Directly relating gas-phase cluster measurements to solution-phase hydrolysis, the absolute standard hydrogen electrode potential, and the absolute proton solvation energy.

PubMed

Donald, William A; Leib, Ryan D; O'Brien, Jeremy T; Williams, Evan R

2009-06-08

Solution-phase, half-cell potentials are measured relative to other half-cell potentials, resulting in a thermochemical ladder that is anchored to the standard hydrogen electrode (SHE), which is assigned an arbitrary value of 0 V. A new method for measuring the absolute SHE potential is demonstrated in which gaseous nanodrops containing divalent alkaline-earth or transition-metal ions are reduced by thermally generated electrons. Energies for the reactions 1) M(H(2)O)(24)(2+)(g) + e(-)(g)-->M(H(2)O)(24)(+)(g) and 2) M(H(2)O)(24)(2+)(g) + e(-)(g)-->MOH(H(2)O)(23)(+)(g) + H(g) and the hydrogen atom affinities of MOH(H(2)O)(23)(+)(g) are obtained from the number of water molecules lost through each pathway. From these measurements on clusters containing nine different metal ions and known thermochemical values that include solution hydrolysis energies, an average absolute SHE potential of +4.29 V vs. e(-)(g) (standard deviation of 0.02 V) and a real proton solvation free energy of -265 kcal mol(-1) are obtained. With this method, the absolute SHE potential can be obtained from a one-electron reduction of nanodrops containing divalent ions that are not observed to undergo one-electron reduction in aqueous solution.

Directly Relating Gas-Phase Cluster Measurements to Solution-Phase Hydrolysis, the Absolute Standard Hydrogen Electrode Potential, and the Absolute Proton Solvation Energy

PubMed Central

Donald, William A.; Leib, Ryan D.; O’Brien, Jeremy T.; Williams, Evan R.

2009-01-01

Solution-phase, half-cell potentials are measured relative to other half-cell potentials, resulting in a thermochemical ladder that is anchored to the standard hydrogen electrode (SHE), which is assigned an arbitrary value of 0 V. A new method for measuring the absolute SHE potential is demonstrated in which gaseous nanodrops containing divalent alkaline-earth or transition-metal ions are reduced by thermally generated electrons. Energies for the reactions 1) M-(H2O)242+(g)+e−(g)→M(H2O)24+(g) and 2) M(H2O)242+(g)+e−(g)→MOH(H2O)23+(g)+H(g) and the hydrogen atom affinities of MOH(H2O)23+(g) are obtained from the number of water molecules lost through each pathway. From these measurements on clusters containing nine different metal ions and known thermochemical values that include solution hydrolysis energies, an average absolute SHE potential of +4.29 V vs. e−(g) (standard deviation of 0.02 V) and a real proton solvation free energy of −265 kcal mol−1 are obtained. With this method, the absolute SHE potential can be obtained from a one-electron reduction of nanodrops containing divalent ions that are not observed to undergo one-electron reduction in aqueous solution. PMID:19440999

Nonadiabatic electron response in the Hasegawa-Wakatani equations

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

Stoltzfus-Dueck, T.; Scott, B. D.; Krommes, J. A.

2013-08-15

Tokamak edge turbulence is strongly influenced by parallel electron physics, which relaxes density and potential fluctuations towards electron adiabatic response. Beginning with the paradigmatic Hasegawa-Wakatani equations (HWEs) for resistive tokamak edge turbulence, a unique decomposition of the electric potential (φ) into adiabatic (a) and nonadiabatic (b) portions is derived, based on the requirement that a neither drive nor respond to the parallel current j{sub ∥}. The form of the decomposition clarifies that, at perpendicular scales large relative to the sound radius, the electron adiabatic response controls the nonzonal φ, not the fluctuating density n. Simple energy balance arguments allow onemore » to rigorously bound the ratio of rms nonzonal nonadiabatic fluctuations (b(tilde sign)) relative to adiabatic ones (ã). The role of the vorticity nonlinearity in transferring energy between adiabatic and nonadiabatic fluctuations aids intuitive understanding of self-sustained turbulence in the HWEs. When the normalized parallel resistivity is weak, b(tilde sign) becomes effectively slaved, allowing the reduction to an approximate one-field model that remains valid for strong turbulence. In addition to guiding physical intuition, the one-field reduction should greatly ease further analytical manipulations. Direct numerical simulation of the 2D HWEs confirms the convergence of the asymptotic formula for b(tilde sign)« less

Acetylacetone as an efficient electron shuttle for concerted redox conversion of arsenite and nitrate in the opposite direction.

PubMed

Chen, Zhihao; Song, Xiaojie; Zhang, Shujuan; Wu, Bingdang; Zhang, Guoyang; Pan, Bingcai

2017-11-01

The redox conversion of arsenite and nitrate has direct effects on their potential environment risks. Due to the similar reduction potentials, there are few technologies that can simultaneously oxidize arsenite and reduce nitrate in one process. Here, we demonstrate that a diketone-mediated photochemical process could efficiently do this. A combined experimental and theoretical investigation was conducted to elucidate the mechanisms behind the redox conversion in the UV/acetylacetone (AA) process. Our key finding is that UV irradiation significantly changed the redox potential of AA. The excited AA, 3 (AA)*, acted as a semiquinone radical-like electron shuttle. For arsenite oxidation, the efficiency of 3 (AA)* was 1-2 orders of magnitude higher than those of quinone-type electron shuttles, whereas the consumption of AA was 2-4 orders of magnitude less than those of benzonquinones. The oxidation of arsenite and reduction of nitrate could be both accelerated when they existed together in UV/AA process. The results indicate that small diketones are some neglected but potent electron shuttles of great application potential in regulating aquatic redox reactions with the combination of UV irradiation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Two-electron Reduction versus One-electron Oxidation of the Type 3 Pair in the Multicopper Oxidases

PubMed Central

Kjaergaard, Christian H.; Jones, Stephen M.; Gounel, Sébastien; Mano, Nicolas; Solomon, Edward I.

2015-01-01

Multicopper Oxidases (MCOs) utilize an electron shuttling Type 1 Cu (T1) site in conjunction with a mononuclear Type 2 (T2) and a binuclear Type 3 (T3) site, arranged in a trinuclear copper cluster (TNC), to reduce O2 to H2O. Reduction of O2 occurs with limited overpotential indicating that all the coppers in the active site can be reduced via high-potential electron donors. Two forms of the resting enzyme have been observed in MCOs: the Alternative Resting form (AR), where only one of the three TNC Cu’s is oxidized, and the Resting Oxidized form (RO), where all three TNC Cu’s are oxidized. In contrast to the AR form, we show that in the RO form of a high-potential MCO, the binuclear T3 Cu(II) site can be reduced via the 700 mV T1 Cu. Systematic spectroscopic evaluation reveals that this proceeds by a two-electron process, where delivery of the first electron, forming a high energy, meta-stable half reduced T3 state, is followed by the rapid delivery of a second energetically favorable electron to fully reduce the T3 site. Alternatively, when this fully reduced binuclear T3 site is oxidized via the T1 Cu, a different thermodynamically favored half oxidized T3 form, i.e. the AR site, is generated. This behavior is evaluated by DFT calculations, which reveal that the protein backbone plays a significant role in controlling the environment of the active site coppers. This allows for the formation of the meta-stable, half reduced state and thus the complete reductive activation of the enzyme for catalysis. PMID:26075678

Electrochemical Behavior of Quinoxalin-2-one Derivatives at Mercury Electrodes and Its Analytical Use

PubMed Central

Zimpl, Milan; Skopalova, Jana; Jirovsky, David; Bartak, Petr; Navratil, Tomas; Sedonikova, Jana; Kotoucek, Milan

2012-01-01

Derivatives of quinoxalin-2-one are interesting compounds with potential pharmacological activity. From this point of view, understanding of their electrochemical behavior is of great importance. In the present paper, a mechanism of electrochemical reduction of quinoxalin-2-one derivatives at mercury dropping electrode was proposed. Pyrazine ring was found to be the main electroactive center undergoing a pH-dependent two-electron reduction process. The molecule protonization of nitrogen in the position 4 precedes the electron acceptance forming a semiquinone radical intermediate which is relatively stable in acidic solutions. Its further reduction is manifested by separated current signal. A positive mesomeric effect of the nonprotonized amino group in the position 7 of the derivative III accelerates the semiquinone reduction yielding a single current wave. The suggested reaction mechanism was verified by means of direct current polarography, differential pulse, cyclic and elimination voltammetry, and coulometry with subsequent GC/MS analysis. The understanding of the mechanism was applied in developing of analytical method for the determination of the studied compounds. PMID:22666117

Humin as an electron donor for enhancement of multiple microbial reduction reactions with different redox potentials in a consortium.

PubMed

Zhang, Dongdong; Zhang, Chunfang; Xiao, Zhixing; Suzuki, Daisuke; Katayama, Arata

2015-02-01

A solid-phase humin, acting as an electron donor, was able to enhance multiple reductive biotransformations, including dechlorination of pentachlorophenol (PCP), dissimilatory reduction of amorphous Fe (III) oxide (FeOOH), and reduction of nitrate, in a consortium. Humin that was chemically reduced by NaBH4 served as an electron donor for these microbial reducing reactions, with electron donating capacities of 0.013 mmol e(-)/g for PCP dechlorination, 0.15 mmol e(-)/g for iron reduction, and 0.30 mmol e(-)/g for nitrate reduction. Two pairs of oxidation and reduction peaks within the humin were detected by cyclic voltammetry analysis. 16S rRNA gene sequencing-based microbial community analysis of the consortium incubated with different terminal electron acceptors, suggested that Dehalobacter sp., Bacteroides sp., and Sulfurospirillum sp. were involved in the PCP dechlorination, dissimilatory iron reduction, and nitrate reduction, respectively. These findings suggested that humin functioned as a versatile redox mediator, donating electrons for multiple respiration reactions with different redox potentials. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Substitution Effects and Linear Free Energy Relationships During Reduction of 4- Benzoyl-n-(4-substituted Benzyl)pyridinium Cations

NASA Technical Reports Server (NTRS)

Leventis, Nicholas; Zhang, Guo-Hui; Rawashdeh, Abdel-Monem M.; Sotiriou-Leventis, Chariklia; Gray, Hugh R. (Technical Monitor)

2003-01-01

In analogy to 4-(para-substituted benzoyl)-N-methylpyridinium cations (1-X's), the title species (2-X's, -X = -OCH3, -CH3, -H, -Br, -COCH3, -NO2) undergo two reversible, well-separated (E(sub 1/2) greater than or equal to 650 mV) one-electron reductions. The effect of substitution on the reduction potentials of 2-X's is much weaker than the effect of the same substituents on 1-X's: the Hammett rho-values are 0.80 and 0.93 for the 1st- and 2nd-e reduction of 2-X's vs. 2.3 and 3.3 for the same reductions of 1-X's, respectively. Importantly, the nitro group of 2-NO2 undergoes reduction before the 2nd-e reduction of the 4-benzoylpyridinium system. These results suggest that the redox potentials of the 4-benzoylpyridinium system can be course-tuned via p-benzoyl substitution and fine-tuned via para-benzyl substitution. Introducing the recently derived substituent constant of the -NO2(sup)- group (sigma para-NO2(sup)- = -0.97) yields an excellent correlation for the 3rd-e reduction of 2- NO2 (corresponding to the reduction of the carbonyl group) with the 2nd-e reduction of the other 2-X's, and confirms the electron donating properties of -NO2(sup)-.

An Electron-bifurcating Caffeyl-CoA Reductase*

PubMed Central

Bertsch, Johannes; Parthasarathy, Anutthaman; Buckel, Wolfgang; Müller, Volker

2013-01-01

A low potential electron carrier ferredoxin (E0′ ≈ −500 mV) is used to fuel the only bioenergetic coupling site, a sodium-motive ferredoxin:NAD+ oxidoreductase (Rnf) in the acetogenic bacterium Acetobacterium woodii. Because ferredoxin reduction with physiological electron donors is highly endergonic, it must be coupled to an exergonic reaction. One candidate is NADH-dependent caffeyl-CoA reduction. We have purified a complex from A. woodii that contains a caffeyl-CoA reductase and an electron transfer flavoprotein. The enzyme contains three subunits encoded by the carCDE genes and is predicted to have, in addition to FAD, two [4Fe-4S] clusters as cofactor, which is consistent with the experimental determination of 4 mol of FAD, 9 mol of iron, and 9 mol of acid-labile sulfur. The enzyme complex catalyzed caffeyl-CoA-dependent oxidation of reduced methyl viologen. With NADH as donor, it catalyzed caffeyl-CoA reduction, but this reaction was highly stimulated by the addition of ferredoxin. Spectroscopic analyses revealed that ferredoxin and caffeyl-CoA were reduced simultaneously, and a stoichiometry of 1.3:1 was determined. Apparently, the caffeyl-CoA reductase-Etf complex of A. woodii uses the novel mechanism of flavin-dependent electron bifurcation to drive the endergonic ferredoxin reduction with NADH as reductant by coupling it to the exergonic NADH-dependent reduction of caffeyl-CoA. PMID:23479729

Reductive electrografting of benzene (p-bisdiazonium hexafluorophosphate): a simple and effective protocol for creating diazonium-functionalized thin films.

PubMed

Marshall, Nicholas; Locklin, Jason

2011-11-01

In this Article, we describe a protocol for surface functionalization of benzenediazonium hexafluorophosphate monolayers by in situ electrochemical reduction of bis(benzenediazonium) hexafluorophosphate. Due to the considerable difference in potential between the first and second reduction of this species, it is possible to form a high density of surface-bound diazonium groups by use of a mild potential which selectively reduces only one diazonium group per ring. The resulting diazonium-containing monolayer reacts readily with solutions of electron-rich aromatic compounds. The reaction with ferrocene produces a dense (2.7 × 10(-10) mol/cm(2)) ferrocene-containing monolayer through a Gomberg-Bachmann type arylation. The resulting ferrocene group exhibits relatively rapid electron transfer to the electrode due to the conjugated linker layer as measured by alternating current voltammetry (ACV) and cyclic voltammetry. Aromatic systems with π-donor substitutents (N,N-dimethylaniline, N,N,N',N'-tetramethyldiaminobenzophenone, and hydroquinone) react through an azo-coupling to form monolayers linked to the surface through an azobenzene moiety. The redox properties of these electron-rich species tethered to the surface were observed and quantified using cyclic voltammetry. This simple and versatile functionalization procedure has a wide variety of potential applications in surface science and materials research.

Effects of Functional Groups in Redox-Active Organic Molecules: A High-Throughput Screening Approach

DOE PAGES

Pelzer, Kenley M.; Cheng, Lei; Curtiss, Larry A.

2016-12-08

Nonaqueous redox flow batteries have attracted recent attention with their potential for high electrochemical storage capacity, with organic electrolytes serving as solvents with a wide electrochemical stability window. Organic molecules can also serve as electroactive species, where molecules with low reduction potentials or high oxidation potentials can provide substantial chemical energy. To identify promising electrolytes in a vast chemical space, high-throughput screening (HTS) of candidate molecules plays an important role, where HTS is used to calculate properties of thousands of molecules and identify a few organic molecules worthy of further attention in battery research. Here, in this work, we presentmore » reduction and oxidation potentials obtained from HTS of 4178 molecules. The molecules are composed of base groups of five- or six-membered rings with one or two functional groups attached, with the set of possible functional groups including both electron-withdrawing and electron-donating groups. In addition to observing the trends in potentials that result from differences in organic base groups and functional groups, we analyze the effects of molecular characteristics such as multiple bonds, Hammett parameters, and functional group position. In conclusion, this work provides useful guidance in determining how the identities of the base groups and functional groups are correlated with desirable reduction and oxidation potentials.« less

Effects of Functional Groups in Redox-Active Organic Molecules: A High-Throughput Screening Approach

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

Pelzer, Kenley M.; Cheng, Lei; Curtiss, Larry A.

Nonaqueous redox flow batteries have attracted recent attention with their potential for high electrochemical storage capacity, with organic electrolytes serving as solvents with a wide electrochemical stability window. Organic molecules can also serve as electroactive species, where molecules with low reduction potentials or high oxidation potentials can provide substantial chemical energy. To identify promising electrolytes in a vast chemical space, high-throughput screening (HTS) of candidate molecules plays an important role, where HTS is used to calculate properties of thousands of molecules and identify a few organic molecules worthy of further attention in battery research. Here, in this work, we presentmore » reduction and oxidation potentials obtained from HTS of 4178 molecules. The molecules are composed of base groups of five- or six-membered rings with one or two functional groups attached, with the set of possible functional groups including both electron-withdrawing and electron-donating groups. In addition to observing the trends in potentials that result from differences in organic base groups and functional groups, we analyze the effects of molecular characteristics such as multiple bonds, Hammett parameters, and functional group position. In conclusion, this work provides useful guidance in determining how the identities of the base groups and functional groups are correlated with desirable reduction and oxidation potentials.« less

Electron-transfer oxidation properties of DNA bases and DNA oligomers.

PubMed

Fukuzumi, Shunichi; Miyao, Hiroshi; Ohkubo, Kei; Suenobu, Tomoyoshi

2005-04-21

Kinetics for the thermal and photoinduced electron-transfer oxidation of a series of DNA bases with various oxidants having the known one-electron reduction potentials (E(red)) in an aqueous solution at 298 K were examined, and the resulting electron-transfer rate constants (k(et)) were evaluated in light of the free energy relationship of electron transfer to determine the one-electron oxidation potentials (E(ox)) of DNA bases and the intrinsic barrier of the electron transfer. Although the E(ox) value of GMP at pH 7 is the lowest (1.07 V vs SCE) among the four DNA bases, the highest E(ox) value (CMP) is only 0.19 V higher than that of GMP. The selective oxidation of GMP in the thermal electron-transfer oxidation of GMP results from a significant decrease in the pH dependent oxidation potential due to the deprotonation of GMP*+. The one-electron reduced species of the photosensitizer produced by photoinduced electron transfer are observed as the transient absorption spectra when the free energy change of electron transfer is negative. The rate constants of electron-transfer oxidation of the guanine moieties in DNA oligomers with Fe(bpy)3(3+) and Ru(bpy)3(3+) were also determined using DNA oligomers containing different guanine (G) sequences from 1 to 10 G. The rate constants of electron-transfer oxidation of the guanine moieties in single- and double-stranded DNA oligomers with Fe(bpy)3(2+) and Ru(bpy)3(3+) are dependent on the number of sequential guanine molecules as well as on pH.

Infrared/visible/ultraviolet spectroscopic detection of one-electron- and two-electron-reduction products of fac-CIR(CO)/sub 3/(4bzpy)/sub 2/ (4bzpy = 4-benzoylpyridine)

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

Shu, C.F.; Wrighton, M.S.

1988-11-16

The results of a spectrochemical investigation of (fac-ClRe(CO)/sub 3/(4bzpy)/sub 2/) (4bzpy = 4-benzoylpyridine) concerning the nature of the products from one- and two-electron reduction of the complex are reported. The ir and uv/visible spectra of the one- and two-electron reduction products are compared. The spectral and electrochemical data obtained are uniformly consistent with the conclusion that the reduced metal complex has the electron(s) localized on the 4bzpy ligand(s). 14 refs., 2 figs., 1 tab.

Investigation of the electronic structure of Be2+He and Be+He, and static dipole polarisabilities of the helium atom

NASA Astrophysics Data System (ADS)

Dhiflaoui, J.; Bejaoui, M.; Farjallah, M.; Berriche, H.

2018-05-01

The potential energy and spectroscopic constants of the ground and many excited states of the Be+He van der Waals system have been investigated using a one-electron pseudo-potential approach, which is used to replace the effect of the Be2+ core and the electron-He interactions by effective potentials. Furthermore, the core-core interactions are incorporated. This permits the reduction of the number of active electrons of the Be+He van der Waals system to only one electron. Therefore, the potential energy of the ground state as well as the excited states is performed at the SCF level and considering the spin-orbit interaction. The core-core interaction for Be2+He ground state is included using accurate CCSD (T) calculations. Then, the spectroscopic properties of the Be+He electronic states are extracted and compared with the previous theoretical and experimental studies. This comparison has shown a very good agreement for the ground and the first excited states. Moreover, the transition dipole moment has been determined for a large and dense grid of internuclear distances including the spin orbit effect. In addition, a vibrational spacing analysis for the Be2+He and Be+He ground states is performed to extract the He atomic polarisability.

Effects of Extrinsic and Intrinsic Proton Activity on The Mechanism of Oxygen Reduction in Ionic Liquids

NASA Astrophysics Data System (ADS)

Zeller, Robert August

Mechanisms for oxygen reduction are proposed for three distinct cases covering two ionic liquids of fundamentally different archetypes and almost thirty orders of magnitude of proton activity. Proton activity is treated both extrinsically by varying the concentration and intrinsically by selecting proton donors with a wide range of aqueous pKa values. The mechanism of oxygen reduction in ionic liquids is introduced by way of the protic ionic liquid (pIL) triethylammonium triflate (TEATf) which shares some similarities with aqueous acid solutions. Oxygen reduction in TEATf begins as the one electron rate limited step to form superoxide, O2 *-, which is then rapidly protonated by the pIL cation forming the perhydroxyl radical, HO2*. The perhydroxyl radical is further reduced to peroxidate (HO2-) and hydrogen peroxide in proportions in accordance with their pKa. The reaction does not proceed beyond this point due to the adsorption of the conjugate base triethylammine interfering with the disproportionation of hydrogen peroxide. This work demonstrates that this mechanism is consistent across Pt, Au, Pd, and Ag electrodes. Two related sets of experiments were performed in the inherently aprotic ionic liquid 1-butyl-2,3-dimethylimidazolium triflate (C4dMImTf). The first involved the titration of acidic species of varying aqueous pKa into the IL while monitoring the extent of oxygen reduction as a function of pKa and potential on Pt and glassy carbon (GC) electrodes. These experiments confirmed the greater propensity of Pt to reduce oxygen by its immediate and abrupt transition from one electron reduction to four electron reduction, while oxygen reduction on GC gradually approaches four electron reduction as the potentials were driven more cathodic. The potential at which oxygen reduction initiates shows general agreement with the Nernst equation and the acid's tabulated aqueous pKa value, however at the extremely acidic end, a small deviation is observed. The second set of experiments in C4dMImTf solicited water as the proton donor for oxygen reduction in an approximation of the aqueous alkaline case. The water content was varied between extremely dry (<0.1 mol% H2O) and saturated (approximately 15.8 mol% H2O). As the water content increased so too did the extent of oxygen reduction eventually approach two electrons on both Pt and GC. However, additional water led to a linear increase in the Tafel slope under enhanced mass transport conditions up to the point of 10 mol% water. This inhibition of oxygen adsorption is the result of the interaction between superoxide and water and more specifically is proposed to be associated with decomposition of theC4dMIm + cation by hydroxide at the elevated temperatures required for the experiment. Oxygen reduction on both Pt and GC follows Nernstian behavior as the water content is increased. Separate mechanisms for oxygen reduction on Pt and GC are proposed based on the nature of the Nernstian response in these systems.

pH-dependent reduction potentials and proton-coupled electron transfer mechanisms in hydrogen-producing nickel molecular electrocatalysts.

PubMed

Horvath, Samantha; Fernandez, Laura E; Appel, Aaron M; Hammes-Schiffer, Sharon

2013-04-01

The nickel-based P2(Ph)N2(Bn) electrocatalysts comprised of a nickel atom and two 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane ligands catalyze H2 production in acetonitrile. Recent electrochemical experiments revealed a linear dependence of the Ni(II/I) reduction potential on pH with a slope of 57 mV/pH unit, implicating a proton-coupled electron transfer (PCET) process with the same number of electrons and protons transferred. The combined theoretical and experimental studies herein provide an explanation for this pH dependence in the context of the overall proposed catalytic mechanism. In the proposed mechanisms, the catalytic cycle begins with a series of intermolecular proton transfers from an acid to the pendant amine ligand and electrochemical electron transfers to the nickel center to produce the doubly protonated Ni(0) species, a precursor to H2 evolution. The calculated Ni(II/I) reduction potentials of the doubly protonated species are in excellent agreement with the experimentally observed reduction potential in the presence of strong acid, suggesting that the catalytically active species leading to the peak observed in these cyclic voltammetry (CV) experiments is doubly protonated. The Ni(I/0) reduction potential was found to be slightly more positive than the Ni(II/I) reduction potential, indicating that the Ni(I/0) reduction occurs spontaneously after the Ni(II/I) reduction, as implied by the experimental observation of a single CV peak. These results suggest that the PCET process observed in the CV experiments is a two-electron/two-proton process corresponding to an initial double protonation followed by two reductions. On the basis of the experimental and theoretical data, the complete thermodynamic scheme and the Pourbaix diagram were generated for this catalyst. The Pourbaix diagram, which identifies the most thermodynamically stable species at each reduction potential and pH value, illustrates that this catalyst undergoes different types of PCET processes for various pH ranges. These thermodynamic insights will aid in the design of more effective molecular catalysts for H2 production.

The reduction potential of nitric oxide (NO) and its importance to NO biochemistry

PubMed Central

Bartberger, Michael D.; Liu, Wei; Ford, Eleonora; Miranda, Katrina M.; Switzer, Christopher; Fukuto, Jon M.; Farmer, Patrick J.; Wink, David A.; Houk, Kendall N.

2002-01-01

A potential of about −0.8 (±0.2) V (at 1 M versus normal hydrogen electrode) for the reduction of nitric oxide (NO) to its one-electron reduced species, nitroxyl anion (3NO−) has been determined by a combination of quantum mechanical calculations, cyclic voltammetry measurements, and chemical reduction experiments. This value is in accord with some, but not the most commonly accepted, previous electrochemical measurements involving NO. Reduction of NO to 1NO− is highly unfavorable, with a predicted reduction potential of about −1.7 (±0.2) V at 1 M versus normal hydrogen electrode. These results represent a substantial revision of the derived and widely cited values of +0.39 V and −0.35 V for the NO/3NO− and NO/1NO− couples, respectively, and provide support for previous measurements obtained by electrochemical and photoelectrochemical means. With such highly negative reduction potentials, NO is inert to reduction compared with physiological events that reduce molecular oxygen to superoxide. From these reduction potentials, the pKa of 3NO− has been reevaluated as 11.6 (±3.4). Thus, nitroxyl exists almost exclusively in its protonated form, HNO, under physiological conditions. The singlet state of nitroxyl anion, 1NO−, is physiologically inaccessible. The significance of these potentials to physiological and pathophysiological processes involving NO and O2 under reductive conditions is discussed. PMID:12177417

Isotopic Probe Illuminates the Role of the Electrode Surface in Proton Coupled Hydride Transfer Electrochemical Reduction of Pyridinium on Pt(111)

DOE PAGES

Zeitler, Elizabeth L.; Ertem, Mehmed Z.; Pander, III, James E.; ...

2015-10-21

A recently proposed mechanism for electrochemical CO 2 reduction on Pt (111) catalyzed by aqueous acidic pyridine solutions suggests that the observed redox potential of ca. -600 mV vs. SCE is due to the one-electron reduction of pyridinium through proton coupled electron transfer (PCET) to form H atoms adsorbed on the Pt surface (H ads). The initial pyridinium reduction was probed isotopically via deuterium substitution. A combined experimental and theoretical analysis found equilibrium isotope effects (EIE) due to deuterium substitution at the acidic pyridinium site. A shift in the cathodic cyclic voltammetric half wave potential of -25 mV was observed,more » consistent with the theoretical prediction of -40 mV based on the recently proposed reaction mechanism where pyridinium is essential to establish a high concentration of Bronsted acid in contact with the substrate CO 2 and with the Pt surface. A prefeature in the cyclic voltammogram was examined under isotopic substitution and indicated an H-ads intermediate in pyridinium reduction. In conclusion, the theoretical prediction and observation of an BM supported the assignment of the cathodic wave to the proposed reduction of pyridinium through PCET forming H ads and eventually H 2 on the Pt surface.« less

Reduction potentials of heterometallic manganese–oxido cubane complexes modulated by redox-inactive metals

PubMed Central

Tsui, Emily Y.; Agapie, Theodor

2013-01-01

Understanding the effect of redox-inactive metals on the properties of biological and heterogeneous water oxidation catalysts is important both fundamentally and for improvement of future catalyst designs. In this work, heterometallic manganese–oxido cubane clusters [MMn3O4] (M = Sr2+, Zn2+, Sc3+, Y3+) structurally relevant to the oxygen-evolving complex (OEC) of photosystem II were prepared and characterized. The reduction potentials of these clusters and other related mixed metal manganese–tetraoxido complexes are correlated with the Lewis acidity of the apical redox-inactive metal in a manner similar to a related series of heterometallic manganese–dioxido clusters. The redox potentials of the [SrMn3O4] and [CaMn3O4] clusters are close, which is consistent with the observation that the OEC is functional only with one of these two metals. Considering our previous studies of [MMn3O2] moieties, the present results with more structurally accurate models of the OEC ([MMn3O4]) suggest a general relationship between the reduction potentials of heterometallic oxido clusters and the Lewis acidities of incorporated cations that applies to diverse structural motifs. These findings support proposals that one function of calcium in the OEC is to modulate the reduction potential of the cluster to allow electron transfer. PMID:23744039

Chromium Isotope Behaviour During Aerobic Microbial Reduction Activities

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Reduction Potentials of [FeFe]-Hydrogenase Accessory Iron-Sulfur Clusters Provide Insights into the Energetics of Proton Reduction Catalysis.

PubMed

Artz, Jacob H; Mulder, David W; Ratzloff, Michael W; Lubner, Carolyn E; Zadvornyy, Oleg A; LeVan, Axl X; Williams, S Garrett; Adams, Michael W W; Jones, Anne K; King, Paul W; Peters, John W

2017-07-19

An [FeFe]-hydrogenase from Clostridium pasteurianum, CpI, is a model system for biological H 2 activation. In addition to the catalytic H-cluster, CpI contains four accessory iron-sulfur [FeS] clusters in a branched series that transfer electrons to and from the active site. In this work, potentiometric titrations have been employed in combination with electron paramagnetic resonance (EPR) spectroscopy at defined electrochemical potentials to gain insights into the role of the accessory clusters in catalysis. EPR spectra collected over a range of potentials were deconvoluted into individual components attributable to the accessory [FeS] clusters and the active site H-cluster, and reduction potentials for each cluster were determined. The data suggest a large degree of magnetic coupling between the clusters. The distal [4Fe-4S] cluster is shown to have a lower reduction potential (∼ < -450 mV) than the other clusters, and molecular docking experiments indicate that the physiological electron donor, ferredoxin (Fd), most favorably interacts with this cluster. The low reduction potential of the distal [4Fe-4S] cluster thermodynamically restricts the Fd ox /Fd red ratio at which CpI can operate, consistent with the role of CpI in recycling Fd red that accumulates during fermentation. Subsequent electron transfer through the additional accessory [FeS] clusters to the H-cluster is thermodynamically favorable.

The Electron Bifurcating FixABCX Protein Complex from Azotobacter vinelandii: Generation of Low-Potential Reducing Equivalents for Nitrogenase Catalysis.

PubMed

Ledbetter, Rhesa N; Garcia Costas, Amaya M; Lubner, Carolyn E; Mulder, David W; Tokmina-Lukaszewska, Monika; Artz, Jacob H; Patterson, Angela; Magnuson, Timothy S; Jay, Zackary J; Duan, H Diessel; Miller, Jacquelyn; Plunkett, Mary H; Hoben, John P; Barney, Brett M; Carlson, Ross P; Miller, Anne-Frances; Bothner, Brian; King, Paul W; Peters, John W; Seefeldt, Lance C

2017-08-15

The biological reduction of dinitrogen (N 2 ) to ammonia (NH 3 ) by nitrogenase is an energetically demanding reaction that requires low-potential electrons and ATP; however, pathways used to deliver the electrons from central metabolism to the reductants of nitrogenase, ferredoxin or flavodoxin, remain unknown for many diazotrophic microbes. The FixABCX protein complex has been proposed to reduce flavodoxin or ferredoxin using NADH as the electron donor in a process known as electron bifurcation. Herein, the FixABCX complex from Azotobacter vinelandii was purified and demonstrated to catalyze an electron bifurcation reaction: oxidation of NADH (E m = -320 mV) coupled to reduction of flavodoxin semiquinone (E m = -460 mV) and reduction of coenzyme Q (E m = 10 mV). Knocking out fix genes rendered Δrnf A. vinelandii cells unable to fix dinitrogen, confirming that the FixABCX system provides another route for delivery of electrons to nitrogenase. Characterization of the purified FixABCX complex revealed the presence of flavin and iron-sulfur cofactors confirmed by native mass spectrometry, electron paramagnetic resonance spectroscopy, and transient absorption spectroscopy. Transient absorption spectroscopy further established the presence of a short-lived flavin semiquinone radical, suggesting that a thermodynamically unstable flavin semiquinone may participate as an intermediate in the transfer of an electron to flavodoxin. A structural model of FixABCX, generated using chemical cross-linking in conjunction with homology modeling, revealed plausible electron transfer pathways to both high- and low-potential acceptors. Overall, this study informs a mechanism for electron bifurcation, offering insight into a unique method for delivery of low-potential electrons required for energy-intensive biochemical conversions.

The Electron Bifurcating FixABCX Protein Complex from Azotobacter vinelandii: Generation of Low-Potential Reducing Equivalents for Nitrogenase Catalysis

DOE PAGES

Ledbetter, Rhesa N.; Garcia Costas, Amaya M.; Lubner, Carolyn E.; ...

2017-07-13

The biological reduction of dinitrogen (N 2) to ammonia (NH 3) by nitrogenase is an energetically demanding reaction that requires low-potential electrons and ATP; however, pathways used to deliver the electrons from central metabolism to the reductants of nitrogenase, ferredoxin or flavodoxin, remain unknown for many diazotrophic microbes. The FixABCX protein complex has been proposed to reduce flavodoxin or ferredoxin using NADH as the electron donor in a process known as electron bifurcation. Herein, the FixABCX complex from Azotobacter vinelandii was purified and demonstrated to catalyze an electron bifurcation reaction: oxidation of NADH (E m = -320 mV) coupled tomore » reduction of flavodoxin semiquinone (E m = -460 mV) and reduction of coenzyme Q (E m = 10 mV). Knocking out fix genes rendered ..delta..rnf A. vinelandii cells unable to fix dinitrogen, confirming that the FixABCX system provides another route for delivery of electrons to nitrogenase. Characterization of the purified FixABCX complex revealed the presence of flavin and iron-sulfur cofactors confirmed by native mass spectrometry, electron paramagnetic resonance spectroscopy, and transient absorption spectroscopy. Transient absorption spectroscopy further established the presence of a short-lived flavin semiquinone radical, suggesting that a thermodynamically unstable flavin semiquinone may participate as an intermediate in the transfer of an electron to flavodoxin. A structural model of FixABCX, generated using chemical cross-linking in conjunction with homology modeling, revealed plausible electron transfer pathways to both high- and low-potential acceptors. Altogether, this study informs a mechanism for electron bifurcation, offering insight into a unique method for delivery of low-potential electrons required for energy-intensive biochemical conversions.« less

On the electron affinity of cytosine in bulk water and at hydrophobic aqueous interfaces.

PubMed

Vöhringer-Martinez, Esteban; Dörner, Ciro; Abel, Bernd

2014-10-01

In the past one possible mechanism of DNA damage in bulk water has been attributed to the presence of hydrated electrons in water. Recently, one important property of hydrated electrons, namely their binding energy, was reported to be smaller at hydrophobic interfaces than in bulk aqueous solution. This possibly opens up new reaction possibilities with different solutes such as the DNA at hydrophobic, aqueous interfaces. Here, we use QM/MM molecular dynamics simulation to study how the molecular environment at the vacuum-water interface and in the bulk alters the electron affinity of cytosine being a characteristic part of the DNA. The electron affinity at the interface is closer to the corresponding binding energy of the partially hydrated electron. The increased energy resonance makes the electron capture process more probable and suggests that hydrated electrons at hydrophobic interfaces may be more reactive than the fully hydrated ones. Additionally, we found that the relaxation of the anionic form after electron attachment also induces a proton transfer from the surrounding solvent that was confirmed by comparison with the experimental reduction potential.

The rise of active-element phased-array radar

NASA Astrophysics Data System (ADS)

Chang, Ike

The War in the Persian Gulf has recently underscored the vast leverage of advanced electronics to U.S. military power. Advanced electronics will likely play an even greater role in the U.S. military in the future. Under declining budgets, the U.S. forces are experiencing drastic reductions in manpower and resources. To offset these reductions, the military has turned to high technology in general as a force multiplier. In terms of projecting air power, a key force multiplier involves the use of electronic sensors for reconnaissance, surveillance, and tracking. One type of sensor for tactical aircraft, fire control radar, has proven to be a crucial element in establishing air superiority over potential adversaries in war. The advantages, history of development, and enabling technologies of a superior and emerging technology for fire control radars are discussed.

Using Hyperfine Electron Paramagnetic Resonance Spectroscopy to Define the Proton-Coupled Electron Transfer Reaction at Fe-S Cluster N2 in Respiratory Complex I.

PubMed

Le Breton, Nolwenn; Wright, John J; Jones, Andrew J Y; Salvadori, Enrico; Bridges, Hannah R; Hirst, Judy; Roessler, Maxie M

2017-11-15

Energy-transducing respiratory complex I (NADH:ubiquinone oxidoreductase) is one of the largest and most complicated enzymes in mammalian cells. Here, we used hyperfine electron paramagnetic resonance (EPR) spectroscopic methods, combined with site-directed mutagenesis, to determine the mechanism of a single proton-coupled electron transfer reaction at one of eight iron-sulfur clusters in complex I, [4Fe-4S] cluster N2. N2 is the terminal cluster of the enzyme's intramolecular electron-transfer chain and the electron donor to ubiquinone. Because of its position and pH-dependent reduction potential, N2 has long been considered a candidate for the elusive "energy-coupling" site in complex I at which energy generated by the redox reaction is used to initiate proton translocation. Here, we used hyperfine sublevel correlation (HYSCORE) spectroscopy, including relaxation-filtered hyperfine and single-matched resonance transfer (SMART) HYSCORE, to detect two weakly coupled exchangeable protons near N2. We assign the larger coupling with A( 1 H) = [-3.0, -3.0, 8.7] MHz to the exchangeable proton of a conserved histidine and conclude that the histidine is hydrogen-bonded to N2, tuning its reduction potential. The histidine protonation state responds to the cluster oxidation state, but the two are not coupled sufficiently strongly to catalyze a stoichiometric and efficient energy transduction reaction. We thus exclude cluster N2, despite its proton-coupled electron transfer chemistry, as the energy-coupling site in complex I. Our work demonstrates the capability of pulse EPR methods for providing detailed information on the properties of individual protons in even the most challenging of energy-converting enzymes.

Redox potential as a master variable controlling pathways of metal reduction by Geobacter sulfurreducens

PubMed Central

Levar, Caleb E; Hoffman, Colleen L; Dunshee, Aubrey J; Toner, Brandy M; Bond, Daniel R

2017-01-01

Geobacter sulfurreducens uses at least two different pathways to transport electrons out of the inner membrane quinone pool before reducing acceptors beyond the outer membrane. When growing on electrodes poised at oxidizing potentials, the CbcL-dependent pathway operates at or below redox potentials of –0.10 V vs the standard hydrogen electrode, whereas the ImcH-dependent pathway operates only above this value. Here, we provide evidence that G. sulfurreducens also requires different electron transfer proteins for reduction of a wide range of Fe(III)- and Mn(IV)-(oxyhydr)oxides, and must transition from a high- to low-potential pathway during reduction of commonly studied soluble and insoluble metal electron acceptors. Freshly precipitated Fe(III)-(oxyhydr)oxides could not be reduced by mutants lacking the high-potential pathway. Aging these minerals by autoclaving did not change their powder X-ray diffraction pattern, but restored reduction by mutants lacking the high-potential pathway. Mutants lacking the low-potential, CbcL-dependent pathway had higher growth yields with both soluble and insoluble Fe(III). Together, these data suggest that the ImcH-dependent pathway exists to harvest additional energy when conditions permit, and CbcL switches on to allow respiration closer to thermodynamic equilibrium conditions. With evidence of multiple pathways within a single organism, the study of extracellular respiration should consider not only the crystal structure or solubility of a mineral electron acceptor, but rather the redox potential, as this variable determines the energetic reward affecting reduction rates, extents, and final microbial growth yields in the environment. PMID:28045456

Designed Proteins as Optimized Oxygen Carriers for Artificial Blood

DTIC Science & Technology

2013-02-01

to the lower energy for electron transfer when coupled to a proton transfer from water (3). Thus we set out to compare the rate of solvent...binding affinities and reduction potentials are the sole result of differences in internal electric fields in these proteins wrought by the surface...serving as the source of potential energy for the hexa- to penta-coordinate conformational change, and one in which the b-position glutamates from

Real-time electron transfer in respiratory complex I

PubMed Central

Verkhovskaya, Marina L.; Belevich, Nikolai; Euro, Liliya; Wikström, Mårten; Verkhovsky, Michael I.

2008-01-01

Electron transfer in complex I from Escherichia coli was investigated by an ultrafast freeze-quench approach. The reaction of complex I with NADH was stopped in the time domain from 90 μs to 8 ms and analyzed by electron paramagnetic resonance (EPR) spectroscopy at low temperatures. The data show that after binding of the first molecule of NADH, two electrons move via the FMN cofactor to the iron–sulfur (Fe/S) centers N1a and N2 with an apparent time constant of ≈90 μs, implying that these two centers should have the highest redox potential in the enzyme. The rate of reduction of center N2 (the last center in the electron transfer sequence) is close to that predicted by electron transfer theory, which argues for the absence of coupled proton transfer or conformational changes during electron transfer from FMN to N2. After fast reduction of N1a and N2, we observe a slow, ≈1-ms component of reduction of other Fe/S clusters. Because all elementary electron transfer rates between clusters are several orders of magnitude higher than this observed rate, we conclude that the millisecond component is limited by a single process corresponding to dissociation of the oxidized NAD+ molecule from its binding site, where it prevents entry of the next NADH molecule. Despite the presence of approximately one ubiquinone per enzyme molecule, no transient semiquinone formation was observed, which has mechanistic implications, suggesting a high thermodynamic barrier for ubiquinone reduction to the semiquinone radical. Possible consequences of these findings for the proton translocation mechanism are discussed. PMID:18316732

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

Tam, Tsz Kin; Chen, Baowei; Lei, Chenghong

NAD/NADH is a coenzyme found in all living cells, carrying electrons from one reaction to another. We report on characterizations of in situ regeneration of NADH via lipoamide dehydrogenase (LD)-catalyzed electron transfer reaction to regenerate NADH using UV-vis spectroelectrochemistry. The Michaelis-Menten constant (Km) and maximum velocity (Vmax) of NADH regeneration were measured as 0.80 {+-} 0.15 mM and 1.91 {+-} 0.09 {micro}M s-1 in a 1-mm thin-layer spectroelectrochemical cell using gold gauze as the working electrode at the applied potential -0.75 V (vs. Ag/AgCl). The electrocatalytic reduction of the NAD system was further coupled with the enzymatic conversion of pyruvatemore » to lactate by lactate dehydrogenase to examine the coenzymatic activity of the regenerated NADH. Although the reproducible electrocatalytic reduction of NAD into NADH is known to be difficult compared to the electrocatalytic oxidation of NADH, our spectroelectrochemical results indicate that the in situ regeneration of NADH via LD-catalyzed electron transfer reaction is fast and sustainable and can be potentially applied to many NAD/NADH-dependent enzyme systems.« less

OXIDATION-REDUCTION POTENTIAL MEASUREMENTS OF IMPORTANT OXIDANTS IN DRINKING WATER

EPA Science Inventory

Oxidation-reduction (redox) reactions are important in drinking water treatment and distribution. Oxidation-reduction potential (ORP) measurements of water reflect the tendency of major constituents in the water to accept or lose electrons. Although ORP measurements are valuable...

Reduction of Flavodoxin by Electron Bifurcation and Sodium Ion-dependent Reoxidation by NAD+ Catalyzed by Ferredoxin-NAD+ Reductase (Rnf)*

PubMed Central

Chowdhury, Nilanjan Pal; Klomann, Katharina; Seubert, Andreas; Buckel, Wolfgang

2016-01-01

Electron-transferring flavoprotein (Etf) and butyryl-CoA dehydrogenase (Bcd) from Acidaminococcus fermentans catalyze the endergonic reduction of ferredoxin by NADH, which is also driven by the concomitant reduction of crotonyl-CoA by NADH, a process called electron bifurcation. Here we show that recombinant flavodoxin from A. fermentans produced in Escherichia coli can replace ferredoxin with almost equal efficiency. After complete reduction of the yellow quinone to the blue semiquinone, a second 1.4 times faster electron transfer affords the colorless hydroquinone. Mediated by a hydrogenase, protons reoxidize the fully reduced flavodoxin or ferredoxin to the semi-reduced species. In this hydrogen-generating system, both electron carriers act catalytically with apparent Km = 0.26 μm ferredoxin or 0.42 μm flavodoxin. Membrane preparations of A. fermentans contain a highly active ferredoxin/flavodoxin-NAD+ reductase (Rnf) that catalyzes the irreversible reduction of flavodoxin by NADH to the blue semiquinone. Using flavodoxin hydroquinone or reduced ferredoxin obtained by electron bifurcation, Rnf can be measured in the forward direction, whereby one NADH is recycled, resulting in the simple equation: crotonyl-CoA + NADH + H+ = butyryl-CoA + NAD+ with Km = 1.4 μm ferredoxin or 2.0 μm flavodoxin. This reaction requires Na+ (Km = 0.12 mm) or Li+ (Km = 0.25 mm) for activity, indicating that Rnf acts as a Na+ pump. The redox potential of the quinone/semiquinone couple of flavodoxin (Fld) is much higher than that of the semiquinone/hydroquinone couple. With free riboflavin, the opposite is the case. Based on this behavior, we refine our previous mechanism of electron bifurcation. PMID:27048649

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

Ledbetter, Rhesa N.; Garcia Costas, Amaya M.; Lubner, Carolyn E.

The biological reduction of dinitrogen (N 2) to ammonia (NH 3) by nitrogenase is an energetically demanding reaction that requires low-potential electrons and ATP; however, pathways used to deliver the electrons from central metabolism to the reductants of nitrogenase, ferredoxin or flavodoxin, remain unknown for many diazotrophic microbes. The FixABCX protein complex has been proposed to reduce flavodoxin or ferredoxin using NADH as the electron donor in a process known as electron bifurcation. Herein, the FixABCX complex from Azotobacter vinelandii was purified and demonstrated to catalyze an electron bifurcation reaction: oxidation of NADH (E m = -320 mV) coupled tomore » reduction of flavodoxin semiquinone (E m = -460 mV) and reduction of coenzyme Q (E m = 10 mV). Knocking out fix genes rendered ..delta..rnf A. vinelandii cells unable to fix dinitrogen, confirming that the FixABCX system provides another route for delivery of electrons to nitrogenase. Characterization of the purified FixABCX complex revealed the presence of flavin and iron-sulfur cofactors confirmed by native mass spectrometry, electron paramagnetic resonance spectroscopy, and transient absorption spectroscopy. Transient absorption spectroscopy further established the presence of a short-lived flavin semiquinone radical, suggesting that a thermodynamically unstable flavin semiquinone may participate as an intermediate in the transfer of an electron to flavodoxin. A structural model of FixABCX, generated using chemical cross-linking in conjunction with homology modeling, revealed plausible electron transfer pathways to both high- and low-potential acceptors. Altogether, this study informs a mechanism for electron bifurcation, offering insight into a unique method for delivery of low-potential electrons required for energy-intensive biochemical conversions.« less

Gemini experiment S026

NASA Technical Reports Server (NTRS)

Medved, D. B.

1971-01-01

The results of the reduction and analysis of data obtained from the S026 experiment from Gemini 10 and 11 flights are presented. The electron and ion sensors were continuously operative throughout both missions from shroud removal (about 6 minutes after Agena liftoff to power-down conditions one week later). Data on ion and electron currents, electron temperature, and vehicle potential were obtained at a sample rate of 32 times per second on positive ions for each of two ion sensors and once every 1.067 seconds for the electron sensor. Only the data reduction of the Gemini plasma wake measurements comprising roughly twenty minutes of data for six maneuvers programed for wake measurements are considered. The intermediate depletion zone, between 1 and 10 vehicle radii downstream from the object, is emphasized. The smallest characteristic radius of interest is 1.34 feet and the largest is 5 feet. This implies a separation span extending from approximately 1.5 feet at the closest approach to at least 50 feet into the far field.

Titanium deposition from ionic liquids - appropriate choice of electrolyte and precursor.

PubMed

Berger, Claudia A; Arkhipova, Maria; Farkas, Attila; Maas, Gerhard; Jacob, Timo

2016-02-14

In this study titanium isopropoxide was dissolved in 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (BMITFSI) and further in a custom-made guanidinium-based ionic liquid (N11N11NpipGuaTFSI). Electrochemical investigations were carried out by means of cyclic voltammetry (CV) and the initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). For BMITFSI we found one large cathodic reduction peak at a potential of -1.2 V vs. Pt, corresponding to the growth of monoatomic high islands. The obtained deposit was identified as elemental titanium by Auger Electron Spectroscopy (AES). Furthermore, we found a corresponding anodic peak at -0.3 V vs. Pt, which is associated with the dissolution of the islands. This observation leads to the assumption that titanium deposition from the imidazolium-based room-temperature ionic liquid (RTIL) proceeds in a one-step electron transfer. In contrast, for the guanidinium-based RTIL we found several peaks during titanium reduction and oxidation, which indicates a multi-step electron transfer in this alternative electrolyte.

Quinone 1 e – and 2 e – /2 H + Reduction Potentials: Identification and Analysis of Deviations from Systematic Scaling Relationships

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

Huynh, Mioy T.; Anson, Colin W.; Cavell, Andrew C.

Quinones participate in diverse electron transfer and proton-coupled electron transfer processes in chemistry and biology. An experimental study of common quinones reveals a non-linear correlation between the 1 e – and 2 e –/2 H + reduction potentials. This unexpected observation prompted a computational study of 128 different quinones, probing their 1 e – reduction potentials, pKa values, and 2 e –/2 H + reduction potentials. The density functional theory calculations reveal an approximately linear correlation between these three properties and an effective Hammett constant associated with the quinone substituent(s). However, deviations from this linear scaling relationship are evident formore » quinones that feature halogen substituents, charged substituents, intramolecular hydrogen bonding in the hydroquinone, and/or sterically bulky substituents. These results, particularly the different substituent effects on the 1 e – versus 2 e – /2 H + reduction potentials, have important implications for designing quinones with tailored redox properties.« less

Reduction Potentials of [FeFe]-Hydrogenase Accessory Iron–Sulfur Clusters Provide Insights into the Energetics of Proton Reduction Catalysis

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

Artz, Jacob H.; Mulder, David W.; Ratzloff, Michael W.

An [FeFe]-hydrogenase from Clostridium pasteurianum, CpI, is a model system for biological H 2 activation. In addition to the catalytic H-cluster, CpI contains four accessory iron-sulfur [FeS] clusters in a branched series that transfer electrons to and from the active site. In this work, potentiometric titrations have been employed in combination with electron paramagnetic resonance (EPR) spectroscopy at defined electrochemical potentials to gain insights into the role of the accessory clusters in catalysis. EPR spectra collected over a range of potentials were deconvoluted into individual components attributable to the accessory [FeS] clusters and the active site H-cluster, and reduction potentialsmore » for each cluster were determined. The data suggest a large degree of magnetic coupling between the clusters. The distal [4Fe-4S] cluster is shown to have a lower reduction potential (~ < -450 mV) than the other clusters, and molecular docking experiments indicate that the physiological electron donor, ferredoxin (Fd), most favorably interacts with this cluster. The low reduction potential of the distal [4Fe-4S] cluster thermodynamically restricts the Fd ox/Fd red ratio at which CpI can operate, consistent with the role of CpI in recycling Fd redthat accumulates during fermentation. In conclusion, subsequent electron transfer through the additional accessory [FeS] clusters to the H-cluster is thermodynamically favorable.« less

Reduction Potentials of [FeFe]-Hydrogenase Accessory Iron–Sulfur Clusters Provide Insights into the Energetics of Proton Reduction Catalysis

DOE PAGES

Artz, Jacob H.; Mulder, David W.; Ratzloff, Michael W.; ...

2017-06-21

An [FeFe]-hydrogenase from Clostridium pasteurianum, CpI, is a model system for biological H 2 activation. In addition to the catalytic H-cluster, CpI contains four accessory iron-sulfur [FeS] clusters in a branched series that transfer electrons to and from the active site. In this work, potentiometric titrations have been employed in combination with electron paramagnetic resonance (EPR) spectroscopy at defined electrochemical potentials to gain insights into the role of the accessory clusters in catalysis. EPR spectra collected over a range of potentials were deconvoluted into individual components attributable to the accessory [FeS] clusters and the active site H-cluster, and reduction potentialsmore » for each cluster were determined. The data suggest a large degree of magnetic coupling between the clusters. The distal [4Fe-4S] cluster is shown to have a lower reduction potential (~ < -450 mV) than the other clusters, and molecular docking experiments indicate that the physiological electron donor, ferredoxin (Fd), most favorably interacts with this cluster. The low reduction potential of the distal [4Fe-4S] cluster thermodynamically restricts the Fd ox/Fd red ratio at which CpI can operate, consistent with the role of CpI in recycling Fd redthat accumulates during fermentation. In conclusion, subsequent electron transfer through the additional accessory [FeS] clusters to the H-cluster is thermodynamically favorable.« less

Density Functional Theory Research into the Reduction Mechanism for the Solvent/Additive in a Sodium-Ion Battery.

PubMed

Liu, Qi; Mu, Daobin; Wu, Borong; Wang, Lei; Gai, Liang; Wu, Feng

2017-02-22

The solid-electrolyte interface (SEI) film in a sodium-ion battery is closely related to capacity fading and cycling stability of the battery. However, there are few studies on the SEI film of sodium-ion batteries and the mechanism of SEI film formation is unclear. The mechanism for the reduction of ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), ethylene sulfite (ES), 1,3-propylene sulfite (PS), and fluorinated ethylene carbonate (FEC) is studied by DFT. The reaction activation energies, Gibbs free energies, enthalpies, and structures of the transition states are calculated. It is indicated that VC, ES, and PS additives in the electrolyte are all easier to form organic components in the anode SEI film by one-electron reduction. The priority of one-electron reduction to produce organic SEI components is in the order of VC>PC>EC; two-electron reduction to produce the inorganic Na 2 CO 3 component is different and follows the order of EC>PC>VC. Two-electron reduction for sulfites ES and PS to form inorganic Na 2 SO 3 is harder than that of carbonate ester reduction. It is also suggested that the one- and two-electron reductive decomposition pathway for FEC is more feasible to produce inorganic NaF components. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Time-resolved generation of membrane potential by ba3 cytochrome c oxidase from Thermus thermophilus coupled to single electron injection into the O and OH states.

PubMed

Siletsky, Sergey A; Belevich, Ilya; Belevich, Nikolai P; Soulimane, Tewfik; Wikström, Mårten

2017-11-01

Two electrogenic phases with characteristic times of ~14μs and ~290μs are resolved in the kinetics of membrane potential generation coupled to single-electron reduction of the oxidized "relaxed" O state of ba 3 oxidase from T. thermophilus (O→E transition). The rapid phase reflects electron redistribution between Cu A and heme b. The slow phase includes electron redistribution from both Cu A and heme b to heme a 3 , and electrogenic proton transfer coupled to reduction of heme a 3 . The distance of proton translocation corresponds to uptake of a proton from the inner water phase into the binuclear center where heme a 3 is reduced, but there is no proton pumping and no reduction of Cu B . Single-electron reduction of the oxidized "unrelaxed" state (O H →E H transition) is accompanied by electrogenic reduction of the heme b/heme a 3 pair by Cu A in a "fast" phase (~22μs) and transfer of protons in "middle" and "slow" electrogenic phases (~0.185ms and ~0.78ms) coupled to electron redistribution from the heme b/heme a 3 pair to the Cu B site. The "middle" and "slow" electrogenic phases seem to be associated with transfer of protons to the proton-loading site (PLS) of the proton pump, but when all injected electrons reach Cu B the electronic charge appears to be compensated by back-leakage of the protons from the PLS into the binuclear site. Thus proton pumping occurs only to the extent of ~0.1 H + /e - , probably due to the formed membrane potential in the experiment. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrochemical evidence that pyranopterin redox chemistry controls the catalysis of YedY, a mononuclear Mo enzyme

PubMed Central

Adamson, Hope; Simonov, Alexandr N.; Kierzek, Michelina; Rothery, Richard A.; Weiner, Joel H.; Bond, Alan M.

2015-01-01

A long-standing contradiction in the field of mononuclear Mo enzyme research is that small-molecule chemistry on active-site mimic compounds predicts ligand participation in the electron transfer reactions, but biochemical measurements only suggest metal-centered catalytic electron transfer. With the simultaneous measurement of substrate turnover and reversible electron transfer that is provided by Fourier-transformed alternating-current voltammetry, we show that Escherichia coli YedY is a mononuclear Mo enzyme that reconciles this conflict. In YedY, addition of three protons and three electrons to the well-characterized “as-isolated” Mo(V) oxidation state is needed to initiate the catalytic reduction of either dimethyl sulfoxide or trimethylamine N-oxide. Based on comparison with earlier studies and our UV-vis redox titration data, we assign the reversible one-proton and one-electron reduction process centered around +174 mV vs. standard hydrogen electrode at pH 7 to a Mo(V)-to-Mo(IV) conversion but ascribe the two-proton and two-electron transition occurring at negative potential to the organic pyranopterin ligand system. We predict that a dihydro-to-tetrahydro transition is needed to generate the catalytically active state of the enzyme. This is a previously unidentified mechanism, suggested by the structural simplicity of YedY, a protein in which Mo is the only metal site. PMID:26561582

Medium Effects are as Important as Catalyst Design for Selectivity in Electrocatalytic Oxygen Reduction by Iron-porphyrin Complexes

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

Rigsby, Matthew L.; Wasylenko, Derek J.; Pegis, Michael L.

2015-04-08

Several substituted iron porphyrin com-plexes were evaluated for oxygen reduction reaction (ORR) electrocatalysis in different homogeneous and heterogeneous media. The selectivity for 4-electron re-duction to H2O vs. 2-electron reduction to H2O2 varies substantially from one medium to another for a given catalyst. In many cases, the influence of the medium in which the catalyst is evaluated has a larger effect on the observed selectivity than the factors attributable to chemical modification of the catalyst. For instance, introduction of potential proton relays has variable effects depending on the catalyst medium. Thus, comparisons of ORR selectivity results need to be interpreted withmore » caution, as the catalysis is a property not just of the catalyst, but also of the larger mesoscale environment be-yond the catalyst. Still, in all the direct pairwise comparisons in the same medium, the catalysts with potential proton relays have similar or better selectivity for the preferred 4e– path. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.« less

Physiological and hydrological controls on mineral redox cycling by long-range electron transport by bacteria in anaerobic sediments

NASA Astrophysics Data System (ADS)

Michelson, K.; Werth, C. J.; Sanford, R. A.; Valocchi, A. J.

2016-12-01

The cycling of iron and manganese oxides plays a critical role in the bioavailability of trace elements and macronutrients, the flux of carbon across terrestrial and atmospheric ecosystems, and the remediation of groundwater contaminated by toxic metals and radionuclides. Bacteria control one half of the redox cycle as the primary drivers of iron and manganese reduction in anaerobic soils and sediments. However, Fe(III) and Mn(IV) are almost exclusively present under anaerobic conditions as insoluble oxides, the reduction of which are facilitated by extracellular electron transport via conductive `nanowires', electron shuttling, and direct contact with outer membrane cytochromes. Our research focus is on the relative contribution of nanowires and electron shuttles under different physiological and hydrological conditions, which remains unexplored. We present a novel microfluidic platform that allows us to directly observe these phenomena under a controlled environment representative of groundwater conditions, monitor the metabolic activity and redox state of bacteria, and determine the presence of reduced products in-situ using Raman spectroscopy. Using Geobacter sulfurreducens and Shewanella oneidensis as model metal-reducing bacteria, and insoluble manganese dioxide (i.e. birnessite) as an electron acceptor, we show that 1) electron shuttling is more effective under static conditions 2) the presence of exogenous shuttles allows efficient electron transport under all flow regimes 3) redox potential of the bulk medium exerts significant control over reduction by both nanowires and electron shuttles 4) shuttling is amplified by orders of magnitude in nanopores.

Catalytic reduction of O2 by cytochrome C using a synthetic model of cytochrome C oxidase.

PubMed

Collman, James P; Ghosh, Somdatta; Dey, Abhishek; Decréau, Richard A; Yang, Ying

2009-04-15

Cytochrome c oxidase (CcO) catalyzes the four-electron reduction of oxygen to water, the one-electron reductant Cytochrome c (Cytc) being the source of electrons. Recently we reported a functional model of CcO that electrochemically catalyzes the four-electron reduction of O(2) to H(2)O (Collman et al. Science 2007, 315, 1565). The current paper shows that the same functional CcO model catalyzes the four-electron reduction of O(2) using the actual biological reductant Cytc in a homogeneous solution. Both single and steady-state turnover kinetics studies indicate that O(2) binding is rate-determining and that O-O bond cleavage and electron transfer from reduced Cytc to the oxidized model complex are relatively fast.

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

PubMed

Zhang, Peng; Yuly, Jonathon L; Lubner, Carolyn E; Mulder, David W; King, Paul W; Peters, John W; Beratan, David N

2017-09-19

How can proteins drive two electrons from a redox active donor onto two acceptors at very different potentials and distances? And how can this transaction be conducted without dissipating very much energy or violating the laws of thermodynamics? Nature appears to have addressed these challenges by coupling thermodynamically uphill and downhill electron transfer reactions, using two-electron donor cofactors that have very different potentials for the removal of the first and second electron. Although electron bifurcation is carried out with near perfection from the standpoint of energy conservation and electron delivery yields, it is a biological energy transduction paradigm that has only come into focus recently. This Account provides an exegesis of the biophysical principles that underpin electron bifurcation. Remarkably, bifurcating electron transfer (ET) proteins typically send one electron uphill and one electron downhill by similar energies, such that the overall reaction is spontaneous, but not profligate. Electron bifurcation in the NADH-dependent reduced ferredoxin: NADP + oxidoreductase I (Nfn) is explored in detail here. Recent experimental progress in understanding the structure and function of Nfn allows us to dissect its workings in the framework of modern ET theory. The first electron that leaves the two-electron donor flavin (L-FAD) executes a positive free energy "uphill" reaction, and the departure of this electron switches on a second thermodynamically spontaneous ET reaction from the flavin along a second pathway that moves electrons in the opposite direction and at a very different potential. The singly reduced ET products formed from the bifurcating flavin are more than two nanometers distant from each other. In Nfn, the second electron to leave the flavin is much more reducing than the first: the potentials are said to be "crossed." The eventually reduced cofactors, NADH and ferredoxin in the case of Nfn, perform crucial downstream redox processes of their own. We dissect the thermodynamics and kinetics of electron bifurcation in Nfn and find that the key features of electron bifurcation are (1) spatially separated transfer pathways that diverge from a two-electron donor, (2) one thermodynamically uphill and one downhill redox pathway, with a large negative shift in the donor's reduction potential after departure of the first electron, and (3) electron tunneling and activation factors that enable bifurcation, producing a 1:1 partitioning of electrons onto the two pathways. Electron bifurcation is found in the CO 2 reducing pathways of methanogenic archaea, in the hydrogen pathways of hydrogenases, in the nitrogen fixing pathway of Fix, and in the mitochondrial charge transfer chain of complex III, cytochrome bc 1 . While crossed potentials may offer the biological advantage of producing tightly regulated high energy reactive species, neither kinetic nor thermodynamic considerations mandate crossed potentials to generate successful electron bifurcation. Taken together, the theoretical framework established here, focusing on the underpinning electron tunneling barriers and activation free energies, explains the logic of electron bifurcation that enables energy conversion and conservation in Nfn, points toward bioinspired schemes to execute multielectron redox chemistry, and establishes a roadmap for examining novel electron bifurcation networks in nature.

Development of Field Guidance for Assessing Feasibility of Intrinsic Bioremediation to Restore Petroleum-Contaminated Soils

DTIC Science & Technology

1994-09-01

Biodegradation, whether aerobic or anaerobic. is an oxidation-reduction or redox reaction . Microbes utilize the redox energy potential from the... redox reaction of organic contaminants and electron acceptors resulting in products such as carbon dioxide and water. According to the figure shown...electron acceptors in the intrinsic bioremediation oxidation/reduction reactions . Redox potentials are from Stumm and Morgan as reported by Bouwer

Detailed electrochemical studies of the tetraruthenium polyoxometalate water oxidation catalyst in acidic media: identification of an extended oxidation series using Fourier transformed alternating current voltammetry.

PubMed

Lee, Chong-Yong; Guo, Si-Xuan; Murphy, Aidan F; McCormac, Timothy; Zhang, Jie; Bond, Alan M; Zhu, Guibo; Hill, Craig L; Geletii, Yurii V

2012-11-05

The electrochemistry of the water oxidation catalyst, Rb(8)K(2)[{Ru(4)O(4)(OH)(2)(H(2)O)(4)}(γ-SiW(10)O(36))(2)] (Rb(8)K(2)-1(0)) has been studied in the presence and absence of potassium cations in both hydrochloric and sulfuric acid solutions by transient direct current (dc) cyclic voltammetry, a steady state dc method in the rotating disk configuration and the kinetically sensitive technique of Fourier transformed large-amplitude alternating current (ac) voltammetry. In acidic media, the presence of potassium ions affects the kinetics (apparent rate of electron transfer) and thermodynamics (reversible potentials) of the eight processes (A'/A to H/H') that are readily detected under dc voltammetric conditions. The six most positive processes (A'/A to F/F'), each involve a one electron ruthenium based charge transfer step (A'/A, B'/B are Ru(IV/V) oxidation and C/C' to F/F' are Ru(IV/III) reduction). The apparent rate of electron transfer of the ruthenium centers in sulfuric acid is higher than in hydrochloric acid. The addition of potassium cations increases the apparent rates and gives rise to a small shift of reversible potential. Simulations of the Fourier transformed ac voltammetry method show that the B'/B, E/E', and F/F' processes are quasi-reversible, while the others are close to reversible. A third Ru(IV/V) oxidation process is observed just prior to the positive potential limit via dc methods. Importantly, the ability of the higher harmonic components of the ac method to discriminate against the irreversible background solvent process allows this (process I) as well as an additional fourth reversible ruthenium based process (J) to be readily identified. The steady-state rotating disk electrode (RDE) method confirmed that all four Ru-centers in Rb(8)K(2)-1(0) are in oxidation state IV. The dc and ac data indicate that reversible potentials of the four ruthenium centers are evenly spaced, which may be relevant to understanding of the water oxidation electrocatalysis. A profound effect of the potassium cation is observed for the one-electron transfer process (G/G') assigned to Ru(III/II) reduction and the multiple electron transfer reduction process (H/H') that arise from the tungstate polyoxometalate framework. A significant shift of E°' to a more positive potential value for process H/H' was observed on removal of K(+) (~100 mV in H(2)SO(4) and ~50 mV in HCl).

Self-Consistent Theory of Shot Noise Suppression in Ballistic Conductors

NASA Astrophysics Data System (ADS)

Bulashenko, O. M.; Rubí, J. M.; Kochelap, V. A.

Shot-noise measurements become a fundamental tool to probe carrier interactions in mesoscopic systems [1]. A matter of particular interest is the significance of Coulomb interaction which may keep nearby electrons more regularly spaced rather than strictly at random and lead to the noise reduction. That effect occurs in different physical situations. Among them are charge-limited ballistic transport, resonant tunneling, single-electron tunneling, etc. In this communication we address the problem of Coulomb correlations in ballistic conductors under the space-charge-limited transport conditions, and present for the first time a semiclassical self-consistent theory of shot noise in these conductors by solving analytically the kinetic equation coupled self-consistently with a Poisson equation. Basing upon this theory, exact results for current noise in a two-terminal ballistic conductor under the action of long-range Coulomb correlations has been derived. The noise reduction factor (in respect to the uncorrelated value) is obtained in a closed analytical form for a full range of biases ranging from thermal to shot-noise limits which describe perfectly the results of the Monte Carlo simulations for a nondegenerate electron gas [2]. The magnitude of the noise reduction exceeds 0.01, which is of interest from the point of view of possible applications. Using these analytical results one may estimate a relative contribution to the noise from different groups of carriers (in energy space and/or real space) and to investigate in great detail the correlations between different groups of carriers. This leads us to suggest an electron energy spectroscopy experiment to probe the Coulomb correlations in ballistic conductors. Indeed, while the injected carriers are uncorrelated, those in the volume of the conductor are strongly correlated, as follows from the derived formulas for the fluctuation of the distribution function. Those correlations may be observed experimentally by making use of a combination of two already realized techniques: a hot-electron spectrometer [3,4] which allows one to analyze different energy groups of electrons collected at the contact and shot-noise measurements [5,6]. Such "shot noise reduction spectroscopy" allows one to measure the novel phenomena. In particular, we predict the (anti)correlation of the "tangent" electrons having the energy close to the potential barrier height, to all other electron energy groups collected at the receiving contact.

Redox properties of structural Fe in clay minerals. 2. Electrochemical and spectroscopic characterization of electron transfer irreversibility in ferruginous smectite, SWa-1.

PubMed

Gorski, Christopher A; Klüpfel, Laura; Voegelin, Andreas; Sander, Michael; Hofstetter, Thomas B

2012-09-04

Structural Fe in clay minerals is an important, albeit poorly characterized, redox-active phase found in many natural and engineered environments. This work develops an experimental approach to directly assess the redox properties of a natural Fe-bearing smectite (ferruginous smectite, SWa-1, 12.6 wt % Fe) with mediated electrochemical reduction (MER) and oxidation (MEO). By utilizing a suite of one-electron-transfer mediating compounds to facilitate electron transfer between structural Fe in SWa-1 and a working electrode, we show that the Fe2+/Fe3+ couple in SWa-1 is redox-active over a large range of potentials (from E(H) = -0.63 V to +0.61 V vs SHE). Electrochemical and spectroscopic analyses of SWa-1 samples that were subject to reduction and re-oxidation cycling revealed both reversible and irreversible structural Fe rearrangements that altered the observed apparent standard reduction potential (E(H)(ø)) of structural Fe. E(H)(ø)-values vary by as much as 0.56 V between SWa-1 samples with different redox histories. The wide range of E(H)-values over which SWa-1 is redox-active and redox history-dependent E(H)(ø)-values underscore the importance of Fe-bearing clay minerals as redox-active phases in a wide range of redox regimes.

The iron-sulfur cluster of electron transfer flavoprotein-ubiquinone oxidoreductase is the electron acceptor for electron transfer flavoprotein.

PubMed

Swanson, Michael A; Usselman, Robert J; Frerman, Frank E; Eaton, Gareth R; Eaton, Sandra S

2008-08-26

Electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) accepts electrons from electron transfer flavoprotein (ETF) and reduces ubiquinone from the ubiquinone pool. It contains one [4Fe-4S] (2+,1+) and one FAD, which are diamagnetic in the isolated oxidized enzyme and can be reduced to paramagnetic forms by enzymatic donors or dithionite. In the porcine protein, threonine 367 is hydrogen bonded to N1 and O2 of the flavin ring of the FAD. The analogous site in Rhodobacter sphaeroides ETF-QO is asparagine 338. Mutations N338T and N338A were introduced into the R. sphaeroides protein by site-directed mutagenesis to determine the impact of hydrogen bonding at this site on redox potentials and activity. The mutations did not alter the optical spectra, EPR g-values, spin-lattice relaxation rates, or the [4Fe-4S] (2+,1+) to FAD point-dipole interspin distances. The mutations had no impact on the reduction potential for the iron-sulfur cluster, which was monitored by changes in the continuous wave EPR signals of the [4Fe-4S] (+) at 15 K. For the FAD semiquinone, significantly different potentials were obtained by monitoring the titration at 100 or 293 K. Based on spectra at 293 K the N338T mutation shifted the first and second midpoint potentials for the FAD from +47 and -30 mV for wild type to -11 and -19 mV, respectively. The N338A mutation decreased the potentials to -37 and -49 mV. Lowering the midpoint potentials resulted in a decrease in the quinone reductase activity and negligible impact on disproportionation of ETF 1e (-) catalyzed by ETF-QO. These observations indicate that the FAD is involved in electron transfer to ubiquinone but not in electron transfer from ETF to ETF-QO. Therefore, the iron-sulfur cluster is the immediate acceptor from ETF.

The Iron-Sulfur Cluster of Electron Transfer Flavoprotein-Ubiquinone Oxidoreductase Is the Electron Acceptor for Electron Transfer Flavoprotein†

PubMed Central

Swanson, Michael A.; Usselman, Robert J.; Frerman, Frank E.; Eaton, Gareth R.; Eaton, Sandra S.

2009-01-01

Electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) accepts electrons from electron transfer flavoprotein (ETF) and reduces ubiquinone from the ubiquinone pool. It contains one [4Fe-4S]2+,1+ and one FAD, which are diamagnetic in the isolated oxidized enzyme and can be reduced to paramagnetic forms by enzymatic donors or dithionite. In the porcine protein, threonine 367 is hydrogen bonded to N1 and O2 of the flavin ring of the FAD. The analogous site in Rhodobacter sphaeroides ETF-QO is asparagine 338. Mutations N338T and N338A were introduced into the R. sphaeroides protein by site-directed mutagenesis to determine the impact of hydrogen bonding at this site on redox potentials and activity. The mutations did not alter the optical spectra, EPR g-values, spin-lattice relaxation rates, or the [4Fe-4S]2+,1+ to FAD point-dipole interspin distances. The mutations had no impact on the reduction potential for the iron-sulfur cluster, which was monitored by changes in the continuous wave EPR signals of the [4Fe-4S]+ at 15 K. For the FAD semiquinone, significantly different potentials were obtained by monitoring the titration at 100 or 293 K. Based on spectra at 293 K the N338T mutation shifted the first and second midpoint potentials for the FAD from +47 and -30 mV for wild type to -11 and -19 mV, respectively. The N338A mutation decreased the potentials to -37 and -49 mV. Lowering the midpoint potentials resulted in a decrease in the quinone reductase activity and negligible impact on disproportionation of ETF1e- catalyzed by ETF-QO. These observations indicate that the FAD is involved in electron transfer to ubiquinone but not in electron transfer from ETF to ETF-QO. Therefore, the iron-sulfur cluster is the immediate acceptor from ETF. PMID:9585549

Studies on the mechanism of electron bifurcation catalyzed by electron transferring flavoprotein (Etf) and butyryl-CoA dehydrogenase (Bcd) of Acidaminococcus fermentans.

PubMed

Chowdhury, Nilanjan Pal; Mowafy, Amr M; Demmer, Julius K; Upadhyay, Vikrant; Koelzer, Sebastian; Jayamani, Elamparithi; Kahnt, Joerg; Hornung, Marco; Demmer, Ulrike; Ermler, Ulrich; Buckel, Wolfgang

2014-02-21

Electron bifurcation is a fundamental strategy of energy coupling originally discovered in the Q-cycle of many organisms. Recently a flavin-based electron bifurcation has been detected in anaerobes, first in clostridia and later in acetogens and methanogens. It enables anaerobic bacteria and archaea to reduce the low-potential [4Fe-4S] clusters of ferredoxin, which increases the efficiency of the substrate level and electron transport phosphorylations. Here we characterize the bifurcating electron transferring flavoprotein (EtfAf) and butyryl-CoA dehydrogenase (BcdAf) of Acidaminococcus fermentans, which couple the exergonic reduction of crotonyl-CoA to butyryl-CoA to the endergonic reduction of ferredoxin both with NADH. EtfAf contains one FAD (α-FAD) in subunit α and a second FAD (β-FAD) in subunit β. The distance between the two isoalloxazine rings is 18 Å. The EtfAf-NAD(+) complex structure revealed β-FAD as acceptor of the hydride of NADH. The formed β-FADH(-) is considered as the bifurcating electron donor. As a result of a domain movement, α-FAD is able to approach β-FADH(-) by about 4 Å and to take up one electron yielding a stable anionic semiquinone, α-FAD, which donates this electron further to Dh-FAD of BcdAf after a second domain movement. The remaining non-stabilized neutral semiquinone, β-FADH(•), immediately reduces ferredoxin. Repetition of this process affords a second reduced ferredoxin and Dh-FADH(-) that converts crotonyl-CoA to butyryl-CoA.

Studies on the Mechanism of Electron Bifurcation Catalyzed by Electron Transferring Flavoprotein (Etf) and Butyryl-CoA Dehydrogenase (Bcd) of Acidaminococcus fermentans*

PubMed Central

Chowdhury, Nilanjan Pal; Mowafy, Amr M.; Demmer, Julius K.; Upadhyay, Vikrant; Koelzer, Sebastian; Jayamani, Elamparithi; Kahnt, Joerg; Hornung, Marco; Demmer, Ulrike; Ermler, Ulrich; Buckel, Wolfgang

2014-01-01

Electron bifurcation is a fundamental strategy of energy coupling originally discovered in the Q-cycle of many organisms. Recently a flavin-based electron bifurcation has been detected in anaerobes, first in clostridia and later in acetogens and methanogens. It enables anaerobic bacteria and archaea to reduce the low-potential [4Fe-4S] clusters of ferredoxin, which increases the efficiency of the substrate level and electron transport phosphorylations. Here we characterize the bifurcating electron transferring flavoprotein (EtfAf) and butyryl-CoA dehydrogenase (BcdAf) of Acidaminococcus fermentans, which couple the exergonic reduction of crotonyl-CoA to butyryl-CoA to the endergonic reduction of ferredoxin both with NADH. EtfAf contains one FAD (α-FAD) in subunit α and a second FAD (β-FAD) in subunit β. The distance between the two isoalloxazine rings is 18 Å. The EtfAf-NAD+ complex structure revealed β-FAD as acceptor of the hydride of NADH. The formed β-FADH− is considered as the bifurcating electron donor. As a result of a domain movement, α-FAD is able to approach β-FADH− by about 4 Å and to take up one electron yielding a stable anionic semiquinone, α-FAD⨪, which donates this electron further to Dh-FAD of BcdAf after a second domain movement. The remaining non-stabilized neutral semiquinone, β-FADH•, immediately reduces ferredoxin. Repetition of this process affords a second reduced ferredoxin and Dh-FADH− that converts crotonyl-CoA to butyryl-CoA. PMID:24379410

Reduction of low potential electron acceptors requires the CbcL inner membrane cytochrome of Geobacter sulfurreducens

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

Zacharoff, Lori; Chan, Chi Ho; Bond, Daniel R.

2015-09-05

The respiration of metals by the bacterium Geobacter sulfurreducens requires electrons generated by metabolism to pass from the interior of the cell to electron acceptors beyond the cell membranes. The G. sulfurreducens inner membrane multiheme c-type cytochrome ImcH is required for respiration to extracellular electron acceptors with redox potentials greater than - 0.1 V vs. SHE, but ImcH is not essential for electron transfer to lower potential acceptors. In contrast, deletion of cbcL, encoding an inner membrane protein consisting of b-type and multiheme c-type cytochrome domains, severely affected reduction of low potential electron acceptors such as Fe(III)-oxides and electrodes poisedmore » at - 0.1 V vs. SHE. Catalytic cyclic voltammetry of a ΔcbcL strain growing on poised electrodes revealed a 50 mV positive shift in driving force required for electron transfer out of the cell. In non-catalytic conditions, low-potential peaks present in wild type biofilms were absent in ΔcbcL mutants. Expression of cbcL in trans increased growth at low redox potential and restored features to cyclic voltammetry. This evidence supports a model where CbcL is a component of a second electron transfer pathway out of the G. sulfurreducens inner membrane that dominates when redox potential is at or below - 0.1 V vs. SHE.« less

Reduction of low potential electron acceptors requires the CbcL inner membrane cytochrome of Geobacter sulfurreducens.

PubMed

Zacharoff, Lori; Chan, Chi Ho; Bond, Daniel R

2016-02-01

The respiration of metals by the bacterium Geobacter sulfurreducens requires electrons generated by metabolism to pass from the interior of the cell to electron acceptors beyond the cell membranes. The G. sulfurreducens inner membrane multiheme c-type cytochrome ImcH is required for respiration to extracellular electron acceptors with redox potentials greater than -0.1 V vs. SHE, but ImcH is not essential for electron transfer to lower potential acceptors. In contrast, deletion of cbcL, encoding an inner membrane protein consisting of b-type and multiheme c-type cytochrome domains, severely affected reduction of low potential electron acceptors such as Fe(III)-oxides and electrodes poised at -0.1 V vs. SHE. Catalytic cyclic voltammetry of a ΔcbcL strain growing on poised electrodes revealed a 50 mV positive shift in driving force required for electron transfer out of the cell. In non-catalytic conditions, low-potential peaks present in wild type biofilms were absent in ∆cbcL mutants. Expression of cbcL in trans increased growth at low redox potential and restored features to cyclic voltammetry. This evidence supports a model where CbcL is a component of a second electron transfer pathway out of the G. sulfurreducens inner membrane that dominates when redox potential is at or below -0.1 V vs. SHE. Copyright © 2015. Published by Elsevier B.V.

INHIBITION OF REDUCTIVE DECHLORINATION BY SULFATE REDUCTION IN MICROCOSMS (ABSTRACT ONLY)

EPA Science Inventory

High sulfate (>1,000 mg/L) concentrations are potentially problematic for field implementation of in situ bioremediation of chlorinated ethenes because its reduction competes for electron donor with reductive dechlorination. As a result of this competition, reductive dechl...

Biological Redox Cycling Of Iron In Nontronite And Its Potential Application In Nitrate Removal

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

Zhao, Linduo; Dong, Hailiang; Kukkadapu, Ravi K.

2015-05-05

Redox cycling of structural Fe in phyllosilicates provides a potential method to remediate nitrate contamination in natural environment. Past research has only studied chemical redox cycles or a single biologically mediated redox cycle of Fe in phyllosilicates. The objective of this research was to study three microbially driven redox cycles of Fe in one phyllosilicate, nontronite (NAu-2). During the reduction phase structural Fe(III) in NAu-2 served as electron acceptor, lactate as electron donor, AQDS as electron shuttle, and dissimilatory Fe(III)-reducing bacteria Shewanella putrefaciens CN32 as mediator in bicarbonate-buffered and PIPES-buffered media. During the oxidation phase, biogenic Fe(II) served an electronmore » donor, nitrate as electron acceptor, and nitrate-dependent Fe(II)-oxidizing bacteria Pseudogulbenkiania sp. strain 2002 as mediator in the same media. For all three cycles, structural Fe in NAu-2 was able to reversibly undergo 3 redox cycles without significant reductive or oxidative dissolution. X-ray diffraction and scanning and transmission electron microscopy revealed that NAu-2 was the dominant residual mineral throughout the 3 redox cycles with some dissolution textures but no significant secondary mineralization. Mössbauer spectroscopy revealed that Fe(II) in bio-reduced samples likely occurred in two distinct environments, at edges and the interior of the NAu-2 structure. Nitrate was completely reduced to nitrogen gas under both buffer conditions and this extent and rate did not change with Fe redox cycles. Mössbauer spectroscopy further revealed that nitrate reduction was coupled to predominant/preferred oxidation of edge Fe(II). These results suggest that structural Fe in phyllosilicates may represent a renewable source to continuously remove nitrate in natural environments.« less

[Vitamin K3-induced activation of molecular oxygen in glioma cells].

PubMed

Krylova, N G; Kulagova, T A; Semenkova, G N; Cherenkevich, S N

2009-01-01

It has been shown by the method of fluorescent analysis that the rate of hydrogen peroxide generation in human U251 glioma cells under the effect of lipophilic (menadione) or hydrophilic (vikasol) analogues of vitamin K3 was different. Analyzing experimental data we can conclude that menadione underwent one- and two-electron reduction by intracellular reductases in glioma cells. Reduced forms of menadione interact with molecular oxygen leading to reactive oxygen species (ROS) generation. The theoretical model of ROS generation including two competitive processes of one- and two-electron reduction of menadione has been proposed. Rate constants of ROS generation mediated by one-electron reduction process have been estimated.

Two-dimensional collective electron magnetotransport, oscillations, and chaos in a semiconductor superlattice

NASA Astrophysics Data System (ADS)

Bonilla, L. L.; Carretero, M.; Segura, A.

2017-12-01

When quantized, traces of classically chaotic single-particle systems include eigenvalue statistics and scars in eigenfuntions. Since 2001, many theoretical and experimental works have argued that classically chaotic single-electron dynamics influences and controls collective electron transport. For transport in semiconductor superlattices under tilted magnetic and electric fields, these theories rely on a reduction to a one-dimensional self-consistent drift model. A two-dimensional theory based on self-consistent Boltzmann transport does not support that single-electron chaos influences collective transport. This theory agrees with existing experimental evidence of current self-oscillations, predicts spontaneous collective chaos via a period doubling scenario, and could be tested unambiguously by measuring the electric potential inside the superlattice under a tilted magnetic field.

Two-dimensional collective electron magnetotransport, oscillations, and chaos in a semiconductor superlattice.

PubMed

Bonilla, L L; Carretero, M; Segura, A

2017-12-01

When quantized, traces of classically chaotic single-particle systems include eigenvalue statistics and scars in eigenfuntions. Since 2001, many theoretical and experimental works have argued that classically chaotic single-electron dynamics influences and controls collective electron transport. For transport in semiconductor superlattices under tilted magnetic and electric fields, these theories rely on a reduction to a one-dimensional self-consistent drift model. A two-dimensional theory based on self-consistent Boltzmann transport does not support that single-electron chaos influences collective transport. This theory agrees with existing experimental evidence of current self-oscillations, predicts spontaneous collective chaos via a period doubling scenario, and could be tested unambiguously by measuring the electric potential inside the superlattice under a tilted magnetic field.

Characterization of the biochemical-pathway of uranium (VI) reduction in facultative anaerobic bacteria.

PubMed

Mtimunye, Phalazane J; Chirwa, Evans M N

2014-10-01

Cultures of U(VI) reducing bacteria sourced from abandoned uranium mine tailing dam were evaluated for their ability to reduce U(VI) to U(IV). The species in the cultures reduced U(VI) in solutions with initial U(VI) concentration up to 400mgL(-)(1) under a near neutral pH of 6.5. The electron flow pathway and fate of reduced species was also analysed in the individual species in order to evaluate the potential for control and optimisation of the reduction potential at the biochemical level. The results showed that U(VI) reduction in live cells was completely blocked by the NADH-dehydrogenase inhibitor, rotenone (C23H22O6), and thioredoxin inhibitor, cadmium chloride (CdCl2), showing that U(VI) reduction involves the electron flow through NADH-dehydrogenase, a primary electron donor to the electron transport respiratory (ETR) system. Mass balance analysis of uranium species aided by visual and electron microscopy suggest that most U(VI) reduction occurred on the cell surface of the isolated species. This finding indicates the possibility of easy uranium recovery for beneficial use through biological remediation. Should the U(VI) be reduced inside the cell, recovery would require complete disruption of the cells and therefore would be difficult. The study contributes new knowledge on the underlying mechanisms in the U(VI) reduction in facultative anaerobes. Copyright © 2014 Elsevier Ltd. All rights reserved.

Reduction of the ionization energy for 1s-electrons in dense aluminum plasmas

NASA Astrophysics Data System (ADS)

Lin, C.; Reinholz, H.; Röpke, G.

2017-02-01

The properties of a bound multi-electron system immersed in a plasma environment are strongly modified by the surrounding plasma. In particular, the modification of the ionization energy is described by the electronic self-energy within the framework of the quantum statistical theory. We present the energy shift of the eigenstates and the lowering of the continuum edge of free electrons in a plasma. The reduction of the ionization potential is determined by their difference. This ionization potential depression for the 1s-levels in dense aluminum plasmas is calculated. Comparisons with other theories and the experimental data are shown for aluminum plasma at solid density 2.7 g/cm3.

Polarity inversion of bioanode for biocathodic reduction of aromatic pollutants.

PubMed

Yun, Hui; Liang, Bin; Kong, De-Yong; Cheng, Hao-Yi; Li, Zhi-Ling; Gu, Ya-Bing; Yin, Hua-Qun; Wang, Ai-Jie

2017-06-05

The enrichment of specific pollutant-reducing consortium is usually required prior to the startup of biocathode bioelectrochemical system (BES) and the whole process is time consuming. To rapidly establish a non-specific functional biocathode, direct polar inversion from bioanode to biocathode is proposed in this study. Based on the diverse reductases and electron transfer related proteins of anode-respiring bacteria (ARB), the acclimated electrochemically active biofilm (EAB) may catalyze reduction of different aromatic pollutants. Within approximately 12 d, the acclimated bioanodes were directly employed as biocathodes for nitroaromatic nitrobenzene (NB) and azo dye acid orange 7 (AO7) reduction. Our results indicated that the established biocathode significantly accelerated the reduction of NB to aniline (AN) and AO7 to discolored products compared with the abiotic cathode and open circuit controls. Several microbes possessing capabilities of nitroaromatic/azo dye reduction and bidirectional electron transfer were maintained or enriched in the biocathode communities. Cyclic voltammetry highlighted the decreased over-potentials and enhanced electron transfer of biocathode as well as demonstrated the ARB Geobacter containing cytochrome c involved in the backward electron transfer from electrode to NB. This study offers new insights into the rapid establishment and modularization of functional biocathodes for the potential treatment of complicated electron acceptors-coexisting wastewaters. Copyright © 2017 Elsevier B.V. All rights reserved.

Graphene-Based Photocatalysts for CO2 Reduction to Solar Fuel.

PubMed

Low, Jingxiang; Yu, Jiaguo; Ho, Wingkei

2015-11-05

Recently, photocatalytic CO2 reduction for solar fuel production has attracted much attention because of its potential for simultaneously solving energy and global warming problems. Many studies have been conducted to prepare novel and efficient photocatalysts for CO2 reduction. Graphene, a two-dimensional material, has been increasingly used in photocatalytic CO2 reduction. In theory, graphene shows several remarkable properties, including excellent electronic conductivity, good optical transmittance, large specific surface area, and superior chemical stability. Attributing to these advantages, fabrication of graphene-based materials has been known as one of the most feasible strategies to improve the CO2 reduction performance of photocatalysts. This Perspective mainly focuses on the recent important advances in the fabrication and application of graphene-based photocatalysts for CO2 reduction to solar fuels. The existing challenges and difficulties of graphene-based photocatalysts are also discussed for future application.

Ab initio evaluation of the thermodynamic and electrochemical properties of alkyl halides and radicals and their mechanistic implications for atom transfer radical polymerization.

PubMed

Lin, Ching Yeh; Coote, Michelle L; Gennaro, Armando; Matyjaszewski, Krzysztof

2008-09-24

High-level ab initio molecular orbital calculations are used to study the thermodynamics and electrochemistry relevant to the mechanism of atom transfer radical polymerization (ATRP). Homolytic bond dissociation energies (BDEs) and standard reduction potentials (SRPs) are reported for a series of alkyl halides (R-X; R = CH 2CN, CH(CH 3)CN, C(CH 3) 2CN, CH 2COOC 2H 5, CH(CH 3)COOCH 3, C(CH 3) 2COOCH 3, C(CH 3) 2COOC 2H 5, CH 2Ph, CH(CH 3)Ph, CH(CH 3)Cl, CH(CH 3)OCOCH 3, CH(Ph)COOCH 3, SO 2Ph, Ph; X = Cl, Br, I) both in the gas phase and in two common organic solvents, acetonitrile and dimethylformamide. The SRPs of the corresponding alkyl radicals, R (*), are also examined. The computational results are in a very good agreement with the experimental data. For all alkyl halides examined, it is found that, in the solution phase, one-electron reduction results in the fragmentation of the R-X bond to the corresponding alkyl radical and halide anion; hence it may be concluded that a hypothetical outer-sphere electron transfer (OSET) in ATRP should occur via concerted dissociative electron transfer rather than a two-step process with radical anion intermediates. Both the homolytic and heterolytic reactions are favored by electron-withdrawing substituents and/or those that stabilize the product alkyl radical, which explains why monomers such as acrylonitrile and styrene require less active ATRP catalysts than vinyl chloride and vinyl acetate. The rate constant of the hypothetical OSET reaction between bromoacetonitrile and Cu (I)/TPMA complex was estimated using Marcus theory for the electron-transfer processes. The estimated rate constant k OSET = approximately 10 (-11) M (-1) s (-1) is significantly smaller than the experimentally measured activation rate constant ( k ISET = approximately 82 M (-1) s (-1) at 25 degrees C in acetonitrile) for the concerted atom transfer mechanism (inner-sphere electron transfer, ISET), implying that the ISET mechanism is preferred. For monomers bearing electron-withdrawing groups, the one-electron reduction of the propagating alkyl radical to the carbanion is thermodynamically and kinetically favored over the one-electron reduction of the corresponding alkyl halide unless the monomer bears strong radical-stabilizing groups. Thus, for monomers such as acrylates, catalysts favoring ISET over OSET are required in order to avoid chain-breaking side reactions.

Geothrix fermentans Secretes Two Different Redox-Active Compounds To Utilize Electron Acceptors across a Wide Range of Redox Potentials

PubMed Central

Mehta-Kolte, Misha G.

2012-01-01

The current understanding of dissimilatory metal reduction is based primarily on isolates from the proteobacterial genera Geobacter and Shewanella. However, environments undergoing active Fe(III) reduction often harbor less-well-studied phyla that are equally abundant. In this work, electrochemical techniques were used to analyze respiratory electron transfer by the only known Fe(III)-reducing representative of the Acidobacteria, Geothrix fermentans. In contrast to previously characterized metal-reducing bacteria, which typically reach maximal rates of respiration at electron acceptor potentials of 0 V versus standard hydrogen electrode (SHE), G. fermentans required potentials as high as 0.55 V to respire at its maximum rate. In addition, G. fermentans secreted two different soluble redox-active electron shuttles with separate redox potentials (−0.2 V and 0.3 V). The compound with the lower midpoint potential, responsible for 20 to 30% of electron transfer activity, was riboflavin. The behavior of the higher-potential compound was consistent with hydrophilic UV-fluorescent molecules previously found in G. fermentans supernatants. Both electron shuttles were also produced when cultures were grown with Fe(III), but not when fumarate was the electron acceptor. This study reveals that Geothrix is able to take advantage of higher-redox-potential environments, demonstrates that secretion of flavin-based shuttles is not confined to Shewanella, and points to the existence of high-potential-redox-active compounds involved in extracellular electron transfer. Based on differences between the respiratory strategies of Geothrix and Geobacter, these two groups of bacteria could exist in distinctive environmental niches defined by redox potential. PMID:22843516

Electronic connection between the quinone and cytochrome C redox pools and its role in regulation of mitochondrial electron transport and redox signaling.

PubMed

Sarewicz, Marcin; Osyczka, Artur

2015-01-01

Mitochondrial respiration, an important bioenergetic process, relies on operation of four membranous enzymatic complexes linked functionally by mobile, freely diffusible elements: quinone molecules in the membrane and water-soluble cytochromes c in the intermembrane space. One of the mitochondrial complexes, complex III (cytochrome bc1 or ubiquinol:cytochrome c oxidoreductase), provides an electronic connection between these two diffusible redox pools linking in a fully reversible manner two-electron quinone oxidation/reduction with one-electron cytochrome c reduction/oxidation. Several features of this homodimeric enzyme implicate that in addition to its well-defined function of contributing to generation of proton-motive force, cytochrome bc1 may be a physiologically important point of regulation of electron flow acting as a sensor of the redox state of mitochondria that actively responds to changes in bioenergetic conditions. These features include the following: the opposing redox reactions at quinone catalytic sites located on the opposite sides of the membrane, the inter-monomer electronic connection that functionally links four quinone binding sites of a dimer into an H-shaped electron transfer system, as well as the potential to generate superoxide and release it to the intermembrane space where it can be engaged in redox signaling pathways. Here we highlight recent advances in understanding how cytochrome bc1 may accomplish this regulatory physiological function, what is known and remains unknown about catalytic and side reactions within the quinone binding sites and electron transfers through the cofactor chains connecting those sites with the substrate redox pools. We also discuss the developed molecular mechanisms in the context of physiology of mitochondria. Copyright © 2015 the American Physiological Society.

Electronic Connection Between the Quinone and Cytochrome c Redox Pools and Its Role in Regulation of Mitochondrial Electron Transport and Redox Signaling

PubMed Central

Sarewicz, Marcin; Osyczka, Artur

2015-01-01

Mitochondrial respiration, an important bioenergetic process, relies on operation of four membranous enzymatic complexes linked functionally by mobile, freely diffusible elements: quinone molecules in the membrane and water-soluble cytochromes c in the intermembrane space. One of the mitochondrial complexes, complex III (cytochrome bc1 or ubiquinol:cytochrome c oxidoreductase), provides an electronic connection between these two diffusible redox pools linking in a fully reversible manner two-electron quinone oxidation/reduction with one-electron cytochrome c reduction/oxidation. Several features of this homodimeric enzyme implicate that in addition to its well-defined function of contributing to generation of proton-motive force, cytochrome bc1 may be a physiologically important point of regulation of electron flow acting as a sensor of the redox state of mitochondria that actively responds to changes in bioenergetic conditions. These features include the following: the opposing redox reactions at quinone catalytic sites located on the opposite sides of the membrane, the inter-monomer electronic connection that functionally links four quinone binding sites of a dimer into an H-shaped electron transfer system, as well as the potential to generate superoxide and release it to the intermembrane space where it can be engaged in redox signaling pathways. Here we highlight recent advances in understanding how cytochrome bc1 may accomplish this regulatory physiological function, what is known and remains unknown about catalytic and side reactions within the quinone binding sites and electron transfers through the cofactor chains connecting those sites with the substrate redox pools. We also discuss the developed molecular mechanisms in the context of physiology of mitochondria. PMID:25540143

Electrodeposition of platinum nanoparticles in a room-temperature ionic liquid.

PubMed

Zhang, Da; Chang, Wan Cheng; Okajima, Takeyoshi; Ohsaka, Takeo

2011-12-06

The electrochemistry of the [PtCl(6)](2-)-[PtCl(4)](2-)-Pt redox system on a glassy carbon (GC) electrode in a room-temperature ionic liquid (RTIL) [i.e., N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMEBF(4))] has been examined. The two-step four-electron reduction of [PtCl(6)](2-) to Pt, i.e., reduction of [PtCl(6)](2-) to [PtCl(4)](2-) and further reduction of [PtCl(4)](2-) to Pt, occurs separately in this RTIL in contrast to the one-step four-electron reduction of [PtCl(6)](2-) to Pt in aqueous media. The cathodic and anodic peaks corresponding to the [PtCl(6)](2-)/[PtCl(4)](2-) redox couple were observed at ca. -1.1 and 0.6 V vs a Pt wire quasi-reference electrode, respectively, while those observed at -2.8 and -0.5 V were found to correspond to the [PtCl(4)](2-)/Pt redox couple. The disproportionation reaction of the two-electron reduction product of [PtCl(6)](2-) (i.e., [PtCl(4)](2-)) to [PtCl(6)](2-) and Pt metal was also found to occur significantly. The electrodeposition of Pt nanoparticles could be carried out on a GC electrode in DEMEBF(4) containing [PtCl(6)](2-) by holding the potential at -3.5 or -2.0 V. At -3.5 V, the four-electron reduction of [PtCl(6)](2-) to Pt can take place, while at -2.0 V the two-electron reduction of [PtCl(6)](2-) to [PtCl(4)](2-) occurs. The results obtained demonstrate that the electrodeposition of Pt at -3.5 V may occur via a series of reductions of [PtCl(6)](2-) to [PtCl(4)](2-) and further [PtCl(4)](2-) to Pt and at -2.0 V via a disproportionation reaction of [PtCl(4)](2-) to [PtCl(6)](2-) and Pt. Furthermore, the deposition potential of Pt nanoparticles was found to largely influence their size and morphology as well as the relative ratio of Pt(110) and Pt(100) crystalline orientation domains. The sizes of the Pt nanoparticles prepared by holding the electrode potential at -2.0 and -3.5 V are almost the same, in the range of ca. 1-2 nm. These small nanoparticles are "grown" to form bigger particles with different morphologies: In the case of the deposition at -2.0 V, the GC electrode surface is totally, relatively compactly covered with Pt particles of relatively uniform size of ca. 10-50 nm. On the other hand, in the case of the electrodeposition at -3.5 V, small particles of ca. 50-100 nm and the grown-up particles of ca. 100-200 nm cover the GC surface irregularly and coarsely. Interestingly, the Pt nanoparticles prepared by holding the potential at -2.0 and -3.5 V are relatively enriched in Pt(100) and Pt(110) facets, respectively. © 2011 American Chemical Society

Plasmon excitation in metal slab by fast point charge: The role of additional boundary conditions in quantum hydrodynamic model

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

Zhang, Ying-Ying; Department of Applied Mathematics, University of Waterloo, Waterloo, Ontario N2L 3G1; An, Sheng-Bai

2014-10-15

We study the wake effect in the induced potential and the stopping power due to plasmon excitation in a metal slab by a point charge moving inside the slab. Nonlocal effects in the response of the electron gas in the metal are described by a quantum hydrodynamic model, where the equation of electronic motion contains both a quantum pressure term and a gradient correction from the Bohm quantum potential, resulting in a fourth-order differential equation for the perturbed electron density. Thus, besides using the condition that the normal component of the electron velocity should vanish at the impenetrable boundary ofmore » the metal, a consistent inclusion of the gradient correction is shown to introduce two possibilities for an additional boundary condition for the perturbed electron density. We show that using two different sets of boundary conditions only gives rise to differences in the wake potential at large distances behind the charged particle. On the other hand, the gradient correction in the quantum hydrodynamic model is seen to cause a reduction in the depth of the potential well closest to the particle, and a reduction of its stopping power. Even for a particle moving in the center of the slab, we observe nonlocal effects in the induced potential and the stopping power due to reduction of the slab thickness, which arise from the gradient correction in the quantum hydrodynamic model.« less

Electrocatalytic Transformation of Carbon Dioxide into Low Carbon Compounds on Conducting Polymers Derived from Multimetallic Porphyrins.

PubMed

Dreyse, Paulina; Honores, Jessica; Quezada, Diego; Isaacs, Mauricio

2015-11-01

The electrochemical reduction of carbon dioxide is studied herein by using conducting polymers based on metallotetraruthenated porphyrins (MTRPs). The polymers on glassy carbon electrodes were obtained by electropolymerization processes of the monomeric MTRP. The linear sweep voltammetry technique resulted in polymeric films that showed electrocatalytic activity toward carbon dioxide reduction with an onset potential of -0.70 V. The reduction products obtained were hydrogen, formic acid, formaldehyde, and methanol, with a tendency for a high production of methanol with a maximum value of turnover frequency equal to 15.07 when using a zinc(II) polymeric surface. Studies of the morphology (AFM) and electrochemical impedance spectroscopy results provide an adequate background to explain that the electrochemical reduction is governed by the roughness of the polymer, for which the possible mechanism involves a series of one-electron reduction reactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Glow discharge based device for solving mazes

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

Dubinov, Alexander E., E-mail: dubinov-ae@yandex.ru; Mironenko, Maxim S.; Selemir, Victor D.

2014-09-15

A glow discharge based device for solving mazes has been designed and tested. The device consists of a gas discharge chamber and maze-transformer of radial-azimuth type. It allows changing of the maze pattern in a short period of time (within several minutes). The device has been tested with low pressure air. Once switched on, a glow discharge has been shown to find the shortest way through the maze from the very first attempt, even if there is a section with potential barrier for electrons on the way. It has been found that ionization waves (striations) can be excited in themore » maze along the length of the plasma channel. The dependancy of discharge voltage on the length of the optimal path through the maze has been measured. A reduction in discharge voltage with one or two potential barriers present has been found and explained. The dependency of the magnitude of discharge ignition voltage on the length of the optimal path through the maze has been measured. The reduction of the ignition voltage with the presence of one or two potential barriers has been observed and explained.« less

Effects of soluble flavin on heterogeneous electron transfer between surface-exposed bacterial cytochromes and iron oxides

NASA Astrophysics Data System (ADS)

Wang, Zheming; Shi, Zhi; Shi, Liang; White, Gaye F.; Richardson, David J.; Clarke, Thomas A.; Fredrickson, Jim K.; Zachara, John M.

2015-08-01

Dissimilatory iron-reducing bacteria can utilize insoluble Fe(Mn)-oxides as a terminal electron acceptor under anaerobic conditions. For Shewanella species specifically, evidence suggests that iron reduction is associated with the secretion of flavin mononucleotide (FMN) and riboflavin. However, the exact mechanism of flavin involvement is unclear; while some indicate that flavins mediate electron transfer (Marsili et al., 2008), others point to flavin serving as co-factors to outer membrane proteins (Okamoto et al., 2013). In this work, we used methyl viologen (MVrad +)-encapsulated, porin-cytochrome complex (MtrCAB) embedded liposomes (MELs) as a synthetic model of the Shewanella outer membrane to investigate the proposed mediating behavior of microbially produced flavins. The reduction kinetics of goethite, hematite and lepidocrocite (200 μM) by MELs ([MVrad +] ∼ 40 μM and MtrABC ⩽ 1 nM) were determined in the presence FMN at pH 7.0 in N2 atmosphere by monitoring the concentrations of MVrad + and FMN through their characteristic UV-visible absorption spectra. Experiments were performed where (i) FMN and Fe(III)-oxide were mixed and then reacted with the reduced MELs and (ii) FMN was reacted with the reduced MELs followed by addition of Fe(III)-oxide. The redox reactions proceeded in two steps: a fast step that was completed in a few seconds, and a slower one lasting over 400 s. For all three Fe(III)-oxides, the initial reaction rate in the presence of a low concentration of FMN (⩽1 μM) was at least a factor of five faster than those with MELs alone, and orders of magnitude faster than those by FMNH2, suggesting that FMN may serve as a co-factor that enhances electron transfer from outer-membrane c-cytochromes to Fe(III)-oxides. The rate and extent of the initial reaction followed the order of lepidocrocite > hematite > goethite, the same as their reduction potentials, implying thermodynamic control on reaction rate. For LEP, with the highest reduction potential among the three Fe(III)-oxides, its reduction by FMNH2 was completed in less than 10 min, suggesting that FMN was capable of mediating electron transfer to LEP. At higher FMN concentrations (>1 μM), the reaction rates for both steps decreased and varied inversely with FMN concentration, indicating that FMN inhibited the MEL to Fe(III)-oxide electron transfer reaction under these conditions. The implications of the observed kinetic behaviors to flavin-mediated Fe(III)-oxide reduction in natural environments are discussed.

Novel composite material polyoxovanadate@MIL-101(Cr): a highly efficient electrocatalyst for ascorbic acid oxidation.

PubMed

Fernandes, Diana M; Barbosa, André D S; Pires, João; Balula, Salete S; Cunha-Silva, Luís; Freire, Cristina

2013-12-26

A novel hybrid composite material, PMo10V2@MIL-101 was prepared by the encapsulation of the tetra-butylammonium (TBA) salt of the vanadium-substituted phosphomolybdate [PMo10V2O40](5-) (PMo10V2) into the porous metal-organic framework (MOF) MIL-101(Cr). The materials characterization by powder X-ray diffraction, Fourier transform infrared spectra and scanning electron microscopy confirmed the preparation of the composite material without disruption of the MOF porous structure. Pyrolytic graphite electrodes modified with the original components (MIL-101(Cr), PMo10V2), and the composite material PMo10V2@MIL-101 were prepared and their electrochemical responses were studied by cyclic voltammetry. Surface confined redox processes were observed for all the immobilized materials. MIL-101(Cr) showed one-electron reduction process due to chromium centers (Cr(III) → Cr(II)), while PMo10V2 presented five reduction processes: the peak at more positive potentials is attributed to two superimposed 1-electron vanadium reduction processes (V(V) → V(IV)) and the other four peaks to Mo-centred two-electron reduction processes (Mo(VI) → Mo(V)). The electrochemical behavior of the composite material PMo10V2@MIL-101 showed both MIL-101(Cr) and PMo10V2 redox features, although with the splitting of the two vanadium processes and the shift of the Mo- and Cr- centered processes to more negative potentials. Finally, PMo10V2@MIL-101 modified electrode showed outstanding enhanced vanadium-based electrocatalytic properties towards ascorbic acid oxidation, in comparison with the free PMo10V2, as a result of its immobilization into the porous structure of the MOF. Furthermore, PMo10V2@MIL-101 modified electrode showed successful simultaneous detection of ascorbic acid and dopamine.

The Iron-Sulfur Cluster of Electron Transfer Flavoprotein-ubiquinone Oxidoreductase (ETF-QO) is the Electron Acceptor for Electron Transfer Flavoprotein†

PubMed Central

Swanson, Michael A.; Usselman, Robert J.; Frerman, Frank E.; Eaton, Gareth R.; Eaton, Sandra S.

2011-01-01

Electron-transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) accepts electrons from electron-transfer flavoprotein (ETF) and reduces ubiquinone from the ubiquinone-pool. It contains one [4Fe-4S]2+,1+ and one FAD, which are diamagnetic in the isolated oxidized enzyme and can be reduced to paramagnetic forms by enzymatic donors or dithionite. In the porcine protein, threonine 367 is hydrogen bonded to N1 and O2 of the flavin ring of the FAD. The analogous site in Rhodobacter sphaeroides ETF-QO is asparagine 338. Mutations N338T and N338A were introduced into the R. sphaeroides protein by site-directed mutagenesis to determine the impact of hydrogen bonding at this site on redox potentials and activity. The mutations did not alter the optical spectra, EPR g-values, spin-lattice relaxation rates, or the [4Fe-4S]2+,1+ to FAD point-dipole interspin distances. The mutations had no impact on the reduction potential for the iron-sulfur cluster, which was monitored by changes in the continuous wave EPR signals of the [4Fe-4S]+ at 15 K. For the FAD semiquinone, significantly different potentials were obtained by monitoring the titration at 100 or 293 K. Based on spectra at 293 K the N338T mutation shifted the first and second midpoint potentials for the FAD from +47 mV and −30 mV for wild type to −11 mV and −19 mV, respectively. The N338A mutation decreased the potentials to −37 mV and −49 mV. Lowering the midpoint potentials resulted in a decrease in the quinone reductase activity and negligible impact on disproportionation of ETF1e− catalyzed by ETF-QO. These observations indicate that the FAD is involved in electron transfer to ubiquinone, but not in electron transfer from ETF to ETF-QO. Therefore the iron-sulfur cluster is the immediate acceptor from ETF. PMID:18672901

Facile one-pot synthesis of platinum nanoparticles decorated nitrogen-graphene with high electrocatalytic performance for oxygen reduction and anodic fuels oxidation

NASA Astrophysics Data System (ADS)

Navaee, Aso; Salimi, Abdollah; Soltanian, Saeid; Servati, Peyman

2015-03-01

Due to exceptional electronic properties of graphene (Gr) and nitrogen doped graphene (N-Gr), they are considered as superior supporting platforms for novel metal nanoparticle decorations. Here, we report, a novel one-step electrochemical method for synthesis of Nitrogen-doped graphene sheets uniformly decorated with platinum nanoparticles (Pt/N-Gr). A graphite rod and platinum wire are respectively used for graphene and platinum nanoparticles production. The potential is cycled from -3V to +3V in acetonitrile solution as a nitrogen dopant source. By increasing the number of cycles the nitrogen-doped graphene/platinum nanoparticles composite is generated. After heat-treating the composite is characterized with various techniques such as FTIR, Raman, XPS, SEM and TEM. The electrocatalytic activity of the prepared composite toward the reduction of O2 and the oxidation of usual anodic fuels such as methanol, ethanol, hydrazine and formic acid is investigated using cyclic voltammetry technique. In comparison to commercial platinum/carbon, the onset potentials and the current densities for both O2 reduction and fuels oxidation are remarkably improved. Furthermore, the modified electrode by this composite shows good long-term stability and poisoning tolerance.

Electric thruster research

NASA Technical Reports Server (NTRS)

Kaufman, H. R.; Robinson, R. S.

1981-01-01

The multipole discharge chamber of an electrostatic ion thruster is discussed. No reductions in discharge losses were obtained, despite repeated demonstration of anode potentials more positive than the bulk of the discharge plasma. The penalty associated with biased anode operation was reduced as the magnetic integral above the biased anodes was increased. The hollow cathode is discussed. The experimental configuration of the Hall current thruster had a uniform field throughout the ion generation and acceleration regions. To obtain reliable ion generation, it was necessary to reduce the magnetic field strength, to the point where excessive electron backflow was required to establish ion acceleration. The theoretical study of ion acceleration with closed electron drift paths resulted in two classes of solutions. One class has the continuous potential variation in the acceleration region that is normally associated with a Hall current accelerator. The other class has an almost discontinuous potential step near the anode end of the acceleration region. This step includes a significant fraction of the total acceleration potential difference.

Iron Reduction and Carbonate Precipitation by Shewanella oneidensis

NASA Astrophysics Data System (ADS)

Zeng, Z.; Tice, M. M.

2011-12-01

This study is to contribute to better understanding of how Archean microbes induced carbonate diagenesis in mats and stromatolites. Previous studies showed sulfate reduction, a common promoter of carbonate precipitation in modern mats[1], is likely to have been less effective in Archean mats in marine fluids lower in sulfate[2]. Alternatively, iron reduction produces far more alkalinity per unit carbon respired than sulfate reduction. Therefore, we hypothesize iron reduction can promote much more carbonate precipitation than sulfate reduction. Our study might also have some relevance to banded iron formation on which microbial iron reduction played a potential role[3]. To test our hypothesis, Shewanella oneidensis MR-1, a dissimilatory iron reducing bacterium will be cultured anaerobically (79%N2, 20%CO2 and 1%H2) in basal medium to trigger iron reduction. Lactate will be used as electron donor, and the electron acceptor will be fresh ferrihydrite. Culture medium will be added with various metal ions, such as Ca2+ and Mg2+, to obtain potential carbonate precipitate. Escherichia coli (with fumarate added as an electron acceptor) will be used to provide a comparison to live but non-iron- reduction cells. After 20 days incubation, precipitate will be collected, washed and identified by X-ray diffraction (XRD). Besides, iron reduction rate (ferrozine assay)[4], PH and amount of precipitate (carbonate and oxidize fractions)[5] will be measured over time to well understand how S. oneidensis drives carbonate precipitation.

Binding and Energetics of Electron Transfer between an Artificial Four-Helix Mn-Protein and Reaction Centers from Rhodobacter sphaeroides.

PubMed

Espiritu, Eduardo; Olson, Tien L; Williams, JoAnn C; Allen, James P

2017-12-12

The ability of an artificial four-helix bundle Mn-protein, P1, to bind and transfer an electron to photosynthetic reaction centers from the purple bacterium Rhodobacter sphaeroides was characterized using optical spectroscopy. Upon illumination of reaction centers, an electron is transferred from P, the bacteriochlorophyll dimer, to Q A , the primary electron acceptor. The P1 Mn-protein can bind to the reaction center and reduce the oxidized bacteriochlorophyll dimer, P + , with a dissociation constant of 1.2 μM at pH 9.4, comparable to the binding constant of c-type cytochromes. Amino acid substitutions of surface residues on the Mn-protein resulted in increases in the dissociation constant to 8.3 μM. The extent of reduction of P + by the P1 Mn-protein was dependent on the P/P + midpoint potential and the pH. Analysis of the free energy difference yielded a midpoint potential of approximately 635 mV at pH 9.4 for the Mn cofactor of the P1 Mn-protein, a value similar to those found for other Mn cofactors in proteins. The linear dependence of -56 mV/pH is consistent with one proton being released upon Mn oxidation, allowing the complex to maintain overall charge neutrality. These outcomes demonstrate the feasibility of designing four-helix bundles and other artificial metalloproteins to bind and transfer electrons to bacterial reaction centers and establish the usefulness of this system as a platform for designing sites to bind novel metal cofactors capable of performing complex oxidation-reduction reactions.

Bioelectrochemically-assisted reductive dechlorination of 1,2-dichloroethane by a Dehalococcoides-enriched microbial culture.

PubMed

Leitão, Patrícia; Rossetti, Simona; Nouws, Henri P A; Danko, Anthony S; Majone, Mauro; Aulenta, Federico

2015-11-01

The aim of this study was to verify the possibility to use a polarized graphite electrode as an electron donor for the reductive dechlorination of 1,2-dichloroethane, an ubiquitous groundwater contaminant. The rate of 1,2-DCA dechlorination almost linearly increased by decreasing the set cathode potential over a broad range of set cathode potentials (i.e., from -300 mV to -900 mV vs. the standard hydrogen electrode). This process was primarily dependent on electrolytic H2 generation. On the other hand, reductive dechlorination proceeded (although quite slowly) with a very high Coulombic efficiency (near 70%) at a set cathode potential of -300 mV, where no H2 production occurred. Under this condition, reductive dechlorination was likely driven by direct electron uptake from the surface of the polarized electrode. Taken as a whole, this study further extends the range of chlorinated contaminants which can be treated with bioelectrochemical systems. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electrogenerated chemiluminescence. 59. Rhenium complexes

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

Richter, M.M.; Debad, J.D.; Bard, A.J.

Re(L)(CO){sub 3}Cl complexes (where L is 1,10-phenanthroline, 2,2`-bipyridine, or a phenanthroline or bipyridine derivative containing methyl groups) are photoluminescent in fluid solution at room temperature. In acetonitrile solutions, these complexes display one chemically reversible one-electron reduction process and one chemically irreversible oxidation process. {lambda}{sub max} for the luminescence is dependent on the nature of L, and a linear relationship between {lambda}{sub max} and the difference in electrode potentials for oxidation and reduction is evident. Electrogenerated chemiluminescence (ECL) was observed in acetonitrile solutions of these complexes (Bu{sub 4}NPF{sub 6} as electrolyte) by stepping the potential of a Pt disk working electrodemore » between potentials sufficient to form the radical anionic and cationic species. The relative amount of light produced during the anodic and cathodic pulses was dependent on the potential limits and pulse duration. ECL was also generated in the presence of coreactants, i.e., with tri-n-propylamine upon stepping the potential sufficiently positive to form the deprotonated tri-n-propylamine radical and the cationic rhenium(II) species Re{sup II}(L)(CO){sub 3}Cl{sup +}. When S{sub 2}O{sub 8}{sup 2-} was present in solution, ECL was also observed for all of the complexes upon stepping to potentials sufficient to form (Re{sup I}(L)(CO){sub 3}Cl){sup -} and the strong oxidant SO{sub 4}{sup .-}. 44 refs., 8 figs.« less

Quantifying Spot Size Reduction of a 1.8 kA Electron Beam for Flash Radiography

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

Burris-Mog, Trevor John; Moir, David C.

The spot size of Axis-I at the Dual Axis Radiographic Hydrodynamic Test facility was reduced by 15.5% by including a small diameter drift tube that acts to aperture the outer diameter of the electron beam. Comparing the measured values to both analytic calculations and results from a particle-in-cell model shows that one-third to one-half of the spot size reduction is due to a drop in beam emittance. We infer that one-half to two-thirds of the spot-size reduction is due to a reduction in beam-target interactions. Sources of emittance growth and the scaling of the final focal spot size with emittancemore » and solenoid aberrations are also presented.« less

Quantifying Spot Size Reduction of a 1.8 kA Electron Beam for Flash Radiography

DOE PAGES

Burris-Mog, Trevor John; Moir, David C.

2018-03-14

The spot size of Axis-I at the Dual Axis Radiographic Hydrodynamic Test facility was reduced by 15.5% by including a small diameter drift tube that acts to aperture the outer diameter of the electron beam. Comparing the measured values to both analytic calculations and results from a particle-in-cell model shows that one-third to one-half of the spot size reduction is due to a drop in beam emittance. We infer that one-half to two-thirds of the spot-size reduction is due to a reduction in beam-target interactions. Sources of emittance growth and the scaling of the final focal spot size with emittancemore » and solenoid aberrations are also presented.« less

Recycling potential for low voltage and high voltage high rupturing capacity fuse links.

PubMed

Psomopoulos, Constantinos S; Barkas, Dimitrios A; Kaminaris, Stavros D; Ioannidis, George C; Karagiannopoulos, Panagiotis

2017-12-01

Low voltage and high voltage high-rupturing-capacity fuse links are used in LV and HV installations respectively, protecting mainly the LV and HV electricity distribution and transportation networks. The Waste Electrical and Electronic Equipment Directive (2002/96/EC) for "Waste of electrical and electronic equipment" is the main related legislation and as it concerns electrical and electronic equipment, it includes electric fuses. Although, the fuse links consist of recyclable materials, only small scale actions have been implemented for their recycling around Europe. This work presents the possibilities for material recovery from this specialized industrial waste for which there are only limited volume data. Furthermore, in order to present the huge possibilities and environmental benefits, it presents the potential for recycling of HRC fuses used by the Public Power Corporation of Greece, which is the major consumer for the country, but one of the smallest ones in Europe and globally, emphasizing in this way in the issue. According to the obtained results, fuse recycling could contribute to the effort for minimize the impacts on the environment through materials recovery and reduction of the wastes' volume disposed of in landfills. Copyright © 2017 Elsevier Ltd. All rights reserved.

Tuning the reactivity of mononuclear nonheme manganese(iv)-oxo complexes by triflic acid

DOE PAGES

Chen, Junying; Yoon, Heejung; Lee, Yong -Min; ...

2015-04-14

Triflic acid (HOTf)-bound nonheme Mn( IV)-oxo complexes, [(L)Mn IV(O)] 2+–(HOTf) 2 (L = N4Py and Bn-TPEN; N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine and Bn-TPEN = N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine), were synthesized by adding HOTf to the solutions of the [(L)Mn IV(O)] 2+ complexes and were characterized by various spectroscopies. The one-electron reduction potentials of the Mn IV(O) complexes exhibited a significant positive shift upon binding of HOTf. The driving force dependences of electron transfer (ET) from electron donors to the Mn IV(O) and Mn IV(O)–(HOTf) 2 complexes were examined and evaluated in light of the Marcus theory of ET to determine the reorganization energies of ET.more » The smaller reorganization energies and much more positive reduction potentials of the [(L)Mn IV(O)] 2+–(HOTf) 2 complexes resulted in greatly enhanced oxidation capacity towards one-electron reductants and para-X-substituted-thioanisoles. The reactivities of the Mn(IV)-oxo complexes were markedly enhanced by binding of HOTf, such as a 6.4 × 10 5-fold increase in the oxygen atom transfer (OAT) reaction (i.e., sulfoxidation). Such a remarkable acceleration in the OAT reaction results from the enhancement of ET from para-X-substituted-thioanisoles to the MnIV(O) complexes as revealed by the unified ET driving force dependence of the rate constants of OAT and ET reactions of [(L)Mn IV(O)] 2+–(HOTf) 2. In contrast, deceleration was observed in the rate of H-atom transfer (HAT) reaction of [(L)Mn IV(O)] 2+–(HOTf) 2 complexes with 1,4-cyclohexadiene as compared with those of the [(L)Mn IV(O)] 2+ complexes. Thus, the binding of two HOTf molecules to the Mn IV(O) moiety resulted in remarkable acceleration of the ET rate when the ET is thermodynamically feasible. When the ET reaction is highly endergonic, the rate of the HAT reaction is decelerated due to the steric effect of the counter anion of HOTf.« less

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

Arlt, T.; Penzkofer H.; Zinth, W.

The energetics of the primary electron donor (the special pair P) in reaction centers from Rhodopseudomonas viridis were modified by site-directed mutagenesis of histidine L168 to phenylalanine. This leads to the loss of a hydrogen bond between the amino acid side chain and the ring I acetyl carbonyl oxygen of the bacteriochlorophyll molecule BChl{sub LP}. As a result of the mutation, a 35 nm blue shift of the Q{sub y} band of the special pair and a decrease of 80 mV in the P/P{sup +} oxidation-reduction potential occur. Femtosecond spectroscopy revealed an acceleration of the first electron transfer step frommore » 3.5 ps in wild type to 1.1 ps in mutant. Analysis of change in the bacteriochlorophyll monomer (B) band of the mutant reaction centers showed strong bleaching. This is direct evidence that bacteriochlorophyll b is real intermediate in electron transfer. The changes in redox potential and time constants allow one to estimate the energetics in the wild-type and mutated reaction centers according to the Marcus electron transfer theory. 32 refs., 6 figs.« less

One-Electron Standard Reduction Potentials of Nitroaromatic and Cyclic Nitramine Explosives

DTIC Science & Technology

2010-01-01

the preparation of solutions. Glassware and plasticware was rinsed with acetone and distilled water prior to soaking overnight in a 5.0 M nitric acid ...prior contact with metal ions was soaked in a 5.0 mM oxalic acid bath overnight before following the above procedure. 40-Nitroacetophenone, 1,3...observable (Colon et al., 2006b) nitrosobenzene and N-hydroxylaniline intermediates to form the final stable product aniline (Fig. 1a). However, NACs

Spectroscopic Investigations of Catalase Compound II: Characterization of an Iron(IV) Hydroxide Intermediate in a Non-thiolate-Ligated Heme Enzyme

PubMed Central

Yosca, Timothy H.; Langston, Matthew C.; Krest, Courtney M.; Onderko, Elizabeth L.; Grove, Tyler L.; Livada, Jovan; Green, Michael T.

2018-01-01

We report on the protonation state of Helicobacter pylori catalase compound II. UV/visible, Mössbauer, and X-ray absorption spectroscopies have been used to examine the intermediate from pH 5 to 14. We have determined that HPC-II exists in an iron(IV) hydroxide state up to pH 11. Above this pH, the iron(IV) hydroxide complex transitions to a new species (pKa = 13.1) with Mössbauer parameters that are indicative of an iron(IV)-oxo intermediate. Recently, we discussed a role for an elevated compound II pKa in diminishing the compound I reduction potential. This has the effect of shifting the thermodynamic landscape toward the two-electron chemistry that is critical for catalase function. In catalase, a diminished potential would increase the selectivity for peroxide disproportionation over off-pathway one-electron chemistry, reducing the buildup of the inactive compound II state and reducing the need for energetically expensive electron donor molecules. PMID:27960340

Microbial Sulfate Reduction Potential in Coal-Bearing Sediments Down to ~2.5 km below the Seafloor off Shimokita Peninsula, Japan

PubMed Central

Glombitza, Clemens; Adhikari, Rishi R.; Riedinger, Natascha; Gilhooly, William P.; Hinrichs, Kai-Uwe; Inagaki, Fumio

2016-01-01

Sulfate reduction is the predominant anaerobic microbial process of organic matter mineralization in marine sediments, with recent studies revealing that sulfate reduction not only occurs in sulfate-rich sediments, but even extends to deeper, methanogenic sediments at very low background concentrations of sulfate. Using samples retrieved off the Shimokita Peninsula, Japan, during the Integrated Ocean Drilling Program (IODP) Expedition 337, we measured potential sulfate reduction rates by slurry incubations with 35S-labeled sulfate in deep methanogenic sediments between 1276.75 and 2456.75 meters below the seafloor. Potential sulfate reduction rates were generally extremely low (mostly below 0.1 pmol cm−3 d−1) but showed elevated values (up to 1.8 pmol cm−3 d−1) in a coal-bearing interval (Unit III). A measured increase in hydrogenase activity in the coal-bearing horizons coincided with this local increase in potential sulfate reduction rates. This paired enzymatic response suggests that hydrogen is a potentially important electron donor for sulfate reduction in the deep coalbed biosphere. By contrast, no stimulation of sulfate reduction rates was observed in treatments where methane was added as an electron donor. In the deep coalbeds, small amounts of sulfate might be provided by a cryptic sulfur cycle. The isotopically very heavy pyrites (δ34S = +43‰) found in this horizon is consistent with its formation via microbial sulfate reduction that has been continuously utilizing a small, increasingly 34S-enriched sulfate reservoir over geologic time scales. Although our results do not represent in-situ activity, and the sulfate reducers might only have persisted in a dormant, spore-like state, our findings show that organisms capable of sulfate reduction have survived in deep methanogenic sediments over more than 20 Ma. This highlights the ability of sulfate-reducers to persist over geological timespans even in sulfate-depleted environments. Our study moreover represents the deepest evidence of a potential for sulfate reduction in marine sediments to date. PMID:27761134

Microbial Sulfate Reduction Potential in Coal-Bearing Sediments Down to ~2.5 km below the Seafloor off Shimokita Peninsula, Japan.

PubMed

Glombitza, Clemens; Adhikari, Rishi R; Riedinger, Natascha; Gilhooly, William P; Hinrichs, Kai-Uwe; Inagaki, Fumio

2016-01-01

Sulfate reduction is the predominant anaerobic microbial process of organic matter mineralization in marine sediments, with recent studies revealing that sulfate reduction not only occurs in sulfate-rich sediments, but even extends to deeper, methanogenic sediments at very low background concentrations of sulfate. Using samples retrieved off the Shimokita Peninsula, Japan, during the Integrated Ocean Drilling Program (IODP) Expedition 337, we measured potential sulfate reduction rates by slurry incubations with 35 S-labeled sulfate in deep methanogenic sediments between 1276.75 and 2456.75 meters below the seafloor. Potential sulfate reduction rates were generally extremely low (mostly below 0.1 pmol cm -3 d -1 ) but showed elevated values (up to 1.8 pmol cm -3 d -1 ) in a coal-bearing interval (Unit III). A measured increase in hydrogenase activity in the coal-bearing horizons coincided with this local increase in potential sulfate reduction rates. This paired enzymatic response suggests that hydrogen is a potentially important electron donor for sulfate reduction in the deep coalbed biosphere. By contrast, no stimulation of sulfate reduction rates was observed in treatments where methane was added as an electron donor. In the deep coalbeds, small amounts of sulfate might be provided by a cryptic sulfur cycle. The isotopically very heavy pyrites (δ 34 S = +43‰) found in this horizon is consistent with its formation via microbial sulfate reduction that has been continuously utilizing a small, increasingly 34 S-enriched sulfate reservoir over geologic time scales. Although our results do not represent in-situ activity, and the sulfate reducers might only have persisted in a dormant, spore-like state, our findings show that organisms capable of sulfate reduction have survived in deep methanogenic sediments over more than 20 Ma. This highlights the ability of sulfate-reducers to persist over geological timespans even in sulfate-depleted environments. Our study moreover represents the deepest evidence of a potential for sulfate reduction in marine sediments to date.

Boron-doped diamond semiconductor electrodes: Efficient photoelectrochemical CO2 reduction through surface modification

NASA Astrophysics Data System (ADS)

Roy, Nitish; Hirano, Yuiri; Kuriyama, Haruo; Sudhagar, Pitchaimuthu; Suzuki, Norihiro; Katsumata, Ken-Ichi; Nakata, Kazuya; Kondo, Takeshi; Yuasa, Makoto; Serizawa, Izumi; Takayama, Tomoaki; Kudo, Akihiko; Fujishima, Akira; Terashima, Chiaki

2016-11-01

Competitive hydrogen evolution and multiple proton-coupled electron transfer reactions limit photoelectrochemical CO2 reduction in aqueous electrolyte. Here, oxygen-terminated lightly boron-doped diamond (BDDL) thin films were synthesized as a semiconductor electron source to accelerate CO2 reduction. However, BDDL alone could not stabilize the intermediates of CO2 reduction, yielding a negligible amount of reduction products. Silver nanoparticles were then deposited on BDDL because of their selective electrochemical CO2 reduction ability. Excellent selectivity (estimated CO:H2 mass ratio of 318:1) and recyclability (stable for five cycles of 3 h each) for photoelectrochemical CO2 reduction were obtained for the optimum silver nanoparticle-modified BDDL electrode at -1.1 V vs. RHE under 222-nm irradiation. The high efficiency and stability of this catalyst are ascribed to the in situ photoactivation of the BDDL surface during the photoelectrochemical reaction. The present work reveals the potential of BDDL as a high-energy electron source for use with co-catalysts in photochemical conversion.

An autotrophic H 2 -oxidizing, nitrate-respiring, Tc(VII)-reducing A cidovorax sp. isolated from a subsurface oxic-anoxic transition zone: H 2 -oxidizing, Tc-reducing Acidovorax spp.

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

Lee, Ji-Hoon; Fredrickson, James K.; Plymale, Andrew E.

2015-04-08

Increasing concentrations of H 2 with depth were observed across a geologic unconformity and associated redox transition zone in the subsurface at the Hanford Site in south-central Washington, USA. An opposing gradient characterized by decreasing O 2 and nitrate concentrations was consistent with microbial-catalyzed biogeochemical processes. Sterile sand was incubated in situ within a multi-level sampler placed across the redox transition zone to evaluate the potential for Tc(VII) reduction and for enrichment of H 2-oxidizing denitrifiers capable of reducing Tc(VII). H 2-driven TcO 4- reduction was detected in sand incubated at all depths but was strongest in material from amore » depth of 17.1 m. Acidovorax spp. were isolated from H 2-nitrate enrichments from colonized sand from 15.1 m, with one representative, strain JHL-9, subsequently characterized. JHL-9 grew on acetate with either O 2 or nitrate as electron acceptor (data not shown) and on medium with bicarbonate, H 2 and nitrate. JHL-9 also reduced pertechnetate (TcO 4-) under denitrifying conditions with H 2 as the electron donor. H 2-oxidizing Acidovorax spp. in the subsurface at Hanford and other locations may contribute to the maintenance of subsurface redox gradients and offer the potential for Tc(VII) reduction.« less

Enhancement of activity of RuSex electrocatalyst by modification with nanostructured iridium towards more efficient reduction of oxygen

NASA Astrophysics Data System (ADS)

Dembinska, Beata; Kiliszek, Malgorzata; Elzanowska, Hanna; Pisarek, Marcin; Kulesza, Pawel J.

2013-12-01

Electrocatalytic activity of carbon (Vulcan XC-72) supported selenium-modified ruthenium, RuSex/C, nanoparticles for reduction of oxygen was enhanced through intentional decoration with iridium nanostructures (dimensions, 2-3 nm). The catalytic materials were characterized in oxygenated 0.5 mol dm-3 H2SO4 using cyclic and rotating ring disk voltammetric techniques as well as using transmission electron microscopy and scanning electron microscopy equipped with X-ray dispersive analyzer. Experiments utilizing gas diffusion electrode aimed at mimicking conditions existing in the low-temperature fuel cell. Upon application of our composite catalytic system, the reduction of oxygen proceeded at more positive potentials, and higher current densities were observed when compared to the behavior of the simple iridium-free system (RuSex/C) investigated under the analogous conditions. The enhancement effect was more pronounced than that one would expect from simple superposition of voltammetric responses for the oxygen reduction at RuSex/C and iridium nanostructures studied separately. Nanostructured iridium acted here as an example of a powerful catalyst for the reduction of H2O2 (rather than O2) and, when combined with such a moderate catalyst as ruthenium-selenium (for O2 reduction), it produced an integrated system of increased electrocatalytic activity in the oxygen reduction process. The proposed system retained its activity in the presence of methanol that could appear in a cathode compartment of alcohol fuel cell.

The interactive biotic and abiotic processes of DDT transformation under dissimilatory iron-reducing conditions.

PubMed

Jin, Xin; Wang, Fang; Gu, Chenggang; Yang, Xinglun; Kengara, Fredrick O; Bian, Yongrong; Song, Yang; Jiang, Xin

2015-11-01

The objective of the study was to elucidate the biotic and abiotic processes under dissimilatory iron reducing conditions involved in reductive dechlorination and iron reduction. DDT transformation was investigated in cultures of Shewanella putrefaciens 200 with/without α-FeOOH. A modified first-order kinetics model was developed and described DDT transformation well. Both the α-FeOOH reduction rate and the dechlorination rate of DDT were positively correlated to the biomass. Addition of α-FeOOH enhanced reductive dechlorination of DDT by favoring the cell survival and generating Fe(II) which was absorbed on the surface of bacteria and iron oxide. 92% of the absorbed Fe(II) was Na-acetate (1M) extractable. However, α-FeOOH also played a negative role of competing for electrons as reflected by the dechlorination rate of DDT was inhibited when increasing the α-FeOOH from 1 g L(-1) to 5 g L(-1). DDT was measured to be toxic to S. putrefaciens 200. The metabolites DDD, DDE and DDMU were recalcitrant to S. putrefaciens 200. The results suggested that iron oxide was not the key factor to promote the dissipation of DDX (DDT and the metabolites), whereas the one-electron reduction potential (E1) of certain organochlorines is the main factor and that the E1 higher than the threshold of the reductive driving forces of DIRB probably ensures the occur of reductive dechlorination. Copyright © 2015 Elsevier Ltd. All rights reserved.

Two-Electron Carbon Dioxide Reduction Catalyzed by Rhenium(I) Bis(imino)acenaphthene Carbonyl Complexes

PubMed Central

Portenkirchner, Engelbert; Kianfar, Elham; Sariciftci, Niyazi Serdar; Knör, Günther

2014-01-01

Rhenium(I) carbonyl complexes carrying substituted bis(arylimino)acenaphthene ligands (BIAN-R) have been tested as potential catalysts for the two-electron reduction of carbon dioxide. Cyclic voltammetric studies as well as controlled potential electrolysis experiments were performed using CO2-saturated solutions of the complexes in acetonitrile and acetonitrile–water mixtures. Faradaic efficiencies of more than 30 % have been determined for the electrocatalytic production of CO. The effects of ligand substitution patterns and water content of the reaction medium on the catalytic performance of the new catalysts are discussed. PMID:24737649

Electrochemical and theoretical analysis of the reactivity of shikonin derivatives: dissociative electron transfer in esterified compounds.

PubMed

Armendáriz-Vidales, Georgina; Frontana, Carlos

2014-09-07

An electrochemical and theoretical analysis of a series of shikonin derivatives in aprotic media is presented. Results showed that the first electrochemical reduction signal is a reversible monoelectronic transfer, generating a stable semiquinone intermediate; the corresponding E(I)⁰ values were correlated with calculated values of electroaccepting power (ω(+)) and adiabatic electron affinities (A(Ad)), obtained with BH and HLYP/6-311++G(2d,2p) and considering the solvent effect, revealing the influence of intramolecular hydrogen bonding and the substituting group at position C-2 in the experimental reduction potential. For the second reduction step, esterified compounds isobutyryl and isovalerylshikonin presented a coupled chemical reaction following dianion formation. Analysis of the variation of the dimensionless cathodic peak potential values (ξ(p)) as a function of the scan rate (v) functions and complementary experiments in benzonitrile suggested that this process follows a dissociative electron transfer, in which the rate of heterogeneous electron transfer is slow (~0.2 cm s(-1)), and the rate constant of the chemical process is at least 10(5) larger.

Photoreduction of Graphene Oxide and Photochemical Synthesis of Graphene-Metal Nanoparticle Hybrids by Ketyl Radicals.

PubMed

Mangadlao, Joey Dacula; Cao, Pengfei; Choi, Diana; Advincula, Rigoberto C

2017-07-26

The photoreduction of graphene oxide (GO) using ketyl radicals is demonstrated for the first time. The use of photochemical reduction through ketyl radicals generated by I-2959 or (1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one) is interesting because it affords spatial and temporal control of the reduction process. Graphene-metal nanoparticle hybrids of Ag, Au, and Pd were also photochemically fabricated in a one-pot procedure. Comprehensive spectroscopic and imaging techniques were carried out to fully characterize the materials. The nanoparticle hybrids showed promising action for the catalytic degradation of model environmental pollutants, namely, 4-nitrophenol, Rose Bengal, and Methyl Orange. The process described can be extended to polymer nanocomposites that can be photopatterned and could be potentially extended to fabricating plastic electronic devices.

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

PubMed

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

2012-09-15

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

Magnetic Field Would Reduce Electron Backstreaming in Ion Thrusters

NASA Technical Reports Server (NTRS)

Foster, John E.

2003-01-01

The imposition of a magnetic field has been proposed as a means of reducing the electron backstreaming problem in ion thrusters. Electron backstreaming refers to the backflow of electrons into the ion thruster. Backstreaming electrons are accelerated by the large potential difference that exists between the ion-thruster acceleration electrodes, which otherwise accelerates positive ions out of the engine to develop thrust. The energetic beam formed by the backstreaming electrons can damage the discharge cathode, as well as other discharge surfaces upstream of the acceleration electrodes. The electron-backstreaming condition occurs when the center potential of the ion accelerator grid is no longer sufficiently negative to prevent electron diffusion back into the ion thruster. This typically occurs over extended periods of operation as accelerator-grid apertures enlarge due to erosion. As a result, ion thrusters are required to operate at increasingly negative accelerator-grid voltages in order to prevent electron backstreaming. These larger negative voltages give rise to higher accelerator grid erosion rates, which in turn accelerates aperture enlargement. Electron backstreaming due to accelerator-gridhole enlargement has been identified as a failure mechanism that will limit ionthruster service lifetime. The proposed method would make it possible to not only reduce the electron backstreaming current at and below the backstreaming voltage limit, but also reduce the backstreaming voltage limit itself. This reduction in the voltage at which electron backstreaming occurs provides operating margin and thereby reduces the magnitude of negative voltage that must be placed on the accelerator grid. Such a reduction reduces accelerator- grid erosion rates. The basic idea behind the proposed method is to impose a spatially uniform magnetic field downstream of the accelerator electrode that is oriented transverse to the thruster axis. The magnetic field must be sufficiently strong to impede backstreaming electrons, but not so strong as to significantly perturb ion trajectories. An electromagnet or permanent magnetic circuit can be used to impose the transverse magnetic field downstream of the accelerator-grid electrode. For example, in the case of an accelerator grid containing straight, parallel rows of apertures, one can apply nearly uniform magnetic fields across all the apertures by the use of permanent magnets of alternating polarity connected to pole pieces laid out parallel to the rows, as shown in the left part of the figure. For low-temperature operation, the pole pieces can be replaced with bar magnets of alternating polarity. Alternatively, for the same accelerator grid, one could use an electromagnet in the form of current-carrying rods laid out parallel to the rows.

Redox-dependent complex formation by an ATP-dependent activator of the corrinoid/iron-sulfur protein

PubMed Central

Hennig, Sandra E.; Jeoung, Jae-Hun; Goetzl, Sebastian; Dobbek, Holger

2012-01-01

Movement, cell division, protein biosynthesis, electron transfer against an electrochemical gradient, and many more processes depend on energy conversions coupled to the hydrolysis of ATP. The reduction of metal sites with low reduction potentials (E0′ < -500 mV) is possible by connecting an energetical uphill electron transfer with the hydrolysis of ATP. The corrinoid-iron/sulfur protein (CoFeSP) operates within the reductive acetyl-CoA pathway by transferring a methyl group from methyltetrahydrofolate bound to a methyltransferase to the [Ni-Ni-Fe4S4] cluster of acetyl-CoA synthase. Methylation of CoFeSP only occurs in the low-potential Co(I) state, which can be sporadically oxidized to the inactive Co(II) state, making its reductive reactivation necessary. Here we show that an open-reading frame proximal to the structural genes of CoFeSP encodes an ATP-dependent reductive activator of CoFeSP. Our biochemical and structural analysis uncovers a unique type of reductive activator distinct from the electron-transferring ATPases found to reduce the MoFe-nitrogenase and 2-hydroxyacyl-CoA dehydratases. The CoFeSP activator contains an ASKHA domain (acetate and sugar kinases, Hsp70, and actin) harboring the ATP-binding site, which is also present in the activator of 2-hydroxyacyl-CoA dehydratases and a ferredoxin-like [2Fe-2S] cluster domain acting as electron donor. Complex formation between CoFeSP and its activator depends on the oxidation state of CoFeSP, which provides evidence for a unique strategy to achieve unidirectional electron transfer between two redox proteins. PMID:22431597

Electron storage in single wall carbon nanotubes. Fermi level equilibration in semiconductor-SWCNT suspensions.

PubMed

Kongkanand, Anusorn; Kamat, Prashant V

2007-08-01

The use of single wall carbon nanotubes (SWCNTs) as conduits for transporting electrons in a photoelectrochemical solar cell and electronic devices requires better understanding of their electron-accepting properties. When in contact with photoirradiated TiO(2) nanoparticles, SWCNTs accept and store electrons. The Fermi level equilibration with photoirradiated TiO(2) particles indicates storage of up to 1 electron per 32 carbon atoms in the SWCNT. The stored electrons are readily discharged on demand upon addition of electron acceptors such as thiazine and oxazine dyes (reduction potential less negative than that of the SWCNT conduction band) to the TiO(2)-SWCNT suspension. The stepwise electron transfer from photoirradiated TiO(2) nanoparticles --> SWCNT --> redox couple has enabled us to probe the electron equilibration process and determine the apparent Fermi level of the TiO(2)-SWCNT system. A positive shift in apparent Fermi level (20-30 mV) indicates the ability of SWCNTs to undergo charge equilibration with photoirradiated TiO(2) particles. The dependence of discharge capacity on the reduction potential of the dye redox couple is compared for TiO(2) and TiO(2)-SWCNT systems under equilibration conditions.

One-Step Laser Patterned Highly Uniform Reduced Graphene Oxide Thin Films for Circuit-Enabled Tattoo and Flexible Humidity Sensor Application.

PubMed

Park, Rowoon; Kim, Hyesu; Lone, Saifullah; Jeon, Sangheon; Kwon, Young Woo; Shin, Bosung; Hong, Suck Won

2018-06-06

The conversion of graphene oxide (GO) into reduced graphene oxide (rGO) is imperative for the electronic device applications of graphene-based materials. Efficient and cost-effective fabrication of highly uniform GO films and the successive reduction into rGO on a large area is still a cumbersome task through conventional protocols. Improved film casting of GO sheets on a polymeric substrate with quick and green reduction processes has a potential that may establish a path to the practical flexible electronics. Herein, we report a facile deposition process of GO on flexible polymer substrates to create highly uniform thin films over a large area by a flow-enabled self-assembly approach. The self-assembly of GO sheets was successfully performed by dragging the trapped solution of GO in confined geometry, which consisted of an upper stationary blade and a lower moving substrate on a motorized translational stage. The prepared GO thin films could be selectively reduced and facilitated from the simple laser direct writing process for programmable circuit printing with the desired configuration and less sample damage due to the non-contact mode operation without the use of photolithography, toxic chemistry, or high-temperature reduction methods. Furthermore, two different modes of the laser operating system for the reduction of GO films turned out to be valuable for the construction of novel graphene-based high-throughput electrical circuit boards compatible with integrating electronic module chips and flexible humidity sensors.

On the correct implementation of Fermi-Dirac statistics and electron trapping in nonlinear electrostatic plane wave propagation in collisionless plasmas

NASA Astrophysics Data System (ADS)

Schamel, Hans; Eliasson, Bengt

2016-05-01

Quantum statistics and electron trapping have a decisive influence on the propagation characteristics of coherent stationary electrostatic waves. The description of these strictly nonlinear structures, which are of electron hole type and violate linear Vlasov theory due to the particle trapping at any excitation amplitude, is obtained by a correct reduction of the three-dimensional Fermi-Dirac distribution function to one dimension and by a proper incorporation of trapping. For small but finite amplitudes, the holes become of cnoidal wave type and the electron density is shown to be described by a ϕ ( x ) 1 / 2 rather than a ϕ ( x ) expansion, where ϕ ( x ) is the electrostatic potential. The general coefficients are presented for a degenerate plasma as well as the quantum statistical analogue to these steady state coherent structures, including the shape of ϕ ( x ) and the nonlinear dispersion relation, which describes their phase velocity.

Photosensitized electron transport across lipid vesicle walls: Enhancement of quantum yield by ionophores and transmembrane potentials

PubMed Central

Laane, Colja; Ford, William E.; Otvos, John W.; Calvin, Melvin

1981-01-01

The photosensitized reduction of heptylviologen in the bulk aqueous phase of phosphatidylcholine vesicles containing EDTA inside and a membrane-bound tris(2,2′-bipyridine)ruthenium(2+) derivative is enhanced by a factor of 6.5 by the addition of valinomycin in the presence of K+. A 3-fold stimulation by gramicidin and carbonyl cyanide m-chlorophenylhydrazone is observed. The results suggest that, under these conditions, the rate of photoinduced electron transfer across vesicle walls in the absence of ion carriers is limited by cotransport of cations. The rate of electron transfer across vesicle walls could be influenced further by generating transmembrane potentials with K+ gradients in the presence of valinomycin. When vesicles are made with transmembrane potentials, interior more negative, the quantum yield of heptylviologen reduction is doubled, and, conversely, when vesicles are made with transmembrane potentials, interior more positive, the quantum yield is decreased and approaches the value found in the absence of valinomycin. PMID:16593002

Selectivity of photoelectrochemical CO2 reduction modulated with electron transfer from size-tunable quantized energy states of CdSe nanocrystals

NASA Astrophysics Data System (ADS)

Cho, Hyunjin; Kim, Whi Dong; Lee, Kangha; Lee, Seokwon; Kang, Gil-Seong; Joh, Han-Ik; Lee, Doh C.

2018-01-01

We investigate the product selectivity of CO2 reduction using NiO photocathodes decorated with CdSe quantum dots (QDs) of varying size in a photoelectrochemical (PEC) cell. Size-tunable and quantized energy states of conduction band in CdSe QDs enable systematic control of electron transfer kinetics from CdSe QDs to NiO. It turns out that different size of CdSe QDs results in variation in product selectivity for CO2 reduction. The energy gap between conduction band edge and redox potential of each reduction product (e.g., CO and CH4) correlates with their production rate. The size dependence of the electron transfer rate estimated from the energy gap is in agreement with the selectivity of CO2 reduction products for all reduction products but CO. The deviation in the case of CO is attributed to sequential conversion of CO into CH4 with CO adsorbed on electrode surface. Based on a premise that the CdSe QDs would exhibit similar surface configuration regardless of QD size, it is concluded that the electron transfer kinetics proves to alter the selectivity of CO2 reduction.

Effect of protons on the redox chemistry of colloidal zinc oxide nanocrystals.

PubMed

Valdez, Carolyn N; Braten, Miles; Soria, Ashley; Gamelin, Daniel R; Mayer, James M

2013-06-12

Electron transfer (ET) reactions of colloidal 3-5 nm diameter ZnO nanocrystals (NCs) with molecular reagents are explored in aprotic solvents. Addition of an excess of the one-electron reductant Cp*2Co (Cp* = pentamethylcyclopentadienyl) gives NCs that are reduced by up to 1-3 electrons per NC. Protons can be added stoichiometrically to the NCs by either a photoreduction/oxidation sequence or by addition of acid. The added protons facilitate the reduction of the ZnO NCs. In the presence of acid, NC reduction by Cp*2Co can be increased to over 15 electrons per NC. The weaker reductant Cp*2Cr transfers electrons only to ZnO NCs in the presence of protons. Cp*2M(+) counterions are much less effective than protons at stabilizing reduced NCs. With excess Cp*2Co or Cp*2Cr, the extent of reduction increases roughly linearly with the number of protons added. Some of the challenges in understanding these results are discussed.

Effective reduction of p-nitrophenol by silver nanoparticle loaded on magnetic Fe3O4/ATO nano-composite

NASA Astrophysics Data System (ADS)

Karki, Hem Prakash; Ojha, Devi Prashad; Joshi, Mahesh Kumar; Kim, Han Joo

2018-03-01

A silver loaded hematite (Fe3O4) and antimony doped tin oxide (ATO) magnetic nano-composite (Ag-Fe3O4/ATO) was successfully synthesized by in situ one pot green and facile hydrothermal process. The formation of nano-composite, its structure, morphology, and stability were characterized by field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HRTEM), electron diffraction spectroscopy (EDS), elemental mapping by high resolution scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infra-red spectroscopy (FTIR). UV-vis spectroscopy was used to monitor the catalytic reduction of p-nitrophenol (PNP) into p-aminophenol (PAP) in presence of Ag-Fe3O4/ATO nano-composite with excess of sodium borohydride (NaBH4). The pseudo-first order kinetic equation could describe the reduction of p-nitrophenol with excess of NaBH4. For the first time, ATO surface was used for hydrothermal growth of silver and iron oxide magnetic nanoparticles. The in situ growth of these nanoparticles provided an effective bonding of components of the nano-composite over the surface of ATO nanoparticles. This nano-composite exhibited easy synthesis, high stability, cost effective and rapid separation using external magnet. The excellent catalytic and anti-bacterial activity of as-synthesized silver nano-composite makes it potential nano-catalyst for waste water treatment as well as biomedical application.

“Feathered” fractal surfaces to minimize secondary electron emission for a wide range of incident angles

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

Swanson, Charles; Kaganovich, Igor D.

Complex structures on a material surface can significantly reduce the total secondary electron emission from that surface. The reduction occurs due to the capture of low-energy, true secondary electrons emitted at one point of the structure and intersecting another. We performed Monte Carlo calculations to demonstrate that fractal surfaces can reduce net secondary electron emission produced by the surface as compared to the flat surface. Specifically, we describe one surface, a “feathered” surface, which reduces the secondary electron emission yield more effectively than other previously considered configurations. Specifically, feathers grown onto a surface suppress secondary electron emission from shallow anglesmore » of incidence more effectively than velvet. Here, we find that, for the surface simulated, secondary electron emission yield remains below 20% of its un-suppressed value, even for shallow incident angles, where the velvet-only surface gives reduction factor of only 50%.« less

“Feathered” fractal surfaces to minimize secondary electron emission for a wide range of incident angles

DOE PAGES

Swanson, Charles; Kaganovich, Igor D.

2017-07-24

Complex structures on a material surface can significantly reduce the total secondary electron emission from that surface. The reduction occurs due to the capture of low-energy, true secondary electrons emitted at one point of the structure and intersecting another. We performed Monte Carlo calculations to demonstrate that fractal surfaces can reduce net secondary electron emission produced by the surface as compared to the flat surface. Specifically, we describe one surface, a “feathered” surface, which reduces the secondary electron emission yield more effectively than other previously considered configurations. Specifically, feathers grown onto a surface suppress secondary electron emission from shallow anglesmore » of incidence more effectively than velvet. Here, we find that, for the surface simulated, secondary electron emission yield remains below 20% of its un-suppressed value, even for shallow incident angles, where the velvet-only surface gives reduction factor of only 50%.« less

"Feathered" fractal surfaces to minimize secondary electron emission for a wide range of incident angles

NASA Astrophysics Data System (ADS)

Swanson, Charles; Kaganovich, Igor D.

2017-07-01

Complex structures on a material surface can significantly reduce the total secondary electron emission from that surface. The reduction occurs due to the capture of low-energy, true secondary electrons emitted at one point of the structure and intersecting another. We performed Monte Carlo calculations to demonstrate that fractal surfaces can reduce net secondary electron emission produced by the surface as compared to the flat surface. Specifically, we describe one surface, a "feathered" surface, which reduces the secondary electron emission yield more effectively than other previously considered configurations. Specifically, feathers grown onto a surface suppress secondary electron emission from shallow angles of incidence more effectively than velvet. We find that, for the surface simulated, secondary electron emission yield remains below 20% of its un-suppressed value, even for shallow incident angles, where the velvet-only surface gives reduction factor of only 50%.

Iron and manganese in anaerobic respiration: environmental significance, physiology, and regulation

NASA Technical Reports Server (NTRS)

Nealson, K. H.; Saffarini, D.

1994-01-01

Dissimilatory iron and/or manganese reduction is known to occur in several organisms, including anaerobic sulfur-reducing organisms such as Geobacter metallireducens or Desulfuromonas acetoxidans, and facultative aerobes such as Shewanella putrefaciens. These bacteria couple both carbon oxidation and growth to the reduction of these metals, and inhibitor and competition experiments suggest that Mn(IV) and Fe(III) are efficient electron acceptors similar to nitrate in redox abilities and capable of out-competing electron acceptors of lower potential, such as sulfate (sulfate reduction) or CO2 (methanogenesis). Field studies of iron and/or manganese reduction suggest that organisms with such metabolic abilities play important roles in coupling the oxidation of organic carbon to metal reduction under anaerobic conditions. Because both iron and manganese oxides are solids or colloids, they tend to settle downward in aquatic environments, providing a physical mechanism for the movement of oxidizing potential into anoxic zones. The resulting biogeochemical metal cycles have a strong impact on many other elements including carbon, sulfur, phosphorous, and trace metals.

Direct Observation by Rapid-Scan FT-IR Spectroscopy of Two-Electron-Reduced Intermediate of Tetraaza Catalyst [Co IIN 4H(MeCN)] 2+ Converting CO 2 to CO

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

Sheng, Hua; Frei, Heinz

In the search for the two-electron-reduced intermediate of the tetraaza catalyst [Co IIN 4H(MeCN)] 2+ (N 4H = 2,12-dimethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),2,11,13,15-pentaene) for CO 2 reduction and elementary steps that result in the formation of CO product, rapid-scan FT-IR spectroscopy of the visible-light-sensitized catalysis, using Ir(ppy) 3 in wet acetonitrile (CD 3CN) solution, led to the observation of two sequential intermediates. The initially formed one-electron-reduced [Co IN 4H] +--CO 2 adduct was converted by the second electron to a transient [Co IN 4H] +--CO 2 - complex that spontaneously converted CO 2 to CO in a rate-limiting step on the second time scalemore » in the dark under regeneration of the catalyst (room temperature). The macrocycle IR spectra of the [Co IN 4H] +--CO 2 - complex and the preceding one-electron [Co IN 4H] +--CO 2 intermediate show close similarity but distinct differences in the carboxylate modes, indicating that the second electron resides mainly on the CO 2 ligand. Vibrational assignments are corroborated by 13C isotopic labeling. The structure and stability of the two-electron-reduced intermediate derived from the time-resolved IR study are in good agreement with recent predictions by DFT electronic structure calculations. This is the first observation of an intermediate of a molecular catalyst for CO 2 reduction during the bond-breaking step producing CO. The reaction pathway for the Co tetraaza catalyst uncovered here suggests that the competition between CO 2 reduction and proton reduction of a macrocyclic multi-electron catalyst is steered toward CO 2 activation if the second electron is directly captured by an adduct of CO 2 and the one-electron-reduced catalyst intermediate.« less

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

Duan, H. Diessel; Lubner, Carolyn E.; Tokmina-Lukaszewska, Monika

A newly-recognized third fundamental mechanism of energy conservation in biology, electron bifurcation, uses free energy from exergonic redox reactions to drive endergonic redox reactions. Flavin-based electron bifurcation furnishes low potential electrons to demanding chemical reactions such as reduction of dinitrogen to ammonia. We employed the heterodimeric flavoenzyme FixAB from the diazotrophic bacterium Rhodopseudomonas palustris to elucidate unique properties that underpin flavin-based electron bifurcation.

Humic substances as a mediator for microbially catalyzed metal reduction

USGS Publications Warehouse

Lovley, D.R.; Fraga, J.L.; Blunt-Harris, E. L.; Hayes, L.A.; Phillips, E.J.P.; Coates, J.D.

1998-01-01

The potential for humic substances to serve as a terminal electron acceptor in microbial respiration and to function as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides was investigated. The Fe(III)-reducing microorganism Geobacter metallireducens conserved energy to support growth from electron transport to humics as evidenced by continued oxidation of acetate to carbon dioxide after as many as nine transfers in a medium with acetate as the electron donor and soil humic acids as the electron acceptor. Growth of G. metallireducens with poorly crystalline Fe(III) oxide as the electron acceptor was greatly stimulated by the addition of as little as 100 ??M of the humics analog, anthraquinone-2,6-disulfonate. Other quinones investigated, including lawsone, menadione, and anthraquinone-2-sulfonate, also stimulated Fe(III) oxide reduction. A wide phylogenetic diversity of microorganisms capable of Fe(III) reduction were also able to transfer electrons to humics. Microorganisms which can not reduce Fe(III) could not reduce humics. Humics stimulated the reduction of structural Fe(III) in clay and the crystalline Fe(III) forms, goethite and hematite. These results demonstrate that electron shuttling between Fe(III)-reducing microorganisms and Fe(III) via humics not only accelerates the microbial reduction of poorly crystalline Fe(III) oxide, but also can facilitate the reduction of Fe(III) forms that are not typically reduced by microorganisms in the absence of humics. Addition of humic substances to enhance electron shuttling between Fe(III)-reducing microorganisms and Fe(III) oxides may be a useful strategy to stimulate the remediation of soils and sediments contaminated with organic or metal pollutants.

Evaluation of homogeneous electrocatalysts by cyclic voltammetry.

PubMed

Rountree, Eric S; McCarthy, Brian D; Eisenhart, Thomas T; Dempsey, Jillian L

2014-10-06

The pursuit of solar fuels has motivated extensive research on molecular electrocatalysts capable of evolving hydrogen from protic solutions, reducing CO2, and oxidizing water. Determining accurate figures of merit for these catalysts requires the careful and appropriate application of electroanalytical techniques. This Viewpoint first briefly presents the fundamentals of cyclic voltammetry and highlights practical experimental considerations before focusing on the application of cyclic voltammetry for the characterization of electrocatalysts. Key metrics for comparing catalysts, including the overpotential (η), potential for catalysis (E(cat)), observed rate constant (k(obs)), and potential-dependent turnover frequency, are discussed. The cyclic voltammetric responses for a general electrocatalytic one-electron reduction of a substrate are presented along with methods to extract figures of merit from these data. The extension of this analysis to more complex electrocatalytic schemes, such as those responsible for H2 evolution and CO2 reduction, is then discussed.

Allosteric control of internal electron transfer in cytochrome cd1 nitrite reductase

PubMed Central

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

2003-01-01

Cytochrome cd1 nitrite reductase is a bifunctional multiheme enzyme catalyzing the one-electron reduction of nitrite to nitric oxide and the four-electron reduction of dioxygen to water. Kinetics and thermodynamics of the internal electron transfer process in the Pseudomonas stutzeri enzyme have been studied and found to be dominated by pronounced interactions between the c and the d1 hemes. The interactions are expressed both in dramatic changes in the internal electron-transfer rates between these sites and in marked cooperativity in their electron affinity. The results constitute a prime example of intraprotein control of the electron-transfer rates by allosteric interactions. PMID:12802018

Pulse-radiolysis studies on the interaction of one-electron reduced species with blue oxidases. Reduction of native and type-2-copper-depleted Vietnamese-lacquer-tree and Japanese-lacquer-tree laccases.

PubMed

O'Neill, P; Fielden, E M; Morpurgo, L; Agostinelli, E

1984-08-15

The interactions of one-electron reduced metronidazole (ArNO2.-) and O2.- with native and Type-2-copper-depleted Vietnamese- and Japanese-lacquer-tree laccases were studied in aqueous solution at pH 6.0 and 7.4 by using the technique of pulse radiolysis. On reaction with ArNO2.-, in the absence of O2, the holo- and the Type-2-copper-depleted proteins accept, with reduction of Type 1 copper, 2 and 1 reducing equivalents respectively. On reaction with O2.- of both holo- and Type-2-copper-depleted Vietnamese-lacquer-tree laccase, almost complete reduction of Type 1 copper was observed and, after completion of the reaction, some (less than 20%) reoxidation of Type 1 copper occurs. Reduction of Type 1 copper of the laccases by these one-electron donors occurs via a bimolecular step; however, the rate of reduction of Vietnamese-lacquer-tree laccase is over 10 times that of Japanese-lacquer-tree laccase. It is inferred that electrons enter the protein via Type 1 copper with, in the case of the holoprotein, subsequent rapid intramolecular transfer of 1 reducing equivalent within the protein. Furthermore it is suggested that intra-molecular electron transfer to Type 3 copper atoms is slow and, in the case of Type-2-copper-depleted protein, may not occur. This slow process may partially account for the variation of the catalytic activities of 'blue' oxidases.

A novel chlorophyll solar cell

NASA Astrophysics Data System (ADS)

Ludlow, J. C.

The photosynthetic process is reviewed in order to produce a design for a chlorophyll solar cell. In a leaf, antenna chlorophyll absorbs light energy and conducts it to an energy trap composed of a protein and two chlorophyll molecules, which perform the oxidation-reduction chemistry. The redox potential of the trap changes from 0.4 to -0.6 V, which is sufficient to reduce nearby molecules with redox potentials in that range. The reduction occurs by transfer of an electron, and a chlorophyll solar cell would direct the transferred electron to a current carrier. Chlorophyll antenna and traps are placed on a metallic support immersed in an electron acceptor solution, and resulting electrons from exposure to light are gathered by a metallic current collector. Spinach chlorophyll extracted, purified, and applied in a cell featuring a Pt collector and an octane water emulsion resulted in intensity independent voltages.

Electrochemistry and electrogenerated chemiluminescence of dithienylbenzothiadiazole derivative. Differential reactivity of donor and acceptor groups and simulations of radical cation-anion and dication-radical anion annihilations.

PubMed

Shen, Mei; Rodríguez-López, Joaquín; Huang, Ju; Liu, Quan; Zhu, Xu-Hui; Bard, Allen J

2010-09-29

We report here the electrochemistry and electrogenerated chemiluminescence (ECL) of a red-emitting dithienylbenzothiadiazole-based molecular fluorophore (4,7-bis(4-(4-sec-butoxyphenyl)-5-(3,5-di(1-naphthyl)phenyl)thiophen-2-yl)-2,1,3-benzothiadiazole, 1b). 1b contains two substituted thiophene groups as strong electron donors at the ends connected directly to a strong electron acceptor, 2,1,3-benzothiadiazole, in the center. Each thiophene moiety is substituted in position 2 by 3,5-di(1-naphthyl)phenyl and in position 3 by 4-sec-butoxyphenyl. Cyclic voltammetry of 1b, with scan rate ranging from 0.05 to 0.75 V/s, shows a single one-electron reduction wave (E°(red) = -1.18 V vs SCE) and two nernstian one-electron oxidation waves (E°(1,ox) = 1.01 V, E°(2,ox) = 1.24 V vs SCE). Reduction of the unsubstituted 2,1,3-benzothiadiazole center shows nernstian behavior with E°(red) = -1.56 V vs SCE. By comparison to a digital simulation, the heterogeneous electron-transfer rate constant for reduction, k(r)° = 1.5 × 10(-3) cm/s, is significantly smaller than those for the oxidations, k(o)° > 0.1 cm/s, possibly indicating that the two substituted end groups have a blocking effect on the reduction of the benzothiadiazole center. The ECL spectrum, produced by electron-transfer annihilation of the reduced and oxidized forms, consists of a single peak with maximum emission at about 635 nm, consistent with the fluorescence of the parent molecule. Relative ECL intensities with respect to 9,10-diphenylanthracene are 330% and 470% for the radical anion-cation and radical anion-dication annihilation, respectively. Radical anion (A(-•))-cation (A(+•)) annihilation produced by potential steps shows symmetric ECL transients during anodic and cathodic pulses, while for anion (A(-•))-dication (A(2+•)) annihilation, transient ECL shows asymmetry in which the anodic pulse is narrower than the cathodic pulse. Digital simulation of the transient ECL experiments showed that the origin of the observed asymmetry is asymmetry in the amount of generated charges rather than instability of the electrogenerated species.

Water nanoelectrolysis: A simple model

NASA Astrophysics Data System (ADS)

Olives, Juan; Hammadi, Zoubida; Morin, Roger; Lapena, Laurent

2017-12-01

A simple model of water nanoelectrolysis—defined as the nanolocalization at a single point of any electrolysis phenomenon—is presented. It is based on the electron tunneling assisted by the electric field through the thin film of water molecules (˜0.3 nm thick) at the surface of a tip-shaped nanoelectrode (micrometric to nanometric curvature radius at the apex). By applying, e.g., an electric potential V1 during a finite time t1, and then the potential -V1 during the same time t1, we show that there are three distinct regions in the plane (t1, V1): one for the nanolocalization (at the apex of the nanoelectrode) of the electrolysis oxidation reaction, the second one for the nanolocalization of the reduction reaction, and the third one for the nanolocalization of the production of bubbles. These parameters t1 and V1 completely control the time at which the electrolysis reaction (of oxidation or reduction) begins, the duration of this reaction, the electrolysis current intensity (i.e., the tunneling current), the number of produced O2 or H2 molecules, and the radius of the nanolocalized bubbles. The model is in good agreement with our experiments.

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

Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.

In this study, a new mechanism for the reduction of vanadyl acetylacetonate, VO(acac)2, to vanadium acetylacetonate, V(acac)3, is introduced. V(acac)3 has been studied for use in redox flow batteries (RFBs) for some time; however, contamination by moisture leads to the formation of VO(acac)2. In previous work, once this transformation occurs, it is no longer reversible because there is a requirement for extreme low potentials for the reduction to occur. Here, we propose that, in the presence of excess acetylacetone (Hacac) and free protons (H+), the reduction can take place between 2.25 and 1.5 V versus Na/Na+ via a one-electron-transfer reduction.more » This reduction can take place in situ during discharge in a novel hybrid Na-based flow battery (HNFB) with a molten Na–Cs alloy as the anode. The in situ recovery of V(acac)3 during discharge is shown to allow the Coulombic efficiency of the HNFB to be ≈100 % with little or no capacity decay over cycles. In addition, utilizing two-electron-transfer redox reactions (i.e., V3+/V4+ and V2+/V3+ redox couples) per V ion to increase the energy density of RFBs becomes possible owing to the in situ recovery of V(acac)3 during discharge. The concept of in situ recovery of material can lead to more advances in maintaining the cycle life of RFBs in the future.« less

Structure and function of NADPH-cytochrome P450 reductase and nitric oxide synthase reductase domain

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

Iyanagi, Takashi

2005-12-09

NADPH-cytochrome P450 reductase (CPR) and the nitric oxide synthase (NOS) reductase domains are members of the FAD-FMN family of proteins. The FAD accepts two reducing equivalents from NADPH (dehydrogenase flavin) and FMN acts as a one-electron carrier (flavodoxin-type flavin) for the transfer from NADPH to the heme protein, in which the FMNH {sup {center_dot}}/FMNH{sub 2} couple donates electrons to cytochrome P450 at constant oxidation-reduction potential. Although the interflavin electron transfer between FAD and FMN is not strictly regulated in CPR, electron transfer is activated in neuronal NOS reductase domain upon binding calmodulin (CaM), in which the CaM-bound activated form canmore » function by a similar mechanism to that of CPR. The oxygenated form and spin state of substrate-bound cytochrome P450 in perfused rat liver are also discussed in terms of stepwise one-electron transfer from CPR. This review provides a historical perspective of the microsomal mixed-function oxidases including CPR and P450. In addition, a new model for the redox-linked conformational changes during the catalytic cycle for both CPR and NOS reductase domain is also discussed.« less

Local, global, and nonlinear screening in twisted double-layer graphene

DOE PAGES

Lu, Chih -Pin; Rodriguez-Vega, Martin; Li, Guohong; ...

2016-06-02

One-atom-thick crystalline layers and their vertical heterostructures carry the promise of designer electronic materials that are unattainable by standard growth techniques. To realize their potential it is necessary to isolate them from environmental disturbances, in particular those introduced by the substrate. However, finding and characterizing suitable substrates, and minimizing the random potential fluctuations they introduce, has been a persistent challenge in this emerging field. In this paper, we show that Landau-level (LL) spectroscopy offers the unique capability to quantify both the reduction of the quasiparticles’ lifetime and the long-range inhomogeneity due to random potential fluctuations. Harnessing this technique together withmore » direct scanning tunneling microscopy and numerical simulations we demonstrate that the insertion of a graphene buffer layer with a large twist angle is a very effective method to shield a 2D system from substrate interference that has the additional desirable property of preserving the electronic structure of the system under study. Finally, we further show that owing to its remarkable nonlinear screening capability a single graphene buffer layer provides better shielding than either increasing the distance to the substrate or doubling the carrier density and reduces the amplitude of the potential fluctuations in graphene to values even lower than the ones in AB-stacked bilayer graphene.« less

Local, global, and nonlinear screening in twisted double-layer graphene

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

Lu, Chih -Pin; Rodriguez-Vega, Martin; Li, Guohong

One-atom-thick crystalline layers and their vertical heterostructures carry the promise of designer electronic materials that are unattainable by standard growth techniques. To realize their potential it is necessary to isolate them from environmental disturbances, in particular those introduced by the substrate. However, finding and characterizing suitable substrates, and minimizing the random potential fluctuations they introduce, has been a persistent challenge in this emerging field. In this paper, we show that Landau-level (LL) spectroscopy offers the unique capability to quantify both the reduction of the quasiparticles’ lifetime and the long-range inhomogeneity due to random potential fluctuations. Harnessing this technique together withmore » direct scanning tunneling microscopy and numerical simulations we demonstrate that the insertion of a graphene buffer layer with a large twist angle is a very effective method to shield a 2D system from substrate interference that has the additional desirable property of preserving the electronic structure of the system under study. Finally, we further show that owing to its remarkable nonlinear screening capability a single graphene buffer layer provides better shielding than either increasing the distance to the substrate or doubling the carrier density and reduces the amplitude of the potential fluctuations in graphene to values even lower than the ones in AB-stacked bilayer graphene.« less

Ultrafast Imaging using Spectral Resonance Modulation

NASA Astrophysics Data System (ADS)

Huang, Eric; Ma, Qian; Liu, Zhaowei

2016-04-01

CCD cameras are ubiquitous in research labs, industry, and hospitals for a huge variety of applications, but there are many dynamic processes in nature that unfold too quickly to be captured. Although tradeoffs can be made between exposure time, sensitivity, and area of interest, ultimately the speed limit of a CCD camera is constrained by the electronic readout rate of the sensors. One potential way to improve the imaging speed is with compressive sensing (CS), a technique that allows for a reduction in the number of measurements needed to record an image. However, most CS imaging methods require spatial light modulators (SLMs), which are subject to mechanical speed limitations. Here, we demonstrate an etalon array based SLM without any moving elements that is unconstrained by either mechanical or electronic speed limitations. This novel spectral resonance modulator (SRM) shows great potential in an ultrafast compressive single pixel camera.

A first principles investigation of electron transfer between Fe(II) and U(VI) on insulating Al- vs. semiconducting Fe-oxide surfaces via the proximity effect

NASA Astrophysics Data System (ADS)

Taylor, S. D.; Marcano, M. C.; Becker, U.

2017-01-01

This study investigates how the intrinsic chemical and electronic properties of mineral surfaces and their associated electron transfer (ET) pathways influence the reduction of U(VI) by surface-associated Fe(II). Density functional theory (DFT), including the Hubbard U correction to the exchange-correlation functional, was used to investigate sorption/redox reactions and ET mechanisms between Fe(II) and U(VI) coadsorbed on isostructural, periodic (0 0 1) surfaces of the insulator corundum (α-Al2O3) vs. the semiconductor hematite (α-Fe2O3). Furthermore, the coadsorbed Fe(II) and U(VI) ions are spatially separated from one another on the surfaces (⩾5.9 Å) to observe whether electronic-coupling through the semiconducting hematite surface facilitates ET between the adsorbates, a phenomenon known as the proximity effect. The calculations show that the different chemical and electronic properties between the isostructural corundum and hematite (0 0 1) surfaces lead to considerably different ET mechanisms between Fe(II) and U(VI). ET on the insulating corundum (0 0 1) surface is limited by the adsorbates' structural configuration. When Fe(II) and U(VI) are spatially separated and do not directly interact with one another (e.g. via an inner-sphere complex), U(VI) reduction by Fe(II) cannot occur as there is no physical pathway enabling ET between the adsorbates. In contrast to the insulating corundum (0 0 1) surface, the hematite (0 0 1) surface can potentially participate in ET reactions due to the high number of electron acceptor sites from the Fe d-states near the Fermi level at the hematite surface. The adsorption of Fe(II) also introduces d-states near the Fermi level as well as shifts unoccupied d-states of the Fe cations at the hematite surface to lower energies, making the surface more conductive. In turn, electronic coupling through the surface can link the spatially separated adsorbates to one another and provide distinct ET pathways for an electron from Fe(II) to travel through the hematite surface and reach U(VI). The progression and extent of ET occurring on the semiconducting hematite (0 0 1) surface via the proximity effect depends on the electronic properties of the surface. ET between the spatially separated U(VI) and Fe(II) occurs most readily when orbitals between the Fe and U adsorbates overlap with those of neighboring O and Fe ions at the hematite surface, as shown by calculations without the Hubbard U correction. Analyses of the spins densities confirm that the U and Fe adsorbates were reduced and oxidized, respectively, (acquiring 0.33 μB and 0.11-0.20 μB, respectively), while Fe cations at the hematite surface were reduced (losing ⩽0.6 μB). If electrons are highly localized, the amount of orbital mixing and electronic coupling through the hematite surface decreases and in turn leads to a lower degree of spin transfer, as predicted by calculations with the Hubbard U correction. Thus, the proximity effect is a potential mechanism on semiconducting surfaces facilitating surface-mediated redox reactions, although its significance varies depending on the electronic properties and subsequent charge-carrying ability of the surface. These results provide insight into ET pathways and mechanisms on insulating Al- and semiconducting Fe oxide surfaces influencing the reduction U(VI) by Fe(II) that may subsequently limit uranium's transport in the subsurface.

Factors that control catalytic two- versus four-electron reduction of dioxygen by copper complexes.

PubMed

Fukuzumi, Shunichi; Tahsini, Laleh; Lee, Yong-Min; Ohkubo, Kei; Nam, Wonwoo; Karlin, Kenneth D

2012-04-25

The selective two-electron reduction of O(2) by one-electron reductants such as decamethylferrocene (Fc*) and octamethylferrocene (Me(8)Fc) is efficiently catalyzed by a binuclear Cu(II) complex [Cu(II)(2)(LO)(OH)](2+) (D1) {LO is a binucleating ligand with copper-bridging phenolate moiety} in the presence of trifluoroacetic acid (HOTF) in acetone. The protonation of the hydroxide group of [Cu(II)(2)(LO)(OH)](2+) with HOTF to produce [Cu(II)(2)(LO)(OTF)](2+) (D1-OTF) makes it possible for this to be reduced by 2 equiv of Fc* via a two-step electron-transfer sequence. Reactions of the fully reduced complex [Cu(I)(2)(LO)](+) (D3) with O(2) in the presence of HOTF led to the low-temperature detection of the absorption spectra due to the peroxo complex [Cu(II)(2)(LO)(OO)] (D) and the protonated hydroperoxo complex [Cu(II)(2)(LO)(OOH)](2+) (D4). No further Fc* reduction of D4 occurs, and it is instead further protonated by HOTF to yield H(2)O(2) accompanied by regeneration of [Cu(II)(2)(LO)(OTF)](2+) (D1-OTF), thus completing the catalytic cycle for the two-electron reduction of O(2) by Fc*. Kinetic studies on the formation of Fc*(+) under catalytic conditions as well as for separate examination of the electron transfer from Fc* to D1-OTF reveal there are two important reaction pathways operating. One is a rate-determining second reduction of D1-OTF, thus electron transfer from Fc* to a mixed-valent intermediate [Cu(II)Cu(I)(LO)](2+) (D2), which leads to [Cu(I)(2)(LO)](+) that is coupled with O(2) binding to produce [Cu(II)(2)(LO)(OO)](+) (D). The other involves direct reaction of O(2) with the mixed-valent compound D2 followed by rapid Fc* reduction of a putative superoxo-dicopper(II) species thus formed, producing D.

Bioelectrochemical ethanol production through mediated acetate reduction by mixed cultures.

PubMed

Steinbusch, Kirsten J J; Hamelers, Hubertus V M; Schaap, Joris D; Kampman, Christel; Buisman, Cees J N

2010-01-01

Biological acetate reduction with hydrogen is a potential method to convert wet biomass waste into ethanol. Since the ethanol concentration and reaction rates are low, this research studies the feasibility of using an electrode, in stead of hydrogen, as an electron donor for biological acetate reduction in conjunction of an electron mediator. Initially, the effect of three selected mediators on metabolic flows during acetate reduction with hydrogen was explored; subsequently, the best performing mediator was used in a bioelectrochemical system to stimulate acetate reduction at the cathode with mixed cultures at an applied cathode potential of -550 mV. In the batch test, methyl viologen (MV) was found to accelerate ethanol production 6-fold and increased ethanol concentration 2-fold to 13.5 +/- 0.7 mM compared to the control. Additionally, MV inhibited n-butyrate and methane formation, resulting in high ethanol production efficiency (74.6 +/- 6%). In the bioelectrochemical system, MV addition to an inoculated cathode led directly to ethanol production (1.82 mM). Hydrogen was coproduced at the cathode (0.0035 Nm(3) hydrogen m(-2) d(-1)), so it remained unclear whether acetate was reduced to ethanol by electrons supplied by the mediator or by hydrogen. As MV reacted irreversibly at the cathode, ethanol production stopped after 5 days.

The Multicenter Aerobic Iron Respiratory Chain of Acidithiobacillus ferrooxidans Functions as an Ensemble with a Single Macroscopic Rate Constant

DOE PAGES

Li, Ting-Feng; Painter, Richard G.; Ban, Bhupal; ...

2015-06-03

Electron transfer reactions among three prominent colored proteins in intact cells of Acidithiobacillus ferrooxidans were monitored using an integrating cavity absorption meter that permitted the acquisition of accurate absorbance data in suspensions of cells that scattered light. The concentrations of proteins in the periplasmic space were estimated to be 350 and 25 mg/ml for rusticyanin and cytochrome c, respectively; cytochrome a was present as one molecule for every 91 nm2 in the cytoplasmic membrane. All three proteins were rapidly reduced to the same relative extent when suspensions of live bacteria were mixed with different concentrations of ferrous ions at pHmore » 1.5. The subsequent molecular oxygen-dependent oxidation of the multicenter respiratory chain occurred with a single macroscopic rate constant, regardless of the proteins' in vitro redox potentials or their putative positions in the aerobic iron respiratory chain. The crowded electron transport proteins in the periplasm of the organism constituted an electron conductive medium where the network of protein interactions functioned in a concerted fashion as a single ensemble with a standard reduction potential of 650 mV. The appearance of product ferric ions was correlated with the reduction levels of the periplasmic electron transfer proteins; the limiting first-order catalytic rate constant for aerobic respiration on iron was 7,400 s -1. The ability to conduct direct spectrophotometric studies under noninvasive physiological conditions represents a new and powerful approach to examine the extent and rates of biological events in situ without disrupting the complexity of the live cellular environment.« less

The short-term reduction of uranium by nanoscale zero-valent iron (nZVI): role of oxide shell, reduction mechanism and the formation of U( v )-carbonate phases

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

Tsarev, Sergey; Collins, Richard N.; Ilton, Eugene S.

Nanoscale zero-valent iron (nZVI) is a potential remediation agent for uranium-contaminated groundwaters, however, a complete mechanistic understanding of the processes that lead to uranium immobilization has yet to be achieved. In this study, the short-term anoxic reaction of U(VI) with fresh, (anoxic) aged and corroded nZVI particles was investigated under aqueous conditions conducive to the formation of thermodynamically stable U(VI)-Ca-CO3 ternary aqueous complexes. The first stage of the reaction between U(VI) and nZVI was assigned to sorption processes with the formation of surface U(VI)-carbonate complexes. Aged nZVI removed U(VI) faster than either fresh or corroded nZVI and it is hypothesizedmore » that U reduction initially occurs through the transfer of one electron from Fe(II) in the nZVI surface oxide layer. Evidence for reduction to U(V) was obtained through X-ray photoelectron spectroscopy and by determination of U-O bond distances of ~2.05 Å and 2.27 Å by U LIII-edge X-ray absorption spectroscopy detection of U-O bond distances at ~2.05 Å and 2.27 Å with these distances , similar to thoseat observed for the U(V) site in the mixed U(V)/U(VI) carbonate mineral wyartite. Scanning transmission electron microscopy also demonstrated that U was present as a nanoparticulate phase after one day of reaction, rather than a surface complex. Further reduction to U(IV), as observed in previous studies, would appear to be rate-limiting and coincident with the transformation of this meta-stable U-carbonate phase to uraninite (UO2).« less

Theoretical studies to understand surface chemistry on carbon anodes for lithium-ion batteries: how does vinylene carbonate play its role as an electrolyte additive?

PubMed

Wang, Yixuan; Nakamura, Shinichiro; Tasaki, Ken; Balbuena, Perla B

2002-04-24

To elucidate the role of vinylene carbonate (VC) as a solvent additive in organic polar solutions for lithium-ion batteries, reductive decompositions for vinylene carbonate (VC) and ethylene carbonate (EC) molecules have been comprehensively investigated both in the gas phase and in solution by means of density functional theory calculations. The salt and solvent effects are incorporated with the clusters (EC)nLi+(VC) (n = 0-3), and further corrections that account for bulk solvent effects are added using the polarized continuum model (PCM). The electron affinities of (EC)nLi+(VC) (n = 0-3) monotonically decrease when the number of EC molecules increases; a sharp decrease of about 20.0 kcal/mol is found from n = 0 to 1 and a more gentle variation for n > 1. For (EC)nLi+(VC) (n = 1-3), the reduction of VC brings about more stable ion-pair intermediates than those due to reduction of the EC molecule by 3.1, 6.1, and 5.3 kcal/mol, respectively. This finding qualitatively agrees with the experimental fact that the reduction potential of VC in the presence of Li salt is more negative than that of EC. The calculated reduction potentials corresponding to radical anion formation are close to the experimental potentials determined with cyclic voltammetry on a gold electrode surface (-2.67, -3.19 eV on the physical scale for VC and EC respectively vs experimental values -2.96 and -2.94 eV). Regarding the decomposition mechanisms, the VC and EC moieties undergo homolytic ring opening from their respective reduction intermediates, and the energy barrier of VC is about one time higher than that of EC (e.g., 20.1 vs 8.8 kcal/mol for (EC)2Li+(VC)); both are weakly affected by the explicit solvent molecules and by a bulk solvent represented by a continuum model. Alternatively, starting from the VC-reduction intermediate, the ring opening of the EC moiety via an intramolecular electron-transfer transition state has also been located; its barrier lies between those of EC and VC (e.g., 17.2 kcal/mol for (EC)2Li+(VC)). On the basis of these results, we suggest the following explanation about the role that VC may play as additive in EC-based lithium-ion battery electrolytes; VC is initially reduced to a more stable intermediate than that from EC reduction. One possibility then is that the reduced VC decomposes to form a radical anion via a barrier of about 20 kcal/mol, which undergoes a series of reactions to give rise to more active film-forming products than those resulting from EC reduction, such as lithium divinylene dicarbonate, Li-C carbides, lithium vinylene dicarbonate, R-O-Li compound, and even oligomers with repeated vinylene and carbonate-vinylene units. Another possibility starting from the VC-reduction intermediate is that the ring opening occurs on the unreduced EC moiety instead of being on the reduced VC, via an intramolecular electron transfer transition state, the energy barrier of which is lower than that of the former, in which VC just helps the intermediate formation and is not consumed. The factors that determine the additive functioning mechanism are briefly discussed, and consequently a general rule for the selection of electrolyte additive is proposed.

A Biochemical Magic Frequency Based on the Reduction Level of Biological Carbon

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

1995-01-01

We have calculated the average number of electron pairs required for the chemical reduction of carbon dioxide to biological carbon using (a) estimates of the reducing equivalents (electron pairs) needed to synthesize biomolecules from carbon dioxide, and (b) measurements of the molecular composition of different organisms. These calculations showed that the carbon of the Earth's biosphere is at the reduction level of formaldehyde that requires two electron pairs per carbon atom to be synthesized from carbon dioxide. This was also the reduction level of cellular carbon when fuel stored as lipid was not used in the estimate. Since this chemical characteristic of life is probably universal, it could be the one thing we know about other carbon-based life in the universe, and the one thing that other intelligent life knows about us. We believe that this common knowledge that biological carbon throughout the universe is at the reduction level of formaldehyde could lead to the selection of the 72.83814 GHz line of the 0, 0, 0 yields 1, 1, 1 rotational transition of formaldehyde as a frequency for interstellar communication.

Sugars as the Optimal Biosynthetic Carbon Substrate of Aqueous Life throughout the Universe

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

1999-01-01

Our previous analysis of the energetics of metabolism showed that both the biosynthesis of amino acids and lipids from sugars, and the fermentation of organic substrates, were energetically driven by electron transfer reactions resulting in carbon redox disproportionation (Weber 1997). Redox disproportionation -- the spontaneous (energetically favorable) direction of carbon group transformation in biosynthesis -- is brought about and driven by the energetically downhill transfer of electron pairs from more oxidized carbon groups (with lower half-cell reduction potentials) to more reduced carbon groups (with higher half-cell reduction potentials). In this report, we compare the redox and kinetic properties of carbon groups in order to evaluate the relative biosynthetic capability of organic substrates, and to identify the optimal biosubstrate. This analysis revealed that sugars (monocarbonyl alditols) are the optimal biosynthetic substrate because they contain the maximum number of biosynthetically useful .high energy electrons/carbon atom , while still containing a single carbonyl group needed to kinetically facilitate their conversion to useful biosynthetic intermediates. This conclusion applies to aqueous life throughout the Universe because it is based on invariant aqueous carbon chemistry -- primarily, the universal reduction potentials of carbon groups.

Sugars as the optimal biosynthetic carbon substrate of aqueous life throughout the universe

NASA Technical Reports Server (NTRS)

Weber, A. L.

2000-01-01

Our previous analysis of the energetics of metabolism showed that both the biosynthesis of amino acids and lipids from sugars, and the fermentation of organic substrates, were energetically driven by electron transfer reactions resulting in carbon redox disproportionation (Weber, 1997). Redox disproportionation--the spontaneous (energetically favorable) direction of carbon group transformation in biosynthesis--is brought about and driven by the energetically downhill transfer of electron pairs from more oxidized carbon groups (with lower half-cell reduction potentials) to more reduced carbon groups (with higher half-cell reduction potentials). In this report, we compare the redox and kinetic properties of carbon groups in order to evaluate the relative biosynthetic capability of organic substrates, and to identify the optimal biosubstrate. This analysis revealed that sugars (monocarbonyl alditols) are the optimal biosynthetic substrate because they contain the maximum number of biosynthetically useful high energy electrons/carbon atom while still containing a single carbonyl group needed to kinetically facilitate their conversion to useful biosynthetic intermediates. This conclusion applies to aqueous life throughout the Universe because it is based on invariant aqueous carbon chemistry--primarily, the universal reduction potentials of carbon groups.

Cooperative Electrocatalytic O 2 Reduction Involving Co(salophen) with p- Hydroquinone as an Electron–Proton Transfer Mediator

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

Anson, Colin W.; Stahl, Shannon S.

2017-12-01

The molecular cobalt complex, Co(salophen), and para-hydroquinone (H2Q) serve as effective cocatalysts for the electrochemical reduction of O2 to water. Mechanistic studies reveal redox cooperativity between Co(salophen) and H2Q. H2Q serves as an electron-proton transfer mediator (EPTM) that enables electrochemical O2 reduction at higher potentials and with faster rates than is observed with Co(salophen) alone. Replacement of H2Q with the higher potential EPTM, 2-chloro-H2Q, allows for faster O2 reduction rates at higher applied potential. These results demonstrate a unique strategy to achieve improved performance with molecular electrocatalyst systems.

Dissection of the Caffeate Respiratory Chain in the Acetogen Acetobacterium woodii: Identification of an Rnf-Type NADH Dehydrogenase as a Potential Coupling Site▿

PubMed Central

Imkamp, Frank; Biegel, Eva; Jayamani, Elamparithi; Buckel, Wolfgang; Müller, Volker

2007-01-01

The anaerobic acetogenic bacterium Acetobacterium woodii couples caffeate reduction with electrons derived from hydrogen to the synthesis of ATP by a chemiosmotic mechanism with sodium ions as coupling ions, a process referred to as caffeate respiration. We addressed the nature of the hitherto unknown enzymatic activities involved in this process and their cellular localization. Cell extract of A. woodii catalyzes H2-dependent caffeate reduction. This reaction is strictly ATP dependent but can be activated also by acetyl coenzyme A (CoA), indicating that there is formation of caffeyl-CoA prior to reduction. Two-dimensional gel electrophoresis revealed proteins present only in caffeate-grown cells. Two proteins were identified by electrospray ionization-mass spectrometry/mass spectrometry, and the encoding genes were cloned. These proteins are very similar to subunits α (EtfA) and β (EtfB) of electron transfer flavoproteins present in various anaerobic bacteria. Western blot analysis demonstrated that they are induced by caffeate and localized in the cytoplasm. Etf proteins are known electron carriers that shuttle electrons from NADH to different acceptors. Indeed, NADH was used as an electron donor for cytosolic caffeate reduction. Since the hydrogenase was soluble and used ferredoxin as an electron acceptor, the missing link was a ferredoxin:NAD+ oxidoreductase. This activity could be determined and, interestingly, was membrane bound. A search for genes that could encode this activity revealed DNA fragments encoding subunits C and D of a membrane-bound Rnf-type NADH dehydrogenase that is a potential Na+ pump. These data suggest the following electron transport chain: H2 → ferredoxin → NAD+ → Etf → caffeyl-CoA reductase. They also imply that the sodium motive step in the chain is the ferredoxin-dependent NAD+ reduction catalyzed by Rnf. PMID:17873051

Photo-driven electron transfer from the highly reducing excited state of naphthalene diimide radical anion to a CO 2 reduction catalyst within a molecular triad

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

Martinez, Jose F.; La Porte, Nathan T.; Mauck, Catherine M.

2017-01-01

The naphthalene-1,4:5,8-bis(dicarboximide) radical anion (NDI -˙), which is easily produced by mild chemical or electrochemical reduction (-0.5 Vvs.SCE), can be photoexcited at wavelengths as long as 785 nm, and has an excited state (NDI -˙*) oxidation potential of -2.1 Vvs.SCE, making it a very attractive choice for artificial photosynthetic systems that require powerful photoreductants, such as CO 2 reduction catalysts. However, once an electron is transferred from NDI -˙* to an acceptor directly bound to it, a combination of strong electronic coupling and favorable free energy change frequently make the back electron transfer rapid. To mitigate this effect, we havemore » designed a molecular triad system comprising an NDI -˙ chromophoric donor, a 9,10-diphenylanthracene (DPA) intermediate acceptor, and a Re(dmb)(CO) 3carbon dioxide reduction catalyst, where dmb is 4,4'-dimethyl-2,2'-bipyridine, as the terminal acceptor. Photoexcitation of NDI -˙ to NDI -˙* is followed by ultrafast reduction of DPA to DPA -˙, which then rapidly reduces the metal complex. The overall time constant for the forward electron transfer to reduce the metal complex is τ = 20.8 ps, while the time constant for back-electron transfer is six orders of magnitude longer, τ = 43.4 μs. Achieving long-lived, highly reduced states of these metal complexes is a necessary condition for their use as catalysts. The extremely long lifetime of the reduced metal complex is attributed to careful tuning of the redox potentials of the chromophore and intermediate acceptor. The NDI -˙–DPA fragment presents many attractive features for incorporation into other photoinduced electron transfer assemblies directed at the long-lived photosensitization of difficult-to-reduce catalytic centers.« less

Thermodynamics of Electron Flow in the Bacterial Deca-heme Cytochrome MtrF

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

Breuer, Marian; Zarzycki, Piotr P.; Blumberger, Jochen

2012-07-01

Electron transporting multiheme cytochromes are essential to the metabolism of microbes that inhabit soils and carry out important biogeochemical processes. Recently the first crystal structure of a prototype bacterial deca-heme cytochrome (MtrF) has been resolved and its electrochemistry characterized. However, the molecular details of electron conductance along heme chains in the cytochrome are difficult to access via experiment due to the nearly identical chemical nature of the heme cofactors. Here we employ large-scale molecular dynamics simulations to compute the reduction potentials of the ten hemes of MtrF in aqueous solution. We find that as a whole they fall within amore » range of about 0.3 V in agreement with experiment. Individual reduction potentials give rise to a free energy profile for electron conduction that is approximately symmetric with respect to the center of the protein. Our calculations indicate that there is no significant potential bias along the orthogonal octa- and tetra-heme chains suggesting that under aqueous conditions MtrF is a nearly reversible two-dimensional conductor.« less

Space electronics technology summary

NASA Technical Reports Server (NTRS)

1976-01-01

An overview is given of current electronics R and D activities, potential future thrusts, and related NASA payoffs. Major increases in NASA mission return and significant concurrent reductions in mission cost appear possible through a focused, long range electronics technology program. The overview covers: guidance assessments, navigation and control, and sensing and data acquisition processing, storage, and transfer.

Investigation on electrochemical behavior and its catalytic effect on oxygen reduction reaction of 3-Ferrocenyl dihydropyrazole derivative as electron relay

NASA Astrophysics Data System (ADS)

Zeng, Han; Huo, Wen-Shan; Zhao, Shu-Xian; Zhang, Yu-He

2017-11-01

Amino group surface tailored multi-wall carbon nano-tubes were covalently tethered to the gold disk electrode and Laccase molecules were covalently coupled to nano-tubes to prepare Lac-based electrode. Derivative of 3-ferrocenyl dihydropyrazole (FDPFFP) was proposed to be electron mediator for mediated oxygen reduction reaction. Investigation in electro-chemical behavior and catalytic performance to enzymatic reaction of FDPFFP indicated that it displayed quasi-reversible characteristics of electro-chemical reaction with rapid dynamics of electron shuttle and had apparent catalytic effect in oxygen reduction (onset potential for catalysis at 450 mV vs NHE). This enzymatic catalysis was restrained by the step in diffusion of substrate.

Electron transfer reactivity of the aqueous iron(IV)–oxo complex. Outer-sphere vs proton-coupled electron transfer

DOE PAGES

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

2016-06-18

Here, the kinetics of oxidation of organic and inorganic reductants by aqueous iron(IV) ions, Fe IV(H 2O) 5O 2+ (hereafter Fe IV aqO 2+), are reported. The substrates examined include several water-soluble ferrocenes, hexachloroiridate(III), polypyridyl complexes M(NN) 3 2+ (M = Os, Fe and Ru; NN = phenanthroline, bipyridine and derivatives), HABTS–/ABTS 2–, phenothiazines, Co II(dmgBF 2) 2, macrocyclic nickel(II) complexes, and aqueous cerium(III). Most of the reductants were oxidized cleanly to the corresponding one-electron oxidation products, with the exception of phenothiazines which produced the corresponding oxides in a single-step reaction, and polypyridyl complexes of Fe(II) and Ru(II) that generatedmore » ligand-modified products. Fe IV aqO 2+ oxidizes even Ce(III) (E 0 in 1 M HClO 4 = 1.7 V) with a rate constant greater than 10 4 M –1 s –1. In 0.10 M aqueous HClO 4 at 25 °C, the reactions of Os(phen) 3 2+ (k = 2.5 × 10 5 M –1 s –1), IrCl 6 3– (1.6 × 10 6), ABTS 2– (4.7 × 10 7), and Fe(cp)(C 5H 4CH 2OH) (6.4 × 10 7) appear to take place by outer sphere electron transfer (OSET). The rate constants for the oxidation of Os(phen) 3 2+ and of ferrocenes remained unchanged in the acidity range 0.05 < [H+] < 0.10 M, ruling out prior protonation of Fe IV aqO 2+ and further supporting the OSET assignment. A fit to Marcus cross-relation yielded a composite parameter (log k 22 + E 0 Fe/0.059) = 17.2 ± 0.8, where k 22 and E 0 Fe are the self-exchange rate constant and reduction potential, respectively, for the Fe IV aqO 2+/Fe III aqO + couple. Comparison with literature work suggests k 22 < 10 –5 M –1 s –1 and thus E 0(Fe IV aqO 2+/Fe III aqO +) > 1.3 V. For proton-coupled electron transfer, the reduction potential is estimated at E 0 (Fe IV aqO 2+, H +/Fe III aqOH 2+) ≥ 1.95 V.« less

Prediction of Reduction Potentials of Copper Proteins with Continuum Electrostatics and Density Functional Theory

PubMed Central

Fowler, Nicholas J.; Blanford, Christopher F.

2017-01-01

Abstract Blue copper proteins, such as azurin, show dramatic changes in Cu2+/Cu+ reduction potential upon mutation over the full physiological range. Hence, they have important functions in electron transfer and oxidation chemistry and have applications in industrial biotechnology. The details of what determines these reduction potential changes upon mutation are still unclear. Moreover, it has been difficult to model and predict the reduction potential of azurin mutants and currently no unique procedure or workflow pattern exists. Furthermore, high‐level computational methods can be accurate but are too time consuming for practical use. In this work, a novel approach for calculating reduction potentials of azurin mutants is shown, based on a combination of continuum electrostatics, density functional theory and empirical hydrophobicity factors. Our method accurately reproduces experimental reduction potential changes of 30 mutants with respect to wildtype within experimental error and highlights the factors contributing to the reduction potential change. Finally, reduction potentials are predicted for a series of 124 new mutants that have not yet been investigated experimentally. Several mutants are identified that are located well over 10 Å from the copper center that change the reduction potential by more than 85 mV. The work shows that secondary coordination sphere mutations mostly lead to long‐range electrostatic changes and hence can be modeled accurately with continuum electrostatics. PMID:28815759

Mechanistic insights into energy conservation by flavin-based electron bifurcation.

PubMed

Lubner, Carolyn E; Jennings, David P; Mulder, David W; Schut, Gerrit J; Zadvornyy, Oleg A; Hoben, John P; Tokmina-Lukaszewska, Monika; Berry, Luke; Nguyen, Diep M; Lipscomb, Gina L; Bothner, Brian; Jones, Anne K; Miller, Anne-Frances; King, Paul W; Adams, Michael W W; Peters, John W

2017-06-01

The recently realized biochemical phenomenon of energy conservation through electron bifurcation provides biology with an elegant means to maximize utilization of metabolic energy. The mechanism of coordinated coupling of exergonic and endergonic oxidation-reduction reactions by a single enzyme complex has been elucidated through optical and paramagnetic spectroscopic studies revealing unprecedented features. Pairs of electrons are bifurcated over more than 1 volt of electrochemical potential by generating a low-potential, highly energetic, unstable flavin semiquinone and directing electron flow to an iron-sulfur cluster with a highly negative potential to overcome the barrier of the endergonic half reaction. The unprecedented range of thermodynamic driving force that is generated by flavin-based electron bifurcation accounts for unique chemical reactions that are catalyzed by these enzymes.

One-pot synthesis of nitrogen and sulfur co-doped onion-like mesoporous carbon vesicle as an efficient metal-free catalyst for oxygen reduction reaction in alkaline solution

NASA Astrophysics Data System (ADS)

Han, Ce; Bo, Xiangjie; Zhang, Yufan; Li, Mian; Guo, Liping

2014-12-01

Nitrogen and sulfur co-doped onion-like mesoporous carbon vesicle (NS-MCV) with multilayer lamellar structure is synthesized as a metal-free catalyst through a convenient and economical procedure. The synthesized materials are systematically characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra, nitrogen adsorption-desorption, and X-ray photoelectron spectroscopy (XPS). The characterization results demonstrate that N and S atoms can be successfully doped into the framework of MCV with little impact on the morphology and structure. The NS-MCV manifests a remarkably high electrocatalytic activity as a metal-free electrocatalyst for the oxygen reduction reaction (ORR) with mainly a four-electron transfer pathway. Moreover, in contrast to the commercially available Pt/C catalyst, the NS-MCV shows much better long-term stability and tolerance toward methanol crossover in an alkaline medium. Such excellent performances can be mainly attributed to the synergistic effect arising from the addition of N and S heteroatom, optimized S content and high surface area. The NS-MCV with a simple synthesis method may further exploited as potentially efficient and inexpensive metal-free ORR catalyst materials.

[The action of quaternary ammonium derivatives on respiration and nitrate reduction in Pseudomonas aeruginosa].

PubMed

Bievskiĭ, A N

1994-01-01

It was revealed that the same dosages of quaternary ammonium derivatives, such as decamethoxin and cetyltrimethylammonium bromide, inhibited the respiratory chains and caused destruction of Pseudomonas aeruginosa under aerobic conditions more effectively than under anaerobic ones when anions of nitric acid were the terminal acceptors of electrons. It was also registered that Pseudomonas were able to dissimilatory nitrate reduction in the media under the polysaccharide layer that was produced by these bacteria: this fact possibly proves the possibility of survival of denitrifying bacteria in solutions with high concentrations of quaternary ammonium salts. The data obtained permit supposing that inhibitors of respiratory chains and oxidizers may be used as potentiators of the antimicrobial action of quaternary ammonium derivatives.

Reduction of Cr(VI) and survival in Cr-contaminated sites by Caulobacter crescentus

NASA Astrophysics Data System (ADS)

Hu, P.; Chakraborty, R.; Brodie, E. L.; Andersen, G. L.; Hazen, T. C.

2008-12-01

The Caulobacter spp. is known to be able to live in low-nutrient environments, a characteristic of most heavy metal-contaminated sites. Recent studies have shown that Caulobacter crescentus can grow in chemically defined medium containing up to 1 mM uranium. Whole-genome transcriptional analysis and electron microscopic imaging of heavy metal stresses in Caulobacter crescentus also provided insight and evidence that the bacterium used an array of defensive mechanisms to deal with heavy metal stresses. In addition to up-regulated enzymes protecting against oxidative stress, DNA repair and down-regulated potential chromium transport, one of the major gene groups respond to chromium stress is "electron transport process and cytochrome oxidases", including cytochrome c oxidases, raising the possibility that the cells can employ the cytochromes to reduce chromium. Analysis of the microbial community at the chromium contaminated DOE site at Hanford, WA revealed the presence of Caulobacter spp. As an oligotroph, Caulobacter can play a significant role in chromium reduction in the environment where the nutrients are limited. This result was confirmed by both 16S rDNA based microarray (Phylochip) as well as by MDA-based clone library data. Based on these results we further investigated the capability of this organism to reduce Cr(VI) using the well known model strain Caulobacter crescentus CB15N. Preliminary cell suspension experiments were set up with glucose as the electron donor and Cr(VI) as the electron acceptor in phosphate based M2 salts buffer. After 22 hours almost 27% of Cr(VI) was reduced in the incubations containing active cells relative to the controls containing heat killed cells. Also, in another set of controls with no electron acceptor added, cells showed no increase in cell density during that time demonstrating that the reduction of Cr(VI) by cells of Caulobacter was due to biological activity. Future experiments will investigate the components responsible and the mechanism of Cr(VI) reduction by Caulobacetr crescentus.

The potential of cinnamon to reduce blood glucose levels in patients with type 2 diabetes and insulin resistance.

PubMed

Kirkham, S; Akilen, R; Sharma, S; Tsiami, A

2009-12-01

Cinnamon has a long history as an antidiabetic spice, but trials involving cinnamon supplementation have produced contrasting results. The aim of this review was to examine the results of randomized controlled clinical trials of cinnamon and evaluate the therapeutic potential amongst patients with diabetes and insulin-resistant patients, particularly the ability to reduce blood glucose levels and inhibit protein glycation. A systematic electronic literature search using the medical subject headings 'cinnamon' and 'blood glucose' was carried out to include randomized, placebo-controlled in vivo clinical trials using Cinnamomum verum or Cinnamomum cassia conducted between January 2003 and July 2008. Five type 2 diabetic and three non-diabetic studies (total N = 311) were eligible. Two of the diabetic studies illustrated significant fasting blood glucose (FBG) reductions of 18-29% and 10.3% (p < 0.05), supported by one non-diabetic trial reporting an 8.4% FBG reduction (p < 0.01) vs. placebo, and another illustrating significant reductions in glucose response using oral glucose tolerance tests (p < 0.05). Three diabetic studies reported no significant results. Whilst definitive conclusions cannot be drawn regarding the use of cinnamon as an antidiabetic therapy, it does possess antihyperglycaemic properties and potential to reduce postprandial blood glucose levels. Further research is required to confirm a possible correlation between baseline FBG and blood glucose reduction and to assess the potential to reduce pathogenic diabetic complications with cinnamon supplementation.

Molecular approaches to the photocatalytic reduction of carbon dioxide for solar fuels.

PubMed

Morris, Amanda J; Meyer, Gerald J; Fujita, Etsuko

2009-12-21

The scientific community now agrees that the rise in atmospheric CO(2), the most abundant green house gas, comes from anthropogenic sources such as the burning of fossil fuels. This atmospheric rise in CO(2) results in global climate change. Therefore methods for photochemically transforming CO(2) into a source of fuel could offer an attractive way to decrease atmospheric concentrations. One way to accomplish this conversion is through the light-driven reduction of carbon dioxide to methane (CH(4(g))) or methanol (CH(3)OH((l))) with electrons and protons derived from water. Existing infrastructure already supports the delivery of natural gas and liquid fuels, which makes these possible CO(2) reduction products particularly appealing. This Account focuses on molecular approaches to photochemical CO(2) reduction in homogeneous solution. The reduction of CO(2) by one electron to form CO(2)(*-) is highly unfavorable, having a formal reduction potential of -2.14 V vs SCE. Rapid reduction requires an overpotential of up to 0.6 V, due at least in part to the kinetic restrictions imposed by the structural difference between linear CO(2) and bent CO(2)(*-). An alternative and more favorable pathway is to reduce CO(2) though proton-assisted multiple-electron transfer. The development of catalysts, redox mediators, or both that efficiently drive these reactions remains an important and active area of research. We divide these reactions into two class types. In Type I photocatalysis, a molecular light absorber and a transition metal catalyst work in concert. We also consider a special case of Type 1 photocatalysis, where a saturated hydrocarbon links the catalyst and the light absorber in a supramolecular compound. In Type II photocatalysis, the light absorber and the catalyst are the same molecule. In these reactions, transition-metal coordination compounds often serve as catalysts because they can absorb a significant portion of the solar spectrum and can promote activation of small molecules. This Account discusses four classes of transition-metal catalysts: (A) metal tetraaza-macrocyclic compounds; (B) supramolecular complexes; (C) metalloporphyrins and related metallomacrocycles; (D) Re(CO)(3)(bpy)X-based compounds where bpy = 2,2'-bipyridine. Carbon monoxide and formate are the primary CO(2) reduction products, and we also propose bicarbonate/carbonate production. For comprehensiveness, we briefly discuss hydrogen formation, a common side reaction that occurs concurrently with CO(2) reduction, though the details of that process are beyond the scope of this Account. It is our hope that drawing attention both to current mechanistic hypotheses and to the areas that are poorly understood will stimulate research that could one day provide an efficient solution to this global problem.

A Biochemical Magic Frequency

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

1993-01-01

Life is composed principally of four classes of biomolecules - protein, nucleic acid, polysaccharide and lipid. Using 1) estimates of the reducing equivalents (electron pairs) needed to synthesize these biomolecules from carbon dioxide, and 2) measurements of the molecular composition of different organisms, we calculated the average number of electron pairs required for the reduction of carbon dioxide to biological carbon (electron pairs/carbon atom). These calculations showed that the carbon of the Earths biosphere is at the reduction level of formaldehyde that requires 2 electron pairs/carbon atom to be synthesized from carbon dioxide. This was also the reduction level of carbon of individual organisms, except for those that stored large amounts of fuel as lipid. Since this chemical property of life is easily discovered and probably universal, it's most likely known by other intelligent life in the universe. It could be the one thing we know about other carbon-based life in the universe, and the one thing that other intelligent life knows about us. We believe this common knowledge that formaldehyde represents the reduction level of life's carbon could lead to the selection of the 72.83814 GHz line of the 0,0,0,1,0,1 ground-state rotational transition of formaldehyde as a frequency for interstellar communication.

Lantana camara Linn leaf extract mediated green synthesis of gold nanoparticles and study of its catalytic activity

NASA Astrophysics Data System (ADS)

Dash, Shib Shankar; Bag, Braja Gopal; Hota, Poulami

2015-03-01

A facile one-step green synthesis of stable gold nanoparticles (AuNPs) has been described using chloroauric acid (HAuCl4) and the leaf extract of Lantana camara Linn (Verbenaceae family) at room temperature. The leaf extract enriched in various types of plant secondary metabolites is highly efficient for the reduction of chloroaurate ions into metallic gold and stabilizes the synthesized AuNPs without any additional stabilizing or capping agents. Detailed characterizations of the synthesized gold nanoparticles were carried out by surface plasmon resonance spectroscopy, transmission electron microscopy, dynamic light scattering, Zeta potential, X-ray diffraction and Fourier transform-infrared spectroscopy studies. The synthesized AuNPs have been utilized as a catalyst for the sodium borohydride reduction of 4-nitrophenol to 4-aminophenol in water at room temperature under mild reaction condition. The kinetics of the reduction reaction has been studied spectrophotometrically.

Harm reduction at the crossroads: the case of e-cigarettes.

PubMed

Maziak, Wasim

2014-10-01

The recent popularity of electronic (e)-cigarettes and their rapid uptake by youth has ignited the debate about their role as a harm-reduction strategy. Harm reduction in the context of tobacco control contends that in societies that have achieved considerable success in curbing smoking, leaving the remaining hard-to-quit smokers with an abstinence-only option is unfair, especially when less-harmful choices are available. On one side of the debate are those who call for caution in endorsing such products until critical pieces of evidence about their safety and potential become available, whereas the other side argues that waiting until all questions about e-cigarettes are answered is dogma driven. In this piece, I try to discuss the unresolvable contention between harm-reduction goals of offering safer options to smokers, and those of e-cigarette makers of being commercially viable and profitable. Copyright © 2014 American Journal of Preventive Medicine. Published by Elsevier Inc. All rights reserved.

Evidence for single metal two electron oxidative addition and reductive elimination at uranium.

PubMed

Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; McInnes, Eric J L; Tuna, Floriana; Wooles, Ashley J; Maron, Laurent; Liddle, Stephen T

2017-12-01

Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido complex in a reaction that satisfies all criteria of a single-metal two-electron oxidative addition. Thermolysis of this complex promotes extrusion of azobenzene, where H-/D-isotopic labelling finds no isotopomer cross-over and the non-reactivity of a nitrene-trap suggests that nitrenes are not generated and thus a reductive elimination has occurred. Though not optimally balanced in this case, this work presents evidence that classical d-block redox chemistry can be performed reversibly by f-block metals, and that uranium can thus mimic elementary transition metal reactivity, which may lead to the discovery of new f-block catalysis.

Spectroscopic and DFT Studies of Second Sphere Variants of the Type 1 Copper Site in Azurin: Covalent and Non-Local Electrostatic Contributions to Reduction Potentials

PubMed Central

Hadt, Ryan G.; Sun, Ning; Marshall, Nicholas M.; Hodgson, Keith O.; Hedman, Britt; Lu, Yi; Solomon, Edward I.

2012-01-01

The reduction potentials (E0) of type 1 (T1) or blue copper (BC) sites in proteins and enzymes with identical first coordination spheres around the redox active copper ion can vary by ~400 mV. Here, we use a combination of low temperature electronic absorption and magnetic circular dichroism, electron paramagnetic resonance, resonance Raman, and S K-edge X-ray absorption spectroscopies to investigate a series of second sphere variants—F114P, N47S, and F114N in Pseudomonas aeruginosa azurin (Az)—which modulate hydrogen bonding to and protein derived dipoles nearby the Cu-S(Cys) bond. Density functional theory (DFT) calculations correlated to the experimental data allow for the fractionation of the contributions to tuning E0 into covalent and non-local electrostatic components. These are found to be significant, comparable in magnitude, and additive for active H-bonds, while passive H-bonds are mostly non-local electrostatic in nature. For dipoles, these terms can be additive to or oppose one another. This study provides a methodology for uncoupling covalency from non-local electrostatics, which, when coupled to X-ray crystallographic data, distinguishes specific local interactions from more long range protein/active interactions, while affording further insight into the second sphere mechanisms available to the protein to tune the E0 of electron transfer sites in biology. PMID:22985400

Distinct properties underlie flavin-based electron bifurcation in a novel electron transfer flavoprotein FixAB from Rhodopseudomonas palustris

DOE PAGES

Duan, H. Diessel; Lubner, Carolyn E.; Tokmina-Lukaszewska, Monika; ...

2018-02-09

A newly-recognized third fundamental mechanism of energy conservation in biology, electron bifurcation, uses free energy from exergonic redox reactions to drive endergonic redox reactions. Flavin-based electron bifurcation furnishes low potential electrons to demanding chemical reactions such as reduction of dinitrogen to ammonia. We employed the heterodimeric flavoenzyme FixAB from the diazotrophic bacterium Rhodopseudomonas palustris to elucidate unique properties that underpin flavin-based electron bifurcation.

Observed Benefits to On-site Medical Services during an Annual 5-day Electronic Dance Music Event with Harm Reduction Services.

PubMed

Munn, Matthew Brendan; Lund, Adam; Golby, Riley; Turris, Sheila A

2016-04-01

With increasing attendance and media attention, large-scale electronic dance music events (EDMEs) are a subset of mass gatherings that have a unique risk profile for attendees and promoters. Shambhala Music Festival (Canada) is a multi-day event in a rural setting with a recognized history of providing harm reduction (HR) services alongside medical care. Study/Objective This manuscript describes the medical response at a multi-day electronic music festival where on-site HR interventions and dedicated medical care are delivered as parallel public health measures. This study was a descriptive case report. Medical encounters and event-related data were documented prospectively using an established event registry database. In 2014, Shambhala Music Festival had 67,120 cumulative attendees over a 7-day period, with a peak daily attendance of 15,380 people. There were 1,393 patient encounters and the patient presentation rate (PPR) was 20.8 per one thousand. The majority of these (90.9%) were for non-urgent complaints. The ambulance transfer rate (ATR) was 0.194 per one thousand and 0.93% of patient encounters were transferred by ambulance. No patients required intubation and there were no fatalities. Harm reduction services included mobile outreach teams, distribution of educational materials, pill checking facilities, a dedicated women's space, and a "Sanctuary" area that provided non-medical peer support for overwhelmed guests. More than 10,000 encounters were recorded by mobile and booth-based preventive and educational services, and 2,786 pills were checked on-site with a seven percent discard rate. Dedicated medical and HR services represent two complementary public health strategies to minimize risk at a multi-day electronic music festival. The specific extent to which HR strategies reduce the need for medical care is not well understood. Incorporation of HR practices when planning on-site medical care has the potential to inform patient management, reduce presentation rates and acuity, and decrease utilization and cost for local, community-based health services.

Genomic, proteomic, and biochemical analysis of the organohalide respiratory pathway in Desulfitobacterium dehalogenans.

PubMed

Kruse, Thomas; van de Pas, Bram A; Atteia, Ariane; Krab, Klaas; Hagen, Wilfred R; Goodwin, Lynne; Chain, Patrick; Boeren, Sjef; Maphosa, Farai; Schraa, Gosse; de Vos, Willem M; van der Oost, John; Smidt, Hauke; Stams, Alfons J M

2015-03-01

Desulfitobacterium dehalogenans is able to grow by organohalide respiration using 3-chloro-4-hydroxyphenyl acetate (Cl-OHPA) as an electron acceptor. We used a combination of genome sequencing, biochemical analysis of redox active components, and shotgun proteomics to study elements of the organohalide respiratory electron transport chain. The genome of Desulfitobacterium dehalogenans JW/IU-DC1(T) consists of a single circular chromosome of 4,321,753 bp with a GC content of 44.97%. The genome contains 4,252 genes, including six rRNA operons and six predicted reductive dehalogenases. One of the reductive dehalogenases, CprA, is encoded by a well-characterized cprTKZEBACD gene cluster. Redox active components were identified in concentrated suspensions of cells grown on formate and Cl-OHPA or formate and fumarate, using electron paramagnetic resonance (EPR), visible spectroscopy, and high-performance liquid chromatography (HPLC) analysis of membrane extracts. In cell suspensions, these components were reduced upon addition of formate and oxidized after addition of Cl-OHPA, indicating involvement in organohalide respiration. Genome analysis revealed genes that likely encode the identified components of the electron transport chain from formate to fumarate or Cl-OHPA. Data presented here suggest that the first part of the electron transport chain from formate to fumarate or Cl-OHPA is shared. Electrons are channeled from an outward-facing formate dehydrogenase via menaquinones to a fumarate reductase located at the cytoplasmic face of the membrane. When Cl-OHPA is the terminal electron acceptor, electrons are transferred from menaquinones to outward-facing CprA, via an as-yet-unidentified membrane complex, and potentially an extracellular flavoprotein acting as an electron shuttle between the quinol dehydrogenase membrane complex and CprA. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Genomic, Proteomic, and Biochemical Analysis of the Organohalide Respiratory Pathway in Desulfitobacterium dehalogenans

PubMed Central

van de Pas, Bram A.; Atteia, Ariane; Krab, Klaas; Hagen, Wilfred R.; Goodwin, Lynne; Chain, Patrick; Boeren, Sjef; Maphosa, Farai; Schraa, Gosse; de Vos, Willem M.; van der Oost, John; Smidt, Hauke

2014-01-01

Desulfitobacterium dehalogenans is able to grow by organohalide respiration using 3-chloro-4-hydroxyphenyl acetate (Cl-OHPA) as an electron acceptor. We used a combination of genome sequencing, biochemical analysis of redox active components, and shotgun proteomics to study elements of the organohalide respiratory electron transport chain. The genome of Desulfitobacterium dehalogenans JW/IU-DC1T consists of a single circular chromosome of 4,321,753 bp with a GC content of 44.97%. The genome contains 4,252 genes, including six rRNA operons and six predicted reductive dehalogenases. One of the reductive dehalogenases, CprA, is encoded by a well-characterized cprTKZEBACD gene cluster. Redox active components were identified in concentrated suspensions of cells grown on formate and Cl-OHPA or formate and fumarate, using electron paramagnetic resonance (EPR), visible spectroscopy, and high-performance liquid chromatography (HPLC) analysis of membrane extracts. In cell suspensions, these components were reduced upon addition of formate and oxidized after addition of Cl-OHPA, indicating involvement in organohalide respiration. Genome analysis revealed genes that likely encode the identified components of the electron transport chain from formate to fumarate or Cl-OHPA. Data presented here suggest that the first part of the electron transport chain from formate to fumarate or Cl-OHPA is shared. Electrons are channeled from an outward-facing formate dehydrogenase via menaquinones to a fumarate reductase located at the cytoplasmic face of the membrane. When Cl-OHPA is the terminal electron acceptor, electrons are transferred from menaquinones to outward-facing CprA, via an as-yet-unidentified membrane complex, and potentially an extracellular flavoprotein acting as an electron shuttle between the quinol dehydrogenase membrane complex and CprA. PMID:25512312

Pulse-radiolysis studies on the interaction of one-electron reduced species with blue oxidases. Reduction of type-2-copper-depleted ascorbate oxidase.

PubMed

O'Neill, P; Fielden, E M; Avigliano, L; Marcozzi, G; Ballini, A; Agrò, F

1984-08-15

The interaction of one-electron reduced metronidazole (ArNO2.-) with native and Type-2-copper-depleted ascorbate oxidase were studied in buffered aqueous solution at pH 6.0 and 7.4 by using the technique of pulse radiolysis. With ArNO2.-, reduction of Type 1 copper of the native enzyme and of the Type-2-copper-depleted ascorbate oxidase occurs via a bimolecular step and at the same rate. Whereas the native protein accepts, in the absence of O2, 6-7 reducing equivalents, Type-2-copper-depleted ascorbate oxidase accepts only 3 reducing equivalents with stoichiometric reduction of Type 1 copper. On reaction of O2.- with ascorbate oxidase under conditions of [O2.-] much greater than [ascorbate oxidase], removal of Type 2 copper results in reduction of all the Type 1 copper atoms, in contrast with reduction of the equivalent of only one Type 1 copper atom in the holoprotein. From observations at 610 nm, the rate of reduction of ascorbate oxidase by O2.- is not dependent on the presence of Type 2 copper. For the holoprotein, no significant optical-absorption changes were observed at 330 nm. It is proposed that electrons enter the protein via Type 1 copper in a rate-determining step followed by a fast intramolecular transfer of electrons within the protein. For the Type-2-copper-depleted protein, intramolecular transfer within the protein, however, is slow or does not occur. In the presence of O2, it is also suggested that re-oxidation of the partially reduced holoprotein occurs at steady state, as inferred from the observations at 330 nm and 610 nm. The role of Type 2 copper in ascorbate oxidase is discussed in terms of its involvement in redistribution of electrons within the protein or structural considerations.

An Overview of Electron Acceptors in Microbial Fuel Cells

PubMed Central

Ucar, Deniz; Zhang, Yifeng; Angelidaki, Irini

2017-01-01

Microbial fuel cells (MFC) have recently received increasing attention due to their promising potential in sustainable wastewater treatment and contaminant removal. In general, contaminants can be removed either as an electron donor via microbial catalyzed oxidization at the anode or removed at the cathode as electron acceptors through reduction. Some contaminants can also function as electron mediators at the anode or cathode. While previous studies have done a thorough assessment of electron donors, cathodic electron acceptors and mediators have not been as well described. Oxygen is widely used as an electron acceptor due to its high oxidation potential and ready availability. Recent studies, however, have begun to assess the use of different electron acceptors because of the (1) diversity of redox potential, (2) needs of alternative and more efficient cathode reaction, and (3) expanding of MFC based technologies in different areas. The aim of this review was to evaluate the performance and applicability of various electron acceptors and mediators used in MFCs. This review also evaluated the corresponding performance, advantages and disadvantages, and future potential applications of select electron acceptors (e.g., nitrate, iron, copper, perchlorate) and mediators. PMID:28469607

Photo-reduction of bromate in drinking water by metallic Ag and reduced graphene oxide (RGO) jointly modified BiVO4 under visible light irradiation.

PubMed

Chen, Fei; Yang, Qi; Zhong, Yu; An, Hongxue; Zhao, Jianwei; Xie, Ting; Xu, Qiuxiang; Li, Xiaoming; Wang, Dongbo; Zeng, Guangming

2016-09-15

Bromate (BrO3(-)), an oxyhalide disinfection by-product (DBP) in drinking water, has been demonstrated to be carcinogenic and genotoxic. In the current work, metallic Ag and reduced graphene oxide (RGO) co-modified BiVO4 was successfully synthesized by a stepwise chemical method coupling with a photo-deposition process and applied in the photo-reduction of BrO3(-) under visible light irradiation. In this composite, metallic Ag acted as an electron donor or mediator and RGO enhanced the BrO3(-) adsorption onto the surface of catalysts as well as an electron acceptor to restrict the recombination of photo-generated electron-hole pairs. The Ag@BiVO4@RGO composite exhibited greater photo-reduction BrO3(-) performance than pure BiVO4, Ag@BiVO4 and RGO@BiVO4 under identical experimental conditions: initial BrO3(-) concentration 150 μg/L, catalyst dosage 0.5 g/L, pH 7.0 and visible light (λ > 420 nm). The photoluminescence spectra (PL), electron-spin resonance (ESR), photocurrent density (PC) and electrochemical impedance spectroscopy (EIS) measurements indicated that the modified BiVO4 enhanced the photo-generated electrons and separated the electron-hole pairs. The photocatalytic reduction efficiency for BrO3(-) removal decreased with the addition of electron quencher K2S2O8, suggesting that electrons were the primary factor in this photo-reduction process. The declining photo-reduction efficiency of BrO3(-) in tap water should attribute to the consumption of photo-generated electrons by coexisting anions and the adsorption of dissolved organic matter (DOM) on graphene surface. The overall results indicate a promising application potential for photo-reduction in the DBPs removal from drinking water. Copyright © 2016 Elsevier Ltd. All rights reserved.

Promotion of Iron Oxide Reduction and Extracellular Electron Transfer in Shewanella oneidensis by DMSO

PubMed Central

Cheng, Yuan-Yuan; Li, Bing-Bing; Li, Dao-Bo; Chen, Jie-Jie; Li, Wen-Wei; Tong, Zhong-Hua; Wu, Chao; Yu, Han-Qing

2013-01-01

The dissimilatory metal reducing bacterium Shewanella oneidensis MR-1, known for its capacity of reducing iron and manganese oxides, has great environmental impacts. The iron oxides reducing process is affected by the coexistence of alternative electron acceptors in the environment, while investigation into it is limited so far. In this work, the impact of dimethyl sulphoxide (DMSO), a ubiquitous chemical in marine environment, on the reduction of hydrous ferric oxide (HFO) by S. oneidensis MR-1 was investigated. Results show that DMSO promoted HFO reduction by both wild type and ΔdmsE, but had no effect on the HFO reduction by ΔdmsB, indicating that such a promotion was dependent on the DMSO respiration. With the DMSO dosing, the levels of extracellular flavins and omcA expression were significantly increased in WT and further increased in ΔdmsE. Bioelectrochemical analysis show that DMSO also promoted the extracellular electron transfer of WT and ΔdmsE. These results demonstrate that DMSO could stimulate the HFO reduction through metabolic and genetic regulation in S. oneidensis MR-1, rather than compete for electrons with HFO. This may provide a potential respiratory pathway to enhance the microbial electron flows for environmental and engineering applications. PMID:24244312

Absolute Standard Hydrogen Electrode Potential Measured by Reduction of Aqueous Nanodrops in the Gas Phase

PubMed Central

Donald, William A.; Leib, Ryan D.; O'Brien, Jeremy T.; Bush, Matthew F.; Williams, Evan R.

2008-01-01

In solution, half-cell potentials are measured relative to those of other half cells, thereby establishing a ladder of thermochemical values that are referenced to the standard hydrogen electrode (SHE), which is arbitrarily assigned a value of exactly 0 V. Although there has been considerable interest in, and efforts toward, establishing an absolute electrochemical half-cell potential in solution, there is no general consensus regarding the best approach to obtain this value. Here, ion-electron recombination energies resulting from electron capture by gas-phase nanodrops containing individual [M(NH3)6]3+, M = Ru, Co, Os, Cr, and Ir, and Cu2+ ions are obtained from the number of water molecules that are lost from the reduced precursors. These experimental data combined with nanodrop solvation energies estimated from Born theory and solution-phase entropies estimated from limited experimental data provide absolute reduction energies for these redox couples in bulk aqueous solution. A key advantage of this approach is that solvent effects well past two solvent shells, that are difficult to model accurately, are included in these experimental measurements. By evaluating these data relative to known solution-phase reduction potentials, an absolute value for the SHE of 4.2 ± 0.4 V versus a free electron is obtained. Although not achieved here, the uncertainty of this method could potentially be reduced to below 0.1 V, making this an attractive method for establishing an absolute electrochemical scale that bridges solution and gas-phase redox chemistry. PMID:18288835

Heterobimetallic Pd–K carbene complexes via one-electron reductions of palladium radical carbenes

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

Cui, Peng; Hoffbauer, Melissa R.; Vyushkova, Mariya

2016-03-24

Unprecedented sequential substitution/reduction synthetic strategy on the Pd radical carbenes afforded heterobimetallic Pd–K carbene complexes, which features novel Pd–C carbene–K structural moieties.

Heterobimetallic Pd–K carbene complexes via one-electron reductions of palladium radical carbenes

DOE PAGES

Cui, Peng; Hoffbauer, Melissa R.; Vyushkova, Mariya; ...

2016-01-01

Unprecedented sequential substitution/reduction synthetic strategy on the Pd radical carbenes afforded heterobimetallic Pd–K carbene complexes, which features novel Pd–C carbene–K structural moieties.

Electronic Structure of Semiconductor Interfaces.

DTIC Science & Technology

1984-11-01

Workshop on Effective One-Electron Potentials In Real Materials, Ossining , New York, Mar. 21-22, 1980 Member, Organizing Committee, Annual Conferences on...Workshop on Effective One-Electron Potentials in Real Materials, Ossining , New York, Mar. 21-22, 1980 (Invited Paper) Electronic Structure of

Electron transfer to nitrogenase in different genomic and metabolic backgrounds.

PubMed

Poudel, Saroj; Colman, Daniel R; Fixen, Kathryn R; Ledbetter, Rhesa N; Zheng, Yanning; Pence, Natasha; Seefeldt, Lance C; Peters, John W; Harwood, Caroline S; Boyd, Eric S

2018-02-26

Nitrogenase catalyzes the reduction of dinitrogen (N 2 ) using low potential electrons from ferredoxin (Fd) or flavodoxin (Fld) through an ATP dependent process. Since its emergence in an anaerobic chemoautotroph, this oxygen (O 2 ) sensitive enzyme complex has evolved to operate in a variety of genomic and metabolic backgrounds including those of aerobes, anaerobes, chemotrophs, and phototrophs. However, whether pathways of electron delivery to nitrogenase are influenced by these different metabolic backgrounds is not well understood. Here, we report the distribution of homologs of Fds, Flds, and Fd/Fld-reducing enzymes in 359 genomes of putative N 2 fixers (diazotrophs). Six distinct lineages of nitrogenase were identified and their distributions largely corresponded to differences in the host cells' ability to integrate O 2 or light into energy metabolism. Predicted pathways of electron transfer to nitrogenase in aerobes, facultative anaerobes, and phototrophs varied from those in anaerobes at the level of Fds/Flds used to reduce nitrogenase, the enzymes that generate reduced Fds/Flds, and the putative substrates of these enzymes. Proteins that putatively reduce Fd with hydrogen or pyruvate were enriched in anaerobes, while those that reduce Fd with NADH/NADPH were enriched in aerobes, facultative anaerobes, and anoxygenic phototrophs. The energy metabolism of aerobic, facultatively anaerobic, and anoxygenic phototrophic diazotrophs often yields reduced NADH/NADPH that is not sufficiently reduced to drive N 2 reduction. At least two mechanisms have been acquired by these taxa to overcome this limitation and to generate electrons with potentials capable of reducing Fd. These include the bifurcation of electrons or the coupling of Fd reduction to reverse ion translocation. IMPORTANCE Nitrogen fixation supplies fixed nitrogen to cells from a variety of genomic and metabolic backgrounds including those of aerobes, facultative anaerobes, chemotrophs, and phototrophs. Here, using informatics approaches applied to genomic data, we show that pathways of electron transfer to nitrogenase in metabolically diverse diazotrophic taxa have diversified primarily in response to host cells' acquired ability to integrate O 2 or light into their energy metabolism. Acquisition of two key enzyme complexes enabled aerobic and facultatively anaerobic phototrophic taxa to generate electrons of sufficiently low potential to reduce nitrogenase: the bifurcation of electrons via the Fix complex or the coupling of Fd reduction to reverse ion translocation via the Rhodobacter nitrogen fixation (Rnf) complex. Copyright © 2018 American Society for Microbiology.

Bookending the Opportunity to Lower Wind’s LCOE by Reducing the Uncertainty Surrounding Annual Energy Production

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

Bolinger, Mark

Reducing the performance risk surrounding a wind project can potentially lead to a lower weighted-average cost of capital (WACC), and hence a lower levelized cost of energy (LCOE), through an advantageous shift in capital structure, and possibly also a reduction in the cost of capital. Specifically, a reduction in performance risk will move the 1-year P99 annual energy production (AEP) estimate closer to the P50 AEP estimate, which in turn reduces the minimum debt service coverage ratio (DSCR) required by lenders, thereby allowing the project to be financed with a greater proportion of low-cost debt. In addition, a reduction inmore » performance risk might also reduce the cost of one or more of the three sources of capital that are commonly used to finance wind projects: sponsor or cash equity, tax equity, and/or debt. Preliminary internal LBNL analysis of the maximum possible LCOE reduction attainable from reducing the performance risk of a wind project found a potentially significant opportunity for LCOE reduction of ~$10/MWh, by reducing the P50 DSCR to its theoretical minimum value of 1.0 (Bolinger 2015b, 2014) and by reducing the cost of sponsor equity and debt by one-third to one-half each (Bolinger 2015a, 2015b). However, with FY17 funding from the U.S. Department of Energy’s Atmosphere to Electrons (A2e) Performance Risk, Uncertainty, and Finance (PRUF) initiative, LBNL has been revisiting this “bookending” exercise in more depth, and now believes that its earlier preliminary assessment of the LCOE reduction opportunity was overstated. This reassessment is based on two new-found understandings: (1) Due to ever-present and largely irreducible inter-annual variability (IAV) in the wind resource, the minimum required DSCR cannot possibly fall to 1.0 (on a P50 basis), and (2) A reduction in AEP uncertainty will not necessarily lead to a reduction in the cost of capital, meaning that a shift in capital structure is perhaps the best that can be expected (perhaps along with a modest decline in the cost of cash equity as new investors enter the market).« less

The obligate respiratory supercomplex from Actinobacteria.

PubMed

Kao, Wei-Chun; Kleinschroth, Thomas; Nitschke, Wolfgang; Baymann, Frauke; Neehaul, Yashvin; Hellwig, Petra; Richers, Sebastian; Vonck, Janet; Bott, Michael; Hunte, Carola

2016-10-01

Actinobacteria are closely linked to human life as industrial producers of bioactive molecules and as human pathogens. Respiratory cytochrome bcc complex and cytochrome aa3 oxidase are key components of their aerobic energy metabolism. They form a supercomplex in the actinobacterial species Corynebacterium glutamicum. With comprehensive bioinformatics and phylogenetic analysis we show that genes for cyt bcc-aa3 supercomplex are characteristic for Actinobacteria (Actinobacteria and Acidimicrobiia, except the anaerobic orders Actinomycetales and Bifidobacteriales). An obligatory supercomplex is likely, due to the lack of genes encoding alternative electron transfer partners such as mono-heme cyt c. Instead, subunit QcrC of bcc complex, here classified as short di-heme cyt c, will provide the exclusive electron transfer link between the complexes as in C. glutamicum. Purified to high homogeneity, the C. glutamicum bcc-aa3 supercomplex contained all subunits and cofactors as analyzed by SDS-PAGE, BN-PAGE, absorption and EPR spectroscopy. Highly uniform supercomplex particles in electron microscopy analysis support a distinct structural composition. The supercomplex possesses a dimeric stoichiometry with a ratio of a-type, b-type and c-type hemes close to 1:1:1. Redox titrations revealed a low potential bcc complex (Em(ISP)=+160mV, Em(bL)=-291mV, Em(bH)=-163mV, Em(cc)=+100mV) fined-tuned for oxidation of menaquinol and a mixed potential aa3 oxidase (Em(CuA)=+150mV, Em(a/a3)=+143/+317mV) mediating between low and high redox potential to accomplish dioxygen reduction. The generated molecular model supports a stable assembled supercomplex with defined architecture which permits energetically efficient coupling of menaquinol oxidation and dioxygen reduction in one supramolecular entity. Copyright © 2016 Elsevier B.V. All rights reserved.

Mechanistic insights into energy conservation by flavin-based electron bifurcation

DOE PAGES

Lubner, Carolyn E.; Jennings, David P.; Mulder, David W.; ...

2017-04-10

The recently realized biochemical phenomenon of energy conservation through electron bifurcation provides biology with an elegant means to maximize utilization of metabolic energy. The mechanism of coordinated coupling of exergonic and endergonic oxidation-reduction reactions by a single enzyme complex has been elucidated through optical and paramagnetic spectroscopic studies revealing unprecedented features. Pairs of electrons are bifurcated over more than 1 volt of electrochemical potential by generating a low-potential, highly energetic, unstable flavin semiquinone and directing electron flow to an iron-sulfur cluster with a highly negative potential to overcome the barrier of the endergonic half reaction. As a result, the unprecedentedmore » range of thermodynamic driving force that is generated by flavin-based electron bifurcation accounts for unique chemical reactions that are catalyzed by these enzymes.« less

Mechanistic insights into energy conservation by flavin-based electron bifurcation

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

Lubner, Carolyn E.; Jennings, David P.; Mulder, David W.

The recently realized biochemical phenomenon of energy conservation through electron bifurcation provides biology with an elegant means to maximize utilization of metabolic energy. The mechanism of coordinated coupling of exergonic and endergonic oxidation-reduction reactions by a single enzyme complex has been elucidated through optical and paramagnetic spectroscopic studies revealing unprecedented features. Pairs of electrons are bifurcated over more than 1 volt of electrochemical potential by generating a low-potential, highly energetic, unstable flavin semiquinone and directing electron flow to an iron-sulfur cluster with a highly negative potential to overcome the barrier of the endergonic half reaction. As a result, the unprecedentedmore » range of thermodynamic driving force that is generated by flavin-based electron bifurcation accounts for unique chemical reactions that are catalyzed by these enzymes.« less

Molecular Cobalt Catalysts for O 2 Reduction: Low-Overpotential Production of H 2 O 2 and Comparison with Iron-Based Catalysts

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

Wang, Yu-Heng; Pegis, Michael L.; Mayer, James M.

A series of mononuclear pseudo-macrocyclic cobalt complexes have been investigated as catalysts for O2 reduction. Each of these complexes, with CoIII/II reduction potentials that span nearly 400 mV, mediate highly selective two- electron reduction of O2 to H2O2 (93–99%) using decamethylferrocene (Fc*) as the reductant and acetic acid as the proton source. Kinetic studies reveal that the rate exhibits a first- order dependence on [Co] and [AcOH], but no dependence on [O2] or [Fc*]. A linear correlation is observed between log(TOF) vs. E1/2(CoIII/II) for the different cobalt complexes (TOF = turnover frequency). The thermodynamic potential for+ O2 reduction to H2O2more » was estimated by measuring the H /H2 open-circuit potential under the reaction conditions. This value provides the basis for direct assessment of the thermodynamic efficiency of the different catalysts and shows that H2O2 is formed with overpotentials as low as 90 mV. These results are compared with a recently reported series of Fe-porphyrin complexes, which catalyze four-electron reduction of O2 to H2O. The data show that the TOFs of the Co complexes exhibit a shallower dependence on E1/2(MIII/II) than the Fe complexes. This behavior, which underlies the low overpotential, is rationalized on the basis of the catalytic rate law.« less

Electronic Tongue for Quantitation of Contaminants in Water

NASA Technical Reports Server (NTRS)

Buehler, Marlin; Kuhlman, Gregory

2004-01-01

An assembly of sensors, denoted an electronic tongue, is undergoing development as a prototype of compact devices for use in measuring concentrations of contaminants in water. Thus far, the electronic tongue has been tested on ions of Cu, Zn, Pb, and Fe and shown to respond to concentrations as low as about 10 parts per million. This electronic tongue is expected to be capable of measuring concentrations of other metal ions and organic compounds. Potential uses for electronic tongues include monitoring the chemical quality of water in a variety of natural, industrial, and laboratory settings; detecting micro-organisms indirectly by measuring microbially influenced corrosion; and characterizing compounds of interest to the pharmaceutical and food industries. This version of the electronic tongue includes a heater, a temperature sensor, an array of ion-specific electrodes, an oxidation/ reduction sensor pair, an electrical-conductivity sensor, and an array of galvanic cells, all on one compact ceramic substrate. Special-purpose electronic excitation and readout circuitry for the sensors has also been constructed. The main advantage of the electronic tongue, relative to electrodes of this type used traditionally to assess water quality, is extreme ruggedness. The types of measurements that can be performed by use of the sensors on the electronic tongue are quite varied. The best combination of types of measurements for a given application depends on the specific contaminants that one seeks to detect. Experimental studies to identify such combinations were in progress at the time of reporting the information for this article.

Prediction of Reduction Potentials of Copper Proteins with Continuum Electrostatics and Density Functional Theory.

PubMed

Fowler, Nicholas J; Blanford, Christopher F; Warwicker, Jim; de Visser, Sam P

2017-11-02

Blue copper proteins, such as azurin, show dramatic changes in Cu 2+ /Cu + reduction potential upon mutation over the full physiological range. Hence, they have important functions in electron transfer and oxidation chemistry and have applications in industrial biotechnology. The details of what determines these reduction potential changes upon mutation are still unclear. Moreover, it has been difficult to model and predict the reduction potential of azurin mutants and currently no unique procedure or workflow pattern exists. Furthermore, high-level computational methods can be accurate but are too time consuming for practical use. In this work, a novel approach for calculating reduction potentials of azurin mutants is shown, based on a combination of continuum electrostatics, density functional theory and empirical hydrophobicity factors. Our method accurately reproduces experimental reduction potential changes of 30 mutants with respect to wildtype within experimental error and highlights the factors contributing to the reduction potential change. Finally, reduction potentials are predicted for a series of 124 new mutants that have not yet been investigated experimentally. Several mutants are identified that are located well over 10 Å from the copper center that change the reduction potential by more than 85 mV. The work shows that secondary coordination sphere mutations mostly lead to long-range electrostatic changes and hence can be modeled accurately with continuum electrostatics. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

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

Lu, Fang; Zhang, Yu; Liu, Shizhong

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

DOE PAGES

Lu, Fang; Zhang, Yu; Liu, Shizhong; ...

2017-05-11

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

New Mechanism for the Reduction of Vanadyl Acetylacetonate to Vanadium Acetylacetonate for Room Temperature Flow Batteries.

PubMed

Shamie, Jack S; Liu, Caihong; Shaw, Leon L; Sprenkle, Vincent L

2017-02-08

In this study, a new mechanism for the reduction of vanadyl acetylacetonate, VO(acac) 2 , to vanadium acetylacetonate, V(acac) 3 , is introduced. V(acac) 3 has been studied for use in redox flow batteries (RFBs) for some time; however, contamination by moisture leads to the formation of VO(acac) 2 . In previous work, once this transformation occurs, it is no longer reversible because there is a requirement for extreme low potentials for the reduction to occur. Here, we propose that, in the presence of excess acetylacetone (Hacac) and free protons (H + ), the reduction can take place between 2.25 and 1.5 V versus Na/Na + via a one-electron-transfer reduction. This reduction can take place in situ during discharge in a novel hybrid Na-based flow battery (HNFB) with a molten Na-Cs alloy as the anode. The in situ recovery of V(acac) 3 during discharge is shown to allow the Coulombic efficiency of the HNFB to be ≈100 % with little or no capacity decay over cycles. In addition, utilizing two-electron-transfer redox reactions (i.e., V 3+ /V 4+ and V 2+ /V 3+ redox couples) per V ion to increase the energy density of RFBs becomes possible owing to the in situ recovery of V(acac) 3 during discharge. The concept of in situ recovery of material can lead to more advances in maintaining the cycle life of RFBs in the future. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anaerobic Methane Oxidation Driven by Microbial Reduction of Natural Organic Matter in a Tropical Wetland

PubMed Central

Valenzuela, Edgardo I.; Prieto-Davó, Alejandra; López-Lozano, Nguyen E.; Hernández-Eligio, Alberto; Vega-Alvarado, Leticia; Juárez, Katy; García-González, Ana Sarahí; López, Mercedes G.

2017-01-01

ABSTRACT Wetlands constitute the main natural source of methane on Earth due to their high content of natural organic matter (NOM), but key drivers, such as electron acceptors, supporting methanotrophic activities in these habitats are poorly understood. We performed anoxic incubations using freshly collected sediment, along with water samples harvested from a tropical wetland, amended with 13C-methane (0.67 atm) to test the capacity of its microbial community to perform anaerobic oxidation of methane (AOM) linked to the reduction of the humic fraction of its NOM. Collected evidence demonstrates that electron-accepting functional groups (e.g., quinones) present in NOM fueled AOM by serving as a terminal electron acceptor. Indeed, while sulfate reduction was the predominant process, accounting for up to 42.5% of the AOM activities, the microbial reduction of NOM concomitantly occurred. Furthermore, enrichment of wetland sediment with external NOM provided a complementary electron-accepting capacity, of which reduction accounted for ∼100 nmol 13CH4 oxidized · cm−3 · day−1. Spectroscopic evidence showed that quinone moieties were heterogeneously distributed in the wetland sediment, and their reduction occurred during the course of AOM. Moreover, an enrichment derived from wetland sediments performing AOM linked to NOM reduction stoichiometrically oxidized methane coupled to the reduction of the humic analogue anthraquinone-2,6-disulfonate. Microbial populations potentially involved in AOM coupled to microbial reduction of NOM were dominated by divergent biota from putative AOM-associated archaea. We estimate that this microbial process potentially contributes to the suppression of up to 114 teragrams (Tg) of CH4 · year−1 in coastal wetlands and more than 1,300 Tg · year−1, considering the global wetland area. IMPORTANCE The identification of key processes governing methane emissions from natural systems is of major importance considering the global warming effects triggered by this greenhouse gas. Anaerobic oxidation of methane (AOM) coupled to the microbial reduction of distinct electron acceptors plays a pivotal role in mitigating methane emissions from ecosystems. Given their high organic content, wetlands constitute the largest natural source of atmospheric methane. Nevertheless, processes controlling methane emissions in these environments are poorly understood. Here, we provide tracer analysis with 13CH4 and spectroscopic evidence revealing that AOM linked to the microbial reduction of redox functional groups in natural organic matter (NOM) prevails in a tropical wetland. We suggest that microbial reduction of NOM may largely contribute to the suppression of methane emissions from tropical wetlands. This is a novel avenue within the carbon cycle in which slowly decaying NOM (e.g., humic fraction) in organotrophic environments fuels AOM by serving as a terminal electron acceptor. PMID:28341676

Anaerobic Methane Oxidation Driven by Microbial Reduction of Natural Organic Matter in a Tropical Wetland.

PubMed

Valenzuela, Edgardo I; Prieto-Davó, Alejandra; López-Lozano, Nguyen E; Hernández-Eligio, Alberto; Vega-Alvarado, Leticia; Juárez, Katy; García-González, Ana Sarahí; López, Mercedes G; Cervantes, Francisco J

2017-06-01

Wetlands constitute the main natural source of methane on Earth due to their high content of natural organic matter (NOM), but key drivers, such as electron acceptors, supporting methanotrophic activities in these habitats are poorly understood. We performed anoxic incubations using freshly collected sediment, along with water samples harvested from a tropical wetland, amended with 13 C-methane (0.67 atm) to test the capacity of its microbial community to perform anaerobic oxidation of methane (AOM) linked to the reduction of the humic fraction of its NOM. Collected evidence demonstrates that electron-accepting functional groups (e.g., quinones) present in NOM fueled AOM by serving as a terminal electron acceptor. Indeed, while sulfate reduction was the predominant process, accounting for up to 42.5% of the AOM activities, the microbial reduction of NOM concomitantly occurred. Furthermore, enrichment of wetland sediment with external NOM provided a complementary electron-accepting capacity, of which reduction accounted for ∼100 nmol 13 CH 4 oxidized · cm -3 · day -1 Spectroscopic evidence showed that quinone moieties were heterogeneously distributed in the wetland sediment, and their reduction occurred during the course of AOM. Moreover, an enrichment derived from wetland sediments performing AOM linked to NOM reduction stoichiometrically oxidized methane coupled to the reduction of the humic analogue anthraquinone-2,6-disulfonate. Microbial populations potentially involved in AOM coupled to microbial reduction of NOM were dominated by divergent biota from putative AOM-associated archaea. We estimate that this microbial process potentially contributes to the suppression of up to 114 teragrams (Tg) of CH 4 · year -1 in coastal wetlands and more than 1,300 Tg · year -1 , considering the global wetland area. IMPORTANCE The identification of key processes governing methane emissions from natural systems is of major importance considering the global warming effects triggered by this greenhouse gas. Anaerobic oxidation of methane (AOM) coupled to the microbial reduction of distinct electron acceptors plays a pivotal role in mitigating methane emissions from ecosystems. Given their high organic content, wetlands constitute the largest natural source of atmospheric methane. Nevertheless, processes controlling methane emissions in these environments are poorly understood. Here, we provide tracer analysis with 13 CH 4 and spectroscopic evidence revealing that AOM linked to the microbial reduction of redox functional groups in natural organic matter (NOM) prevails in a tropical wetland. We suggest that microbial reduction of NOM may largely contribute to the suppression of methane emissions from tropical wetlands. This is a novel avenue within the carbon cycle in which slowly decaying NOM (e.g., humic fraction) in organotrophic environments fuels AOM by serving as a terminal electron acceptor. Copyright © 2017 American Society for Microbiology.

Electron self-injection due to a plasma density downramp and gas ionization in a plasma wakefield accelerator in the blowout regime

NASA Astrophysics Data System (ADS)

Yi, S. A.; D'Avignon, E. C.; Khudik, V.; Shvets, G.

2010-11-01

We study self-injection into a plasma wakefield accelerator (PWFA) in the blowout regime analytically and through particle-in-cell (PIC) simulations. We propose a new injection mechanism into a plasma wakefield accelerator, where growth of the blowout region is enabled through a slow decrease in background plasma density along the direction of propagation. Deepening of the potential well due to this growth causes a reduction of electron Hamiltonian in the co-moving frame. This reduction depends on the shape of the blowout region, its growth rate, and impact parameter of the electron. When the reduction is greater than mc^2 [1,2], the electron becomes trapped inside the bubble. We demonstrate this effect using analytic expressions for the bubble potentials [3], and estimate plasma density gradients, and beam charge and size required for injection. We also apply the injection criterion to electron trapping through gas ionization. This work is supported by the US DOE grants DE-FG02-04ER41321 and DE-FG02-07ER54945. [1] S. Kalmykov, S.A. Yi, V. Khudik, and G. Shvets, Phys. Rev. Lett. 103, 135004 (2009). [2] S.A. Yi, V. Khudik, S. Kalmykov, and G. Shvets, Plasma Phys. Contr. Fus., in press. [3] W. Lu, C. Huang, M. Zhou, M. Tzoufras et al., Phys. Plasmas 13, 056709 (2006).

Investigation of the Redox Chemistry of Anthraquinone Derivatives Using Density Functional Theory

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

Bachman, Jonathan E.; Curtiss, Larry A.; Assary, Rajeev S.

2014-09-25

Application of density functional calculations to compute electrochemical properties such as redox windows, effect of substitution by electron donating and electron withdrawing groups on redox windows, and solvation free energies for ~50 anthraquinone (AQ) derivatives are presented because of their potential as anolytes in all-organic redox flow batteries. Computations suggest that lithium ions can increase (by ~0.4 V) the reduction potential of anthraquinone due to the lithium ion pairing by forming a Lewis base-Lewis acid complex. To design new redox active species, the substitution by electron donating groups are essential to improve the reduction window of AQ with adequate oxidativemore » stability. For instance, a complete methylation of AQ can improve its reduction window by ~0.4 V. The quantum chemical studies of the ~50 AQ derivatives are used to derive a relationship that connects the computed LUMO energy and the reduction potential that can be applied as a descriptor for screening thousands of AQ derivatives. Our computations also suggest that incorporating oxy-methyl dioxolane substituents in the AQ framework can increase its interaction with non-aqueous solvent and improve its solubility. Thermochemical calculations for likely bond breaking decomposition reactions of un-substituted AQ anions suggest that the dianions are relatively stable in the solution. These studies provide ideal platform to perform further combined experimental and theoretical studies to understand the electrochemical reversibility and solubility of new quinone molecules as energy storage materials.« less

Nitric Oxide Reduction to Ammonia by TiO 2 Electrons in Colloid Solution via Consecutive One-Electron Transfer Steps

DOE PAGES

Goldstein, Sara; Behar, David; Rajh, Tijana; ...

2015-03-02

The reaction mechanism of nitric oxide (NO) reduction by excess electrons on TiO 2 nanoparticles (e TiO2–) has been studied under anaerobic conditions. TiO 2 was loaded with 10–130 electrons per particle using γ-irradiation of acidic TiO 2 colloid solutions containing 2-propanol. The study is based on time-resolved kinetics and reactants and products analysis. The reduction of NO by e TiO2– is interpreted in terms of competition between a reaction path leading to formation of NH 3 and a path leading to N 2O and N 2. The proposed mechanism involves consecutive one-electron transfers of NO, and its reduction intermediatesmore » HNO, NH 2O•, and NH 2OH. The results show that e TiO2– does not reduce N 2O and N 2. Second-order rate constants of e TiO2– reactions with NO (740 ± 30 M –1 s –1) and NH 2OH (270 ± 30 M –1 s –1) have been determined employing the rapid-mixing stopped-flow technique and that with HNO (>1.3 × 10 6 M –1 s –1) was derived from fitting the kinetic traces to the suggested reaction mechanism, which is discussed in detail.« less

Fluorinated Dodecaphenylporphyrins: Synthetic and Electrochemical Studies Including the First Evidence of Intramolecular Electron Transfer Between an Fe(II) Porphyrin -Anion Radical and an Fe(I) Porphyrin

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

D'Souza, F.; Forsyth, T.P.; Fukuzumi, S.

1998-10-19

Dodecaphenylporphyrins with varying degrees of fluorination of the peripheral phenyl rings (FXDPPS) were synthesized as model compounds for studying electronic effects in nonplan~ porphyrins, and detailed electrochemical studies of the chloroiron(HI) complexes of these compounds were undertaken. The series of porphyrins, represented as FeDPPCl and as FeFXDPPCl where x = 4, 8 (two isomers), 12, 20,28 or 36, could be reversibly oxidized by two electrons in dichloromethane to give n-cation radicals and n-dications. All of the compounds investigated could also be reduced by three electrons in benzonitrile or pyridine. In benzonitrile, three reversible reductions were observed for the unfluorinated compoundmore » FeDPPC1, whereas the FeFXDPPCl complexes generally exhibited irreversible first and second reductions which were coupled to chemical reactions. The chemical reaction associated with the first reduction involved a loss of the chloride ion after generation of Fe FXDPPC1. The second chemical reaction involved a novel intramolecular electron transfer between the initially generated Fe(H) porphyrin n-anion radical and the final Fe(I) porphyrin reduction product. In pyridine, three reversible one electron reductions were observed with the second reduction affording stable Fe(II) porphyrin o - anion radicals for ail of the complexes investigated.« less

Activation of formylmethanofuran synthesis in cell extracts of Methanobacterium thermoautotrophicum.

PubMed Central

Bobik, T A; Wolfe, R S

1989-01-01

In cell extracts of Methanobacterium thermoautotrophicum, formylmethanofuran (formyl-MFR) synthesis (an essential CO2 fixation reaction that is an early step in CO2 reduction to methane) is subject to a complex activation that involves a heterodisulfide of coenzyme M and N-(7-mercaptoheptanoyl)threonine O3-phosphate (CoM-S-S-HTP). In this paper we report that titanium(III) citrate, a low-potential reducing agent, stimulated CO2 reduction to methane and activated formyl-MFR synthesis in cell extracts. Titanium(III) citrate functioned as the sole source of electrons for formyl-MFR synthesis and enabled this reaction to occur independently of CoM-S-S-HTP. In addition, CoM-S-S-HTP was found to activate an unknown electron carrier that reduced metronidazole. The activation of formyl-MFR synthesis by CoM-S-S-HTP may involve the activation of a low-potential electron carrier. PMID:2921239

Electron Transfer Strategies Regulate Carbonate Mineral and Micropore Formation.

PubMed

Zeng, Zhirui; Tice, Michael M

2018-01-01

Some microbial carbonates are robust biosignatures due to their distinct morphologies and compositions. However, whether carbonates induced by microbial iron reduction have such features is unknown. Iron-reducing bacteria use various strategies to transfer electrons to iron oxide minerals (e.g., membrane-bound enzymes, soluble electron shuttles, nanowires, as well as different mechanisms for moving over or attaching to mineral surfaces). This diversity has the potential to create mineral biosignatures through manipulating the microenvironments in which carbonate precipitation occurs. We used Shewanella oneidensis MR-1, Geothrix fermentans, and Geobacter metallireducens GS-15, representing three different strategies, to reduce solid ferric hydroxide in order to evaluate their influence on carbonate and micropore formation (micro-size porosity in mineral rocks). Our results indicate that electron transfer strategies determined the morphology (rhombohedral, spherical, or long-chained) of precipitated calcium-rich siderite by controlling the level of carbonate saturation and the location of carbonate formation. Remarkably, electron transfer strategies also produced distinctive cell-shaped micropores in both carbonate and hydroxide minerals, thus producing suites of features that could potentially serve as biosignatures recording information about the sizes, shapes, and physiologies of iron-reducing organisms. Key Words: Microbial iron reduction-Micropore-Electron transfer strategies-Microbial carbonate. Astrobiology 18, 28-36.

Total electron acceptor loading and composition affect hexavalent uranium reduction and microbial community structure in a membrane biofilm reactor.

PubMed

Ontiveros-Valencia, Aura; Zhou, Chen; Ilhan, Zehra Esra; de Saint Cyr, Louis Cornette; Krajmalnik-Brown, Rosa; Rittmann, Bruce E

2017-11-15

Molecular microbiology tools (i.e., 16S rDNA gene sequencing) were employed to elucidate changes in the microbial community structure according to the total electron acceptor loading (controlled by influent flow rate and/or medium composition) in a H 2 -based membrane biofilm reactor evaluated for removal of hexavalent uranium. Once nitrate, sulfate, and dissolved oxygen were replaced by U(VI) and bicarbonate and the total acceptor loading was lowered, slow-growing bacteria capable of reducing U(VI) to U(IV) dominated in the biofilm community: Replacing denitrifying bacteria Rhodocyclales and Burkholderiales were spore-producing Clostridiales and Natranaerobiales. Though potentially competing for electrons with U(VI) reducers, homo-acetogens helped attain steady U(VI) reduction, while methanogenesis inhibited U(VI) reduction. U(VI) reduction was reinstated through suppression of methanogenesis by addition of bromoethanesulfonate or by competition from SRB when sulfate was re-introduced. Predictive metagenome analysis further points out community changes in response to alterations in the electron-acceptor loading: Sporulation and homo-acetogenesis were critical factors for strengthening stable microbial U(VI) reduction. This study documents that sporulation was important to long-term U(VI) reduction, whether or not microorganisms that carry out U(VI) reduction mediated by cytochrome c 3 , such as SRB and ferric-iron-reducers, were inhibited. Copyright © 2017 Elsevier Ltd. All rights reserved.

Big Pile or Small Pile?

NASA Astrophysics Data System (ADS)

Branca, Mario; Quidacciolu, Rossana G.; Soletta, Isabella

2013-10-01

The construction of a voltaic pile (battery) is a simple laboratory activity that commemorates the invention of this important device and is of great help in teaching physics. The voltaic pile is often seen as a scientific toy, with the "pile" being constructed from fruit. These toys use some strips of copper and zinc inserted in a piece of fruit to produce a low-intensity electrical current to power a digital device. In a voltaic pile of this type, the zinc acts as an anode while the copper acts as a cathode. The reduction reaction [i.e.,2H+(aq)+2e⇋H2(g)] occurs on the copper (the cathode). The two electrons that are needed for the reduction are taken from the metal (copper), which remains positively charged, while the anode is the zinc, which is oxidized through the reaction Zn∘(m)⇋Zn+2(aq )+2e, and the two electrons remain on the metal, which is negatively charged. If the two pieces of metal are connected by an external conductor, electrons flow from the zinc to the copper. The electromotive force of this system is about 0.76 V, which is the reduction potential of zinc, as can be found in the table of standard reduction potentials.

Structure of electron transfer flavoprotein-ubiquinone oxidoreductase and electron transfer to the mitochondrial ubiquinone pool

PubMed Central

Zhang, Jian; Frerman, Frank E.; Kim, Jung-Ja P.

2006-01-01

Electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) is a 4Fe4S flavoprotein located in the inner mitochondrial membrane. It catalyzes ubiquinone (UQ) reduction by ETF, linking oxidation of fatty acids and some amino acids to the mitochondrial respiratory chain. Deficiencies in ETF or ETF-QO result in multiple acyl-CoA dehydrogenase deficiency, a human metabolic disease. Crystal structures of ETF-QO with and without bound UQ were determined, and they are essentially identical. The molecule forms a single structural domain. Three functional regions bind FAD, the 4Fe4S cluster, and UQ and are closely packed and share structural elements, resulting in no discrete structural domains. The UQ-binding pocket consists mainly of hydrophobic residues, and UQ binding differs from that of other UQ-binding proteins. ETF-QO is a monotopic integral membrane protein. The putative membrane-binding surface contains an α-helix and a β-hairpin, forming a hydrophobic plateau. The UQ—flavin distance (8.5 Å) is shorter than the UQ—cluster distance (18.8 Å), and the very similar redox potentials of FAD and the cluster strongly suggest that the flavin, not the cluster, transfers electrons to UQ. Two possible electron transfer paths can be envisioned. First, electrons from the ETF flavin semiquinone may enter the ETF-QO flavin one by one, followed by rapid equilibration with the cluster. Alternatively, electrons may enter via the cluster, followed by equilibration between centers. In both cases, when ETF-QO is reduced to a two-electron reduced state (one electron at each redox center), the enzyme is primed to reduce UQ to ubiquinol via FAD. PMID:17050691

Structure of electron transfer flavoprotein-ubiquinone oxidoreductase and electron transfer to the mitochondrial ubiquinone pool.

PubMed

Zhang, Jian; Frerman, Frank E; Kim, Jung-Ja P

2006-10-31

Electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) is a 4Fe4S flavoprotein located in the inner mitochondrial membrane. It catalyzes ubiquinone (UQ) reduction by ETF, linking oxidation of fatty acids and some amino acids to the mitochondrial respiratory chain. Deficiencies in ETF or ETF-QO result in multiple acyl-CoA dehydrogenase deficiency, a human metabolic disease. Crystal structures of ETF-QO with and without bound UQ were determined, and they are essentially identical. The molecule forms a single structural domain. Three functional regions bind FAD, the 4Fe4S cluster, and UQ and are closely packed and share structural elements, resulting in no discrete structural domains. The UQ-binding pocket consists mainly of hydrophobic residues, and UQ binding differs from that of other UQ-binding proteins. ETF-QO is a monotopic integral membrane protein. The putative membrane-binding surface contains an alpha-helix and a beta-hairpin, forming a hydrophobic plateau. The UQ-flavin distance (8.5 A) is shorter than the UQ-cluster distance (18.8 A), and the very similar redox potentials of FAD and the cluster strongly suggest that the flavin, not the cluster, transfers electrons to UQ. Two possible electron transfer paths can be envisioned. First, electrons from the ETF flavin semiquinone may enter the ETF-QO flavin one by one, followed by rapid equilibration with the cluster. Alternatively, electrons may enter via the cluster, followed by equilibration between centers. In both cases, when ETF-QO is reduced to a two-electron reduced state (one electron at each redox center), the enzyme is primed to reduce UQ to ubiquinol via FAD.

Floating Potential Probe Langmuir Probe Data Reduction Results

NASA Technical Reports Server (NTRS)

Morton, Thomas L.; Minow, Joseph I.

2002-01-01

During its first five months of operations, the Langmuir Probe on the Floating Potential Probe (FPP) obtained data on ionospheric electron densities and temperatures in the ISS orbit. In this paper, the algorithms for data reduction are presented, and comparisons are made of FPP data with ground-based ionosonde and Incoherent Scattering Radar (ISR) results. Implications for ISS operations are detailed, and the need for a permanent FPP on ISS is examined.

Radiation Shielding Study of Advanced Data and Power Management Systems (ADPMS) Housing Using Geant4

NASA Astrophysics Data System (ADS)

Garcia, F.; Kurvinen, K.; Brander, T.; Orava, R.; Heino, J.; Virtanen, A.; Kettunen, H.; Tenhunen, M.

2008-02-01

A design goal for current space system is to reduce the mass used to enclose components of the spacecraft. One potential target is to reduce the mass of electronics and its housings. The use of composite materials, especially CFRP (Carbon Fiber Reinforced Plastic) is a well known and vastly used approach to mass reduction. A design goal, cost reduction, has increased the use of commercial (non-space qualified) electronics. These commercial circuits and other components cannot tolerate as high radiation levels as space qualified components. Therefore, the use of standard electronics components poses a challenge in terms of the radiation protection capability of the ADPMS housings. The main goal of this study is to provide insight on the radiation shielding protection produced by different configurations of CFRP tungsten laminates of epoxies and cyanate esters and then to compare them to the protection given by the commonly used aluminum. For a spacecraft operating in LEO and MEO orbits the main components of the space radiation environment are energetic electrons and protons, therefore in our study we will compare the experimental and simulation results of the radiation attenuation of different types of laminates for those particles. At the same time the experimental data has been used to validate the Geant4 model of the laminates, which can be used for future optimizations of the laminate structures.

The green hemoproteins of bovine erythrocytes. II. Spectral, ligand-binding, and electrochemical properties.

PubMed

DeFilippi, L J; Hultquist, D E

1978-05-10

The two green hemoproteins isolated from bovine erythrocytes (form I and form II) have been characterized as to spectral, electrochemical, and chemical properties. The absorption spectra of the isolated hemoproteins are typical of high spin ferric states. Reduction of the hemoproteins yields high spin ferrohemoproteins. Complexation of the ferrohemoproteins with CO and the ferrihemoproteins with cyanide yields low spin complexes, demonstrating the presence of an exchangeable weak field ligand in both the ferrous and ferric states of the hemoproteins. The differences in position and intensity of the absorption peaks of the visible spectra allow the two forms to be distinguished from one another. The midpoint potential of forms I and II were found to be +0.075 and +0.019 V, respectively, at pH 6.4 and +0.038 and -0.005 V, respectively, at pH 7.0. This is consistent with the gaining of 1 proton/electron during the reduction. The Nernst plot reveals an unusual 0.5-electron transfer, whereas a quantitative titration demonstrates a 1-electron transfer. Form I binds cyanide more tightly than form II (KD of 84 and 252 micrometer, respectively). The observed spectral, electrochemical, and ligand-binding differences between forms I and II can be explained in terms of a greater electron-withdrawing ability of the side chains of the heme of form I relative to the heme of form II.

Bio-reduction of N-nitrosodimethylamine (NDMA) using a hydrogen-based membrane biofilm reactor.

PubMed

Chung, Jinwook; Ahn, Chang-Hoon; Chen, Zhuo; Rittmann, Bruce E

2008-01-01

N-Nitrosodimethylamine (NDMA) is a disinfection by-product shown to be carcinogenic, mutagenic, and teratogenic. A feasible detoxification pathway for NDMA is a three-step bio-reduction that leads to ammonia and dimethylamine. This study examines the bio-reduction of NDMA in a H2-based membrane biofilm reactor (MBfR) that also is active in nitrate and sulfate reductions. In particular, the study investigates the effects of H2 availability and the relative loadings of NDMA, nitrate, and sulfate, which potentially are competing electron acceptors. The results demonstrate that NDMA was bio-reduced to a major extent (i.e., at least 96%) in a H2-based MBfR in which the electron-equivalent fluxes from H2 oxidation were dominated by nitrate and sulfate reductions. NDMA reduction kinetics responded to NDMA concentration, H2 pressure, and the presence of competing acceptors. The most important factor controlling NDMA-reduction kinetics was the H2 availability, controlled primarily by the H2 pressure, and secondarily by competition from nitrate reduction.

Hydrogen Peroxide as a Sustainable Energy Carrier: Electrocatalytic Production of Hydrogen Peroxide and the Fuel Cell.

PubMed

Fukuzumi, Shunichi; Yamada, Yusuke; Karlin, Kenneth D

2012-11-01

This review describes homogeneous and heterogeneous catalytic reduction of dioxygen with metal complexes focusing on the catalytic two-electron reduction of dioxygen to produce hydrogen peroxide. Whether two-electron reduction of dioxygen to produce hydrogen peroxide or four-electron O 2 -reduction to produce water occurs depends on the types of metals and ligands that are utilized. Those factors controlling the two processes are discussed in terms of metal-oxygen intermediates involved in the catalysis. Metal complexes acting as catalysts for selective two-electron reduction of oxygen can be utilized as metal complex-modified electrodes in the electrocatalytic reduction to produce hydrogen peroxide. Hydrogen peroxide thus produced can be used as a fuel in a hydrogen peroxide fuel cell. A hydrogen peroxide fuel cell can be operated with a one-compartment structure without a membrane, which is certainly more promising for the development of low-cost fuel cells as compared with two compartment hydrogen fuel cells that require membranes. Hydrogen peroxide is regarded as an environmentally benign energy carrier because it can be produced by the electrocatalytic two-electron reduction of O 2 , which is abundant in air, using solar cells; the hydrogen peroxide thus produced could then be readily stored and then used as needed to generate electricity through the use of hydrogen peroxide fuel cells.

Small-volume potentiometric titrations: EPR investigations of Fe-S cluster N2 in mitochondrial complex I.

PubMed

Wright, John J; Salvadori, Enrico; Bridges, Hannah R; Hirst, Judy; Roessler, Maxie M

2016-09-01

EPR-based potentiometric titrations are a well-established method for determining the reduction potentials of cofactors in large and complex proteins with at least one EPR-active state. However, such titrations require large amounts of protein. Here, we report a new method that requires an order of magnitude less protein than previously described methods, and that provides EPR samples suitable for measurements at both X- and Q-band microwave frequencies. We demonstrate our method by determining the reduction potential of the terminal [4Fe-4S] cluster (N2) in the intramolecular electron-transfer relay in mammalian respiratory complex I. The value determined by our method, E m7 =-158mV, is precise, reproducible, and consistent with previously reported values. Our small-volume potentiometric titration method will facilitate detailed investigations of EPR-active centres in non-abundant and refractory proteins that can only be prepared in small quantities. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

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

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

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

Reduced graphene oxide-CdS nanocomposite with enhanced photocatalytic 4-Nitrophenol degradation

NASA Astrophysics Data System (ADS)

Chakraborty, Koushik; Ibrahim, Sk; Das, Poulomi; Ghosh, Surajit; Pal, Tanusri

2017-05-01

We report the photocatalytic activity of reduced graphene oxide cadmium sulfide (RGO-CdS) composite towards the degradation of 4-Nitrophenol (4-NP) under simulated solar light illumination. The solution processable RGO-CdS composite was synthesized by one pot single step low cost solvothermal process, where the reduction of graphene oxide (GO), synthesis and attachment of CdS onto RGO sheets were done simultaneously. The structural and morphological characterization of the RGO-CdS composite and the reduction of GO was confirmed by X-ray diffractometry, TEM imaging and Fourier transform infrared spectroscopy respectively. The photocatalytic efficiency of RGO-CdS composite is 2.6 times higher in compare to controlled CdS. In RGO-CdS composite the photo induced electrons transfer from CdS nanorod to RGO sheets, which reduces the recombination probability of photo generated electron-hole in the CdS. These well separated photoinduced charges enhanced the photocatalytic activity of the RGO-CdS composite. Our study establishes the RGO-CdS composite as a potential photocatalyst for the degradation of organic water pollutant.

Nonlinear Electron Acoustic Waves in Dissipative Plasma with Superthermal Electrons

NASA Astrophysics Data System (ADS)

El-Hanbaly, A. M.; El-Shewy, E. K.; Kassem, A. I.; Darweesh, H. F.

2016-01-01

The nonlinear properties of small amplitude electron-acoustic ( EA) solitary and shock waves in a homogeneous system of unmagnetized collisionless plasma consisted of a cold electron fluid and superthermal hot electrons obeying superthermal distribution, and stationary ions have been investigated. A reductive perturbation method was employed to obtain the Kadomstev-Petviashvili-Burgers (KP-Brugers) equation. Some solutions of physical interest are obtained. These solutions are related to soliton, monotonic and oscillatory shock waves and their behaviour are shown graphically. The formation of these solutions depends crucially on the value of the Burgers term and the plasma parameters as well. By using the tangent hyperbolic (tanh) method, another interesting type of solution which is a combination between shock and soliton waves is obtained. The topology of phase portrait and potential diagram of the KP-Brugers equation is investigated.The advantage of using this method is that one can predict different classes of the travelling wave solutions according to different phase orbits. The obtained results may be helpful in better understanding of waves propagation in various space plasma environments as well as in inertial confinement fusion laboratory plasmas.

Analyzing Residential End-Use Energy Consumption Data to Inform Residential Consumer Decisions and Enable Energy Efficiency Improvements

NASA Astrophysics Data System (ADS)

Carlson, Derrick R.

While renewable energy is in the process of maturing, energy efficiency improvements may provide an opportunity to reduce energy consumption and consequent greenhouse gas emissions to bridge the gap between current emissions and the reductions necessary to prevent serious effects of climate change and will continue to be an integral part of greenhouse gas emissions policy moving forward. Residential energy is a largely untapped source of energy reductions as consumers, who wish to reduce energy consumption for monetary, environmental, and other reasons, face barriers. One such barrier is a lack of knowledge or understanding of how energy is consumed in a home and how to reduce this consumption effectively through behavioral and technological changes. One way to improve understanding of residential energy consumption is through the creation of a model to predict which appliances and electronics will be present and significantly contribute to the electricity consumption of a home on the basis of various characteristics of that home. The basis of this model is publically available survey data from the Residential Energy Consumption Survey (RECS). By predicting how households are likely to consume energy, homeowners, policy makers, and other stakeholders have access to valuable data that enables reductions in energy consumption in the residential sector. This model can be used to select homes that may be ripe for energy reductions and to predict the appliances that are the basis of these potential reductions. This work suggests that most homes in the U.S. have about eight appliances that are responsible for about 80% of the electricity consumption in that home. Characteristics such as census region, floor space, income, and total electricity consumption affect which appliances are likely to be in a home, however the number of appliances is generally around 8. Generally it takes around 4 appliances to reach the 50% threshold and 12 appliances to reach 90% of electricity consumption, which suggests significant diminishing returns for parties interested in monitoring appliance level electricity consumption. Another way to improve understanding of residential energy consumption is through the development of residential use phase energy vectors for use in the Economic Input-Output Life Cycle Assessment (EIO-LCA) model. The EIO-LCA model is a valuable scoping tool to predict the environmental impacts of economic activity. This tool has a gap in its capabilities as residential use phase energy is outside the scope of the model. Adding use phase energy vectors to the EIO-LCA model will improve the modeling, provide a more complete estimation of energy impacts and allow for embedded energy to be compared to use phase energy for the purchase of goods and services in the residential sector. This work adds 21 quads of energy to the residential energy sector for the model and 15 quads of energy for personal transportation. These additions represent one third of the total energy consumption of the United States and a third of the total energy in the EIO-LCA model. This work also demonstrates that for many products such as electronics and household appliances use phase energy demands are much greater than manufacturing energy demands and dominate the life cycles for these products. A final way in which this thesis improves upon the understanding of how use phase energy is consumed in a home is through the exploration of potential energy reductions in a home. This analysis selects products that are used or consumed in a home, and explores the potential for reductions in the embedded manufacturing and use phase energy of that product using EIO-LCA and the energy vectors created in Chapter 3. The results give consumers an understanding of where energy is consumed in the lifecycle of products that they purchase and provide policy makers with valuable information on how to focus or refocus policies that are aimed and reducing energy in the residential sector. This work finds that a majority of the energy consumed by retail products is consumed in the use phase of electronics and appliances. Consequently the largest potential reductions in residential energy use can be found in the same area. The work also shows that targeting reductions in the manufacturing energy for many products is likely to be an ineffective strategy for energy reductions with the exception of a select few products. Supply chain energy reductions may be more promising than manufacturing energy reductions, though neither is likely to be as effective as strategies that target use phase energy reductions.

Oxygen Reduction Reaction on Platinum-Terminated “Onion-structured” Alloy Catalysts

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

Herron, Jeffrey A.; Jiao, Jiao; Hahn, Konstanze

Using periodic, self-consistent density functional theory (GGA-PW91) calculations, a series of onion-structured metal alloys have been investigated for their catalytic performance towards the oxygen reduction reaction (ORR). The onion-structures consist of a varying number of atomic layers of one or two metals each, pseudomorphically deposited on top of one another to form the overall structure. All catalysts studied feature a Pt overlayer, and often consist of at least one Pd layer below the surface. Three distinct ORR mechanisms were analyzed on the close-packed facets of all the structures considered. These mechanisms include a direct route of O2 dissociation and twomore » hydrogen-assisted routes of O–O bond-breaking in peroxyl (OOH) and in hydrogen peroxide (HOOH) intermediates. A thermochemical analysis of the elementary steps provides information on the operating potential, and thereby energy efficiency of each electrocatalyst. A Sabatier analysis of catalytic activity based on thermochemistry of proton/electron transfer steps and activation energy barrier for O–O bond-breaking steps leads to a “volcano” relation between the surfaces’ activity and the binding energy of O. Several of the onion-structured alloys studied here show promise for achieving energy efficiency higher than that of Pt, by being active at potentials higher than the operating potential of Pt. Furthermore, some have at least as good activity as pure Pt at that operating potential. Thus, a number of the onion-structured alloys studied here are promising as cathode electrocatalysts in proton exchange membrane fuel cells.« less

Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity.

PubMed

Wuttig, Anna; Yaguchi, Momo; Motobayashi, Kenta; Osawa, Masatoshi; Surendranath, Yogesh

2016-08-09

CO2 reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H2 We combine in situ surface-enhanced IR absorption spectroscopy (SEIRAS) and electrochemical kinetic studies to probe the mechanistic basis for kinetic bifurcation between H2 and CO production on polycrystalline Au electrodes. Under the conditions of CO2 reduction catalysis, electrogenerated CO species are irreversibly bound to Au in a bridging mode at a surface coverage of ∼0.2 and act as kinetically inert spectators. Electrokinetic data are consistent with a mechanism of CO production involving rate-limiting, single-electron transfer to CO2 with concomitant adsorption to surface active sites followed by rapid one-electron, two-proton transfer and CO liberation from the surface. In contrast, the data suggest an H2 evolution mechanism involving rate-limiting, single-electron transfer coupled with proton transfer from bicarbonate, hydronium, and/or carbonic acid to form adsorbed H species followed by rapid one-electron, one-proton, or H recombination reactions. The disparate proton coupling requirements for CO and H2 production establish a mechanistic basis for reaction selectivity in electrocatalytic fuel formation, and the high population of spectator CO species highlights the complex heterogeneity of electrode surfaces under conditions of fuel-forming electrocatalysis.

Access to Formally Ni(I) States in a Heterobimetallic NiZn System

PubMed Central

Uyeda, Christopher

2014-01-01

Heterobimetallic NiZn complexes featuring metal centers in distinct coordination environments have been synthesized using diimine-dioxime ligands as binucleating scaffolds. A tetramethylfuran-containing ligand derivative enables a stable one-electron-reduced S = 1/2 species to be accessed using Cp2Co as a chemical reductant. The resulting pseudo-square planar complex exhibits spectroscopic and crystallographic characteristics of a ligand-centered radical bound to a Ni(II) center. Upon coordination of a π-acidic ligand such as PPh3, however, a five-coordinate Ni(I) metalloradical is formed. The electronic structures of these reduced species provide insight into the subtle effects of ligand structure on the potential and reversibility of the NiII/I couple for complexes of redox-active tetraazamacrocycles. PMID:25614786

[Participation of oxygen in the reduction of methylviologen, photosensitized by chlorophyll, in an aqueous solution of detergent].

PubMed

Luganskaia, A N; Krasnovskiĭ, A A

1975-01-01

Dependence of chlorophyll "a" photosensitized reduction of methylviologene with tiourea on the temperature of reaction mixture was studied in aerobic conditions in triton X-100 aqueous solution. It was found that the reaction consisted of two stages: the light and dark ones. Photosensitized oxidation of tiourea with air oxygen proceeds at the temperatures up to -70 degrees C. Reduction of methylviologen is a dark stage for which diffusion processes are necessary. The role of hydrogen peroxide in the reaction studied has been investigated. It has been shown that hydrogen peroxide is not the "initiator" of the reaction which results in the reduction of methylviologen. Reduced glutation and the mixture of reduced and oxidized glutations were used as electron donors in photosensitized reaction in the presence of air oxygen. An increase of the depth and rate of the reduction of methylviologen under aerobic conditions as compared to anaerobic ones points to the formation of more active reducers than the initial electron donor.

Electron transfer from a solid-state electrode assisted by methyl viologen sustains efficient microbial reductive dechlorination of TCE.

PubMed

Aulenta, Federico; Catervi, Alessandro; Majone, Mauro; Panero, Stefania; Reale, Priscilla; Rossetti, Simona

2007-04-01

The ability to transfer electrons, via an extracellular path, to solid surfaces is typically exploited by microorganisms which use insoluble electron acceptors, such as iron-or manganese-oxides or inert electrodes in microbial fuel cells. The reverse process, i.e., the use of solid surfaces or electrodes as electron donors in microbial respirations, although largely unexplored, could potentially have important environmental applications, particularly for the removal of oxidized pollutants from contaminated groundwater or waste streams. Here we show, for the first time, that an electrochemical cell with a solid-state electrode polarized at -500 mV (vs standard hydrogen electrode), in combination with a low-potential redox mediator (methyl viologen), can efficiently transfer electrochemical reducing equivalents to microorganisms which respire using chlorinated solvents. By this approach, the reductive transformation of trichloroethene, a toxic yet common groundwater contaminant, to harmless end-products such as ethene and ethane could be performed. Furthermore, using a methyl-viologen-modified electrode we could even demonstrate that dechlorinating bacteria were able to accept reducing equivalents directly from the modified electrode surface. The innovative concept, based on the stimulation of dechlorination reactions through the use of solid-state electrodes (we propose for this process the acronym BEARD: Bio-Electrochemically Assisted Reductive Dechlorination), holds promise for in situ bioremediation of chlorinated-solvent-contaminated groundwater, and has several potential advantages over traditional approaches based on the subsurface injection of organic compounds. The results of this study raise the possibility that immobilization of selected redox mediators may be a general strategy for stimulating and controlling a range of microbial reactions using insoluble electrodes as electron donors.

Microwave-Mediated Synthesis of Bulky Lanthanide Porphyrin-Phthalocyanine Triple-Deckers: Electrochemical and Magnetic Properties.

PubMed

Jin, Hong-Guang; Jiang, Xiaoqin; Kühne, Irina A; Clair, Sylvain; Monnier, Valérie; Chendo, Christophe; Novitchi, Ghenadie; Powell, Annie K; Kadish, Karl M; Balaban, Teodor Silviu

2017-05-01

Five heteroleptic lanthanide porphyrin-bis-phthalocyanine triple-decker complexes with bulky peripheral groups were prepared via microwave-assisted synthesis and characterized in terms of their spectroscopic, electrochemical, and magnetic properties. These compounds, which were easily obtained under our preparative conditions, would normally not be accessible in large quantities using conventional synthetic methods, as a result of the low yield resulting from steric congestion of bulky groups on the periphery of the phthalocyanine and porphyrin ligands. The electrochemically investigated triple-decker derivatives undergo four reversible one-electron oxidations and three reversible one-electron reductions. The sites of oxidation and reduction were assigned on the basis of redox potentials and UV-vis spectral changes during electron-transfer processes monitored by thin-layer spectroelectrochemistry, in conjunction with assignments of electronic absorption bands of the neutral compounds. Magnetic susceptibility measurements on two derivatives containing Tb III and Dy III metal ions reveal the presence of ferromagnetic interactions, probably resulting from magnetic dipolar interactions. The Tb III derivative shows SMM behavior under an applied field of 0.1 T, where the direct and Orbach process can be determined, resulting in an energy barrier of U eff = 132.0 K. However, Cole-Cole plots reveal the presence of two relaxation processes, the second of which takes place at higher frequencies, with the data conforming to a 1/t ∝ T 7 relation, thus suggesting that it can be assigned to a Raman process. Attempts were made to form two-dimensional (2D) self-assembled networks on a highly oriented pyrolytic graphite (HOPG) surface but were unsuccessful due to bulky peripheral groups on the two Pc macrocycles.

alpha Arg-237 in Methylophilus methylotrophus (sp. W3A1) electron-transferring flavoprotein affords approximately 200-millivolt stabilization of the FAD anionic semiquinone and a kinetic block on full reduction to the dihydroquinone.

PubMed

Talfournier, F; Munro, A W; Basran, J; Sutcliffe, M J; Daff, S; Chapman, S K; Scrutton, N S

2001-06-08

The midpoint reduction potentials of the FAD cofactor in wild-type Methylophilus methylotrophus (sp. W3A1) electron-transferring flavoprotein (ETF) and the alphaR237A mutant were determined by anaerobic redox titration. The FAD reduction potential of the oxidized-semiquinone couple in wild-type ETF (E'(1)) is +153 +/- 2 mV, indicating exceptional stabilization of the flavin anionic semiquinone species. Conversion to the dihydroquinone is incomplete (E'(2) < -250 mV), because of the presence of both kinetic and thermodynamic blocks on full reduction of the FAD. A structural model of ETF (Chohan, K. K., Scrutton, N. S., and Sutcliffe, M. J. (1998) Protein Pept. Lett. 5, 231-236) suggests that the guanidinium group of Arg-237, which is located over the si face of the flavin isoalloxazine ring, plays a key role in the exceptional stabilization of the anionic semiquinone in wild-type ETF. The major effect of exchanging alphaArg-237 for Ala in M. methylotrophus ETF is to engineer a remarkable approximately 200-mV destabilization of the flavin anionic semiquinone (E'(2) = -31 +/- 2 mV, and E'(1) = -43 +/- 2 mV). In addition, reduction to the FAD dihydroquinone in alphaR237A ETF is relatively facile, indicating that the kinetic block seen in wild-type ETF is substantially removed in the alphaR237A ETF. Thus, kinetic (as well as thermodynamic) considerations are important in populating the redox forms of the protein-bound flavin. Additionally, we show that electron transfer from trimethylamine dehydrogenase to alphaR237A ETF is severely compromised, because of impaired assembly of the electron transfer complex.

Conducting polymer actuators: From basic concepts to proprioceptive systems

NASA Astrophysics Data System (ADS)

Martinez Gil, Jose Gabriel

Designers and engineers have been dreaming for decades of motors sensing, by themselves, working and surrounding conditions, as biological muscles do originating proprioception. Here bilayer full polymeric artificial muscles were checked up to very high cathodic potential limits (-2.5 V) in aqueous solution by cyclic voltammetry. The electrochemical driven exchange of ions from the conducting polymer film, and the concomitant Faradaic bending movement of the muscle, takes place in the full studied potential range. The presence of trapped counterion after deep reduction was corroborated by EDX determinations giving quite high electronic conductivity to the device. The large bending movement was used as a tool to quantify the amount of water exchanged per reaction unit (exchanged electron or ion). The potential evolutions of self-supported films of conducting polymers or conducting polymers (polypyrrole, polyaniline) coating different microfibers, during its oxidation/reduction senses working mechanical, thermal, chemical or electrical variables. The evolution of the muscle potential from electrochemical artificial muscles based on electroactive materials such as intrinsically conducting polymers and driven by constant currents senses, while working, any variation of the mechanical (trailed mass, obstacles, pressure, strain or stress), thermal or chemical conditions of work. One physically uniform artificial muscle includes one electrochemical motor and several sensors working simultaneously under the same driving reaction. Actuating (current and charge) and sensing (potential and energy) magnitudes are present, simultaneously, in the only two connecting wires and can be read by the computer at any time. From basic polymeric, mechanical and electrochemical principles a physicochemical equation describing artificial proprioception has been developed. It includes and describes, simultaneously, the evolution of the muscle potential during actuation as a function of the motor characteristics (rate and sense of the movement, relative position, and required energy) and the working variables (temperature, electrolyte concentration, mechanical conditions and driving current). By changing working conditions experimental results overlap theoretical predictions. The ensemble computer-generator-muscle-theoretical equation constitutes and describes artificial mechanical, thermal and chemical proprioception of the system. Proprioceptive tools and most intelligent zoomorphic or anthropomorphic soft robots can be envisaged.

A theoretical probe of high-valence uranium and transuranium silylamides: Structural and redox properties

NASA Astrophysics Data System (ADS)

Zhong, Yu-Xi; Guo, Yuan-Ru; Pan, Qing-Jiang

2016-02-01

Relativistic density functional theory was used to explore the structural and redox properties of 18 prototypical actinyl silylamides including a variation of metals (U, Np and Pu), metal oxidation states (VI and V) and equatorial ligands. A theoretical approach associated with implicit solvation and spin-orbit/multiplet corrections was proved to be reliable. A marked shift of reduction potentials of actinyl silylamides caused by changes of equatorial coordination ligands and implicit solvation was elucidated by analyses of electronic structures and single-electron reduction mechanism.

Tapping the Unused Potential of Photosynthesis with a Heterologous Electron Sink.

PubMed

Berepiki, Adokiye; Hitchcock, Andrew; Moore, C Mark; Bibby, Thomas S

2016-12-16

Increasing the efficiency of the conversion of light energy to products by photosynthesis represents a grand challenge in biotechnology. Photosynthesis is limited by the carbon-fixing enzyme Rubisco resulting in much of the absorbed energy being wasted as heat or fluorescence or lost as excess reductant via alternative electron dissipation pathways. To harness this wasted reductant, we engineered the model cyanobacterium Synechococcus PCC 7002 to express the mammalian cytochrome P450 CYP1A1 to serve as an artificial electron sink for excess electrons derived from light-catalyzed water-splitting. This improved photosynthetic efficiency by increasing the maximum rate of photosynthetic electron flow by 31.3%. A simple fluorescent assay for CYP1A1 activity demonstrated that the P450 was functional in the absence of its native reductase, that activity was light-dependent and scaled with irradiance. We show for the first time in live cells that photosynthetic reductant can be redirected to power a heterologous cytochrome P450. Furthermore, Synechococcus PCC 7002 expressing CYP1A1 degraded the herbicide atrazine, which is a widespread environmental pollutant.

Luminosity geometric reduction factor from colliding bunches with different lengths

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

Verdu-Andres, S.

In the interaction point of the future electron-Ion collider eRHIC, the electron beam bunches are at least one order of magnitude shorter than the proton beam bunches. With the introduction of a crossing angle, the actual number of collisions resulting from the bunch collision gets reduced. Here we derive the expression for the luminosity geometric reduction factor when the bunches of the two incoming beams are not equal.

Reduction by symmetries in singular quantum-mechanical problems: General scheme and application to Aharonov-Bohm model

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

Smirnov, A. G., E-mail: smirnov@lpi.ru

2015-12-15

We develop a general technique for finding self-adjoint extensions of a symmetric operator that respects a given set of its symmetries. Problems of this type naturally arise when considering two- and three-dimensional Schrödinger operators with singular potentials. The approach is based on constructing a unitary transformation diagonalizing the symmetries and reducing the initial operator to the direct integral of a suitable family of partial operators. We prove that symmetry preserving self-adjoint extensions of the initial operator are in a one-to-one correspondence with measurable families of self-adjoint extensions of partial operators obtained by reduction. The general scheme is applied to themore » three-dimensional Aharonov-Bohm Hamiltonian describing the electron in the magnetic field of an infinitely thin solenoid. We construct all self-adjoint extensions of this Hamiltonian, invariant under translations along the solenoid and rotations around it, and explicitly find their eigenfunction expansions.« less

A one-pot hydrothermal synthesis of 3D nitrogen-doped graphene aerogels-supported NiS2 nanoparticles as efficient electrocatalysts for the oxygen-reduction reaction

NASA Astrophysics Data System (ADS)

Yuan, Wen-Jing; Li, Ju-Chuan; Chen, Ping; Shen, Yu-Hua; Xie, An-Jian

2014-03-01

Nitrogen-doped graphene aerogels-supported NiS2 nanoparticles (NiS2/NG) were synthesized by a one-pot hydrothermal method. In the process, l-cysteine was used not only as the nitrogen source to form the nitrogen-doped graphene aerogels, but also the sulfur source to form NiS2. The nitrogen-doped graphene (NG) hybrids show an interconnected reticulation of NG sheets with uniform deposition of NiS2 NPs, and the NiS2 NPs are deposited on the NG layers. In studying the effects of the NG and NiS2/NG for the ORR, we found that NiS2/NG shows a more positive onset potential, higher current density, and higher electron transfer number (˜4) for the oxygen-reduction reaction (ORR) in alkaline media than NG. Furthermore, NiS2/NG shows better durability and methanol tolerance than the commercial Pt/C catalyst.

An experimental comparison of the Marcus-Hush and Butler-Volmer descriptions of electrode kinetics applied to cyclic voltammetry. The one electron reductions of europium (III) and 2-methyl-2-nitropropane studied at a mercury microhemisphere electrode

NASA Astrophysics Data System (ADS)

Henstridge, Martin C.; Wang, Yijun; Limon-Petersen, Juan G.; Laborda, Eduardo; Compton, Richard G.

2011-11-01

We present a comparative experimental evaluation of the Butler-Volmer and Marcus-Hush models using cyclic voltammetry at a microelectrode. Numerical simulations are used to fit experimental voltammetry of the one electron reductions of europium (III) and 2-methyl-2-nitropropane, in water and acetonitrile, respectively, at a mercury microhemisphere electrode. For Eu (III) very accurate fits to experiment were obtained over a wide range of scan rates using Butler-Volmer kinetics, whereas the Marcus-Hush model was less accurate. The reduction of 2-methyl-2-nitropropane was well simulated by both models, however Marcus-Hush required a reorganisation energy lower than expected.

Ultrafast Scavenging of the Precursor of H(•) Atom, (e(-), H3O(+)), in Aqueous Solutions.

PubMed

Balcerzyk, Anna; Schmidhammer, Uli; Wang, Furong; de la Lande, Aurélien; Mostafavi, Mehran

2016-09-01

Picosecond pulse radiolysis measurements have been performed in several highly concentrated HClO4 and H3PO4 aqueous solutions containing silver ions at different concentrations. Silver ion reduction is used to unravel the ultrafast reduction reactions observed at the end of a 7 ps electron pulse. Solvated electrons and silver atoms are observed by the pulse (electron beam)-probe (supercontinuum light) method. In highly acidic solutions, ultrafast reduction of silver ions is observed, a finding that is not compatible with a reaction between the H(•) atom and silver ions, which is known to be thermally activated. In addition, silver ion reduction is found to be even more efficient in phosphoric acid solution than that in neutral solution. In the acidic solutions investigated here, the species responsible for the reduction of silver atoms is considered to be the precursor of the H(•) atom. This precursor, denoted (e(-), H3O(+)), is a pair constituting an electron (not fully solvated) and H3O(+). Its structure differs from that of the pair of a solvated electron and a hydronium ion (es(-), H3O(+)), which absorbs in the visible region. The (e(-), H3O(+)) pair , called the pre-H(•) atom here, undergoes ultrafast electron transfer and can, like the presolvated electron, reduce silver ions much faster than the H(•) atom. Moreover, it is found that with the same concentration of H3O(+) the reduction reaction is favored in the phosphoric acid solution compared to that in the perchloric acid solution because of the less-efficient electron solvation process. The kinetics show that among the three reducing species, (e(-), H3O(+)), (es(-), H3O(+)), and H(•) atom, the first one is the most efficient.

Reductive Dissolution of Goethite and Hematite by Reduced Flavins

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

Shi, Zhi; Zachara, John M.; Wang, Zheming

2013-10-02

The abiotic reductive dissolution of goethite and hematite by the reduced forms of flavin mononucleotide (FMNH2) and riboflavin (RBFH2), electron transfer mediators (ETM) secreted by the dissimilatory iron-reducing bacterium Shewanella, was investigated under stringent anaerobic conditions. In contrast to the rapid redox reaction rate observed for ferrihydrite and lepidocrocite (Shi et al., 2012), the reductive dissolution of crystalline goethite and hematite was slower, with the extent of reaction limited by the thermodynamic driving force at circumneutral pH. Both the initial reaction rate and reaction extent increased with decreasing pH. On a unit surface area basis, goethite was less reactive thanmore » hematite between pH 4.0 and 7.0. AH2DS, the reduced form of the well-studied synthetic ETM anthraquinone-2,6-disulfonate (AQDS), yielded higher rates than FMNH2 under most reaction conditions, despite the fact that FMNH2 was a more effective reductant than AH2DS for ferryhydrite and lepidocrocite. Two additional model compounds, methyl viologen and benzyl viologen, were investigated under similar reaction conditions to explore the relationship between reaction rate and thermodynamic properties. Relevant kinetic data from the literature were also included in the analysis to span a broad range of half-cell potentials. Other conditions being equal, the surface area normalized initial reaction rate (ra) increased as the redox potential of the reductant became more negative. A non-linear, parabolic relationship was observed between log ra and the redox potential for eight reducants at pH 7.0, as predicted by Marcus theory for electron transfer. When pH and reductant concentration were fixed, log ra was positively correlated to the redox potential of four Fe(III) oxides over a wide pH range, following a non-linear parabolic relationship as well.« less

Phylogenetic Evidence for H2 based Electron Bifurcation In Early Life

NASA Astrophysics Data System (ADS)

Adams, M. W.; Boyd, E. S.; Schut, G.; Peters, J.

2012-12-01

Energy conservation is a fundamental underpinning of all life and is accomplished by electron transport phosphorylation and/or substrate level phosphorylation. A third mechanism, known as flavin-based electron bifurcation, has recently been established as a mechanism by which life can conserve energy. In this mechanism, a flavin-containing multienzyme complex catalyzes the thermodynamically unfavorable reduction of low potential ferredoxin using electron donors with higher potentials, such as NAD(P)H or H2. Such endergonic reactions are driven forward through the simultaneous oxidation of the electron donor with higher potential acceptors such as NAD+ or heterodisulfide. Membrane associated energy converting [NiFe]hydrogenases (Ech, Eha) link the oxidation of ferredoxin with the production of H2 and in the process conserve energy in the form of an ion (Na+/H+) gradient. Ech/Eha exhibit a modular composition represented by a Na+/H+ antiporter domain and a [NiFe] hydrogenase domain. In addition, Ech/Eha can be accompanied by a formate dehyrogenase, carbon monoxide dehydrogenase, or an FAD/NAD(P)H module that enables coupling with these substrates. Representatives of Ech/Eha have been identified among anaerobic Archaea and Bacteria, including deeply rooted methanogens, sulfur-reducing Crenarcheota/Euryarchaeota as well as Thermotogae. Ech exhibit extensive homology to a number of subunits within the NADH quinone oxidoreductase or complex I family (Nuo, Fpo). Metabolically, Ech generally couple the oxidation of carbon monooxide, formate or ferredoxin to the production of H2. In contrast, the Eha complex couples the translocation of Na+ and the oxidation of H2 to the reduction of ferredoxin, which is then available for the reduction of CO2 in methanogens. In the case of Eha, the gradient of Na+/H+ produced through translocation coupled to ferredoxin oxidation can in be used to drive the phosphorylation of ADP via an ATP synthase complex, thereby representing one of the most simple forms of ATP production supporting life. This finding is consistent with phylogenetic analyses which indicate a close phylogenetic relationship between Ech/Eha and Nuo/Fpo, with [NiFe]-hydrogenase typically involved in H2 oxidation forming divergent lineages. This suggests that Ech/Eha are most likely to represent an ancestor of the Complex I family and the [NiFe]-hydrogenase family. A concatenation and phylogenetic analysis of the large and small subunits of Ech and Nuo was performed and and additional modules enabling coupling with CO2 (Eha), CO (Ech-CODH), and formate (Ech-Fdh) through H2-based electron bifurcation were overlaid on this phylogeny. The results suggest an origin for H2-based electron bifurcation via Ech/Eha among CO2 reducing hydrogenotrophic methanogenic Archaea or sulfur-reducing Archaea, with evolution towards coupling with formate and CO. These results provide insight into the evolutionary relationships between electron bifurcation-enabled ionic gradients capable of driving phosphorylation and electron transport-based phosphorylation. Moreover, these observations suggest that electron bifurcation may have been important in overcoming key metabolic bottlenecks and may have enabled life to access small energetic gradients to support metabolism on early Earth.

Cyclopropyl conjugation and ketyl anions: when do things begin to fall apart?

PubMed

Tanko, J M; Li, Xiangzhong; Chahma, M'hamed; Jackson, Woodward F; Spencer, Jared N

2007-04-11

Results pertaining to the electrochemical reduction of 1,2-diacetylcyclopropane (5), 1-acetyl-2-phenylcyclopropane (6), 1-acetyl-2-benzoylcyclopropane (7), and 1,2-dibenzoylcyclopropane (8) are reported. While 6*- exists as a discrete species, the barrier to ring opening is very small (<1 kcal/mol) and the rate constant for ring opening is >10(7) s(-1). For 7 and 8, the additional resonance stabilization afforded by the benzoyl moieties results in significantly lower rate constants for ring opening, on the order of 10(5)-10(6) s(-1). Electron transfer to 8 serves to initiate an unexpected vinylcyclopropane --> cyclopentene type rearrangement, which occurs via a radical ion chain mechanism. The results for reduction of 5 are less clear-cut: The experimental results suggest that the reduction is unexceptional, with a symmetry coefficient alpha

In-situ sequential laser transfer and laser reduction of graphene oxide films

NASA Astrophysics Data System (ADS)

Papazoglou, S.; Petridis, C.; Kymakis, E.; Kennou, S.; Raptis, Y. S.; Chatzandroulis, S.; Zergioti, I.

2018-04-01

Achieving high quality transfer of graphene on selected substrates is a priority in device fabrication, especially where drop-on-demand applications are involved. In this work, we report an in-situ, fast, simple, and one step process that resulted in the reduction, transfer, and fabrication of reduced graphene oxide-based humidity sensors, using picosecond laser pulses. By tuning the laser illumination parameters, we managed to implement the sequential printing and reduction of graphene oxide flakes. The overall process lasted only a few seconds compared to a few hours that our group has previously published. DC current measurements, X-Ray Photoelectron Spectroscopy, X-Ray Diffraction, and Raman Spectroscopy were employed in order to assess the efficiency of our approach. To demonstrate the applicability and the potential of the technique, laser printed reduced graphene oxide humidity sensors with a limit of detection of 1700 ppm are presented. The results demonstrated in this work provide a selective, rapid, and low-cost approach for sequential transfer and photochemical reduction of graphene oxide micro-patterns onto various substrates for flexible electronics and sensor applications.

Electron-Poor Thiophene 1,1-Dioxides: Synthesis, Characterization, and Application as Electron Relays in Photocatalytic Hydrogen Generation.

PubMed

Tsai, Chia-Hua; Chirdon, Danielle N; Kagalwala, Husain N; Maurer, Andrew B; Kaur, Aman; Pintauer, Tomislav; Bernhard, Stefan; Noonan, Kevin J T

2015-08-03

The synthesis and characterization of electron-poor thiophene 1,1-dioxides bearing cyanated phenyl groups are reported. The electron-accepting nature of these compounds was evaluated by cyclic voltammetry, and highly reversible and facile reductions were observed for several derivatives. Moreover, some of the reduced thiophene dioxides form colorful anions, which were investigated spectroelectrochemically. Photoluminescence spectra of the electron-deficient sulfones were measured in CH2 Cl2, and they emit in the blue-green region with significant variation in the quantum yield depending on the aryl substituents. By expanding the degree of substitution on the phenyl rings, quantum yields up to 34 % were obtained. X-ray diffraction data are reported for two of the thiophene 1,1-dioxides, and the electronic structure was probed for all synthesized derivatives through DFT calculations. The dioxides were also examined as electron relays in a photocatalytic water reduction reaction, and they showed potential to boost the efficiency. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of soluble flavin on heterogeneous electron transfer between surface-exposed bacterial cytochromes and iron oxides

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

Wang, Zheming; Shi, Zhi; Shi, Liang

2015-08-25

Dissimilatory iron-reducing bacteria can utilize insoluble Fe(Mn)-oxides as a terminal electron acceptor under anaerobic conditions. For Shewanella species specifically, some evidence suggests that iron reduction is associated with the secretion of flavin mononucleotide (FMN) and riboflavin that are proposed to mediate electron transfer (Marsili et al., 2008). In this work, we used methyl viologen (MV•+)-encapsulated, porin-cytochrome complex (MtrCAB) embedded liposomes (MELs) as a synthetic model of the Shewanella outer membrane to investigate the proposed mediating behavior of secreted flavins. The reduction kinetics of goethite, hematite and lepidocrocite (200 µM) by MELs ([MV•+] ~ 42 µM and MtrABC ≤ 1 nM)more » were determined in the presence FMN at pH 7.0 in N2 atmosphere by monitoring the concentrations of MV•+ and FMN through their characteristic UV-visible absorption spectra. Experiments were performed where i) FMN and Fe(III)-oxide were mixed and then reacted with the reduced MELs and ii) FMN was reacted with the reduced MELs followed by addition of Fe(III)-oxide. The redox reactions proceeded in two steps: a fast step that was completed in a few seconds, and a slower one lasting over 400 seconds. For all three Fe(III)-oxides, the initial reaction rate in the presence of a low concentration of FMN (≤ 1 µM) was at least a factor of five faster than those with MELs alone, and orders of magnitude faster than those by FMNH2, suggesting that FMN may serve as a co-factor that enhances electron transfer from outer-membrane c-cytochromes to Fe(III)-oxides. The rate and extent of the initial reaction followed the order of lepidocrocite > hematite > goethite, the same as their reduction potentials, implying thermodynamic control on reaction rate. However, at higher FMN concentrations (> 1 µM), the reaction rates for both steps decreased and varied inversely with FMN concentration, indicating that FMN inhibited the MEL to Fe(III)-oxide electron transfer reaction. The implications of the observed kinetic behaviors to flavin-mediated Fe(III) oxide reduction in natural environments are discussed.« less

The Redox Potentials of n-type Colloidal Semiconductor Nanocrystals

NASA Astrophysics Data System (ADS)

Carroll, Gerard Michael

This thesis presents investigations for two related fields of semiconductor electrochemistry: redox potential determination of colloidal semiconductor nanocrystals, and mechanistic analysis of photoelectrochemical water oxidation with electrocatalyst modified mesostructured hematite photoanodes. Adapting electrochemical techniques to colloidal semiconductor nanocrystals (SC NC) is a long-standing challenge for this class of materials. Subject to a variety of complications, standard voltammetric techniques are not as straight forward for SC NCs as they are for small molecules. As a result, researchers have developed creative ways to side step these complications by coupling electrochemistry with NC spectroscopy. Chapter 1 discusses the fundamental electronic and spectroscopic properties of SC NCs at different redox states. We present a brief review of some of the notable studies employing SC NC spectroelectrochemistry that provide the theoretical and experimental context for the following chapters. Chapter 2 presents an investigation on NC redox potentials of photochemically reduced colloidal ZnO NCs using a solvated redox-indicator method. In the one electron limit, conduction band electrons show evidence of quantum confinement, but at higher electron concentrations, the NC Fermi-level becomes dependent on the electron density across all NC sizes. Chapter 3 outlines a poteniometric method for monitoring the NC redox potentials in situ. NC redox potentials for ZnO and CdSe are measured, and as predicted from these measurements, spontaneous electron transfer from CdSe to ZnO is demonstrated. Chapter 4 details the impact of the surface of CdSe NCs on the NC redox potentials. We find that the ratio of Cd2+:Se2- on the surface of CdSe NCs changes both the NC band edge potentials, as well as the maximum electron density achievable by photochemical reduction. These changes are proposed to arise from interfacial dipoles when CdSe has a Se2-rich surface. Chapters 5 and 6 examine the mechanistic pathways of solar water oxidation on Co-Pi modified alpha-Fe2O3 photoanodes. A rate constant analysis of water oxidation and electron-hole recombination paired with the identification of surface-morphology-dependent current-voltage characteristics reveal new insights into the role of the semiconductor/electrocatalyst interface on the overall solar water oxidation efficiency. These findings reconcile disparate observations from previous studies.

Palladium nanoparticles formed on titanium silicate ETS-10.

PubMed

Lin, Christopher C H; Danaie, Mohsen; Mitlin, David; Kuznicki, Steven M

2011-03-01

We report that surface templated and supported palladium nanoparticles self assemble on ETS-10 type molecular sieve surfaces by simple exchange and activation procedures in the absence of a reductant. This procedure is similar to the one previously reported for silver nanoparticle self assembly on ETS-10. We observed a bimodal distribution with particle sizes ranging from 2-5 and 15-30 nm. This simple, economical method generates high concentrations (approximately 12 wt% of total composite) of uniform, metallic palladium nanoparticles that are multiply twinned and thermally stable making them potentially unique for advanced catalytic and electronic applications.

Characterization of 16S rRNA genes from oil field microbial communities indicates the presence of a variety of sulfate-reducing, fermentative, and sulfide-oxidizing bacteria.

PubMed

Voordouw, G; Armstrong, S M; Reimer, M F; Fouts, B; Telang, A J; Shen, Y; Gevertz, D

1996-05-01

Oil field bacteria were characterized by cloning and sequencing of PCR-amplified 16S rRNA genes. A variety of gram-negative, sulfate-reducing bacteria was detected (16 members of the family Desulfovibrionaceae and 8 members of the family Desulfobacteriaceae). In contrast, a much more limited number of anaerobic, fermentative, or acetogenic bacteria was found (one Clostridium sp., one Eubacterium sp., and one Synergistes sp.). Potential sulfide oxidizers and/or microaerophiles (Thiomicrospira, Arcobacter, Campylobacter, and Oceanospirillum spp.) were also detected. The first two were prominently amplified from uncultured production water DNA and represented 28 and 47% of all clones, respectively. Growth on media containing sulfide as the electron donor and nitrate as the electron acceptor and designed for the isolation of Thiomicrospira spp. gave only significant enrichment of the Campylobacter sp., which was shown to be present in different western Canadian oil fields. This newly discovered sulfide oxidizer may provide a vital link in the oil field sulfur cycle by reoxidizing sulfide formed by microbial sulfate or sulfur reduction.

Characterization of 16S rRNA genes from oil field microbial communities indicates the presence of a variety of sulfate-reducing, fermentative, and sulfide-oxidizing bacteria.

PubMed Central

Voordouw, G; Armstrong, S M; Reimer, M F; Fouts, B; Telang, A J; Shen, Y; Gevertz, D

1996-01-01

Oil field bacteria were characterized by cloning and sequencing of PCR-amplified 16S rRNA genes. A variety of gram-negative, sulfate-reducing bacteria was detected (16 members of the family Desulfovibrionaceae and 8 members of the family Desulfobacteriaceae). In contrast, a much more limited number of anaerobic, fermentative, or acetogenic bacteria was found (one Clostridium sp., one Eubacterium sp., and one Synergistes sp.). Potential sulfide oxidizers and/or microaerophiles (Thiomicrospira, Arcobacter, Campylobacter, and Oceanospirillum spp.) were also detected. The first two were prominently amplified from uncultured production water DNA and represented 28 and 47% of all clones, respectively. Growth on media containing sulfide as the electron donor and nitrate as the electron acceptor and designed for the isolation of Thiomicrospira spp. gave only significant enrichment of the Campylobacter sp., which was shown to be present in different western Canadian oil fields. This newly discovered sulfide oxidizer may provide a vital link in the oil field sulfur cycle by reoxidizing sulfide formed by microbial sulfate or sulfur reduction. PMID:8633860

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

USGS Publications Warehouse

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

2009-01-01

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

Slow electron acoustic double layer (SEADL) structures in bi-ion plasma with trapped electrons

NASA Astrophysics Data System (ADS)

Shan, Shaukat Ali; Imtiaz, Nadia

2018-05-01

The properties of ion acoustic double layer (IADL) structures in bi-ion plasma with electron trapping are investigated by using the quasi-potential analysis. The κ-distributed trapped electrons number density expression is truncated to some finite order of the electrostatic potential. By utilizing the reductive perturbation method, a modified Schamel equation which describes the evolution of the slow electron acoustic double layer (SEADL) with the modified speed due to the presence of bi-ion species is investigated. The Sagdeev-like potential has been derived which accounts for the effect of the electron trapping and superthermality in a bi-ion plasma. It is found that the superthermality index, the trapping efficiency of electrons, and ion to electron temperature ratio are the inhibiting parameters for the amplitude of the slow electron acoustic double layers (SEADLs). However, the enhanced population of the cold ions is found to play a supportive role for the low frequency DLs in bi-ion plasmas. The illustrations have been presented with the help of the bi-ion plasma parameters in the Earth's ionosphere F-region.

Ab initio single and multideterminant methods used in the determination of reduction potentials and magnetic properties of Rieske ferredoxins

NASA Astrophysics Data System (ADS)

Powers, Nathan Lee

2008-10-01

The [Fe2S2]2+/[Fe2S 2]+ electronic structure of seven Rieske protein active sites (bovine mitochondrial cytochrome bc1 complex, spinach chloroplast cytochrome b6f complex, Rieske-type ferredoxin associated with biphenyl dioxygenase from Burkholderia cepacia, yeast cytochrome bcl complex from Saccharomyces cerevisiae, Rieske subunit of arsenite oxidase from Alcaligenes faecalis, respiratory-type Rieske protein from Thermus thermophilus, and Rieske protein II (soxF) from Sulfolobus acidocaldarius), which lie in a reduction potential range from -150 mV to 375 mV, have been studied by both single and multi-determinant quantum mechanical methods. Calculated reduction potentials and magnetic properties are found comparable to experimental values.

Increased reactive oxygen species production during reductive stress: The roles of mitochondrial glutathione and thioredoxin reductases.

PubMed

Korge, Paavo; Calmettes, Guillaume; Weiss, James N

2015-01-01

Both extremes of redox balance are known to cause cardiac injury, with mounting evidence revealing that the injury induced by both oxidative and reductive stress is oxidative in nature. During reductive stress, when electron acceptors are expected to be mostly reduced, some redox proteins can donate electrons to O2 instead, which increases reactive oxygen species (ROS) production. However, the high level of reducing equivalents also concomitantly enhances ROS scavenging systems involving redox couples such as NADPH/NADP+ and GSH/GSSG. Here our objective was to explore how reductive stress paradoxically increases net mitochondrial ROS production despite the concomitant enhancement of ROS scavenging systems. Using recombinant enzymes and isolated permeabilized cardiac mitochondria, we show that two normally antioxidant matrix NADPH reductases, glutathione reductase and thioredoxin reductase, generate H2O2 by leaking electrons from their reduced flavoprotein to O2 when electron flow is impaired by inhibitors or because of limited availability of their natural electron acceptors, GSSG and oxidized thioredoxin. The spillover of H2O2 under these conditions depends on H2O2 reduction by peroxiredoxin activity, which may regulate redox signaling in response to endogenous or exogenous factors. These findings may explain how ROS production during reductive stress overwhelms ROS scavenging capability, generating the net mitochondrial ROS spillover causing oxidative injury. These enzymes could potentially be targeted to increase cancer cell death or modulate H2O2-induced redox signaling to protect the heart against ischemia/reperfusion damage. Copyright © 2015 Elsevier B.V. All rights reserved.

A strategy for selecting sexual partners believed to pose little/no risks for HIV: serosorting and its implications for HIV transmission.

PubMed

Eaton, Lisa A; Kalichman, Seth C; O'Connell, Daniel A; Karchner, William D

2009-10-01

A common HIV/AIDS risk reduction strategy among men who have sex with men (MSM) is to limit their unprotected sex partners to those who are of the same HIV status, a practice referred to as serosorting. Decisions to serosort for HIV risk reduction are based on personal impressions and beliefs, and there is limited guidance offered on this community derived strategy from public health services. This paper reviews research on serosorting for HIV risk reduction and offers an evidence-based approach to serosorting guidance. Following a comprehensive electronic and manual literature search, we reviewed 51 studies relating to the implications of serosorting. Studies showed that HIV negative MSM who select partners based on HIV status are inadvertently placing themselves at risk for HIV. Infrequent HIV testing, lack of HIV status disclosure, co-occurring sexually transmitted infections, and acute HIV infection impede the potential protective benefits of serosorting. Public health messages should continue to encourage reductions in numbers of sexual partners and increases in condom use. Risk reduction messages should also highlight the limitations of relying on one's own and partner's HIV status in making sexual risk decisions.

Microbial reduction of uranium

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.; Gorby, Y.A.; Landa, E.R.

1991-01-01

REDUCTION of the soluble, oxidized form of uranium, U(VI), to insoluble U(IV) is an important mechanism for the immobilization of uranium in aquatic sediments and for the formation of some uranium ores1-10. U(VI) reduction has generally been regarded as an abiological reaction in which sulphide, molecular hydrogen or organic compounds function as the reductant1,2,5,11. Microbial involvement in U(VI) reduction has been considered to be limited to indirect effects, such as microbial metabolism providing the reduced compounds for abiological U(VI) reduction and microbial cell walls providing a surface to stimulate abiological U(VI) reduction1,12,13. We report here, however, that dissimilatory Fe(III)-reducing microorganisms can obtain energy for growth by electron transport to U(VI). This novel form of microbial metabolism can be much faster than commonly cited abiological mechanisms for U(VI) reduction. Not only do these findings expand the known potential terminal electron acceptors for microbial energy transduction, they offer a likely explanation for the deposition of uranium in aquatic sediments and aquifers, and suggest a method for biological remediation of environments contaminated with uranium.

Reduction of uranium by Desulfovibrio desulfuricans

USGS Publications Warehouse

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

1992-01-01

The possibility that sulfate-reducing microorganisms contribute to U(VI) reduction in sedimentary environments was investigated. U(VI) was reduced to U(IV) when washed cells of sulfate-grown Desulfovibrio desulfuricans were suspended in a bicarbonate buffer with lactate or H2 as the electron donor. There was no U(VI) reduction in the absence of an electron donor or when the cells were killed by heat prior to the incubation. The rates of U(VI) reduction were comparable to those in respiratory Fe(III)-reducing microorganisms. Azide or prior exposure of the cells to air did not affect the ability of D. desulfuricans to reduce U(VI). Attempts to grow D. desulfuricans with U(VI) as the electron acceptor were unsuccessful. U(VI) reduction resulted in the extracellular precipitation of the U(IV) mineral uraninite. The presence of sulfate had no effect on the rate of U(VI) reduction. Sulfate and U(VI) were reduced simultaneously. Enzymatic reduction of U(VI) by D. desulfuricans was much faster than nonenzymatic reduction of U(VI) by sulfide, even when cells of D. desulfuricans were added to provide a potential catalytic surface for the nonenzymatic reaction. The results indicate that enzymatic U(VI) reduction by sulfate-reducing microorganisms may be responsible for the accumulation of U(IV) in sulfidogenic environments. Furthermore, since the reduction of U(VI) to U(IV) precipitates uranium from solution, D. desulfuricans might be a useful organisms for recovering uranium from contaminated waters and waste streams.

Electrochemical Reduction of Carbon Dioxide to Methanol by Direct Injection of Electrons into Immobilized Enzymes on a Modified Electrode.

PubMed

Schlager, Stefanie; Dumitru, Liviu Mihai; Haberbauer, Marianne; Fuchsbauer, Anita; Neugebauer, Helmut; Hiemetsberger, Daniela; Wagner, Annika; Portenkirchner, Engelbert; Sariciftci, Niyazi Serdar

2016-03-21

We present results for direct bio-electrocatalytic reduction of CO2 to C1 products using electrodes with immobilized enzymes. Enzymatic reduction reactions are well known from biological systems where CO2 is selectively reduced to formate, formaldehyde, or methanol at room temperature and ambient pressure. In the past, the use of such enzymatic reductions for CO2 was limited due to the necessity of a sacrificial co-enzyme, such as nicotinamide adenine dinucleotide (NADH), to supply electrons and the hydrogen equivalent. The method reported here in this paper operates without the co-enzyme NADH by directly injecting electrons from electrodes into immobilized enzymes. We demonstrate the immobilization of formate, formaldehyde, and alcohol dehydrogenases on one-and-the-same electrode for direct CO2 reduction. Carbon felt is used as working electrode material. An alginate-silicate hybrid gel matrix is used for the immobilization of the enzymes on the electrode. Generation of methanol is observed for the six-electron reduction with Faradaic efficiencies of around 10%. This method of immobilization of enzymes on electrodes offers the opportunity for electrochemical application of enzymatic electrodes to many reactions in which a substitution of the expensive sacrificial co-enzyme NADH is desired. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alcohol Electronic Screening and Brief Intervention: A Community Guide Systematic Review.

PubMed

Tansil, Kristin A; Esser, Marissa B; Sandhu, Paramjit; Reynolds, Jeffrey A; Elder, Randy W; Williamson, Rebecca S; Chattopadhyay, Sajal K; Bohm, Michele K; Brewer, Robert D; McKnight-Eily, Lela R; Hungerford, Daniel W; Toomey, Traci L; Hingson, Ralph W; Fielding, Jonathan E

2016-11-01

Excessive drinking is responsible for one in ten deaths among working-age adults in the U.S. annually. Alcohol screening and brief intervention is an effective but underutilized intervention for reducing excessive drinking among adults. Electronic screening and brief intervention (e-SBI) uses electronic devices to deliver key elements of alcohol screening and brief intervention, with the potential to expand population reach. Using Community Guide methods, a systematic review of the scientific literature on the effectiveness of e-SBI for reducing excessive alcohol consumption and related harms was conducted. The search covered studies published from 1967 to October 2011. A total of 31 studies with 36 study arms met quality criteria and were included in the review. Analyses were conducted in 2012. Twenty-four studies (28 study arms) provided results for excessive drinkers only and seven studies (eight study arms) reported results for all drinkers. Nearly all studies found that e-SBI reduced excessive alcohol consumption and related harms: nine study arms reported a median 23.9% reduction in binge-drinking intensity (maximum drinks/binge episode) and nine study arms reported a median 16.5% reduction in binge-drinking frequency. Reductions in drinking measures were sustained for up to 12 months. According to Community Guide rules of evidence, e-SBI is an effective method for reducing excessive alcohol consumption and related harms among intervention participants. Implementation of e-SBI could complement population-level strategies previously recommended by the Community Preventive Services Task Force for reducing excessive drinking (e.g., increasing alcohol taxes and regulating alcohol outlet density). Published by Elsevier Inc.

Effectiveness of mobile electronic devices in weight loss among overweight and obese populations: a systematic review and meta-analysis.

PubMed

Khokhar, Bushra; Jones, Jessica; Ronksley, Paul E; Armstrong, Marni J; Caird, Jeff; Rabi, Doreen

2014-01-01

Mobile electronic devices, such as mobile phones and PDAs, have emerged as potentially useful tools in the facilitation and maintenance of weight loss. While RCTs have demonstrated a positive impact of mobile interventions, the extent to which mobile electronic devices are more effective than usual care methods is still being debated. Electronic databases were systematically searched for RCTs evaluating the effectiveness of mobile electronic device interventions among overweight and obese adults. Weighted mean difference for change in body weight was the primary outcome. The search strategy yielded 559 citations and of the 108 potentially relevant studies, six met the criteria. A total of 632 participants were included in the six studies reporting a mean change in body weight. Using a random-effects model, the WMD for the effect of using mobile electronic devices on reduction in body weight was -1.09 kg (95% CI -2.12, -0.05). When stratified by the type of mobile electronic device used, it suggests that interventions using mobile phones were effective at achieving weight loss, WMD = -1.78 kg (95% CI -2.92, -0.63). This systematic review and meta-analysis suggests that mobile electronic devices have the potential to facilitate weight loss in overweight and obese populations, but further work is needed to understand if these interventions have sustained benefit and how we can make these mHealth tools most effective on a large scale. As the field of healthcare increasingly utilizes novel mobile technologies, the focus must not be on any one specific device but on the best possible use of these tools to measure and understand behavior. As mobile electronic devices continue to increase in popularity and the associated technology continues to advance, the potential for the use of mobile devices in global healthcare is enormous. More RCTs with larger sample sizes need to be conducted to look at the cost-effectiveness, technical and financial feasibility of adapting such mHealth interventions in a real clinical setting.

Effect of N-substituents on redox, optical, and electronic properties of naphthalene bisimides used for field-effect transistors fabrication.

PubMed

Gawrys, Pawel; Djurado, David; Rimarcík, Ján; Kornet, Aleksandra; Boudinet, Damien; Verilhac, Jean-Marie; Lukes, Vladimír; Wielgus, Ireneusz; Zagorska, Malgorzata; Pron, Adam

2010-02-11

Three groups of naphthalene bisimides were synthesized and comparatively studied, namely, alkyl bisimides, alkylaryl ones, and novel bisimides containing the alkylthienyl moiety in the N-substituent. The experimental absorption spectra measured in CHCl(3) exhibit one intensive absorption band that is uniformly detected in the spectral range of 340 to 400 nm for all studied molecules. This band consists of three or four vibronic peaks. The introduction of an alkylthienyl group results in the appearance of an additional band (in the spectral range from 282 to 326 nm, depending on the position of the substituent) that can be ascribed to the pi-pi* transition in the thienyl chromophore. The minimal substituent effect on the lowest electronic transitions was explained using the quantum chemical calculations based on the time-dependent density functional theory. The investigation of the shapes of frontier orbitals have also shown that the oxidation of bisimides containing thiophene moiety is primary connected with the electron abstraction from the thienyl ring. To the contrary, the addition of an electron in the reduction process leads to an increase in the electron density in the central bisimide core. As shown by the electrochemical measurements, the onset of the first reduction potential (so-called "electrochemically determined LUMO level") is sensitive toward the type of the substituent being shifted from about -3.72 eV for bisimides with alkyl substituents to about -3.83 eV for alkylaryl ones and to about -3.94 eV for bisimides with thienyl groups. The presence of the thienyl ring also lowers the energy difference between the HOMO and LUMO orbitals. These experimental data can be well correlated with the DFT calculations in terms of HOMO/LUMO shapes and energies. Taking into account the low position of their LUMO level and their highly ordered supramolecular organization, the new bisimides are good candidates for the use in n-channel field effect transistors, operating in air. The fabricated "all organic" transistors show effective charge carrier mobilities in the range 10(-2) to 10(-4) cm(2) V(-1) s(-1) and the ON/OFF ratios exceed 10(5) for the majority of cases.

Characterization of U(VI) reduction in contaminated sediments with slow-degrading electron donor source

NASA Astrophysics Data System (ADS)

Wu, W.; Watson, D. B.; Zhang, G.; Mehlhorn, T.; Lowe, K.; Earles, J.; Phillips, J.; Kelly, S. D.; Boyanov, M.; Kemner, K. M.; Schadt, C.; Criddle, C. S.; Jardine, P. M.; Brooks, S. C.

2011-12-01

In order to select sustainable, high efficiency and cost effective electron donor source, oleate and emulsified vegetable oil (EVO) were tested uranium (VI) reduction in comparison with ethanol in microcosms using uranium contaminated sediments and groundwater from the US DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) site. The effect of initial sulfate concentration on U(VI) reduction was also tested. Both oleate and EVO were effective electron donor sources for U(VI) reduction. Accumulation of acetate as a major product and the removal of aqueous U(VI) were observed and were associated with sulfate reduction. Both oleate and EVO supported U(VI) reduction but at slower rates with a comparable but slightly lower extent of reduction than ethanol. X-ray absorption near-edge spectroscopy (XANES) analysis confirmed reduction of U(VI) to U(IV). The extent of U(VI) reduction in solid phase was negatively influenced by aqueous calcium concentration. The majority of electrons of the three substrates were consumed by sulfate reduction, Fe(III) reduction, and methanogenesis. Initial U(VI) concentration in the aqueous phase increased with increased sulfate concentration (1 versus 5 mM), likely due to U(VI) desorption from the solid phase. At the higher initial sulfate concentration more U(VI) was reduced and fewer electrons were used in methanogenesis. Analysis of bacterial and archeal populations using 16S rRNA gene libraries showed a significant increase in Deltaproteobacteria after biostimulation. The microbial community structures developed with oleate and EVO were significantly distinct from those developed with ethanol. Bacteria similar to Desulforegula spp. was predominant for oleate and EVO degradation but were not observed in ethanol-amended microcosms. Known U(VI)-reducing bacteria in the microcosms amended with the three electron donor sources included iron(III) reducing Geobacter spp. but in lower abundances than sulfate-reducing Desulfovibrio spp. The test results were used for the design a field test by one-time injection of EVO to the subsurface for U(VI) reduction in Area 2 of the ORIFRC site.

Potential electron mediators to extract electron energies of RBC glycolysis for prolonged in vivo functional lifetime of hemoglobin vesicles.

PubMed

Kettisen, Karin; Bülow, Leif; Sakai, Hiromi

2015-04-15

Developing a functional blood substitute as an alternative to donated blood for clinical use is believed to relieve present and future blood shortages, and to reduce the risks of infection and blood type mismatching. Hemoglobin vesicle (HbV) encapsulates a purified and concentrated human-derived Hb solution in a phospholipid vesicle (liposome). The in vivo safety and efficacy of HbV as a transfusion alternative have been clarified. Auto-oxidation of ferrous Hb in HbV gradually increases the level of ferric methemoglobin (metHb) and impairs the oxygen transport capabilities. The extension of the functional half-life of HbV has recently been proposed using an electron mediator, methylene blue (MB), which acts as a shuttle between red blood cells (RBC) and HbV. MB transfers electron energies of NAD(P)H, produced by RBC glycolysis, to metHb in HbV. Work presented here focuses on screening of 15 potential electron mediators, with appropriate redox potential and water solubility, for electron transfer from RBC to HbV. The results are assessed with regard to the chemical properties of the candidates. The compounds examined in this study were dimethyl methylene blue (DMB), methylene green, azure A, azure B, azure C, toluidine blue (TDB), thionin acetate, phenazine methosulfate, brilliant cresyl blue, cresyl violet, gallocyanine, toluylene blue, indigo carmine, indigotetrasulfonate, and MB. Six candidates were found to be unsuitable because of their insufficient diffusion across membranes, or overly high or nonexistent reactivity with relevant biomolecules. However, 9 displayed favorable metHb reduction. Among the suitable candidates, phenothiazines DMB and TDB exhibited effectiveness like MB did. In comparison to MB, they showed faster reduction by electron-donating NAD(P)H, coupled with showing a lower rate of reoxidation in the presence of molecular oxygen. Ascertaining the best electron mediator can provide a pathway for extending the lifetime and efficiency of potential blood substitutes.

H/D exchange mass spectrometry and statistical coupling analysis reveal a role for allostery in a ferredoxin-dependent bifurcating transhydrogenase catalytic cycle.

PubMed

Berry, Luke; Poudel, Saroj; Tokmina-Lukaszewska, Monika; Colman, Daniel R; Nguyen, Diep M N; Schut, Gerrit J; Adams, Michael W W; Peters, John W; Boyd, Eric S; Bothner, Brian

2018-01-01

Recent investigations into ferredoxin-dependent transhydrogenases, a class of enzymes responsible for electron transport, have highlighted the biological importance of flavin-based electron bifurcation (FBEB). FBEB generates biomolecules with very low reduction potential by coupling the oxidation of an electron donor with intermediate potential to the reduction of high and low potential molecules. Bifurcating systems can generate biomolecules with very low reduction potentials, such as reduced ferredoxin (Fd), from species such as NADPH. Metabolic systems that use bifurcation are more efficient and confer a competitive advantage for the organisms that harbor them. Structural models are now available for two NADH-dependent ferredoxin-NADP + oxidoreductase (Nfn) complexes. These models, together with spectroscopic studies, have provided considerable insight into the catalytic process of FBEB. However, much about the mechanism and regulation of these multi-subunit proteins remains unclear. Using hydrogen/deuterium exchange mass spectrometry (HDX-MS) and statistical coupling analysis (SCA), we identified specific pathways of communication within the model FBEB system, Nfn from Pyrococus furiosus, under conditions at each step of the catalytic cycle. HDX-MS revealed evidence for allosteric coupling across protein subunits upon nucleotide and ferredoxin binding. SCA uncovered a network of co-evolving residues that can provide connectivity across the complex. Together, the HDX-MS and SCA data show that protein allostery occurs across the ensemble of iron‑sulfur cofactors and ligand binding sites using specific pathways that connect domains allowing them to function as dynamically coordinated units. Copyright © 2017 Elsevier B.V. All rights reserved.

Carbon Nanotube-Based Membrane for Light-Driven, Simultaneous Proton and Electron Transport

DOE PAGES

Pilgrim, Gregory A.; Amori, Amanda R.; Hou, Zhentao; ...

2016-12-07

Here we discuss the photon driven transport of protons and electrons over hundreds of microns through a membrane based on vertically aligned single walled carbon nanotubes (SWNTs). Electrons are photogenerated in colloidal CdSe quantum dots that have been noncovalently attached to the carbon nanotube membrane and can be delivered at potentials capable of reducing earth-abundant molecular catalysts that perform proton reduction. Proton transport is driven by the electron photocurrent and is shown to be faster through the SWNT based membrane than through the commercial polymer Nafion. Furthermore, the potential utility of SWNT membranes for solar water splitting applications is demonstratedmore » through their excellent proton and electron transport properties as well as their ability to interact with other components of water splitting systems, such as small molecule electron acceptors.« less

Excitonic gap formation in pumped Dirac materials

NASA Astrophysics Data System (ADS)

Triola, Christopher; Pertsova, Anna; Markiewicz, Robert S.; Balatsky, Alexander V.

2017-05-01

Recent pump-probe experiments demonstrate the possibility that Dirac materials may be driven into transient excited states describable by two chemical potentials, one for the electrons and one for the holes. Given the Dirac nature of the spectrum, such an inverted population allows the optical tunability of the density of states of the electrons and holes, effectively offering control of the strength of the Coulomb interaction. Here we discuss the feasibility of realizing transient excitonic instabilities in optically pumped Dirac materials. We demonstrate, theoretically, the reduction of the critical coupling leading to the formation of a transient condensate of electron-hole pairs and identify signatures of this state. Furthermore, we provide guidelines for experiments by both identifying the regimes in which such exotic many-body states are more likely to be observed and estimating the magnitude of the excitonic gap for a few important examples of existing Dirac materials. We find a set of material parameters for which our theory predicts large gaps and high critical temperatures and which could be realized in future Dirac materials. We also comment on transient excitonic instabilities in three-dimensional Dirac and Weyl semimetals. This study provides an example of a transient collective instability in driven Dirac materials.

Electron beam irradiation of Matricaria chamomilla L. for microbial decontamination

NASA Astrophysics Data System (ADS)

Nemţanu, Monica R.; Kikuchi, Irene Satiko; de Jesus Andreoli Pinto, Terezinha; Mazilu, Elena; Setnic, Silvia; Bucur, Marcela; Duliu, Octavian G.; Meltzer, Viorica; Pincu, Elena

2008-05-01

Wild chamomile (Matricaria chamomilla L.) is one of the most popular herbal materials with both internal and external use to cure different health disturbances. As a consequence of its origin, chamomile could carry various microbial contaminants which offer different hazards to the final consumer. Reduction of the microbial load to the in force regulation limits represents an important phase in the technological process of vegetal materials, and the electron beam treatment might be an efficient alternative to the classical methods of hygienic quality assurance. The purpose of the study was to analyze the potential application of the electron beam treatment in order to assure the microbial safety of the wild chamomile. Samples of chamomile dry inflorescences were treated in electron beam (e-beam) of 6 MeV mean energy, at room temperature and ambient pressure. Some loss of the chemical compounds with bioactive role could be noticed, but the number of microorganisms decreased as a function on the absorbed dose. Consequently, the microbial quality of studied vegetal material inflorescences was improved by e-beam irradiation.

Predicting the Rate Constant of Electron Tunneling Reactions at the CdSe-TiO2 Interface.

PubMed

Hines, Douglas A; Forrest, Ryan P; Corcelli, Steven A; Kamat, Prashant V

2015-06-18

Current interest in quantum dot solar cells (QDSCs) motivates an understanding of the electron transfer dynamics at the quantum dot (QD)-metal oxide (MO) interface. Employing transient absorption spectroscopy, we have monitored the electron transfer rate (ket) at this interface as a function of the bridge molecules that link QDs to TiO2. Using mercaptoacetic acid, 3-mercaptopropionic acid, 8-mercaptooctanoic acid, and 16-mercaptohexadecanoic acid, we observe an exponential attenuation of ket with increasing linker length, and attribute this to the tunneling of the electron through the insulating linker molecule. We model the electron transfer reaction using both rectangular and trapezoidal barrier models that have been discussed in the literature. The one-electron reduction potential (equivalent to the lowest unoccupied molecular orbital) of each molecule as determined by cyclic voltammetry (CV) was used to estimate the effective barrier height presented by each ligand at the CdSe-TiO2 interface. The electron transfer rate (ket) calculated for each CdSe-ligand-TiO2 interface using both models showed the results in agreement with the experimentally determined trend. This demonstrates that electron transfer between CdSe and TiO2 can be viewed as electron tunneling through a layer of linking molecules and provides a useful method for predicting electron transfer rate constants.

Electron Beam-Induced Writing of Nanoscale Iron Wires on a Functional Metal Oxide

PubMed Central

2013-01-01

Electron beam-induced surface activation (EBISA) has been used to grow wires of iron on rutile TiO2(110)-(1 × 1) in ultrahigh vacuum. The wires have a width down to ∼20 nm and hence have potential utility as interconnects on this dielectric substrate. Wire formation was achieved using an electron beam from a scanning electron microscope to activate the surface, which was subsequently exposed to Fe(CO)5. On the basis of scanning tunneling microscopy and Auger electron spectroscopy measurements, the activation mechanism involves electron beam-induced surface reduction and restructuring. PMID:24159366

Formation and characterization of a reactive chromium(v)–oxo complex: mechanistic insight into hydrogen-atom transfer reactions† †Electronic supplementary information (ESI) available: Crystallographic data of 2 and 3 in CIF, ESI-TOF-MS, UV-vis, ESR, DFT calculations, 1H NMR, and GC-MS data. CCDC 1017025 and 1017026. See DOI: 10.1039/c4sc02285h Click here for additional data file.

PubMed Central

Kaida, Suzue; Ishizuka, Tomoya; Sakaguchi, Miyuki; Ogura, Takashi; Shiota, Yoshihito; Yoshizawa, Kazunari

2015-01-01

A mononuclear Cr(v)–oxo complex, [CrV(O)(6-COO–-tpa)](BF4)2 (1; 6-COO–-tpa = N,N-bis(2-pyridylmethyl)-N-(6-carboxylato-2-pyridylmethyl)amine) was prepared through the reaction of a Cr(iii) precursor complex with iodosylbenzene as an oxidant. Characterization of 1 was achieved using ESI-MS spectrometry, electron paramagnetic resonance, UV-vis, and resonance Raman spectroscopies. The reduction potential (E red) of 1 was determined to be 1.23 V vs. SCE in acetonitrile based on analysis of the electron-transfer (ET) equilibrium between 1 and a one-electron donor, [RuII(bpy)3]2+ (bpy = 2,2′-bipyridine). The reorganization energy (λ) of 1 was also determined to be 1.03 eV in ET reactions from phenol derivatives to 1 on the basis of the Marcus theory of ET. The smaller λ value in comparison with that of an Fe(iv)–oxo complex (2.37 eV) is caused by the small structural change during ET due to the dπ character of the electron-accepting LUMO of 1. When benzyl alcohol derivatives (R-BA) with different oxidation potentials were employed as substrates, corresponding aldehydes were obtained as the 2e–-oxidized products in moderate yields as determined from 1H NMR and GC-MS measurements. One-step UV-vis spectral changes were observed in the course of the oxidation reactions of BA derivatives by 1 and a kinetic isotope effect (KIE) was observed in the oxidation reactions for deuterated BA derivatives at the benzylic position as substrates. These results indicate that the rate-limiting step is a concerted proton-coupled electron transfer (PCET) from substrate to 1. In sharp contrast, in the oxidation of trimethoxy-BA (E ox = 1.22 V) by 1, trimethoxy-BA radical cation was observed by UV-vis spectroscopy. Thus, it was revealed that the mechanism of the oxidation reaction changed from one-step PCET to stepwise ET–proton transfer (ET/PT), depending on the redox potentials of R-BA. PMID:29560181

Electron-Transfer Kinetics of Redox Centers Anchored to Metal Surfaces: Weak- versus Strong-Overlap Reaction Pathways.

DTIC Science & Technology

1983-11-01

constants ket are presented for the one-electron electroreduction of various Co1]:I(NH3)5X complexes bound to mercury, platinum, and gold surfaces...electroreduction of various Co^^(NH𔃽)𔃿X complexes bound to mercury, platinum, and gold surfaces via either small inorganic or extended organic ligands X. t...platinum, gold , and copper, to enable values of ke* to be obtained for the one-electron reduction of the surface-Douna_redox center.2.3 These

Manganese inhibition of microbial iron reduction in anaerobic sediments

USGS Publications Warehouse

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

1988-01-01

Potential mechanisms for the lack of Fe(II) accumulation in Mn(IV)-containing anaerobic sediments were investigated. The addition of Mn(IV) to sediments in which Fe(II) reduction was the terminal electron-accepting process removed all the pore-water Fe(II), completely inhibited net Fe(III) reduction, and stimulated Mn(IV) reduction. Results demonstrate that preferential reduction of Mn(IV) by FE(III)-reducing bacteria cannot completely explain the lack of Fe(II) accumulation in anaerobic, Mn(IV)-containing sediments, and indicate that Mn(IV) oxidation of Fe(II) is the mechanism that ultimately prevents Fe(II) accumulation. -Authors

Enhanced Fe2O3 Reducibility via Surface Modification with Pd: Characterizing the Synergy within Pd/Fe Catalysts for Hydrodeoxygenation Reactions

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

Hensley, Alyssa; Hong, Yongchun; Zhang, Renqin

2014-10-03

The synergistic catalysis in the hydrodeoxygenation of phenolic compounds over a Pd/Fe bimetallic surface has been well established. However, the nature of this synergy is still in part a mystery. In this work, we used a combined experimental and theoretical approach to understand a potential function of the surface Pd in the reduction of Pd/Fe2O3. This function of Pd was investigated via the comparison of the reduction properties as well as other physicochemical properties of samples synthesized by the reduction of Fe2O3 nanoparticles with and without surface Pd. Temperature-programmed reduction studies demonstrated the remarkable facilitation of reduction by addition ofmore » Pd, evidenced by a 150 degrees C shift toward lower temperature of the reduction peak of Fe3+. From X-ray photoelectron spectroscopy and theoretical calculation results, the interaction between Pd and the Fe2O3 surface occurs through the exchange of electrons with both the surface Fe and O atoms. This bonding between the Pd and surface oxide elements causes the Pd to partially donate electrons to the oxide surface, making the surface electrons more delocalized. This electron delocalization stabilizes the reduced oxide surfaces, as suggested by the TPR results and theoretical prediction. Therefore, the stabilization of the reduced Fe surface as well as the facilitated water formation by introduction of Pd is expected to significantly contribute to the Pd-Fe synergy in hydrodeoxygenation catalysis.« less

Cadmium poisoning of oxygen reduction on platinum electrode in potassium hydroxide

NASA Technical Reports Server (NTRS)

Miller, R. O.

1972-01-01

Experiment with a rotating disk and ring apparatus showed no poisoning by cadmium in 8.5 M KOH, alone or with Cl(-) or CO3(=). Poisoning does not occur either in 0.1 M KOH supernatant at CdO, but a partially reversible poisoning results from .0001 M CdCl2 and traces of fatty acid are present. Evidence indicates that the catastrophic poisoning affects the four-electron O2 reduction more than it does the one-electron H3O(+) discharge.

Anaerobic reduction of elemental sulfur by Chromatium vinosum and Beggiatoa alba

NASA Technical Reports Server (NTRS)

Schmidt, T. M.

1985-01-01

The effect of sulfur globules on the buoyant density of Chromatium vinosum and Beggiatoa alba was examined. The potential use of sulfur as a terminal electron acceptor in the anaerobic metabolism of Beggiatoa alba is also examined. The effect of the reduction of intracellular sulfur was investigated during dark metabolism on the buoyant density of C. vinosum. It is hypothesized from the results that the sulfur reduction to sulfide is part of an anaerobic energy operating system. Carbon stored as PHB can be oxidized with the concomitant reduction of sulfur to sulfide.

Biomass-derived heteroatoms-doped mesoporous carbon for efficient oxygen reduction in microbial fuel cells.

PubMed

Lu, Yu; Zhu, Nengwu; Yin, Fuhua; Yang, Tingting; Wu, Pingxiao; Dang, Zhi; Liu, Meilin; Wei, Xiaorong

2017-12-15

Currently, the development of less expensive, more active and more stable catalysts like heteroatom-doped carbon based non-precious metal materials are highly desired for the cathodic oxygen reduction reaction (ORR) in microbial fuel cells (MFCs). Comparing with heteroatom sources from chemical reagents, biomass is notably inexpensive and abundant, containing more elements which contribute to ORR activity. Herein, we demonstrate an easy operating one-step and low-cost way to synthesize egg-derived heteroatoms-doped mesoporous carbon (EGC) catalysts utilizing egg as the biomass carbon and other elements source (sulphur, phosphorus, boron and iron), and porous g-C 3 N 4 as both template and nitrogen source. After carbonized, such hybrid materials possess an outstanding electrocatalytic activity towards ORR comparable to the commercial Pt/C catalyst in neutral media. Electrochemical detections as cyclic voltammogram and rotating ring-disk electrode tests show that the potential of oxygen reduction peak of EGC1-10-2 is at + 0.10V, onset potential is at + 0.257V (vs. Ag/AgCl) and electron transfer number of that is 3.84-3.92, which indicate that EGC1-10-2 via a four-electron pathway. Reactor operation shows that the maximum power density of MFC-EGC1-10-2 (737.1mWm -2 ), which is slightly higher than MFC-Pt/C (20%) (704mWm -2 ). The low cost (0.049 $g -1 ), high yield (20.26%) and high performance of EGC1-10-2 provide a promising alternative to noble metal catalysts by using abundant natural biological resources, which contribute a lot to expansion and commercialization of MFCs. Copyright © 2017 Elsevier B.V. All rights reserved.

Arsenic release from shallow aquifers of the Hetao basin, Inner Mongolia: evidence from bacterial community in aquifer sediments and groundwater.

PubMed

Li, Yuan; Guo, Huaming; Hao, Chunbo

2014-12-01

Indigenous microbes play crucial roles in arsenic mobilization in high arsenic groundwater systems. Databases concerning the presence and the activity of microbial communities are very useful in evaluating the potential of microbe-mediated arsenic mobilization in shallow aquifers hosting high arsenic groundwater. This study characterized microbial communities in groundwaters at different depths with different arsenic concentrations by DGGE and one sediment by 16S rRNA gene clone library, and evaluated arsenic mobilization in microcosm batches with the presence of indigenous bacteria. DGGE fingerprints revealed that the community structure changed substantially with depth at the same location. It indicated that a relatively higher bacterial diversity was present in the groundwater sample with lower arsenic concentration. Sequence analysis of 16S rRNA gene demonstrated that the sediment bacteria mainly belonged to Pseudomonas, Dietzia and Rhodococcus, which have been widely found in aquifer systems. Additionally, NO3(-)-reducing bacteria Pseudomonas sp. was the largest group, followed by Fe(III)-reducing, SO4(2-)-reducing and As(V)-reducing bacteria in the sediment sample. These anaerobic bacteria used the specific oxyanions as electron acceptor and played a significant role in reductive dissolution of Fe oxide minerals, reduction of As(V), and release of arsenic from sediments into groundwater. Microcosm experiments, using intact aquifer sediments, showed that arsenic release and Fe(III) reduction were microbially mediated in the presence of indigenous bacteria. High arsenic concentration was also observed in the batch without amendment of organic carbon, demonstrating that the natural organic matter in sediments was the potential electron donor for microbially mediated arsenic release from these aquifer sediments.

Evaluating molecular cobalt complexes for the conversion of N2 to NH3.

PubMed

Del Castillo, Trevor J; Thompson, Niklas B; Suess, Daniel L M; Ung, Gaël; Peters, Jonas C

2015-10-05

Well-defined molecular catalysts for the reduction of N2 to NH3 with protons and electrons remain very rare despite decades of interest and are currently limited to systems featuring molybdenum or iron. This report details the synthesis of a molecular cobalt complex that generates superstoichiometric yields of NH3 (>200% NH3 per Co-N2 precursor) via the direct reduction of N2 with protons and electrons. While the NH3 yields reported herein are modest by comparison to those of previously described iron and molybdenum systems, they intimate that other metals are likely to be viable as molecular N2 reduction catalysts. Additionally, a comparison of the featured tris(phosphine)borane Co-N2 complex with structurally related Co-N2 and Fe-N2 species shows how remarkably sensitive the N2 reduction performance of potential precatalysts is. These studies enable consideration of the structural and electronic effects that are likely relevant to N2 conversion activity, including the π basicity, charge state, and geometric flexibility.

Giant onsite electronic entropy enhances the performance of ceria for water splitting.

PubMed

Naghavi, S Shahab; Emery, Antoine A; Hansen, Heine A; Zhou, Fei; Ozolins, Vidvuds; Wolverton, Chris

2017-08-18

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Ce 4+ /Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.Solid-state entropy of reduction increases the thermodynamic efficiency of ceria for two-step thermochemical water splitting. Here, the authors report a large and different source of entropy, the onsite electronic configurational entropy arising from coupling between orbital and spin angular momenta in f orbitals.

Electrochemical oxygen reduction behavior of selectively deposited platinum atoms on gold nanoparticles.

PubMed

Sarkar, A; Kerr, J B; Cairns, E J

2013-07-22

Carbon-supported Pt@Au "core-shell" nanoparticles with varying surface concentration of platinum atoms have been synthesized using a novel redox-mediated synthesis approach. The synthesis technique allows for a selective deposition of platinum atoms on the surface of prefabricated gold nanoparticles. Energy dispersive spectroscopic analyses in a scanning electron microscope reveal that the platinum to gold atomic ratios are close to the nominal values, validating the synthesis scheme. X-ray diffraction data indicate an un-alloyed structure. The platinum to gold surface atomic ratio determined from cyclic voltammetry and copper under-potential deposition experiments reveal good agreement with the calculated values at low platinum concentration. However, there is an increase in non-uniformity in the deposition process upon increasing the platinum concentration. Koutecky-Levich analysis of the samples indicates a transition of the total number of electrons transferred (n) in the electrochemical oxygen reduction reaction from two to four electrons upon increasing the surface concentration of platinum atoms. Furthermore, the data indicate that isolated platinum atoms can reduce molecular oxygen but via a two-electron route. Moreover, successful four-electron reduction of molecular oxygen requires clusters of platinum atoms. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduction of nitrobenzene with alkaline ascorbic acid: Kinetics and pathways.

PubMed

Liang, Chenju; Lin, Ya-Ting; Shiu, Jia-Wei

2016-01-25

Alkaline ascorbic acid (AA) exhibits the potential to reductively degrade nitrobenzene (NB), which is the simplest of the nitroaromatic compounds. The nitro group (NO2(-)) of NB has a +III oxidation state of the N atom and tends to gain electrons. The effect of alkaline pH ranging from 9 to 13 was initially assessed and the results demonstrated that the solution pH, when approaching or above the pKa2 of AA (11.79), would increase reductive electron transfer to NB. The rate equation for the reactions between NB and AA at pH 12 can be described as r=((0.89±0.11)×10(-4) mM(1-(a+b))h(-1))×[NB](a=1.35±0.10)[AA](b=0.89±0.01). The GC/MS analytical method identified nitrosobenzene, azoxybenzene, and azobenzene as NB reduction intermediates, and aniline (AN) as a final product. These experimental results indicate that the alkaline AA reduction of NB to AN mainly proceeds via the direct route, consisting of a series of two-electron or four-electron transfers, and the condensation reaction plays a minor route. Preliminary evaluation of the remediation of spiked NB contaminated soils revealed that maintenance of alkaline pH and a higher water to soil ratio are essential for a successful alkaline AA application. Copyright © 2015 Elsevier B.V. All rights reserved.

Electronic, Spectral, and Electrochemical Properties of (TPPBr(x)())Zn Where TPPBr(x)() Is the Dianion of beta-Brominated-Pyrrole Tetraphenylporphyrin and x Varies from 0 to 8.

PubMed

D'Souza, Francis; Zandler, Melvin E.; Tagliatesta, Pietro; Ou, Zhongping; Shao, Jianguo; Van Caemelbecke, Eric; Kadish, Karl M.

1998-09-07

The electronic, spectral, and electrochemical characterization of (meso-tetraphenylporphyrinato)zinc(II) complexes bearing between 0 and 8 bromo substituents at the beta-pyrrole positions is reported. The investigated compounds are represented as (TPPBr(x)())Zn where TPPBr(x)() is the dianion of brominated 5,10,15,20-tetraphenylporphyrin and x varies between 0 and 8. Each porphyrin undergoes four well-defined one-electron transfer reactions to yield porphyrin pi-cation radicals and dications upon oxidation and porphyrin pi-anion radicals and dianions upon reduction. Half-wave potentials for the first reduction of (TPPBr(x)())Zn can be described by a single linear free energy relationship, and plots of E(1/2) versus the number of Br groups on the complex show a linear correlation with a positive slope of 63 mV per Br group. This is not the case for the other three electron transfer processes of the compounds where plots of E(1/2) versus the number of Br groups show distinctly different linear correlations for derivatives with 0-4 Br groups and those with 4-8 Br groups. The effect of increasing number of Br groups on the spectral and electrochemical properties of the neutral complexes was examined over the whole series of compounds, and these experimental results are compared to results of theoretical calculations by semiempirical molecular orbital AM1 methods using configurational interactions (CI) over the four Gouterman frontier pi-orbitals. The dihedral angle containing the four porphyrin macrocycle ring nitrogens is proposed as a measure of porphyrin ring nonplanarity, and this value increases with increasing number of Br substituents on (TPPBr(x)())Zn. Results of the AM1-CI = 4 calculations indicate that the spectrally determined HOMO-LUMO gap, i.e., the energy corresponding to the low-energy absorption band, varies in a nonlinear fashion with increasing number of Br substituents on the macrocycle and this is due to both the electronic effect of the substituents and the macrocycle nonplanarity. The HOMO-LUMO gaps theoretically calculated by AM1-CI = 4 methods thus parallel values which are experimentally obtained by electrochemistry or spectroscopy. The lack of well-defined linear free energy relationships for all processes except for the first reduction can be explained on the basis of electronic effects caused by the halogen substituents and nonplanar macrocyclic distortions induced by steric interactions among the peripheral substituents. In the case of porphyrin dication formation, the redox potentials are virtually independent of the bromo substituents.

Self-assembled via axial coordination magnesium porphyrin-imidazole appended fullerene dyad: spectroscopic, electrochemical, computational, and photochemical studies.

PubMed

D'Souza, Francis; El-Khouly, Mohamed E; Gadde, Suresh; McCarty, Amy L; Karr, Paul A; Zandler, Melvin E; Araki, Yasuyaki; Ito, Osamu

2005-05-26

Spectroscopic, redox, and electron transfer reactions of a self-assembled donor-acceptor dyad formed by axial coordination of magnesium meso-tetraphenylporphyrin (MgTPP) and fulleropyrrolidine appended with an imidazole coordinating ligand (C(60)Im) were investigated. Spectroscopic studies revealed the formation of a 1:1 C(60)Im:MgTPP supramolecular complex, and the anticipated 1:2 complex could not be observed because of the needed large amounts of the axial coordinating ligand. The formation constant, K(1), for the 1:1 complex was found to be (1.5 +/- 0.3) x 10(4) M(-1), suggesting fairly stable complex formation. The geometric and electronic structures of the dyads were probed by ab initio B3LYP/3-21G() methods. The majority of the highest occupied frontier molecular orbital (HOMO) was found to be located on the MgTPP entity, while the lowest unoccupied molecular orbital (LUMO) was on the fullerene entity, suggesting that the charge-separated state of the supramolecular complex is C(60)Im(*-):MgTPP(*+). Redox titrations involving MgTPP and C(60)Im allowed accurate determination of the oxidation and reduction potentials of the donor and acceptor entities in the supramolecular complex. These studies revealed more difficult oxidation, by about 100 mV, for MgTPP in the pentacoordinated C(60)Im:MgTPP compared to pristine MgTPP in o-dichlorobenzene. A total of six one-electron redox processes corresponding to the oxidation and reduction of the zinc porphyrin ring and the reduction of fullerene entities was observed within the accessible potential window of the solvent. The excited state events were monitored by both steady state and time-resolved emission as well as transient absorption techniques. In o-dichlorobenzene, upon coordination of C(60)Im to MgTPP, the main quenching pathway involved electron transfer from the singlet excited MgTPP to the C(60)Im moiety. The rate of forward electron transfer, k(CS), calculated from the picosecond time-resolved emission studies was found to be 1.1 x 10(10) s(-1) with a quantum yield, Phi(CS), of 0.99, indicating fast and efficient charge separation. The rate of charge recombination, k(CR), evaluated from nanosecond transient absorption studies, was found to be 8.3 x 10(7) s(-1). A comparison between k(CS) and k(CR) suggested an excellent opportunity to utilize the charge-separated state for further electron-mediating processes.

Direct observation of ultrafast-electron-transfer reactions unravels high effectiveness of reductive DNA damage

PubMed Central

Nguyen, Jenny; Ma, Yuhan; Luo, Ting; Bristow, Robert G.; Jaffray, David A.; Lu, Qing-Bin

2011-01-01

Both water and electron-transfer reactions play important roles in chemistry, physics, biology, and the environment. Oxidative DNA damage is a well-known mechanism, whereas the relative role of reductive DNA damage is unknown. The prehydrated electron (), a novel species of electrons in water, is a fascinating species due to its fundamental importance in chemistry, biology, and the environment. is an ideal agent to observe reductive DNA damage. Here, we report both the first in situ femtosecond time-resolved laser spectroscopy measurements of ultrafast-electron-transfer (UET) reactions of with various scavengers (KNO3, isopropanol, and dimethyl sulfoxide) and the first gel electrophoresis measurements of DNA strand breaks induced by and OH• radicals co-produced by two-UV-photon photolysis of water. We strikingly found that the yield of reductive DNA strand breaks induced by each is twice the yield of oxidative DNA strand breaks induced by each OH• radical. Our results not only unravel the long-standing mystery about the relative role of radicals in inducing DNA damage under ionizing radiation, but also challenge the conventional notion that oxidative damage is the main pathway for DNA damage. The results also show the potential of femtomedicine as a new transdisciplinary frontier and the broad significance of UET reactions of in many processes in chemistry, physics, biology, and the environment. PMID:21730183

Purification and Characterization of Pyranose Oxidase from the White Rot Fungus Trametes multicolor

PubMed Central

Leitner, Christian; Volc, Jindrich; Haltrich, Dietmar

2001-01-01

We purified an intracellular pyranose oxidase from mycelial extracts of the white rot fungus Trametes multicolor by using ammonium sulfate fractionation, hydrophobic interaction, ion-exchange chromatography, and gel filtration. The native enzyme has a molecular mass of 270 kDa as determined by equilibrium ultracentrifugation and is composed of four identical 68-kDa subunits as determined by matrix-assisted laser desorption ionization mass spectrometry. Each subunit contains one covalently bound flavin adenine dinucleotide as its prosthetic group. The enzyme oxidizes several aldopyranoses specifically at position C-2, and its preferred electron donor substrates are d-glucose, d-xylose, and l-sorbose. During this oxidation reaction electrons are transferred to oxygen, yielding hydrogen peroxide. In addition, the enzyme catalyzes the two-electron reduction of 1,4-benzoquinone, several substituted benzoquinones, and 2,6-dichloroindophenol, as well as the one-electron reduction of the ABTS [2,2′-azinobis(3-ethylbenzthiazolinesulfonic acid)] cation radical. As judged by the catalytic efficiencies (kcat/Km), some of these quinone electron acceptors are much better substrates for pyranose oxidase than oxygen. The optimum pH of the pyranose oxidase-catalyzed reaction depends strongly on the electron acceptor employed and varies from 4 to 8. It has been proposed that the main metabolic function of pyranose oxidase is as a constituent of the ligninolytic system of white rot fungi that provides peroxidases with H2O2. An additional function could be reduction of quinones, key intermediates that are formed during mineralization of lignin. PMID:11472941

Wavelets in electronic structure calculations

NASA Astrophysics Data System (ADS)

Modisette, Jason Perry

1997-09-01

Ab initio calculations of the electronic structure of bulk materials and large clusters are not possible on today's computers using current techniques. The storage and diagonalization of the Hamiltonian matrix are the limiting factors in both memory and execution time. The scaling of both quantities with problem size can be reduced by using approximate diagonalization or direct minimization of the total energy with respect to the density matrix in conjunction with a localized basis. Wavelet basis members are much more localized than conventional bases such as Gaussians or numerical atomic orbitals. This localization leads to sparse matrices of the operators that arise in SCF multi-electron calculations. We have investigated the construction of the one-electron Hamiltonian, and also the effective one- electron Hamiltonians that appear in density-functional and Hartree-Fock theories. We develop efficient methods for the generation of the kinetic energy and potential matrices, the Hartree and exchange potentials, and the local exchange-correlation potential of the LDA. Test calculations are performed on one-electron problems with a variety of potentials in one and three dimensions.

Two-electron carbon dioxide reduction catalyzed by rhenium(I) bis(imino)acenaphthene carbonyl complexes.

PubMed

Portenkirchner, Engelbert; Kianfar, Elham; Sariciftci, Niyazi Serdar; Knör, Günther

2014-05-01

Rhenium(I) carbonyl complexes carrying substituted bis(arylimino)acenaphthene ligands (BIAN-R) have been tested as potential catalysts for the two-electron reduction of carbon dioxide. Cyclic voltammetric studies as well as controlled potential electrolysis experiments were performed using CO2-saturated solutions of the complexes in acetonitrile and acetonitrile-water mixtures. Faradaic efficiencies of more than 30 % have been determined for the electrocatalytic production of CO. The effects of ligand substitution patterns and water content of the reaction medium on the catalytic performance of the new catalysts are discussed. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Nanopatterning of Crystalline Silicon Using Anodized Aluminum Oxide Templates for Photovoltaics

NASA Astrophysics Data System (ADS)

Chao, Tsu-An

A novel thin film anodized aluminum oxide templating process was developed and applied to make nanopatterns on crystalline silicon to enhance the optical properties of silicon. The thin film anodized aluminum oxide was created to improve the conventional thick aluminum templating method with the aim for potential large scale fabrication. A unique two-step anodizing method was introduced to create high quality nanopatterns and it was demonstrated that this process is superior over the original one-step approach. Optical characterization of the nanopatterned silicon showed up to 10% reduction in reflection in the short wavelength range. Scanning electron microscopy was also used to analyze the nanopatterned surface structure and it was found that interpore spacing and pore density can be tuned by changing the anodizing potential.

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

Wu, Tao; Kukkadapu, Ravi K.; Griffin, Aron M.

Fe(III)-oxides and Fe(III)-bearing phyllosilicates are the two major iron sources utilized as electron acceptors by dissimilatory iron-reducing bacteria (DIRB) in anoxic soils and sediments. Although there have been many studies of microbial Fe(III)-oxide and Fe(III)-phyllosilicate reduction with both natural and specimen materials, no controlled experimental information is available on the interaction between these two phases when both are available for microbial reduction. In this study, the model DIRB Geobacter sulfurreducens was used to examine the pathways of Fe(III) reduction in Fe(III)-oxide stripped subsurface sediment that was coated with different amounts of synthetic high surface area goethite. Cryogenic (12K) 57Fe Mössbauermore » spectroscopy was used to determine changes in the relative abundances of Fe(III)-oxide, Fe(III)-phyllosilicate, and phyllosilicate-associated Fe(II) (Fe(II)-phyllosilicate) in bioreduced samples. Analogous Mössbauer analyses were performed on samples from abiotic Fe(II) sorption experiments in which sediments were exposed to a quantity of exogenous soluble Fe(II) (FeCl22H2O) comparable to the amount of Fe(II) produced during microbial reduction. A Fe partitioning model was developed to analyze the fate of Fe(II) and assess the potential for abiotic Fe(II)-catalyzed reduction of Fe(III)-phyllosilicatesilicates. The microbial reduction experiments indicated that although reduction of Fe(III)-oxide accounted for virtually all of the observed bulk Fe(III) reduction activity, there was no significant abiotic electron transfer between oxide-derived Fe(II) and Fe(III)-phyllosilicatesilicates, with 26-87% of biogenic Fe(II) appearing as sorbed Fe(II) in the Fe(II)-phyllosilicate pool. In contrast, the abiotic Fe(II) sorption experiments showed that 41 and 24% of the added Fe(II) engaged in electron transfer to Fe(III)-phyllosilicate surfaces in synthetic goethite-coated and uncoated sediment. Differences in the rate of Fe(II) addition and system redox potential may account for the microbial and abiotic reaction systems. Our experiments provide new insight into pathways for Fe(III) reduction in mixed Fe(III)-oxide/Fe(III)-phyllosilicate assemblages, and provide key mechanistic insight for interpreting microbial reduction experiments and field data from complex natural soils and sediments.« less

Nature of electrogenerated intermediates in nitro-substituted nor-β-lapachones: the structure of radical species during successive electron transfer in multiredox centers.

PubMed

Armendáriz-Vidales, Georgina; Hernández-Muñoz, Lindsay S; González, Felipe J; de Souza, Antonio A; de Abreu, Fabiane C; Jardim, Guilherme A M; da Silva, Eufrânio N; Goulart, Marilia O F; Frontana, Carlos

2014-06-06

Electrochemical, spectroelectrochemical, and theoretical studies of the reduction reactions in nor-β-lapachone derivatives including a nitro redox center showed that reduction of the compounds involves the formation of several radical intermediates, including a biradical dianion resultant from the separate reduction of the quinone and nitro groups in the molecules. Theoretical descriptions of the corresponding Fukui functions f(αα)⁺ and f(ββ)⁺(r) and LUMO densities considering finite differences and frozen core approximations for describing the changes in electron and spin densities of the system allowed us to confirm these results. A description of the potential relationship with the obtained results and biological activity selectivity indexes suggests that both the formation of stable biradical dianion species and the stability of the semiquinone intermediates during further reduction are determining factors in the description of their biological activity.

Stability of a Bifunctional Cu-Based Core@Zeolite Shell Catalyst for Dimethyl Ether Synthesis Under Redox Conditions Studied by Environmental Transmission Electron Microscopy and In Situ X-Ray Ptychography.

PubMed

Baier, Sina; Damsgaard, Christian D; Klumpp, Michael; Reinhardt, Juliane; Sheppard, Thomas; Balogh, Zoltan; Kasama, Takeshi; Benzi, Federico; Wagner, Jakob B; Schwieger, Wilhelm; Schroer, Christian G; Grunwaldt, Jan-Dierk

2017-06-01

When using bifunctional core@shell catalysts, the stability of both the shell and core-shell interface is crucial for catalytic applications. In the present study, we elucidate the stability of a CuO/ZnO/Al2O3@ZSM-5 core@shell material, used for one-stage synthesis of dimethyl ether from synthesis gas. The catalyst stability was studied in a hierarchical manner by complementary environmental transmission electron microscopy (ETEM), scanning electron microscopy (SEM) and in situ hard X-ray ptychography with a specially designed in situ cell. Both reductive activation and reoxidation were applied. The core-shell interface was found to be stable during reducing and oxidizing treatment at 250°C as observed by ETEM and in situ X-ray ptychography, although strong changes occurred in the core on a 10 nm scale due to the reduction of copper oxide to metallic copper particles. At 350°C, in situ X-ray ptychography indicated the occurrence of structural changes also on the µm scale, i.e. the core material and parts of the shell undergo restructuring. Nevertheless, the crucial core-shell interface required for full bifunctionality appeared to remain stable. This study demonstrates the potential of these correlative in situ microscopy techniques for hierarchically designed catalysts.

Preliminary research concerning the use of electron accelerators to improve the conservability and to extend the shelf-life of fruits and vegetables

NASA Astrophysics Data System (ADS)

Minea, R.; Oproiu, C.; Pascanu, S.; Matei, C.; Ferdes, O.

1996-06-01

The potential of ionizing radiation treatment for food preservation, shelf-life extension, control of microbial load and reduction of pathogenic microorganism was demonstrated. The irradiations were performed under normal conditions on the Institute of Physics and Technology for Radiation Device's linear electron accelerator, which has the following parameters: 5 μA mean beam current, 6 MeV electron mean energy, pulse period 3.5 μs and dose rates between 100-1500 Gy/min. This research project was aimed at assuring the consumer's acceptance for radiation-treated food and to obtain a significant reduction of food losses. We also propose a promising solution for the radiation processing of some bulk food products at the place of storage, consisting of a mobile electron accelerator. The main characteristics of the mobile electron accelerator are: electron energy 3 to 5 MeV, maximum beam power 5 kW, vertical electron beam; irradiation is possible both with electron beams and with bremsstrahlung. The results of our preliminary research lead to the conclusion that electron-beam irradiation and the use of electron accelerators is a promising solution for food preservation and food safety. Interesting future applications are outlined.

Chloroethene Biodegradation Potential, ADOT/PF Peger Road Maintenance Facility, Fairbanks, Alaska

USGS Publications Warehouse

Bradley, Paul M.; Chapelle, Frances H.

2004-01-01

A series of 14C-radiotracer-based microcosm experiments were conducted to assess: 1) the extent, rate and products of microbial dechlorination of trichloroethene (TCE), cis-dichloroethene (cis-DCE) and vinyl chloride (VC) in sediments at the Peger Road site; 2) the effect of three electron donor amendments (molasses, shrimp and crab chitin, and 'Hydrogen Release Compound' (HRC)) on microbial degradation of TCE in three Peger Road sediments; and 3) the potential significance at the site of chloroethene biodegradation processes other than reductive dechlorination. In these experiments, TCE biodegradation yielded the reduced products, DCE and VC, and the oxidation product CO 2. Biodegradation of DCE and VC involved stoichiometric oxidation to CO 2. Both laboratory microcosm study and field redox assessment results indicated that the predominant terminal electron accepting process in Peger Road plume sediments under anoxic conditions was Mn/Fe-reduction. The rates of chloroethene biodegradation observed in Peger Road sediment microcosms under low temperature conditions (4?C) were within the range of those observed in sediments from temperate (20?C) aquifer systems. This result confirmed that biodegradation can be a significant mechanism for in situ contaminant remediation even in cold temperature aquifers. The fact that CO2 was the sole product of cis-DCE and VC biodegradation detected in Peger Road sediments indicated that a natural attenuation assessment based on reduced daughter product accumulation may significantly underestimate the potential for DCE and VC biodegradation at the Peger Road. Neither HRC nor molasses addition stimulated TCE reductive dechlorination. The fact that molasses and HRC amendment did stimulate Mn/Fe-reduction suggests that addition of these electron donors favored microbial Mn/Fe-reduction to the detriment of microbial TCE dechlorinating activity. In contrast, amendment of sediment microcosms with shrimp and crab chitin resulted in the establishment of mixed Mn/Fe-reducing, SO42--reducing and methanogenic conditions and enhanced TCE biodegradation in two of three Peger Road sediment treatments.

High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

PubMed Central

2015-01-01

Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NOx species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. PMID:27162977

Photosensitized electron transfer processes in SiO2 colloids and sodium lauryl sulfate micellar systems: Correlation of quantum yields with interfacial surface potentials

PubMed Central

Laane, Colja; Willner, Itamar; Otvos, John W.; Calvin, Melvin

1981-01-01

The effectiveness of negatively charged colloidal SiO2 particles in controlling photosensitized electron transfer reactions has been studied and compared with that of the negatively charged sodium lauryl sulfate (NaLauSO4) micellar system. In particular, the photosensitized reduction of the zwitterionic electron acceptor propylviologen sulfonate (PVS0) with tris(2,2′-bipyridinium)ruthenium(II) [Ru(bipy)32+] as the sensitizer and triethanolamine as the electron donor is found to have a quantum yield of 0.033 for formation of the radical anion (PVS[unk]) in the SiO2 colloid compared with 0.005 in the homogeneous system and 0.0086 in a NaLauSO4 micellar solution. The higher quantum yields obtained with the SiO2 colloidal system are attributed to substantial stabilization against back reaction of the intermediate photoproducts—i.e., Ru(bipy)33+ and PVS[unk]—by electrostatic repulsion of the reduced electron acceptor from the negatively charged particle surface. The binding properties of the SiO2 particles and NaLauSO4 micelles were investigated by flow dialysis. The results show that the sensitizer binds to both interfaces and that the SiO2 interface is characterized by a much higher surface potential than the micellar interface (≈-170 mV vs. -85 mV). The effect of ionic strength on the surface potential was estimated from the Gouy-Chapman theory, and the measured quantum yields of photosensitized electron transfer were correlated with surface potential at different ionic strengths. This correlation shows that the quantum yield is not affected by surface potentials smaller than ≈-40 mV. At larger potentials, the quantum yield increases rapidly. The quantum yield obtained in the micellar system at different strengths fits nicely on the correlation curve for the colloid SiO2 system. These results indicate that the surface potential is the dominant factor in the quantum yield improvement for PVS0 reduction. PMID:16593095

Redox reaction characteristics of riboflavin: a fluorescence spectroelectrochemical analysis and density functional theory calculation.

PubMed

Chen, Wei; Chen, Jie-Jie; Lu, Rui; Qian, Chen; Li, Wen-Wei; Yu, Han-Qing

2014-08-01

Riboflavin (RF), the primary redox active component of flavin, is involved in many redox processes in biogeochemical systems. Despite of its wide distribution and important roles in environmental remediation, its redox behaviors and reaction mechanisms in hydrophobic sites remain unclear yet. In this study, spectroelectrochemical analysis and density functional theory (DFT) calculation were integrated to explore the redox behaviors of RF in dimethyl sulfoxide (DMSO), which was used to create a hydrophobic environment. Specifically, cyclic voltafluorometry (CVF) and derivative cyclic voltafluorometry (DCVF) were employed to track the RF concentration changing profiles. It was found that the reduction contained a series of proton-coupled electron transfers dependent of potential driving force. In addition to the electron transfer-chemical reaction-electron transfer process, a disproportionation (DISP1) process was also identified to be involved in the reduction. The redox potential and free energy of each step obtained from the DFT calculations further confirmed the mechanisms proposed based on the experimental results. The combination of experimental and theoretical approaches yields a deep insight into the characteristics of RF in environmental remediation and better understanding about the proton-coupled electron transfer mechanisms. Copyright © 2014 Elsevier B.V. All rights reserved.

Computational chemistry of modified [MFe3S4] and [M2Fe2S4] clusters: assessment of trends in electronic structure and properties.

PubMed

Jensen, Kasper P; Ooi, Bee-Lean; Christensen, Hans E M

2008-12-18

The aim of this work is to understand the molecular evolution of iron-sulfur clusters in terms of electronic structure and function. Metal-substituted models of biological [Fe(4)S(4)] clusters in oxidation states [M(x)Fe(4-x)S(4)](3+/2+/1+) have been studied by density functional theory (M = Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pd, with x = 1 or 2). Most of these clusters have not been characterized before. For those that have been characterized experimentally, very good agreement is obtained, implying that also the predicted structures and properties of new clusters are accurate. Mean absolute errors are 0.024 A for bond lengths ([Fe(4)S(4)], [NiFe(3)S(4)], [CoFe(3)S(4)]) and 0.09 V for shifts in reduction potentials relative to the [Fe(4)S(4)] cluster. All structures form cuboidal geometries similar to the all-iron clusters, except the Pd-substituted clusters, which instead form highly distorted trigonal and tetragonal local sites in compromised, pseudocuboidal geometries. In contrast to other electron-transfer sites, cytochromes, blue copper proteins, and smaller iron-sulfur clusters, we find that the [Fe(4)S(4)] clusters are very insensitive to metal substitution, displaying quite small changes in reorganization energies and reduction potentials upon substitution. Thus, the [Fe(4)S(4)] clusters have an evolutionary advantage in being robust to pollution from other metals, still retaining function. We analyze in detail the electronic structure of individual clusters and rationalize spin couplings and redox activity. Often, several configurations are very close in energy, implying possible use as spin-crossover systems, and spin states are predicted accurately in all but one case ([CuFe(3)S(4)]). The results are anticipated to be helpful in defining new molecular systems with catalytic and magnetic properties.

Control by substrate of the cytochrome p450-dependent redox machinery: mechanistic insights.

PubMed

Hlavica, Peter

2007-08-01

Based on initial studies with bacterial CYP101A1, a popular concept emerged predicting that substrate-induced low-to-high spin conversion of P450s is universally associated with shifts of the midpoint potential to a more positive value to maximize rates of electron transfer and metabolic turnover. However, evaluation of the plethora of observations with pro- and eukaryotic hemoproteins suggests a caveat as to generalization of this principle. Thus, some P450s are inherently high-spin, so that there is no need for a supportive substrate-triggered impulse to electron flow. With other enzymes, high-spin content is not consonant with reductive activity, and spin transition as such is not essential to sustaining substrate oxidation. Also, with certain proteins the low-spin conformer is reduced as swift as the high-spin entity. Moreover, there is not regularly a linear relationship between high-spin level and anodic shift of the reduction potential. Similarly, in given cases turnover may proceed despite insignificant or even lacking substrate-provoked alterations in the redox behaviour. Thus, folding of the disparate and sometimes conflicting data into a harmonized overall picture is a lingering problem. Apart from direct perturbation of the electrochemical properties, substrate docking may entail changes in enzyme conformation such as to favour productive complexation with redox partners or modulate electron transfer conduits within preformed donor/acceptor adducts, resulting in elevated ease of flow of reducing equivalents. Substrate-steered ordering of the oligomeric aggregation state of P450s is likely to impose steric constraints on heterodimers, causing one component to more readily align with electron carriers. Careful uncovering of electrochemical mechanisms in these systems will be fruitful to tailoring of novel bioenergetic machines and redox chains via redox-inspired protein engineering or molecular Lego, capable of generating products of interest or degrading toxic pollutants. Finally, availability of P450 nanobiochips for high-throughput screening of substrate libraries might expedite drug development.

Electrochemistry of Europium(III) Chloride in 3 LiCl – NaCl, 3 LiCl – 2 KCl, LiCl – RbCl, and 3 LiCl – 2 CsCl Eutectics at Various Temperatures

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

Schroll, Cynthia A.; Chatterjee, Sayandev; Levitskaia, Tatiana G.

Here we report the effect of changing the eutectic melt composition on the electrochemical properties of europium(III) chloride under pyroprocessing conditions. The number of electrons transferred, redox potentials and diffusion coefficients were determined using various electrochemical and spectroelectrochemical techniques in four different eutectic mixtures (3 LiCl - NaCl, 3 LiCl - 2 KCl, 3 LiCl - RbCl, and 3 LiCl - 2 CsCl) while varying the temperature of the melt. It was determined that Eu3+ undergoes a one electron reduction to Eu2+ in each melt at all temperatures evaluated. Within all the melts a positive shift in the redox potentialmore » as well as an increase in the diffusion coefficient for Eu3+ was observed as the temperature increased. Also observed was a positive shift in the redox potential and increase in the diffusion coefficient for Eu3+ as the weighted average of the cationic radii for the melt decreased.« less

Reduction of AOX in pharmaceutical wastewater in the cathode chamber of bio-electrochemical reactor.

PubMed

Xie, Yawei; Chen, Lujun; Liu, Rui; Tian, Jinping

2018-06-14

A bio-electrochemical reactor (BER) operating at different cathode potentials ranging from -300 to -1000 mV (vs standard hydrogen electrode, SHE) was used to reduce adsorbable organic halogens (AOX) in pharmaceutical wastewater. Cathode polarization enriched the electron donor of the biological system. Thus, the AOX removal efficiency in the BER improved from 59.9% to 70.2%, and the AOX removal rate increased from 0.87 to 1.17 mg AOX/h when the cathode potential was reduced from -300 to -1000 mV with the addition of methyl viologen, a known redox mediator. The decrease of the cathode potential was also beneficial for methane production, and the inhibition of the methanogenic process enhanced the AOX removal. Additionally, cathode coulombic efficiency analysis demonstrated that the proportion of electrons used for AOX reduction decreases with decreasing potential, from 37.6% at -300 mV to 17.3% at -1000 mV, although the AOX removal efficiency improves. Copyright © 2018 Elsevier Ltd. All rights reserved.

Synthesis of metal nanoparticle and patterning in polymeric films induced by electron beam

NASA Astrophysics Data System (ADS)

Yamamoto, Hiroki; Kozawa, Takahiro; Tagawa, Seiichi; Marignier, Jean-Louis; Mostafavi, Mehran; Belloni, Jacqueline

2018-03-01

Using an electron beam, thin polymeric films loaded with metal nanoparticles of silver were prepared by a one-step irradiation-induced reduction of the metal ions embedded in the polymer. The metal nanoparticles were observed by either optical absorption or microscopy. The mechanism of the reduction of metal ions and of the polymer crosslinking were deduced from the average absorbance measurements. In view of realizing specific patterns of high resolution using the electron beam, electron beam produces 200 nm wide lines that can be separated by unexposed spaces of adjustable width, where precursors were dissolved. The resolution of the electron beam has been exploited to demonstrate the achievement of nanopatterning on polymer films using a direct-writing process. This method supplies interesting applications such as masks, replicas, or imprint molds of improved density and contrast.

High-Potential Electrocatalytic O2 Reduction with Nitroxyl / NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

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

Gerken, James B.; Stahl, Shannon S.

2015-07-15

Efficient reduction of O2 to water is a central challenge in energy conversion and aerobic oxidation catalysis. In the present study, we investigate the electrochemical reduction of O2 with soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl), nor NOx species, such as sodium nitrite, are effective mediators of electrochemical O2 reduction. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction at electrochemical potentials of 0.19–0.33 V (vs. Fc/Fc+) in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalystmore » drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The high potentials observed with this ORR system benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.« less

Evidence for radical anion formation during liquid secondary ion mass spectrometry analysis of oligonucleotides and synthetic oligomeric analogues: a deconvolution algorithm for molecular ion region clusters.

PubMed

Laramée, J A; Arbogast, B; Deinzer, M L

1989-10-01

It is shown that one-electron reduction is a common process that occurs in negative ion liquid secondary ion mass spectrometry (LSIMS) of oligonucleotides and synthetic oligonucleosides and that this process is in competition with proton loss. Deconvolution of the molecular anion cluster reveals contributions from (M-2H).-, (M-H)-, M.-, and (M + H)-. A model based on these ionic species gives excellent agreement with the experimental data. A correlation between the concentration of species arising via one-electron reduction [M.- and (M + H)-] and the electron affinity of the matrix has been demonstrated. The relative intensity of M.- is mass-dependent; this is rationalized on the basis of base-stacking. Base sequence ion formation is theorized to arise from M.- radical anion among other possible pathways.

Tuning the Carbon Nanotube Selectivity: Optimizing Reduction Potentials and Distortion Angles in Perylenediimides.

PubMed

Münich, Peter W; Schierl, Christoph; Dirian, Konstantin; Volland, Michel; Bauroth, Stefan; Wibmer, Leonie; Syrgiannis, Zois; Clark, Timothy; Prato, Maurizio; Guldi, Dirk M

2018-04-25

Different water-soluble perylenediimides (PDIs) have been used to individualize and stabilize single-walled carbon nanotubes (SWCNTs) in aqueous media. A key feature of the PDIs is that they can be substituted at the bay positions via the addition of two and/or four bromines. This enables control over structural and electronic PDI characteristics, which prompted us to conduct comparative assays with focus on SWCNTs' chirality and charge transfer. Electrochemical, microscopic, and spectroscopic experiments were used to investigate the SWCNT chiral selectivity of PDIs, on the one hand, and charge-transfer reactions between SWCNTs and PDIs, on the other hand.

Nickel containing CO dehydrogenases and hydrogenases.

PubMed

Ragsdale, S W

2000-01-01

The two redox catalysts described here can generate very low potential electrons in one direction and perform chemically difficult reductions in the other. The chemical transformations occur at unusual metal clusters. Spectroscopic, crystallographic, and kinetic analyses are converging on answers to how the metals in these clusters are arranged and how they are involved in the chemical and redox steps. The first structure of CO dehydrogenase, which will appear in the next year, will help define a firm chemical basis for future mechanistic studies. In the immediate future, we hope to learn whether the hydride intermediate in hydrogenase or the carbonyl intermediate in CO dehydrogenase bind to the Ni or Fe subsites in these heterometallic clusters. Or perhaps could they be bridged to two metals? Inter- and intramolecular wires have been proposed that connect the catalytic redox machine to proximal redox centers leading eventually to the ultimate redox partners. Elucidating the pathways of electron flow is a priority for the future. There is evidence for molecular channels delivering substrates to the active sites of these enzymes. In the next few years, these channels will be better defined. The products of CO2 and proton reduction are passed to the active sites of other enzymes and, in the case of H2, even passed from one organism to another. In the future, the mechanism of gas transfer will be uncovered. General principles of how these redox reactions are catalyzed are becoming lucid as the reactions are modeled theoretically and experimentally. Proton and CO2 reduction and the generation of C-C bonds from simple precursors are important reactions in industry. H2 could be the clean fuel of the future. Hopefully, the knowledge gained from studies of hydrogenase, CO dehydrogenase, and acetyl-CoA synthase can be used to improve life on earth.

Isolation of Geobacter species from diverse sedimentary environments

USGS Publications Warehouse

Coaxes, J.D.; Phillips, E.J.P.; Lonergan, D.J.; Jenter, H.; Lovley, D.R.

1996-01-01

In an attempt to better understand the microorganisms responsible for Fe(III) reduction in sedimentary environments, Fe(III)-reducing microorganisms were enriched for and isolated from freshwater aquatic sediments, a pristine deep aquifer, and a petroleum-contaminated shallow aquifer. Enrichments were initiated with acetate or toluene as the electron donor and Fe(III) as the electron acceptor. Isolations were made with acetate or benzoate. Five new strains which could obtain energy for growth by dissimilatory Fe(III) reduction were isolated. All five isolates are gram- negative strict anaerobes which grow with acetate as the electron donor and Fe(III) as the electron acceptor. Analysis of the 16S rRNA sequence of the isolated organisms demonstrated that they all belonged to the genus Geobacter in the delta subdivision of the Proteobacteria. Unlike the type strain, Geobacter metallireducens, three of the five isolates could use H2 as an electron donor fur Fe(III) reduction. The deep subsurface isolate is the first Fe(III) reducer shown to completely oxidize lactate to carbon dioxide, while one of the freshwater sediment isolates is only the second Fe(III) reducer known that can oxidize toluene. The isolation of these organisms demonstrates that Geobacter species are widely distributed in a diversity of sedimentary environments in which Fe(III) reduction is an important process.

Mixed-valent metals bridged by a radical ligand: fact or fiction based on structure-oxidation state correlations.

PubMed

Sarkar, Biprajit; Patra, Srikanta; Fiedler, Jan; Sunoj, Raghavan B; Janardanan, Deepa; Lahiri, Goutam Kumar; Kaim, Wolfgang

2008-03-19

Electron-rich Ru(acac)2 (acac- = 2,4-pentanedionato) binds to the pi electron-deficient bis-chelate ligands L, L = 2,2'-azobispyridine (abpy) or azobis(5-chloropyrimidine) (abcp), with considerable transfer of negative charge. The compounds studied, (abpy)Ru(acac)2 (1), meso-(mu-abpy)[Ru(acac)2]2 (2), rac-(mu-abpy)[Ru(acac)2]2 (3), and (mu-abcp)[Ru(acac)2]2 (4), were calculated by DFT to assess the degree of this metal-to-ligand electron shift. The calculated and experimental structures of 2 and 3 both yield about 1.35 A for the length of the central N-N bond which suggests a monoanion character of the bridging ligand. The NBO analysis confirms this interpretation, and TD-DFT calculations reproduce the observed intense long-wavelength absorptions. While mononuclear 1 is calculated with a lower net ruthenium-to-abpy charge shift as illustrated by the computed 1.30 A for d(N-N), compound 4 with the stronger pi accepting abcp bridge is calculated with a slightly lengthened N-N distance relative to that of 2. The formulation of the dinuclear systems with monoanionic bridging ligands implies an obviously valence-averaged Ru(III)Ru(II) mixed-valent state for the neutral molecules. Mixed valency in conjunction with an anion radical bridging ligand had been discussed before in the discussion of MLCT excited states of symmetrically dinuclear coordination compounds. Whereas 1 still exhibits a conventional electrochemical and spectroelectrochemical behavior with metal centered oxidation and two ligand-based one-electron reduction waves, the two one-electron oxidation and two one-electron reduction processes for each of the dinuclear compounds Ru2.5(L*-)Ru2.5 reveal more unusual features via EPR and UV-vis-NIR spectroelectrochemistry. In spite of intense near-infrared absorptions, the EPR results show that the first reduction leads to Ru(II)(L*-)Ru(II) species, with an increased metal contribution for system 4*-. The second reduction to Ru(II)(L2-)Ru(II) causes the disappearance of the NIR band. One-electron oxidation of the Ru2.5(L*-)Ru2.5 species produces a metal-centered spin for which the alternatives RuIII(L0)Ru(II) or Ru(III)(L*-)Ru(III) can be formulated. The absence of NIR bands as common for mixed-valent species with intervalence charge transfer (IVCT) absorption favors the second alternative. The second one-electron oxidation is likely to produce a dication with Ru(III)(L0)Ru(III) formulation. The usefulness and limitations of the increasingly popular structure/oxidation state correlations for complexes with noninnocent ligands is being discussed.

Importance of clay size minerals for Fe(III) respiration in a petroleum-contaminated aquifer

USGS Publications Warehouse

Shelobolina, Evgenya S.; Anderson, Robert T.; Vodyanitskii, Yury N.; Sivtsov, Anatolii V.; Yuretich, Richard; Lovely, Derek R.

2004-01-01

The availability of Fe(III)-bearing minerals for dissimilatory Fe(III) reduction was evaluated in sediments from a petroleum-contaminated sandy aquifer near Bemidji, Minnesota (USA). First, the sediments from a contaminated area of the aquifer, in which Fe(III) reduction was the predominant terminal electron accepting process, were compared with sediments from a nearby, uncontaminated site. Data from 0.5 m HCl extraction of different size fractions of the sediments revealed that the clay size fraction contributed a significant portion of the ‘bio-available’ Fe(III) in the background sediment and was the most depleted in ‘bio-available’ Fe(III) in the iron-reducing sediment. Analytical transmission electron microscopy (TEM) revealed the disappearance of thermodynamically unstable Fe(III) and Mn(IV) hydroxides (ferrihydrite and Fe vernadite), as well as a decrease in the abundance of goethite and lepidocrocite in the clay size fraction from the contaminated sediment. TEM observations and X-ray diffraction examination did not provide strong evidence of Fe(III)-reduction-related changes within another potential source of ‘bio-available’ Fe(III) in the clay size fraction – ferruginous phyllosilicates. However, further testing in the laboratory with sediments from the methanogenic portion of the aquifer that were depleted in microbially reducible Fe(III) revealed the potential for microbial reduction of Fe(III) associated with phyllosilicates. Addition of a clay size fraction from the uncontaminated sediment, as well as Fe(III)-coated kaolin and ferruginous nontronite SWa-1, as sources of poorly crystalline Fe(III) hydroxides and structural iron of phyllosilicates respectively, lowered steady-state hydrogen concentrations consistent with a stimulation of Fe(III) reduction in laboratory incubations of methanogenic sediments. There was no change in hydrogen concentration when non-ferruginous clays or no minerals were added. This demonstrated that Fe(III)-bearing clay size minerals were essential for microbial Fe(III) reduction and suggested that both potential sources of ‘bio-available’ Fe(III) in the clay size fraction, poorly crystalline Fe(III) hydroxides and structural Fe(III) of phyllosilicates, were important sources of electron acceptor for indigenous iron-reducing microorganisms in this aquifer.

NiCo2O4/N-doped graphene as an advanced electrocatalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Zhang, Hui; Li, Huiyong; Wang, Haiyan; He, Kejian; Wang, Shuangyin; Tang, Yougen; Chen, Jiajie

2015-04-01

Developing low-cost catalyst for high-performance oxygen reduction reaction (ORR) is highly desirable. Herein, NiCo2O4/N-doped reduced graphene oxide (NiCo2O4/N-rGO) hybrid is proposed as a high-performance catalyst for ORR for the first time. The well-formed NiCo2O4/N-rGO hybrid is studied by cyclic voltammetry (CV) curves and linear-sweep voltammetry (LSV) performed on the rotating-ring-disk-electrode (RDE) in comparison with N-rGO-free NiCo2O4 and the bare N-rGO. Due to the synergistic effect, the NiCo2O4/N-rGO hybrid exhibits significant improvement of catalytic performance with an onset potential of -0.12 V, which mainly favors a direct four electron pathway in ORR process, close to the behavior of commercial carbon-supported Pt. Also, the benefits of N-incorporation are investigated by comparing NiCo2O4/N-rGO with NiCo2O4/rGO, where higher cathodic currents, much more positive half-wave potential and more electron transfer numbers are observed for the N-doping one, which should be ascribed to the new highly efficient active sites created by N incorporation into graphene. The NiCo2O4/N-rGO hybrid could be used as a promising catalyst for high power metal/air battery.

Synthesis and characterization of lithium oxonitrate (LiNO)

PubMed Central

Switzer, Christopher H.; Miller, Thomas W.; Farmer, Patrick J.; Fukuto, Jon M.

2012-01-01

The oxonitrate (1−) anion (NO−), the one-electron reduction product of nitric oxide and conjugate base of HNO, has not been synthesized and isolated due to the inherent reactivity of this anion. The large scale synthesis and characterization of a stable NO− salt is described here. The lithium salt of oxonitrate (LiNO) was formed by the deprotonation of N-hydroxybenzenesulfonamide with phenyllithium in aprotic, deoxygenated conditions. LiNO exhibited antiferromagnetic paramagnetism as determined by SQUID magnetometry, consistent with a triplet ground state of NO−. LiNO reacted with HCl to yield nitrous oxide consistent with HNO formation and dimerization. LiNO consumed O2 in a pH-dependent manner to initially produce peroxynitrite and eventually nitrite. Consistent with the reduction potential of NO, LiNO exhibited an oxidation potential of approximately +0.80 V as determined by reactions with a series of viologen electron acceptors. LiNO also reacted with ferric tetraphenylporphyrin chloride (Fe(TPP)Cl), potassium tetracyanonickelate (K2Ni(CN)4) and nitrosobenzene in a manner that is identical to other HNO/NO− donors. We conclude that the physical and chemical characteristics of LiNO are indistinguishable from the experimentally and theoretically derived data on oxonitrrate (1−) anion. The bulk synthesis and isolation of a stable 3NO− salt described here allows the chemical and physical properties of this elusive nitrogen oxide to be thoroughly studied as this once elusive nitrogen oxide is now attainable. PMID:23107606

Cathodic Potential Dependence of Electrochemical Reduction of SiO2 Granules in Molten CaCl2

NASA Astrophysics Data System (ADS)

Yang, Xiao; Yasuda, Kouji; Nohira, Toshiyuki; Hagiwara, Rika; Homma, Takayuki

2016-09-01

As part of an ongoing fundamental study to develop a new process for producing solar-grade silicon, this paper examines the effects of cathodic potential on reduction kinetics, current efficiency, morphology, and purity of Si product during electrolysis of SiO2 granules in molten CaCl2 at 1123 K (850 °C). SiO2 granules were electrolyzed potentiostatically at different cathodic potentials (0.6, 0.8, 1.0, and 1.2 V vs Ca2+/Ca). The reduction kinetics was evaluated based on the growth of the reduced Si layer and the current behavior during electrolysis. The results suggest that a more negative cathodic potential is favorable for faster reduction. Current efficiencies in 60 minutes are greater than 65 pct at all the potentials examined. Si wires with sub-micron diameters are formed, and their morphologies show little dependence on the cathodic potential. The impurities in the Si product can be controlled at low level. The rate-determining step for the electrochemical reduction of SiO2 granules in molten CaCl2 changes with time. At the initial stage of electrolysis, the electron transfer is the rate-determining step. At the later stage, the diffusion of O2- ions is the rate-determining step. The major cause of the decrease in reduction rate with increasing electrolysis time is the potential drop from the current collector to the reaction front due to the increased contact resistance among the reduced Si particles.

Suppressing Klein tunneling in graphene using a one-dimensional array of localized scatterers.

PubMed

Walls, Jamie D; Hadad, Daniel

2015-02-13

Graphene's unique physical and chemical properties make it an attractive platform for use in micro- and nanoelectronic devices. However, electrostatically controlling the flow of electrons in graphene can be challenging as a result of Klein tunneling, where electrons normally incident to a one-dimensional potential barrier of height V are perfectly transmitted even as V → ∞. In this study, theoretical and numerical calculations predict that the transmission probability for an electron wave normally incident to a one-dimensional array of localized scatterers can be significantly less than unity when the electron wavelength is smaller than the spacing between scatterers. In effect, placing periodic openings throughout a potential barrier can, somewhat counterintuitively, decrease transmission in graphene. Our results suggest that electrostatic potentials with spatial variations on the order of the electron wavelength can suppress Klein tunneling and could find applications in developing graphene electronic devices.

Direct Reduction of Ferrous Oxides to form an Iron-Rich Alternative Charge Material

NASA Astrophysics Data System (ADS)

Ünal, H. İbrahim; Turgut, Enes; Atapek, Ş. H.; Alkan, Attila

2015-12-01

In this study, production of sponge iron by direct reduction of oxides and the effect of reductant on metallization were investigated. In the first stage of the study, scale formed during hot rolling of slabs was reduced in a rotating furnace using solid and gas reductants. Coal was used as solid reductant and hydrogen released from the combustion reaction of LNG was used as the gas one. The sponge iron produced by direct reduction was melted and solidified. In the second stage, Hematite ore in the form of pellets was reduced using solid carbon in a furnace heated up to 1,100°C for 60 and 120 minutes. Reduction degree of process was evaluated as a function of time and the ratio of Cfix/Fetotal. In the third stage, final products were examined using scanning electron microscope and microanalysis was carried out by energy dispersive x-ray spectrometer attached to the electron microscope. It is concluded that (i) direct reduction using both solid and gas reductants caused higher metallization compared to using only solid reductant, (ii) as the reduction time and ratio of Cfix/Fetotal increased %-reduction of ore increased.

Bio-Reduction of Graphene Oxide Using Sulfate-Reducing Bacteria and Its Implication on Anti-Biocorrosion.

PubMed

Song, Tian-Shun; Tan, Wei-Min; Xie, Jingjing

2018-08-01

In this paper, we developed an environmental friendly, cost effective, simple and green approach to reduce graphene oxide (GO) by a sulfate-reducing bacterium Desulfovibrio desulfuricans. The D. desulfuricans reduces exfoliated GO to reduced graphene oxide (rGO) at 25 °C in an aqueous solution without any toxic and environmentally harmful reducing agents. The rGO was characterized with X-ray Diffraction, Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy, Transmission Electron Microscope, X-ray Photoelectron Spectroscopy and Raman Spectroscopy. The analysis results showed that rGO had excellent properties and multi-layer graphene sheets structure. Furthermore, we demonstrated that D. desulfuricans, one of the primary bacteria responsible for the biocorrosion of various metals, might reduce GO to rGO on the surface of copper and prevented the corrosion of copper, which confirmed that electrophoretic deposition of GO on the surface of metals had great potential on the anti-biocorrosion applications.

Respiratory arsenate reductase as a bidirectional enzyme

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

Richey, Christine; Chovanec, Peter; Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282

2009-05-01

The haloalkaliphilic bacterium Alkalilimnicola ehrlichii is capable of anaerobic chemolithoautotrophic growth by coupling the oxidation of arsenite (As(III)) to the reduction of nitrate and carbon dioxide. Analysis of its complete genome indicates that it lacks a conventional arsenite oxidase (Aox), but instead possesses two operons that each encode a putative respiratory arsenate reductase (Arr). Here we show that one homolog is expressed under chemolithoautotrophic conditions and exhibits both arsenite oxidase and arsenate reductase activity. We also demonstrate that Arr from two arsenate respiring bacteria, Alkaliphilus oremlandii and Shewanella sp. strain ANA-3, is also biochemically reversible. Thus Arr can function asmore » a reductase or oxidase. Its physiological role in a specific organism, however, may depend on the electron potentials of the molybdenum center and [Fe-S] clusters, additional subunits, or constitution of the electron transfer chain. This versatility further underscores the ubiquity and antiquity of microbial arsenic metabolism.« less

Respiratory arsenate reductase as a bidirectional enzyme

USGS Publications Warehouse

Richey, C.; Chovanec, P.; Hoeft, S.E.; Oremland, R.S.; Basu, P.; Stolz, J.F.

2009-01-01

The haloalkaliphilic bacterium Alkalilimnicola ehrlichii is capable of anaerobic chemolithoautotrophic growth by coupling the oxidation of arsenite (As(III)) to the reduction of nitrate and carbon dioxide. Analysis of its complete genome indicates that it lacks a conventional arsenite oxidase (Aox), but instead possesses two operons that each encode a putative respiratory arsenate reductase (Arr). Here we show that one homolog is expressed under chemolithoautotrophic conditions and exhibits both arsenite oxidase and arsenate reductase activity. We also demonstrate that Arr from two arsenate respiring bacteria, Alkaliphilus oremlandii and Shewanella sp. strain ANA-3, is also biochemically reversible. Thus Arr can function as a reductase or oxidase. Its physiological role in a specific organism, however, may depend on the electron potentials of the molybdenum center and [Fe–S] clusters, additional subunits, or constitution of the electron transfer chain. This versatility further underscores the ubiquity and antiquity of microbial arsenic metabolism.

N-benzoylated 1,4,8,11-tetraazacyclotetradecane and their copper(II) and nickel(II) complexes: Spectral, magnetic, electrochemical, crystal structure, catalytic and antimicrobial studies

NASA Astrophysics Data System (ADS)

Nirmala, G.; Rahiman, A. Kalilur; Sreedaran, S.; Jegadeesh, R.; Raaman, N.; Narayanan, V.

2010-09-01

A series of N-benzoylated cyclam ligands incorporating three different benzoyl groups 1,4,8,11-tetra-(benzoyl)-1,4,8,11-tetraazacyclotetradecane (L 1), 1,4,8,11-tetra-(2-nitrobenzoyl)-1,4,8,11-tetraazacyclotetradecane (L 2) and 1,4,8,11-tetra-(4-nitrobenzoyl)-1,4,8,11-tetraazacyclotetradecane (L 3) and their nickel(II) and copper(II) complexes are described. Crystal structure of L 1 is also reported. The ligands and complexes were characterized by elemental analysis, electronic, IR, 1H NMR and 13C NMR spectral studies. N-benzoylation causes red shift in the λmax values of the complexes. The cyclic voltammogram of the complexes of ligand L 1 show one-electron, quasi-reversible reduction wave in the region -1.00 to -1.04 V, whereas that of L 2 and L 3 show two quasi-reversible reduction peaks. Nickel complexes show one-electron quasi-reversible oxidation wave at a positive potential in the range +1.05 to +1.15 V. The ESR spectra of the mononuclear copper(II) complexes show four lines, characteristic of square-planar geometry with nuclear hyperfine spin 3/2. All copper(II) complexes show a normal room temperature magnetic moment values μeff 1.70-1.73 BM which is close to the spin-only value of 1.73 BM. Kinetic studies on the oxidation of pyrocatechol to o-quinone using the copper(II) complexes as catalysts and hydrolysis of 4-nitrophenylphosphate using the copper(II) and nickel(II) complexes as catalysts were carried out. All the ligands and their complexes were also screened for antimicrobial activity against Gram-positive, Gram-negative bacteria and human pathogenic fungi.

Opening the Market for Lower Cost Hearing Aids: Regulatory Change Can Improve the Health of Older Americans.

PubMed

Blustein, Jan; Weinstein, Barbara E

2016-06-01

Hearing loss is a leading cause of disability among older people. Yet only one in seven US adults who could benefit from a hearing aid uses one. This fraction has not increased over the past 30 years, nor have hearing aid prices dropped, despite trends of steady improvements and price reductions in the consumer electronics industry. The President's Council on Science and Technology has proposed changes in the regulation of hearing aids, including the creation of a "basic" low-cost over-the-counter category of devices. We discuss the potential to reduce disability as well as to improve public health, stakeholder responses to the president's council's proposal, and public health efforts to further mitigate the burden of disability stemming from age-related hearing loss.

Enhanced reduction of Fe(III) oxides and methyl orange by Klebsiella oxytoca in presence of anthraquinone-2-disulfonate.

PubMed

Yu, Lei; Wang, Shi; Tang, Qing-Wen; Cao, Ming-Yue; Li, Jia; Yuan, Kun; Wang, Ping; Li, Wen-Wei

2016-05-01

Klebsiella oxytoca GS-4-08 is capable of azo dye reduction, but its quinone respiration and Fe(III) reduction abilities have not been reported so far. In this study, the abilities of this strain were reported in detail for the first time. As the biotic reduction of Fe(III) plays an important role in the biogeochemical cycles, two amorphous Fe(III) oxides were tested as the sole electron acceptor during the anaerobic respiration of strain GS-4-08. For the reduction of goethite and hematite, the biogenic Fe(II) concentrations reached 0.06 and 0.15 mM, respectively. Humic acid analog anthraquinone-2-disulfonate (AQS) was found to serve as an electron shuttle to increase the reduction of both methyl orange (MO) and amorphous Fe(III) oxides, and improve the dye tolerance of the strain. However, the formation of Fe(II) was not accelerated by biologically reduced AQS (B-AH2QS) because of the high bioavailability of soluble Fe(III). For the K. oxytoca strain, high soluble Fe(III) concentrations (above 1 mM) limit its growth and decolorization ability, while lower soluble Fe(III) concentrations produce an electron competition with MO initially, and then stimulate the decolorization after the electron couples of Fe(III)/Fe(II) are formed. With the ability to respire both soluble Fe(III) and insoluble Fe(III) oxides, this formerly known azo-reducer may be used as a promising model organism for the study of the interaction of these potentially competing processes in contaminated environments.

DFT Study on Nitrite Reduction Mechanism in Copper-Containing Nitrite Reductase.

PubMed

Lintuluoto, Masami; Lintuluoto, Juha M

2016-01-12

Dissimilatory reduction of nitrite by copper-containing nitrite reductase (CuNiR) is an important step in the geobiochemical nitrogen cycle. The proposed mechanisms for the reduction of nitrite by CuNiRs include intramolecular electron and proton transfers, and these two events are understood to couple. Proton-coupled electron transfer is one of the key processes in enzyme reactions. We investigated the geometric structure of bound nitrite and the mechanism of nitrite reduction on CuNiR using density functional theory calculations. Also, the proton transfer pathway, the key residues, and their roles in the reaction mechanism were clarified in this study. In our results, the reduction of T2 Cu site promotes the proton transfer, and the hydrogen bond network around the binding site has an important role not only to stabilize the nitrite binding but also to promote the proton transfer to nitrite.

Specific features of electron scattering in uniaxially deformed n-Ge single crystals in the presence of radiation defects

NASA Astrophysics Data System (ADS)

Luniov, S. V.; Zimych, A. I.; Nazarchuk, P. F.; Maslyuk, V. T.; Megela, I. G.

2016-12-01

Temperature dependencies for concentration of electrons and the Hall mobility for unirradiated and irradiated by the flow of electrons ? single crystals ?, with the energy of ?, for different values of uniaxial pressures along the crystallographic directions ?, ? and ? are obtained on the basis of piezo-Hall effect measurements. Non-typical growth of the Hall mobility of electrons for irradiated single crystals ? in comparison with unirradiated with the increasing of value of uniaxial pressures along the crystallographic directions ? (for the entire range of the investigated temperatures) and ? (to temperatures ?) has been revealed. Such an effect of the Hall mobility increase for uniaxially deformed single crystals ? is explained by the reduction of gradients of a resistance as a result of reduction in the amplitude of a large-scale potential with deformation and concentration of charged A-centers in the process of their recharge by the increasing of uniaxial pressure and consequently the probability of scattering on these centers. Theoretical calculations for temperature dependencies of the Hall mobility for uniaxially deformed single crystals ? in terms of the electrons scattering on the ions of shallow donors, acoustic, optical and intervalley phonons, regions of disordering and large-scale potential is good conformed to the corresponding experimental results at temperatures T<220 K for the case of uniaxial pressures along the crystallographic directions ? and ? and for temperatures ? when the uniaxial pressure is directed along the crystallographic directions ?. The mechanism of electron scattering on a charged radiation defects (which correspond to the deep energy levels of A-centers) 'is turned off' for the given temperatures due to the uniaxial pressure. Reduction of the Hall mobility in transition through a maximum of dependence ? with the increasing temperature for cases of the uniaxial deformation of the irradiated single crystals ? along the crystallographic directions ? and ? is explained by the deforming redistribution of electrons between the minima of conduction band of germanium with different mobility.

Electronic Tongue Containing Redox and Conductivity Sensors

NASA Technical Reports Server (NTRS)

Buehler, Martin

2007-01-01

The Electronic Tongue (E-tongue 2) is an assembly of sensors for measuring concentrations of metal ions and possibly other contaminants in water. Potential uses for electronic tongues include monitoring the chemical quality of water in a variety of natural, industrial, and laboratory settings, and detecting micro-organisms indirectly by measuring microbially influenced corrosion. The device includes a heater, a temperature sensor, an oxidation/reduction (redox) sensor pair, an electrical sensor, an array of eight galvanic cells, and eight ion-specific electrodes.

Phyto-reduction of graphene oxide using the aqueous extract of Eichhornia crassipes (Mart.) Solms

NASA Astrophysics Data System (ADS)

Firdhouse, M. Jannathul; Lalitha, P.

2014-10-01

The aqueous extract of Eichhornia crassipes was used as reductant to produce graphene from graphene oxide by refluxing method. The complete reduction of graphene oxide was monitored using UV-Vis spectrophotometer. Characterization of graphene was made through FTIR, XRD, and Raman spectroscopy analysis. The stability of graphene was studied by thermal gravimetric analysis and zeta potential measurements. The nature and surface morphology of the synthesized graphene was analyzed by transmission electron microscopy. The production of graphene using phytoextract as reductant emphasizes on the facile method of synthesis and greener nanotechnology.

Calibration of redox potential in sperm wash media and evaluation of oxidation-reduction potential values in various assisted reproductive technology culture media using MiOXSYS system.

PubMed

Panner Selvam, M K; Henkel, R; Sharma, R; Agarwal, A

2018-03-01

Oxidation-reduction potential describes the balance between the oxidants and antioxidants in fluids including semen. Various artificial culture media are used in andrology and IVF laboratories for sperm preparation and to support the development of fertilized oocytes under in vitro conditions. The composition and conditions of these media are vital for optimal functioning of the gametes. Currently, there are no data on the status of redox potential of sperm processing and assisted reproduction media. The purpose of this study was to compare the oxidation-reduction potential values of the different media and to calibrate the oxidation-reduction potential values of the sperm wash medium using oxidative stress inducer cumene hydroperoxide and antioxidant ascorbic acid. Redox potential was measured in 10 different media ranging from sperm wash media, freezing media and assisted reproductive technology one-step medium to sequential media. Oxidation-reduction potential values of the sequential culture medium and one-step culture medium were lower and significantly different (p < 0.05) from the sperm wash media. Calibration of the sperm wash media using the oxidant cumene hydroperoxide and antioxidant ascorbic acid demonstrated that oxidation-reduction potential and the concentration of oxidant or antioxidant are logarithmically dependent. This study highlights the importance of calibrating the oxidation-reduction potential levels of the sperm wash media in order to utilize it as a reference value to identify the physiological range of oxidation-reduction potential that does not have any adverse effect on normal physiological sperm function. © 2017 American Society of Andrology and European Academy of Andrology.

Isolation of Copper from a 5-Cent Coin: An Example of Electrorefining

ERIC Educational Resources Information Center

Sogo, Steven G.

2004-01-01

Copper is isolated from a 5-cent coin with the help of electrolysis. This experiment is useful for conceptual understanding of the significance of reduction potentials in situation of competition for electrons.

Cyclic Voltammetry Experiment.

ERIC Educational Resources Information Center

Van Benschoten, James J.; And Others

1983-01-01

Describes a three-part experiment designed to introduce cyclic voltammetry to graduate/undergraduate students. Part 1 demonstrates formal reduction potential, redox electron transfer, diffusion coefficient, and electrochemical reversibility. Part 2 investigates electrochemical behavior of acetaminophen. Part 3 examines such experimental variables…

Secondary coordination sphere interactions within the biomimetic iron azadithiolate complexes related to Fe-only hydrogenase: dynamic measure of electron density about the Fe sites.

PubMed

Liu, Yu-Chiao; Tu, Ling-Kuang; Yen, Tao-Hung; Lee, Gene-Hsiang; Yang, Shu-Ting; Chiang, Ming-Hsi

2010-07-19

A series of iron azadithiolate complexes possessing an intramolecular secondary coordination sphere interaction and an ability to reduce HOAc at the potential near the first electron-transfer process are reported. A unique structural feature in which the aza nitrogen has its lone pair point toward the apical carbonyl carbon is observed in [Fe(2)(mu-S(CH(2))(2)NR(CH(2))(2)S)(CO)(6-x)L(x)](2) (R = (n)Pr, x = 0, 1a; R = (i)Pr, x = 0, 1b; R = (n)Pr, L = PPh(3), x = 1, 2; R = (n)Pr, L = P(n)Bu(3), x = 1, 3) as biomimetic models of the active site of Fe-only hydrogenase. The presence of this weak N...C(CO(ap)) interaction provides electronic perturbation at the Fe center. The distance of the N...C(CO(ap)) contact is 3.497 A in 1a. It increases by 0.455 A in 2 when electronic density of the Fe site is slightly enriched by a weak sigma-donating ligand, PPh(3). A longer distance (4.040 A) is observed for the P(n)Bu(3) derivative, 3. This N...C(CO(ap)) distance is thus a dynamic measure of electronic nature of the Fe(2) core. Variation of electronic richness within the Fe(2) moiety among the complexes reflects on their electrochemical response. Reduction of 2 is recorded at the potential of -2.17 V, which is 270 mV more negative than that of 1. Complex 3 requires additional 150 mV for the same reduction. Such cathodic shift results from CO substitution by phosphines. Electrocatalytic hydrogen production from HOAc by both kinds of complexes (all-CO and phosphine-substituted species) requires the potential close to that for reduction of the parent molecules in the absence of acids. The catalytic mechanism of 1a is proposed to involve proton uptake at the Fe(0)Fe(I) redox level instead of the Fe(0)Fe(0) level. This result is the first observation among the all-CO complexes with respect to electrocatalysis of HOAc.

Reconstructing metabolic pathways of a member of the genus Pelotomaculum suggesting its potential to oxidize benzene to carbon dioxide with direct reduction of sulfate.

PubMed

Dong, Xiyang; Dröge, Johannes; von Toerne, Christine; Marozava, Sviatlana; McHardy, Alice C; Meckenstock, Rainer U

2017-03-01

The enrichment culture BPL is able to degrade benzene with sulfate as electron acceptor and is dominated by an organism of the genus Pelotomaculum. Members of Pelotomaculum are usually known to be fermenters, undergoing syntrophy with anaerobic respiring microorganisms or methanogens. By using a metagenomic approach, we reconstructed a high-quality genome (∼2.97 Mbp, 99% completeness) for Pelotomaculum candidate BPL. The proteogenomic data suggested that (1) anaerobic benzene degradation was activated by a yet unknown mechanism for conversion of benzene to benzoyl-CoA; (2) the central benzoyl-CoA degradation pathway involved reductive dearomatization by a class II benzoyl-CoA reductase followed by hydrolytic ring cleavage and modified β-oxidation; (3) the oxidative acetyl-CoA pathway was utilized for complete oxidation to CO2. Interestingly, the genome of Pelotomaculum candidate BPL has all the genes for a complete sulfate reduction pathway including a similar electron transfer mechanism for dissimilatory sulfate reduction as in other Gram-positive sulfate-reducing bacteria. The proteome analysis revealed that the essential enzymes for sulfate reduction were all formed during growth with benzene. Thus, our data indicated that, besides its potential to anaerobically degrade benzene, Pelotomaculum candidate BPL is the first member of the genus that can perform sulfate reduction. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. V. Comparison and Properties of Electrochemical and Chemical Rate Constants

DOE R&D Accomplishments Database

Marcus, R. A.

1962-01-01

Using a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism. (auth)

An assessment of natural biotransformation of petroleum hydrocarbons and chlorinated solvents at an aquifer plume transect

NASA Astrophysics Data System (ADS)

Skubal, Karen L.; Barcelona, Michael J.; Adriaens, Peter

2001-05-01

Field biogeochemical characterization and laboratory microcosm studies were performed to assess the potential for future biotransformation of trichloroethylene (TCE) and toluene in a plume containing petroleum hydrocarbons and chlorinated solvents at the former Wurtsmith Air Force Base in Oscoda, MI. In situ terminal electron accepting processes (TEAPs), contaminant composition and microbial phylogeny were studied at a plume transect 100 m downgradient of the source. The presence of reduced electron acceptors, relevant microbial communities, and elevated dissolved methane and carbon dioxide concentrations at the transect, as well as downgradient accumulation of BTEX metabolites and dechlorination products, indicated that past or current reductive dechlorination at the transect was likely driven by BTEX biodegradation in the methanogenic zone. However, TCE and toluene mineralization in sediment-groundwater microcosms without added electron acceptors did not exceed 5% during 300 days of incubation and was nearly invariant with original sediment TEAP, even following amendments of nitrogen and phosphorus. Mineralization rates were on the order of 0.0015-0.03 μmol/g day. After 8 months, microcosms showed evidence of methanogenesis, but CH 4 and CO 2 production arose from the degradation of contaminants other than toluene. Cis-dichloroethylene was observed in only one methanogenic microcosm after more than 500 days. It appears likely that spatially and temporally dynamic redox zonation at the plume transect will prevent future sustained reductive dehalogenation of highly chlorinated solvents, for during the course of a year, the predominant TEAP at the highly contaminated water table shifted from methanogenesis to iron- and sulfate-reduction. It is recommended that biotransformation studies combine considerations of long-term, spatially relevant changes in redox zonation with laboratory-scale studies of electron donor utilization and cometabolic substrate transformation to yield a more accurate assessment of natural bioattenuation of specific pollutants in aquifers contaminated by undefined organic waste mixtures.

Kinetics of triscarbonato uranyl reduction by aqueous ferrous iron: a theoretical study.

PubMed

Wander, Matthew C F; Kerisit, Sebastien; Rosso, Kevin M; Schoonen, Martin A A

2006-08-10

Uranium is a pollutant whose mobility is strongly dependent on its oxidation state. While U(VI) in the form of the uranyl cation is readily reduced by a range of natural reductants, by contrast complexation of uranyl by carbonate greatly reduces its reduction potential and imposes increased electron transfer (ET) distances. Very little is known about the elementary processes involved in uranium reduction from U(VI) to U(V) to U(IV) in general. In this study, we examine the theoretical kinetics of ET from ferrous iron to triscarbonato uranyl in aqueous solution. A combination of molecular dynamics (MD) simulations and density functional theory (DFT) electronic structure calculations is employed to compute the parameters that enter into Marcus' ET model, including the thermodynamic driving forces, reorganization energies, and electronic coupling matrix elements. MD simulations predict that two ferrous iron atoms will bind in an inner-sphere fashion to the three-membered carbonate ring of triscarbonato uranyl, forming the charge-neutral ternary Fe(2)UO(2)(CO(3))(3)(H(2)O)(8) complex. Through a sequential proton-coupled electron-transfer mechanism (PCET), the first ET step converting U(VI) to U(V) is predicted by DFT to occur with an electronic barrier that corresponds to a rate on the order of approximately 1 s(-1). The second ET step converting U(V) to U(IV) is predicted to be significantly endergonic. Therefore, U(V) is a stabilized end product in this ET system, in agreement with experiment.

Cost-effectiveness analysis of a hospital electronic medication management system

PubMed Central

Gospodarevskaya, Elena; Li, Ling; Richardson, Katrina L; Roffe, David; Heywood, Maureen; Day, Richard O; Graves, Nicholas

2015-01-01

Objective To conduct a cost–effectiveness analysis of a hospital electronic medication management system (eMMS). Methods We compared costs and benefits of paper-based prescribing with a commercial eMMS (CSC MedChart) on one cardiology ward in a major 326-bed teaching hospital, assuming a 15-year time horizon and a health system perspective. The eMMS implementation and operating costs were obtained from the study site. We used data on eMMS effectiveness in reducing potential adverse drug events (ADEs), and potential ADEs intercepted, based on review of 1 202 patient charts before (n = 801) and after (n = 401) eMMS. These were combined with published estimates of actual ADEs and their costs. Results The rate of potential ADEs following eMMS fell from 0.17 per admission to 0.05; a reduction of 71%. The annualized eMMS implementation, maintenance, and operating costs for the cardiology ward were A$61 741 (US$55 296). The estimated reduction in ADEs post eMMS was approximately 80 actual ADEs per year. The reduced costs associated with these ADEs were more than sufficient to offset the costs of the eMMS. Estimated savings resulting from eMMS implementation were A$63–66 (US$56–59) per admission (A$97 740–$102 000 per annum for this ward). Sensitivity analyses demonstrated results were robust when both eMMS effectiveness and costs of actual ADEs were varied substantially. Conclusion The eMMS within this setting was more effective and less expensive than paper-based prescribing. Comparison with the few previous full economic evaluations available suggests a marked improvement in the cost–effectiveness of eMMS, largely driven by increased effectiveness of contemporary eMMs in reducing medication errors. PMID:25670756

Cost-effectiveness analysis of a hospital electronic medication management system.

PubMed

Westbrook, Johanna I; Gospodarevskaya, Elena; Li, Ling; Richardson, Katrina L; Roffe, David; Heywood, Maureen; Day, Richard O; Graves, Nicholas

2015-07-01

To conduct a cost-effectiveness analysis of a hospital electronic medication management system (eMMS). We compared costs and benefits of paper-based prescribing with a commercial eMMS (CSC MedChart) on one cardiology ward in a major 326-bed teaching hospital, assuming a 15-year time horizon and a health system perspective. The eMMS implementation and operating costs were obtained from the study site. We used data on eMMS effectiveness in reducing potential adverse drug events (ADEs), and potential ADEs intercepted, based on review of 1 202 patient charts before (n = 801) and after (n = 401) eMMS. These were combined with published estimates of actual ADEs and their costs. The rate of potential ADEs following eMMS fell from 0.17 per admission to 0.05; a reduction of 71%. The annualized eMMS implementation, maintenance, and operating costs for the cardiology ward were A$61 741 (US$55 296). The estimated reduction in ADEs post eMMS was approximately 80 actual ADEs per year. The reduced costs associated with these ADEs were more than sufficient to offset the costs of the eMMS. Estimated savings resulting from eMMS implementation were A$63-66 (US$56-59) per admission (A$97 740-$102 000 per annum for this ward). Sensitivity analyses demonstrated results were robust when both eMMS effectiveness and costs of actual ADEs were varied substantially. The eMMS within this setting was more effective and less expensive than paper-based prescribing. Comparison with the few previous full economic evaluations available suggests a marked improvement in the cost-effectiveness of eMMS, largely driven by increased effectiveness of contemporary eMMs in reducing medication errors. © The Author 2015. Published by Oxford University Press on behalf of the American Medical Informatics Association.

Gold Decorated Graphene for Rapid Dye Reduction and Efficient Electro Catalytic Oxidation of Ethanol

NASA Astrophysics Data System (ADS)

Siddhardha, R. S.; Kumar v, Lakshman; Kaniyoor, A.; Podila, R.; Kumar, V. S.; Venkataramaniah, K.; Ramaprabhu, S.; Rao, A.; Ramamurthy, S. S.; Clemson University Team; Sri Sathya Sai Institute of Higher Learning Team; IITMadras Team

2013-03-01

A well known disadvantage in fabrication of metal-graphene composite is the use of surfactants that strongly adsorb on the surface and reduce the performance of the catalyst. Here, we demonstrate a novel one pot synthesis of gold nanoparticles (AuNPs) by laser ablation of gold strip and simultaneous decoration of these on functionalized graphene derivatives. Not only the impregnation of AuNPs was linker free, but also the synthesis by itself was surfactant free. This resulted in in-situ decoration of pristine AuNPs on functionalized graphene derivatives. These materials were well characterized and tested for catalytic applications pertaining to dye reduction and electrooxidation. The catalytic reduction rates are 1.4 x 102 and 9.4x102 times faster for Rhodamine B and Methylene Blue dyes respectively, compared to earlier reports. The enhanced rate involves synergistic interplay of electronic relay between AuNPs and the dye, also charge transfer between the graphene system and dye. In addition, the onset potential for ethanol oxidation was found to be more negative ~ 100 mV, an indication of its promising application in direct ethanol fuel cells.

COMPUTATIONAL ELECTROCHEMISTRY: AQUEOUS ONE-ELECTRON OXIDATION POTENTIALS FOR SUBSTITUTED ANILINES

EPA Science Inventory

Semiempirical molecular orbital theory and density functional theory are used to compute one-electron oxidation potentials for aniline and a set of 21 mono- and di-substituted anilines in aqueous solution. Linear relationships between theoretical predictions and experiment are co...

The role of metals in production and scavenging of reactive oxygen species in photosystem II.

PubMed

Pospíšil, Pavel

2014-07-01

Metal ions play a crucial role in enzymatic reactions in all photosynthetic organisms such as cyanobacteria, algae and plants. It well known that metal ions maintain the binding of substrate in the active site of the metalloenzymes and control the redox activity of the metalloenzyme in the enzymatic reaction. A large pigment-protein complex, PSII, known to serve as a water-plastoquinone oxidoreductase, contains three metal centers comprising non-heme iron, heme iron of Cyt b559 and the water-splitting manganese complex. Metal ions bound to PSII proteins maintain the electron transport from water to plastoquinone and regulate the pro-oxidant and antioxidant activity in PSII. In this review, attention is focused on the role of PSII metal centers in (i) the formation of superoxide anion and hydroxyl radicals by sequential one-electron reduction of molecular oxygen and the formation of hydrogen peroxide by incomplete two-electron oxidation of water; and (ii) the elimination of superoxide anion radical by one-electron oxidation and reduction (superoxide dismutase activity) and of hydrogen peroxide by two-electron oxidation and reduction (catalase activity). The balance between the formation and elimination of reactive oxygen species by PSII metal centers is discussed as an important aspect in the prevention of photo-oxidative damage of PSII proteins and lipids. © The Author 2014. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Effect of electrochemical redox reaction on growth and metabolism of Saccharomyces cerevisiae as an environmental factor.

PubMed

Na, Kwan Byung; Hwang, Tae Sik; Lee, Sung Hun; Ahn, Dae Hee; Park, Doo Hyun

2007-03-01

The effect of an electrochemically generated oxidation-reduction potential and electric pulse on ethanol production and growth of Saccharomyces cerevisiae ATCC 26603 was experimented and compared with effects of electron mediators (neutral red, benzyl viologen, and thionine), chemical oxidants (hydrogen peroxide and hypochlorite), chemical reductants (sulfite and nitrite), oxygen, and hydrogen. The oxidation (anodic) and reduction (cathodic) potential and electric pulse activated ethanol production and growth, and changed the total soluble protein pattern of the test strain. Neutral red electrochemically reduced activated ethanol production and growth of the test strain, but benzyl viologen and thionine did not. Nitrite inhibited ethanol production but did not influence growth of the test strain. Hydrogen peroxide, hypochlorite, and sulfite did not influence ethanol production and growth of the test strain. Hydrogen and oxygen also did not influence the growth and ethanol production. It shows that the test strain may perceive electrochemically generated oxidation-reduction potential and electric pulse as an environmental factor.

Reduction and Reoxidation of Humic Acid: Influence on Spectroscopic Properties and Proton Binding

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

Maurer, F.; Christl, I; Kretzschmar, R

2010-01-01

Previous studies on proton and metal binding to humic substances have not considered a potential influence of reduction and oxidation of functional groups. Therefore, we investigated how proton binding of a purified soil humic acid was affected by reduction. Reduction of the humic acid was carried out using an electrochemical cell that allowed us to measure the amounts of electrons and protons involved in reduction reactions. We further applied spectroscopic methods (UV-vis, fluorescence, FT-IR, C-1s NEXAFS) to detect possible chemical changes in the humic acid induced by reduction and reoxidation. The effect of reduction on proton binding was determined withmore » acid-base titrations in the pH range 4-10 under controlled redox conditions. During reduction, 0.54 mol kg{sup -1} protons and 0.55 mol kg{sup -1} electrons were transferred to humic acid. NICA-Donnan modeling revealed an equivalent increase in proton-reactive sites (0.52 mol kg{sup -1}) in the alkaline pH-range. Our results indicate that reduction of humic acid increased the amount of proton-reactive sites by 15% compared to the untreated state. Spectroscopic differences between the untreated and reduced humic acid were minor, apart from a lower UV-vis absorption of the reduced humic acid between 400 and 700 nm.« less

Chemically Conjugated Carbon Nanotubes and Graphene for Carrier Modulation.

PubMed

Kim, Ki Kang; Kim, Soo Min; Lee, Young Hee

2016-03-15

Nanocarbons such as fullerene and carbon nanotubes (CNT) in late 20th century have blossomed nanoscience and nanotechnology in 21st century, which have been further proliferated by the new finding of graphene and have indeed opened a new carbon era. Several new branches of research, for example, zero-dimensional nanoparticles, one-dimensional nanowires, and two-dimensional insulating hexagonal boron nitride, and semiconducting and metallic transition metal dichalcogenides including the recently emerging black phosphorus, have been explored and numerous unprecedented quantum mechanical features have been revealed, that have been hardly accessible otherwise. Extensive research has been done on devices and applications related to such materials. Many experimental instruments have been developed with high sensitivity and improved spatial and temporal resolution to detect such tiny objects. The need for multidisciplinary research has been growing stronger than ever, which will be the tradition in the next few decades. In this Account, we will demonstrate an example of multidisciplinary effort of utilizing CNTs and graphene for electronics by modulating electronic structures. While there are several methods of modifying electronic structures of nanocarbons such as gate bias, contact metal, and conventional substitutional doping, we focus on chemical doping approaches here. We first introduce the concept of chemical doping on CNTs and graphene in terms of electronegativity of molecules and electrochemical potential of CNTs and graphene. To understand the relationship of electrochemical potential of CNTs and graphene to electronegativity of molecules, we propose a simple water bucket model: how to fill or drain water (electrons in CNTs or graphene) in the bucket (density of states) by the chemical dopants. The doping concept is then demonstrated experimentally by tracking the absorption spectroscopy, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, Raman spectroscopy, transmittance, and transport measurements and by relating them to the reduction potential of molecules relative to that of CNTs or graphene. Two effects of chemical doping in electronics, transparent conducting films, and field effect transistors are extensively discussed. One critical issue, the stability of chemical dopants under ambient conditions, is further discussed. We believe that the presented doping concept will be useful tools for other low dimensional materials such as recently emerging transition metal dichalcogenides and black phosphorus.

Nuclear Quantum Effects on Aqueous Electron Attachment and Redox Properties.

PubMed

Rybkin, Vladimir V; VandeVondele, Joost

2017-04-06

Nuclear quantum effects (NQEs) on the reduction and oxidation properties of small aqueous species (CO 2 , HO 2 , and O 2 ) are quantified and rationalized by first-principles molecular dynamics and thermodynamic integration. Vertical electron attachment, or electron affinity, and detachment energies (VEA and VDE) are strongly affected by NQEs, decreasing in absolute value by 0.3 eV going from a classical to a quantum description of the nuclei. The effect is attributed to NQEs that lessen the solvent response upon oxidation/reduction. The reduction of solvent reorganization energy is expected to be general for small solutes in water. In the thermodynamic integral that yields the free energy of oxidation/reduction, these large changes enter with opposite sign, and only a small net effect (0.1 eV) remains. This is not obvious for CO 2 , where the integrand is strongly influenced by NQEs due to the onset of interaction of the reduced orbital with the conduction band of the liquid during thermodynamic integration. We conclude that NQEs might not have to be included in the computation of redox potentials, unless high accuracy is needed, but are important for VEA and VDE calculations.

Quantum-chemical studies on the favored and rare tautomers of neutral and redox adenine.

PubMed

Raczyńska, Ewa D; Makowski, Mariusz; Zientara-Rytter, Katarzyna; Kolczyńska, Katarzyna; Stępniewski, Tomasz M; Hallmann, Małgorzata

2013-02-21

All possible twenty-three prototropic tautomers of neutral and redox adenine (nine amine and fourteen imine forms, including geometric isomerism of the exo ═NH group) were examined in vacuo {DFT(B3LYP)/6-311+G(d,p)}. The NH → NH conversions as well as those usually omitted, NH → CH and CH → CH, were considered. An interesting change of the tautomeric preference occurs when proceeding from neutral to reduced adenine. One-electron reduction favors the nonaromatic amine C8H-N10H tautomer. This tautomeric preference is similar to that (C2H) for reduced imidazole. Water molecules (PCM model) seem to not change this trend. They influence solely the relative energies. The DFT vertical detachment energy in the gas phase is positive for each tautomer, e.g., 0.03 eV for N9H-N10H and 1.84 eV for C8H-N10H. The DFT adiabatic electron affinity for the favored process, neutral N9H-N10H → reduced C8H-N10H (ground states), is equal to 0.18 eV at 0 K (ZPE included). One-electron oxidation does not change the tautomeric preference in the gas phase. The aromatic amine N9H-N10H tautomer is favored for the oxidized molecule similarly as for the neutral one. The DFT adiabatic ionization potential for the favored process, neutral N9H-N10H → oxidized N9H-N10H (ground states), is equal to 8.12 eV at 0 K (ZPE included). Water molecules (PCM model) seem to influence solely the composition of the tautomeric mixture and the relative energies. They change the energies of the oxidation and reduction processes by ca. 2 eV.

Analysis of fast chlorophyll fluorescence rise (O-K-J-I-P) curves in green fruits indicates electron flow limitations at the donor side of PSII and the acceptor sides of both photosystems.

PubMed

Kalachanis, Dimitrios; Manetas, Yiannis

2010-07-01

Limited evidence up to now indicates low linear photosynthetic electron flow and CO(2) assimilation rates in non-foliar chloroplasts. In this investigation, we used chlorophyll fluorescence techniques to locate possible limiting steps in photosystem function in exposed, non-stressed green fruits (both pericarps and seeds) of three species, while corresponding leaves served as controls. Compared with leaves, fruit photosynthesis was characterized by less photon trapping and less quantum yields of electron flow, while the non-photochemical quenching was higher and potentially linked to enhanced carotenoid/chlorophyll ratios. Analysis of fast chlorophyll fluorescence rise curves revealed possible limitations both in the donor (oxygen evolving complex) and the acceptor (Q(A)(-)--> intermediate carriers) sides of photosystem II (PSII) indicating innately low PSII photochemical activity. On the other hand, PSI was characterized by faster reduction of its final electron acceptors and their small pool sizes. We argue that the fast reductive saturation of final PSI electron acceptors may divert electrons back to intermediate carriers facilitating a cyclic flow around PSI, while the partial inactivation of linear flow precludes strong reduction of plastoquinone. As such, the photosynthetic attributes of fruit chloroplasts may act to replenish the ATP lost because of hypoxia usually encountered in sink organs with high diffusive resistance to gas exchange.

Kinetics of the Reduction of Metalloproteins by Chromous Ion

PubMed Central

Dawson, J. W.; Gray, H. B.; Holwerda, R. A.; Westhead, E. W.

1972-01-01

The reduction of Cu(330) in Rhus vernicifera laccase by chromous ion is 30% faster than reduction of Cu(614) at room temperature [pH 4.8, μ = 0.1 (NaCl)], and two parallel first-order paths, attributed to heterogeneity of the protein, are observed at both wavelengths. The reactions of stellacyanin, spinach and French-bean plastocyanins, and cytochrome c with chromous ion under similar conditions are faster than that with laccase by factors of 102 to 104, and are first order in protein concentration. Comparison of rates and activation parameters for the reduction of “blue” copper in laccase, stellacyanin, and the two plastocyanins indicates that reduction of the Cu(614) site in laccase may occur by intramolecular electron transfer from one of the Cu(330) sites. Our value of ΔH‡ (17.4 kcal/mol) for the chromous ion reduction of cytochrome c is consistent with a mechanism in which major conformational changes in the protein must accompany electron transfer. PMID:4500552

Climbing Nitrogenase: Towards a Mechanism of Enzymatic Nitrogen Fixation

PubMed Central

Dean, Dennis R.; Seefeldt, Lance C.

2009-01-01

Conspectus “Nitrogen fixation”—the reduction of dinitrogen (N2) to two ammonia (NH3) molecules—by the Mo-dependent nitrogenase is essential for all life. Despite four decades of research, a daunting number of unanswered questions about the mechanism of nitrogenase make it the ‘Everest of enzymes’. This Account describes our efforts to climb one “face” of this mountain by meeting two interdependent challenges central to determining the mechanism of biological N2 reduction. The first challenge is to determine the reaction pathway: the composition and structure of each of the substrate-derived moieties bound to the catalytic FeMocofactor (FeMo-co) of the molybdenum-iron (MoFe) protein of nitrogenase. To overcome this challenge, we need to discriminate between the two classes of potential reaction pathways: 1) a “distal” (D) pathway, in which H atoms add sequentially at a single N or 2) an “alternating” (A) pathway, in which H atoms add alternately to the two N atoms of N2. Secondly, we need to characterize the dynamics of conversion among intermediates within the accepted Lowe-Thorneley kinetic scheme for N2 reduction. That goal requires us to experimentally determine both the number of electrons/protons delivered to the MoFe protein and their “inventory”—a partition into those residing on each of the reaction components and released as H2 or NH3. The principal obstacle to this “climb” has been the inability to generate N2 reduction intermediates for characterization. A combination of genetic, biochemical, and spectroscopic approaches recently overcame this obstacle. These experiments identified one of the four-iron Fe-S faces of the active-site FeMo-cofactor as the specific site of reactivity, indicated that the sidechain of residue α70V controls access to this face, and supported the involvement of the sidechain of residue α195H in proton delivery. We can now freeze-quench trap N2 reduction pathway intermediates and use ENDOR/ESEEM spectroscopies to characterize them. However, even successful trapping of a N2 reduction intermediate occurs without synchronous electron delivery to the MoFe protein. As a result, the number of electrons and protons, n, delivered to MoFe during its formation is unknown. To determine n and the electron inventory, we initially employed ENDOR spectroscopy to analyze the substrate moiety bound to the FeMo-co and 57Fe within the cofactor. Difficulties in using that approach led us to devise a robust kinetic protocol for determining n of a trapped intermediate. This Account describes strategies that we have formulated to bring this “face” of the nitrogenase mechanism into view and afford approaches to its climb. Although the summit remains distant, we look forward to continued progress in the ascent. PMID:19267458

Cholesterol Hydroperoxide Generation, Translocation, and Reductive Turnover in Biological Systems.

PubMed

Girotti, Albert W; Korytowski, Witold

2017-12-01

Cholesterol is like other unsaturated lipids in being susceptible to peroxidative degradation upon exposure to strong oxidants like hydroxyl radical or peroxynitrite generated under conditions of oxidative stress. In the eukaryotic cell plasma membrane, where most of the cellular cholesterol resides, peroxidation leads to membrane structural and functional damage from which pathological states may arise. In low density lipoprotein, cholesterol and phospholipid peroxidation have long been associated with atherogenesis. Among the many intermediates/products of cholesterol oxidation, hydroperoxide species (ChOOHs) have a number of different fates and deserve special attention. These fates include (a) damage-enhancement via iron-catalyzed one-electron reduction, (b) damage containment via two-electron reduction, and (c) inter-membrane, inter-lipoprotein, and membrane-lipoprotein translocation, which allows dissemination of one-electron damage or off-site suppression thereof depending on antioxidant location and capacity. In addition, ChOOHs can serve as reliable and conveniently detected mechanistic reporters of free radical-mediated reactions vs. non-radical (e.g., singlet oxygen)-mediated reactions. Iron-stimulated peroxidation of cholesterol and other lipids underlies a newly discovered form of regulated cell death called ferroptosis. These and other deleterious consequences of radical-mediated lipid peroxidation will be discussed in this review.

Zirconium and silver co-doped TiO2 nanoparticles as visible light catalyst for reduction of 4-nitrophenol, degradation of methyl orange and methylene blue

NASA Astrophysics Data System (ADS)

Naraginti, Saraschandra; Stephen, Finian Bernard; Radhakrishnan, Adhithya; Sivakumar, A.

2015-01-01

Catalytic activity of Zr and Ag co-doped TiO2 nanoparticles on the reduction of 4-nitrophenol, degradation of methylene blue and methyl orange was studied using sodium borohydride as reducing agent. The nanoparticles were characterized using X-ray diffraction, energy dispersive X-ray, high resolution transmission electron microscopy, selected area electron diffraction and UV-Vis spectroscopy. The rate of the reduction/degradation was found to increase with increasing amount of the photocatalyst which could be attributed to higher dispersity and small size of the nanoparticles. The catalytic activity of Zr and Ag co-doped TiO2 nanoparticles showed no significant difference even after recycling the catalyst four times indicating a promising potential for industrial application of the prepared photocatalyst.

The modern trends in space electromagnetic instrumentation

NASA Astrophysics Data System (ADS)

Korepanov, V. E.

The future trends of the experimental plasma physics development in outer space demand more and more exact and sophisticated scientific instrumentation. Moreover, the situation is complicated by constant reduction of financial support of scientific research, even in leading countries. This resulted in the development of mini; micro and nanosatellites with low price and short preparation time. Consequently, it provoked the creation of new generation of scientific instruments with reduced weight and power consumption but increased level of metrological parameters. The recent state of the development of electromagnetic (EM) sensors for microsatellites is reported. For flux-gate magnetometers (FGM) the reduction of weight as well as power consumption was achieved not only due to the use of new electronic components but also because of the new operation mode development. The scientific and technological study allowed to decrease FGM noise and now the typical noise figure is about 10 picotesla rms at 1 Hz and the record one is below 1 picotesla. The super-light version of search-coil magnetometers (SCM) was created as the result of intensive research. These new SCMs can have about six decades of operational frequency band with upper limit ˜ 1 MHz and noise level of few femtotesla with total weight about 75 grams, including electronics. A new instrument.- wave probe (WP) - which combines three independent sensors in one body - SCM, split Langmuir probe and electric potential sensor - was created. The developed theory confirms that WP can directly measure the wave vector components in space plasmas.

CHARGE-2 rocket observations of vehicle charging and charge neutralization

NASA Astrophysics Data System (ADS)

Banks, P. M.; Gilchrist, B. E.; Neubert, T.; Myers, N.; Raitt, W. J.; Williamson, P. R.; Fraser-Smith, A. C.; Sasaki, S.

Observations of electrical charging and other phenomena have been made in the ionosphere with the CHARGE-2 tethered rocket system. In this experiment, two electrically connected payloads with a variety of plasma instruments measured effects associated with operation of a 1 keV, 40 mA electron gun and a 450-volt dc power supply. During electron beam operations, it was found that both mother and daughter payloads reached high positive potentials as a consequence of the restricted electron current collecting area of the payloads. During neutral gas thruster firings, the payload potentials were dramatically reduced, indicating that electrical discharges could effectively ground each payload to plasma potential. Other thruster-related effects were also seen, including substantial reductions of return current-associated electrical noise at HF and VLF and large increases in 3914 A light in the plasma sheath.

Thermophilic nitrate-reducing microorganisms prevent sulfate reduction in cold marine sediments incubated at high temperature

NASA Astrophysics Data System (ADS)

Nepomnyashchaya, Yana; Rezende, Julia; Hubert, Casey

2014-05-01

Hydrogen sulphide produced during metabolism of sulphate-reducing microorganisms (SRM) is toxic, corrosive and causes detrimental oil reservoir souring. During secondary oil recovery, injecting oil reservoirs with seawater that is rich in sulphate and that also cools high temperature formations provides favourable growth conditions for SRM. Nitrate addition can prevent metabolism of SRM by stimulating nitrate-reducing microorganisms (NRM). The investigations of thermophilic NRM are needed to develop mechanisms to control the metabolism of SRM in high temperature oil field ecosystems. We therefore established a model system consisting of enrichment cultures of cold surface marine sediments from the Baltic Sea (Aarhus Bay) that were incubated at 60°C. Enrichments contained 25 mM nitrate and 40 mM sulphate as potential electron acceptors, and a mixture of the organic substrates acetate, lactate, propionate, butyrate (5 mM each) and yeast extract (0.01%) as potential carbon sources and electron donors. Slurries were incubated at 60°C both with and without initial pasteurization at 80°C for 2 hours. In the enrichments containing both nitrate and sulphate, the concentration of nitrate decreased indicating metabolic activity of NRM. After a four-hour lag phase the rate of nitrate reduction increased and the concentration of nitrate dropped to zero after 10 hours of incubation. The concentration of nitrite increased as the reduction of nitrate progressed and reached 16.3 mM after 12 hours, before being consumed and falling to 4.4 mM after 19-day of incubation. No evidence for sulphate reduction was observed in these cultures during the 19-day incubation period. In contrast, the concentration of sulphate decreased up to 50% after one week incubation in controls containing only sulphate but no nitrate. Similar sulfate reduction rates were seen in the pasteurized controls suggesting the presence of heat resistant SRM, whereas nitrate reduction rates were lower in the pasteurized experiment, suggesting either different populations of NRM or a population of NRM that was not resistant to the 80°C pre-treatment. These results demonstrate that thermophilic NRM exist in cold marine sediments from Aarhus Bay and can be enriched under appropriate conditions. Effective microbial control of SRM activity at high temperature in our Aarhus Bay sediment model system depends on the addition of nitrate to stimulate this group of microorganisms.

The protoelectric potential map (PPM): an absolute two-dimensional chemical potential scale for a global understanding of chemistry.

PubMed

Radtke, Valentin; Himmel, Daniel; Pütz, Katharina; Goll, Sascha K; Krossing, Ingo

2014-04-07

We introduce the protoelectric potential map (PPM) as a novel, two-dimensional plot of the absolute reduction potential (peabs scale) combined with the absolute protochemical potential (Brønsted acidity: pHabs scale). The validity of this thermodynamically derived PPM is solvent-independent due to the scale zero points, which were chosen as the ideal electron gas and the ideal proton gas at standard conditions. To tie a chemical environment to these reference states, the standard Gibbs energies for the transfer of the gaseous electrons/protons to the medium are needed as anchor points. Thereby, the thermodynamics of any redox, acid-base or combined system in any medium can be related to any other, resulting in a predictability of reactions even over different media or phase boundaries. Instruction is given on how to construct the PPM from the anchor points derived and tabulated with this work. Since efforts to establish "absolute" reduction potential scales and also "absolute" pH scales already exist, a short review in this field is given and brought into relation to the PPM. Some comments on the electrochemical validation and realization conclude this concept article. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen reduction reaction catalyzed by platinum nanonetwork prepared by template free one step synthesis for polymer electrolyte membrane fuel cells

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

Narayanamoorthy, B.; Kumar, B.V.V.S. Pavan; Eswaramoorthy, M.

2014-07-01

Highlights: • Supportless Pt nanonetwork (Pt NN) synthesized by novel template free one step method as per our earlier reported procedure. • Electrocatalytic activity of Pt NN studied taking oxygen reduction reaction in acid medium. • Kinetic and thermodynamic parameters were deduced under hydrodynamic conditions. • ORR mechanistic pathway was proposed based on kinetic rate constants. • ADT analysis found enhanced stability (5000 cycles) for Pt NN than Pt NN/VC and reported Pt/C. - Abstract: The reduction reaction of molecular oxygen (ORR) was investigated using supportless Pt nanonetwork (Pt NN) electrocatalyst in sulfuric acid medium. Pt NN was prepared bymore » template free borohydride reduction. The transmission electron microscope images revealed a network like nano-architecture having an average cluster size of 30 nm. The electrochemical characterization of supportless and Vulcan carbon supported Pt NN (Pt NN/VC) was carried out using rotating disc and ring disc electrodes at various temperatures. Kinetic and thermodynamic parameters were estimated under hydrodynamic conditions and compared with Pt NN/VC and reported Pt/C catalysts. The accelerated durability test revealed that supportless Pt NN is quite stable for 5000 potential cycles with 22% reduction in electrochemical surface area (ECSA). While the initial limiting current density has in fact increased by 11.6%, whereas Pt NN/VC suffered nearly 55% loss in ECSA and 13% loss in limiting current density confirming an enhanced stability of supportless Pt NN morphology for ORR compared to conventional Pt/C ORR catalysts in acid medium.« less

Impact of Mutations on the Midpoint Potential of the [4Fe-4S]+1,+2 Cluster and on Catalytic Activity in Electron Transfer Flavoprotein-ubiquinone Oxidoreductase (ETF-QO)†

PubMed Central

Usselman, Robert J.; Fielding, Alistair J.; Frerman, Frank E.; Watmough, Nicholas J.; Eaton, Gareth R.; Eaton, Sandra S.

2011-01-01

Electron transfer flavoprotein - ubiquinone oxidoreductase (ETF-QO) is an iron-sulfur flavoprotein that accepts electrons from electron-transfer flavoprotein (ETF) and reduces ubiquinone from the Q-pool. ETF-QO contains a single [4Fe-4S]2+,1+ cluster and one equivalent of FAD, which are diamagnetic in the isolated oxidized enzyme and can be reduced to paramagnetic forms by enzymatic donors or dithionite. Mutations were introduced by site-directed mutagenesis of amino acids in the vicinity of the iron-sulfur cluster of Rhodobacter sphaeroides ETF-QO. Y501 and T525 are equivalent to Y533 and T558 in the porcine ETF-QO. In the porcine protein, these residues are within hydrogen bonding distance of the Sγ of the cysteine ligands to the iron-sulfur cluster. Y501F, T525A, and Y501F/T525A substitutions were made to determine the effects on midpoint potential, activity, and EPR spectral properties of the cluster. The integrity of the mutated proteins was confirmed by optical spectra, EPR g-values, and spin-lattice relaxation rates, and the cluster to flavin point-dipole distance was determined by relaxation enhancement. Potentiometric titrations were monitored by changes in the CW EPR signals of the cluster and semiquinone. Single mutations decreased the mid-point potentials of the iron-sulfur cluster from +37 mV for wild type to −60 mV for Y501F and T525A and to −128 mV for Y501F/T525A. Lowering the midpoint potential resulted in a decrease in steady-state ubiquinone reductase activity and in ETF semiquinone disproportionation. The decrease in activity demonstrates that reduction of the iron-sulfur cluster is required for activity. There was no detectable effect of the mutations on the flavin midpoint potentials. PMID:18069858

Impact of mutations on the midpoint potential of the [4Fe-4S]+1,+2 cluster and on catalytic activity in electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO).

PubMed

Usselman, Robert J; Fielding, Alistair J; Frerman, Frank E; Watmough, Nicholas J; Eaton, Gareth R; Eaton, Sandra S

2008-01-08

Electron-transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) is an iron-sulfur flavoprotein that accepts electrons from electron-transfer flavoprotein (ETF) and reduces ubiquinone from the Q-pool. ETF-QO contains a single [4Fe-4S]2+,1+ cluster and one equivalent of FAD, which are diamagnetic in the isolated oxidized enzyme and can be reduced to paramagnetic forms by enzymatic donors or dithionite. Mutations were introduced by site-directed mutagenesis of amino acids in the vicinity of the iron-sulfur cluster of Rhodobacter sphaeroides ETF-QO. Y501 and T525 are equivalent to Y533 and T558 in the porcine ETF-QO. In the porcine protein, these residues are within hydrogen-bonding distance of the Sgamma of the cysteine ligands to the iron-sulfur cluster. Y501F, T525A, and Y501F/T525A substitutions were made to determine the effects on midpoint potential, activity, and EPR spectral properties of the cluster. The integrity of the mutated proteins was confirmed by optical spectra, EPR g-values, and spin-lattice relaxation rates, and the cluster to flavin point-dipole distance was determined by relaxation enhancement. Potentiometric titrations were monitored by changes in the CW EPR signals of the cluster and semiquinone. Single mutations decreased the midpoint potentials of the iron-sulfur cluster from +37 mV for wild type to -60 mV for Y501F and T525A and to -128 mV for Y501F/T525A. Lowering the midpoint potential resulted in a decrease in steady-state ubiquinone reductase activity and in ETF semiquinone disproportionation. The decrease in activity demonstrates that reduction of the iron-sulfur cluster is required for activity. There was no detectable effect of the mutations on the flavin midpoint potentials.

Double layers in expanding plasmas and their relevance to the auroral plasma processes

NASA Astrophysics Data System (ADS)

Singh, Nagendra; Khazanov, George

2003-04-01

When a dense plasma consisting of a cold and a sufficiently warm electron population expands, a rarefaction shock forms [, 1978]. In the expansion of the polar wind in the magnetosphere, it has been previously shown that when a sufficiently warm electron population also exists, in addition to the usual cold ionospheric one, a discontinuity forms in the electrostatic potential distribution along the magnetic field lines [, 1984]. Despite the lack of spatial resolution and the assumption of quasi-neutrality in the polar wind models, such discontinuities have been called double layers (DLs). Recently similar discontinuities have been invoked to partly explain the auroral acceleration of electrons and ions in the upward current region [, 2000]. By means of one-dimensional Vlasov simulations of expanding plasmas, for the first time we make here the connection between (1) the rarefaction shocks, (2) the discontinuities in the potential distributions, and (3) DLs. We show that when plasmas expand from opposite directions into a deep density cavity with a potential drop across it and when the plasma on the high-potential side contains hot and cold electron populations, the temporal evolution of the potential and the plasma distribution generates evolving multiple double layers with an extended density cavity between them. One of the DLs is the rarefaction-shock (RFS) and it forms by the reflections of the cold electrons coming from the high-potential side; it supports a part of the potential drop approximately determined by the hot electron temperature. The other DLs evolve from charge separations arising either from reflection of ions coming from the low-potential side or stemming from plasma instabilities; they support the rest of the potential drop. The instabilities forming these additional double layers involve electron-ion (e-i) Buneman or ion-ion (i-i) two-stream interactions. The electron-electron two-stream interactions on the high-potential side of the RFS generate electron-acoustic waves, which evolve into electron phase-space holes. The ion population originating from the low-potential side and trapped by the RFS is energized by the e-i and i-i instabilities and it eventually precipitates into the high-potential plasma along with an electron beam. Applications of these findings to the auroral plasma physics are discussed.

Double Layers in Expanding Plasmas and Their Relevance to the Auroral Plasma Processes

NASA Technical Reports Server (NTRS)

Singh, Nagendra; Khazanov, George

2003-01-01

When a dense plasma consisting of a cold and a sufficiently warm electron population expands, a rarefaction shock forms [Bezzerides et al., 1978]. In the expansion of the polar wind in the magnetosphere, it has been previously shown that when a sufficiently warm electron population also exists, in addition to the usual cold ionospheric one, a discontinuity forms in the electrostatic potential distribution along the magnetic field lines [Barakat and Schunk, 1984]. Despite the lack of spatial resolution and the assumption of quasi-neutrality in the polar wind models, such discontinuities have been called double layers (DLs). Recently similar discontinuities have been invoked to partly explain the auroral acceleration of electrons and ions in the upward current region [Ergun et al., 2000]. By means of one-dimensional Vlasov simulations of expanding plasmas, for the first time we make here the connection between (1) the rarefaction shocks, (2) the discontinuities in the potential distributions, and (3) DLs. We show that when plasmas expand from opposite directions into a deep density cavity with a potential drop across it and when the plasma on the high-potential side contains hot and cold electron populations, the temporal evolution of the potential and the plasma distribution generates evolving multiple double layers with an ,extended density cavity between them. One of the DLs is the rarefaction-shock (RFS) and it forms by the reflections of the cold electrons coming from the high-potential side; it supports a part of the potential drop approximately determined by the hot electron temperature. The other DLs evolve from charge separations arising either from reflection of ions coming from the low-potential side or stemming from plasma instabilities; they support the rest of the potential drop. The instabilities forming these additional double layers involve electron-ion (e-i) Buneman or ion-ion (i-i) two-stream interactions. The electron-electron two-stream interactions on the high-potential side of the RFS generate electron-acoustic waves, which evolve into electron phase-space holes. The ion population originating from the low-potential side and trapped by the RFS is energized by the e-i and i-i instabilities and it eventually precipitates into the high-potential plasma along with an electron beam. Applications of these findings to the auroral plasma physics are discussed.

Recovery of Humic-Reducing Bacteria from a Diversity of Environments

PubMed Central

Coates, John D.; Ellis, Debra J.; Blunt-Harris, Elizabeth L.; Gaw, Catherine V.; Roden, Eric E.; Lovley, Derek R.

1998-01-01

To evaluate which microorganisms might be responsible for microbial reduction of humic substances in sedimentary environments, humic-reducing bacteria were isolated from a variety of sediment types. These included lake sediments, pristine and contaminated wetland sediments, and marine sediments. In each of the sediment types, all of the humic reducers recovered with acetate as the electron donor and the humic substance analog, 2,6-anthraquinone disulfonate (AQDS), as the electron acceptor were members of the family Geobacteraceae. This was true whether the AQDS-reducing bacteria were enriched prior to isolation on solid media or were recovered from the highest positive dilutions of sediments in liquid media. All of the isolates tested not only conserved energy to support growth from acetate oxidation coupled to AQDS reduction but also could oxidize acetate with highly purified soil humic acids as the sole electron acceptor. All of the isolates tested were also able to grow with Fe(III) serving as the sole electron acceptor. This is consistent with previous studies that have suggested that the capacity for Fe(III) reduction is a common feature of all members of the Geobacteraceae. These studies demonstrate that the potential for microbial humic substance reduction can be found in a wide variety of sediment types and suggest that Geobacteraceae species might be important humic-reducing organisms in sediments. PMID:9546186

Rocket measurements of electron temperature in the E region

NASA Technical Reports Server (NTRS)

Zimmerman, R. K., Jr.; Smith, L. G.

1980-01-01

The rocket borne equipment, experimental method, and data reduction techniques used in the measurement of electron temperature in the E region are fully described. Electron temperature profiles from one daytime equatorial flight and two nighttime midlatitude flights are discussed. The last of these three flights, Nike Apache 14.533, showed elevated E region temperatures which are interpreted as the heating effect of a stable auroral red arc.

Structure and function of the tetraheme cytochrome associated to the reaction center of Roseobacter denitrificans.

PubMed

Garcia, D; Richaud, P; Breton, J; Verméglio, A

1994-01-01

We have characterized the tetrahemic RC bound cytochrome isolated from the quasi-photosynthetic bacterium Roseobacter denitrificans in terms of absorption spectrum, redox property and orientation with respect to the membrane plane. The heme, designated H1, which possesses the highest redox midpoint potential (+290 mV), absorbs at 555 nm. Its plane makes an angle of 40 degrees with the membrane plane. The second high potential heme, H2 (+240 mV), peaks at 554 nm and makes a tilt of 55 degrees with the membrane. The two low potential hemes, L1 and L2, present a similar and rather high redox midpoint potential (+90 mV). They absorb at 553 nm and 550 nm. One of these hemes is oriented at 40 degrees while the other makes an angle of 90 degrees with the membrane plane. The soluble cytochrome c551 completes the cyclic electron transfer between the RC and the bc1 complex. Both the oxidation and the re-reduction of cytochrome c551 are diffusible processes. Under semi-aerobic conditions, one of the low potential hemes is photo-oxidized under illumination but only extremely slowly re-reduced. This explains the requirement of high aerobic conditions for growth of Roseobacter denitrificans cells in the light.

Iodate Reduction by Shewanella oneidensis Does Not Involve Nitrate Reductase

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

Mok, Jung Kee; Toporek, Yael J.; Shin, Hyun-Dong

Microbial iodate (IO 3 -) reduction is a major component of the iodine biogeochemical reaction network and is the basis of alternative strategies for remediation of iodine-contaminated environments. The molecular mechanism of microbial IO 3 - reduction, however, is not well understood. In microorganisms displaying IO 3 - and nitrate (NO 3 -) reduction activities, NO 3 - reductase is postulated to reduce IO 3 - as alternate electron acceptor. In the present study, whole genome analyses of 25 NO 3 --reducing Shewanella strains identified various combinations of genes encoding one assimilatory (cytoplasmic Nas) and three dissimilatory (membrane-associated Nar andmore » periplasmic Napα and Napβ) NO 3 - reductases. S. oneidensis was the only Shewanella strain whose genome encoded a single NO 3 - reductase (Napβ). Terminal electron acceptor competition experiments in S. oneidensis batch cultures amended with both NO 3 - and IO 3 - demonstrated that neither NO 3 - nor IO 3 - reduction activities were competitively inhibited by the presence of the competing electron acceptor. The lack of involvement of S. oneidensis Napβ in IO 3 - reduction was confirmed via phenotypic analysis of an in-frame gene deletion mutant lacking napβΑ (encoding the NO 3 --reducing NapβA catalytic subunit). S. oneidensis ΔnapβA was unable to reduce NO 3 -, yet reduced IO 3 - at rates higher than the wild-type strain. Thus, NapβA is required for dissimilatory NO 3 - reduction by S. oneidensis, while neither the assimilatory (Nas) nor dissimilatory (Napα, Napβ, and Nar) NO 3 - reductases are required for IO 3 - reduction. These findings oppose the traditional view that NO 3 - reductase reduces IO 3 - as alternate electron acceptor and indicate that S. oneidensis reduces IO 3 - via an as yet undiscovered enzymatic mechanism.« less

Temperature Independent Catalytic Two-Electron Reduction of Dioxygen by Ferrocenes with a Tris[2-(2-pyridyl)ethyl]amine-Copper(II) Catalyst in the Presence of Perchloric Acid

PubMed Central

Das, Dipanwita; Lee, Yong-Min; Ohkubo, Kei; Nam, Wonwoo; Karlin, Kenneth D.; Fukuzumi, Shunichi

2013-01-01

Selective two-electron plus two-proton (2e−/2H+) reduction of O2 to hydrogen peroxide by ferrocene (Fc) or 1,1′-dimethylferrocene (Me2Fc) in the presence of perchloric acid is catalyzed efficiently by a mononuclear copper(II) complex, [CuII(tepa)]2+ {tepa = tris[2-(2-pyridyl)ethyl]amine} (1) in acetone. The E1/2 value for [CuII(tepa)]2+ as measured by cyclic voltammetry is 0.07 V vs Fc/Fc+ in acetone, being significantly positive, which makes it possible to use relatively weak one-electron reductants such as Fc and Me2Fc for the overall two-electron reduction of O2. Fast electron transfer from Fc or Me2Fc to 1 affords the corresponding CuI complex, [CuI(tepa)]+ (2), which reacts at low temperature (193 K) with O2, however only in presence of HClO4 to afford the hydroperoxo complex, [CuII(tepa)(OOH)]2+ (3). The detailed kinetic study on the homogeneous catalytic system reveals the rate-determining step to be the O2-binding process in the presence of HClO4 at lower temperature as well as at room temperature. The O2-binding kinetics in the presence of HClO4 were studied, demonstrating that the rate of formation of the hydroperoxo complex (3) as well as the overall catalytic reaction remained virtually the same with changing temperature. The apparent lack of an activation energy for the catalytic two-electron reduction of O2 is shown to result from the existence of a pre-equilibrium between 2 and O2 prior to the formation of the hydroperoxo complex 3. No further reduction of [CuII(tepa)(OOH)]2+ (3) by Fc or Me2Fc occurred, and instead 3 is protonated by HClO4 to yield H2O2 accompanied by regeneration of 1, thus completing the catalytic cycle for the two-electron reduction of O2 by Fc or Me2Fc. PMID:23394287

The Adoption of Electronic Benefit Transfer Card for Delivering Food Stamp Benefits in Alabama: Perceptions of College Students Participating in the Food Stamp Program

ERIC Educational Resources Information Center

Zekeri, Andrew A.

2004-01-01

The reasons for moving from paper coupons to delivering food stamps electronically include potential reduction in the cost of administering the system and in fraud, theft and abuse of the system. Furthermore, the use of EBT is believed o reduce social stigma and embarrassment felt by recipients when using paper coupon. Therefore, using survey data…

Thermopower of thermoelectric materials with resonant levels: PbTe:Tl versus PbTe:Na and Cu1 -xNix

NASA Astrophysics Data System (ADS)

Wiendlocha, Bartlomiej

2018-05-01

Electronic transport properties of thermoelectric materials containing resonant levels are discussed by analyzing the two best known examples: copper-nickel metallic alloy (Cu-Ni, constantan) and thallium-doped lead telluride (PbTe:Tl). As a contrasting example of a material with a nonresonant impurity, sodium-doped PbTe is considered. Theoretical calculations of the electronic structure, Bloch spectral functions, and energy-dependent electrical conductivity at T =0 K are done using the Korringa-Kohn-Rostoker method with the coherent potential approximation and the Kubo-Greenwood formalism. The effect of a resonance on the residual resistivity and electronic lifetimes in PbTe is analyzed. By using the full Fermi integrals, room-temperature thermopower is calculated, confirming its increase in PbTe:Tl versus PbTe:Na, due to the presence of the resonant level. In addition, our calculations support the self-compensation model, in which the experimentally observed reduction of carrier concentration in PbTe:Tl against the nominal one is explained by the presence of n -type Te vacancies.

Visible light-driven O2 reduction by a porphyrin-laccase system.

PubMed

Lazarides, Theodore; Sazanovich, Igor V; Simaan, A Jalila; Kafentzi, Maria Chrisanthi; Delor, Milan; Mekmouche, Yasmina; Faure, Bruno; Réglier, Marius; Weinstein, Julia A; Coutsolelos, Athanassios G; Tron, Thierry

2013-02-27

Several recent studies have shown that the combination of photosensitizers with metalloenzymes can support a light-driven multielectron reduction of molecules such as CO(2) or HCN. Here we show that the association of the zinc tetramethylpyridinium porphyrin (ZnTMPyP(4+)) photosensitizer with the multicopper oxidase (MCO) laccase allows to link the oxidation of an organic molecule to the four electrons reduction of dioxygen into water. The enzyme is photoreduced within minutes with porphyrin/enzyme ratio as low as 1:40. With a 1:1 ratio, the dioxygen consumption rate is 1.7 μmol L(-1) s(-1). Flash photolysis experiments support the formation of the triplet excited state of ZnTMPyP(4+) which reduces the enzyme to form a radical cation of the porphyrin with a k(ET) ≈ 10(7) s(-1) M(-1). The long-lived triplet excited state of the ZnTMPyP(4+) (τ(0) = 0.72 ms) accounts for a substantial electron-transfer quantum yield, φ(ET) = 0.35. Consequently, the enzyme-dependent photo-oxidation of the electron donor occurs with a turnover of 8 min(-1) for the one-electron oxidation process, thereby supporting the suitability of such enzyme/sensitizer hybrid systems for aerobic photodriven transformations on substrates. This study is the first example of a phorphyrin-sensitized four-electron reduction of an enzyme of the MCO family, leading to photoreduction of dioxygen into water.

The role of Shewanella oneidensis MR-1 outer surface structures in extracellular electron transfer

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

Bouhenni, Rachida; Vora, Gary J.; Biffinger, Justin C.

2010-04-20

Shewanella oneidensis is a facultative anaerobe that uses more than 14 different terminal electron acceptors for respiration. These include metal oxides and hydroxyoxides, and toxic metals such as uranium and chromium. Mutants deficient in metal reduction were isolated using the mariner transposon derivative, minihimar RB1. These included mutants with transposon insertions in the prepilin peptidase and type II secretion system genes. All mutants were deficient in Fe(III) and Mn(IV) reduction, and exhibited slow growth when DMSO was used as the electron acceptor. The genome sequence of S. oneidensis contains one prepilin peptidase gene, pilD. A similar prepilin peptidase that maymore » function in the processing of type II secretion prepilins was not found. Single and multiple chromosomal deletions of four putative type IV pilin genes did not affect Fe(III) and Mn(IV) reduction. These results indicate that PilD in S. oneidensis is responsible for processing both type IV and type II secretion prepilin proteins. Type IV pili do not appear to be required for Fe(III) and Mn(IV) reduction.« less

The effect of functional groups on reduction and activation of quinone bioreductive agents by DT-diaphorase.

PubMed

Fourie, Jeanne; Oleschuk, Curtis J; Guziec, Frank; Guziec, Lynn; Fiterman, Derek J; Monterrosa, Cielo; Begleiter, Asher

2002-02-01

Bioreductive antitumor agents are an important class of anticancer drugs that include the clinically used drug, mitomycin C, and new agents such as EO9 and tirapazamine that have recently been tested in clinical trials. These agents require activation by reductive enzymes such as DT-diaphorase or NADPH:cytochrome P450 reductase. A major focus for improving cancer chemotherapy has been to increase the selectivity and targeting of antitumor drugs to tumor cells. Bioreductive antitumor agents are ideally suited to improving tumor selectivity by an enzyme-directed approach to tumor targeting. However, none of the bioreductive agents developed to date has been specific for activation by a single reductive enzyme. This is in part due to a lack of knowledge about structural factors that confer selectivity for activation by reductive enzymes. The purpose of this study was to investigate the ability of specific functional groups to modify reduction and activation of quinone bioreductive agents by DT-diaphorase. We used a series of model benzoquinone mustard (BM) bioreductive agents and compared the parent compound BM to MBM, which has a strong electron-donating methoxy group, MeBM, which has a weaker electron-donating methyl group, CBM, which has an electron-withdrawing chloro group, and PBM and its structural isomer, meta-PBM (m-PBM), which both have sterically bulky benzene rings attached to the quinone moiety. We determined the rate of reduction of these agents by purified human DT-diaphorase under hypoxic and aerobic conditions. We also measured the cytotoxic activity of these agents in human tumor cell lines with and without the DT-diaphorase inhibitor, dicoumarol. Under hypoxic conditions in vitro, the t(1/2) values for reduction of the analogs by purified DT-diaphorase were 4, 6, 8, 9, 10 and 21 min for BM, MeBM, CBM, MBM, PBM and m-PBM, respectively. Under aerobic conditions the rank order of redox cycling after two-electron reduction by DT-diaphorase was MBM > MeBM > BM approximately CBM approximately PBM approximately m-PBM. The rate of reduction by DT-diaphorase of HBM, a non-alkylating analog of BM, was similar to that of BM under hypoxic conditions, and the rate of redox cycling under aerobic conditions was comparable to that of BM, suggesting that structural changes to the cytotoxic group of these BMs do not affect DT-diaphorase-mediated reduction and redox cycling potential. MBM, MeBM and PBM were more toxic than BM in the NCI-H661 human non-small-cell lung cancer cells and SK-MEL-28 human melanoma cells, while CBM displayed significantly increased cytotoxic activity compared to BM only in the NCI H661 cells. m-PBM had similar cytotoxic activity compared with BM in both cell lines. These cell lines have moderate to high levels of DT-diaphorase activity. When cells were pretreated with the DT-diaphorase inhibitor, dicoumarol, the cytotoxic activity of BM increased while that of MBM decreased in both cell lines, suggesting that BM was inactivated by DT-diaphorase while MBM was activated by this enzyme. Pretreatment of the SK-MEL-28 melanoma cells with dicoumarol resulted in an increased cytotoxic activity of MeBM, but pretreatment of the NCI-H661 cells did not affect the cytotoxicity of MeBM. This suggests, that similar to the results with BM, DT-diaphorase is an inactivating enzyme for MeBM in the SK-MEL-28 cell line. Dicoumarol had no significant effect on the cytotoxicity of CBM, PBM or m-PBM in both cell lines. These studies demonstrated that functional groups can significantly affect the reduction and activation of bioreductive agents by DT-diaphorase. All the functional groups decreased the rate of reduction of the quinone group by DT-diaphorase. Since MeBM and MBM, with electron-donating functional groups, and CBM with an electron-withdrawing functional group had similar half-lives of reduction by DT-diaphorase, steric rather than electronic effects of the functional groups appear to be more important for modifying the rate of reduction by DT-diaphorase. Steric effects on reduction by DT-diaphorase were also influenced by the position of the functional group on the quinone ring moiety, as the reduction of m-PBM was much slower than the reduction of PBM. The electron-donating methoxy and methyl functional groups increased the ability of the reduced products of MBM and MeBM to undergo redox cycling. DT-diaphorase appeared to be an activating enzyme for MBM. This may have resulted in part from increased formation of reactive oxygen species resulting from the increased redox cycling by MBM. In contrast, DT-diaphorase was an inactivating enzyme for BM, and for MeBM in the SK-MEL-28 melanoma cells, possibly because the hydroquinone product of BM and MeBM may be less cytotoxic than the semiquinone produced by one-electron reduction by NADPH:cytochrome P450 reductase.

Positional effects of second-sphere amide pendants on electrochemical CO2 reduction catalyzed by iron porphyrins† †Electronic supplementary information (ESI) available: Procedures for synthetic, spectroscopic, and electrochemical experiments. CCDC 1582750. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04682k

PubMed Central

Nichols, Eva M.; Derrick, Jeffrey S.; Nistanaki, Sepand K.; Smith, Peter T.

2018-01-01

The development of catalysts for electrochemical reduction of carbon dioxide offers an attractive approach to transforming this greenhouse gas into value-added carbon products with sustainable energy input. Inspired by natural bioinorganic systems that feature precisely positioned hydrogen-bond donors in the secondary coordination sphere to direct chemical transformations occurring at redox-active metal centers, we now report the design, synthesis, and characterization of a series of iron tetraphenylporphyrin (Fe-TPP) derivatives bearing amide pendants at various positions at the periphery of the metal core. Proper positioning of the amide pendants greatly affects the electrocatalytic activity for carbon dioxide reduction to carbon monoxide. In particular, derivatives bearing proximal and distal amide pendants on the ortho position of the phenyl ring exhibit significantly larger turnover frequencies (TOF) compared to the analogous para-functionalized amide isomers or unfunctionalized Fe-TPP. Analysis of TOF as a function of catalyst standard reduction potential enables first-sphere electronic effects to be disentangled from second-sphere through-space interactions, suggesting that the ortho-functionalized porphyrins can utilize the latter second-sphere property to promote CO2 reduction. Indeed, the distally-functionalized ortho-amide isomer shows a significantly larger through-space interaction than its proximal ortho-amide analogue. These data establish that proper positioning of secondary coordination sphere groups is an effective design element for breaking electronic scaling relationships that are often observed in electrochemical CO2 reduction. PMID:29732079

The Competitive Influence of Li+, Na+, K+, Ag+, and H+ on the Fragmentation of a PEGylated Polymeric Excipient

NASA Astrophysics Data System (ADS)

Wei, Juan; Bristow, Anthony W. T.; O'Connor, Peter B.

2015-01-01

The collisionally activated dissociation (CAD) and electron capture dissociation (ECD) of doubly charged tocopheryl polyethylene glycol succinate (TPGS) have been examined. Li+, Na+, K+, Ag+, and H+ were selected in the study, and the competitive influence of each ion was investigated by fragmenting TPGS attached with two different cations, [M + X1 + X2]2+ (X1 and X2 refer to Li+, Na+, K+, Ag+, H+). For metallic adducts, CAD results show that the dissociation of ionic adducts from the precursor is most likely depending on the binding strength, where the affinity of each ion to the TPGS is in the order of Ag+ ≈ Li+ ˃ Na+ ˃ K+. Introducing more strongly bound adducts increases fragmentation. During ECD, however, the silver cation is lost most easily compared with the other alkali metal ions, but silver also shows a dominant role in producing fragmentations. Moreover, the charge carriers are lost in an order (Ag+ ˃ Na+ ˃ K+ ≥ Li+ where the loss of Ag is most easily) that appears to correlate with the standard reduction potential of the metallic ions (Ag+ ˃ Na+ ˃ K+ ˃ Li+). The ECD results suggest that the reduction potential of the charge carrier could be an important factor influencing the fragmentation, where the ion with a high reduction potential is more effective in capturing electrons, but may also be lost easily before leading to any fragmentation. Finally, a proton has the weakest binding with the TPGS according to the CAD results, and its dissociation in ECD follows the order of the reduction potential (Ag+ ˃ H+ ˃ Na+ ˃ K+ > Li+).

Real-Space Multiple-Scattering Theory and Its Applications at Exascale

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

Eisenbach, Markus; Wang, Yang

In recent decades, the ab initio methods based on density functional theory (DFT) (Hohenberg and Kohn 1964, Kohn and Sham 1965) have become a widely used tool in computational materials science, which allows theoretical prediction of physical properties of materials from the first principles and theoretical interpretation of new physical phenomena found in experiments. In the framework of DFT, the original problem that requires solving a quantum mechanical equation for a many-electron system is reduced to a one-electron problem that involves an electron moving in an effective field, while the effective field potential is made up of an electrostatic potential,more » also known as Hartree potential, arising from the electronic and ion charge distribution in space and an exchange–correlation potential, which is a function of the electron density and encapsulates the exchange and correlation effects of the many-electron system. Even though the exact functional form of the exchange-correlation potential is formally unknown, a local density approximation (LDA) or a generalized gradient approximation (GGA) is usually applied so that the calculation of the exchange–correlation potential, as well as the exchange–correlation energy, becomes tractable while a required accuracy is retained. Based on DFT, ab initio electronic structure calculations for a material generally involve a self-consistent process that iterates between two computational tasks: (1) solving an one-electron Schrödinger equation, also known as Kohn–Sham equation, to obtain the electron density and, if needed, the magnetic moment density, and (2) solving the Poisson equation to obtain the electrostatic potential corresponding to the electron density and constructing the effective potential by adding the exchange–correlation potential to the electrostatic potential. This self-consistent process proceeds until a convergence criteria is reached.« less

Design of N-Coordinated Dual-Metal Sites: A Stable and Active Pt-Free Catalyst for Acidic Oxygen Reduction Reaction.

PubMed

Wang, Jing; Huang, Zhengqing; Liu, Wei; Chang, Chunran; Tang, Haolin; Li, Zhijun; Chen, Wenxing; Jia, Chunjiang; Yao, Tao; Wei, Shiqiang; Wu, Yuen; Li, Yadong

2017-12-06

We develop a host-guest strategy to construct an electrocatalyst with Fe-Co dual sites embedded on N-doped porous carbon and demonstrate its activity for oxygen reduction reaction in acidic electrolyte. Our catalyst exhibits superior oxygen reduction reaction performance, with comparable onset potential (E onset , 1.06 vs 1.03 V) and half-wave potential (E 1/2 , 0.863 vs 0.858 V) than commercial Pt/C. The fuel cell test reveals (Fe,Co)/N-C outperforms most reported Pt-free catalysts in H 2 /O 2 and H 2 /air. In addition, this cathode catalyst with dual metal sites is stable in a long-term operation with 50 000 cycles for electrode measurement and 100 h for H 2 /air single cell operation. Density functional theory calculations reveal the dual sites is favored for activation of O-O, crucial for four-electron oxygen reduction.

Direct observation of the oxygenated species during oxygen reduction on a platinum fuel cell cathode

NASA Astrophysics Data System (ADS)

Casalongue, Hernan Sanchez; Kaya, Sarp; Viswanathan, Venkatasubramanian; Miller, Daniel J.; Friebel, Daniel; Hansen, Heine A.; Nørskov, Jens K.; Nilsson, Anders; Ogasawara, Hirohito

2013-12-01

The performance of polymer electrolyte membrane fuel cells is limited by the reduction at the cathode of various oxygenated intermediates in the four-electron pathway of the oxygen reduction reaction. Here we use ambient pressure X-ray photoelectron spectroscopy, and directly probe the correlation between the adsorbed species on the surface and the electrochemical potential. We demonstrate that, during the oxygen reduction reaction, hydroxyl intermediates on the cathode surface occur in several configurations with significantly different structures and reactivities. In particular, we find that near the open-circuit potential, non-hydrated hydroxyl is the dominant surface species. On the basis of density functional theory calculations, we show that the removal of hydration enhances the reactivity of oxygen species. Tuning the hydration of hydroxyl near the triple phase boundary will be crucial for designing more active fuel cell cathodes.

Understanding of the mode of action of Fe(III)-EDDHA as iron chlorosis corrector based on its photochemical and redox behavior.

PubMed

Gómez-Gallego, Mar; Pellico, Daniel; Ramírez-López, Pedro; Mancheño, María J; Romano, Santiago; de la Torre, María C; Sierra, Miguel A

2005-10-07

The very low reduction potential of the chelate Fe(III)-EDDHA (EDDHA = ethylenediamine N,N'-bis(2-hydroxy)phenylacetic acid) makes it unreactive in photochemically or chemically induced electron transfer processes. The lack of reactivity of this complex toward light invalidates photodegradation as an alternative mechanism for environmental elimination. However, in spite of its low reduction potential, the biological reduction of Fe(III)-EDDHA is very effective. Based on electrochemical measurements, it is proposed that Fe(III)-EDDHA itself is not the substrate of the enzyme ferric chelate reductase. Likely, at the more acidic pH in the vicinity of the roots, the ferric chelate in a closed form (FeL-) could generate a vacant coordination site that leads to an open hexacoordinate species (FeHL) where the reduction of the metal by the enzyme takes place.

Preparation and magnetic properties of nickel nanowires by reduction in ethylene glycol medium under the influence of magnetic field

NASA Astrophysics Data System (ADS)

Sun, Wanshuo; Cheng, Junsheng; Li, Lankai; Chen, Shunzhong; Chang, Kun

2017-01-01

Nickel nanowires have successfully been fabricated through a simple liquid reduction in ethylene glycol medium with a 0.3T magnetic field applied. The effect of uniform magnetic field and solvent on the morphology and the crystal structure of magnetic nickel were studied. Scanning electron microscope images and transmission electron scope images s how that the effect of the external magnetic field on the morphology of nickel nanowires. X-ray diffraction shows the crystal structure of as-prepared products. And a energy disperse spectroscopy and a vibrating sample magnetometer are used to analyze the composition and static magnetic properties. The results show that the straight wires with an average diameter of about 100 nm and a length of several microns were obtained and mainly composed by fcc structure in the solvent of ethylene glycol. Magnetic measurements show that the saturation magnetization of the as-obtained products in a 0.3 T external magnetic field is 36 emu/g, less than that of bulk nickel crystal, and the coercivity of them is 186 emu/g, larger than that of bulk crystal with the mole ratio of sodium borohydride to nickel sulfate is 1:1000. This kind of nanowires array has potential applications with the special one-dimensional structures.

Opening the Market for Lower Cost Hearing Aids: Regulatory Change Can Improve the Health of Older Americans

PubMed Central

Weinstein, Barbara E.

2016-01-01

Hearing loss is a leading cause of disability among older people. Yet only one in seven US adults who could benefit from a hearing aid uses one. This fraction has not increased over the past 30 years, nor have hearing aid prices dropped, despite trends of steady improvements and price reductions in the consumer electronics industry. The President’s Council on Science and Technology has proposed changes in the regulation of hearing aids, including the creation of a “basic” low-cost over-the-counter category of devices. We discuss the potential to reduce disability as well as to improve public health, stakeholder responses to the president’s council’s proposal, and public health efforts to further mitigate the burden of disability stemming from age-related hearing loss. PMID:27077339

How oxygen reacts with oxygen-tolerant respiratory [NiFe]-hydrogenases.

PubMed

Wulff, Philip; Day, Christopher C; Sargent, Frank; Armstrong, Fraser A

2014-05-06

An oxygen-tolerant respiratory [NiFe]-hydrogenase is proven to be a four-electron hydrogen/oxygen oxidoreductase, catalyzing the reaction 2 H2 + O2 = 2 H2O, equivalent to hydrogen combustion, over a sustained period without inactivating. At least 86% of the H2O produced by Escherichia coli hydrogenase-1 exposed to a mixture of 90% H2 and 10% O2 is accounted for by a direct four-electron pathway, whereas up to 14% arises from slower side reactions proceeding via superoxide and hydrogen peroxide. The direct pathway is assigned to O2 reduction at the [NiFe] active site, whereas the side reactions are an unavoidable consequence of the presence of low-potential relay centers that release electrons derived from H2 oxidation. The oxidase activity is too slow to be useful in removing O2 from the bacterial periplasm; instead, the four-electron reduction of molecular oxygen to harmless water ensures that the active site survives to catalyze sustained hydrogen oxidation.

How oxygen reacts with oxygen-tolerant respiratory [NiFe]-hydrogenases

PubMed Central

Wulff, Philip; Day, Christopher C.; Sargent, Frank; Armstrong, Fraser A.

2014-01-01

An oxygen-tolerant respiratory [NiFe]-hydrogenase is proven to be a four-electron hydrogen/oxygen oxidoreductase, catalyzing the reaction 2 H2 + O2 = 2 H2O, equivalent to hydrogen combustion, over a sustained period without inactivating. At least 86% of the H2O produced by Escherichia coli hydrogenase-1 exposed to a mixture of 90% H2 and 10% O2 is accounted for by a direct four-electron pathway, whereas up to 14% arises from slower side reactions proceeding via superoxide and hydrogen peroxide. The direct pathway is assigned to O2 reduction at the [NiFe] active site, whereas the side reactions are an unavoidable consequence of the presence of low-potential relay centers that release electrons derived from H2 oxidation. The oxidase activity is too slow to be useful in removing O2 from the bacterial periplasm; instead, the four-electron reduction of molecular oxygen to harmless water ensures that the active site survives to catalyze sustained hydrogen oxidation. PMID:24715724

Giant onsite electronic entropy enhances the performance of ceria for water splitting

DOE PAGES

Naghavi, S. Shahab; Emery, Antoine A.; Hansen, Heine A.; ...

2017-08-18

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Cemore » 4+/Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.« less

Bioreduction of para-chloronitrobenzene in a hydrogen-based hollow-fiber membrane biofilm reactor: effects of nitrate and sulfate.

PubMed

Li, Haixiang; Zhang, Zhiqiang; Xu, Xiaoyin; Liang, Jun; Xia, Siqing

2014-04-01

A continuous-stirred, hydrogen-based, hollow-fiber membrane biofilm reactor (HFMBfR) that was active in nitrate and sulfate reductions was shown to be effective for degradation or detoxification of para-chloronitrobenzene (p-CNB) in water by biotransforming it first to para-chloroaniline (nitro-reduction) and then to aniline (reductive dechlorination) with hydrogen (H2) as an electron donor. A series of short-term experiments examined the effects of nitrate and sulfate on p-CNB bioreduction. The results obtained showed both higher nitrate and sulfate concentration declined the p-CNB bioreduction in the biofilm, and this suggests the competition for H2 caused less H2 available for the p-CNB bioreduction when the H2 demand for the reductions was larger. Denitrification and sulfate reduction intermediates were thought to be potential factors inhibiting the p-CNB bioreduction. Analysis of electron-equivalent fluxes and reaction orders in the biofilm further demonstrated both denitrification and sulfate reduction competed more strongly for H2 availability than p-CNB bioreduction. These findings have significant implications for the HFMBfR used for degrading p-CNB under denitrifying and/or sulfate reducing conditions.

Electron Flow in Multiheme Bacterial Cytochromes is a Balancing Act Between Heme Electronic Interaction and Redox Potentials

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

Breuer, Marian; Rosso, Kevin M.; Blumberger, Jochen

The naturally widespread process of electron transfer from metal reducing bacteria to extracellular solid metal oxides entails unique biomolecular machinery optimized for long-range electron transport. To perform this function efficiently microorganisms have adapted multi-heme c-type cytochromes to arrange heme cofactors into wires that cooperatively span the cellular envelope, transmitting electrons along distances greater than 100 Angstroms. Implications and opportunities for bionanotechnological device design are self-evident. However, at the molecular level how these proteins shuttle electrons along their heme wires, navigating intraprotein intersections and interprotein interfaces effciently, remains a mystery so far inaccessible to experiment. To shed light on this criticalmore » topic, we carried out extensive computer simulations to calculate Marcus theory quantities for electron transfer along the ten heme cofactors in the recently crystallized outer membrane cytochrome MtrF. The combination of electronic coupling matrix elements with free energy calculations of heme redox potentials and reorganization energies for heme-to-heme electron transfer allows the step-wise and overall electron transfer rate to be estimated and understood in terms of structural and dynamical characteristics of the protein. By solving a master equation for electron hopping, we estimate an intrinsic, maximum possible electron flux through solvated MtrF of 104-105 s-1, consistent with recently measured rates for the related MtrCAB protein complex. Intriguingly, this flux must navigate thermodynamically uphill steps past low potential hemes. Our calculations show that the rapid electron transport through MtrF is the result of a clear correlation between heme redox potential and the strength of electronic coupling along the wire: Thermodynamically uphill steps occur only between electronically well connected stacked heme pairs. This suggests that the protein evolved to harbor low potential hemes, presumably necessary for reduction of certain soluble substrates, without slowing down electron ow. These findings are particularly profound in light of the apparently well conserved staggered cross heme wire structural motif in functionally related outer-membrane proteins.« less

Magnetic order and electronic structure of 5d 3 double perovskite Sr 2ScOsO 6

DOE PAGES

Taylor, A. E.; Morrow, R.; Singh, D. J.; ...

2015-03-01

The magnetic susceptibility, crystal and magnetic structures, and electronic structure of double perovskite Sr 2ScOsO 6 are reported. Using both neutron and x-ray powder diffraction we find that the crystal structure is monoclinic P21/n from 3.5 to 300 K. Magnetization measurements indicate an antiferromagnetic transition at TN=92 K, one of the highest transition temperatures of any double perovskite hosting only one magnetic ion. Type I antiferromagnetic order is determined by neutron powder diffraction, with an Os moment of only 1.6(1) muB, close to half the spin-only value for a crystal field split 5d electron state with t2g^3 ground state. Densitymore » functional calculations show that this reduction is largely the result of strong Os-O hybridization, with spin-orbit coupling responsible for only a ~0.1 muB reduction in the moment.« less

Investigation of the reduction process of dopamine using paired pulse voltammetry

PubMed Central

Kim, Do Hyoung; Oh, Yoonbae; Shin, Hojin; Blaha, Charles D.; Bennet, Kevin E.; Lee, Kendall H.; Kim, In Young; Jang, Dong Pyo

2014-01-01

The oxidation of dopamine (DA) around +0.6V potential in anodic sweep and its reduction around −0.1V in cathodic sweep at a relatively fast scanning rate (300 V/s or greater) have been used for identification of DA oxidation in fast-scan cyclic voltammetry (FSCV). However, compared to the oxidation peak of DA, the reduction peak has not been fully examined in analytical studies, although it has been used as one of the representative features to identify DA. In this study, the reduction process of DA was investigated using paired pulse voltammetry (PPV), which consists of two identical triangle-shaped waveforms, separated by a short interval at the holding potential. Especially, the discrepancies between the magnitude of the oxidation and reduction peaks of DA were investigated based on three factors: (1) the instant desorption of the DA oxidation product (dopamine-o-quinone: DOQ) after production, (2) the effect of the holding potential on the reduction process, and (3) the rate-limited reduction process of DA. For the first test, the triangle waveform FSCV experiment was performed on DA with various scanrates (from 400 to 1000 V/s) and durations of switching potentials of the triangle waveform (from 0.0 to 6.0 ms) in order to vary the duration between the applied oxidation potential at +0.6V and the reduction potential at −0.2V. As a result, the ratio of reduction over oxidation peak current response decreased as the duration became longer. To evaluate the effect of holding potentials during the reduction process, FSCV experiments were conducted with holding potential from 0.0V to −0.8V. We found that more negative holding potentials lead to larger amount of reduction process. For evaluation of the rate-limited reduction process of DA, PPV with a 1Hz repetition rate and various delays (2, 8, 20, 40 and 80ms) between the paired scans were utilized to determine how much reduction process occurred during the holding potential (−0.4V). These tests showed that relatively large amounts of DOQ are reduced to DA during the holding potential. The rate-limited reduction process was also confirmed with the increase of reduction in a lower pH environment. In addition to the mechanism of the reduction process of DA, we found that the differences between the responses of primary and secondary pulses in PPV were mainly dependent on the rate-limited reduction process during the holding potential. In conclusion, the reduction process may be one of the important factors to be considered in the kinetic analysis of DA and other electroactive species in brain tissue and in the design of new types of waveform in FSCV. PMID:24926227

Equilibrium and ultrafast kinetic studies manipulating electron transfer: A short-lived flavin semiquinone is not sufficient for electron bifurcation

DOE PAGES

Hoben, John P.; Lubner, Carolyn E.; Ratzloff, Michael W.; ...

2017-06-14

Flavin-based electron transfer bifurcation is emerging as a fundamental and powerful mechanism for conservation and deployment of electrochemical energy in enzymatic systems. In this process, a pair of electrons is acquired at intermediate reduction potential (i.e. intermediate reducing power) and each electron is passed to a different acceptor, one with lower and the other with higher reducing power, leading to 'bifurcation'. It is believed that a strongly reducing semiquinone species is essential for this process, and it is expected that this species should be kinetically short-lived. We now demonstrate that presence of a short-lived anionic flavin semiquinone (ASQ) is notmore » sufficient to infer existence of bifurcating activity, although such a species may be necessary for the process. We have used transient absorption spectroscopy to compare the rates and mechanisms of decay of ASQ generated photochemically in bifurcating NADH-dependent ferredoxin-NADP + oxidoreductase and the non-bifurcating flavoproteins nitroreductase, NADH oxidase and flavodoxin. We found that different mechanisms dominate ASQ decay in the different protein environments, producing lifetimes ranging over two orders of magnitude. Capacity for electron transfer among redox cofactors vs. charge recombination with nearby donors can explain the range of ASQ lifetimes we observe. In conclusion, our results support a model wherein efficient electron propagation can explain the short lifetime of the ASQ of bifurcating NADH-dependent ferredoxin-NADP + oxidoreductase I, and can be an indication of capacity for electron bifurcation.« less

Equilibrium and ultrafast kinetic studies manipulating electron transfer: A short-lived flavin semiquinone is not sufficient for electron bifurcation

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

Hoben, John P.; Lubner, Carolyn E.; Ratzloff, Michael W.

Flavin-based electron transfer bifurcation is emerging as a fundamental and powerful mechanism for conservation and deployment of electrochemical energy in enzymatic systems. In this process, a pair of electrons is acquired at intermediate reduction potential (i.e. intermediate reducing power) and each electron is passed to a different acceptor, one with lower and the other with higher reducing power, leading to 'bifurcation'. It is believed that a strongly reducing semiquinone species is essential for this process, and it is expected that this species should be kinetically short-lived. We now demonstrate that presence of a short-lived anionic flavin semiquinone (ASQ) is notmore » sufficient to infer existence of bifurcating activity, although such a species may be necessary for the process. We have used transient absorption spectroscopy to compare the rates and mechanisms of decay of ASQ generated photochemically in bifurcating NADH-dependent ferredoxin-NADP + oxidoreductase and the non-bifurcating flavoproteins nitroreductase, NADH oxidase and flavodoxin. We found that different mechanisms dominate ASQ decay in the different protein environments, producing lifetimes ranging over two orders of magnitude. Capacity for electron transfer among redox cofactors vs. charge recombination with nearby donors can explain the range of ASQ lifetimes we observe. In conclusion, our results support a model wherein efficient electron propagation can explain the short lifetime of the ASQ of bifurcating NADH-dependent ferredoxin-NADP + oxidoreductase I, and can be an indication of capacity for electron bifurcation.« less

Equilibrium and ultrafast kinetic studies manipulating electron transfer: A short-lived flavin semiquinone is not sufficient for electron bifurcation.

PubMed

Hoben, John P; Lubner, Carolyn E; Ratzloff, Michael W; Schut, Gerrit J; Nguyen, Diep M N; Hempel, Karl W; Adams, Michael W W; King, Paul W; Miller, Anne-Frances

2017-08-25

Flavin-based electron transfer bifurcation is emerging as a fundamental and powerful mechanism for conservation and deployment of electrochemical energy in enzymatic systems. In this process, a pair of electrons is acquired at intermediate reduction potential ( i.e. intermediate reducing power), and each electron is passed to a different acceptor, one with lower and the other with higher reducing power, leading to "bifurcation." It is believed that a strongly reducing semiquinone species is essential for this process, and it is expected that this species should be kinetically short-lived. We now demonstrate that the presence of a short-lived anionic flavin semiquinone (ASQ) is not sufficient to infer the existence of bifurcating activity, although such a species may be necessary for the process. We have used transient absorption spectroscopy to compare the rates and mechanisms of decay of ASQ generated photochemically in bifurcating NADH-dependent ferredoxin-NADP + oxidoreductase and the non-bifurcating flavoproteins nitroreductase, NADH oxidase, and flavodoxin. We found that different mechanisms dominate ASQ decay in the different protein environments, producing lifetimes ranging over 2 orders of magnitude. Capacity for electron transfer among redox cofactors versus charge recombination with nearby donors can explain the range of ASQ lifetimes that we observe. Our results support a model wherein efficient electron propagation can explain the short lifetime of the ASQ of bifurcating NADH-dependent ferredoxin-NADP + oxidoreductase I and can be an indication of capacity for electron bifurcation.

Effects of oxidants and reductants on the efficiency of excitation transfer in green photosynthetic bacteria

NASA Technical Reports Server (NTRS)

Wang, J.; Brune, D. C.; Blankenship, R. E.

1990-01-01

The efficiency of energy transfer in chlorosome antennas in the green sulfur bacteria Chlorobium vibrioforme and Chlorobium limicola was found to be highly sensitive to the redox potential of the suspension. Energy transfer efficiencies were measured by comparing the absorption spectrum of the bacteriochlorophyll c or d pigments in the chlorosome to the excitation spectrum for fluorescence arising from the chlorosome baseplate and membrane-bound antenna complexes. The efficiency of energy transfer approaches 100% at low redox potentials induced by addition of sodium dithionite or other strong reductants, and is lowered to 10-20% under aerobic conditions or after addition of a variety of membrane-permeable oxidizing agents. The redox effect on energy transfer is observed in whole cells, isolated membranes and purified chlorosomes, indicating that the modulation of energy transfer efficiency arises within the antenna complexes and is not directly mediated by the redox state of the reaction center. It is proposed that chlorosomes contain a component that acts as a highly quenching center in its oxidized state, but is an inefficient quencher when reduced by endogenous or exogenous reductants. This effect may be a control mechanism that prevents cellular damage resulting from reaction of oxygen with reduced low-potential electron acceptors found in the green sulfur bacteria. The redox modulation effect is not observed in the green gliding bacterium Chloroflexus aurantiacus, which contains chlorosomes but does not contain low-potential electron acceptors.

Shewanella oneidensis cytochrome c nitrite reductase (ccNiR) does not disproportionate hydroxylamine to ammonia and nitrite, despite a strongly favorable driving force.

PubMed

Youngblut, Matthew; Pauly, Daniel J; Stein, Natalia; Walters, Daniel; Conrad, John A; Moran, Graham R; Bennett, Brian; Pacheco, A Andrew

2014-04-08

Cytochrome c nitrite reductase (ccNiR) from Shewanella oneidensis, which catalyzes the six-electron reduction of nitrite to ammonia in vivo, was shown to oxidize hydroxylamine in the presence of large quantities of this substrate, yielding nitrite as the sole free nitrogenous product. UV-visible stopped-flow and rapid-freeze-quench electron paramagnetic resonance data, along with product analysis, showed that the equilibrium between hydroxylamine and nitrite is fairly rapidly established in the presence of high initial concentrations of hydroxylamine, despite said equilibrium lying far to the left. By contrast, reduction of hydroxylamine to ammonia did not occur, even though disproportionation of hydroxylamine to yield both nitrite and ammonia is strongly thermodynamically favored. This suggests a kinetic barrier to the ccNiR-catalyzed reduction of hydroxylamine to ammonia. A mechanism for hydroxylamine reduction is proposed in which the hydroxide group is first protonated and released as water, leaving what is formally an NH2(+) moiety bound at the heme active site. This species could be a metastable intermediate or a transition state but in either case would exist only if it were stabilized by the donation of electrons from the ccNiR heme pool into the empty nitrogen p orbital. In this scenario, ccNiR does not catalyze disproportionation because the electron-donating hydroxylamine does not poise the enzyme at a sufficiently low potential to stabilize the putative dehydrated hydroxylamine; presumably, a stronger reductant is required for this.

Red blood cells donate electrons to methylene blue mediated chemical reduction of methemoglobin compartmentalized in liposomes in blood.

PubMed

Sakai, Hiromi; Li, Bing; Lim, Wei Lee; Iga, Yumika

2014-07-16

Electron-energy-rich coenzymes in cells, NADH and NADPH, are re-energized repeatedly through the Embden-Meyerhof and pentose-phosphate glycolytic pathways, respectively. This study demonstrates extraction of their electron energies in red blood cells (RBCs) for in vivo extracellular chemical reactions using an electron mediator shuttling across the biomembrane. Hemoglobin-vesicles (HbVs) are an artificial oxygen carrier encapsulating purified and concentrated Hb solution in liposomes. Because of the absence of a metHb-reducing enzymatic system in HbV, HbO2 gradually autoxidizes to form metHb. Wistar rats received HbV suspension (10 mL/kg body weight) intravenously. At the metHb level of around 50%, methylene blue [MB(+); 3,7-bis(dimethylamino)phenothiazinium chloride] was injected. The level of metHb quickly decreased to around 16% in 40 min, remaining for more than 5 h. In vitro mixing of HbV/MB(+) with RBCs recreated the in vivo metHb reduction, but not with plasma. NAD(P)H levels in RBCs decreased after metHb reduction. The addition of glucose facilitated metHb reduction. Liposome-encapsulated NAD(P)H, a model of RBC, reduced metHb in HbV in the presence of MB(+). These results indicate that (i) NAD(P)H in RBCs reacts with MB(+) to convert it to leukomethylene blue (MBH); (ii) MB(+) and MBH shuttle freely between RBC and HbV across the hydrophobic lipid membranes; and (iii) MBH is transferred into HbV and reduces metHb in HbV. Four other electron mediators with appropriate redox potentials appeared to be as effective as MB(+) was, indicating the possibility for further optimization of electron mediators. We established an indirect enzymatic metHb reducing system for HbV using unlimited endogenous electrons created in RBCs in combination with an effective electron mediator that prolongs the functional lifespan of HbV in blood circulation.

Cytochromes and iron sulfur proteins in sulfur metabolism of phototrophic bacteria

NASA Technical Reports Server (NTRS)

Fischer, U.

1985-01-01

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

Anaerobic oxidation of toluene, phenol, and p-cresol by the dissimilatory iron-reducing organism, GS-15

USGS Publications Warehouse

Lovley, D.R.; Lonergan, D.J.

1990-01-01

The dissimilatory Fe(III) reducer, GS-15, is the first microorganism known to couple the oxidation of aromatic compounds to the reduction of Fe(III) and the first example of a pure culture of any kind known to anaerobically oxidize an aromatic hydrocarbon, toluene. In this study, the metabolism of toluene, phenol, and p-cresol by GS-15 was investigated in more detail. GS-15 grew in an anaerobic medium with toluene as the sole electron donor and Fe(III) oxide as the electron acceptor. Growth coincided with Fe(III) reduction. [ring-14C]toluene was oxidized to 14CO2, and the stoichiometry of 14CO2 production and Fe(III) reduction indicated that GS-15 completely oxidized toluene to carbon dioxide with Fe(III) as the electron acceptor. Magnetite was the primary iron end product during toluene oxidation. Phenol and p-cresol were also completely oxidized to carbon dioxide with Fe(III) as the sole electron acceptor, and GS-15 could obtain energy to support growth by oxidizing either of these compounds as the sole electron donor. p-Hydroxybenzoate was a transitory extracellular intermediate of phenol and p-cresol metabolism but not of toluene metabolism. GS-15 oxidized potential aromatic intermediates in the oxidation of toluene (benzylalcohol and benzaldehyde) and p-cresol (p-hydroxybenzylalcohol and p-hydroxybenzaldehyde). The metabolism described here provides a model for how aromatic hydrocarbons and phenols may be oxidized with the reduction of Fe(III) in contaminated aquifers and petroleum-containing sediments.

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

Joel E. Kostka

This project represented a joint effort between Oak Ridge National Laboratory (ORNL), the University of Tennessee (UT), and Florida State University (FSU). ORNL served as the lead in-stitution with Dr. A.V. Palumbo responsible for project coordination, integration, and deliver-ables. In situ uranium bioremediation is focused on biostimulating indigenous microorganisms through a combination of pH neutralization and the addition of large amounts of electron donor. Successful biostimulation of U(VI) reduction has been demonstrated in the field and in the laboratory. However, little data is available on the dynamics of microbial populations capable of U(VI) reduction, and the differences in the microbialmore » community dynamics between proposed electron donors have not been explored. In order to elucidate the potential mechanisms of U(VI) reduction for optimization of bioremediation strategies, structure-function relationships of microbial populations were investigated in microcosms of subsurface materials cocontaminated with radionuclides and nitrate from the Oak Ridge Field Research Center (ORFRC), Oak Ridge, Tennessee.« less

Electronic field emission models beyond the Fowler-Nordheim one

NASA Astrophysics Data System (ADS)

Lepetit, Bruno

2017-12-01

We propose several quantum mechanical models to describe electronic field emission from first principles. These models allow us to correlate quantitatively the electronic emission current with the electrode surface details at the atomic scale. They all rely on electronic potential energy surfaces obtained from three dimensional density functional theory calculations. They differ by the various quantum mechanical methods (exact or perturbative, time dependent or time independent), which are used to describe tunneling through the electronic potential energy barrier. Comparison of these models between them and with the standard Fowler-Nordheim one in the context of one dimensional tunneling allows us to assess the impact on the accuracy of the computed current of the approximations made in each model. Among these methods, the time dependent perturbative one provides a well-balanced trade-off between accuracy and computational cost.

On the Significance of a Carbon-Rich Background in Plasma-Based Graphene Oxide Reduction

DTIC Science & Technology

2016-06-02

can lead to the formation of defects and vacancies. We find that methane provides not only hydrogen but also the carbon necessary to restore the...Graphene oxide Reduction Plasma Argon Hydrogen Methane Office of Naval Research One Liberty Center 875 North Randolph Street, Suite 1425 Arlington, VA...electron-beam generated plasmas produced in argon/ methane (Ar/CH4) backgrounds. However, unlike other reduction approaches [14] the process was found to

Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals in aqueous solutions; electron transfer and proton-coupled electron transfer mechanisms

NASA Astrophysics Data System (ADS)

Matasović, Brunislav; Bonifačić, Marija

2011-06-01

Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals CO2-rad , rad CH 2OH, rad CH(CH 3)OH, and rad CH(CH 3)O - have been studied in oxygen free aqueous solutions in the presence of organic additives: formate, methanol or ethanol. For radicals production 60Co γ-radiolysis was employed and the yield of bromide was measured by means of ion chromatography. Both radical anions have reducing potential negative enough to transfer an electron to BrU producing bromide ion and U rad radical. High yields of bromide have been measured increasing proportional to the concentration of the corresponding organic additives at a constant dose rate. This is characteristic for a chain process where regeneration of radical ions occurs by H-atom abstraction by U rad radical from formate or ethanol. Results with the neutral radicals conformed earlier proposition that the reduction reaction of α-hydroxyalkyl radicals proceeds by the proton-coupled electron transfer mechanism ( Matasović and Bonifačić, 2007). Thus, while both rad CH 2OH and rad CH(CH 3)OH did not react with BrU in water/alcohol solutions, addition of bicarbonate and acetate in mmol dm -3 concentrations, pH 7, brought about chain debromination to occur in the case of rad CH(CH 3)OH radical as reactant. Under the same conditions phosphate buffer, a base with higher bulk proton affinity, failed to have any influence. The results are taken as additional proofs for the specific complex formation of α-hydroxyalkyl radicals with suitable bases which enhances radicals' reduction potential in comparison with only water molecules as proton acceptors. Rate constants for the H-atom abstraction from ethanol and formate by U rad radicals have been estimated to amount to about ≥85 and 1200 dm 3 mol -1 s -1, respectively.

Biodegradation of Polychlorinated Methanes in Methanogenic Systems

DTIC Science & Technology

1991-01-01

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

Electron capture and excitation processes in H+-H collisions in dense quantum plasmas

NASA Astrophysics Data System (ADS)

Jakimovski, D.; Markovska, N.; Janev, R. K.

2016-10-01

Electron capture and excitation processes in proton-hydrogen atom collisions taking place in dense quantum plasmas are studied by employing the two-centre atomic orbital close-coupling (TC-AOCC) method. The Debye-Hückel cosine (DHC) potential is used to describe the plasma screening effects on the Coulomb interaction between charged particles. The properties of a hydrogen atom with DHC potential are investigated as a function of the screening strength of the potential. It is found that the decrease in binding energy of nl levels with increasing screening strength is considerably faster than in the case of the Debye-Hückel (DH) screening potential, appropriate for description of charged particle interactions in weakly coupled classical plasmas. This results in a reduction in the number of bound states in the DHC potential with respect to that in the DH potential for the same plasma screening strength, and is reflected in the dynamics of excitation and electron capture processes for the two screened potentials. The TC-AOCC cross sections for total and state-selective electron capture and excitation cross sections with the DHC potential are calculated for a number of representative screening strengths in the 1-300 keV energy range and compared with those for the DH and pure Coulomb potential. The total capture cross sections for a selected number of screening strengths are compared with the available results from classical trajectory Monte Carlo calculations.

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.

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

Naghavi, S. Shahab; Emery, Antoine A.; Hansen, Heine A.

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Cemore » 4+/Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.« less

Tuning high-harmonic generation by controlled deposition of ultrathin ionic layers on metal surfaces

NASA Astrophysics Data System (ADS)

Aguirre, Néstor F.; Martín, Fernando

2016-12-01

High-harmonic generation (HHG) from semiconductors and insulators has become a very active area of research due to its great potential for developing compact HHG devices. Here we show, that by growing monolayers (ML) of insulators on single-crystal metal surfaces, one can tune the harmonic spectrum by just varying the thickness of the ultrathin layer, rather than the laser properties. This is shown from numerical solutions of the time-dependent Schrödinger equation for Cu(111)/n -ML NaCl systems (n =1 -50 ) based on realistic potentials. Remarkably, the harmonic cutoff increases linearly with n and as much as an order of magnitude when going from n =1 to 30, while keeping the laser intensity low and the wavelength in the near-infrared range. The origin of this behavior is twofold: the initial localization of electrons in a Cu-surface state and the reduction of electronic "friction" when moving from the essentially discrete energy spectrum associated with a few-ML system to the continuous spectrum (bands) inherent in extended periodic systems. Our findings are valid for both few- and multicycle IR pulses and wavelengths ˜1 -2 μ m .

Organic electronic devices using phthalimide compounds

DOEpatents

Hassan, Azad M.; Thompson, Mark E.

2010-09-07

Organic electronic devices comprising a phthalimide compound. The phthalimide compounds disclosed herein are electron transporters with large HOMO-LUMO gaps, high triplet energies, large reduction potentials, and/or thermal and chemical stability. As such, these phthalimide compounds are suitable for use in any of various organic electronic devices, such as OLEDs and solar cells. In an OLED, the phthalimide compounds may serve various functions, such as a host in the emissive layer, as a hole blocking material, or as an electron transport material. In a solar cell, the phthalimide compounds may serve various functions, such as an exciton blocking material. Various examples of phthalimide compounds which may be suitable for use in the present invention are disclosed.

Organic electronic devices using phthalimide compounds

DOEpatents

Hassan, Azad M.; Thompson, Mark E.

2012-10-23

Organic electronic devices comprising a phthalimide compound. The phthalimide compounds disclosed herein are electron transporters with large HOMO-LUMO gaps, high triplet energies, large reduction potentials, and/or thermal and chemical stability. As such, these phthalimide compounds are suitable for use in any of various organic electronic devices, such as OLEDs and solar cells. In an OLED, the phthalimide compounds may serve various functions, such as a host in the emissive layer, as a hole blocking material, or as an electron transport material. In a solar cell, the phthalimide compounds may serve various functions, such as an exciton blocking material. Various examples of phthalimide compounds which may be suitable for use in the present invention are disclosed.

Organic electronic devices using phthalimide compounds

DOEpatents

Hassan, Azad M.; Thompson, Mark E.

2013-03-19

Organic electronic devices comprising a phthalimide compound. The phthalimide compounds disclosed herein are electron transporters with large HOMO-LUMO gaps, high triplet energies, large reduction potentials, and/or thermal and chemical stability. As such, these phthalimide compounds are suitable for use in any of various organic electronic devices, such as OLEDs and solar cells. In an OLED, the phthalimide compounds may serve various functions, such as a host in the emissive layer, as a hole blocking material, or as an electron transport material. In a solar cell, the phthalimide compounds may serve various functions, such as an exciton blocking material. Various examples of phthalimide compounds which may be suitable for use in the present invention are disclosed.

Theranostic reduction-sensitive gemcitabine prodrug micelles for near-infrared imaging and pancreatic cancer therapy

NASA Astrophysics Data System (ADS)

Han, Haijie; Wang, Haibo; Chen, Yangjun; Li, Zuhong; Wang, Yin; Jin, Qiao; Ji, Jian

2015-12-01

A biodegradable and reduction-cleavable gemcitabine (GEM) polymeric prodrug with in vivo near-infrared (NIR) imaging ability was reported. This theranostic GEM prodrug PEG-b-[PLA-co-PMAC-graft-(IR820-co-GEM)] was synthesized by ring-opening polymerization and ``click'' reaction. The as-prepared reduction-sensitive prodrug could self-assemble into prodrug micelles in aqueous solution confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). In vitro drug release studies showed that these prodrug micelles were able to release GEM in an intracellular-mimicking reductive environment. These prodrug micelles could be effectively internalized by BxPC-3 pancreatic cancer cells, which were observed by confocal laser scanning microscopy (CLSM). Meanwhile, a methyl thiazolyl tetrazolium (MTT) assay demonstrated that this prodrug exhibited high cytotoxicity against BxPC-3 cells. The in vivo whole-animal near-infrared (NIR) imaging results showed that these prodrug micelles could be effectively accumulated in tumor tissue and had a longer blood circulation time than IR820-COOH. The endogenous reduction-sensitive gemcitabine prodrug micelles with the in vivo NIR imaging ability might have great potential in image-guided pancreatic cancer therapy.A biodegradable and reduction-cleavable gemcitabine (GEM) polymeric prodrug with in vivo near-infrared (NIR) imaging ability was reported. This theranostic GEM prodrug PEG-b-[PLA-co-PMAC-graft-(IR820-co-GEM)] was synthesized by ring-opening polymerization and ``click'' reaction. The as-prepared reduction-sensitive prodrug could self-assemble into prodrug micelles in aqueous solution confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). In vitro drug release studies showed that these prodrug micelles were able to release GEM in an intracellular-mimicking reductive environment. These prodrug micelles could be effectively internalized by BxPC-3 pancreatic cancer cells, which were observed by confocal laser scanning microscopy (CLSM). Meanwhile, a methyl thiazolyl tetrazolium (MTT) assay demonstrated that this prodrug exhibited high cytotoxicity against BxPC-3 cells. The in vivo whole-animal near-infrared (NIR) imaging results showed that these prodrug micelles could be effectively accumulated in tumor tissue and had a longer blood circulation time than IR820-COOH. The endogenous reduction-sensitive gemcitabine prodrug micelles with the in vivo NIR imaging ability might have great potential in image-guided pancreatic cancer therapy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06734k

Influence of Reactive Transport on the Reduction of U(VI) in the Presence of Fe(III) and Nitrate: Implications for U(VI) Immobilization by Bioremediation / Biobarriers- Final Report

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

B.D. Wood

2007-01-01

Subsurface contamination by metals and radionuclides represent some of the most challenging remediation problems confronting the Department of Energy (DOE) complex. In situ remediation of these contaminants by dissimilatory metal reducing bacteria (DMRB) has been proposed as a potential cost effective remediation strategy. The primary focus of this research is to determine the mechanisms by which the fluxes of electron acceptors, electron donors, and other species can be controlled to maximize the transfer of reductive equivalents to the aqueous and solid phases. The proposed research is unique in the NABIR portfolio in that it focuses on (i) the role ofmore » flow and transport in the initiation of biostimulation and the successful sequestration of metals and radionuclides [specifically U(VI)], (ii) the subsequent reductive capacity and stability of the reduced sediments produced by the biostimulation process, and (iii) the potential for altering the growth of biomass in the subsurface by the addition of specific metabolic uncoupling compounds. A scientifically-based understanding of these phenomena are critical to the ability to design successful bioremediation schemes. The laboratory research will employ Shewanella putrefaciens (CN32), a facultative DMRB that can use Fe(III) oxides as a terminal electron acceptor. Sediment-packed columns will be inoculated with this organism, and the reduction of U(VI) by the DMRB will be stimulated by the addition of a carbon and energy source in the presence of Fe(III). Separate column experiments will be conducted to independently examine: (1) the importance of the abiotic reduction of U(VI) by biogenic Fe(II); (2) the influence of the transport process on Fe(III) reduction and U(VI) immobilization, with emphasis on methods for controlling the fluxes of aqueous species to maximize uranium reduction; (3) the reductive capacity of biologically-reduced sediments (with respect to re-oxidation by convective fluxes of O2 and NO3-) and the long-term stability of immobilized uranium mineral phases after bioremediation processes are complete, and (4) the ability for metabolic uncoupling compounds to maintain microbial growth while limiting biomass production. The results of the laboratory experiments will be used to develop mathematical descriptive models for the coupled transport and reduction processes.« less

Reverse electron transport effects on NADH formation and metmyoglobin reduction.

PubMed

Belskie, K M; Van Buiten, C B; Ramanathan, R; Mancini, R A

2015-07-01

The objective was to determine if NADH generated via reverse electron flow in beef mitochondria can be used for electron transport-mediated reduction and metmyoglobin reductase pathways. Beef mitochondria were isolated from bovine hearts (n=5) and reacted with combinations of succinate, NAD, and mitochondrial inhibitors to measure oxygen consumption and NADH formation. Mitochondria and metmyoglobin were reacted with succinate, NAD, and mitochondrial inhibitors to measure electron transport-mediated metmyoglobin reduction and metmyoglobin reductase activity. Addition of succinate and NAD increased oxygen consumption, NADH formation, electron transport-mediated metmyoglobin reduction, and reductase activity (p<0.05). Addition of antimycin A prevented electron flow beyond complex III, therefore, decreasing oxygen consumption and electron transport-mediated metmyoglobin reduction. Addition of rotenone prevented reverse electron flow, increased oxygen consumption, increased electron transport-mediated metmyoglobin reduction, and decreased NADH formation. Succinate and NAD can generate NADH in bovine tissue postmortem via reverse electron flow and this NADH can be used by both electron transport-mediated and metmyoglobin reductase pathways. Copyright © 2015 Elsevier Ltd. All rights reserved.

Solid state synthesis of starch-capped silver nanoparticles.

PubMed

Hebeish, A; Shaheen, Th I; El-Naggar, Mehrez E

2016-06-01

The present research addresses the establishment of a technique which is solely devoted to environmentally friendly one-pot green synthesis of dry highly stable powdered silver nanoparticles (AgNPs) using starch as both reductant and stabilizing agent in the presence of sodium hydroxide. It is believed that the sodium hydroxide can improve the reduction potential of starch. Thus when the alkali treated starch is submitted to addition of silver nitrate (AgNO3), the alkali treated starch induces the well-established dual role of starch; reduction of silver ions (Ag(+)) to AgNPs and capping the as-formed AgNPs to prevent them from further growth and agglomeration. Beside assessment of AgNPs formation, structural and morphological characteristics of AgNPs are investigated by making use of UV-vis spectroscopy, transmission electron microscopy (TEM), dynamic light scattering (DLS), zeta potential, FT-IR and X-ray diffraction (XRD) analysis. Research outputs signify (a) the absorbance around 410-420nm in the UV-vis spectra of AgNPs appears most, probably owing to the presence of nanosized silver particles and the intensity of this peak increases by increasing AgNO3 concentration; (b) that highly stable AgNPs with well-dispersed particle are successfully prepared using the present research-based innovation; (c) that the size of AgNPs does not exceed 30nm with sphere-like morphology even at the highest Ag(+) concentration employed during synthesis operation; (d) that the XRD and FT-IR confirm the successful preparation of pure AgNPs without noticeable impurities; (d) and that the one-pot synthesis of powdered AgNPs in large scale is clean and easily operated and easily transportation which may be applied as per demands of industries such as textile and painting industry. Copyright © 2016. Published by Elsevier B.V.

Electrodeposition of Zn and Cu-Zn alloy from ZnO/CuO precursors in deep eutectic solvent

NASA Astrophysics Data System (ADS)

Xie, Xueliang; Zou, Xingli; Lu, Xionggang; Lu, Changyuan; Cheng, Hongwei; Xu, Qian; Zhou, Zhongfu

2016-11-01

The electrodeposition of Zn and Cu-Zn alloy has been investigated in choline chloride (ChCl)/urea (1:2 molar ratio) based deep eutectic solvent (DES). Cyclic voltammetry study demonstrates that the reduction of Zn(II) to Zn is a diffusion-controlled quasi-reversible, one-step, two electrons transfer process. Chronoamperometric investigation indicates that the electrodeposition of Zn on a Cu electrode typically involves three-dimensional instantaneous nucleation with diffusion-controlled growth process. Micro/nanostructured Zn films can be obtained by controlling the electrodeposition potential and temperature. The electrodeposited Zn crystals preferentially orient parallel to the (101) plane. The Zn films electrodeposited under more positive potentials and low temperatures exhibit improved corrosion resistance in 3 wt% NaCl solution. In addition, Cu-Zn alloy films have also been electrodeposited directly from CuO-ZnO precursors in ChCl/urea-based DES. The XRD analysis indicates that the phase composition of the electrodeposited Cu-Zn alloy depends on the electrodeposition potential.

Enzyme electrokinetics: hydrogen evolution and oxidation by Allochromatium vinosum [NiFe]-hydrogenase.

PubMed

Léger, Christophe; Jones, Anne K; Roseboom, Winfried; Albracht, Simon P J; Armstrong, Fraser A

2002-12-31

The mechanism of catalytic hydrogen evolution and oxidation by Allochromatium vinosum [NiFe]-hydrogenase has been studied by protein film voltammetry (PFV) with the enzyme adsorbed at a pyrolytic graphite edge electrode. By analyzing the entire shapes of catalytic voltammograms, the energetics of the catalytic cycles (reduction potentials and acidity constants of the active states), including the detailed profiles of activity against pH and the sequences of proton and electron transfers, have been determined, and these are discussed with respect to the mechanism. PFV, which probes rates as a continuous function of the electrochemical potential (i.e., in the "potential domain"), is proven to be an invaluable tool for determining the redox properties of an active site in the presence of its substrate, at room temperature, and during turnover. This is especially relevant in the case of the active states of hydrogenase, since one of its substrates (the proton) is always present at significant levels in the titration medium at physiological pH values.

Reversible superconductor-insulator transition in LiTi2O4 induced by Li-ion electrochemical reaction

PubMed Central

Yoshimatsu, K.; Niwa, M.; Mashiko, H.; Oshima, T.; Ohtomo, A.

2015-01-01

Transition metal oxides display various electronic and magnetic phases such as high-temperature superconductivity. Controlling such exotic properties by applying an external field is one of the biggest continuous challenges in condensed matter physics. Here, we demonstrate clear superconductor-insulator transition of LiTi2O4 films induced by Li-ion electrochemical reaction. A compact electrochemical cell of pseudo-Li-ion battery structure is formed with a superconducting LiTi2O4 film as an anode. Li content in the film is controlled by applying a constant redox voltage. An insulating state is achieved by Li-ion intercalation to the superconducting film by applying reduction potential. In contrast, the superconducting state is reproduced by applying oxidation potential to the Li-ion intercalated film. Moreover, superconducting transition temperature is also recovered after a number of cycles of Li-ion electrochemical reactions. This complete reversible transition originates in difference in potentials required for deintercalation of initially contained and electrochemically intercalated Li+ ions. PMID:26541508

Reversible superconductor-insulator transition in LiTi2O4 induced by Li-ion electrochemical reaction.

PubMed

Yoshimatsu, K; Niwa, M; Mashiko, H; Oshima, T; Ohtomo, A

2015-11-06

Transition metal oxides display various electronic and magnetic phases such as high-temperature superconductivity. Controlling such exotic properties by applying an external field is one of the biggest continuous challenges in condensed matter physics. Here, we demonstrate clear superconductor-insulator transition of LiTi2O4 films induced by Li-ion electrochemical reaction. A compact electrochemical cell of pseudo-Li-ion battery structure is formed with a superconducting LiTi2O4 film as an anode. Li content in the film is controlled by applying a constant redox voltage. An insulating state is achieved by Li-ion intercalation to the superconducting film by applying reduction potential. In contrast, the superconducting state is reproduced by applying oxidation potential to the Li-ion intercalated film. Moreover, superconducting transition temperature is also recovered after a number of cycles of Li-ion electrochemical reactions. This complete reversible transition originates in difference in potentials required for deintercalation of initially contained and electrochemically intercalated Li(+) ions.

The impact of urea-induced unfolding on the redox process of immobilised cytochrome c.

PubMed

Monari, Stefano; Millo, Diego; Ranieri, Antonio; Di Rocco, Giulia; van der Zwan, Gert; Gooijer, Cees; Peressini, Silvia; Tavagnacco, Claudio; Hildebrandt, Peter; Borsari, Marco

2010-11-01

We have studied the effect of urea-induced unfolding on the electron transfer process of yeast iso-1-cytochrome c and its mutant K72AK73AK79A adsorbed on electrodes coated by mixed 11-mercapto-1-undecanoic acid/11-mercapto-1-undecanol self-assembled monolayers. Electrochemical measurements, complemented by surface enhanced resonance Raman studies, indicate two distinct states of the adsorbed proteins that mainly differ with respect to the ligation pattern of the haem. The native state, in which the haem is axially coordinated by Met80 and His18, displays a reduction potential that slightly shifts to negative values with increasing urea concentration. At urea concentrations higher than 6 M, a second state prevails in which the Met80 ligand is replaced by an additional histidine residue. This structural change in the haem pocket is associated with an approximately 0.4 V shift of the reduction potential to negative values. These two states were found for both the wild-type protein and the mutant in which lysine residues 72, 73 and 79 had been substituted by alanines. The analysis of the reduction potentials, the reaction enthalpies and entropies as well as the rate constants indicates that these three lysine residues have an important effect on stabilising the protein structure in the adsorbed state and facilitating the electron transfer dynamics.

[Efficacy and security of electronic cigarette for tobacco harm reduction: Systematic review and meta-analysis].

PubMed

Vanderkam, Paul; Boussageon, Rémy; Underner, Michel; Langbourg, Nicolas; Brabant, Yann; Binder, Philippe; Freche, Bernard; Jaafari, Nematollah

2016-11-01

Smoking is the first cause of preventable death in France and in the world. Without help, it was shown that 80 % of smokers who try to quit smoking relapse after one month with a low long-term success rate. Smoking reduction can concern smokers who did not want to quit or failed in their attempt to weaning. The final aim is to increase attractiveness of drug therapies by developing new products, such as electronic cigarettes, that can compete cigarette without reproducing its harmful effects. Assess the capacity of electronic cigarettes to reduce or stop tobacco use among regular smokers. Consultations MEDLINE and COCHRANE databases. e-cigarette; electronic cigarettes; ENDD (electronic nicotine delivery system); ENDS (electronic nicotine delivery device); vaping were used. Randomized controlled trials (RCTs) comparing the electronic cigarette with nicotine versus placebo device. Two randomized controlled trials were included in the quantitative analysis. The nicotine electronic cigarette users have tobacco consumption significantly decreased compared to the placebo group (RR: 1.30, 95 % CI [1.02 to 1.66]) at 6 months. Smoking cessation rate at 3 months was greater with the electronic cigarette contains nicotine (RR: 2.55, 95 % CI [1.31 to 4.98]). The small number of RCTs included does not allow definitive conclusions about the effectiveness of electronic cigarettes, especially in the medium to long term. The use of electronic cigarette with nicotine decreases tobacco consumption among regular smokers. Further studies are needed to specify electronic cigarettes safety profile and its ability to cause a reduction in consumption and a long-term cessation in smokers. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Oligothiophene/graphene supramolecular ensembles managing light induced processes: preparation, characterization, and femtosecond transient absorption studies leading to charge-separation

NASA Astrophysics Data System (ADS)

Stergiou, A.; Gobeze, H. B.; Petsalakis, I. D.; Zhao, S.; Shinohara, H.; D'Souza, F.; Tagmatarchis, N.

2015-09-01

Advances in organic synthetic chemistry combined with the exceptional electronic properties of carbon allotropes, particularly graphene, is the basis used to design and fabricate novel electron donor-acceptor ensembles with desired properties for technological applications. Thiophene-based materials, which are mainly thiophene-containing polymers, are known for their notable electronic properties. In this frame moving from polymer to oligomer forms, new fundamental information would help for a better understanding of their electrochemical and photophysical properties. Furthermore, a successful combination of their electronic properties with those of graphene is a challenging goal. In this study, two oligothiophene compounds, which consist of three and nine thiophene-rings and are abbreviated 3T and 9T, respectively, were synthesized and noncovalently associated with liquid phase exfoliated few-layered graphene sheets (abbreviated eG), thus forming donor-acceptor 3T/eG and 9T/eG nanoensembes. Markedly, intra-ensemble electronic interactions between the two components in the ground and excited states were evaluated with the aid of UV-Vis and photoluminescence spectroscopy. Furthermore, redox assays revealed the one-electron oxidation of 3T accompanied by one-electron reduction due to eG in 3T/eG, whereas there were two reversible one-electron oxidations of 9T accompanied by one-electron reduction of eG9T/eG. The electrochemical band gap for the 3T/eG and 9T/eG ensembles were calculated and verified, in which the negative free-energy change for the charge-separated state of 3T/eG and 9T/eGvia the singlet excited state of 3T and 9T, respectively, were thermodynamically favorable. Finally, the results of transient pump-probe spectroscopy studies at the femtosecond time scale were supportive of charge transfer type interactions in the 3T/eG and 9T/eG ensembles. The estimated rates for intra-ensemble charge separation were found to be 9.52 × 109 s-1 and 2.2 × 1011 s-1, respectively, for 3T/eG and 9T/eG in THF, which reveal moderate to ultrafast photoinduced events in the oligothiophene/graphene supramolecular ensembles.Advances in organic synthetic chemistry combined with the exceptional electronic properties of carbon allotropes, particularly graphene, is the basis used to design and fabricate novel electron donor-acceptor ensembles with desired properties for technological applications. Thiophene-based materials, which are mainly thiophene-containing polymers, are known for their notable electronic properties. In this frame moving from polymer to oligomer forms, new fundamental information would help for a better understanding of their electrochemical and photophysical properties. Furthermore, a successful combination of their electronic properties with those of graphene is a challenging goal. In this study, two oligothiophene compounds, which consist of three and nine thiophene-rings and are abbreviated 3T and 9T, respectively, were synthesized and noncovalently associated with liquid phase exfoliated few-layered graphene sheets (abbreviated eG), thus forming donor-acceptor 3T/eG and 9T/eG nanoensembes. Markedly, intra-ensemble electronic interactions between the two components in the ground and excited states were evaluated with the aid of UV-Vis and photoluminescence spectroscopy. Furthermore, redox assays revealed the one-electron oxidation of 3T accompanied by one-electron reduction due to eG in 3T/eG, whereas there were two reversible one-electron oxidations of 9T accompanied by one-electron reduction of eG9T/eG. The electrochemical band gap for the 3T/eG and 9T/eG ensembles were calculated and verified, in which the negative free-energy change for the charge-separated state of 3T/eG and 9T/eGvia the singlet excited state of 3T and 9T, respectively, were thermodynamically favorable. Finally, the results of transient pump-probe spectroscopy studies at the femtosecond time scale were supportive of charge transfer type interactions in the 3T/eG and 9T/eG ensembles. The estimated rates for intra-ensemble charge separation were found to be 9.52 × 109 s-1 and 2.2 × 1011 s-1, respectively, for 3T/eG and 9T/eG in THF, which reveal moderate to ultrafast photoinduced events in the oligothiophene/graphene supramolecular ensembles. Electronic supplementary information (ESI) available: NMR, MS, ATR-IR, UV-Vis spectra, CV graphs, femto- and nano-second transient absorption spectra of oligothiophenes and their ensembles with exfoliated graphene. See DOI: 10.1039/c5nr04875c

The link between the microbial ecology, gene expression, and biokinetics of denitrifying polyphosphate-accumulating systems under different electron acceptor combinations.

PubMed

Vieira, A; Ribera-Guardia, A; Marques, R; Barreto Crespo, M T; Oehmen, A; Carvalho, G

2018-06-02

The emission of the greenhouse gas nitrous oxide (N 2 O) can occur during biological nutrient removal. Denitrifying enhanced biological phosphorus removal (d-EBPR) systems are an efficient means of removing phosphate and nitrogen, performed by denitrifying polyphosphate-accumulating organisms (d-PAOs). The aim of this work was to study the effect of various combinations of electron acceptors, nitrate (NO 3 - ), nitrite (NO 2 - ), and N 2 O, on the denitrification pathway of a d-EBPR system. Batch tests were performed with different electron acceptor combinations, to explore the denitrification pathway. Reverse transcriptase-qPCR (RT-qPCR) and high-throughput sequencing, combined with chemical analysis, were used to study gene expression, microbial diversity, and denitrification kinetics. The potential for N 2 O production was greater than the potential for its reduction in most tests. A strong correlation was observed between the N 2 O reduction rate and the relative gene expression of nitrous oxide reductase per nitrite reductase (nosZ/(nirS + nirK)), suggesting that the expression of denitrifying marker genes is a strong predictor of the N 2 O reduction rate. The d-EBPR community maintained a core population with low variations throughout the study. Furthermore, phylogenetic analyses of the studied marker genes revealed that the organisms actively involved in denitrification were closely related to Thauera sp., Candidatus Accumulibacter phosphatis, and Candidatus Competibacter denitrificans. Moreover, Competibacter-related OTUs seem to be important contributors to the N 2 O reduction capacity of the system, likely scavenging the N 2 O produced by other organisms. Overall, this study contributes to a better understanding of the microbial biochemistry and the genetics involving biological denitrification removal, important to minimize N 2 O emissions in wastewater treatment plants.

Cross-field electron transport inside an insulating cylinder of a baffled probe

NASA Astrophysics Data System (ADS)

Raitses, Yevgeny; Alt, Andrew

2017-10-01

Plasma-immersed wall experiments have been performed in a magnetized xenon plasma in a cross-field Penning configuration with density around 1012 cm-3 and an electron temperature around a few eV. A cylinder with an open end and diameter of 1.4 mm was placed across field lines so that electrons were blocked from reaching a wire recessed behind the shield while ions were unimpeded. The reduction of electron current to the wire causes it to float closer to the plasma potential, possibly making a device that can passively measure plasma potential. However, the measured electron current was much higher than expected even when the wire was recessed several electron gyroradii behind the baffle. Possible mechanisms for this electron conduction causing the short circuiting to the bulk plasma have been studied with numerical approaches and with a dedicated experiment designed to isolate this short circuit effect. The obtained results may be important for cross-field transport in a variety of other configurations in magnetized, low-temperature plasmas. This work was supported by DOE contract DE-AC02-09CH11466.

Inhibition of radical-induced DNA strand breaks by water-soluble constituents of coffee: phenolics and caffeine metabolites.

PubMed

Rathod, M A; Patel, D; Das, A; Tipparaju, S R; Shinde, S S; Anderson, R F

2013-07-01

Epidemiological studies have associated coffee consumption with an inverse risk of developing Parkinson's disease, hepatocellular carcinoma and cirrhosis. The molecular mechanisms by which low concentrations of the constituents of coffee measured in human plasma can reduce the incidence of such diseases are not clear. Using an in vitro plasmid DNA system and radiolytically generated reactive oxygen species under constant radical scavenging conditions, we have shown that coffee chlorogenic acid, its derivatives and certain metabolites of caffeine reduce some of the free radical damage sustained to the DNA. A reduction in the amount of prompt DNA single-strand breaks (SSBs) was observed for all compounds whose radical one-electron reduction potential is < 1.0 V. However, except for chlorogenic acid, the compounds were found to be inactive in reducing the amount of radical damage to the DNA bases. These results support a limited antioxidant role for such compounds in their interaction with DNA radicals.

Fabrication of Pd and Pt Nanotubes and Their Catalytic Study on p-Nitrophenol Reduction

NASA Astrophysics Data System (ADS)

Wang, Yinan; Wang, Jiankang; Chen, JingYi

2018-03-01

Pd and Pt nanotubes were fabricated using self-assembled DC8,9PC lipid tubules under mild conditions at room temperature. Scan electron microscope (SEM) show the hollow and open-ended structures of prepared Pd and Pt nanotubes. The Pd and Pt nanotubes demonstrate both high catalytic activity toward p-nitrophenol reduction and excellent stability. This work has indicated the application potentials of lipid tubules in fabricating hollow metal nanomaterials.

Development and characterization of reduced graphene oxide films for transient electronics

NASA Astrophysics Data System (ADS)

Sheikh, Rasel; Bhatkar, Omkar; Smith, David; Rizvi, Reza

2018-03-01

Emerging interests in hardware security as well as environmental concerns have given rise to the field of transient or temporary electronics, which can be decommissioned by an external stimulus with minimal impact to the surrounding environment. In this study, an all graphene based film is produced by a one-step deposition process. The conversion of graphene oxide (GO) to reduced graphene oxide (rGO) depends on an interfacial reduction reaction. Control of processing conditions such as the underlying substrate, pH of GO and the film drying environment results in an ability to tailor the internal architecture of the films and their electronic properties. Furthermore, the ability to create masks for selective reduction of GO during deposition was also demonstrated, which was used to create intricate yet well-defined patterns and connections required in electronic circuits and devices. All graphene based freestanding films with selectively reduced GO were used in transient electronics application as circuitry and RFID tag patterns.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Mechanism of enhanced nitrate reduction via micro-electrolysis at the powdered zero-valent iron/activated carbon interface.

PubMed

Luo, Jinghuan; Song, Guangyu; Liu, Jianyong; Qian, Guangren; Xu, Zhi Ping

2014-12-01

Nitrate reduction by zero-valent iron (Fe(0)) powder always works well only at controlled pH lower than 4 due to the formation of iron (hydr)oxides on its surface. Fe(0) powder combined with activated carbon (AC), i.e., Fe(0)/AC micro-electrolysis system, was first introduced to enhance nitrate reduction in aqueous solution. Comparative study was carried out to investigate nitrate reduction by Fe(0)/AC system and Fe(0) under near-neutral conditions, showing that the Fe(0)/AC system successfully reduced nitrate even at initial pH 6 with the reduction efficiency of up to 73%, whereas for Fe(0) only ∼10%. The effect of Fe(0) to AC mass ratio on nitrate reduction efficiency was examined. Easier nitrate reduction was achieved with more contact between Fe(0) and AC as the result of decreasing Fe(0) to AC mass ratio. Ferrous ion and oxidation-reduction potential were measured to understand the mechanism of enhanced nitrate reduction by Fe(0)/AC micro-electrolysis. The results suggest that a relative potential difference drives much more electrons from Fe(0) to AC, thus generating adsorbed atomic hydrogen which makes it possible for nitrate to be reduced at near-neural pH. Fe(0)/AC micro-electrolysis thus presents a great potential for practical application in nitrate wastewater treatment without excessive pH adjustment. Copyright © 2014 Elsevier Inc. All rights reserved.

Identification of a multi-protein reductive dehalogenase complex in Dehalococcoides mccartyi strain CBDB1 suggests a protein-dependent respiratory electron transport chain obviating quinone involvement.

PubMed

Kublik, Anja; Deobald, Darja; Hartwig, Stefanie; Schiffmann, Christian L; Andrades, Adarelys; von Bergen, Martin; Sawers, R Gary; Adrian, Lorenz

2016-09-01

Dehalococcoides mccartyi strain CBDB1 is an obligate organohalide-respiring bacterium using only hydrogen as electron donor and halogenated organics as electron acceptor. Here, we studied proteins involved in the respiratory chain under non-denaturing conditions. Using blue native gel electrophoresis (BN-PAGE), gel filtration and ultrafiltration an active dehalogenating protein complex with a molecular mass of 250-270 kDa was identified. The active subunit of reductive dehalogenase (RdhA) colocalised with a complex iron-sulfur molybdoenzyme (CISM) subunit (CbdbA195) and an iron-sulfur cluster containing subunit (CbdbA131) of the hydrogen uptake hydrogenase (Hup). No colocalisation between the catalytically active subunits of hydrogenase and reductive dehalogenase was found. By two-dimensional BN/SDS-PAGE the stability of the complex towards detergents was assessed, demonstrating stepwise disintegration with increasing detergent concentrations. Chemical cross-linking confirmed the presence of a higher molecular mass reductive dehalogenase protein complex composed of RdhA, CISM I and Hup hydrogenase and proved to be a potential tool for stabilising protein-protein interactions of the dehalogenating complex prior to membrane solubilisation. Taken together, the identification of the respiratory dehalogenase protein complex and the absence of indications for quinone participation in the respiration suggest a quinone-independent protein-based respiratory electron transfer chain in D. mccartyi. © 2015 Society for Applied Microbiology and John Wiley & Sons Ltd.

Impact of pulmonary arterial endothelial cells on duroquinone redox status.

PubMed

Merker, Marilyn P; Bongard, Robert D; Krenz, Gary S; Zhao, Hongtao; Fernandes, Viola S; Kalyanaraman, Balaraman; Hogg, Neil; Audi, Said H

2004-07-01

The study objective was to use pulmonary arterial endothelial cells to examine kinetics and mechanisms contributing to the disposition of the quinone 2,3,5,6-tetramethyl-1,4-benzoquinone (duroquinone, DQ) observed during passage through the pulmonary circulation. The approach was to add DQ, durohydroquinone (DQH2), or DQ with the cell membrane-impermeant oxidizing agent, ferricyanide (Fe(CN)6(3)-), to the cell medium, and to measure the medium concentrations of substrates and products over time. Studies were carried out under control conditions and with dicumarol, to inhibit NAD(P)H:quinone oxidoreductase 1 (NQO1), or cyanide, to inhibit mitochondrial electron transport. In control cells, DQH2 appears in the extracellular medium of cells incubated with DQ, and DQ appears when the cells are incubated with DQH2. Dicumarol blocked the appearance of DQH2 when DQ was added to the cell medium, and cyanide blocked the appearance of DQ when DQH2 was added to the cell medium, suggesting that the two electron reductase NQO1 dominates DQ reduction and mitochondrial electron transport complex III is the predominant route of DQH2 oxidation. In the presence of cyanide, the addition of DQ also resulted in an increased rate of appearance of DQH2 and stimulation of cyanide-insensitive oxygen consumption. As DQH2 does not autoxidize-comproportionate over the study time course, these observations suggest a cyanide-stimulated one-electron DQ reduction and durosemiquinone (DQ*-) autoxidation. The latter processes are apparently confined to the cell interior, as the cell membrane impermeant oxidant, ferricyanide, did not inhibit the DQ-stimulated cyanide-insensitive oxygen consumption. Thus, regardless of whether DQ is reduced via a one- or two-electron reduction pathway, the net effect in the extracellular medium is the appearance of DQH2. These endothelial redox functions and their apposition to the vessel lumen are consistent with the pulmonary endothelium being an important site of DQ reduction to DQH2 observed in the lungs. Copyright 2004 Elsevier Inc.

Non-enzymatic U(VI) interactions with biogenic mackinawite

NASA Astrophysics Data System (ADS)

Veeramani, H.; Qafoku, N. P.; Kukkadapu, R. K.; Murayama, M.; Hochella, M. F.

2011-12-01

Reductive immobilization of hexavalent uranium [U(VI)] by stimulation of dissimilatory metal and/or sulfate reducing bacteria (DMRB or DSRB) has been extensively researched as a remediation strategy for subsurface U(VI) contamination. These bacteria derive energy by reducing oxidized metals as terminal electron acceptors, often utilizing organic substrates as electron donors. Thus, when evaluating the potential for in-situ uranium remediation in heterogeneous subsurface media, it is important to understand how the presence of alternative electron acceptors such as Fe(III) and sulfate affect U(VI) remediation and the long term behavior and reactivity of reduced uranium. Iron, an abundant subsurface element, represents a substantial sink for electrons from DMRB, and the reduction of Fe(III) leads to the formation of dissolved Fe(II) or to reactive biogenic Fe(II)- and mixed Fe(II)/Fe(III)- mineral phases. Consequently, abiotic U(VI) reduction by reactive forms of biogenic Fe(II) minerals could be a potentially important process for uranium immobilization. In our study, the DMRB Shewanella putrefaciens CN32 was used to synthesize a biogenic Fe(II)-bearing sulfide mineral: mackinawite, that has been characterized by XRD, SEM, HRTEM and Mössbauer spectroscopy. Batch experiments involving treated biogenic mackinawite and uranium (50:1 molar ratio) were carried out at room temperature under strict anoxic conditions. Following complete removal of uranium from solution, the biogenic mackinawite was analyzed by a suite of analytical techniques including XAS, HRTEM and Mössbauer spectroscopy to determine the speciation of uranium and investigate concomitant Fe(II)-phase transformation. Determining the speciation of uranium is critical to success of a remediation strategy. The present work elucidates non-enzymatic/abiotic molecular scale redox interactions between biogenic mackinawite and uranium.

A bio-inspired N-doped porous carbon electrocatalyst with hierarchical superstructure for efficient oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Miao, Yue-E.; Yan, Jiajie; Ouyang, Yue; Lu, Hengyi; Lai, Feili; Wu, Yue; Liu, Tianxi

2018-06-01

The bio-inspired hierarchical "grape cluster" superstructure provides an effective integration of one-dimensional carbon nanofibers (CNF) with isolated carbonaceous nanoparticles into three-dimensional (3D) conductive frameworks for efficient electron and mass transfer. Herein, a 3D N-doped porous carbon electrocatalyst consisting of carbon nanofibers with grape-like N-doped hollow carbon particles (CNF@NC) has been prepared through a simple electrospinning strategy combined with in-situ growth and carbonization processes. Such a bio-inspired hierarchically organized conductive network largely facilitates both the mass diffusion and electron transfer during the oxygen reduction reactions (ORR). Therefore, the metal-free CNF@NC catalyst demonstrates superior catalytic activity with an absolute four-electron transfer mechanism, strong methanol tolerance and good long-term stability towards ORR in alkaline media.

Beam debunching due to ISR-induced energy diffusion

DOE PAGES

Yampolsky, Nikolai A.; Carlsten, Bruce E.

2017-06-20

One of the options for increasing longitudinal coherency of X-ray free electron lasers (XFELs) is seeding with a microbunched electron beam. Several schemes leading to significant amplitude of the beam bunching at X-ray wavelengths were recently proposed. All these schemes rely on beam optics having several magnetic dipoles. While the beam passes through a dipole, its energy spread increases due to quantum effects of synchrotron radiation. As a result, the bunching factor at small wavelengths reduces since electrons having different energies follow different trajectories in the bend. We rigorously calculate the reduction in the bunching factor due to incoherent synchrotronmore » the radiation while the beam travels in an arbitrary beamline. Lastly, we apply general results to estimate reduction of harmonic current in common schemes proposed for XFEL seeding.« less

Anaerobic methane oxidation in two tropical freshwater systems

NASA Astrophysics Data System (ADS)

Roland, Fleur; Darchambeau, François; Crowe, Sean A.; Borges, Alberto V.

2014-05-01

Lake Kivu is one of the East African Great Lakes. It is located at the border between Rwanda and the Democratic Republic of the Congo. It is a deep meromictic lake characterized by huge amounts of methane (CH4) (60 km3 at 0° C and 1 atm) dissolved in its deep waters. Two thirds of the CH4 originates from anoxic bacterial reduction of dissolved carbon dioxide and one third from anaerobic degradation of settling organic material. CH4 then diffuses slowly from the monimolimnion to surface waters where many is oxidised by methanotrophic microorganisms. In Lake Kivu, this biological oxidation of CH4 could occur with different final electron acceptors: oxygen (aerobic oxidation) but also nitrate (NO3-), nitrite, sulfate (SO42-), iron (Fe) or manganese (Mn) in anaerobic conditions. If the anaerobic oxidation of CH4 (AOM) is generally coupled to SO42- reduction in marine waters, electron acceptors of the AOM were rarely investigated in freshwater systems. Five field campaigns were conducted from 2011 to 2013 during periods with contrasted ventilations of the upper water column. The dry season is characterized by a deeper mixing of surface waters ended by a steep gradient of physico-chemical conditions at the redox interface, while during the rainy season the mixed layer is shallower and ended at its deeper part by a NO3- accumulation zone. Sampling was conducted in the main basin of Lake Kivu but also in a particular sub-basin located northeast of the lake, the Kabuno Bay. Both systems are meromictic but differ in terms of morphometry and geochemistry with a shallower permanent chemocline and higher concentrations of CH4, Fe and Mn in the anoxic waters in Kabuno Bay compared to the main lake. Samples were collected for the measurements of CH4 concentrations and the various potential electron acceptors of the AOM. CH4 oxidation rates were measured along vertical profiles at 5 m and 0.5 m depth intervals respectively in the main basin and Kabuno bay water columns. Results indicate high rates of AOM in both main basin (up to 7 μmol L-1 d-1) and Kabuno bay (up to 16 μmol L-1 d-1). In the main basin, we observed a co-occurrence of the AOM and the SO42- reduction in the dry season. During the rainy season, higher oxidation rates occurred in the NO3- accumulation zone, which is in favour of a coupling between AOM and NO3- reduction. In Kabuno Bay, the higher AOM rates were observed at depths with highest particulate Fe concentrations. Our results suggest that AOM coupled with SO42-reduction may occur during the dry season in the main basin, whereas this oxidation could be coupled with NO3- reduction during the rainy season. In Kabuno Bay, the co-occurrence of the Fe [III] peak with high AOM suggests a coupling between the AOM and Fe reduction.

Boron doped graphene wrapped silver nanowires as an efficient electrocatalyst for molecular oxygen reduction

NASA Astrophysics Data System (ADS)

Nair, Anju K.; Thazhe Veettil, Vineesh; Kalarikkal, Nandakumar; Thomas, Sabu; Kala, M. S.; Sahajwalla, Veena; Joshi, Rakesh K.; Alwarappan, Subbiah

2016-12-01

Metal nanowires exhibit unusually high catalytic activity towards oxygen reduction reaction (ORR) due to their inherent electronic structures. However, controllable synthesis of stable nanowires still remains as a daunting challenge. Herein, we report the in situ synthesis of silver nanowires (AgNWs) over boron doped graphene sheets (BG) and demonstrated its efficient electrocatalytic activity towards ORR for the first time. The electrocatalytic ORR efficacy of BG-AgNW is studied using various voltammetric techniques. The BG wrapped AgNWs shows excellent ORR activity, with very high onset potential and current density and it followed four electron transfer mechanism with high methanol tolerance and stability towards ORR. The results are comparable to the commercially available 20% Pt/C in terms of performance.

Effect of collisions on photoelectron sheath in a gas

NASA Astrophysics Data System (ADS)

Sodha, Mahendra Singh; Mishra, S. K.

2016-02-01

This paper presents a study of the effect of the collision of electrons with atoms/molecules on the structure of a photoelectron sheath. Considering the half Fermi-Dirac distribution of photo-emitted electrons, an expression for the electron density in the sheath has been derived in terms of the electric potential and the structure of the sheath has been investigated by incorporating Poisson's equation in the analysis. The method of successive approximations has been used to solve Poisson's equation with the solution for the electric potential in the case of vacuum, obtained earlier [Sodha and Mishra, Phys. Plasmas 21, 093704 (2014)], being used as the zeroth order solution for the present analysis. The inclusion of collisions influences the photoelectron sheath structure significantly; a reduction in the sheath width with increasing collisions is obtained.

Laboratory-scale photoredox catalysis using hydrated electrons sustainably generated with a single green laser.

PubMed

Naumann, Robert; Kerzig, Christoph; Goez, Martin

2017-11-01

The ruthenium-tris-bipyridyl dication as catalyst combined with the ascorbate dianion as bioavailable sacrificial donor provides the first regenerative source of hydrated electrons for chemical syntheses on millimolar scales. This electron generator is operated simply by illumination with a frequency-doubled Nd:YAG laser (532 nm) running at its normal repetition rate. Much more detailed information than by product studies alone was obtained by photokinetical characterization from submicroseconds (time-resolved laser flash photolysis) up to one hour (preparative photolysis). The experiments on short timescales established a reaction mechanism more complex than previously thought, and proved the catalytic action by unchanged concentration traces of the key transients over a number of flashes so large that the accumulated electron total surpassed the catalyst concentration many times. Preparative photolyses revealed that the sacrificial donor greatly enhances the catalyst stability through quenching the initial metal-to-ligand charge-transfer state before destructive dd states can be populated from it, such that the efficiency of this electron generator is no longer limited by catalyst decomposition but by electron scavenging by the accumulating oxidation products of the ascorbate. Applications covered dechlorinations of selected aliphatic and aromatic chlorides and the reduction of a model ketone. All these substrates are impervious to photoredox catalysts exhibiting lower reducing power than the hydrated electron, but the combination of an extremely negative standard potential and a long unquenched life allowed turnover numbers up to 1400 with our method.

Ultrafast dynamics of photogenerated electrons in CdS nanocluster multilayers assembled on solid substrates: effects of assembly and electrode potential.

PubMed

Yagi, Ichizo; Mikami, Kensuke; Okamura, Masayuki; Uosaki, Kohei

2013-07-22

The ultrafast dynamics of photogenerated electrons in multilayer assemblies of CdS nanoparticles prepared on quartz and indium-tin oxide (ITO) substrates were followed by femtosecond (fs) visible-pump/mid-IR probe spectroscopy. Based on the observation of the photoinduced transient absorption spectra in the broad mid-IR range at the multilayer assembly of CdS nanoparticles, the occupation and fast relaxation of higher electronic states (1P(e)) were clarified. As compared with the electron dynamics of isolated (dispersed in solution) nanoparticles, the decay of photoexcited electrons in the multilayer assembly was clearly accelerated probably due to both electron hopping and scattering during interparticle electron tunneling. By using an ITO electrode as a substrate, the effect of the electric field on the photoelectron dynamics in the multilayer assembly was also investigated in situ. Both the amplitude and lifetime of photoexcited electrons gradually reduced as the potential became more positive. This result was explained by considering the reduction of the interparticle tunneling probability and the increase in the electron-transfer rate from the CdS nanoparticle assembly to the ITO electrode. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure-Property Relationships for Tailoring Phenoxazines as Reducing Photoredox Catalysts.

PubMed

McCarthy, Blaine G; Pearson, Ryan M; Lim, Chern-Hooi; Sartor, Steven M; Damrauer, Niels H; Miyake, Garret M

2018-04-18

Through the study of structure-property relationships using a combination of experimental and computational analyses, a number of phenoxazine derivatives have been developed as visible light absorbing, organic photoredox catalysts (PCs) with excited state reduction potentials rivaling those of highly reducing transition metal PCs. Time-dependent density functional theory (TD-DFT) computational modeling of the photoexcitation of N-aryl and core modified phenoxazines guided the design of PCs with absorption profiles in the visible regime. In accordance with our previous work with N, N-diaryl dihydrophenazines, characterization of noncore modified N-aryl phenoxazines in the excited state demonstrated that the nature of the N-aryl substituent dictates the ability of the PC to access a charge transfer excited state. However, our current analysis of core modified phenoxazines revealed that these molecules can access a different type of CT excited state which we posit involves a core substituent as the electron acceptor. Modification of the core of phenoxazine derivatives with electron-donating and electron-withdrawing substituents was used to alter triplet energies, excited state reduction potentials, and oxidation potentials of the phenoxazine derivatives. The catalytic activity of these molecules was explored using organocatalyzed atom transfer radical polymerization (O-ATRP) for the synthesis of poly(methyl methacrylate) (PMMA) using white light irradiation. All of the derivatives were determined to be suitable PCs for O-ATRP as indicated by a linear growth of polymer molecular weight as a function of monomer conversion and the ability to synthesize PMMA with moderate to low dispersity (dispersity less than or equal to 1.5) and initiator efficiencies typically greater than 70% at high conversions. However, only PCs that exhibit strong absorption of visible light and strong triplet excited state reduction potentials maintain control over the polymerization during the entire course of the reaction. The structure-property relationships established here will enable the application of these organic PCs for O-ATRP and other photoredox-catalyzed small molecule and polymer syntheses.

Electrochemical Properties of Boron-Doped Fullerene Derivatives for Lithium-Ion Battery Applications.

PubMed

Sood, Parveen; Kim, Ki Chul; Jang, Seung Soon

2018-03-19

The high electron affinity of fullerene C 60 coupled with the rich chemistry of carbon makes it a promising material for cathode applications in lithium-ion batteries. Since boron has one electron less than carbon, the presence of boron on C 60 cages is expected to generate electron deficiency in C 60 , and thereby to enhance its electron affinity. By using density functional theory (DFT), we studied the redox potentials and electronic properties of C 60 and C 59 B. We have found that doping C 60 with one boron atom results in a substantial increase in redox potential from 2.462 V to 3.709 V, which was attributed to the formation of an open shell system. We also investigated the redox and electronic properties of C 59 B functionalized with various redox-active oxygen containing functional groups (OCFGs). For the combination of functionalization with OCFGs and boron doping, it is found that the enhancement of redox potential is reduced, which is mainly attributed to the open shell structure being changed to a closed-shell one. Nevertheless, the redox potentials are still higher than that of pristine C 60 . From the observation that the lowest unoccupied molecular orbital of closed-shell OCFG- functionalized C 59 B is correlated well with the redox potential, it was confirmed that the spin state is crucial to be considered to understand the relationship between electronic structure and redox properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of strain relaxation in axial [Formula: see text] nanowire heterostructures on their electronic properties.

PubMed

Marquardt, Oliver; Krause, Thilo; Kaganer, Vladimir; Martín-Sánchez, Javier; Hanke, Michael; Brandt, Oliver

2017-05-26

We present a systematic theoretical study of the influence of elastic strain relaxation on the built-in electrostatic potentials and the electronic properties of axial [Formula: see text] nanowire (NW) heterostructures. Our simulations reveal that for a sufficiently large ratio between the thickness of the [Formula: see text] disk and the diameter of the NW, the elastic relaxation leads to a significant reduction of the built-in electrostatic potential in comparison to a planar system of similar layer thickness and In content. In this case, the ground state transition energies approach constant values with increasing thickness of the disk and only depend on the In content, a behavior usually associated to that of a quantum well free of built-in electrostatic potentials. We show that the structures under consideration are by no means field-free, and the built-in potentials continue to play an important role even for ultrathin NWs. In particular, strain and the resulting polarization potentials induce complex confinement features of electrons and holes, which depend on the In content, shape, and dimensions of the heterostructure.

Reduction of Cr(VI) under acidic conditions by the facultative Fe(III)-reducing bacterium Acidiphilium cryptum

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

David E. Cummings; Scott Fendorf; Rajesh K. Sani

2007-01-01

The potential for biological reduction of Cr(VI) under acidic conditions was evaluated with the acidophilic, facultatively metal-reducing bacterium Acidiphilium cryptum strain JF-5 to explore the role of acidophilic microorganisms in the Cr cycle in low-pH environments. An anaerobic suspension of washed A. cryptum cells rapidly reduced 50 M Cr(VI) at pH 3.2; biological reduction was detected from pH 1.7-4.7. The reduction product, confirmed by XANES analysis, was entirely Cr(III) that was associated predominantly with the cell biomass (70-80%) with the residual residing in the aqueous phase. Reduction of Cr(VI) showed a pH optimum similar to that for growth and wasmore » inhibited by 5 mM HgCl2, suggesting that the reaction was enzyme-mediated. Introduction of O2 into the reaction medium slowed the reduction rate only slightly, whereas soluble Fe(III) (as ferric sulfate) increased the rate dramatically, presumably by the shuttling of electrons from bioreduced Fe(II) to Cr(VI) in a coupled biotic-abiotic cycle. Starved cells could not reduce Cr(VI) when provided as sole electron acceptor, indicating that Cr(VI) reduction is not an energy-conserving process in A. cryptum. We speculate, rather, that Cr(VI) reduction is used here as a detoxification mechanism.« less

Development of 8-hydroxyquinoline metal based organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Feng, Xiaodong

Because of its potential application for flat panel displays, solid-state lighting and 1.5 mum emitter for fiber optical communications, organic light-emitting diodes (OLEDs) have been intensively researched. One of the major problems with current OLED technology relates to inefficient electron injection at the cathode interface, which causes high driving voltage and poor device stability. Making a low resistance cathode contact for electron injection is critical to device performance. This work mainly focuses on cathode interface design and engineering. The Ohmic contact using a structure of C60/LiF/Al has been developed in electron only devices. It is found that application of the C60/LiF/Al contact to Alq based OLEDs leads to a dramatic reduction in driving voltages, a significant improvement in power efficiency, and a much slower aging process. A new cathode structure based on metal-organic-metal (MOM) tri-layer films has been developed. It is found that MOM cathodes reduce reflection by deconstructive optical interference from two metal films. The absolute reflectance from the MOM tr-ilayer films can be reduced to as low as 7% in the visible light spectrum. In actual working devices, the reflectance can be reduced from ˜80% to ˜20%. MOM cathodes provide a potential low-cost solution for high contrast full-color OLED displays. Low voltage Erq based OLEDs at 1.5 mum emission have been developed. The Erq/Ag cathode interface has been found to be efficient for electron injection. Dramatic improvement in driving voltage and power efficiency has been realized by implementing Bphen and C60 into Erq devices as an electron transport layer. Integration of Erq devices on Si wafers has also been demonstrated.

Fabrication, electrochemical and catalytic properties of the nanocomposites composed of phosphomolybdic acid and viologen-functionalized multi-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Liu, Jiang; Wang, Jing; Chen, Meng; Qian, Dong-Jin

2017-08-01

Electroactive nanocomposites composed of phosphomolybdic acid (PMA) and viologen-functionalized carbon nanotubes were synthesized and used as heterogeneous catalysts for the electrocatalytic reduction of bromate. Viologen (V) was first covalently anchored on the surface of multi-walled carbon nanotubes (MWNTs) to produce positively charged MWNT-V polyelectrolyte, which was then combined with PMA through electrostatic interaction to form MWNT-V@PMA nanocomposites. Thermogravimetric analysis revealed that the organic species in the MWNT-V polyelectrolyte was about 30% in weight. Composition, structure, and morphology of the nanocomposites were investigated by using UV-vis, infrared, Raman and X-ray photoelectron spectroscopy as well as field emission transition electron microscope. The thickness of organic substituents, viologen, and PMA in the nanocomposites was approximately 10 nm covered on the surface of MWNTs. Cyclic voltammogram measurements for the casting films of MWNT-V@PMA nanocomposites revealed four couples of redox waves with cathodic potentials at about -0.56, -0.19, 0.02, 0.21 V, and anodic ones at about -0.46, -0.11, 0.12, 0.31 V (vs Ag/AgCl), respectively, among which the first one corresponded to the electron transfer process of viologens and others to that of the PMA adsorbed. Finally, the MWNT-V@PMA modified electrodes were used as heterogeneous catalysts for the electrocatalytic bromate reduction, which revealed an almost linear correction between the current density and the bromate concentrations in the concentration range from 1 to 15 mmol/l. [Figure not available: see fulltext.

The electronic cigarette: a knight in shining armour or a Trojan horse?

PubMed

Schluger, Neil W

2014-10-01

Electronic cigarettes have caused a sharp debate in the public health community, with some promoting them as a means of harm reduction for tobacco users and some taking a strong stand against them because of fear of renormalising smoking behaviour and interrupting tobacco control progress. People with mental health problems smoke at high rates and e-cigarettes seem a potentially attractive method of cessation in this population, and their use should be studied carefully.

Rapid isolation of a facultative anaerobic electrochemically active bacterium capable of oxidizing acetate for electrogenesis and azo dyes reduction.

PubMed

Shen, Nan; Yuan, Shi-Jie; Wu, Chao; Cheng, Yuan-Yuan; Song, Xiang-Ning; Li, Wen-Wei; Tong, Zhong-Hua; Yu, Han-Qing

2014-05-01

In this study, 27 strains of electrochemically active bacteria (EAB) were rapidly isolated and their capabilities of extracellular electron transfer were identified using a photometric method based on WO3 nanoclusters. These strains caused color change of WO3 from white to blue in a 24-well agar plate within 40 h. Most of the isolated EAB strains belonged to the genera of Aeromonas and Shewanella. One isolate, Pantoea agglomerans S5-44, was identified as an EAB that can utilize acetate as the carbon source to produce electricity and reduce azo dyes under anaerobic conditions. The results confirmed the capability of P. agglomerans S5-44 for extracellular electron transfer. The isolation of this acetate-utilizing, facultative EBA reveals the metabolic diversity of environmental bacteria. Such strains have great potential for environmental applications, especially at interfaces of aerobic and anaerobic environments, where acetate is the main available carbon source.

Do electronic cigarettes help with smoking cessation?

PubMed

2014-11-01

Smoking causes around 100,000 deaths each year in the UK, and is the leading cause of preventable disease and early mortality. Smoking cessation remains difficult and existing licensed treatments have limited success. Nicotine addiction is thought to be one of the primary reasons that smokers find it so hard to give up, and earlier this year DTB reviewed the effects of nicotine on health. Electronic cigarettes (e-cigarettes) are nicotine delivery devices that aim to mimic the process of smoking but avoid exposing the user to some of the harmful components of traditional cigarettes. However, the increase in the use of e-cigarettes and their potential use as an aid to smoking cessation has been subject to much debate. In this article we consider the regulatory and safety issues associated with the use of e-cigarettes, and their efficacy in smoking cessation and reduction. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

Pendant acid-base groups in molecular catalysts: H-bond promoters or proton relays? Mechanisms of the conversion of CO2 to CO by electrogenerated iron(0)porphyrins bearing prepositioned phenol functionalities.

PubMed

Costentin, Cyrille; Passard, Guillaume; Robert, Marc; Savéant, Jean-Michel

2014-08-20

Two derivatives of iron tetraphenylporphyrin bearing prepositioned phenolic functionalities on two of the opposed phenyl groups prove to be remarkable catalysts for the reduction of CO2 to CO when generated electrochemically at the Fe(0) oxidation state. In one case, the same substituents are present on the two other phenyls, whereas in the other the two other phenyls are perfluorinated. They are taken as examples of the possible role of pendant acid-base groups in molecular catalysis. The prepositioned phenol groups incorporated into the catalyst molecule induce strong stabilization of the initial Fe(0)CO2 adduct through H-bonding, confirmed by DFT calculations. This positive factor is partly counterbalanced by the necessity, resulting from the same stabilization, to inject an additional electron to trigger catalysis. Thanks to the preprotonation of the initial Fe(0)CO2 adduct, the potential required for this second electron transfer is not very distant from the potential at which the adduct is generated by addition of CO2 to the Fe(0) complex. The protonation step involves an internal phenolic group and the reprotonation of the phenoxide ion thus generated by added phenol. The prepositioned phenol groups thus play both the role of H-bonding stabilizers and high-concentration proton donors. They play the same role in the second electron transfer step which closes the catalytic loop concertedly with the breaking of one of the two C-O bonds of CO2 and with proton transfer. It is also remarkable that reprotonation by added phenol is concerted with the three other events.

Rubrolides as model for the development of new lactones and their aza analogs as potential photosynthesis inhibitors.

PubMed

Pereira, Ulisses A; Barbosa, Luiz C A; Demuner, Antônio J; Silva, Antônio A; Bertazzini, Michele; Forlani, Giuseppe

2015-07-01

Natural phytotoxins and their synthetic analogs are a potential source of new bioactive compounds for agriculture. Analogs of rubrolides, a class of γ-alkylidene-γ-lactones isolated from different ascidians, have been shown to interfere with the photosynthetic electron-transport chain, yet their activity needs to be improved. With this aim, ten 5-aryl-6-benzyl-4-bromopyridazin-3(2H)-ones were prepared in yields ranging from 44 to 88% by reaction of their correspondent γ-alkylidene-γ-lactones with NH2 NH2 . The structures of these rubrolide analogs were determined by (1) H- and (13) C-NMR, 2D-NMR (COSY and HETCOR), NOE difference, and MS techniques. These compounds were evaluated for their abilities of interfering with the light-driven reduction of ferricyanide by isolated spinach chloroplasts. Lactones with electron-withdrawing substituents in the para-position of the benzylidene ring were the most effective inhibitors. Characterization of the activity of 11b/11b' suggested a mechanism based on the interaction with the plastoquinone binding site of photosystem II. Addition of several compounds to the culture medium of a cyanobacterial model strain was found to inhibit algal growth. However, the relative effectiveness was not consistent with their activity in vitro, suggesting the occurrence of multiple targets and/or detoxyfication mechanisms. Indeed, the compounds showed differential effects on the heterotrophic growth of some crop species, Cucumis sativus and Sorghum bicolor. Pyridazin-3(2H)-ones 12e, 12i, and 12j, which have been found poorly active against the photosynthetic electron transport, were the most effective in inhibiting the growth of some weeds, Ipomoea grandifolia and Brachiaria decumbens, under greenhouse conditions. Copyright © 2015 Verlag Helvetica Chimica Acta AG, Zürich.

Electric potential distributions at the interface between plasmasheet clouds

NASA Technical Reports Server (NTRS)

Evans, D. S.; Roth, M.; Lemaire, J.

1987-01-01

At the interface between two plasma clouds with different densities, temperatures, and/or bulk velocities, there are large charge separation electric fields which can be modeled in the framework of a collisionless theory for tangential discontinuities. Two different classes of layers were identified: the first one corresponds to (stable) ion layers which are thicker than one ion Lamor radius; the second one corresponds to (unstable) electron layers which are only a few electron Larmor radii thick. It is suggested that these thin electron layers with large electric potential gradients (up to 400 mV/m) are the regions where large-amplitude electrostatic waves are spontaneously generated. These waves scatter the pitch angles of the ambient plasmasheet electron into the atmospheric loss cone. The unstable electron layers can therefore be considered as the seat of strong pitch angle scattering for the primary auroral electrons.

Influence of overconsolidated condition on permeability evolution in silica sand

NASA Astrophysics Data System (ADS)

Kimura, S.; Kaneko, H.; Ito, T.; Nishimura, O.; Minagawa, H.

2013-12-01

Permeability of sediments is important factors for production of natural gas from natural gas hydrate bearing layers. Methane-hydrate is regarded as one of the potential resources of natural gas. As results of coring and logging, the existence of a large amount of methane-hydrate is estimated in the Nankai Trough, offshore central Japan, where many folds and faults have been observed. In the present study, we investigate the permeability of silica sand specimen forming the artificial fault zone after large displacement shear in the ring-shear test under two different normal consolidated and overconsolidated conditions. The significant influence of overconsolidation ratio (OCR) on permeability evolution is not found. The permeability reduction is influenced a great deal by the magnitude of normal stress during large displacement shearing. The grain size distribution and structure observation in the shear zone of specimen after shearing at each normal stress level are analyzed by laser scattering type particle analyzer and scanning electron microscope, respectively. It is indicated that the grain size and porosity reduction due to the particle crushing are the factor of the permeability reduction. This study is financially supported by METI and Research Consortium for Methane Hydrate Resources in Japan (the MH21 Research Consortium).

Plasmonic Control of Multi-Electron Transfer and C-C Coupling in Visible-Light-Driven CO2 Reduction on Au Nanoparticles.

PubMed

Yu, Sungju; Wilson, Andrew J; Heo, Jaeyoung; Jain, Prashant K

2018-04-11

Artificial photosynthesis relies on the availability of synthetic photocatalysts that can drive CO 2 reduction in the presence of water and light. From the standpoint of solar fuel production, it is desirable that these photocatalysts perform under visible light and produce energy-rich hydrocarbons from CO 2 reduction. However, the multistep nature of CO 2 -to-hydrocarbon conversion poses a significant kinetic bottleneck when compared to CO production and H 2 evolution. Here, we show that plasmonic Au nanoparticle photocatalysts can harvest visible light for multielectron, multiproton reduction of CO 2 to yield C 1 (methane) and C 2 (ethane) hydrocarbons. The light-excitation attributes influence the C 2 and C 1 selectivity. The observed trends in activity and selectivity follow Poisson statistics of electron harvesting. Higher photon energies and flux favor simultaneous harvesting of more than one electron from the photocharged Au nanoparticle catalyst, inducing the C-C coupling required for C 2 production. These findings elucidate the nature of plasmonic photocatalysis, which involves strong light-matter coupling, and set the stage for the controlled chemical bond formation by light excitation.

Investigation of excited state, reductive quenching, and intramolecular electron transfer of Ru(II)–Re(I) supramolecular photocatalysts for CO 2 reduction using time-resolved IR measurements

DOE PAGES

Koike, Kazuhide; Grills, David C.; Tamaki, Yusuke; ...

2018-02-14

Supramolecular photocatalysts in which Ru(II) photosensitizer and Re(I) catalyst units are connected to each other by an ethylene linker are among the best known, most effective and durable photocatalytic systems for CO 2 reduction. In this paper we report, for the first time, time-resolved infrared (TRIR) spectra of three of these binuclear complexes to uncover why the catalysts function so efficiently. Selective excitation of the Ru unit with a 532 nm laser pulse induces slow intramolecular electron transfer from the 3MLCT excited state of the Ru unit to the Re unit, with rate constants of (1.0–1.1) × 10 4 smore » -1 as a major component and (3.5–4.3) × 10 6 s -1 as a minor component, in acetonitrile. The produced charge-separated state has a long lifetime, with charge recombination rate constants of only (6.5–8.4) × 10 4 s -1. Thus, although it has a large driving force (-ΔG 0 CR ~ 2.6 eV), this process is in the Marcus inverted region. On the other hand, in the presence of 1-benzyl-1,4-dihydronicotinamide (BNAH), reductive quenching of the excited Ru unit proceeds much faster (k q[BNAH (0.2 M)] = (3.5–3.8) × 10 6 s -1) than the abovementioned intramolecular oxidative quenching, producing the one-electron-reduced species (OERS) of the Ru unit. Nanosecond TRIR data clearly show that intramolecular electron transfer from the OERS of the Ru unit to the Re unit (k ET > 2 × 10 7 s -1) is much faster than from the excited state of the Ru unit, and that it is also faster than the reductive quenching process of the excited Ru unit by BNAH. To measure the exact value of k ET, picosecond TRIR spectroscopy and a stronger reductant were used. Thus, in the case of the binuclear complex with tri(p-fluorophenyl)phosphine ligands (RuRe(FPh)), for which intramolecular electron transfer is expected to be the fastest among the three binuclear complexes, in the presence of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH), k ET was measured as k ET = (1.4 ± 0.1) × 10 9 s -1. This clearly shows that intramolecular electron transfer in these RuRe binuclear supramolecular photocatalysts is not the rate-determining process in the photocatalytic reduction of CO 2, which is one of the main reasons why they work so efficiently.« less

Investigation of excited state, reductive quenching, and intramolecular electron transfer of Ru(II)–Re(I) supramolecular photocatalysts for CO 2 reduction using time-resolved IR measurements

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

Koike, Kazuhide; Grills, David C.; Tamaki, Yusuke

Supramolecular photocatalysts in which Ru(II) photosensitizer and Re(I) catalyst units are connected to each other by an ethylene linker are among the best known, most effective and durable photocatalytic systems for CO 2 reduction. In this paper we report, for the first time, time-resolved infrared (TRIR) spectra of three of these binuclear complexes to uncover why the catalysts function so efficiently. Selective excitation of the Ru unit with a 532 nm laser pulse induces slow intramolecular electron transfer from the 3MLCT excited state of the Ru unit to the Re unit, with rate constants of (1.0–1.1) × 10 4 smore » -1 as a major component and (3.5–4.3) × 10 6 s -1 as a minor component, in acetonitrile. The produced charge-separated state has a long lifetime, with charge recombination rate constants of only (6.5–8.4) × 10 4 s -1. Thus, although it has a large driving force (-ΔG 0 CR ~ 2.6 eV), this process is in the Marcus inverted region. On the other hand, in the presence of 1-benzyl-1,4-dihydronicotinamide (BNAH), reductive quenching of the excited Ru unit proceeds much faster (k q[BNAH (0.2 M)] = (3.5–3.8) × 10 6 s -1) than the abovementioned intramolecular oxidative quenching, producing the one-electron-reduced species (OERS) of the Ru unit. Nanosecond TRIR data clearly show that intramolecular electron transfer from the OERS of the Ru unit to the Re unit (k ET > 2 × 10 7 s -1) is much faster than from the excited state of the Ru unit, and that it is also faster than the reductive quenching process of the excited Ru unit by BNAH. To measure the exact value of k ET, picosecond TRIR spectroscopy and a stronger reductant were used. Thus, in the case of the binuclear complex with tri(p-fluorophenyl)phosphine ligands (RuRe(FPh)), for which intramolecular electron transfer is expected to be the fastest among the three binuclear complexes, in the presence of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH), k ET was measured as k ET = (1.4 ± 0.1) × 10 9 s -1. This clearly shows that intramolecular electron transfer in these RuRe binuclear supramolecular photocatalysts is not the rate-determining process in the photocatalytic reduction of CO 2, which is one of the main reasons why they work so efficiently.« less

Anaerobic ammonium oxidation mediated by Mn-oxides: from sediment to strain level.

PubMed

Javanaud, Cedric; Michotey, Valerie; Guasco, Sophie; Garcia, Nicole; Anschutz, Pierre; Canton, Mathieu; Bonin, Patricia

2011-11-01

Nitrite and (29)N(2) productions in slurry incubations of anaerobically sediment after (15)NO(3) or (15)NH(4) labelling in the presence of Mn-oxides suggested that anaerobic Mn-oxides mediated nitrification coupled with denitrification in muddy intertidal sediments of Arcachon Bay (SW Atlantic French coast). From this sediment, bacterial strains were isolated and physiologically characterized in terms of Mn-oxides and nitrate reduction as well as potential anaerobic nitrification. One of the isolated strain, identified as Marinobacter daepoensis strain M4AY14, was a denitrifier. Nitrous oxide production by this strain was demonstrated in the absence of nitrate and with Mn-oxides and NH(4) amendment, giving indirect proof of anaerobic nitrate or nitrite production. Anaerobic Mn-oxide-mediated nitrification was confirmed by (29)N(2) production in the presence of (15)NO(3) and (14)NH(4) under denitrifying conditions. Anaerobic nitrification by M4AY14 seemed to occur only in the absence of nitrate, or at nitrate levels lower than that of Mn-oxides. Most of the other isolates were affiliated with the Shewanella genus and were able to use both nitrate and Mn-oxides as electron acceptors. When both electron acceptors were present, whatever their concentrations, nitrate and Mn-oxide reduction co-occurred. These data indicate that bacterial Mn-oxide reduction could be an important process in marine sediments with low oxygen concentrations, and demonstrate for the first time the role of bacteria in anaerobic Mn-mediated nitrification. Copyright © 2011 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

Green Perylene Bisimide Dyes: Synthesis, Photophysical and Electrochemical Properties

PubMed Central

Chang, Che-Wei; Tsai, Hsing-Yang; Chen, Kew-Yu

2014-01-01

Three asymmetric amino-substituted perylene bisimide dyes with different n-alkyl chain lengths (n = 6, 12, or 18), 1-(N,N-dialkylamino)perylene bisimides (1a–1c), were synthesized under mild condition in high yields and were characterized by 1H NMR, 13C NMR (nuclear magnetic resonance), HRMS (High Resolution Mass Spectrometer), UV-Vis and fluorescence spectra, as well as cyclic voltammetry (CV). These molecules show intense green color in both solution and solid state and are highly soluble in dichloromethane and even in nonpolar solvents, such as hexane. The shapes of the absorption spectra of 1a–1c in solid state and in solution were found to be virtually the same, indicating that the long alkyl chains could efficiently prevent aggregation. They exhibit a unique charge transfer emission in the near-infrared region, of which the peak wavelengths show strong solvatochromism. The dipole moments of the compounds have been estimated using the Lippert-Mataga equation, and upon excitation, they show larger dipole moment changes than that of 1-aminoperylene bisimide (2). Furthermore, all of the compounds exhibit two quasi-reversible one-electron oxidations and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory (DFT) calculations performed on these dyes are reported in order to rationalize their molecular structures and electronic properties. PMID:28788140

1,7-Bis-(N,N-dialkylamino)perylene Bisimides: Facile Synthesis and Characterization as Near-Infrared Fluorescent Dyes

PubMed Central

Chen, Kew-Yu; Chang, Che-Wei

2014-01-01

Three symmetric alkylamino-substituted perylene bisimides with different n-alkyl chain lengths (n = 6, 12, or 18), 1,7-bis-(N,N-dialkylamino)perylene bisimides (1a–1c), were synthesized under mild condition and were characterized by 1H NMR, 13C NMR and high resolution mass spectroscopy. Their optical and electrochemical properties were measured using UV-Vis and emission spectroscopic techniques as well as cyclic voltammetry (CV). These compounds show deep green color in both solution and solid state, and are highly soluble in dichloromethane and even in nonpolar solvents such as hexane. The shapes of the absorption spectra of 1a–1c in the solution and solid state were found to be almost the same, indicating that the long alkyl chains could efficiently prevent intermolecular contact and aggregation. They show a unique charge transfer emission in the near-infrared region, of which the peak wavelengths exhibit strong solvatochromism. The dipole moments of the molecules have been estimated using the Lippert–Mataga equation, and upon excitation, they show larger dipole moment changes than that of 1,7-diaminoperylene bisimide (2). Moreover, all the dyes exhibit two irreversible one-electron oxidations and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory calculations performed on these chromophores are reported in order to rationalize their electronic structure and optical properties. PMID:28788262

Characterization of a Highly Enriched Microbial Consortium Reductively Dechlorinating 2,3-Dichlorophenol and 2,4,6-Trichlorophenol and the Corresponding cprA Genes from River Sediment.

PubMed

El-Sayed, Wael S

2016-08-26

Anaerobic reductive dechlorination of 2,3-dichlorophenol (2,3DCP) and 2,4,6-trichlorophenol (2,4,6TCP) was investigated in microcosms from River Nile sediment. A stable sediment-free anaerobic microbial consortium reductively dechlorinating 2,3DCP and 2,4,6TCP was established. Defined sediment-free cultures showing stable dechlorination were restricted to ortho chlorine when enriched with hydrogen as the electron donor, acetate as the carbon source, and either 2,3-DCP or 2,4,6-TCP as electron acceptors. When acetate, formate, or pyruvate were used as electron donors, dechlorination activity was lost. Only lactate can replace dihydrogen as an electron donor. However, the dechlorination potential was decreased after successive transfers. To reveal chlororespiring species, the microbial community structure of chlorophenol-reductive dechlorinating enrichment cultures was analyzed by PCR-denaturing gradient gel electrophoresis (DGGE) of 16S rRNA gene fragments. Eight dominant bacteria were detected in the dechlorinating microcosms including members of the genera Citrobacter, Geobacter, Pseudomonas, Desulfitobacterium, Desulfovibrio and Clostridium. Highly enriched dechlorinating cultures were dominated by four bacterial species belonging to the genera Pseudomonas, Desulfitobacterium, and Clostridium. Desulfitobacterium represented the major fraction in DGGE profiles indicating its importance in dechlorination activity, which was further confirmed by its absence resulting in complete loss of dechlorination. Reductive dechlorination was confirmed by the stoichiometric dechlorination of 2,3DCP and 2,4,6TCP to metabolites with less chloride groups and by the detection of chlorophenol RD cprA gene fragments in dechlorinating cultures. PCR amplified cprA gene fragments were cloned and sequenced and found to cluster with the cprA/pceA type genes of Dehalobacter restrictus.

A comparative study of the reduction of silver and gold salts in water by a cathodic microplasma electrode

NASA Astrophysics Data System (ADS)

De Vos, Caroline; Baneton, Joffrey; Witzke, Megan; Dille, Jean; Godet, Stéphane; Gordon, Michael J.; Mohan Sankaran, R.; Reniers, François

2017-03-01

A comparative study of the reduction of aqueous silver (Ag) and gold (Au) salts to colloidal Ag and Au nanoparticles, respectively, by a gaseous, cathodic, atmospheric-pressure microplasma electrode is presented. The resulting nanoparticles (NPs) were characterized by ultraviolet-visible (UV-vis) absorption spectroscopy and transmission electron microscopy (TEM), and the aqueous solution composition before and after experiments was determined by ionic conductivity, electrochemical potential, and/or UV-vis absorption measurements. TEM showed that Ag and Au NPs were spherical and non-agglomerated when synthesized in the presence of a stabilizer, polyvinyl alcohol. The charge injected by the plasma was correlated to the maximum intensity in the absorbance spectra which in turn depends on the nanoparticle concentration. Separately, the charge injected was correlated to the metal cation concentration. Ag and Au reduction rates were found to be directly proportional to the charge injected, independent of plasma current and process time. Differences in the mechanism for Ag and Au reduction were also observed, and solution species generated by the plasma and their role in the reduction process (e.g. H2O2, electrons) is discussed.

Associations with resident physicians' early adoption of electronic cigarettes for smoking cessation.

PubMed

Egnot, Eric; Jordan, Kim; Elliott, John O

2017-06-01

Use of the electronic cigarette for nicotine delivery has increased dramatically in recent years. Information continues to emerge on its role as a smoking cessation aid, but little is known about resident physician use of the device in clinical practice. In 2015, an electronic survey was administered to resident physicians in one healthcare system in Columbus, Ohio. The survey included questions about personal smoking exposure, knowledge, beliefs, attitudes about electronic cigarettes and early adoption of electronic cigarettes with patients. Data were dichotomised based on a 'stages of change' model that assessed resident physician adoption of electronic cigarettes for therapeutic use. Data were analysed through χ 2 tests and logistic regression using ORs and 95% CIs. Of 338 residents, 142 (42%) responded. Of all residents, 25 (17.7%) reported that they have been recommending electronic cigarettes to their patients for the past 6 months or longer. In the multivariate model, residents ≥postgraduate year (PGY)-3 (OR=3.68, 95% CI 1.20 to 11.29), peer-reviewed article exposure (OR=6.65, 95% CI 1.56 to 28.38) and the view that addictive potential is definitely or somewhat less than traditional cigarettes (OR=5.05, 95% CI 1.48 to 17.24) were associated with recommendation of electronic cigarettes. Few residents report recommending electronic cigarettes to patients who smoke. These residents consider the electronic cigarette less addicting than traditional cigarettes, supporting harm reduction strategies over strict abstinence. Most residents require further evidence-based education on efficacy and long-term safety of electronic cigarettes before recommending to their patients. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

Regulatory interactions in the dimeric cytochrome bc(1) complex: the advantages of being a twin.

PubMed

Covian, Raul; Trumpower, Bernard L

2008-09-01

The dimeric cytochrome bc(1) complex catalyzes the oxidation-reduction of quinol and quinone at sites located in opposite sides of the membrane in which it resides. We review the kinetics of electron transfer and inhibitor binding that reveal functional interactions between the quinol oxidation site at center P and quinone reduction site at center N in opposite monomers in conjunction with electron equilibration between the cytochrome b subunits of the dimer. A model for the mechanism of the bc(1) complex has emerged from these studies in which binding of ligands that mimic semiquinone at center N regulates half-of-the-sites reactivity at center P and binding of ligands that mimic catalytically competent binding of ubiquinol at center P regulates half-of-the-sites reactivity at center N. An additional feature of this model is that inhibition of quinol oxidation at the quinone reduction site is avoided by allowing catalysis in only one monomer at a time, which maximizes the number of redox acceptor centers available in cytochrome b for electrons coming from quinol oxidation reactions at center P and minimizes the leakage of electrons that would result in the generation of damaging oxygen radicals.

Facilitated extracellular electron transfer of Shewanella loihica PV-4 by antimony-doped tin oxide nanoparticles as active microelectrodes.

PubMed

Zhang, Xiaojian; Liu, Huan; Wang, Jinrong; Ren, Guangyuan; Xie, Beizhen; Liu, Hong; Zhu, Ying; Jiang, Lei

2015-11-28

Dissimilatory metal reducing bacteria are capable of extracellular electron transfer (EET) to insoluble metal oxides as external electron acceptors for their anaerobic respiration, which is recognized as an important energy-conversion process in natural and engineered environments, such as in mineral cycling, bioremediation, and microbial fuel/electrolysis cells. However, the low EET efficiency remains one of the major bottlenecks for its practical application. We report firstly that the microbial current generated by Shewanella loihica PV-4 (S. loihica PV-4) could be greatly improved that is up to ca. 115 fold, by adding antimony-doped tin oxide (ATO) nanoparticles in the electrochemical reactor. The results demonstrate that the biocompatible, electrically conductive ATO nanoparticles acted as active microelectrodes could facilitate the formation of a cells/ATO composite biofilm and the reduction of the outer membrane c-type cytochromes (OM c-Cyts) that are beneficial for the electron transfer from cells to electrode. Meanwhile, a synergistic effect between the participation of OM c-Cyts and the accelerated EET mediated by cell-secreted flavins may play an important role for the enhanced current generation in the presence of ATO nanoparticles. Moreover, it is worth noting that the TCA cycle in S. loihica PV-4 cells is activated by adding ATO nanoparticles, even if the potential is poised at +0.2 V, thereby also improving the EET process. The results presented here may provide a simple and effective strategy to boost the EET of S. loihica PV-4 cells, which is conducive to providing potential applications in bioelectrochemical systems.

Identical Location Transmission Electron Microscopy Imaging of Site-Selective Pt Nanocatalysts: Electrochemical Activation and Surface Disordering.

PubMed

Arán-Ais, Rosa M; Yu, Yingchao; Hovden, Robert; Solla-Gullón, Jose; Herrero, Enrique; Feliu, Juan M; Abruña, Héctor D

2015-12-02

We have employed identical location transmission electron microscopy (IL-TEM) to study changes in the shape and morphology of faceted Pt nanoparticles as a result of electrochemical cycling; a procedure typically employed for activating platinum surfaces. We find that the shape and morphology of the as-prepared hexagonal nanoparticles are rapidly degraded as a result of potential cycling up to +1.3 V. As few as 25 potential cycles are sufficient to cause significant degradation, and after about 500-1000 cycles the particles are dramatically degraded. We also see clear evidence of particle migration during potential cycling. These finding suggest that great care must be exercised in the use and study of shaped Pt nanoparticles (and related systems) as electrocatlysts, especially for the oxygen reduction reaction where high positive potentials are typically employed.

Susceptibility of Murine Norovirus and Hepatitis A Virus to Electron Beam Irradiation in Oysters and Quantifying the Reduction in Potential Infection Risks

PubMed Central

Praveen, Chandni; Dancho, Brooke A.; Kingsley, David H.; Calci, Kevin R.; Meade, Gloria K.; Mena, Kristina D.

2013-01-01

Consumption of raw oysters is an exposure route for human norovirus (NoV) and hepatitis A virus (HAV). Therefore, efficient postharvest oyster treatment technology is needed to reduce public health risks. This study evaluated the inactivation of HAV and the NoV research surrogate, murine norovirus-1 (MNV-1), in oysters (Crassostrea virginica) by electron beam (E-beam) irradiation. The reduction of potential infection risks was quantified for E-beam irradiation technology employed on raw oysters at various virus contamination levels. The E-beam dose required to reduce the MNV and HAV titer by 90% (D10 value) in whole oysters was 4.05 (standard deviations [SD], ±0.63) and 4.83 (SD, ±0.08) kGy, respectively. Microbial risk assessment suggests that if a typical serving of 12 raw oysters was contaminated with 105 PFU, a 5-kGy treatment would achieve a 12% reduction (from 4.49 out of 10 persons to 3.95 out of 10 persons) in NoV infection and a 16% reduction (from 9.21 out of 10 persons to 7.76 out of 10 persons) in HAV infections. If the serving size contained only 102 PFU of viruses, a 5-kGy treatment would achieve a 26% reduction (2.74 out of 10 persons to 2.03 out of 10 persons) of NoV and 91% reduction (2.1 out of 10 persons to 1.93 out of 100 persons) of HAV infection risks. This study shows that although E-beam processing cannot completely eliminate the risk of viral illness, infection risks can be reduced. PMID:23584781

Susceptibility of murine norovirus and hepatitis A virus to electron beam irradiation in oysters and quantifying the reduction in potential infection risks.

PubMed

Praveen, Chandni; Dancho, Brooke A; Kingsley, David H; Calci, Kevin R; Meade, Gloria K; Mena, Kristina D; Pillai, Suresh D

2013-06-01

Consumption of raw oysters is an exposure route for human norovirus (NoV) and hepatitis A virus (HAV). Therefore, efficient postharvest oyster treatment technology is needed to reduce public health risks. This study evaluated the inactivation of HAV and the NoV research surrogate, murine norovirus-1 (MNV-1), in oysters (Crassostrea virginica) by electron beam (E-beam) irradiation. The reduction of potential infection risks was quantified for E-beam irradiation technology employed on raw oysters at various virus contamination levels. The E-beam dose required to reduce the MNV and HAV titer by 90% (D(10) value) in whole oysters was 4.05 (standard deviations [SD], ±0.63) and 4.83 (SD, ±0.08) kGy, respectively. Microbial risk assessment suggests that if a typical serving of 12 raw oysters was contaminated with 10(5) PFU, a 5-kGy treatment would achieve a 12% reduction (from 4.49 out of 10 persons to 3.95 out of 10 persons) in NoV infection and a 16% reduction (from 9.21 out of 10 persons to 7.76 out of 10 persons) in HAV infections. If the serving size contained only 10(2) PFU of viruses, a 5-kGy treatment would achieve a 26% reduction (2.74 out of 10 persons to 2.03 out of 10 persons) of NoV and 91% reduction (2.1 out of 10 persons to 1.93 out of 100 persons) of HAV infection risks. This study shows that although E-beam processing cannot completely eliminate the risk of viral illness, infection risks can be reduced.

Relative importance of driving force and electrostatic interactions in the reduction of multihaem cytochromes by small molecules.

PubMed

Quintas, Pedro O; Cepeda, Andreia P; Borges, Nuno; Catarino, Teresa; Turner, David L

2013-06-01

Multihaem cytochromes are essential to the energetics of organisms capable of bioremediation and energy production. The haems in several of these cytochromes have been discriminated thermodynamically and their individual rates of reduction by small electron donors were characterized. The kinetic characterization of individual haems used the Marcus theory of electron transfer and assumed that the rates of reduction of each haem by sodium dithionite depend only on the driving force, while electrostatic interactions were neglected. To determine the relative importance of these factors in controlling the rates, we studied the effect of ionic strength on the redox potential and the rate of reduction by dithionite of native Methylophilus methylotrophus cytochrome c″ and three mutants at different pH values. We found that the main factor determining the rate is the driving force and that Marcus theory describes this satisfactorily. This validates the method of the simultaneous fitting of kinetic and thermodynamic data in multihaem cytochromes and opens the way for further investigation into the mechanisms of these proteins. Copyright © 2013 Elsevier B.V. All rights reserved.

The effect of potential electronic nicotine delivery system regulations on nicotine product selection.

PubMed

Pesko, Michael F; Kenkel, Donald S; Wang, Hua; Hughes, Jenna M

2016-04-01

To estimate the effect of potential regulations of electronic nicotine delivery systems (ENDS) among adult smokers, including increasing taxes, reducing flavor availability and adding warning labels communicating various levels of risk. We performed a discrete choice experiment (DCE) among a national sample of 1200 adult smokers. We examined heterogeneity in policy responses by age, cigarette quitting interest and current ENDS use. Our experiment overlapped January 2015 by design, providing exogenous variation in cigarette quitting interest from New Year resolutions. KnowledgePanel, an online panel of recruited respondents. A total of 1200 adult smokers from the United States. Hypothetical purchase choice of cigarettes, nicotine replacement therapy and a disposable ENDS. Increasing ENDS prices from $3 to $6 was associated with a 13.6 percentage point reduction in ENDS selection (P < 0.001). Restricting flavor availability in ENDS to tobacco and menthol was associated with a 2.1 percentage point reduction in ENDS selection (P < 0.001). The proposed Food and Drug Administration (FDA) warning label was associated with a 1.1 percentage point reduction in ENDS selection (P < 0.05) and the MarkTen warning label with a 5.1 percentage point reduction (P < 0.001). We estimated an ENDS price elasticity of -1.8 (P < 0.001) among adult smokers. Statistically significant interaction terms (P < 0.001) imply that price responsiveness was higher among adult smokers 18-24 years of age, smokers who have vaped over the last month and smokers with above the median quitting interest. Young adult smokers were 3.7 percentage points more likely to choose ENDS when multiple flavors were available than older adults (P < 0.001). Young adult smokers and those with above the median cigarette quitting interest were also more likely to reduce cigarette selection and increase ENDS selection in January 2015 (P < 0.001), potentially in response to New Year's resolutions to quit smoking. Increased taxes, a proposed US Food and Drug Administration warning label for electronic nicotine delivery systems and a more severe warning label may discourage adult smokers from switching to electronic nicotine delivery systems. Reducing the availability of flavors may reduce ENDS use by young adult smokers. © 2015 Society for the Study of Addiction.

Observation of warm, higher energy electrons transiting a double layer in a helicon plasma

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

Sung, Yung-Ta, E-mail: ysung2@wisc.edu; Li, Yan; Scharer, John E.

2015-03-15

Measurements of an inductive RF helicon argon plasma double layer with two temperature electron distributions including a fast (>80 eV) tail are observed at 0.17 mTorr Ar pressure. The fast, untrapped electrons observed downstream of the double layer have a higher temperature (13 eV) than the trapped (T{sub e} = 4 eV) electrons. The reduction of plasma potential and density observed in the double layer region would require an upstream temperature ten times the measured 4 eV if occurring via Boltzmann ambipolar expansion. The experimental observation in Madison helicon experiment indicates that fast electrons with substantial density fractions can be created at low helicon operating pressures.

Nonplanar ion acoustic waves with kappa-distributed electrons

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

Sahu, Biswajit

2011-06-15

Using the standard reductive perturbation technique, nonlinear cylindrical and spherical Kadomtsev-Petviashvili equations are derived for the propagation of ion acoustic solitary waves in an unmagnetized collisionless plasma with kappa distributed electrons and warm ions. The influence of kappa-distributed electrons and the effects caused by the transverse perturbation on cylindrical and spherical ion acoustic waves (IAWs) are investigated. It is observed that increase in the kappa distributed electrons (i.e., decreasing {kappa}) decreases the amplitude of the solitary electrostatic potential structures. The numerical results are presented to understand the formation of ion acoustic solitary waves with kappa-distributed electrons in nonplanar geometry. Themore » present investigation may have relevance in the study of propagation of IAWs in space and laboratory plasmas.« less

Ageing and thermal recovery of paramagnetic centers induced by electron irradiation in yttria-stabilized zirconia

NASA Astrophysics Data System (ADS)

Costantini, J. M.; Beuneu, F.

We have used electron spin resonance spectroscopy to study the defects induced in yttria-stabilized zirconia (YSZ) single crystals by 2.5-MeV electron irradiations. Two paramagnetic centers are produced: the first one with an axial <111> symmetry is similar to the trigonal Zr3+ electron center (T center) found after X-ray irradiation or thermo-chemical reduction, whereas the second one is a new oxygen hole center with an axial <100> symmetry different from the orthorhombic O- center induced by X-ray irradiation. At a fluence around 10(18) e/cm(2) , both centers are bleached out near 600 K, like the corresponding X-ray induced defects. At a fluence around 10(19) e/cm(2) , defects are much more stable, since complete thermal bleaching occurs near 1000 K. Accordingly, ageing of as-irradiated samples shows that high-dose defects at more stable than the low-dose ones.

Kinetic and Thermodynamic Characterization of the Cobalt and Manganese Oxyhydroxide Cores Formed in Horse Spleen Ferritin

NASA Technical Reports Server (NTRS)

Zhang, Bo; Harb, John N.; Davis, Robert C.; Kim, Jae-Woo; Chu, Sang-Hyon; Choi, Sang; Miller, Tim; Watt, Gerald D.

2004-01-01

Horse spleen ferritin (HoSF) containing 800-1500 cobalt or 250-1200 manganese atoms as Co(O)OH and Mn(O)OH mineral cores within the HoSF interior (Co-HoSF and Mn-HoSF) was synthesized, and the chemical reactivity, kinetics of reduction, and the reduction potentials were measured. Microcoulometric and chemical reduction of HoSF containing the M(O)OH mineral core (M = Co or Mn) was rapid and quantitative with a reduction stoichiometry of 1.05+/-0.10 e/M forming a stable M(OH)2 mineral core. At pH 9.0, ascorbic acid (AH2), a two-electron reductant, effectively reduced the mineral cores; however, the reaction was incomplete and rapidly reached equilibrium. The addition of excess AH2 shifted the reaction to completion with a M(3+)/AH2 stoichiometry of 1.9-2.1, consistent with a single electron per metal atom reduction. The rate of reaction between M(0)OH and excess AH2 was measured by monitoring the decrease in mineral core absorbance with time. The reaction was first order in each reactant with second-order rate constants of 0.53 and 4.74/M/min, respectively, for Co- and Mn-HoSF at pH 9.0. From the variation of absorbance with increasing AH2 concentration, equilibrium constants at pH 9.0 of 5.0+/-1.9 for Co-HoSF and 2.9+/-0.9 for Mn-HoSF were calculated for 2M(O)OH + AH2 = 2M(OH)2 f D, where AH2 and D are ascorbic acid and dehydroascorbic acid, respectively. Consistent with these equilibrium constants, the standard potential for the reduction of Co(III)-HoSF is 42 mV more positive than that of the ascorbic acid reaction, while the standard potential of Mn(III)-HoSF is 27 mV positive relative to AH2. Fe(2+) in solution with Co- and Mn-HoSF under anaerobic conditions was oxidized to form Fe(O)OH within the HoSF interior, resulting in partial displacement of the Co or Mn by iron.

Role of water and carbonates in photocatalytic transformation of CO{sub 2} to CH{sub 4} on titania.

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

Dimitrijevic, N. M.; Vijayan, B. K.; Poluektov, O. G.

Using the electron paramagnetic resonance technique, we have elucidated the multiple roles of water and carbonates in the overall photocatalytic reduction of carbon dioxide to methane over titania nanoparticles. The formation of H atoms (reduction product) and {center_dot}OH radicals (oxidation product) from water, and CO{sub 3}{sup -} radical anions (oxidation product) from carbonates, was detected in CO{sub 2}-saturated titania aqueous dispersion under UV illumination. Additionally, methoxyl, {center_dot}OCH{sub 3}, and methyl, {center_dot}CH{sub 3}, radicals were identified as reaction intermediates. The two-electron, one-proton reaction proposed as an initial step in the reduction of CO{sub 2} on the surface of TiO{sub 2} ismore » supported by the results of first-principles calculations.« less

Role of Water and Carbonates in Photocatalytic Transformation of CO2 to CH4 on Titania

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

Dimitrijevic, Nada; Vijayan, Baiju K.; Poluektov, Oleg G.

Using the electron paramagnetic resonance technique, we have elucidated the multiple roles of water and carbonates in the overall photocatalytic reduction of carbon dioxide to methane over titania nanoparticles. The formation of H atoms (reduction product) and {sm_bullet}OH radicals (oxidation product) from water, and CO{sub 3}{sup -} radical anions (oxidation product) from carbonates, was detected in CO{sub 2}-saturated titania aqueous dispersion under UV illumination. Additionally, methoxyl, {sm_bullet}OCH{sub 3}, and methyl, {sm_bullet}CH{sub 3}, radicals were identified as reaction intermediates. The two-electron, one-proton reaction proposed as an initial step in the reduction of CO{sub 2}, on the surface of TiO{sub 2}, ismore » supported by the results of first-principles calculations.« less

Biomimetics of [NiFe]-Hydrogenase: Nickel- or Iron-Centered Proton Reduction Catalysis?

PubMed

Tang, Hao; Hall, Michael B

2017-12-13

The [NiFe] hydrogenase (H2ase) has been characterized in the Ni-R state with a hydride bridging between Fe and Ni but displaced toward the Ni. In nearly all of the synthetic Ni-R models reported so far, the hydride ligand is either displaced toward Fe, or terminally bound to Fe. Recently, a structural and functional [NiFe]-H2ase mimic ( Nat. Chem. 2016 , 8 , 1054 - 1060 ) was reported to produce H 2 catalytically via EECC mechanism through a Ni-centered hydride intermediate like the enzyme. Here, a comprehensive DFT study shows a much lower energy route via an E[ECEC] mechanism through an Fe-centered hydride intermediate. Although catalytic H 2 production occurs at the potential corresponding to the complex's second reduction, a third electron is needed to induce the second proton addition from the weak acid. The first two-electron reductions and a proton addition produce a semibridging hydride with a short Fe-H bond like other structured [NiFe]-biomimetics, but this species is not basic enough to add another proton from the weak acid without the third electron. The calculated mechanism provides insight into the origin of this structure in the enzyme.

Decreasing the Hydroxylation Affinity of La 1–x Sr x MnO 3 Perovskites To Promote Oxygen Reduction Electrocatalysis

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

Stoerzinger, Kelsey A.; Hong, Wesley T.; Wang, Xiao Renshaw

Understanding the interaction between oxides and water is critical to design many of their functionalities, including the electrocatalysis of molecular oxygen reduction. In this study, we probed the hydroxylation of model (001)-oriented La(1-x)SrxMnO3 (LSMO) perovskite surfaces, where the electronic structure and manganese valence was controlled by five substitution levels of lanthanum with strontium, using ambient pressure X-ray photoelectron spectroscopy in a humid environment. The degree of hydroxyl formation on the oxide surface correlated with the proximity of the valence band center relative to the Fermi level. LSMO perovskites with a valence band center closer to the Fermi level were moremore » reactive toward water, forming more hydroxyl species at a given relative humidity. More hydroxyl species correlate with greater electron-donating character to the surface free energy in wetting, and reduce the activity to catalyze oxygen reduction reaction (ORR) kinetics in basic solution. New strategies to design more active catalysts should include design of electronically conducting oxides with lower valence band centers relative to the Fermi level at ORR-relevant potentials.« less

Oxidation catalysis by polyoxometalates fundamental electron-transfer phenomena

Treesearch

Yurii V. Geletii; Rajai H. Atalla; Alan J. Bailey; Laurent Delannoy; Craig L. Hill; Ira A. Weinstock

2002-01-01

Early transition-metal oxygen-anion clusters (polyoxometalates, POMs) are a large and rapidly growing class of versatile and tunable oxidation catalysts. All key molecular properties of these clusters (composition, size, shape, charge density, reduction potential, solubility, etc.) can be systematically altered, and the clusters themselves can serve as tunable ligands...

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

PubMed

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

2007-10-30

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

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

NASA Astrophysics Data System (ADS)

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

2007-10-01

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

Positron lifetime spectrometer using a DC positron beam

DOEpatents

Xu, Jun; Moxom, Jeremy

2003-10-21

An entrance grid is positioned in the incident beam path of a DC beam positron lifetime spectrometer. The electrical potential difference between the sample and the entrance grid provides simultaneous acceleration of both the primary positrons and the secondary electrons. The result is a reduction in the time spread induced by the energy distribution of the secondary electrons. In addition, the sample, sample holder, entrance grid, and entrance face of the multichannel plate electron detector assembly are made parallel to each other, and are arranged at a tilt angle to the axis of the positron beam to effectively separate the path of the secondary electrons from the path of the incident positrons.

High-Temperature High-Power Packaging Techniques for HEV Traction Applications

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

Barlow, F.D.; Elshabini, A.

A key issue associated with the wider adoption of hybrid-electric vehicles (HEV) and plug in hybrid-electric vehicles (PHEV) is the implementation of the power electronic systems that are required in these products [1]. To date, many consumers find the adoption of these technologies problematic based on a financial analysis of the initial cost versus the savings available from reduced fuel consumption. Therefore, one of the primary industry goals is the reduction in the price of these vehicles relative to the cost of traditional gasoline powered vehicles. Part of this cost reduction must come through optimization of the power electronics requiredmore » by these vehicles. In addition, the efficiency of the systems must be optimized in order to provide the greatest range possible. For some drivers, any reduction in the range associated with a potential HEV or PHEV solution in comparison to a gasoline powered vehicle represents a significant barrier to adoption and the efficiency of the power electronics plays an important role in this range. Likewise, high efficiencies are also important since lost power further complicates the thermal management of these systems. Reliability is also an important concern since most drivers have a high level of comfort with gasoline powered vehicles and are somewhat reluctant to switch to a less proven technology. Reliability problems in the power electronics or associated components could not only cause a high warranty cost to the manufacturer, but may also taint these technologies in the consumer's eyes. A larger vehicle offering in HEVs is another important consideration from a power electronics point of view. A larger vehicle will need more horsepower, or a larger rated drive. In some ways this will be more difficult to implement from a cost and size point of view. Both the packaging of these modules and the thermal management of these systems at competitive price points create significant challenges. One way in which significant cost reduction of these systems could be achieved is through the use of a single coolant loop for both the power electronics as well as the internal combustion engine (ICE) [2]. This change would reduce the complexity of the cooling system which currently relies on two loops to a single loop [3]. However, the current nominal coolant temperature entering these inverters is 65 C [3], whereas a normal ICE coolant temperature would be much higher at approximately 100 C. This change in coolant temperature significantly increases the junction temperatures of the devices and creates a number of challenges for both device fabrication and the assembly of these devices into inverters and converters for HEV and PHEV applications. With this change in mind, significant progress has been made on the use of SiC devices for inverters that can withstand much higher junction temperatures than traditional Si based inverters [4,5,6]. However, a key problem which the single coolant loop and high temperature devices is the effective packaging of these devices and related components into a high temperature inverter. The elevated junction temperatures that exist in these modules are not compatible with reliable inverters based on existing packaging technology. This report seeks to provide a literature survey of high temperature packaging and to highlight the issues related to the implementation of high temperature power electronic modules for HEV and PHEV applications. For purposes of discussion, it will be assumed in this report that 200 C is the targeted maximum junction temperature.« less

Electron affinities of polycyclic aromatic hydrocarbons by means of B3LYP/6-31+G* calculations.

PubMed

Modelli, Alberto; Mussoni, Laura; Fabbri, Daniele

2006-05-25

The gas-phase experimental adiabatic electron affinities (AEAs) of the polycyclic aromatic hydrocarbons (PAHs) anthracene, tetracene, pentacene, chrysene, pyrene, benzo[a]pyrene, benzo[e]pyrene, and fluoranthene are well reproduced using the hybrid density functional method B3LYP with the 6-31+G* basis set, indicating that the smallest addition of diffuse functions to the basis set is suitable for a correct description of the stable PAH anion states. The calculated AEAs also give a very good linear correlation with available reduction potentials measured in solution. The AEAs (not experimentally available) of the isomeric benzo[ghi]fluoranthene and cyclopenta[cd]pyrene, commonly found in the environment, are predicted to be 0.817 and 1.108 eV, respectively, confirming the enhancement of the electron-acceptor properties associated with fusion of a peripheral cyclopenta ring. The calculated localization properties of the lowest unoccupied MO of cyclopenta[cd]pyrene, together with its relatively high electron affinity, account for a high reactivity at the ethene double bond of this PAH in reductive processes.

How light-harvesting semiconductors can alter the bias of reversible electrocatalysts in favor of H2 production and CO2 reduction.

PubMed

Bachmeier, Andreas; Wang, Vincent C C; Woolerton, Thomas W; Bell, Sophie; Fontecilla-Camps, Juan C; Can, Mehmet; Ragsdale, Stephen W; Chaudhary, Yatendra S; Armstrong, Fraser A

2013-10-09

The most efficient catalysts for solar fuel production should operate close to reversible potentials, yet possess a bias for the fuel-forming direction. Protein film electrochemical studies of Ni-containing carbon monoxide dehydrogenase and [NiFeSe]-hydrogenase, each a reversible electrocatalyst, show that the electronic state of the electrode strongly biases the direction of electrocatalysis of CO2/CO and H(+)/H2 interconversions. Attached to graphite electrodes, these enzymes show high activities for both oxidation and reduction, but there is a marked shift in bias, in favor of CO2 or H(+) reduction, when the respective enzymes are attached instead to n-type semiconductor electrodes constructed from CdS and TiO2 nanoparticles. This catalytic rectification effect can arise for a reversible electrocatalyst attached to a semiconductor electrode if the electrode transforms between semiconductor- and metallic-like behavior across the same narrow potential range (<0.25 V) that the electrocatalytic current switches between oxidation and reduction.

Stable platinum nanoclusters on genomic DNA–graphene oxide with a high oxygen reduction reaction activity

PubMed Central

Tiwari, Jitendra N.; Nath, Krishna; Kumar, Susheel; Tiwari, Rajanish N.; Kemp, K. Christian; Le, Nhien H.; Youn, Duck Hyun; Lee, Jae Sung; Kim, Kwang S.

2013-01-01

Nanosize platinum clusters with small diameters of 2–4 nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2 nm). Here we report the synthesis of platinum clusters (diameter ≤1.4 nm) deposited on genomic double-stranded DNA–graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA–graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA–graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries. PMID:23900456

From chemolithoautotrophs to electrolithoautotrophs: CO2 fixation by Fe(II)-oxidizing bacteria coupled with direct uptake of electrons from solid electron sources.

PubMed

Ishii, Takumi; Kawaichi, Satoshi; Nakagawa, Hirotaka; Hashimoto, Kazuhito; Nakamura, Ryuhei

2015-01-01

At deep-sea vent systems, hydrothermal emissions rich in reductive chemicals replace solar energy as fuels to support microbial carbon assimilation. Until recently, all the microbial components at vent systems have been assumed to be fostered by the primary production of chemolithoautotrophs; however, both the laboratory and on-site studies demonstrated electrical current generation at vent systems and have suggested that a portion of microbial carbon assimilation is stimulated by the direct uptake of electrons from electrically conductive minerals. Here we show that chemolithoautotrophic Fe(II)-oxidizing bacterium, Acidithiobacillus ferrooxidans, switches the electron source for carbon assimilation from diffusible Fe(2+) ions to an electrode under the condition that electrical current is the only source of energy and electrons. Site-specific marking of a cytochrome aa3 complex (aa3 complex) and a cytochrome bc1 complex (bc1 complex) in viable cells demonstrated that the electrons taken directly from an electrode are used for O2 reduction via a down-hill pathway, which generates proton motive force that is used for pushing the electrons to NAD(+) through a bc1 complex. Activation of carbon dioxide fixation by a direct electron uptake was also confirmed by the clear potential dependency of cell growth. These results reveal a previously unknown bioenergetic versatility of Fe(II)-oxidizing bacteria to use solid electron sources and will help with understanding carbon assimilation of microbial components living in electronically conductive chimney habitats.

From chemolithoautotrophs to electrolithoautotrophs: CO2 fixation by Fe(II)-oxidizing bacteria coupled with direct uptake of electrons from solid electron sources

PubMed Central

Ishii, Takumi; Kawaichi, Satoshi; Nakagawa, Hirotaka; Hashimoto, Kazuhito; Nakamura, Ryuhei

2015-01-01

At deep-sea vent systems, hydrothermal emissions rich in reductive chemicals replace solar energy as fuels to support microbial carbon assimilation. Until recently, all the microbial components at vent systems have been assumed to be fostered by the primary production of chemolithoautotrophs; however, both the laboratory and on-site studies demonstrated electrical current generation at vent systems and have suggested that a portion of microbial carbon assimilation is stimulated by the direct uptake of electrons from electrically conductive minerals. Here we show that chemolithoautotrophic Fe(II)-oxidizing bacterium, Acidithiobacillus ferrooxidans, switches the electron source for carbon assimilation from diffusible Fe2+ ions to an electrode under the condition that electrical current is the only source of energy and electrons. Site-specific marking of a cytochrome aa3 complex (aa3 complex) and a cytochrome bc1 complex (bc1 complex) in viable cells demonstrated that the electrons taken directly from an electrode are used for O2 reduction via a down-hill pathway, which generates proton motive force that is used for pushing the electrons to NAD+ through a bc1 complex. Activation of carbon dioxide fixation by a direct electron uptake was also confirmed by the clear potential dependency of cell growth. These results reveal a previously unknown bioenergetic versatility of Fe(II)-oxidizing bacteria to use solid electron sources and will help with understanding carbon assimilation of microbial components living in electronically conductive chimney habitats. PMID:26500609

Effects of water stress on photosynthetic electron transport, photophosphorylation, and metabolite levels of Xanthium strumarium mesophyll cells.

PubMed

Sharkey, T D; Badger, M R

1982-12-01

Several component processes of photosynthesis were measured in osmotically stressed mesophyll cells of Xanthium strumarium L. The ribulose-1,5-bisphosphate regeneration capacity was reduced by water stress. Photophoshorylation was sensitive to water stress but photosynthetic electron transport was unaffected by water potentials down to-40 bar (-4 MPa). The concentrations of several intermediates of the photosynthetic carbon-reduction cycle remained relatively constant and did not indicate that ATP supply was limiting photosynthesis in the water-stressed cells.

The electronic cigarette: a knight in shining armour or a Trojan horse?†

PubMed Central

Schluger, Neil W.

2014-01-01

Electronic cigarettes have caused a sharp debate in the public health community, with some promoting them as a means of harm reduction for tobacco users and some taking a strong stand against them because of fear of renormalising smoking behaviour and interrupting tobacco control progress. People with mental health problems smoke at high rates and e-cigarettes seem a potentially attractive method of cessation in this population, and their use should be studied carefully. PMID:25285216

Theoretical Analysis of Thermal Transport in Graphene Supported on Hexagonal Boron Nitride: The Importance of Strong Adhesion Due to π -Bond Polarization

NASA Astrophysics Data System (ADS)

Pak, Alexander J.; Hwang, Gyeong S.

2016-09-01

One important attribute of graphene that makes it attractive for high-performance electronics is its inherently large thermal conductivity (κ ) for the purposes of thermal management. Using a combined density-functional theory and classical molecular-dynamics approach, we predict that the κ of graphene supported on hexagonal boron nitride (h -BN) can be as large as 90% of the κ of suspended graphene, in contrast to the significant suppression of κ (more than 70% reduction) on amorphous silica. Interestingly, we find that this enhanced thermal transport is largely attributed to increased lifetimes of the in-plane acoustic phonon modes, which is a notable contrast from the dominant contribution of out-of-plane acoustic modes in suspended graphene. This behavior is possible due to the charge polarization throughout graphene that induces strong interlayer adhesion between graphene and h -BN. These findings highlight the potential benefit of layered dielectric substrates such as h -BN for graphene-based thermal management, in addition to their electronic advantages. Furthermore, our study brings attention to the importance of understanding the interlayer interactions of graphene with layered dielectric materials which may offer an alternative technological platform for substrates in electronics.

On the use of electrokinetic phenomena of the second kind for probing electrode kinetic properties of modified electron-conducting surfaces.

PubMed

Duval, Jérôme F L; Sorrenti, Estelle; Waldvogel, Yves; Görner, Tatiana; De Donato, Philippe

2007-04-14

The electrokinetic features of electron-conducting substrates, as measured in a conventional thin-layer electrokinetic cell, strongly depend on the extent of bipolar faradaic depolarisation of the interface formed with the adjacent electrolytic solution. Streaming potential versus applied pressure data obtained for metallic substrates must generally be interpreted on the basis of a modified Helmholtz-Smoluchowski equation corrected by an electronic conduction term-non linear with respect to the lateral potential and applied pressure gradient-that stems from the bipolar electrodic behavior of the metallic surface. In the current study, streaming potential measurements have been performed in KNO(3) solutions on porous plugs made of electron-conducting grains of pyrite (FeS(2)) covered by humic acids. For zero coverage, the extensive bipolar electronic conduction taking place in the plug-depolarized by concomitant and spatially distributed oxidation and reduction reactions of Fe(2+) and Fe(3+) species-leads to the complete extinction of the streaming potential over the entire range of applied pressure examined. For low to intermediate coverage, the local electron-transfer kinetics on the covered regions of the plug becomes more sluggish. The overall bipolar electronic conduction is then diminished which leads to an increase in the streaming potential with a non-linear dependence on the pressure. For significant coverage, a linear response is observed which basically reflects the interfacial double layer properties of the humics surface layer. A tractable, semi-analytical model is presented that reproduces the electrokinetic peculiarities of the complex and composite system FeS(2)/humics investigated. The study demonstrates that the streaming potential technique is a fast and valuable tool for establishing how well the electron transfer kinetics at a partially or completely depolarised bare electron-conducting substrate/electrolyte solution interface is either promoted (catalysis) or blocked (passivation) by the presence of a discontinuous surface layer.

A strategy to minimize the energy offset in carrier injection from excited dyes to inorganic semiconductors for efficient dye-sensitized solar energy conversion.

PubMed

Fujisawa, Jun-Ichi; Osawa, Ayumi; Hanaya, Minoru

2016-08-10

Photoinduced carrier injection from dyes to inorganic semiconductors is a crucial process in various dye-sensitized solar energy conversions such as photovoltaics and photocatalysis. It has been reported that an energy offset larger than 0.2-0.3 eV (threshold value) is required for efficient electron injection from excited dyes to metal-oxide semiconductors such as titanium dioxide (TiO2). Because the energy offset directly causes loss in the potential of injected electrons, it is a crucial issue to minimize the energy offset for efficient solar energy conversions. However, a fundamental understanding of the energy offset, especially the threshold value, has not been obtained yet. In this paper, we report the origin of the threshold value of the energy offset, solving the long-standing questions of why such a large energy offset is necessary for the electron injection and which factors govern the threshold value, and suggest a strategy to minimize the threshold value. The threshold value is determined by the sum of two reorganization energies in one-electron reduction of semiconductors and typically-used donor-acceptor (D-A) dyes. In fact, the estimated values (0.21-0.31 eV) for several D-A dyes are in good agreement with the threshold value, supporting our conclusion. In addition, our results reveal that the threshold value is possible to be reduced by enlarging the π-conjugated system of the acceptor moiety in dyes and enhancing its structural rigidity. Furthermore, we extend the analysis to hole injection from excited dyes to semiconductors. In this case, the threshold value is given by the sum of two reorganization energies in one-electron oxidation of semiconductors and D-A dyes.

Numerical study of the magnetized friction force

NASA Astrophysics Data System (ADS)

Fedotov, A. V.; Bruhwiler, D. L.; Sidorin, A. O.; Abell, D. T.; Ben-Zvi, I.; Busby, R.; Cary, J. R.; Litvinenko, V. N.

2006-07-01

Fundamental advances in experimental nuclear physics will require ion beams with orders of magnitude luminosity increase and temperature reduction. One of the most promising particle accelerator techniques for achieving these goals is electron cooling, where the ion beam repeatedly transfers thermal energy to a copropagating electron beam. The dynamical friction force on a fully ionized gold ion moving through magnetized and unmagnetized electron distributions has been simulated, using molecular dynamics techniques that resolve close binary collisions. We present a comprehensive examination of theoretical models in use by the electron cooling community. Differences in these models are clarified, enabling the accurate design of future electron cooling systems for relativistic ion accelerators.

Boron doped graphene wrapped silver nanowires as an efficient electrocatalyst for molecular oxygen reduction

PubMed Central

Nair, Anju K.; Thazhe veettil, Vineesh; Kalarikkal, Nandakumar; Thomas, Sabu; Kala, M. S.; Sahajwalla, Veena; Joshi, Rakesh K.; Alwarappan, Subbiah

2016-01-01

Metal nanowires exhibit unusually high catalytic activity towards oxygen reduction reaction (ORR) due to their inherent electronic structures. However, controllable synthesis of stable nanowires still remains as a daunting challenge. Herein, we report the in situ synthesis of silver nanowires (AgNWs) over boron doped graphene sheets (BG) and demonstrated its efficient electrocatalytic activity towards ORR for the first time. The electrocatalytic ORR efficacy of BG-AgNW is studied using various voltammetric techniques. The BG wrapped AgNWs shows excellent ORR activity, with very high onset potential and current density and it followed four electron transfer mechanism with high methanol tolerance and stability towards ORR. The results are comparable to the commercially available 20% Pt/C in terms of performance. PMID:27941954

Fast microbial reduction of ferrihydrite colloids from a soil effluent

NASA Astrophysics Data System (ADS)

Fritzsche, Andreas; Bosch, Julian; Rennert, Thilo; Heister, Katja; Braunschweig, Juliane; Meckenstock, Rainer U.; Totsche, Kai U.

2012-01-01

Recent studies on the microbial reduction of synthetic iron oxide colloids showed their superior electron accepting property in comparison to bulk iron oxides. However, natural colloidal iron oxides differ in composition from their synthetic counterparts. Besides a potential effect of colloid size, microbial iron reduction may be accelerated by electron-shuttling dissolved organic matter (DOM) as well as slowed down by inhibitors such as arsenic. We examined the microbial reduction of OM- and arsenic-containing ferrihydrite colloids. Four effluent fractions were collected from a soil column experiment run under water-saturated conditions. Ferrihydrite colloids precipitated from the soil effluent and exhibited stable hydrodynamic diameters ranging from 281 (±146) nm in the effluent fraction that was collected first and 100 (±43) nm in a subsequently obtained effluent fraction. Aliquots of these oxic effluent fractions were added to anoxic low salt medium containing diluted suspensions of Geobacter sulfurreducens. Independent of the initial colloid size, the soil effluent ferrihydrite colloids were quickly and completely reduced. The rates of Fe2+ formation ranged between 1.9 and 3.3 fmol h-1 cell-1, and are in the range of or slightly exceeding previously reported rates of synthetic ferrihydrite colloids (1.3 fmol h-1 cell-1), but greatly exceeding previously known rates of macroaggregate-ferrihydrite reduction (0.07 fmol h-1 cell-1). The inhibition of microbial Fe(III) reduction by arsenic is unlikely or overridden by the concurrent enhancement induced by soil effluent DOM. These organic species may have increased the already high intrinsic reducibility of colloidal ferrihydrite owing to quinone-mediated electron shuttling. Additionally, OM, which is structurally associated with the soil effluent ferrihydrite colloids, may also contribute to the higher reactivity due to increasing solubility and specific surface area of ferrihydrite. In conclusion, ferrihydrite colloids from soil effluents can be considered as highly reactive electron acceptors in anoxic environments.

Ag, Co/graphene interactions and its effect on electrocatalytic oxygen reduction in alkaline media

NASA Astrophysics Data System (ADS)

Qaseem, Adnan; Chen, Fuyi; Wu, Xiaoqiang; Zhang, Nan; Xia, Zhenhai

2017-12-01

Silver nanoparticles supported on cobalt and nitrogen embedded reduced graphene oxide, Ag/Co-NGr, are synthesized by one-step hydrothermal route with remarkable catalytic activity for oxygen reduction reaction (ORR). As-synthesized electrocatalyst exhibits half-wave potential (0.82 V) comparable to commercial Pt/C (0.85 V), specific activity (0.45 mA cm-2) better than commercial Pt/C (0.35 mA cm-2) along with superior stability in alkaline environment (≈95% activity retention after 5000s compared to 80% for Pt/C). Moreover, Ag/Co-NGr is highly tolerant to methanol poisoning during ORR and delivers an excellent specific capacity of 789 mAh.g-1Zn with energy density of 947 Wh. kg-1 at a current density of 20 mA cm-2 in a Zn-air battery. For the first time, it is proven that particle size refinement and electronic perturbation of Ag nanoparticles take place due to metal-support interactions between Ag and Co/NGr. d-band center of Ag in Ag/Co-NGr upshifts toward the Fermi level with respect to the Ag/NGr as a result of charge transfer between Ag and Co/NGr. The superior catalytic activity and excellent stability of Ag/Co-NGr is attributed to the structural and electronic modification of Ag nanoparticles by Co and N elements on graphene.

Identifying involvement of Lys251/Asp252 pair in electron transfer and associated proton transfer at the quinone reduction site of Rhodobacter capsulatus cytochrome bc1.

PubMed

Kuleta, Patryk; Sarewicz, Marcin; Postila, Pekka; Róg, Tomasz; Osyczka, Artur

2016-10-01

Describing dynamics of proton transfers in proteins is challenging, but crucial for understanding processes which use them for biological functions. In cytochrome bc1, one of the key enzymes of respiration or photosynthesis, proton transfers engage in oxidation of quinol (QH2) and reduction of quinone (Q) taking place at two distinct catalytic sites. Here we evaluated by site-directed mutagenesis the contribution of Lys251/Asp252 pair (bacterial numbering) in electron transfers and associated with it proton uptake to the quinone reduction site (Qi site). We showed that the absence of protonable group at position 251 or 252 significantly changes the equilibrium levels of electronic reactions including the Qi-site mediated oxidation of heme bH, reverse reduction of heme bH by quinol and heme bH/Qi semiquinone equilibrium. This implicates the role of H-bonding network in binding of quinone/semiquinone and defining thermodynamic properties of Q/SQ/QH2 triad. The Lys251/Asp252 proton path is disabled only when both protonable groups are removed. With just one protonable residue from this pair, the entrance of protons to the catalytic site is sustained, albeit at lower rates, indicating that protons can travel through parallel routes, possibly involving water molecules. This shows that proton paths display engineering tolerance for change as long as all the elements available for functional cooperation secure efficient proton delivery to the catalytic site. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Ultrashort, high power, and ultralow noise mode-locked optical pulse generation using quantum-dot semiconductor lasers

NASA Astrophysics Data System (ADS)

Choi, Myoung-Taek

This dissertation explores various aspects and potential of optical pulse generation based on active, passive, and hybrid mode-locked quantum dot semiconductor lasers with target applications such as optical interconnect and high speed signal processing. Design guidelines are developed for the single mode operation with suppressed reflection from waveguide discontinuities. The device fabrication procedure is explained, followed by characteristics of FP laser, SOA, and monolithic two-section devices. Short pulse generation from an external cavity mode-locked QD two-section diode laser is studied. High quality, sub-picosecond (960 fs), high peak power (1.2 W) pulse trains are obtained. The sign and magnitude of pulse chirp were measured for the first time. The role of the self-phase modulation and the linewidth enhancement factor in QD mode-locked lasers is addressed. The noise performance of two-section mode-locked lasers and a SOA-based ring laser was investigated. Significant reduction of the timing jitter under hybrid mode-locked operation was achieved owing to more than one order of magnitude reduction of the linewidth in QD gain media. Ultralow phase noise performance (integrated timing jitter of a few fs at a 10 GHz repetition rate) was demonstrated from an actively mode-locked unidirectional ring laser. These results show that quantum dot mode-locked lasers are strong competitors to conventional semiconductor lasers in noise performance. Finally we demonstrated an opto-electronic oscillator (OEO) and coupled opto-electronic oscillators (COEO) which have the potential for both high purity microwave and low noise optical pulse generation. The phase noise of the COEO is measured by the photonic delay line frequency discriminator method. Based on this study we discuss the prospects of the COEO as a low noise optical pulse source.

Selective CO2 reduction conjugated with H2O oxidation utilizing semiconductor/metal-complex hybrid photocatalysts

NASA Astrophysics Data System (ADS)

Morikawa, T.; Sato, S.; Arai, T.; Uemura, K.; Yamanaka, K. I.; Suzuki, T. M.; Kajino, T.; Motohiro, T.

2013-12-01

We developed a new hybrid photocatalyst for CO2 reduction, which is composed of a semiconductor and a metal complex. In the hybrid photocatalyst, ΔG between the position of conduction band minimum (ECBM) of the semiconductor and the CO2 reduction potential of the complex is an essential factor for realizing fast electron transfer from the conduction band of semiconductor to metal complex leading to high photocatalytic activity. On the basis of this concept, the hybrid photocatalyst InP/Ru-complex, which functions in aqueous media, was developed. The photoreduction of CO2 to formate using water as an electron donor and a proton source was successfully achieved as a Z-scheme system by functionally conjugating the InP/Ru-complex photocatalyst for CO2 reduction with a TiO2 photocatalyst for water oxidation. The conversion efficiency from solar energy to chemical energy was ca. 0.04%, which approaches that for photosynthesis in a plant. Because this system can be applied to many other inorganic semiconductors and metal-complex catalysts, the efficiency and reaction selectivity can be enhanced by optimization of the electron transfer process including the energy-band configurations, conjugation conformations, and catalyst structures. This electrical-bias-free reaction is a huge leap forward for future practical applications of artificial photosynthesis under solar irradiation to produce organic species.

Ion acceleration and non-Maxwellian electron distributions in a low collisionality, high power helicon plasma source

NASA Astrophysics Data System (ADS)

Li, Yan; Sung, Yung-Ta; Scharer, John

2015-11-01

Ion acceleration through plasma double layer and non-Maxwellian two temperature electron distributions have been observed in Madison Helicon Experiment (MadHeX) operated in high RF power (>1000 W) and low Ar pressure (0.17 mtorr) inductive mode. By applying Optical Emission Spectroscopy (OES) cross-checked with an RF-compensated Langmuir probe (at 13.56 MHz and its second and third harmonics), the fast (>80 eV), untrapped electrons downstream of the double layer have a higher temperature of 13 eV than the trapped bulk electrons upstream with a temperature of 4 eV. The reduction of plasma potential and density observed in the double layer region require an upstream temperature ten times the measured 4 eV if occurring via Boltzmann ambipolar expansion. The hot tail electrons of the non-Maxwellian electron distribution affect the formation and the potential drop of the double layer region. The mechanism behind this has been explored via several non-invasive plasma diagnostics tools. The OES measured electron temperatures and densities are also cross-checked with Atomic Data and Analysis Structure (ADAS) and a millimeter wave interferometer respectively. The IEDF is measured by a four-grid RPA and also cross-checked with argon 668 nm Laser Induced Fluorescence (LIF). An emissive probe has been used to measure the plasma potential.

Electrochemical behavior of meso-substituted iron porphyrins in alkaline aqueous media

NASA Astrophysics Data System (ADS)

Berezina, N. M.; Bazanov, M. I.; Maksimova, A. A.; Semeikin, A. S.

2017-12-01

The effect meso-substitution in iron porphyrin complexes has on their redox behavior in alkaline aqueous solutions is studied via cyclic voltammetry. The voltammetric features of the reduction of iron pyridylporphyrins suggest that the sites of electron transfer lie at the ligand, the metal ion, and the pyridyl moieties. The electron transfer reactions between the different forms of these compounds, including the oxygen reduction reaction they mediate, are outlined to show the sequence and potential ranges in which they occur in alkaline aqueous media. Under our experimental conditions, the iron porphyrins exist as μ-oxo dimmers whose activity for the electrocatalytic reduction of oxygen displays a considerable dependence on the nature of the substitutents and nitrogen isomerization (for pyridylporphyrins) and grows in the order (Fe( ms-Ph)4P)2O, (Fe[ ms-(Py-3)Ph3]P)2O, (Fe[ ms-(Py-4)4]P)2O, and (Fe[ ms-(Py-3)4]P)2O.

High Performance Reduction of H2O2 with an Electron Transport Decaheme Cytochrome on a Porous ITO Electrode

PubMed Central

2017-01-01

The decaheme cytochrome MtrC from Shewanella oneidensis MR-1 immobilized on an ITO electrode displays unprecedented H2O2 reduction activity. Although MtrC showed lower peroxidase activity in solution compared to horseradish peroxidase, the ten heme cofactors enable excellent electronic communication and a superior activity on the electrode surface. A hierarchical ITO electrode enabled optimal immobilization of MtrC and a high current density of 1 mA cm–2 at 0.4 V vs SHE could be obtained at pH 6.5 (Eonset = 0.72 V). UV–visible and Resonance Raman spectroelectrochemical studies suggest the formation of a high valent iron-oxo species as the catalytic intermediate. Our findings demonstrate the potential of multiheme cytochromes to catalyze technologically relevant reactions and establish MtrC as a new benchmark in biotechnological H2O2 reduction with scope for applications in fuel cells and biosensors. PMID:28221032

Toxin detection using a tyrosinase-coupled oxygen electrode.

PubMed

Smit, M H; Rechnitz, G A

1993-02-15

An enzyme-based "electrochemical canary" is described for the detection of cyanide. The sensing system imitates cyanide's site of toxicity in the mitochondria. The terminal sequence of electron transfer in aerobic respiration is mimicked by mediator coupling of tyrosinase catalysis to an electro-chemical system. An enzyme-coupled oxygen electrode is created which is sensitive to selective poisoning. Biocatalytic reduction of oxygen is promoted by electrochemically supplying tyrosinase with electrons. Thus, ferrocyanide is generated at a cathode and mediates the enzymatic reduction of oxygen to water. An enzyme-dependent reductive current can be monitored which is inhibited by cyanide in a concentration-dependent manner. Oxygen depletion in the reaction layer can be minimized by addressing enzyme activity using a potential pulsing routine. Enzyme activity is electrochemically initiated and terminated and the sensor becomes capable of continuous monitoring. Cyanide poisoning of the biological component is reversible, and it can be reused after rinsing. The resulting sensor detects cyanide based on its biological activity rather than its physical or chemical properties.

Value-based management of design reuse

NASA Astrophysics Data System (ADS)

Carballo, Juan Antonio; Cohn, David L.; Belluomini, Wendy; Montoye, Robert K.

2003-06-01

Effective design reuse in electronic products has the potential to provide very large cost savings, substantial time-to-market reduction, and extra sources of revenue. Unfortunately, critical reuse opportunities are often missed because, although they provide clear value to the corporation, they may not benefit the business performance of an internal organization. It is therefore crucial to provide tools to help reuse partners participate in a reuse transaction when the transaction provides value to the corporation as a whole. Value-based Reuse Management (VRM) addresses this challenge by (a) ensuring that all parties can quickly assess the business performance impact of a reuse opportunity, and (b) encouraging high-value reuse opportunities by supplying value-based rewards to potential parties. In this paper we introduce the Value-Based Reuse Management approach and we describe key results on electronic designs that demonstrate its advantages. Our results indicate that Value-Based Reuse Management has the potential to significantly increase the success probability of high-value electronic design reuse.

Organic photochemical storage of solar energy. Progress report, July 1, 1977--Feburary 28, 1978

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

Jones, G. II

1978-03-01

The prospects for driving endoergic reactions of simple, relatively abundant organic chemicals by photochemical means have been examined. Strategies for utilization of light of varying wavelength involve sensitization mechanisms which depend on the redox properties of energy storing substrates and photosensitizers. Of principal interest is valence isomerization which can be induced by electron donor-acceptor interaction between substrate and sensitizer in an excited complex or exciplex. Photophysical studies show that potentially isomerizable substrates efficiently intercept redox photosensitizers. The quenching of emission of electron acceptor sensitizers by non conjugated hydrocarbon dienes is indeed a function of the reduction potential of the acceptorsmore » (a series of aromatics with varying absorption characteristics) and the oxidation potentials of the substrates. Electron deficient dienes have been shown alternatively to be efficient quenchers of excited donor sensitizers. That exciplexes are formed between isomerizable substrates and donor or acceptor sensitizers has been confirmed by emission spectroscopy. The rearrangement of hexamethyldewarbenzene, a model exciplex isomerization has been examined in some detail.« less

A well-defined terminal vanadium(III) oxo complex.

PubMed

King, Amanda E; Nippe, Michael; Atanasov, Mihail; Chantarojsiri, Teera; Wray, Curtis A; Bill, Eckhard; Neese, Frank; Long, Jeffrey R; Chang, Christopher J

2014-11-03

The ubiquity of vanadium oxo complexes in the V+ and IV+ oxidation states has contributed to a comprehensive understanding of their electronic structure and reactivity. However, despite being predicted to be stable by ligand-field theory, the isolation and characterization of a well-defined terminal mononuclear vanadium(III) oxo complex has remained elusive. We present the synthesis and characterization of a unique terminal mononuclear vanadium(III) oxo species supported by the pentadentate polypyridyl ligand 2,6-bis[1,1-bis(2-pyridyl)ethyl]pyridine (PY5Me2). Exposure of [V(II)(NCCH3)(PY5Me2)](2+) (1) to either dioxygen or selected O-atom-transfer reagents yields [V(IV)(O)(PY5Me2)](2+) (2). The metal-centered one-electron reduction of this vanadium(IV) oxo complex furnishes a stable, diamagnetic [V(III)(O)(PY5Me2)](+) (3) species. The vanadium(III) oxo species is unreactive toward H- and O-atom transfer but readily reacts with protons to form a putative vanadium hydroxo complex. Computational results predict that further one-electron reduction of the vanadium(III) oxo species will result in ligand-based reduction, even though pyridine is generally considered to be a poor π-accepting ligand. These results have implications for future efforts toward low-valent vanadyl chemistry, particularly with regard to the isolation and study of formal vanadium(II) oxo species.

Reduction of chromium (VI) on the hetero-system CuBi2O4/TiO2 under solar light

NASA Astrophysics Data System (ADS)

Lahmar, H.; Benamira, M.; Akika, F. Z.; Trari, M.

2017-11-01

The CuBi2O4/TiO2 heterojunction was tested with success for the photo-catalytic reduction of chromate ions under sunlight. CuBi2O4, prepared by nitrate process, was characterised photo-electrochemically. The oxide is stable against photo corrosion by consumption of holes in presence of oxalic acid. The light absorption promotes electrons in the conduction band of the sensitizer (CuBi2O4) with a very negative potential (-1.74 VSCE) to participate in the exchange of the electron with HCrO4-. The enhanced activity is due to electron injection of activated CuBi2O4 into TiO2-CB (-0.97 VSCE). The band gap of the semiconductor CuBi2O4 is 1.50 eV with a direct optical transition. This compound is a p-type semiconductor with a flat band potential of -0.39 VSCE and activation energy of 0.18 eV. The electrochemical impedance spectroscopy was undertaken to study the semiconductor/electrolyte interfacial phenomena. The photoactivity on the heterojunction is strongly enhanced. A remarkable performance is obtained in less than 4 h for a concentration of 30 mg in (Cr (VI)) at pH ∼ 4 and a dose of 1 mg/mL; a 98% reduction has been obtained. The kinetic of chromate photoreduction is well described by the Langmuir-Hinshelwood model. The chromate elimination obeys to a pseudo-first order kinetic with an apparent rate constant of 0.014 min-1.

Humic acids facilitated microbial reduction of polymeric Pu(IV) under anaerobic conditions.

PubMed

Xie, Jinchuan; Liang, Wei; Lin, Jianfeng; Zhou, Xiaohua; Li, Mei

2018-01-01

Flavins and humic substances have been extensively studied with emphasis on their ability to transfer extracellular electrons to insoluble metal oxides. Nevertheless, whether the low-solubility Pu(IV) polymers are microbially reduced to aqueous Pu(III) remains uncertain. Experiments were conducted under anaerobic and slightly alkaline conditions to study the difference between humic acids and flavins to transport extracellular electrons to Pu(IV) polymers. Our study demonstrates that Shewanella putrefaciens was unable to directly reduce polymeric Pu(IV) with a notably low reduction rate (3.4×10 -12 mol/L Pu(III) aq within 144h). The relatively high redox potential of flavins reveals the thermodynamically unfavorable reduction: E h (PuO 2 (am)/Pu 3+ )

In Situ Industrial Bimetallic Catalyst Characterization using Scanning Transmission Electron Microscopy and X-ray Absorption Spectroscopy at One Atmosphere and Elevated Temperature.

PubMed

Prestat, Eric; Kulzick, Matthew A; Dietrich, Paul J; Smith, Mr Matthew; Tien, Mr Eu-Pin; Burke, M Grace; Haigh, Sarah J; Zaluzec, Nestor J

2017-08-18

We have developed a new experimental platform for in situ scanning transmission electron microscope (STEM) energy dispersive X-ray spectroscopy (EDS) which allows real time, nanoscale, elemental and structural changes to be studied at elevated temperature (up to 1000 °C) and pressure (up to 1 atm). Here we demonstrate the first application of this approach to understand complex structural changes occurring during reduction of a bimetallic catalyst, PdCu supported on TiO 2 , synthesized by wet impregnation. We reveal a heterogeneous evolution of nanoparticle size, distribution, and composition with large differences in reduction behavior for the two metals. We show that the data obtained is complementary to in situ STEM electron energy loss spectroscopy (EELS) and when combined with in situ X-ray absorption spectroscopy (XAS) allows correlation of bulk chemical state with nanoscale changes in elemental distribution during reduction, facilitating new understanding of the catalytic behavior for this important class of materials. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Polyhydroxyalkanoate as a slow-release carbon source for in situ bioremediation of contaminated aquifers: From laboratory investigation to pilot-scale testing in the field.

PubMed

Pierro, Lucia; Matturro, Bruna; Rossetti, Simona; Sagliaschi, Marco; Sucato, Salvatore; Alesi, Eduard; Bartsch, Ernst; Arjmand, Firoozeh; Papini, Marco Petrangeli

2017-07-25

A pilot-scale study aiming to evaluate the potential use of poly-3-hydroxy-butyrate (PHB) as an electron donor source for in situ bioremediation of chlorinated hydrocarbons in groundwater was conducted. Compared with commercially available electron donors, PHB offers a restricted fermentation pathway (i.e., through acetic acid and molecular hydrogen) by avoiding the formation of any residual carbon that could potentially spoil groundwater quality. The pilot study was carried out at an industrial site in Italy, heavily contaminated by different chlorinated aliphatic hydrocarbons (CAHs). Prior to field testing, PHB was experimentally verified as a suitable electron donor for biological reductive dechlorination processes at the investigated site by microcosm studies carried out on site aquifer material and measuring the quantitative transformation of detected CAHs to ethene. Owing to the complex geological characteristics of the aquifer, the use of a groundwater circulation well (GCW) was identified as a potential strategy to enable effective delivery and distribution of electron donors in less permeable layers and to mobilise contaminants. A 3-screened, 30-m-deep GCW coupled with an external treatment unit was installed at the site. The effect of PHB fermentation products on the in situ reductive dechlorination processes were evaluated by quantitative real-time polymerase chain reaction (qPCR). The results from the first 4 months of operation clearly demonstrated that the PHB fermentation products were effectively delivered to the aquifer and positively influenced the biological dechlorination activity. Indeed, an increased abundance of Dehalococcoides mccartyi (up to 6.6 fold) and reduced CAH concentrations at the installed monitoring wells were observed. Copyright © 2016 Elsevier B.V. All rights reserved.

Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species

NASA Astrophysics Data System (ADS)

Eitel, Eryn M.; Taillefert, Martial

2017-10-01

Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.

Role of nonthermal electron on the dynamics of relativistic electromagnetic soliton in the interaction of laser-plasma

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

Rostampooran, Shabnam; Dorranian, Davoud, E-mail: doran@srbiau.ac.ir

A system of nonlinear one-dimensional equations of the electron hydrodynamics with Maxwell's equations was developed to describe electromagnetic (EM) solitons in plasma with nonthermal electrons. Equation of vector potential was derived in relativistic regime by implementing the multiple scales technique, and their solitonic answers were introduced. The allowed regions for bright and dark electromagnetic solitons were discussed in detail. Roles of number density of nonthermal electrons, temperature of electrons, and frequency of fast participate of vector potential on the Sagdeev potential and properties of EM soliton were investigated. Results show that with increasing the number of nonthermal electrons, the amplitudemore » of vector potential of bright solitons increases. By increasing the number of nonthermal electrons, dark EM solitons may be changed to bright solitons. Increasing the energy of nonthermal electrons leads to generation of high amplitude solitons.« less

Fluorescent light mediated a green synthesis of silver nanoparticles using the protein extract of weaver ant larvae.

PubMed

Khamhaengpol, Arunrat; Siri, Sineenat

2016-10-01

Alternative to crude plant extracts, a crude protein extract derived from animal cells is one of the potential sources of biomolecules for mediating a reduction of silver ions and a formation of silver nanoparticles (AgNPs) under a mild condition, which very few works have been reported. This work demonstrated a use of the protein extract of weaver ant larvae as a bio-facilitator for a simple, green synthesis of AgNPs under fluorescent light at room temperature. The protein extract of weaver ant larvae exhibited the reducing and antioxidant activities, which assisted a formation of AgNPs in the reaction containing only silver nitrate under light exposure. Transmission electron microscopy images revealed the dispersed, spherical AgNPs with an average size of 7.87±2.54nm. The maximum surface plasmon resonance (SPR) band of the synthesized AgNPs was at 435nm. The energy-dispersive X-ray analysis revealed that silver was a major element of the particles. The identity of AgNPs was confirmed by X-ray diffraction pattern, selected area electron diffraction and high resolution transmission electron microscopy analyses, which demonstrated the planes of face centered cubic silver. The synthesized AgNPs showed antibacterial activity against both Escherichia coli and Staphylococcus aureus with the minimum bactericidal concentration (MBC) values equally at 250μg/ml, suggesting their potential application as an effective antibacterial agent. Copyright © 2016 Elsevier B.V. All rights reserved.

ortho-Substituted (Aryl)(3-nitrobenzo[b]thiophen-2-yl)amines: Study of the Electrochemical Behavior

NASA Astrophysics Data System (ADS)

Cosimelli, Barbara; Lanza, Camilla Zaira; Scavetta, Erika; Severi, Elda; Spinelli, Domenico; Stenta, Marco; Tonelli, Domenica

2009-08-01

The reduction potentials of the title compounds 4 have been measured by cyclic voltammetry. The effect of the substituents has been evaluated by using a linear free energy relationship treatment, thus evidencing that the present ortho-substituents affect the Epc values basically by electronic effects. A comparison with data previously collected on ortho-substituted (aryl)(2-nitrobenzo[b]thiophen-3-yl)amines 3 has provided some interesting information. Different electrochemical behaviors are observed during the reduction (a reversible process and an irreversible process are operating in 3 and 4, respectively): to elucidate the reasons for this different behavior, the "reversible" reduction potentials of 5 and of 6 have been measured. Moreover, higher susceptibility constants have been calculated for compounds of series 4 with respect to those of series 3 (ρ4 = 329 and ρ3 = 182, respectively). A rationale for all of these findings has been offered.

Powering microbes with electricity: direct electron transfer from electrodes to microbes.

PubMed

Lovley, Derek R

2011-02-01

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. © 2010 Society for Applied Microbiology and Blackwell Publishing Ltd.

Phenazines and Other Redox-Active Antibiotics Promote Microbial Mineral Reduction

PubMed Central

Hernandez, Maria E.; Kappler, Andreas; Newman, Dianne K.

2004-01-01

Natural products with important therapeutic properties are known to be produced by a variety of soil bacteria, yet the ecological function of these compounds is not well understood. Here we show that phenazines and other redox-active antibiotics can promote microbial mineral reduction. Pseudomonas chlororaphis PCL1391, a root isolate that produces phenazine-1-carboxamide (PCN), is able to reductively dissolve poorly crystalline iron and manganese oxides, whereas a strain carrying a mutation in one of the phenazine-biosynthetic genes (phzB) is not; the addition of purified PCN restores this ability to the mutant strain. The small amount of PCN produced relative to the large amount of ferric iron reduced in cultures of P. chlororaphis implies that PCN is recycled multiple times; moreover, poorly crystalline iron (hydr)oxide can be reduced abiotically by reduced PCN. This ability suggests that PCN functions as an electron shuttle rather than an iron chelator, a finding that is consistent with the observation that dissolved ferric iron is undetectable in culture fluids. Multiple phenazines and the glycopeptidic antibiotic bleomycin can also stimulate mineral reduction by the dissimilatory iron-reducing bacterium Shewanella oneidensis MR1. Because diverse bacterial strains that cannot grow on iron can reduce phenazines, and because thermodynamic calculations suggest that phenazines have lower redox potentials than those of poorly crystalline iron (hydr)oxides in a range of relevant environmental pH (5 to 9), we suggest that natural products like phenazines may promote microbial mineral reduction in the environment. PMID:14766572

Suppression of the Polar Tongue of Ionization During the 21 August 2017 Solar Eclipse

NASA Astrophysics Data System (ADS)

Dang, Tong; Lei, Jiuhou; Wang, Wenbin; Burns, Alan; Zhang, Binzheng; Zhang, Shun-Rong

2018-04-01

It has long been recognized that during solar eclipses, the ionosphere-thermosphere system changes greatly within the eclipse shadow, due to the rapid reduction of solar irradiation. However, the concept that a solar eclipse impacts polar ionosphere behavior and dynamics as well as magnetosphere-ionosphere coupling has not been appreciated. In this study, we investigate the potential impact of the 21 August 2017 solar eclipse on the polar tongue of ionization (TOI) using a high-resolution, coupled ionosphere-thermosphere-electrodynamics model. The reduction of electron densities by the eclipse in the middle latitude TOI source region leads to a suppressed TOI in the polar region. The TOI suppression occurred when the solar eclipse moved into the afternoon sector. The Global Positioning System total electron content observations show similar tendency of polar region total electron content suppression. This study reveals that a solar eclipse occurring at middle latitudes may have significant influences on the polar ionosphere and magnetosphere-ionosphere coupling.

Organic substrates as electron donors in permeable reactive barriers for removal of heavy metals from acid mine drainage.

PubMed

Kijjanapanich, P; Pakdeerattanamint, K; Lens, P N L; Annachhatre, A P

2012-12-01

This research was conducted to select suitable natural organic substrates as potential carbon sources for use as electron donors for biological sulphate reduction in a permeable reactive barrier (PRB). A number of organic substrates were assessed through batch and continuous column experiments under anaerobic conditions with acid mine drainage (AMD) obtained from an abandoned lignite coal mine. To keep the heavy metal concentration at a constant level, the AMD was supplemented with heavy metals whenever necessary. Under anaerobic conditions, sulphate-reducing bacteria (SRB) converted sulphate into sulphide using the organic substrates as electron donors. The sulphide that was generated precipitated heavy metals as metal sulphides. Organic substrates, which yielded the highest sulphate reduction in batch tests, were selected for continuous column experiments which lasted over 200 days. A mixture of pig-farm wastewater treatment sludge, rice husk and coconut husk chips yielded the best heavy metal (Fe, Cu, Zn and Mn) removal efficiencies of over 90%.