These are representative sample records from Science.gov related to your search topic.
For comprehensive and current results, perform a real-time search at Science.gov.
1

RELATIONSHIPS BETWEEN OXIDATION-REDUCTION POTENTIAL, OXIDANT, AND PH IN DRINKING WATER  

EPA Science Inventory

Oxidation and reduction (redox) reactions are very important in drinking water. Oxidation-reduction potential (ORP) measurements reflect the redox state of water. Redox measurements are not widely made by drinking water utilities in part because they are not well understood. The ...

2

Assessment of Eccentric Exercise-Induced Oxidative Stress Using Oxidation-Reduction Potential Markers  

PubMed Central

The aim of the present study was to investigate the use of static (sORP) and capacity ORP (cORP) oxidation-reduction potential markers as measured by the RedoxSYS Diagnostic System in plasma, for assessing eccentric exercise-induced oxidative stress. Nineteen volunteers performed eccentric exercise with the knee extensors. Blood was collected before, immediately after exercise, and 24, 48, and 72?h after exercise. Moreover, common redox biomarkers were measured, which were protein carbonyls, thiobarbituric acid-reactive substances, total antioxidant capacity in plasma, and catalase activity and glutathione levels in erythrocytes. When the participants were examined as one group, there were not significant differences in any marker after exercise. However, in 11 participants there was a high increase in cORP after exercise, while in 8 participants there was a high decrease. Thus, the participants were divided in low cORP group exhibiting significant decrease in cORP after exercise and in high cORP group exhibiting significant increase. Moreover, only in the low cORP group there was a significant increase in lipid peroxidation after exercise suggesting induction of oxidative stress. The results suggested that high decreases in cORP values after exercise may indicate induction of oxidative stress by eccentric exercise, while high increases in cORP values after exercise may indicate no existence of oxidative stress. PMID:25874019

Stagos, Dimitrios; Goutzourelas, Nikolaos; Ntontou, Amalia-Maria; Kafantaris, Ioannis; Deli, Chariklia K.; Poulios, Athanasios; Jamurtas, Athanasios Z.; Bar-Or, David; Kouretas, Dimitrios

2015-01-01

3

THE OXIDATION-REDUCTION POTENTIAL OF THE LUCIFERIN-OXYLUCIFERIN SYSTEM.  

PubMed

The oxidation-reduction potential of the Cypridina luciferin-oxyluciferin system determined by a method of "bracketing" lies somewhere between that of anthraquinone 2-6-di Na sulfonate (E(o) (') at pH of 7.7 = -.22) which reduces luciferin, and quinhydrone (E(o) (') at pH of 7.7 = +.24), which oxidizes luciferin. Systems having an E(o) (') value between -.22 and +.24 volt neither reduce oxyluciferin nor oxidize luciferin. If the luciferin-oxyluciferin system were truly reversible considerable reduction and oxidation should occur between -.22 and +.24. The system appears to be an irreversible one, with both "apparent oxidation" and "apparent reduction potentials" in Conant's sense. Hydrosulfites, sulfides, CrCl(2), TiCl(3), and nascent hydrogen reduce oxyluciferin readily in absence of oxygen but without luminescence. Luminescence only appears in water solution if luciferin is oxidized by dissolved oxygen in presence of luciferase. Rapid oxidation of luciferin by oxygen without luciferase or oxidation by K(3)Fe(CN)(6) in presence of luciferase but without oxygen never gives luminescence. PMID:19872330

Harvey, E N

1927-01-20

4

Visible-light assisted reduction of graphene oxide and its potential applications in water treatment  

NASA Astrophysics Data System (ADS)

A novel, environmental-friendly approach for the reduction of graphene oxide (GO) by means of incorporating visible-light sensitive TiO2 and steady state visible-light irradiation was undertaken. Some potential applications of the resultant TiO2-graphene composites as water treatment technique, such as electrosorption and dissolved organic matter removal, have been demonstrated as well.

Li, Haibo; Liang, Sen; Li, Guolong; He, Lijun; Li, Jin

2014-02-01

5

ANAEROBIC DDT BIOTRANSFORMATION: ENHANCEMENT BY APPLICATION OF SURFACTANTS AND LOW OXIDATION REDUCTION POTENTIAL  

EPA Science Inventory

Enhancement of anaerobic DDT (1,1,1-trichloro-2,2-bis( p -chlorophenyl) ethane) biotransformation by mixed cultures was studied with application of surfactants and oxidation reduction potential reducing agents. Without amendments, DDT transformation resulted mainly in the pr...

6

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

PubMed Central

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

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

2002-01-01

7

Microbial reduction of crystalline iron(III) oxides: Influence of oxide surface area and potential for cell growth  

Microsoft Academic Search

Quantitative aspects of microbial crystalline iron(III) oxide reduction were examined using a dissimilatory iron(III) oxide-reducing bacterium (Shewanella alga strain BrY). The initial rate and long-term extent of reduction of a range of synthetic iron(III) oxides were linearly correlated with oxide surface area. Oxide reduction rates reached an asymptote at cell concentrations in excess of =1 x 10⁹\\/m² of oxide surface.

Eric E. Roden; John M. Zachara

1996-01-01

8

Development of Linear Irreversible Thermodynamic Model for Oxidation Reduction Potential in Environmental Microbial System  

PubMed Central

Nernst equation has been directly used to formulate the oxidation reduction potential (ORP) of reversible thermodynamic conditions but applied to irreversible conditions after several assumptions and/or modifications. However, the assumptions are sometimes inappropriate in the quantification of ORP in nonequilibrium system. We propose a linear nonequilibrium thermodynamic model, called microbial related reduction and oxidation reaction (MIRROR Model No. 1) for the interpretation of ORP in biological process. The ORP was related to the affinities of catabolism and anabolism. The energy expenditure of catabolism and anabolism was directly proportional to overpotential (?), straight coefficient of electrode (LEE), and degree of coupling between catabolism and ORP electrode, respectively. Finally, the limitations of MIRROR Model No. 1 were discussed for expanding the applicability of the model. PMID:17496027

Cheng, Hong-Bang; Kumar, Mathava; Lin, Jih-Gaw

2007-01-01

9

Chapter A6. Section 6.5. Reduction-Oxidation Potential (Electrode Method)  

USGS Publications Warehouse

Reduction-oxidation (redox) potential--also referred to as Eh--is a measure of the equilibrium potential, relative to the standard hydrogen electrode, developed at the interface between a noble metal electrode and an aqueous solution containing electroactive chemical species. Measurements of Eh are used to evaluate geochemical speciation models, and Eh data can provide insights on the evolution and status of water chemistry in an aqueous system. Nevertheless, the measurement is fraught with inherent interferences and limitations that must be understood and considered to determine applicability to the aqueous system being studied. For this reason, Eh determination is not one of the field parameters routinely measured by the U.S. Geological Survey (USGS). This section of the National Field Manual (NFM) describes the equipment and procedures needed to measure Eh in water using a platinum electrode. Guidance as to the limitations and interpretation of Eh measurement also is included.

Nordstrom, Darrell Kirk; Wilde, Franceska D.

2005-01-01

10

Electrode measurements of the oxidation reduction potential in the Gotland Deep using a moored profiling instrumentation  

NASA Astrophysics Data System (ADS)

The Gotland Deep Environmental Sampling Station (GODESS) operating between 30 m and 185 m was used to assess the variation of in situ redox potential (Eh) in the stratified water column of the central Baltic Sea, for a period of 56 days (November 2010-January 2011). The aim of this study was to acquire in-depth understanding of redox variations with the overall objective to identify the processes controlling Eh. At an interval of 8 h basic hydro-physical parameters were registered, including the oxidation-reduction potential, dissolved oxygen, chlorophyll a fluorescence, turbidity, temperature and conductivity. In total 170 profiles of all parameters were obtained. The measured Eh (with respect to standard hydrogen electrode, SHE) ranged from -0.055 V to 0.167 V. After temperature and pH correction of the standard reduction potentials, a comparison of the measured Eh with that calculated for the particular redox couples was carried out by applying the Nernst-equation. Furthermore, the concentrations of the most important redox elements such as Fe, Mn, N, O, C and S used for comparison were estimated by using empirical functions or were based on measurements of discrete water samples, taken at the time of deployment and recovery of the mooring. The obtained results reveal that the reduction of Fe(III) and O2 may be the main processes controlling the Eh potential in the Gotland basin. Below the redoxcline the reduction of hematite and then ferric oxyhydroxide could be related to the redox potential and somewhat deeper Fe(III)/Fe(II) was found to be the dominant redox couple. Although mixed potential theory could have been applied, the Fe couples appear to dominate over many other possible redox equilibria. This may be explained by the relatively high exchange current of Fe and by high Fe concentrations (up to 1.5 ?M). Finally, a close correspondence to the Eh potentials measured in the oxic/hypoxic part of the water column was found considering the O2/O2-· and the O2-·/H2O2 couples. This suggests that one-electron transfer reactions determined the Eh under oxic/hypoxic conditions.

Meyer, David; Prien, Ralf D.; Dellwig, Olaf; Waniek, Joanna J.; Schulz–Bull, Detlef E.

2014-03-01

11

OXIDATION-REDUCT ION POTENTIALS AND THE OXIDIZED FLAVOR IN HOMOGENIZED MILK v  

Microsoft Academic Search

Various workers have observed that homogenization tends to stabilize milk against oxidative changes (2, 3, 7, 11, 12, 13), but the mechanism by which the stabilization is produced has not been definitely ascertained. Ross (7), Dahle (1), and Thurston (11) expressed the belief that the ad- sorbed layer around the fat globules is the protective agent involved in homogenization. Earlier,

I. A. GOULD; D G. M. TROUT

12

Analysis of flow decay potential on Galileo. [oxidizer flow rate reduction by iron nitrate precipitates  

NASA Technical Reports Server (NTRS)

The risks posed to the NASA's Galileo spacecraft by the oxidizer flow decay during its extended mission to Jupiter is discussed. The Galileo spacecraft will use nitrogen tetroxide (NTO)/monomethyl hydrazine bipropellant system with one large engine thrust-rated at a nominal 400 N, and 12 smaller engines each thrust-rated at a nominal 10 N. These smaller thrusters, because of their small valve inlet filters and small injector ports, are especially vulnerable to clogging by iron nitrate precipitates formed by NTO-wetted stainless steel components. To quantify the corrosion rates and solubility levels which will be seen during the Galileo mission, corrosion and solubility testing experiments were performed with simulated Galileo materials, propellants, and environments. The results show the potential benefits of propellant sieving in terms of iron and water impurity reduction.

Cole, T. W.; Frisbee, R. H.; Yavrouian, A. H.

1987-01-01

13

Effect of voltage polarity on oxidation-reduction potential by plasma in water  

SciTech Connect

Use of plasma in water for water treatment and medical treatment is growing and raises expectations of finding advanced functions such as an increase of biological compatibility. In the present study with a focus on the variation of oxidation-reduction potential (ORP), relationships between the electrode polarities of plasma in water and the change of water quality such as conductivity, H{sub 2}O{sub 2} concentration, dissolved hydrogen concentration, pH and ORP were revealed. Similar line spectra of radiation at the electrode tip were observed for each case of positive and negative electrode polarity. The emission intensities of OH (309 nm), H? (656 nm), and OI (777 nm) for the positive discharge were significantly higher than those for the negative one, though the energy consumption during the discharge period of both cases was nearly the same. Positive electrode polarity was found to be more suitable than negative electrode polarity for increasing dissolved hydrogen gas and hydrogen peroxide. The ORP for the positive polarity decreased from 460 to 45 mV and that for the negative polarity decreased from 460 to 183 mV, although the pH and conductivity were not significantly changed.

Miyahara, Takashi [Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Naka-ku, Hamamatsu 432-8561 (Japan)] [Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Naka-ku, Hamamatsu 432-8561 (Japan); Oizumi, Masanobu [Graduate School of Engineering, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan (Currently, Nippon Steel and Sumikin Engineering Co. Ltd.) (Japan)] [Graduate School of Engineering, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan (Currently, Nippon Steel and Sumikin Engineering Co. Ltd.) (Japan); Nakatani, Tatsuyuki [Toyo Advanced Technologies Co., Ltd., 5-3-38 Ujinahigashi, Minami-ku, Hiroshima 734-8501 (Japan)] [Toyo Advanced Technologies Co., Ltd., 5-3-38 Ujinahigashi, Minami-ku, Hiroshima 734-8501 (Japan); Sato, Takehiko, E-mail: sato@ifs.tohoku.ac.jp [Institute of Fluid Science, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan)] [Institute of Fluid Science, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan)

2014-04-15

14

Soil Oxidation-Reduction Potential and Plant Photosynthetic Capacity in the Northern Pantanal of Mato Grosso, Brazil  

NASA Astrophysics Data System (ADS)

Plant communities of the Pantanal wetland are able to survive long periods of climatic and physiological stress in the dry and wet seasons. During inundation, soil oxygen demand increases dramatically as reducing soil conditions create stress in the root system with possible impacts on photosynthetic capacity of plants. We look at inundation cycles of a tree island (locally known as a cordilheira) in the Northern Pantanal near Poconé, Mato Grosso, and relate soil oxidation-reduction potential and soil oxygen depletion to the photosynthetic capacity of two plant communities of flooded scrub forest (Vochysia divergens and Curatela americana). Results show a drop in soil oxidation-reduction potential of over 400 mV, to levels below the absolute value of -200 mV, following inundation around the tree island. Both plant species showed increased carbon assimilation at highest soil oxygen demand despite a change in stomatal conductance, suggesting adaptation to the inundated environment. Absolute values of soil oxidation-reduction potential also allow for the determination of specific soil chemical reactions characteristic of the tree island environment, namely the reduction of iron(III), or carbon dioxide which in turn produces methane. Our combined analysis of soil chemistry with plant ecophysiology allows for a better understanding of soil-plant interactions in the Pantanal, specifically the drivers of biogeochemical processes between inundation periods.

Lathuilliere, M. J.; Johnson, M. S.; Dalmagro, H. J.; Pinto Junior, O. B.; Couto, E. G.

2013-12-01

15

Sulfide oxidation and nitrate reduction for potential mitigation of H2S in landfills.  

PubMed

Because H2S emitted by landfill sites has seriously endangered human health, its removal is urgent. H2S removal by use of an autotrophic denitrification landfill biocover has been reported. In this process, nitrate-reducing and sulfide-oxidizing bacteria use a reduced sulfur source as electron donor when reducing nitrate to nitrogen gas and oxidizing sulfur compounds to sulfate. The research presented here was performed to investigate the possibility of endogenous mitigation of H2S by autotrophic denitrification of landfill waste. The sulfide oxidation bioprocess accompanied by nitrate reduction was observed in batch tests inoculated with mineralized refuse from a landfill site. Repeated supply of nitrate resulted in rapid oxidation of the sulfide, indicating that, to a substantial extent, the bioprocess may be driven by functional microbes. This bioprocess can be realized under conditions suitable for the autotrophic metabolic process, because the process occurred without addition of acetate. H2S emissions from landfill sites would be substantially reduced if this bioprocess was introduced. PMID:25680916

Fang, Yuan; Du, Yao; Feng, Huan; Hu, Li-Fang; Shen, Dong-Sheng; Long, Yu-Yang

2015-04-01

16

Oxidation-Reduction Equilibria  

NSDL National Science Digital Library

This 11-page PDF document is part of an environmental geochemistry course taught by Dr. David Sherman at the University of Bristol. Topics include oxidation-reduction reactions and oxidation states, the Nerst Equation, Eh-pH diagrams, and redox environments in nature. Also included are the calculation of Eh from concentrations and the prediction of stable oxidation states. Helpful diagrams accompany the text.

David M. Sherman

17

Effects of sulfide and low redox potential on the inhibition of nitrous oxide reduction by acetylene in Pseudomonas nautica.  

PubMed

Membrane introduction mass spectrometry was used to investigate the inhibitory effect of acetylene on the nitrous oxide reductase activity of intact cells of Pseudomonas nautica. We studied the effects of the concentrations of nitrate and sulfide, and the redox potential, which have all been implicated in causing a decrease in the inhibitory effects of acetylene during measurements of denitrification in natural environments. There was no evidence that the concentration of nitrate influenced the effect of acetylene. Lowering the redox potential with the reductant Ti(III)-nitrilotriacetate caused a slight alleviation of acetylene inhibition. Much greater effects at the same redox potential were obtained with concentrations of sulfide in the range 1-10 microM. PMID:1526461

Jensen, K M; Cox, R P

1992-09-01

18

Using oxidation-reduction potential (ORP) and pH value for process control of shortcut nitrification-denitrification.  

PubMed

A new low cost technology for simultaneous carbon-nitrogen removal from soybean wastewater has been developed in this study. The technology is performed through shortcut nitrification-denitrification. The process operated under realtime control of aeration and mixing time. The shortcut nitrification-denitrification in sequencing batch reactor (SBR) was achieved efficiently and steadily by controlling temperature (28 +/- 0.5 degrees C) and using real-time control strategies. This enabled the prevention of nitrite oxidation, leading to lower operational costs. The feasibility of oxidation-reduction potential (ORP) and pH value as control parameter for shortcut nitrification-denitrification process was also investigated. Results showed that the average removal efficiency of ammonium was more than 95%, and nitrosation rate (NO2(-)-N/NOx(-)-N) was reached to 96%. At the same time, the variation of oxidation--reduction potential (ORP) and pH value was well related to organic matter degradation and ammonium oxidation in SBR. So that judgment on the ending of nitrification and denitrification can be based on the inflection point on the varied curve of ORP and pH throughout each SBR processing cycle, and thus reducing aeration and mixing time for saving energy source. The method saves organic energy up to 40% of chemical oxygen demand (COD) in denitrification process, which should reduce the need for an extra external source of organic carbon. Shorter hydraulic retention time should allow the volume of the reactors to diminish, and thus diminish investment costs. Lower oxygen demand of about 25% gives lower exploitation costs. PMID:14672326

Gao, Da-Wen; Peng, Yong-Zhen; Liang, Hong; Wang, Peng

2003-01-01

19

Oxidation-reduction potentials in a salt marsh: Spatial patterns and interactions with primary production  

Microsoft Academic Search

Spurtina alterniflora oxidizes the sediments in which it grows through both passive oxygen release and active metabolic processes. Eh is higher in the root zone of this grass than in the sediment below the root zone or in unvegetated sediments. Sediments underlying the tall form of S. aZterniJorcl are more oxidized than those under the short form, and sediment redox

BRIAN L. HOWES; ROBERT W. HOWARTH; JOHN M. TEAL; IVAN VALIELA

1981-01-01

20

INTRACELLULAR OXIDATION-REDUCTION STUDIES  

PubMed Central

Twenty-five oxidation-reduction indicators were injected in oxidized or reduced form into Amoeba dubia and Amœba proteus under controlled conditions of oxygen access. (1) Under anaerobiosis the ameba was able to reduce completely all the reversible oxidation-reduction indicators down to and including indigo disulfonate. (2) Under anaerobiosis the ameba was unable to reoxidize six of the most easily oxidizable indicators. (3) Under aerobiosis the ameba was able to reduce completely all the indicators down to and including 1-naphthol-2-sulfonate indo-2, 6-dichlorophenol. Toluylene blue, methylene blue and indigo tetrasulfonate were sometimes completely and sometimes only partly reduced, depending on the quantity of indicator injected and the duration of observation. (4) The time of reduction varied approximately with the size of the injection. Reduction was more rapid under anaerobiosis than under aerobiosis, more rapid in active than in sluggish cells and was retarded by toxic compounds. (5) Sulfonated compounds were somewhat toxic, as a rule. In interpreting reduction phenomena of micro injection, it is necessary to take into consideration the intensity, capacity and rate factors. It then becomes apparent that the ameba has a high reducing potential lying on the rH scale below the zone of indigo disulfonate. The reducing capacity of the ameba seems to be relatively great in the region of the simple indophenols and of a progressively diminishing magnitude as the zone of the indigos is approached. Material of high reduction potential appears to be generated within the ameba at a measurable rate. These phenomena, observed in the interior of the cell with the aid of indicators, parallel very closely those found in reduction electrode studies on bacterial cultures. PMID:19872422

Cohen, Barnett; Chambers, Robert; Reznikoff, Paul

1928-01-01

21

Effect of reducing agents on oxidation-reduction potential and the outgrowth of Clostridium botulinum type E spores.  

PubMed Central

Oxidation-reduction potential (Eh) levels were measured and standardized to pH (Eh7) for Trypticase soy broth containing various concentrations of reducing agents. Prereduced Trypticase soy broth with no added reducing agents exhibited a potential of -141 mV. Ascorbic acid at 0.2 to 0.005% and sodium thioglycolate at concentrations below 0.05% produced an Eh7 higher than the prereduced Trypticase soy broth containing no added reducing agents. The addition of cysteine hydrochloride,2-mercaptoethanol, and sodium formaldehyde sulfoxylate to prereduced Trypticase soy broth resulted in a reduction of Eh7 compared to the system without added reducing agents. The order of relative reducing intensity (from highest to lowest) for the reducing agents when comparing molar concentration was: sodium formaldehyde sulfoxylate,2-mercaptoethanol, cysteine hydrochloride, sodium thioglycolate, and ascorbic acid. Optimal growth of the test organism occurred at low Eh7 and low concentration of the reducing agents. A direct correlation existed between growth of the test organism and -Eh7 x -log concentration of the reducing agent. PMID:384903

Smith, M V; Pierson, M D

1979-01-01

22

Potential Role of Nitrite for Abiotic Fe(II) Oxidation and Cell Encrustation during Nitrate Reduction by Denitrifying Bacteria  

E-print Network

Reduction by Denitrifying Bacteria Nicole Klueglein,a Fabian Zeitvogel,b York-Dieter Stierhof,c Matthias and microoxic conditions. While most of the mix- otrophic nitrate-reducing Fe(II)-oxidizing bacteria become assemblage of Fe(II)-oxidizing bacteria in nature and compli- cates our ability to delineate microbial Fe

Konhauser, Kurt

23

Reversible potentials for steps in methanol and formic acid oxidation to CO2; adsorption energies of intermediates on the ideal electrocatalyst for methanol oxidation and CO2 reduction.  

PubMed

Quantum chemical theory is used to identify the reasons for platinum's limitations as an electrocatalyst for oxidizing methanol at fuel cell anodes. The linear Gibbs energy relation (LGER) method is employed to predict reversible potentials for reaction steps for intermediates on the electrode surface. In this procedure, standard reversible potentials are calculated for the reactions in bulk solution phase and then they are perturbed using calculated adsorption bond strengths to the electrode surface, yielding the equilibrium potentials for each electron transfer step for adsorbed intermediates. Adsorption properties of ideal electrocatalysts for the methanol oxidation are found by imposing the condition that the reversible potential of each electron transfer step equals that for the overall reaction. The adsorption bond strengths that provide the ideal properties also apply to formic acid oxidation and carbon dioxide reduction. It is instructive to think of the ideal electrocatalyst as a lens that focusses the reversible potentials for the n individual electron transfer steps to the reversible potential for the n-electron process. It is found that the ideal catalyst will adsorb many intermediates, including HOOC, CO, OCH, HOC, HOCH, HOCH2, and OCH3 more weakly than platinum, and OOCH and OH more strongly. For example, for one possible pathway it is necessary to weaken adsorption bond strengths for HOCH2, HOCH, OCH, HOOC by about 0.5 eV, weaken adsorption CO by about 1.1 eV and strengthen OH adsorption by about 0.6 eV. These results imply a need for developing new multi-component catalysts. PMID:24741672

Anderson, Alfred B; Asiri, Haleema Aied

2014-06-14

24

Synthesis of poly-hydroxyalkanoates from activated sludge under various oxidation-reduction potentials  

Microsoft Academic Search

The production of poly-hydroxyalkanoates (PHA) from the activated sludge subjected to conditions with various oxidationreduction\\u000a potentials (ORPs) was investigated. By controlling the dissolved oxygen concentration in the cultural media, the ORP were\\u000a kept at preset levels of ?20, ?10, 0, and +10 mV. With glucose as the dedicated carbon source, we have demonstrated a correlating\\u000a relationship with the ORP’s in

Wenfeng Hu; Yujie Wang; Fenglin Hua; Hong Chua; nShirleyngai Sin; Hoifu Yu

2006-01-01

25

Influence of the sewage sludge stabilization process on the value of its oxidation-reduction potential.  

PubMed

The paper presents the study of a sewage sludge subjected to the process of the autothermal thermophilic stabilization (autothermal thermophilic aerobic digestion (ATAD)), which occurs in a two-stage installation. This study was conducted at the municipal wastewater treatment installation in 2010 and 2011. A thickened sludge was examined in an intermediate tank from which it was next being transferred to successive ATAD installation reactors. The content of the dry mass and organic substances was checked in a raw sludge after the first installation stage and after the ATAD process. Also, the levels of the chemical oxygen demand, the pH and the temperature were measured. During the process, the redox potential was measured. Collected results were subjected to statistical analysis. Our main attention was focused on measurements of the redox potential and further the usefulness of this measurement for the evaluation of the process was considered. The way its values were changing was determined. In the thickened sludge prior to the ATAD process, the value of the redox potential oscillated from 329.90 mV to -108.50 mV. In the first-stage reactor, this value dropped significantly and held within a range between -509.80 mV and -214.60 mV. In the second installation stage, this value ranged between -561.60 mV and -306.40 mV. During the study, fully sanitized and stabilized sludge was obtained. The paper presents the evaluation of the conducted research and conclusions ensuing from it. PMID:25145168

Bartkowska, Izabela

2014-01-01

26

Electrode measurements of the oxidation-reduction potential in the Gotland Deep using medium-term moored profiling instrumentation  

NASA Astrophysics Data System (ADS)

The variation of in situ redox potential (Eh) was studied in the stratified water column (30 - 185 m) of the central Baltic Sea, for a period of 56 days (November, 2010 - January, 2011) using the Gotland Deep Environmental Sampling Station (GODESS) in order to identify the processes that control Eh. During the deployment of the mooring 170 profiles of hydro-physical parameters were registered, including the oxidation-reduction potential, pH, dissolved oxygen, chlorophyll a fluorescence, turbidity, temperature and conductivity. In general, the measured Eh (with respect to standard hydrogen electrode, SHE) ranged from - 55 to 167 mV. A comparison of the measured Eh with that calculated for the particular redox couples was carried out by applying the Nernst-equation. The standard reduction potentials were corrected for temperature and pH. Furthermore, the concentrations of the most important redox components such as Fe, Mn, N, O, C and S used for comparison were estimated by using empirical functions or were based on measurements of discrete water samples, taken at the time of deployment and recovery of the mooring. The results reveal that the reduction of Fe(III) essentially controls the electrode potential of the redox sensor in most parts of the anoxic waters. Below the redoxcline the reduction of hematite and then ferric oxyhydroxid could be related to the redox potential and somewhat deeper Fe(III)/Fe(II) was found to be the dominant redox couple. Theoretically a mixed potential theory should have been applied because in natural waters a variety of redox pairs is present but Fe couples appear to dominate all the other redox equlibria. This could be explained by the relatively high exchange current of Fe and by the high concentrations (up to 1.5 µM) present at those depths in the study area. However, there are still gaps in our knowledge about the cycling of redox-sensitive elements and long-term moored profiling instrumentations may help to improve our understanding. Thus, we are pursuing the use of in situ analyzers for electro active compounds on moored systems in the future. In this case, analyzer data would be associated with chemical and physical parameters measured with high resolution in time and space, giving information on mixing processes and reaction kinetics. This approach is required to assess the relevance, for instance, of intrusions of oxygenated waters, vertical eddy-diffusion and fluctuations caused by internal waves on the cycle of redox-sensitive elements. This is particularly important as lateral transport appears to play a dominant role along isopycnal surfaces, especially in medium-sized stratified basins and yet have not been investigated extensively in the Baltic Sea with respect to the cycles of the most electro-active compounds.

Meyer, David; Prien, Ralf; Dellwig, Olaf; Schulz-Bull, Detlef

2013-04-01

27

Use of oxidation reduction potentials in TIE procedures for confirmation of metal toxicity  

SciTech Connect

In support of its ``Policy for the Development of Water Quality-based Toxics Control,`` EPA has developed procedures for isolating and identifying he causes of aquatic toxicity in complex waste mixtures. Chelation procedures using EDTA and sodium thiosulfate are recommended by EPA. While useful to determine whether aquatic toxicity in a water is caused by metals, these tests do not allow for unambiguous identification of toxicity from metal ions. An additional possible method of testing for metal toxicity was investigated, utilizing zero valent metal treatment agents. Metals having high (positive) redox potentials are said to be more noble. These ions can be reduced to the zero valent state and removed from water by metals that are more electronegative. The metal used as a treatment agent must be essentially non-toxic to aquatic test species. Magnesium, iron, and manganese were investigated as zero valent treatment agents. Tests were performed on solutions containing ions of cadmium, copper, nickel, zinc, mercury, cobalt, arsenic, and chrome at 400 ppb in 15% Perrier water or well water prior to treatment. Metals (2--4g) were placed into 0.5 or 1 L of test solutions and shaken for 1 hour. The bulk metal was removed from solution. The solution was aerated for 10 minutes, filtered to remove additional precipitates and pH adjusted to 7.3 with HCl before toxicity testing. ICP-MS and ICP-AES analyses were conducted on aliquots of treated and untreated waters. Magnesium effectively removed all test ions. High concentrations of dissolved magnesium in treated solutions may have interfered with the toxicity tests. Iron metal was effective in removing a number of the metal cations tested, but toxicity was not noticeably reduced. Manganese was not as effective as magnesium in removing all test ions but gave promising test results. Toxicity was markedly decreased after manganese treatment.

McKenzie, D.E.; Wendling, J.M.; Grothe, D.R.; Moser, M. [Monsanto Co., St. Louis, MO (United States). Environmental Sciences Center

1995-12-31

28

Real-time treatment of dairy manure: implications of oxidation reduction potential regimes to nutrient management strategies.  

PubMed

A pilot-scale sequencing batch reactor (SBR) was operated at a dairy farm to test real-time based control in winter operation conditions. A combination of high loading and low oxidation reduction potential (ORP) conditions in the aerobic stage of SBR treatment (an end value of -50 to -150 mV) inhibited nitrification while maintaining carbon removal. After a period of over-aeration over several cycles, the ORP at the end of the aerobic stage increased to values of 50-75 mV. Subsequently, nitrification was observed, accompanied by higher total cycle times. Significant increase in removal efficiencies of ammonical nitrogen (alpha<0.0001) and chemical oxygen demand (alpha<0.001) were observed for the high ORP phase. It is postulated that higher ORP regimes are needed for nitrification. In low ORP regimes, nitrification is absent or occurs at an extremely low rate. It is also noted that nitrifying systems treating high strength animal manure can possibly lead to unacceptably high levels of effluent nitrate+nitrite nitrogen (NO(x)-N). Two manure management schemes are proposed that give the farmer an option to either retain the nutrients, or remove them from the wastewater. Some advantages and disadvantages of the schemes are also discussed. PMID:17467983

Qureshi, Asif; Lo, K Victor; Liao, Ping H; Mavinic, Donald S

2008-03-01

29

Characteristics of oxidation-reduction potential, VFAs, SCOD, N, and P in an ATAD system under different thermophilic temperatures.  

PubMed

One-stage autoheated thermophilic aerobic digestion (ATAD) can stabilize sludge to meet class A standard. In this study, batch experiments were conducted to investigate the characteristics of oxidation-reduction potential (ORP), volatile fatty acids (VFAs), soluble chemical oxygen demand (SCOD), and nutrients at different temperatures (45, 55, and 65 °C) in the one-stage ATAD. Results showed that the ORP values remained between approximately -350 and -120 mV in the primary 5-day digestion despite of excessive aeration in the digester, indicating that the aeration level could be decreased in an ATAD system to save energy. The pH exhibited a poor correlation (R (2)?

Cheng, Jiehong; Kong, Feng; Zhu, Jun; Wu, Xiao

2015-01-01

30

Effects of molecular oxygen, oxidation-reduction potential, and antioxidants upon in vitro replication of Treponema pallidum subsp. pallidum.  

PubMed Central

The effects of various concentrations of dithiothreitol, molecular oxygen, and several antioxidants upon the in vitro replication of Treponema pallidum were studied. The optimal dithiothreitol concentration was between 0.65 and 1.62 mM, and the optimum oxygen concentration was 3.0% +/- 0.5% in both the presence and absence of additional antioxidants. It was discovered that the reduced sulfhydryl concentration and the oxidation-reduction potential of the medium were stabilized after 5 days. The water-soluble antioxidants cobalt chloride, cocarboxylase, mannitol, and histidine were individually tested for their ability to increase treponemal growth in vitro. The optimum concentrations for these antioxidants were 21 nM, 4.3 nM, 0.55 mM, and 0.23 mM, respectively. When combined at these concentrations, the mixture of antioxidants stimulated the in vitro replication of T. pallidum. The number of treponemes in cultures with the antioxidants averaged a 59-fold increase, compared with a 43-fold increase in cultures lacking the antioxidants. It was further demonstrated that histidine and mannitol were the most critical components of this mixture. Catalase and superoxide dismutase were investigated for their ability to promote the growth and maintain viability of T. pallidum in tissue culture. The optimum concentrations for these enzymes were 10,000 U/liter and 25,000 U/liter, respectively. When these enzymes and the above antioxidants were combined and added to a chemically reduced modified Eagle medium, the treponemes increased an average of 70-fold, compared with an average of 35-fold in cultures lacking them. Furthermore, this medium, T. pallidum culture medium, supported the replication of T. pallidum at oxygen concentrations from 5 to 7% with little loss in yield or viability. The lipid-soluble antioxidants vitamin A and vitamin E acetate were also shown to enhance the in vitro growth of T. pallidum in this medium. PMID:2285317

Cox, D L; Riley, B; Chang, P; Sayahtaheri, S; Tassell, S; Hevelone, J

1990-01-01

31

Direct electrochemical reduction of metal-oxides  

DOEpatents

A method of controlling the direct electrolytic reduction of a metal oxide or mixtures of metal oxides to the corresponding metal or metals. A non-consumable anode and a cathode and a salt electrolyte with a first reference electrode near the non-consumable anode and a second reference electrode near the cathode are used. Oxygen gas is produced and removed from the cell. The anode potential is compared to the first reference electrode to prevent anode dissolution and gas evolution other than oxygen, and the cathode potential is compared to the second reference electrode to prevent production of reductant metal from ions in the electrolyte.

Redey, Laszlo I. (Downers Grove, IL); Gourishankar, Karthick (Downers Grove, IL)

2003-01-01

32

A comparison of oxidation-reduction potentials calculated from the As(V)/As(III) and Fe(III)/Fe(II) couples with measured platinum-electrode potentials in groundwater  

NASA Astrophysics Data System (ADS)

Oxidation-reduction (redox) potentials calculated from arsenic speciation showed fair correlation with measured Pt-electrode potentials (Eh) in shallow groundwaters in east-central Illinois. The observed bias in calculated potentials relative to measured Eh values could not be explained by analytical imprecision. Redox potentials calculated from Fe concentrations showed better correlation with measured potentials than the As potentials. Arsenic speciation may be a useful supplement to Eh measurements and concentrations of other solutes, but is probably not a good indicator of redox conditions when used alone.

Holm, Thomas R.; Curtiss, Charles D.

1989-12-01

33

[Growth and proton-potassium exchange in Enterococcus hirae: protonophore effect and the role of oxidation-reduction potential].  

PubMed

Enterococcus hirae ATCC 9790 are able to grow under anaerobic conditions during the fermentation of sugars (pH 8.0) in the presence of the protonophore carbonylcyanide-m-chlorophenylhydrazone at a lesser specific growth rate. As bacteria grow, the acidification of the external medium and a drop in the redox potential from positive to negative (up to -220 mV) values occur. The reducer dithiothreitol, which maintains the negative values of the redox potential, increases the growth rate and acidification of the medium, recovering thereby the effect of the protonophore (without interacting with it). Conversely, the impermeable oxidizer ferricyanide, while maintaining positive values of the redox potential, inhibits the bacterial growth. These results indicate the role of the proton-motive force and importance of reducing processes in bacterial growth. The proton-potassium exchange is inhibited by carbonylcyanide-m-chlorophenylhydazone but is restored with dithiothreitol. Dithiothreiol is able to substitute the proton-motive force; however, ferricyanide and dithiothreitol may also directly affect the bacterial membrane. PMID:16808350

Poladian, A; Kirakosian, G; Trchunian, A

2006-01-01

34

ChemTeacher Resource: Oxidation Reduction Reactions  

NSDL National Science Digital Library

This computer resource goes over oxidation reduction reactions and how they are broken down into half reactions. It explains which half reaction is the oxidation reaction and which one is the reduction, then has some summary questions at the end.

2012-08-02

35

Potential Role of Nitrite for Abiotic Fe(II) Oxidation and Cell Encrustation during Nitrate Reduction by Denitrifying Bacteria  

PubMed Central

Microorganisms have been observed to oxidize Fe(II) at neutral pH under anoxic and microoxic conditions. While most of the mixotrophic nitrate-reducing Fe(II)-oxidizing bacteria become encrusted with Fe(III)-rich minerals, photoautotrophic and microaerophilic Fe(II) oxidizers avoid cell encrustation. The Fe(II) oxidation mechanisms and the reasons for encrustation remain largely unresolved. Here we used cultivation-based methods and electron microscopy to compare two previously described nitrate-reducing Fe(II) oxidizers ( Acidovorax sp. strain BoFeN1 and Pseudogulbenkiania sp. strain 2002) and two heterotrophic nitrate reducers (Paracoccus denitrificans ATCC 19367 and P. denitrificans Pd 1222). All four strains oxidized ?8 mM Fe(II) within 5 days in the presence of 5 mM acetate and accumulated nitrite (maximum concentrations of 0.8 to 1.0 mM) in the culture media. Iron(III) minerals, mainly goethite, formed and precipitated extracellularly in close proximity to the cell surface. Interestingly, mineral formation was also observed within the periplasm and cytoplasm; intracellular mineralization is expected to be physiologically disadvantageous, yet acetate consumption continued to be observed even at an advanced stage of Fe(II) oxidation. Extracellular polymeric substances (EPS) were detected by lectin staining with fluorescence microscopy, particularly in the presence of Fe(II), suggesting that EPS production is a response to Fe(II) toxicity or a strategy to decrease encrustation. Based on the data presented here, we propose a nitrite-driven, indirect mechanism of cell encrustation whereby nitrite forms during heterotrophic denitrification and abiotically oxidizes Fe(II). This work adds to the known assemblage of Fe(II)-oxidizing bacteria in nature and complicates our ability to delineate microbial Fe(II) oxidation in ancient microbes preserved as fossils in the geological record. PMID:24271182

Klueglein, Nicole; Zeitvogel, Fabian; Stierhof, York-Dieter; Floetenmeyer, Matthias; Konhauser, Kurt O.; Obst, Martin

2014-01-01

36

Benzene oxidation coupled to sulfate reduction  

USGS Publications Warehouse

Highly reduced sediments from San Diego Bay, Calif., that were incubated under strictly anaerobic conditions metabolized benzene within 55 days when they were exposed initially to I ??M benzene. The rate of benzene metabolism increased as benzene was added back to the benzene-adapted sediments. When a [14C]benzene tracer was included with the benzene added to benzene-adapted sediments, 92% of the added radioactivity was recovered as 14CO2. Molybdate, an inhibitor of sulfate reduction, inhibited benzene uptake and production of 14CO2 from [14C]benzene. Benzene metabolism stopped when the sediments became sulfate depleted, and benzene uptake resumed when sulfate was added again. The stoichiometry of benzene uptake and sulfate reduction was consistent with the hypothesis that sulfate was the principal electron acceptor for benzene oxidation. Isotope trapping experiments performed with [14C]benzene revealed that there was no production of such potential extracellular intermediates of benzene oxidation as phenol, benzoate, p-hydroxybenzoate, cyclohexane, catechol, and acetate. The results demonstrate that benzene can be oxidized in the absence of O2, with sulfate serving as the electron acceptor, and suggest that some sulfate reducers are capable of completely oxidizing benzene to carbon dioxide without the production of extracellular intermediates. Although anaerobic benzene oxidation coupled to chelated Fe(III) has been documented previously, the study reported here provides the first example of a natural sediment compound that can serve as an electron acceptor for anaerobic benzene oxidation.

Lovley, D.R.; Coates, J.D.; Woodward, J.C.; Phillips, E.J.P.

1995-01-01

37

Oxidation--reduction potentials of molybdenum and iron--sulphur centres in nitrate reductase from Escherichia coli.  

PubMed Central

The potentials of the couples Mo(IV)--(Mo(V) and Mo(V)--Mo(VI) in nitrate reductase from Escherichia coli K12 were measured as + 180 mV and + 220 mV respectively at pH 7.14. The potentials associated with two other e.p.r. signals, believed to be due to iron--sulphur centres, were measured as + 50 mV and + 80 mV. PMID:373749

Vincent, S P

1979-01-01

38

Molecular Modeling of Environmentally Important Processes: Reduction Potentials  

ERIC Educational Resources Information Center

The increasing use of computational quantum chemistry in the modeling of environmentally important processes is described. The employment of computational quantum mechanics for the prediction of oxidation-reduction potential for solutes in an aqueous medium is discussed.

Lewis, Anne; Bumpus, John A.; Truhlar, Donald G.; Cramer, Christopher J.

2004-01-01

39

RELATIONSHIPS BETWEEN OXIDATION-REDUCTION, OXIDANT, AND PH IN DRINKING WATER  

EPA Science Inventory

Oxidation and reduction (redox) reactions are very important in drinking water. Oxidation-reduction potential (ORP) measurements reflect the redox state of water. Redox measurements are not widely made by drinking water utilities in part because they are not well understood. The ...

40

Oxidation and Reduction Reactions in Organic Chemistry  

ERIC Educational Resources Information Center

A variety of approaches to the concept of oxidation and reduction appear in organic textbooks. The method proposed here is different than most published approaches. The oxidation state is calculated by totaling the number of heterogeneous atoms, [pi]-bonds, and rings. A comparison of the oxidation states of reactant and product determine what type…

Shibley, Ivan A., Jr.; Amaral, Katie E.; Aurentz, David J.; McCaully, Ronald J.

2010-01-01

41

Carbothermal reduction of metal-oxide powders by synthetic pitch to carbide and nitride ceramics  

Microsoft Academic Search

The carbothermal reduction potential of mesophase synthetic pitch was investigated. Powders of cobalt oxide, iron oxide, zirconium\\u000a oxide, manganese oxide, silicon oxide, vanadium oxide, tantalum oxide, tungsten oxide, chromium oxide, and titanium oxide\\u000a were mixed with pitch and pyrolyzed at a variety of temperatures up to 1500 °C in nitrogen, 5% hydrogen balance argon, and\\u000a anhydrous ammonia. Pitch was found superior

B. M. Eick; J. P. Youngblood

2009-01-01

42

Polarographic reduction of N-oxides of isoxazolines  

Microsoft Academic Search

1.The polarographic behavior of the N-oxide of 3-carbomethoxyisoxazoline, the N-oxide of 3-phenylisoxazoline, and 3-phenylisoxazoline was investigated, and a mechanism was proposed for their electroreduction.2.The displacement of the half-wave potentials of the electroreduction of the N-oxide of 3-carbomethoxyisoxazoline in the positive direction with increasing pH of the solutions and the anomalous change in the curvature of the wave of the reduction

V. N. Leibzon; S. G. Mairanovskii; É. I. Konnik

1971-01-01

43

Reduction of metal oxides through mechanochemical processing  

DOEpatents

The low temperature reduction of a metal oxide using mechanochemical processing techniques. The reduction reactions are induced mechanically by milling the reactants. In one embodiment of the invention, titanium oxide TiO.sub.2 is milled with CaH.sub.2 to produce TiH.sub.2. Low temperature heat treating, in the range of 400.degree. C. to 700.degree. C., can be used to remove the hydrogen in the titanium hydride.

Froes, Francis H. (Moscow, ID); Eranezhuth, Baburaj G. (Moscow, ID); Senkov, Oleg N. (Moscow, ID)

2000-01-01

44

Stabilized tin-oxide-based oxidation/reduction catalysts  

NASA Technical Reports Server (NTRS)

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony Neal (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor)

2008-01-01

45

High-Resolution Distribution of Temperature, Particle and Oxidation/Reduction Potential Anomalies From a Submarine Hydrothermal System: Brothers Volcano, Kermadec Arc  

NASA Astrophysics Data System (ADS)

The complex relationships between geological setting and hydrothermal venting have, to date, largely been explored with ship-based surveys that effectively examine regional relationships, or with remotely operated vehicles (ROV) and manned submersibles which allow close examination of individual vent fields. Higher- resolution surveys than are possible with ship-based techniques and broader surveys than are practical with ROVs and manned submersibles are necessary for more thoroughly understanding hydrothermal systems and their impact on ocean ecosystems. Autonomous vehicles (AUVs), such as the WHOI Autonomous Benthic Explorer (ABE) can be programmed to conduct high-resolution surveys that systematically cover a broad area of seafloor. Brothers volcano, a hydrothermally active submarine caldera volcano located on the Kermadec arc northwest of New Zealand, was surveyed in July-August 2007 using ABE. Brothers caldera is ~3 km in diameter with a floor depth of 1850 m and walls that rise 290-530 m above the caldera floor. A dacite cone with a summit depth of ~1200 m sits within the caldera, partially merging with the southern caldera wall. Prior to the survey, active hydrothermal vents were known to be perched along the NW caldera wall and located at three sites on the cone. The enclosed caldera, presence of known vent fields with differing geochemical characteristics, and existence of at least one currently inactive site made Brothers volcano an ideal site for a high-resolution survey to explore in greater detail the mass, thermal and geochemical exchanges of hydrothermal systems. During our expedition, the caldera walls and dacite cone (~7 km2) were completely surveyed by ABE with 50-60 m trackline spacing at an altitude of 50 m above the seafloor. Hydrothermal plumes were mapped with ABE's integrated CTD (conductivity- temperature-depth) and sensors measuring optical backscatter (particle concentrations) and oxidation- reduction potential (ORP; indicating the presence of reduced chemical species). This survey resulted in the first high-resolution map of temperature, particle and ORP anomalies within a hydrothermally active submarine caldera. New details about the extent and structure of the known active vent fields were revealed, and a new area of active venting was discovered along the west caldera wall. Additionally, relationships between source vents, buoyant plumes, and neutrally buoyant regional plumes mapped using standard surface ship methods can be compared. Simultaneously acquired bathymetry and magnetic anomaly data show correlations between the geomorphology of the caldera, magnetic alterations and patterns of past and present hydrothermal venting.

Walker, S. L.; Baker, E. T.; de Ronde, C. E.; Yoerger, D.; Embley, R. W.; Davy, B.; Merle, S. G.; Resing, J. A.; Nakamura, K.

2008-12-01

46

Reduction of Metal Oxide to Metal using Ionic Liquids  

SciTech Connect

A novel pathway for the high efficiency production of metal from metal oxide means of electrolysis in ionic liquids at low temperature was investigated. The main emphasis was to eliminate the use of carbon and high temperature application in the reduction of metal oxides to metals. The emphasis of this research was to produce metals such as Zn, and Pb that are normally produced by the application of very high temperatures. The reduction of zinc oxide to zinc and lead oxide to lead were investigated. This study involved three steps in accomplishing the final goal of reduction of metal oxide to metal using ionic liquids: 1) Dissolution of metal oxide in an ionic liquid, 2) Determination of reduction potential using cyclic voltammetry (CV) and 3) Reduction of the dissolved metal oxide. Ionic liquids provide additional advantage by offering a wide potential range for the deposition. In each and every step of the process, more than one process variable has been examined. Experimental results for electrochemical extraction of Zn from ZnO and Pb from PbO using eutectic mixtures of Urea ((NH2)2CO) and Choline chloride (HOC2H4N(CH3)3+Cl-) or (ChCl) in a molar ratio 2:1, varying voltage and temperatures were carried out. Fourier Transform Infra-Red (FTIR) spectroscopy studies of ionic liquids with and without metal oxide additions were conducted. FTIR and induction coupled plasma spectroscopy (ICPS) was used in the characterization of the metal oxide dissolved ionic liquid. Electrochemical experiments were conducted using EG&G potentiostat/galvanostat with three electrode cell systems. Cyclic voltammetry was used in the determination of reduction potentials for the deposition of metals. Chronoamperometric experiments were carried out in the potential range of -0.6V to -1.9V for lead and -1.4V to -1.9V for zinc. The deposits were characterized using XRD and SEM-EDS for phase, morphological and elemental analysis. The results showed that pure metal was deposited on the cathode. Successful extraction of metal from metal oxide dissolved in Urea/ChCl (2:1) was accomplished. The current efficiencies were relatively high in both the metal deposition processes with current efficiency greater than 86% for lead and 95% for zinc. This technology will advance the metal oxide reduction process by increasing the process efficiency and also eliminate the production of CO2 which makes this an environmentally benign technology for metal extraction.

Dr. Ramana Reddy

2012-04-12

47

The oxidation-reduction potential of the reaction-centre chlorophyll (P700) in Photosystem I. Evidence for multiple components in electron-paramagnetic-resonance signal 1 at low temperature.  

PubMed Central

The oxidation-reduction potential of the reaction-centre chlorophyll of Photosystem I (P700) in spinach chloroplasts was determined by using the ability of the reaction centre to photoreduce the bound ferredoxin and to photo-oxidize P700 on illumination at 20K as an indicator of the oxidation state of P700. This procedure shows that P700 is oxidized with Em (pH8.0)(mid-point redox potential at pH8.0)congruent to +375mV. Further oxidation of the chloroplast preparations by high concentrations of K3Fe(CN)6(10mM) in the presence of mediating dyes leads to the appearance of a large radical signal with an apparent Em congruent to +470mVA second, light-inducible, radical also appears over the same potential range. We propose that these signals are due to bulk chlorophyll oxidation and not, as was previously thought [Knaff & Malkin (1973) Arch. Biochem. Biophys. 159, 555-562], to reaction-centre oxidation. A number of optical techniques were used to determine Em of P700. Dual-wavelength spectroscopy (697-720nm) indicates Em congruent to +460-+480mV. The spectrum of the sample during the titration showed a large contribution to the signal by bulk chlorophyll oxidation, in agreement with the electron-paramagnetic-resonance results and those of Ke, Sugahara & Shaw [(1975) Biochim. Biophys. Acta 408, 12-25]. The light-induced absorbance change at 435 nm, usually attributed to P700, showed a potential dependence similar to that of bulk chlorophyll oxidation. Determination of Em of P700 on the basis of the appearance of the P700 signal in oxidized-versus-reduced difference spectra showed Em (pH8.0) congruent to +360mV. Measurements of the effect of potential on the irreversible photo-oxidation of P700 at 77K showed that P700 became oxidized in this potential range. We conclude that the reaction-centre chlorophyll of Photosystem I has Em (pH8.0) congruent to +375mV. PMID:192214

Evans, M C; Sihra, C K; Slabas, A R

1977-01-01

48

41 CFR 101-30.702 - Determining item reduction potential.  

Code of Federal Regulations, 2010 CFR

...2010-07-01 true Determining item reduction potential. 101-30.702 Section 101-30...101-30.702 Determining item reduction potential. Item reduction studies are...determine whether sufficient item reduction potential appears to exist. Item reduction...

2010-07-01

49

Extracellular Dopamine Potentiates Mn-Induced Oxidative Stress, Lifespan Reduction, and Dopaminergic Neurodegeneration in a BLI-3–Dependent Manner in Caenorhabditis elegans  

PubMed Central

Parkinson's disease (PD)-mimicking drugs and pesticides, and more recently PD-associated gene mutations, have been studied in cell cultures and mammalian models to decipher the molecular basis of PD. Thus far, a dozen of genes have been identified that are responsible for inherited PD. However they only account for about 8% of PD cases, most of the cases likely involving environmental contributions. Environmental manganese (Mn) exposure represents an established risk factor for PD occurrence, and both PD and Mn-intoxicated patients display a characteristic extrapyramidal syndrome primarily involving dopaminergic (DAergic) neurodegeneration with shared common molecular mechanisms. To better understand the specificity of DAergic neurodegeneration, we studied Mn toxicity in vivo in Caenorhabditis elegans. Combining genetics and biochemical assays, we established that extracellular, and not intracellular, dopamine (DA) is responsible for Mn-induced DAergic neurodegeneration and that this process (1) requires functional DA-reuptake transporter (DAT-1) and (2) is associated with oxidative stress and lifespan reduction. Overexpression of the anti-oxidant transcription factor, SKN-1, affords protection against Mn toxicity, while the DA-dependency of Mn toxicity requires the NADPH dual-oxidase BLI-3. These results suggest that in vivo BLI-3 activity promotes the conversion of extracellular DA into toxic reactive species, which, in turn, can be taken up by DAT-1 in DAergic neurons, thus leading to oxidative stress and cell degeneration. PMID:20865164

Benedetto, Alexandre; Au, Catherine; Avila, Daiana Silva; Milatovic, Dejan; Aschner, Michael

2010-01-01

50

Role of Ser457 of NADPH-cytochrome P450 oxidoreductase in catalysis and control of FAD oxidation-reduction potential.  

PubMed

Site-directed mutagenesis of Ser457 of NADPH-cytochrome P450 oxidoreductase demonstrates that this residue plays a major role in both hydride transfer from NADPH to FAD and modulation of FAD redox potential. Substitution of Ser457 with alanine or cysteine decreases the rates of reduction of the substrates cytochrome c and potassium ferricyanide approximately 100-fold, while substitution with threonine produces a 20-fold decrease in activity. No changes are observed in k(m)NADPH, KiNADP+, or flavin content, indicating that these substitutions have no effect on cofactor binding but affect catalysis only. k(m)cyt c values are decreased in parallel with the observed decreases in the rates of the reductive half-reaction. Stopped-flow studies with the S457A mutant show a 100-fold decrease in the rate of flavin reduction. The primary deuterium isotope effect on Kcat for cytochrome c reduction increases from 2.7 for the wild-type enzyme to 9.0 for the S457A mutant, consistent with a change in the rate-determining step from NADP+ release in the wild-type enzyme to hydride transfer in the S457A mutant. The primary deuterium isotope effect on K1 for flavin reduction at high ionic strength (I = 535 mM) increases from 12.2 for the wild-type enzyme to > 20 for the S457A mutant, consistent again with an increase in the relative rate limitation of hydride transfer. Furthermore, anaerobic titration of S457A indicates that the redox potential of the FAD semiquinone has been decreased. Data presented in this study support the hypothesis that Ser457 is involved in hydrogen bonding interactions which stabilize both the transition state for hydride transfer and the reduced FAD. PMID:8755724

Shen, A L; Kasper, C B

1996-07-23

51

Ethylene oxide potential toxicity.  

PubMed

The future of ethylene oxide (EO) sterilization has been questioned, owing to its associated toxicity. EO has been around for more than 60 years, mainly due to its recognized characteristics of reliability and effectiveness, coupled with the process flexibility, as well as its compatibility with most mechanical devices. Despite the well-known EO toxicity, the undesirable effects of medical devices' EO residues on the patient's health have not yet been well established. There are limitations related to the current risk-assessment studies. To overcome these drawbacks, demands on greater safety are increasing, which lead to improvements in sterilizers and aeration equipment, as well as the design of the processes. The paper under evaluation highlights risks related to EO sterilization of materials used during processing of stem cells for transplantation, but is an example of a study where the dose of the residues in the devices is not considered. PMID:18452382

da Cunha Mendes, Gisela Cristina; da Silva Brandão, Teresa Ribeiro; Miranda Silva, Cristina Luisa

2008-05-01

52

Potential Reduction Algorithms Kurt M. Anstreicher  

E-print Network

, and a potential function with which to measure the progress of the algorithm. It was quickly shown that the non's original potential function gave rise to potential reduction algorithms having the state­of­the­ art potential functions. In the last section we describe various modifications and extensions of the algorithms

Anstreicher, Kurt M.

53

Suspension Hydrogen Reduction of Iron Oxide Concentrates  

SciTech Connect

The objective of the project is to develop a new ironmaking technology based on hydrogen and fine iron oxide concentrates in a suspension reduction process. The ultimate objective of the new technology is to replace the blast furnace and to drastically reduce CO2 emissions in the steel industry. The goals of this phase of development are; the performance of detailed material and energy balances, thermochemical and equilibrium calculations for sulfur and phosphorus impurities, the determination of the complete kinetics of hydrogen reduction and bench-scale testing of the suspension reduction process using a large laboratory flash reactor.

H.Y. Sohn

2008-03-31

54

Sequential electrolytic oxidation and reduction of aqueous phase energetic compounds.  

PubMed

Contamination of soils and groundwater with energetic compounds has been documented at many former ammunition manufacturing plants and ranges. Recent research at Colorado State University (CSU) has demonstrated the potential utility of electrolytic degradation of organic compounds using an electrolytic permeable reactive barrier (e-barrier). In principle, an electrolytic approach to degrade aqueous energetic compounds such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) or 2,4,6-trinitrotoluene (TNT) can overcome limitations of management strategies that involve solely oxidation or reduction, through sequential oxidation-reduction or reduction-oxidation. The objective of this proof-of-concept research was to evaluate transformation of aqueous phase RDX and TNT in flow-through electrolytic reactors. Laboratory experiments were conducted using six identical column reactors containing porous media and expanded titanium-mixed-metal-oxide electrodes. Three columns tested TNT transformation and three tested RDXtransformation. Electrode sequence was varied between columns and one column for each contaminant acted as a no-voltage control. Over 97% of TNT and 93% of RDX was transformed in the reactors under sequential oxidation-reduction. Significant accumulation of known degradation intermediates was not observed under sequential oxidation-reduction. Removal of approximately 90% of TNT and 40% of RDX was observed under sequential reduction-oxidation. Power requirements on the order of 3 W/m2 were measured during the experiment. This suggests that an in-situ electrolytic approach may be cost-practical for managing groundwater contaminated with explosive compounds. PMID:16382952

Gilbert, David M; Sale, Tom C

2005-12-01

55

Preliminary reduction of oxidized nickel ores  

NASA Astrophysics Data System (ADS)

The laws of gas reduction of oxidized nickel ores (ONOs) are studied. The theoretical prerequisites of the selective reduction of ONO nickel, which are based on the difference between the oxygen partial pressures over the NiO-Ni and FeO-Fe systems, are discussed. The effect of the oxygen partial pressure during reducing roasting of ONOs of ferruginous and magnesia types on the reduction parameters and the quality of the ferronickel formed upon subsequent melting of cinders is experimentally investigated. The optimum conditions of preliminary gas reduction of ONOs are determined. Melting of the cinder of reducing roasting leads to the formation of nickel-rich ferronickel (20-50 wt % Ni for various types of ores) upon the extraction of nickel into ferronickel of >95%, which substantially exceeds the parameters of the existing commercial processes.

Pakhomov, R. A.; Starykh, R. V.

2014-11-01

56

Microbial reduction of manganese oxides - Interactions with iron and sulfur  

NASA Technical Reports Server (NTRS)

Alteromonas putrefaciens (strain MR-1) is capable of rapid Mn(IV) reduction under conditions of neutral pH and temperatures characteristic of the Oneida Lake, New York, sediments from which it was isolated. MR-1 also reduces Fe(3+) to Fe(2+), and disproportionates thiosulfate to sulfide and sulfite; independently, the Fe(2+) and sulfide act as rapid reductants of Mn. The addition of Fe(3+) or thiosulfate to cultures of MR-1 in the presence of oxidized Mn increases the rate and the extent of Mn reduction relative to that observed in the absence of Fe(3+) or thiosulfate. Furthermore, when Fe(3+) and Mn oxides are present conjointly, Fe(2+) does not appear until the reduction of the oxidized Mn is complete. These results demonstrate that the observed rates of Fe(2+) and sulfide production may underestimate the total rates of Fe and sulfate reduction in those environments containing oxidized Mn. These results also demonstrate the potential impact that a single microbe can exert on sediment geochemistry, and provide the basis for preliminary models of the complexity of microbial and geochemical interactions that occur.

Myers, Charles R.; Nealson, Kenneth H.

1988-01-01

57

Some Tungsten Oxidation-Reduction Chemistry: A Paint Pot Titration.  

ERIC Educational Resources Information Center

Reports an oxidation-reduction experiment using tungsten, somewhat analogous to the classical student experiment involving oxidation-reduction of vanadium. Includes experimental procedures, results, and toxicity/cost of tungsten compounds. (Author/JN)

Pickering, Miles; Monts, David L.

1982-01-01

58

Oxidation enthalpies for reduction of ceria surfaces  

NASA Astrophysics Data System (ADS)

The thermodynamic properties of surface ceria were investigated through equilibrium isotherms determined by flow titration and coulometric titration measurements on high-surface-area ceria and ceria supported on La-modified alumina (LA). While the surface area of pure ceria was found to be unstable under redox conditions, the extent of reduction at 873 K and a P(O 2) of 1.6 × 10 -26 atm increased with surface area. Because ceria/LA samples were stable, equilibrium isotherms were determined between 873 and 973 K on a 30-wt% ceria sample. Oxidation enthalpies on ceria/LA were found to vary with the extent of reduction, ranging from -500 kJ/mol O 2 at low extents of reduction to near the bulk value of -760 kJ/mol O 2 at higher extents. To determine whether +3 dopants could affect the oxidation enthalpies for ceria, isotherms were measured for Sm +3-doped ceria (SDC) and Y +3-doped ceria. These dopants were found to remove the phase transition observed in pure ceria below 973 K but appeared to have minimal effect on the oxidation enthalpies. Implications of these results for catalytic applications of ceria are discussed.

Zhou, Gong; Shah, Parag R.; Montini, Tiziano; Fornasiero, Paolo; Gorte, Raymond J.

2007-06-01

59

Oxidation-reduction catalyst and its process of use  

NASA Technical Reports Server (NTRS)

This invention relates generally to a ruthenium stabilized oxidation-reduction catalyst useful for oxidizing carbon monoxide, and volatile organic compounds, and reducing nitrogen oxide species in oxidizing environments, substantially without the formation of toxic and volatile ruthenium oxide species upon said oxidizing environment being at high temperatures.

Jordan, Jeffrey D. (Inventor); Watkins, Anthony Neal (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor)

2008-01-01

60

Whisker growth in reduction of oxides  

SciTech Connect

Cobalt ferrite (CoFe/sub 2/O/sub 4/) was reduced in CO-CO/sub 2/ gas mixtures at 1173 K at total pressure between 6.6 x 10/sup 3/ and 3.3 x 10/sup 4/ Pa, and at CO/CO/sub 2/ ratios between 2.9 and 11.8. The reduction led to the formation of metal whiskers. The experiments and analysis emphasized the behavior of the whisker diameter during reduction. Impurities such as calcium and potassium stimulate metal nucleation but appear to inhibit catalysis of gas reactions at the metal/gas/oxide triple junction. The steady-state whisker diameter was found to be inversely proportional to the total gas pressure at constant CO/CO/sub 2/ ratio. A new model is proposed to explain whisker development. It considers metal/oxide interface diffusion coupled with a metal/oxide/gas triple junction reaction at the whisker base as the process determining the whisker diameter.

Chang, M.; De Jonghe, L.C.

1984-12-01

61

Whisker growth in reduction of oxides  

SciTech Connect

Cobalt ferrite (CoFe/sub 2/O/sub 4/) was reduced in CO-CO/sub 2/ gas mixtures at 1173 K at total pressure between 6.6 X 10/sup 3/ and 3.3 X 10/sup 4/ Pa, and at CO/CO/sub 2/ ratios between 2.9 and 11.8. The reduction led to the formation of metal whiskers. The experiments and analysis emphasized the behavior of the whisker diameter during reduction. Impurities such as calcium and potassium stimulate metal nucleation but appear to inhibit catalysis of gas reactions at the metal/gas/oxide triple junction. The steady state whisker diameter was found to be inversely proportional to the total gas pressure at constant CO/CO/sub 2/ ratio. A new model is proposed to explain whisker development. It considers metal/oxide interface diffusion coupled with a metal/oxide/gas triple junction reaction at the whisker base as the process determining the whisker diameter.

Chang, M.; De Jonghe, L.C.

1984-12-01

62

Lithium metal reduction of plutonium oxide to produce plutonium metal  

DOEpatents

A method is described for the chemical reduction of plutonium oxides to plutonium metal by the use of pure lithium metal. Lithium metal is used to reduce plutonium oxide to alpha plutonium metal (alpha-Pu). The lithium oxide by-product is reclaimed by sublimation and converted to the chloride salt, and after electrolysis, is removed as lithium metal. Zinc may be used as a solvent metal to improve thermodynamics of the reduction reaction at lower temperatures. Lithium metal reduction enables plutonium oxide reduction without the production of huge quantities of CaO--CaCl.sub.2 residues normally produced in conventional direct oxide reduction processes.

Coops, Melvin S. (Livermore, CA)

1992-01-01

63

Biomimetic and microbial reduction of nitric oxide  

SciTech Connect

The biomimetic reduction of nitric oxide (NO) to nitrous oxide (N{sub 2}O) by dithiothreitol in the presence of cyanocobalamin and cobalt-centered porphyrins has been investigated. Reactions were monitored directly using Fourier Transform Infrared (FTIR) Spectroscopy vapor-phase spectra. Reaction rates were twofold faster for the corrin than for the cobalt-centered porphyrins. The stoichiometry showed the loss of two molecules of NO per molecule of N{sub 2}O produced. We have also demonstrated that the facultative anaerobe and chemoautotroph, Thiobacillus denitrificans, can be cultured anoxically in batch reactors using NO as a terminal electron acceptor with reduction to elemental nitrogen (N{sub 2}). We have proposed that the concentrated stream of NO{sub x}, as obtained from certain regenerable processes for the gas desulfurization and NO{sub x} removal, could be converted to N{sub 2} for disposal by contact with a culture of T. denitrificans. Four heterotrophic bacteria have also been identified that may be grown in batch cultures with succinate, yeast extract, or heat and alkali pretreated sewage sludge as carbon and energy sources and NO as a terminal electron acceptor. These are Paracoccus dentrificans, Pseudomonas denitrificans, Alcaligens denitrificans, and Thiophaera pantotropha.

Potter, W.T.; Le, U.; Ronda, S. [Univ. of Tulsa, OK (United States)] [and others

1995-12-31

64

Gaseous reduction of iron oxides: Part III. Reduction-oxidation of porous and dense iron oxides and iron  

Microsoft Academic Search

The internal reduction of high-grade granular hematite ore in hydrogen and carbon monoxide, and also the internal oxidation\\u000a of porous iron granules in CO2-CO mixtures have been investigated. To assist the interpretation of the rate data for porous iron and iron oxides, rate measurements\\u000a have been made also with dense wustite, previously grown on iron by oxidation. The iron formed

E. T. Turkdogan; J. V. Vinters

1972-01-01

65

Plutonium Oxidation and Subsequent Reduction by Mn (IV) Minerals  

SciTech Connect

Plutonium sorbed to rock tuff was preferentially associated with manganese oxides. On tuff and synthetic pyrolusite (Mn{sup IV}O{sub 2}), Pu(IV) or Pu(V) was initially oxidized, but over time Pu(IV) became the predominant oxidation state of sorbed Pu. Reduction of Pu(V/VI), even on non-oxidizing surfaces, is proposed to result from a lower Gibbs free energy of the hydrolyzed Pu(IV) surface species versus that of the Pu(V) or Pu(VI) surface species. This work suggests that despite initial oxidation of sorbed Pu by oxidizing surfaces to more soluble forms, the less mobile form of Pu, Pu(IV), will dominate Pu solid phase speciation during long term geologic storage. The safe design of a radioactive waste or spent nuclear fuel geologic repository requires a risk assessment of radionuclides that may potentially be released into the surrounding environment. Geochemical knowledge of the radionuclide and the surrounding environment is required for predicting subsurface fate and transport. Although difficult even in simple systems, this task grows increasingly complicated for constituents, like Pu, that exhibit complex environmental chemistries. The environmental behavior of Pu can be influenced by complexation, precipitation, adsorption, colloid formation, and oxidation/reduction (redox) reactions (1-3). To predict the environmental mobility of Pu, the most important of these factors is Pu oxidation state. This is because Pu(IV) is generally 2 to 3 orders of magnitude less mobile than Pu(V) in most environments (4). Further complicating matters, Pu commonly exists simultaneously in several oxidation states (5, 6). Choppin (7) reported Pu may exist as Pu(IV), Pu(V), or Pu(VI) oxic natural groundwaters. It is generally accepted that plutonium associated with suspended particulate matter is predominantly Pu(IV) (8-10), whereas Pu in the aqueous phase is predominantly Pu(V) (2, 11-13). The influence of the character of Mn-containing minerals expected to be found in subsurface repository environments on Pu oxidation state distributions has been the subject of much recent research. Kenney-Kennicutt and Morse (14), Duff et al. (15), and Morgenstern and Choppin (16) observed oxidation of Pu facilitated by Mn(IV)-bearing minerals. Conversely, Shaughnessy et al. (17) used X-ray Absorption near-edge spectroscopy (XANES) to show reduction of Pu(VI) by hausmannite (Mn{sup II}Mn{sub 2}{sup III}O{sub 4}) and manganite ({gamma}-Mn{sup III}OOH) and Kersting et al., (18) observed reduction of Pu(VI) by pyrolusite (Mn{sup IV}O{sub 2}). In this paper, we attempt to reconcile the apparently conflicting datasets by showing that Mn-bearing minerals can indeed oxidize Pu, however, if the oxidized species remains on the solid phase, the oxidation step competes with the formation of Pu(IV) that becomes the predominant solid phase Pu species with time. The experimental approach we took was to conduct longer term (approximately two years later) oxidation state analyses on the Pu sorbed to Yucca Mountain tuff (initial analysis reported by Duff et al., (15)) and measure the time-dependant changes in the oxidation state distribution of Pu in the presence of the Mn mineral pyrolusite.

KAPLAN, DANIEL

2005-09-13

66

Nitrogen oxide reduction in Wolinella succinogenes and Campylobacter species.  

PubMed Central

Wolinella succinogenes cells and extracts reduced nitric oxide, and cells, but not extracts, reduced nitrous oxide. Formate-reduced W. succinogenes extracts generated the 573-nm peak in difference spectra seen previously in response to nitric oxide in denitrifiers. The type strains of several Campylobacter species did not reduce either gaseous oxide. Cells, but not extracts, of C. fetus subspecies (fetus and venerealis) reduced nitrous oxide; acetylene inhibited reduction. Neither cells nor extracts reduced nitric oxide. PMID:7130133

Payne, W J; Grant, M A; Shapleigh, J; Hoffman, P

1982-01-01

67

Catalyst for reduction of nitrogen oxides  

DOEpatents

A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N2O was not detected (detection limit: 0.6 percent N2O).

Ott, Kevin C.

2010-04-06

68

REPEATED REDUCTIVE AND OXIDATIVE TREATMENTS ON GRANULAR ACTIVATED CARBON  

EPA Science Inventory

Fenton oxidation and Fenton oxidation preceded by reduction solutions were applied to granular activated carbon (GAC) to chemically regenerate the adsorbent. No adsorbate was present on the GAC so physicochemical effects from chemically aggressive regeneration of the carbon coul...

69

Potential reduction of DSN uplink energy cost  

NASA Technical Reports Server (NTRS)

DSN Earth stations typically transmit more power than that required to meet minimum specifications for uplink performance. Energy and cost savings that could result from matching the uplink power to the amount required for specified performance are studied. The Galileo mission was selected as a case study. Although substantial reduction in transmitted energy is possible, potential savings in source energy (oil or electricity) savings are much less. This is because of the rising inefficiency in power conversion and radio frequency power generation that accompanies reduced power output.

Dolinsky, S.; Degroot, N. F.

1982-01-01

70

Incipient hydrous oxide species as inhibitors of reduction processes at noble metal electrode  

SciTech Connect

Evidence is presented to illustrate the important role of hydrous oxide in noble metal electrocatalysis. It was demonstrated, for instance, that in the case of gold in acid the onset/termination potential, under potential sweep conditions, for hydrazine oxidation and persulfate or iodate reduction occurred at the end of the hydrous oxide reduction peak (recorded for a thick film growth grown by potential multicycling); there was also a maximum in the faradaic ac response for gold in acid in the same region. Both gold and platinum were investigated in acid and base electrolytes. In some cases a range of potential, rather than a discrete value, was found to be involved, different species react with (or are inhibited by) different types (or coverages) of these submonolayer species. In some, possibly electrocatalytically nondemanding, reduction reactions the hydrous oxide seemed to have little effect.

Burke, L.D.; O'Sullivan, J.F.; O'Dwyer, K.J.; Scannell, R.A.; Ahern, M.J.G.; McCarthy, M.M. (Dept. of Chemistry, Univ. College, Cork (IE))

1990-08-01

71

Reduction of Amine N-Oxides by Diboron Reagents  

PubMed Central

Facile reduction of alkylamino-, anilino-, and pyridyl-N-oxides can be achieved via the use of diboron reagents, predominantly bis(pinacolato)- and in some cases bis(catecholato)diboron [(pinB)2 and (catB)2, respectively]. Reductions occur upon simply mixing the amine N-oxide and the diboron reagent in a suitable solvent, at a suitable temperature. Extremely fast reductions of alkylamino- and anilino-N-oxides occur, whereas pyridyl-N-oxides undergo slower reduction. The reaction is tolerant of a variety of functionalities such as hydroxyl, thiol, and cyano groups, as well as halogens. Notably, a sensitive nucleoside N-oxide has also been reduced efficiently. The different rates with which alkylamino- and pyridyl-N-oxides are reduced has been used to perform stepwise reduction of the N,N’-dioxide of (S)-(–)-nicotine. Because it was observed that (pinB)2 was unaffected by the water of hydration in amine oxides, the feasibility of using water as solvent was evaluated. These reactions also proceeded exceptionally well, giving high product yields. In constrast to the reactions with (pinB)2, triethylborane reduced alkylamino-N-oxides, but pyridine N-oxide did not undergo efficient reduction even at elevated temperature. Finally, the mechanism of the reductive process by (pinB)2 has been probed by 1H and 11B NMR. PMID:21812467

Kokatla, Hari Prasad; Thomson, Paul F.; Bae, Suyeal; Doddi, Venkata Ramana; Lakshman, Mahesh K.

2011-01-01

72

Outer Cell Surface Components Essential for Fe(III) Oxide Reduction by Geobacter metallireducens  

PubMed Central

Geobacter species are important Fe(III) reducers in a diversity of soils and sediments. Mechanisms for Fe(III) oxide reduction have been studied in detail in Geobacter sulfurreducens, but a number of the most thoroughly studied outer surface components of G. sulfurreducens, particularly c-type cytochromes, are not well conserved among Geobacter species. In order to identify cellular components potentially important for Fe(III) oxide reduction in Geobacter metallireducens, gene transcript abundance was compared in cells grown on Fe(III) oxide or soluble Fe(III) citrate with whole-genome microarrays. Outer-surface cytochromes were also identified. Deletion of genes for c-type cytochromes that had higher transcript abundance during growth on Fe(III) oxides and/or were detected in the outer-surface protein fraction identified six c-type cytochrome genes, that when deleted removed the capacity for Fe(III) oxide reduction. Several of the c-type cytochromes which were essential for Fe(III) oxide reduction in G. metallireducens have homologs in G. sulfurreducens that are not important for Fe(III) oxide reduction. Other genes essential for Fe(III) oxide reduction included a gene predicted to encode an NHL (Ncl-1–HT2A–Lin-41) repeat-containing protein and a gene potentially involved in pili glycosylation. Genes associated with flagellum-based motility, chemotaxis, and pili had higher transcript abundance during growth on Fe(III) oxide, consistent with the previously proposed importance of these components in Fe(III) oxide reduction. These results demonstrate that there are similarities in extracellular electron transfer between G. metallireducens and G. sulfurreducens but the outer-surface c-type cytochromes involved in Fe(III) oxide reduction are different. PMID:23183974

Smith, Jessica A.; Lovley, Derek R.

2013-01-01

73

Carbothermal Reduction of Manganese Oxide in Different Gas Atmospheres  

Microsoft Academic Search

Carbothermal reduction of manganese oxides was studied in hydrogen, helium, and argon at different temperatures and carbon-to-manganese\\u000a oxide ratios. Isothermal and temperature programmed carbothermal reduction experiments were conducted in a fixed bed reactor\\u000a in a vertical tube furnace, with on-line monitoring of gas composition by the CO-CO2 infrared sensor. The extent of reduction was calculated using the off-gas composition and

Ring Kononov; Oleg Ostrovski; Samir Ganguly

2008-01-01

74

Oxidation-Reduction Resistance of Advanced Copper Alloys  

NASA Technical Reports Server (NTRS)

Resistance to oxidation and blanching is a key issue for advanced copper alloys under development for NASA's next generation of reusable launch vehicles. Candidate alloys, including dispersion-strengthened Cu-Cr-Nb, solution-strengthened Cu-Ag-Zr, and ODS Cu-Al2O3, are being evaluated for oxidation resistance by static TGA exposures in low-p(O2) and cyclic oxidation in air, and by cyclic oxidation-reduction exposures (using air for oxidation and CO/CO2 or H2/Ar for reduction) to simulate expected service environments. The test protocol and results are presented.

Greenbauer-Seng, L. (Technical Monitor); Thomas-Ogbuji, L.; Humphrey, D. L.; Setlock, J. A.

2003-01-01

75

Anaerobic Benzene Oxidation in the Fe(III) Reduction Zone of  

E-print Network

Anaerobic Benzene Oxidation in the Fe(III) Reduction Zone of Petroleum-Contaminated Aquifers R O B North, University of Massachusetts, Amherst, Massachusetts 01003 The potential for anaerobic benzene. [14C]Benzene was not oxidized to 14CO2 at most sites examined, which is consistent with previous

Lovley, Derek

76

Hydrazine-reduction of graphite-and graphene oxide Sungjin Park a,b  

E-print Network

of reduced GO particles was lower than that of reduced graphene oxide and the BET surface area of reduced GO conducting graphene-based platelets on a large scale [7­11], and thus its potential in composites [12Hydrazine-reduction of graphite- and graphene oxide Sungjin Park a,b , Jinho An a , Jeffrey R

77

Plutonium Oxidation and Subsequent Reduction by Mn (IV) Minerals  

Microsoft Academic Search

Plutonium sorbed to rock tuff was preferentially associated with manganese oxides. On tuff and synthetic pyrolusite (Mn{sup IV}Oâ), Pu(IV) or Pu(V) was initially oxidized, but over time Pu(IV) became the predominant oxidation state of sorbed Pu. Reduction of Pu(V\\/VI), even on non-oxidizing surfaces, is proposed to result from a lower Gibbs free energy of the hydrolyzed Pu(IV) surface species versus

2005-01-01

78

In situ UV-visible assessment of extent of reduction during oxidation reactions on oxide catalysts  

E-print Network

to increase with increasing VOx domain size and propane/O2 ratio. Oxidative dehydrogenation (ODH) of alkanes the electronic structure of oxide domains commonly used as alkane ODH catalysts.1,2,4,5 Edge energies dependIn situ UV-visible assessment of extent of reduction during oxidation reactions on oxide catalysts

Bell, Alexis T.

79

Oxidative reduction of glove box wipers with a downdraft thermal oxidation system  

SciTech Connect

Wipers (rags) used for decontamination and glove box cleanup in the Plutonium Finishing Plant often become soaked with acid and plutonium-rich solutions. After use, these wipers are rinsed in a dilute NaOH solution and dried, but the formation of unstable nitrates and the hydrogen gas caused by hydrolysis are concerns that still must be addressed. This report gives the results of testing with a small downdraft thermal oxidation system that was constructed by Pacific Northwest National Laboratory to stabilize glove wiper waste, reduce the waste volume, and reclaim plutonium. Proof-of-principle testing was conducted with eight runs using various combinations of rag moisture and chemical pretreatment. All runs went to planned completion. Results of these tests indicate that the thermal oxidation system has the potential for providing significant reductions in waste volume. Weight reductions of 150:1 were easily obtainable during this project. Modifications could result in weight reductions of over 200:1, with possible volume reductions of 500:1.

Phelps, M.R.; Wilcox, W.A.

1996-04-01

80

Oxidation and Reduction: Too Many Definitions?  

ERIC Educational Resources Information Center

IUPAC gives several different definitions of oxidation: loss of electrons, increase in oxidation state, loss of hydrogen, or gain of oxygen. Most introductory or general chemistry textbooks use all of these definitions at one time or another, which can lead to some confusion in the minds of first-year chemistry students. Some paradoxical…

Silverstein, Todd P.

2011-01-01

81

DEVELOPMENT OF ELECTROCHEMICAL REDUCTION TECHNOLOGY FOR SPENT OXIDE FUELS  

SciTech Connect

The Advanced Spent Fuel Conditioning Process (ACP) has been under development at Korea Atomic Energy Research Institute (KAERI) since 1997. The concept is to convert spent oxide fuel into metallic form and to remove high heat-load fission products such as Cs and Sr from the spent fuel. The heat power, volume, and radioactivity of spent fuel can decrease by a factor of a quarter via this process. For the realization of ACP, a concept of electrochemical reduction of spent oxide fuel in Li2O-LiCl molten salt was proposed and several cold tests using fresh uranium oxides have been carried out. In this new electrochemical reduction process, electrolysis of Li2O and reduction of uranium oxide are taking place simultaneously at the cathode part of electrolysis cell. The conversion of uranium oxide to uranium metal can reach more than 99% ensuring the feasibility of this process.

Hur, Jin-Mok; Seo, Chung-Seok; Kim, Ik-Soo; Hong, Sun-Seok; Kang, Dae-Seung; Park, Seong-Won

2003-02-27

82

REDUCTION OF NITRIC OXIDE WITH METAL SULFIDES  

EPA Science Inventory

The report gives results of research to determine the technical feasibility of using metal sulfide for the chemical reduction of NOx to N2. Nineteen different metal sulfides were investigated, using a test gas of pure NO. Although most sulfides resulted in some NO reduction, BaS,...

83

Reduction of nitrogen oxides in flue gases  

Microsoft Academic Search

In recent years there has been an unprecedented growth and development in flue gas control technologies capable of reducing NOx emissions to the low levels required by current legislation. Major post-combustion technologies include selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR). The current status of these technologies is summarised, and the advantages and disadvantages of both methods are reviewed.

Miroslav Radojevic

1998-01-01

84

Benzene Oxidation Coupled to Sulfate Reduction  

Microsoft Academic Search

(14C)benzene tracer was included with the benzene added to benzene-adapted sediments, 92% of the added radioactivity was recovered as 14CO2. Molybdate, an inhibitor of sulfate reduction, inhibited benzene uptake and production of 14CO2from ( 14 C)benzene. Benzene metabolism stopped when the sediments became sulfate depleted,andbenzeneuptakeresumedwhensulfatewasaddedagain.Thestoichiometryofbenzeneuptakeand sulfate reduction was consistent with the hypothesis that sulfate was the principal electron acceptor for

DEREK R. LOVLEY; JOHN D. COATES; JOAN C. WOODWARD; ANDELIZABETH J. P. PHILLIPS

1995-01-01

85

Reduction–Oxidation Photocycle Dynamics of Flavins in Starch Films  

PubMed Central

The blue-light photo-reduction (conversion of oxidized flavin quinone via flavin semiquinone to fully reduced flavin hydroquinone) and dark re-oxidation of the flavins riboflavin and lumiflavin in starch (?-amylose) films was studied by absorption and luminescence spectroscopy. Blue-light photo-excitation caused an absorption, fluorescence, and phosphorescence decrease which recovered in the dark. The photo-reduction dark-oxidation cycle could be repeated. The efficiency of photo-reduction decreased with exposed excitation energy, and the speed of re-oxidation in the dark slowed down with time after excitation. The absorption did not fully recover. The fluorescence efficiency after a long time of storage in the dark increased beyond the initial flavin quinone fluorescence efficiency. Flavin photo-excitation is thought to cause starch-flavin restructuring (static fluorescence quenching center formation), enabling enhanced photo-induced starch to flavin electron transfer with subsequent flavin reduction and starch oxidation. In the dark, after light switch-off, thermal reversion of flavin reduction and starch oxidation occurred. PMID:22942758

Penzkofer, Alfons

2012-01-01

86

Line Search in Potential Reduction Algorithms for Linear Programming  

E-print Network

of these algorithms are based on reducing a primal­dual potential function that is first appeared in Todd and Ye [9. Since it is a function­driven algorithm, the potential reduction algorithm is quite generic. ManyLine Search in Potential Reduction Algorithms for Linear Programming Yinyu Ye y September 1989

Ye, Yinyu

87

Quadratic Convergence of PotentialReduction Methods for  

E-print Network

­point pure potential­reduction algorithm for linear programming problems is an­ alyzed. This algorithm the Tanabe­Todd­Ye (TTY) potential function. A polynomial time complexity for the method is demonstrated interior­ point potential­reduction algorithms. We consider linear programs in the standard form: (LP ) min

88

Oxide reduction during triggered-lightning fulgurite formation  

NASA Astrophysics Data System (ADS)

In this study triggered-lightning induced fulgurites were formed in 99.9% pure binary oxides of manganese (MnO) and nickel (NiO) in order to study oxide reduction mechanisms. The fulgurite formation process involved packing the oxide in PVC holders and using the standard rocket-and-wire technique to trigger a lightning strike through the oxide at the International Center for Lightning Research and Testing in Camp Blanding, Florida. These two oxides were chosen from the thermodynamic extrapolation of the oxide stability using the Ellingham Diagram. This diagram indicates that NiO is significantly less stable than MnO. Fulgurites from the pure oxides were analyzed in a scanning electron microscope (SEM); secondary electron images, backscattered images and energy dispersive spectroscopy (EDS) were used to determine the microstructure and composition of the fulgurites. SEM/EDS analysis of the NiO and MnO prior to fulgurite formation confirmed they were pure binary oxides with no metallic contamination. After fulgurite formation, it was found that the nickel oxide fulgurite contained metallic nickel particles; the manganese oxide fulgurite showed no metallic phase formation. Transmission electron microscopy (TEM) examination confirmed that the MnO was a pure oxide with no sign of metallic phase formation. However, TEM results of the NiO showed that approximately 50% of the NiO was reduced to metallic face-centered cubic Ni. The Ni and NiO were observed to be coherent with the [1 0 0]Ni//[1 0 0]NiO and [1 1 0]Ni//[1 1 0]NiO. These results are consistent with the aforementioned thermodynamic stability calculations and show that the presence of carbonaceous material or mixtures of oxides is not necessary for oxide reduction during fulgurite formation. These studies do not rule out the possibility that electrolysis plays a role in oxide reduction. However, these fulgurites were made simultaneously during the same lightning strike and therefore were subjected to the same electrical current, and thus it is proposed the thermodynamic stability of the oxide must play a role in oxide reduction.

Jones, B. E.; Jones, K. S.; Rambo, K. J.; Rakov, V. A.; Jerald, J.; Uman, M. A.

2005-03-01

89

Electrochemical investigation of polyhalide ion oxidation–reduction on carbon nanotube electrodes for redox flow batteries  

Microsoft Academic Search

Polyhalide ions, Br?\\/BrCl2-(ClBr2-), are an important redox couple for redox flow batteries. The oxidation–reduction behavior of polyhalide ions on carbon nanotube (CNT) electrodes has been investigated with cyclic voltammetry and electrochemical impedance spectroscopy. The onset oxidation potential of Br?\\/BrCl2-(ClBr2-) is negatively shifted by>100mV, and the redox current peaks are greatly enhanced on the CNT electrode compared with that on the

Yuyan Shao; Mark H. Engelhard; Yuehe Lin

2009-01-01

90

Reductive mobilization of oxide-bound metals  

SciTech Connect

This project is concerned with the mobilization of MnO{sub 2}- and FeOOH-bound toxic metals in subsurface environments arising from an influx of natural organic matter or organic-containing wastes. Our work to date emphasizes the importance of characterizing the reductant, complexant, and adsorptive characteristics of constituent organic chemicals. Organic chemicals may interact with pollutant metals directly, or may bring about changes in speciation and solubility indirectly by acting upon MnO{sub 2} and FeOOH host phases. The primary application of this work is the understanding of metal sorption and release processes within subsurface environments undergoing changes in redox status.

Stone, A.T.

1992-01-01

91

Reduction Kinetics of Graphene Oxide Determined by Temperature Programmed Desorption  

NASA Astrophysics Data System (ADS)

Graphene oxide, which is an electrical insulator, shows promise for use in several technological applications such as dielectric layers in nanoscale electronic devices or as the active region of chemical sensors. In principle, graphene oxide films could also be used as a precursor for the formation of large-scale graphene films by either thermal or chemical reduction of the graphene oxide. In order to determine the thermal stability and reduction kinetics of graphene oxide, temperature program desorption (TPD) measurements have been performed on multilayer films of graphene oxide deposited on SiO2/Si(100) substrates. The graphene oxide was exfoliated from the graphite oxide source material by slow-stirring in aqueous solution, which produces single-layer platelets with an average lateral size of ˜10 ?m. From the TPD measurements, it was determined that the decomposition process begins at ˜80 ^oC. The primary desorption products of the graphene oxide films for temperatures up to 300 ^oC are H2O, CO2, and CO, with only trace amounts of O2 being detected. An activation energy of 1.4 eV/molecule was determined by assuming an Arrhenius dependence for the decomposition process.

Ventrice, Carl; Clark, Nicholas; Field, Daniel; Geisler, Heike; Jung, Inhwa; Yang, Dongxing; Piner, Richard; Ruoff, Rodney

2009-10-01

92

Proton translocation coupled to trimethylamine N-oxide reduction in anaerobically grown Escherichia coli.  

PubMed Central

Proton translocation coupled to trimethylamine N-oxide reduction was studied in Escherichia coli grown anaerobically in the presence of trimethylamine N-oxide. Rapid acidification of the medium was observed when trimethylamine N-oxide was added to anaerobic cell suspensions of E. coli K-10. Acidification was sensitive to the proton conductor 3,5-di-tert-butyl-4-hydroxybenzylidenemalononitrile (SF6847). No pH change was shown in a strain deficient in trimethylamine N-oxide reductase activity. The apparent H+/trimethylamine N-oxide ratio in cells oxidizing endogenous substrates was 3 to 4 g-ions of H+ translocated per mol of trimethylamine N-oxide added. The addition of trimethylamine N-oxide and formate to ethylenediaminetetraacetic acid-treated cell suspension caused fluorescence quenching of 3,3'-dipropylthiacarbocyanine [diS-C3-(5)], indicating the generation of membrane potential. These results indicate that the reduction of trimethylamine N-oxide in E. coli is catalyzed by an anaerobic electron transfer system, resulting in formation of a proton motive force. Trimethylamine N-oxide reductase activity and proton extrusion were also examined in chlorate-resistant mutants. Reduction of trimethylamine N-oxide occurred in chlC, chlG, and chlE mutants, whereas chlA, chlB, and chlD mutants, which are deficient in the molybdenum cofactor, could not reduce it. Protons were extruded in chlC and chlG mutants, but not in chlA, chlB, and chlD mutants. Trimethylamine N-oxide reductase activity in a chlD mutant was restored to the wild-type level by the addition of 100 microM molybdate to the growth medium, indicating that the same molybdenum cofactor as used by nitrate reductase is required for the trimethylamine N-oxide reductase system. PMID:7031034

Takagi, M; Tsuchiya, T; Ishimoto, M

1981-01-01

93

Process for the reduction of nitrogen oxides in an effluent  

SciTech Connect

This patent describes a process for the reduction of the concentration of nitrogen oxides in the effluent from the combustion of a carbonaceous fuel. The process comprises introducing a heterocyclic hydrocarbon selected from the group consisting of piperazine, piperidine, pyrazine, pyrazole, imidazole, oxazolidone, pyrrole and pyrrolidine into the effluent having an effluent temperature of greater than about 1200{sup 0}F. under conditions effective to reduce the concentration of nitrogen oxides in the effluent.

Epperly, W.R.; Sullivan, J.C.; Sprague, B.N.

1989-09-05

94

Carbothermic reduction of copper, nickel, and cobalt oxides and molybdates  

Microsoft Academic Search

The carbothermic reduction of NiO, CoO, CuO, MoO3, and the MMoO4 (M = Ni, Co, Cu) molybdates has been studied by thermogravimetry. The results demonstrate that the reactivity of the molybdates\\u000a with solid carbon, the sequence of reduction reactions, and the composition of reaction intermediates are determined by the\\u000a reactivity of the constituent oxides, which decreases in the order CuO

N. V. Lebukhova; N. F. Karpovich

2008-01-01

95

Pharmacological potential of cerium oxide nanoparticles  

NASA Astrophysics Data System (ADS)

Nanotechnology promises a revolution in pharmacology to improve or create ex novo therapies. Cerium oxide nanoparticles (nanoceria), well-known as catalysts, possess an astonishing pharmacological potential due to their antioxidant properties, deriving from a fraction of Ce3+ ions present in CeO2. These defects, compensated by oxygen vacancies, are enriched at the surface and therefore in nanosized particles. Reactions involving redox cycles between the Ce3+ and Ce4+ oxidation states allow nanoceria to react catalytically with superoxide and hydrogen peroxide, mimicking the behavior of two key antioxidant enzymes, superoxide dismutase and catalase, potentially abating all noxious intracellular reactive oxygen species (ROS) via a self-regenerating mechanism. Hence nanoceria, apparently well tolerated by the organism, might fight chronic inflammation and the pathologies associated with oxidative stress, which include cancer and neurodegeneration. Here we review the biological effects of nanoceria as they emerge from in vitro and in vivo studies, considering biocompatibility and the peculiar antioxidant mechanisms.

Celardo, Ivana; Pedersen, Jens Z.; Traversa, Enrico; Ghibelli, Lina

2011-04-01

96

Nox control for high nitric oxide concentration flows through combustion-driven reduction  

DOEpatents

An improved method for removing nitrogen oxides from concentrated waste gas streams, in which nitrogen oxides are ignited with a carbonaceous material in the presence of substoichiometric quantities of a primary oxidant, such as air. Additionally, reductants may be ignited along with the nitrogen oxides, carbonaceous material and primary oxidant to achieve greater reduction of nitrogen oxides. A scrubber and regeneration system may also be included to generate a concentrated stream of nitrogen oxides from flue gases for reduction using this method.

Yeh, James T. (Bethel Park, PA); Ekmann, James M. (Bethel Park, PA); Pennline, Henry W. (Bethel Park, PA); Drummond, Charles J. (Churchill, PA)

1989-01-01

97

Oxidative stress adaptation in aggressive prostate cancer may be counteracted by the reduction of glutathione reductase  

PubMed Central

Oxidative stress has been associated with prostate cancer development and progression due to an increase of reactive oxygen species (ROS). However, the mechanisms whereby ROS and the antioxidant system participate in cancer progression remain unclear. In order to clarify the influence of oxidative stress in prostate cancer progression, we performed this study in two human prostate cancer cell lines, PC3 and HPV10 (from metastasis and from localized cancer, respectively) and RWPE1 cells derived from normal prostate epithelium. Cells were treated with hydrogen peroxide (H2O2) and PC3 cells were also treated with diethyl maleate (DEM). The effect on cell growth, viability, mitochondria membrane potential and oxidative stress was analysed. Oxidative stress was evaluated based on ROS production, oxidative lesion of lipids (MDA) and on determination of antioxidants, including enzyme activity of glutathione peroxidase (Gl-Px), glutathione reductase (Gl-Red) and on the quantification of glutathione (GSH), glutathione-s-transferase (GST) and total antioxidant status (TAS). PC3 shows higher ROS production but also the highest GSH levels and Gl-Red activity, possibly contributing to oxidative stress resistance. This is also associated with higher mitochondrial membrane potential, TAS and lower lipid peroxidation. On the other hand, we identified Gl-Red activity reduction as a new strategy in overcoming oxidative stress resistance, by inducing H2O2 cytotoxicity. Therefore these results suggest Gl-Red activity reduction as a new potential therapeutic approach, in prostate cancer. PMID:23650590

Freitas, Mariana; Baldeiras, Inês; Proença, Teresa; Alves, Vera; Mota-Pinto, Anabela; Sarmento-Ribeiro, Ana

2012-01-01

98

Methodology for the effective stabilization of tin-oxide-based oxidation/reduction catalysts  

NASA Technical Reports Server (NTRS)

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony N. (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor)

2011-01-01

99

Unification of catalytic water oxidation and oxygen reduction reactions: amorphous beat crystalline cobalt iron oxides.  

PubMed

Catalytic water splitting to hydrogen and oxygen is considered as one of the convenient routes for the sustainable energy conversion. Bifunctional catalysts for the electrocatalytic oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are pivotal for the energy conversion and storage, and alternatively, the photochemical water oxidation in biomimetic fashion is also considered as the most useful way to convert solar energy into chemical energy. Here we present a facile solvothermal route to control the synthesis of amorphous and crystalline cobalt iron oxides by controlling the crystallinity of the materials with changing solvent and reaction time and further utilize these materials as multifunctional catalysts for the unification of photochemical and electrochemical water oxidation as well as for the oxygen reduction reaction. Notably, the amorphous cobalt iron oxide produces superior catalytic activity over the crystalline one under photochemical and electrochemical water oxidation and oxygen reduction conditions. PMID:25469760

Indra, Arindam; Menezes, Prashanth W; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Das, Chittaranjan; Tallarida, Massimo; Schmeißer, Dieter; Strasser, Peter; Driess, Matthias

2014-12-17

100

Direct oxide reduction demonstration, small-scale studies  

Microsoft Academic Search

This project was initiated to provide process design information to the Plutonium Recovery Project (PRP). Although direct oxide reduction (DOR) has been operated in a production mode both at the Rocky Flats Plant (now operated by EG G, Inc.) and Los Alamos National Laboratory, many aspects of the process are ill-defined. Because the PRP plans include significant DOR capability, a

J. L. Long; D. J. Santi; D. C. Fisher; T. J. Humiston

1991-01-01

101

Metal catalyzed carbonylation and oxidation- reduct ion reactions  

Microsoft Academic Search

By the use of rhodium, rhenium, or palladium complexes as cata- lysts, and cyclodextrins or polyethylene glycols as phase transfer cata- lysts, the s elective reduction or oxidation o f carbonyl compounds, as well as t he s ynthesis of t he latter from olefins, occurs under remarkably mild conditions. olefins, epoxides and thiiranes to acids, esters, and lactones are

Howard Alper

1988-01-01

102

Reflectance and structure changes of iridium oxide films by reduction  

SciTech Connect

The reflectance and structure changes of iridium oxide films by reduction were investigated in an attempt to apply the films to optical data storage media. The films were prepared by the thermal oxidation of iridium-carbon composite films. The films were easily reduced by heating them in 5% H/sub 2/ in Ar at temperatures in the range 100/sup 0/-300/sup 0/C. When the films were reduced, the particles size of Ir metal and the reflectance of the films increased with an increase in the reducing temperature. The reduced films were stable against oxidation at temperatures of 250/sup 0/C or higher. Optical writing on the films was carried out with an argon laser at 0.84W power. The writing mechanism was based on changes in the film's optical properties caused by laser-induced reduction.

Sato, Y.; Yanagida, M.; Yamanaka, H.; Tanigawa, H.

1989-03-01

103

Reduction of aqueous transition metal species on the surfaces of Fe(II)-containing oxides  

USGS Publications Warehouse

Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1-7 at 25??C. For an aqueous transition metal m, such reactions are 3[Fe2+Fe3+2]O4(magnetite) + 2/nmz ??? 4[Fe3+2]O3(maghemite) + Fe2+ + 2/nmz-n and 3[Fe2+Ti]O3(ilmenite) + 2/nmz ??? Fe3+2Ti3O9(pseudorutile) + Fe2+ + 2/nmz-n, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] ??? [Fe(III)] is -0.34 to -0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe2+ (-0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 ?? 10-10 mol m-2 s-1. Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe2+ is oxidized homogeneously in solution to Fe3+. X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental solution. In contrast, magnetite weathered under oxidizing vadose conditions show minimum reactivity toward chromate ions. The ability of Fe(II) oxides to reduce transition metals in soils and groundwaters will be strongly dependent on the redox environment.

White, A.F.; Peterson, M.L.

1996-01-01

104

Tyrosine can protect against oxidative stress through ferryl hemoglobin reduction.  

PubMed

The toxic mechanism of hemoglobin (Hb) under oxidative stress is linked to the formations of highly cytotoxic ferryl species and subsequently heme-to-protein cross-linked derivative of Hb (Hb-X). In this study, we have examined the effects of free tyrosine and its analogues (3-chlorotyrosine, phenylalanine) on the stability of ferryl hemoglobin and the formation of Hb-X. The results showed that free tyrosine (not phenylalanine, 10-500 ?M) was an efficient reducing agent of ferryl species and also effective at preventing the formation of cytotoxic Hb-X. Meanwhile, the dimeric tyrosine was formed as the oxidation product of tyrosine during Hb redox reaction. Compared with free tyrosine, 3-chlorotyrosine, an oxidation product of tyrosine and a proposed biomarker for hypochlorous acid (HOCl) in vivo, exhibited stronger antioxidant properties in Hb-induced oxidative stress, which was consistent with its more efficient ability in the reduction of ferryl species. These results showed that the presence of tyrosine and its derivative in vivo and vitro could ameliorate oxidative damage through ferryl heme reduction. The antioxidant ability, therefore, may provide new insights into the nutritional and physiological significance of free tyrosine with redox active heme proteins-related oxidative stress. PMID:24698734

Lu, Naihao; He, Yingjie; Chen, Chao; Tian, Rong; Xiao, Qiang; Peng, Yi-Yuan

2014-08-01

105

ASSESSMENT OF HOUSEHOLD CARBON FOOTPRINT REDUCTION POTENTIALS  

SciTech Connect

The term ?household carbon footprint? refers to the total annual carbon emissions associated with household consumption of energy, goods, and services. In this project, Lawrence Berkeley National Laboratory developed a carbon footprint modeling framework that characterizes the key underlying technologies and processes that contribute to household carbon footprints in California and the United States. The approach breaks down the carbon footprint by 35 different household fuel end uses and 32 different supply chain fuel end uses. This level of end use detail allows energy and policy analysts to better understand the underlying technologies and processes contributing to the carbon footprint of California households. The modeling framework was applied to estimate the annual home energy and supply chain carbon footprints of a prototypical California household. A preliminary assessment of parameter uncertainty associated with key model input data was also conducted. To illustrate the policy-relevance of this modeling framework, a case study was conducted that analyzed the achievable carbon footprint reductions associated with the adoption of energy efficient household and supply chain technologies.

Kramer, Klaas Jan; Homan, Greg; Brown, Rich; Worrell, Ernst; Masanet, Eric

2009-04-15

106

Ion Association, Solubilities, and Reduction Potentials in Aqueous Solution.  

ERIC Educational Resources Information Center

Incorporates the combined effects of ionic strength and ion association to show how calculations involving ionic equilibria are carried out. Examines the variability of reduction potential data for two aqueous redox systems. Provides several examples. (MVL)

Russo, Steven O.; Hanania, George I. H.

1989-01-01

107

Biological reduction of graphene oxide using plant leaf extracts.  

PubMed

Two-dimensional graphene has attracted significant attention due to its unique mechanical, electrical, thermal, and optical properties. Most commonly employed methods to chemically reduce graphene oxide to graphene use hydrazine or its derivatives as the reducing agent. However, they are highly hazardous and explosive. Various phytochemicals obtained from different natural sources such as leaves and peels of a plant are used as reducing agents in the preparation of different gold, silver, copper, and platinum nanoparticles. In this study, seven plant leaf extracts (Cherry, Magnolia, Platanus, Persimmon, Pine, Maple, and Ginkgo) were compared for their abilities to reduce graphene oxide. The optimized reaction conditions for the reduction of graphene oxide were determined as follows. Type of plant: Cherry (Prunus serrulata), reaction time: 12 h, composition of the reaction mixture: 16.7% v/v of plant leaf extract in total suspension, and temperature: 95°C. The degree of reduction caused by Cherry leaf extract was analyzed by elemental analysis and X-ray photoelectron spectroscopy. The reduction of graphene oxide was also confirmed by ultraviolet-visible spectroscopy, Fourier transform-infrared spectroscopy, Raman spectroscopy, X-ray diffraction, transmission electron microscopy, and thermogravimetric analysis. PMID:24375994

Lee, Geummi; Kim, Beom Soo

2014-01-01

108

Selective catalytic reduction of nitric oxide with ammonia over silica-supported vanadium oxide catalyst  

SciTech Connect

The selective catalytic reduction (SCR) of nitric oxide with excess ammonia in the presence of oxygen on silica-supported vanadium oxide catalyst was studied in a packed-bed reactor, and a mathematical model was proposed for the processes occurring in the reactor. Experimental data were presented for evaluation of the accuracy of the proposed model. Good agreement was observed between the measured and calculated values of the conversion in the outlet of the reactor. Once the validity of the proposed model was verified, it was used to examine the effects of different parameters such as feed temperature, inlet feed composition, and gas hourly space velocity (GHSV) on the conversion of NO over V{sub 2}O{sub 5}/SiO{sub 2} catalyst for practical application. The results for the employed catalyst showed that high NO conversion occurred at temperatures of 280-300C, GHSV less than 2000h{sup -1} (STP), and O{sub 2} concentration greater than 10% v/v. These results clearly demonstrate the high potential for this catalyst to be applied commercially for the control of NOx emissions from flue gases of different sources.

Qajar, J.; Mowla, D. [Shiraz University, Shiraz (Iran)

2009-07-01

109

Direct oxide reduction demonstration, small-scale studies  

SciTech Connect

This project was initiated to provide process design information to the Plutonium Recovery Project (PRP). Although direct oxide reduction (DOR) has been operated in a production mode both at the Rocky Flats Plant (now operated by EG&G, Inc.) and Los Alamos National Laboratory, many aspects of the process are ill-defined. Because the PRP plans include significant DOR capability, a well-defined process should minimize capital cost and maximize productivity. Reduced radiation exposure may also be realized. A detailed, statistically valid investigation of the direct oxide reduction process was carried out utilizing 100 grams or less of plutonium dioxide per experiment. Conditions were established for obtaining 95% + yields. Conclusions drawn from the results of the experimental work were utilized to make recommendations for future large-scale investigative and confirmative work as well large-scale production demonstration work. 4 refs., 5 figs., 14 tabs.

Long, J.L.; Santi, D.J.; Fisher, D.C.; Humiston, T.J.

1991-12-09

110

The role of volatiles in the reduction of iron oxides  

NASA Astrophysics Data System (ADS)

With iron ore reduction processes using coal-ore pellets or mixtures, it is possible that volatiles from the coals can contribute to the overall reduction. By identifying the possible reducing species in the volatiles as H2/CO and simulating these constituents, the rates for H2 and CO were investigated in the temperature and reduction range of interest where hydrogen was the major reductant and studied in detail. In the initial stages of the present study, the fundamentals of hydrogen reduction of fine powder were found to be a complex mechanism of chemical kinetics and mass transfer. Complete uniform reduction for porous and dense iron ores were not observed contrary to existing work regarding this subject. Morphological observations of iron ores reduced at low and high temperatures showed a topochemical receding interface to be dominating with an intermediate region developing for higher temperature samples indicating the importance of pore mass transfer at the later stages of reduction. Although the activation energy of 50˜56 kJ/mole for these powder samples were comparable to the literature values for solely chemical kinetics controlled reactions, the reaction rates were not proportional to sample weight and also did not exhibit complete uniform internal reduction. The calculated mass transfer rates were comparable to the observed rate which suggested that bulk mass transfer is important to the mixed-control. The reaction rate at the mixed control regime was found to be first order with respect to hydrogen partial pressure. Results of reducing iron oxide powders in a mixture of He-40%H2 -5%CO and H2-1%H2S showed that H2S and CO which is involved with the volatiles does not affect the rate at the reduction range of interest indicating the role of volatiles is dominated by the hydrogen reduction. The single composite pellet experiments at 900 and 1000°C showed significant fixed carbon reduction to occur above 1000°C. Depending upon the type of carbon reductant in the composite pellet, secondary reactions with carbon and H2O was possible. Sintering of the pellets did not occur until a significant amount of reduction was obtained and thus for volatile reduction it is likely that the effects of sintering was negligible. To determine the possibility of volatile reduction, a layer of Fe 2O3 powders were spread over HV coals resulting in the reduction of the top layer by about 20% at 1000°C after 1000 seconds. The morphology of the reduced Fe2O3 layer indicated that the reduction is higher near the interface of Coal/Fe2O3. The volatile reduction of a single layer of composite pellet was found to be negligible. However, the reduction of Fe2O3 pellets at the top layer by the volatiles from the bottom layers of a three-layer pellet geometry was observed to be about 15%. From the morphological observations and the computed rates of bulk mass transfer, volatile reduction seems to be controlled by a mixed-controlled mechanism of bulk mass transfer and the limited-mixed control. Using the reduction information obtained from the single pellet experiments reduced in hydrogen, an empirical relationship was obtained to approximately predict the amount of volatile reduction up to 20%.

Sohn, Il

111

1. West facade of Plutonium Concentration Facility (Building 233S), ReductionOxidation ...  

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

1. West facade of Plutonium Concentration Facility (Building 233-S), Reduction-Oxidation Building (REDOX-202-S) to the right. Looking east. - Reduction-Oxidation Complex, Plutonium Concentration Facility, 200 West Area, Richland, Benton County, WA

112

Nitrogen oxides reduction by staged combustion of LCV gas  

E-print Network

August 1990 Major Subject: Agricultural Engineering NITROGEN OXIDES REDUCTION BY STAGED COMBUSTION OF LCV GAS A Thesis by JOSE MANUEL CABRERA SIXTO Approved as to style and content by: Calvin B. Parnell, Jr (Chair of Committee) Wayne A. Le...: Dr. Calvin B. Parnell, Jr. This thesis describes the design, construction and testing of a Low-NO?-stagcd combustor to burn LCV gas derived from agricultural wastes. A cycJone combustor was used as the first stage of the staged combustor. Due...

Cabrera Sixto, Jose Manuel

1990-01-01

113

Oxidation Potentials in Iron and Steel Making  

NASA Astrophysics Data System (ADS)

The state of oxidation of a pyrometallurgical process given by the partial pressure of oxygen and the temperature (the oxidation potential) is one of the important properties monitored and controlled in the smelting and refining of iron and the nonferrous metals. Solid electrolyte sensors based on ZrO2 and a reference electrode such as Cr/Cr2O3 to measure the oxygen pressure found early application in the steel industry, followed soon after in copper, nickel, lead, and zinc smelting. Similar devices are installed in automobile postcombustion/exhaust trains as part of emission control systems. The current discussion reviews this technology as applied in the primary steps of iron and steel making and refining.

Matousek, J. W.

2013-11-01

114

Extent of Reduction of Vanadium Oxides during Catalytic Oxidation of Alkanes Measured by in-Situ UV-Visible Spectroscopy  

E-print Network

Extent of Reduction of Vanadium Oxides during Catalytic Oxidation of Alkanes Measured by in-Situ UV to oxidation reactions using lattice oxygens as reactive intermediates. Introduction Oxidative alkane-visible spectroscopy probes the electronic structure of oxide domains commonly used in alkane ODH catalysis.6

Bell, Alexis T.

115

Catalysis of Reduction and Oxidation Reactions for Application in Gas Particle Filters  

SciTech Connect

The present study is a first part of an investigation addressing the simultaneous occurrence of oxidation and reduction reactions in catalytic filters. It has the objectives (a) to assess the state of knowledge regarding suitable (types of) catalysts for reduction and oxidation, (b) to collect and analyze published information about reaction rates of both NOx reduction and VOC oxidation, and (c) to adjust a lab-scale screening method to the requirements of an activity test with various oxidation/reduction catalysts.

Udron, L.; Turek, T.

2002-09-19

116

Dissimilatory selenate reduction potentials in a diversity of sediment types  

USGS Publications Warehouse

We measured potential rates of bacterial dissimilatory reduction of 75SeO42- to 75Se0 in a diversity of sediment types, with salinities ranging from freshwater (salinity = 1 g/liter) to hypersaline (salinity = 320 g/liter and with pH values ranging from 7.1 to 9.8. Significant biological selenate reduction occurred in all samples with salinities from 1 to 250 g/liter but not in samples with a salinity of 320 g/liter. Potential selenate reduction rates (25 nmol of SeO42- per ml of sediment added with isotope) ranged from 0.07 to 22 ??mol of SeO42- reduced liter-1 h-1. Activity followed Michaelis-Menten kinetics in relation to SeO42- concentration (K(m) of selenate = 7.9 to 720 ??M). There was no linear correlation between potential rates of SeO42- reduction and salinity, pH, concentrations of total Se, porosity, or organic carbon in the sediments. However, potential selenate reduction was correlated with apparent K(m) for selenate and with potential rates of denitrification (r = 0.92 and 0.81, respectively). NO3-, NO2-, MoO42-, and WO42- inhibited selenate reduction activity to different extents in sediments from both Hunter Drain and Massie Slough, Nev. Sulfate partially inhibited activity in sediment from freshwater (salinity = 1 g/liter) Massie Slough samples but not from the saline (salinity = 60 g/liter) Hunter Drain samples. We conclude that dissimilatory selenate reduction in sediments is widespread in nature. In addition, in situ selenate reduction is a first-order reaction, because the ambient concentrations of selenium oxyanions in the sediments were orders of magnitude less than their K(m)s.

Steinberg, N.A.; Oremland, R.S.

1990-01-01

117

Pathogenesis of Chronic Hyperglycemia: From Reductive Stress to Oxidative Stress  

PubMed Central

Chronic overnutrition creates chronic hyperglycemia that can gradually induce insulin resistance and insulin secretion impairment. These disorders, if not intervened, will eventually be followed by appearance of frank diabetes. The mechanisms of this chronic pathogenic process are complex but have been suggested to involve production of reactive oxygen species (ROS) and oxidative stress. In this review, I highlight evidence that reductive stress imposed by overflux of NADH through the mitochondrial electron transport chain is the source of oxidative stress, which is based on establishments that more NADH recycling by mitochondrial complex I leads to more electron leakage and thus more ROS production. The elevated levels of both NADH and ROS can inhibit and inactivate glyceraldehyde 3-phosphate dehydrogenase (GAPDH), respectively, resulting in blockage of the glycolytic pathway and accumulation of glycerol 3-phospate and its prior metabolites along the pathway. This accumulation then initiates all those alternative glucose metabolic pathways such as the polyol pathway and the advanced glycation pathways that otherwise are minor and insignificant under euglycemic conditions. Importantly, all these alternative pathways lead to ROS production, thus aggravating cellular oxidative stress. Therefore, reductive stress followed by oxidative stress comprises a major mechanism of hyperglycemia-induced metabolic syndrome. PMID:25019091

Yan, Liang-Jun

2014-01-01

118

Use of ion conductors in the pyrochemical reduction of oxides  

DOEpatents

An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO[sub 2] oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a [beta]-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca[sup o] used for reducing UO[sub 2] and PuO[sub 2] to U and Pu. 2 figures.

Miller, W.E.; Tomczuk, Z.

1994-02-01

119

Use of ion conductors in the pyrochemical reduction of oxides  

DOEpatents

An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO.sub.2 oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a .beta.-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca.degree. used for reducing UO.sub.2 and PuO.sub.2 to U and Pu.

Miller, William E. (Naperville, IL); Tomczuk, Zygmunt (Lockport, IL)

1994-01-01

120

Thermoelectric Powder Using an Oxide-Reduction Process  

NASA Astrophysics Data System (ADS)

The present study focused on synthesis of Bi0.5Sb1.5Te3 thermoelectric powder using an oxide-reduction process. The phase structure and particle size of the synthesized powders were analyzed using x-ray diffractometry and scanning electron microscopy. The synthesized powder was sintered using the spark plasma sintering method. The thermoelectric properties of the sintered body were evaluated by measuring the Seebeck coefficient, electrical resistivity, and thermal conductivity. Bi0.5Sb1.5Te3 powder was synthesized using a combination of mechanical milling, calcination, and reduction processes, using a mixture of Bi2O3, Sb2O3, and TeO2 powders. The sintered body of the oxide-reduction-synthesized Bi0.5Sb1.5Te3 powder showed p-type thermoelectric characteristics. The thermoelectric properties of the sintered bodies depended on the reduction time. After being reduced for 2 h at 663 K, the sintered body of the Bi0.5Sb1.5Te3 powder showed a figure of merit of approximately 1.0 at room temperature.

Lee, Gilgeun; Ha, Gookhyun

2014-06-01

121

Direct printing and reduction of graphite oxide for flexible supercapacitors  

NASA Astrophysics Data System (ADS)

We report direct printing and photo-thermal reduction of graphite oxide (GO) to obtain a highly porous pattern of interdigitated electrodes, leading to a supercapacitor on a flexible substrate. Key parameters optimized include the amount of GO delivered, the suitable photo-thermal energy level for effective flash reduction, and the substrate properties for appropriate adhesion after reduction. Tests with supercapacitors based on the printed-reduced GO showed performance comparable with commercial supercapacitors: the energy densities were 1.06 and 0.87 mWh/cm3 in ionic and organic electrolytes, respectively. The versatility in the architecture and choice of substrate makes this material promising for smart power applications.

Jung, Hanyung; Ve Cheah, Chang; Jeong, Namjo; Lee, Junghoon

2014-08-01

122

Direct printing and reduction of graphite oxide for flexible supercapacitors  

SciTech Connect

We report direct printing and photo-thermal reduction of graphite oxide (GO) to obtain a highly porous pattern of interdigitated electrodes, leading to a supercapacitor on a flexible substrate. Key parameters optimized include the amount of GO delivered, the suitable photo-thermal energy level for effective flash reduction, and the substrate properties for appropriate adhesion after reduction. Tests with supercapacitors based on the printed-reduced GO showed performance comparable with commercial supercapacitors: the energy densities were 1.06 and 0.87 mWh/cm{sup 3} in ionic and organic electrolytes, respectively. The versatility in the architecture and choice of substrate makes this material promising for smart power applications.

Jung, Hanyung [Department of Nano Science and Technology, Graduate School of Convergence Science and Technology, Seoul National University, Seoul (Korea, Republic of); Ve Cheah, Chang [Department of Mechanical and Aerospace Engineering, Seoul National University, Seoul (Korea, Republic of); Jeong, Namjo [Energy Materials and Convergence Research Department, Korea Institute of Energy Research, Daejeon (Korea, Republic of); Lee, Junghoon, E-mail: jleenano@snu.ac.kr [Department of Nano Science and Technology, Graduate School of Convergence Science and Technology, Seoul National University, Seoul (Korea, Republic of); Department of Mechanical and Aerospace Engineering, Seoul National University, Seoul (Korea, Republic of); Division of WCU Multiscale Mechanical Design, School of Mechanical and Aerospace Engineering, Seoul National University, Seoul (Korea, Republic of)

2014-08-04

123

Highly controllable and green reduction of graphene oxide to flexible graphene film with high strength  

SciTech Connect

Graphical abstract: Highly controllable and green reduction of GO to chemical converted graphene (CCG) was achieved with sodium citrate as a facile reductant. Self-assembly of the as-made CCG sheets results in a flexible CCG film, of which the tensile strength strongly depends on the deoxygenation degree of graphene sheets. - Highlights: • Graphene was synthesized by an effective and environmentally friendly approach. • We introduced a facile X-ray diffraction analysis method to investigate the reduction process from graphene oxide to graphene. • Flexible graphene films were prepared by self-assembly of the graphene sheets. • The strength of the graphene films depends on the reduction degree of graphene. - Abstract: Graphene film with high strength was fabricated by the assembly of graphene sheets derived from graphene oxide (GO) in an effective and environmentally friendly approach. Highly controllable reduction of GO to chemical converted graphene (CCG) was achieved with sodium citrate as a facile reductant, in which the reduction process was monitored by XRD analysis and UV–vis absorption spectra. Self-assembly of the as-made CCG sheets results in a flexible CCG film. This method may open an avenue to the easy and scalable preparation of graphene film with high strength which has promising potentials in many fields where strong, flexible and electrically conductive films are highly demanded.

Wan, Wubo [Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Zhao, Zongbin, E-mail: zbzhao@dlut.edu.cn [Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Hu, Han [Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Gogotsi, Yury [Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Department of Materials Science and Engineering, and A.J. Drexel Nanotechnology Institute, Drexel University, Philadelphia, PA 19104 (United States); Qiu, Jieshan, E-mail: jqiu@dlut.edu.cn [Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China)

2013-11-15

124

Reduction of iron-oxide-carbon composites: part III. Shrinkage of composite pellets during reduction  

SciTech Connect

This article involves the evaluation of the volume change of iron-oxide-carbon composite pellets and its implications on reduction kinetics under conditions prevalent in a rotary hearth furnace (RHF) that were simulated in the laboratory. The pellets, in general, were found to shrink considerably during the reduction due to the loss of carbon and oxygen from the system, sintering of the iron-oxide, and formation of a molten slag phase at localized regions inside the pellets due to the presence of binder and coal/wood-charcoal ash at the reduction temperatures. One of the shortcomings of the RHF ironmaking process has been the inability to use multiple layers of composite pellets because of the impediment in heat transport to the lower layers of a multilayer bed. However, pellet shrinkage was found to have a strong effect on the reduction kinetics by virtue of enhancing the external heat transport to the lower layers. The volume change of the different kinds of composite pellets was studied as a function of reduction temperature and time. The estimation of the change in the amount of external heat transport with varying pellet sizes for a particular layer of a multilayer bed was obtained by conducting heat-transfer tests using inert low-carbon steel spheres. It was found that if the pellets of the top layer of the bed shrink by 30 pct, the external heat transfer to the second layer increases by nearly 6 times.

Halder, S.; Fruehan, R.J. [Praxair Inc., Tonawanda, NY (United States). Praxair Technological Center

2008-12-15

125

Potential role of bicarbonate during pyrite oxidation  

SciTech Connect

The need to prevent the development of acid mine drainage (AMD) by oxidation of pyrite has triggered numerous investigations into the mechanisms of its oxidation. According to Frontier molecular orbital (FMO) theory, the surface-exposed sulfur atom of pyrite possesses an unshared electron pair which produces a slightly negatively charged pyrite surface that can attract cations such as Fe{sup 2+}. Because of surface electroneutrality and pH considerations, however, the pyrite surface Fe{sup 2+} coordinates OH. The authors proposed that this surface Fe{sup 2+} OH when in the presence of CO{sub 2} is converted to {minus}FeCO{sub 3} or {minus}FeHCO{sub 3}, depending on pH. In this study, using Fourier transform infrared spectroscopy (FT-IR) they demonstrated that such complexes form on the surface of pyrite and continue to persist even after a significant fraction of the surface Fe{sup 2+} was oxidized to Fe{sup 3+}. FT-IR spectra also showed the presence of two carbonyl absorption bands (1,682 and 1,653 cm{sup {minus}1}) on the surface of pyrite upon exposure to CO{sub 2} which suggested that pyrite surface carbon complexes existed in two different surface chemical environments, pointing out two potential mechanisms of pyrite surface-CO{sub 2} interactions. One potential mechanism involved formation of a pyrite surface-Fe(II)HCO{sub 3} complex, whereas a second potential mechanism involved formation of a pyrite surface-carboxylic acid group complex [{minus}Fe(II)SSCOOFe-(II)].

Evangelou, V.P.; Holt, A. [Univ. of Kentucky, Lexington, KY (United States). Dept. of Agronomy] [Univ. of Kentucky, Lexington, KY (United States). Dept. of Agronomy; Seta, A.K. [Univ. Bengkulu (Indonesia). Fakultas Pertanian] [Univ. Bengkulu (Indonesia). Fakultas Pertanian

1998-07-15

126

Oxidation-Reduction Calculations in the Biochemistry Course  

ERIC Educational Resources Information Center

Redox calculations have the potential to reinforce important concepts in bioenergetics. The intermediacy of the NAD[superscript +]/NADH couple in the oxidation of food by oxygen, for example, can be brought out by such calculations. In practice, students have great difficulty and, even when adept at the calculations, frequently do not understand…

Feinman, Richard D.

2004-01-01

127

THE RELATION OF THE BACTERIOSTATIC ACTION OF CERTAIN DYES TO OXIDATION-REDUCTION PROCESSES  

PubMed Central

Oxidized indophenols and methylene blue are bacteriostatic for Pneumococcus and hemolytic streptococci of human and bovine origin, while the indigoes, malachite green and litmus are not toxic. 2-Chloroindophenol, the most positive of the indicators of oxidation-reduction potentials used, is also the only one to have a bacteriostatic action on cheese strains of Streptococcus hæmolyticus. Methylene blue and the indophenols are no longer bacteriostatic when present in a reduced form in a medium capable of maintaining them in such a condition. A comparison of these results with the growth in plain broth of the organisms studied suggests that the "inhibiting" dyes "poise" the medium at an oxidation potential outside the range in which the inhibited organisms can grow. PMID:19869565

Dubos, René

1929-01-01

128

Cell oxidation-reduction imbalance after modulated radiofrequency radiation.  

PubMed

Abstract Aim of this study was to evaluate an influence of modulated radiofrequency field (RF) of 1800?MHz, strength of 30?V/m on oxidation-reduction processes within the cell. The assigned RF field was generated within Gigahertz Transversal Electromagnetic Mode cell equipped by signal generator, modulator, and amplifier. Cell line V79, was irradiated for 10, 30, and 60?min, specific absorption rate was calculated to be 1.6?W/kg. Cell metabolic activity and viability was determined by MTT assay. In order to define total protein content, colorimetric method was used. Concentration of oxidised proteins was evaluated by enzyme-linked immunosorbent assay. Reactive oxygen species (ROS) marked with fluorescent probe 2',7'-dichlorofluorescin diacetate were measured by means of plate reader device. In comparison with control cell samples, metabolic activity and total protein content in exposed cells did not differ significantly. Concentrations of carbonyl derivates, a product of protein oxidation, insignificantly but continuously increase with duration of exposure. In exposed samples, ROS level significantly (p?oxidation-reduction equilibrium within the growing cells. PMID:25119294

Marjanovic, Ana Marija; Pavicic, Ivan; Trosic, Ivancica

2014-08-13

129

Pre-converted nitric oxide gas in catalytic reduction system  

DOEpatents

A two-stage catalyst comprises an oxidative first stage and a reductive second stage. The first stage is intended to convert NO to NO{sub 2} in the presence of O{sub 2}. The second stage serves to convert NO{sub 2} to environmentally benign gases that include N{sub 2}, CO{sub 2}, and H{sub 2}O. By preconverting NO to NO{sub 2} in the first stage, the efficiency of the second stage for NO{sub x} reduction is enhanced. For example, an internal combustion engine exhaust is connected by a pipe to a first chamber. An oxidizing first catalyst converts NO to NO{sub 2} in the presence of O{sub 2} and includes platinum/alumina, e.g., Pt/Al{sub 2}O{sub 3} catalyst. A flow of hydrocarbons (C{sub x}H{sub y}) is input from a pipe into a second chamber. For example, propene can be used as a source of hydrocarbons. The NO{sub 2} from the first catalyst mixes with the hydrocarbons in the second chamber. The mixture proceeds to a second reduction catalyst that converts NO{sub 2} to N{sub 2}, CO{sub 2}, and H{sub 2}O, and includes a {gamma}-Al{sub 2}O{sub 3}. The hydrocarbons and NO{sub x} are simultaneously reduced while passing through the second catalyst. 9 figs.

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

1999-04-06

130

Pre-converted nitric oxide gas in catalytic reduction system  

DOEpatents

A two-stage catalyst comprises an oxidative first stage and a reductive second stage. The first stage is intended to convert NO to NO.sub.2 in the presence of O.sub.2. The second stage serves to convert NO.sub.2 to environmentally benign gases that include N2, CO2, and H.sub.2 O. By preconverting NO to NO.sub.2 in the first stage, the efficiency of the second stage for NO.sub.x reduction is enhanced. For example, an internal combustion engine exhaust is connected by a pipe to a first chamber. An oxidizing first catalyst converts NO to NO.sub.2 in the presence of O.sub.2 and includes platinum/alumina, e.g., Pt/Al.sub.2 O.sub.3 catalyst. A flow of hydrocarbons (C.sub.x H.sub.y) is input from a pipe into a second chamber. For example, propene can be used as a source of hydrocarbons. The NO.sub.2 from the first catalyst mixes with the hydrocarbons in the second chamber. The mixture proceeds to a second reduction catalyst that converts NO.sub.2 to N2, CO2, and H.sub.2 O, and includes a gamma-alumina .gamma.-Al.sub.2 O.sub.3. The hydrocarbons and NO.sub.x are simultaneously reduced while passing through the second catalyst.

Hsiao, Mark C. (Livermore, CA); Merritt, Bernard T. (Livermore, CA); Penetrante, Bernardino M. (San Ramon, CA); Vogtlin, George E. (Fremont, CA)

1999-01-01

131

Removal of oxides from alkali metal melts by reductive titration to electrical resistance-change end points  

DOEpatents

Alkali metal oxides dissolved in alkali metal melts are reduced with soluble metals which are converted to insoluble oxides. The end points of the reduction is detected as an increase in electrical resistance across an alkali metal ion-conductive membrane interposed between the oxide-containing melt and a material capable of accepting the alkali metal ions from the membrane when a difference in electrical potential, of the appropriate polarity, is established across it. The resistance increase results from blocking of the membrane face by ions of the excess reductant metal, to which the membrane is essentially non-conductive.

Tsang, Floris Y. (Walnut Creek, CA)

1980-01-01

132

An Investigation Into the Potential for PVC Reduction in  

E-print Network

An Investigation Into the Potential for PVC Reduction in Residential Building Drainage Lines A Triple Bottom Line Analysis of PVC vs. HDPE For Penny Martyn, Stakeholder of Project, Green Building for flexibility and cheap cost, PVC comes with numerous harmful side-effects to both the environment

133

Carbon reduction potential from recycling in primary materials manufacturing  

Microsoft Academic Search

This study assesses the potential for energy savings and carbon emissions reduction by increasing the recycled content of energy-intensive materials. Aluminum, steel, paper, plastics, and container glass are considered. Government policies to encourage higher recycling rates and increased recycled materials content are proposed.

1993-01-01

134

Continuous Trajectories for Primal-Dual Potential-Reduction Methods  

E-print Network

- ent primal-dual potential-reduction algorithms for solving linear programming problems. For both Introduction During the past two decades, interior-point methods (IPMs) emerged as very efficient and reliable problem combining measures of proximity to the set of optimal solutions, proximity to the feasible set

135

Landscape planning for agricultural nonpoint source pollution reduction III: Assessing phosphorus and sediment reduction potential  

USGS Publications Warehouse

Riparian buffers have the potential to improve stream water quality in agricultural landscapes. This potential may vary in response to landscape characteristics such as soils, topography, land use, and human activities, including legacies of historical land management. We built a predictive model to estimate the sediment and phosphorus load reduction that should be achievable following the implementation of riparian buffers; then we estimated load reduction potential for a set of 1598 watersheds (average 54 km2) in Wisconsin. Our results indicate that land cover is generally the most important driver of constituent loads in Wisconsin streams, but its influence varies among pollutants and according to the scale at which it is measured. Physiographic (drainage density) variation also influenced sediment and phosphorus loads. The effect of historical land use on present-day channel erosion and variation in soil texture are the most important sources of phosphorus and sediment that riparian buffers cannot attenuate. However, in most watersheds, a large proportion (approximately 70%) of these pollutants can be eliminated from streams with buffers. Cumulative frequency distributions of load reduction potential indicate that targeting pollution reduction in the highest 10% of Wisconsin watersheds would reduce total phosphorus and sediment loads in the entire state by approximately 20%. These results support our approach of geographically targeting nonpoint source pollution reduction at multiple scales, including the watershed scale. ?? 2008 Springer Science+Business Media, LLC.

Diebel, M.W.; Maxted, J.T.; Robertson, D.M.; Han, S.; Vander Zanden, M. J.

2009-01-01

136

Reductive potential - a savior turns stressor in protein aggregation cardiomyopathy.  

PubMed

Redox homeostasis is essential for basal signaling of several physiological processes, but a unilateral shift towards an 'oxidative' or 'reductive' trait will alter intracellular redox milieu. Typically, such an event influences the structure and the native function of a cell or an organelle. Numerous experimental research and clinical trials over the last 6 decades have demonstrated that enhanced oxygen-derived free radicals constitute a major stimulus to trigger damage in several human diseases, including cardiovascular complications supporting the theory of oxidative stress (OS). However, until our key discovery, the dynamic interrelationship between "Reductive Stress (RS)" and cardiac health has been obscured by overwhelming OS studies (Rajasekaran et al., 2007). Notably, this seminal finding spurred considerable interest in investigations of other mechanistic insights, and thus far the results indicate a similar or stronger role for RS, as that of OS. In addition, from our own findings we strongly believe that constitutive activation of pathways that enable sustained generation of reducing equivalents of glutathione (GSH), reduced nicotinamide adenine dinucleotide phosphate (NADPH) will cause RS and impair the basal cellular signaling mechanisms operating through harmless pro-oxidative events, in turn, disrupting single and/or a combination of key cellular processes such as growth, maturation, differentiation, survival, death etc., that govern healthy cell physiology. Here, we have discussed the role of RS as a causal or contributing factor in relevant pathophysiology of a major cardiac disease of human origin. PMID:25446995

Narasimhan, Madhusudhanan; Rajasekaran, Namakkal S

2015-01-01

137

Stable platinum nanoclusters on genomic DNA–graphene oxide with a high oxygen reduction reaction activity  

PubMed Central

Nanosize platinum clusters with small diameters of 2–4?nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2?nm). Here we report the synthesis of platinum clusters (diameter ?1.4?nm) deposited on genomic double-stranded DNA–graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA–graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA–graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries. PMID:23900456

Tiwari, Jitendra N.; Nath, Krishna; Kumar, Susheel; Tiwari, Rajanish N.; Kemp, K. Christian; Le, Nhien H.; Youn, Duck Hyun; Lee, Jae Sung; Kim, Kwang S.

2013-01-01

138

Quinone-Enhanced Reduction of Nitric Oxide by Xanthine/Xanthine Oxidase  

PubMed Central

The quinones 1,4-naphthoquinone, methyl-1,4-naphthoquinone, tetramethyl-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,6-dimethylbenzoquinone, 2,6-dimethoxybenzoquinone, and 9,10-phenanthraquinone enhance the rate of nitric oxide reduction by xanthine/xanthine oxidase in nitrogen-saturated phosphate buffer (pH 7.4). Maximum initial rates of NO reduction (Vmax) and the amount of nitrous oxide produced after 5 min of reaction increase with quinone one- and two-electron redox potentials measured in acetonitrile. One of the most active quinones of those studied is 9,10-phenanthraquinone with a Vmax value 10 times larger than that corresponding to the absence of quinone, under the conditions of this work. Because NO production is enhanced under hypoxia and under certain pathological conditions, the observations obtained in this work are very relevant to such conditions. PMID:19301825

Sanchez-Cruz, Pedro; Alegría, Antonio E.

2009-01-01

139

Oxygen reduction electrocatalyst based on strongly coupled cobalt oxide nanocrystals and carbon nanotubes.  

PubMed

Electrocatalyst for oxygen reduction reaction (ORR) is crucial for a variety of renewable energy applications and energy-intensive industries. The design and synthesis of highly active ORR catalysts with strong durability at low cost is extremely desirable but remains challenging. Here, we used a simple two-step method to synthesize cobalt oxide/carbon nanotube (CNT) strongly coupled hybrid as efficient ORR catalyst by directly growing nanocrystals on oxidized multiwalled CNTs. The mildly oxidized CNTs provided functional groups on the outer walls to nucleate and anchor nanocrystals, while retaining intact inner walls for highly conducting network. Cobalt oxide was in the form of CoO due to a gas-phase annealing step in NH(3). The resulting CoO/nitrogen-doped CNT (NCNT) hybrid showed high ORR current density that outperformed Co(3)O(4)/graphene hybrid and commercial Pt/C catalyst at medium overpotential, mainly through a 4e reduction pathway. The metal oxide/carbon nanotube hybrid was found to be advantageous over the graphene counterpart in terms of active sites and charge transport. Last, the CoO/NCNT hybrid showed high ORR activity and stability under a highly corrosive condition of 10 M NaOH at 80 °C, demonstrating the potential of strongly coupled inorganic/nanocarbon hybrid as a novel catalyst system in oxygen depolarized cathode for chlor-alkali electrolysis. PMID:22957510

Liang, Yongye; Wang, Hailiang; Diao, Peng; Chang, Wesley; Hong, Guosong; Li, Yanguang; Gong, Ming; Xie, Liming; Zhou, Jigang; Wang, Jian; Regier, Tom Z; Wei, Fei; Dai, Hongjie

2012-09-26

140

Enzymatically oxidized lactose and derivatives thereof as potential protein cross-linkers.  

PubMed

The enzyme galactose oxidase [EC 1.1.3.9] was applied to convert lactose, lactylamine and lactobionic acid into their corresponding 6'-aldehyde compounds. The potential protein cross-linking ability of these oxidized lactose and derivatives thereof was investigated using n-butylamine as the model compound. First, oxidized lactose gave double Maillard reaction products that were stable under mild alkaline conditions. Second, reductive amination of lactose followed by enzymatic oxidation gave cross-links that were stable under both neutral and alkaline conditions. Third, stable cross-links were obtained through enzymatic oxidation and amidation of lactobionic acid. PMID:17056020

van Wijk, Arjan; Siebum, Arjan; Schoevaart, Rob; Kieboom, Tom

2006-12-29

141

Landscape Planning for Agricultural Nonpoint Source Pollution Reduction III: Assessing Phosphorus and Sediment Reduction Potential  

Microsoft Academic Search

Riparian buffers have the potential to improve stream water quality in agricultural landscapes. This potential may vary in\\u000a response to landscape characteristics such as soils, topography, land use, and human activities, including legacies of historical\\u000a land management. We built a predictive model to estimate the sediment and phosphorus load reduction that should be achievable\\u000a following the implementation of riparian buffers;

Matthew W. Diebel; Jeffrey T. Maxted; Dale M. Robertson; Seungbong Han; M. Jake Vander Zanden

2009-01-01

142

Role of thickness and intercalated water in the facile reduction of graphene oxide employing camera flash  

NASA Astrophysics Data System (ADS)

Graphene oxide (GO) is a potential precursor for the bulk production of graphene as the synthetic route is simple and cost-effective. Typically, reduction of GO is a time-consuming process and involves either toxic/hazardous reducing agents or high temperature treatment. Herein, we report the role of intercalated water and thickness of GO films towards the reduction of GO employing simple camera flash. A fast, simple and single camera flash instantaneously causes the deoxygenation reaction of GO without employing hazardous/toxic chemical reductants at room temperature. Successful reduction of GO employing camera flash has been verified via XRD, Raman and UV-vis spectroscopic analyses. Flash-reduced graphene shows a relatively high conductivity value of 740 S m-1 with a C/O ratio of around 9.5. Intercalated water molecules facilitate the reduction by electron-hole pair formation. It has also been found that the intercalated water facilitates the reduction of GO up to a certain film thickness. However, the intensity of light passing through to the backside of a too thick film decreases significantly, causing incomplete reduction.

Bose, Saswata; Drzal, Lawrence T.

2014-02-01

143

Design Principles for Oxygen Reduction and Evolution on Oxide Catalysts  

NASA Astrophysics Data System (ADS)

Driven by growing concerns about global warming and the depletion of petroleum resources, developing renewable energy production and storage technologies represent one of the major scientific challenges of the 21^st century. A critical element in pursuit of this quest is the discovery of efficient and cost-effective catalysts used in solar fuel production via electrochemical energy conversion processes such as oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), both of which are central to the efficiencies of direct-solar and electrolytic water-splitting devices, fuel cells, and metal-air batteries. Although the Sabatier's principle provides a qualitative argument in tuning catalytic activity by varying the bond strength between catalyst surface and reactant/product (neither too strong nor too weak leading to the maximum activity at moderate bond strength), it has no predictive power to find catalysts with enhanced activity. Identifying a ``design principle'' that links catalyst properties to the catalytic activity is critical to accelerate the search for highly active catalysts based on abundant elements, and minimize the use of precious metals. Here we establish a molecular principle that governs the activities of oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) for oxide catalysts, where the activities primarily correlate to the ?* orbital (``eg'') occupation of surface transition-metal cations established by systematic examination of more than ten to fifteen transition-metal oxides. The intrinsic ORR and OER activities exhibit a volcano-shaped dependence on the eg occupancy and the activities peak at an eg occupancy close to unity. Our findings reflect the critical influence of the ?* orbital on the energetics of surface reaction intermediates on surface transition metal ions such as the O2^2-/OH^- displacement and the OH^- regeneration, and thus highlight the importance of surface oxide electronic structure in controlling catalytic activities. Using the established molecular principle, we further demonstrate that an alkaline earth cobalt oxide with a chemical formula of Ba0.5Sr0.5Co0.8Fe0.2O3-? (BSCF), catalyzes the OER with intrinsic activity that is at least an order of magnitude higher than the state-of-the-art iridium oxide catalyst in basic solutions. [4pt] [1] J. Suntivich, H.A. Gasteiger, N. Yabuuchi, H. Nakanishi, J. B. Goodenough and Y. Shao-Horn, Design Principles for Oxygen Reduction Activity on Perovskite Oxide Catalysts for Fuel Cells and Metal-Air Batteries, Nature Chemistry, 3, 546--550 (2011).[0pt] [2] Jin Suntivich, Kevin J. May, Hubert A. Gasteiger, John B. Goodenough and Yang Shao-Horn, A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles, ScienceExpress, Science DOI: 10.1126/science.1212858, (2011).

Shao-Horn, Yang

2012-02-01

144

BIOTRANSFORMATIONS OF MORPHINE ALKALOIDS BY FUNGI: N-DEMETHYLATIONS, OXIDATIONS, AND REDUCTIONS  

E-print Network

BIOTRANSFORMATIONS OF MORPHINE ALKALOIDS BY FUNGI: N-DEMETHYLATIONS, OXIDATIONS, AND REDUCTIONS on the occasion of his 85th birthday. Morphine alkaloids and some of its derivatives (morphine, codeine, thebaine. The alkaloids were transformed to a variety of products via biological oxidations, reductions, and oxidative

Hudlicky, Tomas

145

Thermogravimetric study of reduction of oxides present in oxidized nickel-base alloy powders  

NASA Technical Reports Server (NTRS)

Carbon, hydrogen, and hydrogen plus carbon reduction of three oxidized nickel-base alloy powders (a solid solution strengthened alloy both with and without the gamma prime formers aluminum and titanium and the solid solution strengthened alloy NiCrAlY) were evaluated by thermogravimetry. Hydrogen and hydrogen plus carbon were completely effective in reducing an alloy containing chromium, columbium, tantalum, molybdenum, and tungsten. However, with aluminum and titanium present the reduction was limited to a weight loss of about 81 percent. Carbon alone was not effective in reducing any of the alloys, and none of the reducing conditions were effective for use with NiCrAlY.

Herbell, T. P.

1976-01-01

146

Reduction characteristics of copper oxide in cerium and zirconium oxide systems  

Microsoft Academic Search

The reduction of CuO dispersed on fluorite-type oxide catalysts, namely La-doped CeO2 and Y-doped ZrO2 was studied in this work. On both supports distinct copper species were identified as a function of copper content by temperature-programmed reduction (TPR) by H2 and CH4, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and scanning transmission electron microscopy\\/energy dispersive X-ray (STEM\\/EDX) analyses. At

Lj. Kundakovic; M. Flytzani-Stephanopoulos

1998-01-01

147

Novel graphite salts of high oxidizing potential  

SciTech Connect

The intercalation of graphite by the third-transition-series metal hexafluorides has yielded the graphite salts, C/sub 8//sup +/OsF/sub 6//sup -/, C/sub 8//sup +/IrF/sub 6//sup -/ and C/sub 12//sup 2 +/PtF/sub 6//sup 2 -/. The fluoroplatinate salt represents the highest electron withdrawal from the graphite network yet achieved. Analogues to the Os and Ir salts have been obtained both by fluorination of Group V pentaflouride intercalates, C/sub 8/MF/sub 5/ (M = As, Sb), and by the interaction of the dioxygenyl salts with graphite (8C + O/sub 2/MF/sub 6/ ..-->.. C/sub 8/MF/sub 6/ + O/sub 2/+). Non-intercalating binary fluorides have been observed to intercalate in the presence of a fluorine-rich environment (e.g., 8C + PF/sub 5/ + 1/2 F/sub 2/ ..-->.. C/sub 8/PF/sub 6/). GeF/sub 4/, which also does not spontaneously intercalate graphite, has been observed to interact with graphite in the presence of 2 atmospheres of fluorine overpressure to give the fluoroplatinate salt analogue, C/sub 12//sup 2 +/GeF/sub 6//sup 2 -/. This material is in equilibrium with the pentafluorogermanate at ordinary pressures and temperatures. C/sub 12//sup 2 +/GeF/sub 6//sup 2 -/ ..-->.. C/sub 12//sup +/GeF/sub 5//sup -/ + 1/2 F/sub 2/. C/sub 12/GeF/sub 6/ must have an oxidizing potential close to that of fluorine itself. The graphite fluorometallate salts are both electronic and ionic (F/sup -/) conductors. For the C/sub 8//sup +/MF/sub 6//sup -/ salts, a maximum electronic conductivity an order of magnitude greater than the parent graphite has been observed for stage two. The high oxidizing potential, coupled with the fluoride ion transport capability of the graphite salts, has been exploited in the construction of solid-state galvanic cells. These cells use the graphite fluorometallate salts as electrode materials in combination with a superionic fluoride-ion-conducting solid electrolyte.

McCarron, E.M. III

1980-08-01

148

Enzymatically oxidized lactose and derivatives thereof as potential protein cross-linkers  

Microsoft Academic Search

The enzyme galactose oxidase [EC 1.1.3.9] was applied to convert lactose, lactylamine and lactobionic acid into their corresponding 6?-aldehyde compounds. The potential protein cross-linking ability of these oxidized lactose and derivatives thereof was investigated using n-butylamine as the model compound. First, oxidized lactose gave double Maillard reaction products that were stable under mild alkaline conditions. Second, reductive amination of lactose

Arjan van Wijk; Arjan Siebum; Rob Schoevaart; Tom Kieboom

2006-01-01

149

Pollution potential reduction of cheese whey through yeast fermentation  

Microsoft Academic Search

Batch and continuous pilot-scale aerobic fermenters of 4.8 L operating volume were designed and constructed from plexiglass\\u000a materials. The fermenters were used to study the kinetics of cheese whey fermentation using the yeastK. fragillis for pollution potential reduction and single cell protein production. Four retention times (6,12,18, and 24 h) were used\\u000a in this study. The fermentation process was successful

A. E. Ghaly; R. K. Singh

1989-01-01

150

An interior point potential reduction method for constrained equations  

Microsoft Academic Search

We study the problem of solving a constrained system of nonlinear equations by a combination of the classical damped Newton\\u000a method for (unconstrained) smooth equations and the recent interior point potential reduction methods for linear programs,\\u000a linear and nonlinear complementarity problems. In general, constrained equations provide a unified formulation for many mathematical\\u000a programming problems, including complementarity problems of various kinds

Tao Wang; Renato D. C. Monteiro; Jong-shi Pang

1996-01-01

151

Floating Potential Probe Langmuir Probe Data Reduction Results  

NASA Technical Reports Server (NTRS)

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

Morton, Thomas L.; Minow, Joseph I.

2002-01-01

152

Rheostat Re-Wired: Alternative Hypotheses for the Control of Thioredoxin Reduction Potentials  

PubMed Central

Thioredoxins are small soluble proteins that contain a redox-active disulfide (CXXC). These disulfides are tuned to oxidizing or reducing potentials depending on the function of the thioredoxin within the cell. The mechanism by which the potential is tuned has been controversial, with two main hypotheses: first, that redox potential (Em) is specifically governed by a molecular ‘rheostat’—the XX amino acids, which influence the Cys pKa values, and thereby, Em; and second, the overall thermodynamics of protein folding stability regulates the potential. Here, we use protein film voltammetry (PFV) to measure the pH dependence of the redox potentials of a series of wild-type and mutant archaeal Trxs, PFV and glutathionine-equilibrium to corroborate the measured potentials, the fluorescence probe BADAN to measure pKa values, guanidinium-based denaturation to measure protein unfolding, and X-ray crystallography to provide a structural basis for our functional analyses. We find that when these archaeal thioredoxins are probed directly using PFV, both the high and low potential thioredoxins display consistent 2H+:2e- coupling over a physiological pH range, in conflict with the conventional ‘rheostat’ model. Instead, folding measurements reveals an excellent correlation to reduction potentials, supporting the second hypothesis and revealing the molecular mechanism of reduction potential control in the ubiquitous Trx family. PMID:25874934

Bewley, Kathryn D.; Dey, Mishtu; Bjork, Rebekah E.; Mitra, Sangha; Chobot, Sarah E.; Drennan, Catherine L.; Elliott, Sean J.

2015-01-01

153

Reduction of Oxidative Melt Loss of Aluminum and Its Alloys  

SciTech Connect

This project led to an improved understanding of the mechanisms of dross formation. The microstructural evolution in industrial dross samples was determined. Results suggested that dross that forms in layers with structure and composition determined by the local magnesium concentration alone. This finding is supported by fundamental studies of molten metal surfaces. X-ray photoelectron spectroscopy data revealed that only magnesium segregates to the molten aluminum alloy surface and reacts to form a growing oxide layer. X-ray diffraction techniques that were using to investigate an oxidizing molten aluminum alloy surface confirmed for the first time that magnesium oxide is the initial crystalline phase that forms during metal oxidation. The analytical techniques developed in this project are now available to investigate other molten metal surfaces. Based on the improved understanding of dross initiation, formation and growth, technology was developed to minimize melt loss. The concept is based on covering the molten metal surface with a reusable physical barrier. Tests in a laboratory-scale reverberatory furnace confirmed the results of bench-scale tests. The main highlights of the work done include: A clear understanding of the kinetics of dross formation and the effect of different alloying elements on dross formation was obtained. It was determined that the dross evolves in similar ways regardless of the aluminum alloy being melted and the results showed that amorphous aluminum nitride forms first, followed by amorphous magnesium oxide and crystalline magnesium oxide in all alloys that contain magnesium. Evaluation of the molten aluminum alloy surface during melting and holding indicated that magnesium oxide is the first crystalline phase to form during oxidation of a clean aluminum alloy surface. Based on dross evaluation and melt tests it became clear that the major contributing factor to aluminum alloy dross was in the alloys with Mg content. Mg was identified as the primary factor that accelerates dross formation specifically in the transition from two phases to three phase growth. Limiting magnesium oxidation on the surface of molten aluminum therefore becomes the key to minimizing melt loss, and technology was developed to prevent magnesium oxidation on the aluminum surface. This resulted in a lot of the work being focused on the control of Mg oxidation. Two potential molten metal covering agents that could inhibit dross formation during melting and holding consisting of boric acid and boron nitride were identified. The latter was discounted by industry as it resulted in Boron pick up by the melt beyond that allowed by specifications during plant trials. The understanding of the kinetics of dross formation by the industry partners helped them understand how temperature, alloy chemistry and furnace atmosphere (burner controls--e.g. excess air) effected dross formation. This enables them to introduce in their plant process changes that reduced unnecessary holding at high temperatures, control burner configurations, reduce door openings to avoid ingress of air and optimize charge mixes to ensure rapid melting and avoid excess oxidation.

Dr. Subodh K. Das; Shridas Ningileri

2006-03-17

154

Redox-Inactive Metals Modulate the Reduction Potential in Heterometallic Manganese-Oxido Clusters  

PubMed Central

Redox-inactive metals are found in biological and heterogeneous water oxidation catalysts, but their roles in catalysis are currently not well understood. A series of high oxidation state tetranuclear-dioxido clusters comprised of three manganese centers and a redox-inactive metal (M) of various charge is reported. Crystallographic studies show an unprecedented Mn3M(?4-O)(?2-O) core that remains intact upon changing M or the manganese oxidation state. Electrochemical studies reveal that the reduction potentials span a window of 700 mV, dependent upon the Lewis acidity of the second metal. With the pKa of the redox-inactive metal-aqua complex as a measure of Lewis acidity, these compounds display a linear dependence between reduction potential and acidity with a slope of ca. 100 mV per pKa unit. The Sr2+ and Ca2+ compounds show similar potentials, an observation that correlates with the behavior of the OEC, which is active only in the presence of one of these two metals. PMID:23511417

Tsui, Emily Y.; Tran, Rosalie; Yano, Junko; Agapie, Theodor

2013-01-01

155

Catalyst and method for reduction of nitrogen oxides  

DOEpatents

A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

Ott, Kevin C. (Los Alamos, NM)

2008-05-27

156

Catalyst and method for reduction of nitrogen oxides  

DOEpatents

A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

Ott, Kevin C. (Los Alamos, NM)

2008-08-19

157

Oxidation of alpha-ketoglutarate is required for reductive carboxylation in cancer cells with mitochondrial defects  

PubMed Central

Summary Mammalian cells generate citrate by decarboxylating pyruvate in the mitochondria to supply the tricarboxylic acid (TCA) cycle. In contrast, hypoxia and other impairments of mitochondrial function induce an alternative pathway that produces citrate by reductively carboxylating ?-ketoglutarate (AKG) via NADPH-dependent isocitrate dehydrogenase (IDH). It is unknown how cells generate reducing equivalents necessary to supply reductive carboxylation in the setting of mitochondrial impairment. Here we identified shared metabolic features in cells using reductive carboxylation. Paradoxically, reductive carboxylation was accompanied by concomitant AKG oxidation in the TCA cycle. Inhibiting AKG oxidation decreased reducing equivalent availability and suppressed reductive carboxylation. Interrupting transfer of reducing equivalents from NADH to NADPH by nicotinamide nucleotide transhydrogenase increased NADH abundance and decreased NADPH abundance while suppressing reductive carboxylation. The data demonstrate that reductive carboxylation requires bidirectional AKG metabolism along oxidative and reductive pathways, with the oxidative pathway producing reducing equivalents used to operate IDH in reverse. PMID:24857658

Mullen, Andrew R.; Hu, Zeping; Shi, Xiaolei; Jiang, Lei; Boroughs, Lindsey K.; Kovacs, Zoltan; Boriack, Richard; Rakheja, Dinesh; Sullivan, Lucas B.; Linehan, W. Marston; Chandel, Navdeep S.; DeBerardinis, Ralph J.

2014-01-01

158

Lightning-induced reduction of phosphorus oxidation state  

NASA Astrophysics Data System (ADS)

Phosphorus is frequently the limiting nutrient in marine and terrestrial ecosystems, largely owing to its poor solubility and slow movement through the rock cycle. Phosphorus is viewed to exist in geological systems almost exclusively in its fully oxidized state as orthophosphate. However, many microorganisms use the partially oxidized forms-phosphite and hypophosphite-as alternative phosphorus sources, and genomic evidence suggests that this selectivity is ancient. Elucidating the processes that reduce phosphate is therefore key to understanding the biological cycling of phosphorus. Here we show that cloud-to-ground lightning reduces phosphate in lightning-derived glass compounds, termed fulgurites. We analysed the phosphorus chemistry of ten fulgurites retrieved from North America, Africa and Australia, using microprobes and 31P nuclear magnetic resonance. Half of the fulgurites contained reduced phosphorus, mainly in the form of phosphite. The amount and type of reduced phosphorus was dependent on the composition of the fulgurite section examined: carbon-rich sections contained around 22% reduced phosphorus in the form of iron phosphide, whereas other fulgurites contained between 37 and 68% in the form of phosphite. We suggest that lightning provides some portion of the reduced phosphorus used by microbes, and that phosphate reduction by lightning can be locally important to phosphorus biogeochemistry.

Pasek, Matthew; Block, Kristin

2009-08-01

159

Binding of promoter DNA to SoxR protein decreases the reduction potential of the [2Fe-2S] cluster.  

PubMed

The [2Fe-2S] transcriptional factor SoxR, a member of the MerR family, functions as a sensor of oxidative stress in Escherichia coli. The transcriptional activity of SoxR is regulated by the reversible oxidation and reduction of [2Fe-2S] clusters. Electrochemistry measurements on DNA-modified electrodes have shown a dramatic shift in the reduction potential of SoxR from -290 to +200 mV with the promoter DNA-bound [ Gorodetsky , A. A. , Dietrich , L. E. P. , Lee , P. E. , Demple , B. , , Newman , D. K. , and Barton , J. K. ( 2008 ) DNA binding shifts the reduction potential of the transcription factor SoxR , Proc. Natl. Acad. Sci. U.S.A. 105 , 3684 - 3689 ]. To determine the change of the SoxR reduction potential using the new condition, the one-electron oxidation-reduction properties of [2Fe-2S] cluster in SoxR were investigated in the absence and presence of the DNA. The [2Fe-2S] cluster of SoxR was completely reduced by nicotinamide adenine dinucleotide phosphate (NADPH)-cytochrome P450 reductase (CRP) in the presence of a NADPH generating system (glucose 6-dehydrogenase and glucose-6 phosphate), indicating that CRP can serve as an NADPH-dependent electron carrier for SoxR. The reduction potential of SoxR was measured from equilibrium data coupled with NADPH and CRP in the presence of electron mediators. The reduction potentials of DNA-bound and DNA-free states of SoxR were -320 and -293 mV versus NHE (normal hydrogen electrode), respectively. These results indicate that DNA binding causes a moderate shift in the reduction potential of SoxR. PMID:25490746

Kobayashi, Kazuo; Fujikawa, Mayu; Kozawa, Takahiro

2015-01-20

160

Pollution potential reduction of cheese whey through yeast fermentation.  

PubMed

Batch and continuous pilot-scale aerobic fermenters of 4.8 L operating volume were designed and constructed from plexiglass materials. The fermenters were used to study the kinetics of cheese whey fermentation using the yeast K. fragilis for pollution potential reduction and single cell protein production. Four retention times (6, 12, 18, and 24 h) were used in this study. The fermentation process was successful in reducing the total chemical oxygen demand (COD) by 42%, the soluble COD by 65%, the total solids by 53%, and the ammonium nitrogen by 90%. There were also gains in the suspended solids and the organic nitrogen of 60 and 17%, respectively. The reductions in the COD, total solids, and ammonium nitrogen, and the gains in the suspended solids and organic nitrogen were affected by the hydraulic retention time. More soluble material was converted to insoluble microbial cells at the 12-h hydraulic retention time, whereas greater pollution potential reduction was achieved at the 24-h hydraulic retention time for both batch and continuous operations. PMID:2610515

Ghaly, A E; Singh, R K

1989-11-01

161

Electrodeposition and electrochemical reduction of epitaxial metal oxide thin films and superlattices  

NASA Astrophysics Data System (ADS)

The focus of this dissertation is the electrodeposition and electrochemical reduction of epitaxial metal oxide thin films and superlattices. The electrochemical reduction of metal oxides to metals has been studied for decades as an alternative to pyrometallurgical processes for the metallurgy industry. However, the previous work was conducted on bulk polycrystalline metal oxides. Paper I in this dissertation shows that epitaxial face-centered cubic magnetite (Fe3O4 ) thin films can be electrochemically reduced to epitaxial body-centered cubic iron (Fe) thin films in aqueous solution on single-crystalline Au substrates at room temperature. This technique opens new possibilities to produce special epitaxial metal/metal oxide heterojunctions and a wide range of epitaxial metallic alloy films from the corresponding mixed metal oxides. Electrodeposition, like biomineralization, is a soft solution processing method which can produce functional materials with special properties onto conducting or semiconducting solid surfaces. Paper II in this dissertation presents the electrodeposition of cobalt-substituted magnetite (CoxFe3-xO4, 0 of cobalt-substituted magnetite (CoxFe3-xO4, 0potentially used in spintronics and memory devices. Paper III in this dissertation reports the electrodeposition of crystalline cobalt oxide (Co3O4) thin films on stainless steel and Au single-crystalline substrates. The crystalline Co3O4 thin films exhibit high catalytic activity towards the oxygen evolution reaction in an alkaline solution. A possible application of the electrodeposited Co 3O4 is the fabrication of highly active and low-cost photoanodes for photoelectrochemical water-splitting cells.

He, Zhen

162

Radiolytic reactions of nitro blue tetrazolium under oxidative and reductive conditions: a pulse radiolysis study  

NASA Astrophysics Data System (ADS)

The radiolytic reactions of the ditetrazolium salt nitro blue tetrazolium chloride (NBTCl 2) were studied by pulse radiolysis technique in aqueous solution under reducing and oxidising conditions with the aim of potential dosimetry application. Under reducing conditions the fast formation of the tetrazolinyl radical is observed that is followed by the appearance of monoformazan (MF +), i.e. one of the tetrazolium rings is reduced to formazan. The formation of the water-insoluble diformazan, i.e. the result of the second reduction step was not observed in pulse radiolysis. Formazan formation was not found under oxidative conditions.

Kovacs, A.; Wojnarovits, L.; Baranyai, M.; Moussa, A.; Othman, I.; McLaughlin, W. L.

1999-08-01

163

Iron isotope fractionation during microbial dissimilatory iron oxide reduction in simulated Archaean seawater.  

PubMed

The largest Fe isotope excursion yet measured in marine sedimentary rocks occurs in shales, carbonates, and banded iron formations of Neoarchaean and Paleoproterozoic age. The results of field and laboratory studies suggest a potential role for microbial dissimilatory iron reduction (DIR) in producing this excursion. However, most experimental studies of Fe isotope fractionation during DIR have been conducted in simple geochemical systems, using pure Fe(III) oxide substrates that are not direct analogues to phases likely to have been present in Precambrian marine environments. In this study, Fe isotope fractionation was investigated during microbial reduction of an amorphous Fe(III) oxide-silica coprecipitate in anoxic, high-silica, low-sulphate artificial Archaean seawater at 30 °C to determine if such conditions alter the extent of reduction or isotopic fractionations relative to those observed in simple systems. The Fe(III)-Si coprecipitate was highly reducible (c. 80% reduction) in the presence of excess acetate. The coprecipitate did not undergo phase conversion (e.g. to green rust, magnetite or siderite) during reduction. Iron isotope fractionations suggest that rapid and near-complete isotope exchange took place among all Fe(II) and Fe(III) components, in contrast to previous work on goethite and hematite, where exchange was limited to the outer few atom layers of the substrate. Large quantities of low-?(56)Fe Fe(II) (aqueous and solid phase) were produced during reduction of the Fe(III)-Si coprecipitate. These findings shed new light on DIR as a mechanism for producing Fe isotope variations observed in Neoarchaean and Paleoproterozoic marine sedimentary rocks. PMID:21504536

Percak-Dennett, E M; Beard, B L; Xu, H; Konishi, H; Johnson, C M; Roden, E E

2011-05-01

164

Nitrate reduction functional genes and nitrate reduction potentials persist in deeper estuarine sediments. Why?  

PubMed

Denitrification and dissimilatory nitrate reduction to ammonium (DNRA) are processes occurring simultaneously under oxygen-limited or anaerobic conditions, where both compete for nitrate and organic carbon. Despite their ecological importance, there has been little investigation of how denitrification and DNRA potentials and related functional genes vary vertically with sediment depth. Nitrate reduction potentials measured in sediment depth profiles along the Colne estuary were in the upper range of nitrate reduction rates reported from other sediments and showed the existence of strong decreasing trends both with increasing depth and along the estuary. Denitrification potential decreased along the estuary, decreasing more rapidly with depth towards the estuary mouth. In contrast, DNRA potential increased along the estuary. Significant decreases in copy numbers of 16S rRNA and nitrate reducing genes were observed along the estuary and from surface to deeper sediments. Both metabolic potentials and functional genes persisted at sediment depths where porewater nitrate was absent. Transport of nitrate by bioturbation, based on macrofauna distributions, could only account for the upper 10 cm depth of sediment. A several fold higher combined freeze-lysable KCl-extractable nitrate pool compared to porewater nitrate was detected. We hypothesised that his could be attributed to intracellular nitrate pools from nitrate accumulating microorganisms like Thioploca or Beggiatoa. However, pyrosequencing analysis did not detect any such organisms, leaving other bacteria, microbenthic algae, or foraminiferans which have also been shown to accumulate nitrate, as possible candidates. The importance and bioavailability of a KCl-extractable nitrate sediment pool remains to be tested. The significant variation in the vertical pattern and abundance of the various nitrate reducing genes phylotypes reasonably suggests differences in their activity throughout the sediment column. This raises interesting questions as to what the alternative metabolic roles for the various nitrate reductases could be, analogous to the alternative metabolic roles found for nitrite reductases. PMID:24728381

Papaspyrou, Sokratis; Smith, Cindy J; Dong, Liang F; Whitby, Corinne; Dumbrell, Alex J; Nedwell, David B

2014-01-01

165

Nitrate Reduction Functional Genes and Nitrate Reduction Potentials Persist in Deeper Estuarine Sediments. Why?  

PubMed Central

Denitrification and dissimilatory nitrate reduction to ammonium (DNRA) are processes occurring simultaneously under oxygen-limited or anaerobic conditions, where both compete for nitrate and organic carbon. Despite their ecological importance, there has been little investigation of how denitrification and DNRA potentials and related functional genes vary vertically with sediment depth. Nitrate reduction potentials measured in sediment depth profiles along the Colne estuary were in the upper range of nitrate reduction rates reported from other sediments and showed the existence of strong decreasing trends both with increasing depth and along the estuary. Denitrification potential decreased along the estuary, decreasing more rapidly with depth towards the estuary mouth. In contrast, DNRA potential increased along the estuary. Significant decreases in copy numbers of 16S rRNA and nitrate reducing genes were observed along the estuary and from surface to deeper sediments. Both metabolic potentials and functional genes persisted at sediment depths where porewater nitrate was absent. Transport of nitrate by bioturbation, based on macrofauna distributions, could only account for the upper 10 cm depth of sediment. A several fold higher combined freeze-lysable KCl-extractable nitrate pool compared to porewater nitrate was detected. We hypothesised that his could be attributed to intracellular nitrate pools from nitrate accumulating microorganisms like Thioploca or Beggiatoa. However, pyrosequencing analysis did not detect any such organisms, leaving other bacteria, microbenthic algae, or foraminiferans which have also been shown to accumulate nitrate, as possible candidates. The importance and bioavailability of a KCl-extractable nitrate sediment pool remains to be tested. The significant variation in the vertical pattern and abundance of the various nitrate reducing genes phylotypes reasonably suggests differences in their activity throughout the sediment column. This raises interesting questions as to what the alternative metabolic roles for the various nitrate reductases could be, analogous to the alternative metabolic roles found for nitrite reductases. PMID:24728381

Papaspyrou, Sokratis; Smith, Cindy J.; Dong, Liang F.; Whitby, Corinne; Dumbrell, Alex J.; Nedwell, David B.

2014-01-01

166

Biological Oxidation of Fe(II) in Reduced Nontronite Coupled with Nitrate Reduction by Pseudogulbenkiania sp. Strain 2002  

SciTech Connect

Nitrate contamination in soils, sediments, and water bodies is a significant issue. Although much is known about nitrate degradation in these environments, especially via microbial pathways, a complete understanding of all degradation processes, especially in clay mineral-rich soils, is still lacking. The objective of this study was to study the potential of removing nitrate contaminant using structural Fe(II) in clay mineral nontronite. Specifically, the coupled processes of microbial oxidation of Fe(II) in microbially reduced nontronite (NAu-2) and nitrate reduction by Pseudogulbenkiania species strain 2002 was investigated. Bio-oxidation experiments were conducted in bicarbonate-buffered medium under both growth and nongrowth conditions. The extents of Fe(II) oxidation and nitrate reduction were measured by wet chemical methods. X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), and 57Fe-Mössbauer spectroscopy were used to observe mineralogical changes associated with Fe(III) reduction and Fe(II) oxidation in nontronite. The bio-oxidation extent under growth and nongrowth conditions reached 93% and 57%, respectively. Over the same time period, nitrate was completely reduced under both conditions to nitrogen gas (N2), via an intermediate product nitrite. Magnetite was a mineral product of nitrate-dependent Fe(II) oxidation, as evidenced by XRD data and TEM diffraction patterns. The results of this study highlight the importance of iron-bearing clay minerals in the global nitrogen cycle with potential applications in nitrate removal in soils.

Zhao, Linduo; Dong, Hailiang; Kukkadapu, Ravi K.; Agrawal, A.; Liu, Deng; Zhang, Jing; Edelmann, Richard E.

2013-10-15

167

Manipulating Reduction Potentials in an Artificial Safranin Cofactor  

PubMed Central

Safranines hold great promise as artificial flavin-like electron transfer cofactors with tunable properties. We report the design and chemical synthesis of the p-methoxy derivative of safranine O using a new synthetic route based on the Ulmann condensation. Spectroelectrochemical comparison of the purified parent safranine and this derivative demonstrates that the modification increases its two-electron reduction potential by 125 mV, or 5.75 kcal/mol. This modification also causes redshifts in the absorbance and fluorescence spectra of the cofactor, suggesting that it may find future utility in arrayed sensor applications. PMID:23335821

Raju, Gheevarghese; Capo, Joseph; Lichtenstein, Bruce R.; Cerda, Jose F.; Koder, Ronald L.

2013-01-01

168

Potential oxidative stress due to Pb exposure  

E-print Network

The hazards of Pb exposure has been a topic of concern for many years. This research was developed to investigate the possibility of Pb induced oxidative stress. The research objectives were to observe Pb induced lipid peroxidation and Pb induced...

Elms, Rene' Davina

2013-02-22

169

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

PubMed Central

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

Tsui, Emily Y.; Agapie, Theodor

2013-01-01

170

Biological oxidation of Fe(II) in reduced nontronite coupled with nitrate reduction by Pseudogulbenkiania sp. Strain 2002  

NASA Astrophysics Data System (ADS)

The importance of microbial nitrate-dependent Fe(II) oxidation to iron biogeochemistry is well recognized. Past research has focused on oxidation of aqueous Fe2+ and structural Fe(II) in oxides, carbonates, and phosphate, but the importance of structural Fe(II) in phyllosilicates in this reaction is only recently studied. However, the effect of clay mineralogy on the rate and the mechanism of the reaction, and subsequent mineralogical end products are still poorly known. The objective of this research was to study the coupled process of microbial oxidation of Fe(II) in clay mineral nontronite (NAu-2), and nitrate reduction by Pseudogulbenkiania species strain 2002, and to determine mineralogical changes associated with this process. Bio-oxidation experiments were conducted using Fe(II) in microbially reduced nontronite as electron donor and nitrate as electron acceptor in bicarbonate-buffered medium under both growth and nongrowth conditions to investigate cell growth on this process. The extents of Fe(II) oxidation and nitrate reduction were measured by wet chemical methods. X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), and 57Fe-Mössbauer spectroscopy were used to observe mineralogical changes associated with Fe(III) reduction and Fe(II) oxidation in NAu-2. The bio-oxidation extent under growth and nongrowth conditions reached 67% and 57%, respectively. Over the same time period, nitrate was completely reduced under both conditions to nitrogen gas (N2), via an intermediate product nitrite. Abiotic oxidation by nitrite partly accelerated Fe(II) oxidation rate under the growth condition. The oxidized Fe(III) largely remained in the nontronite structure, but secondary minerals such as vivianite, ferrihydrite, and magnetite formed depending on specific experimental conditions. The results of this study highlight the importance of iron-bearing clay minerals in the global nitrogen cycle with potential applications in nitrate removal in natural environments.

Zhao, Linduo; Dong, Hailiang; Kukkadapu, Ravi; Agrawal, Abinash; Liu, Deng; Zhang, Jing; Edelmann, Richard E.

2013-10-01

171

Simulation of catalytic oxidation and selective catalytic NOx reduction in lean-exhaust hybrid vehicles  

SciTech Connect

We utilize physically-based models for diesel exhaust catalytic oxidation and urea-based selective catalytic NOx reduction to study their impact on drive cycle performance of hypothetical light-duty diesel powered hybrid vehicles. The models have been implemented as highly flexible SIMULINK block modules that can be used to study multiple engine-aftertreatment system configurations. The parameters of the NOx reduction model have been adjusted to reflect the characteristics of Cu-zeolite catalysts, which are of widespread current interest. We demonstrate application of these models using the Powertrain System Analysis Toolkit (PSAT) software for vehicle simulations, along with a previously published methodology that accounts for emissions and temperature transients in the engine exhaust. Our results illustrate the potential impact of DOC and SCR interactions for lean hybrid electric and plug-in hybrid electric vehicles.

Gao, Zhiming [ORNL] [ORNL; Daw, C Stuart [ORNL] [ORNL; Chakravarthy, Veerathu K [ORNL] [ORNL

2012-01-01

172

Potential for mercury reduction by microbes in the high arctic.  

PubMed

The contamination of polar regions due to the global distribution of anthropogenic pollutants is of great concern because it leads to the bioaccumulation of toxic substances, methylmercury among them, in Arctic food chains. Here we present the first evidence that microbes in the high Arctic possess and express diverse merA genes, which specify the reduction of ionic mercury [Hg(II)] to the volatile elemental form [Hg(0)]. The sampled microbial biomass, collected from microbial mats in a coastal lagoon and from the surface of marine macroalgae, was comprised of bacteria that were most closely related to psychrophiles that had previously been described in polar environments. We used a kinetic redox model, taking into consideration photoredox reactions as well as mer-mediated reduction, to assess if the potential for Hg(II) reduction by Arctic microbes can affect the toxicity and environmental mobility of mercury in the high Arctic. Results suggested that mer-mediated Hg(II) reduction could account for most of the Hg(0) that is produced in high Arctic waters. At the surface, with only 5% metabolically active cells, up to 68% of the mercury pool was resolved by the model as biogenic Hg(0). At a greater depth, because of incident light attenuation, the significance of photoredox transformations declined and merA-mediated activity could account for up to 90% of Hg(0) production. These findings highlight the importance of microbial redox transformations in the biogeochemical cycling, and thus the toxicity and mobility, of mercury in polar regions. PMID:17293515

Poulain, Alexandre J; Ní Chadhain, Sinéad M; Ariya, Parisa A; Amyot, Marc; Garcia, Edenise; Campbell, Peter G C; Zylstra, Gerben J; Barkay, Tamar

2007-04-01

173

Potential for Mercury Reduction by Microbes in the High Arctic?  

PubMed Central

The contamination of polar regions due to the global distribution of anthropogenic pollutants is of great concern because it leads to the bioaccumulation of toxic substances, methylmercury among them, in Arctic food chains. Here we present the first evidence that microbes in the high Arctic possess and express diverse merA genes, which specify the reduction of ionic mercury [Hg(II)] to the volatile elemental form [Hg(0)]. The sampled microbial biomass, collected from microbial mats in a coastal lagoon and from the surface of marine macroalgae, was comprised of bacteria that were most closely related to psychrophiles that had previously been described in polar environments. We used a kinetic redox model, taking into consideration photoredox reactions as well as mer-mediated reduction, to assess if the potential for Hg(II) reduction by Arctic microbes can affect the toxicity and environmental mobility of mercury in the high Arctic. Results suggested that mer-mediated Hg(II) reduction could account for most of the Hg(0) that is produced in high Arctic waters. At the surface, with only 5% metabolically active cells, up to 68% of the mercury pool was resolved by the model as biogenic Hg(0). At a greater depth, because of incident light attenuation, the significance of photoredox transformations declined and merA-mediated activity could account for up to 90% of Hg(0) production. These findings highlight the importance of microbial redox transformations in the biogeochemical cycling, and thus the toxicity and mobility, of mercury in polar regions. PMID:17293515

Poulain, Alexandre J.; Ní Chadhain, Sinéad M.; Ariya, Parisa A.; Amyot, Marc; Garcia, Edenise; Campbell, Peter G. C.; Zylstra, Gerben J.; Barkay, Tamar

2007-01-01

174

Proton pump inhibitors: potential cost reductions by applying prescribing guidelines  

PubMed Central

Background There are concerns that proton pump inhibitors (PPI) are being over prescribed in both primary and secondary care. This study aims to establish potential cost savings in a community drug scheme for a one year period according to published clinical and cost-effective guidelines for PPI prescribing. Methods Retrospective population-based cohort study in the Republic of Ireland using the Health Services Executive (HSE) Primary Care Reimbursement Services (PCRS) pharmacy claims database. The HSE-PCRS scheme is means tested and provides free health care including medications to approximately 30% of the Irish population. Prescription items are WHO ATC coded and details of every drug dispensed and claimants’ demographic data are available. Potential cost savings (net ingredient cost) were estimated according to UK NICE clinical guidelines for all HSE-PCRS claimants on PPI therapy for ?3 consecutive months starting in 2007 with a one year follow up (n=167,747). Five scenarios were evaluated; (i) change to PPI initiation (cheapest brand); and after 3 months (ii) therapeutic switching (cheaper brand/generic equivalent); (iii) dose reduction (maintenance therapy); (iv) therapeutic switching and dose reduction and (v) therapeutic substitution (H2 antagonist). Results Total net ingredient cost was €88,153,174 for claimants on PPI therapy during 2007. The estimated costing savings for each of the five scenarios in a one year period were: (i) €36,943,348 (42% reduction); (ii) €29,568,475 (34%); (iii) €21,289,322 (24%); (iv) €40,505,013 (46%); (v) €34,991,569 (40%). Conclusion There are opportunities for substantial cost savings in relation to PPI prescribing if implementation of clinical guidelines in terms of generic substitution and step-down therapy is implemented on a national basis. PMID:23163956

2012-01-01

175

Treatment of halogenated phenolic compounds by sequential tri-metal reduction and laccase-catalytic oxidation.  

PubMed

Halogenated phenolic compounds (HPCs) are exerting negative effects on human beings and ecological health. Zero-valence metal reduction can dehalogenate HPCs rapidly but cannot mineralize them. Enzymatic catalysis can oxidize phenolic compounds but fails to dehalogenate efficiently, and sometimes even produces more toxic products. In this study, [Fe|Ni|Cu] tri-metallic reduction (TMR) and laccase-catalytic oxidation (LCO) processes were combined to sequentially remove HPCs, including triclosan, tetrabromobisphenol A, and 2-bromo-4-fluorophenol in water. The kinetics, pH and temperature dependences of TMR and LCO were obtained. The detailed TMR, LCO, and TMR-LCO transformation pathways of three HPCs were well described based on the identification of intermediate products and frontier molecular orbitals (FMOs) theory. The results showed that the two-stage process worked synergically: TMR that reductively dehalogenated HPCs followed by LCO that completely removed dehalogenated products. TMR was proven to not only improve biodegradability of HPCs but also reduce the yield of potential carcinogenic by-products. Furthermore, a TMR-LCO flow reactor was assembled and launched for 256 h, during which >95% HPCs and >75% TOC were removed. Meanwhile, monitored by microorganism indicators, 83.2%-92.7% acute toxicity of HPCs was eliminated, and the genotoxicity, produced by LCO, was also avoided by using TMR as pretreatment process. PMID:25596562

Dai, Yunrong; Song, Yonghui; Wang, Siyu; Yuan, Yu

2015-03-15

176

Reductions in kinesin expression are associated with nitric oxide-induced axonal damage.  

PubMed

Axonal injury is often characterized by axonal transport defects and abnormal accumulation of intra-axonal components. Nitric oxide (NO) has a key role in mediating inflammatory axonopathy in many neurodegenerative diseases, but little is known about how nitrosative/oxidative stress affects axonal transport or whether reductions in kinesin superfamily protein (KIF) expression correlate with axon pathology. KIFs are molecular motors that have a key role in axonal and dendritic transport, and impairment of these mechanisms has been associated with a number of neurological disorders. This study shows that rat cortical neurons exposed to NO display both a time-dependent decrease in KIF gene/protein expression and neurofilament phosphorylation in addition to a reduction in axonal length and neuronal survival. Because mesenchymal stem cells (MSCs) represent a promising therapeutic candidate for neuronal/axonal repair, this study analyzes the capacity of MSCs to protect neurons and axonal transport mechanisms from NO damage. Results show that coculture of MSCs with NO-exposed neurons results in the preservation of KIF expression, axonal length, and neuronal survival. Altogether, these results suggest a potential mechanism involved in the disruption of axonal transport and abnormal accumulation of proteins in axons during nitrosative insult. We hypothesize that impaired axonal transport contributes, per se, to progression of injury and provide further evidence of the therapeutic potential of MSCs for neurodegenerative disorders. © 2015 The Authors. Journal of Neuroscience Research Published by Wiley Periodicals, Inc. PMID:25639260

Redondo, Juliana; Hares, Kelly; Wilkins, Alastair; Scolding, Neil; Kemp, Kevin

2015-06-01

177

Poly(ethylene oxide sulfide): New Poly(ethylene glycol) Derivatives Degradable in Reductive Conditions  

E-print Network

Poly(ethylene oxide sulfide): New Poly(ethylene glycol) Derivatives Degradable in Reductive Received October 1, 2004 Poly(ethylene oxide sulfide) (PEOS), polymers consisting of an internal ethylene. The backbone of these poly(ethylene oxide sulfide) (PEOS) polymers could be degraded into small monomers

Park, Jong-Sang

178

Purified dispersions of graphene in a nonpolar solvent via solvothermal reduction of graphene oxide.  

PubMed

It is demonstrated that oxidative debris can be separated and largely removed during the surfactant assisted phase transfer of graphene oxide from a water/ethanol mixture to dichlorobenzene. The new procedure described provides a facile method to obtain monolayer dispersed graphene sheets in a nonpolar solvent via solvothermal reduction of graphene oxide accompanied by an effective purification process. PMID:25649830

Zheng, Fei; Xu, Wei-Long; Jin, Han-Dong; Zhu, Meng-Qi; Yuan, Wei-Hao; Hao, Xiao-Tao; Ghiggino, Kenneth P

2015-02-17

179

Catalytic reduction of NO by hydrocarbon in oxidizing atmosphere: Importance of hydrocarbon oxidation  

SciTech Connect

The reduction of NO by C{sub 3}H{sub 6} in excess of O{sub 2} was studied over Cu/ZSM-5, Cu/Al{sub 2}O{sub 3}, Pd/ZSM-5, and Au/Al{sub 2}O{sub 3}. The effects of various reaction parameters were examined in detail, especially for Cu/Al{sub 2}O{sub 3}. Under the integral reaction conditions studied, the effects of P(C{sub 3}H{sub 6}) and P(O{sub 2}) on the conversion of NO varied with temperature. There is little effect of P(NO) on the conversion of C{sub 3}H{sub 6} and NO at all temperatures studied. The interrelated effects of the reaction parameters is explained by a proposed mechanism in which one key step is the generation of intermediate(s) from the partial oxidation of C{sub 3}H{sub 6}. Thus, the activity of a catalyst for the selective reduction of NO is related to its activity for hydrocarbon oxidation and is also dependent on reaction conditions.

Jen, H.W.; Gandhi, H.S. [Ford Motor Co., Dearborn, MI (United States)

1993-12-31

180

Particulate Matter Oxidative Potential from Waste Transfer Station Activity  

PubMed Central

Background Adverse cardiorespiratory health is associated with exposure to ambient particulate matter (PM). The highest PM concentrations in London occur in proximity to waste transfer stations (WTS), sites that experience high numbers of dust-laden, heavy-duty diesel vehicles transporting industrial and household waste. Objective Our goal was to quantify the contribution of WTS emissions to ambient PM mass concentrations and oxidative potential. Methods PM with a diameter < 10 ?m (PM10) samples were collected daily close to a WTS. PM10 mass concentrations measurements were source apportioned to estimate local versus background sources. PM oxidative potential was assessed using the extent of antioxidant depletion from a respiratory tract lining fluid model. Total trace metal and bioavailable iron concentrations were measured to determine their contribution to PM oxidative potential. Results Elevated diurnal PM10 mass concentrations were observed on all days with WTS activity (Monday–Saturday). Variable PM oxidative potential, bioavailable iron, and total metal concentrations were observed on these days. The contribution of WTS emissions to PM at the sampling site, as predicted by microscale wind direction measurements, was correlated with ascorbate (r = 0.80; p = 0.030) and glutathione depletion (r = 0.76; p = 0.046). Increased PM oxidative potential was associated with aluminum, lead, and iron content. Conclusions PM arising from WTS activity has elevated trace metal concentrations and, as a consequence, increased oxidative potential. PM released by WTS activity should be considered a potential health risk to the nearby residential community. PMID:20368130

Godri, Krystal J.; Duggan, Sean T.; Fuller, Gary W.; Baker, Tim; Green, David; Kelly, Frank J.; Mudway, Ian S.

2010-01-01

181

A novel synthetic method for the preparation of oxide superconductors: Anionic oxidation-reduction  

NASA Astrophysics Data System (ADS)

A new chemical method for the bulk synthesis of Ba 2YCu 3O 7 powder is described and is applicable to the synthesis of other superconducting oxides. Ionic salt precursors are used which are intimately mixed by spray-drying an aqueous solution of these salts. The anions in the spray-dried mixtures (which in this study are mixtures of nitrate and acetate salts) participate in a low-temperature oxidation-reduction reaction. The exothermic redox reaction and the heat evolved from the reaction completely convert the precursors into their corresponding mixed oxides at temperatures below 300°C in one reaction step. Phase segregation (normally apparent in the decomposition of organic precursors) is not observed in the decomposition of the mixed anion (nitrate/acetate) precursors. The enthalpy of this reaction is strongly dependent upon acetate content in the mixture: -?H (9:4, acetate:nitrate) = 4016 (70) kJ/mole, whereas -?H (5:8, acetate:nitrate) = 890 (70) kJ/mole. These precursors can be reacted at 910°C for 10 min to produce single-phase Ba 2YCu 3O x. Sintered disks of Ba 2YCu 3O 7, prepared from Ba 2YCu 3O x powder, show onset Tc's of 94-95 K and are fully superconducting by 90.5-91 K.

Kourtakis, K.; Robbins, M.; Gallagher, P. K.

1989-10-01

182

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

PubMed

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. PMID:25176636

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

2015-02-01

183

Oxidatively stable nanoporous silicon photocathodes with enhanced onset voltage for photoelectrochemical proton reduction.  

PubMed

Stable and high-performance nanoporous "black silicon" photoelectrodes with electrolessly deposited Pt nanoparticle (NP) catalysts are made with two metal-assisted etching steps. Doubly etched samples exhibit an ?300 mV positive shift in photocurrent onset for photoelectrochemical proton reduction compared to oxide-free planar Si with identical catalysts. We find that the photocurrent onset voltage of black Si photocathodes prepared from single-crystal planar Si wafers by an Ag-assisted etching process increases in oxidative environments (e.g., aqueous electrolyte) owing to a positive flat-band potential shift caused by surface oxidation. However, within 24 h, the surface oxide layer becomes a kinetic barrier to interfacial charge transfer that inhibits proton reduction. To mitigate this issue, we developed a novel second Pt-assisted etch process that buries the Pt NPs deep into the nanoporous Si surface. This second etch shifts the onset voltage positively, from +0.25 V to +0.4 V versus reversible hydrogen electrode, and reduces the charge-transfer resistance with no performance decrease seen for at least two months. PEC performance was stable owing to Pt NP catalysts that were buried deeply in the photoelectrode by the second etch, below a thick surface layer comprised primarily of amorphous SiO2 along with some degree of remaining crystalline Si as observed by scanning and transmission electron micrographs. Electrochemical impedance studies reveal that the second etch leads to a considerably smaller interfacial charge-transfer resistance than samples without the additional etch, suggesting that burying the Pt NPs improves the interfacial contact to the crystalline silicon surface. PMID:25723908

Zhao, Y; Anderson, N C; Zhu, K; Aguiar, J A; Seabold, J A; Lagemaat, J van de; Branz, H M; Neale, N R; Oh, J

2015-04-01

184

The kinetics of formation of h 2 o and co 2 during iron oxide reduction  

Microsoft Academic Search

The kinetics of the chemical reaction-controlled reduction of iron oxides by H2\\/H2O and CO\\/CO2 gas mixtures are discussed. From an analysis of the systems it is concluded that the decomposition of the oxides takes place\\u000a by the two dimensional nucleation and lateral growth of oxygen vacancy clusters at the gas\\/oxide interface. The rates of decomposition\\u000a of the oxides under conditions

P. C. Hayes

1979-01-01

185

Oxidation Potentials in Matte Smelting of Copper and Nickel  

NASA Astrophysics Data System (ADS)

The oxidation potential, given as the base-ten logarithm of the oxygen partial pressure in bars and the temperature [log pO2/ T, °C], defines the state of oxidation of pyrometallurgical extraction and refining processes. This property varies from copper making, [-6/1150]; to lead/zinc smelting, [-10/1200]; to iron smelting, [-13/1600]. The current article extends the analysis to the smelting of copper and nickel/copper sulfide concentrates to produce mattes of the type Cu(Ni)FeS(O) and iron silicate slags, FeOxSiO2—with oxidation potentials of [-7.5/1250].

Matousek, Jan W.

2014-09-01

186

Using FISH-SIMS to Study Marine Methane Oxidation Coupled to the Reduction of Metal Oxides, a Plausible Microbial Metabolism for Subsurface Mars  

NASA Astrophysics Data System (ADS)

In the shallow martian subsurface, microbial life could be supported by methane oxidation coupled to the reduction of sulfate or metal oxides. Here, we report results of efforts to characterize the organisms involved in manganese-dependent marine methane oxidation.

House, C. H.; Beal, E. J.; Orphan, V. J.

2010-04-01

187

Aggregate-scale heterogeneity in iron (hydr)oxide reductive transformations  

SciTech Connect

There is growing awareness of the complexity of potential reaction pathways and the associated solid-phase transformations during the reduction of Fe (hydr)oxides, especially ferrihydrite. An important observation in static and advective-dominated systems is that microbially produced Fe(II) accelerates Ostwald ripening of ferrihydrite, thus promoting the formation of thermodynamically more stable ferric phases (lepidocrocite and goethite) and, at higher Fe(II) surface loadings, the precipitation of magnetite; high Fe(II) levels can also lead to green rust formation, and with high carbonate levels siderite may also be formed. This study expands this emerging conceptual model to a diffusion-dominated system that mimics an idealized micropore of a ferrihydrite-coated soil aggregate undergoing reduction. Using a novel diffusion cell, coupled with micro-x-ray fluorescence and absorption spectroscopies, we determined that diffusion-controlled gradients in Fe{sup 2+}{sub (aq)} result in a complex array of spatially distributed secondary mineral phases. At the diffusive pore entrance, where Fe{sup 2+} concentrations are highest, green rust and magnetite are the dominant secondary Fe (hydr)oxides (30 mol% Fe each). At intermediate distances from the inlet, green rust is not observed and the proportion of magnetite decreases from approximately 30 to <10%. Across this same transect, the proportion of goethite increases from undetectable up to >50%. At greater distances from the advective-diffusive boundary, goethite is the dominant phase, comprising between 40 and 95% of the Fe. In the presence of magnetite, lepidocrocite forms as a transient-intermediate phase during ferrihydrite-to-goethite conversion; in the absence of magnetite, conversion to goethite is more limited. These experimental observations, coupled with results of reactive transport modeling, confirm the conceptual model and illustrate the potential importance of diffusion-generated concentration gradients in dissolved Fe{sup 2+} on the fate of ferrihydrite during reduction in structured soils.

Tufano, K.J.; Benner, S.G.; Mayer, K.U.; Marcus, M.A.; Nico, P.S.; Fendorf, S.

2009-06-15

188

Reduction of Nitrogen Oxide Emissions for lean Burn Engine Technology  

SciTech Connect

Lean-burn engines offer the potential for significant fuel economy improvements in cars and trucks, perhaps the next great breakthrough in automotive technology that will enable greater savings in imported petroleum. The development of lean-burn engines, however, has been an elusive goal among automakers because of the emissions challenges associated with lead-burn engine technology. Presently, cars operate with sophisticated emissions control systems that require the engine's air-fuel ratio to be carefully controlled around the stoichiometric point (chemically correct mixture). Catalysts in these systems are called "three-way" catalysts because they can reduce hydrocarbon, carbon monoxide, and nitrogen oxide emissions simultaneously, but only because of the tight control of the air-fuel ratio. The purpose of this cooperative effort is to develop advanced catalyst systems, materials, and necessary engine control algorithms for reducing NOX emissions in oxygen-rich automotive exhaust (as with lean-burn engine technology) to meet current and near-future mandated Clean Air Act standards. These developments will represent a breakthrough in both emission control technology and automobile efficiency. The total project is a joint effort among five national laboratories, together with US CAR. The role of Lockheed-Martin Energy Systems in the total project is two fold: characterization of catalyst performance through laboratory evaluations from bench-scale flow reactor tests to engine laboratory tests of full-scale prototype catalysts, and microstructural characterization of catalyst material before and after test stand and/or engine testing.

McGill, R.N.

1998-08-04

189

Dissimilatory perchlorate reduction linked to aerobic methane oxidation via chlorite dismutase  

NASA Astrophysics Data System (ADS)

The presence of methane (CH4) in the atmosphere of Mars is controversial yet the evidence has aroused scientific interest, as CH4 could be a harbinger of extant or extinct microbial life. There are various oxidized compounds present on the surface of Mars that could serve as electron acceptors for the anaerobic oxidation of CH4, including perchlorate (ClO4-). We examined the role of perchlorate, chlorate (ClO3-) and chlorite (ClO2-) as oxidants linked to CH4 oxidation. Dissimilatory perchlorate reduction begins with reduction of ClO4- to ClO2- and ends with dismutation of chlorite to yield chloride (Cl-) and molecular oxygen (O2). We explored the potential for aerobic CH4 oxidizing bacteria to couple with oxygen derived from chlorite dismutation during dissimilatory perchlorate reduction. Methane (0.2 kPa) was completely removed within several days from the N2-flushed headspace above cell suspensions of methanotrophs (Methylobacter albus strain BG8) and perchlorate reducing bacteria (Dechloromonas agitata strain CKB) in the presence of 5 mM ClO2-. Similar rates of CH4 consumption were observed for these mixed cultures whether they were co-mingled or segregated under a common headspace, indicating that direct contact of cells was not required for methane consumption to occur. We also observed complete removal of 0.2 kPa CH4 in bottles containing dried soil (enriched in methanotrophs by CH4 additions over several weeks) and D. agitata CKB and in the presence of 10 mM ClO2-. This soil (seasonally exposed sediment) collected from the shoreline of a freshwater lake (Searsville Lake, CA) demonstrated endogenous CH4 uptake as well as perchlorate, chlorate and chlorite reduction/dismutation. However, these experiments required physical separation of soil from the aqueous bacterial culture to allow for the partitioning of O2 liberated from chlorite dismutation into the shared headspace. Although dissimilatory reduction of ClO4- and ClO3- could be inferred from the accumulation of chloride ions either in spent media or in slurries prepared from Searsville Lake soil, neither of these oxyanions evoked methane oxidation when added to either anaerobic mixed cultures or soils enriched in methanotrophs. This result leads us to surmise that the release of O2 during enzymatic perchlorate reduction was low, and that the oxygen produced was unavailable to the aerobic methanotrophs. This was borne out by patterns of O2 and CO2 production during experiments with lake soil, growth media, and pure cultures of dissimilatory perchlorate reducing bacteria. We observed that O2 release during incubation of D. agitata CKB with 10 mM ClO4- or ClO3- was decoupled from metabolism. More O2 was released during incubations without added acetate than with 10 mM acetate and an even greater amount of O2 was released during incubation with heat-killed cells. This suggests a chemical mechanism of O2 production during reaction with ClO4- and ClO3-. Hence, perchlorate reducing bacteria need not be present to facilitate O2 release from the surface of Mars, in support of recent interpretations of Viking LR and GEx experiments.

Oremland, R. S.; Baesman, S. M.; Miller, L. G.

2013-12-01

190

High-Quality Reduced Graphene Oxide by a Dual-Function Chemical Reduction and Healing Process  

NASA Astrophysics Data System (ADS)

A new chemical dual-functional reducing agent, thiophene, was used to produce high-quality reduced graphene oxide (rGO) as a result of a chemical reduction of graphene oxide (GO) and the healing of rGO. Thiophene reduced GO by donation of electrons with acceptance of oxygen while it was converted into an intermediate oxidised polymerised thiophene that was eventually transformed into polyhydrocarbon by loss of sulphur atoms. Surprisingly, the polyhydrocarbon template helped to produce good-quality rGOC (chemically reduced) and high-quality rGOCT after thermal treatment. The resulting rGOCT nanosheets did not contain any nitrogen or sulphur impurities, were highly deoxygenated and showed a healing effect. Thus the electrical properties of the as-prepared rGOCT were superior to those of conventional hydrazine-produced rGO that require harsh reaction conditions. Our novel dual reduction and healing method with thiophene could potentially save energy and facilitate the commercial mass production of high-quality graphene.

Some, Surajit; Kim, Youngmin; Yoon, Yeoheung; Yoo, Heejoun; Lee, Saemi; Park, Younghun; Lee, Hyoyoung

2013-05-01

191

Siderite, oxidation, and neutralization potential determination  

E-print Network

87 Neutralization Potential Determination of IML Samples Neutralization potential values for IML overburden samples, containing FeCOs as confirmed by XRD analysis, determined using 0. 1 M HCI were compared with the total cation concentrations... with CO3 concentration also indicate NP values are attributed to FeCO3 present in the overburden samples (Fig. 41). These data combined with XRD data show that NP values determined using 0. 1 M HCI can be attributed to the presence of FeCO3...

Porter, Elizabeth Brooke

2001-01-01

192

Method for selective catalytic reduction of nitrogen oxides  

DOEpatents

A method for catalytically reducing nitrogen oxide compounds (NO.sub.x, defined as nitric oxide, NO, +nitrogen dioxide, NO.sub.2) in a gas by a material comprising a base metal consisting essentially of CuO and Mn, and oxides of Mn, on an activated metal hydrous metal oxide support, such as HMO:Si. A promoter, such as tungsten oxide or molybdenum oxide, can be added and has been shown to increase conversion efficiency. This method provides good conversion of NO.sub.x to N.sub.2, good selectivity, good durability, resistance to SO.sub.2 aging and low toxicity compared with methods utilizing vanadia-based catalysts.

Mowery-Evans, Deborah L. (Broomfield, CO); Gardner, Timothy J. (Albuquerque, NM); McLaughlin, Linda I. (Albuquerque, NM)

2005-02-15

193

Method For Selective Catalytic Reduction Of Nitrogen Oxides  

DOEpatents

A method for catalytically reducing nitrogen oxide compounds (NO.sub.x, defined as nitric oxide, NO, +nitrogen dioxide, NO.sub.2) in a gas by a material comprising a base metal consisting essentially of CuO and Mn, and oxides of Mn, on an activated metal hydrous metal oxide support, such as HMO:Si. A promoter, such as tungsten oxide or molybdenum oxide, can be added and has been shown to increase conversion efficiency. This method provides good conversion of NO.sub.x to N.sub.2, good selectivity, good durability, resistance to SO.sub.2 aging and low toxicity compared with methods utilizing vanadia-based catalysts.

Mowery-Evans, Deborah L. (Broomfield, CO); Gardner, Timothy J. (Albuquerque, NM); McLaughlin, Linda I. (Albuquerque, NM)

2005-02-15

194

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

NASA Technical Reports Server (NTRS)

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

Myers, Charles R.; Nealson, Kenneth H.

1988-01-01

195

Biomineralization associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals  

USGS Publications Warehouse

Iron-reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so play an important role in the geochemical cycling of iron. This study was undertaken to investigate mineral transformations associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals. A fluid sample from the 2450 m depth of the Chinese Continental Scientific Drilling project was collected, and Fe3+-reducing and Fe2+-oxidizing microorganisms were enriched. The enrichment cultures displayed reduction of Fe3+ in nontronite and ferric citrate, and oxidation of Fe2+ in vivianite, siderite, and monosulfide (FeS). Additional experiments verified that the iron reduction and oxidation was biological. Oxidation of FeS resulted in the formation of goethite, lepidocrocite, and ferrihydrite as products. Although our molecular microbiological analyses detected Thermoan-aerobacter ethanolicus as a predominant organism in the enrichment culture, Fe3+ reduction and Fe2+ oxidation may be accomplished by a consortia of organisms. Our results have important environmental and ecological implications for iron redox cycling in solid minerals in natural environments, where iron mineral transformations may be related to the mobility and solubility of inorganic and organic contaminants.

Zhang, G.; Dong, H.; Jiang, H.; Kukkadapu, R.K.; Kim, J.; Eberl, D.; Xu, Z.

2009-01-01

196

Acetylene inhibition of nitrous oxide reduction by denitrifying bacteria  

Microsoft Academic Search

Acetylene (0.1 atm) caused complete or almost complete inhibition of reduction of NâO by whole cell suspensions of Pseudomonas perfectomarinus, P. aeruginosa and Micrococcus denitrificans. Acetylene did not inhibit reduction of NOâ⁻ or NOâ⁻ by these organisms. In the presence of acetylene there was stoichiometric conversion of NOâ⁻ or NOâ⁻ to NâO with negligible subsequent reduction of the latter. In

T. Yoshinari; R. Knowles

1976-01-01

197

Interfacial Reduction-Oxidation Mechanisms Governing Fate and Transport of Contaminants in the Vadose Zone  

SciTech Connect

There are many soil contamination sites at the Department of Energy (DOE) installations that contain radionuclides and toxic metals such as uranium (U), technetium (Tc), and chromium (Cr). Since these contaminants are the main 'risk drivers' at the Hanford site (WA) and some of them also pose significant risk at other DOE facilities (e.g., Oak Ridge Reservation - TN; Rocky Flats - CO), development of technologies for cost effective site remediation is needed. Current assessment indicates that complete removal of these contaminants for ex-situ disposal is infeasible, thus in-situ stabilization through reduction to insoluble species is considered one of the most important approaches for site remediation. In Situ Gaseous Reduction (ISGR) is a technology developed by Pacific Northwest National Laboratory (PNNL) for vadose zone soil remediation. The ISGR approach uses hydrogen sulfide (H{sub 2}S) for reductive immobilization of contaminants that show substantially lower mobility in their reduced forms (e.g., Tc, U, and Cr). The technology can be applied in two ways: (i) to immobilize or stabilize pre-existing contaminants in the vadose zone soils by direct H{sub 2}S treatment, or (ii) to create a permeable reactive barrier (PRB) that prevents the migration of contaminants. Direct treatment involves reduction of the contaminants by H{sub 2}S to less mobile species. Formation of a PRB is accomplished through reduction of ferric iron species in the vadose zone soils by H{sub 2}S to iron sulfides (e.g., FeS), which provides a means for capturing the contaminants entering the treated zone. Potential future releases may occur during tank closure activities. Thus, the placement of a permeable reactive barrier by ISGR treatment can be part of the leak mitigation program. Deployment of these ISGR approaches, however, requires a better understanding of the immobilization kinetics and mechanisms, and a better assessment of the long-term effectiveness of treatment. The primary objective of this project was to understand the complex interactions among the contaminants (i.e., Cr, Tc, and U), H{sub 2}S, and various soil constituents. The reaction with iron sulfide is also the focus of the research, which could be formed from iron oxide reduction by hydrogen sulfide. Factors controlling the reductive immobilization of these contaminants were identified and quantified. The results and fundamental knowledge obtained from this project shall help better evaluate the potential of in situ gaseous treatment to immobilize toxic and radioactive metals examined.

Principal Investigator: Baolin Deng, University of Missouri, Columbia, MO; Co-Principal Investigator: Silvia Sabine Jurisson, University of Missouri, Columbia, MO; Co-Principal Investigator: Edward C. Thornton, Pacific Northwest National Laboratory Richland, WA; Co-Principal Investigator: Jeff Terry, Illinois Institute of Technology, Chicago, IL

2008-05-12

198

Developing Investigation Skills in an Introductory Multistep Synthesis Using Fluorene Oxidation and Reduction  

ERIC Educational Resources Information Center

A two-step oxidation-reduction sequence that incorporates several important aspects of synthesis into introductory organic chemistry laboratories is described. This experiment is an excellent vehicle for introducing elements of discovery and intermediate yield improvement strategies.

Stocksdale, Mark G; Pointer, Roy D; Benson, Barret W.; Fletcher, Steven E. S.; Henry, Ian; Ogren, Paul J.; Berg, Michael A. G.

2004-01-01

199

Electronic structure of perovskite oxide surfaces at elevated temperatures and its correlation with oxygen reduction reactivity  

E-print Network

The objective is to understand the origin of the local oxygen reduction reaction (ORR) activity on the basis of the local electronic structure at the surface of transition metal oxides at elevated temperatures and in oxygen ...

Chen, Yan, Ph. D. Massachusetts Institute of Technology

2014-01-01

200

IN-SITU CHEMICAL OXIDATION - DNAPL MASS REDUCTION TECHNOLOGY  

EPA Science Inventory

In-situ chemical oxidation (ISCO) is a rapidly developing technology used at hazardous waste sites where oxidants and complimentary reagents are injected into the subsurface to transform organic contaminants into less toxic byproducts. This technology is being used at new sites ...

201

Potentiation of an antimalarial oxidant drug.  

PubMed

In a previous report we described the synergistic antimalarial interaction between two structurally similar compounds, rufigallol and exifone. To explain this phenomenon, we proposed that exifone is transformed inside the parasitized erythrocyte into a xanthone with potent antimalarial properties. We speculated that the transformation process was induced by the prooxidant activity of rufigallol. On the basis of this model we hypothesized that exifone would act synergistically with other oxidant drugs. In the present study we have found a similar synergistic interaction between exifone and ascorbic acid (vitamin C) against both chloroquine-susceptible and multidrug-resistant strains of Plasmodium falciparum. The prooxidant activity of ascorbic acid against Plasmodium-infected erythrocytes is believed to result from an intraerythrocytic Fenton reaction occurring in the acidic food vacuole of the parasite. The hydroxyl radicals produced during this process are believed to attack exifone, which undergoes cyclodehydration to become 2,3,4,5,6-pentahydroxyxanthone (X5). Evidence presented to support this "xanthone hypothesis" includes the demonstration that the exifone ==> X5 transformation occurs readily in vitro under mildly acidic conditions in the presence of iron, ascorbic acid, and oxygen. PMID:9210664

Winter, R W; Ignatushchenko, M; Ogundahunsi, O A; Cornell, K A; Oduola, A M; Hinrichs, D J; Riscoe, M K

1997-07-01

202

Potentiation of an antimalarial oxidant drug.  

PubMed Central

In a previous report we described the synergistic antimalarial interaction between two structurally similar compounds, rufigallol and exifone. To explain this phenomenon, we proposed that exifone is transformed inside the parasitized erythrocyte into a xanthone with potent antimalarial properties. We speculated that the transformation process was induced by the prooxidant activity of rufigallol. On the basis of this model we hypothesized that exifone would act synergistically with other oxidant drugs. In the present study we have found a similar synergistic interaction between exifone and ascorbic acid (vitamin C) against both chloroquine-susceptible and multidrug-resistant strains of Plasmodium falciparum. The prooxidant activity of ascorbic acid against Plasmodium-infected erythrocytes is believed to result from an intraerythrocytic Fenton reaction occurring in the acidic food vacuole of the parasite. The hydroxyl radicals produced during this process are believed to attack exifone, which undergoes cyclodehydration to become 2,3,4,5,6-pentahydroxyxanthone (X5). Evidence presented to support this "xanthone hypothesis" includes the demonstration that the exifone ==> X5 transformation occurs readily in vitro under mildly acidic conditions in the presence of iron, ascorbic acid, and oxygen. PMID:9210664

Winter, R W; Ignatushchenko, M; Ogundahunsi, O A; Cornell, K A; Oduola, A M; Hinrichs, D J; Riscoe, M K

1997-01-01

203

Phenylarsine oxide as a redox modulator of transient receptor potential vanilloid type 1 channel function.  

PubMed

Transient receptor potential vanilloid type 1 (TRPV1) channels are capable of detecting and integrating noxious stimuli and play an important role in nociceptor activation and sensitization. It has been demonstrated that oxidizing agents are capable of positively modulating (sensitizing) the TRPV1 channel. The present study investigates the ability of the thiol-oxidizing agent phenylarsine oxide (PAO) to modulate TRPV1 currents under voltage-clamp conditions. We assessed the ability of PAO to modulate both proton- and capsaicin-activated currents mediated by recombinant human TRPV1 channels as well as native rat and human TRPV1 channels in dorsal root ganglion (DRG) neurons. Experiments with other oxidizing and reducing agents having various membrane-permeating properties supported the intracellular oxidizing mechanism of PAO modulation. The PAO modulation of proton-activated currents was consistent across the cell types studied, with an increase in current across the proton concentrations studied. PAO modulation of the capsaicin-activated current in hTRPV1/Chinese hamster ovary cells consisted of potentiation of the current elicited with low capsaicin concentrations and inhibition of the current at higher concentrations. This same effect was seen with these recombinant cells in calcium imaging experiments and with native TRPV1 channels in rat DRG neurons. Contrary to this, currents in human DRG neurons were potentiated at all capsaicin concentrations tested after PAO treatment. These results could indicate important differences in the reduction-oxidation modulation of human TRPV1 channels in a native cellular environment. PMID:25250537

Carlin, Kevin P; Wu, Gang; Patel, Aniket; Crumley, Gregg; Ilyin, Victor I

2015-02-01

204

Effects of dissimilatory sulfate reduction on FeIII (hydr)oxide reduction and microbial community development  

NASA Astrophysics Data System (ADS)

Although dissimilatory iron and sulfate reduction (DIR and DSR) profoundly affect the biogeochemical cycling of C, Fe, and S in subsurface systems, the dynamics of DIR and DSR in the presence of both FeIII (hydr)oxides and sulfate have not been well-studied with mixed microbial populations. This study examined the response of native microbial communities in subsurface sediment from the U.S. Department of Energy’s Integrated Field Research Challenge site in Rifle, CO to the availability of sulfate and specific FeIII (hydr)oxide minerals in experimental systems containing lactate as the electron donor, with ferrihydrite, goethite, or lepidocrocite and high (10.2 mM) or low (0.2 mM) sulfate as electron acceptors. We observed rapid fermentation of lactate to acetate and propionate. FeIII reduction was slow and limited in the presence of low-sulfate, but the extent of FeIII reduction increased more than 10 times with high-sulfate amendments. Furthermore, the extent of FeIII reduction was higher in ferrihydrite or lepidocrocite incubations than in goethite incubations. Propionate produced during fermentation of lactate was used as the electron donor for DSR. The concurrence of sulfate reduction and FeII production suggests that FeII production was driven primarily by reduction of FeIII by biogenic sulfide. X-ray absorption fine-structure analysis confirmed the formation of ferrous sulfide and the presence of O-coordinated ferrous species. 16S rRNA-based microbial community analysis revealed the development of distinct communities with different FeIII (hydr)oxides. These results highlight the highly coupled nature of C, Fe, and S biogeochemical cycles during DIR and DSR and provide new insight into the effects of electron donor utilization, sulfate concentration, and the presence of specific FeIII (hydr)oxide phases on microbial community development.

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

2014-03-01

205

Coupled reductive and oxidative sulfur cycling in the phototrophic plate of a meromictic lake.  

PubMed

Mahoney Lake represents an extreme meromictic model system and is a valuable site for examining the organisms and processes that sustain photic zone euxinia (PZE). A single population of purple sulfur bacteria (PSB) living in a dense phototrophic plate in the chemocline is responsible for most of the primary production in Mahoney Lake. Here, we present metagenomic data from this phototrophic plate--including the genome of the major PSB, as obtained from both a highly enriched culture and from the metagenomic data--as well as evidence for multiple other taxa that contribute to the oxidative sulfur cycle and to sulfate reduction. The planktonic PSB is a member of the Chromatiaceae, here renamed Thiohalocapsa sp. strain ML1. It produces the carotenoid okenone, yet its closest relatives are benthic PSB isolates, a finding that may complicate the use of okenone (okenane) as a biomarker for ancient PZE. Favorable thermodynamics for non-phototrophic sulfide oxidation and sulfate reduction reactions also occur in the plate, and a suite of organisms capable of oxidizing and reducing sulfur is apparent in the metagenome. Fluctuating supplies of both reduced carbon and reduced sulfur to the chemocline may partly account for the diversity of both autotrophic and heterotrophic species. Collectively, the data demonstrate the physiological potential for maintaining complex sulfur and carbon cycles in an anoxic water column, driven by the input of exogenous organic matter. This is consistent with suggestions that high levels of oxygenic primary production maintain episodes of PZE in Earth's history and that such communities should support a diversity of sulfur cycle reactions. PMID:24976102

Hamilton, T L; Bovee, R J; Thiel, V; Sattin, S R; Mohr, W; Schaperdoth, I; Vogl, K; Gilhooly, W P; Lyons, T W; Tomsho, L P; Schuster, S C; Overmann, J; Bryant, D A; Pearson, A; Macalady, J L

2014-09-01

206

Reversible phenol oxidation and reduction in the structurally well-defined 2-Mercaptophenol-??C protein.  

PubMed

2-Mercaptophenol-??C serves as a biomimetic model for enzymes that use tyrosine residues in redox catalysis and multistep electron transfer. This model protein was tailored for electrochemical studies of phenol oxidation and reduction with specific emphasis on the redox-driven protonic reactions occurring at the phenol oxygen. This protein contains a covalently modified 2-mercaptophenol-cysteine residue. The radical site and the phenol compound were specifically chosen to bury the phenol OH group inside the protein. A solution nuclear magnetic resonance structural analysis (i) demonstrates that the synthetic 2-mercaptophenol-??C model protein behaves structurally as a natural protein, (ii) confirms the design of the radical site, (iii) reveals that the ligated phenol forms an interhelical hydrogen bond to glutamate 13 (phenol oxygen-carboxyl oxygen distance of 3.2 ± 0.5 Å), and (iv) suggests a proton-transfer pathway from the buried phenol OH (average solvent accessible surface area of 3 ± 5%) via glutamate 13 (average solvent accessible surface area of the carboxyl oxygens of 37 ± 18%) to the bulk solvent. A square-wave voltammetry analysis of 2-mercaptophenol-??C further demonstrates that (v) the phenol oxidation-reduction cycle is reversible, (vi) formal phenol reduction potentials can be obtained, and (vii) the phenol-O(•) state is long-lived with an estimated lifetime of ?180 millisecond. These properties make 2-mercaptophenol-??C a unique system for characterizing phenol-based proton-coupled electron transfer in a low-dielectric and structured protein environment. PMID:23373469

Tommos, Cecilia; Valentine, Kathleen G; Martínez-Rivera, Melissa C; Liang, Li; Moorman, Veronica R

2013-02-26

207

Oxidation-reduction Potentials and Capillary Activities of Humic Acids  

Microsoft Academic Search

APART from the effects which humic acids have on the physical properties of the soil, such as its structure, permeability and water retention, and through which they influence the growth of plants, it has been shown that humic acids also have a directly stimulating effect on plant growth1-3. In an attempt to trace the cause of this stimulation, Flaig and

S. A. Visser

1964-01-01

208

DISSOLVED OXYGEN AND OXIDATION-REDUCTION POTENTIALS IN GROUND WATER  

EPA Science Inventory

Water samples were collected from various depths in a pristine sand and gravel water table aquifer at monthly intervals over a period of one year. Dissolved oxygen concentrations were near saturation 9 feet below the water table and decreased to nearly zero at 78 feet below the w...

209

Interfacial Reduction-Oxidation Mechanisms Governing Fate and Transport of Contaminants in the Vadose Zone  

SciTech Connect

The mobility of many contaminants is redox sensitive and thus related to the reduction oxidation characteristics of the environment. Immobilization of certain contaminants (e.g., chromium, uranium, and technetium) can be achieved by reducing the contaminant. One remediation approach to achieving this is the application of diluted hydrogen sulfide gas mixtures, which may have particular value in vadose zone applications. Previous work has shown this approach to be viable for Cr(VI) remediation of soil waste sites. The primary objective of the current research is to assess the potential of in situ gaseous treatment to the immobilization of U(VI) and Tc(VII). This work also addresses basic science aspects of understanding the redox-related aspects of the mobility of these contaminants in the natural environment, thus providing a mechanistic-based understanding needed to successfully achieve remediation.

Thornton, Edward C.; Baolin Deng; Jurisson, Silvia Sabine; Terry, Jeff

2006-06-01

210

Technetium reduction in sediments of a shallow aquifer exhibiting dissimilatory iron reduction potential  

E-print Network

Technetium reduction in sediments of a shallow aquifer exhibiting dissimilatory iron reduction of the Federation of European Microbiological Societies. Keywords: Technetium; Iron reduction; Sediments; Bioremediation 1. Introduction Technetium (99 Tc) is a long-lived (t1=2 ¼ 2:13 Â 105 years) nuclear fission

Roden, Eric E.

211

DEVELOPMENT AND EVALUATION OF A MATHEMATICAL MODEL FOR THE TRANSPORT AND OXIDATION-REDUCTION OF COEDTA  

EPA Science Inventory

Oxidation-reduction reactions, catalyzed by iron and manganese oxides, influence the subsurface mobility of a variety of toxic metals. In the work reported here, we develop a new model for the transport of the redox-sensitive CoEDTA complex, and we test the model against publishe...

212

Santonic acid: Zn-HCl-ether reduction and ceric ammonium nitrate oxidation.  

PubMed

Reduction of santonic acid using Zn-HCl-ether yielded succinic anhydride derivatives via pinacolisation followed by rearrangement, whereas oxidation of santonic acid using ceric ammonium nitrate afforded five oxidative decarboxylation products. Dedicated to Prof. TBH McMurry. PMID:24938372

Fondekar, Kamlesh Pai; Malik, Bhiwa; Paknikar, Shashikumar Keshav

2014-01-01

213

SPATIAL AND TEMPORAL GRADIENTS IN AQUIFER OXIDATION- REDUCTION CONDITIONS  

EPA Science Inventory

The study was undertaken to identify principal oxidizing and reducing chemical species in groundwater with the goal of determining the utility of platinum electrode (Eh) measurements to characterize subsurface redox conditions. Serial measurements of Eh and groundwater analyses w...

214

SPATIAL AND TEMPORAL GRADIENTS IN AQUIFER OXIDATION-REDUCTION CONDITIONS  

EPA Science Inventory

The study was undertaken to identify principal oxidizing and reducing chemical species in groundwater with the goal of determining the utility of platinum electrode (Eh) measurements to characterize subsurface redox conditions. erial measurements of Eh and groundwater analyses we...

215

The Fundamental Role of Nano-Scale Oxide Films in the Oxidation of Hydrogen and the Reduction of Oxygen on Noble Metal Electrocatalysts  

SciTech Connect

The derivation of successful fuel cell technologies requires the development of more effective, cheaper, and poison-resistant electrocatalysts for both the anode (H{sub 2} oxidation in the presence of small amounts of CO from the reforming of carbonaceous fuels) and the cathode (reduction of oxygen in the presence of carried-over fuel). The proposed work is tightly focused on one specific aspect of electrocatalysis; the fundamental role(s) played by nanoscale (1-2 nm thick) oxide (''passive'') films that form on the electrocatalyst surfaces above substrate-dependent, critical potentials, on charge transfer reactions, particularly at elevated temperatures (25 C < T < 200 C). Once the role(s) of these films is (are) adequately understood, we will then use this information to specify, at the molecular level, optimal properties of the passive layer for the efficient electrocatalysis of the oxygen reduction reaction.

Digby Macdonald

2005-04-15

216

Fluidized reduction of oxides on fine metal powders without sintering  

NASA Technical Reports Server (NTRS)

In the process of reducing extremely fine metal particles (av. particle size or = 1000 angstroms) covered with an oxide layer, the metal particles are fluidized by a gas flow contg. H, heated, and reduced. The method uniformly and easily reduces surface oxide layers of the extremely fine metal particles without causing sintering. The metal particles are useful for magnetic recording materials, conductive paste, powder metallurgy materials, chem. reagents, and catalysts.

Hayashi, T.

1985-01-01

217

Author's personal copy Microbial reduction of chlorite and uranium followed by air oxidation  

E-print Network

Author's personal copy Microbial reduction of chlorite and uranium followed by air oxidation, we examined the reduction of structural Fe(III) in chlorite CCa-2 and uranium(VI) by Shewanella Uranium contamination of sediment and groundwater is a problem at many U.S. Department of Energy (DOE

Burgos, William

218

Journal of Power Sources 167 (2007) 265271 Simultaneous oxygen-reduction and methanol-oxidation reactions  

E-print Network

Journal of Power Sources 167 (2007) 265­271 Simultaneous oxygen-reduction and methanol-reduction reaction (ORR) and methanol- oxidation reaction (MOR) at the cathode of a DMFC. Good agreements between a significant poisoning effect on the ORR by the presence of methanol at the cathode. The results also indicated

Zhao, Tianshou

219

Carbon monoxide-induced reduction and healing of graphene oxide Badri Narayanana)  

E-print Network

#12;LETTERS Carbon monoxide-induced reduction and healing of graphene oxide Badri Narayanana, The Netherlands and Dutch Institute for Fundamental Energy Research, 3430 BE, Nieuwegein, The Netherlands Peter monoxide; the energy barriers for reduction by CO are very small and easily overcome at low temperatures

Ciobanu, Cristian

220

Selective reduction of nitric oxides with ammonia using a cellular block catalyst  

SciTech Connect

An aluminum-vanadium cellular block catalyst for selective reduction of nitric oxides with ammonia has been developed. With an average degree of conversion of oxides over 90%, the efficiency of the proposed catalyst is significantly higher than that of industrial catalysts currently used. Such catalyst can be recommended for use in selective plants for purification of waste gases from nitric oxides, which makes it possible to significantly decrease the cost of making a catalyst block.

M.V. D'yakov; A.I. Kozlov; E.S. Lukin [and others] [D.I. Mendeleev Russian Chemical Engineering University, Moscow (Russian Federation)

2004-03-15

221

In-situ X-Ray Absorption Spectroscopy (XAS) Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction  

PubMed Central

In-situ x-ray absorption spectroscopy (XAS) is a powerful technique that can be applied to electrochemical systems, with the ability to elucidate the chemical nature of electrocatalysts under reaction conditions. In this study, we perform in-situ XAS measurements on a bifunctional manganese oxide (MnOx) catalyst with high electrochemical activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Using x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS), we find that exposure to an ORR-relevant potential of 0.7 V vs. RHE produces a disordered Mn3II,III,IIIO4 phase with negligible contributions from other phases. After the potential is increased to a highly anodic value of 1.8 V vs. RHE, relevant to the OER, we observe an oxidation of approximately 80% of the catalytic thin film to form a mixed MnIII,IV oxide, while the remaining 20% of the film consists of a less oxidized phase, likely corresponding to unchanged Mn3II,III,IIIO4. XAS and electrochemical characterization of two thin film catalysts with different MnOx thicknesses reveals no significant influence of thickness on the measured oxidation states, at either ORR or OER potentials, but demonstrates that the OER activity scales with film thickness. This result suggests that the films have porous structure, which does not restrict electrocatalysis to the top geometric layer of the film. As the portion of the catalyst film that is most likely to be oxidized at the high potentials necessary for the OER is that which is closest to the electrolyte interface, we hypothesize that the MnIII,IV oxide, rather than Mn3II,III,IIIO4, is the phase pertinent to the observed OER activity. PMID:23758050

Benck, Jesse D.; Gul, Sheraz; Webb, Samuel M.; Yachandra, Vittal K.; Yano, Junko; Jaramillo, Thomas F.

2013-01-01

222

Solid oxide membrane process for the direct reduction of magnesium from magnesium oxide  

NASA Astrophysics Data System (ADS)

The Solid Oxide Membrane (SOM) process is an emerging generic technology for the environmentally friendly extraction of high-energy-content metals directly from their oxides. This process has the potential to offer a viable, cost effective and cleaner alternative to existing state of the art primary magnesium extraction processes. The SOM process in principle uses a tubular yttria stabilized-zirconia-based solid oxide fuel cell with liquid metal (copper or tin) as an anode in the temperature range of 1100--1300°C. Magnesium oxide is dissolved in a molten ionic flux and oxygen ions are pumped out of the flux through the zirconia membrane and are oxidized at, the liquid metal anode. Magnesium vapor evolves at the cathode and is condensed in a separate chamber (condenser). The proof of concept for the SOM process was initially demonstrated at 1300°C using a magnesium fluoride-based flux. Since the membrane is the most expensive part of the process, its long-term stability is critical to the scale up and eventual commercialization of the process. Temperature, flux chemistry and cell operating conditions have been identified as key process parameters for membrane stability. A new low temperature flux based on the eutectic: magnesium fluoride-calcium fluoride system, has been developed which has lowered the operating temperature of the SOM cell to 1150°C. Additionally, a minor addition of yttrium fluoride to the flux minimized yttria diffusion from the yttria-stabilized-zirconia membrane, thereby further enhancing membrane stability. Important thermo-physical properties of the selected flux compositions critical to the process such as viscosity, density, volatility, solubility and electrical conductivity have been measured. The SOM cell has been electrochemically characterized and concepts related to MgO dissociation voltage, observed leakage current and mass transfer in the SOM cell are explained. The viability of the SOM process has been demonstrated by the operation of a 100 g scale reactor. Preliminary cost estimates and design of a commercial reactor based on this investigation are also discussed.

Krishnan, Ajay

223

Comparative survey of potential nitrate and sulfate reduction rates in aquatic sediments  

NASA Astrophysics Data System (ADS)

Nitrate and sulfate are two major terminal electron acceptors of anaerobic respiration in nearshore sediments. Potential nitrate and sulfate reduction rates (NRR and SRR) were determined on surficial sediments sampled at 14 sites representing a wide range of shallow-water depositional environments. The rates were obtained by supplying undisturbed slices of sediments with nitrate, sulfate or both using a flow-through reactor technique. No external electron donor was added to the sediments. The results indicate that all studied sediments harbored viable and coexisting nitrate- and sulfate-reducing communities, which were able to instantaneously consume the electron acceptors supplied to the reactors. On average, NRR exceeded SRR by about one order of magnitude (309 ± 180 nmol NO3- cm-3 h-1versus 37 ± 29 nmol SO42- cm-3 h-1). The NRR:SRR molar ratio, however, varied significantly from site to site, with values ranging from 1.7 to 59. Nitrite production, indicative of incomplete nitrate reduction, was observed in all studied sediments and, on average, accounted for 45% of NRR (range 3-80%). Production of sulfate under nitrate-reducing conditions was observed in 10 out of 14 of the studied sediments, suggesting a common occurrence of sulfide oxidation coupled to nitrate reduction. Oxidation of sulfide accounted for 0 to 40% of NRR in the nitrate-only experiments. When both electron acceptors were supplied simultaneously, net sulfate consumption decreased on average by 45%. The effect of nitrate on SRR was highly variable, however, ranging from near complete inhibition to a 25% enhancement of SRR. Overall, the results of this study point to the need to critically reassess the model formulations used to represent anaerobic respiration processes and their interactions in early diagenetic models.

Laverman, Anniet M.; Pallud, Céline; Abell, Jeffrey; Cappellen, Philippe Van

2012-01-01

224

Standard reduction potentials of all couples of the peroxidase cycle of lactoperoxidase.  

PubMed

Lactoperoxidase (LPO) is found in mucosal surfaces and exocrine secretions including milk, tears and saliva and has physiological significance in antimicrobial defense. Its predominant physiological role is to convert hydrogen peroxide and thiocyanate in hypothiocyanite. In this study, the standard reduction potentials of all redox couples involved in the halogenation and peroxidase cycle of LPO have been determined by multi-mixing stopped-flow spectroscopy. The standard reduction potentials of the redox couples compound I/native LPO, compound I/compound II of LPO, and compound II/native LPO are (1.09 +/- 0.01) V, (1.14 +/- 0.02) V, and (1.04 +/- 0.02) V, respectively, at pH 7 and 25 degrees C. Thus, for the first time, a full description of these important thermodynamic parameters of lactoperoxidase has been performed, allowing a better understanding in the substantial differences in the oxidation of two- and one-electron donors by LPO and other members of the mammalian heme peroxidase superfamily. PMID:15833345

Furtmüller, Paul Georg; Arnhold, Jürgen; Jantschko, Walter; Zederbauer, Martina; Jakopitsch, Christa; Obinger, Christian

2005-05-01

225

Improved TiO2 photocatalytic reduction by the intrinsic electrostatic potential of BN nanotubes.  

PubMed

We describe the synthesis of novel nanocrystalline TiO(2) closely attached to BN nanotubes (BNNTs). The method involves the reaction of Ti(3+) with the oxidized radicals BN-H(+) to form BN-Ti(4+) bonds first, and then in situ hydrolytic conversion of the attached Ti(4+) into TiO(2). The designed reaction was carried out in a strongly acidic ethanol solution to ensure that the TiO(2) forms on the BNNT surface rather than in solution. We also report the improved photocatalytic reduction properties of TiO(2) when functionalized on BNNT surfaces and take advantage of the strong underlying electrostatic potential of the high-purity nanotubes. PMID:20391468

Tang, Chengchun; Li, Jiguang; Bando, Yoshio; Zhi, Chunyi; Golberg, Dmitri

2010-05-01

226

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

SciTech Connect

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 reduction. The Michaelis-Menten K{sub m} values of 71 {+-} 22 m{sup 2}/L for hematite and 50 {+-} 16 m{sup 2}/L for goethite were calculated as a function of surface area of the two insoluble minerals. V{sub max} was determined to be 123 {+-} 14 and 156 {+-} 13 nmol Fe(II)/min/mg of TM protein for hematite and goethite, respectively. These values are consistent with in vivo rates of reduction reported in the literature. These observations are consistent with our conclusion that the enzymatic reduction of mineral oxides is an effective probe that will allow elucidation of molecular chemistry of the membrane-mineral interface where electron transfer occurs.

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

2006-01-01

227

Kinetics of reduction of iron oxides using microwaves as power source  

SciTech Connect

This work deals with kinetic description of carbothermic reduction of iron oxides using microwaves as power source. Previous researches show that it is possible to conduct this kind of process successfully, but real kinetic comparisons between conventional and microwaves procedure have been presented partially. The aim of this work is to describe reduction kinetics, taking into account how the iron oxide is reduced by microwaves compared with conventional energy supply. In this study the authors used iron ore in pellet shape and dust. They found that both, pellet and dust reduction stops when it reaches approximately 40%, even at whole power.

Gomez, I.; Aguilar, J.; Gonzalez, M.; Morales, J. [Univ. Autonoma de Nuevo Leon, San Nicolas de los Garza (Mexico). Facultad de Ingenieria Mecanica y Electrica

1996-12-31

228

In vitro enzymatic reduction kinetics of mineral oxides by membrane fractions from Shewanella oneidensis MR-1  

NASA Astrophysics Data System (ADS)

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 reduction. The Michaelis-Menten Km values of 71 ± 22 m 2/L for hematite and 50 ± 16 m 2/L for goethite were calculated as a function of surface area of the two insoluble minerals. Vmax was determined to be 123 ± 14 and 156 ± 13 nmol Fe(II)/min/mg of TM protein for hematite and goethite, respectively. These values are consistent with in vivo rates of reduction reported in the literature. These observations are consistent with our conclusion that the enzymatic reduction of mineral oxides is an effective probe that will allow elucidation of molecular chemistry of the membrane-mineral interface where electron transfer occurs.

Ruebush, Shane S.; Icopini, Gary A.; Brantley, Susan L.; Tien, Ming

2006-01-01

229

Study on emission characteristics and reduction strategy of nitrous oxide during wastewater treatment by different processes.  

PubMed

Given the inexorable increase in global wastewater treatment, increasing amounts of nitrous oxide are expected to be emitted from wastewater treatment plants and released to the atmosphere. It has become imperative to study the emission and control of nitrous oxide in the various wastewater treatment processes currently in use. In the present investigation, the emission characteristics and the factors affecting the release of nitrous oxide were studied via full- and pilot-scale experiments in anoxic-oxic, sequencing batch reactor and oxidation ditch processes. We propose an optimal treatment process and relative strategy for nitrous oxide reduction. Our results show that both the bio-nitrifying and bio-denitrifying treatment units in wastewater treatment plants are the predominant sites for nitrous oxide production in each process, while the aerated treatment units are the critical sources for nitrous oxide emission. Compared with the emission of nitrous oxide from the anoxic-oxic (1.37 % of N-influent) and sequencing batch reactor (2.69 % of N-influent) processes, much less nitrous oxide (0.25 % of N-influent) is emitted from the oxidation ditch process, which we determined as the optimal wastewater treatment process for nitrous oxide reduction, given the current technologies. Nitrous oxide emissions differed with various operating parameters. Controlling the dissolved oxygen concentration at a proper level during nitrification and denitrification and enhancing the utilization rate of organic carbon in the influent for denitrification are the two critical methods for nitrous oxide reduction in the various processes considered. PMID:25280506

Sun, Shichang; Bao, Zhiyuan; Sun, Dezhi

2015-03-01

230

Electric coupling between distant nitrate reduction and sulfide oxidation in marine sediment.  

PubMed

Filamentous bacteria of the Desulfobulbaceae family can conduct electrons over centimeter-long distances thereby coupling oxygen reduction at the surface of marine sediment to sulfide oxidation in deeper anoxic layers. The ability of these cable bacteria to use alternative electron acceptors is currently unknown. Here we show that these organisms can use also nitrate or nitrite as an electron acceptor thereby coupling the reduction of nitrate to distant oxidation of sulfide. Sulfidic marine sediment was incubated with overlying nitrate-amended anoxic seawater. Within 2 months, electric coupling of spatially segregated nitrate reduction and sulfide oxidation was evident from: (1) the formation of a 4-6-mm-deep zone separating sulfide oxidation from the associated nitrate reduction, and (2) the presence of pH signatures consistent with proton consumption by cathodic nitrate reduction, and proton production by anodic sulfide oxidation. Filamentous Desulfobulbaceae with the longitudinal structures characteristic of cable bacteria were detected in anoxic, nitrate-amended incubations but not in anoxic, nitrate-free controls. Nitrate reduction by cable bacteria using long-distance electron transport to get privileged access to distant electron donors is a hitherto unknown mechanism in nitrogen and sulfur transformations, and the quantitative importance for elements cycling remains to be addressed. PMID:24577351

Marzocchi, Ugo; Trojan, Daniela; Larsen, Steffen; Meyer, Rikke Louise; Revsbech, Niels Peter; Schramm, Andreas; Nielsen, Lars Peter; Risgaard-Petersen, Nils

2014-08-01

231

Thermogravimetric study of the reduction of oxides of nickel and chromium  

NASA Technical Reports Server (NTRS)

The controlled hydrogen, carbon, and hydrogen-carbon reductions of the oxides of nickel and chromium were evaluated by thermogravimetric means. The materials studied were nickel (nickelous) oxide (NiO) and chromic sesquioxide (Cr2O3), mixed NiO-Cr2O3, and oxidized nickel - 20-percent chromium (Ni-20Cr). NiO was effectively reduced by all three atmospheres, Cr2O3 only by hydrogen-carbon, NiO-Cr2O3 by hydrogen and hydrogen-carbon, and oxidized Ni-20Cr by hydrogen and hydrogen-carbon and to a considerable extent by carbon alone. The results suggest that the presence of nickel promotes the reduction of Cr2O3. However, no definite explanation could be reached for the effectiveness of the hydrogen-carbon reduction of Cr2O3.

Herbell, T. P.

1973-01-01

232

Determination of carbon by the oxidation reduction reaction with chromium  

NASA Technical Reports Server (NTRS)

Free carbon was determined in silicon and boron carbides in ash, oxides, and other materials by oxidation to carbon dioxide with a mixture of K2Cr2O7 + H2SO4. The determination was made from the amount of CR(6) consumed, by adding excess Mohr's salt and titrating with a standard solution of KMnO4. The amount of Cr(6) self reduced was determined in a blank test. Optimum oxidation and conditions were achieved when the volumes of 5% k2Cr2Oz and H2SO4 were equal. The mixture was boiled for 1-2 hours using a reflex condenser. The volume should not be reduced, in order to avoid an increase in the sulfuric acid concentration. The relative error was 4-7% for 0.005-0.04 g C and less than or equal to 3.5% for 0.1 g C.

Mashkovich, L.; Kuteynikov, A. F.

1978-01-01

233

Dramatic reduction of gate leakage current of ultrathin oxides through oxide structure modification q  

E-print Network

]. High-k gate oxides are consid- ered as candidates to replace silicon dioxide or oxynitride [2­4]. However, there are a number of challenging issues facing high-k gate oxides, e.g. threshold and flat­4]. The most difficult issue for high-k gate oxides is the low-k interfacial oxide layer, which dominates

Chen, Zhi

234

Electrochemical preparation of N-doped cobalt oxide nanoparticles with high electrocatalytic activity for the oxygen-reduction reaction.  

PubMed

Nitrogen-doped CoO (N-CoO) nanoparticles with high electrocatalytic activity for the oxygen-reduction reaction (ORR) were fabricated by electrochemical reduction of CoCl2 in acetonitrile solution at cathodic potentials. The initially generated, highly reactive nitrogen-doped Co nanoparticles were readily oxidized to N-CoO nanoparticles in air. In contrast to their N-free counterparts (CoO or Co3 O4 ), N-CoO nanoparticles with a N content of about 4.6?% exhibit remarkable ORR electrocatalytic activity, stability, and immunity to methanol crossover in an alkaline medium. The Co?Nx active sites in the CoO nanoparticles are held responsible for the high ORR activity. This work opens a new path for the preparation of nitrogen-doped transition metal oxide nanomaterials, which are promising electrocatalysts for fuel cells. PMID:24616113

Yu, Hongtao; Li, Yunchao; Li, Xiaohong; Fan, Louzhen; Yang, Shihe

2014-03-17

235

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

USGS Publications Warehouse

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

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

1989-01-01

236

A NEW SOURCE REDUCTION PROJECT: THE POTENTIAL FOR SAFE SUBSTITUTES  

EPA Science Inventory

One of the clean product research projects being funded by the EPA's Pollution Prevention Research Branch in Cincinnati, Ohio, involves evaluating the possibility of dramatic reductions in hazardous waste and toxic chemical exposure associated with commercial products. y identify...

237

Gate oxide leakage current analysis and reduction for VLSI circuits  

Microsoft Academic Search

In this paper we address the growing issue of gate oxide leakage current at the circuit level. Specifically, we develop a fast approach to analyze the total leakage power of a large circuit block, considering both and subthreshold leakage . The interaction between and com- plicates analysis in arbitrary CMOS topologies and we propose simple and accurate heuristics based on

Dongwoo Lee; David Blaauw; Dennis Sylvester

2004-01-01

238

The high-temperature oxidation, reduction, and volatilization reactions of silicon and silicon carbide  

Microsoft Academic Search

A thermochemical analysis was made of the oxidation, reduction, and volatilization reactions which occur in the Si-O-C system. One characteristic feature is the high SiO(g) and SiO(g) + CO(g) pressures at the Si(s)-SiO2 and SiC(s)-SiO2(s) interfaces. Active oxidation with weight losses and passive oxidation with weight gains were found on oxidizing Si(s) and SiC(s) in low oxygen pressures above 1000°C.

Earl A. Gulbransen; Sven A. Jansson

1972-01-01

239

Breakdown into nanoscale of graphene oxide: Confined hot spot atomic reduction and fragmentation  

PubMed Central

Nano-graphene oxide (nano-GO) is a new class of carbon based materials being proposed for biomedical applications due to its small size, intrinsic optical properties, large specific surface area, and easy to functionalize. To fully exploit nano-GO properties, a reproducible method for its production is of utmost importance. Herein we report, the study of the sequential fracture of GO sheets onto nano-GO with controllable lateral width, by a simple, and reproducible method based on a mechanism that we describe as a confined hot spot atomic fragmentation/reduction of GO promoted by ultrasonication. The chemical and structural changes on GO structure during the breakage were monitored by XPS, FTIR, Raman and HRTEM. We found that GO sheets starts breaking from the defects region and in a second phase through the disruption of carbon bonds while still maintaining crystalline carbon domains. The breaking of GO is accompanied by its own reduction, essentially by the elimination of carboxylic and carbonyl functional groups. Photoluminescence and photothermal studies using this nano-GO are also presented highlighting the potential of this nanomaterial as a unique imaging/therapy platform. PMID:25339424

Gonçalves, Gil; Vila, Mercedes; Bdikin, Igor; de Andrés, Alicia; Emami, Nazanin; Ferreira, Rute A. S.; Carlos, Luís D.; Grácio, José; Marques, Paula A. A. P.

2014-01-01

240

Breakdown into nanoscale of graphene oxide: Confined hot spot atomic reduction and fragmentation  

NASA Astrophysics Data System (ADS)

Nano-graphene oxide (nano-GO) is a new class of carbon based materials being proposed for biomedical applications due to its small size, intrinsic optical properties, large specific surface area, and easy to functionalize. To fully exploit nano-GO properties, a reproducible method for its production is of utmost importance. Herein we report, the study of the sequential fracture of GO sheets onto nano-GO with controllable lateral width, by a simple, and reproducible method based on a mechanism that we describe as a confined hot spot atomic fragmentation/reduction of GO promoted by ultrasonication. The chemical and structural changes on GO structure during the breakage were monitored by XPS, FTIR, Raman and HRTEM. We found that GO sheets starts breaking from the defects region and in a second phase through the disruption of carbon bonds while still maintaining crystalline carbon domains. The breaking of GO is accompanied by its own reduction, essentially by the elimination of carboxylic and carbonyl functional groups. Photoluminescence and photothermal studies using this nano-GO are also presented highlighting the potential of this nanomaterial as a unique imaging/therapy platform.

Gonçalves, Gil; Vila, Mercedes; Bdikin, Igor; de Andrés, Alicia; Emami, Nazanin; Ferreira, Rute A. S.; Carlos, Luís D.; Grácio, José; Marques, Paula A. A. P.

2014-10-01

241

Development of molecular electrocatalysts for CO2 reduction and H2 production/oxidation.  

PubMed

The conversion of solar energy to fuels in both natural and artificial photosynthesis requires components for both light-harvesting and catalysis. The light-harvesting component generates the electrochemical potentials required to drive fuel-generating reactions that would otherwise be thermodynamically uphill. This Account focuses on work from our laboratories on developing molecular electrocatalysts for CO(2) reduction and for hydrogen production. A true analog of natural photosynthesis will require the ability to capture CO(2) from the atmosphere and reduce it to a useful fuel. Work in our laboratories has focused on both aspects of this problem. Organic compounds such as quinones and inorganic metal complexes can serve as redox-active CO(2) carriers for concentrating CO(2). We have developed catalysts for CO(2) reduction to form CO based on a [Pd(triphosphine)(solvent)](2+) platform. Catalytic activity requires the presence of a weakly coordinating solvent molecule that can dissociate during the catalytic cycle and provide a vacant coordination site for binding water and assisting C-O bond cleavage. Structures of [NiFe] CO dehydrogenase enzymes and the results of studies on complexes containing two [Pd(triphosphine)(solvent)](2+) units suggest that participation of a second metal in CO(2) binding may also be required for achieving very active catalysts. We also describe molecular electrocatalysts for H(2) production and oxidation based on [Ni(diphosphine)(2)](2+) complexes. Similar to palladium CO(2) reduction catalysts, these species require the optimization of both first and second coordination spheres. In this case, we use structural features of the first coordination sphere to optimize the hydride acceptor ability of nickel needed to achieve heterolytic cleavage of H(2). We use the second coordination sphere to incorporate pendant bases that assist in a number of important functions including H(2) binding, H(2) cleavage, and the transfer of protons between nickel and solution. These pendant bases, or proton relays, are likely to be important in the design of catalysts for a wide range of fuel production and fuel utilization reactions involving multiple electron and proton transfer steps. The generation of fuels from abundant substrates such as CO(2) and water remains a daunting research challenge, requiring significant advances in new inexpensive materials for light harvesting and the development of fast, stable, and efficient electrocatalysts. Although we describe progress in the development of redox-active carriers capable of concentrating CO(2) and molecular electrocatalysts for CO(2) reduction, hydrogen production, and hydrogen oxidation, much more remains to be done. PMID:19645445

Rakowski DuBois, M; DuBois, Daniel L

2009-12-21

242

Anaerobic methane oxidation in metalliferous hydrothermal sediments: influence on carbon flux and decoupling from sulfate reduction.  

PubMed

The anaerobic oxidation of methane (AOM) is a globally significant sink that regulates methane flux from sediments into the oceans and atmosphere. Here we examine mesophilic to thermophilic AOM in hydrothermal sediments recovered from the Middle Valley vent field, on the Juan de Fuca Ridge. Using continuous-flow sediment bioreactors and batch incubations, we characterized (i) the degree to which AOM contributes to net dissolved inorganic carbon flux, (ii) AOM and sulfate reduction (SR) rates as a function of temperature and (iii) the distribution and density of known anaerobic methanotrophs (ANMEs). In sediment bioreactors, inorganic carbon stable isotope mass balances results indicated that AOM accounted for between 16% and 86% of the inorganic carbon produced, underscoring the role of AOM in governing inorganic carbon flux from these sediments. At 90°C, AOM occurred in the absence of SR, demonstrating a striking decoupling of AOM from SR. An abundance of Fe(III)-bearing minerals resembling mixed valent Fe oxides, such as green rust, suggests the potential for a coupling of AOM to Fe(III) reduction in these metalliferous sediments. While SR bacteria were only observed in cooler temperature sediments, ANMEs allied to ANME-1 ribotypes, including a putative ANME-1c group, were found across all temperature regimes and represented a substantial proportion of the archaeal community. In concert, these results extend and reshape our understanding of the nature of high temperature methane biogeochemistry, providing insight into the physiology and ecology of thermophilic anaerobic methanotrophy and suggesting that AOM may play a central role in regulating biological dissolved inorganic carbon fluxes to the deep ocean from the organic-poor, metalliferous sediments of the global mid-ocean ridge hydrothermal vent system. PMID:22827909

Wankel, Scott D; Adams, Melissa M; Johnston, David T; Hansel, Colleen M; Joye, Samantha B; Girguis, Peter R

2012-10-01

243

The Potential Waveform In The Optical Switching Of Hydrated Nickel Oxide  

NASA Astrophysics Data System (ADS)

In this work it has been analyzed the transient of the current flowing in an electrochemical cell in which the working electrode is constituted by a hydrated nickel oxide layer. The analysis of the current, utilizing a model for the diffusion mechanism of protons into the electrochromic material, allows to determine the diffusion coefficient for the oxidation and reduction processes. It ha5been observed that the diffusion coefficient for the bleaching process is larger than that one of the oxidation process. This fact could explain why the transition to the coloured phase occurs more rapidly than the inverse transition and with an apparently more simple function. Attempts have been made to put in correlation the eventual formation of metastable cristallographyc phases, observed by the X-rays diffraction technique, submitting the sample to a periodic potential, with a square waveform, for several cycles.

Pennisi, Agostino; Simone, Francesca

1989-03-01

244

Remote fabrication and irradiation test of recycled nuclear fuel prepared by the oxidation and reduction of spent oxide fuel  

NASA Astrophysics Data System (ADS)

A direct dry recycling process was developed in order to reuse spent pressurized light water reactor (LWR) nuclear fuel in CANDU reactors without the separation of sensitive nuclear materials such as plutonium. The benefits of the dry recycling process are the saving of uranium resources and the reduction of spent fuel accumulation as well as a higher proliferation resistance. In the process of direct dry recycling, fuel pellets separated from spent LWR fuel rods are oxidized from UO2 to U3O8 at 500 °C in an air atmosphere and reduced into UO2 at 700 °C in a hydrogen atmosphere, which is called OREOX (oxidation and reduction of oxide fuel). The pellets are pulverized during the oxidation and reduction processes due to the phase transformation between cubic UO2 and orthorhombic U3O8. Using the oxide powder prepared from the OREOX process, the compaction and sintering processes are performed in a remote manner in a shielded hot cell due to the high radioactivity of the spent fuel. Most of the fission gas and volatile fission products are removed during the OREOX and sintering processes. The mini-elements fabricated by the direct dry recycling process are irradiated in the HANARO research reactor for the performance evaluation of the recycled fuel pellets. Post-irradiation examination of the irradiated fuel showed that microstructural evolution and fission gas release behavior of the dry-recycled fuel were similar to high burnup UO2 fuel.

Jin Ryu, Ho; Chan Song, Kee; Il Park, Geun; Won Lee, Jung; Seung Yang, Myung

2005-02-01

245

Geochemical control of microbial Fe(III) reduction potential in wetlands: Comparison of the rhizosphere to non-rhizosphere soil  

USGS Publications Warehouse

We compared the reactivity and microbial reduction potential of Fe(III) minerals in the rhizosphere and non-rhizosphere soil to test the hypothesis that rapid Fe(III) reduction rates in wetland soils are explained by rhizosphere processes. The rhizosphere was defined as the area immediately adjacent to a root encrusted with Fe(III)-oxides or Fe plaque, and non-rhizosphere soil was 0.5 cm from the root surface. The rhizosphere had a significantly higher percentage of poorly crystalline Fe (66??7%) than non-rhizosphere soil (23??7%); conversely, non-rhizosphere soil had a significantly higher proportion of crystalline Fe (50??7%) than the rhizosphere (18??7%, P<0.05 in all cases). The percentage of poorly crystalline Fe(III) was significantly correlated with the percentage of FeRB (r=0.76), reflecting the fact that poorly crystalline Fe(III) minerals are labile with respect to microbial reduction. Abiotic reductive dissolution consumed about 75% of the rhizosphere Fe(III)-oxide pool in 4 h compared to 23% of the soil Fe(III)-oxide pool. Similarly, microbial reduction consumed 75-80% of the rhizosphere pool in 10 days compared to 30-40% of the non-rhizosphere soil pool. Differences between the two pools persisted when samples were amended with an electron-shuttling compound (AQDS), an Fe(III)-reducing bacterium (Geobacter metallireducens), and organic carbon. Thus, Fe(III)-oxide mineralogy contributed strongly to differences in the Fe(III) reduction potential of the two pools. Higher amounts of poorly crystalline Fe(III) and possibly humic substances, and a higher Fe(III) reduction potential in the rhizosphere compared to the non-rhizosphere soil, suggested the rhizosphere is a site of unusually active microbial Fe cycling. The results were consistent with previous speculation that rapid Fe cycling in wetlands is due to the activity of wetland plant roots. ?? 2004 Federation of European Microbiological Societies. Published by Elsevier B.V. All rights reserved.

Weiss, J.V.; Emerson, D.; Megonigal, J.P.

2004-01-01

246

Bystanding F+ Oxidants Enable Selective Reductive Elimination from High-Valent Metal Centers in Catalysis  

PubMed Central

Reductive elimination from partially or completely oxidized metal centers is a vital step in a myriad of carbon–carbon and carbon–heteroatom bond–forming reactions. One strategy for promoting otherwise challenging reductive elimination reactions is to oxidize the metal center using a two-electron oxidant (i.e., from M(n) to M(n+2)). However, many of the commonly used oxidants for this type of transformation contain oxygen, nitrogen, or halogen moieties that are subsequently capable of participating in reductive elimination, leading to a mixture of products. This minireview examines an emerging solution to this widespread problem in organometallic chemistry, the use of bystanding F+ oxidants, and describes recent applications in Pd(II)/Pd(IV) and Au(I)/Au(III) catalysis. We then briefly discuss a rare example in which one-electron oxidants have been shown to promote selective reductive elimination in Pd(II)-catalyzed C–H functionalization, which we view as a promising future directing in the field. PMID:21264991

Engle, Keary M.; Mei, Tian-Sheng; Wang, Xisheng; Yu, Jin-Quan

2011-01-01

247

Reduction of Iron-Oxide-Carbon Composites: Part I. Estimation of the Rate Constants  

NASA Astrophysics Data System (ADS)

A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO2 and wüstite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbon oxidation and wüstite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wüstite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wüstite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (>1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

Halder, S.; Fruehan, R. J.

2008-12-01

248

Reduction of iron-oxide-carbon composites: part I. Estimation of the rate constants  

SciTech Connect

A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO{sub 2} and wustite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbon oxidation and wustite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wustite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wustite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (> 1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

Halder, S.; Fruehan, R.J. [Praxair Inc., Tonawanda, NY (United States). Technological Center

2008-12-15

249

A simple solvothermal reduction route to copper and cuprous oxide  

Microsoft Academic Search

Pure copper nanocrystallites and cuprous oxide nanorods have been synthesized via solvothermal treatment of CuSO4 or CuSO4·5H2O and NaOH in pure ethanol and mixed solution of ethanol and deionized water at 140 °C for 10 h, respectively. Transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) were used to investigate the different morphologies of the as-synthesized products. X-ray powder diffraction (XRD)

Mingzhen Wei; Ning Lun; Xicheng Ma; Shulin Wen

2007-01-01

250

Nitrite reduction to nitrous oxide by propionibacteria: Detoxication mechanism  

Microsoft Academic Search

Characteristics of dissimilatory nitrate reduction by Propionibacterium acidi-propionici, P. freudenreichii, P. jensenii, P. shermanii and P. thoenii were studied. All strains reduced nitrate to nitrite and further to N2O. Recovery of added nitrite-N as N2O-N approached 100%, so that no other end product existed in a significant quantity. Specific rates of N2O production were 3 to 6 orders of magnitude

Heinrich F. Kaspar

1982-01-01

251

Galvanic interpretation of self-potential signals associated withmicrobial sulfate-reduction  

SciTech Connect

We have evaluated the usefulness of the self-potential (SP)geophysical method to track the onset and location of microbialsulfate-reduction in saturated sediments during organic carbon amendment.Following stimulation of sulfate-reducing bacteria (SRB) by addition oflactate, anomalous voltages exceeding 600 mV correlated in space and timewith the accumulation of dissolved sulfide. Abiotic experiments in whichthe sulfide concentration at the measurement electrode was systematicallyvaried showed a positive correlation between the magnitude of the SPanomaly and differences in the half-cell potential associated with themeasurement and reference electrodes. Thus, we infer that the SPanomaliesresulted from electrochemical differences that developedbetween sulfide-rich regions and areas having higher oxidation potential.In neither experiment did generation of an SP anomaly require thepresence of an in situ electronic conductor, as is required by othermodels. These findings emphasize the importance of incorporation ofelectrochemical effects at electrode surfaces in interpretation of SPdata from geophysical studies. We conclude that SP measurements provide aminimally invasive means for monitoring stimulated sulfate-reductionwithin saturated sediments.

Williams, Kenneth H.; Hubbard, Susan S.; Banfield, Jillian F.

2007-05-02

252

DEVELOPMENT OF IMPROVED CATALYSTS FOR THE SELECTIVE CATALYTIC REDUCTION OF NITROGEN OXIDES WITH HYDROCARBONS  

SciTech Connect

Significant work has been done by the investigators on the cerium oxide-copper oxide based sorbent/catalysts for the combined removal of sulfur and nitrogen oxides from the flue gases of stationary sources. A relatively wide temperature window was established for the use of alumina-supported cerium oxide-copper oxide mixtures as regenerable sorbents for SO{sub 2} removal. Preliminary evaluation of these sorbents as catalysts for the selective reduction of NO{sub x} gave promising results with ammonia, but indicated low selectivity when methane was used as the reductant. Since the replacement of ammonia by another reductant is commercially very attractive, in this project, four research components will be undertaken. The investigation of the reaction mechanism, the first component, will help in the selection of promoters to improve the catalytic activity and selectivity of the sorbents in the SCR with methane. This will result in new catalyst formulations (second component). If this research is successful, the combined SO{sub 2}-NO{sub x} removal process based on alumina-supported copper oxide-ceria sorbent/catalysts will become very attractive for commercial applications. The objective of the third component of the project is to develop an alternative SCR process using another inexpensive fuel, residual fuel oil, instead of natural gas. This innovative proposal is based on very scant evidence concerning the good performance of coked catalysts in the selective reduction of NO and if proven to work the process will certainly be commercially viable. The fourth component of the project involves our industrial partner TDA Research, and the objective is to evaluate long-term stability and durability of the prepared sorbent/catalysts. In the first year of the project, the catalysts were investigated by the temperature-programmed reduction (TPR) technique. The results from TPR indicated that the interaction with support appears to promote reduction at lower temperatures. Copper oxide in excess of monolayer coverage reduces at temperatures close to the reduction temperature of the unsupported copper oxide. Increased dispersion increases the support effect. Low activity of ceria in NO reduction may be due to its resistance to reduction at low temperatures.

Dr. Ates Akyurtlu; Dr. Jale F. Akyurtlu

2001-05-31

253

Microsensor Measurements of Sulfate Reduction and Sulfide Oxidation in Compact Microbial Communities of Aerobic Biofilms  

PubMed Central

The microzonation of O2 respiration, H2S oxidation, and SO42- reduction in aerobic trickling-filter biofilms was studied by measuring concentration profiles at high spatial resolution (25 to 100 ?m) with microsensors for O2, S2-, and pH. Specific reaction rates were calculated from measured concentration profiles by using a simple one-dimensional diffusion reaction model. The importance of electron acceptor and electron donor availability for the microzonation of respiratory processes and their reaction rates was investigated. Oxygen respiration was found in the upper 0.2 to 0.4 mm of the biofilm, whereas sulfate reduction occurred in deeper, anoxic parts of the biofilm. Sulfate reduction accounted for up to 50% of the total mineralization of organic carbon in the biofilms. All H2S produced from sulfate reduction was reoxidized by O2 in a narrow reaction zone, and no H2S escaped to the overlying water. Turnover times of H2S and O2 in the reaction zone were only a few seconds owing to rapid bacterial H2S oxidation. Anaerobic H2S oxidation with NO3- could be induced by addition of nitrate to the medium. Total sulfate reduction rates increased when the availability of SO42- or organic substrate increased as a result of deepening of the sulfate reduction zone or an increase in the sulfate reduction intensity, respectively. PMID:16348687

Kühl, Michael; Jørgensen, Bo Barker

1992-01-01

254

Contrasting effects of Al substitution on microbial reduction of Fe(III) (hydr)oxides  

NASA Astrophysics Data System (ADS)

Aluminum, one of the most abundant elements in soils and sediments, is commonly found co-precipitated with Fe in natural Fe(III) (hydr)oxides; yet, little is known about how Al substitution impacts bacterial Fe(III) reduction. Accordingly, we investigated the reduction of Al substituted (0-13 mol% Al) goethite, lepidocrocite, and ferrihydrite by the model dissimilatory Fe(III)-reducing bacterium (DIRB), Shewanella putrefaciens CN32. Here we reveal that the impact of Al on microbial reduction varies with Fe(III) (hydr)oxide type. No significant difference in Fe(III) reduction was observed for either goethite or lepidocrocite as a function of Al substitution. In contrast, Fe(III) reduction rates significantly decreased with increasing Al substitution of ferrihydrite, with reduction rates of 13% Al-ferrihydrite more than 50% lower than pure ferrihydrite. Although Al substitution changed the minerals' surface area, particle size, structural disorder, and abiotic dissolution rates, we did not observe a direct correlation between any of these physiochemical properties and the trends in bacterial Fe(III) reduction. Based on projected Al-dependent Fe(III) reduction rates, reduction rates of ferrihydrite fall below those of lepidocrocite and goethite at substitution levels equal to or greater than 18 mol% Al. Given the prevalence of Al substitution in natural Fe(III) (hydr)oxides, our results bring into question the conventional assumptions about Fe (hydr)oxide bioavailability and suggest a more prominent role of natural lepidocrocite and goethite phases in impacting DIRB activity in soils and sediments.

Ekstrom, Eileen B.; Learman, Deric R.; Madden, Andrew S.; Hansel, Colleen M.

2010-12-01

255

Technetium reduction in sediments of a shallow aquifer exhibiting dissimilatory iron reduction potential  

Microsoft Academic Search

Pertechnetate ion [Tc(VII)O4?] reduction rate was determined in core samples from a shallow sandy aquifer located on the US Atlantic Coastal Plain. The aquifer is generally low in dissolved O2 (<1 mgL?1) and composed of weakly indurated late Pleistocene sediments differing markedly in physicochemical properties. Thermodynamic calculations, X-ray absorption spectroscopy and statistical analyses were used to establish the dominant reduction

Raymond E. Wildung; Shu-Mei W. Li; Christopher J. Murray; Kenneth M. Krupka; YuLong Xie; Nancy J. Hess; Eric E. Roden

2004-01-01

256

Carbon Isotopic Evidence for Coupled Sulfate Reduction-Methane Oxidation in Amazon Fan Sediments  

NASA Astrophysics Data System (ADS)

Carbon isotope ratios of dissolved inorganic carbon were measured on porewaters from Amazon Fan sediments collected on Ocean Drilling Program Leg 155. Values as low as -49.6‰ vs. PDB were recorded, with the lowest values coinciding with the base of the sulfate reduction zone at each site. The values indicate that on the order of 50-85% of sulfate reduction in Amazon Fan sediments takes place by methane oxidation. Estimated rates of methane oxidation range from 0.3-1.0x10 -5 moles/l/yr. The reasons for the high percentage of sulfate reduction taking place by methane oxidation are thought to be the large decrease in fan sedimentation rates in the early Holocene and the terrestrial source of organic matter in fan sediments.

Burns, Stephen J.

1998-03-01

257

Measurement of the Md3+/Md2+ reduction potential studied with flow electrolytic chromatography.  

PubMed

The reduction behavior of mendelevium (Md) was studied using a flow electrolytic chromatography apparatus. By application of the appropriate potentials on the chromatography column, the more stable Md(3+) is reduced to Md(2+). The reduction potential of the Md(3+) + e(-) ? Md(2+) couple was determined to be -0.16 ± 0.05 V versus a normal hydrogen electrode. PMID:24116851

Toyoshima, Atsushi; Li, Zijie; Asai, Masato; Sato, Nozomi; Sato, Tetsuya K; Kikuchi, Takahiro; Kaneya, Yusuke; Kitatsuji, Yoshihiro; Tsukada, Kazuaki; Nagame, Yuichiro; Schädel, Matthias; Ooe, Kazuhiro; Kasamatsu, Yoshitaka; Shinohara, Atsushi; Haba, Hiromitsu; Even, Julia

2013-11-01

258

Reduction and Oxidation of Copper Oxide Thin Films and Thermal Stability Issues in Copper-Based Metallization.  

NASA Astrophysics Data System (ADS)

This thesis investigates the oxidation and reduction of Cu-oxides and thermal induced reactions of Cu with metals. The combination of ^{16}O( alpha,alpha)^{16}O oxygen resonance and transmission electron microscopy (TEM) provides an effective method of studying the oxidation and reduction of copper oxide thin films. A discontinuous morphology of grain growth of Cu_2O in found in the CuO matrix during reduction. The migration of the Cu_2O-CuO phase boundary is induced by oxygen diffusion along the moving boundary. Grain growth is the dominant process in the transformation from CuO to Cu_2O; nucleation is the dominant process in the reverse transformation, i.e. from Cu_2O to CuO. The reduction and oxidation of copper oxides are asymmetrical; the latter is significantly faster. The metastable phase Cu _4O_3 was formed by ion milling CuO. Carbon and refractory metals such as Ti or Zr can enhance the reduction rate of CuO. Three topics relating to thermal stability issues in Cu-based metallization were investigated: (1) texturing in electroless copper films on epitaxial copper seed layers; (2) predicting first phase formation in Cu/metal bilayer structures; and (3) encapsulation of Cu fine line structures with TiN. (100)- and (111)-textured copper layers were deposited by electroless plating on copper seed layers grown epitaxially on Si (100) and Si (111) substrates, respectively. (111) -textured copper films are more oxidation-resistant. Rutherford backscattering spectrometry (RBS) and in situ transmission electron microscopy (TEM) were used to determine phase formation in Cu-M (M = Ti, Zr, Mg, Sb, Pd and Pt) bilayer systems. An effective heat of formation rule was employed to predict first phase formation in these systems. A TiN-encapsulated copper structure was made by annealing a Cu-10at%Ti alloy film evaporated on a SiO _2/Si(100) substrate at 550^ circC in an NH_3 ambient. Fast heating rates (70^circC/min.) to 550^circC can effectively suppress the formation of Cu_3Ti and enhance TiN_{x} formation near the surface of the copper film. Oxygen incorporation in the TiN_{x} layer was found by Auger depth profiling. This self encapsulated Cu structure exhibits good adhesion to SiO_2 and oxidation resistance.

Li, Jian

259

LC-MS/MS Analysis and Comparison of Oxidative Damages on Peptides Induced by Pathogen Reduction Technologies for Platelets  

NASA Astrophysics Data System (ADS)

Pathogen reduction technologies (PRT) are photochemical processes that use a combination of photosensitizers and UV-light to inactivate pathogens in platelet concentrates (PCs), a blood-derived product used to prevent hemorrhage. However, different studies have questioned the impact of PRT on platelet function and transfusion efficacy, and several proteomic analyses revealed possible oxidative damages to proteins. The present work focused on the oxidative damages produced by the two main PRT on peptides. Model peptides containing residues prone to oxidation (tyrosine, histidine, tryptophane, and cysteine) were irradiated with a combination of amotosalen/UVA (Intercept process) or riboflavin/UVB (Mirasol-like process). Modifications were identified and quantified by liquid chromatography coupled to tandem mass spectrometry. Cysteine-containing peptides formed disulfide bridges (R-SS-R, -2 Da; favored following amotosalen/UVA), sulfenic and sulfonic acids (R-SOH, +16 Da, R-SO3H, +48 Da, favored following riboflavin/UVB) upon treatment and the other amino acids exhibited different oxidations revealed by mass shifts from +4 to +34 Da involving different mechanisms; no photoadducts were detected. These amino acids were not equally affected by the PRT and the combination riboflavin/UVB generated more oxidation than amotosalen/UVA. This work identifies the different types and sites of peptide oxidations under the photochemical treatments and demonstrates that the two PRT may behave differently. The potential impact on proteins and platelet functions may thus be PRT-dependent.

Prudent, Michel; Sonego, Giona; Abonnenc, Mélanie; Tissot, Jean-Daniel; Lion, Niels

2014-04-01

260

Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions.  

PubMed

Development of efficient, affordable electrocatalysts for the oxygen evolution reaction and the oxygen reduction reaction is critical for rechargeable metal-air batteries. Here we present lithium cobalt oxide, synthesized at 400?°C (designated as LT-LiCoO2) that adopts a lithiated spinel structure, as an inexpensive, efficient electrocatalyst for the oxygen evolution reaction. The catalytic activity of LT-LiCoO2 is higher than that of both spinel cobalt oxide and layered lithium cobalt oxide synthesized at 800?°C (designated as HT-LiCoO2) for the oxygen evolution reaction. Although LT-LiCoO2 exhibits poor activity for the oxygen reduction reaction, the chemically delithiated LT-Li1-xCoO2 samples exhibit a combination of high oxygen reduction reaction and oxygen evolution reaction activities, making the spinel-type LT-Li0,5CoO2 a potential bifunctional electrocatalyst for rechargeable metal-air batteries. The high activities of these delithiated compositions are attributed to the Co4O4 cubane subunits and a pinning of the Co(3+/4+):3d energy with the top of the O(2-):2p band. PMID:24862287

Maiyalagan, Thandavarayan; Jarvis, Karalee A; Therese, Soosairaj; Ferreira, Paulo J; Manthiram, Arumugam

2014-01-01

261

Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions  

NASA Astrophysics Data System (ADS)

Development of efficient, affordable electrocatalysts for the oxygen evolution reaction and the oxygen reduction reaction is critical for rechargeable metal-air batteries. Here we present lithium cobalt oxide, synthesized at 400?°C (designated as LT-LiCoO2) that adopts a lithiated spinel structure, as an inexpensive, efficient electrocatalyst for the oxygen evolution reaction. The catalytic activity of LT-LiCoO2 is higher than that of both spinel cobalt oxide and layered lithium cobalt oxide synthesized at 800?°C (designated as HT-LiCoO2) for the oxygen evolution reaction. Although LT-LiCoO2 exhibits poor activity for the oxygen reduction reaction, the chemically delithiated LT-Li1-xCoO2 samples exhibit a combination of high oxygen reduction reaction and oxygen evolution reaction activities, making the spinel-type LT-Li0,5CoO2 a potential bifunctional electrocatalyst for rechargeable metal-air batteries. The high activities of these delithiated compositions are attributed to the Co4O4 cubane subunits and a pinning of the Co3+/4+:3d energy with the top of the O2-:2p band.

Maiyalagan, Thandavarayan; Jarvis, Karalee A.; Therese, Soosairaj; Ferreira, Paulo J.; Manthiram, Arumugam

2014-05-01

262

Reduction and reoxidation of modified multicomponent catalysts of the oxidation of isobutylene  

SciTech Connect

The reduction of modified molybdenum-containing oxide catalysts Co-Mo-Bi-Fe and Co-Mo-Bi-Fe-K by isobutylene at 400/sup 0/C and their reoxidation by the oxygen of the gas phase were studied. The interaction of complex oxide catalytic systems with isobutylene leads to a reduction of the trivalent iron molybdate phase to ..beta..-FeMoO/sub 4/. It was shown that when an alkali metal ion - potassium - is introduced into the catalyst, the mobility of the oxygen of the catalyst lattice increases sharply.

Firsova, A.A.; Vorob'eva, G.A.; Margolis, L.Ya.

1987-04-01

263

Fabrication of palladium/graphene oxide composite by plasma reduction at room temperature  

PubMed Central

Pd nanoparticles were fabricated on graphene oxide (GO) using a deposition-precipitation method with a glow discharge plasma reduction at room temperature. Argon was employed as the plasma-generating gas. The novel plasma method selectively reduces the metal ions. The graphene oxide has no change with this plasma reduction according to the Fourier transform infrared analysis. The Pd nanoparticles on the GO were uniformly distributed with an average diameter of 1.6 nm. The functional groups on the GO not only prevent Pd nanoparticles from further aggregation but also provide a strong hydrophilic property to the Pd/GO composite, which can form stable colloidal dispersions in water. PMID:22533915

2012-01-01

264

Technological Potential for CO 2 Emission Reductions of Passenger Cars  

Microsoft Academic Search

\\u000a Nowadays, the relation between car transport and climate change is according to recent surveys obvious to most people in Europe.\\u000a Despite this cognition the necessary behavioural change only proceeds slowly. Hence, the significance of innovative technologies\\u000a reducing CO2 emissions from cars rises as behavioural change may take longer and remains uncertain. This paper focuses on technically\\u000a feasible CO2 emission reduction

Michael Krail; Wolfgang Schade

265

Superior catalysts for selective catalytic reduction of nitric oxide. Quarterly technical progress report, January 1, 1995--March 31, 1995  

SciTech Connect

During this quarter, progress was made on the following tasks: TPD techniques were employed to study the reaction mechanism of the selective catalytic reduction of nitrogen oxide with ammonia over iron oxide pillared clay catalyst; and a sulfur dioxide resistant iron oxide/titanium oxide catalyst was developed.

Li, W.B.; Yang, R.T.

1995-12-01

266

Nitric oxide reduction in the postflame region of pulverized coal flames  

SciTech Connect

This paper reports on a computer model developed to perform three simulations of nitric oxide reduction in the postflame region of a downflow combustor burning Utah bituminous coal at stoichiometric ratios (SR) of 0.8 and 0.4, where SR = 1/{phi}, and {phi} is fuel equivalence ratio. Comparisons to experiment are made for all three cases. The contributions of both homogeneous and heterogeneous mechanisms to nitric oxide reduction in coal combustion are inferred from the simulations. The first simulation, in which soot was assumed to be the only route for NO reduction, determined the percentage soot yield needed in order for heterogeneous NO reduction on soot to account for the experimental results. The results indicate that required soot yields are consistent with those measured experimentally in pulverized coal flames. The second simulation, in which soot oxidation was added to the first model and where the gas-phase species profiles were calculated using a 119-reaction, 27-species carbon/hydrogen/ oxygen reaction set, showed that all the soot was rapidly oxidized for SR = 0.8, but that no appreciable soot was oxidized at SR = 0.4, due to the much lower OH radical concentrations.

Miller, G.P.; Lester, T.W.; Cheng, M.T. (Dept. of Mechanical Engineering, Louisiana State Univ., Baton Rouge, LA (US))

1991-06-01

267

Reduction of nitrogen oxides with catalytic acid resistant aluminosilicate molecular sieves and ammonia  

DOEpatents

Noxious nitrogen oxides in a waste gas stream such as the stack gas from a fossil-fuel-fired power generation plant or other industrial plant off-gas stream is catalytically reduced to elemental nitrogen and/or innocuous nitrogen oxides employing ammonia as reductant in the presence of a zeolite catalyst in the hydrogen or sodium form having pore openings of about 3 to 10 A.

Pence, Dallas T. (Idaho Falls, ID); Thomas, Thomas R. (Idaho Falls, ID)

1980-01-01

268

Influence of the reaction temperature on the electrochemical promoted catalytic behaviour of platinum impregnated catalysts for the reduction of nitrogen oxides under lean burn conditions  

Microsoft Academic Search

The aim of this work was to study the influence of the reaction temperature on the efficiency of the electrochemical promotion to improve the catalytic performance of a Pt impregnated catalyst for the reduction of nitrogen oxides under lean burn conditions. Open circuit catalytic and potential measurements were carried out in order to explain the potentiostatic behaviour of the electrochemical

Fernando Dorado; Antonio de Lucas-Consuegra; Carmen Jiménez; José Luis Valverde

2007-01-01

269

Evidence of alloy formation during reduction of platinized tin oxide surfaces  

NASA Technical Reports Server (NTRS)

Ion scattering spectroscopy, Auger electron spectroscopy, and electron spectroscopy for chemical analysis have been used to examine a platinized tin oxide catalyst surface before, during, and after reduction by annealing under vacuum at 250 to 450 C. These techniques were then used to examine the reduced surface after a room-temperature, low-pressure oxygen exposure. The spectral results and the behavior of the reduced surface toward oxygen exposure both indicate that a Pt/Sn alloy is produced during reduction.

Gardner, Steven D.; Hoflund, Gar B.; Davidson, Mark R.; Schryer, David R.

1989-01-01

270

THE EFFECT OF GOLD ON THE REDUCTION BEHAVIOUR OF SOME METAL OXIDE CATALYSTS  

Microsoft Academic Search

The results of some temperature programmed reduction experiments are analyzed. One evidences the effects of the gold nanoparticles on the reduction behaviour of several gold promoted metal oxide catalysts: ?-Fe2O3, V2O5\\/TiO2, V2O5\\/ZrO2 and V2O5\\/CeO2. The effects of gold particles on the values of the kinetic parameters are also analyzed.

G. Munteanu; E. Segal; Lyuba Ilieva

271

Potential toxicity of superparamagnetic iron oxide nanoparticles (SPION)  

PubMed Central

Superparamagnetic iron oxide nanoparticles (SPION) are being widely used for various biomedical applications, for example, magnetic resonance imaging, targeted delivery of drugs or genes, and in hyperthermia. Although, the potential benefits of SPION are considerable, there is a distinct need to identify any potential cellular damage associated with these nanoparticles. Besides focussing on cytotoxicity, the most commonly used determinant of toxicity as a result of exposure to SPION, this review also mentions the importance of studying the subtle cellular alterations in the form of DNA damage and oxidative stress. We review current studies and discuss how SPION, with or without different surface coating, may cause cellular perturbations including modulation of actin cytoskeleton, alteration in gene expression profiles, disturbance in iron homeostasis and altered cellular responses such as activation of signalling pathways and impairment of cell cycle regulation. The importance of protein-SPION interaction and various safety considerations relating to SPION exposure are also addressed. PMID:22110864

Singh, Neenu; Jenkins, Gareth J.S.; Asadi, Romisa; Doak, Shareen H.

2010-01-01

272

Catalytic NOx reduction with simultaneous dioxin and furan oxidation.  

PubMed

The engineering, construction, performance and running costs of a catalytic flue gas cleaning component in the low dust area of a municipal waste incinerator is discussed. For this purpose, the case study of a Flemish incineration plant is presented, covering the history, the design procedure of the catalyst, relevant process data and the financial aspects. A reliable PCDD/F-destruction by means of oxidation by the catalyst to typical values of 0.001 ng TEQ/Nm3 has been demonstrated. At the same time, NOx- and CO-emissions are reduced by 90% and 20% to about 50 mg/Nm3 and below 10 mg/Nm3, respectively. PMID:14659429

Goemans, Marcel; Clarysse, Patrick; Joannès, Joseph; De Clercq, Petra; Lenaerts, Silvia; Matthys, Karel; Boels, Kris

2004-03-01

273

Liquid-phase and solid-phase microwave irradiations for reduction of graphite oxide  

NASA Astrophysics Data System (ADS)

In this paper, two microwave irradiation methods: (i) liquid-phase microwave irradiation (MWI) reduction of graphite oxide suspension dissolved in de-ionized water and N, N-dimethylformamide, respectively, and (ii) solid-phase MWI reduction of graphite oxide powder have been successfully carried out to reduce graphite oxide. The reduced graphene oxide products are thoroughly characterized by scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectral analysis, Raman spectroscopy, UV-Vis absorption spectral analysis, and four-point probe conductivity measurements. The results show that both methods can efficiently remove the oxygen-containing functional groups attached to the graphite layers, though the solid-phase MWI reduction method can obtain far more efficiently a higher quality-reduced graphene oxide with fewer defects. The I(D)/I(G) ratio of the solid-phase MWI sample is as low as 0.46, which is only half of that of the liquid-phase MWI samples. The electrical conductivity of the reduced graphene oxide by the solid method reaches 747.9 S/m, which is about 25 times higher than that made by the liquid-phase method.

Zhao, Na; Wen, Chen-Yu; Zhang, David Wei; Wu, Dong-Ping; Zhang, Zhi-Bin; Zhang, Shi-Li

2014-12-01

274

Oxidation potential and state of some vanadium ores and the relation of woody material to their deposition  

USGS Publications Warehouse

Oxidation potential studies with a multiple pH-potential recorder designed and constructed for this purpose demonstrated that some uranium-vanadium ores in the Colorado Plateau were in a reduced state when deposited. Any oxidation which took place occurred after deposition. Experimental and theoretical reducing studies on fresh wood, wood degraded by burial for 450 years, and lignite, indicate that such ores may have been deposited by reduction of oxidized vanadium solutions by woody material. A vanadium (III) mineral, V2O(OH)4, was prepared synthetically by reduction of a vanadium (V) solution with wood. This is the only reported synthesis of any reduced vanadium mineral by any method. It was shown that the origin of almost all vanadium deposits currently of commercial importance involves life processes and products.

Pommer, Alfred Michael

1956-01-01

275

Redox Potentials, Laccase Oxidation, and Antilarval Activities of Substituted Phenols  

PubMed Central

Laccases are copper-containing oxidases that are involved in sclerotization of the cuticle of mosquitoes and other insects. Oxidation of exogenous compounds by insect laccases may have the potential to produce reactive species toxic to insects. We investigated two classes of substituted phenolic compounds, halogenated di- and trihydroxybenzenes and substituted di-tert-butylphenols, on redox potential, oxidation by laccase and effects on mosquito larval growth. An inverse correlation between the oxidation potentials and laccase activity of halogenated hydroxybenzenes was found. Substituted di-tert-butylphenols however were found to impact mosquito larval growth and survival. In particular, 2,4-di-tert-butyl-6-(3-methyl-2-butenyl)phenol (15) caused greater than 98% mortality of Anopheles gambiae larvae in a concentration of 180 nM, whereas 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-methylpropanal oxime (13) and 6,8-di-tert-butyl-2,2-dimethyl-3,4-dihydro-2H-chromene (33) caused 93% and 92% mortalities in concentrations of 3.4 and 3.7 ?M, respectively. Larvae treated with di-tert-butylphenolic compounds died just before pupation. PMID:22300888

Prasain, Keshar; Nguyen, Thi D. T.; Gorman, Maureen J.; Barrigan, Lydia M.; Peng, Zeyu; Kanost, Michael R.; Syed, Lateef U.; Li, Jun; Zhu, Kun Yan; Hua, Duy H.

2012-01-01

276

Redox potentials, laccase oxidation, and antilarval activities of substituted phenols.  

PubMed

Laccases are copper-containing oxidases that are involved in sclerotization of the cuticle of mosquitoes and other insects. Oxidation of exogenous compounds by insect laccases may have the potential to produce reactive species toxic to insects. We investigated two classes of substituted phenolic compounds, halogenated di- and trihydroxybenzenes and substituted di-tert-butylphenols, on redox potential, oxidation by laccase and effects on mosquito larval growth. An inverse correlation between the oxidation potentials and laccase activity of halogenated hydroxybenzenes was found. Substituted di-tert-butylphenols however were found to impact mosquito larval growth and survival. In particular, 2,4-di-tert-butyl-6-(3-methyl-2-butenyl)phenol (15) caused greater than 98% mortality of Anophelesgambiae larvae in a concentration of 180nM, whereas 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-methylpropanal oxime (13) and 6,8-di-tert-butyl-2,2-dimethyl-3,4-dihydro-2H-chromene (33) caused 93% and 92% mortalities in concentrations of 3.4 and 3.7?M, respectively. Larvae treated with di-tert-butylphenolic compounds died just before pupation. PMID:22300888

Prasain, Keshar; Nguyen, Thi D T; Gorman, Maureen J; Barrigan, Lydia M; Peng, Zeyu; Kanost, Michael R; Syed, Lateef U; Li, Jun; Zhu, Kun Yan; Hua, Duy H

2012-03-01

277

Influence of acid-base and oxidation-reduction reactions on the distribution of stable impurities and radionuclides in ``soil-liquid radioactive waste'' system  

NASA Astrophysics Data System (ADS)

During underground disposal of liquid radioactive wastes acid-base and oxidation-reduction reactions proceed between the soil and the solutions, resulting in the changes of the solution pH, oxidation-reduction potential plus a wide spectrum of various precipitation (co-precipitation)—dissolution, complexation, sorption—desorption, etc., reactions. Chemical reactions are followed by redistribution of the elements between the aqueous phase and soil that results in the changes of the soil content, liquid radioactive waste and determines the radionuclides behaviour.

Kozyrev, A. S.; Matyukha, V. A.; Semyonov, E. N.; Larin, V. K.

2003-01-01

278

The low-temperature reduction of Pd-doped transition metal oxide surfaces with hydrogen  

Microsoft Academic Search

The reaction of hydrogen with a series of polyvalent metal oxides (Fe2O3, WO3, MoO3, V2O5, Sb2O3, PbO2, Cr2O3, NiO, CuO, Co3O4, MnO2, PdO, Ag2O) was investigated at low temperatures (77–320K) and pressures (0.001–0.7kPa). Pd-doped (0.1–0.5wt.%) transition metal oxides can be reduced by hydrogen at 77–320K whereas the onset of the reduction of the pure oxides occurs at temperatures higher than

V. M. Belousov; M. A. Vasylyev; L. V. Lyashenko; N. Yu. Vilkova; B. E. Nieuwenhuys

2003-01-01

279

Characterization study of polycrystalline tin oxide surfaces before and after reduction in CO  

NASA Technical Reports Server (NTRS)

Polycrystalline tin oxide surfaces have been examined before and after reduction in 40 Torr of CO at 100 and 175 C using Auger electron spectroscopy (AES), electron spectroscopy for chemical analysis (ESCA), ion scattering spectroscopy (ISS) and electron stimulated desorption (ESD). The changes in the surface composition and chemical states of the surface species generally are subtle for the reductive conditions used. However, significant changes do occur with regard to the amounts and the chemical forms of the hydrogen-containing species remaining after both the 100 and 175 C reductions.

Drawdy, Jean E.; Hoflund, Gar B.; Davidson, Mark R.; Schryer, David R.

1990-01-01

280

Mechanism of Cr(VI) reduction by Aspergillus niger: enzymatic characteristic, oxidative stress response, and reduction product.  

PubMed

Bioremediation of hexavalent chromium by Aspergillus niger was attributed to the reduction product (trivalent chromium) that could be removed in precipitation and immobilized inside the fungal cells and on the surface of mycelium. The site location of reduction was conducted with assays of the permeabilized cells, cell-free extracts, and cell debris, which confirmed that the chromate reductase was mainly located in the soluble fraction of cells. The oxidation-reduction process was accompanied by the increase of reactive oxygen species and antioxidant levels after hexavalent chromium treatment. Michaelis-Menten constant (K m) and maximum reaction rate (V max), obtained from the Lineweaver-Burk plot were 14.68 ?M and 434 ?M min(-1) mg(-1) of protein, respectively. Scanning electron microscopy and Raman spectra analyses manifested that both Cr(VI) and Cr(III) species were present on the mycelium. Fourier transform-infrared spectroscopy analysis suggested that carboxyl, hydroxide, amine, amide, cyano-group, and phosphate groups from the fungal cell wall were involved in chromium binding by the complexation with the Cr(III) and Cr(VI) species. A Cr(VI) removal mechanism of Cr(VI) reduction followed by the surface immobilization and intracellular accumulation of Cr(III) in living A. niger was present. PMID:25408081

Gu, Yanling; Xu, Weihua; Liu, Yunguo; Zeng, Guangming; Huang, Jinhui; Tan, Xiaofei; Jian, Hao; Hu, Xi; Li, Fei; Wang, Dafei

2015-04-01

281

Reduction in Basal Nitric Oxide Activity Causes Albuminuria  

PubMed Central

OBJECTIVE The barrier function of the glomerular filter has been studied for decades. Albuminuria reflects a malfunction of this barrier, and in animals dysfunctional endothelial nitric-oxide (NO) synthase results in albuminuria. We aimed to analyze the importance of NO for the glomerular barrier function in humans. RESEARCH DESIGN AND METHODS To assess the effect of endothelial dysfunction on albuminuria, we measured the urine albumin-to-creatinine ratio (UACR) both before and after the blockade of NO synthases (NOSs) with systemic infusion of NG-monomethyl-l-arginine (l-NMMA) in two distinct study populations. In population A, 62 hypertensive patients with type 2 diabetes and, in population B, 22 patients with hypercholesterolemia but without hypertension or type 2 diabetes were examined. All subjects had normal renal function. RESULTS There was a significant increase in the UACR in response to NOS inhibition with l-NMMA in hypertensive patients with type 2 diabetes (study population A) and in patients with hypercholesterolemia (study population B). Linear regression analyses revealed that the change in mean arterial presssure in response to l-NMMA was not related to the increase in the UACR in response to l-NMMA in either population, even after adjusting for filtration fraction. CONCLUSIONS NOS inhibition provokes albuminuria that is unrelated to changes in blood pressure. It is noteworthy that this finding was evident in patient groups prone to endothelial dysfunction and albuminuria. Thus, acute deterioration of endothelial function by reducing NO activity causes an increase in albuminuria. PMID:21270268

Ott, Christian; Schneider, Markus P.; Delles, Christian; Schlaich, Markus P.; Schmieder, Roland E.

2011-01-01

282

Potential-modulated reflectance study of the oxidation state of iridium in anodic iridium oxide films  

SciTech Connect

In an attempt to identify the changes of oxidation state involved in the electrochromic effect of anodic iridium oxide films (AIROF's) the authors obtained potential-modulated reflectance (PMR) spectra of AIROF's at three pH values: 0.9, 6.7, and 13.0, in the wavelength range 200-650 nm and at an angle of incidence of 45/sup 0/. Depending on pH, the voltammograms show up to four peaks (I-IV) in the anodic scan, the coloration-bleaching process corresponding to the main voltammetric peak II. The PMR spectra measured at a given voltammetric feature were nearly independent of pH, which shows that (i) the chemical composition of the AIROF is largely independent of the pH of the solution in which it was grown; (ii) the reflectance signal is originated by changes of the oxidation state of iridium in the AIROF. The PMR spectra were independent of the thickness of the AIROF, and therefore were not a trivial interference effect. The PMR maximum at 580-610 nm at voltammetric peak II has been tentatively assigned to an Ir(IV) oxide or oxyhydroxide, as have the PMR maximum at 330-360 nm at the minimum between voltammetric peaks II and III and the PMR maximum at 220-260 nm at potentials at or above voltammetric peak III. Apparently an Ir(IV) oxide or oxyhydroxide predominates in the potential range between voltammetric peaks II and IV, and different transitions become possible in this oxide at increasingly positive potentials.

Gutierrez, C.; Sanchez, M.; Pena, J.I.; Martinez, C.; Martinez, M.A.

1987-09-01

283

Pyrite oxidation and reduction - Molecular orbital theory considerations. [for geochemical redox processes  

NASA Technical Reports Server (NTRS)

In this paper, molecular orbital theory is used to explain a heterogeneous reaction mechanism for both pyrite oxidation and reduction. The mechanism demonstrates that the oxidation of FeS2 by Fe(3+) may occur as a result of three important criteria: (1) the presence of a suitable oxidant having a vacant orbital (in case of liquid phase) or site (solid phase) to bind to the FeS2 via sulfur; (2) the initial formation of a persulfido (disulfide) bridge between FeS2 and the oxidant, and (3) an electron transfer from a pi(asterisk) orbital in S2(2-) to a pi or pi(asterisk) orbital of the oxidant.

Luther, George W., III

1987-01-01

284

Potential CO2 Emission Reduction by Development of Non-Grain-Based Bioethanol in China  

NASA Astrophysics Data System (ADS)

Assessment of the potential CO2 emission reduction by development of non-grain-based ethanol in China is valuable for both setting up countermeasures against climate change and formulating bioethanol policies. Based on the land occupation property, feedstock classification and selection are conducted, identifying sweet sorghum, cassava, and sweet potato as plantation feedstocks cultivated from low-quality arable marginal land resources and molasses and agricultural straws as nonplantation feedstocks derived from agricultural by-products. The feedstock utilization degree, CO2 reduction coefficient of bioethanol, and assessment model of CO2 emission reduction potential of bioethanol are proposed and established to assess the potential CO2 emission reduction by development of non-grain-based bioethanol. The results show that China can obtain emission reduction potentials of 10.947 and 49.027 Mt CO2 with non-grain-based bioethanol in 2015 and 2030, which are much higher than the present capacity, calculated as 1.95 Mt. It is found that nonplantation feedstock can produce more bioethanol so as to obtain a higher potential than plantation feedstock in both 2015 and 2030. Another finding is that developing non-grain-based bioethanol can make only a limited contribution to China’s greenhouse gas emission reduction. Moreover, this study reveals that the regions with low and very low potentials for emission reduction will dominate the spatial distribution in 2015, and regions with high and very high potentials will be the majority in 2030.

Li, Hongqiang; Wang, Limao; Shen, Lei

2010-10-01

285

Effect of reduction treatment on microstructure and mechanical properties of fluorite oxides  

NASA Astrophysics Data System (ADS)

Ceria based materials because of their high ionic conductivity at low temperatures are potential candidates as the electrolyte component in the new generation of low temperature solid oxide fuel cells (SOFCs). The effects of operation conditions in SOFCs on microstructure and mechanical integrity of ceria-based materials are evaluated in this research. Pure ceria and gadolinium doped ceria (GDC) were selected to perform this investigation. The state-of-art electrolyte material, yttria-stabilized zirconia (YSZ), was also studied for comparison purposes. The samples were heat treated at 800°C under various oxygen partial pressures ( PO2 s) until equilibrium was reached. The defect concentrations were conserved to room temperature by fast cooling. The crystal structure and the lattice parameter were evaluated by the x-ray diffraction method. Microstructural evaluations and fractographic analyses were conducted using electron microscopy techniques. The intrinsic elastic modulus was evaluated using nanoindentation techniques. The bulk elastic modulus and fracture strength were measured using the four-point-bend testing method and fracture toughness was evaluated using chevron-notched Brazilian disc samples loaded under the mode I condition. The result of this study revealed that microcracks were formed during the reduction heat treatment in ceria and GDC when the PO2 was lower than 10-19 atm. It was also found that ceria samples upon cooling experienced phase transformation that led to the formation of several ordered pseudo-cubic phases. The intrinsic elastic modulus of both ceria and GDC decreased drastically when heat treated at very low PO2 s while the effect was insignificant in YSZ. These results correlate well with our theoretical modeling. Further analysis suggests that an increase in the point defect concentration weakens the attractive forces between atoms. The degradation of bulk elastic modulus of ceria was more pronounced at low PO2 s due to the presence of microcracks caused by the reduction treatments. The results on fracture properties of ceria showed that the flexural strength decreased significantly after reduction in very low PO2 s; however, in contrast, fracture toughness was increased by 30--40% when the PO2 was decreased to the range of 10-20--10-22 atm. Fractographic studies showed that the microcracks developed during reduction treatment are responsible for the decreased strength. In this dissertation, the enhancement in toughness was explained by crack deflection and microcrack toughening mechanisms.

Wang, Yanli

286

Mechanism of oxygen reduction reaction on transition metal oxide catalysts for high temperature fuel cells  

E-print Network

The solid oxide fuel cell (SOFC) with its high energy conversion efficiency, low emissions, silent operation and its ability to utilize commercial fuels has the potential to create a large impact on the energy landscape. ...

La O', Gerardo Jose Cordova

2008-01-01

287

Oxidation Potential, Not Crystal Structure, Controls the Oxidation State of Iron in Perovskite  

NASA Astrophysics Data System (ADS)

The mantle's oxidation state has broad implications on the state and evolution of the earth's interior. The relatively high oxidation potential of the upper mantle is such that iron is predominantly Fe2+ with small amounts of Fe3+ . Fe3+ is more stable than Fe2+ in the dominant lower mantle mineral, perovskite, despite the fact that the effect of pressure is to reduce the oxidizing potential of a system. It is therefore suggested that iron undergoes a disproportionation reaction of 3Fe2+ =2Fe3+ +Fe0 , controlled by the crystallography instead of oxidation potential. We crystallized synthetic enstatite glass with 5% Al2O3, 14% FeO, and 3% Fe2O3 in the laser-heated diamond anvil cell at 25-63 GPa and 1700-2800 K. We find that for temperatures <2200 K, the sample crystallizes to only perovskite, while at higher temperatures, the sample crystallizes to perovskite and stishovite as evident in x-ray diffraction, with 5-50 nm iron precipitates on grain boundaries. The precipitates have small amounts of dissolved oxygen, but are Mg- and Al- free. We interpret that the stishovite is forming due to the oxidation of the ferric iron to ferrous iron according to (Mg2+,Al3+)(Fe3+,Si4+)O3 +SiO2 + Fe0 while the lower-temperature samples crystallizing as approximately (Mg2+ Fe2+ Al3+ )(Fe3+ Al3+ Si4+ )O3. We observe 2.8(2) Å3 volume expansion of the perovskite and a 28(2) GPa decrease in compressibility of the perovskite relative to the perovskite forming at lower temperature, consistent with the proposed compositions of the perovskites. As the increased temperature increases the oxidation potential of the system, we suggest that the oxidation state of iron in perovskite is dependent on oxidation potential as opposed to perovskite's crystal structure. Transmission Electron Microscopy (TEM) coupled with Electron Energy Loss Spectroscopy (EELS) show iron precipitation on grain boundaries supporting the conclusion. We present a discussion of the results and implications for core formation and lower mantle dynamics.

Panero, W. R.; Pigott, J. S.; Watson, H. C.; Scharenberg, M.; Green, H. W.; McComb, D. W.; Williams, R. E.

2013-12-01

288

FINAL REPORT. ADVANCED EXPERIMENTAL ANALYSIS OF CONTROLS ON MICROBIAL FE(III) OXIDE REDUCTION  

EPA Science Inventory

The objectives of this research project were to refine existing models of microbiological and geochemical controls on Fe(III) oxide reduction, using laboratory reactor systems which mimic to varying degrees the physical and chemical conditions of the subsurface. Novel experimenta...

289

In-Situ Chemical Reduction and Oxidation of VOCs in Groundwater: Groundwater Treatability Studies  

NASA Technical Reports Server (NTRS)

This paper presents NASA Marshall Space Flight Center's treatability studies for volatile organic compounds in groundwater. In-Situ groundwater treatment technologies include: 1) Chemical Reduction(Ferox); 2) Chemical Oxidation (Fenton Reagents, Permanganate, and Persulfate); and 3) Thermal (Dynamic Underground Stripping, Six-Phase Heating). This paper is presented in viewgraph form.

Keith, Amy; Glasgow, Jason; McCaleh, Rececca C. (Technical Monitor)

2001-01-01

290

Nitric oxide induced contractile dysfunction is related to a reduction in myocardial energy generation  

Microsoft Academic Search

Objective: It has been suggested that nitric oxide NO is involved in the regulation of myocardial function in a variety of diseases such as dilated cardiomyopathy, myocarditis, heart transplant rejection, and septic shock. However, the underlying mechanism of NO mediated reduction of cardiac contractility has not been clearly established so far. Therefore, we studied the effects of authentic NO on

Malte Kelm; Stefan Schafer; Rudiger Dahmann; Bahar Dolu; Stefan Perings; Ulrich K. M. Decking; Jurgen Schrader; Bodo E. Strauer

1997-01-01

291

CATALYTIC REDUCTION OF NITROGEN OXIDES WITH AMMONIA: UTILITY PILOT PLANT OPERATION  

EPA Science Inventory

The report describes work to demonstrate, on a utility pilot plant scale, the performance, reliability, and practicability of reducing nitrogen oxides (NOx) emissions from steam boilers by reduction of NOx with ammonia over a platinum catalyst. A utility pilot plant treating a sl...

292

Reduction and oxidation of peptide nucleic acid and DNA at mercury and carbon electrodes  

Microsoft Academic Search

Peptide nucleic acid (PNA) is a DNA mimic that binds strongly and specifically to complementary DNA or RNA oligomers, but in contrast to DNA its backbone does not carry any electric charge. We used voltammetry in cyclic and square-wave modes to study reduction and oxidation signals of single stranded (ss)PNA and DNA decamers and pentadecamers with the same base sequences

Miroslav Tomschik; František Jelen; Lud?k Havran; Libuše Trnková; Peter E Nielsen; Emil Pale?ek

1999-01-01

293

The kinetic isotope effect in the bacterial reduction and oxidation of sulfur  

Microsoft Academic Search

The kinetic isotope effect in the bacterial reduction of sulfate to sulfide and oxidation of native sulfur and sulfide to sulfate has been investigated at the temperature of 32°C. In these studies, mixed culture techniques were used in order to more closely approximate isotopic fractionation as it occurs in nature. In addition, the S 34 compositions of sulfur in coexisting

M. L. Jensen; Nobuyuki Nakai

1964-01-01

294

Control of combustion-generated nitrogen oxides by selective non-catalytic reduction  

Microsoft Academic Search

Controlling nitrogen oxides (NOx) emissions is becoming a daunting technical challenge as increasingly strict emission limits are being imposed. The stringent regulations have prompted the innovation and characterization of NOx control technologies suitable for various applications. This paper presents a review on NOx removal techniques with particular reference to selective non-catalytic reduction (SNCR) technology. This includes initially how SNCR emerged

M. Tayyeb Javed; Naseem Irfan; B. M. Gibbs

2007-01-01

295

Emission reduction potential in PTA production plant through cogeneration technology  

Microsoft Academic Search

The focus of this research was to investigate and study the cogeneration potential in PTA production plant for reducing the emission to the environment due to high energy consumption in the respective plant. Currently, the total power requirement of the plant is about 26 MW per month in which fortunately, the Energy Improvement Team manage to locally generate 6 MW

Rozana Azrina Sazali; Norin Zamiah Kassim Shaari; Rohani Mohd Zin

2011-01-01

296

Nitrous oxide reduction by members of the family Rhodospirillaceae and the nitrous oxide reductase of Rhodopseudomonas capsulata.  

PubMed Central

After growth in the absence of nitrogenous oxides under anaerobic phototrophic conditions, several strains of Rhodopseudomonas capsulata were shown to possess a nitrous oxide reductase activity. The enzyme responsible for this activity had a periplasmic location and resembled a nitrous oxide reductase purified from Pseudomonas perfectomarinus. Electron flow to nitrous oxide reductase was coupled to generation of a membrane potential and inhibited by rotenone but not antimycin. It is suggested that electron flow to nitrous oxide reductase branches at the level of ubiquinone from the previously characterized electron transfer components of R. capsulata. This pathway of electron transport could include cytochrome c', a component hitherto without a recognized function. R. capsulata grew under dark anaerobic conditions in the presence of malate as carbon source and nitrous oxide as electron acceptor. This confirms that nitrous oxide respiration is linked to ATP synthesis. Phototrophically and anaerobically grown cultures of nondenitrifying strains of Rhodopseudomonas sphaeroides, Rhodopseudomonas palustris, and Rhodospirillum rubrum also possessed nitrous oxide reductase activity. Images PMID:2997133

McEwan, A G; Greenfield, A J; Wetzstein, H G; Jackson, J B; Ferguson, S J

1985-01-01

297

A simple method for the determination of reduction potentials in heme proteins.  

PubMed

We describe a simple method for the determination of heme protein reduction potentials. We use the method to determine the reduction potentials for the PAS-A domains of the regulatory heme proteins human NPAS2 (Em=-115 mV ± 2 mV, pH 7.0) and human CLOCK (Em=-111 mV ± 2 mV, pH 7.0). We suggest that the method can be easily and routinely applied to the determination of reduction potentials across the family of heme proteins. PMID:24440354

Efimov, Igor; Parkin, Gary; Millett, Elizabeth S; Glenday, Jennifer; Chan, Cheuk K; Weedon, Holly; Randhawa, Harpreet; Basran, Jaswir; Raven, Emma L

2014-03-01

298

A simple method for the determination of reduction potentials in heme proteins  

PubMed Central

We describe a simple method for the determination of heme protein reduction potentials. We use the method to determine the reduction potentials for the PAS-A domains of the regulatory heme proteins human NPAS2 (Em = ?115 mV ± 2 mV, pH 7.0) and human CLOCK (Em = ?111 mV ± 2 mV, pH 7.0). We suggest that the method can be easily and routinely applied to the determination of reduction potentials across the family of heme proteins. PMID:24440354

Efimov, Igor; Parkin, Gary; Millett, Elizabeth S.; Glenday, Jennifer; Chan, Cheuk K.; Weedon, Holly; Randhawa, Harpreet; Basran, Jaswir; Raven, Emma L.

2014-01-01

299

Intermolecular potential energy surface and thermophysical properties of ethylene oxide.  

PubMed

A six-dimensional potential energy hypersurface (PES) for two interacting rigid ethylene oxide (C2H4O) molecules was determined from high-level quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the MP2 and CCSD(T) levels of theory was utilized to determine interaction energies for 10178 configurations of two molecules. An analytical site-site potential function with 19 sites per ethylene oxide molecule was fitted to the interaction energies and fine tuned to agree with data for the second acoustic virial coefficient from accurate speed of sound measurements. The PES was validated by computing the second virial coefficient, shear viscosity, and thermal conductivity. The values of these properties are substantiated by the best experimental data as they tend to fall within the uncertainty intervals and also obey the experimental temperature functions, except for viscosity, where experimental data are insufficient. Due to the lack of reliable data, especially for the transport properties, our calculated values are currently the most accurate estimates for these properties of ethylene oxide. PMID:25362314

Crusius, Johann-Philipp; Hellmann, Robert; Hassel, Egon; Bich, Eckard

2014-10-28

300

Intermolecular potential energy surface and thermophysical properties of ethylene oxide  

SciTech Connect

A six-dimensional potential energy hypersurface (PES) for two interacting rigid ethylene oxide (C{sub 2}H{sub 4}O) molecules was determined from high-level quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the MP2 and CCSD(T) levels of theory was utilized to determine interaction energies for 10178 configurations of two molecules. An analytical site-site potential function with 19 sites per ethylene oxide molecule was fitted to the interaction energies and fine tuned to agree with data for the second acoustic virial coefficient from accurate speed of sound measurements. The PES was validated by computing the second virial coefficient, shear viscosity, and thermal conductivity. The values of these properties are substantiated by the best experimental data as they tend to fall within the uncertainty intervals and also obey the experimental temperature functions, except for viscosity, where experimental data are insufficient. Due to the lack of reliable data, especially for the transport properties, our calculated values are currently the most accurate estimates for these properties of ethylene oxide.

Crusius, Johann-Philipp, E-mail: johann-philipp.crusius@uni-rostock.de; Hassel, Egon [Lehrstuhl für Technische Thermodynamik, Universität Rostock, 18059 Rostock (Germany); Hellmann, Robert; Bich, Eckard [Institut für Chemie, Universität Rostock, 18059 Rostock (Germany)

2014-10-28

301

Intermolecular potential energy surface and thermophysical properties of ethylene oxide  

NASA Astrophysics Data System (ADS)

A six-dimensional potential energy hypersurface (PES) for two interacting rigid ethylene oxide (C2H4O) molecules was determined from high-level quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the MP2 and CCSD(T) levels of theory was utilized to determine interaction energies for 10178 configurations of two molecules. An analytical site-site potential function with 19 sites per ethylene oxide molecule was fitted to the interaction energies and fine tuned to agree with data for the second acoustic virial coefficient from accurate speed of sound measurements. The PES was validated by computing the second virial coefficient, shear viscosity, and thermal conductivity. The values of these properties are substantiated by the best experimental data as they tend to fall within the uncertainty intervals and also obey the experimental temperature functions, except for viscosity, where experimental data are insufficient. Due to the lack of reliable data, especially for the transport properties, our calculated values are currently the most accurate estimates for these properties of ethylene oxide.

Crusius, Johann-Philipp; Hellmann, Robert; Hassel, Egon; Bich, Eckard

2014-10-01

302

Advanced experimental analysis of controls on microbial Fe(III) oxide reduction. First year progress report  

SciTech Connect

'The authors have made considerable progress toward a number of project objectives during the first several months of activity on the project. An exhaustive analysis was made of the growth rate and biomass yield (both derived from measurements of cell protein production) of two representative strains of Fe(III)-reducing bacteria (Shewanellaalga strain BrY and Geobactermetallireducens) growing with different forms of Fe(III) as an electron acceptor. These two fundamentally different types of Fe(III)-reducing bacteria (FeRB) showed comparable rates of Fe(III) reduction, cell growth, and biomass yield during reduction of soluble Fe(III)-citrate and solid-phase amorphous hydrous ferric oxide (HFO). Intrinsic growth rates of the two FeRB were strongly influenced by whether a soluble or a solid-phase source of Fe(III) was provided: growth rates on soluble Fe(III) were 10--20 times higher than those on solid-phase Fe(III) oxide. Intrinsic FeRB growth rates were comparable during reduction of HF0 and a synthetic crystalline Fe(III) oxide (goethite). A distinct lag phase for protein production was observed during the first several days of incubation in solid-phase Fe(III) oxide medium, even though Fe(III) reduction proceeded without any lag. No such lag between protein production and Fe(III) reduction was observed during growth with soluble Fe(III). This result suggested that protein synthesis coupled to solid-phase Fe(III) oxide reduction in batch culture requires an initial investment of energy (generated by Fe(III) reduction), which is probably needed for synthesis of materials (e.g. extracellular polysaccharides) required for attachment of the cells to oxide surfaces. This phenomenon may have important implications for modeling the growth of FeRB in subsurface sedimentary environments, where attachment and continued adhesion to solid-phase materials will be required for maintenance of Fe(III) reduction activity. Despite considerable differences in the rate and pattern of FeRB growth with different Fe(III) forms, a roughly consistent long-term biomass yield of 5 to 15 mg protein per mmol Fe(III) reduced was observed during growth on different forms of Fe(III). These results should prove useful for quantitative modeling of FeRB growth and metabolism in various types of experimental and in situ anaerobic sedimentary systems.'

Roden, E.E.; Urrutia, M.M.

1997-07-01

303

Plasma in-liquid method for reduction of zinc oxide in zinc nanoparticle synthesis  

NASA Astrophysics Data System (ADS)

Metal air-batteries with high-energy density are expected to be increasingly applied in electric vehicles. This will require a method of recycling air batteries, and reduction of metal oxide by generating plasma in liquid has been proposed as a possible method. Microwave-induced plasma is generated in ethanol as a reducing agent in which zinc oxide is dispersed. Analysis by energy-dispersive x-ray spectrometry (EDS) and x-ray diffraction (XRD) reveals the reduction of zinc oxide. According to images by transmission electron microscopy (TEM), cubic and hexagonal metallic zinc particles are formed in sizes of 30 to 200 nm. Additionally, spherical fiber flocculates approximately 180 nm in diameter are present.

Amaliyah, Novriany; Mukasa, Shinobu; Nomura, Shinfuku; Toyota, Hiromichi; Kitamae, Tomohide

2015-02-01

304

Reduction of graphene oxide by aniline with its concomitant oxidative polymerization.  

PubMed

Graphene oxide (GO) nanosheets are readily reduced by aniline above room temperature in an aqueous acid medium, with the aniline simultaneously undergoing oxidative polymerization to produce the reduced graphene oxide-polyaniline nanofiber (RGO-PANi) composites. The resulting RGO-PANi composites and RGO (after dissolution of PANi) were characterized by XPS, XRD analysis, TGA, UV-visible absorption spectroscopy, and TEM. It was also found that the RGO-PANi composites exhibit good specific capacitance during galvanostatic charging-discharging when used as capacitor electrodes. PMID:21480428

Xu, Li Qun; Liu, Yi Liang; Neoh, Koon-Gee; Kang, En-Tang; Fu, Guo Dong

2011-04-19

305

Reduction phases of thin iron-oxide nanowires upon thermal treatment and Li exposure  

NASA Astrophysics Data System (ADS)

Iron oxide nanostructures, a promising alternative to carbon-based anode in lithium-ion batteries, can be produced using a hard template route. This procedure guarantees the formation of Fe2O3 nanowires with comparable diameter and size (average diameter 8 nm) with a dominant cubic ?-phase at the surface. Lithium exposure of the iron oxide nanowires in ultra-high-vacuum (UHV) conditions induces reduction of the Fe ion, leading to a Fe3O4 and then to a Fe2+ phase, as determined by means of core-level photoemission spectroscopy. Mild annealing of Fe2O3 in UHV determines an oxygen content reduction for the nanowires at lower temperature with respect to the bulk phase. The morphology and the evolution of the electronic properties upon reduction have been compared to those of micro-sized bulk-like grains, to unravel the role of the reduced size and surface-volume ratio.

Angelucci, Marco; Frau, Eleonora; Hassoun, Jusef; Hong, Inchul; Grazia Betti, Maria; Panero, Stefania; Scrosati, Bruno; Mariani, Carlo

2014-04-01

306

Bacterial reduction of crystalline Fe{sup 3+} oxides in single phase suspensions and subsurface materials  

SciTech Connect

Microbiologic reduction of synthetic and geologic Fe{sup 3+} oxides associated with four Pleistocene-age, Atlantic coastal plain sediments was investigated using a dissimilatory Fe reducing bacterium (Shewanella putrefaciens, strain CN32) in bicarbonate buffer. Experiments investigated whether phosphate and anthraquinone-2,6-disulfonate, (AQDS, a humic acid analogue) influenced the extent of crystalline Fe{sup 3+} oxide bioreduction and whether crystalline Fe{sup 3+} oxides in geologic materials are more or less reducible than comparable synthetic phases. Anaerobic incubations (10{sup 8} organisms/mL) were performed both with and without PO{sub 4} and AQDS that functions as an electron repository and shuttle. The production of Fe{sup 2+} (solid and aqueous) was followed with time, as was mineralogy by X-ray diffraction. The synthetic oxides were reduced in a qualitative trend consistent with their surface area and free energy: hydrous ferric oxide (HFO) > goethite > hematite. Bacterial reduction of the crystalline oxides was incomplete in spite of excess electron donor. Biogenic formation of vivianite [Fe{sub 3}(PO{sub 4}){sub 2}{center_dot}8H{sub 2}O] and siderite (FeCO{sub 3}) was observed; the conditions of their formation was consistent with their solubility. The geologic Fe{sup 3+} oxides showed a large range in reducibility, approaching 100% in some materials. The natural oxides were equally or more reducible than their synthetic counterparts, in spite of association with non-reducible mineral phases (e.g., kaolinite). The reducibility of the synthetic and geologic oxides was weakly effected by PO{sub 4}, but was accelerated by AQDS. CN32 produced the hydroquinone form of AQDS (AHDS), that, in turn, had thermodynamic power to reduce the Fe{sup 3+} oxides. As a chemical reductant, it could reach physical regions of the oxide not accessible by the organism. Electron microscopy showed that crystallite size was not the primary factor that caused differences in reducibility between natural and synthetic crystalline Fe{sup 3+} oxide phases. Crystalline disorder and microheterogeneities may be more important.

Zachara, J.M.; Fredrickson, J.K.; Li, S.M.; Kennedy, D.W.; Smith, S.C.; Gassman, P.L. [Pacific Northwest National Lab., Richland, WA (United States)

1998-11-01

307

Potential Reduction of Interstitial Myocardial Fibrosis With Renal Denervation  

PubMed Central

Background Hypertensive cardiomyopathy is characterized by myocyte hypertrophy and interstitial fibrosis. The effects of renal denervation (RD) on the heart are poorly understood. New magnetic resonance imaging techniques (extracellular volume fraction) permit the quantitative assessment of myocardial fibrosis. Our aim was to study the effects of RD on myocardial fibrosis. Methods and Results Twenty?three patients with resistant hypertension undergoing RD and 5 resistant hypertensive controls were prospectively included. Cardiac magnetic resonance imaging at 1.5 T was performed before RD and at 6?month follow?up. Indexed left ventricular mass, septal extracellular volume fraction, and indexed absolute extracellular volume (a quantitative measure of extracellular matrix) were quantified. All data are reported as mean±SD deviation (median). Decreases in systolic (161.96±19.09 [160] versus 144.78±16.48 [143] mm Hg, P<0.0001) and diastolic (85.61±12.88 [83] versus 80.39±11.93 [81] mm Hg, P=0.018) blood pressures and in indexed left ventricular mass (41.83±10.20 [41.59] versus 37.72±7.44 [38.49] g/m1.7, P=0.001) were observed at follow?up only in RD patients. No significant differences in extracellular volume were found (26.24±3.92% [26.06%] versus 25.74±4.53% [25.63%], P=0.605). A significant decrease in absolute extracellular volume was observed after 6 months in RD patients exclusively (10.36±2.25 [10.79] versus 9.25±2.38 [9.79] mL/m1.7, P=0.031). This effect was observed independently of blood pressure reduction. Conclusions RD significantly decreases left ventricular mass, while extracellular volume remains stable. Our results suggest that the observed left ventricular mass decrease was due not exclusively to a reversion of myocyte hypertrophy but also to an additional reduction in collagen content, indicating interstitial myocardial fibrosis. PMID:25516438

Doltra, Adelina; Messroghli, Daniel; Stawowy, Philipp; Hassel, Jan?Hendrik; Gebker, Rolf; Leppänen, Olli; Gräfe, Michael; Schneeweis, Christopher; Schnackenburg, Bernhard; Fleck, Eckart; Kelle, Sebastian

2014-01-01

308

Lasofoxifene Is Potential New Option for Breast Cancer Risk Reduction  

Cancer.gov

An investigational agent in the same family of drugs as tamoxifen and raloxifene may be as or more effective in reducing breast cancer risk in some women. The drug, lasofoxifene, also appears to have important benefits for both bone and heart health and, with one exception, appears to lack the rare but potentially serious side effects associated with tamoxifen and raloxifene, according to results published November 4, 2010, in the Journal of the National Cancer Institute.

309

Conifer somatic embryogenesis: improvements by supplementation of medium with oxidation-reduction agents.  

PubMed

A major barrier to the commercialization of somatic embryogenesis technology in loblolly pine (Pinus taeda L.) is recalcitrance of some high-value crosses to initiate embryogenic tissue (ET) and continue early-stage somatic embryo growth. Developing initiation and multiplication media that resemble the seed environment has been shown to decrease this recalcitrance. Glutathione (GSH), glutathione disulfide (GSSG), ascorbic acid and dehydroascorbate analyses were performed weekly throughout the sequence of seed development for female gametophyte and zygotic embryo tissues to determine physiological concentrations. Major differences in stage-specific oxidation-reduction (redox) agents were observed. A simple bioassay was used to evaluate potential growth-promotion of natural and inorganic redox agents added to early-stage somatic embryo growth medium. Compounds showing statistically significant increases in early-stage embryo growth were then tested for the ability to increase initiation of loblolly pine. Low-cost reducing agents sodium dithionite and sodium thiosulfate increased ET initiation for loblolly pine and Douglas fir (Mirb) Franco. Germination medium supplementation with GSSG increased somatic embryo germination. Early-stage somatic embryos grown on medium with or without sodium thiosulfate did not differ in GSH or GSSG content, suggesting that sodium thiosulfate-mediated growth stimulation does not involve GSH or GSSG. We have developed information demonstrating that alteration of the redox environment in vitro can improve ET initiation, early-stage embryo development and somatic embryo germination in loblolly pine. PMID:25716878

Pullman, Gerald S; Zeng, Xiaoyan; Copeland-Kamp, Brandi; Crockett, Jonathan; Lucrezi, Jacob; May, Sheldon W; Bucalo, Kylie

2015-02-01

310

Respiration-linked proton flux in Wolinella succinogenes during reduction of N-oxides  

SciTech Connect

Formate uncoupled proton translocation in formate-grown Wolinella succinogenes cells supplied with N-oxides as terminal electron acceptors. In suspensions containing KSCN (but not valinomycin), H2 supported proton translocation when NO3-, NO2-, and NO were provided as oxidants. H+/N-oxide ratios were 4.77 for NO3-, 2.49 for NO2-, and 1.75 for NO. KSCN inhibits N2O reduction thus precluding use of N2O as oxidant. Repeated exposure of cells to NO inhibited their ability to translocated protons with NO as oxidant but only slightly diminished and did not eliminate their capacity for NO3(-)- or NO2(-)-dependent proton flux. Substituting reduced benzyl viologen for H2 and measuring proton uptake provided results consistent with an extramembranal location for the N- oxide reductases. The uncoupler, carbonyl cyanide m-chlorophenylhydrazone, collapsed proton gradients, permitted uptake of 2 mol H+/mol NO3- or NO2-, but unaccountably inhibited NO3- reduction by 50% while leaving H+ uptake stoichiometry of the cells unaffected.

Shapleigh, J.P.; Payne, W.J.

1986-02-01

311

(11,12/94)(4,5/97)(02,3/07)(01/08) Neuman Chapter 17 Oxidation and Reduction  

E-print Network

(11,12/94)(4,5/97)(02,3/07)(01/08) Neuman Chapter 17 0 Chapter 17 Oxidation and Reduction from. Foundations 1. Organic Molecules and Chemical Bonding 2. Alkanes and Cycloalkanes 3. Haloalkanes, Alcohols and Substitution Reactions 17. Oxidation and Reduction Reactions 18. Reactions of Enolate Ions and Enols 19

Reed, Christopher A.

312

Jet Noise Reduction Potential from Emerging Variable Cycle Technologies  

NASA Technical Reports Server (NTRS)

Acoustic and flow-field experiments were conducted on exhaust concepts for the next generation supersonic, commercial aircraft. The concepts were developed by Lockheed Martin (LM), Rolls-Royce Liberty Works (RRLW), and General Electric Global Research (GEGR) as part of an N+2 (next generation forward) aircraft system study initiated by the Supersonics Project in NASA s Fundamental Aeronautics Program. The experiments were conducted in the Aero-Acoustic Propulsion Laboratory at the NASA Glenn Research Center. The exhaust concepts utilized ejectors, inverted velocity profiles, and fluidic shields. One of the ejector concepts was found to produce stagnant flow within the ejector and the other ejector concept produced discrete-frequency tones that degraded the acoustic performance of the model. The concept incorporating an inverted velocity profile and fluid shield produced overall-sound-pressure-level reductions of 6 dB relative to a single stream nozzle at the peak jet noise angle for some nozzle pressure ratios. Flow separations in the nozzle degraded the acoustic performance of the inverted velocity profile model at low nozzle pressure ratios.

Henderson, Brenda; Bridges, James; Wernet, Mark

2012-01-01

313

Wet air oxidation pretreatment of biomethanated distillery effluent: mapping pretreatment efficiency in terms color, toxicity reduction and biogas generation.  

PubMed

The effluents from molasses-based distilleries after biomethanation are beset with problems of intensified dark brown color, high residual COD, low biodegradability index (BOD/COD ratio <0.2) and toxicity issues for possible land application as a potential fertilizer. Wet air oxidation (WAO) pretreatment of biomethanated distillery effluent resulted in substantial enhancement in the biodegradability index (BI) (up to 0.8). WAO pretreated effluent on anaerobic digestion indicated favorable biogas generation with methane content up to 64% along with concomitant COD reduction up to 54.75%. The HPLC analysis indicated that the pretreatment facilitated degradation of major color containing compounds-namely melanoidins, up to 97.8%. The pretreated effluent with enhanced biodegradability along with substantially reduced color also indicated positive effect on seed germination (up to 100%), implying toxicity reduction of the effluent post WAO pretreatment. PMID:24583914

Sarat Chandra, T; Malik, S N; Suvidha, G; Padmere, M L; Shanmugam, P; Mudliar, S N

2014-04-01

314

Scenario analysis on CO 2 emissions reduction potential in China's electricity sector  

Microsoft Academic Search

With the approach of the year 2012, a new round of international negotiations has energized the entire climate change community. With this, analyses on sector-based emissions reduction and mitigation options will provide the necessary information to form the debate. In order to assess the CO2 emissions reduction potential of China's electricity sector, this research employs three scenarios based on the

Wenjia Cai; Can Wang; Ke Wang; Ying Zhang; Jining Chen

2007-01-01

315

Reduction and Oxidation of the Active Site Iron in Tyrosine Hydroxylase: Kinetics and Specificity†  

PubMed Central

Tyrosine hydroxylase (TyrH) is a pterin-dependent enzyme that catalyzes the hydroxylation of tyrosine to form dihydroxyphenylalanine. The oxidation state of the active site iron atom plays a central role in the regulation of the enzyme. The kinetics of reduction of ferric TyrH by several reductants were determined by anaerobic stopped-flow spectroscopy. Anaerobic rapid freeze–quench EPR confirmed that the change in the near-UV absorbance of TyrH upon adding reductant corresponded to iron reduction. Tetrahydrobiopterin reduces wild-type TyrH following a simple second-order mechanism with a rate constant of 2.8 ± 0.1 mM?1 s?1. 6-Methyltetrahydropterin reduces the ferric enzyme with a second-order rate constant of 6.1 ± 0.1 mM?1 s?1 and exhibits saturation kinetics. No EPR signal for a radical intermediate was detected. Ascorbate, glutathione, and 1,4-benzoquinone all reduce ferric TyrH, but much more slowly than tetrahydrobiopterin, suggesting that the pterin is a physiological reductant. E332A TyrH, which has an elevated Km for tetrahydropterin in the catalytic reaction, is reduced by tetrahydropterins with the same kinetic parameters as those of the wild-type enzyme, suggesting that BH4 does not bind in the catalytic conformation during the reduction. Oxidation of ferrous TyrH by molecular oxygen can be described as a single-step second-order reaction, with a rate constant of 210 mM?1 s?1. S40E TyrH, which mimics the phosphorylated state of the enzyme, has oxidation and reduction kinetics similar to those of the wild-type enzyme, suggesting that phosphorylation does not directly regulate the interconversion of the ferric and ferrous forms. PMID:16475826

Frantom, Patrick A.; Seravalli, Javier; Ragsdale, Stephen W.; Fitzpatrick, Paul F.

2006-01-01

316

Reductions in Northeast Refining Activity: Potential Implications for Petroleum Product Markets  

EIA Publications

This report is the Energy Information Administration's (EIA) initial effort to provide information and analysis on the potential impacts on petroleum product markets from reductions in Northeast petroleum refining activity.

2011-01-01

317

Synthesis and Characterization of Iodine laden Graphene Nano Platelets via reduction of Graphene Oxide Using Hydrogen Iodide  

NASA Astrophysics Data System (ADS)

This research thesis proposes a novel method for the synthesis, analysis and characterization of Iodinated X-Ray contrast agents using Graphene Nanoplatelets (GNPs) for Computed Tomographic Imaging. Graphene Oxide was synthesized using the Hummers Method of Oxidation [1] through oxidative treatment of Graphite with Potassium Permanganate (KMnO4). The resulting Graphene Oxide was chemically reduced using varying concentrations of Hydrogen Iodide or Hydroiodic acid (HI), rather than the conventionally used highly toxic Hydrazine Hydrate (N2H4) to strip off the oxygen functionalities. In the process of chemical reduction using Hydrogen Iodide, we hypothesized that this would result in the incorporation of Iodine into the Graphitic structure. Raman Spectroscopy, EDS along with XRD analysis provided evidence for the reduction of GO. Raman spectra for reduced GNPs showed an increase in ID/IG ratio from that of graphene oxide and also a peak at 154cm-1 attributed to I5 -. EDS/EDX spectra for HI reduced GO showed a peak at X-ray energy level 3.94KeV characteristic of Iodine. Further analysis using Ion-Selective Electrode measurements confirmed the presence of about 10% Iodine in the Hydroiodic acid reduced samples. SEM and TEM images showed a brief morphology of the Graphene Nanoplatelets. Finally, to elucidate the possibility of Iodinated GNPs to be developed into potential CT contrast agents in the near or far future, CT Phantoms of Iodine loaded GNPs at a concentration of 40mg/ml in water showed excellent contrast density with water and dilute Hydroiodic acid as controls.

Sundararaj, Joe Livingston

318

Multifunctional Low-Pressure Turbine for Core Noise Reduction, Improved Efficiency, and Nitrogen Oxide (NOx) Reduction  

NASA Technical Reports Server (NTRS)

This work studied the feasibility of using Helmholtz resonator cavities embedded in low-pressure-turbine (LPT) airfoils to (1) reduce core noise by damping acoustic modes; (2) use the synthetic jets produced by the liner hole acoustic oscillations to improve engine efficiency by maintaining turbulent attached flow in the LPT at low-Reynolds-number cruise conditions; and (3) reduce engine nitrogen oxide emissions by lining the internal cavities with materials capable of catalytic conversion. Flat plates with embedded Helmholtz resonators, designed to resonate at either 3000 or at 400 Hz, were simulated using computational fluid dynamics. The simulations were conducted for two inlet Mach numbers, 0.25 and 0.5, corresponding to Reynolds numbers of 90 000 and 164 000 based on the effective chordwise distance to the resonator orifice. The results of this study are (1) the region of acoustic treatment may be large enough to have a benefit; (2) the jets may not possess sufficient strength to reduce flow separation (based on prior work by researchers in the flow control area); and (3) the additional catalytic surface area is not exposed to a high velocity, so it probably does not have any benefit.

Miller, Christopher J.; Shyam, Vikram; Rigby, David L.

2013-01-01

319

Potential Impacts of Reductions in Refinery Activity on Northeast Petroleum Product Markets  

EIA Publications

Potential Impacts of Reductions in Refinery Activity on Northeast Petroleum Product Markets is an update to a previous Energy Information Administration (EIA) report, Reductions in Northeast Refining Activity: Potential Implications for Petroleum Product Markets, released in December 2011. This update analyzes possible market responses and impacts in the event Sunoco's Philadelphia refinery closes this summer, in addition to the recently idled refineries on the East Coast and in the U.S. Virgin Islands.

2012-01-01

320

Real-time monitoring of graphene oxide reduction in acrylic printable composite inks  

NASA Astrophysics Data System (ADS)

This work reports the electrical characterization of a water-based graphene oxide/acrylic composite material, which was directly inkjet printed to fabricate dissipative patterns. The graphene oxide filler, which is strongly hydrophilic due to its heavily oxygenated surface and can be readily dispersed in water, was reduced by UV irradiation during photo-curing of the polymeric matrix. The concurrent polymerization of the acrylic matrix and reduction of graphene oxide filler was demonstrated by real-time resistance measurements during UV light irradiation. The presence of graphene filler allowed decreasing the resistance of the pure polymeric matrix by nearly five orders of magnitude. This was explained by the fact that clusters of reduced graphene oxide inside the polymer matrix act as preferential pathways for the mobility of charge carriers, thus leading to an overall decrease of the material's resistance.

Porro, S.; Giardi, R.; Chiolerio, A.

2014-06-01

321

Development of Molecular Electrocatalysts for CO2 Reduction and H2 Production/Oxidation  

SciTech Connect

The conversion of solar energy to fuels in both natural and artificial photosynthesis requires components for both light harvesting and catalysis. The light-harvesting component generates the electrochemical potentials required to drive fuel-generating reactions that would otherwise be thermodynamically uphill. This review focuses on work from our laboratories on developing molecular electrocatalysts for CO2 reduction and for hydrogen production. A true analog of natural photosynthesis will require the ability to capture CO2 from the atmosphere and reduce it to a useful fuel. Work in our laboratories has focused on both aspects of this problem. Organic compounds such as quinones and inorganic metal complexes can serve as redox active CO2 carriers for concentrating CO2. Catalysts for CO2 reduction to form CO have also been developed based on a [Pd(triphosphine)(solvent)]2+ platform. A required feature for catalytic activity is the presence of a weakly coordinating solvent molecule that can dissociate during the catalytic cycle and provide a vacant coordination site for binding water and assisting C-O bond cleavage. Participation of a second metal in CO2 binding also appears to be required for achieving very active catalysts as suggested by structures of [NiFe] CO dehydrogenase enzymes and the results of studies on complexes containing two [Pd(triphosphine)(solvent)]2+ units. Molecular electrocatalysts for H2 production and oxidation based on [Ni(diphosphine)2]2+ complexes are also described. These catalysts require the optimization of both first and second coordination spheres similar to that of the palladium CO2 reduction catalysts. In this case, structural features of the first coordination sphere can be used to optimize the hydride acceptor ability of nickel needed to achieve heterolytic cleavage of H2. The second coordination sphere can be used to incorporate pendant bases that assist in a number of important functions including H2 binding, H2 cleavage, and the transfer of protons between nickel and solution. These pendant bases or proton relays are likely to be important in the design of catalysts for a wide range of fuel production and fuel utilization reactions involving multiple electron and proton transfer steps. The work described in this review has been supported by the Chemical Sciences program of the Office of Basic Energy Sciences of the Department of Energy. The Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

Rakowski DuBois, Mary; DuBois, Daniel L.

2009-12-15

322

The potential for diazotrophy in iron-and sulfur-oxidizing acidophilic bacteria  

Microsoft Academic Search

Acetylene reduction was observed with ferrousiron-oxidizingThiobacillus ferrooxidans, as expected from previous studies with this bacterium. Acetylene reduction was also found during the growth ofT. ferrooxidans on tetrathionate. OnlyLeptospirillum ferrooxidans, one of several other phylogenetically diverse, ferrous-iron-and\\/or sulfur-oxidizing acidophilic microorganisms, also reduced\\u000a acetylene. A reduction of the oxygen concentration in the culture atmosphere was necessary to alleviate inhibition of nitrogenase\\u000a activity.

Paul R. Norris; J. Colin Murrell; Deborah Hinson

1995-01-01

323

A dinuclear copper(II) electrocatalyst both water reduction and oxidation  

NASA Astrophysics Data System (ADS)

Splitting water is a key challenge in the production of chemical fuels from electricity. Although several catalysts have been developed for these reactions, substantial challenges remain towards the ultimate goal of an efficient, inexpensive and robust electrocatalyst. Until now, there is as yet no report on both water oxidation and reduction by identical catalyst. Reported here is the first soluble copper-based catalyst, Cu(Me2oxpn)Cu(OH)2] 1 (Me2oxpn: N,N?-bis(2,2?-dimethyl-3-aminopropyl)oxamido) for both electrolytic water oxidation and reduction. Water oxidation occurs at an overpotential of 636 mV vs SHE to give O2 with a turnover frequency (TOF) of ?2.14 s-1. Electrochemical studies also indicate that 1 is a soluble molecular species, that is among the most rapid homogeneous water reduction catalysts, with a TOF of 654 mol of hydrogen per mole of catalyst per hour at an overpotential of 789 mV vs SHE (pH 7.0). Sustained water reduction catalysis occurs at glassy carbon (GC) to give H2 over a 32 h electrolysis period with 95% Faradaic yield and no observable decomposition of the catalyst.

Zhou, Ling-Ling; Fang, Ting; Cao, Jie-Ping; Zhu, Zhi-Hong; Su, Xiao-Ting; Zhan, Shu-Zhong

2015-01-01

324

Enhanced reduction of silicon oxide thin films on silicon under electron beam annealing  

NASA Astrophysics Data System (ADS)

Electron beam annealing is an interesting alternative to other annealing methods as it can provide high temperature, rapid heating and cooling and low level of impurity as it operates under high vacuum environment. Furthermore swamping the materials with electrons can lead to dramatic changes in the component valence states with the mechanism involving oxido-reduction reactions. This is illustrated in the present case with the enhancement of the reduction of SiO2. Commercial thermally grown 100 and 400 nm SiO2 films on Si were annealed under three different environments: furnace annealing in open atmosphere with O2 flow, high vacuum furnace annealing and electron beam annealing. The reduction and oxidation of SiO2 films on Si are investigated using ion beam analysis. The validity of the measurement method was confirmed by measuring the oxidation rate through successive Rutherford backscattering spectrometry (RBS) measurements. The oxidation kinetics were observed to be in excellent agreement with literature values. At 1000 °C reduction of the SiO2 film is observed only with electron beam annealing. A model is proposed to explain the effect of the electron beam.

Kennedy, J.; Leveneur, J.; Fang, F.; Markwitz, A.

2014-08-01

325

Bacterial Reductive Dissolution of Crystalline Fe(III) Oxide in Continuous-Flow Column Reactors  

PubMed Central

Bacterial reductive dissolution of synthetic crystalline Fe(III) oxide-coated sand was studied in continuous-flow column reactors in comparison with parallel batch cultures. The cumulative amount of aqueous Fe(II) exported from the columns over a 6-month incubation period corresponded to (95.0 ± 3.7)% (n = 3) of their original Fe(III) content. Wet-chemical analysis revealed that only (6.5 ± 3.2)% of the initial Fe(III) content remained in the columns at the end of the experiment. The near-quantitative removal of Fe was visibly evidenced by extensive bleaching of color from the sand in the columns. In contrast to the column reactors, Fe(II) production quickly reached an asymptote in batch cultures, and only (13.0 ± 2.2)% (n = 3) of the Fe(III) oxide content was reduced. Sustained bacterial-cell growth occurred in the column reactors, leading to the production and export of a quantity of cells 100-fold greater than that added during inoculation. Indirect estimates of cell growth, based on the quantity of Fe(III) reduced, suggest that only an approximate doubling of initial cell abundance was likely to have occurred in the batch cultures. Our results indicate that removal of biogenic Fe(II) via aqueous-phase transport in the column reactors decreased the passivating influence of surface-bound Fe(II) on oxide reduction activity, thereby allowing a dramatic increase in the extent of Fe(III) oxide reduction and associated bacterial growth. These findings have important implications for understanding the fate of organic and inorganic contaminants whose geochemical behavior is linked to Fe(III) oxide reduction. PMID:10698772

Roden, Eric E.; Urrutia, Matilde M.; Mann, Carroll J.

2000-01-01

326

Effects of microbial iron reduction and oxidation on the immobilization and mobilization of copper in synthesized Fe(III) minerals and Fe-rich soils.  

PubMed

The effects of microbial iron reduction and oxidation on the immobilization and mobilization of copper were investigated in a high concentration of sulfate with synthesized Fe(III) minerals and red earth soils rich in amorphous Fe (hydr)oxides. Batch microcosm experiments showed that red earth soil inoculated with subsurface sediments had a faster Fe(III) bioreduction rate than pure amorphous Fe(III) minerals and resulted in quicker immobilization of Cu in the aqueous fraction. Coinciding with the decrease of aqueous Cu, SO4(2-) in the inoculated red earth soil decreased acutely after incubation. The shift in the microbial community composite in the inoculated soil was analyzed through denaturing gradient gel electrophoresis. Results revealed the potential cooperative effect of microbial Fe(III) reduction and sulfate reduction on copper immobilization. After exposure to air for 144 h, more than 50% of the immobilized Cu was remobilized from the anaerobic matrices; aqueous sulfate increased significantly. Sequential extraction analysis demonstrated that the organic matter/sulfide-bound Cu increased by 52% after anaerobic incubation relative to the abiotic treatment but decreased by 32% after oxidation, indicating the generation and oxidation of Cu-sulfide coprecipitates in the inoculated red earth soil. These findings suggest that the immobilization of copper could be enhanced by mediating microbial Fe(III) reduction with sulfate reduction under anaerobic conditions. The findings have an important implication for bioremediation in Cucontaminated and Fe-rich soils, especially in acid-mine-drainage-affected sites. PMID:24448165

Hu, Chaohua; Zhang, Youchi; Zhang, Lei; Luo, Wensui

2014-04-01

327

HDR reservoir flow impedance and potentials for impedance reduction  

SciTech Connect

The data from flow tests which employed two different production zones in a well at Fenton Hill indicates the flow impedance of a wellbore zone damaged by rapid depressurization was altered, possibly by pressure spallation, which appears to have mechanically propped the joint apertures of outlet flow paths intersecting the altered wellbore. The rapid depressurization and subsequent flow test data derived from the damaged well has led to the hypothesis that pressure spallation and the resultant mechanical propping of outlet flow paths reduced the outlet flow impedance of the damaged wellbore. Furthermore, transient pressure data shows the largest pressure drop between the injection and production wellheads occurs near the production wellbore, so lowering the outlet impedance by increasing the apertures of outlet flow paths will have the greatest effect on reducing the overall reservoir impedance. Fenton Hill data also reveals that increasing the overall reservoir pressure dilates the apertures of flow paths, which likewise serves to reduce the reservoir impedance. Data suggests that either pressure dilating the wellbore connected joints with high production wellhead pressure, or mechanically propping open the outlet flow paths will increase the near-wellbore permeability. Finally, a new method for calculating and comparing near-wellbore outlet impedances has been developed. Further modeling, experimentation, and engineered reservoir modifications, such as pressure dilation and mechanical propping, hold considerable potential for significantly improving the productivity of HDR reservoirs.

DuTeau, R.; Brown, D.

1993-06-01

328

HDR reservoir flow impedance and potential for impedance reduction  

SciTech Connect

The data from flow tests which employed two different production zones in a well at Fenton Hill indicates the flow impedance of a wellbore zone damaged by rapid depressurization was altered, possibly by pressure spallation, which appears to have mechanically propped the joint apertures of outlet flow paths intersecting the altered wellbore. The rapid depressurization and subsequent flow test data derived from the damaged well has led to the hypothesis that pressure spallation and the resultant mechanical propping of outlet flow paths reduced the outlet flow impedance of the damaged wellbore. Furthermore, transient pressure data shows the largest pressure drop between the injection and production wellheads occurs near the production wellbore, so lowering the outlet impedance by increasing the apertures of outlet flow paths will have the greatest effect on reducing the overall reservoir impedance. Fenton Hill data also reveals that increasing the overall reservoir pressure dilates the apertures of flow paths, which likewise serves to reduce the reservoir impedance. Data suggests that either pressure dilating the wellbore connected joints with high production wellhead pressure, or mechanically propping open the outlet flow paths will increase the near-wellbore permeability. Finally, a new method for calculating and comparing near-wellbore outlet impedances has been developed. Further modeling, experimentation, and engineered reservoir modifications, such as pressure dilation and mechanical propping, hold considerable potential for significantly improving the productivity of HDR reservoirs.

Du Teau, Robert; Brown, Donald

1993-01-28

329

HDR reservoir flow impedance and potentials for impedance reduction  

SciTech Connect

The data from flow tests which employed two different production zones in a well at Fenton Hill indicates the flow impedance of a wellbore zone damaged by rapid depressurization was altered, possibly by pressure spallation, which appears to have mechanically propped the joint apertures of outlet flow paths intersecting the altered wellbore. The rapid depressurization and subsequent flow test data derived from the damaged well has led to the hypothesis that pressure spallation and the resultant mechanical propping of outlet flow paths reduced the outlet flow impedance of the damaged wellbore. Furthermore, transient pressure data shows the largest pressure drop between the injection and production wellheads occurs near the production wellbore, so lowering the outlet impedance by increasing the apertures of outlet flow paths will have the greatest effect on reducing the overall reservoir impedance. Fenton Hill data also reveals that increasing the overall reservoir pressure dilates the apertures of flow paths, which likewise serves to reduce the reservoir impedance. Data suggests that either pressure dilating the wellbore connected joints with high production wellhead pressure, or mechanically propping open the outlet flow paths will increase the near-wellbore permeability. Finally, a new method for calculating and comparing near-wellbore outlet impedances has been developed. Further modeling, experimentation, and engineered reservoir modifications, such as pressure dilation and mechanical propping, hold considerable potential for significantly improving the productivity of HDR reservoirs.

DuTeau, R.; Brown, D.

1993-01-01

330

Selective reduction of N-oxides to amines: application to drug metabolism.  

PubMed

Phase I oxidative metabolism of nitrogen-containing drug molecules to their corresponding N-oxides is a common occurrence. There are instances where liquid chromatography/tandem mass spectometry techniques are inadequate to distinguish this pathway from other oxidation processes, including C-hydroxylations and other heteroatom oxidations, such as sulfur to sulfoxide. Therefore, the purpose of the present study was to develop and optimize an efficient and practical chemical method to selectively convert N-oxides to their corresponding amines suitable for drug metabolism applications. Our results indicated that efficient conversion of N-oxides to amines could be achieved with TiCl(3) and poly(methylhydrosiloxane). Among them, we found TiCl(3) to be a facile and easy-to-use reagent, specifically applicable to drug metabolism. There are a few reports describing the use of TiCl(3) to reduce N-O bonds in drug metabolism studies, but this methodology has not been widely used. Our results indicated that TiCl(3) is nearly as efficient when the reductions were carried out in the presence of biological matrices, including plasma and urine. Finally, we have shown a number of examples where TiCl(3) can be successfully used to selectively reduce N-oxides in the presence of sulfoxides and other labile groups. PMID:15319338

Kulanthaivel, Palaniappan; Barbuch, Robert J; Davidson, Rita S; Yi, Ping; Rener, Gregory A; Mattiuz, Edward L; Hadden, Chad E; Goodwin, Lawrence A; Ehlhardt, William J

2004-09-01

331

IMPACTS OF ANTIFOAM ADDITIONS AND ARGON BUBBLING ON DEFENSE WASTE PROCESSING FACILITY REDUCTION/OXIDATION  

SciTech Connect

During melting of HLW glass, the REDOX of the melt pool cannot be measured. Therefore, the Fe{sup +2}/{Sigma}Fe ratio in the glass poured from the melter must be related to melter feed organic and oxidant concentrations to ensure production of a high quality glass without impacting production rate (e.g., foaming) or melter life (e.g., metal formation and accumulation). A production facility such as the Defense Waste Processing Facility (DWPF) cannot wait until the melt or waste glass has been made to assess its acceptability, since by then no further changes to the glass composition and acceptability are possible. therefore, the acceptability decision is made on the upstream process, rather than on the downstream melt or glass product. That is, it is based on 'feed foward' statistical process control (SPC) rather than statistical quality control (SQC). In SPC, the feed composition to the melter is controlled prior to vitrification. Use of the DWPF REDOX model has controlled the balanjce of feed reductants and oxidants in the Sludge Receipt and Adjustment Tank (SRAT). Once the alkali/alkaline earth salts (both reduced and oxidized) are formed during reflux in the SRAT, the REDOX can only change if (1) additional reductants or oxidants are added to the SRAT, the Slurry Mix Evaporator (SME), or the Melter Feed Tank (MFT) or (2) if the melt pool is bubble dwith an oxidizing gas or sparging gas that imposes a different REDOX target than the chemical balance set during reflux in the SRAT.

Jantzen, C.; Johnson, F.

2012-06-05

332

Process for the catalytic reduction of nitrogen oxides in gaseous mixtures  

SciTech Connect

A process for the reductive removal of a nitrogen oxide from a gaseous stream, particularly a stream containing oxygen, water, sulfur dioxide, nitrogen oxide and nitrogen, by contacting the stream with ammonia in the presence of a mixture of two catalysts. The first catalyst comprises copper or a copper compound, preferably copper sulfate supported on a porous carrier material. The second catalyst is a combination of metals or compounds thereof, preferably sulfates of vanadium and iron or tungsten and iron, also dispersed on a porous carrier material.

Ginger, E.A.

1981-05-19

333

Reduction in nitrogen oxides emission on TGME-464 boiler of IRU power plant (Estonia)  

NASA Astrophysics Data System (ADS)

The possibility for realization of measures on a reduction in nitrogen oxides emission on a TGME-464 (plant no. 2) boiler of the IRU power plant (Tallinn, Estonia) is investigated. Low-cost techno-logical measures, namely, nonstoichiometric burning and burning with the moderate controlled chemical underburning, are proposed and experimentally tested. Recommendations on the implementation of low-emission modes of burning natural gas into mode diagrams of the boiler are given. Nitrogen oxides emissions are reduced to the required level as a result of the implementation of the proposed measures.

Roslyakov, P. V.; Ionkin, I. L.

2015-01-01

334

Solid-phase electrochemical reduction of graphene oxide films in alkaline solution.  

PubMed

Graphene oxide (GO) film was evaporated onto graphite and used as an electrode to produce electrochemically reduced graphene oxide (ERGO) films by electrochemical reduction in 6 M KOH solution through voltammetric cycling. Fourier transformed infrared and Raman spectroscopy confirmed the presence of ERGO. Electrochemical impedance spectroscopy characterization of ERGO and GO films in ferrocyanide/ferricyanide redox couple with 0.1 M KCl supporting electrolyte gave results that are in accordance with previous reports. Based on the EIS results, ERGO shows higher capacitance and lower charge transfer resistance compared to GO. PMID:24059434

Basirun, Wan J; Sookhakian, Mehran; Baradaran, Saeid; Mahmoudian, Mohammad R; Ebadi, Mehdi

2013-01-01

335

Xylary pH and Reduction Potential Levels of Iron-stressed Silver Maple (Acer saccharinum L.) 1  

PubMed Central

Xylary fluid pH and reduction potentials were measured on silver maple (Acer saccharinum L.) grown under Fe and pH stress. Although pH and reduction potential (millivolt/59.2) varied significantly in the nutrient solution, xylary pH and reduction potential remained constant. It was concluded that changes in the pH and reduction potential in the xylary fluid of silver maple are not responsible for iron chlorosis. PMID:16661196

Morris, Robert L.; Swanson, Bert T.

1980-01-01

336

Rate of the reduction of the iron oxides in red mud by hydrogen and converted gas  

NASA Astrophysics Data System (ADS)

The drying and gas reduction of the iron oxides in the red mud of bauxite processing are studied. It is shown that at most 25% of aluminum oxide are fixed by iron oxides in this red mud, and the other 75% are fixed by sodium aluminosilicates. A software package is developed to calculate the gas reduction of iron oxides, including those in mud. Small hematite samples fully transform into magnetite in hydrogen at a temperature below 300°C and a heating rate of 500 K/h, and complete reduction of magnetite to metallic iron takes place below 420°C. The densification of a thin red mud layer weakly affects the character and temperature range of magnetizing calcination, and the rate of reduction to iron decreases approximately twofold and reduction covers a high-temperature range (above 900°C). The substitution of a converted natural gas for hydrogen results in a certain delay in magnetite formation and an increase in the temperature of the end of reaction to 375°C. In the temperature range 450-550°C, the transformation of hematite into magnetite in red mud pellets 1 cm in diameter in a converted natural gas is 30-90 faster than the reduction of hematite to iron in hydrogen. The hematite-magnetite transformation rate in pellets is almost constant in the temperature range under study, and reduction occurs in a diffusion mode. At a temperature of ˜500°C, the reaction layer thickness of pellets in a shaft process is calculated to be ˜1 m at a converted-gas flow rate of 0.1 m3/(m2 s) and ˜2.5 m at a flow rate of 0.25 m3/(m2 s). The specific capacity of 1 m2 of the shaft cross section under these conditions is 240 and 600 t/day, respectively. The use of low-temperature gas reduction processes is promising for the development of an in situ optimum red mud utilization technology.

Teplov, O. A.; Lainer, Yu. A.

2013-01-01

337

Inhibition by sulfide of nitric and nitrous oxide reduction by denitrifying Pseudomonas fluorescens  

SciTech Connect

The influence of low redox potentials and H/sub 2/S on NO and N/sub 2/O reduction by resting cells of dentrifying Pseudomonas fluorescens was studied. Hydrogen sulfide and Ti(III) were added to achieve redox potentials near -200 mv. The control without reductant had a redox potential near +200 mv. Production of /sup 13/No, (/sup 13/N)N/sub 2/O, and (/sup 13/N)N/sub 2/ from /sup 13/NO/sub 3//sup -/ and /sup 13/NO/sub 2//sup -/ was followed. Total gas production was similar for all three treatments. The accumulation of /sup 13/NO was most significant in the presence of sulfide. A parallel control with autoclaved cells indicated that the /sup 13/NO production was largely biological. The sulfide inhibition was more dramatic at the level of N/sub 2/O reduction; (/sup 13/N)NO/sub 2/ became the major product instead of (/sup 13/N)N/sub 2/, the dominant product when either no reductant or Ti(III) was present. The results indicate that the specific action of sulfide rather than the low redox potential caused a partial inhibition of NO reduction and a strong inhibition of N/sub 2/O reduction in denitrifying cells.

Sorensen, J.; Tiedje, J.M.; Firestone, R.B.

1980-01-01

338

Nitric Oxide Synthase and Xanthine Oxidase Activities in the Spermatic Vein of Patients with Varicocele: A Potential Role for Nitric Oxide and Peroxynitrite in Sperm Dysfunction  

Microsoft Academic Search

PurposeThe oxidative and reductive stresses within the varicocele veins were estimated. Nitric oxide synthase and xanthine oxidase activities, as well as nitric oxide, S-nitrosothiols and superoxide release within the spermatic vein in patients with varicocele, and the role of the noxious oxidant peroxynitrite formed from nitric oxide and superoxide in sperm dysfunction were determined.

Dionisios Mitropoulos; George Deliconstantinos; Anastasios Zervas; Vassiliki Villiotou; Constantinos Dimopoulos; John Stavrides

1996-01-01

339

Going Wireless: Fe(III) Oxide Reduction without Pili by Geobacter sulfurreducens Strain JS-1  

PubMed Central

Previous studies have suggested that the conductive pili of Geobacter sulfurreducens are essential for extracellular electron transfer to Fe(III) oxides and for optimal long-range electron transport through current-producing biofilms. The KN400 strain of G. sulfurreducens reduces poorly crystalline Fe(III) oxide more rapidly than the more extensively studied DL-1 strain. Deletion of the gene encoding PilA, the structural pilin protein, in strain KN400 inhibited Fe(III) oxide reduction. However, low rates of Fe(III) reduction were detected after extended incubation (>30 days) in the presence of Fe(III) oxide. After seven consecutive transfers, the PilA-deficient strain adapted to reduce Fe(III) oxide as fast as the wild type. Microarray, whole-genome resequencing, proteomic, and gene deletion studies indicated that this adaptation was associated with the production of larger amounts of the c-type cytochrome PgcA, which was released into the culture medium. It is proposed that the extracellular cytochrome acts as an electron shuttle, promoting electron transfer from the outer cell surface to Fe(III) oxides. The adapted PilA-deficient strain competed well with the wild-type strain when both were grown together on Fe(III) oxide. However, when 50% of the culture medium was replaced with fresh medium every 3 days, the wild-type strain outcompeted the adapted strain. A possible explanation for this is that the necessity to produce additional PgcA, to replace the PgcA being continually removed, put the adapted strain at a competitive disadvantage, similar to the apparent selection against electron shuttle-producing Fe(III) reducers in many anaerobic soils and sediments. Despite increased extracellular cytochrome production, the adapted PilA-deficient strain produced low levels of current, consistent with the concept that long-range electron transport through G. sulfurreducens biofilms is more effective via pili. PMID:24814783

Shrestha, Pravin Malla; Snoeyenbos-West, Oona L.; Franks, Ashley E.; Nevin, Kelly P.; Lovley, Derek R.

2014-01-01

340

Reduction of coherence of the human brain electric potentials  

NASA Astrophysics Data System (ADS)

Plenty of technological processes are known to be damaged by magnetic storms. But technology is controlled by men and their functional systems may be damaged as well. We are going to consider the electro-neurophysiological aspect of the general problem: men surrounded by physical fields including ones of cosmic origination. Magnetic storms’ influence had been observed for a group of 13 students (practically healthy girls and boys from 18 to 23 years old, Moscow). To control the main functional systems of the examinees, their electroencephalograms (EEG) were being registered along with electrocardiograms, respiratory rhythms, arterial blood pressure and other characteristics during a year. All of these characteristics, save for the EEG, were within the normal range for all of the examinees during measurements. According to the EEG investigations by implementation of the computer proof-reading test in absence of magnetic storms, the values of the coherence function of time series of the theta-rhythm oscillations (f = 4 - 7.9 Hz, A = 20 ?V) of electric potentials of the frontal-polar and occipital areas of the head belong to the interval [0.3, 0.8] for all of the students under investigation. (As the proof-reading test, it was necessary to choose given symbols from a random sequence of ones demonstrated at a monitor and to enter the number of the symbols discovered in a computer. Everyone was known that the time for determination of symbols is unlimited. On the other hand, nobody was known that the EEG and other registrations mentioned are connected with electromagnetic geophysical researches and geomagnetic storms). Let us formulate the main result: by implementation of the same test during a magnetic storm, 5 ? K ? 6, or no later then 24 hours after its beginning (different types of moderate magnetic storms occurred, the data of IZMIRAN were used), the values of the theta-rhythm frontal - occipital coherence function of all of the students of the group under consideration decreased by a factor of two or more, including the zero coherence function value. The similar result was obtained for another basic low-frequency electro-neurophysiological rhythm delta (f = 0.5 - 3.9 Hz, A = 20 ?V). The usual coherence function values from the interval [0.3, 0.8] were being registered, typically, about 48 hours after the magnetic storm end. The result about decreasing of the coherence of the brain low frequency bioelectric oscillations under a magnetic storm influence was obtained by two methods: 1) comparison of the time series of bioelectric oscillations of a given person without a magnetic storm and under its influence; 2) comparison of two sets of time series of oscillations: a) the set A of time series measured without a magnetic storm and b) the set B of time series measured under its influence, regardless to an individual. Surely, the total number of the EEGs available for the investigation by the set’s approach, i.e. without personification, is more than the number of the EEGs available by the individual approach because there were ones investigated without a magnetic storm only as well as ones investigated under its influence only. By the EEG measurements with closed or open eyes, but without a functional load on the brain in the form of the proof-reading test, a distinctive decrease of the coherence function was not observed during a magnetic storm as well as for pairs of points from other parts of the head (see above) or other rhythms.

Novik, Oleg; Smirnov, Fedor

341

Anion exchange membranes for electrochemical oxidation-reduction energy storage system  

NASA Technical Reports Server (NTRS)

Oxidation-reduction couples in concentrated solutions separated by appropriate ion selective membranes were considered as an attractive approach to bulk electrical energy storage. A key problem is the development of the membrane. Several promising types of anionic membranes are discussed which were developed and evaluated for redox energy storage systems. The copolymers of ethyleneglycoldimethacrylate with either 2-vinylpyridine or vinylbenzl chloride gave stable resistance values compared to the copolymer of vinylbenzlchloride and divinylbenzene which served as the baseline membrane. A polyvinylchloride film aminated with tetraethylenepentamine had a low resistance but a high ion transfer rate. A slurry coated vinylpyridine had the lowest ion transfer rate. All these membranes functioned well in laboratory cells at ambient temperatures with the acidic chloride oxidant/reductant system, Fe 3, Fe 2/Ti 3, Ti 4.

Odonnell, P. M.; Sheibley, D. W.; Gahn, R. F.

1977-01-01

342

Palladium-based electrocatalysts for hydrogen oxidation and oxygen reduction reactions  

NASA Astrophysics Data System (ADS)

Fuel cells, especially low temperature fuel cells are clean energy devices that are expected to help address the energy and environmental problems that have become prevalent in our society. Platinum-based electrocatalysts are usually used as the electrocatalysts for both the anode (hydrogen oxidation) and cathode (oxygen reduction) reactions. The high cost and limited resources of this precious metal hinder the commercialization of fuel cells. Recent efforts have focused on the discovery of palladium-based electrocatalysts with little or no platinum for hydrogen oxidation reaction (HOR) and oxygen reduction reaction (ORR). This paper overviews the recent progress of electrocatalysis of palladium-based materials including both extended surfaces and nanostructured ones for HOR and ORR. The properties of CO and methanol tolerances of palladium-based electrocatalysts are also summarized.

Shao, Minhua

2011-03-01

343

Prediction of the reduction potential of tris(2,2'-bipyridinyl)iron(III/II) derivatives.  

PubMed

The reduction potentials of a tris(2,2'-bipyridinyl)iron (III/II) and iron(III/II) couples complexed with 2,2'-bipyridinyl derivatives in acetonitrile are predicted using density functional theory. The calculation protocol proposed by Kim et al. (Kim, J. Park, Y. S. Lee, J. Comput. Chem. 2013, 34, 2233) showing reliable performance for the reduction potential is used. The four kinds of the functional groups, a methoxy group, a methyl group, a chlorine atom, and a cyanide group, are substituted at the ligands to examine the electronic effect on the reduction potential. Electron donating/withdrawing effect is analyzed by comparing the reduction potential having different substituents at the same position. The influence of the geometrical strain on the reduction potential is investigated. The good correlation between the experimental results and the calculated results is obtained. Not only the general trend, but also the detailed phenomena are correctly reproduced. The maximum deviation from the experimental value is 0.083 V for the methyl substitution at the position 4. The mean absolute error for the seven couples is 0.047 V. The difference of the reduction potential between the chlorine atom substituted at the positions 4 and 5, 0.1 V, is well described. The difference between the CN and the Cl substitution of 0.318 and 0.228 V for the position 4 and 5 is correctly obtained as 0.325 and 0.213 V, respectively. The simple linear relation between the lowest unoccupied molecular orbital (LUMO) energy of the Fe(III) complexes in solution and the calculated reduction potentials is obtained with the R(2) of 0.977. PMID:25348486

Kim, Hyungjun; Park, Joungwon; Lee, Yoon Sup

2015-01-01

344

Scenario analysis on CO 2 emissions reduction potential in China's iron and steel industry  

Microsoft Academic Search

The international climate community has begun to assess a range of possible options for strengthening the international climate change effort after 2012. Analysis of the potential for sector-based emissions reduction and relevant mitigation options will provide the necessary background information for the debate. In order to assess the CO2 abatement potential of China's steel industry, a model was developed using

Ke Wang; Can Wang; Xuedu Lu; Jining Chen

2007-01-01

345

Potential of front-face fluorescence to monitor OM reduction in drinking water during potabilization process  

NASA Astrophysics Data System (ADS)

Elimination of OM in drinking water represents a great challenge for municipalities and technical actors to ensure that it can be safely used for consumption purposes. Indeed, current indicators such as Total Organic Carbon (TOC), turbidity or UV-Absorbance at 254 nm (UVA254) enable only non-specific overview of the amount of organic residuals in water. Fluorescence EEMs are a potent tool for discrimination and deep analysis of OM detailed composition and behaviour. It has been shown that several forms of OM co-exist in raw water, and come from various origins (bacteria, humic compounds…). Potabilization operation is composed of different steps that aim at decreasing all forms of OM using chemical as well as physical methods (ozone oxidation, filtration on activated carbon or sand, flocculation etc.). Unfortunately, it has been observed that reduction of OM during this process was not identical for all the forms, and the process showed a particular lack of efficiency during raining periods. 130 samples of water at various stages of potabilization were analyzed using home-made compact fluorometer, an apparatus composed of UV excitation LEDs. Using chemometrical treatment of spectral data, we put into highlight 5 different forms of OM that were identified according to litterature data. We evidenced the critical steps of the purification on OM reduction, as well as the relative content of each form from raw to product water. In particular, we showed that two forms were less reduced than the other three, so that progressive enrichment of total OM in the former was observed throughout the process. Moreover, a study was carried out in order to establish calibration models over conventional analyses using the spectral information. Highly satisfying models were thus obtained over TOC, turbidity and UVA254, with average RMSEC values of 13%, 7% and 16% respectively. These results demonstrate the potential of the fluorescence analyzer to simultaneously predict three major OM-related quality parameters of water. Finally, study of relationships between the different OM forms, climate parameters (temperature, raw water flow, rainfall) and coagulant amounts showeds that each OM form was specifically linked to these parameters. In particular, we were able to pinpoint one of the five forms that was most associated with the water flow, and also the most flocculated by the coagulant. In conclusion, this work demonstrates that our fluorescence analyzer helps to get improved knowledge of OM behavior during potabilization process. Five different OM forms were identified and their respective evolution was characterized. Furthermore, we evidenced a potential use of a compact and small-size analyzer to monitor water purification steps through simultaneous prediction of quality parameters related to OM content.

Lacotte, Pierre

2014-05-01

346

Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide  

Microsoft Academic Search

Reduction of a colloidal suspension of exfoliated graphene oxide sheets in water with hydrazine hydrate results in their aggregation and subsequent formation of a high-surface-area carbon material which consists of thin graphene-based sheets. The reduced material was characterized by elemental analysis, thermo-gravimetric analysis, scanning electron microscopy, X-ray photoelectron spectroscopy, NMR spectroscopy, Raman spectroscopy, and by electrical conductivity measurements.

Sasha Stankovich; Dmitriy A. Dikin; Richard D. Piner; Kevin A. Kohlhaas; Alfred Kleinhammes; Yuanyuan Jia; Yue Wu; SonBinh T. Nguyen; Rodney S. Ruoff

2007-01-01

347

One-step reduction, characterization and magnetic behaviour of exfoliated graphene oxide  

NASA Astrophysics Data System (ADS)

The functionalized graphene (GO) was fabricated by a simple method of chemical reduction in a polar aprotic solvent. This paper therefore, describes a versatile and synthetic route for the preparation of reduced graphene oxide (RGO) and its behavior when exposed to magnetic field environment. The characterization results of transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman spectroscopy and the attenuated total reflectance-Fourier transform infra-red (ATR-FTIR) analysis indicate that graphite was exfoliated and reduced to graphene layers.

Dikio, E. D.; Thema, F. T.; Farah, A. M.; Shooto, N. D.

2013-01-01

348

Bacterial reductive dissolution of crystalline Fe(III) oxide in continuous-flow column reactors  

Microsoft Academic Search

Bacterial reductive dissolution of synthetic crystalline Fe(III) oxide-coated sand was studied in continuous-flow column reactors in comparison with parallel batch cultures. The cumulative amount of aqueous Fe(II) exported from the columns over a 6-month incubation period corresponded to (95.0 {+-} 3.7)% (n = 3) of their original Fe(III) content. Wet-chemical analysis revealed that only (6.5 {+-} 3.2)% of the initial

ERIC E. RODEN; MATILDE M. URRUTIA; CARROLL J. MANN

2000-01-01

349

Shuttle to Shuttle 2: Subsystem weight reduction potential (estimated 1992 technology readiness date)  

NASA Technical Reports Server (NTRS)

The objective of this study was to make estimates of the weight savings that might be realized on all the subsystems on an advanced rocket-powered shuttle (designated Shuttle 2) by using advanced technologies having a projected maturity date of 1992. The current Shuttle with external tank was used as a baseline from which to make the estimates of weight savings on each subsystem. The subsystems with the greatest potential for weight reduction are the body shell and the thermal protection system. For the body shell, a reduction of 5.2 percent in the weight of the vehicle at main engine cutoff is projected through the application of new technologies, and an additional configuration-based reduction of 5 percent is projected through simplification of body shape. A reduction of 5 percent is projected for the thermal protection system through experience with the current Space Shuttle and the potential for reducing thermal protection system thicknesses in selected areas. Main propellant tanks are expected to increase slightly in weight. The main propulsion system is also projected to increase in weight because of the requirement to operate engines at derated power levels in order to accommodate one-engine-out capability. The projections for weight reductions through improvements in the remaining subsystems are relatively small. By summing all the technology factors, a projected reduction of 16 percent in the vehicle weight at main engine cutoff is obtained. By summarizing the configurational factors, a potential reduction of 12 percent in vehicle weight is obtained.

Macconochie, Ian O.

1988-01-01

350

DEVELOPMENT OF IMPROVED CATALYSTS FOR THE SELECTIVE CATALYTIC REDUCTION OF NITROGEN OXIDES WITH HYDROCARBONS  

SciTech Connect

Significant work has been done by the investigators on the cerium oxide-copper oxide based sorbent/catalysts for the combined removal of sulfur and nitrogen oxides from the flue gases of stationary sources. A relatively wide temperature window was established for the use of alumina-supported cerium oxide-copper oxide mixtures as regenerable sorbents for SO{sub 2} removal. Preliminary evaluation of these sorbents as catalysts for the selective reduction of NO{sub x} gave promising results with ammonia, but indicated low selectivity when methane was used as the reductant. Since the replacement of ammonia by another reductant is commercially very attractive, in this project, four research components will be undertaken. The investigation of the reaction mechanism, the first component, will help in the selection of promoters to improve the catalytic activity and selectivity of the sorbents in the SCR with methane. This will result in new catalyst formulations (second component). If this research is successful, the combined SO{sub 2}-NO{sub x} removal process based on alumina-supported copper oxide-ceria sorbent/catalysts will become very attractive for commercial applications. The objective of the third component of the project is to develop an alternative SCR process using another inexpensive fuel, residual fuel oil, instead of natural gas. This innovative proposal is based on very scant evidence concerning the good performance of coked catalysts in the selective reduction of NO and if proven to work the process will certainly be commercially viable. The fourth component of the project involves our industrial partner TDA Research, and the objective is to evaluate long- term stability and durability of the prepared sorbent/catalysts. In the second year of the project, the catalysts were investigated for their SCR activity with methane in a microreactor setup and also, by the temperature-programmed desorption (TPD) technique. The results from the SCR experiments indicated that manganese is a more effective promoter than rhodium on the supported copper oxide-ceria catalysts under study; the effectiveness of the promoter increases with the increase in Ce/Cu ratio. The TPD profiles of the unpromoted catalyst (Cu/Ce=3) is different than those promoted with 0.1% rhodium.

Ates Akyurtlu; Jale F. Akyurtlu

2001-09-01

351

Oxidative dissolution potential of biogenic and abiogenic TcO 2 in subsurface sediments  

NASA Astrophysics Data System (ADS)

Technetium-99 (Tc) is an important fission product contaminant associated with sites of nuclear fuels reprocessing and geologic nuclear waste disposal. Tc is highly mobile in its most oxidized state [Tc(VII)O4-] and less mobile in the reduced form [Tc(IV)O 2· nH 2O]. Here we investigate the potential for oxidation of Tc(IV) that was heterogeneously reduced by reaction with biogenic Fe(II) in two sediments differing in mineralogy and aggregation state; unconsolidated Pliocene-age fluvial sediment from the upper Ringold (RG) Formation at the Hanford Site and a clay-rich saprolite from the Field Research Center (FRC) background site on the Oak Ridge Site. Both sediments contained Fe(III) and Mn(III/IV) as redox active phases, but FRC also contained mass-dominant Fe-phyllosilicates of different types. Shewanella putrefaciens CN32 reduced Mn(III/IV) oxides and generated Fe(II) that was reactive with Tc(VII) in heat-killed, bioreduced sediment. After bioreduction and heat-killing, biogenic Fe(II) in the FRC exceeded that in RG by a factor of two. More rapid reduction rates were observed in the RG that had lower biogenic Fe(II), and less particle aggregation. EXAFS measurements indicated that the primary reduction product was a TcO 2-like phase in both sediments. The biogenic redox product Tc(IV) oxidized rapidly and completely in RG when contacted with air. Oxidation, in contrast, was slow and incomplete in the FRC, in spite of similar molecular scale speciation of Tc compared to RG. X-ray microprobe, electron microprobe, X-ray absorption spectroscopy, and micro X-ray diffraction were applied to the whole sediment and isolated Tc-containing particles. These analyses revealed that non-oxidizable Tc(IV) in the FRC existed as complexes with octahedral Fe(III) within intra-grain domains of 50-100 ?m-sized, Fe-containing micas presumptively identified as celadonite. The markedly slower oxidation rates in FRC as compared to RG were attributed to mass-transfer-limited migration of O 2 into intra-aggregate and intraparticle domains where Tc(IV) existed; and the formation of unique, oxidation-resistant, intragrain Tc(IV)-Fe(III) molecular species.

Fredrickson, James K.; Zachara, John M.; Plymale, Andrew E.; Heald, Steve M.; McKinley, James P.; Kennedy, David W.; Liu, Chongxuan; Nachimuthu, Ponnusamy

2009-04-01

352

Covalent hybrid of spinel manganese-cobalt oxide and graphene as advanced oxygen reduction electrocatalysts.  

PubMed

Through direct nanoparticle nucleation and growth on nitrogen doped, reduced graphene oxide sheets and cation substitution of spinel Co(3)O(4) nanoparticles, a manganese-cobalt spinel MnCo(2)O(4)/graphene hybrid was developed as a highly efficient electrocatalyst for oxygen reduction reaction (ORR) in alkaline conditions. Electrochemical and X-ray near-edge structure (XANES) investigations revealed that the nucleation and growth method for forming inorganic-nanocarbon hybrids results in covalent coupling between spinel oxide nanoparticles and N-doped reduced graphene oxide (N-rmGO) sheets. Carbon K-edge and nitrogen K-edge XANES showed strongly perturbed C-O and C-N bonding in the N-rmGO sheet, suggesting the formation of C-O-metal and C-N-metal bonds between N-doped graphene oxide and spinel oxide nanoparticles. Co L-edge and Mn L-edge XANES suggested substitution of Co(3+) sites by Mn(3+), which increased the activity of the catalytic sites in the hybrid materials, further boosting the ORR activity compared with the pure cobalt oxide hybrid. The covalently bonded hybrid afforded much greater activity and durability than the physical mixture of nanoparticles and carbon materials including N-rmGO. At the same mass loading, the MnCo(2)O(4)/N-graphene hybrid can outperform Pt/C in ORR current density at medium overpotentials with stability superior to Pt/C in alkaline solutions. PMID:22280461

Liang, Yongye; Wang, Hailiang; Zhou, Jigang; Li, Yanguang; Wang, Jian; Regier, Tom; Dai, Hongjie

2012-02-22

353

Nitrate Reduction to Nitrite, Nitric Oxide and Ammonia by Gut Bacteria under Physiological Conditions  

PubMed Central

The biological nitrogen cycle involves step-wise reduction of nitrogen oxides to ammonium salts and oxidation of ammonia back to nitrites and nitrates by plants and bacteria. Neither process has been thought to have relevance to mammalian physiology; however in recent years the salivary bacterial reduction of nitrate to nitrite has been recognized as an important metabolic conversion in humans. Several enteric bacteria have also shown the ability of catalytic reduction of nitrate to ammonia via nitrite during dissimilatory respiration; however, the importance of this pathway in bacterial species colonizing the human intestine has been little studied. We measured nitrite, nitric oxide (NO) and ammonia formation in cultures of Escherichia coli, Lactobacillus and Bifidobacterium species grown at different sodium nitrate concentrations and oxygen levels. We found that the presence of 5 mM nitrate provided a growth benefit and induced both nitrite and ammonia generation in E.coli and L.plantarum bacteria grown at oxygen concentrations compatible with the content in the gastrointestinal tract. Nitrite and ammonia accumulated in the growth medium when at least 2.5 mM nitrate was present. Time-course curves suggest that nitrate is first converted to nitrite and subsequently to ammonia. Strains of L.rhamnosus, L.acidophilus and B.longum infantis grown with nitrate produced minor changes in nitrite or ammonia levels in the cultures. However, when supplied with exogenous nitrite, NO gas was readily produced independently of added nitrate. Bacterial production of lactic acid causes medium acidification that in turn generates NO by non-enzymatic nitrite reduction. In contrast, nitrite was converted to NO by E.coli cultures even at neutral pH. We suggest that the bacterial nitrate reduction to ammonia, as well as the related NO formation in the gut, could be an important aspect of the overall mammalian nitrate/nitrite/NO metabolism and is yet another way in which the microbiome links diet and health. PMID:25803049

Tiso, Mauro; Schechter, Alan N.

2015-01-01

354

Nitrate Reduction to Nitrite, Nitric Oxide and Ammonia by Gut Bacteria under Physiological Conditions.  

PubMed

The biological nitrogen cycle involves step-wise reduction of nitrogen oxides to ammonium salts and oxidation of ammonia back to nitrites and nitrates by plants and bacteria. Neither process has been thought to have relevance to mammalian physiology; however in recent years the salivary bacterial reduction of nitrate to nitrite has been recognized as an important metabolic conversion in humans. Several enteric bacteria have also shown the ability of catalytic reduction of nitrate to ammonia via nitrite during dissimilatory respiration; however, the importance of this pathway in bacterial species colonizing the human intestine has been little studied. We measured nitrite, nitric oxide (NO) and ammonia formation in cultures of Escherichia coli, Lactobacillus and Bifidobacterium species grown at different sodium nitrate concentrations and oxygen levels. We found that the presence of 5 mM nitrate provided a growth benefit and induced both nitrite and ammonia generation in E.coli and L.plantarum bacteria grown at oxygen concentrations compatible with the content in the gastrointestinal tract. Nitrite and ammonia accumulated in the growth medium when at least 2.5 mM nitrate was present. Time-course curves suggest that nitrate is first converted to nitrite and subsequently to ammonia. Strains of L.rhamnosus, L.acidophilus and B.longum infantis grown with nitrate produced minor changes in nitrite or ammonia levels in the cultures. However, when supplied with exogenous nitrite, NO gas was readily produced independently of added nitrate. Bacterial production of lactic acid causes medium acidification that in turn generates NO by non-enzymatic nitrite reduction. In contrast, nitrite was converted to NO by E.coli cultures even at neutral pH. We suggest that the bacterial nitrate reduction to ammonia, as well as the related NO formation in the gut, could be an important aspect of the overall mammalian nitrate/nitrite/NO metabolism and is yet another way in which the microbiome links diet and health. PMID:25803049

Tiso, Mauro; Schechter, Alan N

2015-01-01

355

Study on the oxidation and reduction of tungsten surface for sub-50 nm patterning process  

SciTech Connect

The oxidation characteristics of tungsten line pattern during the carbon-based mask-layer removal process using oxygen plasmas have been investigated for sub-50 nm patterning processes, in addition to the reduction characteristics of the WO{sub x} layer formed on the tungsten line surface using hydrogen plasmas. The surface oxidation of tungsten lines during the mask layer removal process could be minimized by using low-temperature (300 K) plasma processing for the removal of the carbon-based material. Using this technique, the thickness of WO{sub x} on the tungsten line could be decreased to 25% compared to results from high-temperature processing. The WO{sub x} layer could also be completely removed at a low temperature of 300 K using a hydrogen plasma by supplying bias power to the tungsten substrate to provide a activation energy for the reduction. When this oxidation and reduction technique was applied to actual 40-nm-CD device processing, the complete removal of WO{sub x} formed on the sidewall of tungsten line could be observed.

Kim, Jong Kyu; Nam, Seok Woo; Cho, Sung Il; Jhon, Myung S.; Min, Kyung Suk; Kim, Chan Kyu; Jung, Ho Bum; Yeom, Geun Young [Memory Division Semiconductor Business, Samsung Electronics, San No. 16 Banwol-Ri, Taean-Eup, Hwasung-City, Gyeonggi-Do 449-711, South Korea and Department of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon, Gyeonggi-do 440-746 (Korea, Republic of); Memory Division Semiconductor Business, Samsung Electronics, San No. 16 Banwol-Ri, Taean-Eup, Hwasung-City, Gyeonggi-Do 449-711 (Korea, Republic of); Department of Chemical Engineering and Data Storage Systems Center, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213 (United States); Department of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon, Gyeonggi-do 440-746 (Korea, Republic of)

2012-11-15

356

Nitrous oxide reduction in nodules: denitrification or N/sub 2/ fixation  

SciTech Connect

Detached cowpea nodules that contained a nitrous oxide reductase-positive (Nor/sup +/) rhizobium strain (8A55) and a nitrous oxide reductase-negative (Nor/sup -/) rhizobium strain (32H1) were incubated with 1% /sup 15/N/sub 2/O (95 atom% /sup 15/N) in the following three atmospheres: aerobic with C/sub 2/H/sub 2/ (10%), aerobic without C/sub 2/H/sub 2/, and anaerobic (argon atmosphere) without C/sub 2/H/sub 2/. The greatest production of /sup 15/N/sub 2/ occurred anaerobically with 8A55, yet very little was formed with 32H1. Although acetylene reduction activity was slightly higher with 32H1, about 10 times more /sup 15/N/sub 2/ was produced aerobically by 8A55 than by 32H1 in the absence of acetylene. The major reductive pathway of N/sub 2/O reduction by denitrifying rhizobium strain 8A55 is by nitrous oxide reductase rather than nitrogenase.

Coyne, M.S.; Focht, D.D.

1987-05-01

357

Sulfide Oxidation Coupled to Arsenate Reduction by a Diverse Microbial Community in a Soda Lake†  

PubMed Central

We characterized the arsenate-reducing, sulfide-oxidizing population of Mono Lake, California, by analyzing the distribution and diversity of rrnA, cbbL, and dissimilatory arsenate reductase (arrA) genes in environmental DNA, arsenate-plus sulfide-amended lake water, mixed cultures, and isolates. The arsenate-reducing community was diverse. An organism represented by an rrnA sequence previously retrieved from Mono Lake and affiliated with the Desulfobulbaceae (Deltaproteobacteria) appears to be an important member of the arsenate-reducing, sulfide-oxidizing community. Sulfide oxidation coupled with arsenate reduction appears to proceed via a two-electron transfer, resulting in the production of arsenite and an intermediate S compound that is subsequently disproportionated. A realgar-like As/S mineral was formed in some experiments. PMID:16517653

Hollibaugh, James T.; Budinoff, Charles; Hollibaugh, Ryan A.; Ransom, Briana; Bano, Nasreen

2006-01-01

358

Probing the oxidation reduction properties of terrestrially and microbially derived dissolved organic matter  

NASA Astrophysics Data System (ADS)

Dissolved organic matter (DOM) has been shown to be an integral component in biogeochemical electron transfer reactions due to its demonstrated ability to facilitate redox reactions. While the role of DOM as a facilitator of electron transfer processes has been demonstrated, greater knowledge would lead to better understanding of the structural components responsible for redox behavior, such as quinones and nitrogen and sulfur (N/S) functional groups. This investigation uses direct scan voltammetry (DSV) coupled with fluorescence and NMR spectroscopy as well as thermochemolysis gas chromatography mass spectrometry (GC-MS) and X-ray photoelectron spectroscopy (XPS) to elucidate the organic moieties responsible for facilitating electron transfer reactions. We contrast electrochemical properties and structural details of three organic matter isolates from diverse sources; Great Dismal Swamp DOM (terrestrially derived, highly aromatic), Pony Lake DOM (microbially derived, highly aliphatic) and Toolik Lake (terrestrially derived, photochemically and microbially altered) with juglone (a redox-active model quinone). Aromatic and phenolic constituents were detected (by 13C NMR) and recovered (by thermochemolysis GC-MS) from all three fulvic acid samples, highlighting the ubiquity of these compounds and suggesting that the quinone-phenol redox couple is not limited to DOM derived from lignin precursors. The range of hydroxy-benzene and benzoic acid derivatives may explain the lack of a single pair of well-defined oxidation and reduction peaks in the DSV scans. The presence of a wide-range of hydroxylated benzoic acid isomers and other redox-active aromatic residues implies that native DOM possesses overlapping redox potentials analogous to their characteristic range of p Ka values.

Fimmen, Ryan L.; Cory, Rose M.; Chin, Yu-Ping; Trouts, Tamara D.; McKnight, Diane M.

2007-06-01

359

Oxidative Stress and Redox Modulation Potential in Type 1 Diabetes  

PubMed Central

Redox reactions are imperative to preserving cellular metabolism yet must be strictly regulated. Imbalances between reactive oxygen species (ROS) and antioxidants can initiate oxidative stress, which without proper resolve, can manifest into disease. In type 1 diabetes (T1D), T-cell-mediated autoimmune destruction of pancreatic ?-cells is secondary to the primary invasion of macrophages and dendritic cells (DCs) into the islets. Macrophages/DCs, however, are activated by intercellular ROS from resident pancreatic phagocytes and intracellular ROS formed after receptor-ligand interactions via redox-dependent transcription factors such as NF-?B. Activated macrophages/DCs ferry ?-cell antigens specifically to pancreatic lymph nodes, where they trigger reactive T cells through synapse formation and secretion of proinflammatory cytokines and more ROS. ROS generation, therefore, is pivotal in formulating both innate and adaptive immune responses accountable for islet cell autoimmunity. The importance of ROS/oxidative stress as well as potential for redox modulation in the context of T1D will be discussed. PMID:21647409

Delmastro, Meghan M.; Piganelli, Jon D.

2011-01-01

360

DEVELOPMENT OF IMPROVED CATALYSTS FOR THE SELECTIVE CATALYTIC REDUCTION OF NITROGEN OXIDES WITH HYDROCARBONS  

SciTech Connect

Significant work has been done by the investigators on the cerium oxide-copper oxide based sorbent/catalysts for the combined removal of sulfur and nitrogen oxides from the flue gases of stationary sources. A relatively wide temperature window was established for the use of alumina-supported cerium oxide-copper oxide mixtures as regenerable sorbents for SO{sub 2} removal. Evaluation of these sorbents as catalysts for the selective reduction of NO{sub x} gave promising results with methane. Since the replacement of ammonia by methane is commercially very attractive, in this project, it was planned to investigate the effect of promoters on the activity and selectivity of copper oxide/cerium oxide-based catalysts and to obtain data on the reaction mechanism for the SCR with methane. The investigation of the reaction mechanism will help in the selection of promoters to improve the catalytic activity and selectivity of the sorbents in the SCR with methane. This will result in new catalyst formulations. The last component of the project involves our industrial partner TDA Research, and the objective is to evaluate long- term stability and durability of the prepared sorbent/catalysts. In the second year of the project, the catalysts were investigated for their SCR activity with methane in a microreactor setup and also, by the temperature-programmed desorption (TPD) technique. The results from the SCR experiments indicated that manganese is a more effective promoter than rhodium on the supported copper oxide-ceria catalysts under study; the effectiveness of the promoter increases with the increase in Ce/Cu ratio. The TPD profiles of the unpromoted catalyst (Cu/Ce=3) is different than those promoted with 0.1% rhodium. In the current reporting period, the screening of the promoted catalysts were completed, sufficient amount of the selected catalysts were prepared and delivered to TDA for long term deactivation testing.

Dr. Ates Akyurlu; Dr. Jale F. Akyurtlu

2003-01-28

361

Organic carbon oxidation and suppression of methane production by microbial Fe(III) oxide reduction in vegetated and unvegetated freshwater wetland sediments  

Microsoft Academic Search

High concentrations (20-75 pmol cm-3) of amorphous Fe(III) oxide were observed in unvegetated surface and Juncus eflusus rhizosphere sediments of a freshwater wetland in the southeastern United States. Incu- bation experiments demonstrated that microbial Fe(III) oxide reduction suppressed sulfate reduction and methanogenesis in surface scdimcnts and mediated 240% of depth-integrated (O-10 cm) unvegetated sedi- ment carbon metabolism, compared to I

Eric E. Roden; Robert G. Wetzel

1996-01-01

362

Observations of Oxygen Ion Behavior in the Lithium-Based Electrolytic Reduction of Uranium Oxide  

SciTech Connect

Parametric studies were performed on a lithium-based electrolytic reduction process at bench-scale to investigate the behavior of oxygen ions in the reduction of uranium oxide for various electrochemical cell configurations. Specifically, a series of eight electrolytic reduction runs was performed in a common salt bath of LiCl – 1 wt% Li2O. The variable parameters included fuel basket containment material (i.e., stainless steel wire mesh and sintered stainless steel) and applied electrical charge (i.e., 75 – 150% of the theoretical charge for complete reduction of uranium oxide in a basket to uranium metal). Samples of the molten salt electrolyte were taken at regular intervals throughout each run and analyzed to produce a time plot of Li2O concentrations in the bulk salt over the course of the runs. Following each run, the fuel basket was sectioned and the fuel was removed. Samples of the fuel were analyzed for the extent of uranium oxide reduction to metal and for the concentration of salt constituents, i.e., LiCl and Li2O. Extents of uranium oxide reduction ranged from 43 – 70% in stainless steel wire mesh baskets and 8 – 33 % in sintered stainless steel baskets. The concentrations of Li2O in the salt phase of the fuel product from the stainless steel wire mesh baskets ranged from 6.2 – 9.2 wt%, while those for the sintered stainless steel baskets ranged from 26 – 46 wt%. Another series of tests was performed to investigate the dissolution of Li2O in LiCl at 650 °C across various cathode containment materials (i.e., stainless steel wire mesh, sintered stainless steel and porous magnesia) and configurations (i.e., stationary and rotating cylindrical baskets). Dissolution of identical loadings of Li2O particulate reached equilibrium within one hour for stationary stainless steel wire mesh baskets, while the same took several hours for sintered stainless steel and porous magnesia baskets. Rotation of an annular cylindrical basket of stainless steel wire mesh accelerated the Li2O dissolution rate by more than a factor of six.

Steven D. Herrmann; Shelly X. Li; Brenda E. Serrano-Rodriguez

2009-09-01

363

Hexavalent chromium reduction by tartaric acid and isopropyl alcohol in Mid-Atlantic soils and the role of Mn(III,IV)(hydr)oxides.  

PubMed

Chromium is a naturally occurring transition metal and a soil contaminant in the Cr(VI) oxidation state, but reduction of Cr(VI) to Cr(III) mitigates its toxicity. Tartaric acid reduces Cr(VI) via a termolecular complex with isopropyl alcohol and Cr(VI), but its efficacy in soils has not been demonstrated. Five Mid-Atlantic soils from Maryland, U.S. were examined for their potential to enhance the reduction of Cr(VI). A control treatment (no soil +12 mM tartaric acid + 0.29 M isopropyl alcohol) reduced 0.37 mM Cr(VI) (19%) in 99 h. Reduction was enhanced to 1.97 mM (99%) with addition of a Russett Ap soil horizon (fine-loamy, mixed, semiactive, mesic Typic Hapludult). With a half-life of 18.7 h, the rate of reduction of Cr(VI) with the Russett soil sample was 20 times faster than with no soil (371 h). Soil Mn was solubilized in this reaction and plays a role in the enhanced reduction of Cr(VI). Mn(III/IV)(hydr)oxide-coated quartz sand reduced 1.24 mM (62%) Cr(VI), with all of the Mn(III,IV)(hydr)oxides solubilized. The addition of isopropyl alcohol and tartaric acid to soils enhances the reduction of Cr(VI), and this reduction is further enhanced by the catalytic behavior of Mn(II) from easily reducible Mn(III,IV)(hydr)oxides in soil. PMID:24102200

Brose, Dominic A; James, Bruce R

2013-11-19

364

Quinone reduction by Rhodothermus marinus succinate:menaquinone oxidoreductase is not stimulated by the membrane potential  

SciTech Connect

Succinate:quinone oxidoreductase (SQR), a di-haem enzyme purified from Rhodothermus marinus, reveals an HQNO-sensitive succinate:quinone oxidoreductase activity with several menaquinone analogues as electron acceptors that decreases with lowering the redox midpoint potential of the quinones. A turnover with the low-potential 2,3-dimethyl-1,4-naphthoquinone that is the closest analogue of menaquinone, although low, can be detected in liposome-reconstituted SQR. Reduction of the quinone is not stimulated by an imposed K{sup +}-diffusion membrane potential of a physiological sign (positive inside the vesicles). Nor does the imposed membrane potential increase the reduction level of the haems in R. marinus SQR poised with the succinate/fumarate redox couple. The data do not support a widely discussed hypothesis on the electrogenic transmembrane electron transfer from succinate to menaquinone catalysed by di-haem SQRs. The role of the membrane potential in regulation of the SQR activity is discussed.

Fernandes, Andreia S. [Instituto de Tecnologia Quimica e Biologica, Universidade Nova de Lisboa, Av. da Republica, Apartado 127, 2784-505 Oeiras (Portugal); Konstantinov, Alexander A. [Instituto de Tecnologia Quimica e Biologica, Universidade Nova de Lisboa, Av. da Republica, Apartado 127, 2784-505 Oeiras (Portugal); A.N. Belozersky Institute of Physico-Chemical Biology, Moscow State University, 119992 Moscow (Russian Federation); Teixeira, Miguel [Instituto de Tecnologia Quimica e Biologica, Universidade Nova de Lisboa, Av. da Republica, Apartado 127, 2784-505 Oeiras (Portugal); Pereira, Manuela M. [Instituto de Tecnologia Quimica e Biologica, Universidade Nova de Lisboa, Av. da Republica, Apartado 127, 2784-505 Oeiras (Portugal)]. E-mail: mpereira@itqb.unl.pt

2005-05-06

365

Oxygen transport by oxygen potential gradient in dense ceramic oxide membranes  

Microsoft Academic Search

Numerous studies have been conducted in recent years on the partial oxidation of methane to synthesis gas (syngas: CO+H2) with air as the oxidant. In partial oxidation, a mixed-oxide ceramic membrane selectively transports oxygen from the air; this transport is driven by the oxygen potential gradient. Of the several ceramic materials we have tested, a mixed oxide based on the

P. S. Maiya; U. Balachandran; J. T. Dusek; R. L. Mieville; M. S. Kleefisch; C. A. Udovich

1997-01-01

366

Pulsed laser irradiation for environment friendly reduction of graphene oxide suspensions  

NASA Astrophysics Data System (ADS)

Graphene oxide (GO) sheets were synthesized through a modified Hummers' method. Using high resolution transmission electron microscopy the thickness of the GO sheets in a multilayer structure of stacked GO sheets was found ˜0.8 nm. A nanosecond pulsed laser (with wavelength of 532 nm and average power of 0.3 W) was applied for effective and environment friendly reduction of the GO sheets in an ammonia solution (pH ˜9) at room temperature conditions. The deoxygenation of the GO sheets by the pulsed laser reduction method was confirmed by using UV-visible, Fourier transform infrared, X-ray photoelectron spectroscopy (XPS) and thermo gravimetric analysis. Based on XPS analysis, the O/C ratio of the GO sheets decreased from 49% to 21% after 10 min laser irradiation. This reduction efficiency was comparable with the efficiency achieved by hydrazine which yielded the O/C ratio of 15% at 80 °C after 10 min. Using Raman spectroscopy it was found that the pulsed laser reduction method resulted in nearly no aggregation of the reduced GO sheets in the ammonia solution. These results can help to further promotion and application of pulsed lasers in environment friendly reduction of GO.

Ghadim, Ehsan Ezzatpour; Rashidi, Nasim; Kimiagar, Salimeh; Akhavan, Omid; Manouchehri, Firouzeh; Ghaderi, Elham

2014-05-01

367

Gadolinium oxide nanoparticles as potential multimodal imaging and therapeutic agents.  

PubMed

Potentials of hydrophilic and biocompatible ligand coated gadolinium oxide nanoparticles as multimodal imaging agents, drug carriers, and therapeutic agents are reviewed. First of all, they can be used as advanced T1 magnetic resonance imaging (MRI) contrast agents because they have r1 larger than those of Gd(III)-chelates due to a high density of Gd(III) per nanoparticle. They can be further functionalized by conjugating other imaging agents such as fluorescent imaging (FI), X-ray computed tomography (CT), positron emission tomography (PET), and single photon emission tomography (SPECT) agents. They can be also useful for drug carriers through morphology modifications. They themselves are also potential CT and ultrasound imaging (USI) contrast and thermal neutron capture therapeutic (NCT) agents, which are superior to commercial iodine compounds, air-filled albumin microspheres, and boron ((10)B) compounds, respectively. They, when conjugated with targeting agents such as antibodies and peptides, will provide enhanced images and be also very useful for diagnosis and therapy of diseases (so called theragnosis). PMID:23432005

Kim, Tae Jeong; Chae, Kwon Seok; Chang, Yongmin; Lee, Gang Ho

2013-01-01

368

ON-LINE DEOXYGENATION IN REDUCTIVE (AND OXIDATIVE) AMPEROMETRIC DETECTION: ENVIRONMENTAL APPLICATIONS IN THE LIQUID CHROMATOGRAPHY OF ORGANIC PEROXIDES  

EPA Science Inventory

Cyclic voltammetry was used qualitatively to characterize and determine the feasibility of the oxidation and reduction of selected organic peroxides and hydroperoxides at a glassy carbon electrode. Organic peroxides were determined using reversed-phase high-performance liquid chr...

369

Reinterpretation of reduction potential measurements done by linear sweep voltammetry in silicate melts  

NASA Technical Reports Server (NTRS)

The equilibrium concentrations of Ni between silicate melt and Pt were determined experimentally as a function of oxygen fugacity. The results demonstrate that metallic species derived in linear sweep voltammetry experiments in silicate melts are diffusing into Pt electrodes and not into the melt, as was concluded by previoius studies. This requires reinterpretation of previous linear sweep voltammetry results and recalculation and correction of reported reduction potentials. This paper reports these corrected reduction potentials. Also reported are the activity coefficients for Ni in synthetic basalt and diopsidic melts and for Co in diopsidic melt.

Colson, R. O.; Haskin, L. A.; Keedy, C. R.

1991-01-01

370

Noise and Fuel Burn Reduction Potential of an Innovative Subsonic Transport Configuration  

NASA Technical Reports Server (NTRS)

A study is presented for the noise and fuel burn reduction potential of an innovative double deck concept aircraft with two three-shaft direct-drive turbofan engines. The engines are mounted from the fuselage so that the engine inlet is over the main wing. It is shown that such an aircraft can achieve a cumulative Effective Perceived Noise Level (EPNL) about 28 dB below the current aircraft noise regulations of Stage 4. The combination of high bypass ratio engines and advanced wing design with laminar flow control technologies provide fuel burn reduction and low noise levels simultaneously. For example, the fuselage mounted engine position provides more than 4 EPNLdB of noise reduction by shielding the inlet radiated noise. To identify the potential effect of noise reduction technologies on this concept, parametric studies are presented to reveal the system level benefits of various emerging noise reduction concepts, for both engine and airframe noise reduction. These concepts are discussed both individually to show their respective incremental noise reduction potential and collectively to assess their aggregate effects on the total noise. Through these concepts approximately about 8 dB of additional noise reduction is possible, bringing the cumulative noise level of this aircraft to 36 EPNLdB below Stage 4, if the entire suite of noise reduction technologies would mature to practical application. In a final step, an estimate is made for this same aircraft concept but with higher bypass ratio, geared, turbofan engines. With this geared turbofan propulsion system, the noise is estimated to reach as low as 40-42 dB below Stage 4 with a fuel burn reduction of 43-47% below the 2005 best-in-class aircraft baseline. While just short of the NASA N+2 goals of 42 dB and 50% fuel burn reduction, for a 2025 in service timeframe, this assessment shows that this innovative concept warrants refined study. Furthermore, this design appears to be a viable potential future passenger aircraft, not only in meeting the regulatory requirements, but also in competing with aircraft of different advanced designs within this N+2 timeframe and goal framework.

Guo, Yueping; Nickol, Craig L.; Thomas, Russell H.

2014-01-01

371

Selective CO2 reduction conjugated with H2O oxidation utilizing semiconductor/metal-complex hybrid photocatalysts  

NASA Astrophysics Data System (ADS)

We developed a new hybrid photocatalyst for CO2 reduction, which is composed of a semiconductor and a metal complex. In the hybrid photocatalyst, ?G between the position of conduction band minimum (ECBM) of the semiconductor and the CO2 reduction potential of the complex is an essential factor for realizing fast electron transfer from the conduction band of semiconductor to metal complex leading to high photocatalytic activity. On the basis of this concept, the hybrid photocatalyst InP/Ru-complex, which functions in aqueous media, was developed. The photoreduction of CO2 to formate using water as an electron donor and a proton source was successfully achieved as a Z-scheme system by functionally conjugating the InP/Ru-complex photocatalyst for CO2 reduction with a TiO2 photocatalyst for water oxidation. The conversion efficiency from solar energy to chemical energy was ca. 0.04%, which approaches that for photosynthesis in a plant. Because this system can be applied to many other inorganic semiconductors and metal-complex catalysts, the efficiency and reaction selectivity can be enhanced by optimization of the electron transfer process including the energy-band configurations, conjugation conformations, and catalyst structures. This electrical-bias-free reaction is a huge leap forward for future practical applications of artificial photosynthesis under solar irradiation to produce organic species.

Morikawa, T.; Sato, S.; Arai, T.; Uemura, K.; Yamanaka, K. I.; Suzuki, T. M.; Kajino, T.; Motohiro, T.

2013-12-01

372

Anion adsorption, CO oxidation, and oxygen reduction reaction on a Au(100) surface: The pH effect  

SciTech Connect

The effects of pH on the surface reconstruction of Au(100), on CO oxidation, and on the oxygen reduction reaction (ORR) have been studied by a combination of surface X-ray scattering (SXS), Fourier transform infrared (FTIR) spectroscopy, and rotating ring-disk electrode (RRDE) measurements. In harmony with previous SXS and scanning tunneling microscopy (STM) results, the potential-induced hexagonal (''hex'') to (1 x 1) transition occurs faster in an alkaline electrolyte than in acidic media. In alkaline solution, CO adsorption facilitates the formation of a ''hex'' phase; in acid solution, however, CO has negligible effect on the potential range of thermodynamic stability of the ''hex'' <--> (1 x 1) transition. We propose that in KOH the continuous removal of OHad in the Langmuir-Hinshelwood reaction (CO + OH) CO2 + H+ + e- may stabilize the ''hex'' phase over a much wider potential range than in CO-free solution. In acid solution, where specifically adsorbing anions cannot be displaced by CO from the Au(100) surface, CO has negligible effect on the equilibrium potential for the ''hex'' <--> (1 x 1) transition. Such a mechanism is in agreement with the pH-dependent oxidation of CO. The ORR is also affected by the pH of solution. It is proposed that the pH-dependent kinetics of the ORR on Au(100) can be unraveled by finding the relationship between kinetic rates and two terms: (i) the energetic term of the Au(100)-O2- interaction determines the potential regions where the rate-determining step O2 + e = O2- occurs, and (ii) the preexponential term determines the availability of active sites for the adsorption of O2-.

Blizanac, Berislav B.; Lucas, Chris A.; Gallagher, Mark E.; Arenz, Matthias; Ross, Philip N.; Markovic, Nenad M.

2004-07-29

373

Reduction phases of thin iron-oxide nanowires upon thermal treatment and Li exposure  

SciTech Connect

Iron oxide nanostructures, a promising alternative to carbon-based anode in lithium-ion batteries, can be produced using a hard template route. This procedure guarantees the formation of Fe{sub 2}O{sub 3} nanowires with comparable diameter and size (average diameter 8?nm) with a dominant cubic ?-phase at the surface. Lithium exposure of the iron oxide nanowires in ultra-high-vacuum (UHV) conditions induces reduction of the Fe ion, leading to a Fe{sub 3}O{sub 4} and then to a Fe{sup 2+} phase, as determined by means of core-level photoemission spectroscopy. Mild annealing of Fe{sub 2}O{sub 3} in UHV determines an oxygen content reduction for the nanowires at lower temperature with respect to the bulk phase. The morphology and the evolution of the electronic properties upon reduction have been compared to those of micro-sized bulk-like grains, to unravel the role of the reduced size and surface-volume ratio.

Angelucci, Marco, E-mail: marco.angelucci@gmail.com; Frau, Eleonora; Grazia Betti, Maria [Dipartimento di Fisica, Università di Roma La Sapienza, Piazzale Aldo Moro 2, I-00185 Roma (Italy); Hassoun, Jusef; Hong, Inchul; Panero, Stefania [Dipartimento di Chimica, Università di Roma La Sapienza, Piazzale Aldo Moro 2, I-00185 Roma (Italy); Scrosati, Bruno [IIT, Istituto Italiano di Tecnologia, Genova (Italy); Mariani, Carlo, E-mail: carlo.mariani@uniroma1.it [Dipartimento di Fisica, CNISM, CNIS, Università di Roma La Sapienza, Piazzale Aldo Moro 2, I-00185 Roma (Italy)

2014-04-28

374

Modeling Exposures to the Oxidative Potential of PM10  

PubMed Central

Differences in the toxicity of ambient particulate matter (PM) due to varying particle composition across locations may contribute to variability in results from air pollution epidemiologic studies. Though most studies have used PM mass concentration as the exposure metric, an alternative which accounts for particle toxicity due to varying particle composition may better elucidate whether PM from specific sources is responsible for observed health effects. The oxidative potential (OP) of PM < 10 ?m (PM10) was measured as the rate of depletion of the antioxidant reduced glutathione (GSH) in a model of human respiratory tract lining fluid. Using a database of GSH OP measures collected in greater London, U.K. from 2002 to 2006, we developed and validated a predictive spatiotemporal model of the weekly GSH OP of PM10 that included geographic predictors. Predicted levels of OP were then used in combination with those of weekly PM10 mass to estimate exposure to PM10 weighted by its OP. Using cross-validation (CV), brake and tire wear emissions of PM10 from traffic within 50 m and tailpipe emissions of nitrogen oxides from heavy-goods vehicles within 100 m were important predictors of GSH OP levels. Predictive accuracy of the models was high for PM10 (CV R2=0.83) but only moderate for GSH OP (CV R2 = 0.44) when comparing weekly levels; however, the GSH OP model predicted spatial trends well (spatial CV R2 = 0.73). Results suggest that PM10 emitted from traffic sources, specifically brake and tire wear, has a higher OP than that from other sources, and that this effect is very local, occurring within 50–100 m of roadways. PMID:22731499

2012-01-01

375

Modeling exposures to the oxidative potential of PM10.  

PubMed

Differences in the toxicity of ambient particulate matter (PM) due to varying particle composition across locations may contribute to variability in results from air pollution epidemiologic studies. Though most studies have used PM mass concentration as the exposure metric, an alternative which accounts for particle toxicity due to varying particle composition may better elucidate whether PM from specific sources is responsible for observed health effects. The oxidative potential (OP) of PM < 10 ?m (PM(10)) was measured as the rate of depletion of the antioxidant reduced glutathione (GSH) in a model of human respiratory tract lining fluid. Using a database of GSH OP measures collected in greater London, U.K. from 2002 to 2006, we developed and validated a predictive spatiotemporal model of the weekly GSH OP of PM(10) that included geographic predictors. Predicted levels of OP were then used in combination with those of weekly PM(10) mass to estimate exposure to PM(10) weighted by its OP. Using cross-validation (CV), brake and tire wear emissions of PM(10) from traffic within 50 m and tailpipe emissions of nitrogen oxides from heavy-goods vehicles within 100 m were important predictors of GSH OP levels. Predictive accuracy of the models was high for PM(10) (CV R(2)=0.83) but only moderate for GSH OP (CV R(2) = 0.44) when comparing weekly levels; however, the GSH OP model predicted spatial trends well (spatial CV R(2) = 0.73). Results suggest that PM(10) emitted from traffic sources, specifically brake and tire wear, has a higher OP than that from other sources, and that this effect is very local, occurring within 50-100 m of roadways. PMID:22731499

Yanosky, Jeff D; Tonne, Cathryn C; Beevers, Sean D; Wilkinson, Paul; Kelly, Frank J

2012-07-17

376

Oxidative potential of particulate matter at a German motorway.  

PubMed

Ambient particulate matter (PM10) was sampled alongside a motorway in North-Rhine Westphalia, Germany, during a one-year period. In sum, 120 PM10 samples on quartz fibre filters, 60 samples at each side of the motorway, were taken during clear cross-wind direction situations, i.e. upwind (local background situation) and downwind (traffic influenced). To quantify the traffic-related oxidative potential (OP), or more precisely the hydroxyl radical (OH?) generation potency, these samples were analysed to study their hydrogen peroxide dependent oxidant generation by Electron Paramagnetic Resonance (EPR) spectroscopy using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide. In addition the PM10 mass, the chemical composition and the NOx concentrations were determined. For PM10 mass and traffic tracers like Sb, Ba, elemental and organic carbon as well as for NOx, an additional contribution to the background concentration caused by the traffic was observed (factor: 1.3-6.0). The downwind measurements showed in 72% of cases higher OH? generation potencies with an average factor of 1.4. Significant correlations to OH? were detected for Fe (r > 0.58) and Cu (r > 0.57) for the upwind and overall (upwind + downwind, r > 0.44) dataset. At the downwind side these correlations were absent and are assumed to be covered by the interferences with additional soot particles leading to a quenching of OH?. Accordingly, no significant overall correlation of the OH? generation potency with the traffic intensity was detected. The suggested quenching effect was confirmed via standard diesel soot (SRM 2975) measurements using the EPR approach. In summary, the traffic related PM causes an intrinsic OH? generation via Fenton-like reaction but obviously also leads to interferences and scavenging by traffic related carbonaceous compounds. In consequence, for future studies that would link the intrinsic OP and adverse health effects we suggest to analyse the relationship to EC/OC and to use in parallel also a further OP detection method. PMID:25787944

Hellack, Bryan; Quass, Ulrich; Nickel, Carmen; Wick, Gabriele; Schins, Roel P F; Kuhlbusch, Thomas A J

2015-04-01

377

Overview of artifact reduction and removal in evoked potential and event-related potential recordings.  

PubMed

Artifact in one form or another needs to be contended with in all EEG and EP studies. Various methods have been employed to avoid, eliminate, or minimize artifact. This article has described the methods that have been available for some time and newer methods and their advantages. It is the authors' hope that through the use of these methods the accuracy of all EP and ERP measurements will be improved and promote the validity and general acceptance of EP and ERP recordings. Genuine and valuable data are contained in EPs and ERPs. The challenge is to extract relatively small voltage signals often occurring within a higher voltage background of artifact. The computing power required to perform the artifact removal/reduction procedures now is available with basic laptop and desktop computers, as are the software programs that provide the artifact removal/reduction capabilities. It may be of interest for a prudent researcher to integrate the currently available artifact rejection methods before subjecting the ERP and EP data for further analysis and subsequent publication. PMID:15029896

Ford, Martin R; Sands, Stephen; Lew, Henry L

2004-02-01

378

Changes in pH and redox potential during radiation-induced CO 2 reduction in an aqueous solution containing iron powder  

NASA Astrophysics Data System (ADS)

A study of the radiation induced CO 2 reduction in a solution containing iron powder with a specific surface area as large as 29 m 2/g has revealed that H 2 and hydrocarbons are formed irrespective of whether the solution is irradiated with ?-rays or not and that CO is produced only under ?-ray irradiation. By considering the relation between pH and ORP (oxidation-reduction potential) the results obtained are attributed to the considerable decrease in pH. For an initial period, the rate of H + generation is remarkably enhanced by almost 30 times by a collective effect of ?-rays, CO 2 and iron.

Fujita, Norihiko; Fukuda, Yoshiaki; Matsuura, Chihiro; Saigo, Kazuhiko

1996-04-01

379

Dietary nitrate and reductive polyphenols may potentiate the vascular benefit and alleviate the ulcerative risk of low-dose aspirin.  

PubMed

The recent revelation that daily low-dose aspirin not only lowers risk for vascular events, but also can notably decrease risk for a range of adenocarcinomas, decreasing total cancer mortality by about 20%, makes it highly desirable to implement this protective strategy on a population-wide basis. Nonetheless, the fact that low-dose aspirin approximately doubles risk for serious gastrointestinal bleeding may impede health authorities from recommending its use by people judged to be at low cardiovascular risk. Nitric oxide (NO) exerts gastroprotective effects by boosting blood flow and mucus production in the gastric mucosa - effects which demonstrably oppose the pro-ulcerative impact of aspirin and other NSAIDs. A nitrate-rich diet, as well as ingestion of reductive catechol-bearing polyphenols, can collaborate in promoting NO generation in gastric juice, and they are protective in rodent models of gastric ulceration. Moreover, a high-nitrate diet, as well as certain reductive polyphenols such as epicatechin and quercetin, can exert platelet-stabilizing effects complementary to those of aspirin, and act in other ways to preserve vascular health. Hence, diets rich in nitrate and reductive polyphenols have the potential to amplify the vascular-protective benefits of low-dose aspirin, while diminishing its pro-ulcerative risk. Low-dose aspirin may be more unequivocally recommendable within the context of such a dietary strategy. PMID:23265354

McCarty, Mark F

2013-02-01

380

Accurate oxidation potentials of 40 benzene and biphenyl derivatives with heteroatom substituents.  

PubMed

The redox equilibrium method was used to determine accurate oxidation potentials in acetonitrile for 40 heteroatom-substituted compounds. These include methoxy-substituted benzenes and biphenyls, aromatic amines, and substituted acetanilides. The redox equilibrium method allowed oxidation potentials to be determined with high precision (? ±6 mV). Whereas most of the relative oxidation potentials follow well-established chemical trends, interestingly, the oxidation potentials of substituted N-methylacetanilides were found to be higher than those of the corresponding acetanilides. Density functional theory calculations provided insight into the origin of these surprising results in terms of the preferred conformations of the amides versus their cation radicals. PMID:25184671

Luo, Pu; Feinberg, Adam M; Guirado, Gonzalo; Farid, Samir; Dinnocenzo, Joseph P

2014-10-01

381

High-Index-Contrast AlGaAs Waveguide Scattering Loss Reduction Via Oxidation Smoothing of Sidewall Roughness  

E-print Network

High-Index-Contrast AlGaAs Waveguide Scattering Loss Reduction Via Oxidation Smoothing of Sidewall-6449 Abstract: The propagation loss of single mode high index contrast AlGaAs ridge waveguides is reduced nearly three orders of magnitude (at 1 cm guide length) through application of a nonselective wet oxidation

382

[Fundamental studies in oxidation-reduction in relation to water photolysis]. Progress report, June 26, 1989--November 1, 1990  

SciTech Connect

Objective is to solve problems in photoredox catalysis pertinent to developing membrane-base photoconversion/photostorage systems. The research is divided into: Physical studies (light scattering) on viologen-doped vesicles, transmembrane oxidation-reduction mechanisms, interfacial charge recombination, water oxidation catalysts.

Hurst, J.K.

1990-12-31

383

A high pressure X-ray photoelectron spectroscopy study of oxidation and reduction of Rh(100) and Rh nanoparticles  

NASA Astrophysics Data System (ADS)

We have studied the oxidation and reduction of Rh(100) and SiO2 supported Rh particles using high pressure X-ray photoelectron spectroscopy. We show that the formation and reduction of Rh bulk oxide can be followed in situ in O2 and CO pressures in the range of 0.1 Torr. In general, the oxidation/reduction processes are similar on Rh(100) and the nanoparticles, but there are significant differences in temperature dependence. Already at a sample temperature of 140 °C, the particles show clear signs of a thin bulk oxide, while an ultra-thin so-called surface oxide covers the single crystal at the same temperature. Both of these oxide films, however, hinder further oxidation, and a thick oxide is only found at a temperature of at least 300 °C, for both samples. The reduction, in contrast, starts at a higher temperature on the particles as compared to the single crystal, but once started the particles are completely reduced at lower temperatures.

Blomberg, S.; Westerström, R.; Martin, N. M.; Lundgren, E.; Andersen, J. N.; Messing, M. E.; Gustafson, J.

2014-10-01

384

Temperature variations in the oxygen carrier particles during their reduction and oxidation in a chemical-looping combustion system  

Microsoft Academic Search

A particle reaction model including mass and heat transfer has been developed to know the temperature variations produced inside the oxygen carrier particles during the cyclic reduction and oxidation reactions taking place in a chemical-looping combustion (CLC) system. The reactions of the different oxygen carriers based on Cu, Co, Fe, Mn, and Ni during the reduction with fuel gas (CH4,

Francisco García-Labiano; Luis F. de Diego; Juan Adánez; Alberto Abad; Pilar Gayán

2005-01-01

385

Enzymatic oxidation-reduction processes under magnetic fields up to 8 T (abstract)  

NASA Astrophysics Data System (ADS)

The question of whether magnetic fields affect enzymatic activities or not is of considerable interest in biochemistry and in biomagnetics. Xanthine oxidase, contained in liver, lungs, intestine, and other organs, catalyzes the degradation of hypoxanthine to xanthine, and xanthine to uric acid, which is the terminal waste of purine nucleotides in mammals. During the oxidation of xanthine, the enzyme releases superoxide anion radicals as intermediates which reduce ferricytochrome c (Fe3+). Superoxide anion, as well as any type of free radical, is also paramagnetic. The study is focused on whether these magnetically related enzymatic activities can be affected by magnetic fields. There is a possibility that free radicals, as intermediates, can be modified by magnetic fields of specific intensities. In our previously reported study, we examined a possible effect of magnetic fields up to 1.0 T on biochemical reaction catalyzed by xanthine oxidase, and obtained negative results. In the present abstract, we examine the effect of magnetic fields up to 8 T on this oxidation-reduction process. Reduced cytochrome c (Fe2+) has an absorption maximum at 550 nm which can be detected by a spectrophotometer. Xanthine oxidase was assayed by superoxide dismutase—inhibitable reduction of cytochrome c. We measured optical absorbance of reduced cytochrome c by superoxide anion which was produced by the reaction catalyzed by xanthine oxidase. The absorbances of the mixture exposed to an 8 T magnetic field at 25 °C were higher than control samples in the re-oxidation proces of cytochrome c. The results show that the 8 T magnetic fields altered the rate of reduction of cytochrome c by superoxide anion which was produced by the reaction catalyzed by xanthine oxidase. It may conclude that the electron transfer from xanthine to molecular oxygen or the transfer from superoxide anion to cytochrome c, can be affected by the magnetic fields up to 8 T.

Iwasaka, M.; Ueno, S.

1994-05-01

386

ASYMPTOTIC BEHAVIOR OF CONTINUOUS TRAJECTORIES FOR PRIMAL-DUAL POTENTIAL-REDUCTION METHODS  

E-print Network

by primal- dual potential-reduction algorithms for solving linear programming problems. It is known of the most efficient and reliable techniques for the solution of linear programming problems. The development solution of the given problem combining measures of proximity to the set of optimal solutions, proximity

Tütüncü, Reha

387

CO 2 in the iron and steel industry: an analysis of Japanese emission reduction potentials  

Microsoft Academic Search

A new linear programming model has been developed for the analysis of CO2 emission reduction potentials in the Japanese iron and steel industry. This model is named Steel Environmental strategy Assessment Program. The model can be used to analyse the impact of CO2 taxes on technology selection, iron and steel trade and product demand for the next three decades. The

Dolf Gielen; Yuichi Moriguchi

2002-01-01

388

A primal-dual potential reduction method for problems involving matrix inequalities  

Microsoft Academic Search

We describe a potential reduction method for convex optimization problems involving matrix inequalities. The method is based on the theory developed by Nesterov and Nemirovsky and gener- alizes Gonzaga and Todd's method for linear programming. A worst-case analysis shows that the number of iterations grows as the square root of the problem size, but in practice it appears to grow

Lieven Vandenberghe; Stephen P. Boyd

1995-01-01

389

A model for coupled sulfate reduction and methane oxidation in the sediments of Saanich Inlet  

NASA Astrophysics Data System (ADS)

A methane-sulfate coupled reaction diffusion model has been developed to describe the inverse relationship commonly observed between methane and sulfate concentrations in the pore waters of anoxic marine sediments. The sediment column was divided into two zones; an upper zone where diagenetic reaction rates are limited by the concentration of oxidizable organic matter and a lower zone in which reaction rates are limited by the concentration of oxidizing agent - sulfate. For each zone differential equations describing the distribution of methane and sulfate were derived. The boundary conditions used to solve these equations resulted in a set of four coupled equations. When fit to data from Saanich Inlet (B.C., Canada) and Skan Bay (Alaska) the model not only reproduces the observed methane and sulfate pore water concentration profiles but also accurately predicts the methane oxidation and sulfate reduction rates. Maximum methane oxidation rates occur at the transition boundary from the upper to the lower layer. In Saanich Inlet sediments from 23 to 40% of the downward sulfate flux is consumed in methane oxidation while in Skan Bay this value is only about 12%.

Devol, A. H.; Anderson, J. J.; Kuivila, K.; Murray, J. W.

1984-05-01

390

Graphene-based transition metal oxide nanocomposites for the oxygen reduction reaction.  

PubMed

The development of low cost, durable and efficient nanocatalysts to substitute expensive and rare noble metals (e.g. Pt, Au and Pd) in overcoming the sluggish kinetic process of the oxygen reduction reaction (ORR) is essential to satisfy the demand for sustainable energy conversion and storage in the future. Graphene based transition metal oxide nanocomposites have extensively been proven to be a type of promising highly efficient and economic nanocatalyst for optimizing the ORR to solve the world-wide energy crisis. Synthesized nanocomposites exhibit synergetic advantages and avoid the respective disadvantages. In this feature article, we concentrate on the recent leading works of different categories of introduced transition metal oxides on graphene: from the commonly-used classes (FeOx, MnOx, and CoOx) to some rare and heat-studied issues (TiOx, NiCoOx and Co-MnOx). Moreover, the morphologies of the supported oxides on graphene with various dimensional nanostructures, such as one dimensional nanocrystals, two dimensional nanosheets/nanoplates and some special multidimensional frameworks are further reviewed. The strategies used to synthesize and characterize these well-designed nanocomposites and their superior properties for the ORR compared to the traditional catalysts are carefully summarized. This work aims to highlight the meaning of the multiphase establishment of graphene-based transition metal oxide nanocomposites and its structural-dependent ORR performance and mechanisms. PMID:25502117

Sun, Meng; Liu, Huijuan; Liu, Yang; Qu, Jiuhui; Li, Jinghong

2015-01-28

391

Graphene-based transition metal oxide nanocomposites for the oxygen reduction reaction  

NASA Astrophysics Data System (ADS)

The development of low cost, durable and efficient nanocatalysts to substitute expensive and rare noble metals (e.g. Pt, Au and Pd) in overcoming the sluggish kinetic process of the oxygen reduction reaction (ORR) is essential to satisfy the demand for sustainable energy conversion and storage in the future. Graphene based transition metal oxide nanocomposites have extensively been proven to be a type of promising highly efficient and economic nanocatalyst for optimizing the ORR to solve the world-wide energy crisis. Synthesized nanocomposites exhibit synergetic advantages and avoid the respective disadvantages. In this feature article, we concentrate on the recent leading works of different categories of introduced transition metal oxides on graphene: from the commonly-used classes (FeOx, MnOx, and CoOx) to some rare and heat-studied issues (TiOx, NiCoOx and Co-MnOx). Moreover, the morphologies of the supported oxides on graphene with various dimensional nanostructures, such as one dimensional nanocrystals, two dimensional nanosheets/nanoplates and some special multidimensional frameworks are further reviewed. The strategies used to synthesize and characterize these well-designed nanocomposites and their superior properties for the ORR compared to the traditional catalysts are carefully summarized. This work aims to highlight the meaning of the multiphase establishment of graphene-based transition metal oxide nanocomposites and its structural-dependent ORR performance and mechanisms.

Sun, Meng; Liu, Huijuan; Liu, Yang; Qu, Jiuhui; Li, Jinghong

2015-01-01

392

Direct oxide reduction (DOR) solvent salt recycle in pyrochemical plutonium recovery operations  

SciTech Connect

One method used at Los Alamos for producing plutonium metal is to reduce the oxide with calcium metal in molten CaCl/sub 2/ at 850/sup 0/C. The solvent CaCl/sub 2/ from this reduction step is currently discarded as low-level radioactive waste because it is saturated with the reaction by-product, CaO. We have developed and demonstrated a molten salt technique for rechlorinating the CaO, thereby regenerating the CaCl/sub 2/ and incorporating solvent recycle into the batch PuO/sub 2/ reduction process. We discuss results from the process development experiments and present our plans for incorporating the technique into an advanced design for semicontinuous plutonium metal production.

Fife, K.W.; Bowersox, D.F.; Davis, C.C.; McCormick, E.D.

1987-02-01

393

Photochemically Induced Intramolecular Six-Electron Reductive Elimination and Oxidative Addition of Nitric Oxide by the Nitridoosmate(VIII) Anion.  

PubMed

UV photolysis of the nitridoosmate(VIII) anion, OsO3 N(-) , in low-temperature frozen matrices results in nitrogen-oxygen bond formation to give the Os(II) nitrosyl complex OsO2 (NO)(-) . Photolysis of the Os(II) nitrosyl product with visible wavelengths results in reversion to the parent Os(VIII) complex. Formally a six-electron reductive elimination and oxidative addition, respectively, this represents the first reported example of such an intramolecular transformation. DFT modelling of this reaction proceeds through a step-wise mechanism taking place through a side-on nitroxyl Os(VI) intermediate, OsO2 (?(2) -NO)(-) . PMID:25537499

Thornley, Wyatt A; Bitterwolf, Thomas E

2015-02-01

394

Manganese sulfide formation via concomitant microbial manganese oxide and thiosulfate reduction.  

SciTech Connect

The dissimilatory metal-reducing bacterium, Shewanella oneidensis MR-1 produced ?-MnS (rambergite) nanoparticles under the concurrent reduction of synthetic MnO2 and thiosulfate coupled to H2 oxidation. Using two MR-1 mutants defective in outer membrane c-type cytochromes (?mtrC/?omcA and ?mtrC/?omcA/?mtrF) to eliminate the direct reduction pathway for solid electron acceptors, it was determined that respiratory reduction of MnO2 was dominant relative to chemical reduction by biogenic sulfide generated from bacterial thiosulfate reduction. Although bicarbonate was excluded from the medium, incubations of MR-1 using lactate as the sole electron donor produced MnCO3 (rhodochrosite) as well as MnS in nearly equivalent amounts as estimated by micro X-ray diffraction (micro-XRD) analysis. It was concluded that carbonate released from lactate metabolism promoted MnCO3 formation and that Mn(II) mineralogy was strongly affected by carbonate ions even in the presence of abundant sulfide and weakly alkaline conditions that favor the precipitation of MnS. Formation of the biogenic MnS, as determined by a combination of micro-XRD, transmission electron microscopy, energy dispersive X-ray spectroscopy, and selected area electron diffraction analyses was consistent with equilibrium speciation modeling predictions. Although biogenic MnS likely only forms and is stable over a relatively narrow range of conditions, it may be a significant sink for Mn in anoxic marine basins and terrestrial subsurface sediments where Mn and sulfur compounds are undergoing concurrent reduction.

Lee, Ji-Hoon; Kennedy, David W.; Dohnalkova, Alice; Moore, Dean A.; Nachimuthu, Ponnusamy; Reed, Samantha B.; Fredrickson, Jim K.

2011-12-27

395

Simultaneous no x reduction and soot elimination from diesel exhaust on perovskite-type oxide catalysts  

Microsoft Academic Search

Series of partially substituted manganates belonging to perovskite structure family is prepared and characterized with a view to use them as catalyst for reduction of nitric oxides with carbon black. Catalytic tests show that the series La0.8Sr0.2Mn1?xCuxO3±1 have the best activity among the perovskite samples. La2CuO4, which belongs to K2NiF4 structure family, is more active than the others, but unfortunately

V. Duriez; L. Monceaux; P. Courtine

1995-01-01

396

Reversibly phototunable TiO{sub 2} photonic crystal modulated by Ag nanoparticles' oxidation/reduction  

SciTech Connect

We report a reversibly phototunable photonic crystal system whose reflectance at the stop band position can be modulated by alternating UV/visible (UV/Vis) irradiation. The phototunable system consists of Ag nanoparticles and TiO{sub 2} photonic crystal. The stop bands intensity of Ag loaded TiO{sub 2} photonic crystals were found to be dependent on the redox states of Ag nanoparticles. The quasi 'on' and 'off' states of the stop band were reversibly modulated by the Ag nanoparticles' oxidation/reduction through alternating UV/Vis light irradiation.

Liu Jian; Zhou Jinming; Ye Changqing [Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Organic Solids, Laboratory of New Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Li Mingzhu; Wang Jingxia; Jiang Lei; Song Yanlin [Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Organic Solids, Laboratory of New Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)

2011-01-10

397

Favorite Demonstration: Demonstrating Indigo Carmine Oxidation-Reduction Reactions--A Choreography for Chemical Reactions  

NSDL National Science Digital Library

The indigo carmine demonstration (Ferguson et al. 1973), also referred to as a traffic-light demonstration (Flinn Scientific 2007a), is an example of a set of oxidation-reduction reactions that occurs within one solution. This type of demonstration can be used to introduce the concept of chemical reaction to undergraduate nonscience majors. Through their observations guided by the instructor, students begin to develop and construct the following concepts: color changes, reaction rates, reversible reactions, energy requirements (endothermic/exothermic), and equilibrium.

David M. Majerich

2008-03-01

398

Investigation of NOx Reduction by Low Temperature Oxidation Using Ozone Produced by Dielectric Barrier Discharge  

NASA Astrophysics Data System (ADS)

NOx reduction by low temperature oxidation using ozone produced by a dielectric barrier discharge generator is investigated for different process parameters in a 6 m long reactor in serpentine arrangement using synthetic dry flue gas with NOx levels below 500 ppm, flows up to 50 slm and temperatures up to 80 °C. The role of different mixing schemes and the impact of a steep temperature gradient are also taken into consideration. The process chemistry is monitored by Fourier transform infrared spectroscopy, chemiluminescence and absorption spectroscopy. The kinetic mechanism during the mixing in a cross flow configuration is investigated using three-dimensional simulations.

Stamate, Eugen; Irimiea, Cornelia; Salewski, Mirko

2013-05-01

399

Carbohydrate oxidation coupled to Fe(III) reduction, a novel form of anaerobic metabolism  

USGS Publications Warehouse

An isolate, designated GC-29, that could incompletely oxidize glucose to acetate and carbon dioxide with Fe(III) serving as the electron acceptor was recovered from freshwater sediments of the Potomac River, Maryland. This metabolism yielded energy to support cell growth. Strain GC-29 is a facultatively anaerobic, Gram-negative motile rod which, in addition to glucose, also used sucrose, lactate, pyruvate, yeast extract, casamino acids or H2 as alternative electron donors for Fe(III) reduction. Stain GC-29 could reduce NO-3, Mn(IV), U(VI), fumarate, malate, S2O32-, and colloidal S0 as well as the humics analog, 2,6-anthraquinone disulfonate. Analysis of the almost complete 16S rRNA sequence indicated that strain GC-29 belongs in the Shewanella genus in the epsilon subdivision of the Proteobacteria. The name Shewanella saccharophilia is proposed. Shewanella saccharophilia differs from previously described fermentative microorganisms that metabolize glucose with the reduction of Fe(III) because it transfers significantly more electron equivalents to Fe(III); acetate and carbon dioxide are the only products of glucose metabolism; energy is conserved from Fe(III) reduction; and glucose is not metabolized in the absence of Fe(III). The metabolism of organisms like S. saccharophilia may account for the fact that glucose is metabolized primarily to acetate and carbon dioxide in a variety of sediments in which Fe(III) reduction is the terminal electron accepting process.

Coates, J.D.; Councell, T.; Ellis, D.J.; Lovley, D.R.

1998-01-01

400

Potential Nitrous Oxide Emissions from Municipal Drinking Water  

NASA Astrophysics Data System (ADS)

Nitrous oxide (N2O) is a potent greenhouse gas, having a global warming potential 280 times larger than carbon dioxide. Although the bulk of N2O emissions appear to be related to agricultural activity, various industrial and transportation related emissions exist as well. This study reports the discovery of a new and significant source of potential N2O emissions related to its presence in purified municipal water supplies worldwide. Multiple drinking water samples were obtained from 86 cities in the United States (US) and 44 cities in 16 countries in the Americas, Europe, Asia, and Africa. Samples ranged from 0.004 to 2?mol/L or the equivalent of 60% unsaturated to 200 times supersaturated with respect to ambient atmospheric concentration (320 ppb). Highest N2O contents were from southern US cities. Suspecting nitrification as the cause for the presence of N2O in drinking water, correlation statistics were calculated between N2O concentration and city size, geographical location, mean annual temperature, nitrate, and ammonia concentrations for the total population of samples as well as subsets based on country, water purification method, and raw water source (ground, surface, combination). The highest correlation (r=0.66, p<0.05, N=73) found was between latitude and N2O content for the subset group of large US cities using chloramines to purify water. Continuous year long sampling from a major US city indicated that variance in N2O content is remarkably low through the year within a water supply district. The annual US emission, based on this preliminary analysis, is 8x106 moles or 3.5X108 g N2O. Annual global emissions may be five times larger.

Anderson, D. E.; Thienelt, T.; Tindall, J.; McMahon, P.

2005-12-01

401

Metal oxide-based nanoparticles: revealing their potential to enhance oil recovery in different wettability systems  

NASA Astrophysics Data System (ADS)

This paper presents systematic studies of hydrophilic metal oxide nanoparticles (NPs) dispersed in brine intended to reveal their potential to enhance oil recovery (EOR) in various rock wettability systems. The stability in suspension (nanofluid) of the NPs has been identified as a key factor related to their use as an EOR agent. Experimental techniques have been developed for nanofluid stability using three coupled methods: direct visual observation, surface conductivity and particle size measurements. The use of a dispersant has been investigated and has been shown to successfully improve metal oxide nanofluid stability as a function of its concentration. The dispersant alters the nanofluid properties, i.e. surface conductivity, pH and particle size distribution. A two-phase coreflood experiment was conducted by injecting the stable nanofluids as a tertiary process (nano-EOR) through core plugs with various wettabilities ranging from water-wet to oil-wet. The combination of metal oxide nanofluid and dispersant improved the oil recovery to a greater extent than either silica-based nanofluid or dispersant alone in all wettability systems. The contact angle, interfacial tension (IFT) and effluent were also measured. It was observed that metal oxide-based nanofluids altered the quartz plates to become more water-wet, and the results are consistent with those of the coreflood experiment. The particle adsorption during the transport process was identified from effluent analysis. The presence of NPs and dispersant reduced the IFT, but its reduction is sufficient to yield significant additional oil recovery. Hence, wettability alteration plays a dominant role in the oil displacement mechanism using nano-EOR.

Hendraningrat, Luky; Torsæter, Ole

2015-02-01

402

An epidemiological study of workers potentially exposed to ethylene oxide.  

PubMed Central

This epidemiological study was of 18,728 employees at 14 United States facilities producing sterilised medical supplies and spices, who were potentially exposed to ethylene oxide (EO) for at least 90 days. The mortality of the cohort was studied to the end of 1988. A total of 1353 deaths was identified. The cohort had a significantly lower mortality than the general population from all causes, all cancers, and non-malignant diseases. In the entire cohort, mortality was not significantly increased from any of the cancer sites examined. In particular, no significant increase in mortality was found in the cancer sites of interest based on previous studies--namely, stomach, leukaemia (including major specific cell types), pancreas, and brain. The lack of an increased mortality for these cancer sites was further strengthened by the lack of a dose-response relation with duration of employment and latency. Among the men, a statistically significant increase in mortality from non-Hodgkin's lymphoma was found. There was no indication for a dose-response relation for non-Hodgkin's lymphoma and no specific job categories seemed to be responsible for the increase. Among the women, a deficit of non-Hodgkin's lymphoma was found, which was not consistent with the finding in the men. Therefore, the increase among the men did not seem to be related to exposure to EO. PMID:8494770

Wong, O; Trent, L S

1993-01-01

403

Surface-layer formation by reductive decomposition of LiPF6 at relatively high potentials on negative electrodes in lithium ion batteries and its suppression  

NASA Astrophysics Data System (ADS)

In using a LiPF6/ethylene carbonate-dimethyl carbonate electrolyte for lithium ion batteries (LIBs), a certain reductive reaction is known to occur at a relatively high potential (ca. 2.6 V vs. Li+/Li) on Sn electrode, but its details are still unknown. By means of in-situ X-ray reflectometry, X-ray photoelectron spectroscopy, scanning electron microscopy observations and electrochemical measurements (by using mainly Sn electrode, and additionally Pt, graphite electrodes), we have found out that this reduction eventually forms an inactive passivation-layer consisting mainly of insulative LiF ascribed to the reductive decomposition of LiPF6, which significantly affects the battery cyclability. In contrast, a solid-electrolyte interphase (SEI) is formed by the reductive reaction of the solvent at ca. 1.5 V vs. Li+/Li, which is lower than the reduction potential of LiPF6. However, we have found that the formation of SEI preempts that of the passivation layer when holding the electrode at a potential lower than 1.5 V vs. Li+/Li. Consequently, the cyclability is improved by suppressing the formation of the inactive passivation layer. Such a pretreatment would be quite effective on improvement of the battery cyclability, especially for a relatively noble electrode whose oxidation potential is between 1.5 V and 2.6 V vs. Li+/Li.

Kawaguchi, Tomoya; Shimada, Koki; Ichitsubo, Tetsu; Yagi, Shunsuke; Matsubara, Eiichiro

2014-12-01

404

Syntrophic Effects in a Subsurface Clostridial Consortium on Fe(III)-(Oxyhydr)oxide Reduction and Secondary Mineralization  

SciTech Connect

In this study, we cultivated from subsurface sediments an anaerobic Clostridia 25 consortium that was composed of a fermentative Fe-reducer Clostridium species (designated as 26 strain FGH) and a novel sulfate-reducing bacterium belonging to the Clostridia family 27 Vellionellaceae (designated as strain RU4). In pure culture, Clostridium sp. strain FGH mediated 28 the reductive dissolution/transformation of iron oxides during growth on peptone. When 29 Clostridium sp. FGH was grown with strain RU4 on peptone, the rates of iron oxide reduction 30 were significantly higher. Iron reduction by the consortium was mediated by multiple 31 mechanisms, including biotic reduction by Clostridium sp. FGH and biotic/abiotic reactions 32 involving biogenic sulfide by strain RU4. The Clostridium sp. FGH produced hydrogen during 33 fermentation, and the presence of hydrogen inhibited growth and iron reduction activity. The 34 sulfate-reducing partner strain RU4 was stimulated by the presence of H2 gas and generated 35 reactive sulfide which promoted the chemical reduction of the iron oxides. Characterization of 36 Fe(II) mineral products showed the formation of magnetite during ferrihydrite reduction, and 37 the precipitation of iron sulfides during goethite and hematite reduction. The results suggest an 38 important pathway for iron reduction and secondary mineralization by fermentative sulfate-39 reducing microbial consortia is through syntrophy-driven biotic/abiotic reactions with biogenic 40 sulfide.

Shah, Madhavi; Lin, Chu-Ching; Kukkadapu, Ravi K.; Engelhard, Mark H.; Zhao, Xiuhong; Wang, Yangping; Barkay, Tamar; Yee, Nathan

2013-12-02

405

Structures, electronic properties, and oxidation-reduction reactivity of halogenated iron porphyrins  

SciTech Connect

Molecular structures of both Fe{sup III}(TFPPBr{sub 8}) Cl and Fe{sup II} (TFPPBr{sub 8})(py){sub 2} porphyrins reveal saddle distortions: Fe{sup III-} (TFPPBr{sub 8})Cl in triclinic space group P1, a = 13.649(4) {Angstrom}, c = 14.537 {Angstrom}, {alpha} = 89.26(2){degrees}, {beta} = 67.13(1){degrees}, {gamma} = 71.82(2){degrees}, V = 2494.3(13) {Angstrom}{sup 3}, Z = 2 ; Fe{sup III}(TFPPBr{sub 8})(py){sub 2} in triclinic space group P1, a = 12.459- (7) {Angstrom}, b = 13.125(8) {Angstrom}, c = 20.989(11) {Angstrom}, {alpha} = 84.72(5){degrees}, {beta} = 72.87(4){degrees}, {gamma} = 69.04(5){degrees}, V = 3063(3) {Angstrom}{sup 3}, Z = 2. Similar to other chloro-iron(III) porphyrins. {mu}{sub eff} at room temperature (5.96 {mu}{sub B}) is that of a {sup 6}A{sub 1} state; {mu}{sub eff} at 2 K (4.2{mu}{sub B}) indicates a large zero-field splitting. The Soret bands of both Fe{sup III}(TFPPBr{sub 8})Cl and Fe{sup II}(TFPPBr{sub 8})- (py){sub 2} are red-shifted by approximately 23 nm relative to those of corresponding planar Fe{sup III} porphyrins. The metal and porphyrin reduction potentials of Fe{sup III} (TFPPBr{sub 8})Cl and Fe{sup II}(TFPPBr{sub 8})(py){sub 2} are anodically shifted more than 400 mV from those of Fe{sup III}(TPP)Cl. Although [Fe{sup II}(TFPPBr{sub 8})Cl]- reacts very slowly with dioxygen, it is oxidized rapidly by tert-butyl hydroperoxide (TBHP); these Fe{sup III} reactivity properties taken together with the finding that the corresponding Fe{sup III} complex is reduced rapidly by TBHP provide strong support for the proposal that Fe{sup III}(TFPPBr{sub 8})Cl/O{sub 2}-catalyzed alkane oxygenations occur by a radical chain mechanism in which alkyl hydroperoxide intermediates are decomposed efficiently by both Fe{sup III} and Fe{sup III} species.

Grinstaff, M.W.; Birnbaum, E.R.; Schaefer, W.P. [Arthur Amos Noyes Lab., Pasadena, CA (United States)] [and others

1995-09-13

406

Biogenic iron mineralization accompanying the dissimilatory reduction of hydrous ferric oxide by a groundwater bacterium  

SciTech Connect

The purpose of this research was to investigate the bacterial reduction of hydrous ferric oxide (HFO) by Shewanella putrefaciens and the nature of biogenic secondary phase formation in the presence of different inorganic ligands (PO{sub 4} and HCO{sub 3}) under conditions that may promote or suppress the organism/oxide association (i.e., with and without an electron shuttle). The electron shuttle used, anthraquinone-2,6-disulfonate (AQDS), is both a humic acid analog and a soluble redox indicator. The goal was to provide insights on biogeochemical factors governing dissimilatory biogenic mineralization in sediment or groundwater systems. The authors have investigated the influence of AQDS on the rate and extent of HFO reduction in different buffered systems and utilized X-ray diffraction, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) to evaluate the crystallographic and morphologic features of the biogenic precipitates. The biogenic phase association is interpreted in light of aqueous solution conditions, pe, solid phase thermodynamic stability, and microbiological considerations including metabolic status and growth with the intent of identifying unique microbiological contributions to secondary mineralization.

Fredrickson, J.K.; Zachara, J.M.; Kennedy, D.W.; Li, S.M. [Pacific Northwest National Lab., Richland, WA (United States)] [Pacific Northwest National Lab., Richland, WA (United States); Dong, H.; Onstott, T.C. [Princeton Univ., NJ (United States). Dept. of Geosciences] [Princeton Univ., NJ (United States). Dept. of Geosciences; Hinman, N.W. [Univ. of Montana, Missoula, MT (United States). Dept. of Geology] [Univ. of Montana, Missoula, MT (United States). Dept. of Geology

1998-10-01

407

Submerged Liquid Plasma for the Synchronized Reduction and Functionalization of Graphene Oxide  

PubMed Central

Formation of reduced and functionalized graphene oxide (r-FGO) at ambient temperature and pressure is demonstrated by generating liquid plasma submerged in acetonitrile and graphene oxide solution. The partial restoration of conjugation (sp2 domain) and insertion of fluorophores such as nitrile and amine in r-FGO displays enhanced fluorescence property. Presence of nitrile and amine in r-FGO are confirmed by X-ray photoelectron spectroscopy and Fourier transforms infrared spectroscopy. Morphology and optical property of r-FGO are studied with transmission electron microscopy, scanning tunneling microscopy and Ultraviolet–visible spectroscopy measurements. The nitrile and amine present in r-FGO undergo a surface-controlled reversible redox reaction and sp2- enriched r-FGO acts as an electrical double layer, providing additional hybrid capacitance or pseudocapacitance. r-FGO shows high cyclic stability with a specific capacitance value of 349?F/g at the scan rate of 10?mV/s. Only marginal reduction of specific capacitance (<10% reduction) is observed at the end of 1000 cycles. PMID:24637779

Senthilnathan, Jaganathan; Liu, Yung-Fang; Rao, Kodepelly Sanjeeva; Yoshimura, Masahiro

2014-01-01

408

Silicon nanowire arrays-induced graphene oxide reduction under UV irradiation.  

PubMed

This paper reports on efficient UV irradiation-induced reduction of exfoliated graphene oxide. Direct illumination of an aqueous solution of graphene oxide at ? = 312 nm for 6 h resulted in the formation of graphene nanosheets dispersible in water. X-Ray photoelectron spectroscopy (XPS), UV-vis spectroscopy, atomic force microscopy (AFM) and electrochemical measurements (cyclic voltammetry and electrochemical impedance spectroscopy) suggest a restoration of the sp(2) carbon network. The results were compared with graphene nanosheets prepared by photochemical irradiation of a GO aqueous solution in the presence of hydrogenated silicon nanowire (SiNW) arrays or silicon nanowire arrays decorated with silver (SiNW/Ag NPs) or copper nanoparticles (SiNW/Cu NPs). Graphene nanosheets obtained by illumination of the GO aqueous solution at 312 nm for 6 h in the presence of SiNW/Cu NPs exhibited superior electrochemical charge transfer characteristics. This is mainly due to the higher amount of sp(2)-hybridized carbon in these graphene sheets found by XPS analysis. The high level of extended conjugated carbon network was also evident by the water insoluble nature of the resulting graphene nanosheets, which precipitated upon photochemical reduction. PMID:21960142

Fellahi, Ouarda; Das, Manash R; Coffinier, Yannick; Szunerits, Sabine; Hadjersi, Toufik; Maamache, Mustapha; Boukherroub, Rabah

2011-11-01

409

Silicon nanowire arrays-induced graphene oxide reduction under UV irradiation  

NASA Astrophysics Data System (ADS)

This paper reports on efficient UV irradiation-induced reduction of exfoliated graphene oxide. Direct illumination of an aqueous solution of graphene oxide at ? = 312 nm for 6 h resulted in the formation of graphene nanosheets dispersible in water. X-Ray photoelectron spectroscopy (XPS), UV-vis spectroscopy, atomic force microscopy (AFM) and electrochemical measurements (cyclic voltammetry and electrochemical impedance spectroscopy) suggest a restoration of the sp2 carbon network. The results were compared with graphene nanosheets prepared by photochemical irradiation of a GO aqueous solution in the presence of hydrogenated silicon nanowire (SiNW) arrays or silicon nanowire arrays decorated with silver (SiNW/Ag NPs) or copper nanoparticles (SiNW/Cu NPs). Graphene nanosheets obtained by illumination of the GO aqueous solution at 312 nm for 6 h in the presence of SiNW/Cu NPs exhibited superior electrochemical charge transfer characteristics. This is mainly due to the higher amount of sp2-hybridized carbon in these graphene sheets found by XPS analysis. The high level of extended conjugated carbon network was also evident by the water insoluble nature of the resulting graphene nanosheets, which precipitated upon photochemical reduction.

Fellahi, Ouarda; Das, Manash R.; Coffinier, Yannick; Szunerits, Sabine; Hadjersi, Toufik; Maamache, Mustapha; Boukherroub, Rabah

2011-11-01

410

Photocatalytic carbon dioxide reduction by copper oxide nanocluster-grafted niobate nanosheets.  

PubMed

Amorphous copper oxide (Cu(II)) nanoclusters function as efficient electrocatalysts for the reduction of carbon dioxide (CO2) to carbon monoxide (CO). In addition to promoting electrocatalytic activity, Cu(II) nanoclusters act as efficient cocatalyts for CO2 photoreduction when grafted onto the surface of a semiconductor (light harvester), such as niobate (Nb3O8(-)) nanosheets. Here, the photocatalytic activity and reaction pathway of Cu(II)-grafted Nb3O8(-) nanosheets was investigated using electron spin resonance (ESR) analysis and isotope-labeled molecules (H2(18)O and (13)CO2). The results of the labeling experiments demonstrated that under UV irradiation, electrons are extracted from water to produce oxygen ((18)O2) and then reduce CO2 to produce (13)CO. ESR analysis confirmed that excited holes in the valence band of Nb3O8(-) nanosheets react with water, and that excited electrons in the conduction band of Nb3O8(-) nanosheets are injected into the Cu(II) nanoclusters through the interface and are involved in the reduction of CO2 into CO. The Cu(II) nanocluster-grafted Nb3O8(-) nanosheets are composed of nontoxic and abundant elements and can be facilely synthesized by a wet chemical method. The nanocluster grafting technique described here can be applied for the surface activation of various semiconductor light harvesters, such as metal oxide and/or metal chalcogenides, and is expected to aid in the development of efficient CO2 photoreduction systems. PMID:25629438

Yin, Ge; Nishikawa, Masami; Nosaka, Yoshio; Srinivasan, Nagarajan; Atarashi, Daiki; Sakai, Etsuo; Miyauchi, Masahiro

2015-02-24

411