Effects of ice melting and redox front migration in fractured rocks of low permeability

International Nuclear Information System (INIS)

Guimera, J.; Duro, L.; Jordana, S.; Bruno, J.

1999-09-01

The geochemical stability of a KBS-3 type repository could be adversely affected by oxygenated water inflow during glaciation-deglaciation periods. We have assessed on a quantitative basis the extent and depth of such an oxidising front. This has been done by using limited regional groundwater flow schemes in combination with heterogeneous geochemical models. We consider that the consumption of oxidants under the soil cover will be governed by the reactions between groundwater and redox buffering minerals. The ability of the media to buffer an oxidant intrusion will be dominated by the presence of iron(II) bearing minerals such as chlorite, biotite and pyrite. We approach the problem under two perspectives: the equilibrium approach, where groundwater reaches equilibrium with Fe(II) containing minerals; and the kinetic approach, where the interaction between oxidants and the minerals is governed by kinetic rate laws. The results show that, while the equilibrium approach is applicable to groundwater systems with sufficiently long residence times, the kinetically controlled reactive transport gives more accurate results, provided that characteristic reaction times are longer than groundwater residence time. Multicomponent reactive transport results show that despite the input of melt waters from glacial origin, the ground-water system remains anoxic after periods of thousands of years for most of the scenarios and conceptual models considered. The redox state is governed by the presence of iron(II) in the system. We have performed a sensitivity analysis of the effects of varying the groundwater flow velocity, the available reactive surface and the presence of different Fe(H) minerals. The majority of the simulations indicate that the resulting geochemical composition of the system would not jeopardise the geochemical stability of the spent fuel, at repository depths. Consequently, the intrusion of melting ice water does not pose any threat to the chemical stability of

Effects of ice melting and redox front migration in fractured rocks of low permeability

Energy Technology Data Exchange (ETDEWEB)

Guimera, J.; Duro, L.; Jordana, S.; Bruno, J. [QuantiSci, Barcelona (Spain)

1999-09-01

The geochemical stability of a KBS-3 type repository could be adversely affected by oxygenated water inflow during glaciation-deglaciation periods. We have assessed on a quantitative basis the extent and depth of such an oxidising front. This has been done by using limited regional groundwater flow schemes in combination with heterogeneous geochemical models. We consider that the consumption of oxidants under the soil cover will be governed by the reactions between groundwater and redox buffering minerals. The ability of the media to buffer an oxidant intrusion will be dominated by the presence of iron(II) bearing minerals such as chlorite, biotite and pyrite. We approach the problem under two perspectives: the equilibrium approach, where groundwater reaches equilibrium with Fe(II) containing minerals; and the kinetic approach, where the interaction between oxidants and the minerals is governed by kinetic rate laws. The results show that, while the equilibrium approach is applicable to groundwater systems with sufficiently long residence times, the kinetically controlled reactive transport gives more accurate results, provided that characteristic reaction times are longer than groundwater residence time. Multicomponent reactive transport results show that despite the input of melt waters from glacial origin, the ground-water system remains anoxic after periods of thousands of years for most of the scenarios and conceptual models considered. The redox state is governed by the presence of iron(II) in the system. We have performed a sensitivity analysis of the effects of varying the groundwater flow velocity, the available reactive surface and the presence of different Fe(H) minerals. The majority of the simulations indicate that the resulting geochemical composition of the system would not jeopardise the geochemical stability of the spent fuel, at repository depths. Consequently, the intrusion of melting ice water does not pose any threat to the chemical stability of

Plant redox proteomics

DEFF Research Database (Denmark)

Navrot, Nicolas; Finnie, Christine; Svensson, Birte

2011-01-01

PTMs in regulating enzymatic activities and controlling biological processes in plants. Notably, proteins controlling the cellular redox state, e.g. thioredoxin and glutaredoxin, appear to play dual roles to maintain oxidative stress resistance and regulate signal transduction pathways via redox PTMs......In common with other aerobic organisms, plants are exposed to reactive oxygen species resulting in formation of post-translational modifications related to protein oxidoreduction (redox PTMs) that may inflict oxidative protein damage. Accumulating evidence also underscores the importance of redox....... To get a comprehensive overview of these types of redox-regulated pathways there is therefore an emerging interest to monitor changes in redox PTMs on a proteome scale. Compared to some other PTMs, e.g. protein phosphorylation, redox PTMs have received less attention in plant proteome analysis, possibly...

Formation and properties of electroactive fullerene based films with a covalently attached ferrocenyl redox probe

International Nuclear Information System (INIS)

Wysocka-Zolopa, Monika; Winkler, Krzysztof; Caballero, Ruben; Langa, Fernando

2011-01-01

Highlights: → Formation of redox active films of ferrocene derivatives of C 60 and palladium. → Fullerene moieties are covalently bonded to palladium atoms to form a polymeric network. → Electrochemical activity at both positive and negative potentials. → Charge transfer processes accompanied by transport of supporting electrolyte to and from the polymer layers. - Abstract: Redox active films have been produced via electrochemical reduction in a solution containing palladium(II) acetate and ferrocene derivatives of C 60 (Fc-C 60 and bis-Fc-C 60 ). In these films, fullerene moieties are covalently bonded to palladium atoms to form a polymeric network. Fc-C 60 /Pd and bis-Fc-C 60 /Pd films form uniform and relatively smooth layers on the electrode surface. These films are electrochemically active in both the positive and negative potential regions. At negative potentials, reduction of fullerene moiety takes place resulting in voltammetric behavior resembles typical of conducting polymers. In the positive potential range, oxidation of ferrocene is responsible for the formation of a sharp and symmetrical peak on the voltammograms. In this potential range, studied films behave as typical redox polymers. The charge associated with the oxidation process depends on the number of ferrocene units attached to the C 60 moiety. Oxidation and reduction of these redox active films are accompanied by transport of supporting electrolyte to and from the polymer layer. Films also show a higher permeability to anions than to cations.

Harnessing redox activity for the formation of uranium tris(imido) compounds

Science.gov (United States)

Anderson, Nickolas H.; Odoh, Samuel O.; Yao, Yiyi; Williams, Ursula J.; Schaefer, Brian A.; Kiernicki, John J.; Lewis, Andrew J.; Goshert, Mitchell D.; Fanwick, Phillip E.; Schelter, Eric J.; Walensky, Justin R.; Gagliardi, Laura; Bart, Suzanne C.

2014-10-01

Classically, late transition-metal organometallic compounds promote multielectron processes solely through the change in oxidation state of the metal centre. In contrast, uranium typically undergoes single-electron chemistry. However, using redox-active ligands can engage multielectron reactivity at this metal in analogy to transition metals. Here we show that a redox-flexible pyridine(diimine) ligand can stabilize a series of highly reduced uranium coordination complexes by storing one, two or three electrons in the ligand. These species reduce organoazides easily to form uranium-nitrogen multiple bonds with the release of dinitrogen. The extent of ligand reduction dictates the formation of uranium mono-, bis- and tris(imido) products. Spectroscopic and structural characterization of these compounds supports the idea that electrons are stored in the ligand framework and used in subsequent reactivity. Computational analyses of the uranium imido products probed their molecular and electronic structures, which facilitated a comparison between the bonding in the tris(imido) structure and its tris(oxo) analogue.

Can Mn–S redox cycling drive sedimentary dolomite formation? A hypothesis

Energy Technology Data Exchange (ETDEWEB)

Petrash, Daniel A.; Lalonde, Stefan V.; González-Arismendi, Gabriela; Gordon, Robert A.; Méndez, José A.; Gingras, Murray K.; Konhauser, Kurt O. (CLS); (UCV-Venezuela); (CNRS-UMR); (Alberta)

2016-06-10

The formation of dolomite in modern peritidal environments is linked to the degradation of buried microbial mats, with complexation of Ca and Mg by extracellular polymeric substances (EPSs) and alkalinity generation through organic carbon respiration facilitating the nucleation of dolomite precursors. In the past two decades, microbial sulfate reduction, methanogenesis, and methanotrophy have all been considered as potential drivers of the nucleation process, but it remains unclear why dolomite formation could not also occur in suboxic sediments where abundant alkalinity is produced by processes linked to Mn(IV) and/or Fe(III) reduction coupled with the diffusion and reoxidation of reduced sulfur species. Here we report the interstitial occurrence of spheroidal aggregates of nanometer-scale Ca-rich dolomite rhombohedra within suboxic sediments associated with remnant microbial mats that developed in the peritidal zone of the Archipelago Los Roques, Venezuela. Multiple analytical tools, including EPMA, ICP-MS, synchrotron-based XRF and XRD, and spatially resolved XANES microanalyses, show that the dolomite-cemented interval exhibits depleted bulk iron concentrations, but is interstitially enriched in Mn and elemental sulfur (S⁰). Manganese occurs in several oxidation states, indicating that the dolomite-cemented interval was the locus of complex biological redox transformations characterized by coupled Mn and S cycling. The tight correspondence between sedimentary Mn and MgCO₃ concentrations further hints at a direct role for Mn during dolomitization. While additional studies are required to confirm its relevance in natural settings, we propose a model by which coupled Mn–S redox cycling may promote alkalinity generation and thus dolomite formation in manner similar to, or even more efficiently, than bacterial sulfate reduction alone.

Redox behaviors of iron by absorption spectroscopy and redox potential measurement

International Nuclear Information System (INIS)

Oh, Jae Yong

2010-02-01

This work is performed to study the redox (reduction/oxidation) behaviors of iron in aqueous system by a combination of absorption spectroscopy and redox potential measurements. There are many doubts on redox potential measurements generally showing low accuracies and high uncertainties. In the present study, redox potentials are measured by utilizing various redox electrodes such as Pt, Au, Ag, and glassy carbon (GC) electrodes. Measured redox potentials are compared with calculated redox potentials based on the chemical oxidation speciation of iron and thermodynamic data by absorption spectroscopy, which provides one of the sensitive and selective spectroscopic methods for the chemical speciation of Fe(II/III). From the comparison analyses, redox potential values measured by the Ag redox electrode are fairly consistent with those calculated by the chemical aqueous speciation of iron in the whole system. In summary, the uncertainties of measured redox potentials are closely related with the total Fe concentration and affected by the formation of mixed potentials due to Fe(III) precipitates in the pH range of 6 ∼ 9 beyond the solubility of Fe(III), whilst being independent of the initially prepared concentration ratios between Fe(II) and Fe(III)

Formation of intrathermocline eddies at ocean fronts by wind-driven destruction of potential vorticity

Science.gov (United States)

Thomas, Leif N.

2008-08-01

A mechanism for the generation of intrathermocline eddies (ITEs) at wind-forced fronts is examined using a high resolution numerical simulation. Favorable conditions for ITE formation result at fronts forced by "down-front" winds, i.e. winds blowing in the direction of the frontal jet. Down-front winds exert frictional forces that reduce the potential vorticity (PV) within the surface boundary in the frontal outcrop, providing a source for the low-PV water that is the materia prima of ITEs. Meandering of the front drives vertical motions that subduct the low-PV water into the pycnocline, pooling it into the coherent anticyclonic vortex of a submesoscale ITE. As the fluid is subducted along the outcropping frontal isopycnal, the low-PV water, which at the surface is associated with strongly baroclinic flow, re-expresses itself as water with nearly zero absolute vorticity. This generation of strong anticyclonic vorticity results from the tilting of the horizontal vorticity of the frontal jet, not from vortex squashing. During the formation of the ITE, high-PV water from the pycnocline is upwelled alongside the subducting low-PV surface water. The positive correlation between the ITE's velocity and PV fields results in an upward, along-isopycnal eddy PV flux that scales with the surface frictional PV flux driven by the wind. The relationship between the eddy and wind-induced frictional PV flux is nonlocal in time, as the eddy PV flux persists long after the wind forcing is shut off. The ITE's PV flux affects the large-scale flow by driving an eddy-induced transport or bolus velocity down the outcropping isopycnal layer with a magnitude that scales with the Ekman velocity.

SITE-94. Estimated rates of redox-front migration in granitic rocks

International Nuclear Information System (INIS)

Arthur, R.C.

1996-10-01

Analytical models for the rate of migration of oxidizing groundwaters are derived based on the stationary-state approximation to coupled fluid flow and water-rock interaction, and are constrained by molar concentrations of ferrous silicate, oxide, and sulfide minerals in the granites and associated fractures comprising the host rock beneath Aespoe. Model results indicate that small amounts of ferrous minerals in Aespoe granites and fractures will retard the downward migration of oxidizing conditions that could be generated by infiltration of glacial meltwaters during periods of glacial maxima and retreat. Calculated front velocities are retarded relative to Darcy fluxes observed in conductive fracture zones at Aespoe (0.3 to 3 m/y) by factors ranging from 10 -3 to 10 -4 . Corresponding times for the front to migrate 500 m vary from 5,100 to 4,400,000 years. Retardation efficiency depends on mineralogy and decreases in the order: fractures > altered granites > unaltered granite. The most conductive structures in these rocks are therefore the most efficient in limiting the rate of front migration. Periods of recharge during glaciation are comparable to times required for an oxidizing front to migrate to repository levels. This suggests an oxidizing front could reach repository depths during a single glacial-interglacial event. The persistence of oxidizing conditions could be relatively short lived, however, because reversal of flow conditions driven by the advance and retreat of ice sheets could cause reducing conditions to be restored. 27 refs

Gust-Front and Outflow Related Waterspouts: Timely Warnings, Formation, and Impact on Public Safety

Science.gov (United States)

Cappucci, M.

2013-12-01

Massachusetts may be over a thousand miles away from the traditional "tornado alley", but as the deadly tornadoes that killed four on June 1st 2011 proved, we are not immune to such storms. Over the course of half a century or so, Massachusetts has bore witness to scores of tornadoes, including an F5 twister that touched down on June 9th 1953, resulting in the death of 94 people. Since this tornado, none other in the United States had caused as many deaths, until the Joplin, Missouri catastrophe of May 22, 2011 (161 deaths). In Massachusetts, however, storms of such destructive magnitude are generally confined to the western half of the state, as the June 1, 2011 tornadoes in South Central Massachusetts illustrated. Despite this, a recently observed trend has revealed that the eastern Massachusetts coastline may boast as many, if not more, tornadoes, albeit undocumented. On June 23rd, 2012, a strong thunderstorm produced a spectacular gust front over Boston Harbor. This gust front was associated with intense thunderstorm outflow that helped to spawn a waterspout that roared ashore in Scituate as an EF-0 tornado. This waterspout, however, developed ahead of the gust front, yet merged with the cloud structure of the outflow, hinting at a type of interaction between the thunderstorm downdraft and the waterspout. This tornado caused minor damage. A similar situation occurred in Plymouth, MA, on July 24th, when three waterspouts formed ahead of the gust front of a severe thunderstorm; one of these tempests roared ashore on White Horse Beach as an EF-0 storm, causing minor damage to the sum of a few hundred dollars. Photos taken of these spouts reveal their formation ahead of the gust front, with a downdraft/waterspout interaction similar to the situation of June 23rd. Time-lapse videography of the gust front taken moments after the dissipation of the spouts reveals a horizontally oriented vortex a few hundred meters ahead of the storm's outflow boundary. The spinning of

Formation mechanism of uranium minerals at sandstone-type uranium deposits

International Nuclear Information System (INIS)

Li Shengfu; Zhang Yun

2004-01-01

By analyzing the behavior and existence form of uranium in different geochemical environments, existence form of uranium and uranium minerals species, this paper expounds the formation mechanism of main commercial uranium mineral--pitchblende: (1) uranium is a valence-changeable element. It is reactivated and migrates in oxidized environment, and is reduced and precipitated in reducing environment; (2) [UO 2 (CO 3 ) 3 ] 4- , [UO 2 (CO 3 ) 2 ] 2- coming from oxidized environment react with reductants such as organic matter, sulfide and low-valence iron at the redox front to form simple uranium oxide--pitchblende; (3)the adsorption of uranium by organic matter and clay minerals accelerates the reduction and the concentration of uranium. Therefore, it is considered, that the reduction of SO 4 2- by organic matter to form H 2 S, and the reduction of UO 2 2+ by H 2 S are the main reasons for the formation of pitchblende. This reaction is extensively and universally available in neutral and weakly alkaline carbonate solution. The existense of reductants such as H 2 S is the basic factor leading to the decrease of Eh in environments and the oversaturation of UO 2 2+ at the redox front in groundwater, thus accelerating the adsorption and the precipitation of uranium

Redox Behavior of Fe2+/Fe3+ Redox Couple by Absorption Spectroscopy and Measurement

International Nuclear Information System (INIS)

Oh, J. Y.; Park, S.; Yun, J. I.

2010-01-01

Redox behavior has influences on speciation and other geochemical reactions of radionuclides such as sorption, solubility, and colloid formation, etc. It is one of the factors for evaluation of long-term safety assessment under high-level radioactive waste (HLW) disposal conditions. Accordingly, redox potential (Eh) measurement in aquatic system is important to investigate the redox conditions. Eh is usually measured with redox active electrodes (Pt, Au, glassy carbon, etc.). Nevertheless, Eh measurements by general methods using electrodes provide low accuracy and high uncertainty problem. Therefore, Eh calculated from the concentration of redox active elements with a proper complexing reagent by using UV-Vis absorption spectroscopy is progressed. Iron exists mostly as spent nuclear waste container material and in hydro-geologic minerals. In this system, iron controls the redox condition in near-field area and influences chemical behavior and speciation of radionuclides including redox sensitive actinides such as U, Np, and Pu. In the present work, we present the investigation on redox phenomena of iron in aquatic system by a combination of absorption spectroscopy and redox potential measurements

Chemistry of tetravalent plutonium and zirconium. Hydrolysis, solubility, colloid formation and redox reactions

International Nuclear Information System (INIS)

Cho, Hye-Ryun

2006-01-01

The chemical properties of plutonium and zirconium are important in order to assess nuclear waste disposals with respect to isolation and immobilization of radionuclides. In this study, the hydrolysis, solubility and colloid formation of tetravalent plutonium and zirconium are investigated in 0.5 M HCl/NaCl solution using several complementary methods and the redox behavior of plutonium is investigated in acidic conditions as well. The solubilities of Pu(IV) and Zr(IV) are determined from the onset of colloid formation as a function of pH and metal concentration using LIBD (laser-induced breakdown detection). The investigation of the solubility of Zr(IV) is carried out at different concentrations (log [Zr] = -3 ∝ -7.6) and in a wide pH range (pH = 3 - 9) yielding log K sp (Zr(IV)) = -53.1 ± 0.5 based on the assumption that only mononuclear hydrolysis species exist in solution. Comparing the present results with literature data, the solubilities of Zr can be split in two groups, a crystalline phase with lower solubility and an amorphous phase (Zr(OH) 4 (am)) with higher solubility. The data obtained in the present work set an upper limit for the solubility of freshly formed Zr(OH) 4 (am). To understand this difference of solubilities, the geometrical structure of the dominant solution species is investigated as a function of pH using XAFS (X-ray absorption fine structure). The samples at pH >2, still below the solubility limit determined by LIBD, contain the polynuclear Zr(IV) species probably due to the high concentration ([Zr] = 1 mM) and their structure do not resemble any reported simple ZrO 2 structure. The Zr(IV) colloid species in oversaturated solution under this experimental condition resembles amorphous Zr(IV) hydroxide rather than crystalline ZrO 2 . The solubility of Pu(IV) is investigated in acidic solution below pH 2. Considering only mononuclear hydrolysis species, log K sp (Pu(IV)) = -58.3 ± 0.4 is obtained. Since Pu(IV) is not redox stable even

Dual redox catalysts for oxygen reduction and evolution reactions: towards a redox flow Li-O2 battery.

Science.gov (United States)

Zhu, Yun Guang; Jia, Chuankun; Yang, Jing; Pan, Feng; Huang, Qizhao; Wang, Qing

2015-06-11

A redox flow lithium-oxygen battery (RFLOB) by using soluble redox catalysts with good performance was demonstrated for large-scale energy storage. The new device enables the reversible formation and decomposition of Li2O2 via redox targeting reactions in a gas diffusion tank, spatially separated from the electrode, which obviates the passivation and pore clogging of the cathode.

Systematic front distortion and presence of consecutive fronts in a precipitation system

NARCIS (Netherlands)

Volford, A.; Izsak, F.; Ripszam, M.; Lagzi, I.

2006-01-01

A new simple reaction-diffusion system is presented focusing on pattern formation phenomena as consecutive precipitation fronts and distortion of the precipitation front.The chemical system investigated here is based on the amphoteric property of aluminum hydroxide and exhibits two unique phenomena.

Highly efficient hydrogen storage system based on ammonium bicarbonate/formate redox equilibrium over palladium nanocatalysts.

Science.gov (United States)

Su, Ji; Yang, Lisha; Lu, Mi; Lin, Hongfei

2015-03-01

A highly efficient, reversible hydrogen storage-evolution process has been developed based on the ammonium bicarbonate/formate redox equilibrium over the same carbon-supported palladium nanocatalyst. This heterogeneously catalyzed hydrogen storage system is comparable to the counterpart homogeneous systems and has shown fast reaction kinetics of both the hydrogenation of ammonium bicarbonate and the dehydrogenation of ammonium formate under mild operating conditions. By adjusting temperature and pressure, the extent of hydrogen storage and evolution can be well controlled in the same catalytic system. Moreover, the hydrogen storage system based on aqueous-phase ammonium formate is advantageous owing to its high volumetric energy density. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

HmsC Controls Yersinia pestis Biofilm Formation in Response to Redox Environment

Directory of Open Access Journals (Sweden)

Gai-Xian Ren

2017-08-01

Full Text Available Yersinia pestis biofilm formation, controlled by intracellular levels of the second messenger molecule cyclic diguanylate (c-di-GMP, is important for blockage-dependent plague transmission from fleas to mammals. HmsCDE is a tripartite signaling system that modulates intracellular c-di-GMP levels to regulate biofilm formation in Y. pestis. Previously, we found that Y. pestis biofilm formation is stimulated in reducing environments in an hmsCDE-dependent manner. However, the mechanism by which HmsCDE senses the redox state remains elusive. Using a dsbA mutant and the addition of Cu2+ to simulate reducing and oxidizing periplasmic environments, we found that HmsC protein levels are decreased and the HmsC-HmsD protein-protein interaction is weakened in a reducing environment. In addition, we revealed that intraprotein disulphide bonds are critical for HmsC since breakage lowers protein stability and diminishes the interaction with HmsD. Our results suggest that HmsC might play a major role in sensing the environmental changes.

Hydrogeological analysis applied to regional evaluation of sandstone-type uranium ore-formation in sedimentary basins

International Nuclear Information System (INIS)

Xu Laisheng

2005-01-01

The main purpose of regional evaluation of uranium ore-formation is to preliminarily divide environmental zones and to delineate favourable areas for uranium ore-formation in order to provide basis for further detailed prospecting work. Of the various kinds of prospecting work, the hydrogeologic work should be mainly carried out in following aspects: division of hydrogeological units, the determination of artesian water-bearing system and the identification of prospecting target horizon; the analysis on hydrodynamic regime, the analysis on hydrogeochemical environments, the paleo-hydrogeologic analysis and the delineation of redox front and favourable area for uranium ore-formation. (author)

The Ferredoxin-Like Proteins HydN and YsaA Enhance Redox Dye-Linked Activity of the Formate Dehydrogenase H Component of the Formate Hydrogenlyase Complex.

Science.gov (United States)

Pinske, Constanze

2018-01-01

Formate dehydrogenase H (FDH-H) and [NiFe]-hydrogenase 3 (Hyd-3) form the catalytic components of the hydrogen-producing formate hydrogenlyase (FHL) complex, which disproportionates formate to H 2 and CO 2 during mixed acid fermentation in enterobacteria. FHL comprises minimally seven proteins and little is understood about how this complex is assembled. Early studies identified a ferredoxin-like protein, HydN, as being involved in FDH-H assembly into the FHL complex. In order to understand how FDH-H and its small subunit HycB, which is also a ferredoxin-like protein, attach to the FHL complex, the possible roles of HydN and its paralogue, YsaA, in FHL complex stability and assembly were investigated. Deletion of the hycB gene reduced redox dye-mediated FDH-H activity to approximately 10%, abolished FHL-dependent H 2 -production, and reduced Hyd-3 activity. These data are consistent with HycB being an essential electron transfer component of the FHL complex. The FDH-H activity of the hydN and the ysaA deletion strains was reduced to 59 and 57% of the parental, while the double deletion reduced activity of FDH-H to 28% and the triple deletion with hycB to 1%. Remarkably, and in contrast to the hycB deletion, the absence of HydN and YsaA was without significant effect on FHL-dependent H 2 -production or total Hyd-3 activity; FDH-H protein levels were also unaltered. This is the first description of a phenotype for the E. coli ysaA deletion strain and identifies it as a novel factor required for optimal redox dye-linked FDH-H activity. A ysaA deletion strain could be complemented for FDH-H activity by hydN and ysaA , but the hydN deletion strain could not be complemented. Introduction of these plasmids did not affect H 2 production. Bacterial two-hybrid interactions showed that YsaA, HydN, and HycB interact with each other and with the FDH-H protein. Further novel anaerobic cross-interactions of 10 ferredoxin-like proteins in E. coli were also discovered and described

The effect of a stationary precipitation front on nuclide dissolution and transport

International Nuclear Information System (INIS)

Light, W.B.; Chambre, P.L.; Lee, W.W.L.; Pigford, T.H.

1988-01-01

Waste material in a geologic repository will dissolve and migrate away. For many waste components, this process will be limited by the solubility of the waste matrix and species involved. In this paper the authors deal with a single contaminant species and analyze the effect of a precipitation front caused by a discontinuity in the solubility of the contaminant at some distance from the waste package. The precipitation front may be due to local geochemical changes such as changes in temperature, pH or redox potential, caused by nearby geologic features or the waste itself. The authors provide analytic solutions to the problem of precipitation at a stationary front. Numerical illustrations of these solutions are also presented

Redox-controlled dinitrosyl formation at the diiron-oxo center of NorA.

Science.gov (United States)

Cramm, Rainer; Strube, Katja

2008-01-01

In the denitrifying bacterium Ralstonia eutropha H16, the NorA protein is coproduced with the respiratory nitric oxide (NO) reductase. NorA contains a diiron-oxo center, which can form stable adducts with dioxygen and NO. In contrast to other diiron proteins, the formation of NorA-NO requires both fully reduced protein and additional electrons. A minor fraction of in vitro NorA-NO represents a paramagnetic dinitrosyl iron complex (DNIC), while the major fraction is attributed to a DNIC of the structure {Fe(NO)(2)}, which shows no electron paramagnetic resonance. The NorA-DNIC may be formed either upon direct reaction of the protein with NO or upon incubation with nitrite due to an intrinsic nitrite reduction activity of NorA that liberates NO. NorA can be purified rapidly as a six histidine-tagged derivative from overproducing cells of Escherichia coli. This chapter describes procedures for the preparation of different redox forms of NorA for the formation of NorA adducts with NO, dioxygen, and azide, as well as for the quantification of NorA-bound NO.

Uranium mobility in the natural environment - evidence from sedimentary roll-front deposits

International Nuclear Information System (INIS)

Deutsch, W.J.; Serne, R.J.

1983-04-01

Roll-front deposits consist of naturally occurring ore-grade uranium in selected sandstone aquifers throughout the world. The geochemical environment of these roll-front deposits is analogous to the environment of a radioactive waste repository containing redox-sensitive elements during its post-thermal period. The ore deposits are formed by a combination of dissolution, complexation, sorption/precipitation, and mineral formation processes. The uranium, leached from the soil by percolating rainwater, complexes with dissolved carbonate and moves in the oxidizing ground water at very low concentration (parts per billion) levels. The uranium is extracted from the leaching solution by the chemical processes, over long periods of time, at the interfaces between oxidized and reduced sediments. The Eh of the ground water associated with the reduced sediments (Eh = -100 mv to +100 mv) is higher than the Eh expected for most waste repository environments (Eh = -100 mv to -300 mv); this suggests that uranium solids will not be very soluble in the repositories. Data from in-situ leach mining and restoration of roll-front uranium deposits also provide information on the potential mobility of the waste if oxidizing ground water should enter the repository. Uranium solids probably will be initially very soluble in carbonate ground water; however, as reducing conditions are re-estblished through water/rock interactions, the uranium will reprecipitate and the amount of uranium in solution will again equilibrate with the reduced uranium minerals

Redox Regulation of Endothelial Cell Fate

Science.gov (United States)

Song, Ping; Zou, Ming-Hui

2014-01-01

Endothelial cells (ECs) are present throughout blood vessels and have variable roles in both physiological and pathological settings. EC fate is altered and regulated by several key factors in physiological or pathological conditions. Reactive nitrogen species and reactive oxygen species derived from NAD(P)H oxidases, mitochondria, or nitric oxide-producing enzymes are not only cytotoxic but also compose a signaling network in the redox system. The formation, actions, key molecular interactions, and physiological and pathological relevance of redox signals in ECs remain unclear. We review the identities, sources, and biological actions of oxidants and reductants produced during EC function or dysfunction. Further, we discuss how ECs shape key redox sensors and examine the biological functions, transcriptional responses, and post-translational modifications evoked by the redox system in ECs. We summarize recent findings regarding the mechanisms by which redox signals regulate the fate of ECs and address the outcome of altered EC fate in health and disease. Future studies will examine if the redox biology of ECs can be targeted in pathophysiological conditions. PMID:24633153

Exercise redox biochemistry: Conceptual, methodological and technical recommendations

Directory of Open Access Journals (Sweden)

James N. Cobley

2017-08-01

Full Text Available Exercise redox biochemistry is of considerable interest owing to its translational value in health and disease. However, unaddressed conceptual, methodological and technical issues complicate attempts to unravel how exercise alters redox homeostasis in health and disease. Conceptual issues relate to misunderstandings that arise when the chemical heterogeneity of redox biology is disregarded: which often complicates attempts to use redox-active compounds and assess redox signalling. Further, that oxidised macromolecule adduct levels reflect formation and repair is seldom considered. Methodological and technical issues relate to the use of out-dated assays and/or inappropriate sample preparation techniques that confound biochemical redox analysis. After considering each of the aforementioned issues, we outline how each issue can be resolved and provide a unifying set of recommendations. We specifically recommend that investigators: consider chemical heterogeneity, use redox-active compounds judiciously, abandon flawed assays, carefully prepare samples and assay buffers, consider repair/metabolism, use multiple biomarkers to assess oxidative damage and redox signalling. Keywords: Exercise, Oxidative stress, Free radical, Antioxidants, Redox signalling

Dual-process theory and consumer response to front-of-package nutrition label formats.

Science.gov (United States)

Sanjari, S Setareh; Jahn, Steffen; Boztug, Yasemin

2017-11-01

Nutrition labeling literature yields fragmented results about the effect of front-of-package (FOP) nutrition label formats on healthy food choice. Specifically, it is unclear which type of nutrition label format is effective across different shopping situations. To address this gap, the present review investigates the available nutrition labeling literature through the prism of dual-process theory, which posits that decisions are made either quickly and automatically (system 1) or slowly and deliberately (system 2). A systematically performed review of nutrition labeling literature returned 59 papers that provide findings that can be explained according to dual-process theory. The findings of these studies suggest that the effectiveness of nutrition label formats is influenced by the consumer's dominant processing system, which is a function of specific contexts and personal variables (eg, motivation, nutrition knowledge, time pressure, and depletion). Examination of reported findings through a situational processing perspective reveals that consumers might prefer different FOP nutrition label formats in different situations and can exhibit varying responses to the same label format across situations. This review offers several suggestions for policy makers and researchers to help improve current FOP nutrition label formats. © The Author(s) 2017. Published by Oxford University Press on behalf of the International Life Sciences Institute. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Exercise redox biochemistry: Conceptual, methodological and technical recommendations.

Science.gov (United States)

Cobley, James N; Close, Graeme L; Bailey, Damian M; Davison, Gareth W

2017-08-01

Exercise redox biochemistry is of considerable interest owing to its translational value in health and disease. However, unaddressed conceptual, methodological and technical issues complicate attempts to unravel how exercise alters redox homeostasis in health and disease. Conceptual issues relate to misunderstandings that arise when the chemical heterogeneity of redox biology is disregarded: which often complicates attempts to use redox-active compounds and assess redox signalling. Further, that oxidised macromolecule adduct levels reflect formation and repair is seldom considered. Methodological and technical issues relate to the use of out-dated assays and/or inappropriate sample preparation techniques that confound biochemical redox analysis. After considering each of the aforementioned issues, we outline how each issue can be resolved and provide a unifying set of recommendations. We specifically recommend that investigators: consider chemical heterogeneity, use redox-active compounds judiciously, abandon flawed assays, carefully prepare samples and assay buffers, consider repair/metabolism, use multiple biomarkers to assess oxidative damage and redox signalling. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Measuring intracellular redox conditions using GFP-based sensors

DEFF Research Database (Denmark)

Björnberg, Olof; Ostergaard, Henrik; Winther, Jakob R

2006-01-01

Recent years have seen the development of methods for analyzing the redox conditions in specific compartments in living cells. These methods are based on genetically encoded sensors comprising variants of Green Fluorescent Protein in which vicinal cysteine residues have been introduced at solvent......-exposed positions. Several mutant forms have been identified in which formation of a disulfide bond between these cysteine residues results in changes of their fluorescence properties. The redox sensors have been characterized biochemically and found to behave differently, both spectroscopically and in terms...... of redox properties. As genetically encoded sensors they can be expressed in living cells and used for analysis of intracellular redox conditions; however, which parameters are measured depends on how the sensors interact with various cellular redox components. Results of both biochemical and cell...

Hyporheic exchange and fulvic acid redox reactions in an alpine stream/wetland ecosystem, Colorado front range

Science.gov (United States)

Miller, Matthew P.; McKnight, Diane M.; Cory, R.M.; Williams, Mark W.; Runkel, Robert L.

2006-01-01

The influence of hyporheic zone interactions on the redox state of fulvic acids and other redox active species was investigated in an alpine stream and adjacent wetland, which is a more reducing environment. A tracer injection experiment using bromide (Br-) was conducted in the stream system. Simulations with a transport model showed that rates of exchange between the stream and hyporheic zone were rapid (?? ??? 10-3 s -1). Parallel factor analysis of fluorescence spectra was used to quantify the redox state of dissolved fulvic acids. The rate coefficient for oxidation of reduced fulvic acids (?? = 6.5 ?? 10-3 s -1) in the stream indicates that electron-transfer reactions occur over short time scales. The rate coefficients for decay of ammonium (?? = 1.2 ?? 10-3 s-1) and production of nitrate (?? = -1.0 ?? 10-3 s-1) were opposite in sign but almost equal in magnitude. Our results suggest that fulvic acids are involved in rapid electron-transfer processes in and near the stream channel and may be important in determining ecological energy flow at the catchment scale. ?? 2006 American Chemical Society.

Variability of tidal signals in the Brent Delta Front: New observations on the Rannoch Formation, northern North Sea

Science.gov (United States)

Wei, Xiaojie; Steel, Ronald J.; Ravnås, Rodmar; Jiang, Zaixing; Olariu, Cornel; Li, Zhiyang

2016-04-01

Detailed observations on the Rannoch Formation in several deep Viking Graben wells indicate that the 'classical' wave-dominated Brent delta-front shows coupled storm-tide processes. The tidal signals are of three types: I): alternations of thick cross-laminated sandstone and thin mud-draped sandstone, whereby double mud drapes are prominent but discretely distributed, II): a few tidal bundles within bottomsets and foresets of up to 10 cm-thick sets cross-strata, and III): dm-thick heterolithic lamination showing multiple, well-organized sand-mud couplets. During progradation of the Brent Delta, the Rannoch shoreline system passed upward from 1) a succession dominated by clean-water, storm-event sets and cosets frequently and preferentially interbedded with type I tidal beds, and occasional types II and III tidal deposits, toward 2) very clean storm-event beds less frequently separated by types II and III tidal beds, and then into 3) a thin interval showing muddier storm-event beds mainly alternating with type II tidal beds. It is likely that those variations in preservation bias of storm and tidal beds in each facies succession result from combined effects of 1) the frequency and duration of storms; 2) river discharge; and 3) the absolute and relative strength of tides. Tidal deposits are interpreted as inter-storm, fair-weather deposits, occurred preferentially in longer intermittent fair-weather condition and periods of lower river discharge, and well-pronounced in the distal-reach of delta-front. The formation and preservation of tidal signals between storm beds, indicate that the studied Rannoch Formation was most likely a storm-dominated, tide-influenced delta front 1) near the mouth of a large Brent river, where a significant tidal prism and high tidal range might be expected, and 2) in a setting where there were relatively high sedimentation rates associated with high local subsidence rates, so that the storm waves did not completely rework the inter

Redox-active porous coordination polymer based on trinuclear pivalate: Temperature-dependent crystal rearrangement and redox-behavior

Energy Technology Data Exchange (ETDEWEB)

Lytvynenko, Anton S. [L.V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Prospekt Nauki 31, Kiev 03028 (Ukraine); Kiskin, Mikhail A., E-mail: mkiskin@igic.ras.ru [N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prospect 31, GSP-1, 119991 Moscow (Russian Federation); Dorofeeva, Victoria N.; Mishura, Andrey M.; Titov, Vladimir E.; Kolotilov, Sergey V. [L.V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Prospekt Nauki 31, Kiev 03028 (Ukraine); Eremenko, Igor L.; Novotortsev, Vladimir M. [N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prospect 31, GSP-1, 119991 Moscow (Russian Federation)

2015-03-15

Linking of trinuclear pivalate Fe{sub 2}NiO(Piv){sub 6} (Piv=O{sub 2}CC(CH{sub 3}){sub 3}) by 2,6-bis(4-pyridyl)-4-(1-naphthyl)pyridine (L) resulted in formation of 1D-porous coordination polymer Fe{sub 2}NiO(Piv){sub 6}(L)·Solv, which was characterized in two forms: DMSO solvate Fe{sub 2}NiO(Piv){sub 6}(L)(DMSO)·2.5DMSO (1) or water solvate Fe{sub 2}NiO(Piv){sub 6}(L)(H{sub 2}O) (2). X-ray structure of 1 was determined. Crystal lattice of 1 at 160 K contained open channels, filled by captured solvent, while temperature growth to 296 K led to the crystal lattice rearrangement and formation of closed voids. Redox-behavior of 2 was studied by cyclic voltammetry for a solid compound, deposited on glassy-carbon electrode. Redox-activity of L preserved upon incorporation in the coordination polymer. The presence of pores in desolvated sample Fe{sub 2}NiO(Piv){sub 6}(L) was confirmed by the measurements of N{sub 2} and H{sub 2} adsorption at 77 K. Potential barriers of the different molecules diffusion through pores were estimated by the means of molecular mechanics. - Graphical abstract: Redox-behavior of 1D-porous coordination polymer Fe{sub 2}NiO(Piv){sub 6}(L)(H{sub 2}O) was studied by cyclic voltammetry in thin film, deposited on glassy-carbon electrode. Redox-activity of L preserved upon incorporation in the coordination polymer. Potential barriers of different molecules diffusion through pores were estimated by the means of molecular mechanics. - Highlights: • Porous 1D coordination polymer was synthesized. • Temperature growth led to pores closing due to crystal lattice rearrangement. • Redox-activity of ligand preserved upon incorporation into coordination polymer. • Redox-properties of solid coordination polymer were studied in thin film. • Diffusion barriers were evaluated by molecular mechanics.

TIC/TOC and Redox Sensitive Trace Element (RSTEs) Signals Indicating Redox Conditions of the Lower Part of the Cabo Formation Near Organya (Organya Basin), Catalunya, Spain

Science.gov (United States)

Herdocia, C.; Maurrasse, F. J.

2017-12-01

The thick (> 4.5 km) sedimentary succession of the Organya Basin includes the Cabo Formation [1] which is well exposed in the Cabo valley area and is characteristically composed of black to dark gray marlstones and limestones that accumulated during the greenhouse climate and contain variable amount of organic matter [2-4]. Here we present geochemical results to assess redox conditions of 35.6 m of the Cabo Formation near the Barremian / Aptian boundary, along Catalunya Route C-14, immediately north of the town of Organya. TOC values range between 1 wt% and 5.8 wt%, and peak in all black limestones (0.43 m, 4.38 m, 14.85 m, 29.95 m, and 35.6 m). These TOC values average about 2.0 wt %, except at a height of 0.43 m, where the TOC has a strong peak (5.78 wt%). TIC values oscillated between 86.7 wt% and 96.8 wt%, and averaged at 92.7 wt% and show a strong negative correlation with TOC (r = -0.78). Measured carbon isotope on the organic carbon fraction (δ13Corg) showed fluctuations that ranged from -24.41‰ to -22.15‰. The TOC and δ13Corg curves show a positive correlation (r = 0.58), suggesting that carbon sequestration in the basin followed the overall global signature. Redox sensitive trace elements (V, Ni, Cu, and Mo) correlate with TOC values (r > 0.6), suggesting that dysoxic conditions were responsible for the preservation of organic matter. Biolimiting trace elements (Fe, P) also correlate positively with redox trace elements, and both have highest concentrations at 14.85 m, in concurrence with a high TOC value (2.93 wt%) indicating high primary productivity at that level. Major elements (Al, Si, and Ti) also correlates slightly with TOC (Al: r = 0.39; Si: r = 0.36; Ti: r = 0.43). References: [1] García-Senz, J., 2002, PhD Thesis, University of Barcelona, 310 pp. [2] Bernaus, J.M., et al., 2003. Sedimentary Geology 159 (3-4), 177-201. [3] Caus, E., et al., 1990. Cret. Research 11, 313-320. [4] Sanchez-Hernandez, Y., Maurrasse, F.J-M.R. 2014. Chem

Redox Species of Redox Flow Batteries: A Review.

Science.gov (United States)

Pan, Feng; Wang, Qing

2015-11-18

Due to the capricious nature of renewable energy resources, such as wind and solar, large-scale energy storage devices are increasingly required to make the best use of the renewable power. The redox flow battery is considered suitable for large-scale applications due to its modular design, good scalability and flexible operation. The biggest challenge of the redox flow battery is the low energy density. The redox active species is the most important component in redox flow batteries, and the redox potential and solubility of redox species dictate the system energy density. This review is focused on the recent development of redox species. Different categories of redox species, including simple inorganic ions, metal complexes, metal-free organic compounds, polysulfide/sulfur and lithium storage active materials, are reviewed. The future development of redox species towards higher energy density is also suggested.

Redox Species of Redox Flow Batteries: A Review

Directory of Open Access Journals (Sweden)

Feng Pan

2015-11-01

Full Text Available Due to the capricious nature of renewable energy resources, such as wind and solar, large-scale energy storage devices are increasingly required to make the best use of the renewable power. The redox flow battery is considered suitable for large-scale applications due to its modular design, good scalability and flexible operation. The biggest challenge of the redox flow battery is the low energy density. The redox active species is the most important component in redox flow batteries, and the redox potential and solubility of redox species dictate the system energy density. This review is focused on the recent development of redox species. Different categories of redox species, including simple inorganic ions, metal complexes, metal-free organic compounds, polysulfide/sulfur and lithium storage active materials, are reviewed. The future development of redox species towards higher energy density is also suggested.

Determining redox properties of clay-rich sedimentary deposits in the context of performance assessment of radioactive waste repositories : Conceptual and practical aspects

NARCIS (Netherlands)

Behrends, T.; Bruggeman, Christophe

Redox reactions play a key factor controlling the mobility of redox sensitive radionuclides in clay-rich sediments which might serve as host formations for radioactive waste repositories. Assessing the redox speciation of radionuclides requires information about the redox conditions in the formation

Redox-capacitor to connect electrochemistry to redox-biology.

Science.gov (United States)

Kim, Eunkyoung; Leverage, W Taylor; Liu, Yi; White, Ian M; Bentley, William E; Payne, Gregory F

2014-01-07

It is well-established that redox-reactions are integral to biology for energy harvesting (oxidative phosphorylation), immune defense (oxidative burst) and drug metabolism (phase I reactions), yet there is emerging evidence that redox may play broader roles in biology (e.g., redox signaling). A critical challenge is the need for tools that can probe biologically-relevant redox interactions simply, rapidly and without the need for a comprehensive suite of analytical methods. We propose that electrochemistry may provide such a tool. In this tutorial review, we describe recent studies with a redox-capacitor film that can serve as a bio-electrode interface that can accept, store and donate electrons from mediators commonly used in electrochemistry and also in biology. Specifically, we (i) describe the fabrication of this redox-capacitor from catechols and the polysaccharide chitosan, (ii) discuss the mechanistic basis for electron exchange, (iii) illustrate the properties of this redox-capacitor and its capabilities for promoting redox-communication between biology and electrodes, and (iv) suggest the potential for enlisting signal processing strategies to "extract" redox information. We believe these initial studies indicate broad possibilities for enlisting electrochemistry and signal processing to acquire "systems level" redox information from biology.

On the formation of a moving redox-front by α-radiolysis of compacted water saturated bentonite

International Nuclear Information System (INIS)

Eriksen, T.E.; Ndalamba, P.

1988-12-01

The formation of an expanding volume containing the radiolytically formed oxidants H 2 O 2 and O 2 has been studied in α-irradiated compacted water saturated bentonite (ρ = 2.12 gxcm -3 ). The G-values (0.67±0.05), (0.64±0.07) for H 2 O 2 and O 2 respectively are in fair agreement with the corresponding G-values obtained in experiments with synthetic ground water. From the leaching of γ-irradiated bentonite it is concluded that only a fraction of the Fe 2+ content is easily accessible as scavenger for the radiolytically formed oxidants. (orig.)

Primary uranium mineralization in paleochannels of the Um Bogma formation at Allouga Southwestern Sinai

International Nuclear Information System (INIS)

Bisher, A. H.

2012-12-01

The Um Bogama formation in the Allouga area is within a major Graben trending NNW-SSE. The formation is composed mainly of sandy dolostone. Lactomicin marl, siltstone and carbonaceous shale with a high content of organic matter. The black carbonaceous shale represents the redox-front (reduced facies) at which hexavalent uranium can reduce to the presence state, resulting in the redeposition of uranium mineral. The presence of uranium minerals are increased with an increasing amount of carbonaceous matter in the paleochannels of the Allouga area. Small-scale fault planes also show an increase in the uranium content. The present study reveals the presence of the primary uranium contents, uranium, pitch blends and coffinite, which are recorded for the first time in the area. (Author)

Redox cycling of potential antitumor aziridinylquinones

NARCIS (Netherlands)

Lusthof, Klaas J.; de Mol, Nicolaas J.; Richter, Wilma; Janssen, Lambert H.M.; Butler, John; Hoey, Brigid M.; Verboom, Willem; Reinhoudt, David

1992-01-01

The formation of reactive oxygen intermediates (ROI) during redox cycling of newly synthetized potential antitumor 2,5-bis (1-aziridinyl)-1,4-benzoquinone (BABQ) derivatives has been studied by assaying the production of ROI (superoxide, hydroxyl radical, and hydrogen peroxide) by xanthine oxidase

Simulation of effects of redox and precipitation on diffusion of uranium solution species in backfill

International Nuclear Information System (INIS)

Carnahan, C.L.

1987-12-01

This investigation addresses the problem of prediction of the rate of migration of redox-sensitive solution species within packing and backfill materials under conditions of variable oxidation potential. Effects of changes of oxidation potential and precipitation of stable uranium compounds during diffusion of uranium from a region of high oxidation potential into a region of low oxidation potential were simulated numerically. Questions of particular interest addressed in the investigation were the existence of a moving ''redox front'' and the influence of precipitation-dissolution processes on uranium migration. The simulations showed that no expanding redox fronts existed at any simulated time up to 3.2 x 10 5 years (10 13 s). In simulations where precipitation of stable solids was not allowed, variations of oxidation potential did not affect total uranium concentrations in solution. Concentration profiles could be predicted simply by diffusion of the (constant) source concentrations. In simulations where precipitation of stable solids was allowed, uraninite and calcium uranate accumulated at the source-transport domain interface, while coffinite penetrated further into the transport domain. Total uranium concentrations in regions of precipitation were determined by solubilities of the precipitated solids, and were six to seven orders of magnitude lower than those in the simulations without precipitation, throughout the domain of transport. 14 refs., 7 figs., 2 tabs

Evaluation of in situ sulfate reduction as redox buffer capacity in groundwater flow path

International Nuclear Information System (INIS)

Ioka, Seiichiro; Iwatsuki, Teruki; Amano, Yuki; Furue, Ryoji

2007-01-01

For safety assessment of geological isolation, it is important to evaluate in situ redox buffer capacity in high-permeability zone as groundwater flow path. The study evaluated in situ sulfate reduction as redox buffer capacity in the conglomerate bedding in Toki Lignite-bearing Formation, which occurs at the lowest part of sedimentary rocks overlying basement granite. The bedding plays an important role as the main groundwater flow path. The result showed that in situ redox buffer capacity in the conglomerate bedding has been identified on first nine months, whereas in the following period the redox buffer capacity has not been identified for about fifteen months. This will be caused by the bedding became inappropriate for microbial survival as the organic matter which is needfuel for microbial activity was consumed. Thus, there will be limited redox buffer capacity in groundwater flow path even in formation including organic matter-bearing layer. (author)

The Mechanism of Redox Reaction between Palladium(II Complex Ions and Potassium Formate in Acidic Aqueous Solution

Directory of Open Access Journals (Sweden)

Wojnicki M.

2017-06-01

Full Text Available The kinetics studies of redox reaction between palladium(II chloride complex ions and potassium formate in acidic aqueous solutions was investigated. It was shown, that the reduction reaction of Pd(II is selective in respect to Pd(II complex structure. The kinetic of the process was monitored spectrophotometrically. The influence of chloride ions concentration, Pd(II initial concentration, reductant concentration, ionic strength as well as the temperature were investigated in respect to the process dynamics. Arrhenius equation parameters were determined and are equal to 65.8 kJ/mol, and A = 1.12×1011 s−1.

Ediacaran Redox Fluctuations

Science.gov (United States)

Sahoo, S. K.; Jiang, G.; Planavsky, N. J.; Kendall, B.; Owens, J. D.; Anbar, A. D.; Lyons, T. W.

2013-12-01

Evidence for pervasive oxic conditions, and likely even deep ocean oxygenation has been documented at three intervals in the lower (ca. 632 Ma), middle (ca. 580 Ma) and upper (ca. 551 Ma) Ediacaran. The Doushantuo Formation in South China hosts large enrichments of redox-sensitive trace element (e.g., molybdenum, vanadium and uranium) in anoxic shales, which are indicative of a globally oxic ocean-atmosphere system. However, ocean redox conditions between these periods continue to be a topic of debate and remain elusive. We have found evidence for widespread anoxic conditions through much of the Ediacaran in the deep-water Wuhe section in South China. During most of the Ediacaran-early Cambrian in basinal sections is characterized by Fe speciation data and pyrite morphologies that indicate deposition under euxinic conditions with near-crustal enrichments of redox-sensitive element and positive pyrite-sulfur isotope values, which suggest low levels of marine sulfate and widespread euxinia. Our work reinforces an emerging view that the early Earth, including the Ediacaran, underwent numerous rises and falls in surface oxidation state, rather than a unidirectional rise as originally imagined. The Ediacaran ocean thus experienced repetitive expansion and contraction of marine chalcophilic trace-metal levels that may have had fundamental impact on the slow evolution of early animals and ecosystems. Further, this framework forces us to re-examine the relationship between Neoproterozoic oxygenation and metazoan diversification. Varying redox conditions through the Cryogenian and Ediacaran may help explain molecular clock and biomarker evidence for an early appearance and initial diversification of metazoans but with a delay in the appearance of most major metazoan crown groups until close to Ediacaran-Cambrian boundary.

Formation of high-molecular-weight angiotensinogen during pregnancy is a result of competing redox reactions with the proform of eosinophil major basic protein

DEFF Research Database (Denmark)

Kløverpris, Søren; Skov, Louise Lind; Glerup, Simon

2013-01-01

compared to monomeric AGT and the proMBP-AGT complex. Furthermore, we have used recombinant proteins to analyse the formation of the proMBP-PAPP-A and the proMBP-AGT complexes, and we demonstrate that they are competing reactions, depending on the same cysteine residue of proMBP, but differentially...... on the redox potential, potentially important for the relative amounts of the complexes in vivo. These findings may be important physiologically, since the biochemical properties of the proteins change as a consequence of complex formation....

Characterisation of the Redox Sensitive NMDA Receptor

KAUST Repository

Alzahrani, Ohood

2016-05-01

Glucose entry into the brain and its subsequent metabolism to L-lactate, regulated by astrocytes, plays a major role in synaptic plasticity and memory formation. A recent study has shown that L-lactate produced by the brain upon stimulation of glycolysis, and glycogen-derived L-lactate from astrocytes and its transport into neurons, is crucial for memory formation. A recent study revealed the molecular mechanisms that underlie the role of L-lactate in neuronal plasticity and long-term memory formation. L-lactate was shown to induce a cascade of molecular events via modulation of redox-sensitive N-Methyl-D-aspartate (NMDA) receptor activity that was mimicked by nicotinamide adenine dinucleotide hydride (NADH) co-enzyme. This indicated that changes in cellular redox state, following L-lactate transport inside the cells and its subsequent metabolism, production of NADH, and favouring a reduced state are the key effects of L-lactate. Therefore, we are investigating the role of L-lactate in modulating NMDA receptor function via redox modulatory sites. Accordingly, crucial redox-sensitive cysteine residues, Cys320 and Cys87, of the NR2A NMDA receptor subunit are mutated using site-directed mutation, transfected, and expressed in HEK293 cells. This cellular system will then be used to characterise and monitor its activity upon Llactate stimulation, compared to the wild type. This will be achieved by calcium imaging, using fluorescent microscopy. Our data shows that L-lactate potentiated NMDA receptor activity and increased intracellular calcium influx in NR1/NR2A wild type compared to the control condition (WT NR1/NR2A perfused with (1μM) glutamate and (1μM) glycine agonist only), showing faster response initiation and slower decay rate of the calcium signal to the baseline. Additionally, stimulating with L-lactate associated with greater numbers of cells having high fluorescent intensity (peak amplitude) compared to the control. Furthermore, L-lactate rescued the

Simulation of idealized warm fronts and life cycles of cirrus clouds

Science.gov (United States)

Bense, Vera; Spichtinger, Peter

2013-04-01

One of the generally accepted formation mechanisms of cirrus clouds is connected to warm fronts. As the warm air glides over the cold air mass, it cools through adiabatic expansion and reaches ice supersaturation that eventually leads to the formation of ice clouds. Within this work, the EULAG model (see e.g. Prusa et al., 2008) was used to study the formation and life cycles of cirrus clouds in idealized 2-dimensional simulations. The microphysical processes were modelled with the double-moment bulk scheme of Spichtinger and Gierens (2009), which describes homogeneous and heterogeneous nucleation. In order to represent the gradual gliding of the air along the front, a ramp was chosen as topography. The sensibility of cloud formation to different environmental conditions such as wind shear, aerosol distribution and slope of the front was analyzed. In case of cirrus cloud formation its persistence after the front was studied as well as the change in microphysical properties such as ice crystal number concentrations. References: Prusa, J.M., P.K. Smolarkiewicz, A.A. Wyszogrodzki, 2008: EULAG, a computational model for multiscale flows. Computers and Fluids, doi:10.1016/j.compfluid.2007.12.001. Spichtinger, P., K. M. Gierens, 2009: Modelling of cirrus clouds - Part 1a: Model description and validation, Atmos. Chem. Phys., 9, 685-706.

The Redox Code.

Science.gov (United States)

Jones, Dean P; Sies, Helmut

2015-09-20

The redox code is a set of principles that defines the positioning of the nicotinamide adenine dinucleotide (NAD, NADP) and thiol/disulfide and other redox systems as well as the thiol redox proteome in space and time in biological systems. The code is richly elaborated in an oxygen-dependent life, where activation/deactivation cycles involving O₂ and H₂O₂ contribute to spatiotemporal organization for differentiation, development, and adaptation to the environment. Disruption of this organizational structure during oxidative stress represents a fundamental mechanism in system failure and disease. Methodology in assessing components of the redox code under physiological conditions has progressed, permitting insight into spatiotemporal organization and allowing for identification of redox partners in redox proteomics and redox metabolomics. Complexity of redox networks and redox regulation is being revealed step by step, yet much still needs to be learned. Detailed knowledge of the molecular patterns generated from the principles of the redox code under defined physiological or pathological conditions in cells and organs will contribute to understanding the redox component in health and disease. Ultimately, there will be a scientific basis to a modern redox medicine.

Redox Equilibria in SO2 Oxidation Catalysts

DEFF Research Database (Denmark)

Rasmussen, Søren Birk; Eriksen, Kim Michael; Boghosian, Soghomon

1999-01-01

been carried out regarding the complex and compound formation of V(V) and the formation of V(IV) and V(III) compounds with low solubility causing catalyst deactivation. However, the redox chemistry of vanadium and the complex formation of V(IV) is much less investigated and further information...... on these subjects in pyrosulfate melts is needed to obtain a deeper understanding of the reaction mechanism. The present paper describes our efforts so far to study the V(IV) chemistry using especially spectroscopic and electrochemical methods....

Vascular remodeling: A redox-modulated mechanism of vessel caliber regulation.

Science.gov (United States)

Tanaka, Leonardo Y; Laurindo, Francisco R M

2017-08-01

Vascular remodeling, i.e. whole-vessel structural reshaping, determines lumen caliber in (patho)physiology. Here we review mechanisms underlying vessel remodeling, with emphasis in redox regulation. First, we discuss confusing terminology and focus on strictu sensu remodeling. Second, we propose a mechanobiological remodeling paradigm based on the concept of tensional homeostasis as a setpoint regulator. We first focus on shear-mediated models as prototypes of remodeling closely dominated by highly redox-sensitive endothelial function. More detailed discussions focus on mechanosensors, integrins, extracellular matrix, cytoskeleton and inflammatory pathways as potential of mechanisms potentially coupling tensional homeostasis to redox regulation. Further discussion of remodeling associated with atherosclerosis and injury repair highlights important aspects of redox vascular responses. While neointima formation has not shown consistent responsiveness to antioxidants, vessel remodeling has been more clearly responsive, indicating that despite the multilevel redox signaling pathways, there is a coordinated response of the whole vessel. Among mechanisms that may orchestrate redox pathways, we discuss roles of superoxide dismutase activity and extracellular protein disulfide isomerase. We then discuss redox modulation of aneurysms, a special case of expansive remodeling. We propose that the redox modulation of vascular remodeling may reflect (1) remodeling pathophysiology is dominated by a particularly redox-sensitive cell type, e.g., endothelial cells (2) redox pathways are temporospatially coordinated at an organ level across distinct cellular and acellular structures or (3) the tensional homeostasis setpoint is closely connected to redox signaling. The mechanobiological/redox model discussed here can be a basis for improved understanding of remodeling and helps clarifying mechanisms underlying prevalent hard-to-treat diseases. Copyright © 2017 Elsevier Inc. All

Information processing through a bio-based redox capacitor: signatures for redox-cycling.

Science.gov (United States)

Liu, Yi; Kim, Eunkyoung; White, Ian M; Bentley, William E; Payne, Gregory F

2014-08-01

Redox-cycling compounds can significantly impact biological systems and can be responsible for activities that range from pathogen virulence and contaminant toxicities, to therapeutic drug mechanisms. Current methods to identify redox-cycling activities rely on the generation of reactive oxygen species (ROS), and employ enzymatic or chemical methods to detect ROS. Here, we couple the speed and sensitivity of electrochemistry with the molecular-electronic properties of a bio-based redox-capacitor to generate signatures of redox-cycling. The redox capacitor film is electrochemically-fabricated at the electrode surface and is composed of a polysaccharide hydrogel with grafted catechol moieties. This capacitor film is redox-active but non-conducting and can engage diffusible compounds in either oxidative or reductive redox-cycling. Using standard electrochemical mediators ferrocene dimethanol (Fc) and Ru(NH3)6Cl3 (Ru(3+)) as model redox-cyclers, we observed signal amplifications and rectifications that serve as signatures of redox-cycling. Three bio-relevant compounds were then probed for these signatures: (i) ascorbate, a redox-active compound that does not redox-cycle; (ii) pyocyanin, a virulence factor well-known for its reductive redox-cycling; and (iii) acetaminophen, an analgesic that oxidatively redox-cycles but also undergoes conjugation reactions. These studies demonstrate that the redox-capacitor can enlist the capabilities of electrochemistry to generate rapid and sensitive signatures of biologically-relevant chemical activities (i.e., redox-cycling). Published by Elsevier B.V.

Electrochemical Switching of Conductance with Diarylethene-Based Redox-Active Polymers

DEFF Research Database (Denmark)

Logtenberg, Hella; van der Velde, Jasper H. M.; de Mendoza, Paula

2012-01-01

Reversible switching of conductance using redox triggered switching of a polymer-modified electrode is demonstrated. A bifunctional monomer comprising a central electroswitchable core and two bithiophene units enables formation of a film through anodic electropolymerization. The conductivity...... of the polymer can be switched electrochemically in a reversible manner by redox triggered opening and closing of the diarylethene unit. In the closed state, the conductivity of the modified electrode is higher than in the open state....

Shock-front compression of the magnetic field in the Canis Majoris R1 star-formation region

International Nuclear Information System (INIS)

Vrba, F.J.; Baierlein, R.; Herbst, W.; Wesleyan Univ., Middletown, CT; Van Vleck Observatory, Middletown, CT)

1987-01-01

Results are presented from a linear polarization survey at optical wavelengths of over 140 stars in the direction of the CMa R1 star-formation region; 26 of these are clearly associated with nebulosity within the area. The observations were obtained in order to test the argument of Herbst et al. (1978) that star formation in CMa R1 is driven by a shock wave from a nearby supernova (Herbs and Assousa, 1977 and 1978). The polarizations are found to be consistent with a simple model of the compression by a supernova-induced spherical shock front of an initially uniform interstellar magnetic field. The polarization vectors are inconsistent with a scenario of quiescent cloud collapse along magnetic-field lines. Multicolor polarimetry of the nebular stars provides evidence of grain growth toward increasing cloud optical depth, characterized by a ratio of total-to-selective extinction of R = 3.0 at E(B-V) = 0.23, increasing to R = 4.2 at E(B-V) = 0.7. 15 references

New function of aldoxime dehydratase: Redox catalysis and the formation of an unexpected product.

Science.gov (United States)

Yamada, Masatoshi; Hashimoto, Yoshiteru; Kumano, Takuto; Tsujimura, Seiya; Kobayashi, Michihiko

2017-01-01

In general, hemoproteins are capable of catalyzing redox reactions. Aldoxime dehydratase (OxdA), which is a unique heme-containing enzyme, catalyzes the dehydration of aldoximes to the corresponding nitriles. Its reaction is a rare example of heme directly activating an organic substrate, unlike the utilization of H2O2 or O2 as a mediator of catalysis by other heme-containing enzymes. While it is unknown whether OxdA catalyzes redox reactions or not, we here for the first time detected catalase activity (which is one of the redox activities) of wild-type OxdA, OxdA(WT). Furthermore, we constructed a His320 → Asp mutant of OxdA [OxdA(H320D)], and found it exhibits catalase activity. Determination of the kinetic parameters of OxdA(WT) and OxdA(H320D) revealed that their Km values for H2O2 were similar to each other, but the kcat value of OxdA(H320D) was 30 times higher than that of OxdA(WT). Next, we examined another redox activity and found it was the peroxidase activity of OxdAs. While both OxdA(WT) and OxdA(H320D) showed the activity, the activity of OxdA(H320D) was dozens of times higher than that of OxdA(WT). These findings demonstrated that the H320D mutation enhances the peroxidase activity of OxdA. OxdAs (WT and H320D) were found to catalyze another redox reaction, a peroxygenase reaction. During this reaction of OxdA(H320D) with 1-methoxynaphthalene as a substrate, surprisingly, the reaction mixture changed to a color different from that with OxdA(WT), which was due to the known product, Russig's blue. We purified and identified the new product as 1-methoxy-2-naphthalenol, which has never been reported as a product of the peroxygenase reaction, to the best of our knowledge. These findings indicated that the H320D mutation not only enhanced redox activities, but also significantly altered the hydroxylation site of the substrate.

New function of aldoxime dehydratase: Redox catalysis and the formation of an unexpected product.

Directory of Open Access Journals (Sweden)

Masatoshi Yamada

Full Text Available In general, hemoproteins are capable of catalyzing redox reactions. Aldoxime dehydratase (OxdA, which is a unique heme-containing enzyme, catalyzes the dehydration of aldoximes to the corresponding nitriles. Its reaction is a rare example of heme directly activating an organic substrate, unlike the utilization of H2O2 or O2 as a mediator of catalysis by other heme-containing enzymes. While it is unknown whether OxdA catalyzes redox reactions or not, we here for the first time detected catalase activity (which is one of the redox activities of wild-type OxdA, OxdA(WT. Furthermore, we constructed a His320 → Asp mutant of OxdA [OxdA(H320D], and found it exhibits catalase activity. Determination of the kinetic parameters of OxdA(WT and OxdA(H320D revealed that their Km values for H2O2 were similar to each other, but the kcat value of OxdA(H320D was 30 times higher than that of OxdA(WT. Next, we examined another redox activity and found it was the peroxidase activity of OxdAs. While both OxdA(WT and OxdA(H320D showed the activity, the activity of OxdA(H320D was dozens of times higher than that of OxdA(WT. These findings demonstrated that the H320D mutation enhances the peroxidase activity of OxdA. OxdAs (WT and H320D were found to catalyze another redox reaction, a peroxygenase reaction. During this reaction of OxdA(H320D with 1-methoxynaphthalene as a substrate, surprisingly, the reaction mixture changed to a color different from that with OxdA(WT, which was due to the known product, Russig's blue. We purified and identified the new product as 1-methoxy-2-naphthalenol, which has never been reported as a product of the peroxygenase reaction, to the best of our knowledge. These findings indicated that the H320D mutation not only enhanced redox activities, but also significantly altered the hydroxylation site of the substrate.

New function of aldoxime dehydratase: Redox catalysis and the formation of an expected product

Science.gov (United States)

Kumano, Takuto; Tsujimura, Seiya; Kobayashi, Michihiko

2017-01-01

In general, hemoproteins are capable of catalyzing redox reactions. Aldoxime dehydratase (OxdA), which is a unique heme-containing enzyme, catalyzes the dehydration of aldoximes to the corresponding nitriles. Its reaction is a rare example of heme directly activating an organic substrate, unlike the utilization of H2O2 or O2 as a mediator of catalysis by other heme-containing enzymes. While it is unknown whether OxdA catalyzes redox reactions or not, we here for the first time detected catalase activity (which is one of the redox activities) of wild-type OxdA, OxdA(WT). Furthermore, we constructed a His320 → Asp mutant of OxdA [OxdA(H320D)], and found it exhibits catalase activity. Determination of the kinetic parameters of OxdA(WT) and OxdA(H320D) revealed that their Km values for H2O2 were similar to each other, but the kcat value of OxdA(H320D) was 30 times higher than that of OxdA(WT). Next, we examined another redox activity and found it was the peroxidase activity of OxdAs. While both OxdA(WT) and OxdA(H320D) showed the activity, the activity of OxdA(H320D) was dozens of times higher than that of OxdA(WT). These findings demonstrated that the H320D mutation enhances the peroxidase activity of OxdA. OxdAs (WT and H320D) were found to catalyze another redox reaction, a peroxygenase reaction. During this reaction of OxdA(H320D) with 1-methoxynaphthalene as a substrate, surprisingly, the reaction mixture changed to a color different from that with OxdA(WT), which was due to the known product, Russig’s blue. We purified and identified the new product as 1-methoxy-2-naphthalenol, which has never been reported as a product of the peroxygenase reaction, to the best of our knowledge. These findings indicated that the H320D mutation not only enhanced redox activities, but also significantly altered the hydroxylation site of the substrate. PMID:28410434

Geochemical dispersion associated with uranium deposits in sandstone roll front type and its relationship to the Orinoco Oil Belt, Venezuela

International Nuclear Information System (INIS)

Manrique, J.

2014-01-01

In Venezuela, there is a potential for the formation of uranium deposits in areas such as the Guiana Shield, the south of the Eastern Basin, the Andes and the massif of Baúl, among other areas. Especially great interest is the exploration of uranium redox interface type (roll front), in areas such as the southern part of the Orinoco Oil Belt, north and northwest of the Guiana Shield, where groundwater uranium collecting the weathering shield flowing northward in the sandstones and mudstones of the Cretaceous to Quaternary formations, which constitute the southern boundary of the Eastern basin Venezuela. The presence of gas, extra-heavy crude oil, bitumen and lignite of the Orinoco Oil Belt can be an effective barrier for uranium in solution, which may have precipitated at the redox interface of this groundwater. This process certainly was more effective before the Orinoco river take its course to the east and the waters of small rivers and large draining shield contributed to uranium aquifers became more deep north. This work was based on a qualitative model describing geochemical dispersion associated with uranium deposits in sandstone, roll front type, which indicates that the daughter isotopes "2"3"8U, which can migrate extensively are: "2"2"2Rn, "4He, and in a smaller proportion: "2"2"6Ra and "2"2"2Rn daughters ("2"1"4Bi, "2"1"0Pb). The main exploration methods were established, which can be applied in areas of the Orinoco Oil Belt, north of the Guiana Shield, and areas west of this, among the most important are: soil measurements of radon and helium near faults, sampling soils with gamma spectrometry analysis, log interpretation of oil wells in the area of interest to establish gamma – lithological anomalies, ground water analysis of uranium, radon, radium, helium, vanadium, selenium, molybdenum, analysis of samples oil drilling cores to locate anomalous stratigraphic levels. This research will provide the basis to establish methodologies for uraniferous

Formation of poorly crystalline iron monosulfides: Surface redox reactions on high purity iron, spectroelectrochemical studies

Energy Technology Data Exchange (ETDEWEB)

Hansson, E.B. [Geological Institute, University of Copenhagen, Oster Voldgade 10, Copenhagen K, DK-1350 (Denmark); Odziemkowski, M.S. [Department of Earth Sciences, University of Waterloo, Waterloo, Ont., N2L 3G1 (Canada)]. E-mail: marek@sciborg.uwaterloo.ca; Gillham, R.W. [Department of Earth Sciences, University of Waterloo, Waterloo, Ont., N2L 3G1 (Canada)

2006-11-15

In the use of iron for reductive dehalogenation of chlorinated solvents in ground water, due to presence of sulfate-reducing bacteria the formation of hydrogen sulfide is expected. To simulate those processes the interface between 99.99% pure iron and 0.1 M NaHCO{sub 3} deoxygenated solution with 3.1 x 10{sup -5}-7.8 x 10{sup -3} M Na{sub 2}S . 9H{sub 2}O added was studied. The surface processes were characterised by the in situ normal Raman spectroscopy (NRS) and ex situ techniques; X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive X-ray (EDX). The open circuit potential (OCP) was monitored during in situ NRS measurements, and potentiodynamic anodic polarization measurements were carried out to reveal electrochemical behaviour of iron electrode. Open circuit potential-time transients indicated that the native oxide is unstable in deaerated bicarbonate solution and undergoes reductive dissolution (i.e. autoreduction) leaving the metallic Fe covered by Fe(OH){sub 2}, adsorbed OH{sup -}, and patches of 'magnetite-like' oxide. Immediately upon injection of the Na{sub 2}S-solution the iron interface undergoes complex redox surface processes and a poorly crystalline FeS film forms. Potentiodynamic anodic polarization measurements indicated a mechanical breakdown of the FeS film. The origin and initiation of this breakdown process is not clear but is probably a result of internal stress developed during film growth. Based on surface studies supported by electrochemical measurements, a conceptual model for the complex redox processes occurring at the iron interface is proposed. This model describes the structural development of a poorly crystalline FeS, which breaks down, allowing further dissolution of the Fe and formation of FeOOH at the interface. Simultaneously and despite the existence of thick layer of FeS the entrance of hydrogen was evident as the typical hydrogen cracks in bulk of the

Redox-Enabled, pH-Disabled Pyrazoline-Ferrocene INHIBIT Logic Gates.

Science.gov (United States)

Scerri, Glenn J; Cini, Miriam; Schembri, Jonathan S; da Costa, Paola F; Johnson, Alex D; Magri, David C

2017-07-05

Pyrazoline-ferrocene conjugates with an "electron-donor-spacer-fluorophore-receptor" format are demonstrated as redox-fluorescent two-input INHIBIT logic gates. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Integrated carbon, sulfur, and nitrogen isotope chemostratigraphy of the Ediacaran Lantian Formation in South China: Spatial gradient, ocean redox oscillation, and fossil distribution.

Science.gov (United States)

Wang, W; Guan, C; Zhou, C; Peng, Y; Pratt, L M; Chen, X; Chen, L; Chen, Z; Yuan, X; Xiao, S

2017-07-01

The Ediacaran Doushantuo Formation in South China is a prime target for geobiological investigation because it offers opportunities to integrate chemostratigraphic and paleobiological data. Previous studies were mostly focused on successions in shallow-water shelf facies, but data from deep-water successions are needed to fully understand basinal redox structures. Here, we report δ 13 C carb , δ 13 C org , δ 34 S pyr , δ 34 S CAS , and δ 15 N sed data from a drill core of the fossiliferous Lantian Formation, which is a deep-water equivalent of the Doushantuo Formation. Our data confirm a large (>10‰) spatial gradient in δ 13 C carb in the lower Doushantuo/Lantian formations, but this gradient is probably due to the greater sensitivity of carbonate-poor deep-water sediments to isotopic mixing with 13 C-depleted carbonate cements. A pronounced negative δ 13 C carb excursion (EN3) in the upper Doushantuo/Lantian formations, however, is spatially consistent and may be an equivalent of the Shuram excursion. δ 34 S pyr is more negative in deeper-water facies than in shallow-water facies, particularly in the lower Doushantuo/Lantian formations, and this spatial pattern is interpreted as evidence for ocean redox stratification: Pyrite precipitated in euxinic deep waters has lower δ 34 S pyr than that formed within shallow-water sediments. The Lantian Formation was probably deposited in oscillating oxic and euxinic conditions. Euxinic black shales have higher TOC and TN contents, but lower δ 34 S pyr and δ 15 N sed values. In euxinic environments, pyrite was predominantly formed in the water column and organic nitrogen was predominantly derived from nitrogen fixation or NH 4 + assimilation because of quantitative denitrification, resulting in lower δ 34 S pyr and δ 15 N sed values. Benthic macroalgae and putative animals occur exclusively in euxinic black shales. If preserved in situ, these organisms must have lived in brief oxic episodes punctuating largely

Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility

Science.gov (United States)

Wedege, Kristina; Dražević, Emil; Konya, Denes; Bentien, Anders

2016-01-01

Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined with single cell battery RFB tests on selected redox pairs. Data shows that both the solubility and redox potential are determined by the position of the side groups and only to a small extent by the number of side groups. Additionally, the chemical stability and possible degradation mechanisms leading to capacity loss over time are discussed. The main challenge for the development of all-organic RFBs is to identify a redox pair for the positive side with sufficiently high stability and redox potential that enables battery cell potentials above 1 V. PMID:27966605

Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility

Science.gov (United States)

Wedege, Kristina; Dražević, Emil; Konya, Denes; Bentien, Anders

2016-12-01

Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined with single cell battery RFB tests on selected redox pairs. Data shows that both the solubility and redox potential are determined by the position of the side groups and only to a small extent by the number of side groups. Additionally, the chemical stability and possible degradation mechanisms leading to capacity loss over time are discussed. The main challenge for the development of all-organic RFBs is to identify a redox pair for the positive side with sufficiently high stability and redox potential that enables battery cell potentials above 1 V.

Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility

OpenAIRE

Kristina Wedege; Emil Dražević; Denes Konya; Anders Bentien

2016-01-01

Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined ...

Metabolic Control of Redox and Redox Control of Metabolism in Plants

Science.gov (United States)

Fernie, Alisdair R.

2014-01-01

Abstract Significance: Reduction-oxidation (Redox) status operates as a major integrator of subcellular and extracellular metabolism and is simultaneously itself regulated by metabolic processes. Redox status not only dominates cellular metabolism due to the prominence of NAD(H) and NADP(H) couples in myriad metabolic reactions but also acts as an effective signal that informs the cell of the prevailing environmental conditions. After relay of this information, the cell is able to appropriately respond via a range of mechanisms, including directly affecting cellular functioning and reprogramming nuclear gene expression. Recent Advances: The facile accession of Arabidopsis knockout mutants alongside the adoption of broad-scale post-genomic approaches, which are able to provide transcriptomic-, proteomic-, and metabolomic-level information alongside traditional biochemical and emerging cell biological techniques, has dramatically advanced our understanding of redox status control. This review summarizes redox status control of metabolism and the metabolic control of redox status at both cellular and subcellular levels. Critical Issues: It is becoming apparent that plastid, mitochondria, and peroxisome functions influence a wide range of processes outside of the organelles themselves. While knowledge of the network of metabolic pathways and their intraorganellar redox status regulation has increased in the last years, little is known about the interorganellar redox signals coordinating these networks. A current challenge is, therefore, synthesizing our knowledge and planning experiments that tackle redox status regulation at both inter- and intracellular levels. Future Directions: Emerging tools are enabling ever-increasing spatiotemporal resolution of metabolism and imaging of redox status components. Broader application of these tools will likely greatly enhance our understanding of the interplay of redox status and metabolism as well as elucidating and

Integration of superoxide formation and cristae morphology for mitochondrial redox signaling

Czech Academy of Sciences Publication Activity Database

Plecitá-Hlavatá, Lydie; Ježek, Petr

2016-01-01

Roč. 80, Nov (2016), s. 31-50 ISSN 1357-2725 R&D Projects: GA ČR(CZ) GA16-04788S; GA ČR(CZ) GA16-06700S Institutional support: RVO:67985823 Keywords : redox signaling * mitochondrial cristae morphology * ATP-synthase dimers * OPA1 * MICOS Subject RIV: EA - Cell Biology Impact factor: 3.505, year: 2016

Amplified and in situ detection of redox-active metabolite using a biobased redox capacitor.

Science.gov (United States)

Kim, Eunkyoung; Gordonov, Tanya; Bentley, William E; Payne, Gregory F

2013-02-19

Redox cycling provides a mechanism to amplify electrochemical signals for analyte detection. Previous studies have shown that diverse mediators/shuttles can engage in redox-cycling reactions with a biobased redox capacitor that is fabricated by grafting redox-active catechols onto a chitosan film. Here, we report that redox cycling with this catechol-chitosan redox capacitor can amplify electrochemical signals for detecting a redox-active bacterial metabolite. Specifically, we studied the redox-active bacterial metabolite pyocyanin that is reported to be a virulence factor and signaling molecule for the opportunistic pathogen P. aeruginosa. We demonstrate that redox cycling can amplify outputs from various electrochemical methods (cyclic voltammetry, chronocoulometry, and differential pulse voltammetry) and can lower the detection limit of pyocyanin to 50 nM. Further, the compatibility of this biobased redox capacitor allows the in situ monitoring of the production of redox-active metabolites (e.g., pyocyanin) during the course of P. aeruginosa cultivation. We anticipate that the amplified output of redox-active virulence factors should permit an earlier detection of life-threatening infections by the opportunistic pathogen P. aeruginosa while the "bio-compatibility" of this measurement approach should facilitate in situ study of the spatiotemporal dynamics of bacterial redox signaling.

Heterogeneous-catalytic redox reactions in nitrate - formate systems

International Nuclear Information System (INIS)

Ananiev, A.V.; Shilov, V.P.; Tananaev, I.G.; Brossard, Ph.; Broudic, J.Ch.

2000-01-01

It was found that an intensive destruction of various organic and mineral substances - usual components of aqueous waste solutions (oxalic acid, complexones, urea, hydrazine, ammonium nitrate, etc.) takes place under the conditions of catalytic denitration. Kinetics and mechanisms of urea and ammonium nitrate decomposition in the system HNO 3 - HCOOH - Pt/SiO 2 are comprehensively investigated. The behaviour of uranium, neptunium and plutonium under the conditions of catalytic denitration is studied. It is shown, that under the certain conditions the formic acid is an effective reducer of the uranium (VI), neptunium (VI, V) and plutonium (VI, IV) ions. Kinetics of heterogeneous-catalytic red-ox reactions of uranium (VI), neptunium (VI, V) and plutonium (VI, IV) with formic acid are investigated. The mechanisms of the appropriate reactions are evaluated. (authors)

Improving metabolic efficiency of the reverse beta-oxidation cycle by balancing redox cofactor requirement.

Science.gov (United States)

Wu, Junjun; Zhang, Xia; Zhou, Peng; Huang, Jiaying; Xia, Xiudong; Li, Wei; Zhou, Ziyu; Chen, Yue; Liu, Yinghao; Dong, Mingsheng

2017-11-01

Previous studies have made many exciting achievements on pushing the functional reversal of beta-oxidation cycle (r-BOX) to more widespread adoption for synthesis of a wide variety of fuels and chemicals. However, the redox cofactor requirement for the efficient operation of r-BOX remains unclear. In this work, the metabolic efficiency of r-BOX for medium-chain fatty acid (C 6 -C 10 , MCFA) production was optimized by redox cofactor engineering. Stoichiometric analysis of the r-BOX pathway and further experimental examination identified NADH as a crucial determinant of r-BOX process yield. Furthermore, the introduction of formate dehydrogenase from Candida boidinii using fermentative inhibitor byproduct formate as a redox NADH sink improved MCFA titer from initial 1.2g/L to 3.1g/L. Moreover, coupling of increasing the supply of acetyl-CoA with NADH to achieve fermentative redox balance enabled product synthesis at maximum titers. To this end, the acetate re-assimilation pathway was further optimized to increase acetyl-CoA availability associated with the new supply of NADH. It was found that the acetyl-CoA synthetase activity and intracellular ATP levels constrained the activity of acetate re-assimilation pathway, and 4.7g/L of MCFA titer was finally achieved after alleviating these two limiting factors. To the best of our knowledge, this represented the highest titer reported to date. These results demonstrated that the key constraint of r-BOX was redox imbalance and redox engineering could further unleash the lipogenic potential of this cycle. The redox engineering strategies could be applied to acetyl-CoA-derived products or other bio-products requiring multiple redox cofactors for biosynthesis. Copyright © 2017 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

Redox signaling in the growth and development of colonial hydroids.

Science.gov (United States)

Blackstone, Neil W

2003-02-01

Redox signaling provides a quick and efficient mechanism for clonal or colonial organisms to adapt their growth and development to aspects of the environment, e.g. the food supply. A 'signature' of mitochondrial redox signaling, particularly as mediated by reactive oxygen species (ROS), can be elucidated by experimental manipulation of the electron transport chain. The major sites of ROS formation are found at NADH dehydrogenase of complex I and at the interface between coenzyme Q and complex III. Inhibitors of complex III should thus upregulate ROS from both sites; inhibitors of complex I should upregulate ROS from the first but not the second site, while uncouplers of oxidative phosphorylation should downregulate ROS from both sites. To investigate the possibility of such redox signaling, perturbations of colony growth and development were carried out using the hydroid Podocoryna carnea. Oxygen uptake of colonies was measured to determine comparable physiological doses of antimycin A(1) (an inhibitor of complex III), rotenone (an inhibitor of complex I) and carbonyl cyanide m-chlorophenylhydrazone (CCCP; an uncoupler of oxidative phosphorylation). Using these doses, clear effects on colony growth and development were obtained. Treatment with antimycin A(1) results in 'runner-like' colony growth, with widely spaced polyps and stolon branches, while treatment with CCCP results in 'sheet-like' growth, with closely spaced polyps and stolon branches. Parallel results have been obtained previously with azide, an inhibitor of complex IV, and dinitrophenol, another uncoupler of oxidative phosphorylation. Perhaps surprisingly, rotenone produced effects on colony development similar to those of CCCP. Assays of peroxides using 2',7'-dichlorofluorescin diacetate and fluorescent microscopy suggest a moderate difference in ROS formation between the antimycin and rotenone treatments. The second site of ROS formation (the interface between coenzyme Q and complex III) may thus

A redox-assisted molecular assembly of molybdenum oxide amine composite nanobelts

International Nuclear Information System (INIS)

Luo Haiyan; Wei Mingdeng; Wei Kemei

2011-01-01

Research highlights: → Nanobelts of molybdenum oxide amine were first synthesized via a redox-assisted molecular assembly route. → These nanobelts are highly crystalline with a several tens of micrometers in length and 20-30 nm in thickness. - Abstract: In this paper, the nanobelts of molybdenum oxide amine composite were successfully synthesized via a redox-assisted molecular assembly route under the hydrothermal conditions. The synthesized nanobelts were characterized by XRD, SEM, TEM, TG and FT-IR measurements. The thickness of nanobelts is found to be ca. 20-30 nm and their lengths are up to several tens of micrometers. Based on a series of the experimental results, a possible model, redox-intercalation-exfoliation, was suggested for the formation of nanobelts of molybdenum oxide amine composite.

The Redox Proteome*

Science.gov (United States)

Go, Young-Mi; Jones, Dean P.

2013-01-01

The redox proteome consists of reversible and irreversible covalent modifications that link redox metabolism to biologic structure and function. These modifications, especially of Cys, function at the molecular level in protein folding and maturation, catalytic activity, signaling, and macromolecular interactions and at the macroscopic level in control of secretion and cell shape. Interaction of the redox proteome with redox-active chemicals is central to macromolecular structure, regulation, and signaling during the life cycle and has a central role in the tolerance and adaptability to diet and environmental challenges. PMID:23861437

Chloroplast Redox Poise

DEFF Research Database (Denmark)

Steccanella, Verdiana

the redox status of the plastoquinone pool and chlorophyll biosynthesis. Furthermore, in the plant cell, the equilibrium between redox reactions and ROS signals is also maintained by various balancing mechanisms among which the thioredoxin reductase-thioredoxin system (TR-Trx) stands out as a mediator......The redox state of the chloroplast is maintained by a delicate balance between energy production and consumption and is affected by the need to avoid increased production of reactive oxygen species (ROS). Redox power and ROS generated in the chloroplast are essential for maintaining physiological...... metabolic pathways and for optimizing chloroplast functions. The redox poise of photosynthetic electron transport components like plastoquinone is crucial to initiate signaling cascades and might also be involved in key biosynthetic pathways such as chlorophyll biosynthesis. We, therefore, explored...

A stability comparison of redox-active layers produced by chemical coupling of an osmium redox complex to pre-functionalized gold and carbon electrodes

International Nuclear Information System (INIS)

Boland, Susan; Foster, Kevin; Leech, Donal

2009-01-01

The production of stable redox active layers on electrode surfaces is a key factor for the development of practical electronic and electrochemical devices. Here, we report on a comparison of the stability of redox layers formed by covalently coupling an osmium redox complex to pre-functionalized gold and graphite electrode surfaces. Pre-treatment of gold and graphite electrodes to provide surface carboxylic acid groups is achieved via classical thiolate self-assembled monolayer formation on gold surfaces and the electro-reduction of an in situ generated aryldiazonium salt from 4-aminobenzoic acid on gold, glassy carbon and graphite surfaces. These surfaces have been characterized by AFM and electrochemical blocking studies. The surface carboxylate is then used to tether an osmium complex, [Os(2,2'-bipyridyl) 2 (4-aminomethylpyridine)Cl]PF 6 , to provide a covalently bound redox active layer, E 0 '' of 0.29 V (vs. Ag/AgCl in phosphate buffer, pH 7.4), on the pre-treated electrodes. The aryldiazonium salt-treated carbon-based surfaces showed the greatest stability, represented by a decrease of <5% in the peak current for the Os(II/III) redox transition of the immobilized complex over a 3-day period, compared to a decrease of 19% and 14% for the aryldiazonium salt treated and thiolate treated gold surfaces, respectively, over the same period

Light-Front Holography and the Light-Front Schrodinger Equation

Energy Technology Data Exchange (ETDEWEB)

Brodsky, Stanley J.; de Teramond, Guy

2012-08-15

One of the most important nonperturbative methods for solving QCD is quantization at fixed light-front time {tau} = t+z=c - Dirac's 'Front Form'. The eigenvalues of the light-front QCD Hamiltonian predict the hadron spectrum and the eigensolutions provide the light-front wavefunctions which describe hadron structure. More generally, we show that the valence Fock-state wavefunctions of the light-front QCD Hamiltonian satisfy a single-variable relativistic equation of motion, analogous to the nonrelativistic radial Schrodinger equation, with an effective confining potential U which systematically incorporates the effects of higher quark and gluon Fock states. We outline a method for computing the required potential from first principles in QCD. The holographic mapping of gravity in AdS space to QCD, quantized at fixed light-front time, yields the same light front Schrodinger equation; in fact, the soft-wall AdS/QCD approach provides a model for the light-front potential which is color-confining and reproduces well the light-hadron spectrum. One also derives via light-front holography a precise relation between the bound-state amplitudes in the fifth dimension of AdS space and the boost-invariant light-front wavefunctions describing the internal structure of hadrons in physical space-time. The elastic and transition form factors of the pion and the nucleons are found to be well described in this framework. The light-front AdS/QCD holographic approach thus gives a frame-independent first approximation of the color-confining dynamics, spectroscopy, and excitation spectra of relativistic light-quark bound states in QCD.

Assessment of nitric oxide (NO) redox reactions contribution to nitrous oxide (N2 O) formation during nitrification using a multispecies metabolic network model.

Science.gov (United States)

Perez-Garcia, Octavio; Chandran, Kartik; Villas-Boas, Silas G; Singhal, Naresh

2016-05-01

Over the coming decades nitrous oxide (N2O) is expected to become a dominant greenhouse gas and atmospheric ozone depleting substance. In wastewater treatment systems, N2O is majorly produced by nitrifying microbes through biochemical reduction of nitrite (NO2(-)) and nitric oxide (NO). However it is unknown if the amount of N2O formed is affected by alternative NO redox reactions catalyzed by oxidative nitrite oxidoreductase (NirK), cytochromes (i.e., P460 [CytP460] and 554 [Cyt554 ]) and flavohemoglobins (Hmp) in ammonia- and nitrite-oxidizing bacteria (AOB and NOB, respectively). In this study, a mathematical model is developed to assess how N2O formation is affected by such alternative nitrogen redox transformations. The developed multispecies metabolic network model captures the nitrogen respiratory pathways inferred from genomes of eight AOB and NOB species. The performance of model variants, obtained as different combinations of active NO redox reactions, was assessed against nine experimental datasets for nitrifying cultures producing N2O at different concentration of electron donor and acceptor. Model predicted metabolic fluxes show that only variants that included NO oxidation to NO2(-) by CytP460 and Hmp in AOB gave statistically similar estimates to observed production rates of N2O, NO, NO2(-) and nitrate (NO3(-)), together with fractions of AOB and NOB species in biomass. Simulations showed that NO oxidation to NO2(-) decreased N2O formation by 60% without changing culture's NO2(-) production rate. Model variants including NO reduction to N2O by Cyt554 and cNor in NOB did not improve the accuracy of experimental datasets estimates, suggesting null N2O production by NOB during nitrification. Finally, the analysis shows that in nitrifying cultures transitioning from dissolved oxygen levels above 3.8 ± 0.38 to <1.5 ± 0.8 mg/L, NOB cells can oxidize the NO produced by AOB through reactions catalyzed by oxidative NirK. © 2015 Wiley Periodicals, Inc.

Chloride supporting electrolytes for all-vanadium redox flow batteries.

Science.gov (United States)

Kim, Soowhan; Vijayakumar, M; Wang, Wei; Zhang, Jianlu; Chen, Baowei; Nie, Zimin; Chen, Feng; Hu, Jianzhi; Li, Liyu; Yang, Zhenguo

2011-10-28

This paper examines vanadium chloride solutions as electrolytes for an all-vanadium redox flow battery. The chloride solutions were capable of dissolving more than 2.3 M vanadium at varied valence states and remained stable at 0-50 °C. The improved stability appeared due to the formation of a vanadium dinuclear [V(2)O(3)·4H(2)O](4+) or a dinuclear-chloro complex [V(2)O(3)Cl·3H(2)O](3+) in the solutions over a wide temperature range. The all-vanadium redox flow batteries with the chloride electrolytes demonstrated excellent reversibility and fairly high efficiencies. Only negligible, if any, gas evolution was observed. The improved energy capacity and good performance, along with the ease in heat management, would lead to substantial reduction in capital cost and life-cycle cost, making the vanadium chloride redox flow battery a promising candidate for stationary applications. This journal is © the Owner Societies 2011

Radiation hydrodynamical instabilities in cosmological and galactic ionization fronts

Science.gov (United States)

Whalen, Daniel J.; Norman, Michael L.

2011-11-01

Ionization fronts, the sharp radiation fronts behind which H/He ionizing photons from massive stars and galaxies propagate through space, were ubiquitous in the universe from its earliest times. The cosmic dark ages ended with the formation of the first primeval stars and galaxies a few hundred Myr after the Big Bang. Numerical simulations suggest that stars in this era were very massive, 25-500 solar masses, with H(II) regions of up to 30,000 light-years in diameter. We present three-dimensional radiation hydrodynamical calculations that reveal that the I-fronts of the first stars and galaxies were prone to violent instabilities, enhancing the escape of UV photons into the early intergalactic medium (IGM) and forming clumpy media in which supernovae later exploded. The enrichment of such clumps with metals by the first supernovae may have led to the prompt formation of a second generation of low-mass stars, profoundly transforming the nature of the first protogalaxies. Cosmological radiation hydrodynamics is unique because ionizing photons coupled strongly to both gas flows and primordial chemistry at early epochs, introducing a hierarchy of disparate characteristic timescales whose relative magnitudes can vary greatly throughout a given calculation. We describe the adaptive multistep integration scheme we have developed for the self-consistent transport of both cosmological and galactic ionization fronts.

Probing Fe (III)/Fe (II) redox potential in a clayey material

International Nuclear Information System (INIS)

Tournassat, Christophe; Chainet, Fabien; Betelu, Stephanie; Hadi, Jebril; Gaucher, Eric C.; Ignatiadis, Ioannis; Greneche, Jean-Marc; Charlet, Laurent

2010-01-01

Document available in extended abstract form only. Redox is one of the main factors affecting the migration of redox-sensitive radionuclides. As a consequence reducing conditions are considered of strategic importance for the confinement properties of a clayey formation towards nuclear waste. A representative redox potential of clay formation such as Callovian- Oxfordian (COx) can be derived from thermodynamic calculations considering equilibrium between observed redox phases such as pyrite and siderite. However, there is little information on the reactivity of the different reservoirs of redox constituents in this type of complex material. The present study aims at investigating the reactivity of the Fe(III)/Fe(II) redox couple in the structure of clay minerals using different investigation methods: electrochemistry and O 2 reduction kinetic experiments. Clay modified electrodes were specifically designed to probe Fe(III)/Fe(II) redox potential in the structure of clay minerals. The clay fraction of a Callovian-Oxfordian argillite sample originating from the same level than ANDRA underground research laboratory was used after pre-treatment to remove organic matter and accessory minerals such as pyrite that could influence redox potential measurements. These electrodes were used to verify the validity of the model of Favre et al. (2006) that links the redox potential (E clay ) to the the Fe(II)/Fe tot ratio in the structure (m rel ), the pH and the sodium concentration in solution: equation 1. The good agreement between direct potential measurements and model prediction provides a strong evidence of the relevance of this model in our experimental conditions although the clay composition and its too low Fe content do not a priori fulfil the conditions set by Drits and Manceau (2000) for the calculation of K 0 parameter. Following the verification of the model, we tried to apply it to the specific case of a Callovian-Oxfordian sample that had been very well preserved

Redox regulation of cell proliferation: Bioinformatics and redox proteomics approaches to identify redox-sensitive cell cycle regulators.

Science.gov (United States)

Foyer, Christine H; Wilson, Michael H; Wright, Megan H

2018-03-29

Plant stem cells are the foundation of plant growth and development. The balance of quiescence and division is highly regulated, while ensuring that proliferating cells are protected from the adverse effects of environment fluctuations that may damage the genome. Redox regulation is important in both the activation of proliferation and arrest of the cell cycle upon perception of environmental stress. Within this context, reactive oxygen species serve as 'pro-life' signals with positive roles in the regulation of the cell cycle and survival. However, very little is known about the metabolic mechanisms and redox-sensitive proteins that influence cell cycle progression. We have identified cysteine residues on known cell cycle regulators in Arabidopsis that are potentially accessible, and could play a role in redox regulation, based on secondary structure and solvent accessibility likelihoods for each protein. We propose that redox regulation may function alongside other known posttranslational modifications to control the functions of core cell cycle regulators such as the retinoblastoma protein. Since our current understanding of how redox regulation is involved in cell cycle control is hindered by a lack of knowledge regarding both which residues are important and how modification of those residues alters protein function, we discuss how critical redox modifications can be mapped at the molecular level. Crown Copyright © 2018. Published by Elsevier Inc. All rights reserved.

Redox sensor proteins for highly sensitive direct imaging of intracellular redox state.

Science.gov (United States)

Sugiura, Kazunori; Nagai, Takeharu; Nakano, Masahiro; Ichinose, Hiroshi; Nakabayashi, Takakazu; Ohta, Nobuhiro; Hisabori, Toru

2015-02-13

Intracellular redox state is a critical factor for fundamental cellular functions, including regulation of the activities of various metabolic enzymes as well as ROS production and elimination. Genetically-encoded fluorescent redox sensors, such as roGFP (Hanson, G. T., et al. (2004)) and Redoxfluor (Yano, T., et al. (2010)), have been developed to investigate the redox state of living cells. However, these sensors are not useful in cells that contain, for example, other colored pigments. We therefore intended to obtain simpler redox sensor proteins, and have developed oxidation-sensitive fluorescent proteins called Oba-Q (oxidation balance sensed quenching) proteins. Our sensor proteins derived from CFP and Sirius can be used to monitor the intracellular redox state as their fluorescence is drastically quenched upon oxidation. These blue-shifted spectra of the Oba-Q proteins enable us to monitor various redox states in conjunction with other sensor proteins. Copyright © 2015 Elsevier Inc. All rights reserved.

Redox Regulation of Mitochondrial Function

Science.gov (United States)

Handy, Diane E.

2012-01-01

Abstract Redox-dependent processes influence most cellular functions, such as differentiation, proliferation, and apoptosis. Mitochondria are at the center of these processes, as mitochondria both generate reactive oxygen species (ROS) that drive redox-sensitive events and respond to ROS-mediated changes in the cellular redox state. In this review, we examine the regulation of cellular ROS, their modes of production and removal, and the redox-sensitive targets that are modified by their flux. In particular, we focus on the actions of redox-sensitive targets that alter mitochondrial function and the role of these redox modifications on metabolism, mitochondrial biogenesis, receptor-mediated signaling, and apoptotic pathways. We also consider the role of mitochondria in modulating these pathways, and discuss how redox-dependent events may contribute to pathobiology by altering mitochondrial function. Antioxid. Redox Signal. 16, 1323–1367. PMID:22146081

Graphite felt modified with bismuth nanoparticles as negative electrode in a vanadium redox flow battery.

Science.gov (United States)

Suárez, David J; González, Zoraida; Blanco, Clara; Granda, Marcos; Menéndez, Rosa; Santamaría, Ricardo

2014-03-01

A graphite felt decorated with bismuth nanoparticles was studied as negative electrode in a vanadium redox flow battery (VRFB). The results confirm the excellent electrochemical performance of the bismuth modified electrode in terms of the reversibility of the V(3+) /V(2+) redox reactions and its long-term cycling performance. Moreover a mechanism that explains the role that Bi nanoparticles play in the redox reactions in this negative half-cell is proposed. Bi nanoparticles favor the formation of BiHx , an intermediate that reduces V(3+) to V(2+) and, therefore, inhibits the competitive irreversible reaction of hydrogen formation (responsible for the commonly observed loss of Coulombic efficiency of VRFBs). Thus, the total charge consumed during the cathodic sweep in this electrode is used to reduce V(3+) to V(2+) , resulting in a highly reversible and efficient process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterisation of the Interaction between Toroidal Vortex Structures and Flame Front Propagation

International Nuclear Information System (INIS)

Long, E J; Hargrave, G K; Jarvis, S; Justham, T; Halliwell, N

2006-01-01

Experimental laser diagnostic data is presented for flame characterisation during interactions with toroidal vortices generated in the wake of an annular obstacle. A novel twin section combustion chamber has been utilised to allow the controlled formation of stable eddy structures into which a flame front can propagate. High speed laser sheet visualisation was employed to record the flow field and flame front temporal development and high-speed digital particle image velocimetry was used to quantify the velocity field of the unburnt mixture ahead of the flame front. Results provide characterisation of the toroidal vortex/flame front interaction for a range of vortex scales of and recirculation strengths

Characterisation of the Interaction between Toroidal Vortex Structures and Flame Front Propagation

Energy Technology Data Exchange (ETDEWEB)

Long, E J; Hargrave, G K; Jarvis, S; Justham, T; Halliwell, N [Wolfson School of Mechanical and Manufacturing Engineering, Loughborough University, Loughborough, Leicestershire, LE11 3TU (United Kingdom)

2006-07-15

Experimental laser diagnostic data is presented for flame characterisation during interactions with toroidal vortices generated in the wake of an annular obstacle. A novel twin section combustion chamber has been utilised to allow the controlled formation of stable eddy structures into which a flame front can propagate. High speed laser sheet visualisation was employed to record the flow field and flame front temporal development and high-speed digital particle image velocimetry was used to quantify the velocity field of the unburnt mixture ahead of the flame front. Results provide characterisation of the toroidal vortex/flame front interaction for a range of vortex scales of and recirculation strengths.

Characterisation of the Interaction between Toroidal Vortex Structures and Flame Front Propagation

Science.gov (United States)

Long, E. J.; Hargrave, G. K.; Jarvis, S.; Justham, T.; Halliwell, N.

2006-07-01

Experimental laser diagnostic data is presented for flame characterisation during interactions with toroidal vortices generated in the wake of an annular obstacle. A novel twin section combustion chamber has been utilised to allow the controlled formation of stable eddy structures into which a flame front can propagate. High speed laser sheet visualisation was employed to record the flow field and flame front temporal development and high-speed digital particle image velocimetry was used to quantify the velocity field of the unburnt mixture ahead of the flame front. Results provide characterisation of the toroidal vortex/flame front interaction for a range of vortex scales of and recirculation strengths.

Oxidative Stress in Cardiovascular Diseases: Involvement of Nrf2 Antioxidant Redox Signaling in Macrophage Foam Cells Formation

Directory of Open Access Journals (Sweden)

Bee Kee Ooi

2017-11-01

Full Text Available Oxidative stress is an important risk factor contributing to the pathogenesis of cardiovascular diseases. Oxidative stress that results from excessive reactive oxygen species (ROS production accounts for impaired endothelial function, a process which promotes atherosclerotic lesion or fatty streaks formation (foam cells. Nuclear factor erythroid 2-related factor 2 (Nrf2 is a transcription factor involved in cellular redox homeostasis. Upon exposure to oxidative stress, Nrf2 is dissociated from its inhibitor Keap-1 and translocated into the nucleus, where it results in the transcriptional activation of cell defense genes. Nrf2 has been demonstrated to be involved in the protection against foam cells formation by regulating the expression of antioxidant proteins (HO-1, Prxs, and GPx1, ATP-binding cassette (ABC efflux transporters (ABCA1 and ABCG1 and scavenger receptors (scavenger receptor class B (CD36, scavenger receptor class A (SR-A and lectin-type oxidized LDL receptor (LOX-1. However, Nrf2 has also been reported to exhibit pro-atherogenic effects. A better understanding on the mechanism of Nrf2 in oxidative stress-induced cardiac injury, as well as the regulation of cholesterol uptake and efflux, are required before it can serve as a novel therapeutic target for cardiovascular diseases prevention and treatment.

Inhibition of pH fronts in corrosion cells due to the formation of cerium hydroxide

NARCIS (Netherlands)

Soestbergen, M. van; Erich, S.J.F.; Huinink, H.P.; Adan, O.C.G.

2013-01-01

The effect of cerium-based corrosion inhibitors on the pH front between the alkaline cathode and acidic anode in corrosion cells has been studied. The cerium component of these inhibitors can affect the pH front since it precipitates in an alkaline environment as cerium hydroxide, which is important

Wave fronts and spatiotemporal chaos in an array of coupled Lorenz oscillators

International Nuclear Information System (INIS)

Pazo, Diego; Montejo, Noelia; Perez-Munuzuri, Vicente

2001-01-01

The effects of coupling strength and single-cell dynamics (SCD) on spatiotemporal pattern formation are studied in an array of Lorenz oscillators. Different spatiotemporal structures (stationary patterns, propagating wave fronts, short wavelength bifurcation) arise for bistable SCD, and two well differentiated types of spatiotemporal chaos for chaotic SCD (in correspondence with the transition from stationary patterns to propagating fronts). Wave-front propagation in the bistable regime is studied in terms of global bifurcation theory, while a short wavelength pattern region emerges through a pitchfork bifurcation

pH and redox responsive polymer for antifouling surface coating

International Nuclear Information System (INIS)

Lee, Kang Seok; In, Insik; Park, Sung Young

2014-01-01

Graphical abstract: Dual responsive surface with highly fouling resistance with the formation of a pH-dependent benzoic imine and redox-sensitive disulfide bond has been developed using a catechol/benzoic acid conjugated polymer and disulfide containing amine end-capped Pluronic. - Highlights: • Stimuli-responsive antifouling surface was prepared by layer-by-layer method. • The surface contact angle showed responsive behavior via pH and redox environments. • Simply coated polymer completely prevented cell adhesion onto surfaces. - Abstract: A dual environmentally responsive polymer with a highly fouling-resistant surface has been developed using poly[(hydroxyethyl methacrylate-g-benzoic acid)-co-(dimethylaminoethyl methacrylate-g-2-chloro-3′, 4′-dihydroxyacetophenone)] [poly[(HEMA-BA)-co-(DMAEMA-CCDP)], P1] as a coating material. The redox-sensitive disulfide containing amine end-capped Pluronic [(Plu-S-S-NH 2 ), P2] was then introduced over the P1 surface via the formation of a pH-dependent benzoic imine bond, where the polyethylene glycol (PEG) acts as an antifouling agent. The successful adhesion of P1 and the deposition of P2 onto the P1-coated substrate were ascertained with X-ray photoelectron spectroscopy (XPS). In vitro cell adhesion followed by scanning electron microscopy (SEM) indicated an excellent antifouling nature of the P2 layer. Consequently, the reattachment of Hela cells was strongly observed when P2 layered on P1-coated substrates (P1–P2) was pretreated at lower pH and high redox conditions. The P1–P2 bilayer-coated substrate has exhibited a great advantage in its effective antifouling behaviors with well-tuned cell attachment and detachment

pH and redox responsive polymer for antifouling surface coating

Energy Technology Data Exchange (ETDEWEB)

Lee, Kang Seok [Department of Chemical and Biological Engineering, Korea National University of Transportation, Chungju, 380-702 (Korea, Republic of); In, Insik, E-mail: in1@ut.ac.kr [Department of Polymer Science and Engineering, Korea National University of Transportation, Chungju, 380-702 (Korea, Republic of); Department of IT Convergence, Korea National University of Transportation, Chungju, 380-702 (Korea, Republic of); Park, Sung Young, E-mail: parkchem@ut.ac.kr [Department of Chemical and Biological Engineering, Korea National University of Transportation, Chungju, 380-702 (Korea, Republic of); Department of IT Convergence, Korea National University of Transportation, Chungju, 380-702 (Korea, Republic of)

2014-09-15

Graphical abstract: Dual responsive surface with highly fouling resistance with the formation of a pH-dependent benzoic imine and redox-sensitive disulfide bond has been developed using a catechol/benzoic acid conjugated polymer and disulfide containing amine end-capped Pluronic. - Highlights: • Stimuli-responsive antifouling surface was prepared by layer-by-layer method. • The surface contact angle showed responsive behavior via pH and redox environments. • Simply coated polymer completely prevented cell adhesion onto surfaces. - Abstract: A dual environmentally responsive polymer with a highly fouling-resistant surface has been developed using poly[(hydroxyethyl methacrylate-g-benzoic acid)-co-(dimethylaminoethyl methacrylate-g-2-chloro-3′, 4′-dihydroxyacetophenone)] [poly[(HEMA-BA)-co-(DMAEMA-CCDP)], P1] as a coating material. The redox-sensitive disulfide containing amine end-capped Pluronic [(Plu-S-S-NH{sub 2}), P2] was then introduced over the P1 surface via the formation of a pH-dependent benzoic imine bond, where the polyethylene glycol (PEG) acts as an antifouling agent. The successful adhesion of P1 and the deposition of P2 onto the P1-coated substrate were ascertained with X-ray photoelectron spectroscopy (XPS). In vitro cell adhesion followed by scanning electron microscopy (SEM) indicated an excellent antifouling nature of the P2 layer. Consequently, the reattachment of Hela cells was strongly observed when P2 layered on P1-coated substrates (P1–P2) was pretreated at lower pH and high redox conditions. The P1–P2 bilayer-coated substrate has exhibited a great advantage in its effective antifouling behaviors with well-tuned cell attachment and detachment.

Redox signaling in plants.

Science.gov (United States)

Foyer, Christine H; Noctor, Graham

2013-06-01

Our aim is to deliver an authoritative and challenging perspective of current concepts in plant redox signaling, focusing particularly on the complex interface between the redox and hormone-signaling pathways that allow precise control of plant growth and defense in response to metabolic triggers and environmental constraints and cues. Plants produce significant amounts of singlet oxygen and other reactive oxygen species (ROS) as a result of photosynthetic electron transport and metabolism. Such pathways contribute to the compartment-specific redox-regulated signaling systems in plant cells that convey information to the nucleus to regulate gene expression. Like the chloroplasts and mitochondria, the apoplast-cell wall compartment makes a significant contribution to the redox signaling network, but unlike these organelles, the apoplast has a low antioxidant-buffering capacity. The respective roles of ROS, low-molecular antioxidants, redox-active proteins, and antioxidant enzymes are considered in relation to the functions of plant hormones such as salicylic acid, jasmonic acid, and auxin, in the composite control of plant growth and defense. Regulation of redox gradients between key compartments in plant cells such as those across the plasma membrane facilitates flexible and multiple faceted opportunities for redox signaling that spans the intracellular and extracellular environments. In conclusion, plants are recognized as masters of the art of redox regulation that use oxidants and antioxidants as flexible integrators of signals from metabolism and the environment.

Kinetics of a plasma streamer ionization front

Science.gov (United States)

Taccogna, Francesco; Pellegrini, Fabrizio

2018-02-01

A streamer is a non-linear and non-local gas breakdown mode. Its large-scale coherent structures, such as the ionization front, are the final results of a hierarchical cascade starting from the single particle dynamics. Therefore, this phenomenon covers, by definition, different space and time scales. In this study, we have reproduced the ionization front formation and development by means of a particle-based numerical methodology. The physical system investigated concerns of a high-voltage ns-pulsed surface dielectric barrier discharge. Different reduced electric field regimes ranging from 50 to 500 Td have been considered for two gases: pure atomic Ar and molecular N2. Results have shown the detailed structure of the negative streamer: the leading edge, the head, the interior and the tail. Its dynamical evolution and the front propagation velocity have been calculated for the different cases. Finally, the deviation of the electron energy distribution function from equilibrium behavior has been pointed out as a result of a fast and very localized phenomenon.

Redox calcination study of Synroc D powder containing simulated SRL waste

International Nuclear Information System (INIS)

Chen, C.

1982-01-01

According to Ringwood [A.E. Ringwood, W. Sinclair, and G.M. McLaughlin, Nuclear Waste Immobilization, Lawrence Livermore Laboratory, Livermore, Rept. UCRL-15147 (1979)], the iron oxidation state is important in controlling, the spinel mineralogy and composition if the amount of titania (TiO 2 ) consumed in spinel formation is to be minimized in favor of the formation of the Synroc phases, zirconolite, perovskite, and nepheline. In our redox calcination studies we observed that the iron oxidation state of FeO/Fe 2 O 3 can be controlled by the redoxcalcining atmosphere. In a CO atmosphere, the oxidation state was reduced to less than 7 wt % Fe 2 O 3 . With appropriate CO 2 /CO gas mixtures the resultant iron oxidation states were in the range of 45 to 59 wt % Fe 2 O 3 . Direct rotary redox calcination of spray dried powder at 600 0 C, without prior air calcination, showed increased redox efficiency when compared to powder that had been previously air calcined at 650 0 C. We believe this is caused by a reduction in particle size. Rotary calcination at 800 0 C in argon has no measurable reduction affect on the iron oxidation state of Synroc D powder

Characterization of mammalian selenoprotein o: a redox-active mitochondrial protein.

Science.gov (United States)

Han, Seong-Jeong; Lee, Byung Cheon; Yim, Sun Hee; Gladyshev, Vadim N; Lee, Seung-Rock

2014-01-01

Selenoproteins exhibit diverse biological functions, most of which are associated with redox control. However, the functions of approximately half of mammalian selenoproteins are not known. One such protein is Selenoprotein O (SelO), the largest mammalian selenoprotein with orthologs found in a wide range of organisms, including bacteria and yeast. Here, we report characterization of mammalian SelO. Expression of this protein could be verified in HEK 293T cells by metabolic labeling of cells with 75Se, and it was abolished when selenocysteine was replaced with serine. A CxxU motif was identified in the C-terminal region of SelO. This protein was reversibly oxidized in a time- and concentration-dependent manner in HEK 293T cells when cells were treated with hydrogen peroxide. This treatment led to the formation of a transient 88 kDa SelO-containing complex. The formation of this complex was enhanced by replacing the CxxU motif with SxxC, but abolished when it was replaced with SxxS, suggesting a redox interaction of SelO with another protein through its Sec residue. SelO was localized to mitochondria and expressed across mouse tissues. Its expression was little affected by selenium deficiency, suggesting it has a high priority for selenium supply. Taken together, these results show that SelO is a redox-active mitochondrial selenoprotein.

Characterization of mammalian selenoprotein o: a redox-active mitochondrial protein.

Directory of Open Access Journals (Sweden)

Seong-Jeong Han

Full Text Available Selenoproteins exhibit diverse biological functions, most of which are associated with redox control. However, the functions of approximately half of mammalian selenoproteins are not known. One such protein is Selenoprotein O (SelO, the largest mammalian selenoprotein with orthologs found in a wide range of organisms, including bacteria and yeast. Here, we report characterization of mammalian SelO. Expression of this protein could be verified in HEK 293T cells by metabolic labeling of cells with 75Se, and it was abolished when selenocysteine was replaced with serine. A CxxU motif was identified in the C-terminal region of SelO. This protein was reversibly oxidized in a time- and concentration-dependent manner in HEK 293T cells when cells were treated with hydrogen peroxide. This treatment led to the formation of a transient 88 kDa SelO-containing complex. The formation of this complex was enhanced by replacing the CxxU motif with SxxC, but abolished when it was replaced with SxxS, suggesting a redox interaction of SelO with another protein through its Sec residue. SelO was localized to mitochondria and expressed across mouse tissues. Its expression was little affected by selenium deficiency, suggesting it has a high priority for selenium supply. Taken together, these results show that SelO is a redox-active mitochondrial selenoprotein.

First-principles study of adsorption-desorption kinetics of aqueous V2+/V3+ redox species on graphite in a vanadium redox flow battery.

Science.gov (United States)

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2017-06-14

Vanadium redox flow batteries (VRFBs) represent a promising solution to grid-scale energy storage, and understanding the reactivity of electrode materials is crucial for improving the power density of VRFBs. However, atomistic details about the interactions between vanadium ions and electrode surfaces in aqueous electrolytes are still lacking. Here, we examine the reactivity of the basal (0001) and edge (112[combining macron]0) graphite facets with water and aqueous V 2+ /V 3+ redox species at 300 K employing Car-Parrinello molecular dynamics (CPMD) coupled with metadynamics simulations. The results suggest that the edge surface is characterized by the formation of ketonic C[double bond, length as m-dash]O functional groups due to complete water dissociation into the H/O/H configuration with surface O atoms serving as active sites for adsorption of V 2+ /V 3+ species. The formation of V-O bonds at the surface should significantly improve the kinetics of electron transfer at the edge sites, which is not the case for the basal surface, in agreement with the experimentally hypothesized mechanism.

Osteoma in a blue-fronted Amazon parrot (Amazona aestiva).

Science.gov (United States)

Cardoso, João Felipe Rito; Levy, Marcelo Guilherme Bezerra; Liparisi, Flavia; Romão, Mario Antonio Pinto

2013-09-01

Osteoma is an uncommon bone formation documented in avian species and other animals. A blue-fronted Amazon parrot (Amazona aestiva) with clinical respiratory symptoms was examined because of a hard mass present on the left nostril. Radiographs suggested a bone tumor, and the mass was surgically excised. Histopathologic examination revealed features of an osteoma. To our knowledge, this is the first description of an osteoma in a blue-fronted Amazon parrot. Osteoma should be considered as a differential diagnosis in birds with respiratory distress and swelling of the nostril.

Flavin-catalyzed redox tailoring reactions in natural product biosynthesis.

Science.gov (United States)

Teufel, Robin

2017-10-15

Natural products are distinct and often highly complex organic molecules that constitute not only an important drug source, but have also pushed the field of organic chemistry by providing intricate targets for total synthesis. How the astonishing structural diversity of natural products is enzymatically generated in biosynthetic pathways remains a challenging research area, which requires detailed and sophisticated approaches to elucidate the underlying catalytic mechanisms. Commonly, the diversification of precursor molecules into distinct natural products relies on the action of pathway-specific tailoring enzymes that catalyze, e.g., acylations, glycosylations, or redox reactions. This review highlights a selection of tailoring enzymes that employ riboflavin (vitamin B2)-derived cofactors (FAD and FMN) to facilitate unusual redox catalysis and steer the formation of complex natural product pharmacophores. Remarkably, several such recently reported flavin-dependent tailoring enzymes expand the classical paradigms of flavin biochemistry leading, e.g., to the discovery of the flavin-N5-oxide - a novel flavin redox state and oxygenating species. Copyright © 2017 Elsevier Inc. All rights reserved.

Groundwater redox conditions and conductivity in a contaminant plume from geoelectrical investigations

Directory of Open Access Journals (Sweden)

V. Naudet

2004-01-01

Full Text Available Accurate mapping of the electrical conductivity and of the redox potential of the groundwater is important in delineating the shape of a contaminant plume. A map of redox potential in an aquifer is indicative of biodegradation of organic matter and of concentrations of redox-active components; a map of electrical conductivity provides information on the mineralisation of the groundwater. Both maps can be used to optimise the position of pumping wells for remediation. The self-potential method (SP and electrical resistivity tomography (ERT have been applied to the contaminant plume associated with the Entressen landfill in south-east France. The self-potential depends on groundwater flow (electrokinetic contribution and redox conditions ('electro-redox' contribution. Using the variation of the piezometric head in the aquifer, the electrokinetic contribution is removed from the SP signals. A good linear correlation (R2=0.85 is obtained between the residual SP data and the redox potential values measured in monitoring wells. This relationship is used to draw a redox potential map of the overall contaminated site. The electrical conductivity of the subsoil is obtained from 3D-ERT analysis. A good linear correlation (R2=0.91 is observed between the electrical conductivity of the aquifer determined from the 3D-ERT image and the conductivity of the groundwater measured in boreholes. This indicates that the formation factor is nearly homogeneous in the shallow aquifer at the scale of the ERT. From this correlation, a map of the pore water conductivity of the aquifer is obtained. Keywords: self-potential, redox potential, electrical resistivity tomography, fluid conductivity, contaminant plume

Hemoglobin redox reactions and red blood cell aging.

Science.gov (United States)

Rifkind, Joseph M; Nagababu, Enika

2013-06-10

The physiological mechanism(s) for recognition and removal of red blood cells (RBCs) from circulation after 120 days of its lifespan is not fully understood. Many of the processes thought to be associated with the removal of RBCs involve oxidative stress. We have focused on hemoglobin (Hb) redox reactions, which is the major source of RBC oxidative stress. The importance of Hb redox reactions have been shown to originate in large parts from the continuous slow autoxidation of Hb producing superoxide and its dramatic increase under hypoxic conditions. In addition, oxidative stress has been shown to be associated with redox reactions that originate from Hb reactions with nitrite and nitric oxide (NO) and the resultant formation of highly toxic peroxynitrite when NO reacts with superoxide released during Hb autoxidation. The interaction of Hb, particularly under hypoxic conditions with band 3 of the RBC membrane is critical for the generating the RBC membrane changes that trigger the removal of cells from circulation. These changes include exposure of antigenic sites, increased calcium leakage into the RBC, and the resultant leakage of potassium out of the RBC causing cell shrinkage and impaired deformability. The need to understand the oxidative damage to specific membrane proteins that result from redox reactions occurring when Hb is bound to the membrane. Proteomic studies that can pinpoint the specific proteins damaged under different conditions will help elucidate the cellular aging processes that result in cells being removed from circulation.

Melt front propagation in dielectrics upon femtosecond laser irradiation: Formation dynamics of a heat-affected layer

Energy Technology Data Exchange (ETDEWEB)

Garcia-Lechuga, Mario, E-mail: mario@io.cfmac.csic.es, E-mail: j.siegel@io.cfmac.csic.es; Solis, Javier; Siegel, Jan, E-mail: mario@io.cfmac.csic.es, E-mail: j.siegel@io.cfmac.csic.es [Laser Processing Group, Instituto de Optica, CSIC, Serrano 121, 28006 Madrid (Spain)

2016-04-25

Several studies in dielectrics have reported the presence of a thin heat-affected layer underneath the ablation crater produced by femtosecond laser irradiation. In this work, we present a time-resolved microscopy technique that is capable of monitoring the formation dynamics of this layer and apply it to the study of a phosphate glass exposed to single pulses below the ablation threshold. A few nanoseconds after laser excitation, a melt front interface can be detected, which propagates into the bulk, gradually slowing down its speed. By means of image analysis combined with optical modeling, we are able to determine the temporal evolution of the layer thickness and its refractive index. Initially, a strong transient decrease in the refractive index is observed, which partially recovers afterwards. The layer resolidifies after approximately 1 μs after excitation, featuring a maximum thickness of several hundreds of nanometers.

Melt front propagation in dielectrics upon femtosecond laser irradiation: Formation dynamics of a heat-affected layer

International Nuclear Information System (INIS)

Garcia-Lechuga, Mario; Solis, Javier; Siegel, Jan

2016-01-01

Several studies in dielectrics have reported the presence of a thin heat-affected layer underneath the ablation crater produced by femtosecond laser irradiation. In this work, we present a time-resolved microscopy technique that is capable of monitoring the formation dynamics of this layer and apply it to the study of a phosphate glass exposed to single pulses below the ablation threshold. A few nanoseconds after laser excitation, a melt front interface can be detected, which propagates into the bulk, gradually slowing down its speed. By means of image analysis combined with optical modeling, we are able to determine the temporal evolution of the layer thickness and its refractive index. Initially, a strong transient decrease in the refractive index is observed, which partially recovers afterwards. The layer resolidifies after approximately 1 μs after excitation, featuring a maximum thickness of several hundreds of nanometers.

Method for thermal recovery of hydrocarbons from an underground formation

Energy Technology Data Exchange (ETDEWEB)

1962-11-13

In a thermal recovery procedure for hydrocarbons from an underground formation, an oxygen-containing gas is injected through at least one input well into the formation. A part of the hydrocarbons in the formation is then ignited and an oxidation front is created. This front moves under the influence of the injected gas to at least one production well in the formation. The temperature in the burning front is higher than approximately 200/sup 0/C but lower than approximately 350/sup 0/C. (4 claims)

Case study of mesospheric front dissipation observed over the northeast of Brazil

Science.gov (United States)

Fragoso Medeiros, Amauri; Paulino, Igo; Wrasse, Cristiano Max; Fechine, Joaquim; Takahashi, Hisao; Valentin Bageston, José; Paulino, Ana Roberta; Arlen Buriti, Ricardo

2018-03-01

On 3 October 2005 a mesospheric front was observed over São João do Cariri (7.4° S, 36.5° W). This front propagated to the northeast and appeared in the airglow images on the west side of the observatory. By about 1.5 h later, it dissipated completely when the front crossed the local zenith. Ahead of the front, several ripple structures appeared during the dissipative process of the front. Using coincident temperature profile from the TIMED/SABER satellite and wind profiles from a meteor radar at São João do Cariri, the background of the atmosphere was investigated in detail. On the one hand, it was noted that a strong vertical wind shear in the propagation direction of the front produced by a semidiunal thermal tide was mainly responsible for the formation of duct (Doppler duct), in which the front propagated up to the zenith of the images. On the other hand, the evolution of the Richardson number as well as the appearance of ripples ahead of the main front suggested that a presence of instability in the airglow layer that did not allow the propagation of the front to the other side of the local zenith.

Thioredoxin-dependent Redox Regulation of Chloroplastic Phosphoglycerate Kinase from Chlamydomonas reinhardtii*

Science.gov (United States)

Morisse, Samuel; Michelet, Laure; Bedhomme, Mariette; Marchand, Christophe H.; Calvaresi, Matteo; Trost, Paolo; Fermani, Simona; Zaffagnini, Mirko; Lemaire, Stéphane D.

2014-01-01

In photosynthetic organisms, thioredoxin-dependent redox regulation is a well established mechanism involved in the control of a large number of cellular processes, including the Calvin-Benson cycle. Indeed, 4 of 11 enzymes of this cycle are activated in the light through dithiol/disulfide interchanges controlled by chloroplastic thioredoxin. Recently, several proteomics-based approaches suggested that not only four but all enzymes of the Calvin-Benson cycle may withstand redox regulation. Here, we characterized the redox features of the Calvin-Benson enzyme phosphoglycerate kinase (PGK1) from the eukaryotic green alga Chlamydomonas reinhardtii, and we show that C. reinhardtii PGK1 (CrPGK1) activity is inhibited by the formation of a single regulatory disulfide bond with a low midpoint redox potential (−335 mV at pH 7.9). CrPGK1 oxidation was found to affect the turnover number without altering the affinity for substrates, whereas the enzyme activation appeared to be specifically controlled by f-type thioredoxin. Using a combination of site-directed mutagenesis, thiol titration, mass spectrometry analyses, and three-dimensional modeling, the regulatory disulfide bond was shown to involve the not strictly conserved Cys227 and Cys361. Based on molecular mechanics calculation, the formation of the disulfide is proposed to impose structural constraints in the C-terminal domain of the enzyme that may lower its catalytic efficiency. It is therefore concluded that CrPGK1 might constitute an additional light-modulated Calvin-Benson cycle enzyme with a low activity in the dark and a TRX-dependent activation in the light. These results are also discussed from an evolutionary point of view. PMID:25202015

Effect of long-term fertilization on humic redox mediators in multiple microbial redox reactions.

Science.gov (United States)

Guo, Peng; Zhang, Chunfang; Wang, Yi; Yu, Xinwei; Zhang, Zhichao; Zhang, Dongdong

2018-03-01

This study investigated the effects of different long-term fertilizations on humic substances (HSs), humic acids (HAs) and humins, functioning as redox mediators for various microbial redox biotransformations, including 2,2',4,4',5,5'- hexachlorobiphenyl (PCB 153 ) dechlorination, dissimilatory iron reduction, and nitrate reduction, and their electron-mediating natures. The redox activity of HSs for various microbial redox metabolisms was substantially enhanced by long-term application of organic fertilizer (pig manure). As a redox mediator, only humin extracted from soils with organic fertilizer amendment (OF-HM) maintained microbial PCB 153 dechlorination activity (1.03 μM PCB 153 removal), and corresponding HA (OF-HA) most effectively enhanced iron reduction and nitrate reduction by Shewanella putrefaciens. Electrochemical analysis confirmed the enhancement of their electron transfer capacity and redox properties. Fourier transform infrared analysis showed that C=C and C=O bonds, and carboxylic or phenolic groups in HSs might be the redox functional groups affected by fertilization. This research enhances our understanding of the influence of anthropogenic fertility on the biogeochemical cycling of elements and in situ remediation ability in agroecosystems through microorganisms' metabolisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

Development of clay characterization methods for use in repository design with application to a natural Ca bentonite clay containing a redox front

International Nuclear Information System (INIS)

Karnland, O.; Pusch, R.

1990-12-01

Natural smectite clays in the form of 'true' bentonites formed from volcanic ash, or resulting from in-situ weathering of rock, are suitable for a number of sealing options in repositories, both as tightening component of sand/clay backfills and as highly efficient buffer for embedment of canisters, as well as for fracture sealing. The price and quality, in terms of smectite content and type of smectite, vary considerably and an optimum choice of clay for use in repositories has to be based on quantitative quality data. This requires characterization of the clay material for which a test scheme has been worked out. It comprises determination of the granulometrical, chemical, and mineralogical compositions, as well as of certain physical properties. Recent research shows the importance of the type of smectite for the longevity of buffers in repository environment, beidellite being less favourable and saponite superior to montmorillonite, which is the most common smectite species. The test scheme hence includes means of distinguishing between various smectite minerals. The influence of accessory minerals on the chemical integrity of both the smectite and the canister material requires identification also of such minerals, for which the scheme is useful as well. The report summarizes the various test procedures and gives data from application of the scheme to samples from a natural Ca bentonite containing a redox front. This study suggests that a significant part of the iron in the clay fraction is in the form of Fe 2+ in octahedral positions of the montmorillonite of unoxidized natural clay and that it is converted to Fe 3+ on oxidation. Part of the iron is probably in the form of the Fe 2+ Fe 3+ hydroxy compounds that give the unoxidized clay its bluish colour, while they can be assumed to be transformed to yellowish FeOOH forms on oxidation. (author)

The formation of diffuse discharge by short-front nanosecond voltage pulses and the modification of dielectrics in this discharge

Science.gov (United States)

Orlovskii, V. M.; Panarin, V. A.; Shulepov, M. A.

2014-07-01

The dynamics of diffuse discharge formation under the action of nanosecond voltage pulses with short fronts (below 1 ns) in the absence of a source of additional preionization and the influence of a dielectric film on this process have been studied. It is established that the diffuse discharge is induced by the avalanche multiplication of charge initiated by high-energy electrons and then maintained due to secondary breakdowns propagating via ionized gas channels. If a dielectric film (polyethylene, Lavsan, etc.) is placed on the anode, then multiply repeated discharge will lead to surface and bulk modification of the film material. Discharge-treated polyethylene film exhibits a change in the optical absorption spectrum in the near-IR range.

REDOX IMAGING OF THE p53-DEPENDENT MITOCHONDRIAL REDOX STATE IN COLON CANCER EX VIVO

Science.gov (United States)

XU, HE N.; FENG, MIN; MOON, LILY; DOLLOFF, NATHAN; EL-DEIRY, WAFIK; LI, LIN Z.

2015-01-01

The mitochondrial redox state and its heterogeneity of colon cancer at tissue level have not been previously reported. Nor has how p53 regulates mitochondrial respiration been measured at (deep) tissue level, presumably due to the unavailability of the technology that has sufficient spatial resolution and tissue penetration depth. Our prior work demonstrated that the mitochondrial redox state and its intratumor heterogeneity is associated with cancer aggressiveness in human melanoma and breast cancer in mouse models, with the more metastatic tumors exhibiting localized regions of more oxidized redox state. Using the Chance redox scanner with an in-plane spatial resolution of 200 μm, we imaged the mitochondrial redox state of the wild-type p53 colon tumors (HCT116 p53 wt) and the p53-deleted colon tumors (HCT116 p53−/−) by collecting the fluorescence signals of nicotinamide adenine dinucleotide (NADH) and oxidized flavoproteins [Fp, including flavin adenine dinucleotide (FAD)] from the mouse xenografts snap-frozen at low temperature. Our results show that: (1) both tumor lines have significant degree of intratumor heterogeneity of the redox state, typically exhibiting a distinct bi-modal distribution that either correlates with the spatial core–rim pattern or the “hot/cold” oxidation-reduction patches; (2) the p53−/− group is significantly more heterogeneous in the mitochondrial redox state and has a more oxidized tumor core compared to the p53 wt group when the tumor sizes of the two groups are matched; (3) the tumor size dependence of the redox indices (such as Fp and Fp redox ratio) is significant in the p53−/− group with the larger ones being more oxidized and more heterogeneous in their redox state, particularly more oxidized in the tumor central regions; (4) the H&E staining images of tumor sections grossly correlate with the redox images. The present work is the first to reveal at the submillimeter scale the intratumor heterogeneity pattern

Dissolution of UO2 in redox conditions

International Nuclear Information System (INIS)

Casas, I.; Pablo de, J.; Rovira, M.

1998-01-01

The performance assessment of the final disposal of the spent nuclear fuel in geological formations is strongly dependent on the spent fuel matrix dissolution. Unirradiated uranium (IV) dioxide has shown to be very useful for such purposes. The stability of UO 2 is very dependent on vault redox conditions. At reducing conditions, which are expected in deep groundwaters, the dissolution of the UO 2 -matrix can be explained in terms of solubility, while under oxidizing conditions, the UO 2 is thermodynamically unstable and the dissolution is kinetically controlled. In this report the parameters which affect the uranium solubility under reducing conditions, basically pH and redox potential are discussed. Under oxidizing conditions, UO 2 dissolution rate equations as a function of pH, carbonate concentration and oxidant concentration are reported. Dissolution experiments performed with spent fuel are also reviewed. The experimental equations presented in this work, have been used to model independent dissolution experiments performed with both unirradiated and irradiated UO 2 . (Author)

Iron oxi-hydroxides characterization and associated elements (S, Se, As, Mo, V, Zr) in the redox environments favorable for uranium deposits

International Nuclear Information System (INIS)

Pons, Tony

2015-01-01

This work presents a multi-scale and a multi-technical study for the characterization of iron oxi-hydroxides in three uranium-type deposits and host rock. The choice of sites has focused on a roll front deposit: Zoovch Ovoo in a Cretaceous basin of East Gobi (Mongolia); a tectonic-lithological type: Akola/Ebba in Tim Mersoi basin (Niger) and a Proterozoic unconformity type: Kiggavik in Thelon basin (Canada). A new approach has been implemented to characterize the iron oxi-hydroxides on macroscopic samples: field infrared spectroscopy using the ASD TerraSpec spectrometer. From the original indexes calculated on the spectra, it was possible both to characterize the iron oxi-hydroxides; only hematite and goethite were identified in the different parts of oxidized uranium fronts, and visualize the alteration zonation along the redox front. In addition, the visible part of spectrum was used to quantify the color of samples through the IHS system parameters (Intensity - Hue - Saturation) and the Munsell system. The color setting of the study identified a specific hue for mineralized samples studied: a mixture of yellow and red (2.5 to 10 Yr in Munsell notation). At the crystals scale, the iron-hydroxides were characterized by μ-Raman spectroscopy. The study highlighted a difference in crystallinity of hematite crystals in different fields. From a morphological point of view, the crystals of goethite in the Zoovch Ovoo deposit, is only authigenic iron oxi-hydroxides described in this uranium front, are twinned in the form of six-pointed star, reflecting a low crystallization temperature, compared to Niger and Kiggavik deposits. This crystallization is mainly controlled by the availability of Fe(III) ions in the fluid, released by pyrite dissolution in an oxidizing environment and pH. From a chemical point of view, iron oxi-hydroxides record the fluid passage owing their uranium content. Secondly, the composition in trace elements marks the type of deposit, for example

Redox Pioneer: Professor Vadim N. Gladyshev.

Science.gov (United States)

Hatfield, Dolph L

2016-07-01

Professor Vadim N. Gladyshev is recognized here as a Redox Pioneer, because he has published an article on antioxidant/redox biology that has been cited more than 1000 times and 29 articles that have been cited more than 100 times. Gladyshev is world renowned for his characterization of the human selenoproteome encoded by 25 genes, identification of the majority of known selenoprotein genes in the three domains of life, and discoveries related to thiol oxidoreductases and mechanisms of redox control. Gladyshev's first faculty position was in the Department of Biochemistry, the University of Nebraska. There, he was a Charles Bessey Professor and Director of the Redox Biology Center. He then moved to the Department of Medicine at Brigham and Women's Hospital, Harvard Medical School, where he is Professor of Medicine and Director of the Center for Redox Medicine. His discoveries in redox biology relate to selenoenzymes, such as methionine sulfoxide reductases and thioredoxin reductases, and various thiol oxidoreductases. He is responsible for the genome-wide identification of catalytic redox-active cysteines and for advancing our understanding of the general use of cysteines by proteins. In addition, Gladyshev has characterized hydrogen peroxide metabolism and signaling and regulation of protein function by methionine-R-sulfoxidation. He has also made important contributions in the areas of aging and lifespan control and pioneered applications of comparative genomics in redox biology, selenium biology, and aging. Gladyshev's discoveries have had a profound impact on redox biology and the role of redox control in health and disease. He is a true Redox Pioneer. Antioxid. Redox Signal. 25, 1-9.

Uranium redox transition pathways in acetate-amended sediments

Science.gov (United States)

Bargar, John R.; Williams, Kenneth H.; Campbell, Kate M.; Long, Philip E.; Stubbs, Joanne E.; Suvorova, Elenal I.; Lezama-Pacheco, Juan S.; Alessi, Daniel S.; Stylo, Malgorzata; Webb, Samuel M.; Davis, James A.; Giammar, Daniel E.; Blue, Lisa Y.; Bernier-Latmani, Rizlan

2013-01-01

Redox transitions of uranium [from U(VI) to U(IV)] in low-temperature sediments govern the mobility of uranium in the environment and the accumulation of uranium in ore bodies, and inform our understanding of Earth’s geochemical history. The molecular-scale mechanistic pathways of these transitions determine the U(IV) products formed, thus influencing uranium isotope fractionation, reoxidation, and transport in sediments. Studies that improve our understanding of these pathways have the potential to substantially advance process understanding across a number of earth sciences disciplines. Detailed mechanistic information regarding uranium redox transitions in field sediments is largely nonexistent, owing to the difficulty of directly observing molecular-scale processes in the subsurface and the compositional/physical complexity of subsurface systems. Here, we present results from an in situ study of uranium redox transitions occurring in aquifer sediments under sulfate-reducing conditions. Based on molecular-scale spectroscopic, pore-scale geochemical, and macroscale aqueous evidence, we propose a biotic–abiotic transition pathway in which biomass-hosted mackinawite (FeS) is an electron source to reduce U(VI) to U(IV), which subsequently reacts with biomass to produce monomeric U(IV) species. A species resembling nanoscale uraninite is also present, implying the operation of at least two redox transition pathways. The presence of multiple pathways in low-temperature sediments unifies apparently contrasting prior observations and helps to explain sustained uranium reduction under disparate biogeochemical conditions. These findings have direct implications for our understanding of uranium bioremediation, ore formation, and global geochemical processes.

Geologic map of the greater Denver area, Front Range urban corridor, Colorado

Science.gov (United States)

Trimble, Donald E.; Machette, Michael N.

1979-01-01

This digital map shows the areal extent of surficial deposits and rock stratigraphic units (formations) as compiled by Trimble and Machette from 1973 to 1977 and published in 1979 under the Front Range Urban Corridor Geology Program. Trimble and Machette compiled their geologic map from published geologic maps and unpublished geologic mapping having varied map unit schemes. A convenient feature of the compiled map is its uniform classification of geologic units that mostly matches those of companion maps to the north (USGS I-855-G) and to the south (USGS I-857-F). Published as a color paper map, the Trimble and Machette map was intended for land-use planning in the Front Range Urban Corridor. This map recently (1997-1999) was digitized under the USGS Front Range Infrastructure Resources Project. In general, the mountainous areas in the western part of the map exhibit various igneous and metamorphic bedrock units of Precambrian age, major faults, and fault brecciation zones at the east margin (5-20 km wide) of the Front Range. The eastern and central parts of the map (Colorado Piedmont) depict a mantle of unconsolidated deposits of Quaternary age and interspersed outcroppings of Cretaceous or Tertiary-Cretaceous sedimentary bedrock. The Quaternary mantle comprises eolian deposits (quartz sand and silt), alluvium (gravel, sand, and silt of variable composition), colluvium, and a few landslides. At the mountain front, north-trending, dipping Paleozoic and Mesozoic sandstone, shale, and limestone bedrock formations form hogbacks and intervening valleys.

Morphology evolution and nanostructure of chemical looping transition metal oxide materials upon redox processes

International Nuclear Information System (INIS)

Qin, Lang; Cheng, Zhuo; Guo, Mengqing; Fan, Jonathan A.; Fan, Liang-Shih

2017-01-01

Transition metal are heavily used in chemical looping technologies because of their high oxygen carrying capacity and high thermal reactivity. These oxygen activities result in the oxide formation and oxygen vacancy formation that affect the nanoscale crystal phase and morphology within these materials and their subsequent bulk chemical behavior. In this study, two selected earlier transition metals manganese and cobalt as well as two selected later transition metals copper and nickel that are important to chemical looping reactions are investigated when they undergo cyclic redox reactions. We found Co microparticles exhibited increased CoO impurity presence when oxidized to Co_3O_4 upon cyclic oxidation; CuO redox cycles prefer to be limited to a reduced form of Cu_2O and an oxidized form of CuO; Mn microparticles were oxidized to a mixed phases of MnO and Mn_3O_4, which causes delamination during oxidation. For Ni microparticles, a dense surface were observed during the redox reaction. The atomistic thermodynamics methods and density functional theory (DFT) calculations are carried out to elucidate the effect of oxygen dissociation and migration on the morphological evolution of nanostructures during the redox processes. Our results indicate that the earlier transition metals (Mn and Co) tend to have stronger interaction with O_2 than the later transition metals (Ni and Cu). Also, our modified Brønsted−Evans−Polanyi (BEP) relationship for reaction energies and total reaction barriers reveals that reactions of earlier transition metals are more exergonic and have lower oxygen dissociation barriers than those of later transition metals. In addition, it was found that for these transition metal oxides the oxygen vacancy formation energies increase with the depth. The oxide in the higher oxidation state of transition metal has lower vacancy formation energy, which can facilitate forming the defective nanostructures. The fundamental understanding of these metal

Redox control of iron biomineralization in Magnetospirillum magneticum AMB-1

Science.gov (United States)

Jones, Stephanie Rhianon

Magnetotactic bacteria have evolved complex subcellular machinery to construct linear chains of magnetite nanocrystals that allow the host cell to sense direction. Each mixed-valent iron nanoparticle is mineralized from soluble iron within a membrane-encapsulated vesicle termed the magnetosome, which serves as a specialized compartment that regulates the iron, redox, and pH environment of the growing mineral. In order to dissect the biological components that control this process, we have carried out genetic and biochemical studies of proteins proposed to function in iron mineralization in Magnetospirillum magneticum AMB-1. As iron biomineralization by magnetotactic bacteria represents a particularly interesting case for understanding how the production of nanomaterials can be programmed at the genetic level, we also apply synthetic biology techniques towards the production of new cellular materials and new cellular functions. As the production of magnetite requires both the formation of Fe(II) and Fe(III), the redox components of the magnetosome play an essential role in this process. Using genetic complementation studies, we show that the redox cofactors or heme sites of the two putative redox partners, MamP and MamT, are required for magnetite biomineralization in vivo and that removal of one or both sites leads to defects in mineralization. We develop and optimize a heterologous expression method in the E. coli periplasm to cleanly isolate fully heme-loaded MamP for biochemical studies. Spectrochemical redox titrations show that the reduction potential of MamP lies in a different range than other c-type cytochrome involved in either Fe(III) reduction or Fe(II) oxidation. Nonetheless, in vitro mineralization studies with MamP and Fe(II) show that it is able to catalyze the formation of mixed-valent Fe(II)/Fe(III) oxides such as green rust. Biomineralization also requires lattice-templating proteins that guide the growth of the functional crystalline material. We

Localized structures and front propagation in the Lengyel-Epstein model

DEFF Research Database (Denmark)

Jensen, O.; Pannbacker, Viggo Ole; Mosekilde, Erik

1994-01-01

Pattern selection, localized structure formation, and front propagation are analyzed within the framework of a model for the chlorine dioxide-iodine-malonic acid reaction that represents a key to understanding recently obtained Turing structures. This model is distinguished from previously studied......, simple reaction-diffusion models by producing a strongly subcritical transition to stripes. The wave number for the modes of maximum linear gain is calculated and compared with the dominant wave number for the finally selected, stationary structures grown from the homogeneous steady state or developed...... bifurcation. In the subcritical regime there is an interval where the front velocity vanishes as a result of a pinning of the front to the underlying structure. In 2D, two different nucleation mechanisms for hexagonal structures are illustrated on the Lengyel-Epstein and the Brusselator model. Finally...

The Effects of Acrolein on the Thioredoxin System: Implications for Redox-Sensitive Signaling

Science.gov (United States)

Myers, Charles R.; Myers, Judith M.; Kufahl, Timothy D.; Forbes, Rachel; Szadkowski, Adam

2012-01-01

The reactive aldehyde acrolein is a ubiquitous environmental pollutant and is also generated endogenously. It is a strong electrophile and reacts rapidly with nucleophiles including thiolates. This review focuses on the effects of acrolein on thioredoxin reductase (TrxR) and thioredoxin (Trx), which are major regulators of intracellular protein thiol redox balance. Acrolein causes irreversible effects on TrxR and Trx, which are consistent with the formation of covalent adducts to selenocysteine and cysteine residues that are key to their activity. TrxR and Trx are more sensitive than some other redox-sensitive proteins, and their prolonged inhibition could disrupt a number of redox-sensitive functions in cells. Among these effects are the oxidation of peroxiredoxins and the activation of apoptosis signal regulating kinase (ASK1). ASK1 promotes MAP kinase activation, and p38 activation contributes to apoptosis and a number of other acrolein-induced stress responses. Overall, the disruption of the TrxR/Trx system by acrolein could be significant early and prolonged events that affects many aspects of redox-sensitive signaling and oxidant stress. PMID:21812108

Compromised redox homeostasis, altered nitroso-redox balance, and therapeutic possibilities in atrial fibrillation.

Science.gov (United States)

Simon, Jillian N; Ziberna, Klemen; Casadei, Barbara

2016-04-01

Although the initiation, development, and maintenance of atrial fibrillation (AF) have been linked to alterations in myocyte redox state, the field lacks a complete understanding of the impact these changes may have on cellular signalling, atrial electrophysiology, and disease progression. Recent studies demonstrate spatiotemporal changes in reactive oxygen species production shortly after the induction of AF in animal models with an uncoupling of nitric oxide synthase activity ensuing in the presence of long-standing persistent AF, ultimately leading to a major shift in nitroso-redox balance. However, it remains unclear which radical or non-radical species are primarily involved in the underlying mechanisms of AF or which proteins are targeted for redox modification. In most instances, only free radical oxygen species have been assessed; yet evidence from the redox signalling field suggests that non-radical species are more likely to regulate cellular processes. A wider appreciation for the distinction of these species and how both species may be involved in the development and maintenance of AF could impact treatment strategies. In this review, we summarize how redox second-messenger systems are regulated and discuss the recent evidence for alterations in redox regulation in the atrial myocardium in the presence of AF, while identifying some critical missing links. We also examine studies looking at antioxidants for the prevention and treatment of AF and propose alternative redox targets that may serve as superior therapeutic options for the treatment of AF. © The Author 2016. Published by Oxford University Press on behalf of the European Society of Cardiology.

Engineering redox balance through cofactor systems.

Science.gov (United States)

Chen, Xiulai; Li, Shubo; Liu, Liming

2014-06-01

Redox balance plays an important role in the production of enzymes, pharmaceuticals, and chemicals. To meet the demands of industrial production, it is desirable that microbes maintain a maximal carbon flux towards target metabolites with no fluctuations in redox. This requires functional cofactor systems that support dynamic homeostasis between different redox states or functional stability in a given redox state. Redox balance can be achieved by improving the self-balance of a cofactor system, regulating the substrate balance of a cofactor system, and engineering the synthetic balance of a cofactor system. This review summarizes how cofactor systems can be manipulated to improve redox balance in microbes. Copyright © 2014 Elsevier Ltd. All rights reserved.

Sunlight mediated synthesis of silver nanoparticles using redox phytoprotein and their application in catalysis and colorimetric mercury sensing.

Science.gov (United States)

Ahmed, Khan Behlol Ayaz; Senthilnathan, Rajendran; Megarajan, Sengan; Anbazhagan, Veerappan

2015-10-01

Owing to the benign nature, plant extracts mediated green synthesis of metal nanoparticles (NPs) is rapidly expanding. In this study, we demonstrated the successful green synthesis of silver nanoparticles (AgNPs) by utilizing natural sunlight and redox protein complex composed of ferredoxin-NADP(+) reductase (FNR) and ferredoxin (FD). The capping and stabilization of the AgNPs by the redox protein was confirmed by Fourier transform infrared spectroscopy. Light and redox protein is the prerequisite factor for the formation of AgNPs. The obtained result shows that the photo generated free radicals by the redox protein is responsible for the reduction of Ag(+) to Ag(0). Transmission electron microscopy revealed the formation of spherical AgNPs with size ranging from 10 to 15 nm. As-prepared AgNPs exhibit excellent catalytic activity toward the degradation of hazardous organic dyes, such as methylene blue, methyl orange and methyl red. These bio-inspired AgNPs is highly sensitive and selective in sensing hazardous mercury ions in the water at micromolar concentration. In addition, FNR/FD extract stabilized AgNPs showed good antimicrobial activity against gram positive and gram negative bacteria. Copyright © 2015 Elsevier B.V. All rights reserved.

Redox Homeostasis in Plants under Abiotic Stress: Role of electron carriers, energy metabolism mediators and proteinaceous thiols

Directory of Open Access Journals (Sweden)

Dhriti Kapoor

2015-03-01

Full Text Available Contemporaneous presence of both oxidized and reduced forms of electron carriers is mandatory in efficient flux by plant electron transport cascades. This requirement is considered as redox poising that involves the movement of electron from multiple sites in respiratory and photosynthetic electron transport chains to molecular oxygen. This flux triggers the formation of superoxide, consequently give rise to other reactive oxygen species (ROS under adverse environmental conditions like drought, high or low temperature, heavy metal stress etc. that plants owing during their life span. Plant cells synthesize ascorbate, an additional hydrophilic redox buffer, which protect the plants against oxidative challenge. Large pools of antioxidants also preside over the redox homeostasis. Besides, tocopherol is a liposoluble redox buffer, which efficiently scavenges the ROS like singlet oxygen. In addition, proteinaceous thiol members such as thioredoxin, peroxiredoxin and glutaredoxin, electron carriers and energy metabolism mediators phosphorylated (NADP and non-phosphorylated (NAD+ coenzyme forms interact with ROS, metabolize and maintain redox homeostasis.

Dissecting Redox Biology Using Fluorescent Protein Sensors.

Science.gov (United States)

Schwarzländer, Markus; Dick, Tobias P; Meyer, Andreas J; Morgan, Bruce

2016-05-01

Fluorescent protein sensors have revitalized the field of redox biology by revolutionizing the study of redox processes in living cells and organisms. Within one decade, a set of fundamental new insights has been gained, driven by the rapid technical development of in vivo redox sensing. Redox-sensitive yellow and green fluorescent protein variants (rxYFP and roGFPs) have been the central players. Although widely used as an established standard tool, important questions remain surrounding their meaningful use in vivo. We review the growing range of thiol redox sensor variants and their application in different cells, tissues, and organisms. We highlight five key findings where in vivo sensing has been instrumental in changing our understanding of redox biology, critically assess the interpretation of in vivo redox data, and discuss technical and biological limitations of current redox sensors and sensing approaches. We explore how novel sensor variants may further add to the current momentum toward a novel mechanistic and integrated understanding of redox biology in vivo. Antioxid. Redox Signal. 24, 680-712.

Redox Buffer Strength

Science.gov (United States)

de Levie, Robert

1999-04-01

The proper functioning of enzymes in bodily fluids requires that the pH be maintained within rather narrow limits. The first line of defense against large pH fluctuations in such fluids is the passive control provided by the presence of pH buffers. The ability of pH buffers to stabilize the pH is indicated by the buffer value b introduced in 1922 by van Slyke. It is equally important for many enzymes that the redox potential is kept within a narrow range. In that case, stability of the potential is most readily achieved with a redox buffer. In this communication we define the redox buffer strength by analogy with acid-base buffer strength.

Chromium stable isotope systematic – implications for the redox evolution of the earth

DEFF Research Database (Denmark)

Døssing, Lasse Nørbye

and thus indicate the presence of oxidizing redox species. To track paleo-redox processes deep in the Earth’s history, a number of ancient soil horizons (e.g. the Drakenstein and Nsuze paleosols) formed ~2.2 and ~3.0 billion years ago have been analyzed. These horizons document similar behavior of Cr...... isotopes as modern soil profiles and indicate that oxidative weathering in the terrestrial environment started well before and after the Great Oxidation Event ~2.3 billion years ago. The signals of oxidative weathering on land are traceable in contemporaneous marine sediments such as Banded Iron Formations...

Mechanistic studies of cancer cell mitochondria- and NQO1-mediated redox activation of beta-lapachone, a potentially novel anticancer agent

International Nuclear Information System (INIS)

Li, Jason Z.; Ke, Yuebin; Misra, Hara P.; Trush, Michael A.; Li, Y. Robert; Zhu, Hong; Jia, Zhenquan

2014-01-01

Beta-lapachone (beta-Lp) derived from the Lapacho tree is a potentially novel anticancer agent currently under clinical trials. Previous studies suggested that redox activation of beta-Lp catalyzed by NAD(P)H:quinone oxidoreductase 1 (NQO1) accounted for its killing of cancer cells. However, the exact mechanisms of this effect remain largely unknown. Using chemiluminescence and electron paramagnetic resonance (EPR) spin-trapping techniques, this study for the first time demonstrated the real-time formation of ROS in the redox activation of beta-lapachone from cancer cells mediated by mitochondria and NQO1 in melanoma B16–F10 and hepatocellular carcinoma HepG2 cancer cells. ES936, a highly selective NQO1 inhibitor, and rotenone, a selective inhibitor of mitochondrial electron transport chain (METC) complex I were found to significantly block beta-Lp meditated redox activation in B16–F10 cells. In HepG2 cells ES936 inhibited beta-Lp-mediated oxygen radical formation by ∼ 80% while rotenone exerted no significant effect. These results revealed the differential contribution of METC and NQO1 to beta-lapachone-induced ROS formation and cancer cell killing. In melanoma B16–F10 cells that do not express high NQO1 activity, both NOQ1 and METC play a critical role in beta-Lp redox activation. In contrast, in hepatocellular carcinoma HepG2 cells expressing extremely high NQO1 activity, redox activation of beta-Lp is primarily mediated by NQO1 (METC plays a minor role). These findings will contribute to our understanding of how cancer cells are selectively killed by beta-lapachone and increase our ability to devise strategies to enhance the anticancer efficacy of this potentially novel drug while minimizing its possible adverse effects on normal cells. - Highlights: • Both isolated mitochondria and purified NQO1 are able to generate ROS by beta-Lp. • The differential roles of mitochondria and NQO1 in mediating redox activation of beta-Lp • In cancer cells with

Mechanistic studies of cancer cell mitochondria- and NQO1-mediated redox activation of beta-lapachone, a potentially novel anticancer agent

Energy Technology Data Exchange (ETDEWEB)

Li, Jason Z. [Virginia Tech CRC, Blacksburg, VA (United States); Ke, Yuebin [Shenzhen Center for Disease Control and Prevention, Shenzhen 518055 (China); Misra, Hara P. [Virginia Tech CRC, Blacksburg, VA (United States); Trush, Michael A. [Johns Hopkins University Bloomberg School of Public Health, Baltimore, MD (United States); Li, Y. Robert [Campbell University School of Osteopathic Medicine, Buies Creek, NC (United States); Virginia Tech-Wake Forest University SBES, Blacksburg, VA (United States); Department of Biology, University of North Carolina at Greensboro, NC (United States); Zhu, Hong, E-mail: zhu@campbell.edu [Campbell University School of Osteopathic Medicine, Buies Creek, NC (United States); Jia, Zhenquan, E-mail: z_jia@uncg.edu [Department of Biology, University of North Carolina at Greensboro, NC (United States)

2014-12-15

Beta-lapachone (beta-Lp) derived from the Lapacho tree is a potentially novel anticancer agent currently under clinical trials. Previous studies suggested that redox activation of beta-Lp catalyzed by NAD(P)H:quinone oxidoreductase 1 (NQO1) accounted for its killing of cancer cells. However, the exact mechanisms of this effect remain largely unknown. Using chemiluminescence and electron paramagnetic resonance (EPR) spin-trapping techniques, this study for the first time demonstrated the real-time formation of ROS in the redox activation of beta-lapachone from cancer cells mediated by mitochondria and NQO1 in melanoma B16–F10 and hepatocellular carcinoma HepG2 cancer cells. ES936, a highly selective NQO1 inhibitor, and rotenone, a selective inhibitor of mitochondrial electron transport chain (METC) complex I were found to significantly block beta-Lp meditated redox activation in B16–F10 cells. In HepG2 cells ES936 inhibited beta-Lp-mediated oxygen radical formation by ∼ 80% while rotenone exerted no significant effect. These results revealed the differential contribution of METC and NQO1 to beta-lapachone-induced ROS formation and cancer cell killing. In melanoma B16–F10 cells that do not express high NQO1 activity, both NOQ1 and METC play a critical role in beta-Lp redox activation. In contrast, in hepatocellular carcinoma HepG2 cells expressing extremely high NQO1 activity, redox activation of beta-Lp is primarily mediated by NQO1 (METC plays a minor role). These findings will contribute to our understanding of how cancer cells are selectively killed by beta-lapachone and increase our ability to devise strategies to enhance the anticancer efficacy of this potentially novel drug while minimizing its possible adverse effects on normal cells. - Highlights: • Both isolated mitochondria and purified NQO1 are able to generate ROS by beta-Lp. • The differential roles of mitochondria and NQO1 in mediating redox activation of beta-Lp • In cancer cells with

Redox Flow Batteries, a Review

Energy Technology Data Exchange (ETDEWEB)

Knoxville, U. Tennessee; U. Texas Austin; U, McGill; Weber, Adam Z.; Mench, Matthew M.; Meyers, Jeremy P.; Ross, Philip N.; Gostick, Jeffrey T.; Liu, Qinghua

2011-07-15

Redox flow batteries are enjoying a renaissance due to their ability to store large amounts of electrical energy relatively cheaply and efficiently. In this review, we examine the components of redox flow batteries with a focus on understanding the underlying physical processes. The various transport and kinetic phenomena are discussed along with the most common redox couples.

Post-modelling of images from a laser-induced wavy boiling front

Energy Technology Data Exchange (ETDEWEB)

Matti, R.S., E-mail: ramiz.matti@ltu.se [Luleå University of Technology, Department of Engineering Sciences and Mathematics, SE-971 87 Luleå (Sweden); University of Mosul, College of Engineering, Department of Mechanical Engineering, Mosul (Iraq); Kaplan, A.F.H. [Luleå University of Technology, Department of Engineering Sciences and Mathematics, SE-971 87 Luleå (Sweden)

2015-12-01

Highlights: • New method: post-modelling of high speed images from a laser-induced front. • From the images a wavy cavity and its absorption distribution is calculated. • Histograms enable additional statistical analysis and understanding. • Despite the complex topology the absorptivity is bound to 35–43%. • The new method visualizes valuable complementary information. - Abstract: Processes like laser keyhole welding, remote fusion laser cutting or laser drilling are governed by a highly dynamic wavy boiling front that was recently recorded by ultra-high speed imaging. A new approach has now been established by post-modelling of the high speed images. Based on the image greyscale and on a cavity model the three-dimensional front topology is reconstructed. As a second step the Fresnel absorptivity modulation across the wavy front is calculated, combined with the local projection of the laser beam. Frequency polygons enable additional analysis of the statistical variations of the properties across the front. Trends like shadow formation and time dependency can be studied, locally and for the whole front. Despite strong topology modulation in space and time, for lasers with 1 μm wavelength and steel the absorptivity is bounded to a narrow range of 35–43%, owing to its Fresnel characteristics.

THE STUDY OF REDOX CONDITIONS IN THE DNIESTER RIVER

Directory of Open Access Journals (Sweden)

Viorica Gladchi

2008-06-01

Full Text Available The work presented in the paper discusses the contribution of the Novodnestrovsc water system to the formation of redox conditions in the lower Dniester. The conclusions were drawn on the basis of a long-term protocol of analyses that included the analysis of the oxygen regime, evaluation of the content of hydrogen peroxide, rH2, biological oxygen demand as well as other additional parameters.

Marine redox structure at the culmination of the Great Oxidation Event: Insights from the Zaonega Formation, Karelia, Russia

Science.gov (United States)

Kipp, M.; Lepland, A.; Buick, R.

2017-12-01

The availability of dissolved oxygen is thought to have been the dominant throttle on the evolution and diversification of eukaryotic life during the Proterozoic Eon [1]. In the mid-Proterozoic, during the interval that presaged the rise of eukaryotes to ecological dominance, oxygen scarcity is thought to have relegated eukaryotic organisms to slivers of oxygenated shallow oceans [2]. However, recent work has suggested that oxygen levels rose dramatically during the early Paleoproterozoic Great Oxidation Event before crashing to the low levels of the mid-Proterozoic [3]. Evidence from selenium isotopes in shales [4] and iodate concentrations in carbonates [5] has even suggested that wide swathes of continental shelves were oxic enough to support eukaryotic organisms at this time. How oxic though, and for how long, remain poorly constrained. Here we present new selenium geochemical data from the Zaonega Formation of Karelia, Russia that can help resolve those questions. Previous work has proposed that the Zaonega Formation, and correlative Francevillian Series of Gabon, record the establishment of an oxygen-rich atmosphere at the culmination of the GOE [6]. Our selenium isotope dataset provides a test for this hypothesis, and can also be used to assess the preservation of the geochemical signatures in the Zaonega Formation. These data point to regional redox fluctuations, but due to the short marine residence time of selenium, extrapolating these results to global phenomena remains difficult. 1. Reinhard, et al (2016) PNAS 2. Planavsky, et al (2014) Science 3. Bekker and Holland (2012) EPSL 4. Kipp, et al (2017) PNAS 5. Hardisty, et al (2014) Geology 6. Kump, et al (2011) Science

The redox reaction kinetics of Sinai ore for chemical looping combustion applications

International Nuclear Information System (INIS)

Ksepko, Ewelina; Babiński, Piotr; Nalbandian, Lori

2017-01-01

Highlights: • Redox reaction kinetics of Fe-Mn-rich Sinai ore was determined by TGA. • The most suitable model for reduction was D3, while R3 for oxidation. • Activation energies 35.3 and 16.70 kJ/mole were determined for reduction and oxidation. • Repetitive redox reactions favor the formation of spinel phases in Sinai ore. • Multiple redox cycles induce formation of extensive porosity of the particles. - Abstract: The objective of this work was to study the use of Sinai ore, a Fe–Mn-based ore from Egypt, as a low-cost oxygen carrier (OC) in Chemical Looping Combustion (CLC). The Sinai ore was selected because it possesses relatively high amounts of iron and manganese oxides. Furthermore, those oxides have low cost, very favorable environmental and thermodynamic properties for the CLC process. The performance of the Sinai ore as an OC in CLC was compared to that of ilmenite (Norway Tellnes mine), the most extensively studied naturally occurring Fe-based mineral. The kinetics of the reduction and oxidation reactions with the two minerals were studied using a thermogravimetric analyzer (TGA). Experiments were conducted under isothermal conditions, with multiple redox cycles, at temperatures between 750 and 950 °C. For the reduction and oxidation reactions, different concentrations of CH_4 (10–25 vol.%) and O_2 (5–20 vol.%) were applied, respectively. The kinetic parameters, such as the activation energy (E_a), pre-exponential factor (A_0), and reaction order (n), were determined for the redox reactions. Furthermore, models of the redox reactions were selected by means of a model-fitting method. For the Sinai ore, the D3 model (3-dimensional diffusion) was suitable for modeling reduction reaction kinetics. The calculated E_a was 35.3 kJ/mole, and the reaction order was determined to be approximately 0.76. The best fit for the oxidation reaction was obtained for the R3 model (shrinking core). The oxidation (regeneration) reaction E_a was equal to 16

Rebalancing Redox to Improve Biobutanol Production by Clostridium tyrobutyricum

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Chao Ma

2015-12-01

Full Text Available Biobutanol is a sustainable green biofuel that can substitute for gasoline. Carbon flux has been redistributed in Clostridium tyrobutyricum via metabolic cell engineering to produce biobutanol. However, the lack of reducing power hampered the further improvement of butanol production. The objective of this study was to improve butanol production by rebalancing redox. Firstly, a metabolically-engineered mutant CTC-fdh-adhE2 was constructed by introducing heterologous formate dehydrogenase (fdh and bifunctional aldehyde/alcohol dehydrogenase (adhE2 simultaneously into wild-type C. tyrobutyricum. The mutant evaluation indicated that the fdh-catalyzed NADH-producing pathway improved butanol titer by 2.15-fold in the serum bottle and 2.72-fold in the bioreactor. Secondly, the medium supplements that could shift metabolic flux to improve the production of butyrate or butanol were identified, including vanadate, acetamide, sodium formate, vitamin B12 and methyl viologen hydrate. Finally, the free-cell fermentation produced 12.34 g/L of butanol from glucose using the mutant CTC-fdh-adhE2, which was 3.88-fold higher than that produced by the control mutant CTC-adhE2. This study demonstrated that the redox engineering in C. tyrobutyricum could greatly increase butanol production.

Redox electrode materials for supercapatteries

OpenAIRE

Yu, Linpo; Chen, George Z.

2016-01-01

Redox electrode materials, including transition metal oxides and electronically conducting polymers, are capable of faradaic charge transfer reactions, and play important roles in most electrochemical energy storage devices, such as supercapacitor, battery and supercapattery. Batteries are often based on redox materials with low power capability and safety concerns in some cases. Supercapacitors, particularly those based on redox inactive materials, e.g. activated carbon, can offer high power...

Density-wave fronts on the brink of wet granular condensation

Science.gov (United States)

Huang, Kai; Zippelius, Andreas; Sand lab @ University of Bayreuth Team

2017-11-01

From sand dunes to Faraday heaping, driven granular matter, i.e., large agglomeration of macroscopic particles, is rich pattern forming system. When a granular material is partially wet (e.g., wet sand on the beach), a different pattern forming scenario arises due to the cohesive particle-particle interactions. Here, we focus on the formation of density-wave fronts in an oscillated wet granular layer undergoing a gas-liquid-like transition. The threshold of the instability is governed by the amplitude of the vertical vibrations. Fronts, which are curved into a spiral shape, propagate coherently along the circular rim of the container with leading edges. They are stable beyond a critical distance from the container center. Based on the measurement of the critical distance and the rotation frequency, we propose a model for the pattern formation by considering the competition between the time scale for the collapse of cohesive particles and that of the energy injection resisting this process. Deutsche Forschungsgemeinschaft (Grant No. HU1939 4-1).

Identification of redox-sensitive cysteines in the arabidopsis proteome using OxiTRAQ, a quantitative redox proteomics method

KAUST Repository

Liu, Pei

2014-01-28

Cellular redox status plays a key role in mediating various physiological and developmental processes often through modulating activities of redox-sensitive proteins. Various stresses trigger over-production of reactive oxygen/nitrogen species which lead to oxidative modifications of redox-sensitive proteins. Identification and characterization of redox-sensitive proteins are important steps toward understanding molecular mechanisms of stress responses. Here, we report a high-throughput quantitative proteomic approach termed OxiTRAQ for identifying proteins whose thiols undergo reversible oxidative modifications in Arabidopsis cells subjected to oxidative stress. In this approach, a biotinylated thiol-reactive reagent is used for differential labeling of reduced and oxidized thiols. The biotin-tagged peptides are affinity purified, labeled with iTRAQ reagents, and analyzed using a paralleled HCD-CID fragmentation mode in an LTQ-Orbitrap. With this approach, we identified 195 cysteine-containing peptides from 179 proteins whose thiols underwent oxidative modifications in Arabidopsis cells following the treatment with hydrogen peroxide. A majority of those redox-sensitive proteins, including several transcription factors, were not identified by previous redox proteomics studies. This approach allows identification of the specific redox-regulated cysteine residues, and offers an effective tool for elucidation of redox proteomes. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Factors Controlling the Redox Activity of Oxygen in Perovskites: From Theory to Application for Catalytic Reactions

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Chunzhen Yang

2017-05-01

Full Text Available Triggering the redox reaction of oxygens has become essential for the development of (electro catalytic properties of transition metal oxides, especially for perovskite materials that have been envisaged for a variety of applications such as the oxygen evolution or reduction reactions (OER and ORR, respectively, CO or hydrocarbons oxidation, NO reduction and others. While the formation of ligand hole for perovskites is well-known for solid state physicists and/or chemists and has been widely studied for the understanding of important electronic properties such as superconductivity, insulator-metal transitions, magnetoresistance, ferroelectrics, redox properties etc., oxygen electrocatalysis in aqueous media at low temperature barely scratches the surface of the concept of oxygen ions oxidation. In this review, we briefly explain the electronic structure of perovskite materials and go through a few important parameters such as the ionization potential, Madelung potential, and charge transfer energy that govern the oxidation of oxygen ions. We then describe the surface reactivity that can be induced by the redox activity of the oxygen network and the formation of highly reactive surface oxygen species before describing their participation in catalytic reactions and providing mechanistic insights and strategies for designing new (electro catalysts. Finally, we give a brief overview of the different techniques that can be employed to detect the formation of such transient oxygen species.

Coronal mass ejection shock fronts containing the two types of intermediate shocks

International Nuclear Information System (INIS)

Steinolfson, R.S.; Hundhausen, A.J.

1990-01-01

Numerical solutions of the time-dependent, magnetohydrodynamic (MHD) equations in two dimensions are used to demonstrate the formation of both types of intermediate shocks in a single shock front for physical conditions that are an idealization of those expected to occur in some observed coronal mass ejections. The key to producing such a shock configuration in the simulations is the use of an initial atmosphere containing a magnetic field representative of that in a coronal streamer with open field lines overlying a region of closed field lines. Previous attempts using just open field lines (perpendicular to the surface) produced shock configurations containing just one of the two intermediate shock types. A schematic of such a shock front containing both intermediate shock types has been constructed previously based solely on the known properties of MHD shocks from the Rankine-Hugoniot equations and specific requirements placed on the shock solution at points along the front where the shock normal and upstream magnetic field are aligned. The shock front also contains, at various locations along the front, a hydrodynamic (nonmagnetic) shock, a switch-on shock, and a fast shock in addition to the intermediate shocks. This particular configuration occurs when the shock front speed exceeds the upstream (preshock) intermediate wave speed but is less than a critical speed defined in the paper (equation 1) along at least some portion of the shock front. A distinctive feature of the front is that it is concave upward (away from the surface) near the region where the field in the preshock plasma is normal to the front of near the central portion of the shock front

Formation of physical-gel redox electrolytes through self-assembly of discotic liquid crystals: Applications in dye sensitized solar cells

International Nuclear Information System (INIS)

Khan, Ammar A.; Kamarudin, Muhammad A.; Qasim, Malik M.; Wilkinson, Timothy D.

2017-01-01

The self-assembly of small molecules into ordered structures is of significant interest in electronic applications due to simpler device fabrication and better performance. Here we present work on the development of self-assembled fibrous networks of thermotropic triphenylene discotic liquid crystals, where 2,3,6,7,10,11-Hexakishexyloxytriphenylene (HAT6) is studied. The formation of interconnected molecular fibres in acetonitrile-based solvents facilitates thermally-reversible physical-gel (non-covalent) preparation, with the HAT6 network providing mechanical support and containment of the solvent. Furthermore, gel formation is also achieved using an acetonitrile-based iodide/tri-iodide redox liquid electrolyte, and the resulting gel mixture is utilised as an electrolyte in dye-sensitized solar cells (DSSCs). Our results show that it is indeed possible to achieve in situ gel formation in DSSCs, allowing for easy cell fabrication and electrolyte filling. In addition, the gel phase is found to increase device lifetime by limiting solvent evaporation. Differential scanning calorimetry (DSC) and polarising optical microscopy (POM) are used to study gel formation, and it is identified that the thermally reversible gels are stable up to working temperatures of 40 °C. It is found that DSSCs filled with gel electrolyte exhibit longer electron lifetime in the TiO 2 photo-anode (≈8.4 ms in the liquid electrolyte to ≈11.4 ms in the gel electrolytes), most likely due to electron screening from the electrolyte by HAT6. Current-Voltage (I–V) and electrochemical impedance spectroscopy (EIS) are used to study the effect of gel formation on conductivity and electrochemical properties, and it is found that confinement of the liquid electrolyte into a gel phase does not significantly reduce ionic conductivity, a problem common with solid-state polymer electrolytes. A 3.8 mM HAT6 gel electrolyte DSSC exhibited a PCE of 6.19% vs. a 5.86% liquid electrolyte reference. Extended

Phosphatidylcholine formation by LPCAT1 is regulated by Ca2+ and the redox status of the cell

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Soupene Eric

2012-06-01

Full Text Available Abstract Background Unsaturated fatty acids are susceptible to oxidation and damaged chains are removed from glycerophospholipids by phospholipase A2. De-acylated lipids are then re-acylated by lysophospholipid acyltransferase enzymes such as LPCAT1 which catalyses the formation of phosphatidylcholine (PC from lysoPC and long-chain acyl-CoA. Results Activity of LPCAT1 is inhibited by Ca2+, and a Ca2+-binding motif of the EF-hand type, EFh-1, was identified in the carboxyl-terminal domain of the protein. The residues Asp-392 and Glu-403 define the loop of the hairpin structure formed by EFh-1. Substitution of D392 and E403 to alanine rendered an enzyme insensitive to Ca2+, which established that Ca2+ binding to that region negatively regulates the activity of the acyltransferase amino-terminal domain. Residue Cys-211 of the conserved motif III is not essential for catalysis and not sufficient for sensitivity to treatment by sulfhydryl-modifier agents. Among the several active cysteine-substitution mutants of LPCAT1 generated, we identified one to be resistant to treatment by sulfhydryl-alkylating and sulfhydryl-oxidizer agents. Conclusion Mutant forms of LPCAT1 that are not inhibited by Ca2+ and sulfhydryl-alkylating and –oxidizing agents will provide a better understanding of the physiological function of a mechanism that places the formation of PC, and the disposal of the bioactive species lysoPC, under the control of the redox status and Ca2+ concentration of the cell.

Redox reaction studies by nanosecond pulse radiolysis

International Nuclear Information System (INIS)

Moorthy, P.N.

1979-01-01

Free radicals are formed as intermediates in many chemical and biochemical reactions. An important type of reaction which they can undergo is a one electron or redox process. The direction and rate of such electron transfer reactions is governed by the relative redox potentials of the participating species. Because of the generally short lived nature of free radicals, evaluation of their redox potentials poses a number of problems. Two techniques are described for the experimental determination of the redox potentials of short lived species generated by either a nanosecond electron pulse or laser flash. In the first method, redox titration of the short lived species with stable molecules of known redox potential is carried out, employing the technique of fast kinetic spectrophotometry. Conversely, by the same method it is also possible to evaluate the one electron redox potentials of stable molecules by redox titration with free radicals of known redox potential produced as above. In the second method, electrochemical reduction or oxidation of the short lived species at an appropriate electrode (generally a mercury drop) is carried out at different fixed potentials, and the redox potential evaluated from the current-potential curves (polarograms). Full description of the experimental set up and theoretical considerations for interpretation of the raw data are given. The relative merits of the two methods and their practical applicability are discussed. (auth.)

The roles of different mechanisms related to the tide-induced fronts in the Yellow Sea in summer

Science.gov (United States)

Ren, Shihe; Xie, Jiping; Zhu, Jiang

2014-09-01

In summer, the Yellow Sea Cold Water Mass (YSCWM) is a stable water mass of low temperature lying at the bottom of the central Yellow Sea (YS). It is fringed by some typical tidal fronts, which separate deep, stratified water on the offshore side from the well-mixed, shallow water on the inshore side. Three striking fronts—Subei Bank Front (SBF), Shandong Peninsula Front (SPF), and Mokpo Front (MKF; a front off the southwestern tip of the Korean Peninsula)—have been identified by various studies from both satellite observations and model results. Tide plays an important role in the formation and maintenance of these fronts. However, it is still a matter of debate as to the roles these two kinds of mechanisms of upwelling and tidal mixing play, and how importance they are in the maintenance processes of the above three fronts. Basing a nested high-resolution model HYCOM (the Hybrid Coordinate Ocean Model), this study focuses on the different mechanisms of tidal effects on the thermal fronts in the YS in summertime. Through comparative experiments with and without tidal forcing, the results indicate that the MKF is mainly driven by tide-induced upwelling. For the SPF, tidal mixing is the dominant factor, when lower cold water is stirred upwards along the sloping topography of the western YS. Meanwhile, the combined effect of upwelling and tidal mixing is the main cause of the formation of the SBF. Diagnostic analysis of thermal balance shows that horizontal nonlinear advection induced by strong tidal currents also contributes to the thermal balance of frontal areas.

Front propagation in Rayleigh-Taylor systems with reaction

International Nuclear Information System (INIS)

Scagliarini, A; Biferale, L; Sbragaglia, M; Mantovani, F; Pivanti, M; Schifano, S F; Tripiccione, R; Pozzati, F; Toschi, F

2011-01-01

A special feature of Rayleigh-Taylor systems with chemical reactions is the competition between turbulent mixing and the 'burning processes', which leads to a highly non-trivial dynamics. We studied the problem performing high resolution numerical simulations of a 2d system, using a thermal lattice Boltzmann (LB) model. We spanned the various regimes emerging at changing the relative chemical/turbulent time scales, from slow to fast reaction; in the former case we found numerical evidence of an enhancement of the front propagation speed (with respect to the laminar case), providing a phenomenological argument to explain the observed behaviour. When the reaction is very fast, instead, the formation of sharp fronts separating patches of pure phases, leads to an increase of intermittency in the small scale statistics of the temperature field.

Imaging dynamic redox processes with genetically encoded probes.

Science.gov (United States)

Ezeriņa, Daria; Morgan, Bruce; Dick, Tobias P

2014-08-01

Redox signalling plays an important role in many aspects of physiology, including that of the cardiovascular system. Perturbed redox regulation has been associated with numerous pathological conditions; nevertheless, the causal relationships between redox changes and pathology often remain unclear. Redox signalling involves the production of specific redox species at specific times in specific locations. However, until recently, the study of these processes has been impeded by a lack of appropriate tools and methodologies that afford the necessary redox species specificity and spatiotemporal resolution. Recently developed genetically encoded fluorescent redox probes now allow dynamic real-time measurements, of defined redox species, with subcellular compartment resolution, in intact living cells. Here we discuss the available genetically encoded redox probes in terms of their sensitivity and specificity and highlight where uncertainties or controversies currently exist. Furthermore, we outline major goals for future probe development and describe how progress in imaging methodologies will improve our ability to employ genetically encoded redox probes in a wide range of situations. This article is part of a special issue entitled "Redox Signalling in the Cardiovascular System." Copyright © 2014 Elsevier Ltd. All rights reserved.

A Membrane‐Free Redox Flow Battery with Two Immiscible Redox Electrolytes

OpenAIRE

Navalpotro, Paula; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

2017-01-01

Abstract Flexible and scalable energy storage solutions are necessary for mitigating fluctuations of renewable energy sources. The main advantage of redox flow batteries is their ability to decouple power and energy. However, they present some limitations including poor performance, short‐lifetimes, and expensive ion‐selective membranes as well as high price, toxicity, and scarcity of vanadium compounds. We report a membrane‐free battery that relies on the immiscibility of redox electrolytes ...

Fluid flow and reaction fronts: characterization of physical processes at the microscale using SEM analyses

Science.gov (United States)

Beaudoin, Nicolas; Koehn, Daniel; Toussaint, Renaud; Gomez-Rivas, Enrique; Bons, Paul; Chung, Peter; Martín-Martín, Juan Diego

2014-05-01

Fluid migrations are the principal agent for mineral replacement in the upper crust, leading to dramatic changes in the porosity and permeability of rocks over several kilometers. Consequently, a better understanding of the physical parameters leading to mineral replacement is required to better understand and model fluid flow and rock reservoir properties. Large-scale dolostone bodies are one of the best and most debated examples of such fluid-related mineral replacement. These formations received a lot of attention lately, and although genetic mechanics and implications for fluid volume are understood, the mechanisms controlling the formation and propagation of the dolomitization reaction front remain unclear. This contribution aims at an improvement of the knowledge about how this replacement front propagates over space and time. We study the front sharpness on hand specimen and thin section scale and what the influence of advection versus diffusion of material is on the front development. In addition, we demonstrate how preexisting heterogeneities in the host rock affect the propagation of the reaction front. The rock is normally not homogeneous but contains grain boundaries, fractures and stylolites, and such structures are important on the scale of the front width. Using Scanning Electron Microscopy and Raman Spectroscopy we characterized the reaction front chemistry and morphology in different context. Specimens of dolomitization fronts, collected from carbonate sequences of the southern Maestrat Basin, Spain and the Southwestern Scottish Highlands suggest that the front thickness is about several mm being relatively sharp. Fluid infiltrated grain boundaries and fractures forming mm-scale transition zone. We study the structure of the reaction zone in detail and discuss implications for fluid diffusion-advection models and mineral replacement. In addition we formulate a numerical model taking into account fluid flow, diffusion and advection of the mobile

Role of redox environment on the oligomerization of higher molecular weight adiponectin

Directory of Open Access Journals (Sweden)

Nuñez Martha

2011-05-01

Full Text Available Abstract Background Adiponectin is an adipocyte-secreted hormone with insulin-sensitizing and anti-inflammatory actions. The assembly of trimeric, hexameric, and higher molecular weight (HMW species of adiponectin is a topic of significant interest because physiological actions of adiponectin are oligomer-specific. In addition, adiponectin assembly is an example of oxidative oligomerization of multi-subunit protein complexes in endoplasmic reticulum (ER. Results We previously reported that trimers assemble into HMW adiponectin via intermediates stabilized by disulfide bonds, and complete oxidation of available cysteines locks adiponectin in hexameric conformation. In this study, we examined the effects of redox environment on the rate of oligomer formation and the distribution of oligomers. Reassembly of adiponectin under oxidizing conditions accelerated disulfide bonding but favored formation of hexamers over the HMW species. Increased ratios of HMW to hexameric adiponectin could be achieved rapidly under oxidizing conditions by promoting disulfide rearrangement. Conclusions Based upon these observations, we propose oxidative assembly of multi-subunit adiponectin complexes in a defined and stable redox environment is favored under oxidizing conditions coupled with high rates of disulfide rearrangement.

Negative Ion Density Fronts

International Nuclear Information System (INIS)

Igor Kaganovich

2000-01-01

Negative ions tend to stratify in electronegative plasmas with hot electrons (electron temperature Te much larger than ion temperature Ti, Te > Ti ). The boundary separating a plasma containing negative ions, and a plasma, without negative ions, is usually thin, so that the negative ion density falls rapidly to zero-forming a negative ion density front. We review theoretical, experimental and numerical results giving the spatio-temporal evolution of negative ion density fronts during plasma ignition, the steady state, and extinction (afterglow). During plasma ignition, negative ion fronts are the result of the break of smooth plasma density profiles during nonlinear convection. In a steady-state plasma, the fronts are boundary layers with steepening of ion density profiles due to nonlinear convection also. But during plasma extinction, the ion fronts are of a completely different nature. Negative ions diffuse freely in the plasma core (no convection), whereas the negative ion front propagates towards the chamber walls with a nearly constant velocity. The concept of fronts turns out to be very effective in analysis of plasma density profile evolution in strongly non-isothermal plasmas

Detonative propagation and accelerative expansion of the Crab Nebula shock front.

Science.gov (United States)

Gao, Yang; Law, Chung K

2011-10-21

The accelerative expansion of the Crab Nebula's outer envelope is a mystery in dynamics, as a conventional expanding blast wave decelerates when bumping into the surrounding interstellar medium. Here we show that the strong relativistic pulsar wind bumping into its surrounding nebula induces energy-generating processes and initiates a detonation wave that propagates outward to form the current outer edge, namely, the shock front, of the nebula. The resulting detonation wave, with a reactive downstream, then provides the needed power to maintain propagation of the shock front. Furthermore, relaxation of the curvature-induced reduction of the propagation velocity from the initial state of formation to the asymptotic, planar state of Chapman-Jouguet propagation explains the observed accelerative expansion. Potential richness in incorporating reactive fronts in the description of various astronomical phenomena is expected. © 2011 American Physical Society

Regulatory redox state in tree seeds

Directory of Open Access Journals (Sweden)

Ewelina Ratajczak

2017-12-01

Full Text Available Peroxiredoxins (Prx are important regulators of the redox status of tree seeds during maturation and long-term storage. Thioredoxins (Trx are redox transmitters and thereby regulate Prx activity. Current research is focused on the association of Trx with Prx in tree seeds differing in the tolerance to desiccation. The results will allow for better understanding the regulation of the redox status in orthodox, recalcitrant, and intermediate seeds. The findings will also elucidate the role of the redox status during the loss of viability of sensitive seeds during drying and long-term storage.

Pyritization processes and greigite formation in the advancing sulfidization front in the Upper Pleistocene sediments of the Black Sea

DEFF Research Database (Denmark)

Neretin, LN; Bottcher, ME; Jørgensen, BB

2004-01-01

Pyritization in late Pleistocene sediments of the Black Sea is driven by sulfide formed during anaerobic methane oxidation. A sulfidization front is formed by the opposing gradients of sulfide and dissolved iron. The sulfidization processes are controlled by the diffusion flux of sulfide from above...... and by the solid reactive iron content. Two processes of diffusion-limited pyrite formation were identified. The first process includes pyrite precipitation with the accumulation of iron sulfide precursors with the average chemical composition of FeSn (n = 1.10-1.29), including greigite. Elemental sulfur...... and polysulfides, formed from H,S by a reductive dissolution of Fe(Ill)-containing minerals, serve as intermediates to convert iron sulfides into pyrite. In the second process, a "direct" pyrite precipitation occurs through prolonged exposure of iron-containing minerals to dissolved sulfide. Methane-driven sulfate...

Tuning of redox regulatory mechanisms, reactive oxygen species and redox homeostasis under salinity stress

Directory of Open Access Journals (Sweden)

Hossain eSazzad

2016-05-01

Full Text Available Soil salinity is a crucial environmental constraint which limits biomass production at many sites on a global scale. Saline growth conditions cause osmotic and ionic imbalances, oxidative stress and perturb metabolism, e.g. the photosynthetic electron flow. The plant ability to tolerate salinity is determined by multiple biochemical and physiological mechanisms protecting cell functions, in particular by regulating proper water relations and maintaining ion homeostasis. Redox homeostasis is a fundamental cell property. Its regulation includes control of reactive oxygen species (ROS generation, sensing deviation from and readjustment of the cellular redox state. All these redox related functions have been recognized as decisive factors in salinity acclimation and adaptation. This review focuses on the core response of plants to overcome the challenges of salinity stress through regulation of ROS generation and detoxification systems and to maintain redox homeostasis. Emphasis is given to the role of NADH oxidase (RBOH, alternative oxidase (AOX, the plastid terminal oxidase (PTOX and the malate valve with the malate dehydrogenase isoforms under salt stress. Overwhelming evidence assigns an essential auxiliary function of ROS and redox homeostasis to salinity acclimation of plants.

Cynaropicrin targets the trypanothione redox system in Trypanosoma brucei.

Science.gov (United States)

Zimmermann, Stefanie; Oufir, Mouhssin; Leroux, Alejandro; Krauth-Siegel, R Luise; Becker, Katja; Kaiser, Marcel; Brun, Reto; Hamburger, Matthias; Adams, Michael

2013-11-15

In mice cynaropicrin (CYN) potently inhibits the proliferation of Trypanosoma brucei-the causative agent of Human African Trypanosomiasis-by a so far unknown mechanism. We hypothesized that CYNs α,β-unsaturated methylene moieties act as Michael acceptors for glutathione (GSH) and trypanothione (T(SH)2), the main low molecular mass thiols essential for unique redox metabolism of these parasites. The analysis of this putative mechanism and the effects of CYN on enzymes of the T(SH)2 redox metabolism including trypanothione reductase, trypanothione synthetase, glutathione-S-transferase, and ornithine decarboxylase are shown. A two step extraction protocol with subsequent UPLC-MS/MS analysis was established to quantify intra-cellular CYN, T(SH)2, GSH, as well as GS-CYN and T(S-CYN)2 adducts in intact T. b. rhodesiense cells. Within minutes of exposure to CYN, the cellular GSH and T(SH)2 pools were entirely depleted, and the parasites entered an apoptotic stage and died. CYN also showed inhibition of the ornithine decarboxylase similar to the positive control eflornithine. Significant interactions with the other enzymes involved in the T(SH)2 redox metabolism were not observed. Alongside many other biological activities sesquiterpene lactones including CYN have shown antitrypanosomal effects, which have been postulated to be linked to formation of Michael adducts with cellular nucleophiles. Here the interaction of CYN with biological thiols in a cellular system in general, and with trypanosomal T(SH)2 redox metabolism in particular, thus offering a molecular explanation for the antitrypanosomal activity is demonstrated. At the same time, the study provides a novel extraction and analysis protocol for components of the trypanosomal thiol metabolism. Copyright © 2013 Elsevier Ltd. All rights reserved.

Particle size effect of redox reactions for Co species supported on silica

International Nuclear Information System (INIS)

Chotiwan, Siwaruk; Tomiga, Hiroki; Katagiri, Masaki; Yamamoto, Yusaku; Yamashita, Shohei; Katayama, Misaki; Inada, Yasuhiro

2016-01-01

Conversions of chemical states during redox reactions of two silica-supported Co catalysts, which were prepared by the impregnation method, were evaluated by using an in situ XAFS technique. The addition of citric acid into the precursor solution led to the formation on silica of more homogeneous and smaller Co particles, with an average diameter of 4 nm. The supported Co 3 O 4 species were reduced to metallic Co via the divalent CoO species during a temperature-programmed reduction process. The reduced Co species were quantitatively oxidized with a temperature-programmed oxidation process. The higher observed reduction temperature of the smaller CoO particles and the lower observed oxidation temperature of the smaller metallic Co particles were induced by the higher dispersion of the Co oxide species, which apparently led to a stronger interaction with supporting silica. The redox temperature between CoO and Co 3 O 4 was found to be independent of the particle size. - Graphical abstract: Chemical state conversions of SiO 2 -supported Co species and the particle size effect have been analyzed by means of in situ XAFS technique. The small CoO particles have endurance against the reduction and exist in a wide temperature range. Display Omitted - Highlights: • The conversions of the chemical state of supported Co species during redox reaction are evaluated. • In operando XAFS technique were applied to measure redox properties of small Co particles. • A small particle size affects to the redox temperatures of cobalt catalysts.

Redox thermodynamic data of plutonium in acidic and carbonate media. Pu(V) stability

International Nuclear Information System (INIS)

Capdevila, H.

1992-01-01

Pu redox equilibria are studied in acidic and carbonate media in this thesis, to build a thermodynamic data bank consistent with the TDB (NEA-OECD) one and in connection with radioactive waste disposal programs. Literature is discussed and reinterpreted. The experimental method is tested with Uranium preliminary measurements. The reversible redox potentials (PuO 2 + and Pu 4+ /Pu 3+ ) are measured using the cyclic voltametric technique in perchloric media at several ionic strengths (from 0.5 to 3M) and temperatures (from 0 to 70 deg C). The Specific Interaction Theory (SIT) is used to measured activity coefficients and to extrapolate data to the standard conditions. The potentials variations versus temperature are linear in first approximation: the entropy changes are found constant from 0 to 70 deg C and the heat capacity changes are within uncertainties. The standard constant of PuO 2 + disproportionation into PuO 2 2+ and Pu 3+ is deduced from spectrophotometric measurements performed in perchloric media around pH=1 where Pu 4+ hydrolysis is discussed. The Pu non-reversible standard potentials (PuO 2 2+ /Pu 4+ for instance) are then calculated and validated with a spectrophotometric study of Pu 4+ formation from PuO 2 2+ and Pu 3+ in a 1M perchloric acidic solution. The Pu(VI/V) redox potential, activity coefficients and entropies are measured using the same technique in concentrated carbonate media. The limiting complex standard formation constants and the redox potential shifts (between acidic and carbonate media) are then discussed among the U, Np, Pu and Am actinides. A spectrophotometric study of the equilibrium between the complexes with 5 and 4 carbonate ligands allowed to measure Pu(IV) limiting complex stability at several ionic strengths. (author). 26 tabs., 46 figs., 95 refs

Zinc and the modulation of redox homeostasis

Science.gov (United States)

Oteiza, Patricia I.

2012-01-01

Zinc, a redox inactive metal, has been long viewed as a component of the antioxidant network, and growing evidence points to its involvement in redox-regulated signaling. These actions are exerted through several mechanisms based on the unique chemical and functional properties of zinc. Overall, zinc contributes to maintain the cell redox balance through different mechanisms including: i) the regulation of oxidant production and metal-induced oxidative damage; ii) the dynamic association of zinc with sulfur in protein cysteine clusters, from which the metal can be released by nitric oxide, peroxides, oxidized glutathione and other thiol oxidant species; iii) zinc-mediated induction of the zinc-binding protein metallothionein, which releases the metal under oxidative conditions and act per se scavenging oxidants; iv) the involvement of zinc in the regulation of glutathione metabolism and of the overall protein thiol redox status; and v) a direct or indirect regulation of redox signaling. Findings of oxidative stress, altered redox signaling, and associated cell/tissue disfunction in cell and animal models of zinc deficiency, stress the relevant role of zinc in the preservation of cell redox homeostasis. However, while the participation of zinc in antioxidant protection, redox sensing, and redox-regulated signaling is accepted, the involved molecules, targets and mechanisms are still partially known and the subject of active research. PMID:22960578

Mechanism of formation of subnanosecond current front in high-voltage pulse open discharge

Science.gov (United States)

Schweigert, I. V.; Alexandrov, A. L.; Zakrevsky, Dm. E.; Bokhan, P. A.

2014-11-01

The mechanism of subnanosecond current front rise observed previously in the experiment in high-voltage pulse open discharge in helium is studied in kinetic particle-in-cell simulations. The Boltzmann equations for electrons, ions, and fast atoms are solved self-consistently with the Poisson equations for the electrical potential. The partial contributions to the secondary electron emission from the ions, fast atoms, photons, and electrons, bombarding the electrode, are calculated. In simulations, as in the experiment, the discharge glows between two symmetrical cathodes and the anode grid in the midplane at P =6 Torr and the applied voltage of 20 kV. The electron avalanche development is considered for two experimental situations during the last stage of breakdown: (i) with constant voltage and (ii) with decreasing voltage. For case (i), the subnanosecond current front rise is set by photons from the collisional excitation transfer reactions. For the case (ii), the energetic electrons swamp the cathode during voltage drop and provide the secondary electron emission for the subnanosecond current rise, observed in the experiment.

Real-time monitoring of intracellular redox changes in Methylococcus capsulatus (Bath) for efficient bioconversion of methane to methanol.

Science.gov (United States)

Ishikawa, Masahito; Tanaka, Yuya; Suzuki, Risa; Kimura, Kota; Tanaka, Kenya; Kamiya, Kazuhide; Ito, Hidehiro; Kato, Souichiro; Kamachi, Toshiaki; Hori, Katsutoshi; Nakanishi, Shuji

2017-10-01

This study aimed to develop a novel method for real-time monitoring of the intracellular redox states in a methanotroph Methylococcus capsulatus, using Peredox as a genetically encoded fluorescent sensor of the NADH:NAD + ratio. As expected, the fluorescence derived from the Peredox-expressing M. capsulatus transformant increased by supplementation of electron donor compounds (methane and formate), while it decreased by specifically inhibiting the methanol oxidation reaction. Electrochemical measurements confirmed that the Peredox fluorescence reliably represents the intracellular redox changes. This study is the first to construct a reliable redox-monitoring method for methanotrophs, which will facilitate to develop more efficient methane-to-methanol bioconversion processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries.

Science.gov (United States)

Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

2016-12-23

Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn 4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g -1 based on solid-state redox reaction of oxide ions.

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

Science.gov (United States)

Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

2016-01-01

Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions. PMID:28008955

Catalytic Water Oxidation by a Bio-inspired Nickel Complex with Redox Active Ligand

Science.gov (United States)

Wang, Dong; Bruner, Charlie O.

2017-01-01

The oxidation of water to dioxygen is important in natural photosynthesis. One of nature’s strategies for managing such multi-electron transfer reactions is to employ redox active metal-organic cofactor arrays. One prototype example is the copper-tyrosinate active site found in galactose oxidase. In this work, we have implemented such a strategy to develop a bio-inspired nickel-phenolate complex capable of catalyzing the oxidation of water to O2 electrochemically at neutral pH with a modest overpotential. The employment of the redox-active ligand turned out to be a useful strategy to avoid the formation of high-valent nickel intermediates while a reasonable turnover rate (0.15 s−1) is retained. PMID:29099176

Redox Biology in Neurological Function, Dysfunction, and Aging.

Science.gov (United States)

Franco, Rodrigo; Vargas, Marcelo R

2018-04-23

Reduction oxidation (redox) reactions are central to life and when altered, they can promote disease progression. In the brain, redox homeostasis is recognized to be involved in all aspects of central nervous system (CNS) development, function, aging, and disease. Recent studies have uncovered the diverse nature by which redox reactions and homeostasis contribute to brain physiology, and when dysregulated to pathological consequences. Redox reactions go beyond what is commonly described as oxidative stress and involve redox mechanisms linked to signaling and metabolism. In contrast to the nonspecific nature of oxidative damage, redox signaling involves specific oxidation/reduction reactions that regulate a myriad of neurological processes such as neurotransmission, homeostasis, and degeneration. This Forum is focused on the role of redox metabolism and signaling in the brain. Six review articles from leading scientists in the field that appraise the role of redox metabolism and signaling in different aspects of brain biology including neurodevelopment, neurotransmission, aging, neuroinflammation, neurodegeneration, and neurotoxicity are included. An original research article exemplifying these concepts uncovers a novel link between oxidative modifications, redox signaling, and neurodegeneration. This Forum highlights the recent advances in the field and we hope it encourages future research aimed to understand the mechanisms by which redox metabolism and signaling regulate CNS physiology and pathophysiology. Antioxid. Redox Signal. 00, 000-000.

Turbulence and the Formation of Filaments, Loops, and Shock Fronts in NGC 1275

Science.gov (United States)

Falceta-Gonçalves, D.; de Gouveia Dal Pino, E. M.; Gallagher, J. S.; Lazarian, A.

2010-01-01

NGC 1275, the central galaxy in the Perseus cluster, is the host of gigantic hot bipolar bubbles inflated by active galactic nucleus (AGN) jets observed in the radio as Perseus A. It presents a spectacular Hα-emitting nebulosity surrounding NGC 1275, with loops and filaments of gas extending to over 50 kpc. The origin of the filaments is still unknown, but probably correlates with the mechanism responsible for the giant buoyant bubbles. We present 2.5 and three-dimensional magnetohydrodynamical (MHD) simulations of the central region of the cluster in which turbulent energy, possibly triggered by star formation and supernovae (SNe) explosions, is introduced. The simulations reveal that the turbulence injected by massive stars could be responsible for the nearly isotropic distribution of filaments and loops that drag magnetic fields upward as indicated by recent observations. Weak shell-like shock fronts propagating into the intracluster medium (ICM) with velocities of 100-500 km s-1 are found, also resembling the observations. The isotropic outflow momentum of the turbulence slows the infall of the ICM, thus limiting further starburst activity in NGC 1275. As the turbulence is subsonic over most of the simulated volume, the turbulent kinetic energy is not efficiently converted into heat and additional heating is required to suppress the cooling flow at the core of the cluster. Simulations combining the MHD turbulence with the AGN outflow can reproduce the temperature radial profile observed around NGC 1275. While the AGN mechanism is the main heating source, the SNe are crucial to isotropize the energy distribution.

Analytical redox reactions and redox potentials of tungsten and its concomitants

Energy Technology Data Exchange (ETDEWEB)

Wuensch, G.; Mintrop, L.; Tracht, U.

1985-01-01

It is demonstrated that tungsten can be more effectively determined by redox titrimetry than by gravimetry. In addition to its inherent greater simplicity the volumetric approach offers to determine several components of the sample from consecutive redox titrations. To provide the necessary information the conditional redox potentials of W, Mo, Fe, V, Ti, Sn, Cu, Cr in HCl, HCl + HF and HCl + H/sub 3/PO/sub 4/ have been determined. Use of HF and/or H/sub 3/PO/sub 4/ allows sample preparations without any precipitation of tungstic acid. The influence of these auxiliary complexing agents on the potentials and kinetics is discussed. The titrations can be performed reductimetrically or more conveniently oxidimetrically using potentiometric or amperometric indication. The use of strongly reducing agents restricts the tolerance interval to +-0.6%, so that the gravimetric determination of tungsten remains superior for high precision analyses.

Analytical redox reactions and redox potentials of tungsten and its concomitants

International Nuclear Information System (INIS)

Wuensch, G.; Mintrop, L.; Tracht, U.

1985-01-01

It is demonstrated that tungsten can be more effectively determined by redox titrimetry than by gravimetry. In addition to its inherent greater simplicity the volumetric approach offers to determine several components of the sample from consecutive redox titrations. To provide the necessary information the conditional redox potentials of W, Mo, Fe, V, Ti, Sn, Cu, Cr in HCl, HCl + HF and HCl + H 3 PO 4 have been determined. Use of HF and/or H 3 PO 4 allows sample preparations without any precipitation of tungstic acid. The influence of these auxiliary complexing agents on the potentials and kinetics is discussed. The titrations can be performed reductimetrically or more conveniently oxidimetrically using potentiometric or amperometric indication. The use of strongly reducing agents restricts the tolerance interval to +-0.6%, so that the gravimetric determination of tungsten remains superior for high precision analyses. (orig.) [de

Light-Front Holography, Light-Front Wavefunctions, and Novel QCD Phenomena

Energy Technology Data Exchange (ETDEWEB)

Brodsky, Stanley J.; /SLAC /Southern Denmark U., CP3-Origins; de Teramond, Guy F.; /Costa Rica U.

2012-02-16

Light-Front Holography is one of the most remarkable features of the AdS/CFT correspondence. In spite of its present limitations it provides important physical insights into the nonperturbative regime of QCD and its transition to the perturbative domain. This novel framework allows hadronic amplitudes in a higher dimensional anti-de Sitter (AdS) space to be mapped to frame-independent light-front wavefunctions of hadrons in physical space-time. The model leads to an effective confining light-front QCD Hamiltonian and a single-variable light-front Schroedinger equation which determines the eigenspectrum and the light-front wavefunctions of hadrons for general spin and orbital angular momentum. The coordinate z in AdS space is uniquely identified with a Lorentz-invariant coordinate {zeta} which measures the separation of the constituents within a hadron at equal light-front time and determines the off-shell dynamics of the bound-state wavefunctions, and thus the fall-off as a function of the invariant mass of the constituents. The soft-wall holographic model modified by a positive-sign dilaton metric, leads to a remarkable one-parameter description of nonperturbative hadron dynamics - a semi-classical frame-independent first approximation to the spectra and light-front wavefunctions of meson and baryons. The model predicts a Regge spectrum of linear trajectories with the same slope in the leading orbital angular momentum L of hadrons and the radial quantum number n. The hadron eigensolutions projected on the free Fock basis provides the complete set of valence and non-valence light-front Fock state wavefunctions {Psi}{sub n/H} (x{sub i}, k{sub {perpendicular}i}, {lambda}{sub i}) which describe the hadron's momentum and spin distributions needed to compute the direct measures of hadron structure at the quark and gluon level, such as elastic and transition form factors, distribution amplitudes, structure functions, generalized parton distributions and transverse

Engineered Proteins: Redox Properties and Their Applications

Science.gov (United States)

Prabhulkar, Shradha; Tian, Hui; Wang, Xiaotang; Zhu, Jun-Jie

2012-01-01

Abstract Oxidoreductases and metalloproteins, representing more than one third of all known proteins, serve as significant catalysts for numerous biological processes that involve electron transfers such as photosynthesis, respiration, metabolism, and molecular signaling. The functional properties of the oxidoreductases/metalloproteins are determined by the nature of their redox centers. Protein engineering is a powerful approach that is used to incorporate biological and abiological redox cofactors as well as novel enzymes and redox proteins with predictable structures and desirable functions for important biological and chemical applications. The methods of protein engineering, mainly rational design, directed evolution, protein surface modifications, and domain shuffling, have allowed the creation and study of a number of redox proteins. This review presents a selection of engineered redox proteins achieved through these methods, resulting in a manipulation in redox potentials, an increase in electron-transfer efficiency, and an expansion of native proteins by de novo design. Such engineered/modified redox proteins with desired properties have led to a broad spectrum of practical applications, ranging from biosensors, biofuel cells, to pharmaceuticals and hybrid catalysis. Glucose biosensors are one of the most successful products in enzyme electrochemistry, with reconstituted glucose oxidase achieving effective electrical communication with the sensor electrode; direct electron-transfer-type biofuel cells are developed to avoid thermodynamic loss and mediator leakage; and fusion proteins of P450s and redox partners make the biocatalytic generation of drug metabolites possible. In summary, this review includes the properties and applications of the engineered redox proteins as well as their significance and great potential in the exploration of bioelectrochemical sensing devices. Antioxid. Redox Signal. 17, 1796–1822. PMID:22435347

Radii of Redox Components from Absolute Redox Potentials Compared with Covalent and Aqueous Ionic Radii

Czech Academy of Sciences Publication Activity Database

Heyrovská, Raji

2010-01-01

Roč. 22, č. 9 (2010), s. 903-907 ISSN 1040-0397 Institutional support: RVO:68081707 Keywords : Electrochemistry * Absolute redox potentials * Radii of redox components Subject RIV: BO - Biophysics Impact factor: 2.721, year: 2010

Next generation of optical front-ends for numerical services - 15387

International Nuclear Information System (INIS)

Fullenbaum, M.; Durieux, A.; Dubroca, G.; Fuss, P.

2015-01-01

Visual Inspection and surveillance technology means in environments exhibiting high levels of gamma and neutron radiation are nowadays fulfilled through the use of analog tubes. The images are thus acquired with analog devices whose vast majority relies on 1 and 2/3 inch imaging formats and deliver native analog images. There is a growing demand for real time image processing and distribution through Ethernet services for quicker and seamless process integration throughout many sectors. This will call for the inception of solid state sensor (CCD, CMOS) to generate numerical native images as the first step and building block towards end to end numerical processing (ICT), assuming these sensors can be hardened or protected in the field of the nuclear industry. On the one hand, these sensor sizes will be significantly reduced (by a factor of 2-3) versus those of the tubes, and on the other hand, one will also be presented with the opportunity of increased spatial resolution, stemming from the high pixel count of the solid state technology, for implementation of new or better services or of enhanced pieces of information for decision making purposes. In order to reap the benefits of such sensors, new optical front-ends will have to be designed. Over and beyond the mere aspects of matching the reduced sensor size to the size of the scenes at stake, optical performances of these front-end will also bear an impact on the whole optical chain applications. As an example, detection and tracking needs will be different from a performance standpoint and the overall performances will have to be balanced out in between the optical front-end, the image format, the image processing software capability, processing speed,...just to name a few. In this paper we will review and explain the missing gaps in order to switch to a full numerical optical chain by focusing on the optical front-end and the associated cost trade-offs. Finally, we will conclude by clearly stating the best

Enhanced Colloidal Stability of CeO2 Nanoparticles by Ferrous Ions: Adsorption, Redox Reaction, and Surface Precipitation.

Science.gov (United States)

Liu, Xuyang; Ray, Jessica R; Neil, Chelsea W; Li, Qingyun; Jun, Young-Shin

2015-05-05

Due to the toxicity of cerium oxide (CeO2) nanoparticles (NPs), a better understanding of the redox reaction-induced surface property changes of CeO2 NPs and their transport in natural and engineered aqueous systems is needed. This study investigates the impact of redox reactions with ferrous ions (Fe2+) on the colloidal stability of CeO2 NPs. We demonstrated that under anaerobic conditions, suspended CeO2 NPs in a 3 mM FeCl2 solution at pH 4.8 were much more stable against sedimentation than those in the absence of Fe2+. Redox reactions between CeO2 NPs and Fe2+ lead to the formation of 6-line ferrihydrite on the CeO2 surfaces, which enhanced the colloidal stability by increasing the zeta potential and hydrophilicity of CeO2 NPs. These redox reactions can affect the toxicity of CeO2 NPs by increasing cerium dissolution, and by creating new Fe(III) (hydr)oxide reactive surface layers. Thus, these findings have significant implications for elucidating the phase transformation and transport of redox reactive NPs in the environment.

A redox-based mechanism for the neuroprotective and neurodestructive effects of nitric oxide and related nitroso-compounds.

Science.gov (United States)

Lipton, S A; Choi, Y B; Pan, Z H; Lei, S Z; Chen, H S; Sucher, N J; Loscalzo, J; Singel, D J; Stamler, J S

1993-08-12

Congeners of nitrogen monoxide (NO) are neuroprotective and neurodestructive. To address this apparent paradox, we considered the effects on neurons of compounds characterized by alternative redox states of NO: nitric oxide (NO.) and nitrosonium ion (NO+). Nitric oxide, generated from NO. donors or synthesized endogenously after NMDA (N-methyl-D-aspartate) receptor activation, can lead to neurotoxicity. Here, we report that NO.- mediated neurotoxicity is engendered, at least in part, by reaction with superoxide anion (O2.-), apparently leading to formation of peroxynitrite (ONOO-), and not by NO. alone. In contrast, the neuroprotective effects of NO result from downregulation of NMDA-receptor activity by reaction with thiol group(s) of the receptor's redox modulatory site. This reaction is not mediated by NO. itself, but occurs under conditions supporting S-nitrosylation of NMDA receptor thiol (reaction or transfer of NO+). Moreover, the redox versatility of NO allows for its interconversion from neuroprotective to neurotoxic species by a change in the ambient redox milieu. The details of this complex redox chemistry of NO may provide a mechanism for harnessing neuroprotective effects and avoiding neurotoxicity in the central nervous system.

Modelling sulfamethoxazole degradation under different redox conditions

Science.gov (United States)

Sanchez-Vila, X.; Rodriguez-Escales, P.

2015-12-01

Sulfamethoxazole (SMX) is a low adsorptive, polar, sulfonamide antibiotic, widely present in aquatic environments. Degradation of SMX in subsurface porous media is spatially and temporally variable, depending on various environmental factors such as in situ redox potential, availability of nutrients, local soil characteristics, and temperature. It has been reported that SMX is better degraded under anoxic conditions and by co-metabolism processes. In this work, we first develop a conceptual model of degradation of SMX under different redox conditions (denitrification and iron reducing conditions), and second, we construct a mathematical model that allows reproducing different experiments of SMX degradation reported in the literature. The conceptual model focuses on the molecular behavior and contemplates the formation of different metabolites. The model was validated using the experimental data from Barbieri et al. (2012) and Mohatt et al. (2011). It adequately reproduces the reversible degradation of SMX under the presence of nitrite as an intermediate product of denitrification. In those experiments degradation was mediated by the transient formation of a diazonium cation, which was considered responsible of the substitution of the amine radical by a nitro radical, forming the 4-nitro-SMX. The formation of this metabolite is a reversible process, so that once the concentration of nitrite was back to zero due to further advancement of denitrification, the concentration of SMX was fully recovered. The forward reaction, formation of 4-nitro SMX, was modeled considering a kinetic of second order, whereas the backward reaction, dissociation of 4-nitro-SMX back to the original compound, could be modeled with a first order degradation reaction. Regarding the iron conditions, SMX was degraded due to the oxidation of iron (Fe2+), which was previously oxidized from goethite due to the degradation of a pool of labile organic carbon. As the oxidation of iron occurred on the

Simultaneous anionic and cationic redox

Science.gov (United States)

Jung, Sung-Kyun; Kang, Kisuk

2017-12-01

It is challenging to unlock anionic redox activity, accompanied by full utilization of available cationic redox process, to boost capacity of battery cathodes. Now, material design by tuning the metal-oxygen interaction is shown to be a promising solution.

Membranes for Redox Flow Battery Applications

Science.gov (United States)

Prifti, Helen; Parasuraman, Aishwarya; Winardi, Suminto; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

2012-01-01

The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention. PMID:24958177

Membranes for redox flow battery applications.

Science.gov (United States)

Prifti, Helen; Parasuraman, Aishwarya; Winardi, Suminto; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

2012-06-19

The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention.

Membranes for Redox Flow Battery Applications

Directory of Open Access Journals (Sweden)

Maria Skyllas-Kazacos

2012-06-01

Full Text Available The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention.

Consumer preferences for front-of-pack calories labelling.

Science.gov (United States)

van Kleef, Ellen; van Trijp, Hans; Paeps, Frederic; Fernández-Celemín, Laura

2008-02-01

In light of the emerging obesity pandemic, front-of-pack calories labels may be an important tool to assist consumers in making informed healthier food choices. However, there is little prior research to guide key decisions on whether caloric content should be expressed in absolute terms or relative to recommended daily intake, whether it should be expressed in per serving or per 100 g and whether the information should be further brought alive for consumers in terms of what the extra calorie intake implies in relation to activity levels. The present study aimed at providing more insight into consumers' appreciation of front-of-pack labelling of caloric content of food products and their specific preferences for alternative execution formats for such information in Europe. For this purpose, eight executions of front-of-pack calorie flags were designed and their appeal and information value were extensively discussed with consumers through qualitative research in four different countries (Germany, The Netherlands, France and the UK). The results show that calories are well-understood and that participants were generally positive about front-of-pack flags, particularly when flags are uniform across products. The most liked flags are the simpler flags depicting only the number of calories per serving or per 100 g, while more complex flags including references to daily needs or exercise and the flag including a phrase referring to balanced lifestyle were least preferred. Some relevant differences between countries were observed. Although participants seem to be familiar with the notion of calories, they do not seem to fully understand how to apply them. From the results, managerial implications for the design and implementation of front-of-pack calorie labelling as well as important directions for future research are discussed.

Consumer preferences for front-of-pack calories labelling

Science.gov (United States)

van Kleef, Ellen; van Trijp, Hans; Paeps, Frederic; Fernández-Celemín, Laura

2008-01-01

Objective In light of the emerging obesity pandemic, front-of-pack calories labels may be an important tool to assist consumers in making informed healthier food choices. However, there is little prior research to guide key decisions on whether caloric content should be expressed in absolute terms or relative to recommended daily intake, whether it should be expressed in per serving or per 100 g and whether the information should be further brought alive for consumers in terms of what the extra calorie intake implies in relation to activity levels. The present study aimed at providing more insight into consumers’ appreciation of front-of-pack labelling of caloric content of food products and their specific preferences for alternative execution formats for such information in Europe. Design For this purpose, eight executions of front-of-pack calorie flags were designed and their appeal and information value were extensively discussed with consumers through qualitative research in four different countries (Germany, The Netherlands, France and the UK). Results The results show that calories are well-understood and that participants were generally positive about front-of-pack flags, particularly when flags are uniform across products. The most liked flags are the simpler flags depicting only the number of calories per serving or per 100 g, while more complex flags including references to daily needs or exercise and the flag including a phrase referring to balanced lifestyle were least preferred. Some relevant differences between countries were observed. Although participants seem to be familiar with the notion of calories, they do not seem to fully understand how to apply them. Conclusion From the results, managerial implications for the design and implementation of front-of-pack calorie labelling as well as important directions for future research are discussed. PMID:17601362

Soil phosphorus redistribution among iron-bearing minerals under redox fluctuation

Science.gov (United States)

Lin, Y.; Bhattacharyya, A.; Campbell, A.; Nico, P. S.; Pett-Ridge, J.; Silver, W. L.

2016-12-01

Phosphorus (P) is a key limiting nutrient in tropical forests that governs primary production, litter decomposition, and soil respiration. A large proportion of P in these highly weathered soils is bound to short-range ordered or poorly crystalline iron (Fe) minerals. It is well-documented that these Fe minerals are redox-sensitive; however, little is known about how Fe-redox interactions affect soil P turnover. We evaluated the impacts of oxic/anoxic fluctuation on soil P fractions and reactive Fe species in a laboratory incubation experiment. Soils from a humid tropical forest were amended with plant biomass and incubated for up to 44 days under four redox regimes: static oxic, static anoxic, high frequency fluctuating (4-day oxic/4-day anoxic), and low frequency fluctuating (8-day oxic/4-day anoxic). We found that the static anoxic treatment induced a 10-fold increase in Fe(II) (extracted by hydrochloric acid) and a 1.5-fold increase in poorly crystalline Fe (extracted by ammonium oxalate), suggesting that anoxic conditions drastically increased Fe(III) reduction and the formation of amorphous Fe minerals. Static anoxic conditions also increased Fe-bound P (extracted by sodium hydroxide) and increased the oxalate-extractable P by up to 110% relative to static oxic conditions. In two fluctuating treatments, Fe(II) and oxalate-extractable Fe and P were all increased by short-term reduction events after 30 minutes, but fell back to their initial levels after 3 hours. These results suggest that reductive dissolution of Fe(III) minerals mobilized a significant amount of P; however, this P could be rapidly re-adsorbed. Furthermore, bioavailable P extracted by sodium bicarbonate solution was largely unaffected by redox regimes and was only increased by static anoxic conditions after 20 days. Overall, our data demonstrate that a significant amount of soil P may be liberated and re-adsorbed by Fe minerals during redox fluctuation. Even though bioavailable P appears to be

Redox-assisted Li+-storage in lithium-ion batteries

International Nuclear Information System (INIS)

Huang Qizhao; Wang Qing

2016-01-01

Interfacial charge transfer is the key kinetic process dictating the operation of lithium-ion battery. Redox-mediated charge propagations of the electronic (e − and h + ) and ionic species (Li + ) at the electrode–electrolyte interface have recently gained increasing attention for better exploitation of battery materials. This article briefly summarises the energetic and kinetic aspects of lithium-ion batteries, and reviews the recent progress on various redox-assisted Li + storage approaches. From molecular wiring to polymer wiring and from redox targeting to redox flow lithium battery, the role of redox mediators and the way of the redox species functioning in lithium-ion batteries are discussed. (topical review)

Effect of the soil's redox conditions on the mobility of Se

International Nuclear Information System (INIS)

Darcheville, O.; Fevrier, L.; Martin-Garin, A.

2005-01-01

Full text of publication follows: 79 Se is a long-life fission product found in the nuclear wastes. Understanding its behaviour in soils is of major concern because of its bioavailability with almost all living organisms (plants and animals). This study is part of a wider multi-disciplinary program that aims at studying 'the effect of the geochemical transformations and the microbial activities on the fate of Se in soils' [1]. The first part of this program is focused on the interactions between Se and the organic compartment of soils, including both biotic (microorganisms, plants,...) and abiotic (humic, fulvic substances,...) components. Special attention is paid to their consequence on the mobility of Se. The second part of the study, presented here, aims specifically at understanding the effect of the soil's redox status on the mobility of Se and at identifying the nature of the processes involved (microbiological vs chemical). Different types of experiments are performed under laboratory controlled conditions. They consist in mixing a 2 mm-sieved sandy soil from the Rhone borders (France) with radio-labelled selenite ( 75 SeIV). In batch experiments, the soil is incubated in a closed vessel under various atmospheres (O 2 or N 2 ) and amended with specific nutrients in order to create contrasted redox conditions and to stimulate specific microbial communities. These conditions are also used in column experiments to determine their impact on Se mobility. They are completed by varying the degree of water saturation in the column and the structure of the soil. The percolation front of Se is followed in-situ with a mobile gamma detector without disturbing the system. In both experimental designs, mass recoveries of 75 Se are precisely determined in the soil-solution systems thanks to the quantification of Se concentrations in the aqueous, solid and gaseous phases. In addition, the non reversibly sorbed Se fraction is assessed by performing sequential extractions

Exercise-intensity dependent alterations in plasma redox status do not reflect skeletal muscle redox-sensitive protein signaling.

Science.gov (United States)

Parker, Lewan; Trewin, Adam; Levinger, Itamar; Shaw, Christopher S; Stepto, Nigel K

2018-04-01

Redox homeostasis and redox-sensitive protein signaling play a role in exercise-induced adaptation. The effects of sprint-interval exercise (SIE), high-intensity interval exercise (HIIE) and continuous moderate-intensity exercise (CMIE), on post-exercise plasma redox status are unclear. Furthermore, whether post-exercise plasma redox status reflects skeletal muscle redox-sensitive protein signaling is unknown. In a randomized crossover design, eight healthy adults performed a cycling session of HIIE (5×4min at 75% W max ), SIE (4×30s Wingate's), and CMIE work-matched to HIIE (30min at 50% of W max ). Plasma hydrogen peroxide (H 2 O 2 ), thiobarbituric acid reactive substances (TBARS), superoxide dismutase (SOD) activity, and catalase activity were measured immediately post, 1h, 2h and 3h post-exercise. Plasma redox status biomarkers were correlated with phosphorylation of skeletal muscle p38-MAPK, JNK, NF-κB, and IκBα protein content immediately and 3h post-exercise. Plasma catalase activity was greater with SIE (56.6±3.8Uml -1 ) compared to CMIE (42.7±3.2, pexercise plasma TBARS and SOD activity significantly (pexercise protocol. A significant positive correlation was detected between plasma catalase activity and skeletal muscle p38-MAPK phosphorylation 3h post-exercise (r=0.40, p=0.04). No other correlations were detected (all p>0.05). Low-volume SIE elicited greater post-exercise plasma catalase activity compared to HIIE and CMIE, and greater H 2 O 2 compared to CMIE. Plasma redox status did not, however, adequately reflect skeletal muscle redox-sensitive protein signaling. Copyright © 2017 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

Thiol/disulfide redox states in signaling and sensing

Science.gov (United States)

Go, Young-Mi; Jones, Dean P.

2015-01-01

Rapid advances in redox systems biology are creating new opportunities to understand complexities of human disease and contributions of environmental exposures. New understanding of thiol-disulfide systems have occurred during the past decade as a consequence of the discoveries that thiol and disulfide systems are maintained in kinetically controlled steady-states displaced from thermodynamic equilibrium, that a widely distributed family of NADPH oxidases produces oxidants that function in cell signaling, and that a family of peroxiredoxins utilize thioredoxin as a reductant to complement the well-studied glutathione antioxidant system for peroxide elimination and redox regulation. This review focuses on thiol/disulfide redox state in biologic systems and the knowledge base available to support development of integrated redox systems biology models to better understand the function and dysfunction of thiol-disulfide redox systems. In particular, central principles have emerged concerning redox compartmentalization and utility of thiol/disulfide redox measures as indicators of physiologic function. Advances in redox proteomics show that, in addition to functioning in protein active sites and cell signaling, cysteine residues also serve as redox sensors to integrate biologic functions. These advances provide a framework for translation of redox systems biology concepts to practical use in understanding and treating human disease. Biological responses to cadmium, a widespread environmental agent, are used to illustrate the utility of these advances to the understanding of complex pleiotropic toxicities. PMID:23356510

Redox homeostasis: The Golden Mean of healthy living

Directory of Open Access Journals (Sweden)

Fulvio Ursini

2016-08-01

Full Text Available The notion that electrophiles serve as messengers in cell signaling is now widely accepted. Nonetheless, major issues restrain acceptance of redox homeostasis and redox signaling as components of maintenance of a normal physiological steady state. The first is that redox signaling requires sudden switching on of oxidant production and bypassing of antioxidant mechanisms rather than a continuous process that, like other signaling mechanisms, can be smoothly turned up or down. The second is the misperception that reactions in redox signaling involve “reactive oxygen species” rather than reaction of specific electrophiles with specific protein thiolates. The third is that hormesis provides protection against oxidants by increasing cellular defense or repair mechanisms rather than by specifically addressing the offset of redox homeostasis. Instead, we propose that both oxidant and antioxidant signaling are main features of redox homeostasis. As the redox shift is rapidly reversed by feedback reactions, homeostasis is maintained by continuous signaling for production and elimination of electrophiles and nucleophiles. Redox homeostasis, which is the maintenance of nucleophilic tone, accounts for a healthy physiological steady state. Electrophiles and nucleophiles are not intrinsically harmful or protective, and redox homeostasis is an essential feature of both the response to challenges and subsequent feedback. While the balance between oxidants and nucleophiles is preserved in redox homeostasis, oxidative stress provokes the establishment of a new radically altered redox steady state. The popular belief that scavenging free radicals by antioxidants has a beneficial effect is wishful thinking. We propose, instead, that continuous feedback preserves nucleophilic tone and that this is supported by redox active nutritional phytochemicals. These nonessential compounds, by activating Nrf2, mimic the effect of endogenously produced electrophiles

The effects of metamorphism on iron mineralogy and the iron speciation redox proxy

Science.gov (United States)

Slotznick, Sarah P.; Eiler, John M.; Fischer, Woodward W.

2018-03-01

As the most abundant transition metal in the Earth's crust, iron is a key player in the planetary redox budget. Observations of iron minerals in the sedimentary record have been used to describe atmospheric and aqueous redox environments over the evolution of our planet; the most common method applied is iron speciation, a geochemical sequential extraction method in which proportions of different iron minerals are compared to calibrations from modern sediments to determine water-column redox state. Less is known about how this proxy records information through post-depositional processes, including diagenesis and metamorphism. To get insight into this, we examined how the iron mineral groups/pools (silicates, oxides, sulfides, etc.) and paleoredox proxy interpretations can be affected by known metamorphic processes. Well-known metamorphic reactions occurring in sub-chlorite to kyanite rocks are able to move iron between different iron pools along a range of proxy vectors, potentially affecting paleoredox results. To quantify the effect strength of these reactions, we examined mineralogical and geochemical data from two classic localities where Silurian-Devonian shales, sandstones, and carbonates deposited in a marine sedimentary basin with oxygenated seawater (based on global and local biological constraints) have been regionally metamorphosed from lower-greenschist facies to granulite facies: Waits River and Gile Mountain Formations, Vermont, USA and the Waterville and Sangerville-Vassalboro Formations, Maine, USA. Plotting iron speciation ratios determined for samples from these localities revealed apparent paleoredox conditions of the depositional water column spanning the entire range from oxic to ferruginous (anoxic) to euxinic (anoxic and sulfidic). Pyrrhotite formation in samples highlighted problems within the proxy as iron pool assignment required assumptions about metamorphic reactions and pyrrhotite's identification depended on the extraction techniques

Post-GOE redox insights from Mo isotopes, Ce anomalies, and Mn from the 2.24 Ga Kazput Formation

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Thoby, M.; Konhauser, K.; Philippot, P.; Killingsworth, B.; Warchola, T.; Lalonde, S.

2017-12-01

Following the Great Oxidation event (GOE) defined from 2.45 to 2.2 Ga, an event marking the first appearance of widespread atmospheric oxygen, a combination of decreased Mn(II) supply from land and increased Mn(IV)-precipitation in the oceans should have resulted in lower concentrations of Mn in seawater. Nevertheless, it appears that some early Proterozoic marine sediments record high seawater Mn concentrations hundreds of millions of years after the GOE. Here we investigate a Mn excursion associated with marine carbonates and shales of the 2.31 Ga Kazput Formation. Samples were recovered from drill core collected during the Turee Creek Drilling Project (TCDP). Using molybdenum (Mo) isotope data coupled with cerium (Ce) anomalies, we define the redox condition of the Kazput depositional environment. Initial results show no Mo fractionation and few cerium anomalies in carbonates, pointing to an anoxic basin without Mn oxide precipitates. Additionally, XRF data on the shales indicates an association of Mn with calcium (Ca) suggesting an anoxic environment at the time of their deposition. Our results provide new insights into the nature and environment of the Turee Creek basin and the extent of oxygenation of surface waters after the GOE.

Front-end module readout and control electronics for the PHENIX Multiplicity Vertex Detector

International Nuclear Information System (INIS)

Ericson, M.N.; Allen, M.D.; Boissevain, J.

1997-11-01

Front-end module (FEM) readout and control are implemented as modular, high-density, reprogrammable functions in the PHENIX Multiplicity Vertex Detector. FEM control is performed by the heap manager, an FPGA-based circuit in the FEM unit. Each FEM has 256 channels of front-end electronics, readout, and control, all located on an MCM. Data readout, formatting, and control are performed by the heap manager along with 4 interface units that reside outside the MVD detector cylinder. This paper discusses the application of a generic heap manager and the addition of 4 interface module types to meet the specific control and data readout needs of the MVD. Unit functioning, interfaces, timing, data format, and communication rates will be discussed in detail. In addition, subsystem issues regarding mode control, serial architecture and functions, error handling, and FPGA implementation and programming will be presented

Modes of uranium occurrences in Colorado Front Range

International Nuclear Information System (INIS)

Carpenter, R.H.; Gallagher, J.R.L.; Huber, G.C.

1978-01-01

This report is an analysis of the various types of uranium occurrences in the Colorado Front Range and the environments in which they developed. The early Proterozoic crust of this region is believed to have been a platform on which intermediate to felsic volcanic centers formed. Some units in the volcanic stratigraphy as well as in the sediments which were deposited in the shallow, intervening seaways are thought to have been uraniferous. Tectonism, occurring about 1.7 By ago, was accompanied and followed by three periods of Precambrian igneous activity. The volcanics and sediments were converted to a metavolcanic-metasedimentary sequence known as the Idaho Springs Formation. Some of the syngenetic uranium remaining in the volcanics and sediments after metamorphism may have been mobilized and incorporated within the Silver Plume plutons and the Pikes Peak batholith and concentrated in pegmatite dikes, pegmatites and fractured areas in the hood zones in the apophyses, or along the flanks of these intrusives. Some or most of the uranium found in these sites may have been generated deeper in the continental plate. Uplift of the Front Range in the Late Mississippian and arching during the Laramide with accompanying faulting set the stage for early and mid-Tertiary igneous activity and associated uranium mineralization. The source of the early and mid-Tertiary uranium mineralization is a point of current debate. Exploration for uranium in the igneous and metamorphic terrain of the Front Range is summarized, and models of each major uranium occurrence are described. Finally, the Front Range exploration potential for uranium is outlined

Redox active polymers and colloidal particles for flow batteries

Science.gov (United States)

Gavvalapalli, Nagarjuna; Moore, Jeffrey S.; Rodriguez-Lopez, Joaquin; Cheng, Kevin; Shen, Mei; Lichtenstein, Timothy

2018-05-29

The invention provides a redox flow battery comprising a microporous or nanoporous size-exclusion membrane, wherein one cell of the battery contains a redox-active polymer dissolved in the non-aqueous solvent or a redox-active colloidal particle dispersed in the non-aqueous solvent. The redox flow battery provides enhanced ionic conductivity across the electrolyte separator and reduced redox-active species crossover, thereby improving the performance and enabling widespread utilization. Redox active poly(vinylbenzyl ethylviologen) (RAPs) and redox active colloidal particles (RACs) were prepared and were found to be highly effective redox species. Controlled potential bulk electrolysis indicates that 94-99% of the nominal charge on different RAPs is accessible and the electrolysis products are stable upon cycling. The high concentration attainable (>2.0 M) for RAPs in common non-aqueous battery solvents, their electrochemical and chemical reversibility, and their hindered transport across porous separators make them attractive materials for non-aqueous redox flow batteries based on size-selectivity.

Revisiting the BaO2/BaO redox cycle for solar thermochemical energy storage.

Science.gov (United States)

Carrillo, A J; Sastre, D; Serrano, D P; Pizarro, P; Coronado, J M

2016-03-21

The barium peroxide-based redox cycle was proposed in the late 1970s as a thermochemical energy storage system. Since then, very little attention has been paid to such redox couples. In this paper, we have revisited the use of reduction-oxidation reactions of the BaO2/BaO system for thermochemical heat storage at high temperatures. Using thermogravimetric analysis, reduction and oxidation reactions were studied in order to find the main limitations associated with each process. Furthermore, the system was evaluated through several charge-discharge stages in order to analyse its possible degradation after repeated cycling. Through differential scanning calorimetry the heat stored and released were also determined. Oxidation reaction, which was found to be slower than reduction, was studied in more detail using isothermal tests. It was observed that the rate-controlling step of BaO oxidation follows zero-order kinetics, although at high temperatures a deviation from Arrhenius behaviour was observed probably due to hindrances to anionic oxygen diffusion caused by the formation of an external layer of BaO2. This redox couple was able to withstand several redox cycles without deactivation, showing reaction conversions close to 100% provided that impurities are previously eliminated through thermal pre-treatment, demonstrating the feasibility of this system for solar thermochemical heat storage.

Redox potentials and kinetics of the Ce 3+/Ce 4+ redox reaction and solubility of cerium sulfates in sulfuric acid solutions

Science.gov (United States)

Paulenova, A.; Creager, S. E.; Navratil, J. D.; Wei, Y.

Experimental work was performed with the aim of evaluating the Ce 4+/Ce 3+ redox couple in sulfuric acid electrolyte for use in redox flow battery (RFB) technology. The solubility of cerium sulfates in 0.1-4.0 M sulfuric acid at 20-60 °C was studied. A synergistic effect of both sulfuric acid concentration and temperature on the solubility of cerous sulfate was observed. The solubility of cerous sulfate significantly decreased with rising concentration of sulfuric acid and rising temperature, while the solubility of ceric sulfate goes through a significant maximum at 40 °C. Redox potentials and the kinetics of the cerous/ceric redox reaction were also studied under the same temperature-concentration conditions. The redox potentials were measured using the combined redox electrode (Pt-Ag/AgCl) in equimolar Ce 4+/Ce 3+ solutions (i.e.[Ce 3+]=[Ce 4+]) in sulfuric acid electrolyte. The Ce 3+/Ce 4+ redox potentials significantly decrease (i.e. shift to more negative values) with rising sulfuric acid concentration; a small maximum is observed at 40 °C. Cyclic voltammetric experiments confirmed slow electrochemical kinetics of the Ce 3+/Ce 4+ redox reaction on carbon glassy electrodes (CGEs) in sulfuric acid solutions. The observed dependencies of solubilities, the redox potentials and the kinetics of Ce 3+/Ce 4+ redox reaction on sulfuric acid concentration are thought to be the result of inequivalent complexation of the two redox species by sulfate anions: the ceric ion is much more strongly bound to sulfate than is the cerous ion. The best temperature-concentration conditions for the RFB electrolytes appear to be 40 °C and 1 M sulfuric acid, where the relatively good solubility of both cerium species, the maximum of redox potentials, and the more or less satisfying stability of CGE s were found. Even so, the relatively low solubility of cerium salts in sulfuric acid media and slow redox kinetics of the Ce 3+/Ce 4+ redox reaction at carbon indicate that the Ce 3+/Ce

Polyoxometalate active charge-transfer material for mediated redox flow battery

Energy Technology Data Exchange (ETDEWEB)

Anderson, Travis Mark; Hudak, Nicholas; Staiger, Chad; Pratt, Harry

2017-01-17

Redox flow batteries including a half-cell electrode chamber coupled to a current collecting electrode are disclosed herein. In a general embodiment, a separator is coupled to the half-cell electrode chamber. The half-cell electrode chamber comprises a first redox-active mediator and a second redox-active mediator. The first redox-active mediator and the second redox-active mediator are circulated through the half-cell electrode chamber into an external container. The container includes an active charge-transfer material. The active charge-transfer material has a redox potential between a redox potential of the first redox-active mediator and a redox potential of the second redox-active mediator. The active charge-transfer material is a polyoxometalate or derivative thereof. The redox flow battery may be particularly useful in energy storage solutions for renewable energy sources and for providing sustained power to an electrical grid.

Front Propagation in Stochastic Neural Fields

KAUST Repository

Bressloff, Paul C.

2012-01-01

We analyze the effects of extrinsic multiplicative noise on front propagation in a scalar neural field with excitatory connections. Using a separation of time scales, we represent the fluctuating front in terms of a diffusive-like displacement (wandering) of the front from its uniformly translating position at long time scales, and fluctuations in the front profile around its instantaneous position at short time scales. One major result of our analysis is a comparison between freely propagating fronts and fronts locked to an externally moving stimulus. We show that the latter are much more robust to noise, since the stochastic wandering of the mean front profile is described by an Ornstein-Uhlenbeck process rather than a Wiener process, so that the variance in front position saturates in the long time limit rather than increasing linearly with time. Finally, we consider a stochastic neural field that supports a pulled front in the deterministic limit, and show that the wandering of such a front is now subdiffusive. © 2012 Society for Industrial and Applied Mathematics.

Multiple redox states of multiheme cytochromes may enable bacterial response to changing redox environments

Science.gov (United States)

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

2013-12-01

Multiheme c-type cytochromes (MHCs) are key components in electron-transport pathways that enable some microorganisms to transfer electron byproducts of metabolism to a variety of minerals. As a response to changes in mineral redox potential, microbial communities may shift their membership, or individual organisms may adjust protein expression. Alternatively, the ability to respond may be conferred by the innate characteristics of certain electron-transport-chain components. Here, we used potentiostat-controlled microbial fuel cells (MFCs) to measure the timescale of response to imposed changes in redox conditions, thus placing constraints on the importance of these different mechanisms. In the experiments, a solid electrode acts as an electron-accepting mineral whose redox potential can be precisely controlled. We inoculated duplicate MFCs with a sediment/groundwater mixture from an aquifer at Rifle, Colorado, supplied acetate as an electron donor, and obtained stable, mixed-species biofilms dominated by Geobacter and a novel Geobacter-related family. We poised the anode at potentials spanning the range of natural Fe(III)-reduction, then performed cyclic voltammetry (CV) to characterize the overall biofilm redox signature. The apparent biofilm midpoint potential shifted directly with anode set potential when the latter was changed within the range from about -250 to -50 mV vs. SHE. Following a jump in set potential by 200 mV, the CV-midpoint shift by ~100 mV over a timescale of ~30 minutes to a few hours, depending on the direction of the potential change. The extracellular electron transfer molecules, whose overall CV signature is very similar to those of purified MHCs, appear to span a broad redox range (~200 mV), supporting the hypothesis that MHCs confer substantial redox flexibility. This flexibility may be a principle reason for the abundance of MHCs expressed by microorganisms capable of extracellular electron transfer to minerals.

Radiation-induced non-equilibrium redox chemistry of plutonium: implications for environmental migration

International Nuclear Information System (INIS)

Haschke, J.M.; Siekhaus, W.J.

2009-01-01

Static concentrations of plutonium oxidation states in solution and at surfaces in oxide-water systems are identified as non-equilibrium steady states. These kinetically controlled systems are described by redox cycles based on irreversible disproportionation of Pu(IV), Pu(V), and Pu(VI) in OH-bridged intermediate complexes and at OH-covered oxide surfaces. Steady state is fixed by continuous redox cycles driven by radioactivity-promoted electron-transfer and energetically favorable reactions of Pu(III) and Pu(VII) disproportionation products with H2O. A model based on the redox cycles accounts for the high steady-state (Pu) coexisting with Pu(IV) hydrous oxide at pH 0-15 and for predominance of Pu(V) and Pu(VI) in solution. The steady-state (Pu) depends on pH and the surface area of oxide in solution, but not on the initial Pu oxidation state. PuO 2+x formation is attributed to high Pu(V) concentrations existing at water-exposed oxide surfaces. Results infer that migration of Pu in an aqueous environment is controlled by kinetic factors unique to that site and that the predominant oxidation states in solution are Pu(V) and Pu(VI)

Pyridine nucleotides in regulation of cell death and survival by redox and non-redox reactions.

Science.gov (United States)

Novak Kujundžić, Renata; Žarković, Neven; Gall Trošelj, Koraljka

2014-01-01

Changes of the level and ratios of pyridine nucleotides determine metabolism- dependent cellular redox status and the activity of poly(ADP-ribose) polymerases (PARPs) and sirtuins, thereby influencing several processes closely related to cell survival and death. Pyridine nucleotides participate in numerous metabolic reactions whereby their net cellular level remains constant, but the ratios of NAD+/NADP+ and NADH/NADPH oscillate according to metabolic changes in response to diverse stress signals. In non-redox reactions, NAD+ is degraded and quickly, afterward, resynthesized in the NAD+ salvage pathway, unless overwhelming activation of PARP-1 consumes NAD+ to the point of no return, when the cell can no longer generate enough ATP to accommodate NAD+ resynthesis. The activity of PARP-1 is mandatory for the onset of cytoprotective autophagy on sublethal stress signals. It has become increasingly clear that redox status, largely influenced by the metabolism-dependent composition of the pyridine nucleotides pool, plays an important role in the synthesis of pro-apoptotic and anti-apoptotic sphingolipids. Awareness of the involvement of the prosurvival sphingolipid, sphingosine-1-phosphate, in transition from inflammation to malignant transformation has recently emerged. Here, the participation of pyridine nucleotides in redox and non-redox reactions, sphingolipid metabolism, and their role in cell fate decisions is reviewed.

Redox Regulation in Cancer: A Double-edged Sword with Therapeutic Potential

Directory of Open Access Journals (Sweden)

Asha Acharya

2010-01-01

Full Text Available Oxidative stress, implicated in the etiology of cancer, results from an imbalance in the production of reactive oxygen species (ROS and cell’s own antioxidant defenses. ROS deregulate the redox homeostasis and promote tumor formation by initiating an aberrant induction of signaling networks that cause tumorigenesis. Ultraviolet (UV exposures, γ-radiation and other environmental carcinogens generate ROS in the cells, which can exert apoptosis in the tumors, thereby killing the malignant cells or induce the progression of the cancer growth by blocking cellular defense system. Cancer stem cells take the advantage of the aberrant redox system and spontaneously proliferate. Oxidative stress and gene-environment interactions play a significant role in the development of breast, prostate, pancreatic and colon cancer. Prolonged lifetime exposure to estrogen is associated with several kinds of DNA damage. Oxidative stress and estrogen receptor-associated proliferative changes are suggested to play important roles in estrogen-induced breast carcinogenesis. BRCA1, a tumor suppressor against hormone responsive cancers such as breast and prostate cancer, plays a significant role in inhibiting ROS and estrogen mediated DNA damage; thereby regulate the redox homeostasis of the cells. Several transcription factors and tumor suppressors are involved during stress response such as Nrf2, NFκB and BRCA1. A promising strategy for targeting redox status of the cells is to use readily available natural substances from vegetables, fruits, herbs and spices. Many of the phytochemicals have already been identified to have chemopreventive potential, capable of intervening in carcinogenesis.

Glutathione redox potential in the mitochondrial intermembrane space is linked to the cytosol and impacts the Mia40 redox state

Science.gov (United States)

Kojer, Kerstin; Bien, Melanie; Gangel, Heike; Morgan, Bruce; Dick, Tobias P; Riemer, Jan

2012-01-01

Glutathione is an important mediator and regulator of cellular redox processes. Detailed knowledge of local glutathione redox potential (EGSH) dynamics is critical to understand the network of redox processes and their influence on cellular function. Using dynamic oxidant recovery assays together with EGSH-specific fluorescent reporters, we investigate the glutathione pools of the cytosol, mitochondrial matrix and intermembrane space (IMS). We demonstrate that the glutathione pools of IMS and cytosol are dynamically interconnected via porins. In contrast, no appreciable communication was observed between the glutathione pools of the IMS and matrix. By modulating redox pathways in the cytosol and IMS, we find that the cytosolic glutathione reductase system is the major determinant of EGSH in the IMS, thus explaining a steady-state EGSH in the IMS which is similar to the cytosol. Moreover, we show that the local EGSH contributes to the partially reduced redox state of the IMS oxidoreductase Mia40 in vivo. Taken together, we provide a comprehensive mechanistic picture of the IMS redox milieu and define the redox influences on Mia40 in living cells. PMID:22705944

Characterization of redox conditions in groundwater contaminant plumes

Science.gov (United States)

Christensen, Thomas H.; Bjerg, Poul L.; Banwart, Steven A.; Jakobsen, Rasmus; Heron, Gorm; Albrechtsen, Hans-Jørgen

2000-10-01

Evaluation of redox conditions in groundwater pollution plumes is often a prerequisite for understanding the behaviour of the pollutants in the plume and for selecting remediation approaches. Measuring of redox conditions in pollution plumes is, however, a fairly recent issue and yet relative few cases have been reported. No standardised or generally accepted approach exists. Slow electrode kinetics and the common lack of internal equilibrium of redox processes in pollution plumes make, with a few exceptions, direct electrochemical measurement and rigorous interpretation of redox potentials dubious, if not erroneous. Several other approaches have been used in addressing redox conditions in pollution plumes: redox-sensitive compounds in groundwater samples, hydrogen concentrations in groundwater, concentrations of volatile fatty acids in groundwater, sediment characteristics and microbial tools, such as MPN counts, PLFA biomarkers and redox bioassays. This paper reviews the principles behind the different approaches, summarizes methods used and evaluates the approaches based on the experience from the reported applications.

Sedimentary cobalt concentrations track marine redox evolution

Science.gov (United States)

Swanner, Elizabeth; Planavsky, Noah; Lalonde, Stefan; Robbins, Jamie; Bekker, Andrey; Rouxel, Olivier; Konhauser, Kurt O.; Mojzsis, Stephen J.

2013-04-01

Oxygen production by photosynthesis drove the redox evolution of the atmosphere and ocean. Primary productivity by oxygenic photosynthesizers in the modern surface ocean is limited by trace nutrients such as iron, but previous studies have also observed high Co uptake associated with natural cyanobacterial populations. Constraining the size and variation of the oceanic reservoir of Co through time will help to understand the regulation of primary productivity and hence oxygenation through time. In this study, Co concentrations from iron formations (IF), shales and marine pyrites deposited over nearly 4 billion years of Earth's history are utilized to reconstruct secular changes in the mechanisms of Co removal from the oceanic reservoir. The Co reservoir prior to ~2 Ga was dominated by hydrothermal inputs and Fe(III)oxyhydroxides were likely involved in the removal of Co from the water column. Fe(II) oxidation in the water column resulted in the deposition of IF in the Archean and Paleoproterozoic, and the Co inventory of IF records a large oceanic reservoir of Co during this time. Lower Co concentrations in sediments during the Middle Proterozoic signify a decrease in the oceanic reservoir due to the expansion euxinic environments, corresponding to the results of previous studies. A transition to an oxidized deep ocean in the Phanerozoic is evidenced by correlation between Co and manganese (Mn) concentrations in hydrothermal and exhalative deposits, and in marine pyrites. This relationship between Co and Mn, signifying deposition of Co in association with Mn(IV)oxides, does not occur in the Precambrian. Mn(II) oxidation occurs at higher redox potentials than that required for Fe(II) oxidation, and the extent of Mn redox cycling prior to full ventilation of the oceans at the end of the Neoproterozoic was likely limited to spatially restricted oxic surface waters. In this regard, Co is another valuable redox proxy for tracking the growth and decline in oxygenated

Light-Front QCD

Energy Technology Data Exchange (ETDEWEB)

Brodsky, S.

2004-11-30

In these lectures, I survey a number of applications of light-front methods to hadron and nuclear physics phenomenology and dynamics, including light-front statistical physics. Light-front Fock-state wavefunctions provide a frame-independent representation of hadrons in terms of their fundamental quark and gluon degrees of freedom. Nonperturbative methods for computing LFWFs in QCD are discussed, including string/gauge duality which predicts the power-law fall-off at high momentum transfer of light-front Fock-state hadronic wavefunctions with an arbitrary number of constituents and orbital angular momentum. The AdS/CFT correspondence has important implications for hadron phenomenology in the conformal limit, including an all-orders derivation of counting rules for exclusive processes. One can also compute the hadronic spectrum of near-conformal QCD assuming a truncated AdS/CFT space. Given the LFWFs, one can compute form factors, heavy hadron decay amplitudes, hadron distribution amplitudes, and the generalized parton distributions underlying deeply virtual Compton scattering. The quantum fluctuations represented by the light-front Fock expansion leads to novel QCD phenomena such as color transparency, intrinsic heavy quark distributions, diffractive dissociation, and hidden-color components of nuclear wavefunctions. A new test of hidden color in deuteron photodisintegration is proposed. The origin of leading-twist phenomena such as the diffractive component of deep inelastic scattering, single-spin asymmetries, nuclear shadowing and antishadowing is also discussed; these phenomena cannot be described by light-front wavefunctions of the target computed in isolation. Part of the anomalous NuTeV results for the weak mixing angle {theta}{sub W} could be due to the non-universality of nuclear antishadowing for charged and neutral currents.

Membranes for Redox Flow Battery Applications

OpenAIRE

Prifti, Helen; Parasuraman, Aishwarya; Winardi, Suminto; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

2012-01-01

The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. Th...

Redox-flow battery of actinide complexes

International Nuclear Information System (INIS)

Yamamura, Tomoo; Shiokawa, Yoshinobu

2006-01-01

Np battery and U battery were developed. We suggested that Np redox-flow battery should be (-)|Np 3+ ,Np 4+ ||NpO 2 + ,NpO 2 2+ |(+), and U battery (-)|[U III T 2 ] - ,[U IV T 2 ] 0 ||[U V O 2 T] - ,[U VI O 2 T] 0 |(+). The electromotive force at 50 % charge of Np and U battery is 1.10 V and 1.04 V, respectively. The energy efficiency of 70 mA/cm 2 of Np and U battery shows 99 % and 98 %, respectively. V redox-flow battery, electrode reactions of An battery, Np battery, U battery and future of U battery are described. The concept of V redox-flow battery, comparison of energy efficiency of Np, U and V battery, oxidation state and ionic species of 3d transition metals and main An, Purbe diagram of Np and U aqueous solution, shift of redox potential of β-diketones by pKa, and specifications of three redox-flow batteries are reported. (S.Y.)

Redox kinetics and mechanism in silicate melts

International Nuclear Information System (INIS)

Cochain, B.

2009-12-01

This work contributes to better understand iron redox reactions and mechanisms in silicate melts. It was conducted on compositions in both Na 2 O-B 2 O 3 -SiO 2 -FeO and Na 2 O-Al 2 O 3 -SiO 2 -FeO systems. The influence of boron-sodium and aluminum-sodium substitutions and iron content on properties and structure of glasses and on the iron redox kinetics has been studied by Raman, Moessbauer and XANES spectroscopies at the B and Fe K-edges. In borosilicate glasses, an increase in iron content or in the Fe 3+ /ΣFe redox state implies a structural rearrangement of the BO 4 species in the glass network whereas the BO 3 and BO 4 relative proportions remain nearly constant. In all studied glasses and melts, Fe 3+ is a network former in tetrahedral coordination, unless for aluminosilicates of ratio Al/Na≥1 where Fe 3+ is a network modifier in five-fold coordination. Near Tg, diffusion of network modifying cations controls the iron redox kinetics along with a flux of electron holes. At liquidus temperatures, oxygen diffusion is considered to be the mechanism that governs redox reactions. This study shows the role played by the silicate network polymerization on the redox kinetics. In borosilicate melts, iron redox kinetics depends on the boron speciation between BO 3 and BO 4 that depends itself on the sodium content. Furthermore, an increase in the network-former/network-modifier ratio implies a decrease in oxygen diffusion that results in a slowing down of the redox kinetics. The obtained results allow a description of the iron redox kinetics for more complex compositions as natural lavas or nuclear waste model glasses. (author)

Redox homeostasis: The Golden Mean of healthy living.

Science.gov (United States)

Ursini, Fulvio; Maiorino, Matilde; Forman, Henry Jay

2016-08-01

The notion that electrophiles serve as messengers in cell signaling is now widely accepted. Nonetheless, major issues restrain acceptance of redox homeostasis and redox signaling as components of maintenance of a normal physiological steady state. The first is that redox signaling requires sudden switching on of oxidant production and bypassing of antioxidant mechanisms rather than a continuous process that, like other signaling mechanisms, can be smoothly turned up or down. The second is the misperception that reactions in redox signaling involve "reactive oxygen species" rather than reaction of specific electrophiles with specific protein thiolates. The third is that hormesis provides protection against oxidants by increasing cellular defense or repair mechanisms rather than by specifically addressing the offset of redox homeostasis. Instead, we propose that both oxidant and antioxidant signaling are main features of redox homeostasis. As the redox shift is rapidly reversed by feedback reactions, homeostasis is maintained by continuous signaling for production and elimination of electrophiles and nucleophiles. Redox homeostasis, which is the maintenance of nucleophilic tone, accounts for a healthy physiological steady state. Electrophiles and nucleophiles are not intrinsically harmful or protective, and redox homeostasis is an essential feature of both the response to challenges and subsequent feedback. While the balance between oxidants and nucleophiles is preserved in redox homeostasis, oxidative stress provokes the establishment of a new radically altered redox steady state. The popular belief that scavenging free radicals by antioxidants has a beneficial effect is wishful thinking. We propose, instead, that continuous feedback preserves nucleophilic tone and that this is supported by redox active nutritional phytochemicals. These nonessential compounds, by activating Nrf2, mimic the effect of endogenously produced electrophiles (parahormesis). In summary

Geology of eastern Smith Lake ore trend, Grants mineral belt

International Nuclear Information System (INIS)

Ristorcelli, S.J.

1980-01-01

The sandstones in the Brushy Basin Member of the Morrison Formation (Jurassic) are the ore-bearing horizons of the eastern Smith Lake area. The Brushy Basin Member in this district consists of three sandstones with interbedded mudstones. Only the lower two sandstones contain ore. The sandstones are fine to coarse grained, well rounded, and arkosic, representing continental stream sediments. The lower sandstone contains rollfront ore. The redox interface is laterally extensive and well defined, extending at least 7 mi (11 km) west of the Bluewater fault zone. The ore generally occurs at the redox boundary but occasionally will be up to 1500 ft (450 m) updip. Limonitic alteration, where present, is downdip from the hematitic zone and is 100-1,500 ft (30 to 450 m) wide. The middle sandstone contains both trend ore and roll-front ore. The trend ore occurs downdip from the redox front in unoxidized ground. The redox front in the middle sand is also laterally extensive but displays a wedge shape, rather than a C shape. The clay assemblages of the two types of ore are different: the trend ore occurs in sands with the pore spaces filled with kaolinite; the roll-front ore is associated with altered illite-montmorillonite as grain coatings. Hematitic alteration is asociated with the latter. A second stage of kaolinite coats the illite-montmorillonite. Two periods of mineralization are suggested, but no absolute dates are known. The trend ore is the oldest (Jurassic) and is similar to the ore found in unoxidized ground elsewhere in the Grants region. The rollfront ore could be Laramide or post-Laramide because of its association with local Laramide structures

Ex-situ tracking solid oxide cell electrode microstructural evolution in a redox cycle by high resolution ptychographic nanotomography

DEFF Research Database (Denmark)

De Angelis, Salvatore; Jørgensen, Peter Stanley; Esposito, Vincenzo

2017-01-01

, the nickel and pore networks undergo major reorganization and the formation of internal voids is observed in the nickel-oxide particles after the oxidation. These observations are discussed in terms of reaction kinetics, electrode mechanical stress and the consequences of redox cycling on electrode...... towards this aim by visualizing a complete redox cycle in a solid oxide cell (SOC) electrode. The experiment demonstrates synchrotron-based ptychography as a method of imaging SOC electrodes, providing an unprecedented combination of 3D image quality and spatial resolution among non-destructive imaging...

Unleashing the Power and Energy of LiFePO4-Based Redox Flow Lithium Battery with a Bifunctional Redox Mediator.

Science.gov (United States)

Zhu, Yun Guang; Du, Yonghua; Jia, Chuankun; Zhou, Mingyue; Fan, Li; Wang, Xingzhu; Wang, Qing

2017-05-10

Redox flow batteries, despite great operation flexibility and scalability for large-scale energy storage, suffer from low energy density and relatively high cost as compared to the state-of-the-art Li-ion batteries. Here we report a redox flow lithium battery, which operates via the redox targeting reactions of LiFePO 4 with a bifunctional redox mediator, 2,3,5,6-tetramethyl-p-phenylenediamine, and presents superb energy density as the Li-ion battery and system flexibility as the redox flow battery. The battery has achieved a tank energy density as high as 1023 Wh/L, power density of 61 mW/cm 2 , and voltage efficiency of 91%. Operando X-ray absorption near-edge structure measurements were conducted to monitor the evolution of LiFePO 4 , which provides insightful information on the redox targeting process, critical to the device operation and optimization.

Generation of missiles and destructive shock fronts and their consequences

International Nuclear Information System (INIS)

Porter, W.H.L.

1980-01-01

A general review is given of the generation of missiles and shock fronts from vessels and turbines and the formation and generation of deflagration and detonation waves in the atmosphere after the release of inflammable material. The considerations involved in evaluation the penetration of steel and concrete structures and the effects of pressure waves are presented with particular emphasis on dimensional analysis. The formation and ignition of flammable vapour clouds is considered and the distinction drawn between simple combustion, deflagration and detonation. The rates of release and impulse loadings on vessels resulting from holes or splits are also reviewed. (author)

Front propagation in flipping processes

International Nuclear Information System (INIS)

Antal, T; Ben-Avraham, D; Ben-Naim, E; Krapivsky, P L

2008-01-01

We study a directed flipping process that underlies the performance of the random edge simplex algorithm. In this stochastic process, which takes place on a one-dimensional lattice whose sites may be either occupied or vacant, occupied sites become vacant at a constant rate and simultaneously cause all sites to the right to change their state. This random process exhibits rich phenomenology. First, there is a front, defined by the position of the leftmost occupied site, that propagates at a nontrivial velocity. Second, the front involves a depletion zone with an excess of vacant sites. The total excess Δ k increases logarithmically, Δ k ≅ ln k, with the distance k from the front. Third, the front exhibits ageing-young fronts are vigorous but old fronts are sluggish. We investigate these phenomena using a quasi-static approximation, direct solutions of small systems and numerical simulations

Redox characteristics of the eukaryotic cytosol

DEFF Research Database (Denmark)

López-Mirabal, H Reynaldo; Winther, Jakob R

2007-01-01

The eukaryotic cytoplasm has long been regarded as a cellular compartment in which the reduced state of protein cysteines is largely favored. Under normal conditions, the cytosolic low-molecular weight redox buffer, comprising primarily of glutathione, is highly reducing and reactive oxygen species...... (ROS) and glutathionylated proteins are maintained at very low levels. In the present review, recent progress in the understanding of the cytosolic thiol-disulfide redox metabolism and novel analytical approaches to studying cytosolic redox properties are discussed. We will focus on the yeast model...... organism, Saccharomyces cerevisiae, where the combination of genetic and biochemical approaches has brought us furthest in understanding the mechanisms underlying cellular redox regulation. It has been shown in yeast that, in addition to the enzyme glutathione reductase, other mechanisms may exist...

Vitamin K3 (menadione) redox cycling inhibits cytochrome P450-mediated metabolism and inhibits parathion intoxication

Energy Technology Data Exchange (ETDEWEB)

Jan, Yi-Hua [Department of Environmental and Occupational Medicine, Rutgers Robert Wood Johnson Medical School, Piscataway, NJ (United States); Richardson, Jason R., E-mail: jricha3@eohsi.rutgers.edu [Department of Environmental and Occupational Medicine, Rutgers Robert Wood Johnson Medical School, Piscataway, NJ (United States); Baker, Angela A. [Department of Environmental and Occupational Medicine, Rutgers Robert Wood Johnson Medical School, Piscataway, NJ (United States); Mishin, Vladimir [Department of Pharmacology and Toxicology, Rutgers University, Piscataway, NJ (United States); Heck, Diane E. [Department of Environmental Health Science, New York Medical College, Valhalla, NY (United States); Laskin, Debra L. [Department of Pharmacology and Toxicology, Rutgers University, Piscataway, NJ (United States); Laskin, Jeffrey D., E-mail: jlaskin@eohsi.rutgers.edu [Department of Environmental and Occupational Medicine, Rutgers Robert Wood Johnson Medical School, Piscataway, NJ (United States)

2015-10-01

Parathion, a widely used organophosphate insecticide, is considered a high priority chemical threat. Parathion toxicity is dependent on its metabolism by the cytochrome P450 system to paraoxon (diethyl 4-nitrophenyl phosphate), a cytotoxic metabolite. As an effective inhibitor of cholinesterases, paraoxon causes the accumulation of acetylcholine in synapses and overstimulation of nicotinic and muscarinic cholinergic receptors, leading to characteristic signs of organophosphate poisoning. Inhibition of parathion metabolism to paraoxon represents a potential approach to counter parathion toxicity. Herein, we demonstrate that menadione (methyl-1,4-naphthoquinone, vitamin K3) is a potent inhibitor of cytochrome P450-mediated metabolism of parathion. Menadione is active in redox cycling, a reaction mediated by NADPH-cytochrome P450 reductase that preferentially uses electrons from NADPH at the expense of their supply to the P450s. Using human recombinant CYP 1A2, 2B6, 3A4 and human liver microsomes, menadione was found to inhibit the formation of paraoxon from parathion. Administration of menadione bisulfite (40 mg/kg, ip) to rats also reduced parathion-induced inhibition of brain cholinesterase activity, as well as parathion-induced tremors and the progression of other signs and symptoms of parathion poisoning. These data suggest that redox cycling compounds, such as menadione, have the potential to effectively mitigate the toxicity of organophosphorus pesticides including parathion which require cytochrome P450-mediated activation. - Highlights: • Menadione redox cycles with cytochrome P450 reductase and generates reactive oxygen species. • Redox cycling inhibits cytochrome P450-mediated parathion metabolism. • Short term administration of menadione inhibits parathion toxicity by inhibiting paraoxon formation.

Vitamin K3 (menadione) redox cycling inhibits cytochrome P450-mediated metabolism and inhibits parathion intoxication

International Nuclear Information System (INIS)

Jan, Yi-Hua; Richardson, Jason R.; Baker, Angela A.; Mishin, Vladimir; Heck, Diane E.; Laskin, Debra L.; Laskin, Jeffrey D.

2015-01-01

Parathion, a widely used organophosphate insecticide, is considered a high priority chemical threat. Parathion toxicity is dependent on its metabolism by the cytochrome P450 system to paraoxon (diethyl 4-nitrophenyl phosphate), a cytotoxic metabolite. As an effective inhibitor of cholinesterases, paraoxon causes the accumulation of acetylcholine in synapses and overstimulation of nicotinic and muscarinic cholinergic receptors, leading to characteristic signs of organophosphate poisoning. Inhibition of parathion metabolism to paraoxon represents a potential approach to counter parathion toxicity. Herein, we demonstrate that menadione (methyl-1,4-naphthoquinone, vitamin K3) is a potent inhibitor of cytochrome P450-mediated metabolism of parathion. Menadione is active in redox cycling, a reaction mediated by NADPH-cytochrome P450 reductase that preferentially uses electrons from NADPH at the expense of their supply to the P450s. Using human recombinant CYP 1A2, 2B6, 3A4 and human liver microsomes, menadione was found to inhibit the formation of paraoxon from parathion. Administration of menadione bisulfite (40 mg/kg, ip) to rats also reduced parathion-induced inhibition of brain cholinesterase activity, as well as parathion-induced tremors and the progression of other signs and symptoms of parathion poisoning. These data suggest that redox cycling compounds, such as menadione, have the potential to effectively mitigate the toxicity of organophosphorus pesticides including parathion which require cytochrome P450-mediated activation. - Highlights: • Menadione redox cycles with cytochrome P450 reductase and generates reactive oxygen species. • Redox cycling inhibits cytochrome P450-mediated parathion metabolism. • Short term administration of menadione inhibits parathion toxicity by inhibiting paraoxon formation.

Organic non-aqueous cation-based redox flow batteries

Science.gov (United States)

Jansen, Andrew N.; Vaughey, John T.; Chen, Zonghai; Zhang, Lu; Brushett, Fikile R.

2016-03-29

The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturated moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte is selected to have a higher redox potential than the redox reactant of the negative electrolyte.

Energy storage device including a redox-enhanced electrolyte

Science.gov (United States)

Stucky, Galen; Evanko, Brian; Parker, Nicholas; Vonlanthen, David; Auston, David; Boettcher, Shannon; Chun, Sang-Eun; Ji, Xiulei; Wang, Bao; Wang, Xingfeng; Chandrabose, Raghu Subash

2017-08-08

An electrical double layer capacitor (EDLC) energy storage device is provided that includes at least two electrodes and a redox-enhanced electrolyte including two redox couples such that there is a different one of the redox couples for each of the electrodes. When charged, the charge is stored in Faradaic reactions with the at least two redox couples in the electrolyte and in a double-layer capacitance of a porous carbon material that comprises at least one of the electrodes, and a self-discharge of the energy storage device is mitigated by at least one of electrostatic attraction, adsorption, physisorption, and chemisorption of a redox couple onto the porous carbon material.

Redox activity of airborne particulate matter at different sites in the Los Angeles Basin

International Nuclear Information System (INIS)

Cho, Arthur K.; Sioutas, Constantinos; Miguel, Antonio H.; Kumagai, Yoshito; Schmitz, Debra A.; Singh, Manisha; Eiguren-Fernandez, Arantza; Froines, John R.

2005-01-01

Epidemiologic studies have shown associations between ambient particulate matter (PM) and adverse health outcomes including increased mortality, emergency room visits, and time lost from school and work. The mechanisms of PM-related health effects are still incompletely understood, but a hypothesis under investigation is that many of the adverse health effects may derive from oxidative stress, initiated by the formation of reactive oxygen species (ROS) within affected cells. While the adverse effects from PM have historically been associated with the airborne concentration of PM and more recently fine-particle PM, we considered it relevant to develop an assay to quantitatively measure the ability of PM to catalyze ROS generation as the initial step in the induction of oxidative stress. This ability of PM could then be related to different sources, chemical composition, and physical and spatial/temporal characteristics in the ambient environment. The measurement of ROS-forming ability in relation to sources and other factors will have potential relevance to control of redox-active PM. If oxidative stress represents a relevant mechanism of toxicity from PM, the measurement of redox activity represents a first step in the elucidation of the subsequent downstream processes. We have developed an assay for PM redox activity, utilizing the reduction of oxygen by dithiothreitol which serves as an electron source. We have found that PM will catalyze the reduction of oxygen and have examined the distribution and chemical characteristics of the redox activity of PM fractions collected in different sites in the Los Angeles Basin. Samples of concentrated coarse, fine, and ultrafine PM, obtained with aerosol concentrators, were studied with regard to their chemical properties and redox activity. Redox activity was highest in the ultrafine fraction, in agreement with results indicating ultrafines were the most potent toward inducing that heme oxygenase expression and depleting

Adsorption and desorption experiments in the natural redox milieu over several months, using technetium as an example

International Nuclear Information System (INIS)

Winkler, A.; Bruehl, H.; Trapp, C.

1986-01-01

Complicated experimental equipment has been developed in order to carry out long-term laboratory studies under true to reality, stable conditions simulating the natural milieu of the formation waters, i.e. the redox potential in the range + 200 to -70 mV. The single-pass column experiments have been made with loose rock samples from the Gorleben site and with natural formation water samples in order to study the adsorption and desorption and thus the mobility of technetium, as well as the building up of the geochemical equilibrium state, which has been studied in circulation columns. The results show that the process of Tc fixation in the loose rock in a lower redox milieu is not so much influenced by adsorption or desorption conditions but rather more by changes of the Eh-conditions, i.e. by the oxidation stage of the technetium. (RB) [de

Redox properties of structural Fe in clay minerals: 3. Relationships between smectite redox and structural properties.

Science.gov (United States)

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

2013-01-01

Structural Fe in clay minerals is an important redox-active species in many pristine and contaminated environments as well as in engineered systems. Understanding the extent and kinetics of redox reactions involving Fe-bearing clay minerals has been challenging due to the inability to relate structural Fe(2+)/Fe(total) fractions to fundamental redox properties, such as reduction potentials (EH). Here, we overcame this challenge by using mediated electrochemical reduction (MER) and oxidation (MEO) to characterize the fraction of redox-active structural Fe (Fe(2+)/Fe(total)) in smectites over a wide range of applied EH-values (-0.6 V to +0.6 V). We examined Fe(2+)/Fe(total )- EH relationships of four natural Fe-bearing smectites (SWy-2, SWa-1, NAu-1, NAu-2) in their native, reduced, and reoxidized states and compared our measurements with spectroscopic observations and a suite of mineralogical properties. All smectites exhibited unique Fe(2+)/Fe(total) - EH relationships, were redox active over wide EH ranges, and underwent irreversible electron transfer induced structural changes that were observable with X-ray absorption spectroscopy. Variations among the smectite Fe(2+)/Fe(total) - EH relationships correlated well with both bulk and molecular-scale properties, including Fe(total) content, layer charge, and quadrupole splitting values, suggesting that multiple structural parameters determined the redox properties of smectites. The Fe(2+)/Fe(total) - EH relationships developed for these four commonly studied clay minerals may be applied to future studies interested in relating the extent of structural Fe reduction or oxidation to EH-values.

Catalytic Water Oxidation by a Bio-inspired Nickel Complex with a Redox-Active Ligand.

Science.gov (United States)

Wang, Dong; Bruner, Charlie O

2017-11-20

The oxidation of water (H 2 O) to dioxygen (O 2 ) is important in natural photosynthesis. One of nature's strategies for managing such multi-electron transfer reactions is to employ redox-active metal-organic cofactor arrays. One prototype example is the copper tyrosinate active site found in galactose oxidase. In this work, we have implemented such a strategy to develop a bio-inspired nickel phenolate complex capable of catalyzing the oxidation of H 2 O to O 2 electrochemically at neutral pH with a modest overpotential. Employment of the redox-active ligand turned out to be a useful strategy to avoid the formation of high-valent nickel intermediates while a reasonable turnover rate (0.15 s -1 ) is retained.

Redox interplay between mitochondria and peroxisomes

Directory of Open Access Journals (Sweden)

Celien eLismont

2015-05-01

Full Text Available Reduction-oxidation or ‘redox’ reactions are an integral part of a broad range of cellular processes such as gene expression, energy metabolism, protein import and folding, and autophagy. As many of these processes are intimately linked with cell fate decisions, transient or chronic changes in cellular redox equilibrium are likely to contribute to the initiation and progression of a plethora of human diseases. Since a long time, it is known that mitochondria are major players in redox regulation and signaling. More recently, it has become clear that also peroxisomes have the capacity to impact redox-linked physiological processes. To serve this function, peroxisomes cooperate with other organelles, including mitochondria. This review provides a comprehensive picture of what is currently known about the redox interplay between mitochondria and peroxisomes in mammals. We first outline the pro- and antioxidant systems of both organelles and how they may function as redox signaling nodes. Next, we critically review and discuss emerging evidence that peroxisomes and mitochondria share an intricate redox-sensitive relationship and cooperate in cell fate decisions. Key issues include possible physiological roles, messengers, and mechanisms. We also provide examples of how data mining of publicly-available datasets from ‘omics’ technologies can be a powerful means to gain additional insights into potential redox signaling pathways between peroxisomes and mitochondria. Finally, we highlight the need for more studies that seek to clarify the mechanisms of how mitochondria may act as dynamic receivers, integrators, and transmitters of peroxisome-derived mediators of oxidative stress. The outcome of such studies may open up exciting new avenues for the community of researchers working on cellular responses to organelle-derived oxidative stress, a research field in which the role of peroxisomes is currently highly underestimated and an issue of

Photoionization effects in ionization fronts

International Nuclear Information System (INIS)

Arrayas, Manuel; Fontelos, Marco A; Trueba, Jose L

2006-01-01

In this paper we study the effects of photoionization processes on the propagation of both negative and positive ionization fronts in streamer discharge. We show that negative fronts accelerate in the presence of photoionization events. The appearance and propagation of positive ionization fronts travelling with constant velocity is explained as the result of the combined effects of photoionization and electron diffusion. The photoionization range plays an important role in the selection of the velocity of the ionization front as we show in this work

Photoionization effects in ionization fronts

Energy Technology Data Exchange (ETDEWEB)

Arrayas, Manuel [Departamento de Electromagnetismo, Universidad Rey Juan Carlos, Tulipan s/n, 28933 Mostoles, Madrid (Spain); Fontelos, Marco A [Departamento de Matematicas, Instituto de Matematicas y Fisica Fundamental, Consejo Superior de Investigaciones CientIficas, C/Serrano 123, 28006 Madrid (Spain); Trueba, Jose L [Departamento de Electromagnetismo, Universidad Rey Juan Carlos, Tulipan s/n, 28933 Mostoles, Madrid (Spain)

2006-12-21

In this paper we study the effects of photoionization processes on the propagation of both negative and positive ionization fronts in streamer discharge. We show that negative fronts accelerate in the presence of photoionization events. The appearance and propagation of positive ionization fronts travelling with constant velocity is explained as the result of the combined effects of photoionization and electron diffusion. The photoionization range plays an important role in the selection of the velocity of the ionization front as we show in this work.

Active learning of Pareto fronts.

Science.gov (United States)

Campigotto, Paolo; Passerini, Andrea; Battiti, Roberto

2014-03-01

This paper introduces the active learning of Pareto fronts (ALP) algorithm, a novel approach to recover the Pareto front of a multiobjective optimization problem. ALP casts the identification of the Pareto front into a supervised machine learning task. This approach enables an analytical model of the Pareto front to be built. The computational effort in generating the supervised information is reduced by an active learning strategy. In particular, the model is learned from a set of informative training objective vectors. The training objective vectors are approximated Pareto-optimal vectors obtained by solving different scalarized problem instances. The experimental results show that ALP achieves an accurate Pareto front approximation with a lower computational effort than state-of-the-art estimation of distribution algorithms and widely known genetic techniques.

Redox regulation of plant development.

Science.gov (United States)

Considine, Michael J; Foyer, Christine H

2014-09-20

We provide a conceptual framework for the interactions between the cellular redox signaling hub and the phytohormone signaling network that controls plant growth and development to maximize plant productivity under stress-free situations, while limiting growth and altering development on exposure to stress. Enhanced cellular oxidation plays a key role in the regulation of plant growth and stress responses. Oxidative signals or cycles of oxidation and reduction are crucial for the alleviation of dormancy and quiescence, activating the cell cycle and triggering genetic and epigenetic control that underpin growth and differentiation responses to changing environmental conditions. The redox signaling hub interfaces directly with the phytohormone network in the synergistic control of growth and its modulation in response to environmental stress, but a few components have been identified. Accumulating evidence points to a complex interplay of phytohormone and redox controls that operate at multiple levels. For simplicity, we focus here on redox-dependent processes that control root growth and development and bud burst. The multiple roles of reactive oxygen species in the control of plant growth and development have been identified, but increasing emphasis should now be placed on the functions of redox-regulated proteins, along with the central roles of reductants such as NAD(P)H, thioredoxins, glutathione, glutaredoxins, peroxiredoxins, ascorbate, and reduced ferredoxin in the regulation of the genetic and epigenetic factors that modulate the growth and vigor of crop plants, particularly within an agricultural context.

Monitoring thioredoxin redox with a genetically encoded red fluorescent biosensor.

Science.gov (United States)

Fan, Yichong; Makar, Merna; Wang, Michael X; Ai, Hui-Wang

2017-09-01

Thioredoxin (Trx) is one of the two major thiol antioxidants, playing essential roles in redox homeostasis and signaling. Despite its importance, there is a lack of methods for monitoring Trx redox dynamics in live cells, hindering a better understanding of physiological and pathological roles of the Trx redox system. In this work, we developed the first genetically encoded fluorescent biosensor for Trx redox by engineering a redox relay between the active-site cysteines of human Trx1 and rxRFP1, a redox-sensitive red fluorescent protein. We used the resultant biosensor-TrxRFP1-to selectively monitor perturbations of Trx redox in various mammalian cell lines. We subcellularly localized TrxRFP1 to image compartmentalized Trx redox changes. We further combined TrxRFP1 with a green fluorescent Grx1-roGFP2 biosensor to simultaneously monitor Trx and glutathione redox dynamics in live cells in response to chemical and physiologically relevant stimuli.

ETL 1 kW redox flow cell

International Nuclear Information System (INIS)

Nozaki, K.; Ozawa, T.

1984-01-01

A 1 kW scale redox flow cell system was set up in the laboratory (ETL), while three different types of batteries were also assembled by private companies in early 1983. In this article, this cell system is described. The concept of a modern type redox flow cell is based on a couple of fully soluble redox ions and a highly selective ion-exchange membrane. In the cell, the redox ion stored in a tank is flowed to and reduced on the electrode, while the other ion is also flowed to and oxidized on the other electrode. This electrochemical reaction produces electronic current in the external circuit and ionic current through the membrane sandwiched as a separator between the two electrodes. The reverse reaction proceeds in the charging process. In ETL, the concept was preliminarily tested, and conceptual design and cost estimation of the redox flow cells were carried out to confirm the feasibility; the R and D started on these bases in 1975

Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

Science.gov (United States)

Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

2015-10-01

Vanadium redox reactions have been considered as a key factor affecting the energy efficiency of the all-vanadium redox flow batteries (VRFBs). This redox reaction determines the reaction kinetics of whole cells. However, poor kinetic reversibility and catalytic activity towards the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples on the commonly used carbon substrate limit broader applications of VRFBs. Consequently, modified carbon substrates have been extensively investigated to improve vanadium redox reactions. In this Focus Review, recent progress on metal- and carbon-based nanomaterials as an electrocatalyst for VRFBs is discussed in detail, without the intention to provide a comprehensive review on the whole components of the system. Instead, the focus is mainly placed on the redox chemistry of vanadium ions at a surface of various metals, different dimensional carbons, nitrogen-doped carbon nanostructures, and metal-carbon composites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in base.

Science.gov (United States)

Lyons, Michael E G; Doyle, Richard L; Brandon, Michael P

2011-12-28

Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified via analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec(-1) and ca. 120 mV dec(-1) are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from ca. 3/2 to ca. 1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.

Mitochondrial redox biology and homeostasis in plants.

Science.gov (United States)

Noctor, Graham; De Paepe, Rosine; Foyer, Christine H

2007-03-01

Mitochondria are key players in plant cell redox homeostasis and signalling. Earlier concepts that regarded mitochondria as secondary to chloroplasts as the powerhouses of photosynthetic cells, with roles in cell proliferation, death and ageing described largely by analogy to animal paradigms, have been replaced by the new philosophy of integrated cellular energy and redox metabolism involving mitochondria and chloroplasts. Thanks to oxygenic photosynthesis, plant mitochondria often operate in an oxygen- and carbohydrate-rich environment. This rather unique environment necessitates extensive flexibility in electron transport pathways and associated NAD(P)-linked enzymes. In this review, mitochondrial redox metabolism is discussed in relation to the integrated cellular energy and redox function that controls plant cell biology and fate.

Simultaneous fingering, double-diffusive convection, and thermal plumes derived from autocatalytic exothermic reaction fronts

Science.gov (United States)

Eskew, Matthew W.; Harrison, Jason; Simoyi, Reuben H.

2016-11-01

Oxidation reactions of thiourea by chlorite in a Hele-Shaw cell are excitable, autocatalytic, exothermic, and generate a lateral instability upon being triggered by the autocatalyst. Reagent concentrations used to develop convective instabilities delivered a temperature jump at the wave front of 2.1 K. The reaction zone was 2 mm and due to normal cooling after the wave front, this generated a spike rather than the standard well-studied front propagation. The reaction front has solutal and thermal contributions to density changes that act in opposite directions due to the existence of a positive isothermal density change in the reaction. The competition between these effects generates thermal plumes. The fascinating feature of this system is the coexistence of plumes and fingering in the same solution which alternate in frequency as the front propagates, generating hot and cold spots within the Hele-Shaw cell, and subsequently spatiotemporal inhomogeneities. The small ΔT at the wave front generated thermocapillary convection which competed effectively with thermogravitational forces at low Eötvös Numbers. A simplified reaction-diffusion-convection model was derived for the system. Plume formation is heavily dependent on boundary effects from the cell dimensions. This work was supported by Grant No. CHE-1056366 from the NSF and a Research Professor Grant from the University of KwaZulu-Natal.

Subcellular Redox Targeting: Bridging in Vitro and in Vivo Chemical Biology.

Science.gov (United States)

Long, Marcus J C; Poganik, Jesse R; Ghosh, Souradyuti; Aye, Yimon

2017-03-17

Networks of redox sensor proteins within discrete microdomains regulate the flow of redox signaling. Yet, the inherent reactivity of redox signals complicates the study of specific redox events and pathways by traditional methods. Herein, we review designer chemistries capable of measuring flux and/or mimicking subcellular redox signaling at the cellular and organismal level. Such efforts have begun to decipher the logic underlying organelle-, site-, and target-specific redox signaling in vitro and in vivo. These data highlight chemical biology as a perfect gateway to interrogate how nature choreographs subcellular redox chemistry to drive precision redox biology.

Click-PEGylation - A mobility shift approach to assess the redox state of cysteines in candidate proteins.

Science.gov (United States)

van Leeuwen, Lucie A G; Hinchy, Elizabeth C; Murphy, Michael P; Robb, Ellen L; Cochemé, Helena M

2017-07-01

The redox state of cysteine thiols is critical for protein function. Whereas cysteines play an important role in the maintenance of protein structure through the formation of internal disulfides, their nucleophilic thiol groups can become oxidatively modified in response to diverse redox challenges and thereby function in signalling and antioxidant defences. These oxidative modifications occur in response to a range of agents and stimuli, and can lead to the existence of multiple redox states for a given protein. To assess the role(s) of a protein in redox signalling and antioxidant defence, it is thus vital to be able to assess which of the multiple thiol redox states are present and to investigate how these alter under different conditions. While this can be done by a range of mass spectrometric-based methods, these are time-consuming, costly, and best suited to study abundant proteins or to perform an unbiased proteomic screen. One approach that can facilitate a targeted assessment of candidate proteins, as well as proteins that are low in abundance or proteomically challenging, is by electrophoretic mobility shift assays. Redox-modified cysteine residues are selectively tagged with a large group, such as a polyethylene glycol (PEG) polymer, and then the proteins are separated by electrophoresis followed by immunoblotting, which allows the inference of redox changes based on band shifts. However, the applicability of this method has been impaired by the difficulty of cleanly modifying protein thiols by large PEG reagents. To establish a more robust method for redox-selective PEGylation, we have utilised a Click chemistry approach, where free thiol groups are first labelled with a reagent modified to contain an alkyne moiety, which is subsequently Click-reacted with a PEG molecule containing a complementary azide function. This strategy can be adapted to study reversibly reduced or oxidised cysteines. Separation of the thiol labelling step from the PEG

Neutral Red and Ferroin as Reversible and Rapid Redox Materials for Redox Flow Batteries.

Science.gov (United States)

Hong, Jeehoon; Kim, Ketack

2018-04-17

Neutral red and ferroin are used as redox indicators (RINs) in potentiometric titrations. The rapid response and reversibility that are prerequisites for RINs are also desirable properties for the active materials in redox flow batteries (RFBs). This study describes the electrochemical properties of ferroin and neutral red as a redox pair. The rapid reaction rates of the RINs allow a cell to run at a rate of 4 C with 89 % capacity retention after the 100 th  cycle. The diffusion coefficients, electrode reaction rates, and solubilities of the RINs were determined. The electron-transfer rate constants of ferroin and neutral red are 0.11 and 0.027 cm s -1 , respectively, which are greater than those of the components of all-vanadium and Zn/Br 2 cells. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox shuttles for safer lithium-ion batteries

International Nuclear Information System (INIS)

Chen, Zonghai; Qin, Yan; Amine, Khalil

2009-01-01

Overcharge protection is not only critical for preventing the thermal runaway of lithium-ion batteries during operation, but also important for automatic capacity balancing during battery manufacturing and repair. A redox shuttle is an electrolyte additive that can be used as intrinsic overcharge protection mechanism to enhance the safety characteristics of lithium-ion batteries. The advances on stable redox shuttles are briefly reviewed. Fundamental studies for designing stable redox shuttles are also discussed.

Microfluidic redox battery.

Science.gov (United States)

Lee, Jin Wook; Goulet, Marc-Antoni; Kjeang, Erik

2013-07-07

A miniaturized microfluidic battery is proposed, which is the first membraneless redox battery demonstrated to date. This unique concept capitalizes on dual-pass flow-through porous electrodes combined with stratified, co-laminar flow to generate electrical power on-chip. The fluidic design is symmetric to allow for both charging and discharging operations in forward, reverse, and recirculation modes. The proof-of-concept device fabricated using low-cost materials integrated in a microfluidic chip is shown to produce competitive power levels when operated on a vanadium redox electrolyte. A complete charge/discharge cycle is performed to demonstrate its operation as a rechargeable battery, which is an important step towards providing sustainable power to lab-on-a-chip and microelectronic applications.

Temperature and ionic strength influences on actinide(VI)/(V) redox potentials for carbonate limiting complexes

International Nuclear Information System (INIS)

Capdevila, H.; Vitorge, P.

1998-01-01

Actinide behaviour was studied in two limiting aqueous solutions: acidic and carbonate. Cyclic voltametry was validated with well-known U redox system. SIT was used to account for I influence. Taylor's series expansions to the second order were used to account for T influence. Redox potentials of actinide couples had previously been measured in non complexing media. The above data treatments give standard values for redox potential E 0 , for the corresponding entropy ΔS 0 , enthalpy ΔH 0 and heat capacity ΔC p 0 changes, and also for the corresponding excess values (i.e. the variation of these thermodynamic constants with ionic strength). This methodology was here used in carbonate media to measure the potential of the redox couple PuO 2 (CO 3 ) 3 4- /PuO 2 (CO 3 ) 3 5- from 5 to 70 degC and from I = 0.5 to 4.5 M in Na 2 CO 3 , NaClO 4 media. Experimental details and full results are given for Pu. Only final results are given for Np. Previous and/or published data for U and Am are discussed. E and ΔS variations with T or I were enough to be measured. The values obtained for the fitted SIT coefficients Δε, and for ΔS and ΔCp are similar for U, Np and Pu redox reactions. Using this analogy for Am missing data is discussed. β 3 V /β 3 VI formation constant ratio of the carbonate limiting complexes were deduced from the potential shift from complexing to non complexing media for the Actinide(VI)/Actinide(V) redox couples. β 3 V (U and Pu) and β 3 VI (Np) were finally proposed using published β3 VI (U and Pu) and β 3 V (Np). For Am, this data treatment was used to discuss the AmO 2 2+ / AmO 2 + redox potential

The changes in redox status of ascorbate in stem tissue cells during Scots pine tree growth

Directory of Open Access Journals (Sweden)

G. F. Antonova

2017-02-01

Full Text Available The contents of ascorbate (AsA and dehydroascorbate (DHA and their ratio, showing cellular redox state of AsA, were studied in the cells of the separate tissues at different levels of Pinus sylvestris L. stem during early- and latewood formation. Morphological status of the cells in the tissues and the content of soluble carbohydrates were also estimated. The cellular redox potential of AsA has been found to depend on the type of tissue, cell development degree, the level of stem and the type of forming wood. The content of AsA and AsA/DHA ratio in the cells of non-conducting phloem along the stem were higher than in mature xylem and less during earlywood than latewood formation. The cells of conducting phloem and forming xylem, as the principal tissues taking part in annual ring wood formation, differed in the content of acids in the course of early and late xylem formation. Along the stem, the content of AsA decreased in conducting phloem cells and increased in the cells of forming xylem during both early- and latewood formation. The AsA/DHA of conducting phloem during earlywood formation was greatest below the stem and diminished to the top of the tree, while in the course of latewood development it was similar at all levels. In forming xylem AsA/DHA increased to the top of tree during the early xylem formation and decreased in late xylem that indicates the differences in oxidation-reduction reactions into the cells of two type of forming wood. The data are discussed according to morphological development of cells and the content of carbohydrates.

Managing the cellular redox hub in photosynthetic organisms.

Science.gov (United States)

Foyer, Christine H; Noctor, Graham

2012-02-01

Light-driven redox chemistry is a powerful source of redox signals that has a decisive input into transcriptional control within the cell nucleus. Like photosynthetic electron transport pathways, the respiratory electron transport chain exerts a profound control over gene function, in order to balance energy (reductant and ATP) supply with demand, while preventing excessive over-reduction or over-oxidation that would be adversely affect metabolism. Photosynthetic and respiratory redox chemistries are not merely housekeeping processes but they exert a controlling influence over every aspect of plant biology, participating in the control of gene transcription and translation, post-translational modifications and the regulation of assimilatory reactions, assimilate partitioning and export. The number of processes influenced by redox controls and signals continues to increase as do the components that are recognized participants in the associated signalling pathways. A step change in our understanding of the overall importance of the cellular redox hub to plant cells has occurred in recent years as the complexity of the management of the cellular redox hub in relation to metabolic triggers and environmental cues has been elucidated. This special issue describes aspects of redox regulation and signalling at the cutting edge of current research in this dynamic and rapidly expanding field. © 2011 Blackwell Publishing Ltd.

Unusual thiol-based redox metabolism of parasitic flukes.

Science.gov (United States)

Tripathi, Timir; Suttiprapa, Sutas; Sripa, Banchob

2017-08-01

Parasitic flukes are exposed to free radicals and, to a greater extent, reactive oxygen species (ROS) during their life cycle. Despite being relentlessly exposed to ROS released by activated immune cells, these parasites can survive for many years in the host. Cellular thiol-based redox metabolism plays a crucial role in parasite survival within their hosts. Evidence shows that oxidative stress and redox homeostasis maintenance are important clinical and pathobiochemical as well as effective therapeutic principles in various diseases. The characterization of redox and antioxidant enzymes is likely to yield good target candidates for novel drugs and vaccines. The absence of active catalase in fluke parasites offers great potential for the development of chemotherapeutic agents that act by perturbing the redox equilibrium of the cell. One of the redox-sensitive enzymes, thioredoxin glutathione reductase (TGR), has been accepted as a drug target against blood fluke infections, and related clinical trials are in progress. TGR is the sole enzyme responsible for Trx and GSH reduction in parasitic flukes. The availability of helminth genomes has accelerated the research on redox metabolism of flukes; however, significant achievements have yet to be attained. The present review summarizes current knowledge on the redox and antioxidant system of the parasitic flukes. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Redox Modulations, Antioxidants, and Neuropsychiatric Disorders

Directory of Open Access Journals (Sweden)

Erik A. Fraunberger

2016-01-01

Full Text Available Although antioxidants, redox modulations, and neuropsychiatric disorders have been widely studied for many years, the field would benefit from an integrative and corroborative review. Our primary objective is to delineate the biological significance of compounds that modulate our redox status (i.e., reactive species and antioxidants as well as outline their current role in brain health and the impact of redox modulations on the severity of illnesses. Therefore, this review will not enter into the debate regarding the perceived medical legitimacy of antioxidants but rather seek to clarify their abilities and limitations. With this in mind, antioxidants may be interpreted as natural products with significant pharmacological actions in the body. A renewed understanding of these often overlooked compounds will allow us to critically appraise the current literature and provide an informed, novel perspective on an important healthcare issue. In this review, we will introduce the complex topics of redox modulations and their role in the development of select neuropsychiatric disorders.

Impact of uranium (U) on the cellular glutathione pool and resultant consequences for the redox status of U.

Science.gov (United States)

Viehweger, Katrin; Geipel, Gerhard; Bernhard, Gert

2011-12-01

Uranium (U) as a redox-active heavy metal can cause various redox imbalances in plant cells. Measurements of the cellular glutathione/glutathione disulfide (GSH/GSSG) by HPLC after cellular U contact revealed an interference with this essential redox couple. The GSH content remained unaffected by 10 μM U whereas the GSSG level immediately increased. In contrast, higher U concentrations (50 μM) drastically raised both forms. Using the Nernst equation, it was possible to calculate the half-cell reduction potential of 2GSH/GSSG. In case of lower U contents the cellular redox environment shifted towards more oxidizing conditions whereas the opposite effect was obtained by higher U contents. This indicates that U contact causes a consumption of reduced redox equivalents. Artificial depletion of GSH by chlorodinitrobenzene and measuring the cellular reducing capacity by tetrazolium salt reduction underlined the strong requirement of reduced redox equivalents. An additional element of cellular U detoxification mechanisms is the complex formation between the heavy metal and carboxylic functionalities of GSH. Because two GSH molecules catalyze electron transfers each with one electron forming a dimer (GSSG) two UO(2) (2+) are reduced to each UO(2) (+) by unbound redox sensitive sulfhydryl moieties. UO(2) (+) subsequently disproportionates to UO(2) (2+) and U(4+). This explains that in vitro experiments revealed a reduction to U(IV) of only around 33% of initial U(VI). Cellular U(IV) was transiently detected with the highest level after 2 h of U contact. Hence, it can be proposed that these reducing processes are an important element of defense reactions induced by this heavy metal.

Characterization of redox proteins using electrochemical methods

OpenAIRE

Verhagen, M.

1995-01-01

The use of electrochemical techniques in combination with proteins started approximately a decade ago and has since then developed into a powerfull technique for the study of small redox proteins. In addition to the determination of redox potentials, electrochemistry can be used to obtain information about the kinetics of electron transfer between proteins and about the dynamic behaviour of redox cofactors in proteins. This thesis describes the results of a study, initiated to get a ...

Dihydroxybenzene/benzoquinone-containing polymers: organic redox polymers

Energy Technology Data Exchange (ETDEWEB)

Moulay, S. [Universite de Blida, Lab. de Chimie-Physique Macromoleculaire, Institut de Chimie Industrielle (Algeria)

2000-08-01

Polymers containing hydroquinone, catechol or their corresponding benzoquinones are a special class of redox polymers. Three pathways of their syntheses are possible: condensation polymerization of suitable monomers, addition polymerization of vinyl monomers containing redox moiety, and chemical attachment of redox unit onto pre-made polymeric matrix. A range of functionalized matrices have been employed such as polyethers, polyesters, polycarbonates, polyurethanes, polyamides and others. Protection of their phenolic functionality has conducted to chemically interesting redox polymer precursors. The presence of a redox moiety coupled with the extant functionalization of the polymer matrix makes the materials very valuable, of wide properties and consequently of vast applicability. For instance, in the oil field, some polymers such as carboxy-methyl-cellulose (CMC) are often applied as to bring about a viscosity improvement and therefore to facilitate the oil drilling. In this regard, Patel evaluated sulfo-alkylated polymeric catechol, namely sulfo-methylated and sulfo-ethylated resins. Indeed, polymeric catechol chemically modified as such exhibited a marked ability to control the viscosity, the gel strength, as well as the filtrate loss of aqueous oil drilling fluids.

Chemical behaviour of plutonium in natural, aquatic systems: Hydrolysis, carbonate complexation and redox reactions

International Nuclear Information System (INIS)

Lierse, C.

1985-01-01

In order to clear up the geochemical behaviour of plutonium and its migration mechanisms in groundwater, hydrolysis, redox behaviour, compound formation in carbonate solutions and colloid formation were examined in groundwater conditions, i.e. at pH values between 5 and 8 and at redox potentials of between -300 and +700 mV. Solubility measurements, spectroscopic processes (UV, VIS, IR spectroscopy and laser induced photoacoustic spectroscopy) and electrochemical processes (cyclic voltammetry, differential pulse polarography) are used as methods of investigation. The hydrolysis constants of Pu IV and Pu VI and the solubility product of Pu (OH) 4 were determined and hydrolysis products of divalent and trivalent type are described. From solubility experiments, the stability constants for Pu (IV) carbonate compounds and the solubility product for the carbonate system of stable bodies of Pu (OH) 2 CO 3 were calculated. Using absorption spectroscopy, the disproportionate kinetics of Pu (V) in carbonate was determined at various pH values. A slow, but continuous, reduction in Pu (VI) was found in carbonate solution, which was derived from radiolytic effects. The speed of this auto-reduction was determined, depending on various experimental parameters. (orig./RB) [de

Seabirds and fronts: a brief overview

OpenAIRE

Schneider, David C.

1990-01-01

Oceanographic fronts are the sites of enhanced physical and biological activity, including locally concentrated feeding by marine birds. Two general hypotheses relating marine birds to fronts have been developed. The first is that enhanced primary production at fronts increases prey supply through increased animal growth, reproduction, or immigration. The second is that prey patches develop at fronts either through behavioural responses of prey to thermal or salinity gradients, or through int...

Mesoporous tungsten oxynitride as electrocatalyst for promoting redox reactions of vanadium redox couple and performance of vanadium redox flow battery

Science.gov (United States)

Lee, Wonmi; Jo, Changshin; Youk, Sol; Shin, Hun Yong; Lee, Jinwoo; Chung, Yongjin; Kwon, Yongchai

2018-01-01

For enhancing the performance of vanadium redox flow battery (VRFB), a sluggish reaction rate issue of V2+/V3+ redox couple evaluated as the rate determining reaction should be addressed. For doing that, mesoporous tungsten oxide (m-WO3) and oxyniride (m-WON) structures are proposed as the novel catalysts, while m-WON is gained by NH3 heat treatment of m-WO3. Their specific surface area, crystal structure, surface morphology and component analysis are measured using BET, XRD, TEM and XPS, while their catalytic activity for V2+/V3+ redox reaction is electrochemically examined. As a result, the m-WON shows higher peak current, smaller peak potential difference, higher electron transfer rate constant and lower charge transfer resistance than other catalysts, like the m-WO3, WO3 nanoparticle and mesoporous carbon, proving that it is superior catalyst. Regarding the charge-discharge curve tests, the VRFB single cell employing the m-WON demonstrates high voltage and energy efficiencies, high specific capacity and low capacity loss rate. The excellent results of m-WON are due to the reasons like (i) reduced energy band gap, (ii) reaction familiar surface functional groups and (ii) greater electronegativity.

Redox-active on-surface polymerization of single-site divalent cations from pure metals by a ketone-functionalized phenanthroline

Energy Technology Data Exchange (ETDEWEB)

Skomski, Daniel; Tempas, Christopher D.; Bukowski, Gregory S.; Smith, Kevin A.; Tait, Steven L., E-mail: tait@indiana.edu [Department of Chemistry, Indiana University, 800 E. Kirkwood Ave., Bloomington, Indiana 47405 (United States)

2015-03-14

Metallic iron, chromium, or platinum mixing with a ketone-functionalized phenanthroline ligand on a single crystal gold surface demonstrates redox activity to a well-defined oxidation state and assembly into thermally stable, one dimensional, polymeric chains. The diverging ligand geometry incorporates redox-active sub-units and bi-dentate binding sites. The gold surface provides a stable adsorption environment and directs growth of the polymeric chains, but is inert with regard to the redox chemistry. These systems are characterized by scanning tunnelling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy under ultra-high vacuum conditions. The relative propensity of the metals to interact with the ketone group is examined, and it is found that Fe and Cr more readily complex the ligand than Pt. The formation and stabilization of well-defined transition metal single-sites at surfaces may open new routes to achieve higher selectivity in heterogeneous catalysts.

Redox-Based Regulation of Bacterial Development and Behavior.

Science.gov (United States)

Sporer, Abigail J; Kahl, Lisa J; Price-Whelan, Alexa; Dietrich, Lars E P

2017-06-20

Severe changes in the environmental redox potential, and resulting alterations in the oxidation states of intracellular metabolites and enzymes, have historically been considered negative stressors, requiring responses that are strictly defensive. However, recent work in diverse organisms has revealed that more subtle changes in the intracellular redox state can act as signals, eliciting responses with benefits beyond defense and detoxification. Changes in redox state have been shown to influence or trigger chromosome segregation, sporulation, aerotaxis, and social behaviors, including luminescence as well as biofilm establishment and dispersal. Connections between redox state and complex behavior allow bacteria to link developmental choices with metabolic state and coordinate appropriate responses. Promising future directions for this area of study include metabolomic analysis of species- and condition-dependent changes in metabolite oxidation states and elucidation of the mechanisms whereby the redox state influences circadian regulation.

Hydrodynamic instabilities in an ablation front

International Nuclear Information System (INIS)

Piriz, A R; Portugues, R F

2004-01-01

The hydrodynamic stability of an ablation front is studied for situations in which the wavelength of the perturbations is larger than the distance to the critical surface where the driving radiation is absorbed. An analytical model is presented, and it shows that under conditions in which the thermal flux is limited within the supercritical region of the ablative corona, the front may behave like a flame or like an ablation front, depending on the perturbation wavelength. For relatively long wavelengths the critical and ablation surfaces practically lump together into a unique surface and the front behaves like a flame, whereas for the shortest wavelengths the ablation front substructure is resolved

Hydrodynamic instabilities in an ablation front

Energy Technology Data Exchange (ETDEWEB)

Piriz, A R; Portugues, R F [E.T.S.I. Industriales, Universidad de Castilla-La Mancha, 13071 Ciudad Real (Spain)

2004-06-01

The hydrodynamic stability of an ablation front is studied for situations in which the wavelength of the perturbations is larger than the distance to the critical surface where the driving radiation is absorbed. An analytical model is presented, and it shows that under conditions in which the thermal flux is limited within the supercritical region of the ablative corona, the front may behave like a flame or like an ablation front, depending on the perturbation wavelength. For relatively long wavelengths the critical and ablation surfaces practically lump together into a unique surface and the front behaves like a flame, whereas for the shortest wavelengths the ablation front substructure is resolved.

Redox flow batteries having multiple electroactive elements

Energy Technology Data Exchange (ETDEWEB)

Wang, Wei; Li, Liyu; Yang, Zhenguo; Nie, Zimin

2018-05-01

Introducing multiple redox reactions with a suitable voltage range can improve the energy density of redox flow battery (RFB) systems. One example includes RFB systems utilizing multiple redox pairs in the positive half cell, the negative half cell, or in both. Such RFB systems can have a negative electrolyte, a positive electrolyte, and a membrane between the negative electrolyte and the positive electrolyte, in which at least two electrochemically active elements exist in the negative electrolyte, the positive electrolyte, or both.

Redox reactions in micellar systems. communication 4. Eosin-photosensitized reduction of methylviologen

Energy Technology Data Exchange (ETDEWEB)

Nadtochenko, V.; Dzhabiev, T.S.; Rubtsov, I.V.

1985-12-10

The authors present data on photosensitized reduction of methylviologen (MV/sup 2 +/) by disodium ethylenediaminetetraacetate (EDTA) in micellar systems modeling, in a first approximation, the structural organization of components of the chain of energy and electron transfer in natural photosynthesis. Photosensitized reduction of methylviologen by EDTA in micellar solutions can model photosystem I of plants with structure formation of reagents and transfer of excitation energy before the step of occurrence of a redox reaction in the active center.

Redox behavior of a low-doped Pr-CeO_2(111) surface. A DFT+U study

International Nuclear Information System (INIS)

Milberg, Brian; Juan, Alfredo; Irigoyen, Beatriz

2017-01-01

Highlights: • Pr doping facilitates oxygen donation due to the easy formation of Pr"3"+/Pr"4"+ and Ce"3"+/Ce"4"+ redox couples. • Pr doping also favors the formation of superoxide (O_2"−) radicals on surface O-holes. • CO can be oxidized by superoxide radical forming a CO_2 molecule floating on the surface. • CO can also interact on the (O_2"−)/Pr"3"+ interphase and forms weakly adsorbed carbonate-type intermediates. - Abstract: In this work, we investigated the redox behavior (donation and replenishing of oxygen) of a low praseodymium (Pr)-doped CeO_2(111) surface. We considered a 3.7 at.% Pr doping and performed density functional calculations using the GGA formalism with the ‘U’ correction on Ce(4f) and Pr(4f) orbitals. Our results indicate that Pr doping promotes oxygen donation by lowering the energy necessary to form surface anionic vacancies. When the Ce_0_._9_6_3Pr_0_._0_3_7O_2(111) surface donates one oxygen, the two excess electrons locate on Pr and Ce cations and reduce them to Pr"3"+ and Ce"3"+ ones. Praseodymium doping also favors the activation of O_2 molecule on surface O-holes, leading to formation of a superoxide (O_2"−) radical as well as to reoxidation of the Ce"3"+ cation to Ce"4"+ one. Additionally, we used the CO molecular adsorption for testing the reactivity of those superoxide species. The calculations expose the ability of these radicals to oxidize CO forming a CO_2 molecule floating on the surface. However, when the superoxide is in the immediate vicinity of Pr dopant a carbonate-type species is formed. Our theoretical results may help to gain insight into redox properties and improved catalytic performance of low-doped Pr-CeO_2 solids.

Effects of microbial redox cycling of iron on cast iron pipe corrosion in drinking water distribution systems.

Science.gov (United States)

Wang, Haibo; Hu, Chun; Zhang, Lili; Li, Xiaoxiao; Zhang, Yu; Yang, Min

2014-11-15

Bacterial characteristics in corrosion products and their effect on the formation of dense corrosion scales on cast iron coupons were studied in drinking water, with sterile water acting as a reference. The corrosion process and corrosion scales were characterized by electrochemical and physico-chemical measurements. The results indicated that the corrosion was more rapidly inhibited and iron release was lower due to formation of more dense protective corrosion scales in drinking water than in sterile water. The microbial community and denitrifying functional genes were analyzed by pyrosequencing and quantitative polymerase chain reactions (qPCR), respectively. Principal component analysis (PCA) showed that the bacteria in corrosion products played an important role in the corrosion process in drinking water. Nitrate-reducing bacteria (NRB) Acidovorax and Hydrogenophaga enhanced iron corrosion before 6 days. After 20 days, the dominant bacteria became NRB Dechloromonas (40.08%) with the protective corrosion layer formation. The Dechloromonas exhibited the stronger corrosion inhibition by inducing the redox cycling of iron, to enhance the precipitation of iron oxides and formation of Fe3O4. Subsequently, other minor bacteria appeared in the corrosion scales, including iron-respiring bacteria and Rhizobium which captured iron by the produced siderophores, having a weaker corrosion-inhibition effect. Therefore, the microbially-driven redox cycling of iron with associated microbial capture of iron caused more compact corrosion scales formation and lower iron release. Copyright © 2014 Elsevier Ltd. All rights reserved.

Redox Cycling Realized in Paper-Based Biochemical Sensor for Selective Detection of Reversible Redox Molecules Without Micro/Nano Fabrication Process.

Science.gov (United States)

Yamamoto, So; Uno, Shigeyasu

2018-02-28

This paper describes a paper-based biochemical sensor that realizes redox cycling with close interelectrode distance. Two electrodes, the generator and collector electrodes, can detect steady-state oxidation and reduction currents when suitable potential is held at each electrode. The sensor has two gold plates on both sides of a piece of chromatography paper and defines the interelectrode distance by the thickness of the paper (180 μm) without any micro-fabrication processes. Our proposed sensor geometry has successfully exhibited signatures of redox cycling. As a result, the concentration of ferrocyanide as reversible redox molecules was successfully quantified under the interference by ascorbic acid as a strong irreversible reducing agent. This was possible because the ascorbic acids are completely consumed by the irreversible reaction, while maintaining redox cycling of reversible ferrocyanide. This suggests that a sensor based on the redox cycling method will be suitable for detecting target molecules at low concentration.

Nitric oxide activation by distal redox modulation in tetranuclear iron nitrosyl complexes.

Science.gov (United States)

de Ruiter, Graham; Thompson, Niklas B; Lionetti, Davide; Agapie, Theodor

2015-11-11

A series of tetranuclear iron complexes displaying a site-differentiated metal center was synthesized. Three of the metal centers are coordinated to our previously reported ligand, based on a 1,3,5-triarylbenzene motif with nitrogen and oxygen donors. The fourth (apical) iron center is coordinatively unsaturated and appended to the trinuclear core through three bridging pyrazolates and an interstitial μ4-oxide moiety. Electrochemical studies of complex [LFe3(PhPz)3OFe][OTf]2 revealed three reversible redox events assigned to the Fe(II)4/Fe(II)3Fe(III) (-1.733 V), Fe(II)3Fe(III)/Fe(II)2Fe(III)2 (-0.727 V), and Fe(II)2Fe(III)2/Fe(II)Fe(III)3 (0.018 V) redox couples. Combined Mössbauer and crystallographic studies indicate that the change in oxidation state is exclusively localized at the triiron core, without changing the oxidation state of the apical metal center. This phenomenon is assigned to differences in the coordination environment of the two metal sites and provides a strategy for storing electron and hole equivalents without affecting the oxidation state of the coordinatively unsaturated metal. The presence of a ligand-binding site allowed the effect of redox modulation on nitric oxide activation by an Fe(II) metal center to be studied. Treatment of the clusters with nitric oxide resulted in binding of NO to the apical iron center, generating a {FeNO}(7) moiety. As with the NO-free precursors, the three reversible redox events are localized at the iron centers distal from the NO ligand. Altering the redox state of the triiron core resulted in significant change in the NO stretching frequency, by as much as 100 cm(-1). The increased activation of NO is attributed to structural changes within the clusters, in particular, those related to the interaction of the metal centers with the interstitial atom. The differences in NO activation were further shown to lead to differential reactivity, with NO disproportionation and N2O formation performed by the more

Factors Controlling Redox Speciation of Plutonium and Neptunium in Extraction Separation Processes

Energy Technology Data Exchange (ETDEWEB)

Paulenova, Alena [Principal Investigator; Vandegrift, III, George F. [Collaborator

2013-09-24

The objective of the project was to examine the factors controlling redox speciation of plutonium and neptunium in UREX+ extraction in terms of redox potentials, redox mechanism, kinetics and thermodynamics. Researchers employed redox-speciation extractions schemes in parallel to the spectroscopic experiments. The resulting distribution of redox species w studied uring spectroscopic, electrochemical, and spectro-electrochemical methods. This work reulted in collection of data on redox stability and distribution of redox couples in the nitric acid/nitrate electrolyte and the development of redox buffers to stabilize the desired oxidation state of separated radionuclides. The effects of temperature and concentrations on the redox behavior of neptunium were evaluated.

Multiwalled carbon nanotubes enhance electrochemical properties of titanium to determine in situ bone formation

Energy Technology Data Exchange (ETDEWEB)

Sirivisoot, Sirinrath; Webster, Thomas J [Division of Engineering, Brown University, Providence, RI 02912 (United States)], E-mail: Thomas_Webster@Brown.edu

2008-07-23

Multiwalled carbon nanotubes (MWCNTs) enhance osteoblast (bone-forming cell) calcium deposition compared to currently implanted materials (such as titanium). In this study, MWCNTs were grown out of nanopores anodized on titanium (MWCNT-Ti). The electrochemical responses of MWCNT-Ti were investigated in an attempt to ascertain if MWCNT-Ti can serve as novel in situ sensors of bone formation. For this purpose, MWCNT-Ti was subjected to a ferri/ferrocyanide redox couple and its electrochemical behavior measured. Cyclic voltammograms (CVs) showed an enhanced redox potential for the MWCNT-Ti. These redox signals were superior to that obtained with bare unmodified Ti, which did not sense either oxidation or reduction peaks in the CVs. A further objective of this study was to investigate the redox reactions of MWCNT-Ti in a solution of extracellular components secreted by osteoblasts in vitro. It was found that MWCNT-Ti exhibited well-defined and persistent CVs, similar to the ferri/ferrocyanide redox reaction. The higher electrodic performance and electrocatalytic activity of the MWCNT-Ti compared to the bare titanium observed in this study were likely due to the fact that MWCNTs enhanced direct electron transfer and facilitated double-layer effects, leading to a strong redox signal. Thus these results encourage the further study and modification of MWCNT-Ti to sense new bone growth in situ next to orthopedic implants and perhaps monitor other events (such as infection and/or harmful scar tissue formation) to improve the current clinical diagnosis of orthopedic implants.

Multiwalled carbon nanotubes enhance electrochemical properties of titanium to determine in situ bone formation

International Nuclear Information System (INIS)

Sirivisoot, Sirinrath; Webster, Thomas J

2008-01-01

Multiwalled carbon nanotubes (MWCNTs) enhance osteoblast (bone-forming cell) calcium deposition compared to currently implanted materials (such as titanium). In this study, MWCNTs were grown out of nanopores anodized on titanium (MWCNT-Ti). The electrochemical responses of MWCNT-Ti were investigated in an attempt to ascertain if MWCNT-Ti can serve as novel in situ sensors of bone formation. For this purpose, MWCNT-Ti was subjected to a ferri/ferrocyanide redox couple and its electrochemical behavior measured. Cyclic voltammograms (CVs) showed an enhanced redox potential for the MWCNT-Ti. These redox signals were superior to that obtained with bare unmodified Ti, which did not sense either oxidation or reduction peaks in the CVs. A further objective of this study was to investigate the redox reactions of MWCNT-Ti in a solution of extracellular components secreted by osteoblasts in vitro. It was found that MWCNT-Ti exhibited well-defined and persistent CVs, similar to the ferri/ferrocyanide redox reaction. The higher electrodic performance and electrocatalytic activity of the MWCNT-Ti compared to the bare titanium observed in this study were likely due to the fact that MWCNTs enhanced direct electron transfer and facilitated double-layer effects, leading to a strong redox signal. Thus these results encourage the further study and modification of MWCNT-Ti to sense new bone growth in situ next to orthopedic implants and perhaps monitor other events (such as infection and/or harmful scar tissue formation) to improve the current clinical diagnosis of orthopedic implants

Understanding the nanoscale redox-behavior of iron-anodes for rechargeable iron-air batteries

Energy Technology Data Exchange (ETDEWEB)

Weinrich, Henning [Forschungszentrum Julich (Germany). Inst. for Energy and Climate Research-Fundamental Electrochemistry (IEK-9); RWTH Aachen Univ., Aachen (Germany). Inst. of Physical Chemistry; Come, Jérémy [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Tempel, Hermann [Forschungszentrum Julich (Germany). Inst. for Energy and Climate Research-Fundamental Electrochemistry (IEK-9); Kungl, Hans [Forschungszentrum Julich (Germany). Inst. for Energy and Climate Research-Fundamental Electrochemistry (IEK-9); Eichel, Rüdiger-A. [Forschungszentrum Julich (Germany). Inst. for Energy and Climate Research-Fundamental Electrochemistry (IEK-9); Balke, Nina [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)

2017-10-10

Iron-air cells provide a promising and resource-efficient alternative battery concept with superior area specific power density characteristics compared to state-of-the-art Li-air batteries and potentially superior energy density characteristics compared to present Li-ion batteries. Understanding charge-transfer reactions at the anode-electrolyte interface is the key to develop high-performance cells. By employing in-situ electrochemical atomic force microscopy (in-situ EC-AFM), in-depth insight into the electrochemically induced surface reaction processes on iron in concentrated alkaline electrolyte is obtained. The results highlight the formation and growth of the redox-layer on iron over the course of several oxidation/reduction cycles. By this means, a direct correlation between topography changes and the corresponding electrochemical reactions at the nanoscale could unambiguously be established. Here in this paper, the twofold character of the nanoparticulate redox-layer in terms of its passivating character and its contribution to the electrochemical reactions is elucidated. Furthermore, the evolution of single nanoparticles on the iron electrode surface is evaluated in unprecedented and artifact-free detail. Based on the dedicated topography analysis, a detailed structural model for the evolution of the redox-layer which is likewise elementary for corrosion science and battery research is derived.

Single-molecule conductivity of non-redox and redox molecules at pure and gold-mined Au(111)-electrode surfaces

DEFF Research Database (Denmark)

Zhang, Jingdong; Chi, Qijin; Ulstrup, Jens

The structure, two-dimensional organization, and function of molecules immobilized on solid surfaces can be addressed in a degree of detail that has reached the level of the single-molecule. In this context redox molecules are “smart” molecules adding sophisticated electronic function. Redox meta...

Compartmentation of redox metabolism in malaria parasites.

Directory of Open Access Journals (Sweden)

Sebastian Kehr

Full Text Available Malaria, caused by the apicomplexan parasite Plasmodium, still represents a major threat to human health and welfare and leads to about one million human deaths annually. Plasmodium is a rapidly multiplying unicellular organism undergoing a complex developmental cycle in man and mosquito - a life style that requires rapid adaptation to various environments. In order to deal with high fluxes of reactive oxygen species and maintain redox regulatory processes and pathogenicity, Plasmodium depends upon an adequate redox balance. By systematically studying the subcellular localization of the major antioxidant and redox regulatory proteins, we obtained the first complete map of redox compartmentation in Plasmodium falciparum. We demonstrate the targeting of two plasmodial peroxiredoxins and a putative glyoxalase system to the apicoplast, a non-photosynthetic plastid. We furthermore obtained a complete picture of the compartmentation of thioredoxin- and glutaredoxin-like proteins. Notably, for the two major antioxidant redox-enzymes--glutathione reductase and thioredoxin reductase--Plasmodium makes use of alternative-translation-initiation (ATI to achieve differential targeting. Dual localization of proteins effected by ATI is likely to occur also in other Apicomplexa and might open new avenues for therapeutic intervention.

Bioelectrochemical probing of intracellular redox processes in living yeast cells—application of redox polymer wiring in a microfluidic environment

DEFF Research Database (Denmark)

Heiskanen, Arto; Coman, Vasile; Kostesha, Natalie

2013-01-01

utilizing a new double mediator system to map redox metabolism and screen for genetic modifications in Saccharomyces cerevisiae cells. The function of this new double mediator system based on menadione and osmium redox polymer (PVI-Os) is demonstrated. “Wiring” of S. cerevisiae cells using PVI-Os shows...... that microfluidic bioelectrochemical assays employing the menadione–PVI-Os double mediator system provides an effective means to conduct automated microbial assays. FigureMicrofluidic platform for bioelectrochemical assays using osmium redox polymer “wired” living yeast cells...

Diglycosyl diselenides alter redox homeostasis and glucose consumption of infective African trypanosomes

Directory of Open Access Journals (Sweden)

Jaime Franco

2017-12-01

Full Text Available With the aim to develop compounds able to target multiple metabolic pathways and, thus, to lower the chances of drug resistance, we investigated the anti-trypanosomal activity and selectivity of a series of symmetric diglycosyl diselenides and disulfides. Of 18 compounds tested the fully acetylated forms of di-β-D-glucopyranosyl and di-β-D-galactopyranosyl diselenides (13 and 15, respectively displayed strong growth inhibition against the bloodstream stage of African trypanosomes (EC50 0.54 μM for 13 and 1.49 μM for 15 although with rather low selectivity (SI < 10 assayed with murine macrophages. Nonacetylated versions of the same sugar diselenides proved to be, however, much less efficient or completely inactive to suppress trypanosome growth. Significantly, the galactosyl (15, and to a minor extent the glucosyl (13, derivative inhibited glucose catabolism but not its uptake. Both compounds induced redox unbalance in the pathogen. In vitro NMR analysis indicated that diglycosyl diselenides react with glutathione, under physiological conditions, via formation of selenenylsulfide bonds. Our results suggest that non-specific cellular targets as well as actors of the glucose and the redox metabolism of the parasite may be affected. These molecules are therefore promising leads for the development of novel multitarget antitrypanosomal agents. Keywords: Glutathione, Redox biosensor, Selenosugar, Trypanosome inhibition, Selenium NMR

Creation of a subsurface permeable treatment barrier using in situ redox manipulation

International Nuclear Information System (INIS)

Fruchter, J.S.; Cole, C.R.; Williams, M.D.

1997-01-01

The goal of in situ redox manipulation is to create a permeable treatment zone in the subsurface for remediating redox-sensitive contaminants in groundwater. The permeable treatment zone is created just downstream of the contaminant plume or contaminant source through the injection of reagents and/or microbial nutrients to alter the redox potential of the aquifer fluids and sediments. Contaminant plumes migrating through this manipulated zone can then be destroyed or immobilized. In a field test at the Hanford Site, ∼77,000 L of buffered sodium dithionite solution were successfully injected into the unconfined aquifer at the 100-H Area in September 1995. The target contaminant was chromate. No significant plugging of the well screen or the formation was detected during any phase of the test. Dithionite was detected in monitoring wells at least 7.5 m from the injection point. Data were obtained from all three phases of the test (i.e., injection, reaction, withdrawal). Preliminary core data show that from 60% to 100% of the available reactive iron in the targeted aquifer sediments was reduced by the injected dithionite. One year after the injection, groundwater in the treatment zone remains anoxic. Total and hexavalent chromium levels in groundwater have been reduced from a preexperiment concentration of ∼60 μg/L to below the detection limit of the analytical methods

Redox and pH Responsive Poly (Amidoamine Dendrimer-Heparin Conjugates via Disulfide Linkages for Letrozole Delivery

Directory of Open Access Journals (Sweden)

Thanh Luan Nguyen

2017-01-01

Full Text Available Heparin (Hep conjugated to poly (amidoamine dendrimer G3.5 (P via redox-sensitive disulfide bond (P-SS-Hep was studied. The redox and pH dual-responsive nanocarriers were prepared by a simple method that minimized many complex steps as previous studies. The functional characterization of G3.5 coated Hep was investigated by the proton nuclear magnetic resonance spectroscopy. The size and formation were characterized by the dynamic light scattering, zeta potential, and transmission electron microscopy. P-SS-Hep was spherical in shape with average diameter about 11 nm loaded with more than 20% letrozole. This drug carrier could not only eliminate toxicity to cells and improve the drugs solubility but also increase biocompatibility of the system under reductive environment of glutathione. In particular, P-SS-Hep could enhance the effectiveness of cancer therapy after removing Hep from the surface. These results demonstrated that the P-SS-Hep conjugates could be a promising candidate as redox and pH responsive nanocarriers for cancer chemotherapy.

Redox properties of small semiconductor particles

International Nuclear Information System (INIS)

Liver, N.; Nitzan, A.

1992-01-01

The size dependence of electrical and thermodynamic quantities of intermediate-sized semiconductor particles in an electrolyte solution with a given redox pair are studied. The equilibrium constant for this system is then derived based on the relationship of the electrolytic redox components to the size, charges, and concentration of the semiconductor particles. 25 refs., 9 figs., 1 tab

New tools for redox biology: From imaging to manipulation.

Science.gov (United States)

Bilan, Dmitry S; Belousov, Vsevolod V

2017-08-01

Redox reactions play a key role in maintaining essential biological processes. Deviations in redox pathways result in the development of various pathologies at cellular and organismal levels. Until recently, studies on transformations in the intracellular redox state have been significantly hampered in living systems. The genetically encoded indicators, based on fluorescent proteins, have provided new opportunities in biomedical research. The existing indicators already enable monitoring of cellular redox parameters in different processes including embryogenesis, aging, inflammation, tissue regeneration, and pathogenesis of various diseases. In this review, we summarize information about all genetically encoded redox indicators developed to date. We provide the description of each indicator and discuss its advantages and limitations, as well as points that need to be considered when choosing an indicator for a particular experiment. One chapter is devoted to the important discoveries that have been made by using genetically encoded redox indicators. Copyright © 2016 Elsevier Inc. All rights reserved.

Front-side metallization of silicon solar cells by nickel plating and light induced silver plating

Energy Technology Data Exchange (ETDEWEB)

Aleman, M.; Bay, N.; Barucha, D.; Glunz, S.W.; Preu, R. [Fraunhofer Institut fuer Solare Energiesysteme ISE, Freiburg (Germany)

2009-07-01

At present, screen-printing is the industrial method of choice for forming front-side contacts. Granted, the method is robust, but results in terms of contact width and contact formation, especially for high-efficiency solar cells, are not optimal. For forming these front-side contacts, a new process was developed, not requiring an etching step, but using a laser beam for direct writing of the contact pattern. By making use of the special properties of the semiconductor substrate, a metallising step can be simultaneously carried out. The basic process, involving deposition of nickel, then silver, is described. (orig.)

Gas-phase ion/ion reactions of peptides and proteins: acid/base, redox, and covalent chemistries.

Science.gov (United States)

Prentice, Boone M; McLuckey, Scott A

2013-02-01

Gas-phase ion/ion reactions are emerging as useful and flexible means for the manipulation and characterization of peptide and protein biopolymers. Acid/base-like chemical reactions (i.e., proton transfer reactions) and reduction/oxidation (redox) reactions (i.e., electron transfer reactions) represent relatively mature classes of gas-phase chemical reactions. Even so, especially in regards to redox chemistry, the widespread utility of these two types of chemistries is undergoing rapid growth and development. Additionally, a relatively new class of gas-phase ion/ion transformations is emerging which involves the selective formation of functional-group-specific covalent bonds. This feature details our current work and perspective on the developments and current capabilities of these three areas of ion/ion chemistry with an eye towards possible future directions of the field.

Hydrologic influence on redox dynamics in estuarine environments

Science.gov (United States)

Michael, H. A.; Kim, K. H.; Guimond, J. A.; Heiss, J.; Ullman, W. J.; Seyfferth, A.

2017-12-01

Redox conditions in coastal aquifers control reactions that impact nutrient cycling, contaminant release, and carbon budgets, with implications for water resources and ecosystem health. Hydrologic changes can shift redox boundaries and inputs of reactants, especially in dynamic coastal systems subject to fluctuations on tidal, lunar, and longer timescales. We present two examples of redox shifts in estuarine systems in Delaware, USA: a beach aquifer and a saltmarsh. Beach aquifers are biogeochemical hot spots due to mixing between fresh groundwater and infiltrating seawater. At Cape Henlopen, DE, geochemical measurements identified reactions in the intertidal aquifer that include cycling of carbon, nitrogen, iron, and sulfur. Measurements and modeling illustrate that redox potential as well as the locations of redox reactions shift on tidal to seasonal timescales and in response to changing beach and aquifer properties, impacting overall rates of reactions such as denitrification that reduces N loads to coastal waters. In the St. Jones National Estuarine Research Reserve, tidal fluctuations in channels cause periodic groundwater-surface water exchange, water table movement, and intermittent flooding that varies spatially across the saltmarsh. These changes create shifts in redox potential that are greatest near channels and in the top 20 cm of sediments. The magnitude of redox change depends on hydrologic setting (near channels or in marsh interior), hydrologic conditions (tidal stage, seasonal shifts), as well as prevalence of macropores created by crab burrows that change seasonally with crab activity. These shifts correspond to changes in porewater chemistry that have implications for nutrient cycling and carbon export to the ocean. Understanding hydrologic influence on redox geochemistry is critical for predicting how these systems and their ecosystem services may change in the future in response to anthropogenic and climate change.

Kinetics of Waterborne Alkyd/Acrylic Hybrid Resin Free Radical Polymerization by Two Systems of Redox and Thermal Initiators

Directory of Open Access Journals (Sweden)

shirin Madadi

2012-12-01

Full Text Available Kinetics of radical polymerizations of waterborne alkyd/acrylic hybrid resin via batch mini-emulsion technique was studied using redox initiators (TBHP/Fe2+/EDTA/AsAc  and  TBHP/Fe2+/EDTA/SFS at relatively low temperatures and thermal initiators (BPO, KPS and AIBN at higher temperatures to seek the most suitable initiator system. At the end of all reactions the unreacted monomer content was reduced using post-polymerization technique; consequently, leading to increased monomer conversion and flm formation with improved properties. The kinetics of mini-emulsion polymerization showed that in all redox initiator systems (Fe2+ catalyst + EDTA chelating agent, the radials are produced at relatively low temperature with more effcient control of the reactor temperature. It was found that at 45°C TBHP/Fe2+/EDTA/SFS redox initiator system leads to 98% monomer conversion, a much higher rate than that of systems involved thermal initiators.

Redox chemistry and natural organic matter (NOM): Geochemists' dream, analytical chemists' nightmare

Science.gov (United States)

Macalady, Donald L.; Walton-Day, Katherine

2011-01-01

Natural organic matter (NOM) is an inherently complex mixture of polyfunctional organic molecules. Because of their universality and chemical reversibility, oxidation/reductions (redox) reactions of NOM have an especially interesting and important role in geochemistry. Variabilities in NOM composition and chemistry make studies of its redox chemistry particularly challenging, and details of NOM-mediated redox reactions are only partially understood. This is in large part due to the analytical difficulties associated with NOM characterization and the wide range of reagents and experimental systems used to study NOM redox reactions. This chapter provides a summary of the ongoing efforts to provide a coherent comprehension of aqueous redox chemistry involving NOM and of techniques for chemical characterization of NOM. It also describes some attempts to confirm the roles of different structural moieties in redox reactions. In addition, we discuss some of the operational parameters used to describe NOM redox capacities and redox states, and describe nomenclature of NOM redox chemistry. Several relatively facile experimental methods applicable to predictions of the NOM redox activity and redox states of NOM samples are discussed, with special attention to the proposed use of fluorescence spectroscopy to predict relevant redox characteristics of NOM samples.

Activator Protein-1: redox switch controlling structure and DNA-binding

Energy Technology Data Exchange (ETDEWEB)

Yin, Zhou; Machius, Mischa; Nestler, Eric J.; Rudenko, Gabby (Texas-MED); (Icahn)

2017-09-07

The transcription factor, activator protein-1 (AP-1), binds to cognate DNA under redox control; yet, the underlying mechanism has remained enigmatic. A series of crystal structures of the AP-1 FosB/JunD bZIP domains reveal ordered DNA-binding regions in both FosB and JunD even in absence DNA. However, while JunD is competent to bind DNA, the FosB bZIP domain must undergo a large conformational rearrangement that is controlled by a ‘redox switch’ centered on an inter-molecular disulfide bond. Solution studies confirm that FosB/JunD cannot undergo structural transition and bind DNA when the redox-switch is in the ‘OFF’ state, and show that the mid-point redox potential of the redox switch affords it sensitivity to cellular redox homeostasis. The molecular and structural studies presented here thus reveal the mechanism underlying redox-regulation of AP-1 Fos/Jun transcription factors and provide structural insight for therapeutic interventions targeting AP-1 proteins.

Development of Novel Front Contract Pastes for Crystalline Silicon Solar Cells

Energy Technology Data Exchange (ETDEWEB)

Duty, C.; Jellison, D. G.E. P.; Joshi, P.

2012-04-05

In order to improve the efficiencies of silicon solar cells, paste to silicon contact formation mechanisms must be more thoroughly understood as a function of paste chemistry, wafer properties and firing conditions. Ferro Corporation has been involved in paste development for over 30 years and has extensive expertise in glass and paste formulations. This project has focused on the characterization of the interface between the top contact material (silver paste) and the underlying silicon wafer. It is believed that the interface between the front contact silver and the silicon wafer plays a dominant role in the electrical performance of the solar cell. Development of an improved front contact microstructure depends on the paste chemistry, paste interaction with the SiNx, and silicon (“Si”) substrate, silicon sheet resistivity, and the firing profile. Typical front contact ink contains silver metal powders and flakes, glass powder and other inorganic additives suspended in an organic medium of resin and solvent. During fast firing cycles glass melts, wets, corrodes the SiNx layer, and then interacts with underlying Si. Glass chemistry is also a critical factor in the development of an optimum front contact microstructure. Over the course of this project, several fundamental characteristics of the Ag/Si interface were documented, including a higher-than-expected distribution of voids along the interface, which could significantly impact electrical conductivity. Several techniques were also investigated for the interfacial analysis, including STEM, EDS, FIB, EBSD, and ellipsometry.

QCD and Light-Front Dynamics

International Nuclear Information System (INIS)

Brodsky, Stanley J.; de Teramond, Guy F.

2011-01-01

AdS/QCD, the correspondence between theories in a dilaton-modified five-dimensional anti-de Sitter space and confining field theories in physical space-time, provides a remarkable semiclassical model for hadron physics. Light-front holography allows hadronic amplitudes in the AdS fifth dimension to be mapped to frame-independent light-front wavefunctions of hadrons in physical space-time. The result is a single-variable light-front Schroedinger equation which determines the eigenspectrum and the light-front wavefunctions of hadrons for general spin and orbital angular momentum. The coordinate z in AdS space is uniquely identified with a Lorentz-invariant coordinate ζ which measures the separation of the constituents within a hadron at equal light-front time and determines the off-shell dynamics of the bound state wavefunctions as a function of the invariant mass of the constituents. The hadron eigenstates generally have components with different orbital angular momentum; e.g., the proton eigenstate in AdS/QCD with massless quarks has L = 0 and L = 1 light-front Fock components with equal probability. Higher Fock states with extra quark-anti quark pairs also arise. The soft-wall model also predicts the form of the nonperturbative effective coupling and its β-function. The AdS/QCD model can be systematically improved by using its complete orthonormal solutions to diagonalize the full QCD light-front Hamiltonian or by applying the Lippmann-Schwinger method to systematically include QCD interaction terms. Some novel features of QCD are discussed, including the consequences of confinement for quark and gluon condensates. A method for computing the hadronization of quark and gluon jets at the amplitude level is outlined.

QCD and Light-Front Dynamics

Energy Technology Data Exchange (ETDEWEB)

Brodsky, Stanley J.; de Teramond, Guy F.; /SLAC /Southern Denmark U., CP3-Origins /Costa Rica U.

2011-01-10

AdS/QCD, the correspondence between theories in a dilaton-modified five-dimensional anti-de Sitter space and confining field theories in physical space-time, provides a remarkable semiclassical model for hadron physics. Light-front holography allows hadronic amplitudes in the AdS fifth dimension to be mapped to frame-independent light-front wavefunctions of hadrons in physical space-time. The result is a single-variable light-front Schroedinger equation which determines the eigenspectrum and the light-front wavefunctions of hadrons for general spin and orbital angular momentum. The coordinate z in AdS space is uniquely identified with a Lorentz-invariant coordinate {zeta} which measures the separation of the constituents within a hadron at equal light-front time and determines the off-shell dynamics of the bound state wavefunctions as a function of the invariant mass of the constituents. The hadron eigenstates generally have components with different orbital angular momentum; e.g., the proton eigenstate in AdS/QCD with massless quarks has L = 0 and L = 1 light-front Fock components with equal probability. Higher Fock states with extra quark-anti quark pairs also arise. The soft-wall model also predicts the form of the nonperturbative effective coupling and its {beta}-function. The AdS/QCD model can be systematically improved by using its complete orthonormal solutions to diagonalize the full QCD light-front Hamiltonian or by applying the Lippmann-Schwinger method to systematically include QCD interaction terms. Some novel features of QCD are discussed, including the consequences of confinement for quark and gluon condensates. A method for computing the hadronization of quark and gluon jets at the amplitude level is outlined.

Traveling wave fronts and the transition to saturation

International Nuclear Information System (INIS)

Munier, S.; Peschanski, R.

2004-01-01

We propose a general method to study the solutions to nonlinear QCD evolution equations, based on a deep analogy with the physics of traveling waves. In particular, we show that the transition to the saturation regime of high energy QCD is identical to the formation of the front of a traveling wave. Within this physical picture, we provide the expressions for the saturation scale and the gluon density profile as a function of the total rapidity and the transverse momentum. The application to the Balitskii-Kovchegov equation for both fixed and running coupling constants confirms the effectiveness of this method

Redox proteomics of tomato in response to Pseudomonas syringae infection

Science.gov (United States)

Balmant, Kelly Mayrink; Parker, Jennifer; Yoo, Mi-Jeong; Zhu, Ning; Dufresne, Craig; Chen, Sixue

2015-01-01

Unlike mammals with adaptive immunity, plants rely on their innate immunity based on pattern-triggered immunity (PTI) and effector-triggered immunity (ETI) for pathogen defense. Reactive oxygen species, known to play crucial roles in PTI and ETI, can perturb cellular redox homeostasis and lead to changes of redox-sensitive proteins through modification of cysteine sulfhydryl groups. Although redox regulation of protein functions has emerged as an important mechanism in several biological processes, little is known about redox proteins and how they function in PTI and ETI. In this study, cysTMT proteomics technology was used to identify similarities and differences of protein redox modifications in tomato resistant (PtoR) and susceptible (prf3) genotypes in response to Pseudomonas syringae pv tomato (Pst) infection. In addition, the results of the redox changes were compared and corrected with the protein level changes. A total of 90 potential redox-regulated proteins were identified with functions in carbohydrate and energy metabolism, biosynthesis of cysteine, sucrose and brassinosteroid, cell wall biogenesis, polysaccharide/starch biosynthesis, cuticle development, lipid metabolism, proteolysis, tricarboxylic acid cycle, protein targeting to vacuole, and oxidation–reduction. This inventory of previously unknown protein redox switches in tomato pathogen defense lays a foundation for future research toward understanding the biological significance of protein redox modifications in plant defense responses. PMID:26504582

Redox-active labile iron in fortified flours from the Brazilian market Ferro lábil redox-ativo em farinhas fortificadas do mercado brasileiro

Directory of Open Access Journals (Sweden)

Breno Pannia Espósito

2007-08-01

Full Text Available OBJECTIVE: To quantify the fraction of redox-active labile iron in iron-fortified flours acquired on the Brazilian market. METHODS: Samples of wheat flour, maize flour and breadcrumbs were extracted with buffers that mimic gastric juice, saliva and intestinal juice. Redox-active labile iron levels were assessed through the reaction of autoxidation of ascorbic acid catalyzed by iron in the presence of a fluorescence probe. RESULTS: Redox-active labile iron represents 1% to 9% of the total iron in the flour and breadcrumb samples, with the lowest values found under gastric juice conditions and the highest in the more alkaline media. Redox-active labile iron possibly arises from the decomposition of an iron-phytic acid complex. A positive correlation between redox-active labile iron and total iron was found in saline biomimetic fluids. CONCLUSION: Redox-active labile iron may be a risk factor for people with impaired antioxidant defenses, such as those who are atransferrinemic or iron overloaded (e.g. thalassemic. Total iron can be used to predict redox-active labile iron absorption at each stage of the gastrointestinal tract after ingestion of iron-fortified flours.OBJETIVO: Quantificar a porcentagem de ferro lábil redox ativo em farinhas fortificadas adquiridas no comércio popular. MÉTODOS: Amostras de farinha de trigo, fubá e rosca foram extraídas com tampões miméticos de suco gástrico, saliva e suco intestinal. Os níveis de ferro lábil redox ativo foram determinados por meio da reação de auto-oxidação do ácido ascórbico catalisada pelo ferro, em presença de uma sonda fluorimétrica. RESULTADOS: A fração de ferro lábil redox ativo representa entre 1% e 9% do ferro total nas farinhas estudadas, sendo os menores valores encontrados em condições miméticas do suco gástrico e os maiores nos meios mais alcalinos. Há indícios de que o ferro lábil redox ativo origina-se da decomposição de um complexo entre ferro e ácido f

Fluctuation charge effects in ionization fronts

International Nuclear Information System (INIS)

Arrayas, Manuel; Trueba, Jose L; Baltanas, J P

2008-01-01

In this paper, we study the effects of charge fluctuations on the propagation of both negative and positive ionization fronts in streamer discharges. We show that fronts accelerate when random charge creation events are present. This effect might play a similar role to photoionization in order to make the front move faster

Fluctuation charge effects in ionization fronts

Energy Technology Data Exchange (ETDEWEB)

Arrayas, Manuel; Trueba, Jose L [Area de Electromagnetismo, Universidad Rey Juan Carlos, Camino del Molino s/n, 28943 Fuenlabrada, Madrid (Spain); Baltanas, J P [Departamento de Fisica Aplicada II, Universidad de Sevilla, Av. Reina Mercedes 2, 41012 Sevilla (Spain)

2008-05-21

In this paper, we study the effects of charge fluctuations on the propagation of both negative and positive ionization fronts in streamer discharges. We show that fronts accelerate when random charge creation events are present. This effect might play a similar role to photoionization in order to make the front move faster.

Redox Couples with Unequal Diffusion Coefficients: Effect on Redox Cycling

NARCIS (Netherlands)

Mampallil Augustine, Dileep; Mathwig, Klaus; Kang, Shuo; Lemay, Serge Joseph Guy

2013-01-01

Redox cycling between two electrodes separated by a narrow gap allows dramatic amplification of the faradaic current. Unlike conventional electrochemistry at a single electrode, however, the mass-transport-limited current is controlled by the diffusion coefficient of both the reduced and oxidized

Polyarene mediators for mediated redox flow battery

Science.gov (United States)

Delnick, Frank M.; Ingersoll, David; Liang, Chengdu

2018-01-02

The fundamental charge storage mechanisms in a number of currently studied high energy redox couples are based on intercalation, conversion, or displacement reactions. With exception to certain metal-air chemistries, most often the active redox materials are stored physically in the electrochemical cell stack thereby lowering the practical gravimetric and volumetric energy density as a tradeoff to achieve reasonable power density. In a general embodiment, a mediated redox flow battery includes a series of secondary organic molecules that form highly reduced anionic radicals as reaction mediator pairs for the reduction and oxidation of primary high capacity redox species ex situ from the electrochemical cell stack. Arenes are reduced to stable anionic radicals that in turn reduce a primary anode to the charged state. The primary anode is then discharged using a second lower potential (more positive) arene. Compatible separators and solvents are also disclosed herein.

Symproportionation versus Disproportionation in Bromine Redox Systems

International Nuclear Information System (INIS)

Toporek, Marcin; Michałowska-Kaczmarczyk, Anna M.; Michałowski, Tadeusz

2015-01-01

Graphical abstract: Display Omitted -- Highlights: • The disproportionation and symproportionation of bromine in different media is presented. • All the redox systems are elaborated according to the principles of the generalized approach to electrolytic redox systems (GATES/GEB). • All physicochemical knowledge is involved in the algorithm applied for this purpose. • The graphical representation of the systems is the basis of gaining the detailed physicochemical knowledge on the systems in question. -- Abstract: The paper refers to dynamic (titration) redox systems where symproportionation or disproportionation of bromine species occur. The related systems are modeled according to principles assumed in the Generalized Approach to Electrolytic Redox Systems (GATES), with Generalized Electron Balance (GEB) concept involved in the GATES/GEB software. The results obtained from calculations made with use of iterative computer programs prepared according to MATLAB computational software, are presented graphically, as 2D and 3D graphs

A multi-electron redox mediator for redox-targeting lithium-sulfur flow batteries

Science.gov (United States)

Li, Guochun; Yang, Liuqing; Jiang, Xi; Zhang, Tianran; Lin, Haibin; Yao, Qiaofeng; Lee, Jim Yang

2018-02-01

The lithium-sulfur flow battery (LSFB) is a new addition to the rechargeable lithium flow batteries (LFBs) where sulfur or a sulfur compound is used as the cathode material against the lithium anode. We report here our evaluation of an organic sulfide - dimethyl trisulfide (DMTS), as 1) a catholyte of a LFB and 2) a multi-electron redox mediator for discharging and charging a solid sulfur cathode without any conductive additives. The latter configuration is also known as the redox-targeting lithium-sulfur flow battery (RTLSFB). The LFB provides an initial discharge capacity of 131.5 mAh g-1DMTS (1.66 A h L-1), which decreases to 59 mAh g-1DMTS (0.75 A h L-1) after 40 cycles. The RTLSFB delivers a significantly higher application performance - initial discharge capacity of 1225.3 mAh g-1sulfur (3.83 A h L-1), for which 1030.9 mAh g-1sulfur (3.23 A h L-1) is still available after 40 cycles. The significant increase in the discharge and charge duration of the LFB after sulfur addition indicates that DMTS is better used as a redox mediator in a RTLSFB than as a catholyte in a LFB.

An Excel Workbook for Identifying Redox Processes in Ground Water

Science.gov (United States)

Jurgens, Bryant C.; McMahon, Peter B.; Chapelle, Francis H.; Eberts, Sandra M.

2009-01-01

The reduction/oxidation (redox) condition of ground water affects the concentration, transport, and fate of many anthropogenic and natural contaminants. The redox state of a ground-water sample is defined by the dominant type of reduction/oxidation reaction, or redox process, occurring in the sample, as inferred from water-quality data. However, because of the difficulty in defining and applying a systematic redox framework to samples from diverse hydrogeologic settings, many regional water-quality investigations do not attempt to determine the predominant redox process in ground water. Recently, McMahon and Chapelle (2008) devised a redox framework that was applied to a large number of samples from 15 principal aquifer systems in the United States to examine the effect of redox processes on water quality. This framework was expanded by Chapelle and others (in press) to use measured sulfide data to differentiate between iron(III)- and sulfate-reducing conditions. These investigations showed that a systematic approach to characterize redox conditions in ground water could be applied to datasets from diverse hydrogeologic settings using water-quality data routinely collected in regional water-quality investigations. This report describes the Microsoft Excel workbook, RedoxAssignment_McMahon&Chapelle.xls, that assigns the predominant redox process to samples using the framework created by McMahon and Chapelle (2008) and expanded by Chapelle and others (in press). Assignment of redox conditions is based on concentrations of dissolved oxygen (O2), nitrate (NO3-), manganese (Mn2+), iron (Fe2+), sulfate (SO42-), and sulfide (sum of dihydrogen sulfide [aqueous H2S], hydrogen sulfide [HS-], and sulfide [S2-]). The logical arguments for assigning the predominant redox process to each sample are performed by a program written in Microsoft Visual Basic for Applications (VBA). The program is called from buttons on the main worksheet. The number of samples that can be analyzed

Redox properties of phenosafranine at zeolite-modified electrodes-Effect of surface modification and solution pH

International Nuclear Information System (INIS)

Easwaramoorthi, S.; Natarajan, P.

2008-01-01

Redox properties of cationic dye phenosafranine (3,7-diamino-5-phenylphenazenium chloride) (PS + ) were studied at zeolite-modified electrodes using Zeolite-Y and NaZSM-5. The peak current and peak potential of phenosafranine-adsorbed zeolite were found to be influenced by the pH of the electrolyte solution. Observation of a second redox couple is suggested to be due to formation of new species at low concentration from the reduced phenosafranine at the zeolite-modified electrodes. Titanium dioxide nanoparticles encapsulated in the cavities of the zeolite or anchored on the external surface of the zeolite do not seem to affect the redox properties of adsorbed PS + . When the cyclic voltammograms are recorded immediately after the electrode is immersed into the solution, the redox potential of PS + is found to be sensitive to the nature of the zeolite surface. The peak potential shifts towards positive region under continuous cycles as the surface hydroxyl groups get protonated in acidic electrolyte solution thereby forcing the movement of dye molecules from the zeolite surface to the zeolite electrode solution interface. The electron transfer rate constants for the adsorbed dye at the electrode are calculated to be 2.5 ± 0.2 s -1 and 3.5 ± 0.2 s -1 for the zeolite-Y electrode and the ZSM-5 electrode, respectively by the Laviron equation

Light-Front Holography, Light-Front Wavefunctions, and Novel QCD Phenomena

DEFF Research Database (Denmark)

Brodsky, S. J.; de Teramond, G. F.

2012-01-01

Light-front holography is one of the most remarkable features of the AdS/CFT correspondence. In spite of its present limitations, it provides important physical insights into the non-perturbative regime of QCD and its transition to the perturbative domain. This novel framework allows hadronic...... projected on the free Fock basis provides the complete set of valence and non-valence light-front Fock state wavefunctions Psi(n)/H(x(i), k(perpendicular to i), lambda(i)) which describe the hadron's momentum and spin distributions needed to compute the direct measures of hadron structure at the quark...

Redox phenomena controlling systems - a 7. framework programme collaborative project (2008-2012)

International Nuclear Information System (INIS)

2013-01-01

The objective of this EURATOM collaborative project is to understand Redox phenomena controlling the long-term release/retention of radionuclides (ReCosy programme) in nuclear waste disposal and to provide tools to apply the results to safety assessment. The project has been organized into 6 task forces: 1) implications of Redox for safety, 2) development of Redox determination methods, 3) Redox response of defined and near-natural systems, 4) Redox reactions of radionuclides, 5) Redox processes in radionuclide transport, and 6) Redox reactions affecting the spent fuel source-term

Electronically Induced Redox Barriers for Treatment of Groundwater

National Research Council Canada - National Science Library

Sale, Tom; Gilbert, David

2006-01-01

...) and Colorado State University (CSU). The focus is an innovative electrolytic approach for managing redox-sensitive contaminants in groundwater, referred to as electrically induced redox barrier (e-barriers...

Novel Perspectives from Light-Front QCD, Super-Conformal Algebra, and Light-Front Holography

Energy Technology Data Exchange (ETDEWEB)

Brodsky, Stanley J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2015-12-01

Light-Front Quantization – Dirac’s “Front Form” – provides a physical, frame-independent formalism for hadron dynamics and structure. Observables such as structure functions, transverse momentum distributions, and distribution amplitudes are defined from the hadronic LFWFs. One obtains new insights into the hadronic mass scale, the hadronic spectrum, and the functional form of the QCD running coupling in the nonperturbative domain using light-front holography. In addition, superconformal algebra leads to remarkable supersymmetric relations between mesons and baryons. I also discuss evidence that the antishadowing of nuclear structure functions is nonuniversal; i.e., flavor dependent, and why shadowing and antishadowing phenomena may be incompatible with the momentum and other sum rules for the nuclear parton distribution functions.

Imaging Mitochondrial Redox Potential and Its Possible Link to Tumor Metastatic Potential

Science.gov (United States)

Li, Lin Z.

2012-01-01

Cellular redox states can regulate cell metabolism, growth, differentiation, motility, apoptosis, signaling pathways, and gene expressions etc. Growing body of literature suggest importance of redox status for cancer progression. While most studies on redox state were done on cells and tissue lysates, it is important to understand the role of redox state in tissue in vivo/ex vivo and image its heterogeneity. Redox scanning is a clinically-translatable method for imaging tissue mitochondrial redox potential with a submillimeter resolution. Redox scanning data in mouse models of human cancers demonstrate a correlation between mitochondrial redox state and tumor metastatic potential. I will discuss the significance of this correlation and possible directions for future research. PMID:22895837

Characterization of redox conditions in pollution plumes

DEFF Research Database (Denmark)

Christensen, Thomas Højlund; Bjerg, Poul Løgstrup; Banwart, Steven A.

2000-01-01

Evalution of redox conditions in groundwater pollution plumes is often a prerequisite for understanding the behviour of the pollutants in the plume and for selecting remediation approaches. Measuring of redox conditions in pollution plumes is, however, a fairly recent issue and yet relative few...

Characterization of redox proteins using electrochemical methods

NARCIS (Netherlands)

Verhagen, M.

1995-01-01

The use of electrochemical techniques in combination with proteins started approximately a decade ago and has since then developed into a powerfull technique for the study of small redox proteins. In addition to the determination of redox potentials, electrochemistry can be used to obtain

Chloroplasts as source and target of cellular redox regulation: a discussion on chloroplast redox signals in the context of plant physiology.

Science.gov (United States)

Baier, Margarete; Dietz, Karl-Josef

2005-06-01

During the evolution of plants, chloroplasts have lost the exclusive genetic control over redox regulation and antioxidant gene expression. Together with many other genes, all genes encoding antioxidant enzymes and enzymes involved in the biosynthesis of low molecular weight antioxidants were transferred to the nucleus. On the other hand, photosynthesis bears a high risk for photo-oxidative damage. Concomitantly, an intricate network for mutual regulation by anthero- and retrograde signals has emerged to co-ordinate the activities of the different genetic and metabolic compartments. A major focus of recent research in chloroplast regulation addressed the mechanisms of redox sensing and signal transmission, the identification of regulatory targets, and the understanding of adaptation mechanisms. In addition to redox signals communicated through signalling cascades also used in pathogen and wounding responses, specific chloroplast signals control nuclear gene expression. Signalling pathways are triggered by the redox state of the plastoquinone pool, the thioredoxin system, and the acceptor availability at photosystem I, in addition to control by oxolipins, tetrapyrroles, carbohydrates, and abscisic acid. The signalling function is discussed in the context of regulatory circuitries that control the expression of antioxidant enzymes and redox modulators, demonstrating the principal role of chloroplasts as the source and target of redox regulation.

Albumin-bound fatty acids but not albumin itself alter redox balance in tubular epithelial cells and induce a peroxide-mediated redox-sensitive apoptosis

Science.gov (United States)

Ruggiero, Christine; Elks, Carrie M.; Kruger, Claudia; Cleland, Ellen; Addison, Kaity; Noland, Robert C.

2014-01-01

Albuminuria is associated with metabolic syndrome and diabetes. It correlates with the progression of chronic kidney disease, particularly with tubular atrophy. The fatty acid load on albumin significantly increases in obesity, presenting a proinflammatory environment to the proximal tubules. However, little is known about changes in the redox milieu during fatty acid overload and how redox-sensitive mechanisms mediate cell death. Here, we show that albumin with fatty acid impurities or conjugated with palmitate but not albumin itself compromised mitochondrial and cell viability, membrane potential and respiration. Fatty acid overload led to a redox imbalance which deactivated the antioxidant protein peroxiredoxin 2 and caused a peroxide-mediated apoptosis through the redox-sensitive pJNK/caspase-3 pathway. Transfection of tubular cells with peroxiredoxin 2 was protective and mitigated apoptosis. Mitochondrial fatty acid entry and ceramide synthesis modulators suggested that mitochondrial β oxidation but not ceramide synthesis may modulate lipotoxic effects on tubular cell survival. These results suggest that albumin overloaded with fatty acids but not albumin itself changes the redox environment in the tubules, inducing a peroxide-mediated redox-sensitive apoptosis. Thus, mitigating circulating fatty acid levels may be an important factor in both preserving redox balance and preventing tubular cell damage in proteinuric diseases. PMID:24500687

Propagation study of the ionization fronts in a gas subject to an impulse field

International Nuclear Information System (INIS)

Gayraud, Francois.

1978-01-01

We study the formation of a discharge in nitrogen and in nitrogen-methane mixtures (2,5% to 50% of methane) for pressures of several hundred torr and for electric-field-to-pressure ratio values between 110 and 150 V.cm -1 .torr -1 . The development of the discharge is observed by means of streak camera with a temporal resolution of 400 ps. The analysis of the recording allows to characterise several phases in the ionization fronts development. We give the variation of the speed of the fronts in function of the proportion of methane and of the ratio E/p. We explicit a streamer propagation model, based on the hypothesis that the plasma channel behind the front is assimilable to a perfect conductor. Thus, we obtain analytic expressions of the length and the speed of the streamer. The values obtained from these relations are in excellent agreement with the values measured [fr

Beam front accelerators

International Nuclear Information System (INIS)

Reiser, M.

1982-01-01

An intense relativistic electron beam cannot propagate in a metal drift tube when the current exceeds the space charge limit. Very high charge density and electric field gradients (10 2 to 10 3 MV/m) develop at the beam front and the electrons are reflected. When a neutral gas or a plasma is present, collective acceleration of positive ions occur, and the resulting charge neutralization enables the beam to propagate. Experimental results, theoretical understanding, and schemes to achieve high ion energies by external control of the beam front velocity will be reviewed

Energy conversion at dipolarization fronts

Science.gov (United States)

Khotyaintsev, Yu. V.; Divin, A.; Vaivads, A.; André, M.; Markidis, S.

2017-02-01

We use multispacecraft observations by Cluster in the Earth's magnetotail and 3-D particle-in-cell simulations to investigate conversion of electromagnetic energy at the front of a fast plasma jet. We find that the major energy conversion is happening in the Earth (laboratory) frame, where the electromagnetic energy is being transferred from the electromagnetic field to particles. This process operates in a region with size of the order several ion inertial lengths across the jet front, and the primary contribution to E·j is coming from the motional electric field and the ion current. In the frame of the front we find fluctuating energy conversion with localized loads and generators at sub-ion scales which are primarily related to the lower hybrid drift instability excited at the front; however, these provide relatively small net energy conversion.

Activator Protein-1: redox switch controlling structure and DNA-binding.

Science.gov (United States)

Yin, Zhou; Machius, Mischa; Nestler, Eric J; Rudenko, Gabby

2017-11-02

The transcription factor, activator protein-1 (AP-1), binds to cognate DNA under redox control; yet, the underlying mechanism has remained enigmatic. A series of crystal structures of the AP-1 FosB/JunD bZIP domains reveal ordered DNA-binding regions in both FosB and JunD even in absence DNA. However, while JunD is competent to bind DNA, the FosB bZIP domain must undergo a large conformational rearrangement that is controlled by a 'redox switch' centered on an inter-molecular disulfide bond. Solution studies confirm that FosB/JunD cannot undergo structural transition and bind DNA when the redox-switch is in the 'OFF' state, and show that the mid-point redox potential of the redox switch affords it sensitivity to cellular redox homeostasis. The molecular and structural studies presented here thus reveal the mechanism underlying redox-regulation of AP-1 Fos/Jun transcription factors and provide structural insight for therapeutic interventions targeting AP-1 proteins. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

Impact of Redox Reactions on Colloid Transport in Saturated Porous Media: An Example of Ferrihydrite Colloids Transport in the Presence of Sulfide.

Science.gov (United States)

Liao, Peng; Yuan, Songhu; Wang, Dengjun

2016-10-18

Transport of colloids in the subsurface is an important environmental process with most research interests centered on the transport in chemically stable conditions. While colloids can be formed under dynamic redox conditions, the impact of redox reactions on their transport is largely overlooked. Taking the redox reactions between ferrihydrite colloids and sulfide as an example, we investigated how and to what extent the redox reactions modulated the transport of ferrihydrite colloids in anoxic sand columns over a range of environmentally relevant conditions. Our results reveal that the presence of sulfide (7.8-46.9 μM) significantly decreased the breakthrough of ferrihydrite colloids in the sand column. The estimated travel distance of ferrihydrite colloids in the absence of sulfide was nearly 7-fold larger than that in the presence of 46.9 μM sulfide. The reduced breakthrough was primarily attributed to the reductive dissolution of ferrihydrite colloids by sulfide in parallel with formation of elemental sulfur (S(0)) particles from sulfide oxidation. Reductive dissolution decreased the total mass of ferrihydrite colloids, while the negatively charged S(0) decreased the overall zeta potential of ferrihydrite colloids by attaching onto their surfaces and thus enhanced their retention in the sand. Our findings provide novel insights into the critical role of redox reactions on the transport of redox-sensitive colloids in saturated porous media.

Modern processes of sediment formation in Lake Towuti, Indonesia, as derived from the composition of lake surface sediments

Science.gov (United States)

Hasberg, Ascelina; Melles, Martin; Morlock, Marina; Vogel, Hendrik; Russel, James M.; Bijaksana, Satria

2016-04-01

the shore the grain size and magnetic susceptibility decrease, but the organic carbon vs. total sulfur (C/S) ratio and the redox-sensitive elements such as U, Cd, Mo, and V increase. This suggests that sulfur accumulation in lake Towuti is controlled by autochthoneous pyrite formation, in dependence on differences in redox conditions, rather than gypsum accumulation. Highest silicon (Si) concentrations appear in front of the four major inlets of Lake Towuti, however, a distinct maximum also occurs close to the southeastern shore, where larger river inlets are missing. Hence, the silicon distribution is partly controlled by fluvial input and partly by biogenic silica deposition; the latter is confirmed by high concentrations of pelagic and benthic diatoms as well as sponge spiculae in smear slides from the sediments at the southeastern shore. Hence, the data thus far obtained on the surface sediments of lake Towuti show a strong influence of fluvial sediment supply and water-depth dependent redox conditions on the sediment composition. No indication, in contrast, was found for a significant influence of lake currents on the distribution of the sediments supplied by riverine input.

Blocking-resistant communication through domain fronting

Directory of Open Access Journals (Sweden)

Fifield David

2015-06-01

Full Text Available We describe “domain fronting,” a versatile censorship circumvention technique that hides the remote endpoint of a communication. Domain fronting works at the application layer, using HTTPS, to communicate with a forbidden host while appearing to communicate with some other host, permitted by the censor. The key idea is the use of different domain names at different layers of communication. One domain appears on the “outside” of an HTTPS request—in the DNS request and TLS Server Name Indication—while another domain appears on the “inside”—in the HTTP Host header, invisible to the censor under HTTPS encryption. A censor, unable to distinguish fronted and nonfronted traffic to a domain, must choose between allowing circumvention traffic and blocking the domain entirely, which results in expensive collateral damage. Domain fronting is easy to deploy and use and does not require special cooperation by network intermediaries. We identify a number of hard-to-block web services, such as content delivery networks, that support domain-fronted connections and are useful for censorship circumvention. Domain fronting, in various forms, is now a circumvention workhorse. We describe several months of deployment experience in the Tor, Lantern, and Psiphon circumvention systems, whose domain-fronting transports now connect thousands of users daily and transfer many terabytes per month.

New Redox Polymers that Exhibit Reversible Cleavage of Sulfur Bonds as Cathode Materials.

Science.gov (United States)

Baloch, Marya; Ben Youcef, Hicham; Li, Chunmei; Garcia-Calvo, Oihane; Rodriguez, Lide M; Shanmukaraj, Devaraj; Rojo, Teofilo; Armand, Michel

2016-11-23

Two new cathode materials based on redox organosulfur polymers were synthesized and investigated for rechargeable lithium batteries as a proof-of-concept study. These cathodes offered good cycling performance owing to the absence of polysulfide solubility, which plagues Li/S systems. Herein, an aliphatic polyamine or a conjugated polyazomethine was used as the base to tether the redox-active species. The activity comes from the cleavage and formation of S-S or N-S bonds, which is made possible by the rigid conjugated backbone. The synthesized polymers were characterized through FTIR spectroscopy and thermogravimetric analysis (TGA). Galvanostatic measurements were performed to evaluate the discharge/charge cycles and characterize the performance of the lithium-based cells, which displayed initial discharge capacities of approximately 300 mA h g -1 at C/5 over 100 cycles with approximately 98 % Coulombic efficiency. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery.

Science.gov (United States)

Li, Bin; Nie, Zimin; Vijayakumar, M; Li, Guosheng; Liu, Jun; Sprenkle, Vincent; Wang, Wei

2015-02-24

Redox flow batteries are receiving wide attention for electrochemical energy storage due to their unique architecture and advantages, but progress has so far been limited by their low energy density (~25 Wh l(-1)). Here we report a high-energy density aqueous zinc-polyiodide flow battery. Using the highly soluble iodide/triiodide redox couple, a discharge energy density of 167 Wh l(-1) is demonstrated with a near-neutral 5.0 M ZnI2 electrolyte. Nuclear magnetic resonance study and density functional theory-based simulation along with flow test data indicate that the addition of an alcohol (ethanol) induces ligand formation between oxygen on the hydroxyl group and the zinc ions, which expands the stable electrolyte temperature window to from -20 to 50 °C, while ameliorating the zinc dendrite. With the high-energy density and its benign nature free from strong acids and corrosive components, zinc-polyiodide flow battery is a promising candidate for various energy storage applications.

Redox-responsive theranostic nanoplatforms based on inorganic nanomaterials.

Science.gov (United States)

Han, Lu; Zhang, Xiao-Yong; Wang, Yu-Long; Li, Xi; Yang, Xiao-Hong; Huang, Min; Hu, Kun; Li, Lu-Hai; Wei, Yen

2017-08-10

Spurred on by advances in materials chemistry and nanotechnology, scientists have developed many novel nanopreparations for cancer diagnosis and therapy. To treat complex malignant tumors effectively, multifunctional nanomedicines with targeting ability, imaging properties and controlled drug release behavior should be designed and exploited. The therapeutic efficiency of loaded drugs can be dramatically improved using redox-responsive nanoplatforms which can sense the differences in the redox status of tumor tissues and healthy ones. Redox-sensitive nanocarriers can be constructed from both organic and inorganic nanomaterials; however, at present, drug delivery nanovectors progressively lean towards inorganic nanomaterials because of their facile synthesis/modification and their unique physicochemical properties. In this review, we focus specifically on the preparation and application of redox-sensitive nanosystems based on mesoporous silica nanoparticles (MSNs), carbon nanomaterials, magnetic nanoparticles, gold nanomaterials and other inorganic nanomaterials. We discuss relevant examples of redox-sensitive nanosystems in each category. Finally, we discuss current challenges and future strategies from the aspect of material design and practical application. Copyright © 2017 Elsevier B.V. All rights reserved.

Redox-active and Redox-silent Compounds: Synergistic Therapeutics in Cancer

Czech Academy of Sciences Publication Activity Database

Tomasetti, M.; Santarelli, L.; Alleva, R.; Dong, L.F.; Neužil, Jiří

2015-01-01

Roč. 22, č. 5 (2015), s. 552-568 ISSN 0929-8673 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0109 Institutional support: RVO:86652036 Keywords : Apoptosis * autophagy * redox-active agents Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 3.455, year: 2015

Carbon Redox-Polymer-Gel Hybrid Supercapacitors

Science.gov (United States)

Vlad, A.; Singh, N.; Melinte, S.; Gohy, J.-F.; Ajayan, P.M.

2016-01-01

Energy storage devices that provide high specific power without compromising on specific energy are highly desirable for many electric-powered applications. Here, we demonstrate that polymer organic radical gel materials support fast bulk-redox charge storage, commensurate to surface double layer ion exchange at carbon electrodes. When integrated with a carbon-based electrical double layer capacitor, nearly ideal electrode properties such as high electrical and ionic conductivity, fast bulk redox and surface charge storage as well as excellent cycling stability are attained. Such hybrid carbon redox-polymer-gel electrodes support unprecedented discharge rate of 1,000C with 50% of the nominal capacity delivered in less than 2 seconds. Devices made with such electrodes hold the potential for battery-scale energy storage while attaining supercapacitor-like power performances. PMID:26917470

Titanium nitride as an electrocatalyst for V(II)/V(III) redox couples in all-vanadium redox flow batteries

International Nuclear Information System (INIS)

Yang, Chunmei; Wang, Haining; Lu, Shanfu; Wu, Chunxiao; Liu, Yiyang; Tan, Qinglong; Liang, Dawei; Xiang, Yan

2015-01-01

Titanium nitride nanoparticles (TiN NPs) are proposed as a novel catalyst towards the V(II)/V(III) redox pair for the negative electrode in vanadium redox flow batteries (VRFB). Electrochemical properties of TiN NPs were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results show that TiN NPs demonstrate better electrochemical activity and reversibility for the processes of V(II)/V(III) redox couples as compared with the graphite NPs. TiN NPs facilitate the charge transfer in the V(II)/V(III) redox reaction. Performance of a VRFB using a TiN NPs coated carbon paper as a negative electrode is much higher than that of a VRFB with a raw carbon paper electrode. The columbic efficiency (CE), the voltage efficiency (VE) and the energy efficiency (EE) of the VRFB single cell at charge-discharge current density of 30 mA/cm 2 are 91.74%, 89.11% and 81.74%, respectively. During a 50 charge-discharge cycles test, the CE values of VRFB with TiN NPs consistently remain higher than 90%.

Redox-Flow Batteries: From Metals to Organic Redox-Active Materials.

Science.gov (United States)

Winsberg, Jan; Hagemann, Tino; Janoschka, Tobias; Hager, Martin D; Schubert, Ulrich S

2017-01-16

Research on redox-flow batteries (RFBs) is currently experiencing a significant upturn, stimulated by the growing need to store increasing quantities of sustainably generated electrical energy. RFBs are promising candidates for the creation of smart grids, particularly when combined with photovoltaics and wind farms. To achieve the goal of "green", safe, and cost-efficient energy storage, research has shifted from metal-based materials to organic active materials in recent years. This Review presents an overview of various flow-battery systems. Relevant studies concerning their history are discussed as well as their development over the last few years from the classical inorganic, to organic/inorganic, to RFBs with organic redox-active cathode and anode materials. Available technologies are analyzed in terms of their technical, economic, and environmental aspects; the advantages and limitations of these systems are also discussed. Further technological challenges and prospective research possibilities are highlighted. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Extracellular redox state: refining the definition of oxidative stress in aging.

Science.gov (United States)

Jones, Dean P

2006-01-01

Oxidative stress in aging can result from an imbalance of prooxidants and antioxidants with excessive, destructive free radical chemistry. Thiol systems are important in the control of these processes, both by protecting against damage and serving in redox signaling mechanisms to sense danger and repair the damage. Studies by a number of research groups in collaboration with the Emory Clinical Biomarkers Laboratory show that the redox state of the central tissue antioxidant, glutathione (GSH), can be measured in human plasma and provides a quantitative systemic indicator of oxidative stress. Plasma GSH/GSSG redox in humans becomes oxidized with age, in response to chemotherapy, as a consequence of cigarette smoking, and in association with common age-related diseases (e.g., type 2 diabetes, cardiovascular disease). However, the GSH/GSSG redox is not equilibrated with the larger plasma cysteine/cystine (Cys/CySS) pool, and the Cys/CySS redox varies with age in a pattern that is distinct from that of GSH/GSSG redox. Furthermore, in vitro studies show that variation in Cys/CySS redox over the range found in vivo affects signaling pathways, which control cell proliferation and oxidant-induced apoptosis. The results point to the conclusion that free radical scavenging antioxidants are of increased importance when thiol/disulfide redox states are oxidized. Because thiol/disulfide redox states, per se, function in redox signaling and control as well as antioxidant protection, GSH/GSSG and Cys/CySS redox states may provide central parameters to link environmental influences and progression of changes associated with aging.

Kynurenine pathway metabolites and enzymes involved in redox reactions.

Science.gov (United States)

González Esquivel, D; Ramírez-Ortega, D; Pineda, B; Castro, N; Ríos, C; Pérez de la Cruz, V

2017-01-01

Oxido-reduction reactions are a fundamental part of the life due to support many vital biological processes as cellular respiration and glucose oxidation. In the redox reactions, one substance transfers one or more electrons to another substance. An important electron carrier is the coenzyme NAD + , which is involved in many metabolic pathways. De novo biosynthesis of NAD + is through the kynurenine pathway, the major route of tryptophan catabolism, which is sensitive to redox environment and produces metabolites with redox capacity, able to alter biological functions that are controlled by redox-responsive signaling pathways. Kynurenine pathway metabolites have been implicated in the physiology process and in the physiopathology of many diseases; processes that also share others factors as dysregulation of calcium homeostasis, mitochondrial dysfunction, oxidative stress, inflammation and cell death, which impact the redox environment. This review examines in detail the available evidence in which kynurenine pathway metabolites participate in redox reactions and their effect on cellular redox homeostasis, since the knowledge of the main factors and mechanisms that lead to cell death in many neurodegenative disorders and other pathologies, such as mitochondrial dysfunction, oxidative stress and kynurenines imbalance, will allow to develop therapies using them as targets. This article is part of the Special Issue entitled 'The Kynurenine Pathway in Health and Disease'. Copyright © 2016 Elsevier Ltd. All rights reserved.

Accelerated redox reaction between chromate and phenolic pollutants during freezing

Energy Technology Data Exchange (ETDEWEB)

Ju, Jinjung; Kim, Jaesung [Department of Environmental Sciences and Biotechnology, Hallym University, Chuncheon, Gangwon-do 24252 (Korea, Republic of); Vetráková, Ľubica [Department of Chemistry and Research Centre for Toxic Compounds in the Environment (RECETOX), Faculty of Science, Masaryk University, Kamenice 5, 625 00 Brno (Czech Republic); Seo, Jiwon [School of Urban and Environmental Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919 (Korea, Republic of); Heger, Dominik [Department of Chemistry and Research Centre for Toxic Compounds in the Environment (RECETOX), Faculty of Science, Masaryk University, Kamenice 5, 625 00 Brno (Czech Republic); Lee, Changha [School of Urban and Environmental Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919 (Korea, Republic of); Yoon, Ho-Il [Korea Polar Research Institute (KOPRI), Incheon 21990 (Korea, Republic of); Kim, Kitae, E-mail: ktkim@kopri.re.kr [Korea Polar Research Institute (KOPRI), Incheon 21990 (Korea, Republic of); Kim, Jungwon, E-mail: jwk@hallym.ac.kr [Department of Environmental Sciences and Biotechnology, Hallym University, Chuncheon, Gangwon-do 24252 (Korea, Republic of)

2017-05-05

Highlights: • Redox conversion of 4-CP/Cr(VI) was significantly accelerated during freezing. • Accelerated redox conversion in ice is ascribed to the freeze concentration effect. • 4-CP, Cr(VI), and protons are concentrated in the liquid brine by freezing. • Redox conversions of various phenolic pollutants/Cr(VI) were significant in ice. • Freezing-accelerated redox conversion was observed in real polluted water. - Abstract: The redox reaction between 4-chlorophenol (4-CP) and chromate (Cr(VI)) (i.e., the simultaneous oxidation of 4-CP by Cr(VI) and reduction of Cr(VI) by 4-CP) in ice (i.e., at −20 °C) was compared with the corresponding reaction in water (i.e., at 25 °C). The redox conversion of 4-CP/Cr(VI), which was negligible in water, was significantly accelerated in ice. This accelerated redox conversion of 4-CP/Cr(VI) in ice is ascribed to the freeze concentration effect occurring during freezing, which excludes solutes (i.e., 4-CP and Cr(VI)) and protons from the ice crystals and subsequently concentrates them in the liquid brine. The concentrations of Cr(VI) and protons in the liquid brine were confirmed by measuring the optical image and the UV–vis absorption spectra of cresol red (CR) as a pH indicator of frozen solution. The redox conversion of 4-CP/Cr(VI) was observed in water when the concentrations of 4-CP/protons or Cr(VI)/protons increased by 100/1000-fold. These results corroborate the freeze concentration effect as the reason for the accelerated redox conversion of 4-CP/Cr(VI) in ice. The redox conversion of various phenolic pollutants/Cr(VI) and 4-CP/Cr(VI) in real wastewater was successfully achieved in ice, which verifies the environmental relevance and importance of freezing-accelerated redox conversion of phenolic pollutants/Cr(VI) in cold regions.

Accelerated redox reaction between chromate and phenolic pollutants during freezing

International Nuclear Information System (INIS)

Ju, Jinjung; Kim, Jaesung; Vetráková, Ľubica; Seo, Jiwon; Heger, Dominik; Lee, Changha; Yoon, Ho-Il; Kim, Kitae; Kim, Jungwon

2017-01-01

Highlights: • Redox conversion of 4-CP/Cr(VI) was significantly accelerated during freezing. • Accelerated redox conversion in ice is ascribed to the freeze concentration effect. • 4-CP, Cr(VI), and protons are concentrated in the liquid brine by freezing. • Redox conversions of various phenolic pollutants/Cr(VI) were significant in ice. • Freezing-accelerated redox conversion was observed in real polluted water. - Abstract: The redox reaction between 4-chlorophenol (4-CP) and chromate (Cr(VI)) (i.e., the simultaneous oxidation of 4-CP by Cr(VI) and reduction of Cr(VI) by 4-CP) in ice (i.e., at −20 °C) was compared with the corresponding reaction in water (i.e., at 25 °C). The redox conversion of 4-CP/Cr(VI), which was negligible in water, was significantly accelerated in ice. This accelerated redox conversion of 4-CP/Cr(VI) in ice is ascribed to the freeze concentration effect occurring during freezing, which excludes solutes (i.e., 4-CP and Cr(VI)) and protons from the ice crystals and subsequently concentrates them in the liquid brine. The concentrations of Cr(VI) and protons in the liquid brine were confirmed by measuring the optical image and the UV–vis absorption spectra of cresol red (CR) as a pH indicator of frozen solution. The redox conversion of 4-CP/Cr(VI) was observed in water when the concentrations of 4-CP/protons or Cr(VI)/protons increased by 100/1000-fold. These results corroborate the freeze concentration effect as the reason for the accelerated redox conversion of 4-CP/Cr(VI) in ice. The redox conversion of various phenolic pollutants/Cr(VI) and 4-CP/Cr(VI) in real wastewater was successfully achieved in ice, which verifies the environmental relevance and importance of freezing-accelerated redox conversion of phenolic pollutants/Cr(VI) in cold regions.

Redox-Stability of Alkoxy-BDT Copolymers and their Use for Organic Bioelectronic Devices

KAUST Repository

Giovannitti, Alexander

2018-02-23

Organic semiconductors can be employed as the active layer in accumulation mode organic electrochemical transistors (OECTs), where redox stability in aqueous electrolytes is important for long-term recordings of biological events. It is observed that alkoxy-benzo[1,2-b:4,5-b′]dithiophene (BDT) copolymers can be extremely unstable when they are oxidized in aqueous solutions. The redox stability of these copolymers can be improved by molecular design of the copolymer where it is observed that the electron rich comonomer 3,3′-dimethoxy-2,2′-bithiophene (MeOT2) lowers the oxidation potential and also stabilizes positive charges through delocalization and resonance effects. For copolymers where the comonomers do not have the same ability to stabilize positive charges, irreversible redox reactions are observed with the formation of quinone structures, being detrimental to performance of the materials in OECTs. Charge distribution along the copolymer from density functional theory calculations is seen to be an important factor in the stability of the charged copolymer. As a result of the stabilizing effect of the comonomer, a highly stable OECT performance is observed with transconductances in the mS range. The analysis of the decomposition pathway also raises questions about the general stability of the alkoxy-BDT unit, which is heavily used in donor-acceptor copolymers in the field of photovoltaics.

Redox-Stability of Alkoxy-BDT Copolymers and their Use for Organic Bioelectronic Devices

KAUST Repository

Giovannitti, Alexander; Thorley, Karl J.; Nielsen, Christian B.; Li, Jun; Donahue, Mary J.; Malliaras, George G.; Rivnay, Jonathan; McCulloch, Iain

2018-01-01

Organic semiconductors can be employed as the active layer in accumulation mode organic electrochemical transistors (OECTs), where redox stability in aqueous electrolytes is important for long-term recordings of biological events. It is observed that alkoxy-benzo[1,2-b:4,5-b′]dithiophene (BDT) copolymers can be extremely unstable when they are oxidized in aqueous solutions. The redox stability of these copolymers can be improved by molecular design of the copolymer where it is observed that the electron rich comonomer 3,3′-dimethoxy-2,2′-bithiophene (MeOT2) lowers the oxidation potential and also stabilizes positive charges through delocalization and resonance effects. For copolymers where the comonomers do not have the same ability to stabilize positive charges, irreversible redox reactions are observed with the formation of quinone structures, being detrimental to performance of the materials in OECTs. Charge distribution along the copolymer from density functional theory calculations is seen to be an important factor in the stability of the charged copolymer. As a result of the stabilizing effect of the comonomer, a highly stable OECT performance is observed with transconductances in the mS range. The analysis of the decomposition pathway also raises questions about the general stability of the alkoxy-BDT unit, which is heavily used in donor-acceptor copolymers in the field of photovoltaics.

Manganese and iron geochemistry in sediments underlying the redox-stratified Fayetteville Green Lake

Science.gov (United States)

Herndon, Elizabeth M.; Havig, Jeff R.; Singer, David M.; McCormick, Michael L.; Kump, Lee R.

2018-06-01

Manganese and iron are redox-sensitive elements that yield clues about biogeochemistry and redox conditions both in modern environments and in the geologic past. Here, we investigated Mn and Fe-bearing minerals preserved in basin sediments underlying Fayetteville Green Lake, a redox-stratified lake that serves as a geochemical analogue for Paleoproterozoic oceans. Synchrotron-source microprobe techniques (μXRF, μXANES, and μXRD) and bulk geochemical analyses were used to examine the microscale distribution and speciation of Mn, Fe, and S as a function of depth in the top 48 cm of anoxic lake sediments. Manganese was primarily associated with calcite grains as a manganese-rich carbonate that precipitated in the chemocline of the water column and settled through the euxinic basin to collect in lake sediments. Iron was preserved in framboidal iron sulfides that precipitated in euxinic bottom waters and underwent transformation to pyrite and marcasite in the sediments. Previous studies attribute the formation of manganese-rich carbonates to the diagenetic alteration of manganese oxides deposited in basins underlying oxygenated water. Our study challenges this paradigm by providing evidence that Mn-bearing carbonates form in the water column and accumulate in sediments below anoxic waters. Consequently, manganoan carbonates preserved in the rock record do not necessarily denote the presence of oxygenated bottom waters in ocean basins.

Organic non-aqueous cation-based redox flow batteries

Science.gov (United States)

Zhang, Lu; Huang, Jinhua; Burrell, Anthony

2018-05-08

The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturated moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte comprises a tetrafluorohydroquinone ether compound or a tetrafluorocatechol ether compound.

Redox shuttles for overcharge protection of lithium batteries

Science.gov (United States)

Amine, Khalil; Chen, Zonghai; Wang, Qingzheng

2010-12-14

The present invention is generally related to electrolytes containing novel redox shuttles for overcharge protection of lithium-ion batteries. The redox shuttles are capable of thousands hours of overcharge tolerance and have a redox potential at about 3-5.5 V vs. Li and particularly about 4.4-4.8 V vs. Li. Accordingly, in one aspect the invention provides electrolytes comprising an alkali metal salt; a polar aprotic solvent; and a redox shuttle additive that is an aromatic compound having at least one aromatic ring with four or more electronegative substituents, two or more oxygen atoms bonded to the aromatic ring, and no hydrogen atoms bonded to the aromatic ring; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

De Novo Construction of Redox Active Proteins.

Science.gov (United States)

Moser, C C; Sheehan, M M; Ennist, N M; Kodali, G; Bialas, C; Englander, M T; Discher, B M; Dutton, P L

2016-01-01

Relatively simple principles can be used to plan and construct de novo proteins that bind redox cofactors and participate in a range of electron-transfer reactions analogous to those seen in natural oxidoreductase proteins. These designed redox proteins are called maquettes. Hydrophobic/hydrophilic binary patterning of heptad repeats of amino acids linked together in a single-chain self-assemble into 4-alpha-helix bundles. These bundles form a robust and adaptable frame for uncovering the default properties of protein embedded cofactors independent of the complexities introduced by generations of natural selection and allow us to better understand what factors can be exploited by man or nature to manipulate the physical chemical properties of these cofactors. Anchoring of redox cofactors such as hemes, light active tetrapyrroles, FeS clusters, and flavins by His and Cys residues allow cofactors to be placed at positions in which electron-tunneling rates between cofactors within or between proteins can be predicted in advance. The modularity of heptad repeat designs facilitates the construction of electron-transfer chains and novel combinations of redox cofactors and new redox cofactor assisted functions. Developing de novo designs that can support cofactor incorporation upon expression in a cell is needed to support a synthetic biology advance that integrates with natural bioenergetic pathways. © 2016 Elsevier Inc. All rights reserved.

Effect of the oxidation front penetration on in-clad hydrogen migration

Science.gov (United States)

Feria, F.; Herranz, L. E.

2018-03-01

In LWR fuel claddings the embrittlement due to hydrogen precipitates (i.e., hydrides) is a degrading mechanism that concerns in nuclear safety, particularly in dry storage. A relevant factor is the radial distribution of the hydrogen absorbed, especially the hydride rim formed. Thus, a reliable assessment of fuel performance should account for hydrogen migration. Based on the current state of modelling of hydrogen dynamics in the cladding, a 1D radial model has been derived and coupled with the FRAPCON code. The model includes the effect of the oxidation front progression on in-clad hydrogen migration, based on experimental observations found (i.e., dissolution/diffusion/re-precipitation of the hydrogen in the matrix ahead of the oxidation front). A remarkable quantitative impact of this new contribution has been shown by analyzing the hydrogen profile across the cladding of several high burnup fuel scenarios (>60 GW d/tU); other potential contributions like thermodiffusion and diffusion in the hydride phase hardly make any difference. Comparisons against PIE measurements allow concluding that the model accuracy notably increases when the effect of the oxidation front is accounted for in the hydride rim formation. In spite of the promising results, further validation would be needed.

Dimensional behavior of Ni-YSZ composites during redox cycling

DEFF Research Database (Denmark)

Pihlatie, Mikko; Kaiser, Andreas; Larsen, Peter Halvor

2009-01-01

The dimensional behavior of Ni-yttria-stabilized zirconia (YSZ) cermets during redox cycling was tested in dilatometry within the temperature range 600-1000 degrees C. The effect Of humidity oil redox stability was investigated at intermediate and low temperatures. We show that both the sintering...... of nickel depending on temperature of the initial reduction and the operating conditions, and the temperature of reoxidation are very important for the size of the dimensional change. Cumulative redox strain (CRS) is shown to be correlated with temperature. Measured maximum CRS after three redox cycles...... varies within 0.25-3.2% dL/L in dry gas and respective temperature range of 600-1000 degrees C. A high degree of redox reversibility was reached at low temperature. however. reversibility is lost at elevated temperatures. We found that at 850 degrees C, 6% steam and a very high p(H2O)/p(H2) ratio...

NAD(H) and NADP(H) Redox Couples and Cellular Energy Metabolism.

Science.gov (United States)

Xiao, Wusheng; Wang, Rui-Sheng; Handy, Diane E; Loscalzo, Joseph

2018-01-20

The nicotinamide adenine dinucleotide (NAD + )/reduced NAD + (NADH) and NADP + /reduced NADP + (NADPH) redox couples are essential for maintaining cellular redox homeostasis and for modulating numerous biological events, including cellular metabolism. Deficiency or imbalance of these two redox couples has been associated with many pathological disorders. Recent Advances: Newly identified biosynthetic enzymes and newly developed genetically encoded biosensors enable us to understand better how cells maintain compartmentalized NAD(H) and NADP(H) pools. The concept of redox stress (oxidative and reductive stress) reflected by changes in NAD(H)/NADP(H) has increasingly gained attention. The emerging roles of NAD + -consuming proteins in regulating cellular redox and metabolic homeostasis are active research topics. The biosynthesis and distribution of cellular NAD(H) and NADP(H) are highly compartmentalized. It is critical to understand how cells maintain the steady levels of these redox couple pools to ensure their normal functions and simultaneously avoid inducing redox stress. In addition, it is essential to understand how NAD(H)- and NADP(H)-utilizing enzymes interact with other signaling pathways, such as those regulated by hypoxia-inducible factor, to maintain cellular redox homeostasis and energy metabolism. Additional studies are needed to investigate the inter-relationships among compartmentalized NAD(H)/NADP(H) pools and how these two dinucleotide redox couples collaboratively regulate cellular redox states and cellular metabolism under normal and pathological conditions. Furthermore, recent studies suggest the utility of using pharmacological interventions or nutrient-based bioactive NAD + precursors as therapeutic interventions for metabolic diseases. Thus, a better understanding of the cellular functions of NAD(H) and NADP(H) may facilitate efforts to address a host of pathological disorders effectively. Antioxid. Redox Signal. 28, 251-272.

Pattern-oriented Agent-based Monte Carlo simulation of Cellular Redox Environment

DEFF Research Database (Denmark)

Tang, Jiaowei; Holcombe, Mike; Boonen, Harrie C.M.

/CYSS) and mitochondrial redox couples. Evidence suggests that both intracellular and extracellular redox can affect overall cell redox state. How redox is communicated between extracellular and intracellular environments is still a matter of debate. Some researchers conclude based on experimental data...... cells. Biochimica Et Biophysica Acta-General Subjects, 2008. 1780(11): p. 1271-1290. 5. Jones, D.P., Redox sensing: orthogonal control in cell cycle and apoptosis signalling. J Intern Med, 2010. 268(5): p. 432-48. 6. Pogson, M., et al., Formal agent-based modelling of intracellular chemical interactions...

Redox processes in the safety case of deep geological repositories of radioactive wastes. Contribution of the European RECOSY Collaborative Project

International Nuclear Information System (INIS)

Duro, L.; Bruno, J.; Grivé, M.; Montoya, V.; Kienzler, B.; Altmaier, M.; Buckau, G.

2014-01-01

Highlights: • The RECOSY project produced results relevant for the Safety Case of nuclear disposal. • We classify the safety related features where RECOSY has contributed. • Redox processes effect the retention of radionuclides in all repository subsystems. - Abstract: Redox processes influence key geochemical characteristics controlling radionuclide behaviour in the near and far field of a nuclear waste repository. A sound understanding of redox related processes is therefore of high importance for developing a Safety Case, the collection of scientific, technical, administrative and managerial arguments and evidence in support of the safety of a disposal facility. This manuscript presents the contribution of the specific research on redox processes achieved within the EURATOM Collaborative Project RECOSY (REdox phenomena COntrolling SYstems) to the Safety Case of nuclear waste disposal facilities. Main objectives of RECOSY were related to the improved understanding of redox phenomena controlling the long-term release or retention of radionuclides in nuclear waste disposal and providing tools to apply the results to Performance Assessment and the Safety Case. The research developed during the project covered aspects of the near-field and the far-field aspects of the repository, including studies relevant for the rock formations considered in Europe as suitable for hosting an underground repository for radioactive wastes. It is the intention of this paper to highlight in which way the results obtained from RECOSY can feed the scientific process understanding needed for the stepwise development of the Safety Case associated with deep geological disposal of radioactive wastes

Breast Cancer Redox Heterogeneity Detectable with Chemical Exchange Satruation Transfer (CEST) MRI

Science.gov (United States)

Cai, Kejia; Xu, He N.; Singh, Anup; Moon, Lily; Haris, Mohammad; Reddy, Ravinder; Li, Lin

2014-01-01

Purpose Tissue redox state is an important mediator of various biological processes in health and diseases such as cancer. Previously, we discovered that the mitochondrial redox state of ex vivo tissues detected by redox scanning (an optical imaging method) revealed interesting tumor redox state heterogeneity that could differentiate tumor aggressiveness. Because the noninvasive chemical exchange saturation transfer (CEST) MRI can probe the proton transfer and generate contrasts from endogenous metabolites, we aim to investigate if the in vivo CEST contrast is sensitive to proton transfer of the redox reactions so as to reveal the tissue redox states in breast cancer animal models. Procedures CEST MRI has been employed to characterize tumor metabolic heterogeneity and correlated with the redox states measured by the redox scanning in two human breast cancer mouse xenograft models, MDA-MB-231 and MCF-7. The possible biological mechanism on the correlation between the two imaging modalities was further investigated by phantom studies where the reductants and the oxidants of the representative redox reactions were measured. Results The CEST contrast is found linearly correlated with NADH concentration and the NADH redox ratio with high statistical significance, where NADH is the reduced form of nicotinamide adenine dinucleotide. The phantom studies showed that the reductants of the redox reactions have more CEST contrast than the corresponding oxidants, indicating that higher CEST effect corresponds to the more reduced redox state. Conclusions This preliminary study suggests that CEST MRI, once calibrated, might provide a novel noninvasive imaging surrogate for the tissue redox state and a possible diagnostic biomarker for breast cancer in the clinic. PMID:24811957

Hydrogen peroxide and central redox theory for aerobic life: A tribute to Helmut Sies: Scout, trailblazer, and redox pioneer.

Science.gov (United States)

Jones, Dean P

2016-04-01

When Rafael Radi and I wrote about Helmut Sies for the Redox Pioneer series, I was disappointed that the Editor restricted us to the use of "Pioneer" in the title. My view is that Helmut was always ahead of the pioneers: He was a scout discovering paths for exploration and a trailblazer developing strategies and methods for discovery. I have known him for nearly 40 years and greatly enjoyed his collegiality as well as brilliance in scientific scholarship. He made monumental contributions to 20th century physiological chemistry beginning with his first measurement of H2O2 in rat liver. While continuous H2O2 production is dogma today, the concept of H2O2 production in mammalian tissues was largely buried for half a century. He continued this leadership in research on oxidative stress, GSH, selenium, and singlet oxygen, during the timeframe when physiological chemistry and biochemistry transitioned to contemporary 21st century systems biology. His impact has been extensive in medical and health sciences, especially in nutrition, aging, toxicology and cancer. I briefly summarize my interactions with Helmut, stressing our work together on the redox code, a set of principles to link mitochondrial respiration, bioenergetics, H2O2 metabolism, redox signaling and redox proteomics into central redox theory. Copyright © 2015 The Author. Published by Elsevier Inc. All rights reserved.

Redox signaling in acute pancreatitis

Science.gov (United States)

Pérez, Salvador; Pereda, Javier; Sabater, Luis; Sastre, Juan

2015-01-01

Acute pancreatitis is an inflammatory process of the pancreatic gland that eventually may lead to a severe systemic inflammatory response. A key event in pancreatic damage is the intracellular activation of NF-κB and zymogens, involving also calcium, cathepsins, pH disorders, autophagy, and cell death, particularly necrosis. This review focuses on the new role of redox signaling in acute pancreatitis. Oxidative stress and redox status are involved in the onset of acute pancreatitis and also in the development of the systemic inflammatory response, being glutathione depletion, xanthine oxidase activation, and thiol oxidation in proteins critical features of the disease in the pancreas. On the other hand, the release of extracellular hemoglobin into the circulation from the ascitic fluid in severe necrotizing pancreatitis enhances lipid peroxidation in plasma and the inflammatory infiltrate into the lung and up-regulates the HIF–VEGF pathway, contributing to the systemic inflammatory response. Therefore, redox signaling and oxidative stress contribute to the local and systemic inflammatory response during acute pancreatitis. PMID:25778551

Redox signaling in acute pancreatitis

Directory of Open Access Journals (Sweden)

Salvador Pérez

2015-08-01

Full Text Available Acute pancreatitis is an inflammatory process of the pancreatic gland that eventually may lead to a severe systemic inflammatory response. A key event in pancreatic damage is the intracellular activation of NF-κB and zymogens, involving also calcium, cathepsins, pH disorders, autophagy, and cell death, particularly necrosis. This review focuses on the new role of redox signaling in acute pancreatitis. Oxidative stress and redox status are involved in the onset of acute pancreatitis and also in the development of the systemic inflammatory response, being glutathione depletion, xanthine oxidase activation, and thiol oxidation in proteins critical features of the disease in the pancreas. On the other hand, the release of extracellular hemoglobin into the circulation from the ascitic fluid in severe necrotizing pancreatitis enhances lipid peroxidation in plasma and the inflammatory infiltrate into the lung and up-regulates the HIF–VEGF pathway, contributing to the systemic inflammatory response. Therefore, redox signaling and oxidative stress contribute to the local and systemic inflammatory response during acute pancreatitis.

Arteriovenous oscillations of the redox potential: Is the redox state influencing blood flow?

Science.gov (United States)

Poznanski, Jaroslaw; Szczesny, Pawel; Pawlinski, Bartosz; Mazurek, Tomasz; Zielenkiewicz, Piotr; Gajewski, Zdzislaw; Paczek, Leszek

2017-09-01

Studies on the regulation of human blood flow revealed several modes of oscillations with frequencies ranging from 0.005 to 1 Hz. Several mechanisms were proposed that might influence these oscillations, such as the activity of vascular endothelium, the neurogenic activity of vessel wall, the intrinsic activity of vascular smooth muscle, respiration, and heartbeat. These studies relied typically on non-invasive techniques, for example, laser Doppler flowmetry. Oscillations of biochemical markers were rarely coupled to blood flow. The redox potential difference between the artery and the vein was measured by platinum electrodes placed in the parallel homonymous femoral artery and the femoral vein of ventilated anesthetized pigs. Continuous measurement at 5 Hz sampling rate using a digital nanovoltmeter revealed fluctuating signals with three basic modes of oscillations: ∼ 1, ∼ 0.1 and ∼ 0.01 Hz. These signals clearly overlap with reported modes of oscillations in blood flow, suggesting coupling of the redox potential and blood flow. The amplitude of the oscillations associated with heart action was significantly smaller than for the other two modes, despite the fact that heart action has the greatest influence on blood flow. This finding suggests that redox potential in blood might be not a derivative but either a mediator or an effector of the blood flow control system.

Instability of an infiltration-driven dissolution-precipitation front with a nonmonotonic porosity profile

Science.gov (United States)

Kondratiuk, Paweł; Dutka, Filip; Szymczak, Piotr

2016-04-01

Infiltration of a rock by an external fluid very often drives it out of chemical equilibrium. As a result, alteration of the rock mineral composition occurs. It does not however proceed uniformly in the entire rock volume. Instead, one or more reaction fronts are formed, which are zones of increased chemical activity, separating the altered (product) rock from the yet unaltered (primary) one. The reaction fronts propagate with velocities which are usually much smaller than those of the infiltrating fluid. One of the simplest examples of such alteration is the dissolution of some of the minerals building the primary rock. For instance, calcium carbonate minerals in the rock matrix can be dissolved by infiltrating acidic fluids. In such a case the product rock has higher porosity and permeability than the primary one. Due to positive feedbacks between the reactant transport, fluid flow, and porosity generation, the reaction fronts in porosity-generating replacement systems are inherently unstable. An arbitrarily small protrusion of the front gets magnified and develops into a highly porous finger-like or funnel-like structure. This feature of dissolution fronts, dubbed the "reactive-infiltration instability" [1], is responsible for the formation of a number of geological patterns, such as solution pipes or various karst forms. It is also of practical importance, since spontaneous front breakup and development of localized highly porous flow paths (a.k.a. "wormholes") is favourable by petroleum engineers, who apply acidization to oil-bearing reservoirs in order to increase their permeability. However, more complex chemical reactions might occur during infiltration of a rock by a fluid. In principle, the products of dissolution might react with other species present either in the fluid or in the rock and reprecipitate [2]. The dissolution and precipitation fronts develop and and begin to propagate with equal velocities, forming a single dissolution-precipitation front

Biogeochemical Barriers: Redox Behavior of Metals and Metalloids

Science.gov (United States)

Redox conditions and pH are arguably the most important geochemical parameters that control contaminant transport and fate in groundwater systems. Oxidation-reduction (redox) reactions mediate the chemical behavior of both inorganic and organic chemical constituents by affecting...

Quantitative proteomic characterization of redox-dependent post-translational modifications on protein cysteines

Energy Technology Data Exchange (ETDEWEB)

Duan, Jicheng; Gaffrey, Matthew J.; Qian, Wei-Jun

2017-01-01

Protein cysteine thiols play a crucial role in redox signaling, regulation of enzymatic activity and protein function, and maintaining redox homeostasis in living systems. The unique chemical reactivity of thiol groups makes cysteine susceptible to oxidative modifications by reactive oxygen and nitrogen species to form a broad array of reversible and irreversible protein post-translational modifications (PTMs). The reversible modifications in particular are one of the major components of redox signaling and are involved in regulation of various cellular processes under physiological and pathological conditions. The biological significance of these redox PTMs in health and diseases has been increasingly recognized. Herein, we review the recent advances of quantitative proteomic approaches for investigating redox PTMs in complex biological systems, including the general considerations of sample processing, various chemical or affinity enrichment strategies, and quantitative approaches. We also highlight a number of redox proteomic approaches that enable effective profiling of redox PTMs for addressing specific biological questions. Although some technological limitations remain, redox proteomics is paving the way towards a better understanding of redox signaling and regulation in human health and diseases.

Engineering redox homeostasis to develop efficient alcohol-producing microbial cell factories.

Science.gov (United States)

Zhao, Chunhua; Zhao, Qiuwei; Li, Yin; Zhang, Yanping

2017-06-24

The biosynthetic pathways of most alcohols are linked to intracellular redox homeostasis, which is crucial for life. This crucial balance is primarily controlled by the generation of reducing equivalents, as well as the (reduction)-oxidation metabolic cycle and the thiol redox homeostasis system. As a main oxidation pathway of reducing equivalents, the biosynthesis of most alcohols includes redox reactions, which are dependent on cofactors such as NADH or NADPH. Thus, when engineering alcohol-producing strains, the availability of cofactors and redox homeostasis must be considered. In this review, recent advances on the engineering of cellular redox homeostasis systems to accelerate alcohol biosynthesis are summarized. Recent approaches include improving cofactor availability, manipulating the affinity of redox enzymes to specific cofactors, as well as globally controlling redox reactions, indicating the power of these approaches, and opening a path towards improving the production of a number of different industrially-relevant alcohols in the near future.

QCD and Light-Front Holography

Energy Technology Data Exchange (ETDEWEB)

Brodsky, Stanley J.; /SLAC /Southern Denmark U., CP3-Origins; de Teramond, Guy F.; /Costa Rica U.

2010-10-27

The soft-wall AdS/QCD model, modified by a positive-sign dilaton metric, leads to a remarkable one-parameter description of nonperturbative hadron dynamics. The model predicts a zero-mass pion for zero-mass quarks and a Regge spectrum of linear trajectories with the same slope in the leading orbital angular momentum L of hadrons and the radial quantum number N. Light-Front Holography maps the amplitudes which are functions of the fifth dimension variable z of anti-de Sitter space to a corresponding hadron theory quantized on the light front. The resulting Lorentz-invariant relativistic light-front wave equations are functions of an invariant impact variable {zeta} which measures the separation of the quark and gluonic constituents within the hadron at equal light-front time. The result is to a semi-classical frame-independent first approximation to the spectra and light-front wavefunctions of meson and baryon light-quark bound states, which in turn predict the behavior of the pion and nucleon form factors. The theory implements chiral symmetry in a novel way: the effects of chiral symmetry breaking increase as one goes toward large interquark separation, consistent with spectroscopic data, and the the hadron eigenstates generally have components with different orbital angular momentum; e.g., the proton eigenstate in AdS/QCD with massless quarks has L = 0 and L = 1 light-front Fock components with equal probability. The soft-wall model also predicts the form of the non-perturbative effective coupling {alpha}{sub s}{sup AdS} (Q) and its {beta}-function which agrees with the effective coupling {alpha}{sub g1} extracted from the Bjorken sum rule. The AdS/QCD model can be systematically improved by using its complete orthonormal solutions to diagonalize the full QCD light-front Hamiltonian or by applying the Lippmann-Schwinger method in order to systematically include the QCD interaction terms. A new perspective on quark and gluon condensates is also reviewed.

Redox Stable Anodes for Solid Oxide Fuel Cells

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Guoliang eXiao

2014-06-01

Full Text Available Solid oxide fuel cells (SOFCs can convert chemical energy from the fuel directly to electrical energy with high efficiency and fuel flexibility. Ni-based cermets have been the most widely adopted anode for SOFCs. However, the conventional Ni-based anode has low tolerance to sulfur-contamination, is vulnerable to deactivation by carbon build-up (coking from direct oxidation of hydrocarbon fuels, and suffers volume instability upon redox cycling. Among these limitations, the redox instability of the anode is particularly important and has been intensively studied since the SOFC anode may experience redox cycling during fuel cell operations even with the ideal pure hydrogen as the fuel. This review aims to highlight recent progresses on improving redox stability of the conventional Ni-based anode through microstructure optimization and exploration of alternative ceramic-based anode materials.

Novel VEGFR-2 kinase inhibitor identified by the back-to-front approach

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Sanphanya, Kingkan; Phowichit, Suwadee; Wattanapitayakul, Suvara K.; Fokin, Valery V.; Vajragupta, Opa

2013-01-01

Novel lead was developed as VEGFR-2 inhibitor by the back-to-front approach. Docking experiment guided that the 3-chloromethylphenylurea motif occupied the back pocket of the VEGFR-2 kinase. The attempt to enhance the binding affinity of 1 was made by expanding structure to access the front pocket using triazole as linker. A library of 1,4-(disubsituted)-1H-1,2,3-triazoles were screened in silico and one lead compound (VH02) was identified with enzymatic IC50 against VEGFR-2 of 0.56 μM. VH02 showed antiangiogenic effect by inhibiting the tube formation of HUVEC cells (EA.hy926) at 0.3 μM which was 13 times lower than its cytotoxic dose. The enzymatic and cellular activities suggested the potential of VH02 as a lead for further optimization. PMID:23562241

Thermo-Kinetic Investigation of Comparative Ligand Effect on Cysteine Iron Redox Reaction

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Masood Ahmad Rizvi

2015-03-01

Full Text Available Transition metal ions in their free state bring unwanted biological oxidations generating oxidative stress. The ligand modulated redox potential can be indispensable in prevention of such oxidative stress by blocking the redundant bio-redox reactions. In this study we investigated the comparative ligand effect on the thermo-kinetic aspects of biologically important cysteine iron (III redox reaction using spectrophotometric and potentiometric methods. The results were corroborated with the complexation effect on redox potential of iron(III-iron(II redox couple. The selected ligands were found to increase the rate of cysteine iron (III redox reaction in proportion to their stability of iron (II complex (EDTA < terpy < bipy < phen. A kinetic profile and the catalytic role of copper (II ions by means of redox shuttle mechanism for the cysteine iron (III redox reaction in presence of 1,10-phenanthroline (phen ligand is also reported.

Redox processes in radiation biology and cancer

International Nuclear Information System (INIS)

Greenstock, C.L.

1981-01-01

Free-radical intermediates, particularly the activated oxygen species OH, O - 2 , and 1 O 2 , are implicated in many types of radiation damage to biological systems. In addition, these same species may be formed, either directly or indirectly through biochemical redox reactions, in both essential and aberrant metabolic processes. Cell survival and adaptation to an environment containing ionizing radiation and other physical and chemical carcinogens ultimately depend upon the cell's ability to maintain optimal function in response to free-radical damage at the chemical level. Many of these feedback control mechanisms are redox controlled. Radiation chemical techniques using selective radical scavengers, such as product analysis and pulse radiolysis, enable us to generate, observe, and characterize individually the nature and reactivity of potentially damaging free radicals. From an analysis of the chemical kinetics of free-radical involvement in biological damage, redox mechanisms are proposed to describe the early processes of radiation damage, redox mechanisms are proposed to describe the early processes of radiation damage, its protection and sensitization, and the role of free radicals in radiation and chemical carcinogenesis

Differential alkylation-based redox proteomics - Lessons learnt

DEFF Research Database (Denmark)

Wojdyla, Katarzyna; Rogowska-Wrzesinska, Adelina

2015-01-01

Cysteine is one of the most reactive amino acids. This is due to the electronegativity of sulphur atom in the side chain of thiolate group. It results in cysteine being present in several distinct redox forms inside the cell. Amongst these, reversible oxidations, S-nitrosylation and S-sulfenylati......Cysteine is one of the most reactive amino acids. This is due to the electronegativity of sulphur atom in the side chain of thiolate group. It results in cysteine being present in several distinct redox forms inside the cell. Amongst these, reversible oxidations, S-nitrosylation and S......-sulfenylation are crucial mediators of intracellular redox signalling, with known associations to health and disease. Study of their functionalities has intensified thanks to the development of various analytical strategies, with particular contribution from differential alkylation-based proteomics methods. Presented here...... is a critical evaluation of differential alkylation-based strategies for the analysis of S-nitrosylation and S-sulfenylation. The aim is to assess the current status and to provide insights for future directions in the dynamically evolving field of redox proteomics. To achieve that we collected 35 original...

Development of redox stable, multifunctional substrates for anode supported SOFCS

DEFF Research Database (Denmark)

Sudireddy, Bhaskar Reddy; Foghmoes, Søren Preben Vagn; Ramos, Tania

2017-01-01

Redox stable solid oxide fuel cells are beneficial in many aspects such as tolerance against system failures e.g fuel cut off and emergency shut down, but also allow for higher fuel utilization, which increases efficiency. State-ofthe-art Ni-cermet based anodes suffer from microstructural changes...... with a multifunctional anode support, the development of a two layer fuel electrode based on a redox stable strontium titanate layer for the electrochemically active layer and a redox stable Ni-YSZ support was pursued. Half-cells with well adhearing strontium titante anode layers on stateof-the-art Ni-YSZ cermet...... supports have been achieved. Redox tolerance of the half-cell depends could be increased by optimizing the redox stability of the cermet support....

Redox chemistry of americium in nitric acid media

Energy Technology Data Exchange (ETDEWEB)

Picart, S.; Jobelin, I.; Armengol, G.; Adnet, JM

2004-07-01

The redox properties of the actinides are very important parameters for speciation studies and spent nuclear fuel reprocessing based on liquid-liquid extraction of actinides at different oxidation states (as in the Purex or Sesame process). They are also very useful for developing analytical tools including coulometry and redox titration. This study addressed the americium(IV)/americium(III) and americium(VI)/americium(V) redox couples, focusing on exhaustive acquisition of the thermodynamic and kinetic parameters of americium oxidation at an electrode in a complexing nitric acid medium. (authors)

Redox chemistry of americium in nitric acid media

International Nuclear Information System (INIS)

Picart, S.; Jobelin, I.; Armengol, G.; Adnet, JM.

2004-01-01

The redox properties of the actinides are very important parameters for speciation studies and spent nuclear fuel reprocessing based on liquid-liquid extraction of actinides at different oxidation states (as in the Purex or Sesame process). They are also very useful for developing analytical tools including coulometry and redox titration. This study addressed the americium(IV)/americium(III) and americium(VI)/americium(V) redox couples, focusing on exhaustive acquisition of the thermodynamic and kinetic parameters of americium oxidation at an electrode in a complexing nitric acid medium. (authors)

Redox Equilibria Involving Chromium Minerals in Aqueous Fluids in the Deep Earth - Implications for Diamond Formation

Science.gov (United States)

Huang, J.; Huang, F.; Hao, J.; Sverjensky, D. A.

2017-12-01

Diamonds are often associated with inclusions of garnet that are characteristically Cr-rich and Ca-poor, suggesting metasomatic reactions involving fluids [1]. To investigate these reactions, we developed a thermodynamic characterization of Cr-bearing minerals and integrated it with our database for the thermodynamic properties of aqueous Cr-species [2]. We retrieved thermodynamic properties of picrochromite (MgCr2O4), and knorringite (Mg3Cr2Si3O12) consistent with minerals in the Berman (1988) using calorimetric data and experimental phase equilibria involving the reactions: MgCr2O4 + SiO2 = Cr2O3 + MgSiO3 [2] and MgCr2O4 + 4MgSiO3 = Mg3Cr2Si3O12 + Mg2SiO4 [3], respectively.At high temperatures and pressures, neutral pH and FMQ, the predicted solubilities of eskolaite and knorringite equilibrium with Cr2+ in a pure water system are very low. However, we found that complexes of Cr2+ and Cl- could increase the solubilities of chromium minerals significantly. At 500°C and 0.2 - 1.0 GPa, we retrieved the CrCl(OH)0 neutral complex from experiments on the solubility of Cr2O3 in HCl solutions [4]. At 1,000°C and 4.0 GPa, we retrieved the properties of a CrCl3- complex from experiments on the solubility of Cr2O3 in KCl solutions [5]. The predicted solubility of a garnet containing 23 mole% of knorringite in equilibrium with CrCl3- in a peridotitic diamond-forming fluid is 22 millimolal (1,144 ppm). This result suggests that a redox reaction relating to diamond formation might involveMg3Al2Si3O12 + 0.5CO2(aq) + 2 CrCl3- + 2H+ = Mg3Cr2Si3O12 + 0.5C-Diamond + 2Al3+ + 6Cl-. In this way, high temperature and pressure fluids containing Cr(II)-complexes might promote the mobility of chromium and be involved in metasomatic reactions and diamond formation.[1]Boyd et al. (1993)[2] Hao et al. (submitted to Geochem. Persp. Letters)[3] Berman (1988)[4] Klemme et al. (2000)[5] Klemme et al. (2004)[6] Watenphul et al. (2014)[7] Klein-BenDavid et al. (2011)

Redox reactions of the α-synuclein-Cu(2+) complex and their effects on neuronal cell viability.

Science.gov (United States)

Wang, Chengshan; Liu, Lin; Zhang, Lin; Peng, Yong; Zhou, Feimeng

2010-09-21

α-Synuclein (α-syn), a presynaptic protein believed to play an important role in neuropathology in Parkinson's disease (PD), is known to bind Cu(2+). Cu(2+) has been shown to accelerate the aggregation of α-syn to form various toxic aggregates in vitro. Copper is also a redox-active metal whose complexes with amyloidogenic proteins/peptides have been linked to oxidative stress in major neurodegenerative diseases. In this work, the formation of the Cu(2+) complex with α-syn or with an N-terminal peptide, α-syn(1-19), was confirmed with electrospray-mass spectrometry (ES-MS). The redox potentials of the Cu(2+) complex with α-syn (α-syn-Cu(2+)) and α-syn(1-19) were determined to be 0.018 and 0.053 V, respectively. Furthermore, the Cu(2+) center(s) can be readily reduced to Cu(+), and possible reactions of α-syn-Cu(2+) with cellular species (e.g., O(2), ascorbic acid, and dopamine) were investigated. The occurrence of a redox reaction can be rationalized by comparing the redox potential of the α-syn-Cu(2+) complex to that of the specific cellular species. For example, ascorbic acid can directly reduce α-syn-Cu(2+) to α-syn-Cu(+), setting up a redox cycle in which O(2) is reduced to H(2)O(2) and cellular redox species is continuously exhausted. In addition, the H(2)O(2) generated was demonstrated to reduce viability of the neuroblastoma SY-HY5Y cells. Although our results ruled out the direct oxidation of dopamine by α-syn-Cu(2+), the H(2)O(2) generated in the presence of α-syn-Cu(2+) can oxidize dopamine. Our results suggest that oxidative stress is at least partially responsible for the loss of dopaminergic cells in PD brain and reveal the multifaceted role of the α-syn-Cu(2+) complex in oxidative stress associated with PD symptoms.

The N-Terminus of the Floral Arabidopsis TGA Transcription Factor PERIANTHIA Mediates Redox-Sensitive DNA-Binding.

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Nora Gutsche

Full Text Available The Arabidopsis TGA transcription factor (TF PERIANTHIA (PAN regulates the formation of the floral organ primordia as revealed by the pan mutant forming an abnormal pentamerous arrangement of the outer three floral whorls. The Arabidopsis TGA bZIP TF family comprises 10 members, of which PAN and TGA9/10 control flower developmental processes and TGA1/2/5/6 participate in stress-responses. For the TGA1 protein it was shown that several cysteines can be redox-dependently modified. TGA proteins interact in the nucleus with land plant-specific glutaredoxins, which may alter their activities posttranslationally. Here, we investigated the DNA-binding of PAN to the AAGAAT motif under different redox-conditions. The AAGAAT motif is localized in the second intron of the floral homeotic regulator AGAMOUS (AG, which controls stamen and carpel development as well as floral determinacy. Whereas PAN protein binds to this regulatory cis-element under reducing conditions, the interaction is strongly reduced under oxidizing conditions in EMSA studies. The redox-sensitive DNA-binding is mediated via a special PAN N-terminus, which is not present in other Arabidopsis TGA TFs and comprises five cysteines. Two N-terminal PAN cysteines, Cys68 and Cys87, were shown to form a disulfide bridge and Cys340, localized in a C-terminal putative transactivation domain, can be S-glutathionylated. Comparative land plant analyses revealed that the AAGAAT motif exists in asterid and rosid plant species. TGA TFs with N-terminal extensions of variable length were identified in all analyzed seed plants. However, a PAN-like N-terminus exists only in the rosids and exclusively Brassicaceae homologs comprise four to five of the PAN N-terminal cysteines. Redox-dependent modifications of TGA cysteines are known to regulate the activity of stress-related TGA TFs. Here, we show that the N-terminal PAN cysteines participate in a redox-dependent control of the PAN interaction with a highly

Metabolic and redox barriers in the skin exposed to drugs and xenobiotics.

Science.gov (United States)

Korkina, Liudmila

2016-01-01

Growing exposure of human skin to environmental and occupational hazards, to numerous skin care/beauty products, and to topical drugs led to a biomedical concern regarding sustainability of cutaneous chemical defence that is essential for protection against intoxication. Since skin is the largest extra-hepatic drug/xenobiotic metabolising organ where redox-dependent metabolic pathways prevail, in this review, publications on metabolic processes leading to redox imbalance (oxidative stress) and its autocrine/endocrine impact to cutaneous drug/xenobiotic metabolism were scrutinised. Chemical and photo-chemical skin barriers contain metabolic and redox compartments: their protective and homeostatic functions. The review will examine the striking similarity of adaptive responses to exogenous chemical/photo-chemical stressors and endogenous toxins in cutaneous metabolic and redox system; the role(s) of xenobiotics/drugs and phase II enzymes in the endogenous antioxidant defence and maintenance of redox balance; redox regulation of interactions between metabolic and inflammatory responses in skin cells; skin diseases sharing metabolic and redox problems (contact dermatitis, lupus erythematosus, and vitiligo) Due to exceptional the redox dependence of cutaneous metabolic pathways and interaction of redox active metabolites/exogenous antioxidants with drug/xenobiotic metabolism, metabolic tests of topical xenobiotics/drugs should be combined with appropriate redox analyses and performed on 3D human skin models.

Enhanced energy density of carbon-based supercapacitors using Cerium (III) sulphate as inorganic redox electrolyte

International Nuclear Information System (INIS)

Díaz, Patricia; González, Zoraida; Santamaría, Ricardo; Granda, Marcos; Menéndez, Rosa; Blanco, Clara

2015-01-01

Highlights: •Ce 2 (SO 4 ) 3 /H 2 SO 4 redox electrolyte as a new route to increase the energy density of SCs. •Increased operating cell voltage with no electrolyte decomposition. •Redox reactions on the battery-type electrode. •The negative electrode retains its capacitor behaviour. •Outstanding energy density values compared to those measured in H 2 SO 4 . -- ABSTRACT: The energy density of carbon based supercapacitors (CBSCs) was significantly increased by the addition of an inorganic redox species [Ce 2 (SO 4 ) 3 ] to an aqueous electrolyte (H 2 SO 4 ). The development of the faradaic processes on the positive electrode not only significantly increased the capacitance but also the operational cell voltage of these devices (up to 1.5 V) due to the high redox potentials at which the Ce 3+ /Ce 4+ reactions occur. Therefore, in asymmetric CBSCs assembled using an activated carbon as negative electrode and MWCNTs as the positive one, the addition of Ce 2 (SO 4 ) 3 moderately increases the energy density of the device (from 1.24 W h kg −1 to 5.08 W h kg −1 ). When a modified graphite felt is used as positive electrode the energy density of the cell reaches values as high as 13.84 W h kg −1 . The resultant systems become asymmetric hybrid devices where energy is stored due to the electrical double layer formation in the negative electrode and the development of the faradaic process in the positive electrode, which acts as a battery-type electrode

Redox Modulation Matters: Emerging Functions for Glutaredoxins in Plant Development and Stress Responses

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Shutian Li

2014-11-01

Full Text Available Glutaredoxins (GRXs are small ubiquitous glutathione (GSH-dependent oxidoreductases that catalyze the reversible reduction of protein disulfide bridges or protein-GSH mixed disulfide bonds via a dithiol or monothiol mechanism, respectively. Three major classes of GRXs, with the CPYC-type, the CGFS-type or the CC-type active site, have been identified in many plant species. In spite of the well-characterized roles for GRXs in Escherichia coli, yeast and humans, the biological functions of plant GRXs have been largely enigmatic. The CPYC-type and CGFS-type GRXs exist in all organisms, from prokaryotes to eukaryotes, whereas the CC-type class has thus far been solely identified in land plants. Only the number of the CC-type GRXs has enlarged dramatically during the evolution of land plants, suggesting their participation in the formation of more complex plants adapted to life on land. A growing body of evidence indicates that plant GRXs are involved in numerous cellular pathways. In this review, emphasis is placed on the recently emerging functions for GRXs in floral organ development and disease resistance. Notably, CC-type GRXs have been recruited to participate in these two seemingly unrelated processes. Besides, the current knowledge of plant GRXs in the assembly and delivery of iron-sulfur clusters, oxidative stress responses and arsenic resistance is also presented. As GRXs require GSH as an electron donor to reduce their target proteins, GSH-related developmental processes, including the control of flowering time and the development of postembryonic roots and shoots, are further discussed. Profiling the thiol redox proteome using high-throughput proteomic approaches and measuring cellular redox changes with fluorescent redox biosensors will help to further unravel the redox-regulated physiological processes in plants.

Quantitative redox imaging biomarkers for studying tissue metabolic state and its heterogeneity

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He N. Xu

2014-03-01

Full Text Available NAD+/NADH redox state has been implicated in many diseases such as cancer and diabetes as well as in the regulation of embryonic development and aging. To fluorimetrically assess the mitochondrial redox state, Dr. Chance and co-workers measured the fluorescence of NADH and oxidized flavoproteins (Fp including flavin–adenine–dinucleotide (FAD and demonstrated their ratio (i.e. the redox ratio is a sensitive indicator of the mitochondrial redox states. The Chance redox scanner was built to simultaneously measure NADH and Fp in tissue at submillimeter scale in 3D using the freeze-trap protocol. This paper summarizes our recent research experience, development and new applications of the redox scanning technique in collaboration with Dr. Chance beginning in 2005. Dr. Chance initiated or actively involved in many of the projects during the last several years of his life. We advanced the redox scanning technique by measuring the nominal concentrations (in reference to the frozen solution standards of the endogenous fluorescent analytes, i.e., [NADH] and [Fp] to quantify the redox ratios in various biological tissues. The advancement has enabled us to identify an array of the redox indices as quantitative imaging biomarkers (including [NADH], [Fp], [Fp]/([NADH]+[Fp], [NADH]/[Fp], and their standard deviations for studying some important biological questions on cancer and normal tissue metabolism. We found that the redox indices were associated or changed with (1 tumorigenesis (cancer versus non-cancer of human breast tissue biopsies; (2 tumor metastatic potential; (3 tumor glucose uptake; (4 tumor p53 status; (5 PI3K pathway activation in pre-malignant tissue; (6 therapeutic effects on tumors; (7 embryonic stem cell differentiation; (8 the heart under fasting. Together, our work demonstrated that the tissue redox indices obtained from the redox scanning technique may provide useful information about tissue metabolism and physiology status in normal

Characterization of Redox properties of humic materials

International Nuclear Information System (INIS)

Choppin, G.R.

1995-01-01

An important aspect of humic materials is the presence of stable free radicals as shown by the width of 1 H-NMR lines of humic acid in solution as well as ESR spectra of solid samples. Presumably, these are due to quinohdrone functional groups in the humic structure. These free radicals are assumed to be a source of the redox effects of humics in metal cations. Phenolic groups have also been proposed as a source of reduction potential in these substances. The reduction potential of humic material is 0.5-0.7 V (vs. the normal hydrogen electrode). In addition to this inherent redox property, humics undergo photolysis by sunlight in surface waters which results in the production of hydrogen peroxide. The latter can also result in redox reactions with metal cations. Such direct and indirect redox capability can have significant effects on the migration of reducible cations. Studies of the reduction of hexavalent actinide cations by humic acid showed the reactions Np O 2 2+ -> Np O 2 + (E 1/2 0 = 1.47 V) and Pu O 2 2+ -> Pu +4 (E 1/2 0 = 1.04 V) while U O 2 2+ was not reduced. The reduction of plutonium in sea water by humics is discussed. Evidence of the effects of redox by humic material on metal cations in natural waters and sediments are also reviewed. (authors). 16 refs., 2 figs., 1 tab

Cost-driven materials selection criteria for redox flow battery electrolytes

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Dmello, Rylan; Milshtein, Jarrod D.; Brushett, Fikile R.; Smith, Kyle C.

2016-10-01

Redox flow batteries show promise for grid-scale energy storage applications but are presently too expensive for widespread adoption. Electrolyte material costs constitute a sizeable fraction of the redox flow battery price. As such, this work develops a techno-economic model for redox flow batteries that accounts for redox-active material, salt, and solvent contributions to the electrolyte cost. Benchmark values for electrolyte constituent costs guide identification of design constraints. Nonaqueous battery design is sensitive to all electrolyte component costs, cell voltage, and area-specific resistance. Design challenges for nonaqueous batteries include minimizing salt content and dropping redox-active species concentration requirements. Aqueous battery design is sensitive to only redox-active material cost and cell voltage, due to low area-specific resistance and supporting electrolyte costs. Increasing cell voltage and decreasing redox-active material cost present major materials selection challenges for aqueous batteries. This work minimizes cost-constraining variables by mapping the battery design space with the techno-economic model, through which we highlight pathways towards low price and moderate concentration. Furthermore, the techno-economic model calculates quantitative iterations of battery designs to achieve the Department of Energy battery price target of 100 per kWh and highlights cost cutting strategies to drive battery prices down further.

The role of grain boundaries and transient porosity increase as fluid pathways for reaction front propagation

Science.gov (United States)

Jonas, Laura; John, Timm; Geisler, Thorsten; Putnis, Andrew

2013-04-01

The pseudomorphic replacement of Carrara marble by calcium phosphates was studied as a model system to examine the influence of different fluid pathways for reaction front propagation induced by fluid-rock interaction. In this model system, the grain boundaries present in the rock and the transient porosity structures developing throughout the replacement reaction enable the reaction front to progress further into the rock as well as to the center of each single grain until complete transformation. Hydrothermal treatment of the marble using phosphate bearing solutions at temperature levels of 150° C and 200° C for different durations lead to the formation of two product phases which were identified as hydroxyapatite [Ca5(PO4)3OH] as well as β-tricalcium phosphate [β-Ca3(PO4)2] (β-TCP). The formation of β-TCP was probably favored by the presence of ~0.6wt.% of Mg in the parent phase. Completely transformed single grains show a distinctive zoning, both in composition and texture. Whereas areas next to the grain boundary consist of nearly pure hydroxyapatite and show a coarse porosity, areas close to the center of the single grains show a high amount of β-TCP and a very fine porous microstructure. If F was added as an additional solution component, the formation of β-TCP was avoided and up to 3wt.% of F were incorporated into the product apatite. The use of the isotope 18O as a chronometer for the replacement reaction makes it possible to reconstruct the chronological development of the calcium phosphate reaction front. Raman analysis revealed that the incorporation of 18O in the PO4 tetrahedron of hydroxyapatite results in the development of distinct profiles in the calcium phosphate reaction front perpendicular to the grain boundaries of the marble. Through the use of the 18O chronometer, it is possible to estimate and compare the time effectiveness of the different fluid pathways in this model system. The results show that the grain boundaries serve as a

Facile approach to prepare pH and redox-responsive nanogels via Diels-Alder click reaction

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C. M. Q. Le

2018-08-01

Full Text Available A novel pH and redox responsive system of sub-100 nm nanogels was prepared by arm-first approach via Diels-Alder click reaction. First, well-defined poly(ethylene glycol-block-poly(styrene-alt-maleic anhydride (PEG-b-PSM was synthesized and subsequently functionalized with furfuryl amine, leading to the formation of the dual-functional block copolymer of PEG-b-PSMf. The furfuryl groups in the PSMf block were employed to incorporate a redox-responsive linkage and the carboxylic acid moieties generated through functionalization acted as a pH-responsive part. The Diels-Alder click reaction between a bismaleimide crosslinker and PEG-b-PSMf was conducted at 60 °C, affording star-like nanogel structures. Doxorubicin, a model anticancer drug, was loaded into to the core of the nanogels primarily by the ionic interaction with carboxylates of core blocks and a highest drug loading capacity of 38.1% was obtained. Furthermore, the in vitro profile showed a low release percentage (11.2% of DOX at PBS pH 7.4, whereas a burst release (62% at pH 5.0 in the presence of 10 mM glutathione, indicating the effective pH and redox responsive characteristic of the PEG-b-PSMf nanogels.

A spatial database of bedding attitudes to accompany Geologic map of the greater Denver area, Front Range Urban Corridor, Colorado

Science.gov (United States)

Trimble, Donald E.; Machette, Michael N.; Brandt, Theodore R.; Moore, David W.; Murray, Kyle E.

2003-01-01

This digital map shows bedding attitude symbols display over the geographic extent of surficial deposits and rock stratigraphic units (formations) as compiled by Trimble and Machette 1973-1977 and published in 1979 (U.S. Geological Survey Map I-856-H) under the Front Range Urban Corridor Geology Program. Trimble and Machette compiled their geologic map from published geologic maps and unpublished geologic mapping having varied map unit schemes. A convenient feature of the compiled map is its uniform classification of geologic units that mostly matches those of companion maps to the north (USGS I-855-G) and to the south (USGS I-857-F). Published as a color paper map, the Trimble and Machette map was intended for land-use planning in the Front Range Urban Corridor. This map recently (1997-1999), was digitized under the USGS Front Range Infrastructure Resources Project (see cross-reference). In general, the mountainous areas in the west part of the map exhibit various igneous and metamorphic bedrock units of Precambrian age, major faults, and fault brecciation zones at the east margin (5-20 km wide) of the Front Range. The eastern and central parts of the map (Colorado Piedmont) depict a mantle of unconsolidated deposits of Quaternary age and interspersed outcroppings of Cretaceous or Tertiary-Cretaceous sedimentary bedrock. The Quaternary mantle is comprised of eolian deposits (quartz sand and silt), alluvium (gravel, sand, and silt of variable composition), colluvium, and few landslides. At the mountain front, north-trending, dipping Paleozoic and Mesozoic sandstone, shale, and limestone bedrock formations form hogbacks and intervening valleys.

Cleavage and synthesis function of high and low redox potential laccases towards 4-morpholinoaniline and aminated as well as chlorinated phenols.

Science.gov (United States)

Hahn, Veronika; Mikolasch, Annett; Schauer, Frieder

2014-02-01

Laccases are able to mediate both cleavage and synthesis processes. The basis for this dual reaction capability lies in the property of the enzyme laccase to oxidize phenolic, and to some extent non-phenolic substances, to reactive radicals which can undergo on the one hand separations of small substitutents or large molecule parts from the parent compound and on the other hand coupling reactions with other radicals or molecules which are not themselves oxidizable by laccase. The cleavage of the non-phenolic compound 4-morpholinoaniline as well as the deamination of 4-aminophenol and the dechlorination of 4-chlorophenol resulted in the formation of 1,4-hydroquinone which is immediately oxidized by laccase to 1,4-benzoquinone. The formation of the 1,4-hydroquinone/1,4-benzoquinone is the rate limiting step for the synthesis of the heteromolecular dimers and trimers composed of 1,4-benzoquinone and one or two molecules of morpholine. In addition to the synthesis of new compounds from the cleavage products, 4-morpholinoaniline polymerized probably via azo groups and C-N bonds to a homomolecular dimer and trimer. Similarities and differences in cleavage and synthesis reactions catalyzed by the low redox potential laccase of Myceliophthora thermophila (0.46 V) and the high redox potential laccase of Pycnoporus cinnabarinus (0.79 V) were determined. In addition, the dependency of the cleavage and synthesis efficiencies on the (a) structure and redox potential of the laccase, (b) structure and redox potential of the substrate, (c) pH value of the buffer used, (d) incubation temperature, (e) solvent concentration, and (f) laccase activity is discussed in general.

Sharp fronts within geochemical transport problems

International Nuclear Information System (INIS)

Grindrod, P.

1995-01-01

The authors consider some reactive geochemical transport problems in groundwater systems. When incoming fluid is in disequilibrium with the mineralogy sharp transition fronts may develop. They show that this is a generic property for a class of systems where the timescales associated with reaction and diffusion phenomena are much shorter than those associated with advective transport. Such multiple timescale problems are relevant to a variety of processes in natural systems: mathematically methods of singular perturbation theory reduce the dimension of the problems to be solved locally. Furthermore, they consider how spatial heterogeneous mineralogy can impact upon the propagation of sharp geochemical fronts. The authors developed an asymptotic approach in which they solve equations for the evolving geometry of the front and indicate how the non-smooth perturbations due to natural heterogeneity of the mineralogy on underlying ground water flow field are balanced against the smoothing effect of diffusion/dispersive processes. Fronts are curvature damped, and the results here indicate the generic nature of separate front propagation within both model (idealized) and natural (heterogeneous) geochemical systems

Light-Front Quantization of Gauge Theories

Energy Technology Data Exchange (ETDEWEB)

Brodsky, Stanley J.

2003-03-25

Light-front wavefunctions provide a frame-independent representation of hadrons in terms of their physical quark and gluon degrees of freedom. The light-front Hamiltonian formalism provides new nonperturbative methods for obtaining the QCD spectrum and eigensolutions, including resolvant methods, variational techniques, and discretized light-front quantization. A new method for quantizing gauge theories in light-cone gauge using Dirac brackets to implement constraints is presented. In the case of the electroweak theory, this method of light-front quantization leads to a unitary and renormalizable theory of massive gauge particles, automatically incorporating the Lorentz and 't Hooft conditions as well as the Goldstone boson equivalence theorem. Spontaneous symmetry breaking is represented by the appearance of zero modes of the Higgs field leaving the light-front vacuum equal to the perturbative vacuum. I also discuss an ''event amplitude generator'' for automatically computing renormalized amplitudes in perturbation theory. The importance of final-state interactions for the interpretation of diffraction, shadowing, and single-spin asymmetries in inclusive reactions such as deep inelastic lepton-hadron scattering is emphasized.

Light-Front Quantization of Gauge Theories

Energy Technology Data Exchange (ETDEWEB)

Brodskey, Stanley

2002-12-01

Light-front wavefunctions provide a frame-independent representation of hadrons in terms of their physical quark and gluon degrees of freedom. The light-front Hamiltonian formalism provides new nonperturbative methods for obtaining the QCD spectrum and eigensolutions, including resolvant methods, variational techniques, and discretized light-front quantization. A new method for quantizing gauge theories in light-cone gauge using Dirac brackets to implement constraints is presented. In the case of the electroweak theory, this method of light-front quantization leads to a unitary and renormalizable theory of massive gauge particles, automatically incorporating the Lorentz and 't Hooft conditions as well as the Goldstone boson equivalence theorem. Spontaneous symmetry breaking is represented by the appearance of zero modes of the Higgs field leaving the light-front vacuum equal to the perturbative vacuum. I also discuss an ''event amplitude generator'' for automatically computing renormalized amplitudes in perturbation theory. The importance of final-state interactions for the interpretation of diffraction, shadowing, and single-spin asymmetries in inclusive reactions such as deep inelastic lepton-hadron scattering is emphasized.

Redox-induced reversible luminescence switching of cerium-doped upconversion nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Huang, Yanan [College of Sciences, Shanghai University, Shanghai 200444 (China); International Laboratory for Adaptive Bio-nanotechnology, Suzhou Institute of Nano-tech and Nano-bionics (SINANO), Chinese Academy of Science, Suzhou 215123 (China); Xiao, Qingbo, E-mail: qbxiao2011@sinano.ac.cn [International Laboratory for Adaptive Bio-nanotechnology, Suzhou Institute of Nano-tech and Nano-bionics (SINANO), Chinese Academy of Science, Suzhou 215123 (China); Wang, Jian [College of Sciences, Shanghai University, Shanghai 200444 (China); International Laboratory for Adaptive Bio-nanotechnology, Suzhou Institute of Nano-tech and Nano-bionics (SINANO), Chinese Academy of Science, Suzhou 215123 (China); Xi, Yonglan [Laboratory for Agricultural Wastes Treatment and Recycling Institute of Agricultural Resources and Environment, Jiangsu Academy of Agricultural Science, Nanjing 210014 (China); Li, Fujin [International Laboratory for Adaptive Bio-nanotechnology, Suzhou Institute of Nano-tech and Nano-bionics (SINANO), Chinese Academy of Science, Suzhou 215123 (China); Feng, Yamin [College of Sciences, Shanghai University, Shanghai 200444 (China); International Laboratory for Adaptive Bio-nanotechnology, Suzhou Institute of Nano-tech and Nano-bionics (SINANO), Chinese Academy of Science, Suzhou 215123 (China); Shi, Liyi [College of Sciences, Shanghai University, Shanghai 200444 (China); Lin, Hongzhen, E-mail: hzlin2010@sinano.ac.cn [International Laboratory for Adaptive Bio-nanotechnology, Suzhou Institute of Nano-tech and Nano-bionics (SINANO), Chinese Academy of Science, Suzhou 215123 (China)

2016-05-15

Smart upconversion nanophosphors (UCNPs) that can be reversibly switched between two or more luminescent states by certain external stimuli have attracted considerable attention due to their great potential in biological applications. Here we report for the first time a type of redox-switchable UCNPs by codoping NaGdF{sub 4}:Yb/Er nanorods with the redox-active Ce{sup 3+}/Ce{sup 4+} ion pairs. A reversible switching of their UC luminescence intensity was observed upon the variation of the surrounding redox environments. We show solid proof that the luminescence switching is caused by the tailoring of the NaGdF{sub 4} host crystal structure in response to changing redox state of the codoped cerium ions. A proof-of-concept example is further demonstrated by using these UCNPs for probing the dynamical variation of redox environments in biological tissues. - Highlights: • Synthesis of upconversion nanoparticles doped with Ce{sup 3+}/Ce{sup 4+} ions. • The precise and reversible modification of crystal structure by redox reactions. • Tuning the upconversion luminescence by tailoring the crystal structure.

A study of redox kinetic in silicate melt

International Nuclear Information System (INIS)

Magnien, V.

2005-12-01

The aim of this thesis is to understand better iron redox reactions and mechanisms in silicate glasses and melts. Particular interest has been paid to the influence of temperature and chemical composition. For this purpose, the influence of alkali element content, iron content and network formers on the kinetics of redox reactions has been determined through XANES and Raman spectroscopy experiments performed either near the glass transition or above the liquidus temperature. As a complement, electrical conductivity and RBS spectroscopy experiments have been made to characterize the diffusivity of the species that transport electrical charges and the reaction morphology, respectively. Temperature and composition variations can induce changes in the dominating redox mechanism. At a given temperature, the parameters that exert the strongest influence on redox mechanisms are the presence or lack of divalent cations and the existing decoupling between the mobility of network former and modifier elements. Near Tg, the diffusion of divalent cations, when present in the melt, controls the kinetics of iron redox reactions along with a flux of electron holes. Composition, through the degree of polymerization and the silicate network structure, influences the kinetics and the nature of the involved cations, but not the mechanisms of the reaction. Without alkaline earth elements, the kinetics of redox reactions are controlled by the diffusion of oxygen species. With increasing temperatures, the diffusivities of all ionic species tend to become similar. The decoupling between ionic fluxes then is reduced so that several mechanisms become kinetically equivalent and can thus coexist. (author)

Le reazioni redox: un pasticcio concettuale?

Directory of Open Access Journals (Sweden)

Elena Ghibaudi

2015-10-01

Full Text Available Le reazioni di ossidoriduzione costituiscono un argomento centrale di qualsiasi corso di base di chimica, sia a livello scolastico che universitario. Il loro apprendimento comporta il superamento di svariati ostacoli concettuali, la cui difficoltà può risultare amplificata da prassi didattiche inadeguate. Gli errori più ricorrenti nel presentare l’argomento sono di due tipi: i fare implicitamente riferimento a modelli esplicativi distinti (es. il numero di ossidazione e il trasferimento elettronico, senza esplicitarli e senza evidenziarne la differente natura e il campo di validità; ii confondere il livello della spiegazione formale con quello della realtà fisica. I fenomeni redox sono normalmente interpretati sulla base di tre distinti modelli empirici, che fanno riferimento al trasferimento di atomi di ossigeno, di atomi di idrogeno, di elettroni; e di un quarto modello, formale, fondato sul cambiamento del numero di ossidazione. La confusione tra questi modelli può generare considerevoli problemi di apprendimento. Il presente lavoro riporta un’analisi critica delle implicazioni concettuali della didattica dei processi redox. L’analisi è articolata in tre sezioni: i disamina della evoluzione storica del concetto di ossidoriduzione; ii analisi dei modelli redox e del loro campo di validità; iii discussione di alcuni aspetti epistemologici inerenti i processi redox che sono rilevanti per la didattica della chimica.

How Reducing was the Late Devonian Ocean? The Role of Extensive Expansion of Anoxia in Marine Biogeochemical Cycles of Redox Sensitive Metals.

Science.gov (United States)

Sahoo, S. K.; Jin, H.

2017-12-01

The evolution of Earth's biogeochemical cycles is intimately linked to the oxygenation of the oceans and atmosphere. The Late Devonian is no exception as its characterized with mass extinction and severe euxinia. Here we use concentrations of Molybdenum (Mo), Vanadium (V), Uranium (U) and Chromium (Cr) in organic rich black shales from the Lower Bakken Formation of the Williston Basin, to explore the relationship between extensive anoxia vs. euxinia and it's relation with massive release of oxygen in the ocean atmosphere system. XRF data from 4 core across the basin shows that modern ocean style Mo, U and Cr enrichments are observed throughout the Lower Bakken Formation, yet V is not enriched until later part of the formation. Given the coupling between redox-sensitive-trace element cycles and ocean redox, various models for Late Devonian ocean chemistry imply different effects on the biogeochemical cycling of major and trace nutrients. Here, we examine the differing redox behavior of molybdenum and vanadium under an extreme anoxia and relatively low extent of euxinia. The model suggests that Late Devonian was perhaps extensively anoxic- 40-50% compared to modern seafloor area, and a very little euxinia. Mo enrichments extend up to 500 p.p.m. throughout the section, representative of a modern reducing ocean. However, coeval low V enrichments only support towards anoxia, where anoxia is a source of V, and a sink for Mo. Our model suggests that the oceanic V reservoir is extremely sensitive to perturbations in the extent of anoxic condition, particularly during post glacial times.

Generalized kinetic model of reduction of molecular oxidant by metal containing redox

International Nuclear Information System (INIS)

Kravchenko, T.A.

1986-01-01

Present work is devoted to kinetics of reduction of molecular oxidant by metal containing redox. Constructed generalized kinetic model of redox process in the system solid redox - reagent solution allows to perform the general theoretical approach to research and to obtain new results on kinetics and mechanism of interaction of redox with oxidants.

Molecular Orbital Principles of Oxygen-Redox Battery Electrodes.

Science.gov (United States)

Okubo, Masashi; Yamada, Atsuo

2017-10-25

Lithium-ion batteries are key energy-storage devices for a sustainable society. The most widely used positive electrode materials are LiMO 2 (M: transition metal), in which a redox reaction of M occurs in association with Li + (de)intercalation. Recent developments of Li-excess transition-metal oxides, which deliver a large capacity of more than 200 mAh/g using an extra redox reaction of oxygen, introduce new possibilities for designing higher energy density lithium-ion batteries. For better engineering using this fascinating new chemistry, it is necessary to achieve a full understanding of the reaction mechanism by gaining knowledge on the chemical state of oxygen. In this review, a summary of the recent advances in oxygen-redox battery electrodes is provided, followed by a systematic demonstration of the overall electronic structures based on molecular orbitals with a focus on the local coordination environment around oxygen. We show that a π-type molecular orbital plays an important role in stabilizing the oxidized oxygen that emerges upon the charging process. Molecular orbital principles are convenient for an atomic-level understanding of how reversible oxygen-redox reactions occur in bulk, providing a solid foundation toward improved oxygen-redox positive electrode materials for high energy-density batteries.

Synthesis and characterization of redox-active ferric nontronite

Energy Technology Data Exchange (ETDEWEB)

Ilgen, A. G.; Kukkadapu, R. K.; Dunphy, D. R.; Artyushkova, K.; Cerrato, J. M.; Kruichak, J. N.; Janish, M. T.; Sun, C. J.; Argo, J. M.; Washington, R. E.

2017-10-01

Heterogeneous redox reactions on clay mineral surfaces control mobility and bioavailability of redox-sensitive nutrients and contaminants. Iron (Fe) residing in clay mineral structures can either catalyze or directly participate in redox reactions; however, chemical controls over its reactivity are not fully understood. In our previous work we demonstrated that converting a minor portion of Fe(III) to Fe(II) (partial reduction) in the octahedral sheet of natural Fe-rich clay mineral nontronite (NAu-1) activates its surface, making it redox-active. In this study we produced and characterized synthetic ferric nontronite (SIP), highlighting structural and chemical similarities and differences between this synthetic nontronite and its natural counterpart NAu-1, and probed whether mineral surface is redox-active by reacting it with arsenic As(III) under oxic and anoxic conditions. We demonstrate that synthetic nontronite SIP undergoes the same activation as natural nontronite NAu-1 following the partial reduction treatment. Similar to NAu-1, SIP oxidized As(III) to As(V) under both oxic (catalytic pathway) and anoxic (direct oxidation) conditions. The similar reactivity trends observed for synthetic nontronite and its natural counterpart make SIP an appropriate analog for laboratory studies. The development of chemically pure analogs for ubiquitous soil minerals will allow for systematic research of the fundamental properties of these minerals.

Inhibition of Ape1 Redox Activity Promotes Odonto/osteogenic Differentiation of Dental Papilla Cells.

Science.gov (United States)

Chen, Tian; Liu, Zhi; Sun, Wenhua; Li, Jingyu; Liang, Yan; Yang, Xianrui; Xu, Yang; Yu, Mei; Tian, Weidong; Chen, Guoqing; Bai, Ding

2015-12-07

Dentinogenesis is the formation of dentin, a substance that forms the majority of teeth, and this process is performed by odontoblasts. Dental papilla cells (DPCs), as the progenitor cells of odontoblasts, undergo the odontogenic differentiation regulated by multiple cytokines and paracrine signal molecules. Ape1 is a perfect paradigm of the function complexity of a biological macromolecule with two major functional regions for DNA repair and redox regulation, respectively. To date, it remains unclear whether Ape1 can regulate the dentinogenesis in DPCs. In the present study, we firstly examed the spatio-temporal expression of Ape1 during tooth germ developmental process, and found the Ape1 expression was initially high and then gradually reduced along with the tooth development. Secondly, the osteo/odontogenic differentiation capacity of DPCs was up-regulated when treated with either Ape1-shRNA or E3330 (a specific inhibitor of the Ape1 redox function), respectively. Moreover, we found that the canonical Wnt signaling pathway was activated in this process, and E3330 reinforced-osteo/odontogenic differentiation capacity was suppressed by Dickkopf1 (DKK1), a potent antagonist of canonical Wnt signaling pathway. Taken together, we for the first time showed that inhibition of Ape1 redox regulation could promote the osteo/odontogenic differentiation capacity of DPCs via canonical Wnt signaling pathway.

PKI 166 induced redox signalling and apoptosis through activation of p53, MAP kinase and caspase pathway in epidermoid carcinoma.

Science.gov (United States)

Das, Subhasis; Dey, Kaushik Kumar; Bharti, Rashmi; MaitiChoudhury, Sujata; Maiti, Sukumar; Mandal, Mahitosh

2012-01-01

Cellular redox changes have emerged as a pivotal and proximal event in cancer. PKI 166 is used to determine the effects of redox sensitive inhibition of EGFR, metastasis and apoptosis in epidermoid carcinoma. Cytotoxicity study of PKI 166 (IC50 1.0 microM) treated A431 cells were performed by MTT assay for 48 and 72 hrs. Morphological analysis of PKI 166 treated A431 cells for 48 hrs. revealed the cell shrinkage, loss of filopodia and lamellipodia by phase contrast and SEM images in dose dependent manner. It has cytotoxic effects through inhibiting cellular proliferation, leads to the induction of apoptosis, as increased fraction of sub-G1 phase of the cell cycle, chromatin condensation and DNA ladder. It inhibited cyclin-D1 and cyclin-E expression and induced p53, p21 expression in dose dependent manner. Consequently, an imbalance of Bax/Bcl-2 ratio triggered caspase cascade and subsequent cleavage of PARP, thereby shifting the balance in favour of apoptosis. PKI 166 treatment actively stimulated reactive oxygen species (ROS) and mitochondrial membrane depolarization. It inhibited some metastatic properties of A431 cells supressing colony formation by soft agar assay and inhibition of MMP 9 activity by gelatin zymography and western blot analysis. PKI 166 inhibited growth factor induced phosphorylation of EGFR, Akt, MAPK, JNK and colony formation in A431 cells. Thus the inhibition of proliferation was associated with redox regulation of the caspase cascade, EGFR, Akt/PI3K, MAPK/ ERK and JNK pathway. On the other hand, increased antioxidant activity leads to decreased ROS generation inhibit the anti-proliferative and apoptotic properties of PKI 166 in A431 cells. These observations indicated PKI 166 induced redox signalling dependent inhibition of cell proliferation, metastatic properties and induction of apoptotic potential in epidermoid carcinoma.

Anticancer Activity of Metal Complexes: Involvement of Redox Processes

Science.gov (United States)

Jungwirth, Ute; Kowol, Christian R.; Keppler, Bernhard K.; Hartinger, Christian G.; Berger, Walter; Heffeter, Petra

2012-01-01

Cells require tight regulation of the intracellular redox balance and consequently of reactive oxygen species for proper redox signaling and maintenance of metal (e.g., of iron and copper) homeostasis. In several diseases, including cancer, this balance is disturbed. Therefore, anticancer drugs targeting the redox systems, for example, glutathione and thioredoxin, have entered focus of interest. Anticancer metal complexes (platinum, gold, arsenic, ruthenium, rhodium, copper, vanadium, cobalt, manganese, gadolinium, and molybdenum) have been shown to strongly interact with or even disturb cellular redox homeostasis. In this context, especially the hypothesis of “activation by reduction” as well as the “hard and soft acids and bases” theory with respect to coordination of metal ions to cellular ligands represent important concepts to understand the molecular modes of action of anticancer metal drugs. The aim of this review is to highlight specific interactions of metal-based anticancer drugs with the cellular redox homeostasis and to explain this behavior by considering chemical properties of the respective anticancer metal complexes currently either in (pre)clinical development or in daily clinical routine in oncology. PMID:21275772

In-situ irradiation of cerium precursors in TEM to study nanocrystal formation

Science.gov (United States)

Asghar, Muhammad Sajid Ali; Sabri, Mohammed Mohammed; Tian, Zijian; Möbus, Günter

2017-09-01

Three of the most commonly used precursor chemicals for wet-chemical nano-ceria synthesis are examined by means of direct dry electron irradiation in TEM. Transformation reactions of micron-size carbonate, chloride, and nitrate grains into nanocrystallites (internal or external) are recorded in situ. Progress of possible redox-changes of cerium is tracked by EELS. We find a straight local oxidation reaction for carbonates, but external nanorod formation by condensation in the case of chlorides, while nitrates show a multi-stage complex redox behaviour.

The Development of the Redox Concept Inventory as a Measure of Students' Symbolic and Particulate Redox Understandings and Confidence

Science.gov (United States)

Brandriet, Alexandra R.; Bretz, Stacey Lowery

2014-01-01

This article describes the development of the Redox Concept Inventory (ROXCI) as a measure of students' understandings and confidence of both the symbolic and particulate domains of oxidation-reduction (redox) reactions. The ROXCI was created using a mixed-methods design in which the items were developed based upon themes that emerged from…

Front propagation and clustering in the stochastic nonlocal Fisher equation

Science.gov (United States)

Ganan, Yehuda A.; Kessler, David A.

2018-04-01

In this work, we study the problem of front propagation and pattern formation in the stochastic nonlocal Fisher equation. We find a crossover between two regimes: a steadily propagating regime for not too large interaction range and a stochastic punctuated spreading regime for larger ranges. We show that the former regime is well described by the heuristic approximation of the system by a deterministic system where the linear growth term is cut off below some critical density. This deterministic system is seen not only to give the right front velocity, but also predicts the onset of clustering for interaction kernels which give rise to stable uniform states, such as the Gaussian kernel, for sufficiently large cutoff. Above the critical cutoff, distinct clusters emerge behind the front. These same features are present in the stochastic model for sufficiently small carrying capacity. In the latter, punctuated spreading, regime, the population is concentrated on clusters, as in the infinite range case, which divide and separate as a result of the stochastic noise. Due to the finite interaction range, if a fragment at the edge of the population separates sufficiently far, it stabilizes as a new cluster, and the processes begins anew. The deterministic cutoff model does not have this spreading for large interaction ranges, attesting to its purely stochastic origins. We show that this mode of spreading has an exponentially small mean spreading velocity, decaying with the range of the interaction kernel.

Light front quantum chromodynamics: Towards phenomenology

Indian Academy of Sciences (India)

Light front dynamics; quantum chromodynamics; deep inelastic scattering. PACS Nos 11.10. ... What makes light front dynamics appealing from high energy phenomenology point of view? .... given in terms of Poincarй generators by. MВ = W P ...

Redox homeostasis: the linchpin in stem cell self-renewal and differentiation.

Science.gov (United States)

Wang, Kui; Zhang, Tao; Dong, Qiang; Nice, Edouard Collins; Huang, Canhua; Wei, Yuquan

2013-03-14

Stem cells are characterized by their unique ability of self-renewal to maintain the so-called stem cell pool. Over the past decades, reactive oxygen species (ROS) have been recognized as toxic aerobic metabolism byproducts that are harmful to stem cells, leading to DNA damage, senescence or cell death. Recently, a growing body of literature has shown that stem cells reside in redox niches with low ROS levels. The balance of Redox homeostasis facilitates stem cell self-renewal by an intricate network. Thus, to fully decipher the underlying molecular mechanisms involved in the maintenance of stem cell self-renewal, it is critical to address the important role of redox homeostasis in the regulation of self-renewal and differentiation of stem cells. In this regard, we will discuss the regulatory mechanisms involved in the subtly orchestrated balance of redox status in stem cells by scavenger antioxidant enzyme systems that are well monitored by the hypoxia niches and crucial redox regulators including forkhead homeobox type O family (FoxOs), apurinic/apyrimidinic (AP) endonuclease1/redox factor-1 (APE1/Ref-1), nuclear factor erythroid-2-related factor 2 (Nrf2) and ataxia telangiectasia mutated (ATM). We will also introduce several pivotal ROS-sensitive molecules, such as hypoxia-inducible factors, p38 mitogen-activated protein kinase (p38) and p53, involved in the redox-regulated stem cell self-renewal. Specifically, all the aforementioned molecules can act as 'redox sensors' by virtue of redox modifications of their cysteine residues, which are critically important in the control of protein function. Given the importance of redox homeostasis in the regulation of stem cell self-renewal, understanding the underlying molecular mechanisms involved will provide important new insights into stem cell biology.

Electrochemical redox processes involving soluble cerium species

International Nuclear Information System (INIS)

Arenas, L.F.; Ponce de León, C.; Walsh, F.C.

2016-01-01

Highlights: • The relevance of cerium in laboratory and industrial electrochemistry is considered. • The history of fundamental electrochemical studies and applications is considered. • The chemistry, redox thermodynamics and electrode kinetics of cerium are summarised. • The uses of cerium ions in synthesis, energy storage, analysis and environmental treatment are illustrated. • Research needs and development perspectives are discussed. - Abstract: Anodic oxidation of cerous ions and cathodic reduction of ceric ions, in aqueous acidic solutions, play an important role in electrochemical processes at laboratory and industrial scale. Ceric ions, which have been used for oxidation of organic wastes and off-gases in environmental treatment, are a well-established oxidant for indirect organic synthesis and specialised cleaning processes, including oxide film removal from tanks and process pipework in nuclear decontamination. They also provide a classical reagent for chemical analysis in the laboratory. The reversible oxidation of cerous ions is an important reaction in the positive compartment of various redox flow batteries during charge and discharge cycling. A knowledge of the thermodynamics and kinetics of the redox reaction is critical to an understanding of the role of cerium redox species in these applications. Suitable choices of electrode material (metal or ceramic; coated or uncoated), geometry/structure (2-or 3-dimensional) and electrolyte flow conditions (hence an acceptable mass transport rate) are critical to achieving effective electrocatalysis, a high performance and a long lifetime. This review considers the electrochemistry of soluble cerium species and their diverse uses in electrochemical technology, especially for redox flow batteries and mediated electrochemical oxidation.

Are bioassays useful tools to assess redox processes and biodegradation?

DEFF Research Database (Denmark)

Albrechtsen, Hans-Jørgen; Pedersen, Philip Grinder; Ludvigsen, L.

2002-01-01

sensitive hydrochemical or geochemical parameters, levels of hydrogen, and redox potential. However, all these approaches have to be evaluated against TEAP-bioassays as the most direct measure. We assessed successfully ongoing microbial-mediated redox processes by TEAP-bioassays in degradation studies...... of aromatic and chlorinated aliphatic compounds in landfill leachate plumes, and of pesticides in aquifers with various redox conditions....

Front Propagation in Stochastic Neural Fields

KAUST Repository

Bressloff, Paul C.; Webber, Matthew A.

2012-01-01

We analyze the effects of extrinsic multiplicative noise on front propagation in a scalar neural field with excitatory connections. Using a separation of time scales, we represent the fluctuating front in terms of a diffusive-like displacement

Thiol Redox Transitions in Cell Signaling: a Lesson from N-Acetylcysteine

Directory of Open Access Journals (Sweden)

Tiziana Parasassi

2010-01-01

Full Text Available The functional status of cells is under the control of external stimuli affecting the function of critical proteins and eventually gene expression. Signal sensing and transduction by messengers to specific effectors operate by post-translational modification of proteins, among which thiol redox switches play a fundamental role that is just beginning to be understood. The maintenance of the redox status is, indeed, crucial for cellular homeostasis and its dysregulation towards a more oxidized intracellular environment is associated with aberrant proliferation, ultimately related to diseases such as cancer, cardiovascular disease, and diabetes. Redox transitions occur in sensitive cysteine residues of regulatory proteins relevant to signaling, their evolution to metastable disulfides accounting for the functional redox switch. N-acetylcysteine (NAC is a thiol-containing compound that is able to interfere with redox transitions of thiols and, thus, in principle, able to modulate redox signaling. We here review the redox chemistry of NAC, then screen possible mechanisms to explain the effects observed in NAC-treated normal and cancer cells; such effects involve a modification of global gene expression, thus of functions and morphology, with a leitmotif of a switch from proliferation to terminal differentiation. The regulation of thiol redox transitions in cell signaling is, therefore, proposed as a new tool, holding promise not only for a deeper explanation of mechanisms, but indeed for innovative pharmacological interventions.

Exercise and Glycemic Control: Focus on Redox Homeostasis and Redox-Sensitive Protein Signaling

Science.gov (United States)

Parker, Lewan; Shaw, Christopher S.; Stepto, Nigel K.; Levinger, Itamar

2017-01-01

Physical inactivity, excess energy consumption, and obesity are associated with elevated systemic oxidative stress and the sustained activation of redox-sensitive stress-activated protein kinase (SAPK) and mitogen-activated protein kinase signaling pathways. Sustained SAPK activation leads to aberrant insulin signaling, impaired glycemic control, and the development and progression of cardiometabolic disease. Paradoxically, acute exercise transiently increases oxidative stress and SAPK signaling, yet postexercise glycemic control and skeletal muscle function are enhanced. Furthermore, regular exercise leads to the upregulation of antioxidant defense, which likely assists in the mitigation of chronic oxidative stress-associated disease. In this review, we explore the complex spatiotemporal interplay between exercise, oxidative stress, and glycemic control, and highlight exercise-induced reactive oxygen species and redox-sensitive protein signaling as important regulators of glucose homeostasis. PMID:28529499

Investigation of a redox-sensitive predictive model of mouse embryonic stem cells differentiation using quantitative nuclease protection assays and glutathione redox status

Science.gov (United States)

Investigation of a redox-sensitive predictive model of mouse embryonic stem cell differentiation via quantitative nuclease protection assays and glutathione redox status Chandler KJ,Hansen JM, Knudsen T,and Hunter ES 1. U.S. Environmental Protection Agency, Research Triangl...

Redox behavior of a low-doped Pr-CeO{sub 2}(111) surface. A DFT+U study

Energy Technology Data Exchange (ETDEWEB)

Milberg, Brian [ITHES, UBA-CONICET, Departamento de Ingeniería Química, Pabellón de Industrias, Ciudad Universitaria, 1428 Buenos Aires (Argentina); Juan, Alfredo [Departamento de Física & IFISUR, UNS-CONICET, Avda. Alem 1253, 8000 Bahía Blanca (Argentina); Irigoyen, Beatriz, E-mail: beatriz@di.fcen.uba.ar [ITHES, UBA-CONICET, Departamento de Ingeniería Química, Pabellón de Industrias, Ciudad Universitaria, 1428 Buenos Aires (Argentina)

2017-04-15

Highlights: • Pr doping facilitates oxygen donation due to the easy formation of Pr{sup 3+}/Pr{sup 4+} and Ce{sup 3+}/Ce{sup 4+} redox couples. • Pr doping also favors the formation of superoxide (O{sub 2}{sup −}) radicals on surface O-holes. • CO can be oxidized by superoxide radical forming a CO{sub 2} molecule floating on the surface. • CO can also interact on the (O{sub 2}{sup −})/Pr{sup 3+} interphase and forms weakly adsorbed carbonate-type intermediates. - Abstract: In this work, we investigated the redox behavior (donation and replenishing of oxygen) of a low praseodymium (Pr)-doped CeO{sub 2}(111) surface. We considered a 3.7 at.% Pr doping and performed density functional calculations using the GGA formalism with the ‘U’ correction on Ce(4f) and Pr(4f) orbitals. Our results indicate that Pr doping promotes oxygen donation by lowering the energy necessary to form surface anionic vacancies. When the Ce{sub 0.963}Pr{sub 0.037}O{sub 2}(111) surface donates one oxygen, the two excess electrons locate on Pr and Ce cations and reduce them to Pr{sup 3+} and Ce{sup 3+} ones. Praseodymium doping also favors the activation of O{sub 2} molecule on surface O-holes, leading to formation of a superoxide (O{sub 2}{sup −}) radical as well as to reoxidation of the Ce{sup 3+} cation to Ce{sup 4+} one. Additionally, we used the CO molecular adsorption for testing the reactivity of those superoxide species. The calculations expose the ability of these radicals to oxidize CO forming a CO{sub 2} molecule floating on the surface. However, when the superoxide is in the immediate vicinity of Pr dopant a carbonate-type species is formed. Our theoretical results may help to gain insight into redox properties and improved catalytic performance of low-doped Pr-CeO{sub 2} solids.

MMIC front-ends for optical communication systems

DEFF Research Database (Denmark)

Petersen, Anders Kongstad

1993-01-01

Two different types of optical front-end MMIC amplifiers for a 2.5-Gb/s coherent heterodyne optical receiver are presented. A bandwidth of 6-12 GHz has been obtained for a tuned front-end and 3-13 GHz for a distributed front-end. An input noise current density of 5-15 pA/√Hz has been obtained for...

High-energy redox-flow batteries with hybrid metal foam electrodes.

Science.gov (United States)

Park, Min-Sik; Lee, Nam-Jin; Lee, Seung-Wook; Kim, Ki Jae; Oh, Duk-Jin; Kim, Young-Jun

2014-07-09

A nonaqueous redox-flow battery employing [Co(bpy)3](+/2+) and [Fe(bpy)3](2+/3+) redox couples is proposed for use in large-scale energy-storage applications. We successfully demonstrate a redox-flow battery with a practical operating voltage of over 2.1 V and an energy efficiency of 85% through a rational cell design. By utilizing carbon-coated Ni-FeCrAl and Cu metal foam electrodes, the electrochemical reactivity and stability of the nonaqueous redox-flow battery can be considerably enhanced. Our approach intoduces a more efficient conversion of chemical energy into electrical energy and enhances long-term cell durability. The cell exhibits an outstanding cyclic performance of more than 300 cycles without any significant loss of energy efficiency. Considering the increasing demands for efficient energy storage, our achievement provides insight into a possible development pathway for nonaqueous redox-flow batteries with high energy densities.

Application of up-front licensing

Energy Technology Data Exchange (ETDEWEB)

Grant, S D [Atomic Energy of Canada Ltd., Saskatoon, SK (Canada); Snell, V G [Atomic Energy of Canada Ltd., Mississauga, ON (Canada)

1996-12-31

AECL has been pioneering `up-front` licensing of new reactor designs. The CANDU 3 design has been formally reviewed by AECB staff for a number of years. The CANDU 9 design has just started the up-front licensing process. The process gives designers, regulators and potential customers early confidence in the licensability of future plants. (author). 4 refs., 2 tabs.

Application of up-front licensing

International Nuclear Information System (INIS)

Grant, S.D.; Snell, V.G.

1995-01-01

AECL has been pioneering 'up-front' licensing of new reactor designs. The CANDU 3 design has been formally reviewed by AECB staff for a number of years. The CANDU 9 design has just started the up-front licensing process. The process gives designers, regulators and potential customers early confidence in the licensability of future plants. (author). 4 refs., 2 tabs

Redox non-innocent ligands: versatile new tools to control catalytic reactions

NARCIS (Netherlands)

Lyaskovskyy, V.; de Bruin, B.

2012-01-01

In this (tutorial overview) perspective we highlight the use of "redox non-innocent" ligands in catalysis. Two main types of reactivity in which the redox non-innocent ligand is involved can be specified: (A) The redox active ligand participates in the catalytic cycle only by accepting/donating

Redox behavior of Ce(IV)/Ce(III) in the presence of nitrilotriacetic acid: a surrogate study for An(IV)/An(III) redox behavior

International Nuclear Information System (INIS)

Suzuki, Y.; Nankawa, T.; Ohnuki, T.; Francis, A.J.

2010-01-01

Using cyclic voltammetry, we investigated the redox behavior of Ce(IV)/Ce(III), which is a surrogate for An(IV)/An(III) (An = actinides), in a solution of nitrilotriacetic acid (NTA) at 25 C. The cyclic voltammogram of Ce in a 0.1 M NTA solution at pH 6 showed a reversible one-electron redox reaction for Ce(IV)/Ce(III) at 0.51 V vs. Ag/AgCl. This redox potential was much lower than that obtained in 1 M nitric acid, indicating that Ce(IV) was preferentially stabilized by complexation with NTA. The redox potential in the NTA solution was independent of the Ce concentration from 2 to 20 mM, NTA concentration from 5 to 200 mM and pH between 3 and 7. These results indicated that no polymerization and no additional coordination of NTA and OH to the Ce(III)-NTA complex took place during the redox reaction. As the speciation calculation of Ce(III) in the NTA solution showed that the predominant species was Ce III (nta) 2 3 (H 3 nta = NTA), the redox reaction of the Ce-NTA complex was expressed by the following: Ce IV (nta) 2 2- + e - ↔ Ce III (nta) 2 3 . The logarithm of the stability constant of Ce IV (nta) 2 2- was calculated to be 38.6 ± 0.8 for I = 0 from the redox potential shift of Ce(IV)/Ce(III) in the NTA solution. The value was in good accordance with the stability constant of the Np IV (nta) 2 2- complex, demonstrating that the aqueous coordination chemistry of Ce(IV) with NTA is quite similar to that of An(IV). These results strongly suggest that a negative shift of the Pu(IV)/Pu(III) redox potential in the NTA solution should make Pu(IV) more stable than Pu(III) even in a reducing environment. (orig.)

Wintertime sea surface temperature fronts in the Taiwan Strait

Science.gov (United States)

Chang, Yi; Shimada, Teruhisa; Lee, Ming-An; Lu, Hsueh-Jung; Sakaida, Futoki; Kawamura, Hiroshi

2006-12-01

We present wintertime variations and distributions of sea surface temperature (SST) fronts in the Taiwan Strait by applying an entropy-based edge detection method to 10-year (1996-2005) satellite SST images with grid size of 0.01°. From climatological monthly mean maps of SST gradient magnitude in winter, we identify four significant SST fronts in the Taiwan Strait. The Mainland China Coastal Front is a long frontal band along the 50-m isobath near the Chinese coast. The sharp Peng-Chang Front appears along the Peng-Hu Channel and extends northward around the Chang-Yuen Ridge. The Taiwan Bank Front evolves in early winter. As the winter progresses, the front becomes broad and moves toward the Chinese coast, connecting to the Mainland China Coastal Front. The Kuroshio Front extends northeastward from the northeastern tip of Taiwan with a semicircle-shape curving along the 100-m isobath.

Redox Control of Skeletal Muscle Regeneration.

Science.gov (United States)

Le Moal, Emmeran; Pialoux, Vincent; Juban, Gaëtan; Groussard, Carole; Zouhal, Hassane; Chazaud, Bénédicte; Mounier, Rémi

2017-08-10

Skeletal muscle shows high plasticity in response to external demand. Moreover, adult skeletal muscle is capable of complete regeneration after injury, due to the properties of muscle stem cells (MuSCs), the satellite cells, which follow a tightly regulated myogenic program to generate both new myofibers and new MuSCs for further needs. Although reactive oxygen species (ROS) and reactive nitrogen species (RNS) have long been associated with skeletal muscle physiology, their implication in the cell and molecular processes at work during muscle regeneration is more recent. This review focuses on redox regulation during skeletal muscle regeneration. An overview of the basics of ROS/RNS and antioxidant chemistry and biology occurring in skeletal muscle is first provided. Then, the comprehensive knowledge on redox regulation of MuSCs and their surrounding cell partners (macrophages, endothelial cells) during skeletal muscle regeneration is presented in normal muscle and in specific physiological (exercise-induced muscle damage, aging) and pathological (muscular dystrophies) contexts. Recent advances in the comprehension of these processes has led to the development of therapeutic assays using antioxidant supplementation, which result in inconsistent efficiency, underlying the need for new tools that are aimed at precisely deciphering and targeting ROS networks. This review should provide an overall insight of the redox regulation of skeletal muscle regeneration while highlighting the limits of the use of nonspecific antioxidants to improve muscle function. Antioxid. Redox Signal. 27, 276-310.

Sorption of redox-sensitive elements: critical analysis

International Nuclear Information System (INIS)

Strickert, R.G.

1980-12-01

The redox-sensitive elements (Tc, U, Np, Pu) discussed in this report are of interest to nuclear waste management due to their long-lived isotopes which have a potential radiotoxic effect on man. In their lower oxidation states these elements have been shown to be highly adsorbed by geologic materials occurring under reducing conditions. Experimental research conducted in recent years, especially through the Waste Isolation Safety Assessment Program (WISAP) and Waste/Rock Interaction Technology (WRIT) program, has provided extensive information on the mechanisms of retardation. In general, ion-exchange probably plays a minor role in the sorption behavior of cations of the above three actinide elements. Formation of anionic complexes of the oxidized states with common ligands (OH - , CO -- 3 ) is expected to reduce adsorption by ion exchange further. Pertechnetate also exhibits little ion-exchange sorption by geologic media. In the reduced (IV) state, all of the elements are highly charged and it appears that they form a very insoluble compound (oxide, hydroxide, etc.) or undergo coprecipitation or are incorporated into minerals. The exact nature of the insoluble compounds and the effect of temperature, pH, pe, other chemical species, and other parameters are currently being investigated. Oxidation states other than Tc (IV,VII), U(IV,VI), Np(IV,V), and Pu(IV,V) are probably not important for the geologic repository environment expected, but should be considered especially when extreme conditions exist (radiation, temperature, etc.). Various experimental techniques such as oxidation-state analysis of tracer-level isotopes, redox potential measurement and control, pH measurement, and solid phase identification have been used to categorize the behavior of the various valence states

Sorption of redox-sensitive elements: critical analysis

Energy Technology Data Exchange (ETDEWEB)

Strickert, R.G.

1980-12-01

The redox-sensitive elements (Tc, U, Np, Pu) discussed in this report are of interest to nuclear waste management due to their long-lived isotopes which have a potential radiotoxic effect on man. In their lower oxidation states these elements have been shown to be highly adsorbed by geologic materials occurring under reducing conditions. Experimental research conducted in recent years, especially through the Waste Isolation Safety Assessment Program (WISAP) and Waste/Rock Interaction Technology (WRIT) program, has provided extensive information on the mechanisms of retardation. In general, ion-exchange probably plays a minor role in the sorption behavior of cations of the above three actinide elements. Formation of anionic complexes of the oxidized states with common ligands (OH/sup -/, CO/sup - -//sub 3/) is expected to reduce adsorption by ion exchange further. Pertechnetate also exhibits little ion-exchange sorption by geologic media. In the reduced (IV) state, all of the elements are highly charged and it appears that they form a very insoluble compound (oxide, hydroxide, etc.) or undergo coprecipitation or are incorporated into minerals. The exact nature of the insoluble compounds and the effect of temperature, pH, pe, other chemical species, and other parameters are currently being investigated. Oxidation states other than Tc (IV,VII), U(IV,VI), Np(IV,V), and Pu(IV,V) are probably not important for the geologic repository environment expected, but should be considered especially when extreme conditions exist (radiation, temperature, etc.). Various experimental techniques such as oxidation-state analysis of tracer-level isotopes, redox potential measurement and control, pH measurement, and solid phase identification have been used to categorize the behavior of the various valence states.

A catalytic approach to estimate the redox potential of heme-peroxidases

International Nuclear Information System (INIS)

Ayala, Marcela; Roman, Rosa; Vazquez-Duhalt, Rafael

2007-01-01

The redox potential of heme-peroxidases varies according to a combination of structural components within the active site and its vicinities. For each peroxidase, this redox potential imposes a thermodynamic threshold to the range of oxidizable substrates. However, the instability of enzymatic intermediates during the catalytic cycle precludes the use of direct voltammetry to measure the redox potential of most peroxidases. Here we describe a novel approach to estimate the redox potential of peroxidases, which directly depends on the catalytic performance of the activated enzyme. Selected p-substituted phenols are used as substrates for the estimations. The results obtained with this catalytic approach correlate well with the oxidative capacity predicted by the redox potential of the Fe(III)/Fe(II) couple

An experimental and theoretical method for determination of standard electrode potential for the redox couple diphenyl sulfone/diphenyl sulfide

Science.gov (United States)

Song, Y. Z.; Wei, K. X.; Lv, J. S.

2013-12-01

DFT calculations were performed for diphenyl sulfide and diphenyl sulfone. The electrochemistry of diphenyl sulfide on the gold electrode was investigated by cyclic voltammety and the results show that standard electrode potential for redox couple diphenyl sulfone/diphenyl sulfide is 1.058 V, which is consistent with that of 1.057 calculated at B3LYP/6-31++G( d, p)-IEFPCM level. The front orbit theory and Mulliken charges of molecular explain well on the oxidation of diphenyl sulfide in oxidative desulfurization. According to equilibrium theory the experimental equilibrium constant in the oxidative desulfurization of H2O2, is 1.17 × 1048, which is consistent with the theoretical equilibrium constant is 2.18 × 1048 at B3LYP/6-31++G( d, p)-IEFPCM level.

Fenton Redox Chemistry : Arsenite Oxidation by Metallic Surfaces

NARCIS (Netherlands)

Borges Freitas, S.C.; Van Halem, D.; Badruzzaman, A.B.M.; Van der Meer, W.G.J.

2014-01-01

Pre-oxidation of As(III) is necessary in arsenic removal processes in order to increase its efficiency. Therefore, the Fenton Redox Chemistry is defined by catalytic activation of H2O2 and currently common used for its redox oxidative properties. In this study the effect of H2O2 production catalysed

Hourly and daily variation of sediment redox potential in tidal wetland sediments

Science.gov (United States)

Catallo, W. James

1999-01-01

Variation of electrochemical oxidation-reduction (redox) potential was examined in surface salt march sediments under conditions of flooding and tidal simulation in mesocosms and field sites. Time series were generated of redox potential measured in sediment profiles at 2-10 cm depth using combination Pt-Ag/AgCl (ORP) electrodes. Redox potential data were acquired at rapid rates (1-55 samples/h) over extended periods (3-104 days) along with similar times series of temperature (water, air, soil) and pH. It was found that redox potential vaired as a result of water level changes and was unrelated to diurnal changes in temperature or pH, the latter of which changed by 370 mV redox potential decrease in under 48 hours). Attenuatoin of microbial activity by [gamma] y-radiation and toxic chemicals elimintated this response. In tidal salt marsh mesocosms where the sediment-plant assemblages were exposed to a simulated diurnal tide, redox potenial oscillations of 40-300 mV amplitude were recoded that has the same periodicity as the flood-drain cycle. Periodic redoc potential time series were observed repeatedly in sediments receiving tidal pulsing but not in those sediments exposed to static hydrological conditions. Data collected over 12 days from a coastal marsh site experiencing diurnal tides showed similar fluctuations in redox potential. Data from the experimentents indicated that (a) redox potential can be a dynamic, nonlinear variable in coastal and estuarine wetland sediments over hourly and daily scales, and the designs of biogeochemical experiments should reflect this, (b) redox potential can change rapidly and signigicantly in coastal wetland sediments in response of flooding and draining, (c) microbial community processes are primarily determinants of the time course of redox potential in wetland sediments, and elimination of inhibition of microbial activity (e.g. by pollutants) can significantly alter that behavior, and (d) fast redox potential dynamics appear

Characterizing Ion Flows Across a Dipolarization Front

Science.gov (United States)

Arnold, H.; Drake, J. F.; Swisdak, M.

2017-12-01

In light of the Magnetospheric Multiscale Mission (MMS) moving to study predominately symmetric magnetic reconnection in the Earth's magnetotail, it is of interest to investigate various methods for determining the relative location of the satellites with respect to the x line or a dipolarization front. We use a 2.5 dimensional PIC simulation to explore the dependence of various characteristics of a front, or flux bundle, on the width of the front in the dawn-dusk direction. In particular, we characterize the ion flow in the x-GSM direction across the front. We find a linear relationship between the width of a front, w, and the maximum velocity of the ion flow in the x-GSM direction, Vxi, for small widths: Vxi/VA=w/di*1/2*(mVA2)/Ti*Bz/Bxwhere m, VA, di, Ti, Bz, and Bx are the ion mass, upstream Alfven speed, ion inertial length, ion temperature, and magnetic fields in the z-GSM and x-GSM directions respectively. However, once the width reaches around 5 di, the relationship gradually approaches the well-known theoretical limit for ion flows, the upstream Alfven speed. Furthermore, we note that there is a reversal in the Hall magnetic field near the current sheet on the positive y-GSM side of the front. This reversal is most likely due to conservation of momentum in the y-GSM direction as the ions accelerate towards the x-GSM direction. This indicates that while the ions are primarily energized in the x-GSM direction by the front, they transfer energy to the electromagnetic fields in the y-GSM direction. The former energy transfer is greater than the latter, but the reversal of the Hall magnetic field drags the frozen-in electrons along with it outside of the front. These simulations should better able researchers to determine the relative location of a satellite crossing a dipolarization front.

Hydrogen production of Enterobacter aerogenes altered by extracellular and intracellular redox states

Energy Technology Data Exchange (ETDEWEB)

Nakashimada, Y.; Rachman, M.A.; Kakizono, T.; Nishio, N. [Hiroshima University, Higashi-Hiroshima (Japan). Graduate School of Advanced Sciences of Matter, Department of Molecular Biotechnology

2002-12-01

Enterobacter aerogenes HU-101, tested for its hydrogen production in batch cultures on various substrates, produced the highest amount of hydrogen when the substrate was glycerol. The yield of hydrogen is a function of the degree to which the substrates are reduced. To examine the effect of intracellular redox state on hydrogen yield, glucose-limiting chemostat cultures were carried out at various pH using strain HU-101 and its mutant AY-2. For both strains, the molar yield and the production rate of hydrogen and the hydrogenase activity in the cell-free extract were optimal at the culture pH of 6.3. The highest NADH/NAD ratio in both strains was also observed at pH 6.3, at which the ratio in AY-2 was more than two-fold that of HU-101. Furthermore, NAD(P)H-dependent hydrogen formation was observed in the cell-free extract of AY-2, and hydrogenase activity was found not in the cytoplasmic but in the cell membrane fraction, suggesting that a high intracellular redox state, that is a high NADH/NAD ratio, would accelerate hydrogen production by driving membrane-bound NAD(P)H-dependent hydrogenase. (author)

Optical imaging the redox status change during cell apoptosis

Science.gov (United States)

Su, Ting; Zhang, Zhihong; Lin, Juqiang; Luo, Qingming

2007-02-01

Many cellular events involve the alteration in redox equilibrium, globally or locally. In many cases, excessive reactive oxygen species (ROS) production is the underlying cause. Several green fluoresecence protein based indicators are constructed to measure redox status in cells, e.g, rxYFP and roGFPs, which allow real time detection. reduction and oxidization-sensitive GFP (RoGFPs) are more useful due to ratiometric variation by excitation, making the measurement more accurate. Utilizing one of those roGFPs called roGFP1, we establish a mitochondrial redox state probing platform in HeLa cells with laser scan confocal microscopy (LSCM) as detection system. Control experiments confirmed that our platform could produce stable ratiometric values, which made the data more accurately reflect the real environmental changes of redox status that roGFP1 probed. Using exogenous H IIO II and DTT, we evaluated the reactivity and reversibility of roGFP1. The minimal hydrogen peroxide concentration that roGFP1 could show detectable ratiometric changes in our system was about 200μM. Preliminarily applying our platform to exploring the redox status during apoptosis, we observed an increase in ratiometric, suggesting an excessive ROS production.

TEMPOL increases NAD+ and improves redox imbalance in obese mice

Directory of Open Access Journals (Sweden)

Mayumi Yamato

2016-08-01

Full Text Available Continuous energy conversion is controlled by reduction–oxidation (redox processes. NAD+ and NADH represent an important redox couple in energy metabolism. 4-Hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPOL is a redox-cycling nitroxide that promotes the scavenging of several reactive oxygen species (ROS and is reduced to hydroxylamine by NADH. TEMPOL is also involved in NAD+ production in the ascorbic acid–glutathione redox cycle. We utilized the chemical properties of TEMPOL to investigate the effects of antioxidants and NAD+/NADH modulators on the metabolic imbalance in obese mice. Increases in the NAD+/NADH ratio by TEMPOL ameliorated the metabolic imbalance when combined with a dietary intervention, changing from a high-fat diet to a normal diet. Plasma levels of the superoxide marker dihydroethidium were higher in mice receiving the dietary intervention compared with a control diet, but were normalized with TEMPOL consumption. These findings provide novel insights into redox regulation in obesity.

Improved electrochemical performances of binder-free CoMoO4 nanoplate arrays@Ni foam electrode using redox additive electrolyte

Science.gov (United States)

Veerasubramani, Ganesh Kumar; Krishnamoorthy, Karthikeyan; Kim, Sang Jae

2016-02-01

Herein, we are successfully prepared cobalt molybdate (CoMoO4) grown on nickel foam as a binder free electrode by hydrothermal approach for supercapacitors and improved their electrochemical performances using potassium ferricyanide (K3Fe(CN)6) as redox additive. The formation of CoMoO4 on Ni foam with high crystallinity is confirmed using XRD, Raman, and XPS measurements. The nanoplate arrays (NPAs) of CoMoO4 are uniformly grown on Ni foam which is confirmed by FE-SEM analysis. The prepared binder-free CoMoO4 NPAs achieved maximum areal capacity of 227 μAh cm-2 with KOH electrolyte at 2.5 mA cm-2. This achieved areal capacity is further improved about three times using the addition of K3Fe(CN)6 as redox additive. The increased electrochemical performances of CoMoO4 NPAs on Ni foam electrode via redox additive are discussed in detail and the mechanism has been explored. Moreover, the assembled CoMoO4 NPAs on Ni foam//activated carbon asymmetric supercapacitor device with an extended operating voltage window of 1.5 V exhibits an excellent performances such as high energy density and cyclic stability. The overall performances of binder-free CoMoO4 NPAs on Ni foam with redox additives suggesting their potential use as positive electrode material for high performance supercapacitors.

Syntactic and FSP Aspects of Fronting as a Style Marker

Directory of Open Access Journals (Sweden)

Libuše Dušková

2017-07-01

Full Text Available The paper examines contextual and emphatic fronting in academic prose, fiction narrative and fiction dialogue in order to ascertain whether the types of fronting can serve as a style marker. The differences in the distribution and their effect on style are assumed to be connected with the respective FSP structures: in emphatic fronting the fronted element is the rheme, whereas in contextual fronting it is the diatheme. Hence emphatic fronting displays a prominent deviation from the basic distribution of communicative dynamism, whereas contextual fronting achieves agreement with it. As compared with the unmarked postverbal ordering, emphatic fronting intensifies the emphatic/emotional character of the content being expressed, which is a feature of speech, while contextual fronting serves as a direct link with what precedes, hence contributes to textual cohesion, which is a characteristic of academic prose, with fiction narrative presumably occupying an intermediate position. The results of the study show more types of fronting with diversified structures and less clear-cut relations between the types of frontings and the examined text sorts.

The effects of variable front persistence and intensity on mesopelagic fish communities: a comparison of three fronts in the California Current Ecosystem

Science.gov (United States)

Netburn, A. N.; Koslow, J. A.

2016-02-01

Although the strong physical gradients at fronts are primarily realized in the epipelagic, the biological impacts of frontal ecosystems can extend into mesopelagic waters. In 2008, Lara-Lopez et al. (2012) observed a significant shift in total biomass and community composition of migrating mesopelagic fishes at a strong persistent front off of the Pt. Conception area of the southern California Current Ecosystem. Through the California Current Ecosystem Long-Term Ecological Research Program, two additional intensive sampling cruises have been conducted on frontal systems in the general region. In 2011 and 2012, paired day and night midwater Matsuda-Oozeki-Hu trawls were conducted at stations located on either side of the fronts and at the fronts themselves, a suite of concurrent observations of the physical environment measured, and lower trophic levels sampled. Using satellite imagery, we estimate front duration of each of the 2008, 2011, and 2012 fronts, and investigate changes to the relative abundance and community composition across these systems, comparing the resolved patterns in 2011 and 2012 to those published from 2008. Results of this work will help address the questions: (1) What are the timescales required for front presence to impact mesopelagic fish communities? (2) Do different types of frontal systems (e.g., an eddy front vs. a "classic" front) result in different patterns of mesopelagic fish abundance and community composition? These answers will provide insight into the mechanisms of accumulation of fishes at fronts. As many mesopelagic fishes are important forage species for oceanic predators, understanding their response to the high productivity frontal systems is key to understanding ecosystem-wide impacts of fronts.

Redox Cycling, pH Dependence, and Ligand Effects of Mn(III) in Oxalate Decarboxylase from Bacillus subtilis.

Science.gov (United States)

Twahir, Umar T; Ozarowski, Andrew; Angerhofer, Alexander

2016-11-29

This contribution describes electron paramagnetic resonance (EPR) experiments on Mn(III) in oxalate decarboxylase of Bacillus subtilis, an interesting enzyme that catalyzes the redox-neutral dissociation of oxalate into formate and carbon dioxide. Chemical redox cycling provides strong evidence that both Mn centers can be oxidized, although the N-terminal Mn(II) appears to have the lower reduction potential and is most likely the carrier of the +3 oxidation state under moderate oxidative conditions, in agreement with the general view that it represents the active site. Significantly, Mn(III) was observed in untreated OxDC in succinate and acetate buffers, while it could not be directly observed in citrate buffer. Quantitative analysis showed that up to 16% of the EPR-visible Mn is in the +3 oxidation state at low pH in the presence of succinate buffer. The fine structure and hyperfine structure parameters of Mn(III) are affected by small carboxylate ligands that can enter the active site and have been recorded for formate, acetate, and succinate. The results from a previous report [Zhu, W., et al. (2016) Biochemistry 55, 429-434] could therefore be reinterpreted as evidence of formate-bound Mn(III) after the enzyme is allowed to turn over oxalate. The pH dependence of the Mn(III) EPR signal compares very well with that of enzymatic activity, providing strong evidence that the catalytic reaction of oxalate decarboxylase is driven by Mn(III), which is generated in the presence of dioxygen.

Techno-Economic Modeling and Analysis of Redox Flow Battery Systems

Directory of Open Access Journals (Sweden)

Jens Noack

2016-08-01

Full Text Available A techno-economic model was developed to investigate the influence of components on the system costs of redox flow batteries. Sensitivity analyses were carried out based on an example of a 10 kW/120 kWh vanadium redox flow battery system, and the costs of the individual components were analyzed. Particular consideration was given to the influence of the material costs and resistances of bipolar plates and energy storage media as well as voltages and electric currents. Based on the developed model, it was possible to formulate statements about the targeted optimization of a developed non-commercial vanadium redox flow battery system and general aspects for future developments of redox flow batteries.

Light-front QCD. II. Two-component theory

International Nuclear Information System (INIS)

Zhang, W.; Harindranath, A.

1993-01-01

The light-front gauge A a + =0 is known to be a convenient gauge in practical QCD calculations for short-distance behavior, but there are persistent concerns about its use because of its ''singular'' nature. The study of nonperturbative field theory quantizing on a light-front plane for hadronic bound states requires one to gain a priori systematic control of such gauge singularities. In the second paper of this series we study the two-component old-fashioned perturbation theory and various severe infrared divergences occurring in old-fashioned light-front Hamiltonian calculations for QCD. We also analyze the ultraviolet divergences associated with a large transverse momentum and examine three currently used regulators: an explicit transverse cutoff, transverse dimensional regularization, and a global cutoff. We discuss possible difficulties caused by the light-front gauge singularity in the applications of light-front QCD to both old-fashioned perturbative calculations for short-distance physics and upcoming nonperturbative investigations for hadronic bound states

Evaluation of electrolytes for redox flow battery applications

International Nuclear Information System (INIS)

Chakrabarti, M.H.; Dryfe, R.A.W.; Roberts, E.P.L.

2007-01-01

A number of redox systems have been investigated in this work with the aim of identifying electrolytes suitable for testing redox flow battery cell designs. The criteria for the selection of suitable systems were fast electrochemical kinetics and minimal cross-contamination of active electrolytes. Possible electrolyte systems were initially selected based on cyclic voltammetry data. Selected systems were then compared by charge/discharge experiments using a simple H-type cell. The all-vanadium electrolyte system has been developed as a commercial system and was used as the starting point in this study. The performance of the all-vanadium system was significantly better than an all-chromium system which has recently been reported. Some metal-organic and organic redox systems have been reported as possible systems for redox flow batteries, with cyclic voltammetry data suggesting that they could offer near reversible kinetics. However, Ru(acac) 3 in acetonitrile could only be charged efficiently to 9.5% of theoretical charge, after which irreversible side reactions occurred and [Fe(bpy) 3 ](ClO 4 ) 2 in acetonitrile was found to exhibit poor charge/discharge performance

Control of a laser front wave

International Nuclear Information System (INIS)

Akaoka, K.; Wakaida, I.

1996-01-01

We controlled the laser wave front through a laser beam simulation experiment propagating through medium. Thus, we confirmed that the RMS, defined as the quadratic mean of the laser beam wave front, dropped to the 1/3 - 1/6 of the pre-control value

A Membrane‐Free Redox Flow Battery with Two Immiscible Redox Electrolytes

Science.gov (United States)

Navalpotro, Paula; Palma, Jesus; Anderson, Marc

2017-01-01

Abstract Flexible and scalable energy storage solutions are necessary for mitigating fluctuations of renewable energy sources. The main advantage of redox flow batteries is their ability to decouple power and energy. However, they present some limitations including poor performance, short‐lifetimes, and expensive ion‐selective membranes as well as high price, toxicity, and scarcity of vanadium compounds. We report a membrane‐free battery that relies on the immiscibility of redox electrolytes and where vanadium is replaced by organic molecules. We show that the biphasic system formed by one acidic solution and one ionic liquid, both containing quinoyl species, behaves as a reversible battery without any membrane. This proof‐of‐concept of a membrane‐free battery has an open circuit voltage of 1.4 V with a high theoretical energy density of 22.5 Wh L−1, and is able to deliver 90 % of its theoretical capacity while showing excellent long‐term performance (coulombic efficiency of 100 % and energy efficiency of 70 %). PMID:28658538

A Membrane-Free Redox Flow Battery with Two Immiscible Redox Electrolytes.

Science.gov (United States)

Navalpotro, Paula; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

2017-10-02

Flexible and scalable energy storage solutions are necessary for mitigating fluctuations of renewable energy sources. The main advantage of redox flow batteries is their ability to decouple power and energy. However, they present some limitations including poor performance, short-lifetimes, and expensive ion-selective membranes as well as high price, toxicity, and scarcity of vanadium compounds. We report a membrane-free battery that relies on the immiscibility of redox electrolytes and where vanadium is replaced by organic molecules. We show that the biphasic system formed by one acidic solution and one ionic liquid, both containing quinoyl species, behaves as a reversible battery without any membrane. This proof-of-concept of a membrane-free battery has an open circuit voltage of 1.4 V with a high theoretical energy density of 22.5 Wh L -1 , and is able to deliver 90 % of its theoretical capacity while showing excellent long-term performance (coulombic efficiency of 100 % and energy efficiency of 70 %). © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Fast front-end electronics for COMPASS MWPCs

CERN Document Server

Colantoni, M L; Ferrero, A; Frolov, V; Grasso, A; Heinz, S; Maggiora, A; Maggiora, M G; Panzieri, D; Popov, A; Tchalyshev, V

2000-01-01

In the COMPASS experiment, under construction at CERN, about 23000 channels of MWPCs will be used. The very high rate of the muon and hadron beams, and the consequently high trigger rate, require front- end electronics with innovative conceptual design. A new MWPC front- end electronics that fulfills the main COMPASS requirement to have a fast DAQ with a minimum dead-time has been designed. The general concept of the front-end cards is described; the comparative tests of two front-end chips, and different fast gas mixtures, are also shown. The commissioning of the experiment will start in the summer 2000, and production running, using the muon beam, is foreseen for the year 2001. (8 refs).

Redox regulation of Rac1 by thiol oxidation

Science.gov (United States)

Hobbs, G. Aaron; Mitchell, Lauren E.; Arrington, Megan E.; Gunawardena, Harsha P.; DeCristo, Molly J.; Loeser, Richard F.; Chen, Xian; Cox, Adrienne D.; Campbell, Sharon L.

2016-01-01

The Rac1 GTPase is an essential and ubiquitous protein that signals through numerous pathways to control critical cellular processes, including cell growth, morphology, and motility. Rac1 deletion is embryonic lethal, and its dysregulation or mutation can promote cancer, arthritis, cardiovascular disease, and neurological disorders. Rac1 activity is highly regulated by modulatory proteins and posttranslational modifications. Whereas much attention has been devoted to guanine nucleotide exchange factors that act on Rac1 to promote GTP loading and Rac1 activation, cellular oxidants may also regulate Rac1 activation by promoting guanine nucleotide exchange. Herein, we show that Rac1 contains a redox-sensitive cysteine (Cys18) that can be selectively oxidized at physiological pH because of its lowered pKa. Consistent with these observations, we show that Rac1 is glutathiolated in primary chondrocytes. Oxidation of Cys18 by glutathione greatly perturbs Rac1 guanine nucleotide binding and promotes nucleotide exchange. As aspartate substitutions have been previously used to mimic cysteine oxidation, we characterized the biochemical properties of Rac1C18D. We also evaluated Rac1C18S as a redox-insensitive variant and found that it retains structural and biochemical properties similar to those of Rac1WT but is resistant to thiol oxidation. In addition, Rac1C18D, but not Rac1C18S, shows greatly enhanced nucleotide exchange, similar to that observed for Rac1 oxidation by glutathione. We employed Rac1C18D in cell-based studies to assess whether this fast-cycling variant, which mimics Rac1 oxidation by glutathione, affects Rac1 activity and function. Expression of Rac1C18D in Swiss 3T3 cells showed greatly enhanced GTP-bound Rac1 relative to Rac1WT and the redox-insensitive Rac1C18S variant. Moreover, expression of Rac1C18D in HEK-293T cells greatly promoted lamellipodia formation. Our results suggest that Rac1 oxidation at Cys18 is a novel posttranslational modification that

Redox Regulation in Amyotrophic Lateral Sclerosis

Science.gov (United States)

Parakh, Sonam; Spencer, Damian M.; Halloran, Mark A.; Soo, Kai Y.; Atkin, Julie D.

2013-01-01

Amyotrophic lateral sclerosis (ALS) is a neurodegenerative disease that results from the death of upper and lower motor neurons. Due to a lack of effective treatment, it is imperative to understand the underlying mechanisms and processes involved in disease progression. Regulations in cellular reduction/oxidation (redox) processes are being increasingly implicated in disease. Here we discuss the possible involvement of redox dysregulation in the pathophysiology of ALS, either as a cause of cellular abnormalities or a consequence. We focus on its possible role in oxidative stress, protein misfolding, glutamate excitotoxicity, lipid peroxidation and cholesterol esterification, mitochondrial dysfunction, impaired axonal transport and neurofilament aggregation, autophagic stress, and endoplasmic reticulum (ER) stress. We also speculate that an ER chaperone protein disulphide isomerase (PDI) could play a key role in this dysregulation. PDI is essential for normal protein folding by oxidation and reduction of disulphide bonds, and hence any disruption to this process may have consequences for motor neurons. Addressing the mechanism underlying redox regulation and dysregulation may therefore help to unravel the molecular mechanism involved in ALS. PMID:23533690

Zero modes in discretized light-front quantization

International Nuclear Information System (INIS)

Martinovic, E.

1997-01-01

The current understanding of the role of bosonic zero modes in field-theoretical models quantized at the equal light-front time is reviewed. After a brief discussion of the main features of the light-front field theories - in particular the simplicity of the physical vacuum - the light-front canonical formalism for the quantum electrodynamics and the Yukawa model is sketched. The zero mode of Maskawa and Yamawaki is reviewed. Reasons for the appearance of the constrained and/or dynamical zero modes are explained along with the subtleties of the gauge fixing in presence of boundary conditions. Perturbative treatment of the corresponding constraint equations in the Yukawa model and quantum electrodynamics (3+1) is outlined. The next topic is the manifestation of the symmetry breaking in the light-front field theory. A pattern of multiple solutions to the zero-mode constraint equations replacing physical picture of multiple vacua of the conventionally quantized field theories is illustrated on an example of 2-dimensional theory. The importance of a (regularized) constrained zero mode of the pion field for the consistency of the Nambu-Goldstone phase of the discretized light-front linear a/model is demonstrated. Finally, a non-trivial physical vacuum based on the dynamical zero mode is constructed for the two-dimensional light-front quantum electrodynamics. (authors)

Role of ionization fronts in the colliding wind model of planetary nebulae

International Nuclear Information System (INIS)

Giuliani, J.L. Jr.

1981-01-01

A similarity transformation is used to study the expansion of a planetary nebula which is driven by a fast stellar wind as well as an expanding H II region. The undisturbed gas is taken to be the remnant of a slow, red giant wind. The present analysis improves upon Kwok, Purton, and FitzGerald's colliding wind model for the formation of planetary nebulae since it includes the dynamical influence of ionization fronts, and calculates the variation of velocity and density within the flow

Redox active molecules cytochrome c and vitamin C enhance heme-enzyme peroxidations by serving as non-specific agents for redox relay

International Nuclear Information System (INIS)

Gade, Sudeep Kumar; Bhattacharya, Subarna; Manoj, Kelath Murali

2012-01-01

Highlights: ► At low concentrations, cytochrome c/vitamin C do not catalyze peroxidations. ► But low levels of cytochrome c/vitamin C enhance diverse heme peroxidase activities. ► Enhancement positively correlates to the concentration of peroxide in reaction. ► Reducible additives serve as non-specific agents for redox relay in the system. ► Insight into electron transfer processes in routine and oxidative-stress states. -- Abstract: We report that incorporation of very low concentrations of redox protein cytochrome c and redox active small molecule vitamin C impacted the outcome of one-electron oxidations mediated by structurally distinct plant/fungal heme peroxidases. Evidence suggests that cytochrome c and vitamin C function as a redox relay for diffusible reduced oxygen species in the reaction system, without invoking specific or affinity-based molecular interactions for electron transfers. The findings provide novel perspectives to understanding – (1) the promiscuous role of cytochrome b 5 in the metabolism mediated by liver microsomal xenobiotic metabolizing systems and (2) the roles of antioxidant molecules in affording relief from oxidative stress.

Accelerated redox reaction between chromate and phenolic pollutants during freezing.

Science.gov (United States)

Ju, Jinjung; Kim, Jaesung; Vetráková, Ľubica; Seo, Jiwon; Heger, Dominik; Lee, Changha; Yoon, Ho-Il; Kim, Kitae; Kim, Jungwon

2017-05-05

The redox reaction between 4-chlorophenol (4-CP) and chromate (Cr(VI)) (i.e., the simultaneous oxidation of 4-CP by Cr(VI) and reduction of Cr(VI) by 4-CP) in ice (i.e., at -20°C) was compared with the corresponding reaction in water (i.e., at 25°C). The redox conversion of 4-CP/Cr(VI), which was negligible in water, was significantly accelerated in ice. This accelerated redox conversion of 4-CP/Cr(VI) in ice is ascribed to the freeze concentration effect occurring during freezing, which excludes solutes (i.e., 4-CP and Cr(VI)) and protons from the ice crystals and subsequently concentrates them in the liquid brine. The concentrations of Cr(VI) and protons in the liquid brine were confirmed by measuring the optical image and the UV-vis absorption spectra of cresol red (CR) as a pH indicator of frozen solution. The redox conversion of 4-CP/Cr(VI) was observed in water when the concentrations of 4-CP/protons or Cr(VI)/protons increased by 100/1000-fold. These results corroborate the freeze concentration effect as the reason for the accelerated redox conversion of 4-CP/Cr(VI) in ice. The redox conversion of various phenolic pollutants/Cr(VI) and 4-CP/Cr(VI) in real wastewater was successfully achieved in ice, which verifies the environmental relevance and importance of freezing-accelerated redox conversion of phenolic pollutants/Cr(VI) in cold regions. Copyright © 2017 Elsevier B.V. All rights reserved.

Redox induces diverse effects on recombinant human wild-type PrP and mutated PrP with inserted or deleted octarepeats.

Science.gov (United States)

Shi, Qi; Chen, Cao; Zhang, Bao-Yun; Zhou, Wei; Xiao, Kang; Dong, Xiao-Ping

2018-04-01

Normal prion protein (PrP) contains two cysteines at amino acids 179 and 214, which may form intra‑ and interpeptide disulfide bonds. To determine the possible effects of this disulfide bridge on the biochemical features of PrP, prokaryotic recombinant human wild‑type PrP (PG5), and mutated PrPs with seven extra octarepeats (PG12) or with all five octarepeats removed (PG0), were subjected to redox in vitro. Sedimentation assays revealed a large portion of aggregation in redox‑treated PG5, but not in PG0 and PG12. Circular dichroism analysis detected increased β‑sheet and decreased α‑helix in PG5 subjected to redox, increased random‑coil and decreased β‑sheet in PG0, and increased random‑coil, but limited changes to β‑sheet content, in PG12. Thioflavin T fluorescence tests indicated that fluorescent value was increased in PG5 subjected to redox. In addition, proteinase K (PK) digestions indicated that PK resistance was stronger in PG12 and PG0 compared with in PG5; redox enhanced the PK resistance of all three PrP constructs, particularly PG0 and PG12. These data indicated that formation of a disulfide bond induces marked alterations in the secondary structure and biochemical characteristics of PrP. In addition, the octarepeat region within the PrP peptide markedly influences the effects of redox on the biochemical phenotypes of PrP, thus highlighting the importance of the number of octarepeats in the biological functions of PrP.

Supersymmetric Properties of Hadron Physics from Light-Front Holography and Superconformal Algebra and other Advances in Light-Front QCD

Science.gov (United States)

Brodsky, Stanley J.

2018-05-01

Light-front holography, together with superconformal algebra, have provided new insights into the physics of color confinement and the spectroscopy and dynamics of hadrons. As shown by de Alfaro, Fubini and Furlan, a mass scale can appear in the equations of motion without affecting the conformal invariance of the action if one adds a term to the Hamiltonian proportional to the dilatation operator or the special conformal operator. If one applies the procedure of de Alfaro et al. to the frame-independent light-front Hamiltonian, it leads uniquely to a confining q \\bar{q} potential κ ^4 ζ ^2, where ζ ^2 is the light-front radial variable related in momentum space to the q \\bar{q} invariant mass. The same result, including spin terms, is obtained using light-front holography—the duality between the front form and AdS_5, the space of isometries of the conformal group—if one modifies the action of AdS_5 by the dilaton e^{κ ^2 z^2} in the fifth dimension z. When one generalizes this procedure using superconformal algebra, the resulting light-front eigensolutions lead to a a unified Regge spectroscopy of meson, baryon, and tetraquarks, including supersymmetric relations between their masses and their wavefunctions. One also predicts hadronic light-front wavefunctions and observables such as structure functions, transverse momentum distributions, and the distribution amplitudes. The mass scale κ underlying confinement and hadron masses can be connected to the parameter Λ_{\\overline{MS}} in the QCD running coupling by matching the nonperturbative dynamics to the perturbative QCD regime. The result is an effective coupling α _s(Q^2) defined at all momenta. The matching of the high and low momentum transfer regimes determines a scale Q_0 which sets the interface between perturbative and nonperturbative hadron dynamics. I also discuss a number of applications of light-front phenomenology.

Redox Flow Batteries, Hydrogen and Distributed Storage.

Science.gov (United States)

Dennison, C R; Vrubel, Heron; Amstutz, Véronique; Peljo, Pekka; Toghill, Kathryn E; Girault, Hubert H

2015-01-01

Social, economic, and political pressures are causing a shift in the global energy mix, with a preference toward renewable energy sources. In order to realize widespread implementation of these resources, large-scale storage of renewable energy is needed. Among the proposed energy storage technologies, redox flow batteries offer many unique advantages. The primary limitation of these systems, however, is their limited energy density which necessitates very large installations. In order to enhance the energy storage capacity of these systems, we have developed a unique dual-circuit architecture which enables two levels of energy storage; first in the conventional electrolyte, and then through the formation of hydrogen. Moreover, we have begun a pilot-scale demonstration project to investigate the scalability and technical readiness of this approach. This combination of conventional energy storage and hydrogen production is well aligned with the current trajectory of modern energy and mobility infrastructure. The combination of these two means of energy storage enables the possibility of an energy economy dominated by renewable resources.

Muon front end for the neutrino factory

CERN Document Server

Rogers, C T; Prior, G; Gilardoni, S; Neuffer, D; Snopok, P; Alekou, A; Pasternak, J

2013-01-01

In the neutrino factory, muons are produced by firing high-energy protons onto a target to produce pions. The pions decay to muons and pass through a capture channel known as the muon front end, before acceleration to 12.6 GeV. The muon front end comprises a variable frequency rf system for longitudinal capture and an ionization cooling channel. In this paper we detail recent improvements in the design of the muon front end.

Potential redox behaviour on industrial wastes treatment; Evolucion del potencial redox en tratamiento y depuracion industrial de aguas

Energy Technology Data Exchange (ETDEWEB)

Marin Galvin, R.; rodriguez Mellado, J. M.; Ruiz Montoya, M.; Jimenez Gamero, C. [Departamento Quimica Fisica y Termodinamica aplicada, Facultad de ciencias, Universidad de Cordoba (Spain)

1995-12-31

A study over the behaviour of redox potential in waters and wastewaters under industrial treatment processes has been carried out. In both cases, the potential-time curves obtained were in a logarithmical shape being more strongly distorted when the waters contained more dissolved and suspended compounds. Oxygen fundamentally leads the redox state in wastewaters, although ozone and chlorine almost oxygen lead the redox potential in raw waters intended to drinking water production. In this way, by increasing 210 m V the E{sub H} value of water or maintaining the rH>21.8 it can be industrially sterilized the drinking water. On the other hand, increases of 350 mV in the EH values from wastewaters influent to plant to the treated waters, allowed discarding 450 mg/l of DQO and 9 mg/l of NH{sub 3} from the former. Finally, the exploitation of the Wastewaters Treatment Plant by regulation of the E{sub H} values can suppose a good practice. (Author) 14 refs.

Redox pioneer:Professor Christine Helen Foyer.

Science.gov (United States)

Del Río, Luis A

2011-10-15

Dr. Christine Foyer (B.Sc. 1974; Ph.D. 1977) is recognized here as a Redox Pioneer because she has published an article on redox biology that has been cited more than 1000 times, 4 other articles that have been cited more than 500 times, and a further 32 articles that have been each cited more than 100 times. During her Ph.D. at the Kings College, University of London, United Kingdom, Dr. Foyer discovered that ascorbate and glutathione and enzymes linking NADPH, glutathione, and ascorbate are localized in isolated chloroplast preparations. These observations pioneered the discovery of the ascorbate-glutathione cycle, now known as Foyer-Halliwell-Asada pathway after the names of the three major contributors, a crucial mechanism for H(2)O(2) metabolism in both animals and plants. Dr. Foyer has made a very significant contribution to our current understanding of the crucial roles of ascorbate and glutathione in redox biology, particularly in relation to photosynthesis, respiration, and chloroplast and mitochondrial redox signaling networks. "My view is that science…is compulsive and you have to keep with it all the time and not get despondent when things do not work well. Being passionate about science is what carries you through the hard times so that it isn't so much work, as a hobby that you do for a living. It is the thrill of achieving a better understanding and finding real pleasure in putting new ideas together, explaining data and passing on knowledge that keeps you going no matter what!" --Prof. Christine Helen Foyer.

RPC performance vs. front-end electronics

International Nuclear Information System (INIS)

Cardarelli, R.; Aielli, G.; Camarri, P.; Di Ciaccio, A.; Di Stante, L.; Liberti, B.; Pastori, E.; Santonico, R.; Zerbini, A.

2012-01-01

Moving the amplification from the gas to the front-end electronics was a milestone in the development of Resistive Plate Chambers. Here we discuss the historical evolution of RPCs and we show the results obtained with newly developed front-end electronics with threshold in the fC range.

Nuclear Physics on the Light Front

OpenAIRE

Miller, Gerald A.

1999-01-01

High energy scattering experiments involving nuclei are typically analyzed in terms of light front variables. The desire to provide realistic, relativistic wave functions expressed in terms of these variables led me to try to use light front dynamics to compute nuclear wave functions. The progress is summarized here.

Differentiating cancerous from normal breast tissue by redox imaging

Science.gov (United States)

Xu, He N.; Tchou, Julia; Feng, Min; Zhao, Huaqing; Li, Lin Z.

2015-02-01

Abnormal metabolism can be a hallmark of cancer occurring early before detectable histological changes and may serve as an early detection biomarker. The current gold standard to establish breast cancer (BC) diagnosis is histological examination of biopsy. Previously we have found that pre-cancer and cancer tissues in animal models displayed abnormal mitochondrial redox state. Our technique of quantitatively measuring the mitochondrial redox state has the potential to be implemented as an early detection tool for cancer and may provide prognostic value. We therefore in this present study, investigated the feasibility of quantifying the redox state of tumor samples from 16 BC patients. Tumor tissue aliquots were collected from both normal and cancerous tissue from the affected cancer-bearing breasts of 16 female patients (5 TNBC, 9 ER+, 2 ER+/Her2+) shortly after surgical resection. All specimens were snap-frozen with liquid nitrogen on site and scanned later with the Chance redox scanner, i.e., the 3D cryogenic NADH/oxidized flavoprotein (Fp) fluorescence imager. Our preliminary results showed that both NADH and Fp (including FAD, i.e., flavin adenine dinucleotide) signals in the cancerous tissues roughly tripled to quadrupled those in the normal tissues (pcancerous tissues than in the normal ones (pcancer and non-cancer breast tissues in human patients and this novel redox scanning procedure may assist in tissue diagnosis in freshly procured biopsy samples prior to tissue fixation. We are in the process of evaluating the prognostic value of the redox imaging indices for BC.

Characterization of plasma thiol redox potential in a common marmoset model of aging

Directory of Open Access Journals (Sweden)

James R. Roede

2013-01-01

Full Text Available Due to its short lifespan, ease of use and age-related pathologies that mirror those observed in humans, the common marmoset (Callithrix jacchus is poised to become a standard nonhuman primate model of aging. Blood and extracellular fluid possess two major thiol-dependent redox nodes involving cysteine (Cys, cystine (CySS, glutathione (GSH and glutathione disulfide (GSSG. Alteration in these plasma redox nodes significantly affects cellular physiology, and oxidation of the plasma Cys/CySS redox potential (EhCySS is associated with aging and disease risk in humans. The purpose of this study was to determine age-related changes in plasma redox metabolites and corresponding redox potentials (Eh to further validate the marmoset as a nonhuman primate model of aging. We measured plasma thiol redox states in marmosets and used existing human data with multivariate adaptive regression splines (MARS to model the relationships between age and redox metabolites. A classification accuracy of 70.2% and an AUC of 0.703 were achieved using the MARS model built from the marmoset redox data to classify the human samples as young or old. These results show that common marmosets provide a useful model for thiol redox biology of aging.

A novel iron-lead redox flow battery for large-scale energy storage

Science.gov (United States)

Zeng, Y. K.; Zhao, T. S.; Zhou, X. L.; Wei, L.; Ren, Y. X.

2017-04-01

The redox flow battery (RFB) is one of the most promising large-scale energy storage technologies for the massive utilization of intermittent renewables especially wind and solar energy. This work presents a novel redox flow battery that utilizes inexpensive and abundant Fe(II)/Fe(III) and Pb/Pb(II) redox couples as redox materials. Experimental results show that both the Fe(II)/Fe(III) and Pb/Pb(II) redox couples have fast electrochemical kinetics in methanesulfonic acid, and that the coulombic efficiency and energy efficiency of the battery are, respectively, as high as 96.2% and 86.2% at 40 mA cm-2. Furthermore, the battery exhibits stable performance in terms of efficiencies and discharge capacities during the cycle test. The inexpensive redox materials, fast electrochemical kinetics and stable cycle performance make the present battery a promising candidate for large-scale energy storage applications.

The Redox Flow System for solar photovoltaic energy storage

Science.gov (United States)

Odonnell, P.; Gahn, R. F.; Pfeiffer, W.

1976-01-01

The interfacing of a Solar Photovoltaic System and a Redox Flow System for storage was workable. The Redox Flow System, which utilizes the oxidation-reduction capability of two redox couples, in this case iron and titanium, for its storage capacity, gave a relatively constant output regardless of solar activity so that a load could be run continually day and night utilizing the sun's energy. One portion of the system was connected to a bank of solar cells to electrochemically charge the solutions, while a separate part of the system was used to electrochemically discharge the stored energy.