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Sample records for metmyoglobin reduction electronic

  1. Influence of different production strategies on the stability of color, oxygen consumption and metmyoglobin reducing activity of meat from Ningxia Tan sheep.

    Science.gov (United States)

    Gao, Xiaoguang; Wang, Zhenyu; Miao, Jing; Xie, Li; Dai, Yan; Li, Xingmin; Chen, Yong; Luo, Hailing; Dai, Ruitong

    2014-02-01

    Fifty male Ningxia Tan sheep were randomly divided into five groups (10 per group). Different feeding strategies were applied to each group for 120 days prior to slaughter. The sheep belong to five groups were pastured for 0 h (feedlot-fed), 2h, 4h, 8h, 12h per day on a natural grazing ground, respectively. M. semitendinosus muscle from Tan sheep was obtained after slaughter. Instrumental color, pH values, oxygen consumption rate, metmyoglobin reducing activity and relative metmyoglobin percentages were analyzed after 1, 3, 5, 7 and 9 days of refrigerated storage. Long-term daily grazing and herbage-based diet were conducive to maintain a lower oxygen consumption rate, higher metmyoglobin reducing activity and lower metmyoglobin accumulation. The combination of pasture-fed and feedlot-fed was conducive to weight gain, and at the same time, increased the color stability of the meat from Ningxia Tan sheep. © 2013.

  2. Reducing effects of polyphenols on metmyoglobin and the in vitro regeneration of bright meat color by polyphenols in the presence of cysteine.

    Science.gov (United States)

    Miura, Yukari; Inai, Miyuki; Honda, Sari; Masuda, Akiko; Masuda, Toshiya

    2014-10-01

    The effect of polyphenols and related phenolic compounds on the reduction of metmyoglobin (MetMb) to oxymyoglobin (MbO2), in the presence of cysteine, was investigated. Caffeic acid, dihydrocaffeic acid, and hydroxtyrosol (600 μmol/L) did not show any reducing activity individually. However, their highly potent activity in the reduction of MetMb to MbO2 was observed in the presence of equimolar amounts of cysteine. On the basis of the analytical results for the redox reaction products generated during the MetMb-reducing reaction of caffeic acid, we proposed a mechanism for the polyphenol-mediated reduction of MetMb. As per the proposed mechanism, the antioxidant polyphenols having a catechol substructure can effectively reduce MetMb to MbO2 with chemical assistance from nucleophilic reactive thiol compounds such as cysteine. Moreover, cysteine-coupled polyphenols such as cysteinylcaffeic acids (which are coupling products of caffeic acid and cysteine) can be used as preserving agents for retaining the fresh meat color, because of their powerful reducing effect on MetMb. The reduction of MetMb to MbO2 changes the color of meat from brown to the more desirable bright red.

  3. Met-myoglobin formation, accumulation, degradation, and myoglobin oxygenation monitoring based on multiwavelength attenuance measurement in porcine meat

    Science.gov (United States)

    Nguyen, Thien; Phan, Kien Nguyen; Lee, Jee-Bum; Kim, Jae Gwan

    2016-05-01

    We propose a simple, rapid, and nondestructive method to investigate formation, accumulation, and degradation of met-myoglobin (met-Mb) and myoglobin oxygenation from the interior of porcine meat. For the experiment, color photos and attenuance spectra of porcine meat (well-bled muscle, fat, and mixed) were collected daily to perform colorimetric analysis and to obtain the differences of attenuance between 578 and 567 nm (A578-A567) and between 615 and 630 nm (A630-A615), respectively. Oxy-, deoxy-, and met-myoglobin concentration changes over storage time were also calculated using Beer-Lamberts' law with reflectance intensities at 557, 582, and 630 nm. The change of A578-A567 was well matched with the change of myoglobin oxygenation, and the change of A630-A615 corresponded well with the formation and degradation of met-Mb. In addition, attenuation differences, A578-A567 and A630-A615, were able to show the formation of met-Mb earlier than colorimetric analysis. Therefore, the attenuance differences between wavelengths can be indicators for estimating myoglobin oxygenation and met-Mb formation, accumulation, and degradation, which enable us to design a simple device to monitor myoglobin activities in porcine meat.

  4. LC-MS of Metmyoglobin at pH = 2: Separation and Characterization of Apomyoglobin and Heme by ESI-MS and UV-Vis

    Science.gov (United States)

    Stynes, Helen Cleary; Layo, Araceli; Smith, Richard W.

    2004-01-01

    The protein species of apomyoglobin (apoMb) and heme are freed and segregated from the aqueous protein solution of metmyoglobin by liquid chromatography, and are distinguished by UV-Vis absorption or electrospray ionization mass spectrometry (ESI-MS). This is an ingenious and effective approach to characterize apomyoglobin and heme, while students…

  5. Lipid oxidation in human low-density lipoprotein induced by metmyoglobin/H2O2

    DEFF Research Database (Denmark)

    Witting, P K; Willhite, C A; Davies, Michael Jonathan

    1999-01-01

    Metmyoglobin (metMb) and H(2)O(2) can oxidize low-density lipoprotein (LDL) in vitro, and oxidized LDL may be atherogenic. The role of alpha-tocopherol (alpha-TOH) in LDL oxidation by peroxidases such as metMb is unclear. Herein, we show that during metMb/H(2)O(2)-induced oxidation of native LDL...... of CE-O(O)H is dependent on, and correlates with, LDL's alpha-TOH content, yet does not require preformed lipid hydroperoxides or H(2)O(2). This indicates that in native LDL alpha-TOH can act as a phase-transfer agent and alpha-TO(*) as a chain-transfer agent propagating LDL lipid peroxidation via...

  6. Nitroxide radicals as research tools: Elucidating the kinetics and mechanisms of catalase-like and "suicide inactivation" of metmyoglobin.

    Science.gov (United States)

    Samuni, Uri; Czapski, Gideon; Goldstein, Sara

    2016-07-01

    Metmyoglobin (MbFe(III)) reaction with H(2)O(2) has been a subject of study over many years. H(2)O(2) alone promotes heme destruction frequently denoted "suicide inactivation," yet the mechanism underlying H(2)O(2) dismutation associated with MbFe(III) inactivation remains obscure. MbFe(III) reaction with excess H(2)O(2) in the absence and presence of the nitroxide was studied at pH 5.3-8.1 and 25°C by direct determination of reaction rate constants using rapid-mixing stopped-flow technique, by following H(2)O(2) depletion, O(2) evolution, spectral changes of the heme protein, and the fate of the nitroxide by EPR spectroscopy. The rates of both H(2)O(2) dismutation and heme inactivation processes depend on [MbFe(III)], [H(2)O(2)] and pH. Yet the inactivation stoichiometry is independent of these variables and each MbFe(III) molecule catalyzes the dismutation of 50±10 H(2)O(2) molecules until it is inactivated. The nitroxide catalytically enhances the catalase-like activity of MbFe(III) while protecting the heme against inactivation. The rate-determining step in the absence and presence of the nitroxide is the reduction of MbFe(IV)O by H(2)O(2) and by nitroxide, respectively. The nitroxide effects on H(2)O(2) dismutation catalyzed by MbFe(III) demonstrate that MbFe(IV)O reduction by H(2)O(2) is the rate-determining step of this process. The proposed mechanism, which adequately fits the pro-catalytic and protective effects of the nitroxide, implies the intermediacy of a compound I-H(2)O(2) adduct, which decomposes to a MbFe(IV)O and an inactivated heme at a ratio of 25:1. The effects of nitroxides are instrumental in elucidating the mechanism underlying the catalysis and inactivation routes of heme proteins. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Sequential Proton Loss Electron Transfer in Deactivation of Iron(IV) Binding Protein by Tyrosine Based Food Components.

    Science.gov (United States)

    Tang, Ning; Skibsted, Leif H

    2017-08-02

    The iron(IV) binding protein ferrylmyoglobin, MbFe(IV)═O, was found to be reduced by tyrosine based food components in aqueous solution through a sequential proton loss electron transfer reaction mechanism without binding to the protein as confirmed by isothermal titration calorimetry. Dopamine and epinephrine are the most efficient food components reducing ferrylmyoglobin to oxymyoglobin, MbFe(II)O 2 , and metmyoglobin, MbFe(III), as revealed by multivariate curve resolution alternating least-squares with second order rate constants of 33.6 ± 2.3 L/mol/s (ΔH ⧧ of 19 ± 5 kJ/mol, ΔS ⧧ of -136 ± 18 J/mol K) and 228.9 ± 13.3 L/mol/s (ΔH ⧧ of 110 ± 7 kJ/mol, ΔS ⧧ of 131 ± 25 J/mol K), respectively, at pH 7.4 and 25 °C. The other tyrosine based food components were found to reduce ferrylmyoglobin to metmyoglobin with similar reduction rates at pH 7.4 and 25 °C. These reduction reactions were enhanced by protonation of ferrylmyoglobin and facilitated proton transfer at acidic conditions. Enthalpy-entropy compensation effects were observed for the activation parameters (ΔH ⧧ and ΔS ⧧ ), indicating the common reaction mechanism. Moreover, principal component analysis combined with heat map were performed to understand the relationship between density functional theory calculated molecular descriptors and kinetic data, which was further modeled by partial least squares for quantitative structure-activity relationship analysis. In addition, a three tyrosine residue containing protein, lysozyme, was also found to be able to reduce ferrylmyoglobin with a second order rate constant of 66 ± 28 L/mol/s as determined by a competitive kinetic method.

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

    Science.gov (United States)

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

    2016-01-01

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

  9. Synthesis of AuPd alloyed nanoparticles via room-temperature electron reduction with argon glow discharge as electron source.

    Science.gov (United States)

    Yang, Manman; Wang, Zongyuan; Wang, Wei; Liu, Chang-Jun

    2014-01-01

    Argon glow discharge has been employed as a cheap, environmentally friendly, and convenient electron source for simultaneous reduction of HAuCl4 and PdCl2 on the anodic aluminum oxide (AAO) substrate. The thermal imaging confirms that the synthesis is operated at room temperature. The reduction is conducted with a short time (30 min) under the pressure of approximately 100 Pa. This room-temperature electron reduction operates in a dry way and requires neither hydrogen nor extra heating nor chemical reducing agent. The analyses using X-ray photoelectron spectroscopy (XPS) confirm all the metallic ions have been reduced. The characterization with X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) shows that AuPd alloyed nanoparticles are formed. There also exist some highly dispersed Au and Pd monometallic particles that cannot be detected by XRD and transmission electron microscopy (TEM) because of their small particle sizes. The observed AuPd alloyed nanoparticles are spherical with an average size of 14 nm. No core-shell structure can be observed. The room-temperature electron reduction can be operated in a larger scale. It is an easy way for the synthesis of AuPd alloyed nanoparticles.

  10. Cobamide-mediated enzymatic reductive dehalogenation via long-range electron transfer.

    Science.gov (United States)

    Kunze, Cindy; Bommer, Martin; Hagen, Wilfred R; Uksa, Marie; Dobbek, Holger; Schubert, Torsten; Diekert, Gabriele

    2017-07-03

    The capacity of metal-containing porphyrinoids to mediate reductive dehalogenation is implemented in cobamide-containing reductive dehalogenases (RDases), which serve as terminal reductases in organohalide-respiring microbes. RDases allow for the exploitation of halogenated compounds as electron acceptors. Their reaction mechanism is under debate. Here we report on substrate-enzyme interactions in a tetrachloroethene RDase (PceA) that also converts aryl halides. The shape of PceA's highly apolar active site directs binding of bromophenols at some distance from the cobalt and with the hydroxyl substituent towards the metal. A close cobalt-substrate interaction is not observed by electron paramagnetic resonance spectroscopy. Nonetheless, a halogen substituent para to the hydroxyl group is reductively eliminated and the path of the leaving halide is traced in the structure. Based on these findings, an enzymatic mechanism relying on a long-range electron transfer is concluded, which is without parallel in vitamin B 12 -dependent biochemistry and represents an effective mode of RDase catalysis.

  11. Evidence for Single Metal Two Electron Oxidative Addition and Reductive Elimination at Uranium

    OpenAIRE

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

    2017-01-01

    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 compl...

  12. Determination of one-electron reduction potentials of some radiosensitive compounds by pulse radiolysis

    International Nuclear Information System (INIS)

    Zuo Zhihua; Yao Side; Li Hucheng; Lin Nianyun; Jin Yizun

    1994-01-01

    One-electron reduction potential (E 7 1 ) is one of the important parameters of radiosensitive compound with high electron affinity. In this work one-electron reduction potentials of some radiosensitizers, such as Miso, 911, CMNa, SMU-1, SMU-2, SMD, SNN, S 3 and BSO, were determined pulse radiolytically by using anthraquinone-2-sulfate (AQS), duroquinone (DQ) and methyl viologen (MV 2+ ) as references

  13. Methanol as electron donor for thermophilic biological sulfate and sulfite reduction

    OpenAIRE

    Weijma, J.

    2000-01-01

    Sulfur oxyanions (e.g. sulfate, sulfite) can be removed from aqueous waste- and process streams by biological reduction with a suitable electron donor to sulfide, followed by partial chemical or biological oxidation of sulfide to elemental sulfur. The aim of the research described in this thesis was to make this biological process more broadly applicable for desulfurization of flue-gases and ground- and wastewaters by using the cheap chemical methanol as electron donor for the reduct...

  14. Challenges in reduction of dinitrogen by proton and electron transfer.

    Science.gov (United States)

    van der Ham, Cornelis J M; Koper, Marc T M; Hetterscheid, Dennis G H

    2014-08-07

    Ammonia is an important nutrient for the growth of plants. In industry, ammonia is produced by the energy expensive Haber-Bosch process where dihydrogen and dinitrogen form ammonia at a very high pressure and temperature. In principle one could also reduce dinitrogen upon addition of protons and electrons similar to the mechanism of ammonia production by nitrogenases. Recently, major breakthroughs have taken place in our understanding of biological fixation of dinitrogen, of molecular model systems that can reduce dinitrogen, and in the electrochemical reduction of dinitrogen at heterogeneous surfaces. Yet for efficient reduction of dinitrogen with protons and electrons major hurdles still have to be overcome. In this tutorial review we give an overview of the different catalytic systems, highlight the recent breakthroughs, pinpoint common grounds and discuss the bottlenecks and challenges in catalytic reduction of dinitrogen.

  15. Reduction of electron density in a plasma by injection of liquids

    Science.gov (United States)

    Sodha, M. S.; Evans, J. S.

    1974-01-01

    In this paper, the authors have investigated the physics of various processes relevant to the reduction of electron density in a plasma by addition of water droplets; two processes have in particular been analyzed in some detail, viz, the electron attachment to charged dielectric droplets and the emission of negative ions by vaporization from these droplets. The results of these analyses have been applied to a study of the kinetics of reduction of electron density and charging of droplets in an initially overionized plasma, after addition of water droplets. A number of simplifying assumptions including uniform size and charge on droplets and negligible change in the radius of the droplet due to evaporation have been made.

  16. Localized conductive patterning via focused electron beam reduction of graphene oxide

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Songkil; Henry, Mathias [George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States); Kulkarni, Dhaval D.; Zackowski, Paul; Jang, Seung Soon; Tsukruk, Vladimir V. [School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States); Fedorov, Andrei G., E-mail: agf@gatech.edu [George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States); Parker H. Petit Institute for Bioengineering and Bioscience, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States)

    2015-03-30

    We report on a method for “direct-write” conductive patterning via reduction of graphene oxide (GO) sheets using focused electron beam induced deposition (FEBID) of carbon. FEBID treatment of the intrinsically dielectric graphene oxide between two metal terminals opens up the conduction channel, thus enabling a unique capability for nanoscale conductive domain patterning in GO. An increase in FEBID electron dose results in a significant increase of the domain electrical conductivity with improving linearity of drain-source current vs. voltage dependence, indicative of a change of graphene oxide electronic properties from insulating to semiconducting. Density functional theory calculations suggest a possible mechanism underlying this experimentally observed phenomenon, as localized reduction of graphene oxide layers via interactions with highly reactive intermediates of electron-beam-assisted dissociation of surface-adsorbed hydrocarbon molecules. These findings establish an unusual route for using FEBID as nanoscale lithography and patterning technique for engineering carbon-based nanomaterials and devices with locally tailored electronic properties.

  17. Investigation of industrial-scale carbon dioxide reduction using pulsed electron beams

    Energy Technology Data Exchange (ETDEWEB)

    Petrov, G. M.; Apruzese, J. P.; Petrova, Tz. B.; Wolford, M. F. [Plasma Physics Division, Naval Research Laboratory, 4555 Overlook Ave. SW, Washington, DC 20375-5346 (United States)

    2016-03-14

    Carbon dioxide is the most important greenhouse gas contributing to global warming. To help mitigate increasing CO{sub 2} concentrations, we investigate a method of carbon dioxide reduction using high-power electron beams, which can be used on an industrial scale. A series of experiments are conducted in which the reduction of CO{sub 2} is measured for different gas compositions and power deposition rates. An electron beam deposition model is applied to compute reduction rates of CO{sub 2} and energy cost for breaking a CO{sub 2} molecule in flue gas and pure carbon dioxide at atmospheric pressure. For flue gas consisting of 82% N{sub 2}, 6% O{sub 2}, and 12% CO{sub 2}, the calculated energy cost is 85 eV per molecule. In order to dissociate 50% of the CO{sub 2} molecules, beam energy density deposition on the order of 20 J/cm{sup 3} is required. Electron beam irradiation of 12.6 liter gas volume containing 90% CO{sub 2} and 10% CH{sub 4} at beam energy density deposition of 4.2 J/cm{sup 3}, accumulated over 43 shots in a 20 min interval, reduced the CO{sub 2} concentration to 78%. Analogous experiments with a gas mixture containing 11.5% CO{sub 2}, 11.5% CH{sub 4}, and balance of Ar, reduced the CO{sub 2} concentration to below 11% with energy deposition 0.71 J/cm{sup 3}, accumulated over 10 shots in a 5 min interval. The experimental data and the theoretical predictions of CO{sub 2} reduction using pulsed electron beams are in agreement within the experimental error. Other techniques to enhance the removal of CO{sub 2} with pulsed electron beams are also explored, yielding new possible avenues of research.

  18. NOx reduction by compact electron beam processing

    International Nuclear Information System (INIS)

    Penetrante, B.M.; Hsiao, M.C.; Merritt, B.T.; Wallman, P.H.; Vogtlin, G.E.

    1995-01-01

    Among the new methods being investigated for the post-combustion removal of nitrogen oxides (NO x ) are based on non-thermal plasmas. These plasmas can be produced by electrical discharge methods or electron beam irradiation. The application of electron beam irradiation for NO x removal in power plant flue gases has been investigated since the early 1970's in both laboratory- and pilot-scale experiments. Electrical discharge methods are relatively new entrants in the field of flue gas cleanup. Pulsed corona and dielectric-barrier discharge techniques are two of the more commonly used electrical discharge methods for producing nonthermal plasmas at atmospheric pressure. There are basically two types of reactions responsible for the depletion of NO by non-thermal plasmas: oxidation and reduction

  19. Formation of methemoglobin and metmyoglobin using 8-aminoquinoline derivatives or sodium nitrite and subsequent reaction with cyanide.

    Science.gov (United States)

    Steinhaus, R K; Baskin, S I; Clark, J H; Kirby, S D

    1990-10-01

    The kinetics of the oxidation of hemoglobin (Hb) and myoglobin (Mb) by sodium nitrite, 8-[(4-amino-1-methylbutyl)amino]-6-methoxy-quinoline diphosphate (primaquine), 6-methoxy-8-(6-diethylaminohexylamino)-4-methyl-quinoline dihydrochloride (WR6026) and 8-[(4-amino-1-methylbutyl)amino]-2,6-dimethoxy-4-methyl- 5-[(3-trifluoromethyl)phenoxy]quinoline succinate (WR238,605) were studied at pH values ranging from 7.4 to 7.6 and at 37 +/- 1 degrees C. The reaction between Hb and primaquine, WR6026 and WR238,605 resulted in precipitation, as did the reaction between Mb and WR238,605. The reaction between nitrite ion (NO2-) and Hb showed a lag period followed by an autocatalytic phase. The data in this study are consistent with and substantiate the proposed mechanism for the Hb-NO2- oxidation reaction. The reaction between Mb and NO2- at higher NO2- concentrations also showed a lag period followed by an autocatalytic period, while at lower NO2- concentrations no lag period was seen. The data suggest a shift in rate constant at these lower NO2- concentrations. The reaction between Mb and both WR6026 and primaquine followed a two-term rate law with oxidant-dependent and -independent terms. Concentration-effect curve data, along with these results, suggest the presence of a catalytic pathway. The rates of formation of cyanomethemoglobin and cyanometmyoglobin complexes from cyanide ion and methemoglobin (MHb) and metmyoglobin (MMb), respectively, were followed in the presence of the heme oxidants. The rate constants were all within a narrow range and suggest that complexation of cyanide by MHb and MMb is not affected by the presence of oxidants.

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

    Science.gov (United States)

    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.

  1. Observation of reduction of secondary electron emission from helium ion impact due to plasma-generated nanostructured tungsten fuzz

    International Nuclear Information System (INIS)

    Hollmann, E M; Doerner, R P; Nishijima, D; Pigarov, A Yu

    2017-01-01

    Growth of nanostructured fuzz on a tungsten target in a helium plasma is found to cause a significant (∼3×) reduction in ion impact secondary electron emission in a linear plasma device. The ion impact secondary electron emission is separated from the electron impact secondary electron emission by varying the target bias voltage and fitting to expected contributions from electron impact, both thermal and non-thermal; with the non-thermal electron contribution being modeled using Monte-Carlo simulations. The observed (∼3×) reduction is similar in magnitude to the (∼2×) reduction observed in previous work for the effect of tungsten fuzz formation on secondary electron emission due to electron impact. It is hypothesized that the observed reduction results from re-absorption of secondary electrons in the tungsten fuzz. (paper)

  2. One-electron standard reduction potentials of nitroaromatic and cyclic nitramine explosives

    International Nuclear Information System (INIS)

    Uchimiya, Minori; Gorb, Leonid; Isayev, Olexandr; Qasim, Mohammad M.; Leszczynski, Jerzy

    2010-01-01

    Extensive studies have been conducted in the past decades to predict the environmental abiotic and biotic redox fate of nitroaromatic and nitramine explosives. However, surprisingly little information is available on one-electron standard reduction potentials (E o (R-NO 2 /R-NO 2 - )). The E o (R-NO 2 /R-NO 2 - ) is an essential thermodynamic parameter for predicting the rate and extent of reductive transformation for energetic residues. In this study, experimental (linear free energy relationships) and theoretical (ab initio calculation) approaches were employed to determine E o (R-NO 2 /R-NO 2 - ) for nitroaromatic, (caged) cyclic nitramine, and nitroimino explosives that are found in military installations or are emerging contaminants. The results indicate a close agreement between experimental and theoretical E o (R-NO 2 /R-NO 2 - ) and suggest a key trend: E o (R-NO 2 /R-NO 2 - ) value decreases from di- and tri-nitroaromatic (e.g., 2,4-dinitroanisole) to nitramine (e.g., RDX) to nitroimino compound (e.g., nitroguanidine). The observed trend in E o (R-NO 2 /R-NO 2 - ) agrees with reported rate trends for reductive degradation, suggesting a thermodynamic control on the reduction rate under anoxic/suboxic conditions. - Reduction of explosives becomes less thermodynamically favorable as the one-electron standard reduction potential decreases from di- and tri-nitroaromatic, nitramine, to nitroimino compounds.

  3. Optimisation of 12 MeV electron beam simulation using variance reduction technique

    International Nuclear Information System (INIS)

    Jayamani, J; Aziz, M Z Abdul; Termizi, N A S Mohd; Kamarulzaman, F N Mohd

    2017-01-01

    Monte Carlo (MC) simulation for electron beam radiotherapy consumes a long computation time. An algorithm called variance reduction technique (VRT) in MC was implemented to speed up this duration. This work focused on optimisation of VRT parameter which refers to electron range rejection and particle history. EGSnrc MC source code was used to simulate (BEAMnrc code) and validate (DOSXYZnrc code) the Siemens Primus linear accelerator model with the non-VRT parameter. The validated MC model simulation was repeated by applying VRT parameter (electron range rejection) that controlled by global electron cut-off energy 1,2 and 5 MeV using 20 × 10 7 particle history. 5 MeV range rejection generated the fastest MC simulation with 50% reduction in computation time compared to non-VRT simulation. Thus, 5 MeV electron range rejection utilized in particle history analysis ranged from 7.5 × 10 7 to 20 × 10 7 . In this study, 5 MeV electron cut-off with 10 × 10 7 particle history, the simulation was four times faster than non-VRT calculation with 1% deviation. Proper understanding and use of VRT can significantly reduce MC electron beam calculation duration at the same time preserving its accuracy. (paper)

  4. One-electron standard reduction potentials of nitroaromatic and cyclic nitramine explosives

    Energy Technology Data Exchange (ETDEWEB)

    Uchimiya, Minori, E-mail: sophie.uchimiya@ars.usda.go [Environmental Laboratory, U.S. Army Engineer Research and Development Center, Vicksburg, MS 39180 (United States); Gorb, Leonid [SpecPro Inc, 3909 Halls Ferry Road, Vicksburg, MS 39180 (United States); Isayev, Olexandr [Department of Chemistry, Case Western Reserve University, Cleveland, OH 44106 (United States); Qasim, Mohammad M. [Environmental Laboratory, U.S. Army Engineer Research and Development Center, Vicksburg, MS 39180 (United States); Leszczynski, Jerzy [Environmental Laboratory, U.S. Army Engineer Research and Development Center, Vicksburg, MS 39180 (United States); Interdisciplinary Center for Nanotoxicity, Jackson State University, Jackson, MS 39217 (United States)

    2010-10-15

    Extensive studies have been conducted in the past decades to predict the environmental abiotic and biotic redox fate of nitroaromatic and nitramine explosives. However, surprisingly little information is available on one-electron standard reduction potentials (E{sup o}(R-NO{sub 2}/R-NO{sub 2}{sup -})). The E{sup o}(R-NO{sub 2}/R-NO{sub 2}{sup -}) is an essential thermodynamic parameter for predicting the rate and extent of reductive transformation for energetic residues. In this study, experimental (linear free energy relationships) and theoretical (ab initio calculation) approaches were employed to determine E{sup o}(R-NO{sub 2}/R-NO{sub 2}{sup -}) for nitroaromatic, (caged) cyclic nitramine, and nitroimino explosives that are found in military installations or are emerging contaminants. The results indicate a close agreement between experimental and theoretical E{sup o}(R-NO{sub 2}/R-NO{sub 2}{sup -}) and suggest a key trend: E{sup o}(R-NO{sub 2}/R-NO{sub 2}{sup -}) value decreases from di- and tri-nitroaromatic (e.g., 2,4-dinitroanisole) to nitramine (e.g., RDX) to nitroimino compound (e.g., nitroguanidine). The observed trend in E{sup o}(R-NO{sub 2}/R-NO{sub 2}{sup -}) agrees with reported rate trends for reductive degradation, suggesting a thermodynamic control on the reduction rate under anoxic/suboxic conditions. - Reduction of explosives becomes less thermodynamically favorable as the one-electron standard reduction potential decreases from di- and tri-nitroaromatic, nitramine, to nitroimino compounds.

  5. Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction.

    Science.gov (United States)

    Zhu, Di; Zhang, Linghong; Ruther, Rose E; Hamers, Robert J

    2013-09-01

    The photocatalytic reduction of N₂ to NH₃ is typically hampered by poor binding of N₂ to catalytic materials and by the very high energy of the intermediates involved in this reaction. Solvated electrons directly introduced into the reactant solution can provide an alternative pathway to overcome such limitations. Here we demonstrate that illuminated hydrogen-terminated diamond yields facile electron emission into water, thus inducing reduction of N₂ to NH₃ at ambient temperature and pressure. Transient absorption measurements at 632 nm reveal the presence of solvated electrons adjacent to the diamond after photoexcitation. Experiments using inexpensive synthetic diamond samples and diamond powder show that photocatalytic activity is strongly dependent on the surface termination and correlates with the production of solvated electrons. The use of diamond to eject electrons into a reactant liquid represents a new paradigm for photocatalytic reduction, bringing electrons directly to reactants without requiring molecular adsorption to the surface.

  6. Biotechnological aspects of sulfate reduction with methane as electron donor

    NARCIS (Netherlands)

    Meulepas, R.J.W.; Stams, A.J.M.; Lens, P.N.L.

    2010-01-01

    Biological sulfate reduction can be used for the removal and recovery of oxidized sulfur compounds and metals from waste streams. However, the costs of conventional electron donors, like hydrogen and ethanol, limit the application possibilities. Methane from natural gas or biogas would be a more

  7. Competitive microbial reduction of perchlorate and nitrate with a cathode directly serving as the electron donor

    International Nuclear Information System (INIS)

    Xie, Daohai; Yu, Hui; Li, Chenchen; Ren, Yuan; Wei, Chaohai; Feng, Chunhua

    2014-01-01

    Microbial reduction of perchlorate with an electrode as the electron donor represents an emerging technology for remediation of perchlorate contamination; it is important to know how perchlorate reduction behaves when nitrate, a co-contaminant of perchlorate is present. We reported that electrons derived from the electrode can be directly transferred to the bacteria with perchlorate or nitrate as the sole electron acceptor. The presence of nitrate, even at the 0.07 mM level, can slow reduction of perchlorate (0.70 mM) as a poised potential of -0.50 V (vs. SCE) was applied to the inoculated cathode. Increasing the concentration of nitrate resulted in a noticeable inhibitory effect on perchlorate reduction. When the nitrate concentration was 2.10 mM, reduction of 0.70 mM perchlorate was totally inhibited. Bacterial community analyses based on 16S rDNA gene analysis with denaturing gradient gel electrophoresis (DGGE) revealed that most of the bacteria newly enriched on the nitrate and/or perchlorate biocathodes were the known electrochemically active denitrifiers, which possibly prefer to reduce nitrate over perchlorate. These results show that nitrate is a more favorable electron acceptor than perchlorate in the bioelectrochemical system where the cathode directly serves as the electron donor

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

    Science.gov (United States)

    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.

  9. Performance Limits of Photoelectrochemical CO2 Reduction Based on Known Electrocatalysts and the Case for Two-Electron Reduction Products

    DEFF Research Database (Denmark)

    Vesborg, Peter Christian Kjærgaard; Seger, Brian

    2016-01-01

    Solar-drivenreduction of CO2 to solar fuels as an alternative to H2 via water splitting is an intriguing proposition. We modelthe solar-to-fuel (STF) efficiencies using realistic parameters basedon recently reported CO2 reduction catalysts with a highperformance tandem photoabsorber structure. CO...... due to excessiveoverpotentials and poor selectivity. This work considers breakingup the multielectron reduction pathway into individually optimized,separate two-electron steps as a way forward....

  10. Pulse-radiolytic one-electron reduction of anthraquinone and chloro-anthraquinones in aqueous-isopropanol-acetone mixed solvent

    International Nuclear Information System (INIS)

    Rath, M.C.; Pal, H.; Mukherjee, T.

    1996-01-01

    One-electron reduction of 9,10-anthraquinone and some chloro-anthraquinones and the characteristics of the semiquinones thus formed have been investigated in aqueous-isipropanol-acetone mixed solvent using electron pulse radiolysis technique. Spectroscopic characteristics, kinetic parameters of formation and decay, and the acid/base behaviour of the semiquinones have been investigated. The one-electron reduction potential of the quinones have been measured following electron transfer equilibria with a reference redox system (methyl viologen) and the values thus obtained have been compared with those of some other anthrasemiquinone systems. An analysis of the characteristics of the semiquinones shows that α-chloro substituents adjacent to the C=O group act as electron withdrawing groups. (author)

  11. Methanol as electron donor for thermophilic biological sulfate and sulfite reduction

    NARCIS (Netherlands)

    Weijma, J.

    2000-01-01

    Sulfur oxyanions (e.g. sulfate, sulfite) can be removed from aqueous waste- and process streams by biological reduction with a suitable electron donor to sulfide, followed by partial chemical or biological oxidation of sulfide to elemental sulfur. The aim of the research described in this

  12. Characterization of alternate reductant binding and electron transfer in the dopamine β-monooxygenase reaction

    International Nuclear Information System (INIS)

    Stewart, L.C.; Klinman, J.P.

    1987-01-01

    The steady-state limiting kinetic parameters V/sub max/, V/K/sub DA/, and V/K/sub O 2 /, together with deuterium isotope effects on these parameters, have been determined for the dopamine β-monooxygenase (DβM) reaction in the presence of structurally distinct reductants. The results show the one-electron reductant ferrocyanide to be nearly as kinetically competent as the presumed in vivo reductant ascrobate. Further, a reductant system of ferricyanide plus substrate dopamine yields steady-state kinetic parameters and isotope effects very similar to those measured solely in the presence of ferrocyanide, indicating a role for catecholamine in the rapid recycling of oxidized ferrocyanide. Use of substrate dopamine as the sole reductant is found to lead to a highly unusual kinetic independence of oxygen concentration, as well as significantly reduced values of V/sub max/ and V/K/sub DA/, and the authors conclude that dopamine reduces enzymic copper in a rate-limiting step that is 40-fold slower than with ascorbate. The near-identical kinetic parameters measured in the presence of either ascorbate or ferrocyanide, together with markedly reduced rates with dopamine, are interpreted in terms of a binding site for reductant that is physically distinct from the substrate binding site. This view is supported by molecular modeling, which reveals ascorbate and ferrocyanide to possess an unexpected similarity in potential sites for interaction with enzymic residues. With regard to electron flux, identical values of V/K/sub O 2 / have been measured with [2,2- 2 H 2 ]dopamine as substrate both in the presence and in the absence of added ascorbate. This key result unambiguously rules out an entry of electrons to enzyme forms leading from the enzyme-dopamine complex to enzyme-bound product and, hence, reaction mechanisms involving a reductive activation of the putative Cu(II)-OOH prior to substrate hydroxylation

  13. Application of a CADIS-like variance reduction technique to electron transport

    International Nuclear Information System (INIS)

    Dionne, B.; Haghighat, A.

    2004-01-01

    This paper studies the use of approximate deterministic importance functions to calculate the lower-weight bounds of the MCNP5 weight-window variance reduction technique when applied to electron transport simulations. This approach follows the CADIS (Consistent Adjoint Driven Importance Sampling) methodology developed for neutral particles shielding calculations. The importance functions are calculated using the one-dimensional CEPXS/ONELD code package. Considering a simple 1-D problem, this paper shows that our methodology can produce speedups up to ∼82 using an approximate electron importance function distributions computed in ∼8 seconds. (author)

  14. Promotion of multi-electron transfer for enhanced photocatalysis: A review focused on oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Changhua [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China); College of Chemistry and Biology, Beihua University, Jilin 132013 (China); Zhang, Xintong, E-mail: xtzhang@nenu.edu.cn [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China); Liu, Yichun [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China)

    2015-12-15

    Highlights: • Oxygen reduction reaction (ORR) in photocatalysis process is focused. • Multi-electron transfer ORR is reviewed. • This review provides a guide to access to enhanced photocatalysis via multi-electron transfer. - Abstract: Semiconductor photocatalysis has attracted significant interest for solar light induced environmental remediation and solar fuel generation. As is well known, photocatalytic performance is determined by three steps: photoexcitation, separation and transport of photogenerated charge carriers, and surface reactions. To achieve higher efficiency, significant efforts have been made on improvement of efficiency of above first two steps, which have been well documented in recent review articles. In contrast, this review intends to focus on strategies moving onto the third step of improvement for enhanced photocatalysis wherein active oxygen species including superoxide radical, hydrogen peroxide, hydroxyl radical are in situ detected. Particularly, surface electron-transfer reduction of oxygen over single component photocatalysts is reviewed and systems enabling multi-electron transfer induced oxygen reduction reaction (ORR) are highlighted. It is expected this review could provide a guideline for readers to better understand the critical role of ORR over photocatalyst in charge carrier separation and transfer and obtain reliable results for enhanced aerobic photocatalysis.

  15. Molecular dynamics simulation of the first electron transfer step in the oxygen reduction reaction

    NARCIS (Netherlands)

    Hartnig, C.B.; Koper, M.T.M.

    2002-01-01

    We present a molecular dynamics simulation of solvent reorganization in the first electron transfer step in the oxygen reduction reaction, i.e. O2+e-¿O2-, modeled as taking place in the outer Helmholtz plane. The first electron transfer step is usually considered the rate-determining step from many

  16. Influence of Carbon Sources and Electron Shuttles on Ferric Iron Reduction by Cellulomonas sp. Strain ES6

    Energy Technology Data Exchange (ETDEWEB)

    Erin K. Field; Robin Gerlach; Sridhar Viamajala; Laura K. Jennings; Alfred B. Cunningham; Brent M. Peyton; William A. Apel

    2011-09-01

    The reduction of hexavalent chromium, Cr(VI), to trivalent chromium, Cr(III), can be an important aspect of remediation processes at Department of Energy (DOE) and other contaminated sites. Cellulomonas species are found at several Cr(VI) contaminated and uncontaminated locations at the DOE site in Hanford, Washington. Members of this genus have demonstrated the ability to effectively reduce Cr(VI) to Cr(III) fermentatively and therefore play a potential role in hexavalent chromium remediation at this site. Batch studies were conducted with Cellulomonas sp. strain ES6 to assess the influence of various carbon sources, iron minerals, and electron shuttling compounds on Cr(VI) reduction. These chemical species are likely to be present in these terrestrial environments during in situ bioremediation. Results indicated that there were a number of interactions between these compounds that influenced Cr(VI) reduction rates. The type of carbon source as well as the type of electron shuttle present influenced Cr(VI) reduction rates. When an electron shuttle, such as anthraquinone-2,6-disulfonate (AQDS), was present in the system, reduction rates increased significantly. Biologically reduced AQDS (AHDS) reduced Cr(VI) almost instantaneously. The presence of iron minerals and their concentrations did not significantly influence Cr(VI) reduction rates. However, strain ES6 or AQDS could directly reduce surface-associated Fe(III) to Fe(II) which was capable of reducing Cr(VI) at a near instantaneous rate. These results suggest the rate limiting step in these systems is the transfer of electrons from strain ES6 to the intermediate or terminal electron acceptor whether that is Cr(VI), Fe(III), or AQDS.

  17. Study of microbial perchlorate reduction: Considering of multiple pH, electron acceptors and donors

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Xing [Key Laboratory of Water Pollution Control and Recycling (Shandong), School of Environmental Science and Engineering, Shandong University, Jinan 250100 (China); Gao, Baoyu, E-mail: bygao@sdu.edu.cn [Key Laboratory of Water Pollution Control and Recycling (Shandong), School of Environmental Science and Engineering, Shandong University, Jinan 250100 (China); Jin, Bo [School of Chemical Engineering, The University of Adelaide, Adelaide SA 5005,Australia (Australia); Zhen, Hu [Key Laboratory of Water Pollution Control and Recycling (Shandong), School of Environmental Science and Engineering, Shandong University, Jinan 250100 (China); Wang, Xiaoyi [CSIRO Land and Water, Gate 5, Waite Road, Urrbrae, SA 5064 (Australia); Dai, Ming [School of Chemical Engineering, The University of Adelaide, Adelaide SA 5005,Australia (Australia)

    2015-03-21

    Graphical abstract: Schemes of perchlorate reduction in ClO{sub 4}{sup −}/ClO{sub 3}{sup −}–NO{sub 3}{sup −} e{sup −}acceptor systems. - Highlights: • We created a multiple electron acceptor/donor system for ClO{sub 4}{sup −} reduction. • Nitrate reduction was inhibited when using perchlorate-grown Azospira sp. KJ. • Reduction proceeded as an order of ClO{sub 3}{sup −}, ClO{sub 4}{sup −}and NO{sub 3}{sup −}. • Oxidation of acetate was inhibited by succinate in acetate–succinate series. - Abstract: Bioremediation of perchlorate-cotaminated water by a heterotrophic perchlorate reducing bacterium creates a multiple electron acceptor-donor system. We experimentally determined the perchlorate reduction by Azospira sp. KJ at multiple pH, electron acceptors and donors systems; this was the aim of this study. Perchlorate reduction was drastically inhibited at the pH 6.0, and the maximum reduction of perchlorate by Azospira sp. KJ was observed at pH value of 8.0. Perchlorate reduction was retarded in ClO{sub 4}{sup −}–ClO{sub 3}{sup −}, ClO{sub 4}{sup −}–ClO{sub 3}{sup −}–NO{sub 3}{sup −},and ClO{sub 4}{sup −}–NO{sub 3}{sup −} acceptor systems, while being completely inhibited by the additional O{sub 2} in the ClO{sub 4}{sup −}–O{sub 2} acceptor system. The reduction proceeded as an order of ClO{sub 3}{sup −}, ClO{sub 4}{sup −}, and NO{sub 3}{sup −} in the ClO{sub 4}{sup −}–ClO{sub 3}{sup −}–NO{sub 3}{sup −} system. K{sub S,}v{sub max}, and q{sub max} obtained at different e{sup −} acceptor and donor conditions are calculated as 140.5–190.6 mg/L, 8.7–13.2 mg-perchlorate/L-h, and 0.094–0.16 mg-perchlorate/mg-DW-h, respectively.

  18. The Mechanisms of Oxygen Reduction in the Terminal Reducing Segment of the Chloroplast Photosynthetic Electron Transport Chain.

    Science.gov (United States)

    Kozuleva, Marina A; Ivanov, Boris N

    2016-07-01

    The review is dedicated to ascertainment of the roles of the electron transfer cofactors of the pigment-protein complex of PSI, ferredoxin (Fd) and ferredoxin-NADP reductase in oxygen reduction in the photosynthetic electron transport chain (PETC) in the light. The data regarding oxygen reduction in other segments of the PETC are briefly analyzed, and it is concluded that their participation in the overall process in the PETC under unstressful conditions should be insignificant. Data concerning the contribution of Fd to the oxygen reduction in the PETC are examined. A set of collateral evidence as well as results of direct measurements of the involvement of Fd in this process in the presence of isolated thylakoids led to the inference that this contribution in vivo is negligible. The increase in oxygen reduction rate in the isolated thylakoids in the presence of either Fd or Fd plus NADP + under increasing light intensity was attributed to the increase in oxygen reduction executed by the membrane-bound oxygen reductants. Data are presented which imply that a main reductant of the O 2 molecule in the terminal reducing segment of the PETC is the electron transfer cofactor of PSI, phylloquinone. The physiological significance of characteristic properties of oxygen reductants in this segment of the PETC is discussed. © The Author 2016. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  19. Human low density lipoprotein (LDL) oxidation by metmyoglobin/H2O2: involvement of α-tocopheroxyl and phosphatidylcholine alkoxyl radicals

    International Nuclear Information System (INIS)

    Witting, P.K.; Willhite, C.A.; Stocker, R.; Davies, M.J.

    1998-01-01

    Full text: Metmyoglobin (metMb) and H 2 O 2 can oxidize low density lipoprotein (LDL) in vitro; formation of such oxidized LDL may be atherogenic. The role of α-tocopherol (α-TOH) in LDL oxidation by peroxidases, such as metMb is unclear. Herein we show that during metMb/H 2 O 2 -induced oxidation of native, α-TOH-containing, LDL, α-tocopheroxyl radical (α-TO) and hydroperoxides and hydroxides of cholesteryl esters (CE-O(O)H) and phosphatidylcholine (PC-O(O)H) accumulated concomitantly with α-TOH consumption. Accumulation of CE-O(O)H was dependent on, and correlated with, LDL's α-TOH content indicating that α-TO . acted as a chain-transfer agent and propagated LDL lipid peroxidation via tocopherol-mediated peroxidation (TMP). Further, the ratio of accumulating CE-O(O)H to PC-O(O)H remained constant in the presence α-TOH. Subsequent to α-TOH depletion, CE-O(O)H continued to accumulate, albeit at a lower rate than in the presence of α-TOH. This was accompanied by depletion of PC-OOH, a rapid increase in the CE-O(O)H/PC-O(O)H ratio, formation of lipid-derived alkoxyl radicals and phosphatidylcholine hydroxides (PC-OH), and accumulation of a second organic radical, characterized by a broad singlet EPR signal. The latter persisted for several hours at 37 deg C. We conclude that metMb/H 2 O 2 -induced peroxidation of LDL lipids is not inhibited by α-TOH and occurs initially via TMP. After α-TOH depletion, cholesteryl esters peroxidize at higher fractional rates than surface phospholipids, and this appears to be mediated via reactions involving alkoxyl radicals derived from the peroxidatic activity of metMb on PC-OO

  20. In situ Reduction and Oxidation of Nickel from Solid Oxide Fuel Cells in a Transmission Electron Microscope

    DEFF Research Database (Denmark)

    Faes, Antonin; Jeangros, Quentin; Wagner, Jakob Birkedal

    2009-01-01

    Environmental transmission electron microscopy was used to characterize in situ the reduction and oxidation of nickel from a Ni/YSZ solid oxide fuel cell anode support between 300-500{degree sign}C. The reduction is done under low hydrogen pressure. The reduction initiates at the NiO/YSZ interface...

  1. Topotactic reduction of YBa2Cu4O8 under the electron beam

    International Nuclear Information System (INIS)

    Domenges, B.; Hervieu, M.; Raveau, B.; Karpinski, J.; Kaldis, E.; Rusiecki, S.

    1991-01-01

    The stability of the high oxygen-pressure 80K-superconductor YBa 2 Cu 4 O 8 under the electron beam was studied by high resolution electron microscopy. Several topotactic reductions were observed for which models are proposed. The most important feature deals with the topotactic transformation of YBa 2 Cu 4 O 8 into the 125-type phase Y 1+x Ba 2+2x Cu 5-3x O 9 (x = 0.14) involving order-disorder phenomena

  2. Impact of Fe(III) as an effective electron-shuttle mediator for enhanced Cr(VI) reduction in microbial fuel cells: Reduction of diffusional resistances and cathode overpotentials

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Qiang [Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Huang, Liping, E-mail: lipinghuang@dlut.edu.cn [Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Pan, Yuzhen [College of Chemistry, Dalian University of Technology, Dalian 116024 (China); Quan, Xie [Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Li Puma, Gianluca, E-mail: g.lipuma@lboro.ac.uk [Environmental Nanocatalysis & Photoreaction Engineering, Department of Chemical Engineering, Loughborough University, Loughborough LE11 3TU (United Kingdom)

    2017-01-05

    Highlights: • Fe(III) shuttles electrons for enhanced reduction of Cr(VI) in MFCs. • The coulombic efficiency increases by 1.6 fold in the presence of Fe(III). • The reduction of Cr(VI) occurs via an indirect Fe(III) mediation mechanism. • Fe(III) decreases the diffusional resistances and the cathode overpotentials. - Abstract: The role of Fe(III) was investigated as an electron-shuttle mediator to enhance the reduction rate of the toxic heavy metal hexavalent chromium (Cr(VI)) in wastewaters, using microbial fuel cells (MFCs). The direct reduction of chromate (CrO{sub 4}{sup −}) and dichromate (Cr{sub 2}O{sub 7}{sup 2−}) anions in MFCs was hampered by the electrical repulsion between the negatively charged cathode and Cr(VI) functional groups. In contrast, in the presence of Fe(III), the conversion of Cr(VI) and the cathodic coulombic efficiency in the MFCs were 65.6% and 81.7%, respectively, 1.6 times and 1.4 folds as those recorded in the absence of Fe(III). Multiple analytical approaches, including linear sweep voltammetry, Tafel plot, cyclic voltammetry, electrochemical impedance spectroscopy and kinetic calculations demonstrated that the complete reduction of Cr(VI) occurred through an indirect mechanism mediated by Fe(III). The direct reduction of Cr(VI) with cathode electrons in the presence of Fe(III) was insignificant. Fe(III) played a critical role in decreasing both the diffusional resistance of Cr(VI) species and the overpotential for Cr(VI) reduction. This study demonstrated that the reduction of Cr(VI) in MFCs was effective in the presence of Fe(III), providing an alternative and environmentally benign approach for efficient remediation of Cr(VI) contaminated sites with simultaneous production of renewable energy.

  3. Impact of Fe(III) as an effective electron-shuttle mediator for enhanced Cr(VI) reduction in microbial fuel cells: Reduction of diffusional resistances and cathode overpotentials

    International Nuclear Information System (INIS)

    Wang, Qiang; Huang, Liping; Pan, Yuzhen; Quan, Xie; Li Puma, Gianluca

    2017-01-01

    Highlights: • Fe(III) shuttles electrons for enhanced reduction of Cr(VI) in MFCs. • The coulombic efficiency increases by 1.6 fold in the presence of Fe(III). • The reduction of Cr(VI) occurs via an indirect Fe(III) mediation mechanism. • Fe(III) decreases the diffusional resistances and the cathode overpotentials. - Abstract: The role of Fe(III) was investigated as an electron-shuttle mediator to enhance the reduction rate of the toxic heavy metal hexavalent chromium (Cr(VI)) in wastewaters, using microbial fuel cells (MFCs). The direct reduction of chromate (CrO_4"−) and dichromate (Cr_2O_7"2"−) anions in MFCs was hampered by the electrical repulsion between the negatively charged cathode and Cr(VI) functional groups. In contrast, in the presence of Fe(III), the conversion of Cr(VI) and the cathodic coulombic efficiency in the MFCs were 65.6% and 81.7%, respectively, 1.6 times and 1.4 folds as those recorded in the absence of Fe(III). Multiple analytical approaches, including linear sweep voltammetry, Tafel plot, cyclic voltammetry, electrochemical impedance spectroscopy and kinetic calculations demonstrated that the complete reduction of Cr(VI) occurred through an indirect mechanism mediated by Fe(III). The direct reduction of Cr(VI) with cathode electrons in the presence of Fe(III) was insignificant. Fe(III) played a critical role in decreasing both the diffusional resistance of Cr(VI) species and the overpotential for Cr(VI) reduction. This study demonstrated that the reduction of Cr(VI) in MFCs was effective in the presence of Fe(III), providing an alternative and environmentally benign approach for efficient remediation of Cr(VI) contaminated sites with simultaneous production of renewable energy.

  4. [Efficacy and security of electronic cigarette for tobacco harm reduction: Systematic review and meta-analysis].

    Science.gov (United States)

    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.

  5. Supramolecular tetracluster-cobalt porphyrin: a four-electron transfer catalyst for dioxygen reduction

    International Nuclear Information System (INIS)

    Winnischofer, Herbert; Otake, Vesper Yoshiyuki; Dovidauskas, Sergio; Nakamura, Marcelo; Toma, Henrique Eisi; Araki, Koiti

    2004-01-01

    Electrocatalysis by CoTCP {CoTCP meso-tetrakis(4-pyridyl)porphynatocobalt(III)} coordinated to four [Ru 3 (μ 3 -O)(μ 2 -CH 3 CO 2 ) 6 (py) 2 ] + complexes in the four-electron reduction of dioxygen, has been unequivocally demonstrated in this work by using two types of electrostatically assembled films of CoTCP and anionic zinc or free-base meso-tetrakis(4-sulfonatophenyl)porphyrins (ZnTPPS or H 2 TPPS), as well as, by employing different electrode materials. An enhanced electrocatalytic activity has been observed, in spite of the fact that the typical bis-coordination of dioxygen to two cobalt porphyrin sites is precluded in such CoTCP/ZnTPPS or CoTCP/H 2 TPPS bilayered films. In addition, negligible ring currents have been observed in ring-disk voltammetry measurements, yielding straight Levich and Koutecky-Levich plots, whose slopes approached the theoretical 4e - curve in air, or in O 2 saturated solutions (pH 3-5). The use of gold instead of glassy carbon (GC) electrodes has not also significantly perturbed the mechanism. By ruling out any influence from the electrode materials, a well known critical point in the catalysis by cobalt porphyrins, the results have shown that CoTCP is acting as a four-electron transfer catalyst for dioxygen reduction. Also, by excluding the possibility of bis-coordination of dioxygen, it was shown that the electronic and supramolecular effects exerted by the peripheral ruthenium cluster complexes should be triggering the four-electron catalytic activity of the cobalt porphyrin center

  6. Electron Transfer Pathways Facilitating U(VI) Reduction by Fe(II) on Al- vs Fe-Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, S. D. [Pacific Northwest National Laboratory, Physical Sciences Division, P.O. Box; Becker, U. [The University of Michigan, Department of Earth; Rosso, K. M. [Pacific Northwest National Laboratory, Physical Sciences Division, P.O. Box

    2017-09-06

    This study continues mechanistic development of heterogeneous electron transfer (ET) pathways at mineral surfaces in aquatic environments that enable the reduction U(VI) by surface-associated Fe(II). Using computational molecular simulation within the framework of Marcus Theory, our findings highlight the importance of the configurations and interaction of the electron donor and acceptor species with the substrate, with respect to influencing its electronic structure and thereby the ability of semiconducting minerals to facilitate ET. U(VI) reduction by surface-associated Fe(II) (adsorbed or structurally incorporated into the lattice) on an insulating, corundum (001) surface (α-Al2O3) occurs when proximal inner-sphere (IS) surface complexes are formed, such that ET occurs through a combination of direct exchange (i.e., Fe d- and U f-orbitals overlap through space) and superexchange via intervening surface oxygen atoms. U(VI) reduction by coadsorbed Fe(II) on the isostructural semiconducting hematite (α-Fe2O3) basal surface requires either their direct electronic interaction (e.g., IS complexation) or mediation of this interaction indirectly through the surface via an intrasurface pathway. Conceptually possible longer-range ET by charge-hopping through surface Fe atoms was investigated to determine whether this indirect pathway is competitive with direct ET. The calculations show that energy barriers are large for this conduction-based pathway; interfacial ET into the hematite surface is endothermic (+80.1 kJ/mol) and comprises the rate-limiting step (10–6 s–1). The presence of the IS adsorbates appears to weaken the electronic coupling between underlying Fe ions within the surface, resulting in slower intra-surface ET (10–5 s–1) than expected in the bulk basal plane. Our findings lay out first insights into donor-acceptor communication via a charge-hopping pathway through the surface for heterogeneous reduction of U(VI) by Fe(II) and help provide a basis

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

    Energy Technology Data Exchange (ETDEWEB)

    Ayala-Parra, Pedro; Sierra-Alvarez, Reyes; Field, Jim A., E-mail: jimfield@email.arizona.edu

    2016-11-05

    Highlights: • Algal biomass can serve as an electron donor to drive reduction of sulfate to sulfide. • Biogenic sulfide precipitates Cu{sup 2+} as stable sulfide mineral. • Cu{sup +2} removal in sulfidogenic bioreactors amended with algal biomass exceeded 99.5%. • Acidity in synthetic acid rock drainage was consumed by sulfate reduction. - Abstract: This study assessed bioremediation of acid rock drainage in simulated permeable reactive barriers (PRB) using algae, Chlorella sorokiniana, as the sole electron donor for sulfate-reducing bacteria. Lipid extracted algae (LEA), the residues of biodiesel production, were compared with whole cell algae (WCA) as an electron donor to promote sulfate-reducing activity. Inoculated columns containing anaerobic granular sludge were fed a synthetic medium containing H{sub 2}SO{sub 4} and Cu{sup 2+}. Sulfate, sulfide, Cu{sup 2+} and pH were monitored throughout the experiment of 123 d. Cu recovered in the column packing at the end of the experiment was evaluated using sequential extraction. Both WCA and LEA promoted 80% of sulfate removal (12.7 mg SO{sub 4}{sup 2−} d{sup −1}) enabling near complete Cu removal (>99.5%) and alkalinity generation raising the effluent pH to 6.5. No noteworthy sulfate reduction, alkalinity formation and Cu{sup 2+} removal were observed in the endogenous control. In algae amended-columns, Cu{sup 2+} was precipitated with biogenic H{sub 2}S produced by sulfate reduction. Formation of CuS was evidenced by sequential extraction and X-ray diffraction. LEA and WCA provided similar levels of electron donor based on the COD balance. The results demonstrate an innovative passive remediation system using residual algae biomass from the biodiesel industry.

  8. Electron irradiation induced reduction of the permittivity in chalcogenide glass (As2S3) thin film

    KAUST Repository

    San Roman Alerigi, Damian; Anjum, Dalaver H.; Zhang, Yaping; Yang, Xiaoming; Ben Slimane, Ahmed; Ng, Tien Khee; Hedhili, Mohamed N.; Alsunaidi, Mohammad; Ooi, Boon S.

    2013-01-01

    In this paper, we investigate the effect of electron beam irradiation on the dielectric properties of As 2 S 3 chalcogenide glass. By means of low-loss electron energy loss spectroscopy, we derive the permittivity function, its dispersive relation, and calculate the refractive index and absorption coefficients under the constant permeability approximation. The measured and calculated results show a heretofore unseen phenomenon: a reduction in the permittivity of ? 40 %. Consequently a reduction of the refractive index of 20%, hence, suggests a conspicuous change in the optical properties of the material under irradiation with a 300 keV electron beam. The plausible physical phenomena leading to these observations are discussed in terms of the homopolar and heteropolar bond dynamics under high energy absorption. The reported phenomena, exhibited by As 2 S 3-thin film, can be crucial for the development of photonics integrated circuits using electron beam irradiation method. © 2013 American Institute of Physics.

  9. Influence of Bicarbonate, Sulfate, and Electron Donors on Biological reduction of Uranium and Microbial Community Composition

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Wensui [ORNL; Zhou, Jizhong [ORNL; Wu, Weimin [ORNL; Yan, Tingfen [ORNL; Criddle, Craig [ORNL; Jardine, Philip M [ORNL; Gu, Baohua [ORNL

    2007-01-01

    A microcosm study was performed to investigate the effect of ethanol and acetate on uranium(VI) biological reduction and microbial community changes under various geochemical conditions. Each microcosm contained an uranium-contaminated sediment (up to 2.8 g U/kg) suspended in buffer with bicarbonate at concentrations of either 1 mM or 40 mM and sulfate at either 1.1 or 3.2 mM. Ethanol or acetate was used as an electron donor. Results indicate that ethanol yielded in significantly higher U(VI) reduction rates than acetate. A low bicarbonate concentration (1 mM) was favored for U(VI) bioreduction to occur in sediments, but high concentrations of bicarbonate (40 mM) and sulfate (3.2 mM) decreased the reduction rates of U(VI). Microbial communities were dominated by species from the Geothrix genus and Proteobacteria phylum in all microcosms. However, species in the Geobacteraceae family capable of reducing U(VI) were significantly enriched by ethanol and acetate in low bicarbonate buffer. Ethanol increased the population of unclassified Desulfuromonales, while acetate increased the population of Desulfovibrio. Additionally, species in the Geobacteraceae family were not enriched in high bicarbonate buffer, but the Geothrix and the unclassified Betaproteobacteria species were enriched. This study concludes that ethanol could be a better electron donor than acetate for reducing U(VI) under given experimental conditions, and electron donor and geoundwater geochemistry alter microbial communities responsible for U(VI) reduction.

  10. Influence of bicarbonate, sulfate, and electron donors on biological reduction of uranium and microbial community composition

    Energy Technology Data Exchange (ETDEWEB)

    Luo Wensui [Oak Ridge Inst. for Science and Education, TN (United States); Oak Ridge National Lab., TN (United States). Environmental Sciences Div.; Wu Wei-Min; Criddle, C.S. [Stanford Univ., CA (United States). Dept. of Civil and Environmental Engineering; Yan Tingfen [Oak Ridge Inst. for Science and Education, TN (United States); Jardine, P.M.; Gu Baohua [Oak Ridge National Lab., TN (United States). Environmental Sciences Div.; Zhou Jizhong [Oklahoma Univ., Norman, OK (United States). Dept. of Botany and Microbiology

    2007-12-15

    A microcosm study was performed to investigate the effect of ethanol and acetate on uranium(VI) biological reduction and microbial community changes under various geochemical conditions. Each microcosm contained an uranium-contaminated sediment (up to 2.8 g U/kg) suspended in buffer with bicarbonate at concentrations of either 1 or 40 mM and sulfate at either 1.1 or 3.2 mM. Ethanol or acetate was used as an electron donor. Results indicate that ethanol yielded in significantly higher U(VI) reduction rates than acetate. A low bicarbonate concentration (1 mM) was favored for U(VI) bioreduction to occur in sediments, but high concentrations of bicarbonate (40 mM) and sulfate (3.2 mM) decreased the reduction rates of U(VI). Microbial communities were dominated by species from the Geothrix genus and Proteobacteria phylum in all microcosms. However, species in the Geobacteraceae family capable of reducing U(VI) were significantly enriched by ethanol and acetate in low-bicarbonate buffer. Ethanol increased the population of unclassified Desulfuromonales, while acetate increased the population of Desulfovibrio. Additionally, species in the Geobacteraceae family were not enriched in high-bicarbonate buffer, but the Geothrix and the unclassified Betaproteobacteria species were enriched. This study concludes that ethanol could be a better electron donor than acetate for reducing U(VI) under given experimental conditions, and electron donor and groundwater geochemistry alter microbial communities responsible for U(VI) reduction. (orig.)

  11. Reduction of the Glauber amplitude for electron impact rotational excitation of quadrupolar molecular ions

    International Nuclear Information System (INIS)

    Mathur, K.C.; Gupta, G.P.; Pundir, R.S.

    1981-06-01

    A reduction of the Glauber amplitude for the rotational excitation of pure quadrupolar molecular ions by electron impact is presented in a form suitable for numerical evaluation. The differential cross-section is expressed in terms of one dimensional integrals over impact parameter. (author)

  12. Projection-reduction method applied to deriving non-linear optical conductivity for an electron-impurity system

    Directory of Open Access Journals (Sweden)

    Nam Lyong Kang

    2013-07-01

    Full Text Available The projection-reduction method introduced by the present authors is known to give a validated theory for optical transitions in the systems of electrons interacting with phonons. In this work, using this method, we derive the linear and first order nonlinear optical conductivites for an electron-impurity system and examine whether the expressions faithfully satisfy the quantum mechanical philosophy, in the same way as for the electron-phonon systems. The result shows that the Fermi distribution function for electrons, energy denominators, and electron-impurity coupling factors are contained properly in organized manners along with absorption of photons for each electron transition process in the final expressions. Furthermore, the result is shown to be represented properly by schematic diagrams, as in the formulation of electron-phonon interaction. Therefore, in conclusion, we claim that this method can be applied in modeling optical transitions of electrons interacting with both impurities and phonons.

  13. Reduction of 1/f noise in graphene after electron-beam irradiation

    International Nuclear Information System (INIS)

    Zahid Hossain, Md.; Rumyantsev, Sergey; Shur, Michael S.; Balandin, Alexander A.

    2013-01-01

    We investigated experimentally the effect of the electron-beam irradiation on the level of the low-frequency 1/f noise in graphene devices. It was found that 1/f noise in graphene reduces with increasing concentration of defects induced by irradiation. The increased amount of structural disorder in graphene under irradiation was verified with micro-Raman spectroscopy. The bombardment of graphene devices with 20-keV electrons reduced the noise spectral density, S I /I 2 (I is the source-drain current) by an order-of magnitude at the radiation dose of 10 4 μC/cm 2 . We analyzed the observed noise reduction in the limiting cases of the mobility and carrier number fluctuation mechanisms. The obtained results are important for the proposed graphene applications in analog, mixed-signal, and radio-frequency systems, integrated circuits and sensors.

  14. Electron transfer capacity dependence of quinone-mediated Fe(III) reduction and current generation by Klebsiella pneumoniae L17.

    Science.gov (United States)

    Li, Xiaomin; Liu, Liang; Liu, Tongxu; Yuan, Tian; Zhang, Wei; Li, Fangbai; Zhou, Shungui; Li, Yongtao

    2013-06-01

    Quinone groups in exogenous electron shuttles can accelerate extracellular electron transfer (EET) from bacteria to insoluble terminal electron acceptors, such as Fe(III) oxides and electrodes, which are important in biogeochemical redox processes and microbial electricity generation. However, the relationship between quinone-mediated EET performance and electron-shuttling properties of the quinones remains incompletely characterized. This study investigates the effects of a series of synthetic quinones (SQs) on goethite reduction and current generation by a fermenting bacterium Klebsiella pneumoniae L17. In addition, the voltammetric behavior and electron transfer capacities (ETCs) of SQ, including electron accepting (EAC) and donating (EDC) capacities, is also examined using electrochemical methods. The results showed that SQ can significantly increase both the Fe(III) reduction rates and current outputs of L17. Each tested SQ reversibly accepted and donated electrons as indicated by the cyclic voltammograms. The EAC and EDC results showed that Carmine and Alizarin had low relative capacities of electron transfer, whereas 9,10-anthraquinone-2,6-disulfonic acid (AQDS), 2-hydroxy-1,4-naphthoquinone (2-HNQ), and 5-hydroxy-1,4-naphthoquinone (5-HNQ) showed stronger relative ETC, and 9,10-anthraquinone-2-carboxylic acid (AQC) and 9,10-anthraquinone-2-sulfonic acid (AQS) had high relative ETC. Enhancement of microbial goethite reduction kinetics and current outputs by SQ had a good linear relationship with their ETC, indicating that the effectiveness of quinone-mediated EET may be strongly dependent on the ETC of the quinones. Therefore, the presence of quinone compounds and fermenting microorganisms may increase the diversity of microbial populations that contribute to element transformation in natural environments. Moreover, ETC determination of different SQ would help to evaluate their performance for microbial EET under anoxic conditions. Copyright © 2013 Elsevier

  15. Influence of Carbon Sources and Electron Shuttles on Ferric Iron Reduction by Cellulomonas sp. Strain ES6

    Energy Technology Data Exchange (ETDEWEB)

    Dr Robin Gerlach; Erin K. Field; Sridhar Viamajala; Brent M. Peyton; William A. Apel; Al B. Cunningham

    2011-09-01

    Microbially reduced iron minerals can reductively transform a variety of contaminants including heavy metals, radionuclides, chlorinated aliphatics, and nitroaromatics. A number of Cellulomonas spp. strains, including strain ES6, isolated from aquifer samples obtained at the U.S. Department of Energy's Hanford site in Washington, have been shown to be capable of reducing Cr(VI), TNT, natural organic matter, and soluble ferric iron [Fe(III)]. This research investigated the ability of Cellulomonas sp. strain ES6 to reduce solid phase and dissolved Fe(III) utilizing different carbon sources and various electron shuttling compounds. Results suggest that Fe(III) reduction by and growth of strain ES6 was dependent upon the type of electron donor, the form of iron present, and the presence of synthetic or natural organic matter, such as anthraquinone-2,6-disulfonate (AQDS) or humic substances. This research suggests that Cellulomonas sp. strain ES6 could play a significant role in metal reduction in the Hanford subsurface and that the choice of carbon source and organic matter addition can allow for independent control of growth and iron reduction activity.

  16. Nitrogen Starvation Acclimation in Synechococcus elongatus: Redox-Control and the Role of Nitrate Reduction as an Electron Sink

    Directory of Open Access Journals (Sweden)

    Alexander Klotz

    2015-03-01

    Full Text Available Nitrogen starvation acclimation in non-diazotrophic cyanobacteria is characterized by a process termed chlorosis, where the light harvesting pigments are degraded and the cells gradually tune down photosynthetic and metabolic activities. The chlorosis response is governed by a complex and poorly understood regulatory network, which converges at the expression of the nblA gene, the triggering factor for phycobiliprotein degradation. This study established a method that allows uncoupling metabolic and redox-signals involved in nitrogen-starvation acclimation. Inhibition of glutamine synthetase (GS by a precise dosage of l-methionine-sulfoximine (MSX mimics the metabolic situation of nitrogen starvation. Addition of nitrate to such MSX-inhibited cells eliminates the associated redox-stress by enabling electron flow towards nitrate/nitrite reduction and thereby, prevents the induction of nblA expression and the associated chlorosis response. This study demonstrates that nitrogen starvation is perceived not only through metabolic signals, but requires a redox signal indicating over-reduction of PSI-reduced electron acceptors. It further establishes a cryptic role of nitrate/nitrite reductases as electron sinks to balance conditions of over-reduction.

  17. Nitrogen Starvation Acclimation in Synechococcus elongatus: Redox-Control and the Role of Nitrate Reduction as an Electron Sink

    Science.gov (United States)

    Klotz, Alexander; Reinhold, Edgar; Doello, Sofía; Forchhammer, Karl

    2015-01-01

    Nitrogen starvation acclimation in non-diazotrophic cyanobacteria is characterized by a process termed chlorosis, where the light harvesting pigments are degraded and the cells gradually tune down photosynthetic and metabolic activities. The chlorosis response is governed by a complex and poorly understood regulatory network, which converges at the expression of the nblA gene, the triggering factor for phycobiliprotein degradation. This study established a method that allows uncoupling metabolic and redox-signals involved in nitrogen-starvation acclimation. Inhibition of glutamine synthetase (GS) by a precise dosage of l-methionine-sulfoximine (MSX) mimics the metabolic situation of nitrogen starvation. Addition of nitrate to such MSX-inhibited cells eliminates the associated redox-stress by enabling electron flow towards nitrate/nitrite reduction and thereby, prevents the induction of nblA expression and the associated chlorosis response. This study demonstrates that nitrogen starvation is perceived not only through metabolic signals, but requires a redox signal indicating over-reduction of PSI-reduced electron acceptors. It further establishes a cryptic role of nitrate/nitrite reductases as electron sinks to balance conditions of over-reduction. PMID:25780959

  18. One-electron reduction of anthraquinone sulphonates: a pulse radiolysis study

    International Nuclear Information System (INIS)

    Pal, H.; Palit, D.K.; Mukherjee, T.; Mittal, J.P.

    1991-01-01

    Semiquinone free radicals, derived from 2-sulphonate, 1,5-disulphonate and 2,6-disulphonate derivatives of 9,10-anthraquinone, have been studied using pulse radiolysis and kinetic absorption spectrophotometry techniques. Spectroscopic characteristics of both neutral and anionic species have been ascertained. Kinetics of formation and decay, reactivity with oxygen and one-electron reduction potential values have been estimated. The semiquinone radicals have been shown to be very stable under suitable pH conditions where the equilibrium (2 semiquinone ↔ quinone + hydroquinone) lies predominantly to the left. From a measurement of the equilibrium constants at different pH, values of E 2 and E m have been calculated. (author)

  19. The need for novel model order reduction techniques in the electronics industry (Chapter 1)

    NARCIS (Netherlands)

    Schilders, W.H.A.; Benner, P.; Hinze, M.; Maten, ter E.J.W.

    2011-01-01

    In this paper, we discuss the present and future needs of the electronics industry with regard to model order reduction. The industry has always been one of the main motivating fields for the development of MOR techniques, and continues to play this role. We discuss the search for provably passive

  20. Quantifying spot size reduction of a 1.8 kA electron beam for flash radiography

    Science.gov (United States)

    Burris-Mog, T. J.; Moir, D. C.

    2018-03-01

    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 emittance and solenoid aberrations are also presented.

  1. Enhanced catalytic four-electron dioxygen (O2) and two-electron hydrogen peroxide (H2O2) reduction with a copper(II) complex possessing a pendant ligand pivalamido group.

    Science.gov (United States)

    Kakuda, Saya; Peterson, Ryan L; Ohkubo, Kei; Karlin, Kenneth D; Fukuzumi, Shunichi

    2013-05-01

    A copper complex, [(PV-tmpa)Cu(II)](ClO4)2 (1) [PV-tmpa = bis(pyrid-2-ylmethyl){[6-(pivalamido)pyrid-2-yl]methyl}amine], acts as a more efficient catalyst for the four-electron reduction of O2 by decamethylferrocene (Fc*) in the presence of trifluoroacetic acid (CF3COOH) in acetone as compared with the corresponding copper complex without a pivalamido group, [(tmpa)Cu(II)](ClO4)2 (2) (tmpa = tris(2-pyridylmethyl)amine). The rate constant (k(obs)) of formation of decamethylferrocenium ion (Fc*(+)) in the catalytic four-electron reduction of O2 by Fc* in the presence of a large excess CF3COOH and O2 obeyed first-order kinetics. The k(obs) value was proportional to the concentration of catalyst 1 or 2, whereas the k(obs) value remained constant irrespective of the concentration of CF3COOH or O2. This indicates that electron transfer from Fc* to 1 or 2 is the rate-determining step in the catalytic cycle of the four-electron reduction of O2 by Fc* in the presence of CF3COOH. The second-order catalytic rate constant (k(cat)) for 1 is 4 times larger than the corresponding value determined for 2. With the pivalamido group in 1 compared to 2, the Cu(II)/Cu(I) potentials are -0.23 and -0.05 V vs SCE, respectively. However, during catalytic turnover, the CF3COO(-) anion present readily binds to 2 shifting the resulting complex's redox potential to -0.35 V. The pivalamido group in 1 is found to inhibit anion binding. The overall effect is to make 1 easier to reduce (relative to 2) during catalysis, accounting for the relative k(cat) values observed. 1 is also an excellent catalyst for the two-electron two-proton reduction of H2O2 to water and is also more efficient than is 2. For both complexes, reaction rates are greater than for the overall four-electron O2-reduction to water, an important asset in the design of catalysts for the latter.

  2. Evaluation of the participation of ferredoxin in oxygen reduction in the photosynthetic electron transport chain of isolated pea thylakoids.

    Science.gov (United States)

    Kozuleva, Marina A; Ivanov, Boris N

    2010-07-01

    The contribution to reduction of oxygen by ferredoxin (Fd) to the overall reduction of oxygen in isolated pea thylakoids was studied in the presence of Fd versus Fd + NADP(+). The overall rate of electron transport was measured using a determination of Photosystem II quantum yield from chlorophyll fluorescence parameters, and the rate of oxidation of Fd was measured from the light-induced redox changes of Fd. At low light intensity, increasing Fd concentration from 5 to 30 microM in the absence of NADP(+) increased the proportion of oxygen reduction by Fd from 25-35 to 40-60% in different experiments. This proportion decreased with increasing light intensity. When NADP(+) was added in the presence of 15 microM Fd, which was optimal for the NADP(+) reduction rate, the participation of Fd in the reduction of oxygen was low, no more than 10%, and it also decreased with increasing light intensity. At high light intensity, the overall oxygen reduction rates in the presence of Fd + NADP(+) and in the presence of Fd alone were comparable. The significance of reduction of dioxygen either by water-soluble Fd or by the membrane-bound carriers of the photosynthetic electron transport chain for redox signaling under different light intensities is discussed.

  3. In-situ reduction of promoted cobalt oxide supported on alumina by environmental transmission electron microscopy

    DEFF Research Database (Denmark)

    Dehghan, Roya; Hansen, Thomas Willum; Wagner, Jakob Birkedal

    2011-01-01

    the reactivity of the nanoparticles and the importance of controlling the gas composition and specimen temperature during this type of experiment. Similar behaviour was observed for a non-promoted catalyst. Imaging and analysis of the promoted sample before and after reduction indicated a uniform distribution...... resolution transmission electron microscopy and scanning transmission electron microscopy imaging. The cobalt particles were mainly face centred cubic while some hexagonal close packed particles were also found. Reoxidation of the sample upon cooling to room temperature, still under flowing H2, underlines...

  4. Recovery of gold from hydrometallurgical leaching solution of electronic waste via spontaneous reduction by polyaniline

    Directory of Open Access Journals (Sweden)

    Yuanzhao Wu

    2017-08-01

    Full Text Available The present study is primarily designed to develop an environmentally-benign approach for the recovery of precious metals, especially gold, from the ever increasingly-discarded electronic wastes (e-waste. By coupling the metal reduction process with an increase in the intrinsic oxidation state of the aniline polymers, and the subsequent re-protonation and reduction of the intrinsically oxidized polymer to the protonated emeraldine (EM salt, polyaniline (PANi films and polyaniline coated cotton fibers are able to recover metallic gold from acid/halide leaching solutions of electronic wastes spontaneously and sustainably. The current technique, which does not require the use of extensive extracting reagents or external energy input, can recover as much as 90% of gold from the leaching acidic solutions. The regeneration of polyaniline after gold recovery, as confirmed by the X-ray photoelectron spectroscopy measurements, promises the continuous operation using the current approach. The as-recovered elemental gold can be further concentrated and purified by incineration in air.

  5. Pulse radiolytic one-electron reduction of 2-hydroxy- and 2,6-dihydroxy-9,10-anthraquinones

    International Nuclear Information System (INIS)

    Pal, Haridas; Mukherjee, Tulsi; Mittal, J.P.

    1994-01-01

    The semiquinone free radicals produced by one-electron reduction of 2-hydroxy-9-10-anthraquinone (2HAQ) and 2,6-dihydroxy-9,10-anthraquinone (26DHAQ) in aqueous formate solution, water-isopropyl alcohol-acetone mixed solvent and isopropyl alcohol have been studied using the pulse radiolysis technique. The absorption characteristics, kinetic parameters of formation and decay, acid-base behaviour and redox characteristics of the semiquinones have been investigated and compared with the corresponding characteristics of a few intramolecularly hydro-bonded anthrasemiquinone derivatives. The non-hydrogen-bonded semiquinones show two pKsub(a) values (4.7 and 10.7 for 2HAQ and 5.4 and 8.7 for 26DHAQ, respectively) within the pH range 1-14, whereas other intramolecularly hydrogen-bonded semiquinones show only one pKsub(a). The one-electron reduction potential (E' 7 ) values for 2HAQ (-440 mV) and 26DHAQ (- 400 mV) are more negative than those of the intramolecularly hydrogen-bonded systems. (Author)

  6. Functionalized Cobalt Triarylcorrole Covalently Bonded with Graphene Oxide: A Selective Catalyst for the Two- or Four-Electron Reduction of Oxygen.

    Science.gov (United States)

    Tang, Jijun; Ou, Zhongping; Guo, Rui; Fang, Yuanyuan; Huang, Dong; Zhang, Jing; Zhang, Jiaoxia; Guo, Song; McFarland, Frederick M; Kadish, Karl M

    2017-08-07

    A cobalt triphenylcorrole (CorCo) was covalently bonded to graphene oxide (GO), and the resulting product, represented as GO-CorCo, was characterized by UV-vis, FT-IR, and micro-Raman spectroscopy as well as by HRTEM, TGA, XRD, XPS, and AFM. The electrocatalytic activity of GO-CorCo toward the oxygen reduction reaction (ORR) was then examined in air-saturated 0.1 M KOH and 0.5 M H 2 SO 4 solutions by cyclic voltammetry and linear sweep voltammetry using a rotating disk electrode and/or a rotating ring-disk electrode. An overall 4-electron reduction of O 2 is obtained in alkaline media while under acidic conditions a 2-electron process is seen. The ORR results thus indicate that covalently bonded GO-CoCor can be used as a selective catalyst for either the 2- or 4-electron reduction of oxygen, the prevailing reaction depending upon the acidity of the solution.

  7. Complete bromate and nitrate reduction using hydrogen as the sole electron donor in a rotating biofilm-electrode reactor

    International Nuclear Information System (INIS)

    Zhong, Yu; Li, Xin; Yang, Qi; Wang, Dongbo; Yao, Fubing; Li, Xiaoming; Zhao, Jianwei; Xu, Qiuxiang; Zhang, Chang; Zeng, Guangming

    2016-01-01

    Graphical abstract: Main mechanism of simultaneous bromate and nitrate removal in the RBER. - Highlights: • Cathode of RBER was designed to automatically rotate. • Simultaneous bromate and nitrate removal was achieved by auto-hydrogenotrophic reduction. • The maximum bromate reduction rate estimated by the Monod equation was 109.12 μg/L h. • An electron transfer process and main reaction mechanism in RBER was explored. - Abstract: Simultaneous reduction of bromate and nitrate was investigated using a rotating biofilm-electrode reactor (RBER) with graphite carbon (GC) rods as anode and activated carbon fiber (ACF) bonded with steel ring as cathode. In RBER, the community of denitrifying bacteria immobilized on the cathode surface could completely utilize hydrogen (H 2 ) as the electron donor, which was internally produced by the electrolysis of water. The short-term test confirmed that the RBER system could reduce 150–800 μg/L bromate to below 10 μg/L under autotrophic conditions. The reduced bromate was considered to be roughly equivalent to the amount of bromide in effluent, indicating that bromate was completely reduced to bromide without accumulation of by-products. The long-term test (over 120 days) showed that the removal fluxes of bromate and nitrate could be improved by increasing the electric current and decreasing the hydraulic retention time (HRT). But nitrite in effluent was significantly accumulated when the electric current was beyond 10 mA and the HRT was less than 6 h. The maximum bromate reduction rate estimated by the Monod equation was 109.12 μg/L h when the electric current was 10 mA and HRT was 12 h. It was proposed that the electron transfer process in RBER produced H 2 on the surface of the ACF cathode, and the microbial cultures attached closely on the cathode which could completely utilize H 2 as electron donors for reduction of bromate and nitrate.

  8. Complete bromate and nitrate reduction using hydrogen as the sole electron donor in a rotating biofilm-electrode reactor

    Energy Technology Data Exchange (ETDEWEB)

    Zhong, Yu; Li, Xin [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Yang, Qi, E-mail: yangqi@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Wang, Dongbo [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Advanced Water Management Centre, The University of Queensland, QLD 4072 (Australia); Yao, Fubing [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Li, Xiaoming, E-mail: xmli@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Zhao, Jianwei; Xu, Qiuxiang; Zhang, Chang; Zeng, Guangming [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China)

    2016-04-15

    Graphical abstract: Main mechanism of simultaneous bromate and nitrate removal in the RBER. - Highlights: • Cathode of RBER was designed to automatically rotate. • Simultaneous bromate and nitrate removal was achieved by auto-hydrogenotrophic reduction. • The maximum bromate reduction rate estimated by the Monod equation was 109.12 μg/L h. • An electron transfer process and main reaction mechanism in RBER was explored. - Abstract: Simultaneous reduction of bromate and nitrate was investigated using a rotating biofilm-electrode reactor (RBER) with graphite carbon (GC) rods as anode and activated carbon fiber (ACF) bonded with steel ring as cathode. In RBER, the community of denitrifying bacteria immobilized on the cathode surface could completely utilize hydrogen (H{sub 2}) as the electron donor, which was internally produced by the electrolysis of water. The short-term test confirmed that the RBER system could reduce 150–800 μg/L bromate to below 10 μg/L under autotrophic conditions. The reduced bromate was considered to be roughly equivalent to the amount of bromide in effluent, indicating that bromate was completely reduced to bromide without accumulation of by-products. The long-term test (over 120 days) showed that the removal fluxes of bromate and nitrate could be improved by increasing the electric current and decreasing the hydraulic retention time (HRT). But nitrite in effluent was significantly accumulated when the electric current was beyond 10 mA and the HRT was less than 6 h. The maximum bromate reduction rate estimated by the Monod equation was 109.12 μg/L h when the electric current was 10 mA and HRT was 12 h. It was proposed that the electron transfer process in RBER produced H{sub 2} on the surface of the ACF cathode, and the microbial cultures attached closely on the cathode which could completely utilize H{sub 2} as electron donors for reduction of bromate and nitrate.

  9. One-electron reduction of 2- and 6-methyl-1,4-naphthoquinone bioreductive alkylating agents

    International Nuclear Information System (INIS)

    Wilson, I.; Wardman, P.; Lin, T.S.; Sartorelli, A.C.

    1986-01-01

    The semiquinones, Q.-, of derivatives of 2- and 6-methyl-1,4-naphthoquinones, some incorporating leaving groups with substituents such as CH 2 Br or CH 2 OCONHCH 3 , have been produced by radiolytic reduction of Q by (CH 3 )2COH radicals. The absorption spectra and decay kinetics of Q.- were all closely similar to that produced from 2-methyl-1,4-naphthoquinone, with no evidence for unimolecular elimination of a leaving group in the semiquinone form, but immediate loss of leaving group upon two-electron reduction of Q to the hydroquinone. The redox equilibria between Q/Q.- and O2/O2.- were characterized, and reduction potentials of the couples Q/Q.- in water at pH 7.6 were calculated. The implications of these observations for the use of these compounds as bioreductive alkylating agents or as radiosensitizers with potential selective activity toward hypoxic cells are discussed

  10. Catalytic activity of dual catalysts system based on nano-manganese oxide and cobalt octacyanophthalocyanine toward four-electron reduction of oxygen in alkaline media

    International Nuclear Information System (INIS)

    Zhang, Dun; Chi, Dahe; Okajima, Takeyoshi; Ohsaka, Takeo

    2007-01-01

    The electrocatalysis of the dual functional catalysts system composed of electrolytic nano-manganese oxide (nano-MnOx) and cobalt octacyanophthalocyanine (CoPcCN) toward 4-electron reduction of oxygen (O 2 ) in alkaline media was studied. Nano-MnOx electrodeposited on the CoPcCN monolayer-modified glassy carbon (GC) electrode was clarified as the nano-rods with ca. 10-20 nm diameter by scanning electron microscopy. The peak current for O 2 reduction at the dual catalysts-modified GC electrode increases largely and the peak potential shifts by ca. 160 mV to the positive direction in cyclic voltammograms compared with those obtained at the bare GC electrode. The Koutecky-Levich plots indicate that the O 2 reduction at the dual catalysts-modified GC electrode is an apparent 4-electron process. Collection efficiencies obtained at the dual catalysts-modified GC electrode are much lower than those at the GC electrode and are almost similar to those at the Pt nano-particles modified GC electrode. The obtained results demonstrate that the dual catalysts system possesses a bifuctional catalytic activity for redox-mediating 2-electron reduction of O 2 to HO 2 - by CoPcCN as well as catalyzing the disproportionation of HO 2 - to OH - and O 2 by nano-MnOx, and enables an apparent 4-electron reduction of O 2 at a relatively low overpotential in alkaline media. In addition, it has been found that the cleaning of the dual catalysts-modified electrode by soaking in 0.1 M sulfuric acid solution enhances its catalytic activity toward the reduction of O 2

  11. Structure of bound water and refinement of acid metmyoglobin

    International Nuclear Information System (INIS)

    Raghaven, N.V.; Schoenborn, B.P.

    1982-06-01

    The structure of myoglobin has been determined by x-ray diffraction for the acidmet, deoxy, and the oxy forms. Neutron diffraction work, done in this laboratory, has demonstrated that hydrogen and deuterium positions can be located. In addition to the localization of H and D, neutron diffraction provides a unique method for studying the water structure because of the strong scattering ability of D 2 O. The scattering factor of deuterium is nearly twice as large as that of hydrogen, and it increases the visibility of water molecules in Fourier maps, so that in a neutron map a water molecule appears about three times as strong as in an equivalent electron-density map. (DT)

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

    Science.gov (United States)

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

    2016-11-05

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

  13. Electron-beam-induced reduction of Fe3+ in iron phosphate dihydrate, ferrihydrite, haemosiderin and ferritin as revealed by electron energy-loss spectroscopy

    International Nuclear Information System (INIS)

    Pan, Ying-Hsi; Vaughan, Gareth; Brydson, Rik; Bleloch, Andrew; Gass, Mhairi; Sader, Kasim; Brown, Andy

    2010-01-01

    The effect of high-energy electron irradiation on ferritin/haemosiderin cores (in an iron-overloaded human liver biopsy), its mineral analogue; six-line ferrihydrite (6LFh), and iron phosphate dihydrate (which has similar octahedral ferric iron to oxygen coordination to that in ferrihydrite and ferritin/haemosiderin cores) has been investigated using electron energy-loss spectroscopy (EELS). Fe L 2,3 -ionisation edges were recorded on two types of electron microscope: a 200 keV transmission electron microscope (TEM) and a 100 keV scanning transmission electron microscope (STEM), in order to investigate the damage mechanisms in operation and to establish a methodology for minimum specimen alteration during analytical electron microscopic characterisation. A specimen damage mechanism dominated by radiolysis that results in the preferential loss of iron co-ordinating ligands (O, OH and H 2 O) is discussed. The net result of irradiation is structural re-organisation and reduction of iron within the iron hydroxides. At sufficiently low electron fluence and particularly in the lower incident energy, finer probe diameter STEM, the alteration is shown to be minimal. All the materials examined exhibit damage which as a function of cumulative fluence is best fitted by an inverse power-law, implying that several chemical and structural changes occur in response to the electron beam and we suggest that these are governed by secondary processes arising from the primary ionisation event. This work affirms that electron fluence and current density should be considered when measuring mixed valence ratios with EELS.

  14. Heterogeneous electron transfer and oxygen reduction reaction at nanostructured iron(II) phthalocyanine and its MWCNTs nanocomposites

    CSIR Research Space (South Africa)

    Mamuru, SA

    2010-05-01

    Full Text Available species within the porous layers of MWCNTs. Electron transfer process is much easier at the EPPGE-MWCNT and EPPGE-MWCNT-nanoFePc compared to the other electrodes. The best response for oxygen reduction reaction was at the EPPGE-MWCNTnanoFePc, yielding a 4...

  15. Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals in aqueous solutions; electron transfer and proton-coupled electron transfer mechanisms

    Science.gov (United States)

    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.

  16. Reduction of charge trapping and electron tunneling in SIMOX by supplemental implantation of oxygen

    International Nuclear Information System (INIS)

    Stahlbush, R.E.; Hughes, H.L.; Krull, W.A.

    1993-01-01

    Silicon-on-insulator, SOI, technologies are being aggressively pursued to produce high density, high speed, radiation tolerant electronics. The dielectric isolation of the buried oxide makes it possible to design integrated circuits that greatly minimize single event upset and eliminate dose-rate induced latchup and upset. The reduction of excess-silicon related defects in SIMOX by the supplemental implantation of oxygen has been examined. The supplemental implant is 6% of the oxygen dose used to form the buried oxide, and is followed by a 1,000 C anneal, in contrast to the >1,300 C anneal used to form the buried oxide layer of SIMOX. The defects examined include shallow electron traps, deep hole traps, and silicon clusters. The radiation-induced shallow electron and deep hole trapping are measured by cryogenic detrapping and isothermal annealing techniques. The low-field (3 to 6 MV/cm) electron tunneling is interpreted as due to a two phase mixture of stoichiometric SiO 2 and Si clusters a few nm in size. Single and triple SIMOS samples have been examined. All of the defects are reduced by the supplemental oxygen processing. Shallow electron trapping is reduced by an order of magnitude. Because of the larger capture cross section for hole trapping, hole trapping is not reduced as much. The low-field electron tunneling due to Si clusters is also significantly reduced. Both uniform and nonuniform electron tunneling have been observed in SIMOX samples without supplement processing. In samples exhibiting only uniform tunneling, electron capture at holes has been observed. The nonuniform tunneling is superimposed upon the uniform tunneling and is characterized by current spiking

  17. Ant colony method to control variance reduction techniques in the Monte Carlo simulation of clinical electron linear accelerators

    International Nuclear Information System (INIS)

    Garcia-Pareja, S.; Vilches, M.; Lallena, A.M.

    2007-01-01

    The ant colony method is used to control the application of variance reduction techniques to the simulation of clinical electron linear accelerators of use in cancer therapy. In particular, splitting and Russian roulette, two standard variance reduction methods, are considered. The approach can be applied to any accelerator in a straightforward way and permits, in addition, to investigate the 'hot' regions of the accelerator, an information which is basic to develop a source model for this therapy tool

  18. Using environmental transmission electron microscope to study the in-situ reduction of Co3O4 supported on α-Al2O3

    DEFF Research Database (Denmark)

    Dehghan-Niri, R.; Hansen, Thomas Willum; Wagner, Jakob Birkedal

    in specialized Transmission Electron Microscope (TEM) instruments with differentially pumped columns at pressures in the range up to 20 mbar. 1-3 The objective of this work is to study the reduction of Co3O4 nanoparticles directly and observe their morphology and crystallography. The catalysts were produced...... by dispersion of crushed powder directly on steel grids and gold grids. TEM analysis was performed with an FEI TITAN E-cell electron microscope operating at 300 kV. Reduction was done at 360°C and 3.4 mbar H2 flow. The samples were studied before and after reduction by High Resolution TEM (HRTEM) imaging, high...

  19. Effect of high electron donor supply on dissimilatory nitrate reduction pathways in a bioreactor for nitrate removal

    DEFF Research Database (Denmark)

    Behrendt, Anna; Tarre, Sheldon; Beliavski, Michael

    2014-01-01

    The possible shift of a bioreactor for NO3- removal from predominantly denitrification (DEN) to dissimilatory nitrate reduction to ammonium (DNRA) by elevated electron donor supply was investigated. By increasing the C/NO3- ratio in one of two initially identical reactors, the production of high...... sulfide concentrations was induced. The response of the dissimilatory NO3- reduction processes to the increased availability of organic carbon and sulfide was monitored in a batch incubation system. The expected shift from a DEN- towards a DNRA-dominated bioreactor was not observed, also not under...

  20. Single-Step versus Stepwise Two-Electron Reduction of Polyarylpyridiniums: Insights from the Steric Switching of Redox Potential Compression

    Czech Academy of Sciences Publication Activity Database

    Fortage, J.; Peltier, C.; Perruchot, Ch.; Takemoto, Y.; Teki, Y.; Bedioui, F.; Marvand, V.; Dupeyre, G.; Pospíšil, Lubomír; Adamo, C.; Hromadová, Magdaléna; Ciofini, I.; Lainé, P. P.

    2012-01-01

    Roč. 134, č. 5 (2012), s. 2691-2705 ISSN 0002-7863 Institutional research plan: CEZ:AV0Z40400503 Keywords : FUNCTIONALIZED TERPYRIDYL LIGANDS * GATED PHOTOINDUCED PROCESSES * ONE-ELECTRON REDUCTION Subject RIV: CG - Electrochemistry Impact factor: 10.677, year: 2012

  1. Ant colony method to control variance reduction techniques in the Monte Carlo simulation of clinical electron linear accelerators

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Pareja, S. [Servicio de Radiofisica Hospitalaria, Hospital Regional Universitario ' Carlos Haya' , Avda. Carlos Haya, s/n, E-29010 Malaga (Spain)], E-mail: garciapareja@gmail.com; Vilches, M. [Servicio de Fisica y Proteccion Radiologica, Hospital Regional Universitario ' Virgen de las Nieves' , Avda. de las Fuerzas Armadas, 2, E-18014 Granada (Spain); Lallena, A.M. [Departamento de Fisica Atomica, Molecular y Nuclear, Universidad de Granada, E-18071 Granada (Spain)

    2007-09-21

    The ant colony method is used to control the application of variance reduction techniques to the simulation of clinical electron linear accelerators of use in cancer therapy. In particular, splitting and Russian roulette, two standard variance reduction methods, are considered. The approach can be applied to any accelerator in a straightforward way and permits, in addition, to investigate the 'hot' regions of the accelerator, an information which is basic to develop a source model for this therapy tool.

  2. Electron-beam-induced reduction of Fe{sup 3+} in iron phosphate dihydrate, ferrihydrite, haemosiderin and ferritin as revealed by electron energy-loss spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Ying-Hsi; Vaughan, Gareth; Brydson, Rik [Institute for Materials Research, SPEME, University of Leeds, Leeds LS2 9JT (United Kingdom); Bleloch, Andrew; Gass, Mhairi [SuperSTEM, Daresbury Laboratories, Warrington WA4 4AD (United Kingdom); Sader, Kasim [Institute for Materials Research, SPEME, University of Leeds, Leeds LS2 9JT (United Kingdom); SuperSTEM, Daresbury Laboratories, Warrington WA4 4AD (United Kingdom); Brown, Andy, E-mail: a.p.brown@leeds.ac.uk [Institute for Materials Research, SPEME, University of Leeds, Leeds LS2 9JT (United Kingdom)

    2010-07-15

    The effect of high-energy electron irradiation on ferritin/haemosiderin cores (in an iron-overloaded human liver biopsy), its mineral analogue; six-line ferrihydrite (6LFh), and iron phosphate dihydrate (which has similar octahedral ferric iron to oxygen coordination to that in ferrihydrite and ferritin/haemosiderin cores) has been investigated using electron energy-loss spectroscopy (EELS). Fe L{sub 2,3}-ionisation edges were recorded on two types of electron microscope: a 200 keV transmission electron microscope (TEM) and a 100 keV scanning transmission electron microscope (STEM), in order to investigate the damage mechanisms in operation and to establish a methodology for minimum specimen alteration during analytical electron microscopic characterisation. A specimen damage mechanism dominated by radiolysis that results in the preferential loss of iron co-ordinating ligands (O, OH and H{sub 2}O) is discussed. The net result of irradiation is structural re-organisation and reduction of iron within the iron hydroxides. At sufficiently low electron fluence and particularly in the lower incident energy, finer probe diameter STEM, the alteration is shown to be minimal. All the materials examined exhibit damage which as a function of cumulative fluence is best fitted by an inverse power-law, implying that several chemical and structural changes occur in response to the electron beam and we suggest that these are governed by secondary processes arising from the primary ionisation event. This work affirms that electron fluence and current density should be considered when measuring mixed valence ratios with EELS.

  3. Four-electron deoxygenative reductive coupling of carbon monoxide at a single metal site

    Science.gov (United States)

    Buss, Joshua A.; Agapie, Theodor

    2016-01-01

    Carbon dioxide is the ultimate source of the fossil fuels that are both central to modern life and problematic: their use increases atmospheric levels of greenhouse gases, and their availability is geopolitically constrained. Using carbon dioxide as a feedstock to produce synthetic fuels might, in principle, alleviate these concerns. Although many homogeneous and heterogeneous catalysts convert carbon dioxide to carbon monoxide, further deoxygenative coupling of carbon monoxide to generate useful multicarbon products is challenging. Molybdenum and vanadium nitrogenases are capable of converting carbon monoxide into hydrocarbons under mild conditions, using discrete electron and proton sources. Electrocatalytic reduction of carbon monoxide on copper catalysts also uses a combination of electrons and protons, while the industrial Fischer-Tropsch process uses dihydrogen as a combined source of electrons and electrophiles for carbon monoxide coupling at high temperatures and pressures. However, these enzymatic and heterogeneous systems are difficult to probe mechanistically. Molecular catalysts have been studied extensively to investigate the elementary steps by which carbon monoxide is deoxygenated and coupled, but a single metal site that can efficiently induce the required scission of carbon-oxygen bonds and generate carbon-carbon bonds has not yet been documented. Here we describe a molybdenum compound, supported by a terphenyl-diphosphine ligand, that activates and cleaves the strong carbon-oxygen bond of carbon monoxide, enacts carbon-carbon coupling, and spontaneously dissociates the resulting fragment. This complex four-electron transformation is enabled by the terphenyl-diphosphine ligand, which acts as an electron reservoir and exhibits the coordinative flexibility needed to stabilize the different intermediates involved in the overall reaction sequence. We anticipate that these design elements might help in the development of efficient catalysts for

  4. Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals in aqueous solutions; electron transfer and proton-coupled electron transfer mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Matasovic, Brunislav [Division of Physical Chemistry, ' Ruder Boskovic' Institute, Bijenicka c. 54, HR-10000 Zagreb (Croatia); Bonifacic, Marija, E-mail: bonifacic@irb.h [Division of Physical Chemistry, ' Ruder Boskovic' Institute, Bijenicka c. 54, HR-10000 Zagreb (Croatia)

    2011-06-15

    Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals {sup {center_dot}C}O{sub 2}{sup -}, {sup {center_dot}C}H{sub 2}OH, {sup {center_dot}C}H(CH{sub 3})OH, and {sup {center_dot}C}H(CH{sub 3})O{sup -} have been studied in oxygen free aqueous solutions in the presence of organic additives: formate, methanol or ethanol. For radicals production {sup 60}Co {gamma}-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{sup {center_dot}} 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{sup {center_dot}} radical from formate or ethanol. Results with the neutral radicals conformed earlier proposition that the reduction reaction of {alpha}-hydroxyalkyl radicals proceeds by the proton-coupled electron transfer mechanism (). Thus, while both {sup {center_dot}C}H{sub 2}OH and {sup {center_dot}C}H(CH{sub 3})OH did not react with BrU in water/alcohol solutions, addition of bicarbonate and acetate in mmol dm{sup -3} concentrations, pH 7, brought about chain debromination to occur in the case of {sup {center_dot}C}H(CH{sub 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 {alpha}-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{sup {center_dot}} radicals have been estimated to amount to about {>=}85 and 1200 dm{sup 3} mol{sup -1} s{sup -1

  5. Electronic and Optical Properties of Aluminum Oxide Before and After Surface Reduction by Ar+ Bombardment

    Directory of Open Access Journals (Sweden)

    D. Tahir

    2014-08-01

    Full Text Available The electronic and optical properties of a-Al2O3 after induced by 3-keV Ar+ sputtering have been studied quantitatively by use of reflection electron energy loss spectroscopy (REELS spectra. The band gap values of a-Al2O3 was determined from the onset values of the energy loss spectrum to the background level of REELS spectra as a function of time Ar+ bombardment. The bandgap changes from 8.4 eV before sputtering to 6.2 eV after 4 minutes of sputtering.The optical properties of α-Al2O3 thin films have been determined by comparing the experimental cross section obtained from reflection electron energy loss spectroscopy with the theoretical inelastic scattering cross section, deduced from the simulated energy loss function (ELF by using QUEELS-ε(k-REELS software. The peak assignments are based on ELF and compared with reported data on the electronic structure of α-Al2O3 obtained using different techniques. The results demonstrate that the electronic and optical properties before and after surface reduction will provide further understanding in the fundamental properties of α-Al2O3 which will be useful in the design, modeling and analysis of devices applications performance.

  6. Topotactic reduction yielding black titanium oxide nanostructures as metallic electronic conductors.

    Science.gov (United States)

    Tominaka, Satoshi

    2012-10-01

    Detailed analyses of reduced, single crystal, rutile-type TiO(2) via high-resolution transmission electron microscopy (TEM) are reported which reveal that the reduction proceeds topotactically via interstitial diffusion of Ti ions at low temperature, around 350 °C. This important finding encouraged the production of various nanostructured reduced titanium oxides from TiO(2) precursors with morphology retention, and in the process, the synthesis of black titanium oxide nanorods using TiO(2) nanorods was demonstrated. Interestingly, as opposed to the semiconductive behavior of Ti(2)O(3) synthesized at high temperature, topotactically synthesized Ti(2)O(3) exhibits metallic electrical resistance, and the value at room temperature is quite low (topotactically synthesized Ti(2)O(3). This work shows that topotactically reduced titanium oxides can have fascinating properties as well as nanostructures.

  7. Reduction of hexavalent chromium by Pannonibacter phragmitetus LSSE-09 stimulated with external electron donors under alkaline conditions

    International Nuclear Information System (INIS)

    Xu Lin; Luo Mingfang; Li Wangliang; Wei Xuetuan; Xie Keng; Liu Lijun; Jiang Chengying; Liu Huizhou

    2011-01-01

    Research highlights: → Growing cells have high Cr (VI) resistant and reducing ability aerobically. → Resting cells show strong anaerobic-reduction potential. → Acetate can highly stimulate both aerobic and anaerobic reduction process. - Abstract: A novel Cr (VI) resistant bacterial strain LSSE-09, identified as Pannonibacter phragmitetus, was isolated from industrial sludge. It has strong aerobic and anaerobic Cr (VI)-reduction potential under alkaline conditions. At 37 o C and pH 9.0, growing cells of strain LSSE-09 could completely reduce 100 and 1000 mg L -1 Cr (VI)-Cr (III) within 9 and 24 h, respectively under aerobic condition. Resting cells showed higher anaerobic reduction potential with the rate of 1.46 mg g -1 (dryweight) min -1 , comparing with their aerobic reduction rate, 0.21 mg g -1 min -1 . External electron donors, such as lactate, acetate, formate, pyruvate, citrate and glucose could highly increase the reduction rate, especially for aerobic reduction. The presence of 3000 mg L -1 acetate enhanced anaerobic and aerobic Cr (VI)-reduction rates up to 9.47 mg g -1 min -1 and 4.42 mg g -1 min -1 , respectively, which were 5 and 20 times faster than those without it. Strain LSSE-09 retained high activities over six batch cycles and NO 3 - and SO 4 2- had slightly negative effects on Cr (VI)-reduction rates. The results suggest that strain LSSE-09 has potential application for Cr (VI) detoxification in alkaline wastewater.

  8. Catabolic thiosulfate disproportionation and carbon dioxide reduction in strain DCB-1, a reductively dechlorinating anaerobe

    Energy Technology Data Exchange (ETDEWEB)

    Mohn, W.W.; Tiedje, J.M. (Michigan State Univ., East Lansing (USA))

    1990-04-01

    Strain DCB-1 is a strict anaerobe capable of reductive dehalogenation. We elucidated metabolic processes in DCB-1 which may be related to dehalogenation and which further characterize the organism physiologically. Sulfoxy anions and CO2 were used by DCB-1 as catabolic electron acceptors. With suitable electron donors, sulfate and thiosulfate were reduced to sulfide. Sulfate and thiosulfate supported growth with formate or hydrogen as the electron donor and thus are probably respiratory electron acceptors. Other electron donors supporting growth with sulfate were CO, lactate, pyruvate, butyrate, and 3-methoxybenzoate. Thiosulfate also supported growth without an additional electron donor, being disproportionated to sulfide and sulfate. In the absence of other electron acceptors, CO2 reduction to acetate plus cell material was coupled to pyruvate oxidation to acetate plus CO2. Pyruvate could not be fermented without an electron acceptor. Carbon monoxide dehydrogenase activity was found in whole cells, indicating that CO2 reduction probably occurred via the acetyl coenzyme A pathway. Autotrophic growth occurred on H2 plus thiosulfate or sulfate. Diazotrophic growth occurred, and whole cells had nitrogenase activity. On the basis of these physiological characteristics, DCB-1 is a thiosulfate-disproportionating bacterium unlike those previously described.

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

    Science.gov (United States)

    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.

  10. The autoprotonation in reduction mechanism of pesticide ioxynil

    Energy Technology Data Exchange (ETDEWEB)

    Sokolova, Romana, E-mail: sokolova@jh-inst.cas.c [J. Heyrovsky Institute of Physical Chemistry, v.v.i., Academy of Sciences of the Czech Republic, Dolejskova 3, 18223 Prague (Czech Republic); Hromadova, Magdalena; Ludvik, Jiri; Pospisil, Lubomir [J. Heyrovsky Institute of Physical Chemistry, v.v.i., Academy of Sciences of the Czech Republic, Dolejskova 3, 18223 Prague (Czech Republic); Giannarelli, Stefania [Department of Chemistry and Industrial Chemistry, University of Pisa, Via Risorgimento 35, 56100 Pisa (Italy)

    2010-11-30

    The reduction mechanism of ioxynil (3,5-diiodo-4-hydroxy-benzonitrile) was studied in dimethylsulfoxide using the electrochemical methods (tast polarography, cyclic voltammetry and controlled potential electrolysis) combined with GC/MS identification of products. The reduction is accompanied by the cleavage of iodide yielding 3-iodo-4-hydroxybenzonitrile. Surprisingly, this process requires only one electron for the exhaustive electrolysis of the starting compound. We showed that the apparent one electron reduction observed in the aprotic solvent is due to the autoprotonation by another molecule of ioxynil. The overall one electron reduction (uptake of two electrons per two molecules of ioxynil) is changed in the presence of a strong proton donor to a two electron process per one molecule.

  11. Reductive dechlorination of trichloroethylene (TCE) in competition with Fe and Mn oxides – observed dynamics in H2-dependent terminal electron accepting processes

    DEFF Research Database (Denmark)

    Paul, Laiby; Jakobsen, Rasmus; Smolders, Erik

    2016-01-01

    The determination of hydrogen (H2) concentration together with the products of microbial reduction reactions in a trichloroethylene dechlorinating system is conducted to delineate the ongoing predominant terminal electron accepting processes (TEAP). Formate was used as electron donor and synthetic...

  12. Model Order Reduction for Electronic Circuits:

    DEFF Research Database (Denmark)

    Hjorth, Poul G.; Shontz, Suzanne

    Electronic circuits are ubiquitous; they are used in numerous industries including: the semiconductor, communication, robotics, auto, and music industries (among many others). As products become more and more complicated, their electronic circuits also grow in size and complexity. This increased...... in the semiconductor industry. Circuit simulation proceeds by using Maxwell’s equations to create a mathematical model of the circuit. The boundary element method is then used to discretize the equations, and the variational form of the equations are then solved on the graph network....

  13. Reductive dechlorination of trichloroethene DNAPL source zones: source zone architecture versus electron donor availability

    Science.gov (United States)

    Krol, M.; Kokkinaki, A.; Sleep, B.

    2014-12-01

    The persistence of dense-non-aqueous-phase liquids (DNAPLs) in the subsurface has led practitioners and regulatory agencies to turn towards low-maintenance, low-cost remediation methods. Biological degradation has been suggested as a possible solution, based on the well-proven ability of certain microbial species to break down dissolved chlorinated ethenes under favorable conditions. However, the biodegradation of pure phase chlorinated ethenes is subject to additional constraints: the continuous release of electron acceptor at a rate governed by mass transfer kinetics, and the temporal and spatial heterogeneity of DNAPL source zones which leads to spatially and temporally variable availability of the reactants for reductive dechlorination. In this work, we investigate the relationship between various DNAPL source zone characteristics and reaction kinetics using COMPSIM, a multiphase groundwater model that considers non-equilibrium mass transfer and Monod-type kinetics for reductive dechlorination. Numerical simulations are performed for simple, homogeneous trichloroethene DNAPL source zones to demonstrate the effect of single source zone characteristics, as well as for larger, more realistic heterogeneous source zones. It is shown that source zone size, and mass transfer kinetics may have a decisive effect on the predicted bio-enhancement. Finally, we evaluate the performance of DNAPL bioremediation for realistic, thermodynamically constrained, concentrations of electron donor. Our results indicate that the latter may be the most important limitation for the success of DNAPL bioremediation, leading to reduced bio-enhancement and, in many cases, comparable performance with water flooding.

  14. Experimental Observations of In-Situ Secondary Electron Yield Reduction in the PEP-II Particle Accelerator Beam Line

    International Nuclear Information System (INIS)

    Pivi, Mauro

    2010-01-01

    Beam instability caused by the electron cloud has been observed in positron and proton storage rings and it is expected to be a limiting factor in the performance of the positron Damping Ring (DR) of future Linear Colliders (LC) such as ILC and CLIC. To test a series of promising possible electron cloud mitigation techniques as surface coatings and grooves, in the Positron Low Energy Ring (LER) of the PEP-II accelerator, we have installed several test vacuum chambers including (i) a special chamber to monitor the variation of the secondary electron yield of technical surface materials and coatings under the effect of ion, electron and photon conditioning in situ in the beam line; (ii) chambers with grooves in a straight magnetic-free section; and (iii) coated chambers in a dedicated newly installed 4-magnet chicane to study mitigations in a magnetic field region. In this paper, we describe the ongoing R and D effort to mitigate the electron cloud effect for the LC damping ring, focusing on the first experimental area and on results of the reduction of the secondary electron yield due to in situ conditioning.

  15. Spin relaxation of iron in mixed state hemoproteins

    International Nuclear Information System (INIS)

    Wajnberg, E.; Kalinowski, H.J.; Bemski, G.; Helman, J.S.

    1984-01-01

    In pure states hemoproteins the relaxation of iron depends on its spin state. It is found that in both mixed state met-hemoglobin and met-myoglobin, the low and high spin states relax through an Orbach-like process. Also, very short (approx. 1 ns) and temperature independent transverse relaxation times T 2 were estimated. This peculiar behaviour of the relaxation may result from the unusual electronic structure of mixed state hemoproteins that allows thermal equilibrium and interconversion of the spin states. (Author) [pt

  16. Biochemistry of Catabolic Reductive Dehalogenation.

    Science.gov (United States)

    Fincker, Maeva; Spormann, Alfred M

    2017-06-20

    A wide range of phylogenetically diverse microorganisms couple the reductive dehalogenation of organohalides to energy conservation. Key enzymes of such anaerobic catabolic pathways are corrinoid and Fe-S cluster-containing, membrane-associated reductive dehalogenases. These enzymes catalyze the reductive elimination of a halide and constitute the terminal reductases of a short electron transfer chain. Enzymatic and physiological studies revealed the existence of quinone-dependent and quinone-independent reductive dehalogenases that are distinguishable at the amino acid sequence level, implying different modes of energy conservation in the respective microorganisms. In this review, we summarize current knowledge about catabolic reductive dehalogenases and the electron transfer chain they are part of. We review reaction mechanisms and the role of the corrinoid and Fe-S cluster cofactors and discuss physiological implications.

  17. Electron transfer study on graphene modified glassy carbon substrate via electrochemical reduction and the application for tris(2,2'-bipyridyl)ruthenium(II) electrochemiluminescence sensor fabrication.

    Science.gov (United States)

    Xu, Yuanhong; Cao, Mengmei; Liu, Huihui; Zong, Xidan; Kong, Na; Zhang, Jizhen; Liu, Jingquan

    2015-07-01

    In this study, electron transfer behavior of the graphene nanosheets attachment on glassy carbon electrode (GCE) via direct electrochemical reduction of graphene oxide (GO) is investigated for the first time. The graphene modified electrode was achieved by simply dipping the GCE in GO suspension, followed by cyclic voltammetric scanning in the potential window from 0V to -1.5V. Tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)3(2+)] was immobilized on the graphene modified electrode and used as the redox probe to evaluate the electron transfer behavior. The electron transfer rate constant (Ks) was calculated to be 61.9±5.8s(-1), which is much faster than that of tiled graphene modified GCE (7.1±0.6s(-1)). The enhanced electron transfer property observed with the GCE modified by reductively deposited graphene is probably due to its standing configuration, which is beneficial to the electron transfer comparing with the tiled one. Because the abundant oxygen-containing groups are mainly located at the edges of GO, which should be much easier for the reduction to start from, the reduced GO should tend to stand on the electrode surface as evidenced by scanning electron microscopy analysis. In addition, due to the favored electron transfer and standing configuration, the Ru(bpy)3(2+) electrochemiluminescence sensor fabricated with standing graphene modified GCE provided much higher and more stable efficiency than that fabricated with tiled graphene. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. V. Comparison and Properties of Electrochemical and Chemical Rate Constants

    Science.gov (United States)

    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)

  19. Effect of an electronic nicotine delivery device (e-Cigarette on smoking reduction and cessation: a prospective 6-month pilot study

    Directory of Open Access Journals (Sweden)

    Papale Gabriella

    2011-10-01

    Full Text Available Abstract Background Cigarette smoking is a tough addiction to break. Therefore, improved approaches to smoking cessation are necessary. The electronic-cigarette (e-Cigarette, a battery-powered electronic nicotine delivery device (ENDD resembling a cigarette, may help smokers to remain abstinent during their quit attempt or to reduce cigarette consumption. Efficacy and safety of these devices in long-term smoking cessation and/or smoking reduction studies have never been investigated. Methods In this prospective proof-of-concept study we monitored possible modifications in smoking habits of 40 regular smokers (unwilling to quit experimenting the 'Categoria' e-Cigarette with a focus on smoking reduction and smoking abstinence. Study participants were invited to attend a total of five study visits: at baseline, week-4, week-8, week-12 and week-24. Product use, number of cigarettes smoked, and exhaled carbon monoxide (eCO levels were measured at each visit. Smoking reduction and abstinence rates were calculated. Adverse events and product preferences were also reviewed. Results Sustained 50% reduction in the number of cig/day at week-24 was shown in 13/40(32.5% participants; their median of 25 cigs/day decreasing to 6 cigs/day (p Conclusion The use of e-Cigarette substantially decreased cigarette consumption without causing significant side effects in smokers not intending to quit (http://ClinicalTrials.gov number NCT01195597.

  20. NiO/YSZ Reduction for SOFC/SOEC Studied In Situ by Environmental Transmission Electron Microscopy

    DEFF Research Database (Denmark)

    Simonsen, Søren Bredmose; Agersted, Karsten; Hansen, Karin Vels

    2014-01-01

    SOFCs/SOECs are typically composed of ceramic materials, which are highly complex at the nano-scale. Scanning and transmission electron microscopy (SEM and TEM) are routinely applied for studying these nano-scaled structures post mortem, but only few SOFC/SOEC studies have applied environmental T...... and constant temperature ramping rate of 1°C/min. The NiO observed in the first image at 320°C is dense. From the lower left corner a front of porous Ni is progressing until full reduction at 340°C. [Formula]...

  1. Reduction of radiation damage on organic material at very low object temperatures in an electron microscope with supraconductive lenses

    International Nuclear Information System (INIS)

    Knapek, E.

    1981-01-01

    As a result of this study, the increase in structure conservation by cooling the object to very low temperatures (cryoprotection) as compared with the conditions at room temperature was higher than the values at low temperatures reached so far by one to two orders of magnitude. The experiments carried out with an electron microscope with supraconductive lenses (SLEM) showed, depending of the organic substance, that in tests with an electron diffraction of about 4.2 K the reduction of radiation damage as compared with room temperature was by a factor between 30 and 350. (orig./PW) [de

  2. Ion current reduction in pinched electron beam diodes

    International Nuclear Information System (INIS)

    Quintenz, J.P.; Poukey, J.W.

    1977-01-01

    A new version of a particle-in-cell diode code has been written which permits the accurate treatment of higher-current diodes with greater physical dimensions. Using this code, we have studied ways to reduce the ion current in large-aspect-ratio pinched electron beam diodes. In particular, we find that allowing the ions to reflex in such diodes lowers the ion to electron current ratio considerably. In a 3-MV R/d=24 case this ratio was lowered by a factor of 6--8 compared with the corresponding nonreflexing-ion diode, while still producing a superpinched electron beam

  3. Kinetics and mechanisms of photoinduced electron-transfer reaction of zinc myoglobin

    International Nuclear Information System (INIS)

    Tsukahara, Keiichi; Asami, Satoko; Okada, Mihoko; Sakurai, Takeshi.

    1994-01-01

    Photoinduced electron transfer (ET) between zinc myoglobin (ZnPPMb) and a variety of quenchers, such as hexacyanoferrate(III)([Fe(CN) 6 ] 3- ) and hexaammineruthenium(III)(Ru(NH 3 ) 6 ] 3+ ions, cationic viologens, copper(II) protein (stellacyanin), and metmyoglobins, has been studied in aqueous degassed solutions. The excited triplet state of ZnPPMb( * ZnPPMb) was quenched by [Fe(CN) 6 ] 3- in a self-associated complex. Both quenching rate constant and formation constant of the self-associated complex decrease with increasing ionic strengths. The thermal backward ET reaction for this system was not observed; it is most likely that the backward ET step is much faster than the quenching reaction. All of the cationic quenchers examined in this work did not form a self-associated complex with * ZnPPMb, and the intermolecular quenching occurred. The thermal backward ET reaction was observed for these cationic quenchers. Not only photoinduced ET but also thermal backward ET reactions were insensitive to the driving force of the reactions, suggesting that the reactions are controlled by conformational changes in ZnPPMb. The quenching rate constants increase with increasing ionic strength for the cationic quenchers. The effects of poly-L-lysine hydrochloride, sodium poly-L-glutamate, and sodium cyclo-hexaphosphate were also examined. The active site of the * ZnPPMb toward both anionic and cationic quenchers is assumed to be the positively charged site near the heme pocket. (author)

  4. One electron reduction of triphenyl methane dyes by hydrated electrons

    Energy Technology Data Exchange (ETDEWEB)

    Bhasikuttan, A C; Shastri, L V; Sapre, A V; Rama Rao, K V.S. [Bhabha Atomic Research Centre, Bombay (India). Chemistry Div.

    1994-12-31

    Electron reaction rates for the triphenylmethane (TPM) dyes have been evaluated. Spectral characteristics of the resulting dye radicals have been determined. Evolution of the transient spectra shows intramolecular rearrangement in the radical from brilliant green and malachite green. (author). 3 refs., 1 fig., 1 tab.

  5. One electron reduction of triphenyl methane dyes by hydrated electrons

    International Nuclear Information System (INIS)

    Bhasikuttan, A.C.; Shastri, L.V.; Sapre, A.V.; Rama Rao, K.V.S.

    1994-01-01

    Electron reaction rates for the triphenylmethane (TPM) dyes have been evaluated. Spectral characteristics of the resulting dye radicals have been determined. Evolution of the transient spectra shows intramolecular rearrangement in the radical from brilliant green and malachite green. (author). 3 refs., 1 fig., 1 tab

  6. One-electron reduction of mitomycin c by rat liver : role of cytochrome P-450 and NADPH-cytochrome P-450 reductase

    NARCIS (Netherlands)

    Vromans, R M; Van de Straat, R; Groeneveld, M.; Vermeulen, N P

    1. The role of cytochrome P-450 in the one-electron reduction of mitomycin c was studied in rat hepatic microsomal systems and in reconstituted systems of purified cytochrome P-450. Formation of H2O2 from redox cycling of the reduced mitomycin c in the presence of O2 and the alkylation of

  7. Energy Spread Reduction of Electron Beams Produced via Laser Wake

    Energy Technology Data Exchange (ETDEWEB)

    Pollock, Bradley Bolt [Univ. of California, San Diego, CA (United States)

    2012-01-01

    Laser wakefield acceleration of electrons holds great promise for producing ultra-compact stages of GeV scale, high quality electron beams for applications such as x-ray free electron lasers and high energy colliders. Ultra-high intensity laser pulses can be self-guided by relativistic plasma waves over tens of vacuum diffraction lengths, to give >1 GeV energy in cm-scale low density plasma using ionization-induced injection to inject charge into the wake at low densities. This thesis describes a series of experiments which investigates the physics of LWFA in the self-guided blowout regime. Beginning with high density gas jet experiments the scaling of the LWFA-produced electron beam energy with plasma electron density is found to be in excellent agreement with both phenomenological theory and with 3-D PIC simulations. It is also determined that self-trapping of background electrons into the wake exhibits a threshold as a function of the electron density, and at the densities required to produce electron beams with energies exceeding 1 GeV a different mechanism is required to trap charge into low density wakes. By introducing small concentrations of high-Z gas to the nominal He background the ionization-induced injection mechanism is enabled. Electron trapping is observed at densities as low as 1.3 x 1018 cm-3 in a gas cell target, and 1.45 GeV electrons are demonstrated for the first time from LWFA. This is currently the highest electron energy ever produced from LWFA. The ionization-induced trapping mechanism is also shown to generate quasi-continuous electron beam energies, which is undesirable for accelerator applications. By limiting the region over which ionization-induced trapping occurs, the energy spread of the electron beams can be controlled. The development of a novel two-stage gas cell target provides the capability to tailor the gas composition in the longitudinal direction, and confine the trapping process to occur only in a

  8. Electronic nicotine delivery systems and/or electronic non-nicotine delivery systems for tobacco smoking cessation or reduction: a systematic review and meta-analysis.

    Science.gov (United States)

    El Dib, Regina; Suzumura, Erica A; Akl, Elie A; Gomaa, Huda; Agarwal, Arnav; Chang, Yaping; Prasad, Manya; Ashoorion, Vahid; Heels-Ansdell, Diane; Maziak, Wasim; Guyatt, Gordon

    2017-02-23

    A systematic review and meta-analysis to investigate the impact of electronic nicotine delivery systems (ENDS) and/or electronic non-nicotine delivery systems (ENNDS) versus no smoking cessation aid, or alternative smoking cessation aids, in cigarette smokers on long-term tobacco use. Searches of MEDLINE, EMBASE, PsycInfo, CINAHL, CENTRAL and Web of Science up to December 2015. Randomised controlled trials (RCTs) and prospective cohort studies. Three pairs of reviewers independently screened potentially eligible articles, extracted data from included studies on populations, interventions and outcomes and assessed their risk of bias. We used the Grading of Recommendations Assessment, Development and Evaluation approach to rate overall certainty of the evidence by outcome. Three randomised trials including 1007 participants and nine cohorts including 13 115 participants proved eligible. Results provided by only two RCTs suggest a possible increase in tobacco smoking cessation with ENDS in comparison with ENNDS (RR 2.03, 95% CI 0.94 to 4.38; p=0.07; I 2 =0%, risk difference (RD) 64/1000 over 6 to 12 months, low-certainty evidence). Results from cohort studies suggested a possible reduction in quit rates with use of ENDS compared with no use of ENDS (OR 0.74, 95% CI 0.55 to 1.00; p=0.051; I 2 =56%, very low certainty). There is very limited evidence regarding the impact of ENDS or ENNDS on tobacco smoking cessation, reduction or adverse effects: data from RCTs are of low certainty and observational studies of very low certainty. The limitations of the cohort studies led us to a rating of very low-certainty evidence from which no credible inferences can be drawn. Lack of usefulness with regard to address the question of e-cigarettes' efficacy on smoking reduction and cessation was largely due to poor reporting. This review underlines the need to conduct well-designed trials measuring biochemically validated outcomes and adverse effects. Published by the BMJ

  9. Improvement of electron emission characteristics of porous silicon emitter by using cathode reduction and electrochemical oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Li, He; Wenjiang, Wang, E-mail: wwj@mail.xjtu.edu.cn; Xiaoning, Zhang

    2017-03-31

    Highlights: • An electron emitter based on porous silicon having the strong application potential was prepared in the studying. • A new simple and convenient post-treat technique was proposed to improve the electron emission properties of the PS emitter. • It demonstrated that the improving of the PS morphology and the oxygen distribution is very important to the PS emitter. - Abstract: A new simple and convenient post-treat technique combined the cathode reduction (CR) and electrochemical oxidation (ECO) was proposed to improve the electron emission properties of the surface-emitting cold cathodes based on the porous silicon (PS). It is demonstrated here that by introducing this new technique combined CR and ECO, the emission properties of the diode have been significantly improved than those as-prepared samples. The experimental results showed that the emission current densities and efficiencies of sample treated by CR were 62 μA/cm{sup 2} and 12.10‰, respectively, nearly 2 orders of magnitude higher than those of as-prepared sample. Furthermore, the CR-treated PS emitter shows higher repeatability and stability compared with the as-prepared PS emitter. The scanning electron microscope (SEM), atomic force microscope (AFM), energy dispersive spectrometer (EDS), furier transformed infrared (FTIR) spectroscopy results indicated that the improved mechanism is mainly due to the passivation of the PS, which not only improve the PS morphology by the passivation of the H{sup +} but also improve the uniformity of the oxygen content distribution in the whole PS layer. Therefore, the method combined the CR treatment and ECO is expected to be a valuable technique to enhance the electron emission characteristics of the PS emitter.

  10. Improvement of electron emission characteristics of porous silicon emitter by using cathode reduction and electrochemical oxidation

    International Nuclear Information System (INIS)

    Li, He; Wenjiang, Wang; Xiaoning, Zhang

    2017-01-01

    Highlights: • An electron emitter based on porous silicon having the strong application potential was prepared in the studying. • A new simple and convenient post-treat technique was proposed to improve the electron emission properties of the PS emitter. • It demonstrated that the improving of the PS morphology and the oxygen distribution is very important to the PS emitter. - Abstract: A new simple and convenient post-treat technique combined the cathode reduction (CR) and electrochemical oxidation (ECO) was proposed to improve the electron emission properties of the surface-emitting cold cathodes based on the porous silicon (PS). It is demonstrated here that by introducing this new technique combined CR and ECO, the emission properties of the diode have been significantly improved than those as-prepared samples. The experimental results showed that the emission current densities and efficiencies of sample treated by CR were 62 μA/cm"2 and 12.10‰, respectively, nearly 2 orders of magnitude higher than those of as-prepared sample. Furthermore, the CR-treated PS emitter shows higher repeatability and stability compared with the as-prepared PS emitter. The scanning electron microscope (SEM), atomic force microscope (AFM), energy dispersive spectrometer (EDS), furier transformed infrared (FTIR) spectroscopy results indicated that the improved mechanism is mainly due to the passivation of the PS, which not only improve the PS morphology by the passivation of the H"+ but also improve the uniformity of the oxygen content distribution in the whole PS layer. Therefore, the method combined the CR treatment and ECO is expected to be a valuable technique to enhance the electron emission characteristics of the PS emitter.

  11. 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

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, Jose F. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA; La Porte, Nathan T. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA; Mauck, Catherine M. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA; Wasielewski, Michael R. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA

    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 CO2 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 have 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.

  12. A comparative study of electrochemical reduction of isatin and its ...

    Indian Academy of Sciences (India)

    Administrator

    hibit a single irreversible two-electron reduction wave in contrast with the two discrete one-electron transfer reduction ... experiments. The working electrode was a Static Mercury Drop Elec- ..... Women Scientist Scheme (WOS-A), is gratefully.

  13. Gold Nanofilm Redox Catalysis for Oxygen Reduction at Soft Interfaces

    International Nuclear Information System (INIS)

    Smirnov, Evgeny; Peljo, Pekka; Scanlon, Micheál D.; Girault, Hubert H.

    2016-01-01

    ABSTRACT: Functionalization of a soft or liquid-liquid interface by a one gold nanoparticle thick “nanofilm” provides a conductive pathway to facilitate interfacial electron transfer from a lipophilic electron donor to a hydrophilic electron acceptor in a process known as interfacial redox catalysis. The gold nanoparticles in the nanofilm are charged by Fermi level equilibration with the lipophilic electron donor and act as an interfacial reservoir of electrons. Additional thermodynamic driving force can be provided by electrochemically polarising the interface. Using these principles, the biphasic reduction of oxygen by a lipophilic electron donor, decamethylferrocene, dissolved in α,α,α-trifluorotoluene was catalysed at a gold nanoparticle nanofilm modified water-oil interface. A recently developed microinjection technique was utilised to modify the interface reproducibly with the mirror-like gold nanoparticle nanofilm, while the oxidised electron donor species and the reduction product, hydrogen peroxide, were detected by ion transfer voltammetry and UV/vis spectroscopy, respectively. Metallization of the soft interface allowed the biphasic oxygen reduction reaction to proceed via an alternative mechanism with enhanced kinetics and at a significantly lower overpotential in comparison to a bare soft interface. Weaker lipophilic reductants, such as ferrocene, were capable of charging the interfacial gold nanoparticle nanofilm but did not have sufficient thermodynamic driving force to significantly elicit biphasic oxygen reduction.

  14. Studies on the heterogeneous electron transport and oxygen reduction reaction at metal (Co, Fe) octabutylsulphonylphthalocyanines supported on multi-walled carbon nanotube modified graphite electrode

    CSIR Research Space (South Africa)

    Mamuru, SA

    2010-09-01

    Full Text Available Heterogeneous electron transfer dynamics and oxygen reduction reaction (ORR) activities using octabutylsulphonylphthalocyanine complexes of iron (FeOBSPc) and cobalt (CoOBSPc) supported on multi-walled carbon nanotube (MWCNT) platforms have been...

  15. Electron uptake by iron-oxidizing phototrophic bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Bose, A; Gardel, EJ; Vidoudez, C; Parra, EA; Girguis, PR

    2014-02-26

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

  16. Titanium oxidation-reduction at low oxygen pressure under electron bombardment

    International Nuclear Information System (INIS)

    Brasca, R.; Passeggi, M.C.G.; Ferron, J.

    2006-01-01

    The effect of the electron bombardment on the first stages of the titanium oxidation process has been studied by means of Auger Electron Spectroscopy. Using Factor Analysis and the valence electron dependence behaviour of the titanium LMV Auger transition, we found that the process is strongly dependent on the oxygen pressure and electron current density. Depending on the irradiation conditions, films of different thickness and Ti oxidized states are obtained

  17. A Series of Supramolecular Complexes for Solar Energy Conversion via Water Reduction to Produce Hydrogen: An Excited State Kinetic Analysis of Ru(II,Rh(III,Ru(II Photoinitiated Electron Collectors

    Directory of Open Access Journals (Sweden)

    Shamindri M. Arachchige

    2011-12-01

    Full Text Available Mixed-metal supramolecular complexes have been designed that photochemically absorb solar light, undergo photoinitiated electron collection and reduce water to produce hydrogen fuel using low energy visible light. This manuscript describes these systems with an analysis of the photophysics of a series of six supramolecular complexes, [{(TL2Ru(dpp}2RhX2](PF65 with TL = bpy, phen or Ph2phen with X = Cl or Br. The process of light conversion to a fuel requires a system to perform a number of complicated steps including the absorption of light, the generation of charge separation on a molecular level, the reduction by one and then two electrons and the interaction with the water substrate to produce hydrogen. The manuscript explores the rate of intramolecular electron transfer, rate of quenching of the supramolecules by the DMA electron donor, rate of reduction of the complex by DMA from the 3MLCT excited state, as well as overall rate of reduction of the complex via visible light excitation. Probing a series of complexes in detail exploring the variation of rates of important reactions as a function of sub-unit modification provides insight into the role of each process in the overall efficiency of water reduction to produce hydrogen. The kinetic analysis shows that the complexes display different rates of excited state reactions that vary with TL and halide. The role of the MLCT excited state is elucidated by this kinetic study which shows that the 3MLCT state and not the 3MMCT is likely that key contributor to the photoreduction of these complexes. The kinetic analysis of the excited state dynamics and reactions of the complexes are important as this class of supramolecules behaves as photoinitiated electron collectors and photocatalysts for the reduction of water to hydrogen.

  18. Tracking the Structural and Electronic Configurations of a Cobalt Proton Reduction Catalyst in Water

    Energy Technology Data Exchange (ETDEWEB)

    Moonshiram, Dooshaye; Gimbert-Suriñach, Carolina [Institute; Guda, Alexander [International; Picon, Antonio; Lehmann, C. Stefan; Zhang, Xiaoyi; Doumy, Gilles; March, Anne Marie; Benet-Buchholz, Jordi [Institute; Soldatov, Alexander [International; Llobet, Antoni [Institute; Departament; Southworth, Stephen H.

    2016-08-09

    Time resolved X-ray absorption spectroscopy (X-TAS) has been used to study the light induced hydrogen evolution reaction catalyzed by a highly stable cobalt complex, [Ru(bpy)3]2+ photosensitizer and an equimolar mixture of sodium ascorbate/ascorbic acid electron donor in pure water. XANES and EXAFS analysis of a binary mixture of the octahedral Co(III) pre-catalyst and [Ru(bpy)3]2+ after illumination, revealed in-situ formation of a square pyramidal Co(II) intermediate, with electron transfer kinetics of 51 ns. On the other hand, X-TAS experiments of the complete photocatalytic system in the presence of the electron donor showed the formation of a square planar Co(I) intermediate species within a few nanoseconds followed by its decay in the microsecond timescales. The Co(I) structural assignment is supported by calculations based on density functional theory (DFT). At longer reaction times, we observe the formation of the initial Co(III) species concomitant to the decay of Co(I), thus closing the catalytic cycle. The experimental X-ray absorption spectra of the molecular species formed along the catalytic cycle are modeled using a combination of molecular orbital DFT calculations (DFT-MO) and Finite Difference Method (FDM). These findings allowed us to unequivocally assign the full mechanistic pathway followed by the catalyst as well as to determine the rate limiting step of the process, which consists in the protonation of the Co(I). This study provides a complete kinetics scheme for the hydrogen evolution reaction by a cobalt catalyst, revealing unique information for the development of better catalysts for the reductive side of hydrogen fuel cells.

  19. Impact of the electron donor on in situ microbial nitrate reduction in Opalinus Clay: results from the Mont Terri rock laboratory (Switzerland)

    Energy Technology Data Exchange (ETDEWEB)

    Bleyen, N.; Smets, S. [Belgian Nuclear Research Centre SCK-CEN, Mol (Belgium); Small, J. [National Nuclear Laboratory NLL, Warrington (United Kingdom); and others

    2017-04-15

    At the Mont Terri rock laboratory (Switzerland), an in situ experiment is being carried out to examine the fate of nitrate leaching from nitrate-containing bituminized radioactive waste, in a clay host rock for geological disposal. Such a release of nitrate may cause a geochemical perturbation of the clay, possibly affecting some of the favorable characteristics of the host rock. In this in situ experiment, combined transport and reactivity of nitrate is studied inside anoxic and water-saturated chambers in a borehole in the Opalinus Clay. Continuous circulation of the solution from the borehole to the surface equipment allows a regular sampling and online monitoring of its chemical composition. In this paper, in situ microbial nitrate reduction in the Opalinus Clay is discussed, in the presence or absence of additional electron donors relevant for the disposal concept and likely to be released from nitrate-containing bituminized radioactive waste: acetate (simulating bitumen degradation products) and H{sub 2} (originating from radiolysis and corrosion in the repository). The results of these tests indicate that - in case microorganisms would be active in the repository or the surrounding clay - microbial nitrate reduction can occur using electron donors naturally present in the clay (e.g. pyrite, dissolved organic matter). Nevertheless, non-reactive transport of nitrate in the clay is expected to be the main process. In contrast, when easily oxidizable electron donors would be available (e.g. acetate and H{sub 2}), the microbial activity will be strongly stimulated. Both in the presence of H{sub 2} and acetate, nitrite and nitrogenous gases are predominantly produced, although some ammonium can also be formed when H{sub 2} is present. The reduction of nitrate in the clay could have an impact on the redox conditions in the pore-water and might also lead to a gas-related perturbation of the host rock, depending on the electron donor used during denitrification

  20. In situ oxidation and reduction of triangular nickel nanoplates via environmental transmission electron microscopy

    KAUST Repository

    LAGROW, A.P.

    2017-08-29

    Understanding the oxidation and reduction mechanisms of transition metals, such as nickel (Ni), is important for their use in industrial applications of catalysis. A powerful technique for investigating the redox reactive species is in situ environmental transmission electron microscopy (ETEM), where oxidation and reduction can be tracked in real time. One particular difficulty in understanding the underlying reactions is understanding the underlying morphology of the starting structure in a reaction, in particular the defects contained in the material, and the exposed surface facets. Here-in, we use a colloidal nanoparticle synthesis in a continuous flow reactor to form nanoplates of nickel coated with oleylamine as a capping agent. We utilise an in situ heating procedure at 300 °C in vacuum to remove the oleylamine ligands, and then oxidise the Ni nanoparticles at 25 °C with 2 Pa oxygen, and follow the nanoparticles initial oxidation. After that, the nanoparticles are oxidised at 200 and 300 °C, making the size of the oxide shell increase to ∼4 nm. The oxide shell could be reduced under 2 Pa hydrogen at 500 °C to its initial size of ∼1 nm. High temperature oxidation encouraged the nanoparticles to form pure NiO nanoparticles, which occurred via the Kirkendall effect leading to hollowing and void formation.

  1. In situ oxidation and reduction of triangular nickel nanoplates via environmental transmission electron microscopy

    KAUST Repository

    LAGROW, A.P.; AlYami, Noktan; LLOYD, D.C.; Bakr, Osman; BOYES, E.D.; GAI, P.L.

    2017-01-01

    Understanding the oxidation and reduction mechanisms of transition metals, such as nickel (Ni), is important for their use in industrial applications of catalysis. A powerful technique for investigating the redox reactive species is in situ environmental transmission electron microscopy (ETEM), where oxidation and reduction can be tracked in real time. One particular difficulty in understanding the underlying reactions is understanding the underlying morphology of the starting structure in a reaction, in particular the defects contained in the material, and the exposed surface facets. Here-in, we use a colloidal nanoparticle synthesis in a continuous flow reactor to form nanoplates of nickel coated with oleylamine as a capping agent. We utilise an in situ heating procedure at 300 °C in vacuum to remove the oleylamine ligands, and then oxidise the Ni nanoparticles at 25 °C with 2 Pa oxygen, and follow the nanoparticles initial oxidation. After that, the nanoparticles are oxidised at 200 and 300 °C, making the size of the oxide shell increase to ∼4 nm. The oxide shell could be reduced under 2 Pa hydrogen at 500 °C to its initial size of ∼1 nm. High temperature oxidation encouraged the nanoparticles to form pure NiO nanoparticles, which occurred via the Kirkendall effect leading to hollowing and void formation.

  2. Evaluation of toxicity reduction of sodium dodecyl sulfate submitted to electron beam radiation

    Science.gov (United States)

    Romanelli, M. F.; Moraes, M. C. F.; Villavicencio, A. L. C. H.; Borrely, S. I.

    2004-09-01

    Surfactants, as detergent active substances, are an important source of pollution causing biological adverse effects to aquatic organisms. Several data have been showing ecological disturbance due to the high concentration of surfactants on receiving waters and on wastewater treatment plants. Ionizing radiation has been proved as an effective technology to decompose organic substances and few papers have included ecotoxicological aspects. This paper shows the reduction of acute toxicity of a specific surfactant, sodium dodecyl sulfate (SDS), when diluted in distilled water and submitted to electron beam radiation. The study included two test-organisms, the marine bacteria Vibrio fischeri and the crustacean Daphnia similis. Radiation processing resulted in an important acute toxicity removal for both assays, which can be summarized between 70% and 96%, using 3.0, 6.0, 9.0 and 12.0 kGy as radiation doses. Nevertheless, lower doses demonstrated better effect than 9.0 and 12.0 kGy and the bacterium assay was more sensitive to SDS than crustacean assay.

  3. Pulse radiolytic one-electron reduction of 1,4-amino and hydroxy disubstituted 9,10-anthraquinones

    International Nuclear Information System (INIS)

    Pal, H.; Palit, D.K.; Mukherjee, T.; Mittal, J.P.

    1992-01-01

    The semiquinone radicals produced by one-electron reduction of 1-amino-4-hydroxy-9,10-anthraquinone and 1,4-diamino-9,10-anthraquinone have been studied in aqueous-organic mixed solvent using pulse radiolysis technique. Spectroscopic characteristics, kinetic characteristics of formation and decay, acid/base behaviour and redox characteristics of the semiquinones have been investigated and compared with those of some similar systems studied earlier. It has been shown that the variation of the disproportionation equilibria involving the reduced semiquinone radicals, the parent quinone and the fully reduced hydroquinone with pH of the solutions follow a similar trend as observed in the case of other dihydroxy quinones. Stability of the semiquinones over a broad pH range and their thermodynamic properties have been correlated. (Author)

  4. The reduction of nitrate, nitrite and hydroxylamine to ammonia by enzymes from Cucurbita pepo L. in the presence of reduced benzyl viologen as electron donor

    Science.gov (United States)

    Cresswell, C. F.; Hageman, R. H.; Hewitt, E. J.; Hucklesby, D. P.

    1965-01-01

    1. Enzyme systems from Cucurbita pepo have been shown to catalyse the reduction of nitrite and hydroxylamine to ammonia in yields about 90–100%. 2. Reduced benzyl viologen serves as an efficient electron donor for both systems. Activity of the nitrite-reductase system is directly related to degree of dye reduction when expressed in terms of the function for oxidation–reduction potentials, but appears to decrease to negligible activity below about 9% dye reduction. 3. NADH and NADPH alone produce negligible nitrite loss, but NADPH can be linked to an endogenous diaphorase system to reduce nitrite to ammonia in the presence of catalytic amounts of benzyl viologen. 4. The NADH– or NADPH–nitrate-reductase system that is also present can accept electrons from reduced benzyl viologen, but shows relationships opposite to that for the nitrite-reductase system with regard to effect of degree of dye reduction on activity. The product of nitrate reduction may be nitrite alone, or nitrite and ammonia, or ammonia alone, according only to the degree of dye reduction. 5. The relative activities of nitrite-reductase and hydroxylamine-reductase systems show different relationships with degree of dye reduction and may become reversed in magnitude when effects of degree of dye reduction are tested over a suitable range. 6. Nitrite severely inhibits the rate of reduction of hydroxylamine without affecting the yield of ammonia as a percentage of total substrate loss, but hydroxylamine has a negligible effect on the activity of the nitrite-reductase system. 7. The apparent Km for nitrite (1 μm) is substantially less than that for hydroxylamine, for which variable values between 0·05 and 0·9mm (mean 0·51 mm) have been observed. 8. The apparent Km values for reduced benzyl viologen differ for the nitrite-reductase and hydroxylamine-reductase systems: 60 and 7·5 μm respectively. 9. It is concluded that free hydroxylamine may not be an intermediate in the reduction of nitrite

  5. Reduction of dose enhancement from backscattered radiation at tissue-metal interfaces irradiated with 6MeV electrons

    International Nuclear Information System (INIS)

    Steel, B.

    1996-01-01

    Due to Electron Back Scatter (EBS), electron irradiation of tissue having under lying lead shielding results in an increase in dose to the tissue on the entrance side of the lead. In these situations dose increases as high as 80% have been reported in the literature. Saunders (British Journal of Radiology, 47, 467-470) noted that dose enhancement is dependent on atomic number of the under lying material approximately as Z 0.5 , and it increases at lower incident electron energies. In our clinic we use 2mm of lead shielding to protect under lying normal tissue when 6MeV electrons are used to treat lips and ears. The object of this study was to find the thinnest combination of materials to reduce the total dose to an acceptable level, with the provisos that; the patient does not come into contact with the lead or other metals, the finished shield could comfortabley be placed between the patient's lip and teeth, and that the materials are sufficietly malleable to work into custom shields. Various combinations of dental wax and aluminium were trialed. That which proved to give the best compromise between reduction of EBS and total shielding thickness was, 1mm of aluminim on the beam side of the lead with 1mm of dental wax to completely enclose the shield. In practice the manufactured shields are approximately 6 mm thick, and are usually not uncomfortable for the patient. (author)

  6. One-electron reduction reactions with enzymes in solution

    International Nuclear Information System (INIS)

    Bisby, R.H.; Cundall, R.B.; Redpath, J.L.; Adams, G.E.

    1976-01-01

    At pH 8 and above, hydrated electrons react with ribonuclease lysozyme and α-chymotrypsin to form transient products whose spectra resemble, but are not identical to, those for the RSSR - radical anion already known for simple disulphides. Assuming a value for the extinction coefficient similar to that for RSSR - in simple disulphides, only a fraction of the hydrated electrons are shown to react with the disulphide bridges: the remainder react at other sites in the protein molecule, such as histidine, tyrosine and, in lysozyme, tryptophan residues, giving rise to comparatively weak optical absorptions between 300 and 400 nm. This has been substantiated by studying the reaction of e - sub(aq) with subtilisin Novo (an enzyme which does not contain disulphide bridges), with enzymes in which the sulphur bridges have been oxidised and with some amino acid derivatives. On lowering the pH of the solution the intensity of the RSSR - absorption diminishes as the protonated histidine residues become the favoured reaction sites. In acid solutions (pH 2 to 3) the transient optical absoptions observed are due to reactions of hydrogen atoms with the aromatic amino acids tyrosine, tryptophan and phenylalanine. The CO - 2 radical anion is only observed to transfer an electron to disulphide groups in ribonuclease, although the effect of repeated pulsing shows that some reaction must occur elsewhere in the protein molecule. In acid solutions, protonation of the electron adduct appears to produce the RSSRH. radical, whose spectrum has a maximum at 340 nm. (author)

  7. Anelasticity of olivine single crystals investigated by stress-reduction tests and high-angular resolution electron backscatter diffraction

    Science.gov (United States)

    Wallis, D.; Hansen, L. N.; Kempton, I.; Wilkinson, A. J.

    2017-12-01

    Geodynamic phenomena, including glacial isostatic adjustment and postseismic deformation, can involve transient deformation in response to changes in differential stress acting on mantle rocks. As such, rheological models of transient deformation are incorporated in predictions of associated processes, including sea-level rise and stress redistribution after earthquakes. However, experimental constraints on rheological models for transient deformation of mantle materials are sparse. In particular, experiments involving stress reductions have been lacking. Moreover, a material's response to a reduction in stress can provide clues to the microphysical processes controlling deformation. To constrain models of transient deformation of mantle rocks we performed stress-reduction tests on single crystals of olivine at 1250-1300°C. Mechanical and piezoelectric actuators controlled constant initial stress during creep. At various strain intervals stress was reduced near-instantaneously using the piezoelectric actuator, inducing both elastic and anelastic (time-dependent) lengthening of the samples. A range of magnitudes of stress reduction were applied, typically unloading 10-90% of the initial stress. High-angular resolution electron backscatter diffraction (HR-EBSD), based on cross-correlation of diffraction patterns, was used to map dislocation density and elastic strain distributions in the recovered samples. Magnitudes of anelastic back-strain increase with increasing magnitudes of stress reduction and show a marked increase when stress reductions exceed 50% of the initial stress, consistent with previous observations in metals and alloys. This observation is inconsistent with the Burgers rheological model commonly used to describe transient behaviour and suggests that the style of rheological behaviour depends on the magnitude of stress change. HR-EBSD maps reveal that the crystal lattices are smoothly curved and generally lack subgrain boundaries and elastic strain

  8. Toxicity reduction for pharmaceuticals mixture in water by electron beam irradiation

    International Nuclear Information System (INIS)

    Boiani, Nathalia Fonseca; Tominaga, Flavio Kiyoshi; Borrely, Sueli Ivone

    2015-01-01

    The incorrect disposal of products is committing the environment quality once the aquatic environment is the main vehicle for dispersion of pollutants. Among the highlighted contaminants there are the pharmaceuticals, which are also released to the aquatic environment through the domestic sewage, hospitals and effluents. The monitoring of these pharmaceuticals in the environment has grown, showing many of them as persistent pollutants. Pharmaceuticals from different therapeutic classes have been detected in domestic sewage, surface water and groundwater around the world. Several studies evidenced Fluoxetine Hydrochloride residues in waters. Another important product is the Propranolol, used for heart disease treatments as far as fluoxetine is applied for treating mental diseases. The objective of this study was to apply the radiation processing for the abatement of pollutant in waters. Electron beam accelerator was used during irradiation of the mixture (Propranolol + Fluoxetine Hydrochloride) in aqueous solution. Acute toxicity assays were carried out for Vibrio fischeri marine bacterium, 15 minutes exposure. The results showed that irradiation (2.5kGy and 5.0kGy) enhanced the average effective concentration of the mixture, which means reduction of toxicity (56.34%, 55.70% respectively). Inverse effect was obtained with 7.5 kGy and 10 kGy. (author)

  9. Toxicity reduction for pharmaceuticals mixture in water by electron beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Boiani, Nathalia Fonseca; Tominaga, Flavio Kiyoshi; Borrely, Sueli Ivone, E-mail: flavio_tominaga@hotmail.com, E-mail: sborrely@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2015-07-01

    The incorrect disposal of products is committing the environment quality once the aquatic environment is the main vehicle for dispersion of pollutants. Among the highlighted contaminants there are the pharmaceuticals, which are also released to the aquatic environment through the domestic sewage, hospitals and effluents. The monitoring of these pharmaceuticals in the environment has grown, showing many of them as persistent pollutants. Pharmaceuticals from different therapeutic classes have been detected in domestic sewage, surface water and groundwater around the world. Several studies evidenced Fluoxetine Hydrochloride residues in waters. Another important product is the Propranolol, used for heart disease treatments as far as fluoxetine is applied for treating mental diseases. The objective of this study was to apply the radiation processing for the abatement of pollutant in waters. Electron beam accelerator was used during irradiation of the mixture (Propranolol + Fluoxetine Hydrochloride) in aqueous solution. Acute toxicity assays were carried out for Vibrio fischeri marine bacterium, 15 minutes exposure. The results showed that irradiation (2.5kGy and 5.0kGy) enhanced the average effective concentration of the mixture, which means reduction of toxicity (56.34%, 55.70% respectively). Inverse effect was obtained with 7.5 kGy and 10 kGy. (author)

  10. Microstructural characterization of Ni/YSZ based SOFC anodes after cyclic reduction and oxidation using electron microscopy

    International Nuclear Information System (INIS)

    Waldbillig, D.; He, A.; Ivey, D.

    2003-01-01

    The effect of redox cycling on the microstructure, of an SOFC anode, was studied using two approaches. Bulk samples were redox cycled and then examined in the SEM. In addition, electron transparent samples were prepared, redox cycled, and then examined in the TEM. Significant microstructural changes were observed. The anode in the as received condition consists of NiO particles several microns in size, YSZ grains about one micron in size and intergranular porosity. After the first reduction, the overall Ni grain size remains the same as the consumed NiO and epitaxial growth of Ni crystals on NiO grains is observed. The amount of intergranular porosity increases and very fine (50 nm) intragranular pores are formed throughout the Ni grains. This increase in the amount of porosity is expected due to the large volume change that occurs upon reduction. When samples are reoxidized the NiO particles in the SEM images appear spongy with much smaller pores than the as received, oxidized samples. The reoxidized anode consists of fine (<100 nm), randomly oriented grains of NiO. The grain refinement that occurs upon reoxidation is likely due to the large number of intragranular pores that occur upon reduction, which serve as nucleation sites. Rereduced samples were also very fine grained (<200 nm) and contained significant amounts of small intergranular porosity. The YSZ grains were unaffected by the redox cycles. (author)

  11. Electron transfer to sulfides:

    International Nuclear Information System (INIS)

    Meneses, Ana Belen; Antonello, Sabrina; Arevalo, Maria Carmen; Maran, Flavio

    2005-01-01

    The problem of characterizing the steps associated with the dissociative reduction of sulfides has been addressed. The electrochemical reduction of diphenylmethyl para-methoxyphenyl sulfide in N,N-dimethylformamide, on both glassy carbon and mercury electrodes, was chosen as a test system. The electrode process involves the slow heterogeneous outer-sphere electron transfer to the sulfide, the fast cleavage of the C-S bond, the reduction of the ensuing carbon radical, and the self-protonation triggered by the generation of the strong base Ph 2 CH - . The latter reaction is rather slow, in agreement with the large intrinsic barriers characterizing proton transfers between CH-acids and carbon bases. The dissociative reduction was studied in the presence of an exogenous acid. The results, obtained by convolution analysis, point to a stepwise DET mechanism in which the ET step is accompanied by rather large reorganization energy. Similar results were obtained on both electrode materials. Analysis of the heterogeneous electron transfer and associated C-S bond cleavage indicate that the reduction of this and other sulfides lies between the stepwise dissociative electron transfers leading to the formation of stiff π* radical anions and those going through the intermediacy of loose σ* radical anions

  12. Reduction of Ferrrihydrite and Akaganeite by Shewanella alga (PAH93)

    Science.gov (United States)

    Jung, M.; Kim, Y.; Lee, Y.; Kwon, K.; Roh, Y.

    2009-12-01

    Shewanella species are capable of oxidizing diverse organic acids coupled to reducing Fe(III) (oxy)hydroxides to crystalline Fe(II)-containing phases such as magnetite, siderite, and vivianite. The objective of this study was to examine reduction of ferrihydrite and akaganeite as the electron acceptors using various organic acids as the electron donors by Shewanella alga (PAH93) isolated from Yeosu, South Korea. Microbial reduction of akaganeite (40 mM) and ferrihydrite (40 mM) was examined using acetate (10 mM), glucose (10 mM), and lactate (10 mM) as electron donors at room temperature. Ferrozine method was used to analyze both water soluble and HCl soluble Fe(II) concentrations during the microbial Fe(III) reduction. XRD and TEM-EDX analyses were used to characterize biominerals formed by PAH93. PAH93 was completely reduced ferrihydrite to Fe(II), which transformed as siderite (FeCO3). PAH93 was oxidized acetate, glucose, and lactate coupled to reducing akaganeite to magnetite or green rust. Microbial reduction of ferrihydrite resulted in higher soluble Fe(II) concentration (446 - 498 mg/L) than the reduction of akaganeite (255 - 284 mg/L) within 6 days of incubation. For 21 days of incubation, souble Fe(II) concentration during akaganeite reduction (945 - 1316 mg/L) was higher than ferrihydrite reduction (120 - 738 mg/L). It may be attributed to the differences of crystallinity of the iron minerals used for microbial iron reduction. This study indicates types of the electron acceptors, ferrihydrite and akaganeite, affect Fe(II) reduction rate and types of the biotransformed minerals.

  13. Validity of the use of the neutron-reduction factor in assessing displacement damage to electronics in armoured vehicles

    Energy Technology Data Exchange (ETDEWEB)

    Cousins, T.; Jamieson, T.J.

    1990-02-01

    The degree of protection from neutron irradiation afforded to electronics by armoured vehicles is most currently defined by the outside-to-inside ratio of the 1 MeV equivalent neutron fluence for Silicon. It has been proposed that this factor may be approximated by an experimentally measurable parameter - the neutron (tissue kerma) reduction factor. This report examines the validity of this assumption for a variety of realistic nuclear battlefield scenarios, calculated using the computer code VPF2. In addition the response of two neutron dosimeters in the calculated fields is examined.

  14. A Synthetic Pseudo-Rh: NOx Reduction Activity and Electronic Structure of Pd-Ru Solid-solution Alloy Nanoparticles

    Science.gov (United States)

    Sato, Katsutoshi; Tomonaga, Hiroyuki; Yamamoto, Tomokazu; Matsumura, Syo; Zulkifli, Nor Diana Binti; Ishimoto, Takayoshi; Koyama, Michihisa; Kusada, Kohei; Kobayashi, Hirokazu; Kitagawa, Hiroshi; Nagaoka, Katsutoshi

    2016-06-01

    Rh is one of the most important noble metals for industrial applications. A major fraction of Rh is used as a catalyst for emission control in automotive catalytic converters because of its unparalleled activity toward NOx reduction. However, Rh is a rare and extremely expensive element; thus, the development of Rh alternative composed of abundant elements is desirable. Pd and Ru are located at the right and left of Rh in the periodic table, respectively, nevertheless this combination of elements is immiscible in the bulk state. Here, we report a Pd-Ru solid-solution-alloy nanoparticle (PdxRu1-x NP) catalyst exhibiting better NOx reduction activity than Rh. Theoretical calculations show that the electronic structure of Pd0.5Ru0.5 is similar to that of Rh, indicating that Pd0.5Ru0.5 can be regarded as a pseudo-Rh. Pd0.5Ru0.5 exhibits better activity than natural Rh, which implies promising applications not only for exhaust-gas cleaning but also for various chemical reactions.

  15. One-electron reduction of 1,2-dihydroxy-9,10-anthraquinone and some of its transition metal complexes in aqueous solution and in aqueous isopropanol-acetone-mixed solvent: a steady-state and pulse radiolysis study

    International Nuclear Information System (INIS)

    Das, S.; Bhattacharya, A.; Mandal, P.C.; Rath, M.C.; Mukherjee, T.

    2002-01-01

    One-electron reduction of 1,2-dihydroxy-9,10-anthraquinone (DHA) and its complexes with Cu(II), Ni(II) and Fe(III), by acetone ketyl radical, (CH 3 ) 2 C·OH, was carried out in aqueous solution and in aqueous isopropanol acetone mixed solvent using both steady-state gamma radiolysis and pulse radiolysis techniques. The rate constants for the reduction of DHA at different pH values by the ketyl radical are in the order of ∼10 9 dm 3 mol -1 s -1 , whereas those for the metal complexes are comparatively less. These rate constants are, however, in conformity with the one-electron reduction potentials of the ligand in free DHA and in its metal complexes. Decay kinetics of the one-electron reduced semiquinones of the free ligand and its metal complexes suggest disproportionation of the semiquinone in the case of the free ligand and intermolecular electron transfer from the co-ordinated semiquinone radical to the metal centre in the case of the metal complexes

  16. Kinetic analysis and modeling of oleate and ethanol stimulated uranium (VI) bio-reduction in contaminated sediments under sulfate reduction conditions

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Fan, E-mail: zhangfan@itpcas.ac.cn [Key Laboratory of Tibetan Environment Changes and Land Surface Processes, Institute of Tibetan Plateau Research, Chinese Academy of Sciences, P.O. Box 2871, Beijing 100085 (China); Wu Weimin [Department of Civil and Environmental Engineering, Stanford University, Stanford, CA 94305 (United States); Parker, Jack C. [Department of Civil and Environmental Engineering, University of Tennessee, Knoxville, TN 37996 (United States); Mehlhorn, Tonia [Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Kelly, Shelly D.; Kemner, Kenneth M. [Biosciences Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Zhang, Gengxin [Key Laboratory of Tibetan Environment Changes and Land Surface Processes, Institute of Tibetan Plateau Research, Chinese Academy of Sciences, P.O. Box 2871, Beijing 100085 (China); Schadt, Christopher; Brooks, Scott C. [Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Criddle, Craig S. [Department of Civil and Environmental Engineering, Stanford University, Stanford, CA 94305 (United States); Watson, David B. [Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Jardine, Philip M. [Biosystems Engineering and Soil Science Department, University of Tennessee, Knoxville, TN 37996 (United States)

    2010-11-15

    Microcosm tests with uranium contaminated sediments were performed to explore the feasibility of using oleate as a slow-release electron donor for U(VI) reduction in comparison to ethanol. Oleate degradation proceeded more slowly than ethanol with acetate produced as an intermediate for both electron donors under a range of initial sulfate concentrations. A kinetic microbial reduction model was developed and implemented to describe and compare the reduction of sulfate and U(VI) with oleate or ethanol. The reaction path model considers detailed oleate/ethanol degradation and the production and consumption of intermediates, acetate and hydrogen. Although significant assumptions are made, the model tracked the major trend of sulfate and U(VI) reduction and describes the successive production and consumption of acetate, concurrent with microbial reduction of aqueous sulfate and U(VI) species. The model results imply that the overall rate of U(VI) bioreduction is influenced by both the degradation rate of organic substrates and consumption rate of intermediate products.

  17. Kinetic analysis and modeling of oleate and ethanol stimulated uranium (VI) bio-reduction in contaminated sediments under sulfate reduction conditions

    International Nuclear Information System (INIS)

    Zhang Fan; Wu Weimin; Parker, Jack C.; Mehlhorn, Tonia; Kelly, Shelly D.; Kemner, Kenneth M.; Zhang, Gengxin; Schadt, Christopher; Brooks, Scott C.; Criddle, Craig S.; Watson, David B.; Jardine, Philip M.

    2010-01-01

    Microcosm tests with uranium contaminated sediments were performed to explore the feasibility of using oleate as a slow-release electron donor for U(VI) reduction in comparison to ethanol. Oleate degradation proceeded more slowly than ethanol with acetate produced as an intermediate for both electron donors under a range of initial sulfate concentrations. A kinetic microbial reduction model was developed and implemented to describe and compare the reduction of sulfate and U(VI) with oleate or ethanol. The reaction path model considers detailed oleate/ethanol degradation and the production and consumption of intermediates, acetate and hydrogen. Although significant assumptions are made, the model tracked the major trend of sulfate and U(VI) reduction and describes the successive production and consumption of acetate, concurrent with microbial reduction of aqueous sulfate and U(VI) species. The model results imply that the overall rate of U(VI) bioreduction is influenced by both the degradation rate of organic substrates and consumption rate of intermediate products.

  18. Electron Bifurcation and Confurcation in Methanogenesis and Reverse Methanogenesis

    Directory of Open Access Journals (Sweden)

    Zhen Yan

    2018-06-01

    Full Text Available Reduction of the disulfide of coenzyme M and coenzyme B (CoMS–SCoB by heterodisulfide reductases (HdrED and HdrABC is the final step in all methanogenic pathways. Flavin-based electron bifurcation (FBEB by soluble HdrABC homologs play additional roles in driving essential endergonic reactions at the expense of the exergonic reduction of CoMS–SCoM. In the first step of the CO2 reduction pathway, HdrABC complexed with hydrogenase or formate dehydrogenase generates reduced ferredoxin (Fdx2- for the endergonic reduction of CO2 coupled to the exergonic reduction of CoMS–SCoB dependent on FBEB of electrons from H2 or formate. Roles for HdrABC:hydrogenase complexes are also proposed for pathways wherein the methyl group of methanol is reduced to methane with electrons from H2. The HdrABC complexes catalyze FBEB-dependent oxidation of H2 for the endergonic reduction of Fdx driven by the exergonic reduction of CoMS–SCoB. The Fdx2- supplies electrons for reduction of the methyl group to methane. In H2- independent pathways, three-fourths of the methyl groups are oxidized producing Fdx2- and reduced coenzyme F420 (F420H2. The F420H2 donates electrons for reduction of the remaining methyl groups to methane requiring transfer of electrons from Fdx2- to F420. HdrA1B1C1 is proposed to catalyze FBEB-dependent oxidation of Fdx2- for the endergonic reduction of F420 driven by the exergonic reduction of CoMS–SCoB. In H2- independent acetotrophic pathways, the methyl group of acetate is reduced to methane with electrons derived from oxidation of the carbonyl group mediated by Fdx. Electron transport involves a membrane-bound complex (Rnf that oxidizes Fdx2- and generates a Na+ gradient driving ATP synthesis. It is postulated that F420 is reduced by Rnf requiring HdrA2B2C2 catalyzing FBEB-dependent oxidation of F420H2 for the endergonic reduction of Fdx driven by the exergonic reduction of CoMS–SCoB. The Fdx2- is recycled by Rnf and HdrA2B2C2 thereby

  19. Decal electronics for printed high performance cmos electronic systems

    KAUST Repository

    Hussain, Muhammad Mustafa

    2017-11-23

    High performance complementary metal oxide semiconductor (CMOS) electronics are critical for any full-fledged electronic system. However, state-of-the-art CMOS electronics are rigid and bulky making them unusable for flexible electronic applications. While there exist bulk material reduction methods to flex them, such thinned CMOS electronics are fragile and vulnerable to handling for high throughput manufacturing. Here, we show a fusion of a CMOS technology compatible fabrication process for flexible CMOS electronics, with inkjet and conductive cellulose based interconnects, followed by additive manufacturing (i.e. 3D printing based packaging) and finally roll-to-roll printing of packaged decal electronics (thin film transistors based circuit components and sensors) focusing on printed high performance flexible electronic systems. This work provides the most pragmatic route for packaged flexible electronic systems for wide ranging applications.

  20. Catalytic activity of lanthanum oxide for the reduction of cyclohexanone

    International Nuclear Information System (INIS)

    Sugunan, S.; Sherly, K.B.

    1994-01-01

    Lanthanum oxides, La 2 O 3 has been found to be an effective catalyst for the liquid phase reduction of cyclohexanone. The catalytic activities of La 2 O 3 activated at 300, 500 and 800 degC and its mixed oxides with alumina for the reduction of cylcohexanone with 2-propanol have been determined and the data parallel that of the electron donating properties of the catalysts. The electron donating properties of the catalysts have been determined from the adsorption of electron acceptors of different electron affinities on the surface of these oxides. (author). 15 refs., 2 figs., 1 tab

  1. One-electron reduction of 9,10-anthraquinone, 1-amino-9,10-anthraquinone and 1-hydroxy-9,10-anthraquinone in aqueous-isopropanol-acetone mixed solvent: a pulse radiolysis study

    International Nuclear Information System (INIS)

    Pal, H.; Mukherjee, T.; Mittal, J.P.

    1994-01-01

    The semiquinone radicals produced by one-electron reduction of 9,10-anthraquinone, 1-amino- 9,10-anthraquinone and 1-hydroxy-9,10-anthraquinone have been characterized in aqueous-organic mixed solvent comprising of 30.2 mol dm -3 water, 5 mol dm -3 isopropanol and 1 mol dm -3 acetone, using the pulse radiolysis technique. Spectroscopic characteristics, the kinetic parameters of formation and decay and one acid dissociation constants of the semiquinones and one-electron reduction potentials of the quinones have been estimated. The characteristics of the present semiquinone systems have been compared with those of other similar systems. The observed differences in characteristics of the semiquinones due to different substitutions have been analysed. (Author)

  2. Quantification and reduction of peripheral dose from leakage radiation on Siemens Primus accelerators in electron therapy mode.

    Science.gov (United States)

    Yeboah, Collins; Karotki, Alex; Hunt, Dylan; Holly, Rick

    2010-06-15

    In this work, leakage radiation from EA200 series electron applicators on Siemens Primus accelerators is quantified, and its penetration ability in water and/or the shielding material Xenolite-NL established. Initially, measurement of leakage from 10 x 10 - 25 x 25 cm2 applicators was performed as a function of height along applicator and of lateral distance from applicator body. Relative to central-axis ionization maximum in solid water, the maximum leakage in air observed with a cylindrical ion chamber with 1 cm solid water buildup cap at a lateral distance of 2 cm from the front and right sidewalls of applicators were 17% and 14%, respectively; these maxima were recorded for 18 MeV electron beams and applicator sizes of >or=20 x 20 cm2. In the patient plane, the applicator leakage gave rise to a broad peripheral dose off-axis distance peak that shifted closer to the field edge as the electron energy increases. The maximum peripheral dose from normally incident primary electron beams at a depth of 1 cm in a water phantom was observed to be equal to 5% of the central-axis dose maximum and as high as 9% for obliquely incident beams with angles of obliquity dose curves showed that the "practical range" of the leakage electrons in water varies from approximately 1.4 to 5.7 cm as the primary electron beam energy is raised from 6 to 18 MeV. Next, transmission measurements of leakage radiation through the shielding material Xenolite-NL showed a 4 mm thick sheet of this material is required to attenuate the leakage from 9 MeV beams by two-thirds, and that for every additional 3 MeV increase in the primary electron beam energy, an additional Xenolite-NL thickness of roughly 2 mm is needed to achieve the aforementioned attenuation level. Finally, attachment of a 1 mm thick sheet of lead to the outer surface of applicator sidewalls resulted in a reduction of the peripheral dose by up to 80% and 74% for 9 and 18MeV beams, respectively. This sidewall modification had an

  3. Electrochemical reduction of imazamethabenz methyl on mercury and carbon electrodes

    International Nuclear Information System (INIS)

    Ruiz Montoya, Mercedes; Pintado, Sara; Rodriguez Mellado, Jose Miguel

    2010-01-01

    This paper presents polarographic and voltammetric studies of the reduction of the herbicide imazamethabenz methyl (2/3-methyl-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-p-toluate), on mercury and carbon electrodes. The electrochemical studies were performed in strongly acidic media (0.1-2.7 M H 2 SO 4 ) as well as in the pH range of 1-12. The overall reduction process involves the uptake of two electrons. The results obtained in polarography show that there is the reduction of two species, related via an acid-base equilibrium, and having very close reduction potentials. The voltammetric results obtained with a glassy carbon electrode were very similar to those observed on mercury electrodes. The reducible group in the molecule is the imidazolinone ring. In strongly acidic media (pH a ), the reaction mechanism proposed is the reduction of the protonated herbicide by an electrochemical-chemical-electrochemical (ECE) process, being the r.d.s. the second electron transfer. At pH > pK a the neutral form of the herbicide is reduced and the second electron transfer becomes reversible or quasi-reversible. In basic media, the species reduced is the deprotonated imazamethabenz methyl and the r.d.s. is the second electron transfer.

  4. Electrochemical reduction of imazamethabenz methyl on mercury and carbon electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz Montoya, Mercedes, E-mail: mmontoya@uhu.e [Departamento de Ingenieria Quimica, Quimica Fisica y Quimica Organica, Universidad de Huelva, Campus El Carmen, Facultad de Ciencias Experimentales, E-21071 Huelva (Spain); Pintado, Sara; Rodriguez Mellado, Jose Miguel [Departamento de Quimica Fisica y Termodinamica Aplicada, Universidad de Cordoba, Campus Universitario de Rabanales, edificio ' Marie Curie' , E-14014 Cordoba (Spain)

    2010-03-30

    This paper presents polarographic and voltammetric studies of the reduction of the herbicide imazamethabenz methyl (2/3-methyl-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-p-toluate), on mercury and carbon electrodes. The electrochemical studies were performed in strongly acidic media (0.1-2.7 M H{sub 2}SO{sub 4}) as well as in the pH range of 1-12. The overall reduction process involves the uptake of two electrons. The results obtained in polarography show that there is the reduction of two species, related via an acid-base equilibrium, and having very close reduction potentials. The voltammetric results obtained with a glassy carbon electrode were very similar to those observed on mercury electrodes. The reducible group in the molecule is the imidazolinone ring. In strongly acidic media (pH < pK{sub a}), the reaction mechanism proposed is the reduction of the protonated herbicide by an electrochemical-chemical-electrochemical (ECE) process, being the r.d.s. the second electron transfer. At pH > pK{sub a} the neutral form of the herbicide is reduced and the second electron transfer becomes reversible or quasi-reversible. In basic media, the species reduced is the deprotonated imazamethabenz methyl and the r.d.s. is the second electron transfer.

  5. A study on relation between nitroxyl radical reduction potency and X-ray irradiation on mouse lung using L-band electron spin resonance

    International Nuclear Information System (INIS)

    Taneike, Makoto; Sho, Keizen; Morita, Rikushi

    1999-01-01

    Changes in nitroxy radical reduction potency (''reduction potency''), caused by different doses and different number of fractions of X-ray irradiation were studied using a L-band electron spin resonance system on mouse lungs into which 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (hydroxy-TEMPO) was introduced through the trachea. The ''reduction potency'' lineally decreased as the irradiation dose increased from 1.0 to 5.0 Gy, but no further decrease was observed at higher doses of 7.5 and 10 Gy. The reduction potency'' dropped at 20 min after each irradiation, but it recovered to the control levels after 1 week in all 3 groups of single dose of 10 Gy, 3 fractions and 5 fractions in a similar manner. Although the levels of the ''reduction potency'' were kept high in the groups of fractionated irradiation through 1-4 weeks after irradiation, the levels dropped again in the single dose group at 1 week and the levels were kept significantly low until 4 weeks after irradiation. suggesting that the fractionation of X-ray irradiation would also be effective to prevent the deterioration of the ''reduction potency''. Pre-treatment with sufficient ascorbic acid inhibited the lowering effects of radiation on the ''reduction potency'' in a dose dependent manner. Furthermore the levels of the reduction potency'' ever elevated higher than those of controls with the large amount of ascorbic acid of 750 mg/kg or more, suggesting that the large amounts of ascorbic acid could prevent the adverse effects associated with radiation therapy for the lung malignancy. (author)

  6. Modelling the autoxidation of myoglobin in fresh meat under modified atmosphere packing conditions

    DEFF Research Database (Denmark)

    Tofteskov, Jon; Hansen, Jesper Schmidt; Bailey, Nicholas

    2017-01-01

    pigment concentration data is obtained, but only by substantially increasing the value of the oxygen consumption rate. Application of the model to meat stored at 5 °C shows that the metmyoglobin layer forms under the surface over a time scale of 24 h; The metmyoglobin layer forms deeper inside the meat......Modified atmosphere packing (MAP) is a technique to increase the shelf life of fresh meat. Continuing development of MAP requires better understanding of the physical and chemical processes taking place, in particular the diffusion of oxygen and its reaction with myoglobin. We model these processes...... proportional to the logarithm of the headspace oxygen partial pressure, thus improving the colour appearance of the meat....

  7. Quinone reduction via secondary B-branch electron transfer in mutant bacterial reaction centers.

    Science.gov (United States)

    Laible, Philip D; Kirmaier, Christine; Udawatte, Chandani S M; Hofman, Samuel J; Holten, Dewey; Hanson, Deborah K

    2003-02-18

    Symmetry-related branches of electron-transfer cofactors-initiating with a primary electron donor (P) and terminating in quinone acceptors (Q)-are common features of photosynthetic reaction centers (RC). Experimental observations show activity of only one of them-the A branch-in wild-type bacterial RCs. In a mutant RC, we now demonstrate that electron transfer can occur along the entire, normally inactive B-branch pathway to reduce the terminal acceptor Q(B) on the time scale of nanoseconds. The transmembrane charge-separated state P(+)Q(B)(-) is created in this manner in a Rhodobacter capsulatus RC containing the F(L181)Y-Y(M208)F-L(M212)H-W(M250)V mutations (YFHV). The W(M250)V mutation quantitatively blocks binding of Q(A), thereby eliminating Q(B) reduction via the normal A-branch pathway. Full occupancy of the Q(B) site by the native UQ(10) is ensured (without the necessity of reconstitution by exogenous quinone) by purification of RCs with the mild detergent, Deriphat 160-C. The lifetime of P(+)Q(B)(-) in the YFHV mutant RC is >6 s (at pH 8.0, 298 K). This charge-separated state is not formed upon addition of competitive inhibitors of Q(B) binding (terbutryn or stigmatellin). Furthermore, this lifetime is much longer than the value of approximately 1-1.5 s found when P(+)Q(B)(-) is produced in the wild-type RC by A-side activity alone. Collectively, these results demonstrate that P(+)Q(B)(-) is formed solely by activity of the B-branch carriers in the YFHV RC. In comparison, P(+)Q(B)(-) can form by either the A or B branches in the YFH RC, as indicated by the biexponential lifetimes of approximately 1 and approximately 6-10 s. These findings suggest that P(+)Q(B)(-) states formed via the two branches are distinct and that P(+)Q(B)(-) formed by the B side does not decay via the normal (indirect) pathway that utilizes the A-side cofactors when present. These differences may report on structural and energetic factors that further distinguish the functional

  8. A False Alarm Reduction Method for a Gas Sensor Based Electronic Nose

    Directory of Open Access Journals (Sweden)

    Mohammad Mizanur Rahman

    2017-09-01

    Full Text Available Electronic noses (E-Noses are becoming popular for food and fruit quality assessment due to their robustness and repeated usability without fatigue, unlike human experts. An E-Nose equipped with classification algorithms and having open ended classification boundaries such as the k-nearest neighbor (k-NN, support vector machine (SVM, and multilayer perceptron neural network (MLPNN, are found to suffer from false classification errors of irrelevant odor data. To reduce false classification and misclassification errors, and to improve correct rejection performance; algorithms with a hyperspheric boundary, such as a radial basis function neural network (RBFNN and generalized regression neural network (GRNN with a Gaussian activation function in the hidden layer should be used. The simulation results presented in this paper show that GRNN has more correct classification efficiency and false alarm reduction capability compared to RBFNN. As the design of a GRNN and RBFNN is complex and expensive due to large numbers of neuron requirements, a simple hyperspheric classification method based on minimum, maximum, and mean (MMM values of each class of the training dataset was presented. The MMM algorithm was simple and found to be fast and efficient in correctly classifying data of training classes, and correctly rejecting data of extraneous odors, and thereby reduced false alarms.

  9. Lamb meat colour stability as affected by dietary tannins

    Directory of Open Access Journals (Sweden)

    Pietro Pennisi

    2010-01-01

    Full Text Available Twenty-one male Comisana lambs were divided into three groups at 45 days of age and were individually penned for 60 days. Seven lambs were fed a concentrate-based diet (C, seven lambs received the same concentrate with the addiction of tannins from quebracho (Schinopsis lorentzii; T, whereas the remaining animals were fed exclusively fresh vetch (Vicia sativa; H. Colour descriptors (a*, b* and H* and metmyoglobin (MMb percentages were measured on minced semimembranosus muscle over 14 days of refrigerated storage in a high oxygen atmosphere. Regardless of dietary treatment, meat redness decreased, while yellowness and hue angle increased (P < 0.001 over storage duration. However, higher a* values, lower b* values and lower H* values were observed in meat from both H- and T-fed animals as compared to meat from C-fed lambs (P = 0.012; P = 0.02; P = 0.003, respectively. Metmyoglobin formation increased over time (P < 0.001, but H diet resulted in lower metmyoglobin percentages than C diet (P = 0.007. We conclude that the inclusion of tannins into the concentrate improved meat colour stability compared to a tannin-free concentrate. Moreover, the protective effect of tannins against meat discolouration was comparable to that obtained by feeding lambs fresh herbage.

  10. Influence of Diet and Postmortem Ageing on Oxidative Stability of Lipids, Myoglobin and Myofibrillar Proteins and Quality Attributes of Gluteus Medius Muscle in Goats

    Science.gov (United States)

    Adeyemi, Kazeem Dauda; Shittu, Rafiat Morolayo; Sabow, Azad Behnan; Ebrahimi, Mahdi; Sazili, Awis Qurni

    2016-01-01

    This study appraised the effects of dietary blend of 80% canola oil and 20% palm oil and postmortem ageing on oxidative stability, fatty acids and quality attributes of gluteus medius (GM) muscle in goats. Twenty-four Boer bucks were randomly allotted to diet supplemented with 0, 4 and 8% oil blend, fed for 100 days and slaughtered, and the GM muscle was subjected to a 7 d chill storage (4±1°C). Diet had no effect (P> 0.05) on the colour, drip loss, thiobarbituric acid-reactive substances (TBARS) value, free thiol, carbonyl, myoglobin and metmyoglobin contents, metmyoglobin reducing activity (MRA), antioxidant enzyme activities and abundance of myosin heavy chain (MHC) and actin in the GM muscle in goats. The meat from goats fed 4 and 8% oil blend had higher (Pgoats. The GM muscle from the oil-supplemented goats had lower (Pgoats. Nonetheless, diet did not affect (Pgoats. Regardless of the diet, the free thiol and myoglobin contents, concentration of tocopherol and total carotenoids, MHC and MRA in the GM muscle decreased (P< 0.05) while carbonyl content, TBARS, drip loss and metmyoglobin content increased over storage. Dietary blend of 80% canola oil and 20% palm oil beneficially altered tissue lipids without hampering the oxidative stability of chevon. PMID:27138001

  11. Pulse radiolytic reduction of amino and hydroxy disubstituted anthraquinones (Preprint no. RC-15)

    International Nuclear Information System (INIS)

    Pal, H.; Palit, D.K.; Mukherjee, T.; Mittal, J.P.

    1991-01-01

    One-electron reduction of 1-amino-4-hydroxy-9, 10-anthraquinone (AHAQ) and 1,4-diamino-9, 10-anthraquinone (DAAQ) in various matrices has been investigated by electron pulse radiolysis. Spectroscopic and kinetic parameters, acid dissociation constants (pK a ) of the reduced semiquinone radicals and one-electron reduction potential for AHAQ have been measured. (author). 2 tabs

  12. Chemodynamics of chromium reduction in soils: Implications to bioavailability

    Energy Technology Data Exchange (ETDEWEB)

    Choppala, Girish [Centre for Environmental Risk Assessment and Remediation, Building-X, University of South Australia, Mawson Lakes, South Australia 5095 (Australia); Cooperative Research Centre for Contamination Assessment and Remediation of the Environment, PO Box 486, Salisbury, South Australia 5106 (Australia); Bolan, Nanthi, E-mail: Nanthi.Bolan@unisa.edu.au [Centre for Environmental Risk Assessment and Remediation, Building-X, University of South Australia, Mawson Lakes, South Australia 5095 (Australia); Cooperative Research Centre for Contamination Assessment and Remediation of the Environment, PO Box 486, Salisbury, South Australia 5106 (Australia); Seshadri, Balaji [Centre for Environmental Risk Assessment and Remediation, Building-X, University of South Australia, Mawson Lakes, South Australia 5095 (Australia); Cooperative Research Centre for Contamination Assessment and Remediation of the Environment, PO Box 486, Salisbury, South Australia 5106 (Australia)

    2013-10-15

    Highlights: • Examined the effects of sorption, pH and C sources on Cr(VI) reduction and toxicity. • The rate of Cr(VI) reduction decreased with an increase in Cr(VI) adsorption and pH. • The proton dynamics in Cr(VI) reduction was assessed in relation to remediation. • A novel black carbon showed the highest reduction rate of Cr(VI) in soils. • Black carbon decreased the bioavailability and phytotoxicity of Cr(VI) in soils. -- Abstract: Chromium toxicity in soils can be mitigated by reduction of Cr(VI) to Cr(III) which is influenced by the presence of free Cr(VI) species in soil solution, and the supply of protons and electrons. In this study, the effects of Cr(VI) adsorption (i.e. availability of free Cr(VI) species in soil solution), soil pH (i.e. supply of protons) and three electron donor carbon sources [black carbon (BC), chicken manure biochar (CMB) and cow manure (CM)] on the reduction of Cr(VI) to Cr(III) in soils were investigated. The results indicated that the rate of Cr(VI) reduction decreased with an increase in Cr(VI) adsorption and soil pH, which is attributed to decreased supply of free Cr(VI) ions and protons, respectively. Among the three different amendments tested, BC showed the highest rate of Cr(VI) reduction followed by CM and CMB. Furthermore, addition of BC, CM and CMB decreased the bioavailability of Cr(VI) in contaminated soils. The high efficiency of BC on Cr(VI) reduction was due to the electron donor's functional groups such as phenolic, hydroxyl, carbonyl and amides. The study demonstrated that free form of Cr(VI) ions in soil solution and carbon amendments enriched with acidic functional groups favored the reduction of Cr(VI), thereby mitigating its bioavailability and toxicity in contaminated soils.

  13. Cyclic voltammetry and reduction mechanistic studies of styrylpyrylium perchlorates

    Directory of Open Access Journals (Sweden)

    Y. L. Bonzi-Coulibaly

    2013-04-01

    Full Text Available The reduction and oxidation potentials of methylated 4-styrylpyrylium and 6-styrylpyrylium perchlorates have been evaluated using cyclic voltammetry, in comparison to their non-methylated derivatives values. The reduction peak of all studied compounds remained chemically irreversible. The presence of the electron-donating methyl group on pyrylium ring leads to a shift of the styrylpyrylium perchlorates reduction potential towards cathodic values. Kinetic studies on platinum electrodes based on the variation of the peak potential at different scan rates and upon substrate concentrations confirm, in another way, the mechanism of electron transfer.DOI: http://dx.doi.org/10.4314/bcse.v27i1.12

  14. Reduction of organic solvent emission by industrial use of electron-beam curable coatings

    International Nuclear Information System (INIS)

    Haering, E.

    1982-01-01

    Most industrial finishing processes operate by the use of liquid organic coating materials drying by solvent evaporation and subsequent chemical crosslinking reactions, in many cases also releasing cleavage products. These organic emissions contribute to air pollution and therefore many countries have issued restrictions in order to protect the environment. Complementary to other modern methods for reducing this problem, radiation chemistry enables an approach by radical chain polymerization which can be induced by exposure to electron radiation. This procedure is known as electron-beam curing of coatings or the EBC process. It utilizes well-developed accelerator equipment with voltages of 150 to 400kV at a minimum energy consumption. There is no necessity to use irradiation facilities based on the decay of radioisotopes. Free radical polymerization requires unsaturated resins as pain binders and polymerizable liquid compounds (monomers) as reactive diluents. Their crosslinking yields a high molecular network, the coating, without any emission of organic solvents or cleavage products. Moreover, the radiochemical formation of the paint film occurs extremely rapidly. The technical application of EBC coatings began by coating automotive plastic parts; a little later the finishing of wood products gained more industrial use as a non-polluting and energy-saving coating technology. Application methods in coating plastic foils in combination with vacuum metallizing and the production of decorative laminating papers for furniture followed. In 1981 new EBC pilot lines were installed for curing top coats on PVC foil and also for the coating of prefinished steel wheels for automobiles. In comparison with conventional solvent-based methods the industrial EBC process results in a nearly complete reduction of organic solvent emission avoiding air pollution and saving valuable petrochemical raw materials. This paper reviews the development of EBC during the last decade. (author)

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    Highlights: • Alkaline ascorbic acid (a.k.a. vitamin C) is capable of reductively degrading NB. • The pH above the pK_a_2 of ascorbic acid increases reductive electron transfer to NB. • The rate equation for the reactions between NB and AA is determined. • NSB, AZOXY, and AZO are identified as intermediates and aniline as a final product. • Alkaline pH is essential for AA remediation of NB contaminated soils. - Abstract: Alkaline ascorbic acid (AA) exhibits the potential to reductively degrade nitrobenzene (NB), which is the simplest of the nitroaromatic compounds. The nitro group (NO_2"−) 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 pK_a_2 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"."3"5 "± "0"."1"0[AA]"b "= "0"."8"9 "± "0"."0"1. 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.

  16. Nickel oxide reduction studied by environmental TEM

    DEFF Research Database (Denmark)

    Jeangros, Q.; Hansen, Thomas Willum; Wagner, Jakob Birkedal

    2012-01-01

    In situ reduction of an industrial NiO powder is performed under 1.3 mbar of H2 (2 mlN/min) in a differentially pumped FEI Titan 80-300 environmental transmission electron microscope (ETEM). Images, diffraction patterns and electron energy loss spectra (EELS) are acquired to monitor the structura...

  17. Electron transfer reactions in structural units of copper proteins

    International Nuclear Information System (INIS)

    Faraggi, M.

    1975-01-01

    In previous pulse radiolysis studies it was suggested that the reduction of the Cu(II) ions in copper proteins by the hydrated electron is a multi-step electron migration process. The technique has been extended to investigate the reduction of some structural units of these proteins. These studies include: the reaction of the hydrated electron with peptides, the reaction of the disulphide bridge with formate radical ion and radicals produced by the reduction of peptides, and the reaction of Cu(II)-peptide complex with esub(aq)sup(-) and CO 2 - . Using these results the reduction mechanism of copper and other proteins will be discussed. (author)

  18. Metallothermic reduction of molybdate

    International Nuclear Information System (INIS)

    Mukherjee, T.K.; Bose, D.K.

    1987-01-01

    This paper gives a brief account of the investigations conducted so far on metallothermic reduction of high grade molybdenite with particular emphasis on the work carried out in Bhabha Atomic Research Centre. Based on thermochemical considerations, the paper first introduces a number of metallic reductants suitable for use in metallothermic reduction of molybdenite. Aluminium, sodium and tin are found to be suitable reducing agents and very rightly they have found most applications in the research and development efforts on metallothermic reduction of molybdenite. The reduction with tin was conducted on fairly large scale both in vacuum and hydrogen atmosphere. The reaction was reported to be invariant depending mainly on the reduction temperature and a temperature of the order of 1250deg to 1300degC was required for good metal recovery. In comparison to tin, aluminothermic reduction of molybdenite was studied more extensively and it was conducted in closed bomb, vacuum and also in open atmosphere. In aluminothermic reduction, the influence of amount of reducing agent, amount of heat booster, preheating temperature and charging procedure on these metal yield was studied in detail. The reduction generally yielded massive molybdenum metal contaminated with aluminium as the major impurity element. Efforts were made to purify the reduced metal by arc melting, electron beam melting and molten salt electrorefining. 9 refs. (author)

  19. Influence of the particle size reduction on magnetic properties of electron-doped Ca1-xYxMnO3

    OpenAIRE

    Alqat Aboalqasim; Gebrel Zohra; Spasojević Vojislav; Kusigerski Vladan; Bošković Snežana; Blanuša Jovan

    2012-01-01

    The electron-doped magnetic nanoparticles of Ca1-xYxMnO3 (x = 0, 0.05, 0.10, 0.15, 0.20, and 0.30) manganite with an average particle size of 50 nm are analyzed and discussed in relation to their bulk counterparts. Nanoparticle samples show dominant anti-ferromagnetic ordering with a significant increase of coercivity, with the maximum value of 0.9 T for x = 0. Particle size reduction in Ca1-xYxMnO3 retains the bulk-like magnetic behavior of samples having up to 15% of Y3+, with the sma...

  20. Enema reduction of intussusception: the success rate of hydrostatic and pneumatic reduction.

    Science.gov (United States)

    Khorana, Jiraporn; Singhavejsakul, Jesda; Ukarapol, Nuthapong; Laohapensang, Mongkol; Wakhanrittee, Junsujee; Patumanond, Jayanton

    2015-01-01

    Intussusception is a common surgical emergency in infants and children. The incidence of intussusception is from one to four per 2,000 infants and children. If there is no peritonitis, perforation sign on abdominal radiographic studies, and nonresponsive shock, nonoperative reduction by pneumatic or hydrostatic enema can be performed. The purpose of this study was to compare the success rates of both the methods. Two institutional retrospective cohort studies were performed. All intussusception patients (ICD-10 code K56.1) who had visited Chiang Mai University Hospital and Siriraj Hospital from January 2006 to December 2012 were included in the study. The data were obtained by chart reviews and electronic databases, which included demographic data, symptoms, signs, and investigations. The patients were grouped according to the method of reduction followed into pneumatic reduction and hydrostatic reduction groups with the outcome being the success of the reduction technique. One hundred and seventy episodes of intussusception occurring in the patients of Chiang Mai University Hospital and Siriraj Hospital were included in this study. The success rate of pneumatic reduction was 61% and that of hydrostatic reduction was 44% (P=0.036). Multivariable analysis and adjusting of the factors by propensity scores were performed; the success rate of pneumatic reduction was 1.48 times more than that of hydrostatic reduction (P=0.036, 95% confidence interval [CI] =1.03-2.13). Both pneumatic and hydrostatic reduction can be performed safely according to the experience of the radiologist or pediatric surgeon and hospital setting. This study showed that pneumatic reduction had a higher success rate than hydrostatic reduction.

  1. Reductant-dependent electron distribution among redox sites of laccase

    DEFF Research Database (Denmark)

    Farver, O; Goldberg, M; Wherland, S

    1978-01-01

    Rhus laccase (monophenol monooxygenase, monophenol,dihydroxyphenylalanine:oxygen oxidoreductase, EC 1.14.18.1) an O2/H2O oxidoreductase containing four copper ions bound to three redox sites (type 1, type 2, and type 3 Cu pair), was titrated anaerobically with several reductants having various ch...

  2. Demonstration of electronic pattern switching and 10x pattern demagnification in a maskless micro-ion beam reduction lithography system

    International Nuclear Information System (INIS)

    Ngo, V.V.; Akker, B.; Leung, K.N.; Noh, I.; Scott, K.L.; Wilde, S.

    2002-01-01

    A proof-of-principle ion projection lithography (IPL) system called Maskless Micro-ion beam Reduction Lithography (MMRL) has been developed and tested at the Lawrence Berkeley National Laboratory (LBNL) for future integrated circuits (ICs) manufacturing and thin film media patterning [1]. This MMRL system is aimed at completely eliminating the first stage of the conventional IPL system [2] that contains the complicated beam optics design in front of the stencil mask and the mask itself. It consists of a multicusp RF plasma generator, a multi-beamlet pattern generator, and an all-electrostatic ion optical column. Results from ion beam exposures on PMMA and Shipley UVII-HS resists using 75 keV H+ are presented in this paper. Proof-of-principle electronic pattern switching together with 10x reduction ion optics (using a pattern generator made of nine 50-(micro)m switchable apertures) has been performed and is reported in this paper. In addition, the fabrication of a micro-fabricated pattern generator [3] on an SOI membrane is also presented

  3. Pulse radiolysis study of the reduction mechanism of an antitumor antibiotic, mitomycin C

    International Nuclear Information System (INIS)

    Machtalere, G.; Houee-Levin, C.; Gardes-Albert, M.; Ferradini, C.; Hickel, B.

    1988-01-01

    Mitomycin C is a quinonic antitumor metabolized in vivo by one-electron reduction. We have studied the mechanism of the one-electron reduction of this drug by pulse radiolysis using C00 .- free radicals as reductants. Semiquinonic and hydroquinonic intermediates are formed. The hydroquinonic form undergoes a methanol elimination leading to a transient which can disappear in one of two ways: by either internal redox reaction or hydrolysis of the aziridine. 17 refs [fr

  4. Electrochemical reduction of oxygen on gold and boron-doped diamond electrodes in ambient temperature, molten acetamide-urea-ammonium nitrate eutectic melt

    International Nuclear Information System (INIS)

    Dilimon, V.S.; Venkata Narayanan, N.S.; Sampath, S.

    2010-01-01

    The electrochemical reduction of oxygen has been studied on gold, boron-doped diamond (BDD) and glassy carbon (GC) electrodes in a ternary eutectic mixture of acetamide (CH 3 CONH 2 ), urea (NH 2 CONH 2 ) and ammonium nitrate (NH 4 NO 3 ). Cyclic voltammetry (CV), differential pulse voltammetry (DPV), chronoamperometry and rotating disk electrode (RDE) voltammetry techniques have been employed to follow oxygen reduction reaction (ORR). The mechanism for the electrochemical reduction of oxygen on polycrystalline gold involves 2-step, 2-electron pathways of O 2 to H 2 O 2 and further reduction of H 2 O 2 to H 2 O. The first 2-electron reduction of O 2 to H 2 O 2 passes through superoxide intermediate by 1-electron reduction of oxygen. Kinetic results suggest that the initial 1-electron reduction of oxygen to HO 2 is the rate-determining step of ORR on gold surfaces. The chronoamperometric and RDE studies show a potential dependent change in the number of electrons on gold electrode. The oxygen reduction reaction on boron-doped diamond (BDD) seems to proceed via a direct 4-electron process. The reduction of oxygen on the glassy carbon (GC) electrode is a single step, irreversible, diffusion limited 2-electron reduction process to peroxide.

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

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Chenju, E-mail: cliang@nchu.edu.tw [Department of Environmental Engineering, National Chung Hsing University 250, Kuo-kuang Road, Taichung 402, Taiwan (China); Lin, Ya-Ting [Department of Environmental Engineering, Chung Yuan Christian University, 200 Chung Pei Road, Chung Li District, Taoyuan City 320, Taiwan (China); Shiu, Jia-Wei [Department of Environmental Engineering, National Chung Hsing University 250, Kuo-kuang Road, Taichung 402, Taiwan (China)

    2016-01-25

    Highlights: • Alkaline ascorbic acid (a.k.a. vitamin C) is capable of reductively degrading NB. • The pH above the pK{sub a2} of ascorbic acid increases reductive electron transfer to NB. • The rate equation for the reactions between NB and AA is determined. • NSB, AZOXY, and AZO are identified as intermediates and aniline as a final product. • Alkaline pH is essential for AA remediation of NB contaminated soils. - Abstract: Alkaline ascorbic acid (AA) exhibits the potential to reductively degrade nitrobenzene (NB), which is the simplest of the nitroaromatic compounds. The nitro group (NO{sub 2}{sup −}) 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 pK{sub a2} 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{sup −4} mM{sup 1−(a} {sup +} {sup b)} h{sup −1}) × [NB]{sup a} {sup =} {sup 1.35} {sup ±} {sup 0.10}[AA]{sup b} {sup =} {sup 0.89} {sup ±} {sup 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.

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

    Science.gov (United States)

    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

  7. Reduction of uranium(IV) and its mixtures with an olefin or an alkyne in tetrahydrofuran solutions by solvated electrons

    International Nuclear Information System (INIS)

    Koulkes-Pujo, A.M.; Le Marechal, J.F.; Le Motais, B.; Folcher, G.

    1985-01-01

    The reduction of UCl 4 and its mixtures with different olefins (stilbene, St, diphenylethylene, DPE, acenaphtylene, Ac or with diphenylacetylene (DPA) was studied by pulse radiolysis of tetrahydrofuran (THF) solutions. U(III) was formed by U(IV) reaction either with the solvated electrons created by THF radiolysis or with the transitory anions St - and DPA - . In the latter case, the reaction proceeds via a first step leading to [St-U(IV)] - or [DPA-U(IV)] - . In the case of DPE - the first species, [DPE-U(IV)] - , does not lead to U(III) but is destroyed by THF(H) + giving DPE(H). and U(IV). Ac - does not react with U(IV). A mechanistic scheme of this electron attachment is discussed as well as its implication in catalytic hydrogenation of olefins in LiAlH 4 -UCl 4 solutions. It is concluded that the catalytic effect observed is rather the result of a hydride transfer from a uranium transient compound to the alkenes. 22 references, 8 figures, 1 table

  8. Reduction of U(VI) and Toxic Metals by Desulfovibrio Cytochrome C3

    Energy Technology Data Exchange (ETDEWEB)

    Wall, Judy D

    2013-04-11

    The central objective of our proposed research was twofold: 1) to investigate the structure-function relationship of Desulfovibrio desulfuricans (now Desulfovibrio alaskensis G20) cytochrome c3 with uranium and 2) to elucidate the mechanism for uranium reduction in vitro and in vivo. Physiological analysis of a mutant of D. desulfuricans with a mutation of the gene encoding the type 1 tetraheme cytochrome c3 had demonstrated that uranium reduction was negatively impacted while sulfate reduction was not if lactate were the electron donor. This was thought to be due to the presence of a branched pathway of electron flow from lactate leading to sulfate reduction. Our experimental plan was to elucidate the structural and mechanistic details of uranium reduction involving cytochrome c3.

  9. Reduction in unnecessary red blood cell folate testing by restricting computerized physician order entry in the electronic health record.

    Science.gov (United States)

    MacMillan, Thomas E; Gudgeon, Patrick; Yip, Paul M; Cavalcanti, Rodrigo B

    2018-05-02

    Red blood cell folate is a laboratory test with limited clinical utility. Previous attempts to reduce physician ordering of unnecessary laboratory tests, including folate, have resulted in only modest success. The objective of this study was to assess the effectiveness and impacts of restricting red blood cell folate ordering in the electronic health record. This was a retrospective observational study from January 2010 to December 2016 at a large academic healthcare network in Toronto, Canada. All inpatients and outpatients who underwent at least 1 red blood cell folate or vitamin B12 test during the study period were included. Red blood cell folate ordering was restricted to clincians in gastroenterology and hematology and was removed from other physicians' computerized order entry screen in the electronic health record in June 2013. Red blood cell folate testing decreased by 94.4% during the study, from a mean of 493.0 (SD 48.0) tests/month before intervention to 27.6 (SD 10.3) tests/month after intervention (P<.001). Restricting red blood cell folate ordering in the electronic health record resulted in a large and sustained reduction in red blood cell folate testing. Significant cost savings estimated at over a quarter-million dollars (CAD) over three years were achieved. There was no significant clinical impact of the intervention on the diagnosis of folate deficiency. Copyright © 2018. Published by Elsevier Inc.

  10. Studies Of Oxidation And Thermal Reduction Of The Cu(100) Surface Using Positron Annihilation Induced Auger Electron Spectroscopy

    Science.gov (United States)

    Fazleev, N. G.; Nadesalingam, M. P.; Maddox, W.; Weiss, A. H.

    2011-06-01

    Positron annihilation induced Auger electron spectroscopy (PAES) measurements from the surface of an oxidized Cu(100) single crystal show a large increase in the intensity of the annihilation induced Cu M2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 °C. The PAES intensity then decreases monotonically as the annealing temperature is increased to ˜550 °C. Experimental positron annihilation probabilities with Cu 3p and O 1s core electrons are estimated from the measured intensities of the positron annihilation induced Cu M2,3VV and O KLL Auger transitions. PAES results are analyzed by performing calculations of positron surface states and annihilation probabilities of the surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface and various surface structures associated with low and high oxygen coverages. The variations in atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface are found to affect localization and spatial extent of the positron surface state wave function. The computed positron binding energy and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface. Theoretical positron annihilation probabilities with Cu 3p and O 1s core electrons computed for the oxidized Cu(100) surface are compared with experimental ones. The obtained results provide a demonstration of thermal reduction of the copper oxide surface after annealing at 300 °C followed by re-oxidation of the Cu(100) surface at higher annealing temperatures presumably due to diffusion of subsurface oxygen to the surface.

  11. Studies Of Oxidation And Thermal Reduction Of The Cu(100) Surface Using Positron Annihilation Induced Auger Electron Spectroscopy

    International Nuclear Information System (INIS)

    Fazleev, N. G.; Nadesalingam, M. P.; Maddox, W.; Weiss, A. H.

    2011-01-01

    Positron annihilation induced Auger electron spectroscopy (PAES) measurements from the surface of an oxidized Cu(100) single crystal show a large increase in the intensity of the annihilation induced Cu M2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 deg. C. The PAES intensity then decreases monotonically as the annealing temperature is increased to ∼550 deg. C. Experimental positron annihilation probabilities with Cu 3p and O 1s core electrons are estimated from the measured intensities of the positron annihilation induced Cu M 2,3 VV and O KLL Auger transitions. PAES results are analyzed by performing calculations of positron surface states and annihilation probabilities of the surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface and various surface structures associated with low and high oxygen coverages. The variations in atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface are found to affect localization and spatial extent of the positron surface state wave function. The computed positron binding energy and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface. Theoretical positron annihilation probabilities with Cu 3p and O 1s core electrons computed for the oxidized Cu(100) surface are compared with experimental ones. The obtained results provide a demonstration of thermal reduction of the copper oxide surface after annealing at 300 deg. C followed by re-oxidation of the Cu(100) surface at higher annealing temperatures presumably due to diffusion of subsurface oxygen to the surface.

  12. Preparation of hafnium metal by calciothermic reduction of HfO2

    International Nuclear Information System (INIS)

    Sharma, I.G.; Vijay, P.L.; Sehra, J.C.; Sundaram, C.V.

    1975-01-01

    Hafnium metal powder has been produced by the calciothermic reduction of hafnium oxide. The influence of various experimental parameters - such as amount of calcium in excess of stoichiometric requirement, temperature, and time of reduction - on the yield and purity of the metal has been studied. The metal powder obtained by reduction at 960 0 C (two hours) with a calcium excess of 70% analysed 600 ppm of oxygen and 147 ppm of nitrogen. A reduction efficiency of 96% has been achieved under these conditions. The refining of the powder by electron beam melting, fused salt electrolysis, and iodide process has been studied. The oxygen content in the metal could be brought down from 6900 to 148 ppm by electron beam melt-refining. (author)

  13. Increased Patient Satisfaction and a Reduction in Pre-Analytical Errors Following Implementation of an Electronic Specimen Collection Module in Outpatient Phlebotomy.

    Science.gov (United States)

    Kantartjis, Michalis; Melanson, Stacy E F; Petrides, Athena K; Landman, Adam B; Bates, David W; Rosner, Bernard A; Goonan, Ellen; Bixho, Ida; Tanasijevic, Milenko J

    2017-08-01

    Patient satisfaction in outpatient phlebotomy settings typically depends on wait time and venipuncture experience, and many patients equate their experiences with their overall satisfaction with the hospital. We compared patient service times and preanalytical errors pre- and postimplementation of an integrated electronic health record (EHR)-laboratory information system (LIS) and electronic specimen collection module. We also measured patient wait time and assessed patient satisfaction using a 5-question survey. The percentage of patients waiting less than 10 minutes increased from 86% preimplementation to 93% postimplementation of the EHR-LIS (P ≤.001). The median total service time decreased significantly, from 6 minutes (IQR, 4-8 minutes), to 5 minutes (IQR, 3-6 minutes) (P = .005). The preanalytical errors decreased significantly, from 3.20 to 1.93 errors per 1000 specimens (P ≤.001). Overall patient satisfaction improved, with an increase in excellent responses for all 5 questions (P ≤.001). We found several benefits of implementing an electronic specimen collection module, including decreased wait and service times, improved patient satisfaction, and a reduction in preanalytical errors. © American Society for Clinical Pathology, 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com

  14. Electronic prescribing reduces prescribing error in public hospitals.

    Science.gov (United States)

    Shawahna, Ramzi; Rahman, Nisar-Ur; Ahmad, Mahmood; Debray, Marcel; Yliperttula, Marjo; Declèves, Xavier

    2011-11-01

    To examine the incidence of prescribing errors in a main public hospital in Pakistan and to assess the impact of introducing electronic prescribing system on the reduction of their incidence. Medication errors are persistent in today's healthcare system. The impact of electronic prescribing on reducing errors has not been tested in developing world. Prospective review of medication and discharge medication charts before and after the introduction of an electronic inpatient record and prescribing system. Inpatient records (n = 3300) and 1100 discharge medication sheets were reviewed for prescribing errors before and after the installation of electronic prescribing system in 11 wards. Medications (13,328 and 14,064) were prescribed for inpatients, among which 3008 and 1147 prescribing errors were identified, giving an overall error rate of 22·6% and 8·2% throughout paper-based and electronic prescribing, respectively. Medications (2480 and 2790) were prescribed for discharge patients, among which 418 and 123 errors were detected, giving an overall error rate of 16·9% and 4·4% during paper-based and electronic prescribing, respectively. Electronic prescribing has a significant effect on the reduction of prescribing errors. Prescribing errors are commonplace in Pakistan public hospitals. The study evaluated the impact of introducing electronic inpatient records and electronic prescribing in the reduction of prescribing errors in a public hospital in Pakistan. © 2011 Blackwell Publishing Ltd.

  15. PIC simulation of the electron-ion collision effects on suprathermal electrons

    International Nuclear Information System (INIS)

    Wu Yanqing; Han Shensheng

    2000-01-01

    The generation and transportation of suprathermal electrons are important to both traditional ICF scheme and 'Fast Ignition' scheme. The author discusses the effects of electron-ion collision on the generation and transportation of the suprathermal electrons by parametric instability. It indicates that the weak electron-ion term in the PIC simulation results in the enhancement of the collisional absorption and increase of the hot electron temperature and reduction in the maximum electrostatic field amplitude while wave breaking. Therefore the energy and distribution of the suprathermal electrons are changed. They are distributed more close to the phase velocity of the electrostatic wave than the case without electron-ion collision term. The electron-ion collision enhances the self-consistent field and impedes the suprathermal electron transportation. These factors also reduce the suprathermal electron energy. In addition, the authors discuss the effect of initial condition on PIC simulation to ensure that the results are correct

  16. Knorr-Rabe partial reduction of pyrroles: Application to the synthesis of indolizidine alkaloids

    Directory of Open Access Journals (Sweden)

    Ryan John H

    2008-01-01

    Full Text Available Abstract Background The Birch reduction of electron rich pyrroles does not occur readily. However, dissolving metal reduction with zinc under acidic conditions gives 3-pyrrolines (2,5-dihydropyrroles in reasonable yield. This dissolving metal reduction was first reported by Knorr and Rabe in 1901 but since then has only been reported for the reduction of electron rich pyrroles. Results The partial reduction of bicyclic α-ketopyrrole derivatives has been performed under dissolving metal conditions with zinc and hydrochloric acid to give excellent yields of hexahydroindolizidines. This reduction method has been utilised for the diastereoselective synthesis of 5-alkylindolizidines and the stereoselectivity obtained is opposite to that of catalytic hydrogenation. Conclusion An efficient stereoselective synthesis of indolizidine alkaloids has been developed from α-ketopyrrole intermediates using a modified version of Knorr and Rabe's pyrrole reduction.

  17. Electronic noise in CT detectors: Impact on image noise and artifacts.

    Science.gov (United States)

    Duan, Xinhui; Wang, Jia; Leng, Shuai; Schmidt, Bernhard; Allmendinger, Thomas; Grant, Katharine; Flohr, Thomas; McCollough, Cynthia H

    2013-10-01

    The objective of our study was to evaluate in phantoms the differences in CT image noise and artifact level between two types of commercial CT detectors: one with distributed electronics (conventional) and one with integrated electronics intended to decrease system electronic noise. Cylindric water phantoms of 20, 30, and 40 cm in diameter were scanned using two CT scanners, one equipped with integrated detector electronics and one with distributed detector electronics. All other scanning parameters were identical. Scans were acquired at four tube potentials and 10 tube currents. Semianthropomorphic phantoms were scanned to mimic the shoulder and abdominal regions. Images of two patients were also selected to show the clinical values of the integrated detector. Reduction of image noise with the integrated detector depended on phantom size, tube potential, and tube current. Scans that had low detected signal had the greatest reductions in noise, up to 40% for a 30-cm phantom scanned using 80 kV. This noise reduction translated into up to 50% in dose reduction to achieve equivalent image noise. Streak artifacts through regions of high attenuation were reduced by up to 45% on scans obtained using the integrated detector. Patient images also showed superior image quality for the integrated detector. For the same applied radiation level, the use of integrated electronics in a CT detector showed a substantially reduced level of electronic noise, resulting in reductions in image noise and artifacts, compared with detectors having distributed electronics.

  18. Synthesis of carbon nanorods by reduction of carbon bisulfide

    International Nuclear Information System (INIS)

    Lou Zhengsong; He Minglong; Zhao Dejian; Li Zhongchun; Shang Tongming

    2010-01-01

    Research highlights: Our manuscript is a concise preliminary account of original and of significant research, which illuminates carbon nanorods and variously shaped Y-junction carbon nanorods are successfully fabricated on a large scale through a carbon bisulfide thermal reduction process. Various shaped Y-junction carbon nanorods can be used as studying the electronic and transport properties of the nano-meter carbon material. - Abstract: Carbon nanorods are synthesized at large scale by the reduction of carbon bisulfide at 600 o C. Moreover, novel Y-junction carbon nanorods are detected in the samples. The X-ray power diffraction pattern indicates that the products are hexagonal graphite. Scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy and N 2 physisorption studies show that carbon nanorods predominate in the product. Based on the supercritical carbon bisulfide system, the possible growth mechanism of the carbon nanorods was discussed. This method provides a simple and cheap route to large-scale synthesis of carbon nanorods.

  19. TH-CD-202-02: A Preliminary Study Evaluating Beam-Hardening Artifact Reduction On CT Direct Electron-Density Images

    Energy Technology Data Exchange (ETDEWEB)

    Li, H; Dolly, S; Zhao, T; Anastasio, M; Mutic, S [Washington University School of Medicine, Saint Louis, MO (United States); Ritter, A; Colombo, V; Raupach, R; Huenemohr, N [Siemens Healthcare GmbH, Deutschland (Germany); Mistry, N [Siemens Medical Solutions USA, Malvern, PA (United States); Yu, L [Mayo Clinic, Rochester, MN (United States)

    2016-06-15

    Purpose: A prototype reconstruction algorithm that can provide direct electron density (ED) images from single energy CT scans is being currently developed by Siemens Healthcare GmbH. This feature can eliminate the need for kV specific calibration curve for radiation treatemnt planning. An added benefit is that beam-hardening artifacts are also reduced on direct-ED images due to the underlying material decomposition. This study is to quantitatively analyze the reduction of beam-hardening artifacts on direct-ED images and suggest additional clinical usages. Methods: HU and direct-ED images were reconstructed on a head phantom scanned on a Siemens Definition AS CT scanner at five tube potentials of 70kV, 80kV, 100kV, 120kV and 140kV respectively. From these images, mean, standard deviation (SD), and local NPS were calculated for regions of interest (ROI) of same locations and sizes. A complete analysis of beam-hardening artifact reduction and image quality improvement was conducted. Results: Along with the increase of tube potentials, ROI means and SDs decrease on both HU and direct-ED images. The mean value differences between HU and direct-ED images are up to 8% with absolute value of 2.9. Compared to that on HU images, the SDs are lower on direct-ED images, and the differences are up to 26%. Interestingly, the local NPS calculated from direct-ED images shows consistent values in the low spatial frequency domain for images acquired from all tube potential settings, while varied dramatically on HU images. This also confirms the beam -hardening artifact reduction on ED images. Conclusions: The low SDs on direct-ED images and relative consistent NPS values in the low spatial frequency domain indicate a reduction of beam-hardening artifacts. The direct-ED image has the potential to assist in more accurate organ contouring, and is a better fit for the desired purpose of CT simulations for radiotherapy.

  20. Menadione-mediated WST1 reduction assay for the determination of metabolic activity of cultured neural cells.

    Science.gov (United States)

    Stapelfeldt, Karsten; Ehrke, Eric; Steinmeier, Johann; Rastedt, Wiebke; Dringen, Ralf

    2017-12-01

    Cellular reduction of tetrazolium salts to their respective formazans is frequently used to determine the metabolic activity of cultured cells as an indicator of cell viability. For membrane-impermeable tetrazolium salts such as WST1 the application of a membrane-permeable electron cycler is usually required to mediate the transfer of intracellular electrons for extracellular WST1 reduction. Here we demonstrate that in addition to the commonly used electron cycler M-PMS, menadione can also serve as an efficient electron cycler for extracellular WST1 reduction in cultured neural cells. The increase in formazan absorbance in glial cell cultures for the WST1 reduction by menadione involves enzymatic menadione reduction and was twice that recorded for the cytosolic enzyme-independent WST1 reduction in the presence of M-PMS. The optimized WST1 reduction assay allowed within 30 min of incubation a highly reliable detection of compromised cell metabolism caused by 3-bromopyruvate and impaired membrane integrity caused by Triton X-100, with a sensitivity as good as that of spectrophotometric assays which determine cellular MTT reduction or lactate dehydrogenase release. The short incubation period of 30 min and the observed good sensitivity make this optimized menadione-mediated WST1 reduction assay a quick and reliable alternative to other viability and toxicity assays. Copyright © 2017 Elsevier Inc. All rights reserved.

  1. Applications of time-dependent Raman scattering theory to the one-electron reduction of 4-cyano-n-methylpyridinium

    International Nuclear Information System (INIS)

    Johnson, C.S.

    1992-01-01

    Activation barrier heights, and therefore rates, for molecule-based electron-transfer (ET) reactions are governed by redox thermodynamics and Frank-Condon effects. Quantitative assessment of the latter requires a detailed, quantitative knowledge of all internal and external normal-coordinate displacements, together with appropriate vibrational frequencies (v) or force constants (f). In favorable cases, the desire internal or vibrational displacement information can be satisfactorily estimated from redox-induced bond-length changes as provided, for example, by x-ray crystallography or extended x-ray absorption fine structure (EXAFS) measurements. Other potentially useful methods include Franck-Condon analysis of structured emission or absorption spectra, hole burning techniques, and application of empirical structure/frequency relationships (E.g., Badger's rules). There are, however, a number of limitations. The most obvious limitations for crystallography are that measurements can be made only in a crystalline environment and that experiments cannot be done on short-lived electron-transfer excited states or on systems which suffer from chemical decomposition following oxidation or reduction. For EXAFS there are additional constrains in that only selected elements display useful scattering and only atoms in close proximity to the scattering center may be detected. This report contains the first successful applications of the Raman methodology to a much larger class of ET reactions, namely, outer-sphere reactions. The report also necessarily represents the first application to a monomeric redox system

  2. Reduction of angular spread at nonadiabatic electron motion in magnetically insulated diode

    Energy Technology Data Exchange (ETDEWEB)

    Arzhannikov, A V; Sinitskij, S L [Institute of Nuclear Physics, Novosibirsk (Russian Federation)

    1997-12-31

    The behavior of the electron pitch-angle was investigated by analytical and numerical methods for the case of a magnetically insulated diode with a ribbon geometry. It is shown that at the boundary of the adiabaticity of the electron motion the angle can be multiply reduced by choice of a special inhomogeneity of the magnetic field. Analytic expressions for the final pitch-angle of the beam electrons are given. (author). 2 figs., 3 refs.

  3. Periplasmic Cytochrome c(3) of Desulfovibrio vulgaris Is Directly Involved in H2-Mediated Metal but Not Sulfate Reduction

    International Nuclear Information System (INIS)

    Elias, Dwayne A.; Suflita, Joseph M.; McInerney, Michael J.; Krumholz, Lee R.

    2004-01-01

    Kinetic parameters and the role of cytochrome c3 in sulfate, Fe(III), and U(VI) reduction were investigated in Desulfovibrio vulgaris Hildenborough. While sulfate reduction followed Michaelis-Menten kinetics (Km 220 uM), loss of Fe(III) and U(VI) was first-order at all concentrations tested. Initial reduction rates of all electron acceptors were similar for cells grown with H2 and sulfate, while cultures grown using lactate and sulfate had similar rates of metal loss but lower sulfate reduction activities. The similarities in metal, but not sulfate, reduction with H2 and lactate suggest divergent pathways. Respiration assays and reduced minus oxidized spectra were carried out to determine c-type cytochrome involvement in electron acceptor reduction. c-type cytochrome oxidation was immediate with Fe(III) and U(VI) in the presence of H2, lactate, or pyruvate. Sulfidogenesis occurred with all three electron donors and effectively oxidized the c-type cytochrome in lactate or pyruvate-reduced, but not H2-reduced cells. Correspondingly, electron acceptor competition assays with lactate or pyruvate as electron donors showed that Fe(III) inhibited U(VI) reduction, and U(VI) inhibited sulfate loss. However, sulfate reduction was slowed but not halted when H2 was the electron donor in the presence of Fe(III) or U(VI). U(VI) loss was still impeded by Fe(III) when H2 was used. Hence, we propose a modified pathway for the reduction of sulfate, Fe(III), and U(VI) which helps explain why these bacteria cannot grow using these metals. We further propose that cytochrome c3 is an electron carrier involved in lactate and pyruvate oxidation and is the reductase for alternate electron acceptors with higher redox potentials than sulfate

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

    Science.gov (United States)

    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.

  5. Special raster scanning for reduction of charging effects in scanning electron microscopy.

    Science.gov (United States)

    Suzuki, Kazuhiko; Oho, Eisaku

    2014-01-01

    A special raster scanning (SRS) method for reduction of charging effects is developed for the field of SEM. Both a conventional fast scan (horizontal direction) and an unusual scan (vertical direction) are adopted for acquiring raw data consisting of many sub-images. These data are converted to a proper SEM image using digital image processing techniques. About sharpness of the image and reduction of charging effects, the SRS is compared with the conventional fast scan (with frame-averaging) and the conventional slow scan. Experimental results show the effectiveness of SRS images. By a successful combination of the proposed scanning method and low accelerating voltage (LV)-SEMs, it is expected that higher-quality SEM images can be more easily acquired by the considerable reduction of charging effects, while maintaining the resolution. © 2013 Wiley Periodicals, Inc.

  6. Benzene degradation coupled with chlorate reduction in soil column study

    NARCIS (Netherlands)

    Tan, N.C.G.; Doesburg, van W.C.J.; Langenhoff, A.A.M.; Stams, A.J.M.

    2006-01-01

    Perchlorate and chlorate are electron acceptors that during reduction result in the formation of molecular oxygen. The produced oxygen can be used for activation of anaerobic persistent pollutants, like benzene. In this study chlorate was tested as potential electron acceptor to stimulate benzene

  7. Bioelectrochemical ethanol production through mediated acetate reduction by mixed cultures.

    Science.gov (United States)

    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.

  8. Optical absorption of copper met-myoglobin complexes

    International Nuclear Information System (INIS)

    Lamy, M.T.; Ribeiro, P.C.; Nascimento, O.R.; Bemski, G.

    1976-01-01

    It is reported on the use of a known denaturing agent, namely Cu 2+ ions, to induce a gradual change in the optical spectrum of Mb solutions, in order to identify the absorption bands that undergo similar changes which may be attributed to the transitions between correlated energy levels [pt

  9. System reduction for nanoscale IC design

    CERN Document Server

    2017-01-01

    This book describes the computational challenges posed by the progression toward nanoscale electronic devices and increasingly short design cycles in the microelectronics industry, and proposes methods of model reduction which facilitate circuit and device simulation for specific tasks in the design cycle. The goal is to develop and compare methods for system reduction in the design of high dimensional nanoelectronic ICs, and to test these methods in the practice of semiconductor development. Six chapters describe the challenges for numerical simulation of nanoelectronic circuits and suggest model reduction methods for constituting equations. These include linear and nonlinear differential equations tailored to circuit equations and drift diffusion equations for semiconductor devices. The performance of these methods is illustrated with numerical experiments using real-world data. Readers will benefit from an up-to-date overview of the latest model reduction methods in computational nanoelectronics.

  10. Inhibition of bacterial U(VI) reduction by calcium

    International Nuclear Information System (INIS)

    Brooks, Scott C.; Fredrickson, Jim K.; Carroll, S. L.; Kennedy, David W.; Zachara, John M.; Plymale, Andrew E.; Kelly, S. D.; Kemner, K. M.; Fendorf, S.

    2003-01-01

    The rapid kinetics of bacterial U(VI) reduction and low solubility of uraninite (UO2,cr) make this process an attractive option for removing uranium from groundwater. Nevertheless, conditions that may promote or inhibit U(VI) reduction are not well-defined. Recent descriptions of Ca-UO2-CO3 complexes indicate that these species may dominate the aqueous speciation of U(VI) in many environments. We monitored the bacterial reduction of U(VI) in bicarbonate-buffered solution in the presence and absence of Ca. XAFS measurements confirmed the presence of a Ca-U(VI)-CO3 complex in the initial solutions containing calcium. Calcium, at millimolar concentrations (0.45-5 mM), caused a significant decrease in the rate and extent of bacterial U(VI) reduction. Both facultative (Shewanella putrefaciens strain CN32) and obligate (Desulfovibrio desulfuricans, Geobacter sulfurreducens) anaerobic bacteria were affected by the presence of calcium. Reduction of U(VI) ceased when the calculated system Eh re ached -0.046+/- 0.001 V, based on the Ca2UO2(CO3)(3) -- > UO2,cr couple. The results are consistent with the hypothesis that U is a less energetically favorable electron acceptor when the Ca-UO2-CO3 complexes are present. The results do not support Ca inhibition caused by direct interactions with the cells or with the electron donor as the reduction of fumarate or Tc(VII)O-4(-) under identical conditions was unaffected by the presence of Ca

  11. Susceptibility of murine norovirus and hepatitis A virus to electron beam irradiation in oysters and quantifying the reduction in potential infection risks.

    Science.gov (United States)

    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.

  12. Reduction of heavy metals in residues from the dismantling of waste electrical and electronic equipment before incineration

    International Nuclear Information System (INIS)

    Long, Yu-Yang; Feng, Yi-Jian; Cai, Si-Shi; Hu, Li-Fang; Shen, Dong-Sheng

    2014-01-01

    Highlights: • The highest metal reduction occurs at a 2.36 mm sieving size. • Washing promotes heavy metal recycling without secondary pollution. • Sieving and washing are environmentally friendly pretreatments for WEEE wastes. - Abstract: Residues disposal from the dismantling of waste electrical and electronic equipment are challenging because of the large waste volumes, degradation-resistance, low density and high heavy metal content. Incineration is advantageous for treating these residues but high heavy metal contents may exist in incinerator input and output streams. We have developed and studied a specialized heavy metal reduction process, which includes sieving and washing for treating residues before incineration. The preferable screen aperture for sieving was found to be 2.36 mm (8 meshes) in this study; using this screen aperture resulted in the removal of approximately 47.2% Cu, 65.9% Zn, 26.5% Pb, 55.4% Ni and 58.8% Cd from the residues. Subsequent washing further reduces the heavy metal content in the residues larger than 2.36 mm, with preferable conditions being 400 rpm rotation speed, 5 min washing duration and liquid-to-solid ratio of 25:1. The highest cumulative removal efficiencies of Cu, Zn, Pb, Ni and Cd after sieving and washing reached 81.1%, 61.4%, 75.8%, 97.2% and 72.7%, respectively. The combined sieving and washing process is environmentally friendly, can be used for the removal of heavy metals from the residues and has benefits in terms of heavy metal recycling

  13. Reduction of heavy metals in residues from the dismantling of waste electrical and electronic equipment before incineration

    Energy Technology Data Exchange (ETDEWEB)

    Long, Yu-Yang; Feng, Yi-Jian; Cai, Si-Shi [Zhejiang Provincial Key Laboratory of Solid Waste Treatment and Recycling, School of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310012 (China); Hu, Li-Fang [College of Quality and Safety Engineering, China Jiliang University, Hangzhou 310018 (China); Shen, Dong-Sheng, E-mail: shends@zju.edu.cn [Zhejiang Provincial Key Laboratory of Solid Waste Treatment and Recycling, School of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310012 (China)

    2014-05-01

    Highlights: • The highest metal reduction occurs at a 2.36 mm sieving size. • Washing promotes heavy metal recycling without secondary pollution. • Sieving and washing are environmentally friendly pretreatments for WEEE wastes. - Abstract: Residues disposal from the dismantling of waste electrical and electronic equipment are challenging because of the large waste volumes, degradation-resistance, low density and high heavy metal content. Incineration is advantageous for treating these residues but high heavy metal contents may exist in incinerator input and output streams. We have developed and studied a specialized heavy metal reduction process, which includes sieving and washing for treating residues before incineration. The preferable screen aperture for sieving was found to be 2.36 mm (8 meshes) in this study; using this screen aperture resulted in the removal of approximately 47.2% Cu, 65.9% Zn, 26.5% Pb, 55.4% Ni and 58.8% Cd from the residues. Subsequent washing further reduces the heavy metal content in the residues larger than 2.36 mm, with preferable conditions being 400 rpm rotation speed, 5 min washing duration and liquid-to-solid ratio of 25:1. The highest cumulative removal efficiencies of Cu, Zn, Pb, Ni and Cd after sieving and washing reached 81.1%, 61.4%, 75.8%, 97.2% and 72.7%, respectively. The combined sieving and washing process is environmentally friendly, can be used for the removal of heavy metals from the residues and has benefits in terms of heavy metal recycling.

  14. Effect of flavin compounds on uranium(VI) reduction- kinetic study using electrochemical methods with UV-vis spectroscopy

    International Nuclear Information System (INIS)

    Yamasaki, Shinya; Tanaka, Kazuya; Kozai, Naofumi; Ohnuki, Toshihiko

    2017-01-01

    The reduction of uranium hexavalent (U(VI)) to tetravalent (U(IV)) is an important reaction because of the change in its mobility in the natural environment. Although the flavin mononucleotide (FMN) has acted as an electron shuttle for the U(VI) reduction in vivo system, which is called an electron mediator, only the rate constant for the electron transfer from FMN to U(VI) has been determined. This study examined the rate constant for the U(VI) reduction process by three flavin analogues (riboflavin, flavin mononucleotide, flavin adenine dinucleotide) to elucidate their substituent group effect on the U(VI) reduction rate by electrochemical methods. The formation of the U(IV) was monitored by UV-vis spectrometry at 660 nm during the constant potential electrolysis of the U(VI) solution in the presence of the mediator. The cyclic voltammograms indicated that the three flavin analogues behaved as electron mediator to reduce U(VI). The logarithmic rate constant for the U(VI) reduction was related to the standard redox potential of the mediators. This linear relationship indicated that the redox-active group of the mediator and the substituent group of the mediator dominate capability of the U(VI) reduction and its rate, respectively. The apparent reduction potential of U(VI) increased about 0.2 V in the presence of the mediators, which strongly suggests that the biological electron mediator makes the U(VI) reduction possible even under more oxidative conditions. - Highlights: • The rate constant for the U(VI) reduction by flavin analogues was determined. • The flavins showed a mediator effect on the U(VI) reduction. • The logarithmic rate constants for the U(VI) reduction was proportional to redox potential of the mediator. • The presence of the mediator increased about 0.2 V apparent redox potential of U(VI) to U(IV).

  15. Fast microbial reduction of ferrihydrite colloids from a soil effluent

    Science.gov (United States)

    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

  16. Reactivity of Trapped and Accumulated Electrons in Titanium Dioxide Photocatalysis

    Directory of Open Access Journals (Sweden)

    Shigeru Kohtani

    2017-10-01

    Full Text Available Electrons, photogenerated in conduction bands (CB and trapped in electron trap defects (Tids in titanium dioxide (TiO2, play crucial roles in characteristic reductive reactions. This review summarizes the recent progress in the research on electron transfer in photo-excited TiO2. Particularly, the reactivity of electrons accumulated in CB and trapped at Tids on TiO2 is highlighted in the reduction of molecular oxygen and molecular nitrogen, and the hydrogenation and dehalogenation of organic substrates. Finally, the prospects for developing highly active TiO2 photocatalysts are discussed.

  17. Secondary electron emission in nanostructured porous silicon

    Energy Technology Data Exchange (ETDEWEB)

    Ruano, G D; Ferron, J; Koropecki, R R, E-mail: gdruano@ceride.gov.a [INTEC-UNL-CONICET, Gueemes 3450 - 3000 Santa Fe (Argentina)

    2009-05-01

    We studied the reversible reduction induced by ion bombardment of the secondary electron emission (SEE) yield. This effect has been modelled as due to changes in dynamically sustained dipoles related with ions and electrons penetration ranges. Such charge configuration precludes the escape of electrons from the nanoporous silicon, making the SEE dependent on the flux of impinging ions. Since this dipolar momentum depends on the electric conduction of the porous medium, by controlled oxidation of the nanoporous structure we change the conduction features of the sample, studying the impact on the SEE reduction effect. Li ion bombardment was also used with the intention of changing the parameters determining the effect. FT-IR and Auger electron spectroscopy were used to characterize the oxidation degree of the samples at different depth scales

  18. Fullerene-catalyzed reduction of azo derivatives in water under UV irradiation

    KAUST Repository

    Guo, Yong; Li, Wengang; Yan, Jingjing; Moosa, Basem; Amad, Maan H.; Werth, Charles; Khashab, Niveen M.

    2012-01-01

    Metal-free fullerene (C60) was found to be an effective catalyst for the reduction of azo groups in basic aqueous solution under UV irradiation in the presence of NaBH4. Use of NaBH4 by itself is not sufficient to reduce the azo dyes without the assistance of a metal catalyst such as Pd and Ag. Experimental and theoretical results suggest that C 60 catalyzes this reaction by using its vacant orbital to accept the electron in the bonding orbital of azo dyes, which leads to the activation of the N=N bond. UV irradiation increases the ability of C60 to interact with electron-donor moieties in azo dyes. Filling a vacancy: Experimental and theoretical methods have been combined to show that C60-catalyzed reductions of azo compounds form aromatic amines under UV irradiation (see scheme). The obtained results show that C60 acts as an electron acceptor to catalyze the reduction of azo compounds, and the role of UV irradiation is to increase the ability of C60 to interact with electron-donor moieties in azo compounds. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Fullerene-catalyzed reduction of azo derivatives in water under UV irradiation

    KAUST Repository

    Guo, Yong

    2012-09-27

    Metal-free fullerene (C60) was found to be an effective catalyst for the reduction of azo groups in basic aqueous solution under UV irradiation in the presence of NaBH4. Use of NaBH4 by itself is not sufficient to reduce the azo dyes without the assistance of a metal catalyst such as Pd and Ag. Experimental and theoretical results suggest that C 60 catalyzes this reaction by using its vacant orbital to accept the electron in the bonding orbital of azo dyes, which leads to the activation of the N=N bond. UV irradiation increases the ability of C60 to interact with electron-donor moieties in azo dyes. Filling a vacancy: Experimental and theoretical methods have been combined to show that C60-catalyzed reductions of azo compounds form aromatic amines under UV irradiation (see scheme). The obtained results show that C60 acts as an electron acceptor to catalyze the reduction of azo compounds, and the role of UV irradiation is to increase the ability of C60 to interact with electron-donor moieties in azo compounds. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Microbiological reduction of Sb(V) in anoxic freshwater sediments

    Science.gov (United States)

    Oremland, Ronald S.; Kulp, Thomas R.; Miller, Laurence G.; Braiotta, Franco; Webb, Samuel M.; Kocar, Benjamin D; Blum, Jodi S.

    2014-01-01

    Microbiological reduction of millimolar concentrations of Sb(V) to Sb(III) was observed in anoxic sediments from two freshwater settings: (1) a Sb- and As-contaminated mine site (Stibnite Mine) in central Idaho and 2) an uncontaminated suburban lake (Searsville Lake) in the San Francisco Bay Area. Rates of Sb(V) reduction in anoxic sediment microcosms and enrichment cultures were enhanced by amendment with lactate or acetate as electron donors but not by H2, and no reduction occurred in sterilized controls. Addition of 2-14C-acetate to Stibnite Mine microcosms resulted in the production of 14CO2 coupled to Sb(V) reduction, suggesting that this process proceeds by a dissimilatory respiratory pathway in those sediments. Antimony(V) reduction in Searsville Lake sediments was not coupled to acetate mineralization and may be associated with Sb-resistance. The microcosms and enrichment cultures also reduced sulfate, and the precipitation of insoluble Sb(III)-sulfide complexes was a major sink for reduced Sb. The reduction of Sb(V) by Stibnite Mine sediments was inhibited by As(V), suggesting that As(V) is a preferred electron acceptor for the indigenous community. These findings indicate a novel pathway for anaerobic microbiological respiration and suggest that communities capable of reducing high concentrations of Sb(V) commonly occur naturally in the environment.

  1. Electrochemical reduction of graphited materials in LiClO{sub 4}-EC and LiClO{sub 4}-PC media: characterization of interface products by transmission electron microscopy; Reduction electrochimique de materiaux graphites en milieux LiCIO{sub 4}-EC et LiCIO{sub 4}-PC: caracterisation des produits d`interface par microscopie electronique a transmission

    Energy Technology Data Exchange (ETDEWEB)

    Billaud, D.; Naji, A.; Ghanbaja, J. [Universite Henri Poincare Nancy, 54 - Vandoeuvre-les-Nancy (France); Willmann, P. [Centre National d`Etudes Spatiales (CNES), 31 - Toulouse (France)

    1996-12-31

    The electrochemical intercalation of non-solvated lithium in different graphited materials has been performed in LiClO{sub 4}-ethylene carbonate (EC) medium. The irreversible capacity observed during the first output is mainly due to the formation of a passivation layer made of electrolyte reduction products. These products have been characterized for different electrode reduction potentials using transmission electron microscopy (image, diffraction) and electron energy loss spectroscopy (EELS). EC reduction on the electrode surface in presence of LiClO{sub 4} leads to the formation of Li{sub 2}CO{sub 3} for potentials close to 0.8 V vs Li{sup +}/Li. For lower potentials, the electrolyte reduction reaction goes on with the formation of different lithium alkyl-carbonates. In LiClO{sub 4}-propylene carbonate (PC) medium, the interface phenomena are different. The reduction of a graphite electrode is characterized by the exfoliation phenomenon which hinders lithium intercalation. On the contrary, the formation of the passivation layer by graphite reduction in LiClO{sub 4}-EC medium allows the cycling of the electrode in the LiClO{sub 4}-PC electrolyte. In this case, the irreversible capacity observed during the first output depends on the experimental conditions of formation of the passivation layer. Abstract only. (J.S.)

  2. Electrochemical reduction of graphited materials in LiClO{sub 4}-EC and LiClO{sub 4}-PC media: characterization of interface products by transmission electron microscopy; Reduction electrochimique de materiaux graphites en milieux LiCIO{sub 4}-EC et LiCIO{sub 4}-PC: caracterisation des produits d`interface par microscopie electronique a transmission

    Energy Technology Data Exchange (ETDEWEB)

    Billaud, D; Naji, A; Ghanbaja, J [Universite Henri Poincare Nancy, 54 - Vandoeuvre-les-Nancy (France); Willmann, P [Centre National d` Etudes Spatiales (CNES), 31 - Toulouse (France)

    1997-12-31

    The electrochemical intercalation of non-solvated lithium in different graphited materials has been performed in LiClO{sub 4}-ethylene carbonate (EC) medium. The irreversible capacity observed during the first output is mainly due to the formation of a passivation layer made of electrolyte reduction products. These products have been characterized for different electrode reduction potentials using transmission electron microscopy (image, diffraction) and electron energy loss spectroscopy (EELS). EC reduction on the electrode surface in presence of LiClO{sub 4} leads to the formation of Li{sub 2}CO{sub 3} for potentials close to 0.8 V vs Li{sup +}/Li. For lower potentials, the electrolyte reduction reaction goes on with the formation of different lithium alkyl-carbonates. In LiClO{sub 4}-propylene carbonate (PC) medium, the interface phenomena are different. The reduction of a graphite electrode is characterized by the exfoliation phenomenon which hinders lithium intercalation. On the contrary, the formation of the passivation layer by graphite reduction in LiClO{sub 4}-EC medium allows the cycling of the electrode in the LiClO{sub 4}-PC electrolyte. In this case, the irreversible capacity observed during the first output depends on the experimental conditions of formation of the passivation layer. Abstract only. (J.S.)

  3. Electron acoustic solitary waves in a magnetized plasma with nonthermal electrons and an electron beam

    Energy Technology Data Exchange (ETDEWEB)

    Singh, S. V., E-mail: satyavir@iigs.iigm.res.in; Lakhina, G. S., E-mail: lakhina@iigs.iigm.res.in [Indian Institute of Geomagnetism, New Panvel (W), Navi Mumbai (India); University of the Western Cape, Belville (South Africa); Devanandhan, S., E-mail: devanandhan@gmail.com [Indian Institute of Geomagnetism, New Panvel (W), Navi Mumbai (India); Bharuthram, R., E-mail: rbharuthram@uwc.ac.za [University of the Western Cape, Belville (South Africa)

    2016-08-15

    A theoretical investigation is carried out to study the obliquely propagating electron acoustic solitary waves having nonthermal hot electrons, cold and beam electrons, and ions in a magnetized plasma. We have employed reductive perturbation theory to derive the Korteweg-de-Vries-Zakharov-Kuznetsov (KdV-ZK) equation describing the nonlinear evolution of these waves. The two-dimensional plane wave solution of KdV-ZK equation is analyzed to study the effects of nonthermal and beam electrons on the characteristics of the solitons. Theoretical results predict negative potential solitary structures. We emphasize that the inclusion of finite temperature effects reduces the soliton amplitudes and the width of the solitons increases by an increase in the obliquity of the wave propagation. The numerical analysis is presented for the parameters corresponding to the observations of “burst a” event by Viking satellite on the auroral field lines.

  4. Sheath and heat flow of a two-electron-temperature plasma in the presence of electron emission

    International Nuclear Information System (INIS)

    Sato, Kunihiro; Miyawaki, Fujio

    1992-01-01

    The electrostatic sheath and the heat flow of a two-electron-temperature plasma in the presence of electron emission are investigated analytically. It is shown that the energy flux is markedly enhanced to a value near the electron free-flow energy flux as a result of considerable reduction of the sheath potential due to electron emission if the fraction of hot electrons at the sheath edge is much smaller than one. If the hot- to cold-electron temperature ratio is of the order of ten and the hot electron density is comparable to the cold electron density, the action of the sheath as a thermal insulator is improved as a result of suppression of electron emission due to the space-charge effect of hot electrons. (author)

  5. Effects of mechanical activation on the carbothermal reduction of chromite with metallurgical coke

    Directory of Open Access Journals (Sweden)

    Kenan Yıldız

    2010-06-01

    Full Text Available The carbothermal reduction of mechanically activated chromite with metallurgical coke under an argon atmosphere was investigated at temperatures between 1100 and 1400°C and the effects of the mechanical activation on chromite structure were analyzed by x-ray diffraction (XRD and scanning electron microscopy (SEM. An increase in specific surface area resulted in more contact points. The activation procedure led to amorphization and structural disordering in chromite and accelerated the degree of reduction and metalization in the mixture of chromite and metallurgical coke. Carbothermal reduction products were analzed by using scanning electron microscopy (SEM/EDS.

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

    Science.gov (United States)

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

    2010-04-01

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

  7. Electron irradiation of power transistors

    International Nuclear Information System (INIS)

    Hower, P.L.; Fiedor, R.J.

    1982-01-01

    A method for reducing storage time and gain parameters in a semiconductor transistor includes the step of subjecting the transistor to electron irradiation of a dosage determined from measurements of the parameters of a test batch of transistors. Reduction of carrier lifetime by proton bombardment and gold doping is mentioned as an alternative to electron irradiation. (author)

  8. Noise reduction in the beam current monitor

    International Nuclear Information System (INIS)

    Arai, Shigeaki.

    1982-02-01

    A simple noise reduction system using a pulse transformer and a pair of L C low pass filters has been introduced to the beam current monitor of a current transformer type at the INS electron linac. With this system, the pick-up noise has been reduced to be 1% of the noise without noise reduction. Signal deformation caused by this system is relatively small and the beam current pulse down to 20 mA is successfully monitored in the actual accelerator operation. (author)

  9. Reduction and immobilization of molybdenum by Desulfovibrio desulfuricans

    Energy Technology Data Exchange (ETDEWEB)

    Tucker, M.D.; Barton, L.L.; Thomson, B.M. [Sandia National Laboratories, Albuquerque, NM (United States)

    1997-07-01

    Molybdenum contamination of groundwater occurs through activities such as molybdenum and copper mining and processing, shale oil production and power generation from coal-fired power plants. The mobility of Mo in the environment is strongly dependent on its chemical oxidation state. Under oxidizing conditions, Mo occurs as highly soluble and mobile Mo(VI) and Mo(V) compounds. However, under reducing conditions Mo usually forms insoluble Mo(IV) phases. The objective of this study was to demonstrate the ability of the sulfate-reducing bacterium, Desulfovibrio desulfuricans, to reduce Mo(IV) to Mo(IV) in anaerobic environments. Molybdenum-VI was reduced to Mo(IV) by washed cells of D. desulfuricans suspended in bicarbonate buffer solution with either lactate or H{sub 2} as the electron donor and Mo(VI) as the electron acceptor. Molybdenum-VIi reduction by D. desulfuricans in the presence of sulfide resulted in the extracelluar precipitation of the mineral molybdenite. Molybdenum-VI reduction did not occur in the absence of an electron donor or in the presence of heat-killed cells of D. desulfuricans. The results indicate that enzymatic reduction of Mo(VI) by sulfate-reducing bacteria may contribute to the accumulation of Mo(IV) in anaerobic environments and that there organisms may be useful for removing soluble Mo from contaminated water. 20 refs., 6 figs., 4 tabs.

  10. Electronic nose with a new feature reduction method and a multi-linear classifier for Chinese liquor classification

    Energy Technology Data Exchange (ETDEWEB)

    Jing, Yaqi; Meng, Qinghao, E-mail: qh-meng@tju.edu.cn; Qi, Peifeng; Zeng, Ming; Li, Wei; Ma, Shugen [Tianjin Key Laboratory of Process Measurement and Control, Institute of Robotics and Autonomous Systems, School of Electrical Engineering and Automation, Tianjin University, Tianjin 300072 (China)

    2014-05-15

    An electronic nose (e-nose) was designed to classify Chinese liquors of the same aroma style. A new method of feature reduction which combined feature selection with feature extraction was proposed. Feature selection method used 8 feature-selection algorithms based on information theory and reduced the dimension of the feature space to 41. Kernel entropy component analysis was introduced into the e-nose system as a feature extraction method and the dimension of feature space was reduced to 12. Classification of Chinese liquors was performed by using back propagation artificial neural network (BP-ANN), linear discrimination analysis (LDA), and a multi-linear classifier. The classification rate of the multi-linear classifier was 97.22%, which was higher than LDA and BP-ANN. Finally the classification of Chinese liquors according to their raw materials and geographical origins was performed using the proposed multi-linear classifier and classification rate was 98.75% and 100%, respectively.

  11. Electronic nose with a new feature reduction method and a multi-linear classifier for Chinese liquor classification

    International Nuclear Information System (INIS)

    Jing, Yaqi; Meng, Qinghao; Qi, Peifeng; Zeng, Ming; Li, Wei; Ma, Shugen

    2014-01-01

    An electronic nose (e-nose) was designed to classify Chinese liquors of the same aroma style. A new method of feature reduction which combined feature selection with feature extraction was proposed. Feature selection method used 8 feature-selection algorithms based on information theory and reduced the dimension of the feature space to 41. Kernel entropy component analysis was introduced into the e-nose system as a feature extraction method and the dimension of feature space was reduced to 12. Classification of Chinese liquors was performed by using back propagation artificial neural network (BP-ANN), linear discrimination analysis (LDA), and a multi-linear classifier. The classification rate of the multi-linear classifier was 97.22%, which was higher than LDA and BP-ANN. Finally the classification of Chinese liquors according to their raw materials and geographical origins was performed using the proposed multi-linear classifier and classification rate was 98.75% and 100%, respectively

  12. electrocatalytic reduction of oxygen at vapor phase polymerized poly ...

    African Journals Online (AJOL)

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    In all fuel cell devices, the reduction of O2 to H2O plays a critical role. The sluggish nature of the oxygen reduction reaction requires an expensive electrocatalyst like platinum. The high .... equations. The Levich equation is expressed as equation 1: ... solution is not a two electron reaction via the formation of H2O2. Similar ...

  13. Influence of Calcium on Microbial Reduction of Solid Phase Uranium (VI)

    International Nuclear Information System (INIS)

    Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M.; Wang, Zheming

    2007-01-01

    The effect of calcium on microbial reduction of a solid phase U(VI), sodium boltwoodite (NaUO2SiO3OH · 1.5H2O), was evaluated in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. Batch experiments were performed in a non-growth bicarbonate medium with lactate as electron donor at pH 7 buffered with PIPES. Calcium increased both the rate and extent of Na-boltwoodite dissolution by increasing its solubility through the formation of a ternary aqueous calcium-uranyl-carbonate species. The ternary species, however, decreased the rates of microbial reduction of aqueous U(VI). Laser-induced fluorescence spectroscopy (LIFS) and transmission electron microscopy (TEM) revealed that microbial reduction of solid phase U(VI) is a sequentially coupled process of Na-boltwoodite dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) to U(IV) that accumulated on bacterial surfaces/periplasm. The overall rates of microbial reduction of solid phase U(VI) can be described by the coupled rates of dissolution and microbial reduction that were both influenced by calcium. The results demonstrated that dissolved U(VI) concentration during microbial reduction was a complex function of solid phase U(VI) dissolution kinetics, aqueous U(VI) speciation, and microbial activity

  14. The Study of NADPH-Dependent Flavoenzyme-Catalyzed Reduction of Benzo[1,2-c]1,2,5-oxadiazole N-Oxides (Benzofuroxans

    Directory of Open Access Journals (Sweden)

    Jonas Šarlauskas

    2014-12-01

    Full Text Available The enzymatic reactivity of a series of benzo[1,2-c]1,2,5-oxadiazole N-oxides (benzofuroxans; BFXs towards mammalian single-electron transferring NADPH:cytochrome P-450 reductase (P-450R and two-electron (hydride transferring NAD(PH:quinone oxidoreductase (NQO1 was examined in this work. Since the =N+ (→OO− moiety of furoxan fragments of BFXs bears some similarity to the aromatic nitro-group, the reactivity of BFXs was compared to that of nitro-aromatic compounds (NACs whose reduction mechanisms by these and other related flavoenzymes have been extensively investigated. The reduction of BFXs by both P-450R and NQO1 was accompanied by O2 uptake, which was much lower than the NADPH oxidation rate; except for annelated BFXs, whose reduction was followed by the production of peroxide. In order to analyze the possible quantitative structure-activity relationships (QSARs of the enzymatic reactivity of the compounds, their electron-accepting potency and other reactivity indices were assessed by quantum mechanical methods. In P-450R-catalyzed reactions, both BFXs and NACs showed the same reactivity dependence on their electron-accepting potency which might be consistent with an “outer sphere” electron transfer mechanism. In NQO1-catalyzed two-electron (hydride transferring reactions, BFXs acted as more efficient substrates than NACs, and the reduction efficacy of BFXs by NQO1 was in general higher than by single-electron transferring P-450R. In NQO1-catalyzed reactions, QSARs obtained showed that the reduction efficacy of BFXs, as well as that of NACs, was determined by their electron-accepting potency and could be influenced by their binding mode in the active center of NQO1 and by their global softness as their electronic characteristic. The reductive conversion of benzofuroxan by both flavoenzymes yielded the same reduction product of benzofuroxan, 2,3-diaminophenazine, with the formation of o-benzoquinone dioxime as a putative primary

  15. 2-Nitrophenol reduction promoted by S. putrefaciens 200 and biogenic ferrous iron: The role of different size-fractions of dissolved organic matter

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Zhenke [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Tao, Liang, E-mail: taoliang@soil.gd.cn [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Li, Fangbai, E-mail: cefbli@soil.gd.cn [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China)

    2014-08-30

    Graphical abstract: - Highlights: • Dissolved organic matter (DOM) act as electron shuttle in redox reactions. • Different molecular weight DOM fractions have different electron transfer capacity. • A higher electron transfer capacities value indicates a higher reduction rate. • DOM transfer electron from S. putrefaciens 200 to 2-nitrophenol (2-NP) and Fe(III). • DOM and biogenic Fe(II) synergistically enhanced the 2-NP reductive transformation. - Abstract: The reduction of nitroaromatic compounds (listed as a priority pollutant) in natural subsurface environments typically coexists with dissimilatory reduction of iron oxides effected by dissolved organic matter (DOM). Investigating the impact of the DOM that influences those reduction processes is crucial for understanding and predicting the geochemical fate of these environmental species. This study investigated the impact of different molecular weight DOM fractions (DMWDs) on the 2-nitrophenol (2-NP) reduction by S. putrefaciens 200 (SP200) and α-Fe{sub 2}O{sub 3} with lactate (excluding electron donor interference). Kinetic measurements demonstrated that 2-NP reduction rates were affected by the redox reactivity of active species under DMWDs (denoted as L-DOM, M-DOM, and H-DOM). The enhanced reduction rates are consistent with the negative shifts in peak oxidation potential values, the increases in HA-like/FA-like values, aromaticity index values and electron transfer capacity values. L-DOM acted mainly as ligands to complex Fe(II), whereas the significant role of H-DOM in reductive reactions should be acting as an electron shuttle, transferring electrons from SP200 to Fe(III) and 2-NP and from biogenic Fe(II) to 2-NP, further accelerating the 2-NP reductions. Those observations provide valuable insights into the role of DOM in the biogeochemical redox processes and the remediation of contaminated soil in a natural environment.

  16. Functional separation of oxidation–reduction reactions and electron transport in PtRu/ND and conductive additive hybrid electrocatalysts during methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yan; Wang, Yanhui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Bian, Linyan [College of Physics and Chemistry, Henan Polytechnic University, Jiaozuo, Henan 454000 (China); Lu, Rui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Zang, Jianbing, E-mail: jbzang@ysu.edu.cn [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China)

    2016-02-28

    Graphical abstract: - Highlights: • Functional separation of reactions and electron transport in PtRu/ND + AB (or CNT). • A conductive network was formed after the addition of AB or CNT. • PtRu/ND + AB (or CNT) exhibited enhanced activity and stability than PtRu/ND. - Abstract: Undoped nanodiamond (ND) supported PtRu (PtRu/ND) electrocatalyst for methanol oxidation reactions (MOR) in direct methanol fuel cells was prepared by a microwave-assisted polyol reduction method. Sp{sup 3}-bonded ND possesses high electrochemical stability but low conductivity, while sp{sup 2}-bonded carbon nanomaterials with high conductivity are prone to oxidation. Therefore, the functions of the supporting material were separated in this study. ND (sp{sup 3}), as a support, and AB or CNTs (sp{sup 2}), as a conductive additive, were combined to form the hybrid electrocatalysts PtRu/ND + AB and PtRu/ND + CNT for MOR. The morphology of the electrocatalysts was characterized by scanning electron microscopy and electrochemical measurements were performed using an electrochemical workstation. The results indicated that the electrocatalytic activity of PtRu/ND for MOR was improved with the addition of AB or CNTs as a conductive additive. Moreover, adding CNTs to PtRu/ND as a conductive additive showed better electrocatalytic activities than adding AB, which can be ascribed to the better electron-transfer ability of CNTs.

  17. Preparation and characterization of electronically conducting polypyrrole-montmorillonite nanocomposite and its potential application as a cathode material for oxygen reduction

    International Nuclear Information System (INIS)

    Rajapakse, R.M.G.; Murakami, Kenji; Bandara, H.M.N.; Rajapakse, R.M.M.Y.; Velauthamurti, K.; Wijeratne, S.

    2010-01-01

    Simple wet chemical processes were deployed to prepare low-cost conducting nanocomposites based on natural clays with 2:1 layered structures such as sodium montmorillonite (MMT). Ce(IV) modified MMT was used for the spontaneous polymerization of pyrrole within clay interlayers. The resulted clay-conducting polypyrrole nanocomposites containing the reduced form of the oxidising agent, have been extensively characterized by X-ray diffraction (XRD) technique for interlayer spacing variations and by Fourier transform infra red (FT-IR) spectroscopy to study the interactions between the clay and polymer functional groups. DC polarization technique with both blocking and non-blocking electrodes was used to distinguish between the ionic and electronic transport numbers and to recognize the type of mobile ionic species. AC impedance analysis further resolved the electrical conduction of these materials. Bulk conductivity analysis implied that the polypyrrole (PPY) formed within Ce(IV) modified MMT posses dominant electronic conductivity. The low-cost, light-weight and stable polymer-clay nanocomposite prepared by Ce(IV) intercalated MMT, [Ce(III)-PPY-MMT], seems to be a promising cathode material for oxygen reduction and hence may find applications in fuel cell industries.

  18. Importance of c-Type cytochromes for U(VI reduction by Geobacter sulfurreducens

    Directory of Open Access Journals (Sweden)

    Leang Ching

    2007-03-01

    Full Text Available Abstract Background In order to study the mechanism of U(VI reduction, the effect of deleting c-type cytochrome genes on the capacity of Geobacter sulfurreducens to reduce U(VI with acetate serving as the electron donor was investigated. Results The ability of several c-type cytochrome deficient mutants to reduce U(VI was lower than that of the wild type strain. Elimination of two confirmed outer membrane cytochromes and two putative outer membrane cytochromes significantly decreased (ca. 50–60% the ability of G. sulfurreducens to reduce U(VI. Involvement in U(VI reduction did not appear to be a general property of outer membrane cytochromes, as elimination of two other confirmed outer membrane cytochromes, OmcB and OmcC, had very little impact on U(VI reduction. Among the periplasmic cytochromes, only MacA, proposed to transfer electrons from the inner membrane to the periplasm, appeared to play a significant role in U(VI reduction. A subpopulation of both wild type and U(VI reduction-impaired cells, 24–30%, accumulated amorphous uranium in the periplasm. Comparison of uranium-accumulating cells demonstrated a similar amount of periplasmic uranium accumulation in U(VI reduction-impaired and wild type G. sulfurreducens. Assessment of the ability of the various suspensions to reduce Fe(III revealed no correlation between the impact of cytochrome deletion on U(VI reduction and reduction of Fe(III hydroxide and chelated Fe(III. Conclusion This study indicates that c-type cytochromes are involved in U(VI reduction by Geobacter sulfurreducens. The data provide new evidence for extracellular uranium reduction by G. sulfurreducens but do not rule out the possibility of periplasmic uranium reduction. Occurrence of U(VI reduction at the cell surface is supported by the significant impact of elimination of outer membrane cytochromes on U(VI reduction and the lack of correlation between periplasmic uranium accumulation and the capacity for uranium

  19. Electronic Correlation Strength of Pu

    DEFF Research Database (Denmark)

    Svane, A.; C. Albers, R.; E. Christensen, N.

    2013-01-01

    A new electronic quantity, the correlation strength, is defined as a necessary step for understanding the properties and trends in strongly correlated electronic materials. As a test case, this is applied to the different phases of elemental Pu. Within the GW approximation we have surprisingly...... found a "universal" scaling relationship, where the f-electron bandwidth reduction due to correlation effects is shown to depend only upon the local density approximation (LDA) bandwidth and is otherwise independent of crystal structure and lattice constant....

  20. High Efficient Reduction of Graphene Oxide via Nascent Hydrogen at Room Temperature

    Directory of Open Access Journals (Sweden)

    Qiqi Zhuo

    2018-02-01

    Full Text Available To develop a green and efficient method to synthesize graphene in relative milder conditions is prerequisite for graphene applications. A chemical reducing method has been developed to high efficiently reduce graphene oxide (GO using Fe2O3 and NH3BH3 as catalyst and reductants, respectively. During the process, environmental and strong reductive nascent hydrogen were generated surrounding the surface of GO sheets by catalyst hydrolysis reaction of NH3BH3 and were used for reduction of GO. The reduction process was studied by ultraviolet absorption spectroscopy, Raman spectroscopy, and Fourier transform infrared spectrum. The structure and morphology of the reduced GO were characterized with scanning electron microscopy and transmission electron microscopy. Compared to metal (Mg/Fe/Zn/Al particles and acid system which also use nascent hydrogen to reduce GO, this method exhibited higher reduction efficiency (43.6%. Also the reduction was carried out at room temperature condition, which is environmentally friendly. As a supercapacitor electrode, the reversible capacity of reduced graphene oxide was 113.8 F g−1 at 1 A g−1 and the capacitance retention still remained at 90% after 200 cycles. This approach provides a new method to reduce GO with high reduction efficiency by green reductant.

  1. Evaluation of the antioxidant activity of Betula pendula leaves extract and its effects on model foods.

    Science.gov (United States)

    Azman, Nurul Aini Mohd; Skowyra, Monika; Muhammad, Kwestan; Gallego, María Gabriela; Almajano, Maria Pilar

    2017-12-01

    Betula pendula Roth (Betulaceae) exhibits many pharmacological activities in humans including anticancer, antibacterial, and antiviral effects. However, the antioxidant activity of BP towards lipid degradation has not been fully determined. The BP ethanol and methanol extracts were evaluated to determine antioxidant activity by an in vitro method and lyophilized extract of BP was added to beef patties to study oxidative stability. Antioxidant activities of extracts of BP were determined by measuring scavenging radical activity against methoxy radical generated by Fenton reaction 2,2'-azino-bis-3-ethylbenzothiazoline-6-sulphonic acid (TEAC) radical cation, the oxygen radical absorbance capacity (ORAC) and the ferric reducing antioxidant power (FRAP) assays. The lipid deterioration in beef patties containing 0.1% and 0.3% (w/w) of lyophilized extract of BP stored in 80:20 (v/v) O 2 :CO 2 modified atmosphere (MAP) at 4 °C for 10 days was determined using thiobarbituric acid reacting substances (TBARS), % metmyoglobin and colour value. The BP methanol extract revealed the presence of catechin, myricetin, quercetin, naringenin, and p-coumaric acid. The BP ethanol (50% w/w) extract showed scavenging activity in TEAC, ORAC and FRAP assays with values of 1.45, 2.81, 1.52 mmol Trolox equivalents (TE)/g DW, respectively. Reductions in lipid oxidation were found in samples treated with lyophilized BP extract (0.1% and 0.3% w/w) as manifested by the changes of colour and metmyoglobin concentration. A preliminary study film with BP showed retard degradation of lipid in muscle food. The present results indicated that the BP extracts can be used as natural food antioxidants.

  2. Immediate remediation of heavy metal (Cr(VI)) contaminated soil by high energy electron beam irradiation

    International Nuclear Information System (INIS)

    Zhang, Jing; Zhang, Guilong; Cai, Dongqing; Wu, Zhengyan

    2015-01-01

    Highlights: • An immediate remediation method for Cr(VI) contaminated soil (CCS) was developed. • High energy electron beam (HEEB) irradiation could reduce Cr(VI) in CCS to Cr(III). • This effect was attributed to electrons, hydrated electrons, and reductive radicals. • This remediation method was effective, environmentally friendly, and low-cost. - Abstract: This work developed an immediate and high-performance remediation method for Cr(VI) contaminated soil (CCS) using high energy electron beam (HEEB) irradiation. The result indicated that, compared with γ-ray irradiation, HEEB irradiation displayed a significant reduction efficiency on Cr(VI) in CCS to Cr(III) with substantially lower toxicity, which was mainly attributed to the reduction effects of electrons, hydrated electrons, and reductive radicals generated in the irradiation process of HEEB. This work could provide a one-step and effective method for the remediation of heavy metal contaminated soil (HMCS)

  3. Immediate remediation of heavy metal (Cr(VI)) contaminated soil by high energy electron beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jing; Zhang, Guilong [Key Laboratory of Ion Beam Bioengineering, Hefei Institutes of Physical Science, Chinese Academy of Sciences and Anhui Province, Hefei 230031 (China); Bioenergy Forest Research Center of State Forestry Administration, Hefei 230031 (China); Cai, Dongqing, E-mail: dqcai@ipp.ac.cn [Key Laboratory of Ion Beam Bioengineering, Hefei Institutes of Physical Science, Chinese Academy of Sciences and Anhui Province, Hefei 230031 (China); Bioenergy Forest Research Center of State Forestry Administration, Hefei 230031 (China); Wu, Zhengyan, E-mail: zywu@ipp.ac.cn [Key Laboratory of Ion Beam Bioengineering, Hefei Institutes of Physical Science, Chinese Academy of Sciences and Anhui Province, Hefei 230031 (China); Bioenergy Forest Research Center of State Forestry Administration, Hefei 230031 (China)

    2015-03-21

    Highlights: • An immediate remediation method for Cr(VI) contaminated soil (CCS) was developed. • High energy electron beam (HEEB) irradiation could reduce Cr(VI) in CCS to Cr(III). • This effect was attributed to electrons, hydrated electrons, and reductive radicals. • This remediation method was effective, environmentally friendly, and low-cost. - Abstract: This work developed an immediate and high-performance remediation method for Cr(VI) contaminated soil (CCS) using high energy electron beam (HEEB) irradiation. The result indicated that, compared with γ-ray irradiation, HEEB irradiation displayed a significant reduction efficiency on Cr(VI) in CCS to Cr(III) with substantially lower toxicity, which was mainly attributed to the reduction effects of electrons, hydrated electrons, and reductive radicals generated in the irradiation process of HEEB. This work could provide a one-step and effective method for the remediation of heavy metal contaminated soil (HMCS)

  4. Dissimilatory oxidation and reduction of elemental sulfur in thermophilic archaea.

    Science.gov (United States)

    Kletzin, Arnulf; Urich, Tim; Müller, Fabian; Bandeiras, Tiago M; Gomes, Cláudio M

    2004-02-01

    The oxidation and reduction of elemental sulfur and reduced inorganic sulfur species are some of the most important energy-yielding reactions for microorganisms living in volcanic hot springs, solfataras, and submarine hydrothermal vents, including both heterotrophic, mixotrophic, and chemolithoautotrophic, carbon dioxide-fixing species. Elemental sulfur is the electron donor in aerobic archaea like Acidianus and Sulfolobus. It is oxidized via sulfite and thiosulfate in a pathway involving both soluble and membrane-bound enzymes. This pathway was recently found to be coupled to the aerobic respiratory chain, eliciting a link between sulfur oxidation and oxygen reduction at the level of the respiratory heme copper oxidase. In contrast, elemental sulfur is the electron acceptor in a short electron transport chain consisting of a membrane-bound hydrogenase and a sulfur reductase in (facultatively) anaerobic chemolithotrophic archaea Acidianus and Pyrodictium species. It is also the electron acceptor in organoheterotrophic anaerobic species like Pyrococcus and Thermococcus, however, an electron transport chain has not been described as yet. The current knowledge on the composition and properties of the aerobic and anaerobic pathways of dissimilatory elemental sulfur metabolism in thermophilic archaea is summarized in this contribution.

  5. Application of electron beam irradiation, (1). Development and application of electron beam processors

    International Nuclear Information System (INIS)

    Katsumura, Yosuke

    1994-01-01

    This paper deals with characteristics, equipment (principle and kinds), present conditions, and future issues in the application of electron beam irradiation. Characteristics of electron beams are described in terms of the following: chemical and biological effects of radiation; energy and penetrating power of electron beams; and principle and kinds of electron beam accelerator. Industrial application of electron beam irradiation has advantages of high speed procedure and producibility, less energy, avoidance of poisonous gas, and extreme reduction of organic solvents to be used. The present application of electron beam irradiation cen be divided into the following: (1) hardening of resin or coated membrane; (2) improvement of macromolecular materials; (3) environmental protection; (4) sterilization; (5) food sterilization. The present equipment for electron beam irradiation is introduced according to low energy, medium energy, and high energy equipment. Finally, future issues focuses on (1) the improvement of traceability system and development of electron dosimetric techniques and (2) food sterilization. (N.K.)

  6. Visible light-driven O2 reduction by a porphyrin-laccase system.

    Science.gov (United States)

    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.

  7. Allosteric control of internal electron transfer in cytochrome cd1 nitrite reductase

    DEFF Research Database (Denmark)

    Farver, Ole; Kroneck, Peter M H; Zumft, Walter G

    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....

  8. Spin polarized electron source technology transferred from HE accelerators to electron microscopes

    International Nuclear Information System (INIS)

    Nakanishi, Tsutomu

    2009-01-01

    For many years, we have developed a technology of spin-polarized-electron-source (PES) for a future linear collider project (ILC). Various new techniques for achieving high polarization, high quantum efficiency, high current density, sub-nanosecond multi-bunch generation etc. were developed. Two fundamental technologies; reduction of dark current and preparation of extremely high vacuum environment to protect the Negative Electron Affinity (NEA) surface have been also developed. Using these PES technologies and a new transmission type photocathode, we recently succeeded in producing the high brightness and high polarization electron beam for the low energy electron microscope (LEEM). Our Spin-LEEM system enables the world-first dynamic observation of surface magnetic domain formed by evaporation on the metal substrate with ∼ 20 nm space resolutions. (author)

  9. Mechanisms of bacterially catalyzed reductive dehalogenation

    Energy Technology Data Exchange (ETDEWEB)

    Picardal, Flynn William [Univ. of Arizona, Tucson, AZ (United States)

    1992-01-01

    Nine bacteria were tested for the ability to dehalogenate tetrachloromethane (CT), tetrachloroethene (PCE), and 1, 1, 1-trichloroethane (TCA) under anaerobic conditions. Three bacteria were able to reductively dehalogenate CT. Dehalogenation ability was not readily linked to a common metabolism or changes in culture redox potential. None of the bacteria tested were able to dehalogenate PCE or TCA. One of the bacteria capable of dehalogenating CT, Shewanella putrefaciens, was chosen as a model organism to study mechanisms of bacterially catalyzed reductive dehalogenation. The effect of a variety of alternate electron acceptors on CT dehalogenation ability by S. putrefaciens was determined. oxygen and nitrogen oxides were inhibitory but Fe (III), trimethylamine oxide, and fumarate were not. A model of the electron transport chain of S. putrefaciens was developed to explain inhibition patterns. A period of microaerobic growth prior to CT exposure increased the ability of S. putrefaciens to dehalogenate CT. A microaerobic growth period also increased cytochrome concentrations. A relationship between cytochrome content and dehalogenation ability was developed from studies in which cytochrome concentrations in S. putrefaciens were manipulated by changing growth conditions. Stoichiometry studies using 14C-CT suggested that CT was first reduced to form a trichloromethyl radical. Reduction of the radical to produce chloroform and reaction of the radical with cellular biochemicals explained observed product distributions. Carbon dioxide or other fully dehalogenated products were not found.

  10. Velocity Spread Reduction for Axis-encircling Electron Beam Generated by Single Magnetic Cusp

    Science.gov (United States)

    Jeon, S. G.; Baik, C. W.; Kim, D. H.; Park, G. S.; Sato, N.; Yokoo, K.

    2001-10-01

    Physical characteristics of an annular Pierce-type electron gun are investigated analytically. An annular electron gun is used in conjunction with a non-adiabatic magnetic reversal and an adiabatic compression to produce an axis-encircling electron beam. Velocity spread close to zero is realized with an initial canonical angular momentum spread at the cathode when the beam trajectory does not coincide with the magnetic flux line. Both the analytical calculation and the EGUN code simulation confirm this phenomenon.

  11. The role of humic substances in the anaerobic reductive dechlorination of 2,4-dichlorophenoxyacetic acid by Comamonas koreensis strain CY01

    Energy Technology Data Exchange (ETDEWEB)

    Wang Yibo [College of Life Sciences, South China Normal University, Guangdong Key Lab of Biotechnology for Plant Development, Guangzhou, 510631 (China)] [Guangdong Institute of Eco-environment and Soil Sciences, Guangzhou, 510650 (China)] [College of Life Science and Chemistry, Tianshui Normal University, Tianshui, 741000 (China); Wu Chunyuan [Guangdong Institute of Eco-environment and Soil Sciences, Guangzhou, 510650 (China); Wang Xiaojing, E-mail: wangyb02@163.com [College of Life Sciences, South China Normal University, Guangdong Key Lab of Biotechnology for Plant Development, Guangzhou, 510631 (China); Zhou Shungui, E-mail: sgzhou@soil.gd.cn [Guangdong Institute of Eco-environment and Soil Sciences, Guangzhou, 510650 (China)

    2009-05-30

    The role of the humic model compound, anthraquinone-2,6-disulfonate (AQDS), in the anaerobic reductive dechlorination of 2,4-dichlorophenoxyacetic acid (2,4-D) by the Fe(III)- and humic substances (HS)-reducing bacterium, Comamonas koreensis strain CY01 was investigated. The results taken as a whole indicated that (i) strain CY01 could couple glucose oxidation to 2,4-D reductive dechlorination; (ii) reductive dechlorination of 2,4-D by strain CY01 was greatly stimulated by the addition of AQDS; (iii) the transfer of electrons from biogenic AH{sub 2}QDS to 2,4-D was an abiotic process which can take place in the absence of microorganisms; and (iv) AH{sub 2}QDS was reoxidized during the chemical reaction, AQDS can serve again as electron acceptor for microorganisms, thus acting as electron shuttles. All the results suggested that 2,4-D reductive dechlorination by CY01 strain was a biochemical process that oxidizes the electron donors and transfers the electron to the acceptors through redox mediator, AQDS. We proposed the possible mechanism for the HS dependent reduction of 2,4-D. Our results suggested that microbial reduction of HS and subsequent chemical reduction of organic pollutants represent an important path of electron flow in anoxic natural environments. This work is a necessary preliminary step for better understanding the biodegradation of 2,4-D in subsurface soil.

  12. Reduction and precipitation of neptunium(V) by sulfate-reducing bacteria

    International Nuclear Information System (INIS)

    Banaszak, J. E.; Rittmann, B. E.; Reed, D. T.

    1999-01-01

    Migration of neptunium, as NpO 2 + , has been identified as a potentially important pathway for actinide release at nuclear waste repositories and existing sites of subsurface contamination. Reduction of Np(V) to Np(IV) will likely reduce its volubility, resulting in lowered subsurface migration. The ability of sulfate-reducing bacteria (SRB) to utilize Np(V) as an electron acceptor was investigated, because these bacteria are active in many anaerobic aquifers and are known to facilitate the reduction of metals and radionuclides. Pure and mixed cultures of SRB were able to precipitate neptunium during utilization of pyruvate, lactate, and hydrogen as electron donors in the presence and absence of sulfate. The neptunium in the precipitate was identified as Np(IV) using X-ray absorption near edge spectroscopy (XANES) analysis. In mixed-culture studies, the addition of hydrogen to consortia grown by pyruvate fermentation stimulated neptunium reduction and precipitation. Experiments with pure cultures of Desulfovibrio vulgaris, growing by lactate fermentation in the absence of sulfate or by sulfate reduction, confirm that the organism is active in neptunium reduction and precipitation. Based on our results, the activity of SRB in the subsurface may have a significant, and potentially beneficial, impact on actinide mobility by reducing neptunium volubility

  13. Hexavalent chromium reduction in a sulfur reducing packed-bed bioreactor

    Energy Technology Data Exchange (ETDEWEB)

    Sahinkaya, Erkan, E-mail: erkansahinkaya@yahoo.com [Department of Bioengineering, Istanbul Medeniyet University, Goeztepe, Istanbul (Turkey); Kilic, Adem [Department of Environmental Engineering, Harran University, Osmanbey Campus, 63000 Sanliurfa (Turkey); Altun, Muslum [Department of Chemistry, Hacettepe University, Beytepe, Ankara (Turkey); Komnitsas, Kostas [Department of Mineral Resources Engineering, Technical University of Crete, 73100 Chania (Greece); Lens, Piet N.L. [Unesco-IHE Institute for Water Education, Westvest 7, Delft 2611 AX (Netherlands)

    2012-06-15

    Highlights: Black-Right-Pointing-Pointer Elemental sulfur can be used as electron acceptor for sulfide production. Black-Right-Pointing-Pointer Biogenically produced sulfide reduces Cr(VI) to the much less toxic and immobile form of Cr(III). Black-Right-Pointing-Pointer Sulfur packed bioreactor is efficient for Cr(VI) containing wastewater treatment. Black-Right-Pointing-Pointer Reduced form of chromium precipitates in the bioreactor. - Abstract: The most commonly used approach for the detoxification of hazardous industrial effluents and wastewaters containing Cr(VI) is its reduction to the much less toxic and immobile form of Cr(III). This study investigates the cleanup of Cr(VI) containing wastewaters using elemental sulfur as electron acceptor, for the production of hydrogen sulfide that induces Cr(VI) reduction. An elemental sulfur reducing packed-bed bioreactor was operated at 28-30 Degree-Sign C for more than 250 days under varying influent Cr(VI) concentrations (5.0-50.0 mg/L) and hydraulic retention times (HRTs, 0.36-1.0 day). Ethanol or acetate (1000 mg/L COD) was used as carbon source and electron donor. The degree of COD oxidation varied between 30% and 85%, depending on the operating conditions and the type of organic carbon source. The oxidation of organic matter was coupled with the production of hydrogen sulfide, which reached a maximum concentration of 750 mg/L. The biologically produced hydrogen sulfide reduced Cr(VI) chemically to Cr(III) that precipitated in the reactor. Reduction of Cr(VI) and removal efficiency of total chromium always exceeded 97% and 85%, respectively, implying that the reduced chromium was retained in the bioreactor. This study showed that sulfur can be used as an electron acceptor to produce hydrogen sulfide that induces efficient reduction and immobilization of Cr(VI), thus enabling decontamination of Cr(VI) polluted wastewaters.

  14. Optimizing Metalloporphyrin-Catalyzed Reduction Reactions for In Situ Remediation of DOE Contaminants

    International Nuclear Information System (INIS)

    Schlautman, Mark A.

    2013-01-01

    Past activities have resulted in a legacy of contaminated soil and groundwater at Department of Energy facilities nationwide. Uranium and chromium are among the most frequently encountered and highest-priority metal and radionuclide contaminants at DOE installations. Abiotic chemical reduction of uranium and chromium at contaminated DOE sites can be beneficial because the reduced metal species are less soluble in water, less mobile in the environment, and less toxic to humans and ecosystems. Although direct biological reduction has been reported for U(VI) and Cr(VI) in laboratory studies and at some field sites, the reactions can sometimes be slow or even inhibited due to unfavorable environmental conditions. One promising approach for the in-situ remediation of DOE contaminants is to develop electron shuttle catalysts that can be delivered precisely to the specific subsurface locations where contaminants reside. Previous research has shown that reduction of oxidized organic and inorganic contaminants often can be catalyzed by electron shuttle systems. Metalloporphyrins and their derivatives are well known electron shuttles for many biogeochemical systems, and thus were selected to study their catalytic capabilities for the reduction of chromium and uranium in the presence of reducing agents. Zero valent iron (ZVI) was chosen as the primary electron donor in most experimental systems. Research proceeded in three phases and the key findings of each phase are reported here. Phase I examined Cr(VI) reduction and utilized micro- and nano-sized ZVI as the electron donors. Electron shuttle catalysts tested were cobalt- and iron-containing metalloporphyrins and Vitamin B12. To aid in the recycle and reuse of the nano-sized ZVI and soluble catalysts, sol-gels and calcium-alginate gel beads were tested as immobilization/support matrices. Although the nano-sized ZVI could be incorporated within the alginate gel beads, preliminary attempts to trap it in sol-gels were not

  15. Optimizing Metalloporphyrin-Catalyzed Reduction Reactions for In Situ Remediation of DOE Contaminants

    Energy Technology Data Exchange (ETDEWEB)

    Schlautman, Mark A. [Clemson University, Clemson, SC (United States)

    2013-07-14

    Past activities have resulted in a legacy of contaminated soil and groundwater at Department of Energy facilities nationwide. Uranium and chromium are among the most frequently encountered and highest-priority metal and radionuclide contaminants at DOE installations. Abiotic chemical reduction of uranium and chromium at contaminated DOE sites can be beneficial because the reduced metal species are less soluble in water, less mobile in the environment, and less toxic to humans and ecosystems. Although direct biological reduction has been reported for U(VI) and Cr(VI) in laboratory studies and at some field sites, the reactions can sometimes be slow or even inhibited due to unfavorable environmental conditions. One promising approach for the in-situ remediation of DOE contaminants is to develop electron shuttle catalysts that can be delivered precisely to the specific subsurface locations where contaminants reside. Previous research has shown that reduction of oxidized organic and inorganic contaminants often can be catalyzed by electron shuttle systems. Metalloporphyrins and their derivatives are well known electron shuttles for many biogeochemical systems, and thus were selected to study their catalytic capabilities for the reduction of chromium and uranium in the presence of reducing agents. Zero valent iron (ZVI) was chosen as the primary electron donor in most experimental systems. Research proceeded in three phases and the key findings of each phase are reported here. Phase I examined Cr(VI) reduction and utilized micro- and nano-sized ZVI as the electron donors. Electron shuttle catalysts tested were cobalt- and iron-containing metalloporphyrins and Vitamin B12. To aid in the recycle and reuse of the nano-sized ZVI and soluble catalysts, sol-gels and calcium-alginate gel beads were tested as immobilization/support matrices. Although the nano-sized ZVI could be incorporated within the alginate gel beads, preliminary attempts to trap it in sol-gels were not

  16. Single step preparation of NdFeB alloy by magnesiothermic reduction-diffusion process

    International Nuclear Information System (INIS)

    Singha, Vinay Kant; Surendranathana, A.O.; John Berchmans, L.

    2014-01-01

    Magnesiothermic reduction is a new approach to produce the NdFeB alloy on a commercial scale. Similar studies were conducted for the preparation of LaNi 5 and SmCo 5 using magnesium as the reductant. In the present investigation NdFeB Hard magnetic bulk materials were synthesized by metallothermic 'Reduction – Diffusion (R-D) Process' using Magnesium as a reductant. For this process oxide precursors of Nd, Fe and B were blended with flux (LiCl/CaCl 2 ) and Mg chips were sandwiched in alternate layers. Thermal analysis (TGA/DTA) was carried out to find the dissociation and decomposition temperature of the reactants. The phase analysis, structure, and elemental composition were assessed by X-ray diffraction (XRD) and electron dispersive spectrometry (EDS). The infrared (IR) spectra were recorded by Fourier transform infrared spectrometer (FTIR). The morphological features and particle size was assessed by scanning electron microscope (SEM). The magnetic behaviour of the alloy was assessed using electron paramagnetic resonance (EPR) and vibratory sample magnetometer (VSM). From these studies it has been concluded that the NdFeB magnetic particles can be prepared using magnesium as the reductant. The process is faster and consumes very less amount of energy for the completion as compared to conventional calciothermic reduction process. Traces of MgO were detected in the alloy which increases the perpendicular anisotropy, thus increasing the coercivity of the material

  17. In Vitro Enzymatic Reduction Kinetics of Mineral Oxides by Membrane Fractions from Shewanella oneidensis MR-1

    International Nuclear Information System (INIS)

    Ruebush, S.; Icopini, G.; Brantley, S.; Tien, M.

    2006-01-01

    This study documents the first example of in vitro solid-phase mineral oxide reduction by enzyme-containing membrane fractions. Previous in vitro studies have only reported the reduction of aqueous ions. Total membrane (TM) fractions from iron-grown cultures of Shewanella oneidensis MR-1 were isolated and shown to catalyze the reduction of goethite, hematite, birnessite, and ramsdellite/pyrolusite using formate. In contrast, nicotinamide adenine dinucleotide (NADH) and succinate cannot function as electron donors. The significant implications of observations related to this cell-free system are: (i) both iron and manganese mineral oxides are reduced by the TM fraction, but aqueous U(VI) is not; (ii) TM fractions from anaerobically grown, but not aerobically grown, cells can reduce the mineral oxides; (iii) electron shuttles and iron chelators are not needed for this in vitro reduction, documenting conclusively that reduction can occur by direct contact with the mineral oxide; (iv) electron shuttles and EDTA stimulate the in vitro Fe(III) reduction, documenting that exogenous molecules can enhance rates of enzymatic mineral reduction; and (v) multiple membrane components are involved in solid-phase oxide reduction. The membrane fractions, consisting of liposomes of cytoplasmic and outer membrane segments, contain at least 100 proteins including the enzyme that oxidizes formate, formate dehydrogenase. Mineral oxide reduction was inhibited by the addition of detergent Triton X-100, which solubilizes membranes and their associated proteins, consistent with the involvement of multiple electron carriers that are disrupted by detergent addition. In contrast, formate dehydrogenase activity was not inhibited by Triton X-100. The addition of anthraquinone-2,6-disulfonate (AQDS) and menaquinone-4 was unable to restore activity; however, menadione (MD) restored 33% of the activity. The addition of AQDS and MD to reactions without added detergent increased the rate of goethite

  18. Electronic market places in the energy

    International Nuclear Information System (INIS)

    Mons, L.

    2001-12-01

    Electronic market places in the energy domain occurred at the end of the 90's in the US and have started to develop in Europe in the year 2000. About 60 platforms are registered today and this development can be explained by the advantages raised by such an infrastructure: simplification of purchase procedures, reduction of delays in the purchase decision, reduction of administrative costs etc.. However, today none of these electronic market places is profitable and several have closed down. On the other hand, this tool will certainly become necessary in the future and all energy actors are developing projects in this way. This study analyzes the electronic market places phenomenon in the energy domain using 10 market places examples with their key-factors of success. It draws out a complete status of the initiatives developed today and presents some scenarios of evolution. (J.S.)

  19. Spin polarized and density modulated phases in symmetric electron-electron and electron-hole bilayers.

    Science.gov (United States)

    Kumar, Krishan; Moudgil, R K

    2012-10-17

    We have studied symmetric electron-electron and electron-hole bilayers to explore the stable homogeneous spin phase and the feasibility of inhomogeneous charge-/spin-density ground states. The former is resolved by comparing the ground-state energies in states of different spin polarizations, while the latter is resolved by searching for a divergence in the wavevector-dependent static charge/spin susceptibility. For this endeavour, we have used the dielectric approach within the self-consistent mean-field theory of Singwi et al. We find that the inter-layer interactions tend to change an abrupt spin-polarization transition of an isolated layer into a nearly gradual one, even though the partially spin-polarized phases are not clearly stable within the accuracy of our calculation. The transition density is seen to decrease with a reduction in layer spacing, implying a suppression of spin polarization by inter-layer interactions. Indeed, the suppression shows up distinctly in the spin susceptibility computed from the spin-polarization dependence of the ground-state energy. However, below a critical layer spacing, the unpolarized liquid becomes unstable against a charge-density-wave (CDW) ground state at a density preceding full spin polarization, with the transition density for the CDW state increasing on further reduction in the layer spacing. Due to attractive e-h correlations, the CDW state is found to be more pronounced in the e-h bilayer. On the other hand, the static spin susceptibility diverges only in the long-wavelength limit, which simply represents a transition to the homogeneous spin-polarized phase.

  20. An Integrated Assessment of Geochemical and Community Structure Determinants of Metal Reduction Rates in Subsurface Sediments. Final report

    International Nuclear Information System (INIS)

    Pfiffner, Susan

    2010-01-01

    The objective of this research was to examine the importance of microbial community structure in influencing uranium reduction rates in subsurface sediments. If the redox state alone is the key to metal reduction, then any organisms that can utilize the oxygen and nitrate in the subsurface can change the geochemical conditions so metal reduction becomes an energetically favored reaction. Thus, community structure would not be critical in determining rates or extent of metal reduction unless community structure influenced the rate of change in redox. Alternatively, some microbes may directly catalyze metal reduction (e.g., specifically reduce U). In this case the composition of the community may be more important and specific types of electron donors may promote the production of communities that are more adept at U reduction. Our results helped determine if the type of electron donor or the preexisting community is important in the bioremediation of metal-contaminated environments subjected to biostimulation. In a series of experiments at the DOE FRC site in Oak Ridge we have consistently shown that all substrates promoted nitrate reduction, while glucose, ethanol, and acetate always promoted U reduction. Methanol only occasionally promoted extensive U reduction which is possibly due to community heterogeneity. There appeared to be limitations imposed on the community related to some substrates (e.g. methanol and pyruvate). Membrane lipid analyses (phospholipids and respiratory quinones) indicated different communities depending on electron donor used. Terminal restriction fragment length polymorphism and clone libraries indicated distinct differences among communities even in treatments that promoted U reduction. Thus, there was enough metabolic diversity to accommodate many different electron donors resulting in the U bioimmobilization.

  1. Simultaneous reduction and nitrogen functionalization of graphene oxide using lemon for metal-free oxygen reduction reaction

    Science.gov (United States)

    Begum, Halima; Ahmed, Mohammad Shamsuddin; Cho, Sung; Jeon, Seungwon

    2017-12-01

    Inspire by the vision of finding a simple and green method for simultaneous reduction and nitrogen (N)-functionalization of graphene oxide (GO), a N-rich reduced graphene oxide (rGO) has been synthesized through a facile and ecofriendly hydrothermal strategy while most of the existing methods are involving with multiple steps and highly toxic reducing agents that are harmful to human health and environment. In this paper, the simultaneous reduction and N-functionalization of GO using as available lemon juice (denoted as Lem-rGO) for metal-free electrocatalysis towards oxygen reduction reaction (ORR) is described. The proposed method is based on the reduction of GO using of the reducing and the N-precursor capability of ascorbic acid and citric acid as well as the nitrogenous compounds, respectively, that containing in lemon juice. The resultant Lem-rGO has higher reduction degree, higher specific surface area and better crystalline nature with N-incorporation than that of well investigated ascorbic acid and citric acid treated rGO. As a result, it shows better ORR electrocatalytic activity in respect to the improved onset potential, electron transfer rate and kinetics than those typical rGO catalysts. Moreover, it shows a significant tolerance to the anodic fuels and durability than the Pt/C during ORR.

  2. Syntrophic Growth via Quinone-Mediated Interspecies Electron Transfer

    Directory of Open Access Journals (Sweden)

    Jessica A Smith

    2015-02-01

    Full Text Available The mechanisms by which microbial species exchange electrons are of interest because interspecies electron transfer can expand the metabolic capabilities of microbial communities. Previous studies with the humic substance analog anthraquinone-2,6-disulfonate (AQDS suggested that quinone-mediated interspecies electron transfer (QUIET is feasible, but it was not determined if sufficient energy is available from QUIET to support the growth of both species. Furthermore, there have been no previous studies on the mechanisms for the oxidation of anthrahydroquinone-2,6-disulfonate (AHQDS. A co-culture of Geobacter metallireducens and Geobacter sulfurreducens metabolized ethanol with the reduction of fumarate much faster in the presence of AQDS, and there was an increase in cell protein. G. sulfurreducens was more abundant, consistent with G. sulfurreducens obtaining electrons from acetate that G. metallireducens produced from ethanol, as well as from AHQDS. Cocultures initiated with a citrate synthase-deficient strain of G. sulfurreducens that was unable to use acetate as an electron donor also metabolized ethanol with the reduction of fumarate and cell growth, but acetate accumulated over time. G. sulfurreducens and G. metallireducens were equally abundant in these co-cultures reflecting the inability of the citrate synthase-deficient strain of G. sulfurreducens to metabolize acetate. Evaluation of the mechanisms by which G. sulfurreducens accepts electrons from AHQDS demonstrated that a strain deficient in outer-surface c-type cytochromes that are required for AQDS reduction was as effective at QUIET as the wild-type strain. Deletion of additional genes previously implicated in extracellular electron transfer also had no impact on QUIET. These results demonstrate that QUIET can yield sufficient energy to support the growth of both syntrophic partners, but that the mechanisms by which electrons are derived from extracellular hydroquinones require

  3. Reduction of nickel oxide particles by hydrogen studied in an environmental TEM

    DEFF Research Database (Denmark)

    Jeangros, Q.; Hansen, Thomas Willum; Wagner, Jakob Birkedal

    2013-01-01

    In situ reduction of nickel oxide (NiO) particles is performed under 1.3 mbar of hydrogen gas (H2) in an environmental transmission electron microscope (ETEM). Images, diffraction patterns and electron energy-loss spectra (EELS) are acquired to monitor the structural and chemical evolution of the...

  4. Review on the processes of reduction and refining of metallic vanadium

    International Nuclear Information System (INIS)

    Mourao, M.B.; Capocchi, J.D.T.

    1982-01-01

    A literature survey on the processes of vanadium reduction and refining is presented. The results achieved by several research workers are comented. Enphasis is given to the aluminothermic reduction of V 2 O 5 followed by purification of the crude metal in an electron beam melting furnace or by high temperature molten salts electrolitic processes. (Author) [pt

  5. Kinetics of U(VI) reduction control kinetics of U(IV) reoxidation

    International Nuclear Information System (INIS)

    Senko, J.M.; Minyard, M.L.; Dempsey, B.A.; Roden, E.E.; Yeh, G.-T.; Burgos, W.D.

    2006-01-01

    For the in situ reductive immobilization of U to be an acceptable strategy for the removal of that element from groundwater, the long-term stability of U(IV) must be determined. Rates of biotransformation of Fe species influence the mineralogy of the resulting products (Fredrickson et al., 2003; Senko et al., 2005), and we hypothesize that the rate of U(VI) reduction influences the mineralogy of resultant U(IV) precipitates. We hypothesize that slower rates of U(VI) reduction will yield U(IV) phases that are more resistant to reoxidation, and will therefore be more stable upon cessation of electron donor addition. U(IV) phases formed by relatively slow reduction may be more crystalline or larger in comparison to their relatively rapidly-formed counterparts (Figure 1), thus limiting the reactivity of slowly-formed U(IV) phases toward various oxidants. The physical location of U(IV) precipitates relative to bacterial cells may also limit the reactivity of biogenic U(IV) phases. In this situation, we expect that precipitation of U(IV) within the bacterial cell may protect U(IV) from reoxidation by limiting physical contact between U(IV) and oxidants (Figure 1). We assessed the effect of U(VI) reduction rate on the subsequent reoxidation of biogenic U(IV) and are currently conducting column scale studies to determine whether U(VI) reduction rate can be manipulated by varying the electron donor concentration used to stimulate U(VI) reduction

  6. Structural changes in graphene oxide thin film by electron-beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Tyagi, Chetna, E-mail: tchetna91@gmail.com [Materials Science Group, Inter University Accelerator Centre, New Delhi 67 (India); Lakshmi, G.B.V.S.; Kumar, Sunil; Tripathi, Ambuj [Materials Science Group, Inter University Accelerator Centre, New Delhi 67 (India); Avasthi, D.K. [Amity University, Noida 201313, Uttar Pradesh (India)

    2016-07-15

    Although we have a whole class of 2D materials, graphene has drawn much attention for its excellent electronic, optical, thermal and mechanical properties. Recent researches have shown its large scale production by the reduction of graphene oxide either thermally, chemically or electrochemically. Although the structure of graphene oxide is inhomogeneous and hence complicated due to the presence of organic moieties e.g. epoxy, carboxylic acid, hydroxyl groups etc., its properties can be tuned by reduction according to desired application. The aim of this work is to synthesize continuous thin film of graphene oxide using commercially available graphene oxide solution and to study its reduction by 25 keV electron beam irradiation at fluences varying from 2 × 10{sup 11} to 2 × 10{sup 13} e{sup −}/cm{sup 2}. Our studies using X-ray diffraction, Raman microscopy and UV–Vis spectroscopy showed that electron-beam irradiation is an effective tool for reduction of graphene oxide and for tuning its band gap.

  7. Dimensional reduction of a generalized flux problem

    International Nuclear Information System (INIS)

    Moroz, A.

    1992-01-01

    In this paper, a generalized flux problem with Abelian and non-Abelian fluxes is considered. In the Abelian case we shall show that the generalized flux problem for tight-binding models of noninteracting electrons on either 2n- or (2n + 1)-dimensional lattice can always be reduced to an n-dimensional hopping problem. A residual freedom in this reduction enables one to identify equivalence classes of hopping Hamiltonians which have the same spectrum. In the non-Abelian case, the reduction is not possible in general unless the flux tensor factorizes into an Abelian one times are element of the corresponding algebra

  8. One electron reduction of 1,2 dihydroxy 9,10 anthraquinone and its transition metal complexes in aqueous-isopropanol-acetone mixed solvent: a steady state-state and pulse radiolysis study

    International Nuclear Information System (INIS)

    Das, Saurabh; Mandal, Parikshit C.; Rath, Madhab C.; Mukherjee, Tulsi

    1998-01-01

    One electron reduction of 1,2 dihydroxy 9,10 anthraquinone and its Cu(II) and Ni(II) and Fe(III) complexes have been studied in aqueous-isopropanol-acetone solvent. Results indicate that the reducing ketyl radical generated reacts with the ligand forming semiquinones which undergoes a disproportionation reaction. Formation and decay rates of semiquinones was calculated using pulse radiolysis. (author)

  9. Effect of salt on color and warmed over flavor in charqui meat processing

    Directory of Open Access Journals (Sweden)

    Youssef Elza Y.

    2003-01-01

    Full Text Available A combination of salt (NaCl high concentration and curing salt was investigated for their role in warmed-over flavor (WOF and color changes during charqui meats processing. WOF was measured by TBARS method in uncured charqui meat (CH and in cured charqui known in Brazil as Jerked beef (JB. WOF occurred substantially in CH and sodium nitrite was able to inhibit 40-45% (p<0.05 in JB samples stored for 30 days. Color parameters also changed as evaluated by CIELAB system. The a*/b* ratio showed that CH samples presented brown color indicating the formation of metmyoglobin (Fe3+ whilst JB samples presented deep red color an indication of nitrosylmyoglobin (Fe2+ formation. Under cooking, a*/b* ratio indicated the presence of denatured metmyoglobin (Fe3+ in CH and formation of nitrosylmyochromogen (Fe2+ in JB samples. The actual iron state influenced the color of charqui meat and apparently nitrite was able to chelate Fe ions, thus inhibiting development of WOF.

  10. The estimated reduction in the odds of loss-of-control type crashes for sport utility vehicles equipped with electronic stability control.

    Science.gov (United States)

    Green, Paul E; Woodrooffe, John

    2006-01-01

    Using data from the NASS General Estimates System (GES), the method of induced exposure was used to assess the effects of electronic stability control (ESC) on loss-of-control type crashes for sport utility vehicles. Sport utility vehicles were classified into crash types generally associated with loss of control and crash types most likely not associated with loss of control. Vehicles were then compared as to whether ESC technology was present or absent in the vehicles. A generalized additive model was fit to assess the effects of ESC, driver age, and driver gender on the odds of loss of control. In addition, the effects of ESC on roads that were not dry were compared to effects on roads that were dry. Overall, the estimated percentage reduction in the odds of a loss-of-control crash for sport utility vehicles equipped with ESC was 70.3%. Both genders and all age groups showed reduced odds of loss-of-control crashes, but there was no significant difference between males and females. With respect to driver age, the maximum percentage reduction of 73.6% occurred at age 27. The positive effects of ESC on roads that were not dry were significantly greater than on roads that were dry.

  11. Reduction reactions of water soluble cyano-cobalt(III)-porphyrins: Metal versus ligand centered processes

    International Nuclear Information System (INIS)

    Mosseri, S.; Neta, P.; Harriman, A.; Hambright, P.

    1990-01-01

    Reduction reactions of dicyano-cobalt(III)-porphyrins [potential in vivo cyanide scavenger drugs] were studied by radiolytic and electrochemical methods using the water soluble tetrakis(4-sulfonatophenyl)porphyrin (TPPS) and tetrakis(N-methyl-4-pyridyl)porphyrin (TMPyP). For [(CN)2CoIIITPPS]-, reduction occurs stepwise to the CoII, CoI, and finally to the phlorin anion. This behavior is similar to that of the cobalt porphyrins in the absence of cyanide, except that the cyanide ligand shifts the reduction potentials to much more negative values. On the other hand, under radiolytic conditions, [(CN)2CoIIITMPyP]- is reduced on the porphyrin macrocycle by one electron to give the CoIII pi-radical anion, which disproportionates into the initial complex and the two-electron ring reduced CoIII phlorin. The radical anion is also formed by intramolecular electron transfer subsequent to the reaction of CoIITMPyP and cyanide. The results are compared with the chemistry of Vitamin B-12

  12. Disinfection of wastewaters: high-energy electron vs gamma irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Farooq, S [King Fahd Univ. of Petroleum and Minerals, Dhahran (Saudi Arabia). Dept. of Civil Engineering; Kurucz, C N; Waite, T D [Miami Univ., Coral Gables, FL (United States); Cooper, W J [Florida International Univ., Miami, FL (United States). Drinking Water Research Center

    1993-07-01

    A study was undertaken to examine the sensitivity of a wastewater population of coliphage, total coliforms and total flora present in raw sewage and secondary effluent after irradiating with similar doses delivered by a high-energy electron beam and [gamma]-radiation. The electron beam study was conducted on a large scale at the Virginia Key Wastewater Treatment Plant, Miami, Florida. The facility is equipped with a 1.5 MeV, 50 mA electron accelerator, with a wastewater flow rate of 8ls[sup -1]. Concurrent [gamma]-radiation studies were conducted at laboratory scale using a 5000 Ci, [sup 60]Co [gamma]-source. Three logs reduction of all three test organisms were observed at an electron beam dose of 500 krads, while at least four logs reduction were observed at the same dose utilizing the [gamma]'source. (Author).

  13. Identification of a multi-protein reductive dehalogenase complex in Dehalococcoides mccartyi strain CBDB1 suggests a protein-dependent respiratory electron transport chain obviating quinone involvement

    DEFF Research Database (Denmark)

    Kublik, Anja; Deobald, Darja; Hartwig, Stefanie

    2016-01-01

    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...... 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....

  14. Impact of an electronic cigarette on smoking reduction and cessation in schizophrenic smokers: a prospective 12-month pilot study.

    Science.gov (United States)

    Caponnetto, Pasquale; Auditore, Roberta; Russo, Cristina; Cappello, Giorgio Carlo; Polosa, Riccardo

    2013-01-28

    Cigarette smoking is a tough addiction to break. This dependence is the most common dual diagnosis for individuals with schizophrenia. Currently three effective drugs are approved for smoking cessation: nicotine replacement therapy (NRT), varenicline and bupropion. However, some serious side effects of varenicline have been reported, including depression, suicidal thoughts, and suicide. The use of bupropion also has side effects. It should not be used by people who have epilepsy or any condition that lowers the seizure threshold, nor by people who take a specific class of drugs called monoamine oxidase inhibitors. Hence, there are pharmacodynamic reason to believe they could precipitate or exacerbate psychosis. For its capacity to deliver nicotine and provide a coping mechanism for conditioned smoking cues by replacing some of the rituals associated with smoking gestures, electronic-cigarettes may reduce nicotine withdrawal symptoms without serious side effects. Our recent work with ECs in healthy smokers not intending to quit consistently show surprisingly high success rates. We hypothesised that these positive findings could be replicated in difficult patients with schizophrenia This tool may help smokers with schizophrenia remain abstinent during their quitting attempts or to reduce cigarette consumption. Efficacy and safety of these devices in long-term smoking cessation and/or smoking reduction studies have never been investigated for this special population. In this study we monitored possible modifications in smoking habits of 14 smokers (not intending to quit) with schizophrenia experimenting with the "Categoria" e-Cigarette with a focus on smoking reduction and smoking abstinence. Study participants were invited to attend six study visits: at baseline, week-4, week-8, week-12 week-24 and week 52. Product use, number of cigarettes smoked, carbon monoxide in exhaled breath (eCO) and positive and negative symptoms of schizophrenia levels were measured at each

  15. Fatty acids, lipid and protein oxidation, metmyoglobin reducing ...

    African Journals Online (AJOL)

    user

    2016-05-23

    May 23, 2016 ... attributes of biceps femoris muscle in goats fed a canola and palm oil blend ... The 4% and 8% BCPO meat had lower C14:0, but ... oil had no effect on feed intake and growth performance in goats (Adeyemi et al., 2015c). .... temperature was set at 100 ºC for 2 min, and warmed to 170 ºC at 10 ºC/min, held ...

  16. A hydrogen-donating monohydroxamate scavenges ferryl myoglobin radicals

    DEFF Research Database (Denmark)

    Cooper, C E; Green, E S; Rice-Evans, C A

    1994-01-01

    The addition of 25 microM hydrogen peroxide to 20 microM metmyoglobin produces ferryl (FeIV = O) myoglobin. Optical spectroscopy shows that the ferryl species reaches a maximum concentration (60-70% of total haem) after 10 minutes and decays slowly (hours). Low temperature EPR spectroscopy of the...

  17. Graphene oxide reduction by microwave heating

    International Nuclear Information System (INIS)

    Longo, Angela; Carotenuto, Gianfranco

    2016-01-01

    The possibility to prepare thermal reduced graphene oxide (Tr-GO) colloidal suspensions by microwave heating of graphene oxide (GO) suspensions in N-methyl-2-pyrrolidone (NMP) has been investigated. According to transmission electron microscopy (TEM) and absorption and emission spectroscopy characterization, such a type of thermal reduction does not lead to graphene quantum dots formation because only mono-functional oxygen-containing groups are removed.

  18. Graphene oxide reduction by microwave heating

    Energy Technology Data Exchange (ETDEWEB)

    Longo, Angela; Carotenuto, Gianfranco [Institute for Polymers, Composites, and Biomaterials, National Research Council, Piazzale Enrico Fermi 1, 80055 Portici (Italy)

    2016-05-18

    The possibility to prepare thermal reduced graphene oxide (Tr-GO) colloidal suspensions by microwave heating of graphene oxide (GO) suspensions in N-methyl-2-pyrrolidone (NMP) has been investigated. According to transmission electron microscopy (TEM) and absorption and emission spectroscopy characterization, such a type of thermal reduction does not lead to graphene quantum dots formation because only mono-functional oxygen-containing groups are removed.

  19. Ion-acoustic solitons in a plasma with electron beam

    International Nuclear Information System (INIS)

    Esfandyari, A. R.; Khorram, S.

    2001-01-01

    Ion-acoustic solitons in a collisionless plasma consisting of warm ions, hot isothermal electrons and a electron beam are studied by using the reductive perturbation method. The basic set of fluid equations is reduced to Korteweg-de Vries and modified Korteweg-de Vries temperature and electron beam on ion acoustic equations. The effect of ion solitons are investigated

  20. Electron transfer pathways in microbial oxygen biocathodes

    Energy Technology Data Exchange (ETDEWEB)

    Freguia, Stefano, E-mail: stefano@kais.kyoto-u.ac.j [Bio-analytical and Physical Chemistry Laboratory, Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8205 (Japan); Tsujimura, Seiya, E-mail: seiya@kais.kyoto-u.ac.j [Bio-analytical and Physical Chemistry Laboratory, Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8205 (Japan); Kano, Kenji, E-mail: kkano@kais.kyoto-u.ac.j [Bio-analytical and Physical Chemistry Laboratory, Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8205 (Japan)

    2010-01-01

    The ability of some bacteria to enhance the rate of cathodic oxygen reduction to water has been recently discovered, opening the way to an entirely renewable and environmentally friendly concept of biocathode. In this study we reveal that several mechanisms may induce catalytic effects by bacteria. These comprise mechanisms that are putatively beneficial to the bacteria as well as mechanisms which are merely side effects, including quinone autoxidation and direct O{sub 2} reduction by heme compounds. Here we showed that 1 muM of ACNQ is able to generate a significant catalytic wave for oxygen reduction, with onset at approximately 0 V vs. SHE. Similarly, adsorption of hemin on a carbon surface catalyses O{sub 2} reduction to H{sub 2}O{sub 2} with an onset of +0.2 V vs. SHE. To evaluate the catalytic pathways of live cells on cathodic oxygen reduction, two species of electrochemically active bacteria were selected as pure cultures, namely Acinetobacter calcoaceticus and Shewanella putrefaciens. The former appears to exploit a self-excreted redox compound with redox characteristics matching those of pyrroloquinoline quinone (PQQ) for extracellular electron transfer. The latter appears to utilise outer membrane-bound redox compounds. Interaction of quinones and cytochromes with the membrane-bound electron transfer chain is yet to be proven.

  1. Anaerobic oxidation of methane coupled to thiosulfate reduction in a biotrickling filter.

    Science.gov (United States)

    Cassarini, Chiara; Rene, Eldon R; Bhattarai, Susma; Esposito, Giovanni; Lens, Piet N L

    2017-09-01

    Microorganisms from an anaerobic methane oxidizing sediment were enriched with methane gas as the substrate in a biotrickling filter (BTF) using thiosulfate as electron acceptor for 213days. Thiosulfate disproportionation to sulfate and sulfide were the dominating sulfur conversion process in the BTF and the sulfide production rate was 0.5mmoll -1 day -1 . A specific group of sulfate reducing bacteria (SRB), belonging to the Desulforsarcina/Desulfococcus group, was enriched in the BTF. The BTF biomass showed maximum sulfate reduction rate (0.38mmoll -1 day -1 ) with methane as sole electron donor, measured in the absence of thiosulfate in the BTF. Therefore, a BTF fed with thiosulfate as electron acceptor can be used to enrich SRB of the DSS group and activate the inoculum for anaerobic oxidation of methane coupled to sulfate reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Microbiological evidence for Fe(III) reduction on early Earth

    Science.gov (United States)

    Vargas, Madeline; Kashefi, Kazem; Blunt-Harris, Elizabeth L.; Lovley, Derek R.

    1998-09-01

    It is generally considered that sulphur reduction was one of the earliest forms of microbial respiration, because the known microorganisms that are most closely related to the last common ancestor of modern life are primarily anaerobic, sulphur-reducing hyperthermophiles. However, geochemical evidence indicates that Fe(III) is more likely than sulphur to have been the first external electron acceptor of global significance in microbial metabolism. Here we show that Archaea and Bacteria that are most closely related to the last common ancestor can reduce Fe(III) to Fe(II) and conserve energy to support growth from this respiration. Surprisingly, even Thermotoga maritima, previously considered to have only a fermentative metabolism, could grow as a respiratory organism when Fe(III) was provided as an electron acceptor. These results provide microbiological evidence that Fe(III) reduction could have been an important process on early Earth and suggest that microorganisms might contribute to Fe(III) reduction in modern hot biospheres. Furthermore, our discovery that hyperthermophiles that had previously been thought to require sulphur for cultivation can instead be grown without the production of toxic and corrosive sulphide, should aid biochemical investigations of these poorly understood organisms.

  3. IN SITU DESTRUCTION OF CHLORINATED HYDROCARBON COMPOUNDS IN GROUNDWATER USING CATALYTIC REDUCTIVE REDUCTIVE DEHALOGENATION IN A REACTIVE WELL: TESTING AND OPERATIONAL EXPERIENCES. (R825421)

    Science.gov (United States)

    A groundwater treatment technology based on catalytic reductive dehalogenation has been developed to efficiently destroy chlorinated hydrocarbons in situ using a reactive well approach. The treatment process utilizes dissolved H2 as an electron donor, in...

  4. Luminosity geometric reduction factor from colliding bunches with different lengths

    Energy Technology Data Exchange (ETDEWEB)

    Verdu-Andres, S. [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2017-09-29

    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.

  5. In situ studies of NO reduction by H

    NARCIS (Netherlands)

    Roobol, S. B.; Onderwaater, W. G.; van Spronsen, M. A.; Carla, F; Balmes, O; Navarro-Paredes, V; Vendelbo, S.B.; Kooyman, P.J.; Elkjær, C. F.; Helveg, S; Felici, R; Frenken, J. W.M.; Groot, I.M.N.

    2017-01-01

    In situ surface X-ray diffraction and transmission electron microscopy at 1 bar show massive material transport of platinum during high-temperature NO reduction with H2. A Pt(110) single-crystal surface shows a wide variety of surface reconstructions and extensive faceting of the

  6. Monte Carlo 20 and 45 MeV Bremsstrahlung and dose-reduction calculations

    Energy Technology Data Exchange (ETDEWEB)

    Goosman, D.R.

    1984-08-14

    The SANDYL electron-photon coupled Monte Carlo code has been compared with previously published experimental bremsstrahlung data at 20.9 MeV electron energy. The code was then used to calculate forward-directed spectra, angular distributions and dose-reduction factors for three practical configurations. These are: 20 MeV electrons incident on 1 mm of W + 59 mm of Be, 45 MeV electrons of 1 mm of W and 45 MeV electrons on 1 mm of W + 147 mm of Be. The application of these results to flash radiography is discussed. 7 references, 12 figures, 1 table.

  7. Monte Carlo 20 and 45 MeV Bremsstrahlung and dose-reduction calculations

    International Nuclear Information System (INIS)

    Goosman, D.R.

    1984-01-01

    The SANDYL electron-photon coupled Monte Carlo code has been compared with previously published experimental bremsstrahlung data at 20.9 MeV electron energy. The code was then used to calculate forward-directed spectra, angular distributions and dose-reduction factors for three practical configurations. These are: 20 MeV electrons incident on 1 mm of W + 59 mm of Be, 45 MeV electrons of 1 mm of W and 45 MeV electrons on 1 mm of W + 147 mm of Be. The application of these results to flash radiography is discussed. 7 references, 12 figures, 1 table

  8. Harvesting multiple electron-hole pairs generated through plasmonic excitation of Au nanoparticles.

    Science.gov (United States)

    Kim, Youngsoo; Smith, Jeremy G; Jain, Prashant K

    2018-05-07

    Multi-electron redox reactions, although central to artificial photosynthesis, are kinetically sluggish. Amidst the search for synthetic catalysts for such processes, plasmonic nanoparticles have been found to catalyse multi-electron reduction of CO 2 under visible light. This example motivates the need for a general, insight-driven framework for plasmonic catalysis of such multi-electron chemistry. Here, we elucidate the principles underlying the extraction of multiple redox equivalents from a plasmonic photocatalyst. We measure the kinetics of electron harvesting from a gold nanoparticle photocatalyst as a function of photon flux. Our measurements, supported by theoretical modelling, reveal a regime where two-electron transfer from the excited gold nanoparticle becomes prevalent. Multiple electron harvesting becomes possible under continuous-wave, visible-light excitation of moderate intensity due to strong interband transitions in gold and electron-hole separation accomplished using a hole scavenger. These insights will help expand the utility of plasmonic photocatalysis beyond CO 2 reduction to other challenging multi-electron, multi-proton transformations such as N 2 fixation.

  9. Reduction in alert fatigue in an assisted electronic prescribing system, through the Lean Six Sigma methodology.

    Science.gov (United States)

    Cuéllar Monreal, Mª Jesús; Reig Aguado, Jorge; Font Noguera, Isabel; Poveda Andrés, José Luis

    2017-01-01

    To reduce the alert fatigue in our Assisted Electronic Prescribing System (AEPS), through the Lean Six Sigma (LSS) methodology. An observational (transversal) and retrospective study, in a general hospital with 850 beds and AEPS. The LSS methodology was followed in order to evaluate the alert fatigue situation in the AEPS system, to implement improvements, and to assess outcomes. The alerts generated during two trimesters studied (before and after the intervention) were analyzed. In order to measure the qualitative indicators, the most frequent alert types were analyzed, as well as the molecules responsible for over 50% of each type of alert. The action by the prescriber was analyzed in a sample of 496 prescriptions that generated such alerts. For each type of alert and molecule, there was a prioritization of the improvements to be implemented according to the alert generated and its quality. A second survey evaluated the pharmacist action for the alerts most highly valued by physicians. The problem, the objective, the work team and the project schedule were defined. A survey was designed in order to understand the opinion of the client about the alert system in the program. Based on the surveys collected (n = 136), the critical characteristics and the quanti/qualitative indicators were defined. Sixty (60) fields in the alert system were modified, corresponding to 32 molecules, and this led to a 28% reduction in the total number of alerts. Regarding quality indicators, false po sitive results were reduced by 25% (p < 0.05), 100% of those alerts ignored with justification were sustained, and there were no significant differences in user adherence to the system. The project improvements and outcomes were reviewed by the work team. LSS methodology has demonstrated being a valid tool for the quantitative and qualitative improvement of the alert system in an Assisted Electronic Prescription Program, thus reducing alert fatigue. Copyright AULA MEDICA EDICIONES 2014

  10. Volatile fatty acids as substrates for iron and sulfate reduction in Arctic marine sediments, Svalbard

    Science.gov (United States)

    Finke, N.; Vandieken, V.; Jorgensen, B. B.

    2006-12-01

    Anaerobic degradation of complex organic material in aquatic systems is a multi-step process. The metabolic products of fermentative bacteria serve as electron donors for the terminal oxidizing bacteria. In marine sediments, iron reduction and sulfate reduction are generally the most important terminal oxidation processes in the upper anoxic zone [1]. Microorganisms that reduce iron and sulfate may use a broad range of electron donors, yet the list of potential substrates provides little information about the substrates used in situ by these organisms. Investigations on the electron donors for sulfate reducers in marine sediments have shown that volatile fatty acids (VFA), and in particular acetate, together with hydrogen are the major substrates (e.g. [2-4]). Similar investigations for iron reduction or simultaneous iron and sulfate reduction are lacking for marine sediments. Furthermore, most of these studies were made in temperate sediments and little is known about the substrates for sulfate reducers in permanently cold sediments, which account for >90% of the ocean floor [5]. We investigated the relative contributions of iron reduction and sulfate reduction to the terminal oxidation of organic carbon and the importance of acetate, lactate, propionate, and isobutyrate as electron donors for iron and sulfate reduction in permanently cold, Arctic sediments from Svalbard. In the surface layer (0-2 cm) sulfate reduction accounted for 2/3 of the organic carbon oxidation (determined as DIC production), the remaining 1/3 were attributed to iron reduction. In the 5-9 cm layer sulfate reduction was the sole important terminal oxidation step. The contribution of acetate to terminal oxidation was determined by radiotracer incubation as well as from the accumulation after the inhibition of sulfate reduction by selenate. The rates determined with the two methods varied by less than 20%. Acetate turnover, determined with the tracer incubations, accounted for 10 and 40% of

  11. Inhibition Mechanism of Uranyl Reduction Induced by Calcium-Carbonato Complexes

    Science.gov (United States)

    Jones, M. E.; Bargar, J.; Fendorf, S. E.

    2015-12-01

    Uranium mobility in the subsurface is controlled by the redox state and chemical speciation, generally as minimally soluble U(IV) or soluble U(VI) species. In the presence of even low carbonate concentrations the uranyl-carbonato complex quickly becomes the dominant aqueous species; they are, in fact, the primary aqueous species in most groundwaters. Calcium in groundwater leads to ternary calcium-uranyl-carbonato complexes that limit the rate and extent of U(VI) reduction. This decrease in reduction rate has been attributed to surface processes, thermodynamic limitations, and kinetic factors. Here we present a new mechanism for the inhibition of ferrous iron reduction of uranyl-carbonato species in the presence of calcium. A series of experiments under variable Ca conditions were preformed to determine the role of Ca in the inhibition of U reduction by ferrous iron. Calcium ions in the Ca2UO2(CO3)3 complex sterically prevent the interaction of Fe(II) with U(VI), in turn preventing the Fe(II)-U(VI) distance required for electron transfer. The mechanism described here helps to predict U redox transformations in suboxic environments and clarifies the role of Ca in the fate and mobility of U. Electrochemical measurements further show the decrease of the U(VI) to U(V) redox potential of the uranyl-carbonato complex with decreasing pH suggesting the first electron transfer is critical determining the rate and extent of uranium reduction.

  12. CuZn Alloy- Based Electrocatalyst for CO2 Reduction

    KAUST Repository

    Alazmi, Amira

    2014-01-01

    , especially when the electronic energy is derived from renewable energies, such as solar, wind, geo-thermal and tidal. To achieve this goal, the development of an efficient electrocatalyst for CO2 reduction is essential. In this thesis, studies on CuZn alloys

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

    Science.gov (United States)

    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.

  14. Novel mode of microbial energy metabolism: organic carbon oxidation coupled to dissimilatory reduction of iron or manganese.

    Science.gov (United States)

    Lovley, D R; Phillips, E J

    1988-06-01

    A dissimilatory Fe(III)- and Mn(IV)-reducing microorganism was isolated from freshwater sediments of the Potomac River, Maryland. The isolate, designated GS-15, grew in defined anaerobic medium with acetate as the sole electron donor and Fe(III), Mn(IV), or nitrate as the sole electron acceptor. GS-15 oxidized acetate to carbon dioxide with the concomitant reduction of amorphic Fe(III) oxide to magnetite (Fe(3)O(4)). When Fe(III) citrate replaced amorphic Fe(III) oxide as the electron acceptor, GS-15 grew faster and reduced all of the added Fe(III) to Fe(II). GS-15 reduced a natural amorphic Fe(III) oxide but did not significantly reduce highly crystalline Fe(III) forms. Fe(III) was reduced optimally at pH 6.7 to 7 and at 30 to 35 degrees C. Ethanol, butyrate, and propionate could also serve as electron donors for Fe(III) reduction. A variety of other organic compounds and hydrogen could not. MnO(2) was completely reduced to Mn(II), which precipitated as rhodochrosite (MnCO(3)). Nitrate was reduced to ammonia. Oxygen could not serve as an electron acceptor, and it inhibited growth with the other electron acceptors. This is the first demonstration that microorganisms can completely oxidize organic compounds with Fe(III) or Mn(IV) as the sole electron acceptor and that oxidation of organic matter coupled to dissimilatory Fe(III) or Mn(IV) reduction can yield energy for microbial growth. GS-15 provides a model for how enzymatically catalyzed reactions can be quantitatively significant mechanisms for the reduction of iron and manganese in anaerobic environments.

  15. Enzymatic U(VI) reduction by Desulfosporosinus species

    International Nuclear Information System (INIS)

    Suzuki, Y.; Kelly, S.D.; Kemner, K.M.; Banfield, J.F.

    2004-01-01

    Here we tested U(VI) reduction by a Desulfosporosinus species (sp.) isolate and type strain (DSM 765) in cell suspensions (pH 7) containing 1 mM U(VI) and lactate, under an atmosphere containing N 2 -CO 2 -H 2 (90: 5: 5). Although neither Desulfosporosinus species (spp.) reduced U(VI) in cell suspensions with 0.25% Na-bicarbonate or 0.85% NaCl, U(VI) was reduced in these solutions by a control strain, desulfovibrio desulfuricans (ATCC 642). However, both Desulfosporosinus strains reduced U(VI) in cell suspensions depleted in bicarbonate and NaCl. No U(VI) reduction was observed without lactate and H 2 electron donors or with heat-killed cells, indicating enzymatic U(VI) reduction. Uranium(VI) reduction by both strains was inhibited when 1 mM CuCl 2 was added to the cell suspensions. Because the Desulfosporosinus DSM 765 does not contain cytochrome c 3 used by Desulfovibrio spp. to reduce U(VI), Desulfosporosinus species reduce uranium via a different enzymatic pathway. (orig.)

  16. Extracellular Electron Transport Coupling Biogeochemical Processes Centimeters

    DEFF Research Database (Denmark)

    Risgaard-Petersen, Nils; Fossing, Henrik; Christensen, Peter Bondo

    2010-01-01

    of the oxygen uptake in laboratory incubations of initially homogenized and stabilized sediment. Using microsensors and process rate measurements we further investigated the effect of the electric currents on sediment biogeochemistry. Dissolved sulfide readily donated electrons to the networks and could...... confirmed the depth range of the electric communication and indicated donation of electrons directly from organotrophic bacteria. The separation of oxidation and reduction processes created steep pH gradients eventually causing carbonate precipitation at the surface. The results indicate that electron...... exchanging organisms have major biogeochemical importance as they allow widely separated electron donors and acceptors to react with one another....

  17. Bacterial chromate reduction and product characterization

    International Nuclear Information System (INIS)

    Mehlhorn, R.J.; Buchanan, B.B.; Leighton, T.

    1992-11-01

    Bacillus subtilis reduced hexavalent chromate to trivalent chromium under either aerobic or anaerobic conditions. Reduction of CR(VI) and appearance of extracellular Cr(III) were demonstrated by electron spin resonance and spectrophotometry. Chromate reduction was stimulated more than five-fold by freeze-thawing, indicating that intracellular reductases or chemical reductants reduce chromate more rapidly than do intact cells. Moderately concentrated cells (10% pellet volume after centrifugation) reduced approximately 40 μM chromate/min (2 mg Cr/1-min) when exposed to 100 μM chromate (5 mg Cr/1). Highly concentrated cells (70% pellet volume) reduced more than 99.8% of 2 mM chromate (100 mg Cr/1) within 15 min. This rate of chromate reduction was of the same order of magnitude as the rate of respiration in aerobic cells. A substantial fraction of the reduction product (ca. 75%) was extracellular Cr(M), which could readily be separated from the cells by centrifugation. At high chromate concentrations, some fraction of reduced CR(VI) appeared to be taken up by cells, consistent with a detection of intracellular paramagnetic products. At low chromate concentrations, undefined growth medium alone reduced Cr(VI), but at a slow rate, relative to cells. Under appropriate conditions, B. subtilis appears to be an organism of choice for detoxifying chromate-contaminated soil and water

  18. Impact of an Electronic Cigarette on Smoking Reduction and Cessation in Schizophrenic Smokers: A Prospective 12-Month Pilot Study

    Directory of Open Access Journals (Sweden)

    Pasquale Caponnetto

    2013-01-01

    Full Text Available Background: Cigarette smoking is a tough addiction to break. This dependence is the most common dual diagnosis for individuals with schizophrenia. Currently three effective drugs are approved for smoking cessation: nicotine replacement therapy (NRT, varenicline and bupropion. However, some serious side effects of varenicline have been reported, including depression, suicidal thoughts, and suicide. The use of bupropion also has side effects. It should not be used by people who have epilepsy or any condition that lowers the seizure threshold, nor by people who take a specific class of drugs called monoamine oxidase inhibitors. Hence, there are pharmacodynamic reason to believe they could precipitate or exacerbate psychosis. For its capacity to deliver nicotine and provide a coping mechanism for conditioned smoking cues by replacing some of the rituals associated with smoking gestures, electronic-cigarettes may reduce nicotine withdrawal symptoms without serious side effects. Our recent work with ECs in healthy smokers not intending to quit consistently show surprisingly high success rates. We hypothesised that these positive findings could be replicated in difficult patients with schizophrenia This tool may help smokers with schizophrenia remain abstinent during their quitting attempts or to reduce cigarette consumption. Efficacy and safety of these devices in long-term smoking cessation and/or smoking reduction studies have never been investigated for this special population. Methods: In this study we monitored possible modifications in smoking habits of 14 smokers (not intending to quit with schizophrenia experimenting with the “Categoria” e-Cigarette with a focus on smoking reduction and smoking abstinence. Study participants were invited to attend six study visits: at baseline, week-4, week-8, week-12 week-24 and week 52. Product use, number of cigarettes smoked, carbon monoxide in exhaled breath (eCO and positive and negative symptoms of

  19. Study on Effects of Electron Donors on Phosphine Production from Anaerobic Activated Sludge

    Directory of Open Access Journals (Sweden)

    Jianping Cao

    2017-07-01

    Full Text Available The effects of different types and concentrations of electron donors (glucose, starch, methanol and sodium acetate on the formation of phosphine from anaerobic activated sludge that has been domesticated for a prolonged period were studied in small batch experiments. The results show that types and concentrations of electron donor have significant effects on the production of phosphine from anaerobic activated sludge. Among them, glucose was the most favourable electron donor, whereas sodium acetate was the least favourable electron donor for the removal of phosphorus and the production of phosphine. Higher concentrations of electron donors were more favourable for the reduction of phosphate into phosphine, and supplying more than nine times the amount of electron donor as theoretically required for the reduction of phosphate into phosphine was favourable for the production of phosphine.

  20. Effects of Enhanced Eathode Electron Emission on Hall Thruster Operation

    International Nuclear Information System (INIS)

    Raitses, Y.; Smirnov, A.; Fisch, N.J.

    2009-01-01

    Interesting discharge phenomena are observed that have to do with the interaction between the magnetized Hall thruster plasma and the neutralizing cathode. The steadystate parameters of a highly ionized thruster discharge are strongly influenced by the electron supply from the cathode. The enhancement of the cathode electron emission above its self-sustained level affects the discharge current and leads to a dramatic reduction of the plasma divergence and a suppression of large amplitude, low frequency discharge current oscillations usually related to an ionization instability. These effects correlate strongly with the reduction of the voltage drop in the region with the fringing magnetic field between the thruster channel and the cathode. The measured changes of the plasma properties suggest that the electron emission affects the electron cross-field transport in the thruster discharge. These trends are generalized for Hall thrusters of various configurations.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Junwei [Iowa State Univ., Ames, IA (United States)

    1999-11-08

    Surface plasmon resonance was utilized to enhance the electron transfer at silver/solution interfaces. Photoelectrochemical reductions of nitrite, nitrate, and CO2 were studied on electrochemically roughened silver electrode surfaces. The dependence of the photocurrent on photon energy, applied potential and concentration of nitrite demonstrates that the photoelectrochemical reduction proceeds via photoemission process followed by the capture of hydrated electrons. The excitation of plasmon resonances in nanosized metal structures resulted in the enhancement of the photoemission process. In the case of photoelectrocatalytic reduction of CO2, large photoelectrocatalytic effect for the reduction of CO2 was observed in the presence of surface adsorbed methylviologen, which functions as a mediator for the photoexcited electron transfer from silver metal to CO2 in solution. Photoinduced reduction of microperoxidase-11 adsorbed on roughened silver electrode was also observed and attributed to the direct photoejection of free electrons of silver metal. Surface plasmon assisted electron transfer at nanostructured silver particle surfaces was further determined by EPR method.

  2. Simulation Study of Electronic Damping of Microphonic Vibrations in Superconducting Cavities

    International Nuclear Information System (INIS)

    Alicia Hofler; Jean Delayen

    2005-01-01

    Electronic damping of microphonic vibrations in superconducting rf cavities involves an active modulation of the cavity field amplitude in order to induce ponderomotive forces that counteract the effect of ambient vibrations on the cavity frequency. In lightly beam loaded cavities, a reduction of the microphonics-induced frequency excursions leads directly to a reduction of the rf power required for phase and amplitude stabilization. Jefferson Lab is investigating such an electronic damping scheme that could be applied to the JLab 12 GeV upgrade, the RIA driver, and possibly to energy-recovering superconducting linacs. This paper discusses a model and presents simulation results for electronic damping of microphonic vibrations

  3. Organic electronic devices using phthalimide compounds

    Science.gov (United States)

    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.

  4. Achieving high field-effect mobility in amorphous indium-gallium-zinc oxide by capping a strong reduction layer.

    Science.gov (United States)

    Zan, Hsiao-Wen; Yeh, Chun-Cheng; Meng, Hsin-Fei; Tsai, Chuang-Chuang; Chen, Liang-Hao

    2012-07-10

    An effective approach to reduce defects and increase electron mobility in a-IGZO thin-film transistors (a-IGZO TFTs) is introduced. A strong reduction layer, calcium, is capped onto the back interface of a-IGZO TFT. After calcium capping, the effective electron mobility of a-IGZO TFT increases from 12 cm(2) V(-1) s(-1) to 160 cm(2) V(-1) s(-1). This high mobility is a new record, which implies that the proposed defect reduction effect is key to improve electron transport in oxide semiconductor materials. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Reduction of Magnetite in the Presence of Activated Carbon Using Mechanical Alloying

    Directory of Open Access Journals (Sweden)

    Ledwaba Harry Moloto

    2013-01-01

    Full Text Available The reduction behaviour of magnetite using graphite under ball-milling conditions (using a planetary mono mill, Fritsch Pulverisette 6 has been investigated. The reaction of magnetite and graphite at different milling conditions leads to the formation of Fe2+ and Fe3+ species, the former increasing at the expense of Fe3O4. Fe3O4 completely disappeared after a ball to powder ratio of 50 : 1 and beyond. The Fe2+ species were confirmed to be due to FeO using Mössbauer Spectroscopy and X-ray diffraction techniques. Scanning electron microscopy and transmission electron microscopy analyses confirm the reduction of magnetite to wüstite.

  6. Fundamental limits on gas-phase chemical reduction of NOx in a plasma

    Energy Technology Data Exchange (ETDEWEB)

    Penetrante, B.M.; Hsiao, M.C.; Merritt, B.T.; Vogtlin, G.E. [Lawrence Livermore National Lab., CA (United States)

    1997-12-31

    In the plasma, the electrons do not react directly with the NOx molecules. The electrons collide mainly with the background gas molecules like N{sub 2}, O{sub 2} and H{sub 2}O. Electron impact on these molecules result partly in dissociation reactions that produce reactive species like N, O and OH. The NOx in the engine exhaust gas initially consist mostly of NO. The ground state nitrogen atom, N, is the only species that could lead to the chemical reduction of NO to N{sub 2}. The O radical oxidizes NO to NO{sub 2} leaving the same amount of NOx. The OH radical converts NO{sub 2} to nitric acid. Acid products in the plasma can easily get adsorbed on surfaces in the plasma reactor and in the pipes. When undetected, the absence of these oxidation products can often be mistaken for chemical reduction of NOx. In this paper the authors will examine the gas-phase chemical reduction of NOx. They will show that under the best conditions, the plasma can chemically reduce 1.6 grams of NOx per brake-horsepower-hour [g(NOx)/bhp-hr] when 5% of the engine output energy is delivered to the plasma.

  7. Metaproteomics Identifies the Protein Machinery Involved in Metal and Radionuclide Reduction in Subsurface Microbiomes and Elucidates Mechanisms and U(VI) Reduction Immobilization

    Energy Technology Data Exchange (ETDEWEB)

    Pfiffner, Susan M. [Univ. of Tennessee, Knoxville, TN (United States); Löffler, Frank [Univ. of Tennessee, Knoxville, TN (United States); Ritalahti, Kirsti [Univ. of Tennessee, Knoxville, TN (United States); Sayler, Gary [Univ. of Tennessee, Knoxville, TN (United States); Layton, Alice [Univ. of Tennessee, Knoxville, TN (United States); Hettich, Robert [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-08-31

    analyses, and gene expression studies to support the metaproteomics characterizations. Growth experiments of target microorganisms (Anaeromyxobacter, Shewanella, Geobacter) revealed tremendous respiratory versatility, as evidenced by the ability to utilize a range of electron donors (e.g. acetate, hydrogen, pyruvate, lactate, succinate, formate) and electron acceptors (e.g. nitrate, fumarate, halogenated phenols, ferric iron, nitrous oxide, etc.). In particular, the dissimilatory metabolic reduction of metals, including radionuclides, by target microorganisms spurred interest for in situ bioremediation of contaminated soils and sediments. Distinct c-type cytochrome expression patterns were observed in target microorganisms grown with the different electron acceptors. For each target microorganism, the core proteome covered almost all metabolic pathways represented by their corresponding pan-proteomes. Unique proteins were detected for each target microorganism, and their expression and possible functionalities were linked to specific growth conditions through proteomics measurements. Optimization of the proteomic tools included in-depth comprehensive metagenomic and metaproteomic analyses on a limited number of samples. The optimized metaproteomic analyses were then applied to Oak Ridge IFRC field samples from the slow-release substrate biostimulation. Metaproteomic analysis and pathway mapping results demonstrated the distinct effects of metal and non-metal growth conditions on the proteome expression. With these metaproteomic tools, we identified which previously hypothetical metabolic pathways were active during the analyzed time points of the slow release substrate biostimulation. Thus, we demonstrated the utility of these tools for site assessment, efficient implementation of bioremediation and long-term monitoring. This research of detailed protein analysis linked with metal reduction activity did (1) show that c-type cytochrome isoforms, previously associated with

  8. Effect of electron temperature on small-amplitude electron acoustic solitary waves in non-planar geometry

    Science.gov (United States)

    Bansal, Sona; Aggarwal, Munish; Gill, Tarsem Singh

    2018-04-01

    Effects of electron temperature on the propagation of electron acoustic solitary waves in plasma with stationary ions, cold and superthermal hot electrons is investigated in non-planar geometry employing reductive perturbation method. Modified Korteweg-de Vries equation is derived in the small amplitude approximation limit. The analytical and numerical calculations of the KdV equation reveal that the phase velocity of the electron acoustic waves increases as one goes from planar to non planar geometry. It is shown that the electron temperature ratio changes the width and amplitude of the solitary waves and when electron temperature is not taken into account,our results completely agree with the results of Javidan & Pakzad (2012). It is found that at small values of τ , solitary wave structures behave differently in cylindrical ( {m} = 1), spherical ( {m} = 2) and planar geometry ( {m} = 0) but looks similar at large values of τ . These results may be useful to understand the solitary wave characteristics in laboratory and space environments where the plasma have multiple temperature electrons.

  9. Design of electromagnetically compatible electronics

    NARCIS (Netherlands)

    Reitsma, G.P.

    2005-01-01

    EMC is a channel capacity problem, where with the help of adaptation the signal coding and signal processing and reduction of unintentional coupling, the chance of corruption of the transferred signal information is minimized. For the topology of an electronic circuit this implies that with the help

  10. Electron Bunch Timing with Femtosecond Precision in a Superconducting Free-Electron Laser

    Science.gov (United States)

    Löhl, F.; Arsov, V.; Felber, M.; Hacker, K.; Jalmuzna, W.; Lorbeer, B.; Ludwig, F.; Matthiesen, K.-H.; Schlarb, H.; Schmidt, B.; Schmüser, P.; Schulz, S.; Szewinski, J.; Winter, A.; Zemella, J.

    2010-04-01

    High-gain free-electron lasers (FELs) are capable of generating femtosecond x-ray pulses with peak brilliances many orders of magnitude higher than at other existing x-ray sources. In order to fully exploit the opportunities offered by these femtosecond light pulses in time-resolved experiments, an unprecedented synchronization accuracy is required. In this Letter, we distributed the pulse train of a mode-locked fiber laser with femtosecond stability to different locations in the linear accelerator of the soft x-ray FEL FLASH. A novel electro-optic detection scheme was applied to measure the electron bunch arrival time with an as yet unrivaled precision of 6 fs (rms). With two beam-based feedback systems we succeeded in stabilizing both the arrival time and the electron bunch compression process within two magnetic chicanes, yielding a significant reduction of the FEL pulse energy jitter.

  11. Electron Bunch Timing with Femtosecond Precision in a Superconducting Free-Electron Laser

    International Nuclear Information System (INIS)

    Loehl, F.; Arsov, V.; Felber, M.; Hacker, K.; Lorbeer, B.; Ludwig, F.; Matthiesen, K.-H.; Schlarb, H.; Schmidt, B.; Winter, A.; Jalmuzna, W.; Schmueser, P.; Schulz, S.; Zemella, J.; Szewinski, J.

    2010-01-01

    High-gain free-electron lasers (FELs) are capable of generating femtosecond x-ray pulses with peak brilliances many orders of magnitude higher than at other existing x-ray sources. In order to fully exploit the opportunities offered by these femtosecond light pulses in time-resolved experiments, an unprecedented synchronization accuracy is required. In this Letter, we distributed the pulse train of a mode-locked fiber laser with femtosecond stability to different locations in the linear accelerator of the soft x-ray FEL FLASH. A novel electro-optic detection scheme was applied to measure the electron bunch arrival time with an as yet unrivaled precision of 6 fs (rms). With two beam-based feedback systems we succeeded in stabilizing both the arrival time and the electron bunch compression process within two magnetic chicanes, yielding a significant reduction of the FEL pulse energy jitter.

  12. Kinetic Isotope Effects in the Reduction of Methyl Iodide

    DEFF Research Database (Denmark)

    Holm, Torkil

    1999-01-01

    a Grignard reagent to methyl iodide, and for reduction of methyl iodide with tributyltin hydride or with gaseous hydrogen iodide. Very small KIE's were found for electron transfer to methyl iodide from magnesium in ether or from sodium in ammonia. The reason may be that these reactions are transport...

  13. Green reduction of graphene oxide using alanine.

    Science.gov (United States)

    Wang, Jiabin; Salihi, Elif Caliskan; Šiller, Lidija

    2017-03-01

    There remains a real need for the easy, eco-friendly and scalable preparation method of graphene due to various potential applications. Chemical reduction is the most versatile method for the large scale production of graphene. Here we report the operating conditions for a one-step, economical and green synthesis method for the reduction of graphene oxide using a biomolecule (alanine). Graphene oxide was produced by the oxidation and exfoliation of natural graphite flake with strong oxidants using Hummers method (Hummers and Offeman, 1958), but the method was revised in our laboratory to set up a safe and environmentally friendly route. The reduction of graphene oxide was investigated using alanine at various operating conditions in order to set up optimum conditions (treatment time, temperature and concentration of the reagent). Samples have been characterized by using UV-Visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, Raman spectroscopy and X-ray diffraction analysis. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

  14. Electrochemical reduction of nitroaromatic compounds by single sheet iron oxide coated electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Li-Zhi, E-mail: lizhi@plen.ku.dk [Department of Plant and Environmental Sciences, University of Copenhagen, Thorvaldsensvej 40, DK–1871 Frederiksberg C (Denmark); Hansen, Hans Christian B. [Department of Plant and Environmental Sciences, University of Copenhagen, Thorvaldsensvej 40, DK–1871 Frederiksberg C (Denmark); Bjerrum, Morten Jannik [Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK–2100 København Ø (Denmark)

    2016-04-05

    Highlights: • Composite layers of single sheet iron oxides were coated on indium tin oxide electrodes. • Single sheet iron oxide is an electro-catalyst for reduction of nitroaromatic compounds in aqueous solution. • The reduction is well explained by a diffusion layer model. • The charge properties of the nitrophenols have an important influence on reduction. • Low-cost iron oxide based materials are promising electro-catalyst for water treatment. - Abstract: Nitroaromatic compounds are substantial hazard to the environment and to the supply of clean drinking water. We report here the successful reduction of nitroaromatic compounds by use of iron oxide coated electrodes, and demonstrate that single sheet iron oxides formed from layered iron(II)-iron(III) hydroxides have unusual electrocatalytic reactivity. Electrodes were produced by coating of single sheet iron oxides on indium tin oxide electrodes. A reduction current density of 10 to 30 μA cm{sup −2} was observed in stirred aqueous solution at pH 7 with concentrations of 25 to 400 μM of the nitroaromatic compound at a potential of −0.7 V vs. SHE. Fast mass transfer favors the initial reduction of the nitroaromatic compound which is well explained by a diffusion layer model. Reduction was found to comprise two consecutive reactions: a fast four-electron first-order reduction of the nitro-group to the hydroxylamine-intermediate (rate constant = 0.28 h{sup −1}) followed by a slower two-electron zero-order reduction resulting in the final amino product (rate constant = 6.9 μM h{sup −1}). The zero-order of the latter reduction was attributed to saturation of the electrode surface with hydroxylamine-intermediates which have a more negative half-wave potential than the parent compound. For reduction of nitroaromatic compounds, the SSI electrode is found superior to metal electrodes due to low cost and high stability, and superior to carbon-based electrodes in terms of high coulombic efficiency and

  15. A Comparative Study of Physiological Monitoring with a Wearable Opto-Electronic Patch Sensor (OEPS for Motion Reduction

    Directory of Open Access Journals (Sweden)

    Abdullah Alzahrani

    2015-06-01

    Full Text Available This paper presents a comparative study in physiological monitoring between a wearable opto-electronic patch sensor (OEPS comprising a three-axis Microelectromechanical systems (MEMs accelerometer (3MA and commercial devices. The study aims to effectively capture critical physiological parameters, for instance, oxygen saturation, heart rate, respiration rate and heart rate variability, as extracted from the pulsatile waveforms captured by OEPS against motion artefacts when using the commercial probe. The protocol involved 16 healthy subjects and was designed to test the features of OEPS, with emphasis on the effective reduction of motion artefacts through the utilization of a 3MA as a movement reference. The results show significant agreement between the heart rates from the reference measurements and the recovered signals. Significance of standard deviation and error of mean yield values of 2.27 and 0.65 beats per minute, respectively; and a high correlation (0.97 between the results of the commercial sensor and OEPS. T, Wilcoxon and Bland-Altman with 95% limit of agreement tests were also applied in the comparison of heart rates extracted from these sensors, yielding a mean difference (MD: 0.08. The outcome of the present work incites the prospects of OEPS on physiological monitoring during physical activities.

  16. Electron tunneling in carbon nanotube composites

    International Nuclear Information System (INIS)

    Gau, C; Kuo, Cheng-Yung; Ko, H S

    2009-01-01

    Nanocomposites, such as polymer blending with carbon nanotubes (CNTs), have been shown to have a drastic reduction in the resistivity and become conductive when the CNTs concentration has reached a certain percolation threshold. The reduction could be more than a millionth of the original polymer material. This has been realized as the formation of an infinite cluster of connected CNTs or pathways. Therefore, the conductivity of a nanocomposite should follow that of CNTs. Here we show that the resistivity of a nanocomposite is not governed by the interconnected CNTs, but the polymer between neighboring CNTs. That is, polymer-CNTs exhibit the nature of a conducting polymer, which can be explained as the tunneling of electrons one by one from the first CNT electrode to the next-nearest CNT electrode, forming a CNT/polymer pathway. A conduction model based on the tunneling of electrons passing, one by one, through the polymer gap between two neighboring CNT electrodes is formulated and derived. This model can accurately predict the significant reduction of the polymer-CNTs' resistivity with the addition of CNTs. The temperature effect can be readily incorporated to account for resistivity variation with the temperature of this nanocomposites.

  17. From chemolithoautotrophs to electrolithoautotrophs: CO2 fixation by Fe(II)-oxidizing bacteria coupled with direct uptake of electrons from solid electron sources.

    Science.gov (United States)

    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.

  18. Reduction mechanisms of ethylene carbonate on si anodes of lithium-ion batteries: effects of degree of lithiation and nature of exposed surface.

    Science.gov (United States)

    Martinez de la Hoz, Julibeth M; Leung, Kevin; Balbuena, Perla B

    2013-12-26

    Ab initio molecular dynamics simulations are used to identify mechanisms of reduction of ethylene carbonate on Si surfaces at various degrees of lithiation, where the low-coordinated surface Si atoms are saturated with O, OH, or H functional groups. The lowest Si content surfaces are represented by quasi-amorphous LiSi4 and LiSi2; intermediate lithiation is given by LiSi crystalline facets, and the highest Li content is studied through Li13Si4 surfaces. It is found that ethylene carbonate (EC) reduction mechanisms depend significantly on the degree of lithiation of the surface. On LiSi surfaces EC is reduced according to two different two-electron mechanisms (one simultaneous and one sequential), which are independent of specific surface functionalization or nature of exposed facets. On the less lithiated surfaces, the simultaneous two-electron reduction is found more frequently. In that mechanism, the EC reduction is initiated by the formation of a C-Si bond that allows adsorption of the intact molecule to the surface and is followed by electron transfer and ring-opening. Strongly lithiated Li13Si4 surfaces are found to be highly reactive. Reduction of adsorbed EC molecules occurs via a four-electron mechanism yielding as reduction products CO(2-) and O(C2H4)O(2-). Direct transfer of two electrons to EC molecules in liquid phase is also possible, resulting in the presence of O(C2H4)OCO(2-) anions in the liquid phase.

  19. A simple electron-beam lithography system

    DEFF Research Database (Denmark)

    Mølhave, Kristian; Madsen, Dorte Nørgaard; Bøggild, Peter

    2005-01-01

    A large number of applications of electron-beam lithography (EBL) systems in nanotechnology have been demonstrated in recent years. In this paper we present a simple and general-purpose EBL system constructed by insertion of an electrostatic deflector plate system at the electron-beam exit...... of the column of a scanning electron microscope (SEM). The system can easily be mounted on most standard SEM systems. The tested setup allows an area of up to about 50 x 50 pm to be scanned, if the upper limit for acceptable reduction of the SEM resolution is set to 10 run. We demonstrate how the EBL system can...... be used to write three-dimensional nanostructures by electron-beam deposition. (C) 2004 Elsevier B.V. All rights reserved....

  20. Enzymology of Electron Transport: Energy Generation with Geochemical Consequences

    Energy Technology Data Exchange (ETDEWEB)

    Dichristina, Thomas J.; Fredrickson, Jim K.; Zachara, John M.

    2005-12-20

    Dissimilatory metal-reducing bacteria (DMRB) are important components of the microbial community residing in redox-stratified freshwater and marine environments. DMRB occupy a central position in the biogeochemical cycles of metals, metalloids and radionuclides, and serve as catalysts for a variety of other environmentally important processes including biomineralization, biocorrosion, bioremediation and mediators of ground water quality. DMRB are presented, however, with a unique physiological challenge: they are required to respire anaerobically on terminal electron acceptors which are either highly insoluble (e.g., Fe(III)- and Mn(IV)-oxides) and reduced to soluble end-products or highly soluble (e.g., U(VI) and Tc(VII)) and reduced to insoluble end-products. To overcome physiological problems associated with metal and radionuclide solubility, DMRB are postulated to employ a variety of novel respiratory strategies not found in other gram-negative bacteria which respire on soluble electron acceptors such as O2, NO3- and SO42-. The novel respiratory strategies include (1) direct enzymatic reduction at the outer membrane, (2) electron shuttling pathways and (3) metal solubilization by exogenous or bacterially-produced organic ligands followed by reduction of soluble organic-metal compounds. The first section of this chapter highlights the latest findings on the enzymatic mechanisms of metal and radionuclide reduction by two of the most extensively studied DMRB (Geobacter and Shewanella), with particular emphasis on electron transport chain enzymology. The second section emphasizes the geochemical consequences of DMRB activity, including the direct and indirect effects on metal solubility, the reductive transformation of Fe- and Mn-containing minerals, and the biogeochemical cycling of metals at redox interfaces in chemically stratified environments.

  1. Enzymology of Electron Transport: Energy Generation with Geochemical Consequences

    International Nuclear Information System (INIS)

    Dichristina, Thomas J.; Fredrickson, Jim K.; Zachara, John M.

    2005-01-01

    Dissimilatory metal-reducing bacteria (DMRB) are important components of the microbial community residing in redox-stratified freshwater and marine environments. DMRB occupy a central position in the biogeochemical cycles of metals, metalloids and radionuclides, and serve as catalysts for a variety of other environmentally important processes including biomineralization, biocorrosion, bioremediation and mediators of ground water quality. DMRB are presented, however, with a unique physiological challenge: they are required to respire anaerobically on terminal electron acceptors which are either highly insoluble (e.g., Fe(III)- and Mn(IV)-oxides) and reduced to soluble end-products or highly soluble (e.g., U(VI) and Tc(VII)) and reduced to insoluble end-products. To overcome physiological problems associated with metal and radionuclide solubility, DMRB are postulated to employ a variety of novel respiratory strategies not found in other gram-negative bacteria which respire on soluble electron acceptors such as O2, NO3- and SO42-. The novel respiratory strategies include (1) direct enzymatic reduction at the outer membrane, (2) electron shuttling pathways and (3) metal solubilization by exogenous or bacterially-produced organic ligands followed by reduction of soluble organic-metal compounds. The first section of this chapter highlights the latest findings on the enzymatic mechanisms of metal and radionuclide reduction by two of the most extensively studied DMRB (Geobacter and Shewanella), with particular emphasis on electron transport chain enzymology. The second section emphasizes the geochemical consequences of DMRB activity, including the direct and indirect effects on metal solubility, the reductive transformation of Fe- and Mn-containing minerals, and the biogeochemical cycling of metals at redox interfaces in chemically stratified environments

  2. Investigation of the charge-transfer in photo-excited nanoparticles for CO2 reduction in non-aqueous media

    Directory of Open Access Journals (Sweden)

    Dimitrijević Nada M.

    2013-01-01

    Full Text Available Photoinduced charge separation in TiO2 and Cu2O semiconductor nanoparticles was examined using Electron Paramagnetic Resonance spectroscopy in order to get insight into the photocatalytic reduction of CO2 in nonaqueous media. For dissolution/grafting of CO2 we have used carboxy-PEG4-amine, and as a solvent poly(ethylene glycol 200. We have found that, in this system, reduction of CO2 starts at potential of -0.5 V vs Ag/AgCl, which is significantly more positive than the potential for electrochemical reduction of CO2 in most organic solvents and water (-2.0 V vs. Ag/AgCl. The electron transfer from excited nanoparticles to CO2 is governed both by thermodynamic and kinetic parameters, namely by the redox potential of conduction band electrons and adsorption/binding of CO2 on the surface of nanoparticles.

  3. Novel Insights Into Microbial Uranium Reduction and Immobilization

    Science.gov (United States)

    Loeffler, F. E.; Fletcher, K.; Thomas, S.; Kemner, K. M.; Boyanov, M.; Sanford, R.

    2010-12-01

    Many ferric iron- and manganese oxide-reducing bacteria affect the oxidation state and complexation of toxic radionuclides in subsurface environments. Relevant to uranium (U) speciation are bacteria that reduce predominantly water-soluble and mobile U(VI) to U(IV), which has reduced solubility and typically forms the uraninite (UO2) mineral. Gram-negative model organisms including Shewanella spp., Geobacter spp., and more recently Anaeromyxobacter spp. use U(VI) as growth-supporting electron acceptor; however, the biomass yields are lower than predicted based on the theoretical free energy changes associated with U(VI)-to-U(IV) reduction. Recent findings demonstrated that U(VI) reduction is not limited to Gram-negative bacteria, and members of the genus Desulfitobacterium, which are commonly found in soil and subsurface environments, share the ability to reduce U(VI). Interestingly, extended X-ray absorption fine structure (EXAFS) analysis demonstrated that the U(IV) produced in cultures of five Desulfitobacterium spp. was not UO2 but rather a phase or mineral composed of mononuclear U(IV) atoms. Since the properties of the reduced product influence U(IV) fate, knowledge of the diversity of U reduction mechanisms and the stability of the end products is desirable for controlling and predicting U fate. For example, UO2 is susceptible to reoxidation by oxidants, and oxic/anoxic interface processes are controlling the stability of the precipitated material. In other words, metal reducers that thrive at the oxic/anoxic interface are likely key players affecting long-term U fate. Anaeromyxobacter spp. are facultative microaerophiles and grow with oxygen as electron acceptor at partial pressures equal to or below 0.18 atm. Thus, Anaeromyxobacter are uniquely adapted to life at the oxic-anoxic interface where they consume oxygen and take advantage of oxidized metal species including U(VI) as electron acceptors. The application of 16S rRNA gene-targeted qPCR approaches

  4. Studies on biological reduction of chromate by Streptomyces griseus

    International Nuclear Information System (INIS)

    Poopal, Ashwini C.; Laxman, R. Seeta

    2009-01-01

    Chromium is a toxic heavy metal used in various industries and leads to environmental pollution due to improper handling. The most toxic form of chromium Cr(VI) can be converted to less toxic Cr(III) by reduction. Among the actinomycetes tested for chromate reduction, thirteen strains reduced Cr(VI) to Cr(III), of which one strain of Streptomyces griseus (NCIM 2020) was most efficient showing complete reduction within 24 h. The organism was able to use a number of carbon sources as electron donors. Sulphate, nitrate, chloride and carbonate had no effect on chromate reduction during growth while cations such as Cd, Ni, Co and Cu were inhibitory to varying degrees. Chromate reduction was associated with the bacterial cells and sonication was the best method of cell breakage to release the enzyme. The enzyme was constitutive and did not require presence of chromate during growth for expression of activity. Chromate reduction with cell free extract (CFE) was observed without added NADH. However, addition of NAD(P)H resulted in 2-3-fold increase in activity. Chromate reductase showed optimum activity at 28 deg. C and pH 7.

  5. Green reduction of graphene oxide using alanine

    International Nuclear Information System (INIS)

    Wang, Jiabin; Salihi, Elif Caliskan; Šiller, Lidija

    2017-01-01

    There remains a real need for the easy, eco-friendly and scalable preparation method of graphene due to various potential applications. Chemical reduction is the most versatile method for the large scale production of graphene. Here we report the operating conditions for a one-step, economical and green synthesis method for the reduction of graphene oxide using a biomolecule (alanine). Graphene oxide was produced by the oxidation and exfoliation of natural graphite flake with strong oxidants using Hummers method (Hummers and Offeman, 1958), but the method was revised in our laboratory to set up a safe and environmentally friendly route. The reduction of graphene oxide was investigated using alanine at various operating conditions in order to set up optimum conditions (treatment time, temperature and concentration of the reagent). Samples have been characterized by using UV–Visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, Raman spectroscopy and X-ray diffraction analysis. - Highlights: • An environmentally friendly route was reported for the chemical reduction of graphene oxide (GO). • Alanine could reduce GO to rGO (reduced graphene oxide) without using any stabilizer or alcaline medium. • Characterization studies confirmed the successful deoxygenation of GO.

  6. Green reduction of graphene oxide using alanine

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jiabin [Newcastle University, School of Chemical Engineering and Advanced Materials, Newcastle upon Tyne NE1 7RU (United Kingdom); Salihi, Elif Caliskan, E-mail: caliskanelif@gmail.com [Newcastle University, School of Chemical Engineering and Advanced Materials, Newcastle upon Tyne NE1 7RU (United Kingdom); Marmara University, Faculty of Pharmacy, Department of Basic Pharmaceutical Sciences, 34668 Istanbul (Turkey); Šiller, Lidija [Newcastle University, School of Chemical Engineering and Advanced Materials, Newcastle upon Tyne NE1 7RU (United Kingdom)

    2017-03-01

    There remains a real need for the easy, eco-friendly and scalable preparation method of graphene due to various potential applications. Chemical reduction is the most versatile method for the large scale production of graphene. Here we report the operating conditions for a one-step, economical and green synthesis method for the reduction of graphene oxide using a biomolecule (alanine). Graphene oxide was produced by the oxidation and exfoliation of natural graphite flake with strong oxidants using Hummers method (Hummers and Offeman, 1958), but the method was revised in our laboratory to set up a safe and environmentally friendly route. The reduction of graphene oxide was investigated using alanine at various operating conditions in order to set up optimum conditions (treatment time, temperature and concentration of the reagent). Samples have been characterized by using UV–Visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, Raman spectroscopy and X-ray diffraction analysis. - Highlights: • An environmentally friendly route was reported for the chemical reduction of graphene oxide (GO). • Alanine could reduce GO to rGO (reduced graphene oxide) without using any stabilizer or alcaline medium. • Characterization studies confirmed the successful deoxygenation of GO.

  7. Reductive Dehalogenation of Trichloroacetic Acid by Trichlorobacter thiogenes gen. nov., sp. nov.

    Science.gov (United States)

    De Wever, Helene; Cole, James R.; Fettig, Michael R.; Hogan, Deborah A.; Tiedje, James M.

    2000-01-01

    A bacterium able to grow via reductive dechlorination of trichloroacetate was isolated from anaerobic soil enrichments. The isolate, designated strain K1, is a member of the δ proteobacteria and is related to other known sulfur and ferric iron reducers. In anaerobic mineral media supplemented with acetate and trichloroacetate, its doubling time was 6 h. Alternative electron donor and acceptors were acetoin and sulfur or fumarate, respectively. Trichloroacetate dehalogenation activity was constitutively present, and the dechlorination product was dichloroacetate and chloride. Trichloroacetate conversion seemed to be coupled to a novel sulfur-sulfide redox cycle, which shuttled electrons from acetate oxidation to trichloroacetate reduction. In view of its unique physiological characteristics, the name Trichlorobacter thiogenes is suggested for strain K1. PMID:10831402

  8. Electrocatalysis of oxygen reduction on nitrogen-containing multi-walled carbon nanotube modified glassy carbon electrodes

    International Nuclear Information System (INIS)

    Vikkisk, Merilin; Kruusenberg, Ivar; Joost, Urmas; Shulga, Eugene; Tammeveski, Kaido

    2013-01-01

    Highlights: ► Pyrolysis in the presence of urea was used for nitrogen doping of carbon nanotubes. ► N-doped carbon nanotubes were used as catalysts for the oxygen reduction reaction. ► N-doped carbon material showed a high catalytic activity for ORR in alkaline media. ► N-containing CNT material is an attractive cathode catalyst for alkaline membrane fuel cells. - Abstract: The electrochemical reduction of oxygen was studied on nitrogen-doped multi-walled carbon nanotube (NCNT) modified glassy carbon (GC) electrodes employing the rotating disk electrode (RDE) method. Nitrogen doping was achieved by simple pyrolysis of the carbon nanotube material in the presence of urea. The surface morphology and composition of the NCNT samples were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The SEM images revealed a rather uniform distribution of NCNTs on the GC electrode substrate. The XPS analysis showed a successful doping of carbon nanotubes with nitrogen species. The RDE results revealed that in alkaline solution the N-doped nanotube materials showed a remarkable electrocatalytic activity towards oxygen reduction. At low overpotentials the reduction of oxygen followed a two-electron pathway on undoped carbon nanotube modified GC electrodes, whereas on NCNT/GC electrodes a four-electron pathway of O 2 reduction predominated. The results obtained are significant for the development of nitrogen-doped carbon-based cathodes for alkaline membrane fuel cells.

  9. Reductive Dissolution of Goethite and Hematite by Reduced Flavins

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Zhi; Zachara, John M.; Wang, Zheming; Shi, Liang; Fredrickson, Jim K.

    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 than 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.

  10. Long distance electron transport in marine sediments: Microbial and geochemical implications

    DEFF Research Database (Denmark)

    Risgaard-Petersen, Nils; Larsen, Steffen; Pfeffer, Christian

    and promotes the formation of Mg-calcite and iron oxides in the oxic zone. Oxygen seems to be the major electron acceptor, and more than 40% of the oxygen consumption in sediments can be driven by long distance electron transfer from distant electron donors. The major e-donor is sulfide, which is oxidized......Anaerobic oxidation of organic matter in marine sediment is traditionally considered to be coupled to oxygen reduction via a cascade of redox processes and transport of intermittent electron donors and acceptors. Electric currents have been found to shortcut this cascade and directly couple...... oxidation of sulphide centimeters down in marine sediment to the reduction of oxygen at the very surface1 . This electric coupling of spatially separated redox half-reactions seems to be mediated by centimeter long filamentous Desulfubulbus affiliated bacteria with morphological and ultra...

  11. pH-dependent electron transfer reaction and direct bioelectrocatalysis of the quinohemoprotein pyranose dehydrogenase

    Energy Technology Data Exchange (ETDEWEB)

    Takeda, Kouta [Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan); Matsumura, Hirotoshi; Ishida, Takuya [Department of Biomaterial Sciences, Graduate School of Agriculture and Life Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-8657 (Japan); Yoshida, Makoto [Department of Environmental and Natural Resource Science, Tokyo University of Agriculture and Technology, Fuchu, Tokyo 183-8509 (Japan); Igarashi, Kiyohiko; Samejima, Masahiro [Department of Biomaterial Sciences, Graduate School of Agriculture and Life Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-8657 (Japan); Ohno, Hiroyuki [Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan); Nakamura, Nobuhumi, E-mail: nobu1@cc.tuat.ac.jp [Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)

    2016-08-26

    A pyranose dehydrogenase from Coprinopsis cinerea (CcPDH) is an extracellular quinohemoeprotein, which consists a b-type cytochrome domain, a pyrroloquinoline-quinone (PQQ) domain, and a family 1-type carbohydrate-binding module. The electron transfer reaction of CcPDH was studied using some electron acceptors and a carbon electrode at various pH levels. Phenazine methosulfate (PMS) reacted directly at the PQQ domain, whereas cytochrome c (cyt c) reacted via the cytochrome domain of intact CcPDH. Thus, electrons are transferred from reduced PQQ in the catalytic domain of CcPDH to heme b in the N-terminal cytochrome domain, which acts as a built-in mediator and transfers electron to a heterogenous electron transfer protein. The optimal pH values of the PMS reduction (pH 6.5) and the cyt c reduction (pH 8.5) differ. The catalytic currents for the oxidation of L-fucose were observed within a range of pH 4.5 to 11. Bioelectrocatalysis of CcPDH based on direct electron transfer demonstrated that the pH profile of the biocatalytic current was similar to the reduction activity of cyt c characters. - Highlights: • pH dependencies of activity were different for the reduction of cyt c and DCPIP. • DET-based bioelectrocatalysis of CcPDH was observed. • The similar pH-dependent profile was found with cyt c and electrode. • The present results suggested that IET reaction of CcPDH shows pH dependence.

  12. Solid-phase reduction of silico-12-molybdic acid H4SiMo12O40 by some organic oxygen containing compounds

    International Nuclear Information System (INIS)

    Chuvaev, V.F.; Pinchuk, I.N.; Spitsyn, V.I.

    1982-01-01

    A study is made on reduction reactions of anhydrous silico-12-molybdic acid by vapors of organic oxygen-containing compounds at 170 deg C: alcohols, simple carbonyl compounds. Methods of thermal analysis, electron paramagnetic resonance, paramagnetic resonance were used to established that depending on the nature of organic reagent and temperature, H 6 SiMo 2 5 Mo 10 6 O 40 two-electron or H 8 SiMo 4 5 Mo 8 6 O 40 four-electron flues form. It is shown that the increase of heterogeneous reduction temperature can lead to formation of anhydrous phases of SiMo 12 O 38 -(n/2), able to attach water reversibly with formation of corresponding blue. Characteristics of blues, prepared during solid-phase reduction of silico-12-molybdic acid and mixed valent forms with corresponding reduction degree, separated from water solutions, were compared

  13. Synthesis and electrocatalytic activity towards oxygen reduction reaction of gold-nanostars

    OpenAIRE

    Oyunbileg G; Batnyagt G; Enkhsaruul B; T Takeguchi

    2018-01-01

    The oxygen reduction reaction (ORR) is a characteristic reaction which determines the performance of fuel cells which convert a chemical energy into an electrical energy. Aims of this study are to synthesize Au-based nanostars (AuNSs) and determine their preliminary electro-catalytic activities towards ORR by a rotating-disk electrode method in alkaline electrolyte. The images obtained from a scanning electron microscope (SEM) and a transmission electron microscope (TEM) analyses confirm the ...

  14. Reduction of combinatorical background in the mass spectrum of electron pairs

    International Nuclear Information System (INIS)

    Tonse, S.

    1992-01-01

    Among the aims of the PHENIX experiment are the identification and measurement of the properties of the ρ, ω, φ and J/ψ vector mesons that have decayed through the e + e - channel. The main obstacle to identifying vector mesons (VM) using the e + e - invariant mass, is the significant number of e + and e - from other sources, which causes a large combinatorical background in the invariant mass spectrum. The work we have done aims to reduce this background by identifying background sources through kinematical cuts and removing them along with their combinatorical effects, while at the same time preserving as much as possible of the signal, i.e. the electrons from VM decay. A measurement of electron pairs (e + and e - ) from π-π and q bar q thermal sources is also a possibility, and a clear identification of the ''easier'' vector mesons (ω, φ) will be an indication of how well the thermal measurement can be done. To determine the nature and values of the kinematical cuts we have used a computer simulation to generate particles according to predetermined phase-space (rapidity and P T ) and multiplicity distributions

  15. Enrichment of Geobacter species in response to stimulation of Fe(III) reduction in sandy aquifer sediments

    Science.gov (United States)

    Snoeyenbos-West, O.L.; Nevin, K.P.; Anderson, R.T.; Lovely, D.R.

    2000-01-01

    Engineered stimulation of Fe(III) has been proposed as a strategy to enhance the immobilization of radioactive and toxic metals in metal-contaminated subsurface environments. Therefore, laboratory and field studies were conducted to determine which microbial populations would respond to stimulation of Fe(III) reduction in the sediments of sandy aquifers. In laboratory studies, the addition of either various organic electron donors or electron shuttle compounds stimulated Fe(III) reduction and resulted in Geobacter sequences becoming important constituents of the Bacterial 16S rDNA sequences that could be detected with PCR amplification and denaturing gradient gel electrophoresis (DGGE). Quantification of Geobacteraceae sequences with a PCR most-probable-number technique indicated that the extent to which numbers of Geobacter increased was related to the degree of stimulation of Fe(III) reduction. Geothrix species were also enriched in some instances, but were orders of magnitude less numerous than Geobacter species. Shewanella species were not detected, even when organic compounds known to be electron donors for Shewanella species were used to stimulate Fe(III) reduction in the sediments. Geobacter species were also enriched in two field experiments in which Fe(III) reduction was stimulated with the addition of benzoate or aromatic hydrocarbons. The apparent growth of Geobacter species concurrent with increased Fe(III) reduction suggests that Geobacter species were responsible for much of the Fe(III) reduction in all of the stimulation approaches evaluated in three geographically distinct aquifers. Therefore, strategies for subsurface remediation that involve enhancing the activity of indigenous Fe(III)-reducing populations in aquifers should consider the physiological properties of Geobacter species in their treatment design.

  16. Electronic and transport properties of kinked graphene

    DEFF Research Database (Denmark)

    Rasmussen, Jesper Toft; Gunst, Tue; Bøggild, Peter

    2013-01-01

    Local curvature, or bending, of a graphene sheet is known to increase the chemical reactivity presenting an opportunity for templated chemical functionalisation. Using first-principles calculations based on density functional theory (DFT), we investigate the reaction barrier reduction for the ads......Local curvature, or bending, of a graphene sheet is known to increase the chemical reactivity presenting an opportunity for templated chemical functionalisation. Using first-principles calculations based on density functional theory (DFT), we investigate the reaction barrier reduction...... for the adsorption of atomic hydrogen at linear bends in graphene. We find a significant barrier lowering (≈15%) for realistic radii of curvature (≈20 Å) and that adsorption along the linear bend leads to a stable linear kink. We compute the electronic transport properties of individual and multiple kink lines......, and demonstrate how these act as efficient barriers for electron transport. In particular, two parallel kink lines form a graphene pseudo-nanoribbon structure with a semimetallic/semiconducting electronic structure closely related to the corresponding isolated ribbons; the ribbon band gap translates...

  17. Investigation of Reduction of the Uncertainty of Monte Carlo Dose Calculations in Oncor® Clinical Linear Accelerator Simulation Using the DBS Variance Reduction Technique in Monte Carlo Code BEAMnrc

    Directory of Open Access Journals (Sweden)

    Amin Asadi

    2017-10-01

    Full Text Available Purpose: To study the benefits of Directional Bremsstrahlung Splitting (DBS dose variance reduction technique in BEAMnrc Monte Carlo (MC code for Oncor® linac at 6MV and 18MV energies. Materials and Method: A MC model of Oncor® linac was built using BEAMnrc MC Code and verified by the measured data for 6MV and 18MV energies of various field sizes. Then Oncor® machine was modeled running DBS technique, and the efficiency of total fluence and spatial fluence for electron and photon, the efficiency of dose variance reduction of MC calculations for PDD on the central beam axis and lateral dose profile across the nominal field was measured and compared. Result: With applying DBS technique, the total fluence of electron and photon increased in turn 626.8 (6MV and 983.4 (6MV, and 285.6 (18MV and 737.8 (18MV, the spatial fluence of electron and photon improved in turn 308.6±1.35% (6MV and 480.38±0.43% (6MV, and 153±0.9% (18MV and 462.6±0.27% (18MV. Moreover, by running DBS technique, the efficiency of dose variance reduction for PDD MC dose calculations before maximum dose point and after dose maximum point enhanced 187.8±0.68% (6MV and 184.6±0.65% (6MV, 156±0.43% (18MV and 153±0.37% (18MV, respectively, and the efficiency of MC calculations for lateral dose profile remarkably on the central beam axis and across the treatment field raised in turn 197±0.66% (6MV and 214.6±0.73% (6MV, 175±0.36% (18MV and 181.4±0.45% (18MV. Conclusion: Applying dose variance reduction technique of DBS for modeling Oncor® linac with using BEAMnrc MC Code surprisingly improved the fluence of electron and photon, and it therefore enhanced the efficiency of dose variance reduction for MC calculations. As a result, running DBS in different kinds of MC simulation Codes might be beneficent in reducing the uncertainty of MC calculations. 

  18. Electrochemical reduction of oxygen catalyzed by a wide range of bacteria including Gram-positive

    Energy Technology Data Exchange (ETDEWEB)

    Cournet, Amandine [Universite de Toulouse, UPS, LU49, Adhesion Bacterienne et Formation de Biofilms, 35 chemin des Maraichers, 31 062 Toulouse cedex 09 (France); Laboratoire de Genie Chimique CNRS, Universite de Toulouse, 4 allee Emile Monso, BP 84234, 31432 Toulouse cedex 04 (France); Delia, Marie-Line; Bergel, Alain [Laboratoire de Genie Chimique CNRS, Universite de Toulouse, 4 allee Emile Monso, BP 84234, 31432 Toulouse cedex 04 (France); Roques, Christine; Berge, Mathieu [Universite de Toulouse, UPS, LU49, Adhesion Bacterienne et Formation de Biofilms, 35 chemin des Maraichers, 31 062 Toulouse cedex 09 (France)

    2010-04-15

    Most bacteria known to be electrochemically active have been harvested in the anodic compartments of microbial fuel cells (MFCs) and are able to use electrodes as electron acceptors. The reverse phenomenon, i.e. using solid electrodes as electron donors, is not so widely studied. To our knowledge, most of the electrochemically active bacteria are Gram-negative. The present study implements a transitory electrochemical technique (cyclic voltammetry) to study the microbial catalysis of the electrochemical reduction of oxygen. It is demonstrated that a wide range of aerobic and facultative anaerobic bacteria are able to catalyze oxygen reduction. Among these electroactive bacteria, several were Gram-positive. The transfer of electrons was direct since no activity was obtained with the filtrate. These findings, showing a widespread property among bacteria including Gram-positive ones, open new and interesting routes in the field of electroactive bacteria research. (author)

  19. Bioelectrochemical Ethanol Production through Mediated Acetate Reduction by Mixed Cultures

    NARCIS (Netherlands)

    Steinbusch, K.J.J.; Hamelers, H.V.M.; Schaap, J.D.; Kampman, C.; Buisman, C.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

  20. Electron beam treatment of industrial wastewater

    International Nuclear Information System (INIS)

    Han, Bumsoo; Kim, JinKyu; Kim, Yuri

    2004-01-01

    For industrial wastewater with low impurity levels such as contaminated ground water, cleaning water and etc., purification only with electron beam is possible, but it should be managed carefully with reducing required irradiation doses as low as possible. Also for industrial wastewater with high impurity levels such as dyeing wastewater, leachate and etc., purification only with electron beam requires high amount of doses and far beyond economies. Electron beam treatment combined with conventional purification methods such as coagulation, biological treatment, etc. is suitable for reduction of non-biodegradable impurities in wastewater and will extend the application area of electron beam. A pilot plant with electron beam for treating 1,000 m 3 /day of wastewater from dyeing industries has constructed and operated continuously since Oct 1998. Electron beam irradiation instead of chemical treatment shows much improvement in removing impurities and increases the efficiency of biological treatment. Actual plant is under consideration based upon the experimental results. (author)

  1. Nonequilibrium electron energy-loss kinetics in metal clusters

    CERN Document Server

    Guillon, C; Fatti, N D; Vallee, F

    2003-01-01

    Ultrafast energy exchanges of a non-Fermi electron gas with the lattice are investigated in silver clusters with sizes ranging from 4 to 26 nm using a femtosecond pump-probe technique. The results yield evidence for a cluster-size-dependent slowing down of the short-time energy losses of the electron gas when it is strongly athermal. A constant rate is eventually reached after a few hundred femtoseconds, consistent with the electron gas internal thermalization kinetics, this behaviour reflecting evolution from an individual to a collective electron-lattice type of coupling. The timescale of this transient regime is reduced in small nanoparticles, in agreement with speeding up of the electron-electron interactions with size reduction. The experimental results are in quantitative agreement with numerical simulations of the electron kinetics.

  2. Chemical changes induced on a TiO2 surface by electron bombardment

    International Nuclear Information System (INIS)

    Vergara, L.I.; Passeggi, M.C.G.; Ferron, J.

    2007-01-01

    We study the TiO 2 (Ti 4+ ) chemical reduction induced by electron bombardment using Auger electron spectroscopy and factor analysis. We show that the electron irradiation of a TiO 2 sample is characterized by the appearance of a lower Ti oxidation state, Ti 2 O 3 (Ti 3+ ), followed by a further deposition of carbon, which is present inevitably in the environment even under ultra-high vacuum conditions. The appearance of C over the surface is found to be a complex mechanism which affects the reduction process through passivation of the electron-induced oxygen desorption and formation of titanium carbide. For very high irradiation doses, we also found that the chemical changes on the surface are stopped due to the deposition of carbon in a graphitic form

  3. New possibilities for superconductor electronics

    International Nuclear Information System (INIS)

    Likharev, K.K.; Semenov, V.K.; Zorin, A.B.

    1989-01-01

    Situation in the superconducting electronics, the field being developed since mid '60s has changed drastically recently as a result of not only discovery of the high-T c superconductivity, but also of the nearly simultaneous invention of several novel electronic devices. A detailed analysis of the new situation and prospects of this important field was carried out recently by the present authors of this paper. A complete report on our analysis is being published elsewhere, while in this paper we are presenting a brief summary of its results. The analysis has shown that the virtually only advantage which can arise from applications of the high-T c superconductors in electronics is a drastic reduction of the refrigeration costs, rather than an improvement of the device performance

  4. Role of Reversible Histidine Coordination in Hydroxylamine Reduction by Plant Hemoglobins (Phytoglobins).

    Science.gov (United States)

    Athwal, Navjot Singh; Alagurajan, Jagannathan; Andreotti, Amy H; Hargrove, Mark S

    2016-10-18

    Reduction of hydroxylamine to ammonium by phytoglobin, a plant hexacoordinate hemoglobin, is much faster than that of other hexacoordinate hemoglobins or pentacoordinate hemoglobins such as myoglobin, leghemoglobin, and red blood cell hemoglobin. The reason for differences in reactivity is not known but could be intermolecular electron transfer between protein molecules in support of the required two-electron reduction, hydroxylamine binding, or active site architecture favoring the reaction. Experiments were conducted with phytoglobins from rice, tomato, and soybean along with human neuroglobin and soybean leghemoglobin that reveal hydroxylamine binding as the rate-limiting step. For hexacoordinate hemoglobins, binding is limited by the dissociation rate constant for the distal histidine, while leghemoglobin is limited by an intrinsically low affinity for hydroxylamine. When the distal histidine is removed from rice phytoglobin, a hydroxylamine-bound intermediate is formed and the reaction rate is diminished, indicating that the distal histidine imidazole side chain is critical for the reaction, albeit not for electron transfer but rather for direct interaction with the substrate. Together, these results demonstrate that phytoglobins are superior at hydroxylamine reduction because they have distal histidine coordination affinity constants near 1, and facile rate constants for binding and dissociation of the histidine side chain. Hexacoordinate hemoglobins such as neuroglobin are limited by tighter histidine coordination that blocks hydroxylamine binding, and pentacoordinate hemoglobins have intrinsically lower hydroxylamine affinities.

  5. Electron-transfer reactions of extremely small AgI colloids

    International Nuclear Information System (INIS)

    Vucemilovic, M.I.; Micic, O.I.

    1988-01-01

    Small colloidal AgI particles (particle diameter 20-50 A) have been prepared in water and acetonitrile, and optical effects due to size quantization have been observed. Electron transfer reactions involving electron donors and electron acceptors with AgI have been studied by pulse radiolysis techniques. Both reduction and oxidation of the colloids led to transient bleaching of semiconductor absorption. The recovery of the bleaching has been attributed to corrosion processes. Electrons injected into AgI colloids produce metallic silver and hydrogen. Hydrogen evolution is catalyzed by metallic silver formation. (author)

  6. Sulphate reduction in the Aespoe HRL tunnel

    International Nuclear Information System (INIS)

    Gustafson, G.; Pedersen, K.; Tullborg, E.L.; Wallin, B.; Wikberg, P.

    1995-12-01

    Evidence and indications of sulphate reduction based on geological, hydrogeological, groundwater, isotope and microbial data gathered in and around the Aespoe Hard Rock Laboratory tunnel have been evaluated. This integrated investigation showed that sulphate reduction had taken place in the past but is most likely also an ongoing process. Anaerobic sulphate-reducing bacteria can live in marine sediments, in the tunnel sections under the sea and in deep groundwaters, since there is no access to oxygen. The sulphate-reducing bacteria seem to thrive when the Cl - concentration of the groundwater is 4000-6000 mg/l. Sulphate reduction is an in situ process but the resulting hydrogen-sulphide rich water can be transported to other locations. A more vigorous sulphate reduction takes place when the organic content in the groundwater is high (>10 mg/l DOC) which is the case in the sediments and in the groundwaters under the sea. Some bacteria use hydrogen as an electron donor instead of organic carbon and can therefore live in deep environments where access to organic material is limited. The sulphate-reducing bacteria seem to adapt to changing flow situations caused by the tunnel construction relatively fast. Sulphate reduction seems to have occurred and will probably occur where conditions are favourable for the sulphate-reducing bacteria such as anaerobic brackish groundwater with dissolved sulphate and organic carbon or hydrogen. 59 refs, 37 figs, 6 tabs

  7. Short circuit current changes in electron irradiated GaAlAs/GaAs solar cells

    Science.gov (United States)

    Walker, G. H.; Conway, E. J.

    1978-01-01

    Heteroface p-GaAlAs/p-GaAs/n-GaAs solar cells with junction depths of 0.8, 1.5, and 4 microns were irradiated with 1 MeV electrons. The short-circuit current for the 4 micron junction depth cells is significantly reduced by the electron irradiation. Reduction of the junction depth to 1.5 microns improves the electron radiation resistance of the cells while further reduction of the junction depth to 0.8 microns improves the stability of the cells even more. Primary degradation is in the blue region of the spectrum. Considerable recovery of lost response is obtained by annealing the cells at 200 C. Computer modeling shows that the degradation is caused primarily by a reduction in the minority carrier diffusion length in the p-GaAs.

  8. Tokamak startup with electron cyclotron heating

    International Nuclear Information System (INIS)

    Holly, D.J.; Prager, S.C.; Shepard, D.A.; Sprott, J.C.

    1980-04-01

    Experiments are described in which the startup voltage in a tokamak is reduced by approx. 60% by the use of a modest amount of electron cyclotron resonance heating power for preionization. A 50% reduction in volt-second requirement and impurity reflux are also observed

  9. Tokamak startup with electron cyclotron heating

    Energy Technology Data Exchange (ETDEWEB)

    Holly, D J; Prager, S C; Shepard, D A; Sprott, J C

    1980-04-01

    Experiments are described in which the startup voltage in a tokamak is reduced by approx. 60% by the use of a modest amount of electron cyclotron resonance heating power for preionization. A 50% reduction in volt-second requirement and impurity reflux are also observed.

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

    Science.gov (United States)

    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.

  11. Study of nonlinear electron-acoustic solitary and shock waves in a dissipative, nonplanar space plasma with superthermal hot electrons

    Energy Technology Data Exchange (ETDEWEB)

    Han, Jiu-Ning, E-mail: hanjiuning@126.com; He, Yong-Lin; Luo, Jun-Hua; Nan, Ya-Gong; Han, Zhen-Hai; Dong, Guang-Xing [College of Physics and Electromechanical Engineering, Hexi University, Zhangye 734000 (China); Duan, Wen-Shan [College of Physics and Electronic Engineering, Northwest Normal University, Lanzhou 730070 (China); Li, Jun-Xiu [College of Civil Engineering, Hexi University, Zhangye 734000 (China)

    2014-01-15

    With the consideration of the superthermal electron distribution, we present a theoretical investigation about the nonlinear propagation of electron-acoustic solitary and shock waves in a dissipative, nonplanar non-Maxwellian plasma comprised of cold electrons, superthermal hot electrons, and stationary ions. The reductive perturbation technique is used to obtain a modified Korteweg-de Vries Burgers equation for nonlinear waves in this plasma. We discuss the effects of various plasma parameters on the time evolution of nonplanar solitary waves, the profile of shock waves, and the nonlinear structure induced by the collision between planar solitary waves. It is found that these parameters have significant effects on the properties of nonlinear waves and collision-induced nonlinear structure.

  12. Using Electronic Surveys: Advice from Survey Professionals.

    Directory of Open Access Journals (Sweden)

    David M. Shannon

    2002-01-01

    Full Text Available The study reports the perceptions and recommendations of sixty-two experienced survey..researchers from the American Educational Research Association regarding the use of..electronic surveys. The most positive aspects cited for the use of electronic surveys were..reduction of costs (i.e., postage, phone charges, the use of electronic mail for pre-notification or..follow-up purposes, and the compatibility of data with existing software programs. These..professionals expressed limitations in using electronic surveys pertaining to the limited..sampling frame as well as issues of confidentiality, privacy, and the credibility of the sample...They advised that electronic surveys designed with the varied technological background and..capabilities of the respondent in mind, follow sound principles of survey construction, and be..administered to pre-notified, targeted populations with published email addresses.

  13. Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species

    Science.gov (United States)

    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.

  14. The contribution of fermentative bacteria and methanogenic archaea to azo dye reduction by a thermophilic anaerobic consortium

    NARCIS (Netherlands)

    Santos, dos A.B.; Cervantes, F.J.; Madrid, de M.P.; Bok, de F.A.M.; Stams, A.J.M.; Lier, van J.B.

    2006-01-01

    The contribution of fermentative bacteria and methanogenic archaea to azo dye reduction by a thermophilic anaerobic consortium was studied. Additionally, the effects of different electron-donating substrates and the redox mediator riboflavin on dye reduction were assessed by using either a

  15. Electron self-exchange in hemoglobins revealed by deutero-hemin substitution.

    Science.gov (United States)

    Athwal, Navjot Singh; Alagurajan, Jagannathan; Sturms, Ryan; Fulton, D Bruce; Andreotti, Amy H; Hargrove, Mark S

    2015-09-01

    Hemoglobins (phytoglobins) from rice plants (nsHb1) and from the cyanobacterium Synechocystis (PCC 6803) (SynHb) can reduce hydroxylamine with two electrons to form ammonium. The reaction requires intermolecular electron transfer between protein molecules, and rapid electron self-exchange might play a role in distinguishing these hemoglobins from others with slower reaction rates, such as myoglobin. A relatively rapid electron self-exchange rate constant has been measured for SynHb by NMR, but the rate constant for myoglobin is equivocal and a value for nsHb1 has not yet been measured. Here we report electron self-exchange rate constants for nsHb1 and Mb as a test of their role in hydroxylamine reduction. These proteins are not suitable for analysis by NMR ZZ exchange, so a method was developed that uses cross-reactions between each hemoglobin and its deutero-hemin substituted counterpart. The resulting electron transfer is between identical proteins with low driving forces and thus closely approximates true electron self-exchange. The reactions can be monitored spectrally due to the distinct spectra of the prosthetic groups, and from this electron self-exchange rate constants of 880 (SynHb), 2900 (nsHb1), and 0.05M(-1) s(-1) (Mb) have been measured for each hemoglobin. Calculations of cross-reactions using these values accurately predict hydroxylamine reduction rates for each protein, suggesting that electron self-exchange plays an important role in the reaction. Copyright © 2015 Elsevier Inc. All rights reserved.

  16. A systematic way for the cost reduction of density fitting methods

    International Nuclear Information System (INIS)

    Kállay, Mihály

    2014-01-01

    We present a simple approach for the reduction of the size of auxiliary basis sets used in methods exploiting the density fitting (resolution of identity) approximation for electron repulsion integrals. Starting out of the singular value decomposition of three-center two-electron integrals, new auxiliary functions are constructed as linear combinations of the original fitting functions. The new functions, which we term natural auxiliary functions (NAFs), are analogous to the natural orbitals widely used for the cost reduction of correlation methods. The use of the NAF basis enables the systematic truncation of the fitting basis, and thereby potentially the reduction of the computational expenses of the methods, though the scaling with the system size is not altered. The performance of the new approach has been tested for several quantum chemical methods. It is demonstrated that the most pronounced gain in computational efficiency can be expected for iterative models which scale quadratically with the size of the fitting basis set, such as the direct random phase approximation. The approach also has the promise of accelerating local correlation methods, for which the processing of three-center Coulomb integrals is a bottleneck

  17. Enhanced Cr(VI) reduction and As(III) oxidation in ice phase: Important role of dissolved organic matter from biochar

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Xiaoling [Department of Soil and Water Science, University of Florida, Gainesville, FL 32611 (United States); Ma, Lena Q., E-mail: lqma@ufl.edu [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Jiangsu 210046 (China); Department of Soil and Water Science, University of Florida, Gainesville, FL 32611 (United States); Gress, Julia; Harris, Willie [Department of Soil and Water Science, University of Florida, Gainesville, FL 32611 (United States); Li, Yuncong [Soil and Water Science Department, Tropical Research and Education Center, University of Florida, Homestead, FL 33031-3314 (United States)

    2014-02-01

    Graphical abstract: - Highlights: • Biochar-derived dissolved organic matter (DOM) effectively reduced Cr(VI) and oxidized As(III). • Cr(VI) and As(III) could serve as a redox couple. • Cr(VI) and As(III) redox conversion was more effective in the ice phase than aqueous phase. • FTIR and ESR showed that biochar DOM served as both electron donor and acceptor. - Abstract: This study evaluated the impact of DOM from two biochars (sugar beet tailing and Brazilian pepper) on Cr(VI) reduction and As(III) oxidation in both ice and aqueous phases with a soil DOM as control. Increasing DOM concentration from 3 to 300 mg C L{sup −1} enhanced Cr(VI) reduction from 20% to 100% and As(III) oxidation from 6.2% to 25%; however, Cr(VI) reduction decreased from 80–86% to negligible while As(III) oxidation increased from negligible to 18–19% with increasing pH from 2 to 10. Electron spin resonance study suggested semiquinone radicals in DOM were involved in As(III) oxidation while Fourier transform infrared analysis suggested that carboxylic groups in DOM participated in both Cr(VI) reduction and As(III) oxidation. During Cr(VI) reduction, part of DOM (∼10%) was oxidized to CO{sub 2}. The enhanced conversion of Cr(VI) and As(III) in the ice phase was due to the freeze concentration effect with elevated concentrations of electron donors and electron acceptors in the grain boundary. Though DOM enhanced both Cr(VI) reduction and As(III)oxidation, Cr(VI) reduction coupled with As(III) oxidation occurred in absence of DOM. The role of DOM, Cr(VI) and/or As(III) in Cr and As transformation may provide new insights into their speciation and toxicity in cold regions.

  18. Development of readout electronics for monolithic integration with diode strip detectors

    International Nuclear Information System (INIS)

    Hosticka, B.J.; Wrede, M.; Zimmer, G.; Kemmer, J.; Hofmann, R.; Lutz, G.

    1984-03-01

    Parallel in - serial out analog readout electronics integrated with silicon strip detectors will bring a reduction of two orders of magnitude in external electronics. The readout concept and the chosen CMOS technology solve the basic problem of low noise and low power requirements. A hybrid solution is an intermediate step towards the final goal of monolithic integration of detector and electronics. (orig.)

  19. Electron-ionic technology of storage of foodstuffs

    International Nuclear Information System (INIS)

    Tsoj, A.P.

    1996-01-01

    Work is trained on reduction of food suffer losses under cold store due to its drying and spoiling. Experimental cold store of fruits in 'microclimates' in electron-ionic medium created with help of pilot unit is carried out

  20. CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane

    OpenAIRE

    Khadka, Nimesh; Dean, Dennis R.; Smith, Dayle; Hoffman, Brian M.; Raugei, Simone; Seefeldt, Lance C.

    2016-01-01

    The reduction of N2 to NH3 by Mo-dependent nitrogenase at its active-site metal cluster FeMo-cofactor utilizes reductive elimination (re) of Fe-bound hydrides with obligatory loss of H2 to activate the enzyme for binding/reduction of N2. Earlier work showed that wild type nitrogenase and a nitrogenase having amino acid substitutions in the MoFe protein near FeMo-cofactor can catalytically reduce CO2 by 2 or 8 electrons/protons to carbon monoxide (CO) and methane (CH4) at low rates. Here, it i...

  1. Dynamic behavior of ion acoustic waves in electron-positron-ion magnetoplasmas with superthermal electrons and positrons

    Science.gov (United States)

    Saha, Asit; Pal, Nikhil; Chatterjee, Prasanta

    2014-10-01

    The dynamic behavior of ion acoustic waves in electron-positron-ion magnetoplasmas with superthermal electrons and positrons has been investigated in the framework of perturbed and non-perturbed Kadomtsev-Petviashili (KP) equations. Applying the reductive perturbation technique, we have derived the KP equation in electron-positron-ion magnetoplasma with kappa distributed electrons and positrons. Bifurcations of ion acoustic traveling waves of the KP equation are presented. Using the bifurcation theory of planar dynamical systems, the existence of the solitary wave solutions and the periodic traveling wave solutions has been established. Two exact solutions of these waves have been derived depending on the system parameters. Then, using the Hirota's direct method, we have obtained two-soliton and three-soliton solutions of the KP equation. The effect of the spectral index κ on propagations of the two-soliton and the three-soliton has been shown. Considering an external periodic perturbation, we have presented the quasi periodic behavior of ion acoustic waves in electron-positron-ion magnetoplasmas.

  2. Dynamic behavior of ion acoustic waves in electron-positron-ion magnetoplasmas with superthermal electrons and positrons

    Energy Technology Data Exchange (ETDEWEB)

    Saha, Asit, E-mail: asit-saha123@rediffmail.com, E-mail: prasantachatterjee1@rediffmail.com [Department of Mathematics, Sikkim Manipal Institute of Technology, Majitar, Rangpo, East-Sikkim 737136 (India); Department of Mathematics, Siksha Bhavana, Visva Bharati University, Santiniketan-731235 (India); Pal, Nikhil; Chatterjee, Prasanta, E-mail: asit-saha123@rediffmail.com, E-mail: prasantachatterjee1@rediffmail.com [Department of Mathematics, Siksha Bhavana, Visva Bharati University, Santiniketan-731235 (India)

    2014-10-15

    The dynamic behavior of ion acoustic waves in electron-positron-ion magnetoplasmas with superthermal electrons and positrons has been investigated in the framework of perturbed and non-perturbed Kadomtsev-Petviashili (KP) equations. Applying the reductive perturbation technique, we have derived the KP equation in electron-positron-ion magnetoplasma with kappa distributed electrons and positrons. Bifurcations of ion acoustic traveling waves of the KP equation are presented. Using the bifurcation theory of planar dynamical systems, the existence of the solitary wave solutions and the periodic traveling wave solutions has been established. Two exact solutions of these waves have been derived depending on the system parameters. Then, using the Hirota's direct method, we have obtained two-soliton and three-soliton solutions of the KP equation. The effect of the spectral index κ on propagations of the two-soliton and the three-soliton has been shown. Considering an external periodic perturbation, we have presented the quasi periodic behavior of ion acoustic waves in electron-positron-ion magnetoplasmas.

  3. Electron uptake and delivery sites on plastocyanin in its reactions with the photosynthetic electron transport system

    DEFF Research Database (Denmark)

    Farver, O; Shahak, Y; Pecht, I

    1982-01-01

    French bean plastocyanin is stoichiometrically and specifically labeled upon reduction by Cr(II)aq ions, yielding a substitution-inert (Cr(III) adduct at the protein surface. The effect of the modification on the activity of plastocyanin in electron transfer between photosystems II and I has been...... and Cr-labeled plastocyanin were indistinguishable, the rates of photooxidation of the modified protein were markedly attenuated relative to those of the native one. This difference in reactivity clearly reflects the perturbation of the electron transfer pathway to P700. These findings, in conjunction...... with the structure of plastocyanin and the locus of CR(III) binding on its surface, lead to the following interpretation: (a) There are most probably two physiologically significant, electron transfer sites on plastocyanin. (b) The site involved in the electron transfer to P700 is most likely in the region...

  4. An Exploratory Study on the Pathways of Cr (VI) Reduction in Sulfate-reducing Up-flow Anaerobic Sludge Bed (UASB) Reactor.

    Science.gov (United States)

    Qian, Jin; Wei, Li; Liu, Rulong; Jiang, Feng; Hao, Xiaodi; Chen, Guang-Hao

    2016-03-29

    Electroplating wastewater contains both Cr (VI) and sulfate. So Cr (VI) removal under sulfate-rich condition is quite complicated. This study mainly investigates the pathways for Cr (VI) removal under biological sulfate-reducing condition in the up-flow anaerobic sludge bed (UASB) reactor. Two potential pathways are found for the removal of Cr (VI). The first one is the sulfidogenesis-induced Cr (VI) reduction pathway (for 90% Cr (VI) removal), in which Cr (VI) is reduced by sulfide generated from biological reduction of sulfate. The second one leads to direct reduction of Cr (VI) which is utilized by bacteria as the electron acceptor (for 10% Cr (VI) removal). Batch test results confirmed that sulfide was oxidized to elemental sulfur instead of sulfate during Cr (VI) reduction. The produced extracellular polymeric substances (EPS) provided protection to the microbes, resulting in effective removal of Cr (VI). Sulfate-reducing bacteria (SRB) genera accounted for 11.1% of the total bacterial community; thus they could be the major organisms mediating the sulfidogenesis-induced reduction of Cr (VI). In addition, chromate-utilizing genera (e.g. Microbacterium) were also detected, which were possibly responsible for the direct reduction of Cr (VI) using organics as the electron donor and Cr (VI) as the electron acceptor.

  5. An Exploratory Study on the Pathways of Cr (VI) Reduction in Sulfate-reducing Up-flow Anaerobic Sludge Bed (UASB) Reactor

    Science.gov (United States)

    Qian, Jin; Wei, Li; Liu, Rulong; Jiang, Feng; Hao, Xiaodi; Chen, Guang-Hao

    2016-01-01

    Electroplating wastewater contains both Cr (VI) and sulfate. So Cr (VI) removal under sulfate-rich condition is quite complicated. This study mainly investigates the pathways for Cr (VI) removal under biological sulfate-reducing condition in the up-flow anaerobic sludge bed (UASB) reactor. Two potential pathways are found for the removal of Cr (VI). The first one is the sulfidogenesis-induced Cr (VI) reduction pathway (for 90% Cr (VI) removal), in which Cr (VI) is reduced by sulfide generated from biological reduction of sulfate. The second one leads to direct reduction of Cr (VI) which is utilized by bacteria as the electron acceptor (for 10% Cr (VI) removal). Batch test results confirmed that sulfide was oxidized to elemental sulfur instead of sulfate during Cr (VI) reduction. The produced extracellular polymeric substances (EPS) provided protection to the microbes, resulting in effective removal of Cr (VI). Sulfate-reducing bacteria (SRB) genera accounted for 11.1% of the total bacterial community; thus they could be the major organisms mediating the sulfidogenesis-induced reduction of Cr (VI). In addition, chromate-utilizing genera (e.g. Microbacterium) were also detected, which were possibly responsible for the direct reduction of Cr (VI) using organics as the electron donor and Cr (VI) as the electron acceptor. PMID:27021522

  6. An Exploratory Study on the Pathways of Cr (VI) Reduction in Sulfate-reducing Up-flow Anaerobic Sludge Bed (UASB) Reactor

    Science.gov (United States)

    Qian, Jin; Wei, Li; Liu, Rulong; Jiang, Feng; Hao, Xiaodi; Chen, Guang-Hao

    2016-03-01

    Electroplating wastewater contains both Cr (VI) and sulfate. So Cr (VI) removal under sulfate-rich condition is quite complicated. This study mainly investigates the pathways for Cr (VI) removal under biological sulfate-reducing condition in the up-flow anaerobic sludge bed (UASB) reactor. Two potential pathways are found for the removal of Cr (VI). The first one is the sulfidogenesis-induced Cr (VI) reduction pathway (for 90% Cr (VI) removal), in which Cr (VI) is reduced by sulfide generated from biological reduction of sulfate. The second one leads to direct reduction of Cr (VI) which is utilized by bacteria as the electron acceptor (for 10% Cr (VI) removal). Batch test results confirmed that sulfide was oxidized to elemental sulfur instead of sulfate during Cr (VI) reduction. The produced extracellular polymeric substances (EPS) provided protection to the microbes, resulting in effective removal of Cr (VI). Sulfate-reducing bacteria (SRB) genera accounted for 11.1% of the total bacterial community; thus they could be the major organisms mediating the sulfidogenesis-induced reduction of Cr (VI). In addition, chromate-utilizing genera (e.g. Microbacterium) were also detected, which were possibly responsible for the direct reduction of Cr (VI) using organics as the electron donor and Cr (VI) as the electron acceptor.

  7. Biogeochemical Modeling of In Situ U(VI) Reduction and Immobilization with Emulsified Vegetable Oil as the Electron Donor at a Field Site in Oak Ridge, Tennessee

    Science.gov (United States)

    Tang, G.; Parker, J.; Wu, W.; Schadt, C. W.; Watson, D. B.; Brooks, S. C.; Orifrc Team

    2011-12-01

    A comprehensive biogeochemical model was developed to quantitatively describe the coupled hydrologic, geochemical and microbiological processes that occurred following injection of emulsified vegetable oil (EVO) as the electron donor to immobilize U(VI) at the Oak Ridge Integrated Field Research Challenge site (ORIFRC) in Tennessee. The model couples the degradation of EVO, production and oxidation of long-chain fatty acids (LCFA), glycerol, hydrogen and acetate, reduction of nitrate, manganese, ferrous iron, sulfate and uranium, and methanoganesis with growth of multiple microbial groups. The model describes the evolution of geochemistry and microbial populations not only in the aqueous phase as typically observed, but also in the mineral phase and therefore enables us to evaluate the applicability of rates from the literature for field scale assessment, estimate the retention and degradation rates of EVO and LCFA, and assess the influence of the coupled processes on fate and transport of U(VI). Our results suggested that syntrophic bacteria or metal reducers might catalyze LCFA oxidation in the downstream locations when sulfate was consumed, and competition between methanogens and others for electron donors and slow growth of methanogen might contribute to the sustained reducing condition. Among the large amount of hydrologic, geochemical and microbiological parameter values, the initial biomass, and the interactions (e.g., inhibition) of the microbial functional groups, and the rate and extent of Mn and Fe oxide reduction appear as the major sources of uncertainty. Our model provides a platform to conduct numerical experiments to study these interactions, and could be useful for further iterative experimental and modeling investigations into the bioreductive immobiliztion of radionuclide and metal contaminants in the subsurface.

  8. TEM investigation of U6+ and Re7+ reduction by Desulfovibrio desulfuricans, a sulfate-reducing bacterium

    International Nuclear Information System (INIS)

    XU, HUIFANG; BARTON, LARRY L.; CHOUDHURY, KEKA; ZHANG, PENGCHU; WANG, YIFENG

    2000-01-01

    Uranium and its fission product Tc in aerobic environment will be in the forms of UO 2 2+ and TcO 4 - . Reduced forms of tetravalent U and Tc are sparingly soluble. As determined by transmission electron microscopy, the reduction of uranyl acetate by immobilized cells of Desulfovibrio desulfuricans results in the production of black uraninite nanocrystals precipitated outside the cell. Some nanocrystals are associated with outer membranes of the cell as revealed from cross sections of these metabolic active sulfate-reducing bacteria. The nanocrystals have an average diameter of 5 nm and have anhedral shape. The reduction of Re 7+ by cells of Desulfovibrio desulfuricans is fast in media containing H 2 an electron donor, and slow in media containing lactic acid. It is proposed that the cytochrome in these cells has an important role in the reduction of uranyl and Re 7+ is (a chemical analogue for Tc 7+ ) through transferring an electron from molecular hydrogen or lactic acid to the oxyions of UO 2 2+ and TcO 4 -

  9. Effect of electron (de)localization and pairing in the electrochemistry of polyoxometalates: study of Wells-Dawson molybdotungstophosphate derivatives.

    Science.gov (United States)

    Parent, Loïc; Aparicio, Pablo A; de Oliveira, Pedro; Teillout, Anne-Lucie; Poblet, Josep M; López, Xavier; Mbomekallé, Israël M

    2014-06-16

    Polyoxometalates (POMs) are inorganic entities featuring extensive and sometimes unusual redox properties. In this work, several experimental techniques as well as density functional theory (DFT) calculations have been applied to identify and assess the relevance of factors influencing the redox potentials of POMs. First, the position of the Mo substituent atom in the Wells-Dawson structure, α1- or α2-P2W17Mo, determines the potential of the first 1e(-) reduction wave. For P2W(18-x)Mox systems containing more than one Mo atom, reduction takes place at successively more positive potentials. We attribute this fact to the higher electron delocalization when some Mo oxidizing atoms are connected. After having analyzed the experimental and theoretical data for the monosubstituted α1- and α2-P2W17Mo anions, some relevant facts arise that may help to rationalize the redox behavior of POMs in general. Three aspects concern the stability of systems: (i) the favorable electron delocalization, (ii) the unfavorable e(-)-e(-) electrostatic repulsion, and (iii) the favorable electron pairing. They explain trends such as the second reduction wave occurring at more positive potentials in α1- than in α2-P2W17Mo, and also the third electron reduction taking place at a less negative potential in the case of α2, reversing the observed behavior for the first and the second waves. In P2W17V derivatives, the nature of the first "d" electron is more localized because of the stronger oxidant character of V(V). Thus, the reduction potentials as well as the computed reduction energies (REs) for the second reduction of either isomer are closer to each other than in Mo-substituted POMs. This may be explained by the lack of electron delocalization in monoreduced P2W17V(IV) systems.

  10. Reduction of heavy metals in residues from the dismantling of waste electrical and electronic equipment before incineration.

    Science.gov (United States)

    Long, Yu-Yang; Feng, Yi-Jian; Cai, Si-Shi; Hu, Li-Fang; Shen, Dong-Sheng

    2014-05-15

    Residues disposal from the dismantling of waste electrical and electronic equipment are challenging because of the large waste volumes, degradation-resistance, low density and high heavy metal content. Incineration is advantageous for treating these residues but high heavy metal contents may exist in incinerator input and output streams. We have developed and studied a specialized heavy metal reduction process, which includes sieving and washing for treating residues before incineration. The preferable screen aperture for sieving was found to be 2.36mm (8 meshes) in this study; using this screen aperture resulted in the removal of approximately 47.2% Cu, 65.9% Zn, 26.5% Pb, 55.4% Ni and 58.8% Cd from the residues. Subsequent washing further reduces the heavy metal content in the residues larger than 2.36mm, with preferable conditions being 400rpm rotation speed, 5min washing duration and liquid-to-solid ratio of 25:1. The highest cumulative removal efficiencies of Cu, Zn, Pb, Ni and Cd after sieving and washing reached 81.1%, 61.4%, 75.8%, 97.2% and 72.7%, respectively. The combined sieving and washing process is environmentally friendly, can be used for the removal of heavy metals from the residues and has benefits in terms of heavy metal recycling. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. One-electron transfer reactions of the couple NAD./NADH

    International Nuclear Information System (INIS)

    Grodkowski, J.; Neta, P.; Carlson, B.W.; Miller, L.

    1983-01-01

    One-electron transfer reactions involving nicotinamide-adenine dinucleotide in its oxidized and reducd forms (NAD./NADH) were studied by pulse radiolysis in aqueous solutions. One-electron oxidation of NADH by various phenoxyl radicals and phenothiazine cation radicals was found to take place with rate constants in the range of 10 5 to 10 8 M -1 s -1 , depending on the redox potential of the oxidizing species. In all cases, NAD. is formed quantitatively with no indication for the existence of the protonated form (NADH + .). The spectrum of NAD., as well as the rates of oxidation of NADH by phenoxyl and by (chlorpromazine) + . were independent of pH between pH 4.5 and 13.5. Reaction of deuterated NADH indicated only a small kinetic isotope effect. All these findings point to an electron transfer mechanism. On the other hand, attempts to observe the reverse electron transfer, i.e., one-electron reduction of NAD. to NADH by radicals such as semiquinones, showed that k was less than 10 4 to 10 5 M -1 s -1 , so that it was unobservable. Consequently, it was not possible to achieve equilibrium conditions which would have permitted the direct measurement of the redox potential for NAD./NADH. One-electron reduction of NAD. appears to be an unlikely process. 1 table

  12. Contribution of Higher-Order Dispersion to Nonlinear Electron-Acoustic Solitary Waves in a Relativistic Electron Beam Plasma System

    International Nuclear Information System (INIS)

    Zahran, M.A.; El-Shewy, E.K.

    2008-01-01

    The nonlinear properties of solitary wave structures are reported in an unmagnetized collisionless plasma comprising of cold relativistic electron fluid, Maxwellian hot electrons, relativistic electron beam, and stationary ions. The Korteweg--de Vries (KdV) equation has been derived using a reductive perturbation theory. As the wave amplitude increases, the width and velocity of the soliton deviate from the prediction of the KdV equation i.e. the breakdown of the KdV approximation. On the other hand, to overcome this weakness we extend our analysis to obtain the KdV equation with fifth-order dispersion term. The solution of the resulting equation has been obtained

  13. Advances in electron cooling in heavy-ion storage rings

    International Nuclear Information System (INIS)

    Danared, H.

    1994-01-01

    The efficiency of electron cooling can be improved by reducing the temperature of the electrons. If the magnetic field at the location of the electron gun is stronger than in the region where the electrons interact with the ions, and the field gradient is adiabatic with respect to the cyclotron motion of the electrons, the resulting expansion of the electron beam reduces its transverse temperature by a factor equal to the ratio between the two fields. A ten times expanded electron beam was introduced in the CRYRING electron cooler in the summer of 1993, and similar arrangements have since then been made at the TSR ring in Heidelberg and at ASTRID in Aarhus. The reduction of the transverse electron temperature has increased cooling rates with large factors, and improves the energy resolution and increases count rates when the cooler is used as an electron target for ion-electron recombination experiments

  14. Cholesterol Hydroperoxide Generation, Translocation, and Reductive Turnover in Biological Systems.

    Science.gov (United States)

    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.

  15. Spectrum analysis of the reduction degree of two-step reduced graphene oxide (GO) and the polymer/r-GO composites

    Energy Technology Data Exchange (ETDEWEB)

    She, Xilin, E-mail: xlshe@qdu.edu.cn [College of Chemical and Environmental Engineering, Qingdao University, Qingdao 266071 (China); Liu, Tongchao; Wu, Nan [College of Chemical and Environmental Engineering, Qingdao University, Qingdao 266071 (China); Xu, Xijin [School of Physics and Technology, University of Jinan, Jinan 250022 (China); Li, Jianjiang [College of Chemical and Environmental Engineering, Qingdao University, Qingdao 266071 (China); Yang, Dongjiang, E-mail: d.yang@qdu.edu.cn [College of Chemical and Environmental Engineering, Qingdao University, Qingdao 266071 (China); School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001 (Australia); Frost, Ray [School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001 (Australia)

    2013-12-16

    In this paper, the reduction degree of graphene oxide (GO) reduced using chemical reduction and thermal reduction methods was characterized by spectrum analysis. The optimized conditions of reducing GO were determined that the hydrazine hydrate is the best reducing agent and the appropriate thermal reduction temperature is at 240 °C. The obtained GO solution was mixed with polystyrene (PS) solution to prepare PS/r-GO composites by using two-step reduction technique under the optimized conditions. The structure and micro-morphology of GO, r-GO and PS/r-GO composites were characterized by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) respectively. It is also observed that the two-step reduction pathway is more effective than one-step reduction for improving the reduction degree of GO. Accordingly, the electric conductivity of PS/r-GO composites prepared by two-step reduction technique is as high as 21.45 S m{sup −1}, which is much higher than that of composites fabricated by one-step reduction method. The spectrum techniques will highlight new opportunities for investigating the reduction degree of GO in polymer composites. - Highlights: • Spectrum analysis on the reduction degree of GO reduced by different methods. • Determine the optimized reduction conditions of GO and polymer/r-GO composites. • The two-step reduction is more effective than one-step reduction.

  16. Spectrum analysis of the reduction degree of two-step reduced graphene oxide (GO) and the polymer/r-GO composites

    International Nuclear Information System (INIS)

    She, Xilin; Liu, Tongchao; Wu, Nan; Xu, Xijin; Li, Jianjiang; Yang, Dongjiang; Frost, Ray

    2013-01-01

    In this paper, the reduction degree of graphene oxide (GO) reduced using chemical reduction and thermal reduction methods was characterized by spectrum analysis. The optimized conditions of reducing GO were determined that the hydrazine hydrate is the best reducing agent and the appropriate thermal reduction temperature is at 240 °C. The obtained GO solution was mixed with polystyrene (PS) solution to prepare PS/r-GO composites by using two-step reduction technique under the optimized conditions. The structure and micro-morphology of GO, r-GO and PS/r-GO composites were characterized by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) respectively. It is also observed that the two-step reduction pathway is more effective than one-step reduction for improving the reduction degree of GO. Accordingly, the electric conductivity of PS/r-GO composites prepared by two-step reduction technique is as high as 21.45 S m −1 , which is much higher than that of composites fabricated by one-step reduction method. The spectrum techniques will highlight new opportunities for investigating the reduction degree of GO in polymer composites. - Highlights: • Spectrum analysis on the reduction degree of GO reduced by different methods. • Determine the optimized reduction conditions of GO and polymer/r-GO composites. • The two-step reduction is more effective than one-step reduction

  17. Reductive decolourisation of azo dyes by mesophilic and thermophilic methanogenic consortia

    NARCIS (Netherlands)

    Cervantes, F.J.; Santos, dos A.B.; Madrid, de M.P.; Stams, A.J.M.; Lier, van J.B.

    2005-01-01

    The contribution of acidogenic bacteria and methanogenic archaea on the reductive decolourisation of azo dyes was assessed in anaerobic granular sludge. Acidogenic bacteria appeared to play an important role in the decolourising processes when glucose was provided as an electron donor; whereas

  18. Model reduction of nonlinear systems subject to input disturbances

    KAUST Repository

    Ndoye, Ibrahima

    2017-07-10

    The method of convex optimization is used as a tool for model reduction of a class of nonlinear systems in the presence of disturbances. It is shown that under some conditions the nonlinear disturbed system can be approximated by a reduced order nonlinear system with similar disturbance-output properties to the original plant. The proposed model reduction strategy preserves the nonlinearity and the input disturbance nature of the model. It guarantees a sufficiently small error between the outputs of the original and the reduced-order systems, and also maintains the properties of input-to-state stability. The matrices of the reduced order system are given in terms of a set of linear matrix inequalities (LMIs). The paper concludes with a demonstration of the proposed approach on model reduction of a nonlinear electronic circuit with additive disturbances.

  19. Low voltage electron beam accelerators

    International Nuclear Information System (INIS)

    Ochi, Masafumi

    2003-01-01

    Widely used electron accelerators in industries are the electron beams with acceleration voltage at 300 kV or less. The typical examples are shown on manufactures in Japan, equipment configuration, operation, determination of process parameters, and basic maintenance requirement of the electron beam processors. New electron beam processors with acceleration voltage around 100 kV were introduced maintaining the relatively high dose speed capability of around 10,000 kGy x mpm at production by ESI (Energy Science Inc. USA, Iwasaki Electric Group). The application field like printing and coating for packaging requires treating thickness of 30 micron or less. It does not require high voltage over 110 kV. Also recently developed is a miniature bulb type electron beam tube with energy less than 60 kV. The new application area for this new electron beam tube is being searched. The drive force of this technology to spread in the industries would be further development of new application, process and market as well as the price reduction of the equipment, upon which further acknowledgement and acceptance of the technology to societies and industries would entirely depend. (Y. Tanaka)

  20. Low voltage electron beam accelerators

    Energy Technology Data Exchange (ETDEWEB)

    Ochi, Masafumi [Iwasaki Electric Co., Ltd., Tokyo (Japan)

    2003-02-01

    Widely used electron accelerators in industries are the electron beams with acceleration voltage at 300 kV or less. The typical examples are shown on manufactures in Japan, equipment configuration, operation, determination of process parameters, and basic maintenance requirement of the electron beam processors. New electron beam processors with acceleration voltage around 100 kV were introduced maintaining the relatively high dose speed capability of around 10,000 kGy x mpm at production by ESI (Energy Science Inc. USA, Iwasaki Electric Group). The application field like printing and coating for packaging requires treating thickness of 30 micron or less. It does not require high voltage over 110 kV. Also recently developed is a miniature bulb type electron beam tube with energy less than 60 kV. The new application area for this new electron beam tube is being searched. The drive force of this technology to spread in the industries would be further development of new application, process and market as well as the price reduction of the equipment, upon which further acknowledgement and acceptance of the technology to societies and industries would entirely depend. (Y. Tanaka)

  1. Electron Transfer Strategies Regulate Carbonate Mineral and Micropore Formation.

    Science.gov (United States)

    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.

  2. NMR studies of transmembrane electron transport in human erythrocytes

    International Nuclear Information System (INIS)

    Kennett, E.C.; Bubb, W.A.; Kuchel, P.W.

    2002-01-01

    Full text: Electron transport systems exist in the plasma membranes of all cells. These systems appear to play a role in cell growth and proliferation, intracellular signalling, hormone responses, apoptotic events, cell defence and perhaps most importantly they enable the cell to respond to changes in the redox state of both the intra- and extracellular environments. Previously, 13 C NMR has been used to study transmembrane electron transport in human erythrocytes, specifically the reduction of extracellular 13 C-ferricyanide. NMR is a particularly useful tool for studying such systems as changes in the metabolic state of the cell can be observed concomitantly with extracellular reductase activity. We investigated the oxidation of extracellular NADH by human erythrocytes using 1 H and 31 P NMR spectroscopy. Recent results for glucose-starved human erythrocytes indicate that, under these conditions, extracellular NADH can be oxidised at the plasma membrane with the electron transfer across the membrane resulting in reduction of intracellular NAD + . The activity is inhibited by known trans-plasma membrane electron transport inhibitors (capsaicin and atebrin) and is unaffected by inhibition of the erythrocyte Band 3 anion transporter. These results suggest that electron import from extracellular NADH allows the cell to re-establish a reducing environment after the normal redox balance is disturbed

  3. Tuning of CO2 Reduction Selectivity on Metal Electrocatalysts.

    Science.gov (United States)

    Wang, Yuhang; Liu, Junlang; Wang, Yifei; Al-Enizi, Abdullah M; Zheng, Gengfeng

    2017-11-01

    Climate change, caused by heavy CO 2 emissions, is driving new demands to alleviate the rising concentration of atmospheric CO 2 levels. Enlightened by the photosynthesis of green plants, photo(electro)chemical catalysis of CO 2 reduction, also known as artificial photosynthesis, is emerged as a promising candidate to address these demands and is widely investigated during the past decade. Among various artificial photosynthetic systems, solar-driven electrochemical CO 2 reduction is widely recognized to possess high efficiencies and potentials for practical application. The efficient and selective electroreduction of CO 2 is the key to the overall solar-to-chemical efficiency of artificial photosynthesis. Recent studies show that various metallic materials possess the capability to play as electrocatalysts for CO 2 reduction. In order to achieve high selectivity for CO 2 reduction products, various efforts are made including studies on electrolytes, crystal facets, oxide-derived catalysts, electronic and geometric structures, nanostructures, and mesoscale phenomena. In this Review, these methods for tuning the selectivity of CO 2 electrochemical reduction of metallic catalysts are summarized. The challenges and perspectives in this field are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Secondary electron emission characteristics of oxide electrodes in flat electron emission lamp

    Directory of Open Access Journals (Sweden)

    Chang-Lin Chiang

    2016-01-01

    Full Text Available The present study concerns with the secondary electron emission coefficient, γ, of the cathode materials used in the newly developed flat electron emission lamp (FEEL devices, which essentially integrates the concept of using cathode for fluorescent lamp and anode for cathode ray tube (CRT to obtain uniform planar lighting. Three different cathode materials, namely fluorine-doped tin oxide (FTO, aluminum oxide coated FTO (Al2O3/FTO and magnesium oxide coated FTO (MgO/FTO were prepared to investigate how the variations of γ and working gases influence the performance of FEEL devices, especially in lowering the breakdown voltage and pressure of the working gases. The results indicate that the MgO/FTO bilayer cathode exhibited a relatively larger effective secondary electron emission coefficient, resulting in significant reduction of breakdown voltage to about 3kV and allowing the device to be operated at the lower pressure to generate the higher lighting efficiency.

  5. Secondary electron emission characteristics of oxide electrodes in flat electron emission lamp

    Energy Technology Data Exchange (ETDEWEB)

    Chiang, Chang-Lin, E-mail: CLChiang@itri.org.tw; Li, Chia-Hung [Green Energy and Environment Research Laboratories, Industrial Technology Research Institute, 195, Sec. 4, Chung Hsing Road, Chutung 310, Taiwan (China); Department of Electrophysics, National Chiao Tung University, 1001 Ta Hsueh Road, Hsinchu 300, Taiwan (China); Zeng, Hui-Kai [Department of Electronic Engineering, Chung Yuan Christian University, 200 Chung Pei Road, Chung Li 320, Taiwan (China); Li, Jung-Yu, E-mail: JY-Lee@itri.org.tw; Chen, Shih-Pu; Lin, Yi-Ping [Green Energy and Environment Research Laboratories, Industrial Technology Research Institute, 195, Sec. 4, Chung Hsing Road, Chutung 310, Taiwan (China); Hsieh, Tai-Chiung; Juang, Jenh-Yih, E-mail: jyjuang@cc.nctu.edu.tw [Department of Electrophysics, National Chiao Tung University, 1001 Ta Hsueh Road, Hsinchu 300, Taiwan (China)

    2016-01-15

    The present study concerns with the secondary electron emission coefficient, γ, of the cathode materials used in the newly developed flat electron emission lamp (FEEL) devices, which essentially integrates the concept of using cathode for fluorescent lamp and anode for cathode ray tube (CRT) to obtain uniform planar lighting. Three different cathode materials, namely fluorine-doped tin oxide (FTO), aluminum oxide coated FTO (Al{sub 2}O{sub 3}/FTO) and magnesium oxide coated FTO (MgO/FTO) were prepared to investigate how the variations of γ and working gases influence the performance of FEEL devices, especially in lowering the breakdown voltage and pressure of the working gases. The results indicate that the MgO/FTO bilayer cathode exhibited a relatively larger effective secondary electron emission coefficient, resulting in significant reduction of breakdown voltage to about 3kV and allowing the device to be operated at the lower pressure to generate the higher lighting efficiency.

  6. Hexavalent uranium reduction from solid phase by thermophilic bacterium Thermoterrabacterium ferrireducens

    International Nuclear Information System (INIS)

    Khijniak, T.V.; Slobodkin, A.I.; Bonch-Osmolovskaya, E.A.; Medvedeva-Lyalikova, N.N.; Coker, V.; Lloyd, J.R.; Birkeland, N.K.

    2005-01-01

    Full text of publication follows: It has been reported that in uranium-contaminated sites, solid-phase U(VI) present in sediments is resistant to microbial reduction. Also, it was demonstrated that mesophilic iron and sulfate-reducing bacteria can reduce hexavalent uranium and sulphate-reducing bacteria were able to grow via uranium reduction. Among thermophilic microorganisms reduction of hexavalent uranium has been demonstrated only for cell suspensions of two genera: Pyrobaculum and Thermus. In the present study, Thermoterrabacterium ferrireducens was tested for reduction of U(VI), a thermophilic, gram-positive anaerobic bacterium capable for growth with the reduction of various electron acceptors including Fe(III). Kinetic of bacterial growth, uranium reduction and influence of different uranium concentrations were investigated at 65 deg. C. Due to presence of phosphate in the basal medium yellow uranium phosphate precipitate was formed after addition of uranyl acetate. After 68 h of incubation control tubes without bacteria were contained yellow precipitate whereas in presence of bacteria precipitate turned to the grey color. In the control tubes uranium phosphates and other elements formed a uniform mixture of crystals, but in presence of bacteria the round shape particles, containing uranium, were found by Environmental Scan Electron Microscopy of air-dried or frozen samples. To determine valent state speciation spectroscopic investigations were performed also. Initial yellow uranium phosphate precipitate was separated and identified as uramphite - (NH 4 )(UO 2 )(PO 4 )*3H 2 O by X-Ray Powder Diffraction. Grey precipitate, which was formed by bacterial reduction, was identified as ningyoite - CaU(PO 4 ) 2 *H 2 O. The fact that final grey precipitate contain U(IV) was also confirmed by EXAFS investigation. High concentration of uranium has toxic effect. 1 and 2.5 mM of uranium (VI) support bacterial growth and bacterial biomass was accumulated, but if 5 or 10

  7. Cadmium poisoning of oxygen reduction on platinum electrode in potassium hydroxide

    Science.gov (United States)

    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.

  8. Phase transformation behavior of titanium during carbothermic reduction of titanomagnetite ironsand

    Institute of Scientific and Technical Information of China (English)

    Yi-ran Liu; Jian-liang Zhang; Zheng-jian Liu; Xiang-dong Xing

    2016-01-01

    The reduction of titanomagnetite (TTM) ironsand, which contains 11.41wt% TiO2 and 55.63wt% total Fe, by graphite was per-formed using a thermogravimetric analysis system under an argon gas atmosphere at 1423–1623 K. The behavior and effects of titanium in TTM ironsand during the reduction process were investigated by means of thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. During the reduction procedure, the titanium concentrated in the slag phase, where the phase transformation followed this sequence: FeO + FeTiO3→ Fe2TiO4→ FeTiO3→ FeTi2O5→ TiO2. The calculated results for the reduction kinetics showed that the carbothermic reduction was controlled by the diffusion of ions through the product layer. Furthermore, the apparent activation energy was 170.35 kJ·mol−1.

  9. Application of the Marcus theory to description of the kinetics of reduction processes of organic cations

    International Nuclear Information System (INIS)

    Bogillo, V.I.; Lobanov, V.V.; Gragerov, I.P.

    1987-01-01

    The calculation of the rate constants for the processes in the reduction of diazonium, tropylium, verdazylium, and pyrylium cations by various organic electron donors, using the equations of the Marcus theory with allowance for the reorganization energy of only the outer coordination sphere, leads to values which are one to seven orders of magnitude higher than the experimental values. By quantum-chemical calculations it was shown that the reduction of diazonium and tropylium cations to the corresponding radicals is accompanied by a substantial change in the structure of the reagents. This leads to high values for the reorganization energy of the inner coordination sphere of the cations, which must be taken into account during calculation of the rate constants. The differences in the rate constants of the processes of direct electron transfer from the electron donors to the organic cations and the recombination of these reagents depend on the dissociation energy of the bond of the cation with the donor leading to the electron transfer products

  10. Redox reactions in micellar systems. communication 4. Eosin-photosensitized reduction of methylviologen

    Energy Technology Data Exchange (ETDEWEB)

    Nadtochenko, V.; Dzhabiev, T.S.; Rubtsov, I.V.

    1985-12-10

    The authors present data on photosensitized reduction of methylviologen (MV/sup 2 +/) by disodium ethylenediaminetetraacetate (EDTA) in micellar systems modeling, in a first approximation, the structural organization of components of the chain of energy and electron transfer in natural photosynthesis. Photosensitized reduction of methylviologen by EDTA in micellar solutions can model photosystem I of plants with structure formation of reagents and transfer of excitation energy before the step of occurrence of a redox reaction in the active center.

  11. Electronic coupling induced high performance of N, S-codoped graphene supported CoS2 nanoparticles for catalytic reduction and evolution of oxygen

    Science.gov (United States)

    Chen, Bohong; Jiang, Zhongqing; Zhou, Lingshan; Deng, Binglu; Jiang, Zhong-Jie; Huang, Jianlin; Liu, Meilin

    2018-06-01

    A simple synthetic method is developed for the synthesis of CoS2/N, S-codoped graphene. The result shows the existence of a strong electronic coupling between CoS2 and N, S-codoped graphene. The pyrrolic and pyridinic type nitrogen and S in the form of C-S-C in N, S-codoped graphene are found to be the anchoring sites of the CoS2 nanoparticles. As a bifunctional catalyst, the CoS2/N, S-codoped graphene exhibits an oxygen reduction onset potential of 0.963 V vs. RHE and delivers an oxygen evolution overpotential of 393 mV at the current density of 10 mA cm-2. Its oxygen reduction and evolution catalytic activities are comparable to those of the Pt/C and the state-of-art RuO2/C, respectively. Most impressively, the CoS2/N, S-codoped graphene exhibits a potential gap of 771 mV. This value is lower than those of most bifuntional catalysts reported, clearly indicating its potential use as the bifunctional catalyst to replace the noble-metal based catalysts for practical applications. Additionally, our results also suggest a great importance to prepare a single pure phase CoS2 in improving the catalytic bifunctionality of the CoS2/N, S-codoped graphene. The primary Zn-air battery with CoS2/N, S-codoped graphene shows a higher discharge peak power density than that with Pt/C.

  12. Catalysis of the reduction of Tl+ and of CH2Cl2 by colloidal silver in aqueous solution

    International Nuclear Information System (INIS)

    Henglein, A.

    1979-01-01

    (CH 3 ) 2 COH radicals (1-hydroxy-1-methylethyl) do not reduce Tl + or CH 2 Cl 2 in homogeneous aqueous solution. In the presence of 2.5 x 10 -4 g atom/L of colloidal silver, Tl + is reduced to yield colloidal thallium, and CH 2 Cl 2 to yield Cl - plus CH 3 Cl. These reactions occur in competition with the silver-catalyzed reduction of water. Tl + is reduced in a one-electron transfer reaction and CH 2 Cl 2 in a two-electron transfer process. The effects are understood in terms of the colloidal particles acting as a pool for electrons that is continuously charged by the organic radicals and discharged by water or dissolved substrates. The specific rate for the CH 2 Cl 2 reduction at the silver pool is 4.3 x 10 3 times greater than that of the water reduction. Electrochemical considerations are carried out to estimate a stationary potential of -0.62 V (vs the standard hydrogen electrode) for the electron pool and to discuss the energetics of the observed reactions and the possible role of adsorbed hydrogen atoms. Colloidal silver and organic radicals were radiolytically produced. 7 figures

  13. Catalysis of the reduction of Tl+ and of CH2Cl2 by colloidal silver in aqueous solution

    International Nuclear Information System (INIS)

    Henglein, A.

    1979-01-01

    (CH 3 ) 2 COH radicals (1-hydroxy-1-methylethyl) do not reduce Tl + or CH 2 CL 2 in homogeneous aqueous solution. In the presence of 2.5 x 10 -4 g atom/L of colloidal silver, Tl + is reduced to yield colloidal thallium, and CH 2 Cl 2 to yield Cl - plus CH 3 Cl. These reactions occur in competition with the silver-catalyzed reduction of water. Tl + is reduced in a one-electron transfer reaction and CH 2 Cl 2 in a two-electron transfer process. The effects are understood in terms of the colloidal particles acting as a pool for electrons that is continuously charged by the organic radicals and discharged by water or dissolved substrates. The specific rate for the CH 2 Cl 2 reduction at the silver pool is 4.3 x 10 3 times greater than that of the water reduction. Electrochemical considerations are carried out to estimate a stationary potential of -0.62 V (vs the standard hydrogen electrode) for the electron pool and to discuss the energetics of the observed reactions and tha materials handling point of view, are being determined

  14. Oxygen reduction at platinum nanoparticles supported on carbon cryogel in alkaline solution

    Directory of Open Access Journals (Sweden)

    N. R. ELEZOVIC

    2007-07-01

    Full Text Available The oxygen reduction reaction was investigated in 0.1 M NaOH solution, on a porous coated electrode formed of Pt particles supported on carbon cryogel. The Pt/C catalyst was characterized by the X-ray diffraction (XRD, transmission electron microscopy (TEM and cyclic voltammetry techniques. The results demonstrated a successful reduction of Pt to metallic form and homogenous Pt particle size distribution with a mean particle size of about 2.7 nm. The ORR kinetics was investigated by linear sweep polarization at a rotating disc electrode. The results showed the existence of two E – log j regions, usually referred to polycrystalline Pt in acid and alkaline solution. At low current densities (lcd, the Tafel slope was found to be close to –2.3RT/F, while at high current densities (hcd it was found to be close to –2×2.3RT/F. It is proposed that the main path in the ORR mechanism on Pt particles was the direct four-electron process, with the transfer of the first electron as the rate determining step. If the activities are expressed through the specific current densities, a small enhancement of the catalytic activity for Pt/C was observed compared to that of polycrystalline Pt. The effect of the Pt particle size on the electrocatalysis of oxygen reduction was ascribed to the predominant (111 facets of the platinum crystallites.

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

    Science.gov (United States)

    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

  16. Reduction of secondary electron yield for E-cloud mitigation by laser ablation surface engineering

    Energy Technology Data Exchange (ETDEWEB)

    Valizadeh, R., E-mail: reza.valizadeh@stfc.ac.uk [ASTeC, STFC Daresbury Laboratory, Warrington WA4 4AD (United Kingdom); Malyshev, O.B. [ASTeC, STFC Daresbury Laboratory, Warrington WA4 4AD (United Kingdom); Wang, S. [ASTeC, STFC Daresbury Laboratory, Warrington WA4 4AD (United Kingdom); Department of Physics, Loughborough University, Loughborough LE11 3TU (United Kingdom); Sian, T. [ASTeC, STFC Daresbury Laboratory, Warrington WA4 4AD (United Kingdom); The Photon Science Institute, The University of Manchester, Manchester M13 9PL (United Kingdom); Cropper, M.D. [Department of Physics, Loughborough University, Loughborough LE11 3TU (United Kingdom); Sykes, N. [Micronanics Ltd., Didcot, Oxon OX11 0QX (United Kingdom)

    2017-05-15

    Highlights: • SEY below 1 can be achieved with Laser ablation surface engineering. • SEY <1 surface can be produced with different types of nanosecond lasers. • Both microstructure (groves) and nano-structures are playing a role in reducing SEY. - Abstract: Developing a surface with low Secondary Electron Yield (SEY) is one of the main ways of mitigating electron cloud and beam-induced electron multipacting in high-energy charged particle accelerators. In our previous publications, a low SEY < 0.9 for as-received metal surfaces modified by a nanosecond pulsed laser was reported. In this paper, the SEY of laser-treated blackened copper has been investigated as a function of different laser irradiation parameters. We explore and study the influence of micro- and nano-structures induced by laser surface treatment in air of copper samples as a function of various laser irradiation parameters such as peak power, laser wavelength (λ = 355 nm and 1064 nm), number of pulses per point (scan speed and repetition rate) and fluence, on the SEY. The surface chemical composition was determined by x-ray photoelectron spectroscopy (XPS) which revealed that heating resulted in diffusion of oxygen into the bulk and induced the transformation of CuO to sub-stoichiometric oxide. The surface topography was examined with high resolution scanning electron microscopy (HRSEM) which showed that the laser-treated surfaces are dominated by microstructure grooves and nanostructure features.

  17. Kinetics of U(VI) reduction by a dissimilatory Fe(III)-reducing bacterium under non-growth conditions

    International Nuclear Information System (INIS)

    Truex, M.J.; Peyton, B.M.; Valentine, N.B.; Gorby, Y.A.

    1997-01-01

    Dissimilatory metal-reducing microorganisms may be useful in processes designed for selective removal of uranium from aqueous streams. These bacteria can use U(VI) as an electron acceptor and thereby reduce soluble U(VI) to insoluble U(IV). While significant research has been devoted to demonstrating and describing the mechanism of dissimilatory metal reduction, the reaction kinetics necessary to apply this for remediation processes have not been adequately defined. In this study, pure culture Shewanella alga strain BrY reduced U(VI) under non-growth conditions in the presence of excess lactate as the electron donor. Initial U(VI) concentrations ranged from 13 to 1,680microM. A maximum specific U(VI) reduction rate of 2.37 micromole-U(VI)/(mg-biomass h) and Monod half-saturation coefficient of 132 microM-U(VI) were calculated from measured U(VI) reduction rates. U(VI) reduction activity was sustained at 60% of this rate for at least 80 h. The initial presence of oxygen at a concentration equal to atmospheric saturation at 22 C delays but does not prevent U(VI) reduction. The rate of U(VI) reduction by BrY is comparable or better than rates reported for other metal reducing species. BrY reduces U(VI) at a rate that is 30% of its Fe(III) reduction rate

  18. Electron - polar acoustical phonon interactions in nitride based diluted magnetic semiconductor quantum well via hot electron magnetotransport

    International Nuclear Information System (INIS)

    Pandya, Ankur; Shinde, Satyam; Jha, Prafulla K.

    2015-01-01

    In this paper the hot electron transport properties like carrier energy and momentum scattering rates and electron energy loss rates are calculated via interactions of electrons with polar acoustical phonons for Mn doped BN quantum well in BN nanosheets via piezoelectric scattering and deformation potential mechanisms at low temperatures with high electric field. Electron energy loss rate increases with the electric field. It is observed that at low temperatures and for low electric field the phonon absorption is taking place whereas, for sufficient large electric field, phonon emission takes place. Under the piezoelectric (polar acoustical phonon) scattering mechanism, the carrier scattering rate decreases with the reduction of electric field at low temperatures wherein, the scattering rate variation with electric field is limited by a specific temperature beyond which there is no any impact of electric field on such scattering

  19. First results from the commissioning of the FERMI@Elettra free electron laser by means of the Photon Analysis Delivery and Reduction System (PADReS)

    Science.gov (United States)

    Zangrando, M.; Cudin, I.; Fava, C.; Gerusina, S.; Gobessi, R.; Godnig, R.; Rumiz, L.; Svetina, C.; Parmigiani, F.; Cocco, D.

    2011-06-01

    The Italian Free Electron Laser (FEL) facility FERMI@Elettra has started to produce photon radiation at the end of 2010. The photon beam is presently delivered by the first undulator chain (FEL1) that is supposed to produce photons in the 100-20 nm wavelength range. A second undulator chain (FEL2) will be commissioned at the end of 2011, and it will produce radiation in the 20-4nm range. The Photon Analysis Delivery and Reduction System (PADReS) was designed to collect the radiation coming from both the undulator chains (FEL1 and FEL2), to characterize and control it, and to redirect it towards the following beamlines. The first parameters that are checked are the pulse-resolved intensity and beam position. For each of these parameters two dedicated monitors are installed along PADReS on each FEL line. In this way it possible to determine the intensity reduction that is realized by the gas reduction system, which is capable of cutting the intensity by up to four orders of magnitude. The energy distribution of each single pulse is characterized by an online spectrometer installed in the experimental hall. Taking advantage of a variable line-spacing grating it can direct the almost-full beam to the beamlines, while it uses a small fraction of the beam itself to determine the spectral distribution of each pulse delivered by the FEL. The first light of FERMI@Elettra, delivered to the PADReS section in late 2010, is used for the first commissioning runs and some preliminary experiments whose results are reported and discussed in detail.

  20. Green reduction of graphene oxide by ascorbic acid

    Science.gov (United States)

    Khosroshahi, Zahra; Kharaziha, Mahshid; Karimzadeh, Fathallah; Allafchian, Alireza

    2018-01-01

    Graphene, a single layer of sp2-hybridized carbon atoms in a hexagonal (two-dimensional honey-comb) lattice, has attracted strong scientific and technological interest due to its novel and excellent optical, chemical, electrical, mechanical and thermal properties. The solution-processable chemical reduction of Graphene oxide (GO is considered as the most favorable method regarding mass production of graphene. Generally, the reduction of GO is carried out by chemical approaches using different reductants such as hydrazine and sodium borohydride. These components are corrosive, combustible and highly toxic which may be dangerous for personnel health and the environment. Hence, these reducing agents are not promising choice for reducing of graphene oxide (GO). As a consequence, it is necessary for further development and optimization of eco-friendly, natural reducing agent for clean and effective reduction of GO. Ascorbic acid, an eco-friendly and natural reducing agents, having a mild reductive ability and nontoxic property. So, the aim of this research was to green synthesis of GO with ascorbic acid. For this purpose, the required amount of NaOH and ascorbic acid were added to GO solution (0.5 mg/ml) and were heated at 95 °C for 1 hour. According to the X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and electrochemical results, GO were reduced with ascorbic acid like hydrazine with better electrochemical properties and ascorbic acid is an ideal substitute for hydrazine in the reduction of graphene oxide process.

  1. The effects of electron beam irradiation on additives present in food-contact polymers

    International Nuclear Information System (INIS)

    Crowson, Andrew.

    1991-09-01

    A range of additives (Irganox 1010, Irganox 1076, Irganox 1330, Irgafos 168 and Tinuvin 622) has been incorporated into a variety of food-contact polymers including polypropylene and low density polyethylene. Samples of these stabilized polymers were subjected to electron-beam or gamma irradiation to receive doses of 1,5,10,25 and 50 kGy. The effects of electron-beam irradiation on the amount of extractable antioxidant in polymers were determined. Using hplc techniques it was found that there was a dose-related reduction in the amount of extractable antioxidant similar to that caused by gamma irradiation. The magnitude of this reduction was found to be dependent upon the nature of both the antioxidant and the polymer type. Electron-beam irradiation was also found to cause a dose-related reduction in the levels of the antioxidants Irganox 1010 and Irganox 1076 migrating from polymers into a food simulant. This effect was similar to that caused by gamma irradiation. (author)

  2. Mechanisms for Electron Transfer Through Pili to Fe(III) Oxide in Geobacter

    Energy Technology Data Exchange (ETDEWEB)

    Lovley, Derek R. [Univ. of Massachusetts, Amherst, MA (United States)

    2015-03-09

    The purpose of these studies was to aid the Department of Energy in its goal of understanding how microorganisms involved in the bioremediation of metals and radionuclides sustain their activity in the subsurface. This information is required in order to incorporate biological processes into decision making for environmental remediation and long-term stewardship of contaminated sites. The proposed research was designed to elucidate the mechanisms for electron transfer to Fe(III) oxides in Geobacter species because Geobacter species are abundant dissimilatory metal-reducing microorganisms in a diversity of sites in which uranium is undergoing natural attenuation via the reduction of soluble U(VI) to insoluble U(IV) or when this process is artificially stimulated with the addition of organic electron donors. This study investigated the novel, but highly controversial, concept that the final conduit for electron transfer to Fe(III) oxides are electrically conductive pili. The specific objectives were to: 1) further evaluate the conductivity along the pili of Geobacter sulfurreducens and related organisms; 2) determine the mechanisms for pili conductivity; and 3) investigate the role of pili in Fe(III) oxide reduction. The studies demonstrated that the pili of G. sulfurreducens are conductive along their length. Surprisingly, the pili possess a metallic-like conductivity similar to that observed in synthetic organic conducting polymers such as polyaniline. Detailed physical analysis of the pili, as well as studies in which the structure of the pili was genetically modified, demonstrated that the metallic-like conductivity of the pili could be attributed to overlapping pi-pi orbitals of aromatic amino acids. Other potential mechanisms for conductivity, such as electron hopping between cytochromes associated with the pili were definitively ruled out. Pili were also found to be essential for Fe(III) oxide reduction in G. metallireducens. Ecological studies demonstrated

  3. Nanocomposite films containing Au nanoparticles formed by electrochemical reduction of metal ions in the multilayer films as electrocatalyst for dioxygen reduction

    International Nuclear Information System (INIS)

    Huang Minghua; Shen Yan; Cheng Wenlong; Shao Yong; Sun Xuping; Liu Baifeng; Dong Shaojun

    2005-01-01

    Through electrostatic layer-by-layer assembly, AuCl 4 - anions and [tetrakis(N-methylpyridyl)porphyrinato] cobalt (CoTMPyP) cations were alternately deposited on indium tin oxide (ITO) substrates, and 4-aminobenzoic acid modified glassy carbon electrode. Electrochemical reduction of AuCl 4 - anions sandwiched between CoTMPyP layers leads to the in situ formation of Au nanoparticles in the multilayer films. Regular growth of the multilayer films is monitored by UV-vis spectroscopy. UV-vis spectroscopy, X-ray photoelectron spectroscopy and cyclic voltammetry confirm the formation of Au nanoparticles in the multilayer films after electrochemical reduction of AuCl 4 - anions. Atomic force spectroscopy verifies that the as-prepared Au nanoparticles are uniformly distributed with average particles diameters of 20-25 nm. The resulting composite films containing Au nanoparticles with high stability exhibit high electrocatalytic activity for the reduction of dioxygen. Rotating disk electrode voltammetry and rotating ring-disk electrode voltammetry demonstrate the Au nanoparticles-containing films can catalyze two-electron reduction of O 2 to H 2 O 2 in O 2 -saturated 0.1 M H 2 SO 4 solution

  4. Effectiveness of the Electronic Cigarette: An Eight-Week Flemish Study with Six-Month Follow-up on Smoking Reduction, Craving and Experienced Benefits and Complaints

    Directory of Open Access Journals (Sweden)

    Karolien Adriaens

    2014-10-01

    Full Text Available Background: Smoking reduction remains a pivotal issue in public health policy, but quit rates obtained with traditional quit-smoking therapies remain disappointingly low. Tobacco Harm Reduction (THR, aiming at less harmful ways of consuming nicotine, may provide a more effective alternative. One promising candidate for THR are electronic cigarettes (e-cigs. The aim of this study was to investigate the efficacy of second-generation e-cigs both in terms of acute craving-reduction in the lab and in terms of smoking reduction and experienced benefits/complaints in an eight-month Randomized Controlled Trial (RCT. Design: RCT with three arms. Methods: Participants (N = 48 unwilling to quit smoking were randomized into two e-cig groups and one control group. During three lab sessions (over two months participants, who had been abstinent for four hours, vaped/smoked for five minutes, after which we monitored the effect on craving and withdrawal symptoms. eCO and saliva cotinine levels were also measured. In between lab sessions, participants in the e-cig groups could use e-cigs or smoke ad libitum, whereas the control group could only smoke. After the lab sessions, the control group also received an e-cig. The RCT included several questionnaires, which repeatedly monitored the effect of ad libitum e-cig use on the use of tobacco cigarettes and the experienced benefits/complaints up to six months after the last lab session. Results: From the first lab session on, e-cig use after four hours of abstinence resulted in a reduction in cigarette craving which was of the same magnitude as when a cigarette was smoked, while eCO was unaffected. After two months, we observed that 34% of the e-cig groups had stopped smoking tobacco cigarettes, versus 0% of the control group (difference p < 0.01. After five months, the e-cig groups demonstrated a total quit-rate of 37%, whereas the control group showed a quit rate of 38% three months after initiating e-cig use. At

  5. CuO reduction induced formation of CuO/Cu2O hybrid oxides

    Science.gov (United States)

    Yuan, Lu; Yin, Qiyue; Wang, Yiqian; Zhou, Guangwen

    2013-12-01

    Reduction of CuO nanowires results in the formation of a unique hierarchical hybrid nanostructure, in which the parent oxide phase (CuO) works as the skeleton while the lower oxide (Cu2O) resulting from the reduction reaction forms as partially embedded nanoparticles that decorate the skeleton of the parent oxide. Using in situ transmission electron microscopy observations of the reduction process of CuO nanowires, we demonstrate that the formation of such a hierarchical hybrid oxide structure is induced by topotactic nucleation and growth of Cu2O islands on the parent CuO nanowires.

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

    Science.gov (United States)

    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)-.

  7. Reductive dechlorination of trichloroacetic acid (TCAA) by electrochemical process over Pd-In/Al_2O_3 catalyst

    International Nuclear Information System (INIS)

    Liu, Yanzhen; Mao, Ran; Tong, Yating; Lan, Huachun; Zhang, Gong; Liu, Huijuan; Qu, Jiuhui

    2017-01-01

    Highlights: • TCAA was efficiently removed by Pd-In/Al_2O_3 based electro-reductive process. • The active species for TCAA electroreduction involved electron (e"−) and atomic H*. • The atomic H* played a major contribution to TCAA removal. - Abstract: Electrochemical reduction treatment was found to be a promising method for dechlorination of Trichloroacetic acid (TCAA), and acceleration of electron transfer or enhancement of the concentration of atomic H* significantly improve the electrochemical dechlorination process. Bimetallic Pd-based catalysts have the unique property of simultaneously catalyzing the production of atomic H* and reducing target pollutants. Herein, a bimetallic Pd–In electrocatalyst with atomic ratio of 1:1 was evenly deposited on an Al_2O_3 substrate, and the bimetallic Pd-In structure was confirmed via X-ray photoelectron spectroscopy (XPS). Electrochemical removal of trichloroacetic acid (TCAA) by the Pd-In/Al_2O_3 catalyst was performed in a three-dimensional reactor. 94% of TCAA with the initial concentration of 500 μg L"−"1 could be degraded within 30 min under a relatively low current density (0.9 mA cm"−"2). In contrast to the presence of refractory intermediates (dichloroacetic acid (DCAA)) found in the Pd/Al_2O_3 system, TCAA could be thoroughly reduced to monochloroacetic acid (MCAA) using Pd-In/Al_2O_3 catalysts. According to scavenger experiments, an electron transfer process and atomic H* formation function both existed in the TCAA reduction process, and the enhanced indirect atomic H* reduction process (confirmed by ESR signals) played a chief role in the TCAA removal. Moreover, the synergistic effects of Pd and In were proven to be able to enhance both direct electron transfer and indirect atomic H* formation, indicating a promising prospect for bimetallic electrochemical reduction treatment.

  8. Chemical changes of titanium and titanium dioxide under electron bombardment

    Directory of Open Access Journals (Sweden)

    Romins Brasca

    2007-09-01

    Full Text Available The electron induced effect on the first stages of the titanium (Ti0 oxidation and titanium dioxide (Ti4+ chemical reduction processes has been studied by means of Auger electron spectroscopy. Using factor analysis we found that both processes are characterized by the appearance of an intermediate Ti oxidation state, Ti2O3 (Ti3+.

  9. SVC or VSC for reduction of voltage sags and flicker. Trends in power electronics

    Energy Technology Data Exchange (ETDEWEB)

    Haeusler, M; Schnettler, A [ABB Calor Emag Schaltanlagen AG, Mannheim (Germany); Halvarsson, P [ABB Power Systems AB, Vaesteraas (Sweden)

    1997-07-01

    In the past complaints about insufficient power quality were often caused by flicker observed in the neighbourhood of industrial networks. Voltage sags due to faults in the power system pass, however, mostly unnoticed as not-so-common events. Now electronic controls are penetrating more and more in industry. Electronic controllers on factory machines - particularly those for variable speed motors - are vulnerable to voltage sags. A one-tenth second sag can cause a $200.000 downtime incident in a big factory. Therefore the demands on power quality are rising in industry as well. The costly separation in clean networks for residential areas and dirty networks for industrial grids is no perfect solution to avoid such problems. Static VAr Compensators (SVC) are traditionally one means to control the voltage in industrial networks. Because of the recent development of powerful gate turn-off semiconductor devices another type of converter has gained new interest for mitigation of system disturbances, the voltage-source converter (VSC). The characteristics of both types of power electronics in view of their possibilities for this application are presented. (orig.)

  10. Integrated methodology for production related risk management of vehicle electronics (IMPROVE)

    OpenAIRE

    Geis, Stefan Rafael

    2006-01-01

    This scientific work is designated to provide an innovative and integrated conceptional approach to improve the assembly quality of automotive electronics. This is achieved by the reduction and elimination of production related risks of automotive electronics and the implementation of a sustainable solution process. The focus is the development and implementation of an integrated technical risk management approach for automotive electronics throughout the vehicle life cycle and the vehicle pr...

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

    Science.gov (United States)

    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.

  12. Reversed Microstructures and Tensile Properties after Various Cold Rolling Reductions in AISI 301LN Steel

    Directory of Open Access Journals (Sweden)

    Antti Järvenpää

    2018-02-01

    Full Text Available Heavy cold rolling is generally required for efficient grain size refinement in the martensitic reversion process, which is, however, not desirable in practical processing. In the present work, the influence of cold rolling reductions of 32%, 45% and 63% on the microstructure evolution and mechanical properties of a metastable austenitic AISI 301LN type steel were investigated in detail adopting scanning electron microscopy with the electron backscatter diffraction method and mechanical testing. A completely austenitic microstructure and a partially reversed counterpart were created. It was found that the fraction of grains with a size of 3 µm or larger, called medium-sized grains, increased with decreasing the prior cold rolling reduction. These grains are formed mainly from the shear-reversed austenite, transformed from slightly-deformed martensite, by gradual evolution of subgrains to grains. However, in spite of significant amounts of medium-sized grains, the tensile properties after the 32% or 45% cold rolling reductions were practically equal to those after the 63% reduction. The austenite stability against the formation of deformation-induced martensite in subsequent straining was reduced by lowering the cold rolling reduction, due to the larger grain size of medium-sized grains and the shift of their orientation towards {211} .

  13. Metal porphyrin intercalated reduced graphene oxide nanocomposite utilized for electrocatalytic oxygen reduction

    Directory of Open Access Journals (Sweden)

    Mingyan Wang

    2017-07-01

    Full Text Available In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin –MtTMPyP (Mt= Cobalt (II, Manganese (III, or Iron (III; TMPyP = 5, 10, 15, 20-tetrakis (N-methylpyridinium-4-yl porphyrin intercalated into the layer of graphene oxide (GO by the cooperative effects of electrostatic and π–π stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2D MtTMPyP/rGOn were fabricated. The as-prepared 2D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction (ORR in an alkaline medium. The MtTMPyP/rGOn hybrids, especially CoTMPyP/rGO5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries. Keywords: Metal porphyrin, Reduced graphene oxide, Intercalation, Oxygen reduction reaction, Catalyst

  14. Nitrate reduction in an unconfined sandy aquifer

    DEFF Research Database (Denmark)

    Postma, Diederik Jan; Boesen, Carsten; Kristiansen, Henning

    1991-01-01

    of total dissolved ions in the NO3- free anoxic zone indicates the downward migration of contaminants and that active nitrate reduction is taking place. Nitrate is apparently reduced to N2 because both nitrite and ammonia are absent or found at very low concentrations. Possible electron donors......Nitrate distribution and reduction processes were investigated in an unconfined sandy aquifer of Quaternary age. Groundwater chemistry was studied in a series of eight multilevel samplers along a flow line, deriving water from both arable and forested land. Results show that plumes of nitrate...... processes of O2 and NO3- occur at rates that are fast compared to the rate of downward water transport. Nitrate-contaminated groundwater contains total contents of dissolved ions that are two to four times higher than in groundwater derived from the forested area. The persistence of the high content...

  15. Evaluation of the effects of different filters and helium bag on the reduction of electron contamination in photon beam of Neptune linac

    International Nuclear Information System (INIS)

    Bahreyni Toosi, M. T.; Saberi, H.; Momen Nejad, M.

    2005-01-01

    Skin sparing is one of the most desirable characteristics of high energy photon beams. However, the photons emerging from the target of linacs are contaminated by secondary electrons as a result of their interactions with air, collimators, flattening filter and any other objects in their path. This phenomenon tends to increase the skin dose received by the patients. A practical and simple way to reduce the contribution of electron contamination is to place a sheet of medium to high Z material just after the secondary collimator. In this study, filters having different thickness and atomic number were applied and their effectiveness on the reduction of skin dose was evaluated. Materials and Methods: The filters of different thickness and atomic number were applied. The percent depth dose values were determined by the direct measurements made in a Scanditronix water phantom using a PTW 31006 Pin Point chamber having a sensitive volume of 0.015 cm 3 . A Perspex filter holder was made to be installed on the accessory slot. A plastic bag containing helium was also made using thin plastic sheet to study the effect of the helium bag when it replaces the air column between the head of the linac and the phantom. All of the measurements were carried out for the three field sizes of 10*10, 20*20 and 25*25 cm 2 . The setups were adjusted for SSD 100 cm. The ratio of the surface dose to maximum dose (Ds) was used as the criterion to determine the optimum filter. Results: The dosimetry results obtained in the water phantom indicated that a 0.4 mm thick Pb filter is the most effective one. This filter reduces the Ds for the field sizes of 10*10, 20*20 and 25*25 cm 2 by 5.7, 7.9 and 9.6%, respectively. Also the simultaneous use of the optimum filter and He bag is more effective than the filter alone. It reduces the Ds by 6.3, 10.1 and 12.3% for the field sizes of 10*10,20*20 and 25*25 cm 2 , respectively. Discussion and Conclusion: Based on the results of this work it is evident

  16. Acetate, lactate, propionate, and isobutyrate as electron donors for iron and sulfate reduction in Arctic marine sediments, Svalbard

    DEFF Research Database (Denmark)

    Finke, Niko; Vandieken, Verona; Jørgensen, Bo Barker

    2007-01-01

    The contribution of volatile fatty acids (VFA) as e--donors for anaerobic terminal oxidation of organic carbon through iron and sulfate reduction was studied in Arctic fjord sediment. Dissolved inorganic carbon, Fe2+, VFA concentrations, and sulfate reduction were monitored in slurries from...... by alternative e--donors. The accumulation of VFA in the selenate-inhibited 0-2 cm slurry did not enhance iron reduction, indicating that iron reducers were not limited by VFA availability....

  17. Nonlinear Electron Acoustic Waves in Dissipative Plasma with Superthermal Electrons

    Science.gov (United States)

    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.

  18. Effect of Organic Substrates on the Photocatalytic Reduction of Cr(VI by Porous Hollow Ga2O3 Nanoparticles

    Directory of Open Access Journals (Sweden)

    Jin Liu

    2018-04-01

    Full Text Available Porous hollow Ga2O3 nanoparticles were successfully synthesized by a hydrolysis method followed by calcination. The prepared samples were characterized by field emission scanning electron microscope, transmission electron microscope, thermogravimetry and differential scanning calorimetry, UV-vis diffuse reflectance spectra and Raman spectrum. The porous structure of Ga2O3 nanoparticles can enhance the light harvesting efficiency, and provide lots of channels for the diffusion of Cr(VI and Cr(III. Photocatalytic reduction of Cr(VI, with different initial pH and degradation of several organic substrates by porous hollow Ga2O3 nanoparticles in single system and binary system, were investigated in detail. The reduction rate of Cr(VI in the binary pollutant system is markedly faster than that in the single Cr(VI system, because Cr(VI mainly acts as photogenerated electron acceptor. In addition, the type and concentration of organic substrates have an important role in the photocatalytic reduction of Cr(VI.

  19. Effect of Organic Substrates on the Photocatalytic Reduction of Cr(VI) by Porous Hollow Ga2O3 Nanoparticles

    Science.gov (United States)

    Liu, Jin; Gan, Huihui; Wu, Hongzhang; Zhang, Xinlei; Zhang, Jun; Li, Lili; Wang, Zhenling

    2018-01-01

    Porous hollow Ga2O3 nanoparticles were successfully synthesized by a hydrolysis method followed by calcination. The prepared samples were characterized by field emission scanning electron microscope, transmission electron microscope, thermogravimetry and differential scanning calorimetry, UV-vis diffuse reflectance spectra and Raman spectrum. The porous structure of Ga2O3 nanoparticles can enhance the light harvesting efficiency, and provide lots of channels for the diffusion of Cr(VI) and Cr(III). Photocatalytic reduction of Cr(VI), with different initial pH and degradation of several organic substrates by porous hollow Ga2O3 nanoparticles in single system and binary system, were investigated in detail. The reduction rate of Cr(VI) in the binary pollutant system is markedly faster than that in the single Cr(VI) system, because Cr(VI) mainly acts as photogenerated electron acceptor. In addition, the type and concentration of organic substrates have an important role in the photocatalytic reduction of Cr(VI). PMID:29690548

  20. Mechanism of electron density reduction in the region of stable subauroral red arcs

    International Nuclear Information System (INIS)

    Pavlov, A.V.

    1993-01-01

    For geomagnetic storm on 18.12.71 are fulfilled calculations of electron density N e and temperature Te and intensity of the atmosphere luminescence at 630 nm in the region of the subauroral red are and outside its

  1. Anaerobic degradation of benzene by enriched consortia with humic acids as terminal electron acceptors

    Energy Technology Data Exchange (ETDEWEB)

    Cervantes, Francisco J., E-mail: fjcervantes@ipicyt.edu.mx [Division de Ciencias Ambientales, Instituto Potosino de Investigacion Cientifica y Tecnologica (IPICyT), Camino a la Presa San Jose 2055, Col. Lomas 4a. Seccion, San Luis Potosi, SLP, 78216 Mexico (Mexico); Mancilla, Ana Rosa; Toro, E. Emilia Rios-del [Division de Ciencias Ambientales, Instituto Potosino de Investigacion Cientifica y Tecnologica (IPICyT), Camino a la Presa San Jose 2055, Col. Lomas 4a. Seccion, San Luis Potosi, SLP, 78216 Mexico (Mexico); Alpuche-Solis, Angel G.; Montoya-Lorenzana, Lilia [Division de Biologia Molecular, Instituto Potosino de Investigacion Cientifica y Tecnologica (IPICyT), Camino a la Presa San Jose 2055, Col. Lomas 4a. Seccion, San Luis Potosi, SLP, 78216 Mexico (Mexico)

    2011-11-15

    Highlights: {yields} Enriched consortia were able to couple the anaerobic degradation of benzene to the reduction of humic acids. {yields} Electron-equivalents derived from anaerobic benzene oxidation were highly recovered as reduced humic acids. {yields} Several species from classes {beta}-, {delta}- and {gamma}-Proteobacteria were enriched during the anaerobic degradation of benzene. - Abstract: The anaerobic degradation of benzene coupled to the reduction of humic acids (HA) was demonstrated in two enriched consortia. Both inocula were able to oxidize benzene under strict anaerobic conditions when the humic model compound, anthraquinone-2,6-disulfonate (AQDS), was supplied as terminal electron acceptor. An enrichment culture originated from a contaminated soil was also able to oxidize benzene linked to the reduction of highly purified soil humic acids (HPSHA). In HPSHA-amended cultures, 9.3 {mu}M of benzene were degraded, which corresponds to 279 {+-} 27 micro-electron equivalents ({mu}Eq) L{sup -1}, linked to the reduction of 619 {+-} 81 {mu}Eq L{sup -1} of HPSHA. Neither anaerobic benzene oxidation nor reduction of HPSHA occurred in sterilized controls. Anaerobic benzene oxidation did not occur in soil incubations lacking HPSHA. Furthermore, negligible reduction of HPSHA occurred in the absence of benzene. The enrichment culture derived from this soil was dominated by two {gamma}-Proteobacteria phylotypes. A benzene-degrading AQDS-reducing enrichment originated from a sediment sample showed the prevalence of different species from classes {beta}-, {delta}- and {gamma}-Proteobacteria. The present study provides clear quantitative demonstration of anaerobic degradation of benzene coupled to the reduction of HA.

  2. Anaerobic degradation of benzene by enriched consortia with humic acids as terminal electron acceptors

    International Nuclear Information System (INIS)

    Cervantes, Francisco J.; Mancilla, Ana Rosa; Toro, E. Emilia Rios-del; Alpuche-Solis, Angel G.; Montoya-Lorenzana, Lilia

    2011-01-01

    Highlights: → Enriched consortia were able to couple the anaerobic degradation of benzene to the reduction of humic acids. → Electron-equivalents derived from anaerobic benzene oxidation were highly recovered as reduced humic acids. → Several species from classes β-, δ- and γ-Proteobacteria were enriched during the anaerobic degradation of benzene. - Abstract: The anaerobic degradation of benzene coupled to the reduction of humic acids (HA) was demonstrated in two enriched consortia. Both inocula were able to oxidize benzene under strict anaerobic conditions when the humic model compound, anthraquinone-2,6-disulfonate (AQDS), was supplied as terminal electron acceptor. An enrichment culture originated from a contaminated soil was also able to oxidize benzene linked to the reduction of highly purified soil humic acids (HPSHA). In HPSHA-amended cultures, 9.3 μM of benzene were degraded, which corresponds to 279 ± 27 micro-electron equivalents (μEq) L -1 , linked to the reduction of 619 ± 81 μEq L -1 of HPSHA. Neither anaerobic benzene oxidation nor reduction of HPSHA occurred in sterilized controls. Anaerobic benzene oxidation did not occur in soil incubations lacking HPSHA. Furthermore, negligible reduction of HPSHA occurred in the absence of benzene. The enrichment culture derived from this soil was dominated by two γ-Proteobacteria phylotypes. A benzene-degrading AQDS-reducing enrichment originated from a sediment sample showed the prevalence of different species from classes β-, δ- and γ-Proteobacteria. The present study provides clear quantitative demonstration of anaerobic degradation of benzene coupled to the reduction of HA.

  3. Impact of natural organic matter coatings on the microbial reduction of iron oxides

    Science.gov (United States)

    Poggenburg, Christine; Mikutta, Robert; Schippers, Axel; Dohrmann, Reiner; Guggenberger, Georg

    2018-03-01

    Iron (Fe) oxyhydroxides are important constituents of the soil mineral phase known to stabilize organic matter (OM) under oxic conditions. In an anoxic milieu, however, these Fe-organic associations are exposed to microbial reduction, releasing OM into soil solution. At present, only few studies have addressed the influence of adsorbed natural OM (NOM) on the reductive dissolution of Fe oxyhydroxides. This study therefore examined the impact of both the composition and concentration of adsorbed NOM on microbial Fe reduction with regard to (i) electron shuttling, (ii) complexation of Fe(II,III), (iii) surface site coverage and/or pore blockage, and (iv) aggregation. Adsorption complexes with varying carbon loadings were synthesized using different Fe oxyhydroxides (ferrihydrite, lepidocrocite, goethite, hematite, magnetite) and NOM of different origin (extracellular polymeric substances from Bacillus subtilis, OM extracted from soil Oi and Oa horizons). The adsorption complexes were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), N2 gas adsorption, electrophoretic mobility and particle size measurements, and OM desorption. Incubation experiments under anaerobic conditions were conducted for 16 days comparing two different strains of dissimilatory Fe(III)-reducing bacteria (Shewanella putrefaciens, Geobacter metallireducens). Mineral transformation during reduction was assessed via XRD and FTIR. Microbial reduction of the pure Fe oxyhydroxides was controlled by the specific surface area (SSA) and solubility of the minerals. For Shewanella putrefaciens, the Fe reduction of adsorption complexes strongly correlated with the concentration of potentially usable electron-shuttling molecules for NOM concentrations <2 mg C L-1, whereas for Geobacter metallireducens, Fe reduction depended on the particle size and thus aggregation of the adsorption complexes. These diverging results suggest that

  4. Effect of Smoking Abstinence and Reduction in Asthmatic Smokers Switching to Electronic Cigarettes: Evidence for Harm Reversal

    Directory of Open Access Journals (Sweden)

    Riccardo Polosa

    2014-05-01

    Full Text Available Electronic cigarettes (e-cigs are marketed as safer alternatives to tobacco cigarettes and have shown to reduce their consumption. Here we report for the first time the effects of e-cigs on subjective and objective asthma parameters as well as tolerability in asthmatic smokers who quit or reduced their tobacco consumption by switching to these products. We retrospectively reviewed changes in spirometry data, airway hyper-responsiveness (AHR, asthma exacerbations and subjective asthma control in smoking asthmatics who switched to regular e-cig use. Measurements were taken prior to switching (baseline and at two consecutive visits (Follow-up/1 at 6 (±1 and Follow-up/2 at 12 (±2 months. Eighteen smoking asthmatics (10 single users, eight dual users were identified. Overall there were significant improvements in spirometry data, asthma control and AHR. These positive outcomes were noted in single and dual users. Reduction in exacerbation rates was reported, but was not significant. No severe adverse events were noted. This small retrospective study indicates that regular use of e-cigs to substitute smoking is associated with objective and subjective improvements in asthma outcomes. Considering that e-cig use is reportedly less harmful than conventional smoking and can lead to reduced cigarette consumption with subsequent improvements in asthma outcomes, this study shows that e-cigs can be a valid option for asthmatic patients who cannot quit smoking by other methods.

  5. Artificial electron acceptors decouple archaeal methane oxidation from sulfate reduction.

    Science.gov (United States)

    Scheller, Silvan; Yu, Hang; Chadwick, Grayson L; McGlynn, Shawn E; Orphan, Victoria J

    2016-02-12

    The oxidation of methane with sulfate is an important microbial metabolism in the global carbon cycle. In marine methane seeps, this process is mediated by consortia of anaerobic methanotrophic archaea (ANME) that live in syntrophy with sulfate-reducing bacteria (SRB). The underlying interdependencies within this uncultured symbiotic partnership are poorly understood. We used a combination of rate measurements and single-cell stable isotope probing to demonstrate that ANME in deep-sea sediments can be catabolically and anabolically decoupled from their syntrophic SRB partners using soluble artificial oxidants. The ANME still sustain high rates of methane oxidation in the absence of sulfate as the terminal oxidant, lending support to the hypothesis that interspecies extracellular electron transfer is the syntrophic mechanism for the anaerobic oxidation of methane. Copyright © 2016, American Association for the Advancement of Science.

  6. Elastic scattering by hot electrons and apparent lifetime of longitudinal optical phonons in gallium nitride

    Energy Technology Data Exchange (ETDEWEB)

    Khurgin, Jacob B., E-mail: jakek@jhu.edu [Department of Electrical and Computer Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Bajaj, Sanyam; Rajan, Siddharth [Department of Electrical and Computer Engineering, The Ohio State University, Columbus, Ohio 43210 (United States)

    2015-12-28

    Longitudinal optical (LO) phonons in GaN generated in the channel of high electron mobility transistors (HEMT) are shown to undergo nearly elastic scattering via collisions with hot electrons. The net result of these collisions is the diffusion of LO phonons in the Brillouin zone causing reduction of phonon and electron temperatures. This previously unexplored diffusion mechanism explicates how an increase in electron density causes reduction of the apparent lifetime of LO phonons, obtained from the time resolved Raman studies and microwave noise measurements, while the actual decay rate of the LO phonons remains unaffected by the carrier density. Therefore, the saturation velocity in GaN HEMT steadily declines with increased carrier density, in a qualitative agreement with experimental results.

  7. Catastrophic Failure and Fault-Tolerant Design of IGBT Power Electronic Converters - An Overview

    DEFF Research Database (Denmark)

    Wu, Rui; Blaabjerg, Frede; Wang, Huai

    2013-01-01

    Reliability is one of the key issues for the application of Insulated Gate Bipolar Transistors (IGBTs) in power electronic converters. Many efforts have been devoted to the reduction of IGBT wear out failure induced by accumulated degradation and catastrophic failure triggered by single-event ove......Reliability is one of the key issues for the application of Insulated Gate Bipolar Transistors (IGBTs) in power electronic converters. Many efforts have been devoted to the reduction of IGBT wear out failure induced by accumulated degradation and catastrophic failure triggered by single...

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

    Science.gov (United States)

    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

  9. Intramolecular photoinduced electron-transfer in azobenzene-perylene diimide

    International Nuclear Information System (INIS)

    Feng Wen-Ke; Wang Shu-Feng; Gong Qi-Huang; Feng Yi-Yu; Feng Wei; Yi Wen-Hui

    2010-01-01

    This paper studies the intramolecular photoinduced electron-transfer (PET) of covalent bonded azobenzene-perylene diimide (AZO-PDI) in solvents by using steady-state and time-resolved fluorescence spectroscopy together with ultrafast transient absorption spectroscopic techniques. Fast fluorescence quenching is observed when AZO-PDI is excited at characteristic wavelengths of AZO and perylene moieties. Reductive electron-transfer with transfer rate faster than 10 11 s −1 is found. This PET process is also consolidated by femtosecond transient absorption spectra

  10. Plasma-assisted reduction of silver ions impregnated into a natural zeolite framework

    Science.gov (United States)

    Osonio, Airah P.; Vasquez, Magdaleno R.

    2018-02-01

    A green, dry, and energy-efficient method for the fabrication of silver-zeolite (AgZ) composite via 13.56 MHz radio-frequency plasma reduction is demonstrated. Impregnation by soaking and ion-exchange deposition were performed to load the silver ions (Ag+) into the sodium-zeolite samples. Characterization was performed by optical emission spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and Brunauer-Emmett-Teller analyses. Results indicate the successful reduction of Ag+ to its metallic state on the surface of the zeolite with a mean diameter of 165 nm. This plasma-induced reduction technique opens possibilities in several areas including catalysis, adsorption, water treatment, and medicine.

  11. New shower maximum trigger for electrons and photons at CDF

    International Nuclear Information System (INIS)

    Amidei, D.; Burkett, K.; Gerdes, D.; Miao, C.; Wolinski, D.

    1994-01-01

    For the 1994 Tevatron collider run, CDF has upgraded the electron and photo trigger hardware to make use of shower position and size information from the central shower maximum detector. For electrons, the upgrade has resulted in a 50% reduction in backgrounds while retaining approximately 90% of the signal. The new trigger also eliminates the background to photon triggers from single-phototube spikes

  12. New shower maximum trigger for electrons and photons at CDF

    International Nuclear Information System (INIS)

    Gerdes, D.

    1994-08-01

    For the 1994 Tevatron collider run, CDF has upgraded the electron and photon trigger hardware to make use of shower position and size information from the central shower maximum detector. For electrons, the upgrade has resulted in a 50% reduction in backgrounds while retaining approximately 90% of the signal. The new trigger also eliminates the background to photon triggers from single-phototube discharge

  13. Decomposition and reduction of AUC in hydrogen

    International Nuclear Information System (INIS)

    Ge Qingren; Kang Shifang; Zhou Meng

    1987-01-01

    AUC (Ammonium Uranyl Carbonate) conversion processes have been adopted extensively in nuclear fuel cycle. The kinetics investigation of these processes, however, has not yet been reported in detail at the published literatures. In the present work, the decomposition kinetics of AUC in hydrogen has been determined by non-isothermal method. DSC curves are solved with computer by Ge Qingren method. The results show that the kinetics obeys Avrami-Erofeev equation within 90% conversion. The apparent activation energy and preexponent are found to be 113.0 kJ/mol and 7.11 x 10 11 s -1 respectively. The reduction kinetics of AUC decomposition product in hydrogen at the range of 450 - 600 deg C has been determined by isothermal thermogravimetric method. The results show that good linear relationship can be obtained from the plot of conversion vs time, and that the apparent activation energy is found to be 113.9 kJ/mol. The effects of particle size and partial pressure of hydrogen are examined in reduction of AUC decomposition product. The reduction mechanism and the structure of particle are discussed according to the kinetics behaviour and SEM (scanning electron microscope) photograph

  14. pH control for enhanced reductive bioremediation of chlorinated solvent source zones

    International Nuclear Information System (INIS)

    Robinson, Clare; Barry, D.A.; McCarty, Perry L.; Gerhard, Jason I.; Kouznetsova, Irina

    2009-01-01

    Enhanced reductive dehalogenation is an attractive treatment technology for in situ remediation of chlorinated solvent DNAPL source areas. Reductive dehalogenation is an acid-forming process with hydrochloric acid and also organic acids from fermentation of the electron donors typically building up in the source zone during remediation. This can lead to groundwater acidification thereby inhibiting the activity of dehalogenating microorganisms. Where the soils' natural buffering capacity is likely to be exceeded, the addition of an external source of alkalinity is needed to ensure sustained dehalogenation. To assist in the design of bioremediation systems, an abiotic geochemical model was developed to provide insight into the processes influencing the groundwater acidity as dehalogenation proceeds, and to predict the amount of bicarbonate required to maintain the pH at a suitable level for dehalogenating bacteria (i.e., > 6.5). The model accounts for the amount of chlorinated solvent degraded, site water chemistry, electron donor, alternative terminal electron-accepting processes, gas release and soil mineralogy. While calcite and iron oxides were shown to be the key minerals influencing the soil's buffering capacity, for the extensive dehalogenation likely to occur in a DNAPL source zone, significant bicarbonate addition may be necessary even in soils that are naturally well buffered. Results indicated that the bicarbonate requirement strongly depends on the electron donor used and availability of competing electron acceptors (e.g., sulfate, iron (III)). Based on understanding gained from this model, a simplified model was developed for calculating a preliminary design estimate of the bicarbonate addition required to control the pH for user-specified operating conditions.

  15. Primary oxidation and reduction products in x-irradiated aspartic acid

    International Nuclear Information System (INIS)

    Adams, S.M.; Budzinski, E.E.; Box, H.C.

    1976-01-01

    The primary reduction products identified by ESR--ENDOR spectroscopy in single crystals of DL-aspartic acid hydrochloride irradiated at 4.2degreeK are anions formed by addition of an electron to the carbonyl oxygen atoms of the carboxylic acid groups. The main consequence of the oxidation process is to produce a hole centered mainly on atomic chlorine

  16. The mechanism of electron gating in proton pumping cytochrome c oxidase: the effect of pH and temperature on internal electron transfer.

    Science.gov (United States)

    Brzezinski, P; Malmström, B G

    1987-10-29

    Electron-transfer reactions following flash photolysis of the mixed-valence cytochrome oxidase-CO complex have been measured at 445, 598 and 830 nm between pH 5.2 and 9.0 in the temperature range of 0-25 degrees C. There is a rapid electron transfer from the cytochrome a3-CuB pair to CuA (time constant: 14200 s-1), which is followed by a slower electron transfer to cytochrome a. Both the rate and the amplitude of the rapid phase are independent of pH, and the rate in the direction from CuA to cytochrome a3-CuB is practically independent of temperature. The second phase depends strongly on pH due to the titration of an acid-base group with pKa = 7.6. The equilibrium at pH 7.4 corresponds to reduction potentials of 225 and 345 mV for cytochrome a and a3, respectively, from which it is concluded that the enzyme is in a different conformation compared to the fully oxidized form. The results have been used to suggest a series of reaction steps in a cycle of the oxidase as a proton pump. Application of the electron-transfer theory to the temperature-dependence data suggests a mechanism for electron gating in the pump. Reduction of both cytochrome a and CuA leads to a conformational change, which changes the structure of cytochrome a3-CuB in such a way that the reorganizational barrier for electron transfer is removed and the driving force is increased.

  17. Charge transfer induced activity of graphene for oxygen reduction

    International Nuclear Information System (INIS)

    Shen, Anli; Xia, Weijun; Dou, Shuo; Wang, Shuangyin; Zhang, Lipeng; Xia, Zhenhai

    2016-01-01

    Tetracyanoethylene (TCNE), with its strong electron-accepting ability, was used to dope graphene as a metal-free electrocatalyst for the oxygen reduction reaction (ORR). The charge transfer process was observed from graphene to TCNE by x-ray photoelectron spectroscopy and Raman characterizations. Our density functional theory calculations found that the charge transfer behavior led to an enhancement of the electrocatalytic activity for the ORR. (paper)

  18. Radiolytic preparation of thin Au film directly on resin substrate using high-energy electron beam

    Energy Technology Data Exchange (ETDEWEB)

    Ohkubo, Yuji, E-mail: okubo@upst.eng.osaka-u.ac.jp [Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan); Seino, Satoshi; Nakagawa, Takashi; Kugai, Junichiro [Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan); Ueno, Koji [Japan Electron Beam Irradiation Service Ltd., 5-3 Ozushima, Izumiohtsu, Osaka 595-0074 (Japan); Yamamoto, Takao A. [Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan)

    2016-04-01

    A novel method for preparing thin Au films directly on resin substrates using an electron beam was developed. The thin Au films were prepared on a resin substrate by the reduction of Au ions in an aqueous solution via irradiation with a high-energy electron beam (4.8 MeV). This reduction method required 7 s of the irradiation time of the electron beam. Furthermore, no reductant or catalyst was needed. As the concentration of Au ions in the precursor solution was increased, the amount of Au deposited on the resin substrate increased, too, and the structure of the prepared Au film changed. As a result, the film color changed as well. Cross-sectional scanning electron microscope images of the thus-prepared Au film indicated that the Au films were consisted of two layers: a particle layer and a bottom bulk layer. There was strong adhesion between the Au films and the underlying resin substrates. This was confirmed by the tape-peeling test and through ultrasonic cleaning. After both processes, Au remained on the resin substrates, while most of the particle-like moieties were removed. This indicated that the thin Au films prepared via irradiation with a high-energy electron beam adhered strongly to the resin substrates. - Highlights: • A thin gold (Au) film was formed by EBIRM for the first time. • The irradiation time of the electron beam was less than 10 s. • Thin Au films were obtained without reductant or catalyst. • Au films were consisted of two layers: a particle layer and a bottom bulk layer. • There was strong adhesion between the bottom bulk layer and the underlying resin substrates.

  19. Laser-Induced Reductive Sintering of Nickel Oxide Nanoparticles under Ambient Conditions

    KAUST Repository

    Paeng, Dongwoo; Lee, Daeho; Yeo, Junyeob; Yoo, Jae-Hyuck; Allen, Frances I.; Kim, Eunpa; So, Hongyun; Park, Hee K.; Minor, Andrew M.; Grigoropoulos, Costas P.

    2015-01-01

    © 2015 American Chemical Society. This work is concerned with the kinetics of laser-induced reductive sintering of nonstoichiometric crystalline nickel oxide (NiO) nanoparticles (NPs) under ambient conditions. The mechanism of photophysical reductive sintering upon irradiation using a 514.5 nm continuous-wave (CW) laser on NiO NP thin films has been studied through modulating the laser power density and illumination time. Protons produced due to high-temperature decomposition of the solvent present in the NiO NP ink, oxygen vacancies in the NiO NPs, and electronic excitation in the NiO NPs by laser irradiation all affect the early stage of the reductive sintering process. Once NiO NPs are reduced by laser irradiation to Ni, they begin to coalesce, forming a conducting material. In situ optical and electrical measurements during the reductive sintering process take advantage of the distinct differences between the oxide and the metallic phases to monitor the transient evolution of the process. We observe four regimes: oxidation, reduction, sintering, and reoxidation. A characteristic time scale is assigned to each regime.

  20. Reductive dehalogenase structure suggests a mechanism for B12-dependent dehalogenation.

    Science.gov (United States)

    Payne, Karl Ap; Quezada, Carolina P; Fisher, Karl; Dunstan, Mark S; Collins, Fraser A; Sjuts, Hanno; Levy, Colin; Hay, Sam; Rigby, Stephen Ej; Leys, David

    2015-01-22

    Organohalide chemistry underpins many industrial and agricultural processes, and a large proportion of environmental pollutants are organohalides. Nevertheless, organohalide chemistry is not exclusively of anthropogenic origin, with natural abiotic and biological processes contributing to the global halide cycle. Reductive dehalogenases are responsible for biological dehalogenation in organohalide respiring bacteria, with substrates including polychlorinated biphenyls or dioxins. Reductive dehalogenases form a distinct subfamily of cobalamin (B12)-dependent enzymes that are usually membrane associated and oxygen sensitive, hindering detailed studies. Here we report the characterization of a soluble, oxygen-tolerant reductive dehalogenase and, by combining structure determination with EPR (electron paramagnetic resonance) spectroscopy and simulation, show that a direct interaction between the cobalamin cobalt and the substrate halogen underpins catalysis. In contrast to the carbon-cobalt bond chemistry catalysed by the other cobalamin-dependent subfamilies, we propose that reductive dehalogenases achieve reduction of the organohalide substrate via halogen-cobalt bond formation. This presents a new model in both organohalide and cobalamin (bio)chemistry that will guide future exploitation of these enzymes in bioremediation or biocatalysis.

  1. Laser-Induced Reductive Sintering of Nickel Oxide Nanoparticles under Ambient Conditions

    KAUST Repository

    Paeng, Dongwoo

    2015-03-19

    © 2015 American Chemical Society. This work is concerned with the kinetics of laser-induced reductive sintering of nonstoichiometric crystalline nickel oxide (NiO) nanoparticles (NPs) under ambient conditions. The mechanism of photophysical reductive sintering upon irradiation using a 514.5 nm continuous-wave (CW) laser on NiO NP thin films has been studied through modulating the laser power density and illumination time. Protons produced due to high-temperature decomposition of the solvent present in the NiO NP ink, oxygen vacancies in the NiO NPs, and electronic excitation in the NiO NPs by laser irradiation all affect the early stage of the reductive sintering process. Once NiO NPs are reduced by laser irradiation to Ni, they begin to coalesce, forming a conducting material. In situ optical and electrical measurements during the reductive sintering process take advantage of the distinct differences between the oxide and the metallic phases to monitor the transient evolution of the process. We observe four regimes: oxidation, reduction, sintering, and reoxidation. A characteristic time scale is assigned to each regime.

  2. Nonplanar ion acoustic waves with kappa-distributed electrons

    International Nuclear Information System (INIS)

    Sahu, Biswajit

    2011-01-01

    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 κ) 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. The present investigation may have relevance in the study of propagation of IAWs in space and laboratory plasmas.

  3. On the nature of organic and inorganic centers that bifurcate electrons, coupling exergonic and endergonic oxidation-reduction reactions.

    Science.gov (United States)

    Peters, John W; Beratan, David N; Schut, Gerrit J; Adams, Michael W W

    2018-04-19

    Bifurcating electrons to couple endergonic and exergonic electron-transfer reactions has been shown to have a key role in energy conserving redox enzymes. Bifurcating enzymes require a redox center that is capable of directing electron transport along two spatially separate pathways. Research into the nature of electron bifurcating sites indicates that one of the keys is the formation of a low potential oxidation state to satisfy the energetics required of the endergonic half reaction, indicating that any redox center (organic or inorganic) that can exist in multiple oxidation states with sufficiently separated redox potentials should be capable of electron bifurcation. In this Feature Article, we explore a paradigm for bifurcating electrons down independent high and low potential pathways, and describe redox cofactors that have been demonstrated or implicated in driving this unique biochemistry.

  4. Reduction of graphene oxide and its effect on square resistance of reduced graphene oxide films

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Zhaoxia; Zhou, Yin; Li, Guang Bin; Wang, Shaohong; Wang, Mei Han; Hu, Xiaodan; Li, Siming [Liaoning Province Key Laboratory of New Functional Materials and Chemical Technology, School ofMechanical Engineering, Shenyang University, Shenyang (China)

    2015-06-15

    Graphite oxide was prepared via the modified Hummers’ method and graphene via chemical reduction. Deoxygenation efficiency of graphene oxide was compared among single reductants including sodium borohydride, hydrohalic acids, hydrazine hydrate, and vitamin C. Two-step reduction of graphene oxide was primarily studied. The reduced graphene oxide was characterized by XRD, TG, SEM, XPS, and Raman spectroscopy. Square resistance was measured as well. Results showed that films with single-step N2H4 reduction have the best transmittance and electrical conductivity with square resistance of ~5746 Ω/sq at 70% transmittance. This provided an experimental basis of using graphene for electronic device applications.

  5. Reduction reactions applied for synthesizing different nano-structured materials

    Energy Technology Data Exchange (ETDEWEB)

    Albuquerque Brocchi, Eduardo de; Correia de Siqueira, Rogério Navarro [Department of Materials Engineering, PUC-Rio, Rua Marquês de São Vicente, 225, Gávea, 22453-900 Rio de Janeiro, RJ (Brazil); Motta, Marcelo Senna [Basck Ltd. (United Kingdom); Moura, Francisco José, E-mail: moura@puc-rio.br [Department of Materials Engineering, PUC-Rio, Rua Marquês de São Vicente, 225, Gávea, 22453-900 Rio de Janeiro, RJ (Brazil); Solórzano-Naranjo, Ivan Guillermo [Department of Materials Engineering, PUC-Rio, Rua Marquês de São Vicente, 225, Gávea, 22453-900 Rio de Janeiro, RJ (Brazil)

    2013-06-15

    Different materials have been synthesized by alternative routes: nitrates thermal decomposition to prepare oxide or co-formed oxides and reduction by hydrogen or graphite to obtain mixed oxides, composites or alloys. These chemical-based synthesis routes are described and thermodynamics studies and kinetics data are presented to support its feasibility. In addition, selective reduction reactions have been applied to successfully produce metal/ceramic composites, and alloys. Structural characterization has been carried out by X-ray Diffraction and, more extensively, Transmission Electron Microscopy operating in conventional diffraction contrast (CTEM) and high-resolution mode (HRTEM), indicated the possibility of obtaining oxide and alloy crystals of sizes ranging between 20 and 40 nm. - Highlights: • The viability in obtaining Ni–Co, Cu–Al, Mn–Al co-formed nano oxides was evaluated. • Partial and complete H{sub 2} reduction were used to produce alloy, composite and Spinel. • XRD, TEM and HREM techniques were used to characterize the obtained nanostructures.

  6. Improved core electron confinement on JET

    International Nuclear Information System (INIS)

    Litaudon, X.; Baranov, Y.; Voitsekhovitch, I.

    1999-01-01

    Formation of core regions with reduced electron transport is reported in regimes with current profile shaping at JET. The electron heat diffusivity (Χ c ) is reduced down to 0.5 m 2 /s in the region of low magnetic shear with an ICRH power of 1 MW with no indication of a threshold. In the high performance optimised shear regime, obtained in scenarios dominated by ion heating, internal transport barriers on the ion temperature profiles are simultaneously accompanied by a significant reduction of the electron heat diffusivity at two-third of the plasma radius. In this regime, recent results and measurements obtained with the new gas-box divertor configuration are reported together with their transport analyses. The results indicate that Χ c is reduced by one order of magnitude in a spatially localised region. (authors)

  7. Electron-beam flue-gas treatment system

    International Nuclear Information System (INIS)

    Aoki, Sinji; Suzuki, Ryoji

    1994-01-01

    The damage of forests in the world due to acid rain has become serious problems, and the development of high efficiency and economical desulfurization and denitration technologies for combustion exhaust gas has been desired. Japan leads the world in exhaust gas treatment technology. The conventional technologies have been the desulfurization by lime gypsum process and the denitration by ammonia catalytic reduction process. The solution by entirely new concept is the electron beam treatment technology for exhaust gas. This technology is a dry process without drain, and does not require catalyst. The byproduct from this technology was approved as a fertilizer. The electron beam treatment technology is called EBA (electron beam with ammonia). The exhaust gas treatment technology by electron beam process is constituted by the cooling of exhaust gas, ammonia addition, electron beam irradiation and the separation of byproduct. The features of the technology are the simultaneous removal of sulfur and nitrogen oxides, dry process, the facilities are simple and the operation is easy, easy following to load variation and the utilization of byproduct. The reaction mechanism of desulfurization and denitration, the course of development, the electron beam generator, and the verifying test are reported. (K.I.)

  8. X-ray absorption spectroscopy study on the thermal and hydrazine reduction of graphene oxide

    International Nuclear Information System (INIS)

    Liang, Xianqing; Wang, Yu; Zheng, Huiyuan; Wu, Ziyu

    2014-01-01

    Highlights: • XAS study of GO and reduced GO was performed. • Detailed evolution of the electronic structures and chemical bonding of GO was revealed. • A new efficient route for the reduction of GO is proposed. - Abstract: X-ray absorption spectroscopy (XAS) was applied to systemically investigate the deoxygenation of graphene oxide (GO) via annealing and hydrazine treatment. Detailed evolution of the electronic structures and chemical bonding of GO was presented. The enhanced intensity of π * resonance and the appearance of splitting σ * resonance in C K-edge XAS spectra suggest high extents of recoveries of π-conjugation upon reduction using thermal annealing or hydrazine. Experimental results revealed that the carboxyl as well as epoxide and hydroxyl groups on the surface of GO were thermally reduced first, followed by the more difficult removal of carbonyl and cyclic ether groups at higher temperatures. The hydrazine reduction could remove epoxide, hydroxyl and carboxyl groups effectively, whereas the carbonyl groups were partially reduced with the incorporation of nitrogen species simultaneously. The residual oxygen functional groups on hydrazine-reduced GO could be further removed after modest thermal annealing. It was proposed that a combination of both types of reductions would give the best deoxygenation efficiency for the production of graphene

  9. Theoretical study of the electron paramagnetic resonance ...

    Indian Academy of Sciences (India)

    conveniently investigated by means of electron paramagnetic resonance (EPR). In ... ion Ir2+ can experience the Jahn–Teller effect by means of vibration interaction, ... Similarly, k. (and k ) are the orbital reduction factors arising from the anisotropic interactions of the orbital angular momentum operator. From the cluster ...

  10. Electron transfer reactions involving porphyrins and chlorophyll a

    International Nuclear Information System (INIS)

    Neta, P.; Scherz, A.; Levanon, H.

    1979-01-01

    Electron transfer reactions involving porphyrins (P) and quinones (Q) have been studied by pulse radiolysis. The porphyrins used were tetraphenylporphyrin (H 2 TPP), its tetracarboxy derivative (H 2 TCPP), the sodium and zinc compounds (Na 2 TPP and ZnTPP), and chlorophyll a (Chl a). These compounds were found to be rapidly reduced by electron transfer from (CH 3 ) 2 CO - . Reduction by (CH 3 ) 2 COH was rapid in aqueous solutions but relatively slow in i-PrOH solutions. Transient spectra of the anion radicals were determined and, in the case of H 2 TCPP - ., a pK = 9.7 was derived for its protonation. Electron-transfer reactions from the anion radical of H 2 TCPP to benzoquinone, duroquinone, 9,10-anthraquinone 2-sulfonate, and methylviologen occur in aqueous solutions with rate constants approx. 10 7 -10 9 M -1 s -1 which depend on the pH and the quinone reduction potential. Reactions of Na 2 TPP - ., ZnTPP - ., and Chl a - . with anthraquinone in basic i-PrOH solutions occur with rate constants approx. 10 9 M -1 s -1 . The spectral changes associated with these electron-transfer reactions as observed over a period of approx. 1 ms indicated, in some cases, the formation of an intermediate complex [P...Q - .]. 8 figures, 2 tables

  11. Carbon-supported cubic CoSe2 catalysts for oxygen reduction reaction in alkaline medium

    International Nuclear Information System (INIS)

    Feng Yongjun; Alonso-Vante, Nicolas

    2012-01-01

    Highlights: ► Cubic CoSe 2 a non-precious metal electrocatalyst for oxygen reduction in KOH. ► The catalyst shows four-electron transfer pathway in overall reaction. ► Catalyst has higher methanol tolerance than commercial Pt/C catalyst. - Abstract: A Carbon-supported CoSe 2 nanocatalyst has been developed as an alternative non-precious metal electrocatalyst for oxygen reduction reaction (ORR) in alkaline medium. The catalyst was prepared via a surfactant-free route and its electrocatalytic activity for the ORR has been investigated in detail in 0.1 M KOH electrolyte at 25 °C using rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) techniques. The prepared catalyst showed promising catalytic activity towards ORR in a four-electron transfer pathway and higher tolerance to methanol compared to commercial Pt/C catalyst in 0.1 M KOH. To some extent, the increase of CoSe 2 loading on the electrode favors a faster reduction of H 2 O 2 intermediate to H 2 O.

  12. Flow-through Column Experiments and Modeling of Microbially Mediated Cr(VI) Reduction at Hanford 100H

    Science.gov (United States)

    Yang, L.; Molins, S.; Beller, H. R.; Brodie, E. L.; Steefel, C.; Nico, P. S.; Han, R.

    2010-12-01

    Microbially mediated Cr(VI) reduction at the Hanford 100H area was investigated by flow-through column experiments. Three separate experiments were conducted to promote microbial activities associated with denitrification, iron and sulfate reduction, respectively. Replicate columns packed with natural sediments from the site under anaerobic environment were injected with 5mM Lactate as the electron donor and 5 μM Cr(VI) in all experiments. Sulfate and nitrate solutions were added to act as the main electron acceptors in the respective experiments, while iron columns relied on the indigenous sediment iron (and manganese) oxides as electron acceptors. Column effluent solutions were analyzed by IC and ICP-MS to monitor the microbial consumption/conversion of lactate and the associated Cr(VI) reduction. Biogeochemical reactive transport modeling was performed to gain further insights into the reaction mechanisms and Cr(VI) bioreduction rates. All experimental columns showed a reduction of the injected Cr(VI). Columns under denitrifying conditions showed the least Cr(VI) reduction at early stages (simulations indicated that biomass growth completely depleted influent ammonium, and called for an additional source of N to account for the measured reduction rates. Iron columns were the least active with undetectable consumption of the injected lactate, slowest cell growth, and the smallest change in Cr(VI) concentrations during the course of the experiment. In contrast, columns under sulfate-reducing/fermentative conditions exhibited the greatest Cr(VI) reduction capacity. Two sulfate columns evolved to complete lactate fermentation with acetate and propionate produced in the column effluent after 40 days of experiments. These fermenting columns showed a complete removal of injected Cr(VI), visible precipitation of sulfide minerals, and a significant increase in effluent Fe and Mn concentrations. Reactive transport simulations suggested that direct reduction of Cr(VI) by

  13. Dissimilatory Fe(III) and Mn(IV) reduction.

    Science.gov (United States)

    Lovley, D R

    1991-06-01

    The oxidation of organic matter coupled to the reduction of Fe(III) or Mn(IV) is one of the most important biogeochemical reactions in aquatic sediments, soils, and groundwater. This process, which may have been the first globally significant mechanism for the oxidation of organic matter to carbon dioxide, plays an important role in the oxidation of natural and contaminant organic compounds in a variety of environments and contributes to other phenomena of widespread significance such as the release of metals and nutrients into water supplies, the magnetization of sediments, and the corrosion of metal. Until recently, much of the Fe(III) and Mn(IV) reduction in sedimentary environments was considered to be the result of nonenzymatic processes. However, microorganisms which can effectively couple the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV) have recently been discovered. With Fe(III) or Mn(IV) as the sole electron acceptor, these organisms can completely oxidize fatty acids, hydrogen, or a variety of monoaromatic compounds. This metabolism provides energy to support growth. Sugars and amino acids can be completely oxidized by the cooperative activity of fermentative microorganisms and hydrogen- and fatty-acid-oxidizing Fe(III) and Mn(IV) reducers. This provides a microbial mechanism for the oxidation of the complex assemblage of sedimentary organic matter in Fe(III)- or Mn(IV)-reducing environments. The available evidence indicates that this enzymatic reduction of Fe(III) or Mn(IV) accounts for most of the oxidation of organic matter coupled to reduction of Fe(III) and Mn(IV) in sedimentary environments. Little is known about the diversity and ecology of the microorganisms responsible for Fe(III) and Mn(IV) reduction, and only preliminary studies have been conducted on the physiology and biochemistry of this process.

  14. Kinetic Alfven waves and electron physics. II. Oblique slow shocks

    International Nuclear Information System (INIS)

    Yin, L.; Winske, D.; Daughton, W.

    2007-01-01

    One-dimensional (1D) particle-in-cell (PIC; kinetic ions and electrons) and hybrid (kinetic ions; adiabatic and massless fluid electrons) simulations of highly oblique slow shocks (θ Bn =84 deg. and β=0.1) [Yin et al., J. Geophys. Res., 110, A09217 (2005)] have shown that the dissipation from the ions is too weak to form a shock and that kinetic electron physics is required. The PIC simulations also showed that the downstream electron temperature becomes anisotropic (T e parallel )>T e perpendicular ), as observed in slow shocks in space. The electron anisotropy results, in part, from the electron acceleration/heating by parallel electric fields of obliquely propagating kinetic Alfven waves (KAWs) excited by ion-ion streaming, which cannot be modeled accurately in hybrid simulations. In the shock ramp, spiky structures occur in density and electron parallel temperature, where the ion parallel temperature decreases due to the reduction of the ion backstreaming speed. In this paper, KAW and electron physics in oblique slow shocks are further examined under lower electron beta conditions. It is found that as the electron beta is reduced, the resonant interaction between electrons and the wave parallel electric fields shifts to the tail of the electron velocity distribution, providing more efficient parallel heating. As a consequence, for β e =0.02, the electron physics is shown to influence the formation of a θ Bn =75 deg. shock. Electron effects are further enhanced at a more oblique shock angle (θ Bn =84 deg.) when both the growth rate and the range of unstable modes on the KAW branch increase. Small-scale electron and ion phase-space vortices in the shock ramp formed by electron-KAW interactions and the reduction of the ion backstreaming speed, respectively, are observed in the simulations and confirmed in homogeneous geometries in one and two spatial dimensions in the accompanying paper [Yin et al., Phys. Plasmas 14, 062104 (2007)]. Results from this study

  15. Synthesis and photocatalytic CO2 reduction performance of Cu2O/Coal-based carbon nanoparticle composites

    Science.gov (United States)

    Dedong, Zhang; Maimaiti, Halidan; Awati, Abuduheiremu; Yisilamu, Gunisakezi; Fengchang, Sun; Ming, Wei

    2018-05-01

    The photocatalytic reduction of CO2 into hydrocarbons provides a promising approach to overcome the challenges of environmental crisis and energy shortage. Here we fabricated a cuprous oxide (Cu2O) based composite photocatalyst consisting of Cu2O/carbon nanoparticles (CNPs). To prepare the CNPs, coal samples from Wucaiwan, Xinjiang, China, were first treated with HNO3, followed by hydrogen peroxide (H2O2) oxidation to strip nanocrystalline carbon from coal. After linking with oxygen-containing group such as hydroxyl, coal-based CNPs with sp2 carbon structure and multilayer graphene lattice structure were synthesized. Subsequently, the CNPs were loaded onto the surface of Cu2O nanoparticles prepared by in-situ reduction of copper chloride (CuCl2·2H2O). The physical properties and chemical structure of the Cu2O/CNPs as well as photocatalytic activity of CO2/H2O reduction into CH3OH were measured. The results demonstrate that the Cu2O/CNPs are composed of spherical particles with diameter of 50 nm and mesoporous structure, which are suitable for CO2 adsorption. Under illumination of visible light, electron-hole pairs are generated in Cu2O. Thanks to the CNPs, the fast recombination of electron-hole pairs is suppressed. The energy gradient formed on the surface of Cu2O/CNPs facilitates the efficient separation of electron-hole pairs for CO2 reduction and H2O oxidation, leading to enhanced photocatalytic activity.

  16. Electrocatalytic reduction of nitrite on tetraruthenated metalloporphyrins/Nafion glassy carbon modified electrode

    Energy Technology Data Exchange (ETDEWEB)

    Calfuman, Karla [Facultad de Ciencias, Departamento de Quimica, Universidad de Chile, Las Palmeras 3425, Casilla 653, Nunoa, Santiago (Chile); Aguirre, Maria Jesus [Facultad de Quimica y Biologia, Departamento de Quimica de los Materiales, Universidad de Santiago de Chile, Santiago (Chile); Canete-Rosales, Paulina; Bollo, Soledad [Facultad de Ciencias Quimicas y Farmaceuticas, Departamento de Quimica Farmacologica y Toxicologica, Universidad de Chile, Santiago (Chile); Llusar, Rosa [Departamento de Quimica Fisica y Analitica, Universidad de Jaume I, Castellon (Spain); Isaacs, Mauricio, E-mail: misaacs@uchile.cl [Facultad de Ciencias, Departamento de Quimica, Universidad de Chile, Las Palmeras 3425, Casilla 653, Nunoa, Santiago (Chile)

    2011-10-01

    Highlights: > Preparation and characterization of modified electrodes with M(II) Tetraruthenated porphyrins onto a Nafion film. > The electrodes were characterized by SEM, TEM, AFM and SECM techniques. > The modified electrodes are active in the electrochemical reduction of nitrite at -660 mV vs Ag/AgCl. > GC/Nf/CoTRP modified electrode is more electrochemically active than their Ni and Zn analogues. - Abstract: This paper describes the electrochemical reduction of nitrite ion in neutral aqueous solution mediated by tetraruthenated metalloporphyrins (Co(II), Ni(II) and Zn(II)) electrostatically assembled onto a Nafion film previously adsorbed on glassy carbon or ITO electrodes. Scanning electron microscope (SEM-EDX) and transmission electron microscopy (TEM) results have shown that on ITO electrodes the macrocycles forms multiple layers with a disordered stacking orientation over the Nafion film occupying hydrophobic and hydrophilic sites in the polyelectrolyte. Atomic force microscopy (AFM) results demonstrated that the Nafion film is 35 nm thick and tetraruthenated metalloporphyrins layers 190 nm thick presenting a thin but compacted morphology. Scanning electrochemical microscopy (SECM) images shows that the Co(II) tetraruthenated porphyrins/Nf/GC modified electrode is more electrochemically active than their Ni and Zn analogues. These modified electrodes are able to reduce nitrite at -660 mV showing enhanced reduction current and a decrease in the required overpotential compared to bare glassy carbon electrode. Controlled potential electrolysis experiments verify the production of ammonia, hydrazine and hydroxylamine at potentials where reduction of solvent is plausible demonstrating some selectivity toward the nitrite ion. Rotating disc electrode voltammetry shows that the factor that governs the kinetics of nitrite reduction is the charge propagation in the film.

  17. Oxygen control of nif gene expression in Klebsiella pneumoniae depends on NifL reduction at the cytoplasmic membrane by electrons derived from the reduced quinone pool.

    Science.gov (United States)

    Grabbe, Roman; Schmitz, Ruth A

    2003-04-01

    In Klebsiella pneumoniae, the flavoprotein, NifL regulates NifA mediated transcriptional activation of the N2-fixation (nif) genes in response to molecular O2 and ammonium. We investigated the influence of membrane-bound oxidoreductases on nif-regulation by biochemical analysis of purified NifL and by monitoring NifA-mediated expression of nifH'-'lacZ reporter fusions in different mutant backgrounds. NifL-bound FAD-cofactor was reduced by NADH only in the presence of a redox-mediator or inside-out vesicles derived from anaerobically grown K. pneumoniae cells, indicating that in vivo NifL is reduced by electrons derived from membrane-bound oxidoreductases of the anaerobic respiratory chain. This mechanism is further supported by three lines of evidence: First, K. pneumoniae strains carrying null mutations of fdnG or nuoCD showed significantly reduced nif-induction under derepressing conditions, indicating that NifL inhibition of NifA was not relieved in the absence of formate dehydrogenase-N or NADH:ubiquinone oxidoreductase. The same effect was observed in a heterologous Escherichia coli system carrying a ndh null allele (coding for NADH dehydrogenaseII). Second, studying nif-induction in K. pneumoniae revealed that during anaerobic growth in glycerol, under nitrogen-limitation, the presence of the terminal electron acceptor nitrate resulted in a significant decrease of nif-induction. The final line of evidence is that reduced quinone derivatives, dimethylnaphthoquinol and menadiol, are able to transfer electrons to the FAD-moiety of purified NifL. On the basis of these data, we postulate that under anaerobic and nitrogen-limited conditions, NifL inhibition of NifA activity is relieved by reduction of the FAD-cofactor by electrons derived from the reduced quinone pool, generated by anaerobic respiration, that favours membrane association of NifL. We further hypothesize that the quinol/quinone ratio is important for providing the signal to NifL.

  18. Electrochemical Reduction of Oxygen on Anthraquinone/Carbon Nanotubes Nanohybrid Modified Glassy Carbon Electrode in Neutral Medium

    Directory of Open Access Journals (Sweden)

    Zheng Gong

    2013-01-01

    Full Text Available The electrochemical behaviors of monohydroxy-anthraquinone/multiwall carbon nanotubes (MHAQ/MWCNTs nanohybrid modified glassy carbon (MHAQ/MWCNTs/GC electrodes in neutral medium were investigated; also reported was their application in the electrocatalysis of oxygen reduction reaction (ORR. The resulting MHAQ/MWCNTs nanohybrid was characterized by scanning electron microscope (SEM and transmission electron microscope (TEM. It was found that the ORR at the MHAQ/MWCNTs/GC electrode occurs irreversibly at a potential about 214 mV less negative than at a bare GC electrode in pH 7.0 buffer solution. Cyclic voltammetric and rotating disk electrode (RDE techniques indicated that the MHAQ/MWCNTs nanohybrid has high electrocatalytic activity for the two-electron reduction of oxygen in the studied potential range. The kinetic parameters of ORR at the MHAQ/MWCNTs nanohybrid modified GC electrode were also determined by RDE and EIS techniques.

  19. Electronic-level interactions of tungsten oxide with unsupported Se/Ru electrocatalytic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Lewera, Adam; Miecznikowski, Krzysztof [Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland); Hunger, Ralf [Institute of Materials Science, Darmstadt University of Technology, Darmstadt (Germany); Kolary-Zurowska, Aneta [Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland); Wieckowski, Andrzej [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL (United States); Kulesza, Pawel J., E-mail: pkulesza@chem.uw.edu.p [Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland)

    2010-11-01

    Se/Ru nanoparticles - a potent non-platinum catalyst towards oxygen reduction reaction - were modified by hydrated WO{sub 3} and investigated using the rotating disk/ring electrode methods and by synchrotron X-ray photoelectron spectroscopy. The modification resulted in an enhanced catalytic activity towards oxygen reduction reaction (ORR). Our data indicate that the oxygen reduction current starts ca. 70 mV more positive and formation of undesirable hydrogen peroxide has significantly decreased following the modification of Se/Ru with WO{sub 3}. X-ray photoelectron spectroscopy reveals that WO{sub 3} interacts electronically with Se/Ru as the W 4f and Se 3d line-shapes change. We therefore conclude that the electronic interactions between Se/Ru and WO{sub 3} are primarily responsible for the increase in activity and selectivity of the WO{sub 3}-modified Se/Ru towards ORR.

  20. Electronic-level interactions of tungsten oxide with unsupported Se/Ru electrocatalytic nanoparticles

    International Nuclear Information System (INIS)

    Lewera, Adam; Miecznikowski, Krzysztof; Hunger, Ralf; Kolary-Zurowska, Aneta; Wieckowski, Andrzej; Kulesza, Pawel J.

    2010-01-01

    Se/Ru nanoparticles - a potent non-platinum catalyst towards oxygen reduction reaction - were modified by hydrated WO 3 and investigated using the rotating disk/ring electrode methods and by synchrotron X-ray photoelectron spectroscopy. The modification resulted in an enhanced catalytic activity towards oxygen reduction reaction (ORR). Our data indicate that the oxygen reduction current starts ca. 70 mV more positive and formation of undesirable hydrogen peroxide has significantly decreased following the modification of Se/Ru with WO 3 . X-ray photoelectron spectroscopy reveals that WO 3 interacts electronically with Se/Ru as the W 4f and Se 3d line-shapes change. We therefore conclude that the electronic interactions between Se/Ru and WO 3 are primarily responsible for the increase in activity and selectivity of the WO 3 -modified Se/Ru towards ORR.

  1. New approximations of the differential electron-atom elastic scattering cross-sections

    International Nuclear Information System (INIS)

    Niculescu, V.I.R.; Catana, D.

    1994-01-01

    In the present note concerning the electron-atom interaction a cubic Spline method was used to obtain approximations of the differential cross-sections. These approximations gave a 20 times reduction of the computing time preserving also the accuracy (2%). The example is for Al in the 1-256 keV electron energy range. (Author) 2 Tabs., 3 Refs

  2. Real-Time Electronic Tracking of Diarrheal Episodes and Laxative Therapy Enables Verification of Clostridium difficile Clinical Testing Criteria and Reduction of Clostridium difficile Infection Rates.

    Science.gov (United States)

    Truong, Cynthia Y; Gombar, Saurabh; Wilson, Richard; Sundararajan, Gopalakrishnan; Tekic, Natasa; Holubar, Marisa; Shepard, John; Madison, Alexandra; Tompkins, Lucy; Shah, Neil; Deresinski, Stan; Schroeder, Lee F; Banaei, Niaz

    2017-05-01

    Health care-onset health care facility-associated Clostridium difficile infection (HO-CDI) is overdiagnosed for several reasons, including the high prevalence of C. difficile colonization and the inability of hospitals to limit testing to patients with clinically significant diarrhea. We conducted a quasiexperimental study from 22 June 2015 to 30 June 2016 on consecutive inpatients with C. difficile test orders at an academic hospital. Real-time electronic patient data tracking was used by the laboratory to enforce testing criteria (defined as the presence of diarrhea [≥3 unformed stools in 24 h] and absence of laxative intake in the prior 48 h). Outcome measures included C. difficile test utilization, HO-CDI incidence, oral vancomycin utilization, and clinical complications. During the intervention, 7.1% (164) and 9.1% (211) of 2,321 C. difficile test orders were canceled due to absence of diarrhea and receipt of laxative therapy, respectively. C. difficile test utilization decreased upon implementation from an average of 208.8 tests to 143.0 tests per 10,000 patient-days ( P difficile results. Real-time electronic clinical data tracking is an effective tool for verification of C. difficile clinical testing criteria and safe reduction of inflated HO-CDI rates. Copyright © 2017 American Society for Microbiology.

  3. Whole acute toxicity removal from industrial and domestic effluents treated by electron beam radiation: emphasis on anionic surfactants

    International Nuclear Information System (INIS)

    Moraes, M.C.F.; Romanelli, M.F; Sena, H.C.; Pasqualini da Silva, G.; Sampa, M.H.O.; Borrely, S.I.

    2004-01-01

    Electron beam radiation has been applied to improve real industrial and domestic effluents received by Suzano wastewater treatment plant. Radiation efficacy has been evaluated as toxicity reduction, using two biological assays. Three sites were sampled and submitted for toxicity assays, anionic surfactant determination and electron beam irradiation. This paper shows the reduction of acute toxicity for both test-organisms, the marine bacteria Vibrio fischeri and the crustacean Daphnia similis. The raw toxic effluents exibitted from 0.6 ppm up to 11.67 ppm for anionic surfactant before being treated by the electron beam. Radiation processing resulted in reduction of the acute toxicity as well as surfactant removal. The final biological effluent was in general less toxic than other sites but the presence of anionic surfactants was evidenced

  4. Whole acute toxicity removal from industrial and domestic effluents treated by electron beam radiation: emphasis on anionic surfactants

    Energy Technology Data Exchange (ETDEWEB)

    Moraes, M.C.F. E-mail: mariacristinafm@uol.com.br; Romanelli, M.F; Sena, H.C.; Pasqualini da Silva, G.; Sampa, M.H.O.; Borrely, S.I

    2004-10-01

    Electron beam radiation has been applied to improve real industrial and domestic effluents received by Suzano wastewater treatment plant. Radiation efficacy has been evaluated as toxicity reduction, using two biological assays. Three sites were sampled and submitted for toxicity assays, anionic surfactant determination and electron beam irradiation. This paper shows the reduction of acute toxicity for both test-organisms, the marine bacteria Vibrio fischeri and the crustacean Daphnia similis. The raw toxic effluents exibitted from 0.6 ppm up to 11.67 ppm for anionic surfactant before being treated by the electron beam. Radiation processing resulted in reduction of the acute toxicity as well as surfactant removal. The final biological effluent was in general less toxic than other sites but the presence of anionic surfactants was evidenced.

  5. Influence of riboflavin on the reduction of radionuclides by Shewanella oneidenis MR-1.

    Science.gov (United States)

    Cherkouk, Andrea; Law, Gareth T W; Rizoulis, Athanasios; Law, Katie; Renshaw, Joanna C; Morris, Katherine; Livens, Francis R; Lloyd, Jonathan R

    2016-03-28

    Uranium (as UO2(2+)), technetium (as TcO4(-)) and neptunium (as NpO2(+)) are highly mobile radionuclides that can be reduced enzymatically by a range of anaerobic and facultatively anaerobic microorganisms, including Shewanella oneidensis MR-1, to poorly soluble species. The redox chemistry of Pu is more complicated, but the dominant oxidation state in most environments is highly insoluble Pu(IV), which can be reduced to Pu(III) which has a potentially increased solubility which could enhance migration of Pu in the environment. Recently it was shown that flavins (riboflavin and flavin mononucleotide (FMN)) secreted by Shewanella oneidensis MR-1 can act as electron shuttles, promoting anoxic growth coupled to the accelerated reduction of poorly-crystalline Fe(III) oxides. Here, we studied the role of riboflavin in mediating the reduction of radionuclides in cultures of Shewanella oneidensis MR-1. Our results demonstrate that the addition of 10 μM riboflavin enhances the reduction rate of Tc(VII) to Tc(IV), Pu(IV) to Pu(III) and to a lesser extent, Np(V) to Np(IV), but has no significant influence on the reduction rate of U(VI) by Shewanella oneidensis MR-1. Thus riboflavin can act as an extracellular electron shuttle to enhance rates of Tc(VII), Np(V) and Pu(IV) reduction, and may therefore play a role in controlling the oxidation state of key redox active actinides and fission products in natural and engineered environments. These results also suggest that the addition of riboflavin could be used to accelerate the bioremediation of radionuclide-contaminated environments.

  6. Electron beam generation in the fore-vacuum pressure range

    CERN Document Server

    Burachevskij, Y A; Kuzemchenko, M N; Mytnikov, A V; Oks, E M

    2001-01-01

    One presents the results of investigations to generate electron beams within 0.01-0.1 Torr gas pressure range. To generate a beam one used a plasma source based on a hollow cathode discharge in combination with a plane accelerating gap. Peculiar features of electron emission and acceleration within the mentioned pressure range are associated with high probability of gas ionization in an accelerating gap and with generation of ion flow meeting electron beam. It results in reduction of discharge combustion intensification, as well as, in plasma concentration range. The developed design of an electron source enables to generate cylindrical beams with up to 1 A current and with up to 10 keV energy

  7. The roles of polycarboxylates in Cr(VI)/sulfite reaction system: Involvement of reactive oxygen species and intramolecular electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Bo, E-mail: bjiang86upc@163.com [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China); School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266033 (China); Wang, Xianli; Liu, Yukun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China); Wang, Zhaohui [College of Environmental Science and Engineering, Donghua University, Shanghai 201620 (China); Southern Cross GeoScience, Southern Cross University, Lismore, NSW 2480 (Australia); Zheng, Jingtang, E-mail: jtzheng03@163.com [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China); Wu, Mingbo, E-mail: wumb@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China)

    2016-03-05

    Highlights: • The formations of SO{sub 4}·{sup −} and OH·, involve in Cr(VI) reduction induced by S(IV). • Affinity of polycarboxylate to Cr(VI) accelerates Cr(VI) reduction rate. • Polycarboxylates can act as electron donors for Cr(VI) reduction retrenching S(IV). • Only oxalate can enhance the formations of SO{sub 4}·{sup −} and OH· in Cr(VI)/S(IV) system. - Abstract: In this study, the effects of polycarboxylates on both Cr(VI) reduction and S(IV) consumption in Cr(VI)/S(IV) system was investigated in acidic solution. Under aerobic condition, the productions of reactive oxygen species (ROS), i.e., SO{sub 4}·{sup −} and OH·, have been confirmed in S(IV) reducing Cr(VI) process by using electron spin resonance and fluorescence spectrum techniques, leading to the excess consumption of S(IV). However, when polycarboxylates (oxalic, citric, malic and tartaric acid) were present in Cr(VI)/S(IV) system, the affinity of polycarboxylates to CrSO{sub 6}{sup 2−} can greatly promote the reduction of Cr(VI) via expanding the coordination of Cr(VI) species from tetrahedron to hexahedron. Besides, as alternatives to S(IV), these polycarboxylates can also act as electron donors for Cr(VI) reduction via intramolecular electron transfer reaction, which is dependent on the energies of the highest occupied molecular orbital of these polycarboxylates. Notably, the variant electron donating capacity of these polycarboxylates resulted in different yield of ROS and therefore the oxidation efficiencies of other pollutants, e.g., rhodamine B and As(III). Generally, this study does not only shed light on the mechanism of S(IV) reducing Cr(VI) process mediated by polycarboxylates, but also provides an escalated, cost-effective and green strategy for the remediation of Cr(VI) using sulfite as a reductant.

  8. Reduction of Aflatoxins in Apricot Kernels by Electronic and Manual Color Sorting

    OpenAIRE

    Zivoli, Rosanna; Gambacorta, Lucia; Piemontese, Luca; Solfrizzo, Michele

    2016-01-01

    The efficacy of color sorting on reducing aflatoxin levels in shelled apricot kernels was assessed. Naturally-contaminated kernels were submitted to an electronic optical sorter or blanched, peeled, and manually sorted to visually identify and sort discolored kernels (dark and spotted) from healthy ones. The samples obtained from the two sorting approaches were ground, homogenized, and analysed by HPLC-FLD for their aflatoxin content. A mass balance approach was used to measure the distributi...

  9. Reduction of hexavalent chromium by the thermophilic methanogen Methanothermobacter thermautotrophicus

    Science.gov (United States)

    Singh, Rajesh; Dong, Hailiang; Liu, Deng; Zhao, Linduo; Marts, Amy R.; Farquhar, Erik; Tierney, David L.; Almquist, Catherine B.; Briggs, Brandon R.

    2015-01-01

    Despite significant progress on iron reduction by thermophilic microorganisms, studies on their ability to reduce toxic metals are still limited, despite their common co-existence in high temperature environments (up to 70 °C). In this study, Methanothermobacter thermautotrophicus, an obligate thermophilic methanogen, was used to reduce hexavalent chromium. Experiments were conducted in a growth medium with H2/CO2 as substrate with various Cr6+ concentrations (0.2, 0.4, 1, 3, and 5 mM) in the form of potassium dichromate (K2Cr2O7). Time-course measurements of aqueous Cr6+ concentrations using 1,5-diphenylcarbazide colorimetric method showed complete reduction of the 0.2 and 0.4 mM Cr6+ solutions by this methanogen. However, much lower reduction extents of 43.6%, 13.0%, and 3.7% were observed at higher Cr6+ concentrations of 1, 3 and 5 mM, respectively. These lower extents of bioreduction suggest a toxic effect of aqueous Cr6+ to cells at this concentration range. At these higher Cr6+ concentrations, methanogenesis was inhibited and cell growth was impaired as evidenced by decreased total cellular protein production and live/dead cell ratio. Likewise, Cr6+ bioreduction rates decreased with increased initial concentrations of Cr6+ from 13.3 to 1.9 μM h-1. X-ray absorption near-edge structure (XANES) spectroscopy revealed a progressive reduction of soluble Cr6+ to insoluble Cr3+ precipitates, which was confirmed as amorphous chromium hydroxide by selected area electron diffraction pattern. However, a small fraction of reduced Cr occurred as aqueous Cr3+. Scanning and transmission electron microscope observations of M. thermautotrophicus cells after Cr6+ exposure suggest both extra- and intracellular chromium reduction mechanisms. Results of this study demonstrate the ability of M. thermautotrophicus cells to reduce toxic Cr6+ to less toxic Cr3+ and its potential application in metal bioremediation, especially at high temperature subsurface radioactive waste disposal

  10. Development of novel low-voltage free-electron lasers in the 5-500GHz region

    International Nuclear Information System (INIS)

    Zhong, Xiehe

    2002-01-01

    The electromagnetic spectrum from 5GHz to 500GHz is important for many industrial, commercial, and scientific applications. In particular for the 100 - 500GHz region, free electron lasers (FELs) are usually the only viable radiation sources with sizeable output power and as such are an attractive enabling technology for many applications. One major issue for widespread application of free electron lasers is to reduce their cost and size. This is particularly challenging because of the expensive electron accelerator system they employ. To make it significantly more attractive economically for many important applications, the electron energy has to be reduced to below 300keV. In this thesis two novel electron-energy-reduction techniques are investigated for FEL systems operated in the spectrum from 5GHz to 500GHz with the development of a suite of suitable FEL codes. In the microwave to millimetre-wave region, a novel energy reduction technique based on second harmonic waveguide FELs is studied. It is shown that the required electron voltage is approximately half of what is normally required for comparable conventional waveguide FELs. Effect of electron energy spread is studied for second harmonic waveguide FELs both in microwave and millimetre-wave regions. It is shown that strong wiggler field enhances electron hunching thereby increasing the small-signal gain as well as the insusceptibility to electron voltage spread. Saturation behaviour of second harmonic waveguide FELs is also studied because it is important for evaluation of output power. For FEL generation above 300GHz, it is found that second harmonic waveguide FELs need to increase electron energy above 300keV. To this end, a second energy reduction technique is considered based on a novel quasiperiodic wiggler. It is established that by changing the initial phase angle between the two component wigglers, strong radiation can be generated near 1THz with electron energy below 300keV. (author)

  11. Solved? The reductive radiation chemistry of alanine.

    Science.gov (United States)

    Pauwels, Ewald; De Cooman, Hendrik; Waroquier, Michel; Hole, Eli O; Sagstuen, Einar

    2014-02-14

    The structural changes throughout the entire reductive radiation-induced pathway of l-α-alanine are solved on an atomistic level with the aid of periodic DFT and nudged elastic band (NEB) simulations. This yields unprecedented information on the conformational changes taking place, including the protonation state of the carboxyl group in the "unstable" and "stable" alanine radicals and the internal transformation converting these two radical variants at temperatures above 220 K. The structures of all stable radicals were verified by calculating EPR properties and comparing those with experimental data. The variation of the energy throughout the full radiochemical process provides crucial insight into the reason why these structural changes and rearrangements occur. Starting from electron capture, the excess electron quickly localizes on the carbon of a carboxyl group, which pyramidalizes and receives a proton from the amino group of a neighboring alanine molecule, forming a first stable radical species (up to 150 K). In the temperature interval 150-220 K, this radical deaminates and deprotonates at the carboxyl group, the detached amino group undergoes inversion and its methyl group sustains an internal rotation. This yields the so-called "unstable alanine radical". Above 220 K, triggered by the attachment of an additional proton on the detached amino group, the radical then undergoes an internal rotation in the reverse direction, giving rise to the "stable alanine radical", which is the final stage in the reductive radiation-induced decay of alanine.

  12. Structural changes induced by electron irradiation

    International Nuclear Information System (INIS)

    Koike, J.; Pedraza, D.F.

    1993-01-01

    Highly oriented pyrolytic graphite was irradiated at room temperature with 300 kV electrons. Transmission electron microscopy and electron energy loss spectroscopy were employed to study the structural changes produced by irradiation. The occurrence of a continuous ring intensity in the selected area diffraction (SAD) pattern obtained on a specimen irradiated with the electron beam parallel to the c-crystallographic axis indicated that microstructural changes had occurred. However, from the SAD pattern obtained for the specimens tilted relative to the irradiation direction, it was found that up to a fluence of 1.1x10 27 e/m 2 graphite remained crystalline. An SAD pattern of a specimen irradiated with the electron beam perpendicular to the c-axis confirmed the persistence of crystalline order. High resolution electron microscopy showed that ordering along the c-axis direction remained. A density reduction of 8.9% due to irradiation was determined from the plasmon frequency shift. A qualitative model is proposed to explain these observations. A new determination of the threshold displacement energy, Ed, of carbon atoms in graphite was done by examining the appearance of a continuous ring in the SAD pattern at various electron energies. A value of 30 eV was obtained whether the incident electron beam was parallel or perpendicular to the c-axis, demonstrating that Ed is independent of the displacement direction

  13. The reduction of MoO3 at low temperatures

    International Nuclear Information System (INIS)

    Thoeni, W.; Gai, P.L.; Hirsch, P.B.

    1977-01-01

    New observations of the surface defects generated in MoO 3 on reduction in H 2 in situ in a high voltage electron microscope have revealed an error in the previous interpretation (Thoni and Hirsch, Phil. Mag.; 33:639 (1976)). The defects are now shown to be partial screw dislocations, with Burgers vector 1/2 , which accommodate the misfit between the reduced surface layer and the underlying matrix. (author)

  14. Electrocatalytic Reduction-oxidation of Chlorinated Phenols using a Nanostructured Pd-Fe Modified Graphene Catalyst

    International Nuclear Information System (INIS)

    Shi, Qin; Wang, Hui; Liu, Shaolei; Pang, Lei; Bian, Zhaoyong

    2015-01-01

    A Pd-Fe modified graphene (Pd-Fe/G) catalyst was prepared by the Hummers oxidation method and bimetallic co-deposition method. The catalyst was then characterized by various characterization techniques and its electrochemical property toward the electrocatalytic reduction-oxidation of chlorinated phenols was investigated by using cyclic voltammetry and differential pulse voltammetry. The results of the characterization show that the Pd-Fe/G catalyst in which the weight proportion of Pd and Fe is 1:1 has an optimal surface performance. The diameter of the Pd-Fe particles is approximately 5.2 ± 0.3 nm, with a uniform distribution on the supporting graphene. This is smaller than the Pd particles of a Pd-modified graphene (Pd/G) catalyst. The Pd-Fe/G catalyst shows a higher electrocatalytic activity than the Pd/G catalyst for reductive dechlorination when feeding with hydrogen gas. The reductive peak potentials of −0.188 V, −0.836 V and −0.956 V in the DPV curves are attributed to the dechlorination of ortho-Cl, meta-Cl, and para-Cl in 2-chlorophenol, 3-chlorophenol and 4-chlorophenol, respectively. In accordance with an analysis of the frontier orbital theory, the order of ease of dechlorination with Pd-Fe/G catalyst is 2-chlorophenol > 3-chlorophenol > 4-chlorophenol. The Pd-Fe/G catalyst has a greater activity than the Pd/G catalyst in accelerating the two-electron reduction of O_2 to H_2O_2, which is attributed to the higher current of the reduction peak at approximately −0.40 V when feeding with oxygen gas. Therefore, the Pd-Fe/G catalyst exhibits a higher electrocatalytic activity than the Pd/G catalyst for the reductive dechlorination and acceleration of the two-electron reduction of O_2 to H_2O_2.

  15. Large Reduction of Hot Spot Temperature in Graphene Electronic Devices with Heat-Spreading Hexagonal Boron Nitride.

    Science.gov (United States)

    Choi, David; Poudel, Nirakar; Park, Saungeun; Akinwande, Deji; Cronin, Stephen B; Watanabe, Kenji; Taniguchi, Takashi; Yao, Zhen; Shi, Li

    2018-04-04

    Scanning thermal microscopy measurements reveal a significant thermal benefit of including a high thermal conductivity hexagonal boron nitride (h-BN) heat-spreading layer between graphene and either a SiO 2 /Si substrate or a 100 μm thick Corning flexible Willow glass (WG) substrate. At the same power density, an 80 nm thick h-BN layer on the silicon substrate can yield a factor of 2.2 reduction of the hot spot temperature, whereas a 35 nm thick h-BN layer on the WG substrate is sufficient to obtain a factor of 4.1 reduction. The larger effect of the h-BN heat spreader on WG than on SiO 2 /Si is attributed to a smaller effective heat transfer coefficient per unit area for three-dimensional heat conduction into the thick, low-thermal conductivity WG substrate than for one-dimensional heat conduction through the thin oxide layer on silicon. Consequently, the h-BN lateral heat-spreading length is much larger on WG than on SiO 2 /Si, resulting in a larger degree of temperature reduction.

  16. Electrocatalytic reduction of oxygen at glassy carbon electrode modified by polypyrrole/anthraquinones composite film in various pH media

    International Nuclear Information System (INIS)

    Valarselvan, S.; Manisankar, P.

    2011-01-01

    Graphical abstract: The electrocatalytic reduction of dioxygen by one mono and four dihydroxy derivatives of 9,10-anthraquinone (AQ) incorporated in polypyrrole (PPy) matrix on glassy carbon electrode has been investigated. AQ and PPy composite film showed excellent electrocatalytic performance for the reduction of O 2 to H 2 O 2 . Highlights: → Hydroxyl derivatives of anthraquinones as electrocatalysts for dioxygen reduction. → AQ/PPy composite film on GC electrode exhibits potent electrocatalytic activity. → Substituent groups influence electrocatalytic dioxygen reduction. → Surface coverage varies the rate of electrocatalytic dioxygen reduction. - Abstract: The electrocatalytic reduction of dioxygen by one mono and four dihydroxy derivatives of 9,10-anthraquinone (AQ) incorporated in polypyrrole (PPy) matrix on glassy carbon electrode has been investigated. The electrochemical behaviour of the modified electrodes was examined in various pH media and both the formal potential of anthraquinones and reduction potential of dioxygen exhibited pH dependence. AQ and PPy composite film showed excellent electrocatalytic performance for the reduction of O 2 to H 2 O 2 . pH 6.0 was chosen as the most suitable medium to study the electrocatalysis by comparing the peak potential of oxygen reduction and enhancement in peak current for oxygen reduction. The diffusion coefficient values of AQ at the modified electrodes and the number of electrons involved in AQ reduction were evaluated by chronoamperometric and chronocoulometric techniques, respectively. In addition, hydrodynamic voltammetric studies showed the involvement of two electrons in O 2 reduction. The mass specific activity of AQ used, the diffusion coefficient of oxygen and the heterogeneous rate constants for the oxygen reduction at the surface of modified electrodes were also determined by rotating disk voltammetry.

  17. Mechanisms for the reduction of actinide ions by Geobacter sulfurreducens

    International Nuclear Information System (INIS)

    Renshaw, J.C.; Livens, F.R.; May, I.; Lloyd, J.R.

    2005-01-01

    Full text of publication follows: Three of the most problematic radioactive contaminants are the actinide elements uranium, neptunium and plutonium. All three pose considerable long-term environmental risks. The most stable environmental oxidation states of uranium and neptunium are VI and V, respectively, as the di-oxo cations [UO 2 ] 2+ and [NpO 2 ] + ; both are highly soluble and so are relatively mobile and biologically available in the environment. In similar conditions, plutonium mainly exists as Pu(IV), which forms a highly insoluble hydrous oxide, although is also environmentally stable in the more soluble III, V and VI oxidation states. The bio-reduction of U(VI) by anaerobic subsurface microorganisms has been the focus of much recent interest. Both Fe(III)- and sulfate-reducing bacteria have been shown to reduce soluble [U VI O 2 ] 2+ to insoluble U IV O 2 , with c-type cytochromes involved in electron transfer to the actinide. Such transformations offer a strategy for the bio-remediation of uranium contaminated groundwater and a potential mechanism for the bio-deposition of uranium ores. The mechanism of U(VI). reduction has important implications for the potential microbial reduction of transuranic elements with environmentally stable lower oxidation states. Reduction of mobile 237 Np(V) to Np(IV) and subsequent precipitation may be advantageous whilst remobilization of immobile Pu(IV) as more soluble Pu(III) species could have important environmental implications. Conversely, selective reduction might allow targeting of particular radionuclide species. The model anaerobic bacterium Geobacter sulfurreducens is typical of those found in contaminated subsurface environments and has been shown to reduce soluble [U VI O 2 ] 2+ to insoluble U IV O 2 . In the course of this study we use X-ray absorption spectroscopy (XAS) to show that G. sulfurreducens reduces U(VI) by a one-electron reduction, forming an unstable [UO 2 ] + species which subsequently

  18. Monte-Carlo calculations of forward directed bremsstrahlung produced by 20 and 45 MeV electrons on tungsten

    International Nuclear Information System (INIS)

    Goosman, D.R.

    1983-01-01

    The SANDYL Monte-Carlo code has been used to calculate the Bremsstrahlung photon production from beams of parallel electrons incident upon three target geometries. These are 20 MeV electrons onto 1 mm of tungsten + 59 mm of Be, which simulates the operating parameters of the FXR electron accelerator at LLNL Bldg. 801, 45 MeV electrons onto 1 mm of tungsten, and finally 45 MeV electrons onto 1 mm of tungsten and 147 mm of Be. The latter two situations simulate possible future modifications to the FXR accelerator. Graphs of the spectral shape of the Bremsstrahlung photons emitted with angles between 0 0 and 1 0 to the electron direction, the angular distribution of photon-MeV, and the dose reduction curves for each of the three geometries are given. The latter dose reduction curves allow one to calculate forward-directed photon fluxes in real-life situations where the electron beam has non-zero angular divergence

  19. The Nernst equation applied to oxidation-reduction reactions in myoglobin and hemoglobin. Evaluation of the parameters.

    Science.gov (United States)

    Saroff, Harry A

    Analyses of the binding of oxygen to monomers such as myoglobin employ the Mass Action equation. The Mass Action equation, as such, is not directly applicable for the analysis of the binding of oxygen to oligomers such as hemoglobin. When the binding of oxygen to hemoglobin is analyzed, models incorporating extensions of mass action are employed. Oxidation-reduction reactions of the heme group in myoglobin and hemoglobin involve the binding and dissociation of electrons. This reaction is described with the Nernst equation. The Nernst equation is applicable only to a monomeric species even if the number of electrons involved is greater than unity. To analyze the oxidation-reduction reaction in a molecule such as hemoglobin a model is required which incorporates extensions of the Nernst equation. This communication develops models employing the Nernst equation for oxidation-reduction reactions analogous to those employed for hemoglobin in the analysis of the oxygenation (binding of oxygen) reaction.

  20. An Integrated Assessment of Geochemical and Community Structure Determinants of Metal Reduction Rates in Subsurface Sediments

    International Nuclear Information System (INIS)

    Kostka, Joel E.

    2008-01-01

    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 microbial 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.

  1. Single crystalline multi-petal Cd nanoleaves prepared by thermal reduction of CdO

    International Nuclear Information System (INIS)

    Khan, Waheed S.; Cao, Chuanbao; Aslam, Imran; Ali, Zulfiqar; Butt, Faheem K.; Mahmood, Tariq; Nabi, Ghulam; Ihsan, Ayesha; Usman, Zahid; Rehman, Asma

    2013-01-01

    Highlights: ► Cd nanoleaves are obtained on abraded Cu substrate by thermal reduction of CdO. ► Vapour solid (VS) growth mechanism governs the formation of Cd nanoleaves (CdNLs). ► PL spectrum for CdNLs exhibits a strong ultraviolet (UV) emission band at 353 nm. ► UV band is attributed to interband radiative recombination under Xe illumination. -- Abstract: Multi-petal cadmium metal nanoleaves with 30–40 nm thickness were fabricated on abraded copper substrate by simple thermal reduction of cadmium oxide (CdO) powder at 1050 °C inside horizontal tube furnace (HTF) under nitrogen gas flow. The structural, compositional and morphological characterizations of the as-prepared cadmium nanoleaves (CdNLs) were performed by X-ray diffraction, energy dispersive X-ray spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy and selected area electron diffraction. Non-catalytic vapour–solid (VS) process based growth mechanism governing the formation of CdNLs has been proposed and discussed briefly. Photoluminescence (PL) spectrum for CdNLs measured at room temperature exhibited a single prominent emission band at 353 nm which may either be ascribed to surface oxidation effects or interband radiative recombination under Xe light illumination.

  2. Single crystalline multi-petal Cd nanoleaves prepared by thermal reduction of CdO

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Waheed S. [Research Centre of Materials Science, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); National Institute for Biotechnology and Genetic Engineering (NIBGE), P.O. Box No. 577, Jhang Road, Faisalabad (Pakistan); Cao, Chuanbao, E-mail: cbcao@bit.edu.cn [Research Centre of Materials Science, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Aslam, Imran; Ali, Zulfiqar; Butt, Faheem K.; Mahmood, Tariq; Nabi, Ghulam [Research Centre of Materials Science, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Ihsan, Ayesha [National Institute for Biotechnology and Genetic Engineering (NIBGE), P.O. Box No. 577, Jhang Road, Faisalabad (Pakistan); Usman, Zahid [Research Centre of Materials Science, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Rehman, Asma [National Institute for Biotechnology and Genetic Engineering (NIBGE), P.O. Box No. 577, Jhang Road, Faisalabad (Pakistan)

    2013-02-15

    Highlights: ► Cd nanoleaves are obtained on abraded Cu substrate by thermal reduction of CdO. ► Vapour solid (VS) growth mechanism governs the formation of Cd nanoleaves (CdNLs). ► PL spectrum for CdNLs exhibits a strong ultraviolet (UV) emission band at 353 nm. ► UV band is attributed to interband radiative recombination under Xe illumination. -- Abstract: Multi-petal cadmium metal nanoleaves with 30–40 nm thickness were fabricated on abraded copper substrate by simple thermal reduction of cadmium oxide (CdO) powder at 1050 °C inside horizontal tube furnace (HTF) under nitrogen gas flow. The structural, compositional and morphological characterizations of the as-prepared cadmium nanoleaves (CdNLs) were performed by X-ray diffraction, energy dispersive X-ray spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy and selected area electron diffraction. Non-catalytic vapour–solid (VS) process based growth mechanism governing the formation of CdNLs has been proposed and discussed briefly. Photoluminescence (PL) spectrum for CdNLs measured at room temperature exhibited a single prominent emission band at 353 nm which may either be ascribed to surface oxidation effects or interband radiative recombination under Xe light illumination.

  3. Molecular Underpinnings of Fe(III Oxide Reduction by Shewanella oneidensis MR-1

    Directory of Open Access Journals (Sweden)

    Liang eShi

    2012-02-01

    Full Text Available In the absence of O2 and other electron acceptors, the Gram-negative bacterium Shewanella oneidensis MR-1 can use ferric [Fe(III] (oxy(hydroxide minerals as the terminal electron acceptors for anaerobic respiration. At circumneutral pH and in the absence of strong complexing ligands, Fe(III oxides are relatively insoluble and thus are external to the bacterial cells. S. oneidensis MR-1 has evolved the machinery (i.e., metal-reducing or Mtr pathway for transferring electrons across the entire cell envelope to the surface of extracellular Fe(III oxides. The protein components identified to date for the Mtr pathway include CymA, MtrA, MtrB, MtrC and OmcA. CymA is an inner-membrane tetraheme c-type cytochrome (c-Cyt that is proposed to oxidize the quinol in the inner-membrane and transfers the released electrons to redox proteins in the periplasm. Although the periplasmic proteins receiving electrons from CymA during Fe(III oxidation have not been identified, they are believed to relay the electrons to MtrA. A decaheme c-Cyt, MtrA is thought to be embedded in the trans outer-membrane and porin-like protein MtrB. Together, MtrAB deliver the electrons across the outer-membrane to the MtrC and OmcA on the outmost bacterial surface. Functioning as terminal reductases, the outer membrane and decaheme c-Cyts MtrC and OmcA can bind the surface of Fe(III oxides and transfer electrons directly to these minerals. To increase their reaction rates, MtrC and OmcA can use the flavins secreted by S. oneidensis MR-1 cells as diffusible co-factors for reduction of Fe(III oxides. MtrC and OmcA can also serve as the terminal reductases for soluble forms of Fe(III. Although our understanding of the Mtr pathway is still far from complete, it is the best characterized microbial pathway used for extracellular electron exchange. Characterizations of the Mtr pathway have made significant contributions to the molecular understanding of microbial reduction of Fe(III oxides.

  4. Electron/Photon Verification Calculations Using MCNP4B

    Energy Technology Data Exchange (ETDEWEB)

    D. P. Gierga; K. J. Adams

    1999-04-01

    MCNP4BW was released in February 1997 with significant enhancements to electron/photon transport methods. These enhancements have been verified against a wide range of published electron/photon experiments, spanning high energy bremsstrahlung production to electron transmission and reflection. The impact of several MCNP tally options and physics parameters was explored in detail. The agreement between experiment and simulation was usually within two standard deviations of the experimental and calculational errors. Furthermore, sub-step artifacts for bremsstrahlung production were shown to be mitigated. A detailed suite of electron depth dose calculations in water is also presented. Areas for future code development have also been explored and include the dependence of cell and detector tallies on different bremsstrahlung angular models and alternative variance reduction splitting schemes for bremsstrahlung production.

  5. One electron reduction and absorption characteristics of Cresyl violet in micellar medium

    International Nuclear Information System (INIS)

    Gawandi, Vijay B.; Guha, S.N.; Hari Mohan

    2000-01-01

    Effect of surfactant micelles on absorption characteristics of Cresyl violet (CV) and on its redox reactions have been studied. Among the various surfactants investigated anionic surfactants particularly sodium lauryl sulfate (SLS) and sodium dodecyl benzene sulfonate (SDDBS) showed marked effect on these properties. Reactions of hydrated electron in these micellar media were studied using the technique of nanosecond pulse radiolysis. Results of other surfactants, viz.BSS, CTAB and TritonX-100 have also been presented. (author)

  6. Electrochemical Reduction of Quinones in Different Media: A Review

    Directory of Open Access Journals (Sweden)

    Partha Sarathi Guin

    2011-01-01

    Full Text Available The electron transfer reactions involving quinones, hydroquinones, and catechols are very important in many areas of chemistry, especially in biological systems. The therapeutic efficiency as well as toxicity of anthracycline anticancer drugs, a class of anthraquinones, is governed by their electrochemical properties. Other quinones serve as important functional moiety in various biological systems like electron-proton carriers in the respiratory chain and their involvement in photosynthetic electron flow systems. The present paper summarizes literatures on the reduction of quinones in different solvents under various conditions using different electrochemical methods. The influence of different reaction conditions including pH of the media, nature of supporting electrolytes, nature of other additives, intramolecular or intermolecular hydrogen bonding, ion pair formation, polarity of the solvents, stabilization of the semiquinone and quinone dianion, catalytic property, and adsorption at the electrode surface, are discussed and relationships between reaction conditions and products formed have been presented.

  7. pH control for enhanced reductive bioremediation of chlorinated solvent source zones

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, Clare, E-mail: clare.robinson@epfl.ch [Laboratoire de technologie ecologique, Institut d' ingenierie de l' environnement, Station No. 2, Ecole Polytechnique Federale de Lausanne, CH-1015 Lausanne (Switzerland); Now at: Department of Civil and Environmental Engineering, University of Western Ontario, London, Canada N6A 5B9 (Canada); Barry, D.A., E-mail: andrew.barry@epfl.ch [Laboratoire de technologie ecologique, Institut d' ingenierie de l' environnement, Station No. 2, Ecole Polytechnique Federale de Lausanne, CH-1015 Lausanne (Switzerland); McCarty, Perry L., E-mail: pmccarty@stanford.edu [Department of Civil and Environmental Engineering, Stanford University, Stanford, CA 94305-4020 (United States); Gerhard, Jason I., E-mail: j.gerhard@ed.ac.uk [Now at: Department of Civil and Environmental Engineering, University of Western Ontario, London, Canada N6A 5B9 (Canada); Institute for Infrastructure and Environment, University of Edinburgh, Edinburgh, EH9 3JL (United Kingdom); Kouznetsova, Irina, E-mail: irina.kouznetsova@ed.ac.uk [Institute for Infrastructure and Environment, University of Edinburgh, Edinburgh, EH9 3JL (United Kingdom)

    2009-08-01

    Enhanced reductive dehalogenation is an attractive treatment technology for in situ remediation of chlorinated solvent DNAPL source areas. Reductive dehalogenation is an acid-forming process with hydrochloric acid and also organic acids from fermentation of the electron donors typically building up in the source zone during remediation. This can lead to groundwater acidification thereby inhibiting the activity of dehalogenating microorganisms. Where the soils' natural buffering capacity is likely to be exceeded, the addition of an external source of alkalinity is needed to ensure sustained dehalogenation. To assist in the design of bioremediation systems, an abiotic geochemical model was developed to provide insight into the processes influencing the groundwater acidity as dehalogenation proceeds, and to predict the amount of bicarbonate required to maintain the pH at a suitable level for dehalogenating bacteria (i.e., > 6.5). The model accounts for the amount of chlorinated solvent degraded, site water chemistry, electron donor, alternative terminal electron-accepting processes, gas release and soil mineralogy. While calcite and iron oxides were shown to be the key minerals influencing the soil's buffering capacity, for the extensive dehalogenation likely to occur in a DNAPL source zone, significant bicarbonate addition may be necessary even in soils that are naturally well buffered. Results indicated that the bicarbonate requirement strongly depends on the electron donor used and availability of competing electron acceptors (e.g., sulfate, iron (III)). Based on understanding gained from this model, a simplified model was developed for calculating a preliminary design estimate of the bicarbonate addition required to control the pH for user-specified operating conditions.

  8. Electron cloud effects in SIS-18 and SIS-100

    Energy Technology Data Exchange (ETDEWEB)

    Petrov, Fedor; Boine-Frankenheim, Oliver [Technische Universitaet Darmstadt, Institut fuer Theorie Elektromagnetischer Felder (TEMF) (Germany); Gesellschaft fuer Schwerionenforschung (GSI) GmbH, Darmstadt (Germany); Weiland, Thomas [Technische Universitaet Darmstadt, Institut fuer Theorie Elektromagnetischer Felder (TEMF) (Germany)

    2011-07-01

    Electron cloud build-up and associated instabilities are studied in simulations under conditions relevant to SIS-18 and to the projected SIS-100 heavy ion synchrotrons. In both rings coasting beams are foreseen during slow extraction of the beam. Trapped electrons could lead to a reduction of the extraction efficiency. We present the results of electron cloud studies for bunched and for coasting beams. In these two regimes the main production mechanisms are significantly different. For coasting beams the most important mechanism is residual gas ionization, for bunched beam the main source of electrons is secondary emission. In the case of coasting beams electrons are generated in the vicinity of the beam center and a two-stream instability may occur for the projected intensities.Electron clouds due to bunched beams are of concern in SIS-100 because no special coating of the stainless steel beam pipe is presently foreseen. Finally we also discuss experimental studies of electron cloud generation in SIS-18.

  9. Quenching of excited uranyl ion during its photochemical reduction by triphenylphosphine: Part III

    International Nuclear Information System (INIS)

    Sidhu, M.S.; Chahal, P.; Singh, R.J.

    1993-01-01

    Relative rates of bimolecular quenching of excited uranyl ion by some mono and di-substituted benzene derivatives have been measured during its photochemical reduction with triphenylphosphine. For the related compounds in a series it has been found that substituent groups enriching the aromatic π-electron cloud due to resonance stabilization, show an enhanced photophysical quenching action. The substituents decreasing the π-electron cloud and delocalization of positive charger over the benzene ring decrease the quenching action. (author). 16 refs., 2 figs., 1 tab

  10. Analog Electronic Filters Theory, Design and Synthesis

    CERN Document Server

    Dimopoulos, Hercules G

    2012-01-01

    Filters are essential subsystems in a huge variety of electronic systems. Filter applications are innumerable; they are used for noise reduction, demodulation, signal detection, multiplexing, sampling, sound and speech processing, transmission line equalization and image processing, to name just a few. In practice, no electronic system can exist without filters. They can be found in everything from power supplies to mobile phones and hard disk drives and from loudspeakers and MP3 players to home cinema systems and broadband Internet connections. This textbook introduces basic concepts and methods and the associated mathematical and computational tools employed in electronic filter theory, synthesis and design.  This book can be used as an integral part of undergraduate courses on analog electronic filters. Includes numerous, solved examples, applied examples and exercises for each chapter. Includes detailed coverage of active and passive filters in an independent but correlated manner. Emphasizes real filter...

  11. Evaluation of electronic speed limit signs on US 30.

    Science.gov (United States)

    2011-09-01

    This study documents the speed : reduction impacts of two dynamic, : electronic school zone speed limit signs : at United Community Schools between : Ames and Boone, Iowa. The school : facility is situated along US Highway 30, : a rural four-lane div...

  12. A CsPbBr3 Perovskite Quantum Dot/Graphene Oxide Composite for Photocatalytic CO2 Reduction.

    Science.gov (United States)

    Xu, Yang-Fan; Yang, Mu-Zi; Chen, Bai-Xue; Wang, Xu-Dong; Chen, Hong-Yan; Kuang, Dai-Bin; Su, Cheng-Yong

    2017-04-26

    Halide perovskite quantum dots (QDs), primarily regarded as optoelectronic materials for LED and photovoltaic devices, have not been applied for photochemical conversion (e.g., water splitting or CO 2 reduction) applications because of their insufficient stability in the presence of moisture or polar solvents. Herein, we report the use of CsPbBr 3 QDs as novel photocatalysts to convert CO 2 into solar fuels in nonaqueous media. Under AM 1.5G simulated illumination, the CsPbBr 3 QDs steadily generated and injected electrons into CO 2 , catalyzing CO 2 reduction at a rate of 23.7 μmol/g h with a selectivity over 99.3%. Additionally, through the construction of a CsPbBr 3 QD/graphene oxide (CsPbBr 3 QD/GO) composite, the rate of electron consumption increased 25.5% because of improved electron extraction and transport. This study is anticipated to provide new opportunities to utilize halide perovskite QD materials in photocatalytic applications.

  13. Effects of deformation on the electronic properties of B-C-N nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Azevedo, S., E-mail: sazevedo@fisica.ufpb.br [Departamento de Fisica, Universidade Federal da Paraiba, Caixa Postal 5008, 58059-900 Joao Pessoa-PB (Brazil); Rosas, A. [Departamento de Fisica, Universidade Federal da Paraiba, Caixa Postal 5008, 58059-900 Joao Pessoa-PB (Brazil); Machado, M. [Departamento de Fisica, Universidade Federal de Pelotas, Caixa Postal 354, 96010-900 Pelotas-RS (Brazil); Kaschny, J.R. [Instituto Federal da Bahia-Campus Vitoria da Conquista, Av. Amazonas 3150, 45030-220 Vitoria da Conquista-BA (Brazil); Chacham, H. [Departamento de Fisica, ICEX, Universidade Federal de Minas Gerais, Caixa Postal 702, 30123-970 Belo Horizonte-MG (Brazil)

    2013-01-15

    We apply first-principles methods, using density functional theory, to investigate the effects of flattening deformation on the electronic properties of BC{sub 2}N and C-doped BNNTs. Four different types of BC{sub 2}N structures are considered. Two of them are semiconductors, and the radial compression produces a significant reduction of the energy band gap. The other two types of structures are metallic, and the effect of radial compression is quite distinct. For one of them it is found the opening of a small band gap, and for the other one no changes are observed. For C-doped tubes, it is also found that the electronic properties undergo significant modifications when subjected to radial compression. - Graphical Abstract: We apply first-principles methods, using density functional theory, to investigate the effects of flattening deformation on the electronic properties of BC{sub 2}N and C-doped BNNTs. Four different types of BC{sub 2}N structures are considered. Two of them are semiconductors, and the radial compression produces a significant reduction of the energy band gap. The other two types of structures are metallic, and the effect of radial compression is quite distinct. For one of them it is found the opening of a small band gap, and for the other one no changes are observed. For C-doped tubes, it is also found that the electronic properties undergo significant modifications when subjected to radial compression. Highlights: Black-Right-Pointing-Pointer We investigated electronic properties of flattened BC{sub 2}N nanotubes. Black-Right-Pointing-Pointer The electronic states depend strongly on compression. Black-Right-Pointing-Pointer It is studied flattened BN nanotubes doped with a carbon atom. Black-Right-Pointing-Pointer The flattened C-doped structures, presents a significant reduction of the gap.

  14. Simultaneous nitrate reduction and acetaminophen oxidation using the continuous-flow chemical-less VUV process as an integrated advanced oxidation and reduction process.

    Science.gov (United States)

    Moussavi, Gholamreza; Shekoohiyan, Sakine

    2016-11-15

    This work was aimed at investigating the performance of the continuous-flow VUV photoreactor as a novel chemical-less advanced process for simultaneously oxidizing acetaminophen (ACT) as a model of pharmaceuticals and reducing nitrate in a single reactor. Solution pH was an important parameter affecting the performance of VUV; the highest ACT oxidation and nitrate reduction attained at solution pH between 6 and 8. The ACT was oxidized mainly by HO while the aqueous electrons were the main working agents in the reduction of nitrate. The performance of VUV photoreactor improved with the increase of hydraulic retention time (HRT); the complete degradation of ACT and ∼99% reduction of nitrate with 100% N2 selectivity achieved at HRT of 80min. The VUV effluent concentrations of nitrite and ammonium at HRT of 80min were below the drinking water standards. The real water sample contaminated with the ACT and nitrate was efficiently treated in the VUV photoreactor. Therefore, the VUV photoreactor is a chemical-less advanced process in which both advanced oxidation and advanced reduction reactions are accomplished. This unique feature possesses VUV photoreactor as a promising method of treating water contaminated with both pharmaceutical and nitrate. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Reduction Rates for Higher Americium Oxidation States in Nitric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Grimes, Travis Shane [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mincher, Bruce Jay [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schmitt, Nicholas C [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-09-30

    The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

  16. Facile synthesis of SiO{sub 2}@Cu{sub x}O@TiO{sub 2} heterostructures for catalytic reductions of 4-nitrophenol and 2-nitroaniline organic pollutants

    Energy Technology Data Exchange (ETDEWEB)

    Zelekew, Osman Ahmed; Kuo, Dong-Hau, E-mail: dhkuo@mail.ntust.edu.tw

    2017-01-30

    Highlights: • The synthesis of SiO{sub 2}@Cu{sub x}O@TiO{sub 2}catalystwasillustrated (*). • The p-n junction between p-type Cu{sub x}O and n-type TiO{sub 2} built electric field. • The electric field results in avoiding the recombination of electron and hole. • The n-type TiO{sub 2} rich in electron outward facilitates the reduction. - Abstract: Herein, we designed the p-type Cu{sub x}O (x = 1 or 2) nanoparticles deposited on SiO{sub 2} spherical particle inside and coated with thin layered n-type TiO{sub 2} semiconductors outside for reduction purpose. The composite material, abbreviated as SiO{sub 2}@Cu{sub x}O@TiO{sub 2}, was characterized. The catalytic performance of the composite was tested for the reductions of 4-nitrophenol (4-NP) and 2-nitroaniline (2-NA). Complete reductions of 4-NP and 2-NA took, 210 and 150 s, respectively. The catalytic efficiency of the composite material may be associated with electron and hole separation resulted from the p-n junction formation between p-type Cu{sub x}O and n-type TiO{sub 2} and the built-in electric field. Moreover, the hydride ion and electrons released from NaBH{sub 4} together with outward electrons from n-type TiO{sub 2}, synergistically, are also responsible for the reduction of nitro aromatic compounds. Our design of composite material from low-priced metal oxides was successful towards reduction of nitro-aromatic compounds.

  17. Electron cyclotron waves transmission: new approach for the characterization of electron distribution functions in Tokamak hot plasmas

    International Nuclear Information System (INIS)

    Michelot, Y.

    1995-10-01

    Fast electrons are one of the basic ingredients of plasma operations in many existing thermonuclear fusion research devices. However, the understanding of fast electrons dynamics during creation and sustainment of the superthermal electrons tail is far for being satisfactory. For this reason, the Electron Cyclotron Transmission (ECT) diagnostic was implemented on Tore Supra tokamak. It consists on a microwave transmission system installed on a vertical chord crossing the plasma center and working in the frequency range 77-109 GHz. Variations of the wave amplitude during the propagation across the plasma may be due to refraction and resonant absorption. For the ECT, the most common manifestation of refraction is a reduction of the received power density with respect to the signal detected in vacuum, due to the spreading and deflection of the wave beam. Wave absorption is observed in the vicinity of the electron cyclotron harmonics and may be due both to thermal plasma and to superthermal electron tails. It has a characteristic frequency dependence due to the relativistic mass variation in the wave-electron resonance condition. This thesis presents the first measurements of: the extraordinary mode optical depth at the third harmonics, the electron temperature from the width of a cyclotron absorption line and the relaxation times of the electron distribution during lower hybrid current drive from the ordinary mode spectral superthermal absorption line at the first harmonic. (J.S.). 175 refs., 110 figs., 9 tabs., 3 annexes

  18. Nitrate effects on chromate reduction in a methane-based biofilm.

    Science.gov (United States)

    Zhong, Liang; Lai, Chun-Yu; Shi, Ling-Dong; Wang, Kai-Di; Dai, Yu-Jie; Liu, Yao-Wei; Ma, Fang; Rittmann, Bruce E; Zheng, Ping; Zhao, He-Ping

    2017-05-15

    The effects of nitrate (NO 3 - ) on chromate (Cr(VI)) reduction in a membrane biofilm reactor (MBfR) were studied when CH 4 was the sole electron donor supplied with a non-limiting delivery capacity. A high surface loading of NO 3 - gave significant and irreversible inhibition of Cr(VI) reduction. At a surface loading of 500 mg Cr/m 2 -d, the Cr(VI)-removal percentage was 100% when NO 3 - was absent (Stage 1), but was dramatically lowered to PCoA and UniFrac analyses proved that the introduction of NO 3 - had a strong impact on the microbial community in the biofilms, and the changes possibly were linked to the irreversible inhibition of Cr(VI) reduction. For example, Meiothermus, the main genus involved in Cr(VI) reduction at first, declined with introduction of NO 3 - . The denitrifier Chitinophagaceae was enriched after the addition of NO 3 - , while Pelomonas became important when nitrate was removed, suggesting its potential role as a Cr(VI) reducer. Moreover, introducing NO 3 - led to a decrease in the number of genes predicted (by PICRUSt) to be related to chromate reduction, but genes predicted to be related to denitrification, methane oxidation, and fermentation increased. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Light-Induced Reduction of Cuprous Oxide in an Environmental Transmission Electron Microscope

    DEFF Research Database (Denmark)

    Cavalca, Filippo Carlo; Laursen, Anders Bo; Wagner, Jakob Birkedal

    2013-01-01

    Photocatalysts for solar fuel production are subject to intensive investigation as they constitute one viable route for solar energy harvesting. Cuprous oxide (Cu2O) is a working photocatalyst for hydrogen evolution but it photocorrodes upon light illumination in an aqueous environment....... Environmental transmission electron microscopy (ETEM) makes it possible to obtain insight into the local structure, composition and reactivity of catalysts in their working environment, which is of fundamental interest for sustainable energy research and is essential for further material optimization. Herein...

  20. Exogenous electron shuttle-mediated extracellular electron transfer of Shewanella putrefaciens 200: electrochemical parameters and thermodynamics.

    Science.gov (United States)

    Wu, Yundang; Liu, Tongxu; Li, Xiaomin; Li, Fangbai

    2014-08-19

    Despite the importance of exogenous electron shuttles (ESs) in extracellular electron transfer (EET), a lack of understanding of the key properties of ESs is a concern given their different influences on EET processes. Here, the ES-mediated EET capacity of Shewanella putrefaciens 200 (SP200) was evaluated by examining the electricity generated in a microbial fuel cell. The results indicated that all the ESs substantially accelerated the current generation compared to only SP200. The current and polarization parameters were linearly correlated with both the standard redox potential (E(ES)(0)) and the electron accepting capacity (EAC) of the ESs. A thermodynamic analysis of the electron transfer from the electron donor to the electrode suggested that the EET from c-type cytochromes (c-Cyts) to ESs is a crucial step causing the differences in EET capacities among various ESs. Based on the derived equations, both E(ES)(0) and EAC can quantitatively determine potential losses (ΔE) that reflect the potential loss of the ES-mediated EET. In situ spectral kinetic analysis of ES reduction by c-Cyts in a living SP200 suspension was first investigated with the E(ES), E(c-Cyt), and ΔE values being calculated. This study can provide a comprehensive understanding of the role of ESs in EET.

  1. Web-based computational chemistry education with CHARMMing III: Reduction potentials of electron transfer proteins.

    Directory of Open Access Journals (Sweden)

    B Scott Perrin

    2014-07-01

    Full Text Available A module for fast determination of reduction potentials, E°, of redox-active proteins has been implemented in the CHARMM INterface and Graphics (CHARMMing web portal (www.charmming.org. The free energy of reduction, which is proportional to E°, is composed of an intrinsic contribution due to the redox site and an environmental contribution due to the protein and solvent. Here, the intrinsic contribution is selected from a library of pre-calculated density functional theory values for each type of redox site and redox couple, while the environmental contribution is calculated from a crystal structure of the protein using Poisson-Boltzmann continuum electrostatics. An accompanying lesson demonstrates a calculation of E°. In this lesson, an ionizable residue in a [4Fe-4S]-protein that causes a pH-dependent E° is identified, and the E° of a mutant that would test the identification is predicted. This demonstration is valuable to both computational chemistry students and researchers interested in predicting sequence determinants of E° for mutagenesis.

  2. Enhanced selective photocatalytic CO{sub 2} reduction into CO over Ag/CdS nanocomposites under visible light

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Zezhou; Qin, Jiani; Jiang, Min; Ding, Zhengxin; Hou, Yidong, E-mail: ydhou@fzu.edu.cn

    2017-01-01

    Highlights: • Ag/CdS nanocomposites were prepared by a facile photodeposition method. • Ag/CdS was more effective as a photocatalyst for CO{sub 2} reduction than CdS. • Ag as cocatalyst served as electron trap as well as active site for CO{sub 2} reduction reaction. - Abstract: Photocatalytic reduction of carbon dioxide can convert chemically inert carbon dioxide into useful chemical fuel in a mild manner. Herein, Ag-CdS nanocomposites were prepared by photodeposition method and examined for photocatalytic CO{sub 2} reduction under visible light. Meanwhile, the nanocomposites were characterized by XRD, SEM, TEM, XPS, DRS and PL in detail. The results show that, the deposition of Ag improves the photocatalytic performance of CdS, especially in the selectivity of CO{sub 2}-to-CO. The highest photocatalytic activity is achieved over 1.0 wt.% Ag/CdS, with an increase by 3 times in comparison to CdS. In this reaction system, Ag can serve as electron trap as well as active site for CO{sub 2} reduction, which is probably responsible for the enhanced activity and selectivity of CO{sub 2} to CO over Ag/CdS. The possible mechanism of CO{sub 2} photoreduction over Ag/CdS was proposed in view of the abovementioned analysis.

  3. Vertical activity distribution of dissimilatory nitrate reduction in coastal marine sediments

    DEFF Research Database (Denmark)

    Behrendt, A.; de Beer, D.; Stief, P.

    2013-01-01

    The relative importance of two dissimilatory nitrate reduction pathways, denitrification (DEN) and dissimilatory nitrate reduction to ammonium (DNRA), was investigated in intact sediment cores from five different coastal marine field sites (Dorum, Aarhus Bight, Mississippi Delta, Limfjord...... reduction was clearly dominated by DEN (59-131% of the total NO3- reduced) rather than by DNRA, irrespective of the sedimentary inventories of electron donors such as organic carbon, sulfide, and iron. Highest ammonium production via DNRA, accounting for up to 8.9% of the total NO3- reduced, was found...... was detected accounting for 37-77% of the total NO3- reduced. These contradictory results might be explained by enhanced NO3- availability for DNRA bacteria in the sediment slurries compared to the core-incubated sediments in which diffusion of NO3- from the water column may only reach DEN bacteria...

  4. Application of Macro Response Monte Carlo method for electron spectrum simulation

    International Nuclear Information System (INIS)

    Perles, L.A.; Almeida, A. de

    2007-01-01

    During the past years several variance reduction techniques for Monte Carlo electron transport have been developed in order to reduce the electron computation time transport for absorbed dose distribution. We have implemented the Macro Response Monte Carlo (MRMC) method to evaluate the electron spectrum which can be used as a phase space input for others simulation programs. Such technique uses probability distributions for electron histories previously simulated in spheres (called kugels). These probabilities are used to sample the primary electron final state, as well as the creation secondary electrons and photons. We have compared the MRMC electron spectra simulated in homogeneous phantom against the Geant4 spectra. The results showed an agreement better than 6% in the spectra peak energies and that MRMC code is up to 12 time faster than Geant4 simulations

  5. Electronic Power Transformer for Power Distribution Networks

    Directory of Open Access Journals (Sweden)

    Ermuraсhi Iu.V.

    2017-12-01

    Full Text Available Reducing losses in electricity distribution networks is a current technical problem. This issue also has social and environmental aspects. As a promising solution one can examine the direct distribution from the medium voltage power network using new equipment based on the use of power electronics. The aim of the paper is to propose and argue an innovative technical solution for the realization of the Solid State Transformer (SST in order to decrease the number of energy transformation stages compared to the known solutions, simplifying the topology of the functional scheme with the reduction of production costs and the loss of energy in transformers used in electrical distribution networks. It is proposed the solution of simplifying the topology of the AC/AC electronic transformer by reducing the number of passive electronic components (resistors, inductors, capacitors and active (transistors. The inverter of the SST transformer ensures the switching mode of the transistors, using for this purpose the inductance of the magnetic leakage flux of the high frequency transformer. The robustness of the laboratory sample of the SST 10 / 0.22 kV transformer with the power of 20 kW was manufactured and tested. Testing of the laboratory sample confirmed the functionality of the proposed scheme and the possibility of switching of the transistors to at zero current (ZCS mode with the reduction of the energy losses. In the proposed converter a single high-frequency transformer with a simplified construction with two windings is used, which reduces its mass and the cost of making the transformer. The reduction in the manufacturing cost of the converter is also due to the decrease in the number of links between the functional elements.

  6. Recharge processes drive sulfate reduction in an alluvial aquifer contaminated with landfill leachate

    Science.gov (United States)

    Scholl, M.A.; Cozzarelli, I.M.; Christenson, S.C.

    2006-01-01

    Natural attenuation of contaminants in groundwater depends on an adequate supply of electron acceptors to stimulate biodegradation. In an alluvial aquifer contaminated with leachate from an unlined municipal landfill, the mechanism of recharge infiltration was investigated as a source of electron acceptors. Water samples were collected monthly at closely spaced intervals in the top 2 m of the saturated zone from a leachate-contaminated well and an uncontaminated well, and analyzed for ??18O, ??2H, non-volatile dissolved organic carbon (NVDOC), SO42-, NO3- and Cl-. Monthly recharge amounts were quantified using the offset of the ??18O or ??2H from the local meteoric water line as a parameter to distinguish water types, as evaporation and methanogenesis caused isotopic enrichment in waters from different sources. Presence of dissolved SO42- in the top 1 to 2??m of the saturated zone was associated with recharge; SO42- averaged 2.2??mM, with maximum concentrations of 15??mM. Nitrate was observed near the water table at the contaminated site at concentrations up to 4.6??mM. Temporal monitoring of ??2H and SO42- showed that vertical transport of recharge carried SO42- to depths up to 1.75??m below the water table, supplying an additional electron acceptor to the predominantly methanogenic leachate plume. Measurements of ??34S in SO42- indicated both SO42- reduction and sulfide oxidation were occurring in the aquifer. Depth-integrated net SO42- reduction rates, calculated using the natural Cl- gradient as a conservative tracer, ranged from 7.5 ?? 10- 3 to 0.61??mM??d- 1 (over various depth intervals from 0.45 to 1.75??m). Sulfate reduction occurred at both the contaminated and uncontaminated sites; however, median SO42- reduction rates were higher at the contaminated site. Although estimated SO42- reduction rates are relatively high, significant decreases in NVDOC were not observed at the contaminated site. Organic compounds more labile than the leachate NVDOC may be

  7. Recharge processes drive sulfate reduction in an alluvial aquifer contaminated with landfill leachate.

    Science.gov (United States)

    Scholl, Martha A; Cozzarelli, Isabelle M; Christenson, Scott C

    2006-08-10

    Natural attenuation of contaminants in groundwater depends on an adequate supply of electron acceptors to stimulate biodegradation. In an alluvial aquifer contaminated with leachate from an unlined municipal landfill, the mechanism of recharge infiltration was investigated as a source of electron acceptors. Water samples were collected monthly at closely spaced intervals in the top 2 m of the saturated zone from a leachate-contaminated well and an uncontaminated well, and analyzed for delta(18)O, delta(2)H, non-volatile dissolved organic carbon (NVDOC), SO(4)(2-), NO(3)(-) and Cl(-). Monthly recharge amounts were quantified using the offset of the delta(18)O or delta(2)H from the local meteoric water line as a parameter to distinguish water types, as evaporation and methanogenesis caused isotopic enrichment in waters from different sources. Presence of dissolved SO(4)(2-) in the top 1 to 2 m of the saturated zone was associated with recharge; SO(4)(2-) averaged 2.2 mM, with maximum concentrations of 15 mM. Nitrate was observed near the water table at the contaminated site at concentrations up to 4.6 mM. Temporal monitoring of delta(2)H and SO(4)(2-) showed that vertical transport of recharge carried SO(4)(2-) to depths up to 1.75 m below the water table, supplying an additional electron acceptor to the predominantly methanogenic leachate plume. Measurements of delta(34)S in SO(4)(2-) indicated both SO(4)(2-) reduction and sulfide oxidation were occurring in the aquifer. Depth-integrated net SO(4)(2-) reduction rates, calculated using the natural Cl(-) gradient as a conservative tracer, ranged from 7.5x10(-3) to 0.61 mM.d(-1) (over various depth intervals from 0.45 to 1.75 m). Sulfate reduction occurred at both the contaminated and uncontaminated sites; however, median SO(4)(2-) reduction rates were higher at the contaminated site. Although estimated SO(4)(2-) reduction rates are relatively high, significant decreases in NVDOC were not observed at the contaminated

  8. Cathodic reduction of benzil in acetone and in dichloromethane

    Energy Technology Data Exchange (ETDEWEB)

    Quintanilla, Gloria [Departamento de Quimica Organica, Universidad de Alcala, 28871 Alcala de Henares, Madrid (Spain)], E-mail: gloria.quintanilla@uah.es; Liebeck, Miriam; Bengtsson, Carina; Arnold, Lena; Barba, Fructuoso [Departamento de Quimica Organica, Universidad de Alcala, 28871 Alcala de Henares, Madrid (Spain)

    2008-02-15

    The cathodic reduction of benzil has been carried out at a controlled potential on a mercury cathode in two different SSE (solvent-supporting-electrolyte) conditions: (a) acetone/lithium perchlorate in absence of electrophile where 2,3-diphenyl-5-methyl-furan and 1,2-diphenyl-2-hydroxy-1,4-pentanedione were obtained as main products and (b) dichloromethane/tetrabuthylammonium chloride with the addition of oxalyl chloride as electrophile, where a fast electron transfer took place.

  9. The electrochemical reduction of biotin (vitamin B7) and conversion into its ester

    International Nuclear Information System (INIS)

    Lauw, Sherman J.L.; Ganguly, Rakesh; Webster, Richard D.

    2013-01-01

    Highlights: •Biotin can be reduced electrochemically, by one-electron, at a platinum electrode. •The reduction likely follows a direct discharge mechanism of the carboxyl group. •Electrochemically generated biotin carboxylate was reacted with iodomethane (91%). •ATR–FTIR characterization of biotin, its carboxylate anion, and its methyl ester. -- Abstract: An electrochemical study on biotin (vitamin B7), performed in aprotic solvents and at a platinum electrode, revealed that at approximately E f 0 =−1.6to−1.8 vs. (Fc/Fc + )/V (E f 0 =formal reduction potential and Fc=ferrocene), biotin is reduced by one-electron to form its carboxylate anion and dihydrogen via a direct discharge of the carboxylic acid at the platinum surface. The electrochemical reduction process appeared to be chemically reversible on the time-frame of cyclic voltammetry (CV) (t ≤ s), but not over the extended period of controlled potential electrolysis (CPE) (t ≥ min) where the conversion of biotin into its carboxylate anion was found to be chemically irreversible. A strategy to functionalize biotin's carboxyl group was established by performing a bulk reductive electrolysis, and then reacting the electrochemically generated carboxylate anion with iodomethane to afford biotin methyl ester in excellent yield (91%). Attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopy was successful in identifying several distinct and characteristic carbonyl absorbance peaks associated with the analogous forms of biotin available before electrolysis, after electrolysis, and after methylation

  10. UK intussusception audit: A national survey of practice and audit of reduction rates

    International Nuclear Information System (INIS)

    Hannon, Edward; Williams, Rhianydd; Allan, Rosemary; Okoye, Bruce

    2014-01-01

    Aim: To define current UK reduction practice and the reductions rates achieved. Materials and methods: Electronic surveys were sent to radiologists at 26 UK centres. This assessed methods of reduction, equipment, personnel, and protocol usage. Standardized audit proforma were also sent to evaluate all reductions performed in 2011. Results: Twenty-two of 26 centres (85%) replied. All used air enema under fluoroscopic guidance. Equipment was not standardized but could be broadly categorized into hand-pumped air-supply systems (seven centres) and pressurized air systems (15 centres). Seventeen centres followed a protocol based on British Society of Paediatric Radiologists (BSPR) guidelines. In 21 of the 22 centres a consultant paediatric radiologist led reductions and only 12 centres reported a surgeon being present. Three hundred and ten cases were reported across 22 centres. Cases per centre ranged from 0–31 (median 14). Reduction rates varied from 38–90% (median 71%). The overall perforation rate was 2.5%. Caseload did not significantly correlate with reduction rate, and there was no significant difference between the two types of equipment used. Median reduction rates were 15% higher in centres with a surgeon present at reduction (p < 0.05). Conclusion: Intussusception care in the UK lacks standardization of equipment and personnel involved. National reduction rates are lower than in current international literature. Improved standardization may lead to an improvement in reduction rates and a surgeon should always be present at reduction

  11. Metal-free reduction of the greenhouse gas sulfur hexafluoride, formation of SF5 containing ion pairs and the application in fluorinations

    KAUST Repository

    Rueping, Magnus; Nikolaienko, Pavlo; Lebedev, Yury; Adams, Alina

    2017-01-01

    A protocol for the fast and selective two-electron reduction of the potent greenhouse gas sulfur hexafluoride (SF6) by organic electron donors at ambient temperature has been developed. The reaction yields solid ion pairs consisting of donor

  12. Studies of transfer reactions of photosensitized electrons involving complexes of transition metals in view of solar energy storage

    International Nuclear Information System (INIS)

    Takakubo, Masaaki

    1984-01-01

    This research thesis addresses electron transfer reactions occurring during photosynthesis, for example, photosensitized reaction in which chlorophyll is the sensitizer. More specifically, the author studied experimentally electron photo-transfers with type D sensitizers (riboflavin, phenoxazine and porphyrin), and various complexes of transition metals. After a presentation of these experiments, the author describes the photosensitisation process (photo-physics of riboflavin, oxygen deactivation, sensitized photo-oxidation and photo-reduction). The theoretical aspect of electron transfer is then addressed: generalities, deactivation of the riboflavin triplet, initial efficiency of electron transfer. Experimental results on three basic processes (non-radiative deactivation, energy transfer, electron transfer) are interpreted in a unified way by using the non-radiative transfer theory. Some applications are described: photo-electrochemical batteries, photo-oxidation and photo-reduction of the cobalt ion

  13. Simulation of electron beam in a MET as charged particles flux

    International Nuclear Information System (INIS)

    Hernandez-Valle, Alberto; Valverde-Noguera, Vanessa; Lopez-Gomez, Ignacio; Chine-Polito, Bruno; Esquivel-Isern, Ricardo; Chaves-Noguera, Juan

    2015-01-01

    The behavior of an electron beam is simulated in a transmission electron microscope (TEM). The simulation is performed according to the acceleration voltage, the excitation current of the lenses and the relative permeability of the pole pieces, through the software COMSOL Multiphysics version 4.2a. The dispersed electrons filtered by diaphragms have showed a low vertical speed as result. Graphics have exposed an increase in the magnetic flux density, intensifying the magnetic permeability of the polar pieces, the angle of the divergent electrons and vertical velocity reduction. Observations have showed that the number of electrons in the system remains unaffected in the general behavior of the beam and the magnitude of the magnetic flux density. (Author) [es

  14. Animal Research on Nicotine Reduction: Current Evidence and Research Gaps.

    Science.gov (United States)

    Smith, Tracy T; Rupprecht, Laura E; Denlinger-Apte, Rachel L; Weeks, Jillian J; Panas, Rachel S; Donny, Eric C; Sved, Alan F

    2017-09-01

    A mandated reduction in the nicotine content of cigarettes may improve public health by reducing the prevalence of smoking. Animal self-administration research is an important complement to clinical research on nicotine reduction. It can fill research gaps that may be difficult to address with clinical research, guide clinical researchers about variables that are likely to be important in their own research, and provide policy makers with converging evidence between clinical and preclinical studies about the potential impact of a nicotine reduction policy. Convergence between clinical and preclinical research is important, given the ease with which clinical trial participants can access nonstudy tobacco products in the current marketplace. Herein, we review contributions of preclinical animal research, with a focus on rodent self-administration, to the science of nicotine reduction. Throughout this review, we highlight areas where clinical and preclinical research converge and areas where the two differ. Preclinical research has provided data on many important topics such as the threshold for nicotine reinforcement, the likelihood of compensation, moderators of the impact of nicotine reduction, the impact of environmental stimuli on nicotine reduction, the impact of nonnicotine cigarette smoke constituents on nicotine reduction, and the impact of nicotine reduction on vulnerable populations. Special attention is paid to current research gaps including the dramatic rise in alternative tobacco products, including electronic nicotine delivery systems (ie, e-cigarettes). The evidence reviewed here will be critical for policy makers as well as clinical researchers interested in nicotine reduction. This review will provide policy makers and clinical researchers interested in nicotine reduction with an overview of the preclinical animal research conducted on nicotine reduction and the regulatory implications of that research. The review also highlights the utility of

  15. Nonadiabatic electron response in the Hasegawa-Wakatani equations

    International Nuclear Information System (INIS)

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

    2013-01-01

    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 ∥ . 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 one 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)

  16. Synthesis of silicon carbide by carbothermal reduction of silica

    International Nuclear Information System (INIS)

    Abel, Joao Luis

    2009-01-01

    The production of silicon carbide (SiC) in an industrial scale still by carbothermal reduction of silica. This study aims to identify, in a comparative way, among the common reducers like petroleum coke, carbon black, charcoal and graphite the carbothermal reduction of silica from the peat. It is shown, that the peat, also occurs in nature together with high purity silica sand deposits, where the proximity of raw materials and their quality are key elements that determine the type, purity and cost of production of SiC. Tests were running from samples produced in the electric resistance furnace with controlled atmosphere at temperatures of 1550 degree C, 1600 degree C and 1650 degree C, both the precursors and products of reaction of carbothermal reduction were characterized by applying techniques of X-ray diffraction, scanning electron microscopy (SEM) and Energy-Dispersive X-ray analysis Spectroscopy (EDS). The results showed the formation of SiC for all common reducers, as well as for peat, but it was not possible to realize clearly the difference between them, being necessary, specific tests. (author)

  17. Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

    Science.gov (United States)

    Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.; Roubelakis, Manolis M.; Maher, Andrew G.; Lee, Chang Hoon; Chambers, Matthew B.; Hammes-Schiffer, Sharon; Nocera, Daniel G.

    2014-01-01

    The hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We conclude that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring. PMID:25298534

  18. The Use of an Edible Mushroom-Derived Renewable Carbon Material as a Highly Stable Electrocatalyst towards Four-Electron Oxygen Reduction

    Directory of Open Access Journals (Sweden)

    Chaozhong Guo

    2015-12-01

    Full Text Available The development of highly stable and efficient electrocatalysts for sluggish oxygen reduction reaction (ORR is exceedingly significant for the commercialization of fuel cells but remains a challenge. We here synthesize a new nitrogen-doped biocarbon composite material (N-BC@CNP-900 as a nitrogen-containing carbon-based electrocatalyst for the ORR via facile all-solid-state multi-step pyrolysis of bioprotein-enriched enoki mushroom as a starting material, and inexpensive carbon nanoparticles as the inserting matrix and conducting agent at controlled temperatures. Results show that the N-BC@CNP-900 catalyst exhibits the best ORR electrocatalytic activity with an onset potential of 0.94 V (versus reversible hydrogen electrode, RHE and high stability. Meanwhile, this catalyst significantly exhibits good selectivity of the four-electron reaction pathway in an alkaline electrolyte. It is notable that pyridinic- and graphtic-nitrogen groups that play a key role in the enhancement of the ORR activity may be the catalytically active structures for the ORR. We further propose that the pyridinic-nitrogen species can mainly stabilize the ORR activity and the graphitic-nitrogen species can largely enhance the ORR activity. Besides, the addition of carbon support also plays an important role in the pyrolysis process, promoting the ORR electrocatalytic activity.

  19. The Use of an Edible Mushroom-Derived Renewable Carbon Material as a Highly Stable Electrocatalyst towards Four-Electron Oxygen Reduction.

    Science.gov (United States)

    Guo, Chaozhong; Sun, Lingtao; Liao, Wenli; Li, Zhongbin

    2015-12-23

    The development of highly stable and efficient electrocatalysts for sluggish oxygen reduction reaction (ORR) is exceedingly significant for the commercialization of fuel cells but remains a challenge. We here synthesize a new nitrogen-doped biocarbon composite material (N-BC@CNP-900) as a nitrogen-containing carbon-based electrocatalyst for the ORR via facile all-solid-state multi-step pyrolysis of bioprotein-enriched enoki mushroom as a starting material, and inexpensive carbon nanoparticles as the inserting matrix and conducting agent at controlled temperatures. Results show that the N-BC@CNP-900 catalyst exhibits the best ORR electrocatalytic activity with an onset potential of 0.94 V ( versus reversible hydrogen electrode, RHE) and high stability. Meanwhile, this catalyst significantly exhibits good selectivity of the four-electron reaction pathway in an alkaline electrolyte. It is notable that pyridinic- and graphtic-nitrogen groups that play a key role in the enhancement of the ORR activity may be the catalytically active structures for the ORR. We further propose that the pyridinic-nitrogen species can mainly stabilize the ORR activity and the graphitic-nitrogen species can largely enhance the ORR activity. Besides, the addition of carbon support also plays an important role in the pyrolysis process, promoting the ORR electrocatalytic activity.

  20. Electron heating using lower hybrid waves in the PLT tokamak

    International Nuclear Information System (INIS)

    Bell, R.E.; Bernabei, S.; Cavallo, A.; Chu, T.K.; Luce, T.; Motley, R.; Ono, M.; Stevens, J.; von Goeler, S.

    1987-06-01

    Lower hybrid waves with a narrow high velocity wave spectrum have been used to achieve high central electron temperatures in a tokamak plasma. Waves with a frequency of 2.45 GHz launched by a 16-waveguide grill at a power level less than 600 kW were used to increase the central electron temperature of the PLT plasma from 2.2 keV to 5 keV. The magnitude of the temperature increase depends strongly on the phase difference between the waveguides and on the direction of the launched wave. A reduction in the central electron thermal diffusivity is associated with the peaked electron temperature profiles of lower hybrid current-driven plasmas. 16 refs