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Sample records for eh redox potential

  1. Methods of simulating low redox potential (Eh) for a basalt repository

    International Nuclear Information System (INIS)

    Jantzen, C.M.

    1983-01-01

    Basalt groundwaters have inherently low redox potentials, approximately -0.4V, which can be measured with platinum electrodes, but are difficult to reproduce during leaching experiments. In the presence of deionized water, crushed basalt reaches the measured Eh-pH values of a basalt repository. Other waste package components, such as iron, will interact with groundwater in different ways under oxic or anoxic conditions since the presence of any redox active solid will affect the groundwater Eh. 26 references, 4 figures

  2. Practical improvements in soil redox potential (Eh) measurement for characterisation of soil properties. Application for comparison of conventional and conservation agriculture cropping systems

    Energy Technology Data Exchange (ETDEWEB)

    Husson, Olivier, E-mail: Olivier.husson@cirad.fr [CIRAD/PERSYST/UPR 115 AIDA and AfricaRice Centre, 01 BP 2031 Cotonou (Benin); Husson, Benoit, E-mail: bhusson@ideeaquaculture.com [IDEEAQUACULTURE, Parc Euromédecine 2, 39 Rue Jean Giroux, 34080 Montpellier (France); Brunet, Alexandre, E-mail: brunet.alexandre@outlook.com [CIRAD/US 49 Analyse, Avenue Agropolis, TA B-49/01, 34398 Montpellier Cedex (France); Babre, Daniel, E-mail: Daniel.babre@cirad.fr [CIRAD/US 49 Analyse, Avenue Agropolis, TA B-49/01, 34398 Montpellier Cedex (France); Alary, Karine, E-mail: Karine.alary@cirad.fr [CIRAD/US 49 Analyse, Avenue Agropolis, TA B-49/01, 34398 Montpellier Cedex (France); Sarthou, Jean-Pierre, E-mail: sarthou@ensat.fr [ENSAT/INRA/INP UMR AGIR. BP 52627, Chemin de Borde Rouge, 31326 Castanet-Tolosan Cedex (France); Charpentier, Hubert, E-mail: Charpentier.hub@wanadoo.fr [La Boisfarderie, Brives 36100 (France); Durand, Michel, E-mail: earldeslacs@orange.fr [Le Cazals, Castanet 81 150 (France); Benada, Jaroslav, E-mail: benada@vukrom.cz [Agrotest fyto, Kromeriz Institute, Havlíckova 2787, 76701 Kromeriz (Czech Republic); Henry, Marc, E-mail: henry@unistra.fr [UMR CNRS/UdS 7140, Université de Strasbourg, Institut Le Bel, 4, rue Blaise Pascal, CS 90032, Strasbourg 67081 (France)

    2016-02-04

    The soil redox potential (Eh) can provide essential information to characterise soil conditions. In practice, however, numerous problems may arise regarding: (i) Eh determination in soils, especially aerobic soils, e.g. variations in the instrumentation and methodology for Eh measurement, high spatial and temporal Eh variability in soils, irreversibility of the redox reaction at the surface electrode, chemical disequilibrium; and (ii) measurement interpretation. This study aimed at developing a standardised method for redox potential measurement in soils, in order to use Eh as a soil quality indicator. This paper presents practical improvements in soil Eh measurement, especially regarding the control of electromagnetic perturbations, electrode choice and preparation, soil sample preparation (drying procedure) and soil:water extraction rate. The repeatability and reproducibility of the measurement method developed are highlighted. The use of Eh corrected at pH7, pe+pH or rH{sub 2}, which are equivalent notions, is proposed to facilitate interpretation of the results. The application of this Eh measurement method allows characterisation of soil conditions with sufficient repeatability, reproducibility and accuracy to demonstrate that conservation agriculture systems positively alter the protonic and electronic balance of soil as compared to conventional systems. - Highlights: • Electromagnetic fields can dramatically perturb soil Eh measurement. • Our method overcomes the main difficulties in soil Eh measurement. • Accurate and reproducible measurement of mean soil Eh are achieved. • Eh{sub pH7}, pe+pH and rH{sub 2} are equivalent notions characterising electron activity. • Agricultural practices alter soil protonic and electronic characteristics.

  3. Laboratory Eh simulations in relation to the Redox conditions in natural granitic groundwaters

    International Nuclear Information System (INIS)

    Wikberg, P.

    1992-01-01

    Redox conditions are one of the prime parameters affecting the sorption of radionuclides released from a nuclear waste repository. The swedish granitic groundwaters are all reducing from a depth of approximately 100 m, the vast majority already from a depth of a few tens of metres. The contents of ferrous iron reaches a maximum at the same depth due to the weathering of iron rich minerals. At greater depths the iron content decreases while sulphide contents increases. The redox buffering capacity (in groundwater) lies mainly in the rock. The contents of iron, sulphide and manganese constitute the buffer in the groundwater. The redox potential (Eh) is controlled by the iron system in the groundwater and the rock. Sulphate is not involved in the groundwater redox processes. Laboratory simulations of the groundwater rock interactions with respect to the redox conditions have been realized, but there is still a difference compared to the natural system. This difference is due to the fact that traces of oxygen diffuses into the laboratory system causing a continuous oxidation. 20 refs., 4 figs., 1 tab

  4. Investigation of Eh, pH and corrosion potential of steel in anoxic groundwater

    Energy Technology Data Exchange (ETDEWEB)

    Peat, R.; Brabon, S.; Fennell, P.A.H.; Rance, A.P.; Smart, N.R. [AEA Technology (United Kingdom)

    2001-01-01

    SKB intend to dispose of the spent nuclear fuel produced by Sweden's eleven nuclear reactors by encapsulating it in corrosion-resistant copper canisters containing a cast iron or carbon steel insert. After encapsulation, the fuel will be transported to a geological repository, where the containers will be deposited at a depth of 500 to 700 m in granitic rock and surrounded by a bentonite clay backfill material. If, or when the copper corrosion shield fails, the iron insert will be in contact with oxygen-free water and hydrogen-producing, anaerobic corrosion will start. SKB have carried out modelling calculations of the oxidising power (Eh) of groundwater and wished to confirm the results by carrying out experimental measurements. The objective of the work described in this report was to demonstrate the feasibility of monitoring Eh, pH and corrosion potential in a cell where anaerobic corrosion of steel in artificial groundwater was occurring. To this end, gas cells similar to those used previously for anaerobic corrosion rate measurements were used as the basis for the design of an electrochemical cell. The cell incorporated electrodes to provide an in situ measurement of the redox potential, Eh, the pH and the corrosion potential of carbon steel. The main stages of the work were: Design of the electrochemical cell; Preparation of silver-silver chloride and calomel reference electrodes; Calibration of the reference electrodes and commercial glass pH electrodes against a standard hydrogen electrode; Assembly of the test cell under anoxic conditions; Monitoring the cell before and after the addition of steel wires to the test solution. Details of the design of the test cell and the experimental procedures used are described. Two cells were set up. The first employed a silver-silver chloride reference electrode, which was failed after approximately 400 hours, and the second cell therefore used a calomel reference electrode. The results of the electrode

  5. 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.

  6. Do microbial exudates control EH electrode measurements?

    Science.gov (United States)

    Markelova, E.; Parsons, C. T.; Smeaton, C. M.; Van Cappellen, P.

    2017-12-01

    Redox electrodes are widely used as simple, inexpensive monitoring devices to rapidly measure redox potentials (EH) of waterlogged soils, sediments, and aquifers. While a variety of physicochemical and biogeochemical factors have been involved to explain measured EH values, the role of microorganisms remains comparatively understudied and uncertain. Besides catalyzing many inorganic redox reactions (e.g., nitrate reduction), microorganisms produce a variety of redox-active organic compounds (e.g., NAD+/NADH, GSSG/2GSH, FAD/FADH2), which can be released into the surrounding environment via active secretion, passive diffusion, or cell lysis. To isolate different microbial effects on EH measurements, we performed batch experiments using S. oneidensis MR-I as a model heterotrophic microorganism and flavins as example microbial exudates [1]. We monitored EH and pH along with flavin production (fluorescence measurements) during dissimilatory nitrate reduction to ammonium (DNRA). Dissolved flavins increased to 0.2 mM (riboflavin equivalent) under anoxic conditions during complete consumption of 1 mM nitrate by DNRA at pH 7.4 and 30 °C over 80 hours. The observed redox cascade from +255 to -250 mV did not follow the EH predicted for the reduction of NO3- to NO2- and NO2- to NH4+ by the Nernst equation. However, a set of separate abiotic experiments on the photoreduction of synthetic flavins (LMC, RF, FMN, and FAD, Sigma Aldrich) under the same conditions indicated that measured EH values are buffered at +270 ± 20 mV and -230 ± 50 mV when oxidized and reduced flavin species dominate, respectively. Moreover, based on the temporal changes in EH, we speculate that NO3- reduction by S. oneidensis consumes reduced flavins (i.e., NO3- accepts electrons from reduced flavins) and generates oxidized flavins, thus buffering EH at +255 mV. By contrast, NO2- reduction to NH4+ is independent of flavin speciation, which leads to the accumulation of reduced flavins in the solution and

  7. 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 ...

  8. 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

  9. 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

  10. Measurement of Redox Potential in Nanoecotoxicological Investigations

    Directory of Open Access Journals (Sweden)

    Ratna Tantra

    2012-01-01

    Full Text Available Redox potential has been identified by the Organisation for Economic Co-operation and Development (OECD as one of the parameters that should be investigated for the testing of manufactured nanomaterials. There is still some ambiguity concerning this parameter, i.e., as to what and how to measure, particularly when in a nanoecotoxicological context. In this study the redox potentials of six nanomaterials (either zinc oxide (ZnO or cerium oxide (CeO2 dispersions were measured using an oxidation-reduction potential (ORP electrode probe. The particles under testing differed in terms of their particle size and dispersion stability in deionised water and in various ecotox media. The ORP values of the various dispersions and how they fluctuate relative to each other are discussed. Results show that the ORP values are mainly governed by the type of liquid media employed, with little contributions from the nanoparticles. Seawater was shown to have reduced the ORP value, which was attributed to an increase in the concentration of reducing agents such as sulphites or the reduction of dissolved oxygen concentration. The lack of redox potential value contribution from the particles themselves is thought to be due to insufficient interaction of the particles at the Pt electrode of the ORP probe.

  11. Measurement of redox potential in nanoecotoxicological investigations.

    Science.gov (United States)

    Tantra, Ratna; Cackett, Alex; Peck, Roger; Gohil, Dipak; Snowden, Jacqueline

    2012-01-01

    Redox potential has been identified by the Organisation for Economic Co-operation and Development (OECD) as one of the parameters that should be investigated for the testing of manufactured nanomaterials. There is still some ambiguity concerning this parameter, i.e., as to what and how to measure, particularly when in a nanoecotoxicological context. In this study the redox potentials of six nanomaterials (either zinc oxide (ZnO) or cerium oxide (CeO(2))) dispersions were measured using an oxidation-reduction potential (ORP) electrode probe. The particles under testing differed in terms of their particle size and dispersion stability in deionised water and in various ecotox media. The ORP values of the various dispersions and how they fluctuate relative to each other are discussed. Results show that the ORP values are mainly governed by the type of liquid media employed, with little contributions from the nanoparticles. Seawater was shown to have reduced the ORP value, which was attributed to an increase in the concentration of reducing agents such as sulphites or the reduction of dissolved oxygen concentration. The lack of redox potential value contribution from the particles themselves is thought to be due to insufficient interaction of the particles at the Pt electrode of the ORP probe.

  12. 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.

  13. 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)

  14. Iron and manganese in oxide minerals and in glasses: preliminary consideration of Eh buffering potential at Yucca Mountain, Nevada

    International Nuclear Information System (INIS)

    Caporuscio, F.A.; Vaniman, D.T.

    1985-04-01

    The tuffs of Yucca Mountain at the Nevada Test Site are currently under investigation as a possible deep burial site for high-level radioactive waste disposal. One of the main concerns is the effect of oxidizing groundwater on the transport of radionuclides. Rock components that may affect the oxygen content of groundwater include Fe-Ti oxides, Mn oxides, and glasses that contain ferrous iron. Some phenocryst Fe-Ti oxides at Yucca Mountain are in reduced states, whereas groundmass Fe-Ti oxides have been oxidized to hematite, rutile, and pseudobrookite (Fe 3+ -bearing phases) exclusively. Estimates of Fe 2+ -bearing oxides indicate that less than 0.33 vol% phenocrysts is available to act as solid buffering agents of Eh. Of this percentage, significant amounts of Fe-Ti oxides are isolated from effective interaction with groundwater because they occur in densely welded, devitrified tuffs that have low interstitial permeability. Manganese oxides occur primarily along fractures in the ash-flow tuffs. Because the Mn oxides are concentrated along the same pathways (fractures) where transport has occurred in the past, these small volume percentages could act as buffers. However, the oxidation states of actual Mn-oxide phases are high (Mn 4+ ), and these minerals have virtually no potential for reducing groundwater Eh. Manganese oxides may even act as oxidizing agents. However, regardless of their poor capabilities as reducing agents, the Mn oxides could be important as sorbents of heavy metals at Yucca Mountain. The lack of accessible, pristine Fe-Ti oxides and the generally high oxidation states of Mn oxides seem to rule out these oxides as Eh buffers of the Yucca Mountain groundwater system. Reduction of ferrous iron within glassy tuffs may have some effect on Eh, but further study is needed. At present it is prudent to assume that minerals and glasses have little or no capacity for reducing oxygen-rich groundwater at Yucca Mountain. 25 refs., 3 figs., 12 tabs

  15. 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

  16. 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.

  17. Redox potential dynamics in a grassed swale used for storage and treatment

    Science.gov (United States)

    Vorenhout, Michel; Boogaard, Floris Cornelis

    2016-04-01

    Treatment wetlands are used to remove pollutants from water. Most swales are designed to infiltrate stormwater into the subsurface. A combination of both functions can help to enhance water quality and reduce flooding risks in urban areas. The chemical forms and possible removal of pollutants such as nitrate and heavy metals in wetlands are highly dependent on the redox conditions. The redox conditions are expected to be highly dynamic and dependent on water levels and flow. We studied the correlation between these factors in an urban grassed swale system, and show that more factors play a role in these systems than water levels alone. The study system is located in the World Heritage site "Bryggen" in the city of Bergen, Norway. It consists of a series of SUDS, a socalled treatment train. The system is fed by storm water, which is at first stored in a rain garden then led to grassed swales. Water infiltrates into the subsurface in the swales. The reason for implementation of the system at this site is the protection of the highly organic archaeological layers at the site, which requires reduced conditions. Swales 1 and 2 were equipped with pressure loggers and multi-level redox and temperature probes (-2, -5, -10 and -20cm from surface). Redox and temperature probes were connected to a HYPNOS system. Measurements were taken for more than 1 year at 15 minute interval. A weather station supplemented the dataset with precipitation measurements. The redox potential in the swales show a strong correlation with water level. The regularly flooded swale 2 shows frequent anoxic events (Eh < 200mV) where as swale 1 shows oxic conditions (Eh = 650mV) throughout the same measurement period. Swale 1 has fewer flooding events than Swale 2 and a more coarse soil with less organic matter than swale 2. These redox results are as expected given the local conditions, and show that redox conditions are localised phenomena that depend on local soil conditions. Analysis of the redox

  18. Integrating life cycle assessment into managing potential EHS risks of engineered nanomaterials: reviewing progress to date

    International Nuclear Information System (INIS)

    Walker, William C.; Bosso, Christopher J.; Eckelman, Matthew; Isaacs, Jacqueline A.; Pourzahedi, Leila

    2015-01-01

    The 2011 National Nanotechnology Initiative’s Environmental Health and Safety Research Strategy stressed the need for research to integrate life cycle considerations into risk management and, then, to better integrate risk assessment into decisionmaking on environmental, health, and safety (EHS) dimensions of nanomanufacturing. This paper reviews scholarly articles published 2010–2015 that in some way apply life cycle analysis to nanotechnology to assess the extent to which current research reflects the priorities lain out in the NNI report. As the NNI’s focus was primarily on the “responsible development of nanotechnology” we also focus our examination on the ways in which LCA, in concert with other methodologies, can provide utility to decision makers facing the challenge of implementing that broad goal. We explore some of the challenges and opportunities inherent in using LCA, a tool built to optimize manufacturing decisions, as a guide for policy formulation or tool for policy implementation

  19. Integrating life cycle assessment into managing potential EHS risks of engineered nanomaterials: reviewing progress to date

    Energy Technology Data Exchange (ETDEWEB)

    Walker, William C.; Bosso, Christopher J., E-mail: c.bosso@neu.edu [Northeastern University, School of Public Policy and Urban Affairs (United States); Eckelman, Matthew [Northeastern University, Department of Civil and Environmental Engineering (United States); Isaacs, Jacqueline A. [Northeastern University, Department of Mechanical and Industrial Engineering (United States); Pourzahedi, Leila [Northeastern University, Department of Civil and Environmental Engineering (United States)

    2015-08-15

    The 2011 National Nanotechnology Initiative’s Environmental Health and Safety Research Strategy stressed the need for research to integrate life cycle considerations into risk management and, then, to better integrate risk assessment into decisionmaking on environmental, health, and safety (EHS) dimensions of nanomanufacturing. This paper reviews scholarly articles published 2010–2015 that in some way apply life cycle analysis to nanotechnology to assess the extent to which current research reflects the priorities lain out in the NNI report. As the NNI’s focus was primarily on the “responsible development of nanotechnology” we also focus our examination on the ways in which LCA, in concert with other methodologies, can provide utility to decision makers facing the challenge of implementing that broad goal. We explore some of the challenges and opportunities inherent in using LCA, a tool built to optimize manufacturing decisions, as a guide for policy formulation or tool for policy implementation.

  20. Development of pH-Eh multi-stat system and its application to uranium chemistry

    International Nuclear Information System (INIS)

    Kirishima, A.; Kitatsuji, Y.; Kimura, T.

    2005-01-01

    Full text of publication follows: Redox potential Eh is one of the most important thermodynamic parameters beside pH and ionic strength. Since uranium, neptunium and plutonium may exist in various oxidation states in aqueous solution, a shift in Eh changes their chemical behavior drastically. The conventional ways of Eh adjustment in a sample solution can be classified into two types, that is, dissolution of suitable amounts of reductants or oxidants, and the electrochemical technique consisting of a potentiostat and electrodes. Coexistence of a certain amount of redox reagents generates Eh values being homogeneous in a whole solution system, while it is difficult to adjust Eh precisely to a designated value by varying the concentration of redox reagents. On the other hand, a potentiostat controls the Eh just on the electrode surface, and, therefore, the Eh of the bulk solution is never controlled when the concentration of the existing redox ion pairs is low. Because of these demerits of both techniques, bulk Eh of the solution system has not been quantitatively controlled so far unlike to pH and ionic strength. When it comes to the thermodynamical aspects of actinide speciation, the factor that governs the system is not an electrode surface Eh but the bulk solution Eh. Therefore, to study actinide reactions occurring with Eh shifts in a given pH region more quantitatively, the present work focuses on the development of a pH-Eh multi-stat system which makes it possible to select Eh and pH values independently and keep them constant. The system consists of two automatic burettes injecting acid or alkaline solution, 1. 10 -3 M of supporting redox ion pairs such as [Fe 3+ /Fe 2+ ] and the bulk potentiostatic electrolysis equipment made up of a potentiostat and a Pt-black working electrode etc. The voltage applied to the working electrode controls the fraction of supporting redox ion pairs, which determine the bulk Eh of the system. A supporting redox ion pair [Fe 2

  1. Redox potential characterization and soil greenhouse gas concentration across a hydrological gradient in a Gulf coast forest

    Science.gov (United States)

    Yu, K.; Faulkner, S.P.; Patrick, W.H.

    2006-01-01

    Soil redox potential (Eh), concentrations of oxygen (O2) and three greenhouse gases (CO2, CH4, and N2O) were measured in the soil profile of a coastal forest at ridge, transition, and swamp across a hydrological gradient. The results delineated a distinct boundary in soil Eh and O2 concentration between the ridge and swamp with essentially no overlap between the two locations. Critical soil Eh to initiate significant CH4 production under this field conditions was about +300 mV, much higher than in the homogenous soils (about -150 mV). The strength of CH4 source to the atmosphere was strong for the swamp, minor for the transition, and negligible or even negative (consumption) for the ridge. Maximum N2O concentration in the soils was found at about Eh +250 mV, and the soil N2O emission was estimated to account for less than 4% for the ridge and transition, and almost negligible for the swamp in the cumulative global warming potential (GWP) of these three gases. The dynamic nature of this study site in response to water table fluctuations across a hydrological gradient makes it an ideal model of impact of future sea level rise to coastal ecosystems. Soil carbon (C) sequestration potential due to increasing soil water content upon sea level rise and subsidence in this coastal forest was likely limited and temporal, and at the expense of increasing soil CH4 production and emission. ?? 2005 Elsevier Ltd. All rights reserved.

  2. 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

  3. 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.

  4. 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

  5. REDOX POTENTIAL AND DYNAMICS OF PROTEIN AND FAT DESTRUCTION DURING STORAGE OF CANNED MEAT IN PIECES

    Directory of Open Access Journals (Sweden)

    V. B. Krylova

    2016-01-01

    Full Text Available The studies on the dynamics of the redox potential of systems and its relationship with the processes of protein and fat destruction in canned foods during their storage are fragmented and not systemized, which highlight their topicality. The aim of the research was to obtain the experimental data on the Eh values and physico-chemical indicators of canned food quality during storage in order to establish their possible correlation. It was shown that the dynamics of Eh, the content of free amino acids and fatty acid fractions in the canned products from beef and pork was different during storage. For example, a decrease in the Eh value and free amino acid content in the canned products from beef had a smooth character, while in the canned products from pork several periods were observed, which differed in the character of the change in the quality indicators.A linear character of the changes in the proportion of fatty acid fractions during storage of the canned products from beef and pork was noticed. With that, both canned food items had an increase in the saturated fatty acid content at the concomitant decrease in the sum of mono- and polyunsaturated fatty acids. The value of an increase in the proportion of saturated fatty acids associated with the process of reduction of mono- and polyunsaturated fatty acids did not depend on the kind of meat in the canned foods and was on average 6%. A decrease in the proportion of mono- and polyunsaturated fatty acids in the canned products from pork was about 4 times more intensive compared to the canned products from beef.

  6. 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

  7. Redox Potentials of Ligands and Complexes – a DFT Approach

    African Journals Online (AJOL)

    NICO

    A review of the limited literature concerned with theoretical ways to predict experimentally measured redox potentials of ligands and ... electrode surface, over-potentials and high solvent resistance, ... A correlation coefficient of 0.969 in the linear relation with ... of E0' were performed in two steps, i.e. calculation of the free.

  8. EH domain of EHD1

    Energy Technology Data Exchange (ETDEWEB)

    Kieken, Fabien; Jovic, Marko; Naslavsky, Naava; Caplan, Steve, E-mail: scaplan@unmc.edu; Sorgen, Paul L. [University of Nebraska Medical Center, Department of Biochemistry and Molecular Biology and Eppley Cancer Center (United States)], E-mail: psorgen@unmc.edu

    2007-12-15

    EHD1 is a member of the mammalian C-terminal Eps15 homology domain (EH) containing protein family, and regulates the recycling of various receptors from the endocytic recycling compartment to the plasma membrane. The EH domain of EHD1 binds to proteins containing either an Asn-Pro-Phe or Asp-Pro-Phe motif, and plays an important role in the subcellular localization and function of EHD1. Thus far, the structures of five N-terminal EH domains from other proteins have been solved, but to date, the structure of the EH domains from the four C-terminal EHD family paralogs remains unknown. In this study, we have assigned the 133 C-terminal residues of EHD1, which includes the EH domain, and solved its solution structure. While the overall structure resembles that of the second of the three N-terminal Eps15 EH domains, potentially significant differences in surface charge and the structure of the tripeptide-binding pocket are discussed.

  9. EH domain of EHD1

    International Nuclear Information System (INIS)

    Kieken, Fabien; Jovic, Marko; Naslavsky, Naava; Caplan, Steve; Sorgen, Paul L.

    2007-01-01

    EHD1 is a member of the mammalian C-terminal Eps15 homology domain (EH) containing protein family, and regulates the recycling of various receptors from the endocytic recycling compartment to the plasma membrane. The EH domain of EHD1 binds to proteins containing either an Asn-Pro-Phe or Asp-Pro-Phe motif, and plays an important role in the subcellular localization and function of EHD1. Thus far, the structures of five N-terminal EH domains from other proteins have been solved, but to date, the structure of the EH domains from the four C-terminal EHD family paralogs remains unknown. In this study, we have assigned the 133 C-terminal residues of EHD1, which includes the EH domain, and solved its solution structure. While the overall structure resembles that of the second of the three N-terminal Eps15 EH domains, potentially significant differences in surface charge and the structure of the tripeptide-binding pocket are discussed

  10. Redox potentials of free radicals. III. Reevaluation of the method

    International Nuclear Information System (INIS)

    Rao, P.S.; Hayon, E.

    1974-01-01

    A reevaluation of the method described in ref 1 and 2 to determine the redox potentials of free radicals (.RH) in water using the techniques of pulse radiolysis and absorption spectrophotometry is presented. This method is based on the dependence of the percentage efficiency for the one-electron oxidation (or reduction) of .RH radicals on the redox potentials E 01 of the electron acceptors, A. The reaction .RH + A → .A - + R + H + (kappa/sub ox/) is not reversible for most radicals under the experimental conditions used, and the derived potentials are, therefore, not thermodynamic values. A reinterpretation of the results is made on the basis of the kinetic competition between the above reaction and .RH + A → .RHA (kappa/sub add/) (radical adducts). Based on kappa/ sub ox/ and kappa/sub add/, it is concluded that the observed experimental ''titration'' curves do represent a measure of the redox property of the free radicals. From the midpoint on the curves, the kinetic potential, E/sub kappa/ 01 : of the free radicals can be derived based on the known two-electron redox potentials of the electron acceptors. These and other questions are discussed. (U.S.)

  11. 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.

  12. 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.

  13. The fairytale of the GSSG/GSH redox potential.

    Science.gov (United States)

    Flohé, Leopold

    2013-05-01

    The term GSSG/GSH redox potential is frequently used to explain redox regulation and other biological processes. The relevance of the GSSG/GSH redox potential as driving force of biological processes is critically discussed. It is recalled that the concentration ratio of GSSG and GSH reflects little else than a steady state, which overwhelmingly results from fast enzymatic processes utilizing, degrading or regenerating GSH. A biological GSSG/GSH redox potential, as calculated by the Nernst equation, is a deduced electrochemical parameter based on direct measurements of GSH and GSSG that are often complicated by poorly substantiated assumptions. It is considered irrelevant to the steering of any biological process. GSH-utilizing enzymes depend on the concentration of GSH, not on [GSH](2), as is predicted by the Nernst equation, and are typically not affected by GSSG. Regulatory processes involving oxidants and GSH are considered to make use of mechanistic principles known for thiol peroxidases which catalyze the oxidation of hydroperoxides by GSH by means of an enzyme substitution mechanism involving only bimolecular reaction steps. The negligibly small rate constants of related spontaneous reactions as compared with enzyme-catalyzed ones underscore the superiority of kinetic parameters over electrochemical or thermodynamic ones for an in-depth understanding of GSH-dependent biological phenomena. At best, the GSSG/GSH potential might be useful as an analytical tool to disclose disturbances in redox metabolism. This article is part of a Special Issue entitled Cellular Functions of Glutathione. Copyright © 2012 Elsevier B.V. All rights reserved.

  14. The EH network

    DEFF Research Database (Denmark)

    Santolini, E; Salcini, A E; Kay, B K

    1999-01-01

    . Moreover, a number of cellular ligands of the domain have been identified and demonstrated to define a complex network of protein-protein interactions in the eukaryotic cell. Interestingly, many of the EH-containing and EH-binding proteins display characteristics of endocytic "accessory" proteins......, suggesting that the principal function of the EH network is to regulate various steps in endocytosis. In addition, recent evidence suggests that the EH network might work as an "integrator" of signals controlling cellular pathways as diverse as endocytosis, nucleocytosolic export, and ultimately cell...

  15. Redox potential and mobility of contaminant oxyanions (As, Sb, Cr) in argillaceous rock subjected to oxic and anoxic cycles

    International Nuclear Information System (INIS)

    Markelova, Ekaterina

    2016-01-01

    Electron transfer (redox) reactions are key processes in the biogeochemical functioning of natural systems. Redox reactions control the speciation and mobility of major elements (e.g., carbon, nitrogen, iron, and manganese) and environmentally important contaminants such as arsenic (As), antimony (Sb), and chromium (Cr). Nonetheless, the characterization of redox conditions and their effects on biogeochemical cycling and contaminant fate remain incompletely understood. The first part of this thesis focused on the interpretation of redox potential (EH) measurements using results obtained in synthetic biogeochemical systems of increasing complexity under dynamic, redox-oscillating conditions. By progressively combining inorganic solutes, an organic electron donor (lactate), an aqueous electron acceptor (nitrate), a metabolically versatile heterotrophic bacterium (Shewanella oneidensis), and a solid-state electron acceptor (goethite), a full redox cascade from +500 to -350 mV (pH ∼7.4) was reproduced in the laboratory. The experimental results revealed that a conventional Pt redox electrode responds to a variety of physical, chemical, and microbial factors. In particular, the presence of the bacteria always led to lower EH readings. In contrast, measurements of EH in argillaceous suspensions were insensitive to changes in chemical ratios of the redox-sensitive, but non-electro-active, couples, including O 2 /H 2 O, CrO 4 2- /Cr(OH) 3 , NO 3 - /NO 2 - /NH 4 + , HAsO 4 2- /H3AsO 3 , and Sb(OH) 6 - /Sb 2 O 3 . Therefore, EH measurements are shown to have limited usefulness in the natural systems depleted in electro-active redox couples, such as α-FeOOH(s)/Fe 2+ (aq). The second part of the thesis focused on the behavior of oxy-anion contaminants under redox-oscillating conditions in the argillaceous subsoil suspensions. Successive cycles of oxic and anoxic conditions were imposed on the argillaceous suspensions amended with a mixture of oxidized Cr(VI), As(V), Sb

  16. Thermal Coefficient of Redox Potential of Alkali Metals

    Science.gov (United States)

    Fukuzumi, Yuya; Hinuma, Yoyo; Moritomo, Yutaka

    2018-05-01

    The thermal coefficient (α) of redox potential (V) is a significant physical quantity that converts the thermal energy into electric energy. In this short note, we carefully determined α of alkali metals (A = Li and Na) against electrolyte solution. The obtained α is much larger than that expected from the specific heat (CpA) of solid A and depends on electrolyte solution. These observations indicate that the solvent has significant effect on α.

  17. Online monitoring of Mezcal fermentation based on redox potential measurements.

    Science.gov (United States)

    Escalante-Minakata, P; Ibarra-Junquera, V; Rosu, H C; De León-Rodríguez, A; González-García, R

    2009-01-01

    We describe an algorithm for the continuous monitoring of the biomass and ethanol concentrations as well as the growth rate in the Mezcal fermentation process. The algorithm performs its task having available only the online measurements of the redox potential. The procedure combines an artificial neural network (ANN) that relates the redox potential to the ethanol and biomass concentrations with a nonlinear observer-based algorithm that uses the ANN biomass estimations to infer the growth rate of this fermentation process. The results show that the redox potential is a valuable indicator of the metabolic activity of the microorganisms during Mezcal fermentation. In addition, the estimated growth rate can be considered as a direct evidence of the presence of mixed culture growth in the process. Usually, mixtures of microorganisms could be intuitively clear in this kind of processes; however, the total biomass data do not provide definite evidence by themselves. In this paper, the detailed design of the software sensor as well as its experimental application is presented at the laboratory level.

  18. [Determination of the redox potential of water saturated with hydrogen].

    Science.gov (United States)

    Piskarev, I M; Ushkanov, V A; Aristova, N A; Likhachev, P P; Myslivets, T C

    2010-01-01

    It has been shown that the redox potential of water saturated with hydrogen is -500--700 mV. The time of the establishment of the potential is 24 h. The potential somewhat increases with increasing volume of hydrogen introduced to a reservoir with water and practically does not depend on the presence of additions in water, provided these additions are not reduced by hydrogen. The pH value of water does not change after the addition of water. In a glass vessel with a metallic cover resting on the side, no decrease in potential during the 2.5-month storage was observed. In plastic bottles, the content of hydrogen decreased; on storage for more than two weeks, it disappeared almost completely, and as a result, the potential increased after storage for three to four weeks to a level near zero. In an open vessel, the potential remained negative for two days.

  19. Ab initio optical potentials applied to low-energy e-H2 and e-N2 collisions in the linear-algebraic approach

    International Nuclear Information System (INIS)

    Schneider, B.I.; Collins, L.A.

    1983-01-01

    We propose a method for constructing an effective optical potential through which correlation effects can be introduced into the electron-molecule scattering formulation. The optical potential is based on a nonperturbative, Feshbach projection-operator procedure and is evaluated on an L 2 basis. The optical potential is incorporated into the scattering equations by means of a separable expansion, and the resulting scattering equations are solved by a linear-algebraic method based on the integral-equation formulation. We report the results of scattering calculations, which include polarization effects, for low-energy e-H 2 and e-N 2 collisions. The agreement with other theoretical and with experimental results is quite good

  20. The Effects of Fiddler Crabs (Uca sp on C/N Ratio and Redox Potential of Soil in Mangrove Ecosystems

    Directory of Open Access Journals (Sweden)

    Mulyanto Mulyanto

    2017-08-01

    Full Text Available Research has been done in Ketapang mangrove area of  Probolinggo city in months of September-November 2015. The objectives are to observe the fiddler crab community stucture and to analyze the effects of fiddler crabs on C/N ratio and redox potential of soil in mangrove ecosystems. The samples of fiddler crabs were taken during the low tides at 4 station (20 transects with sizes of 1 m2. Data of the fiddler crabs were measured from the soil digging insides the transect. The soil samples were taken from these crab holes wall (at the surface and at the depth of 20 cm, under the holes at the depth of 40 cm as well as from the locations that undwells by these animals at the same depth. The fiddler crab identified are U. Triangularis between 2 – 6 ind/m2, U paradussumieri 1 – 3 ind/m2, U perplexa 14 – 32 ind/m2, U dussumieri 12 – 27 ind/m2 and U. Tetragonon 3 – 6 ind/m2. The diversity is moderate (H = 1.7 and the dominance index was low (C = 0.37. C/N ratio soil were inhabited by fiddler crab between 6 – 14, the undwelled area were 14 – 20. Soil C/N ratio was inhabited by the fiddler crab at the surface and depth of 20 cm in average of 9 cm while at 40 cm in avergae of 12. The low of C/N ratio at surface and depth of 20 cm causing the organic matter turnover faster because the high nitorgen content. Soil potential redox (Eh the undwelled areas was found –0.647 mV, meanwhile the soil Eh in the dwelled areas was positive (0.68 till 0.87 mV. This mean, the decpmposition was occured during aerobic condition and will produce untoxic subtances.

  1. 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

  2. IRON DYNAMICS AND ITS RELATION TO SOIL REDOX POTENTIAL AND PLANT GROWTH IN ACID SULPHATE SOIL OF SOUTH KALIMANTAN, INDONESIA

    Directory of Open Access Journals (Sweden)

    Wahida Annisa

    2017-01-01

    Full Text Available Organic matter has a function to maintain reductive conditions and to chelate toxic elements in acid sulphate soils. The study aimed to assess the dynamics of ferrous iron (Fe2+ in acid sulphate soil and its correlation with soil redox potential (Eh and plant growth. The experiment was arranged in two factorial randomized block design with three replications. The first factor was two types of organic matter: (1 control (without organic matter, (2 rice straw and (3 rush weed (Eleocharis dulcis. The second factor was time of decomposition of organic matter: I1 = 2 weeks, I2 = 4 weeks, I3 = 8 weeks, and I4 = 12 weeks (farmer practice. The results showed that concentration of ferrous iron in the soil ranged from 782 to 1308 mg kg-1 during the rice growing season. The highest constant rate of iron reduction (k F2+ was observed on application of rice straw and rush weed with decomposition time of 8 weeks with the k Fe2+ value of 0.016 and 0.011 per day, respectively, while the ferrous iron formation without organic matter had the k Fe2+ value of 0.077 per day. The ferric iron (Fe3+ reduction served as a function of soil Eh as indicated by the negative correlation of ferrous iron and Eh (r = -0.856*. Organic matter decreased exchangeable iron due to chelating reaction. Iron concentration in roots was negatively correlated with soil soluble iron (r = -0.62*. Application of rice straw decomposed for 8 weeks increased the height of rice plant up to 105.67 cm. The score of Fe2+ toxicity at 8 weeks after planting ranged from 2 to 3, so rice crop did not show iron toxicity symptoms. 

  3. Development of an investigation method for redox condition of rocks by self potential (SP) method

    International Nuclear Information System (INIS)

    Kubota, Kenji; Inohara, Yoshiki; Oyama, Takahiro

    2012-01-01

    One of the major issues in subsurface disposal of low level radioactive wastes is that long term behaviors of sedimentary rocks can be affected by geochemical factors. Redox conditions can affect to corrosion of metal included in artificial barrier or wastes and adsorption characteristics of a nuclide. Therefore, it is necessary to develop a method for evaluating the redox conditions around natural barrier at waste facilities. In general, geochemical properties are acquired by rock samples or water sampling at a borehole. However, there is a possibility not to acquire data we want to evaluate. If geophysical methods are applied, redox conditions can be evaluated widely and briefly. There is a possibility that self potential (SP) and redox conditions have a correlation. So we have conducted self potential method around test caverns where redox front can be observed at the Rokkasho site. The results demonstrated that self potential decreased around redox front. There was a positive correlation between self potential and pH. One of the factors of self potential change is difference of elevation, however, self potential change around redox front was larger than that expected from elevation difference. Zeta potential is one of the important factors for determination of self potential, and it had a correlation with self potential or pH. Therefore, there is a possibility that self potential change occurs by geochemical condition changes around redox front, and redox condition can be detected by self potential method. (author)

  4. Effects of soil type, moisture content, redox potential and methyl bromide fumigation on Kd values of radio-selenium in soil

    International Nuclear Information System (INIS)

    Ashworth, D.J.; Moore, J.; Shaw, G.

    2008-01-01

    Understanding the processes that determine the solid-liquid partitioning (K d value) of Se is of fundamental importance in assessing the risk associated with the disposal of radio-selenium-containing waste. Using a mini-column (rather than batch) approach, K d values for 75 Se were determined over time in relation to soil moisture content (field capacity or saturated), redox potential and methyl bromide fumigation (used to disrupt the soil microbial population) in three contrasting soil types: clay loam, organic and sandy loam. The K d values were generally in the range 50-500 L kg -1 , with mean soil K d increasing with increasing organic matter content. Saturation with water lowered the measured redox potentials in the soils. However, only in the sandy loam soil did redox potential become negative, and this led to an increase in 75 Se K d value in this soil. Comparison of the data with the Eh-pH stability diagram for Se suggested that such strong reduction may have been consistent with the formation of the insoluble Se species, selenide. These findings, coupled with the fact that methyl bromide fumigation had no discernible effect on 75 Se K d value in the sandy loam soil, suggest that geochemical, rather than microbial, processes controlled 75 Se partitioning. The inter-relations between soil moisture content, redox potential and Se speciation should be considered in the modelling and assessment of radioactive Se fate and transport in the environment

  5. Effect of dissolved oxygen on redox potential and milk acidification by lactic acid bacteria isolated from a DL-starter culture.

    Science.gov (United States)

    Larsen, Nadja; Werner, Birgit Brøsted; Vogensen, Finn Kvist; Jespersen, Lene

    2015-03-01

    Milk acidification by DL-starter cultures [cultures containing Lactococcus lactis diacetylactis (D) and Leuconostoc (L) species] depends on the oxidation-reduction (redox) potential in milk; however, the mechanisms behind this effect are not completely clear. The objective of this study was to investigate the effect of dissolved oxygen on acidification kinetics and redox potential during milk fermentation by lactic acid bacteria (LAB). Fermentations were conducted by single strains isolated from mixed DL-starter culture, including Lactococcus lactis ssp. lactis, Lactococcus lactis ssp. cremoris, and Leuconostoc mesenteroides ssp. cremoris, by the DL-starter culture, and by the type strains. High and low levels of oxygen were produced by flushing milk with oxygen or nitrogen, respectively. The kinetics of milk acidification was characterized by the maximum rate and time of acidification (Vamax and Tamax), the maximum rate and time of reduction (Vrmax and Trmax), the minimum redox potential (Eh7 final), and time of reaching Eh7 final (Trfinal). Variations in kinetic parameters were observed at both the species and strain levels. Two of the Lc. lactis ssp. lactis strains were not able to lower redox potential to negative values. Kinetic parameters of the DL-starter culture were comparable with the best acidifying and reducing strains, indicating their additive effects. Acidification curves were mostly diauxic at all oxygen levels, displaying 2 maxima of acidification rate: before (aerobic maximum) and after (anaerobic maximum) oxygen depletion. The redox potential decreased concurrently with oxygen consumption and continued to decrease at slower rate until reaching the final values, indicating involvement of both oxygen and microbiological activity in the redox state of milk. Oxygen flushing had a negative effect on reduction and acidification capacity of tested LAB. Reduction was significantly delayed at high initial oxygen, exhibiting longer Trmax, Trfinal, or both

  6. Oxidative shift in tissue redox potential increases beat-to-beat variability of action potential duration.

    Science.gov (United States)

    Kistamás, Kornél; Hegyi, Bence; Váczi, Krisztina; Horváth, Balázs; Bányász, Tamás; Magyar, János; Szentandrássy, Norbert; Nánási, Péter P

    2015-07-01

    Profound changes in tissue redox potential occur in the heart under conditions of oxidative stress frequently associated with cardiac arrhythmias. Since beat-to-beat variability (short term variability, SV) of action potential duration (APD) is a good indicator of arrhythmia incidence, the aim of this work was to study the influence of redox changes on SV in isolated canine ventricular cardiomyocytes using a conventional microelectrode technique. The redox potential was shifted toward a reduced state using a reductive cocktail (containing dithiothreitol, glutathione, and ascorbic acid) while oxidative changes were initiated by superfusion with H2O2. Redox effects were evaluated as changes in "relative SV" determined by comparing SV changes with the concomitant APD changes. Exposure of myocytes to the reductive cocktail decreased SV significantly without any detectable effect on APD. Application of H2O2 increased both SV and APD, but the enhancement of SV was the greater, so relative SV increased. Longer exposure to H2O2 resulted in the development of early afterdepolarizations accompanied by tremendously increased SV. Pretreatment with the reductive cocktail prevented both elevation in relative SV and the development of afterdepolarizations. The results suggest that the increased beat-to-beat variability during an oxidative stress contributes to the generation of cardiac arrhythmias.

  7. Convergence of an L2-approach in the coupled-channels optical potential method for e-H scattering

    International Nuclear Information System (INIS)

    Bray, I.; Konovalov, D.A.; McCarthy, I.E.

    1990-08-01

    An L 2 approach to the coupled-channels optical method is studied. The investigation is done for electron-hydrogen elastic scattering at projectile energies of 30, 50, 100 and 200 eV. Weak coupling, free-particle Green's function and no exchange in Q-space are appoximations used to calculate the polarization potential. This model problem is solved exactly using actual hydrogen discrete and continuum functions. The convergence of an L 2 approach with the Laguerre basis to the exact result is investigated. It is found that a basis of 10 Laguerre functions is sufficient for convergence of approximately 5% in the polarization potential matrix elements and 2% in the differential cross sections for non-large angles. The convergence is faster for smaller energies. In general, the convergence to the exact result is slow. 12 refs., 2 tabs., 2 figs

  8. Efecto del potencial rédox sobre los parámetros del cultivo de Trypanosoma cruzi desarrollado en medio líquido agitado Effect of redox potential on culture parameters of Trypanosoma cruzi developed in liquid stirred media.

    Directory of Open Access Journals (Sweden)

    R.A. Martínez

    2005-12-01

    Full Text Available El potencial rédox (Eh es una propiedad fisicoquímica que presentan los solutos capaces de intercambiar electrones con un electrodo inerte. El potencial rédox influye en el crecimiento bacteriano en forma independiente del oxígeno disuelto. Es escasa la información disponible en relación a cultivos in vitro de protozoarios, en particular de Trypanosoma cruzi. Para determinar el efecto del Eh sobre los parámetros de cultivos, se empleó la cepa Tulahuén 0, desarrollada en medio CIEN líquido en agitación y se ensayaron valores de Eh entre 310 mV (testigo y 110 mV en 11 réplicas diferentes y duplicadas. Se determinaron pH, velocidad específica de desarrollo (µ, Eh, rH, velocidad de consumo de glucosa y rendimiento. Los resultados muestran que µ varía en forma directa con el Eh. Se establece una alta correlación (r = 0,93; P The redox potential (Eh is a physico-chemical property presented by solutes able to interchange electrons with an inert electrode. The redox potential influences bacterial growth in an independent way from dissolved oxygen. The available information about protozoaries in vitro grown is scarce, being Trypanosoma cruzi main example. T. cruzi Tulahuén 0 strain, developed in CIEN liquid stirred media, was used to determine the Eh effect on growth parameters. Eh values between 310 mV (reference and 110 mV were measured in 11 different samples and by duplicate. pH, m, Eh, rH, consume glucose rate and efficiency were determined. Results show that specific rate of development (µ varies in a direct way with Eh. A high correlation (r = 0.93; P < 0.01 between rH (rH = Eh(V+ 0.06 pH and µ was established, even when dissolved oxygen concentration remained constant. Other parameters in the growing medium showed no significant variations. It is concluded that changes on Eh in the medium significantly affect of T. cruzi's growth being a variable to take into account when potential trypanocide substances are analyzed.

  9. Age-dependent oxidation of extracellular cysteine/cystine redox state (Eh(Cys/CySS)) in mouse lung fibroblasts is mediated by a decline in Slc7a11 expression.

    Science.gov (United States)

    Zheng, Yuxuan; Ritzenthaler, Jeffrey D; Burke, Tom J; Otero, Javier; Roman, Jesse; Watson, Walter H

    2018-04-01

    Aging is associated with progressive oxidation of the extracellular environment. The redox state of human plasma, defined by the concentrations of cysteine (Cys) and cystine (CySS), becomes more oxidized as we age. Recently, we showed that fibroblasts isolated from the lungs of young and old mice retain this differential phenotype; old cells produce and maintain a more oxidizing extracellular redox potential (E h (Cys/CySS)) than young cells. Microarray analysis identified down-regulation of Slc7a11, the light subunit of the CySS/glutamate transporter, as a potential mediator of age-related oxidation in these cells. The purpose of the present study was to investigate the mechanistic link between Slc7a11 expression and extracellular E h (Cys/CySS). Sulforaphane treatment or overexpression of Slc7a11 was used to increase Slc7a11 in lung fibroblasts from old mice, and sulfasalazine treatment or siRNA-mediated knock down was used to decrease Slc7a11 in young fibroblasts. Slc7a11 mRNA levels were measured by real-time PCR, Slc7a11 activity was determined by measuring the rate of glutamate release, Cys, CySS, glutathione (GSH) and its disulfide (GSSG) were measured by HPLC, and E h (Cys/CySS) was calculated from the Nernst equation. The results showed that both E h (Cys/CySS) and E h (GSH/GSSG) were more oxidized in the conditioned media of old cells than in young cells. Up-regulation of Slc7a11 via overexpression or sulforaphane treatment restored extracellular E h (Cys/CySS) in cultures of old cells, whereas down-regulation reproduced the oxidizing E h (Cys/CySS) in young cells. Only sulforaphane treatment was able to increase total GSH and restore E h (GSH/GSSG), whereas overexpression, knock down and sulfasalazine had no effect on these parameters. In addition, inhibition of GSH synthesis with buthionine sulfoximine had no effect on the ability of cells to restore their extracellular redox potential in response to an oxidative challenge. In conclusion, our study

  10. 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

  11. Redox reactions with empirical potentials: Atomistic battery discharge simulations

    OpenAIRE

    Dapp, Wolf B.; Müser, Martin H.

    2013-01-01

    Batteries are pivotal components in overcoming some of today's greatest technological challenges. Yet to date there is no self-consistent atomistic description of a complete battery. We take first steps toward modeling of a battery as a whole microscopically. Our focus lies on phenomena occurring at the electrode-electrolyte interface which are not easily studied with other methods. We use the redox split-charge equilibration (redoxSQE) method that assigns a discrete ionization state to each ...

  12. 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

  13. Redox reactions with empirical potentials: atomistic battery discharge simulations.

    Science.gov (United States)

    Dapp, Wolf B; Müser, Martin H

    2013-08-14

    Batteries are pivotal components in overcoming some of today's greatest technological challenges. Yet to date there is no self-consistent atomistic description of a complete battery. We take first steps toward modeling of a battery as a whole microscopically. Our focus lies on phenomena occurring at the electrode-electrolyte interface which are not easily studied with other methods. We use the redox split-charge equilibration (redoxSQE) method that assigns a discrete ionization state to each atom. Along with exchanging partial charges across bonds, atoms can swap integer charges. With redoxSQE we study the discharge behavior of a nano-battery, and demonstrate that this reproduces the generic properties of a macroscopic battery qualitatively. Examples are the dependence of the battery's capacity on temperature and discharge rate, as well as performance degradation upon recharge.

  14. [Effect of the medium redox potential on the growth and metabolism of anaerobic bacteria].

    Science.gov (United States)

    Vasilian, A; Trchunian, A

    2008-01-01

    Based on the available literature data on a decrease in the redox potential of medium to low negative values and a decrease in pH during the growth of sugar-fermenting anaerobic bacteria, it was concluded that these processes cannot be described by the theory of redox potential. A theory was developed according to which the regulation of bacterial metabolism is accomplished through changes in the redox potential. The theory considers the redox potential as a factor determining the growth of anaerobic bacteria, which is regulated by oxidizers and reducers. The assumption is put forward that, under anaerobic conditions, bacteria are sensitive to changes in the redox potential and have a redox taxis. The effect of the redox potential on the transport of protons and other substances through membranes and the activity of membrane-bound enzymes, including the proton F1-F0-ATPase, whose mechanisms of action involve changes in the proton conductance of the membrane, the generation of proton-driving force, and dithiol-disulfide transitions in proteins was studied.

  15. Superconducting magnet for EHS

    International Nuclear Information System (INIS)

    Desportes, H.; Duthil, R.; Celebart, J.C.; Leschevin, C.; Lesmond, C.

    1980-10-01

    A 55 Mjoules Magnet has been installed and commissioned at CERN for the Rapid Cycling Bubble Chamber of the EHS experiment (European Hybrid Spectrometer). The magnet consists of two separate circular coils, assembled with their axis horizontal into a massive iron structure, and provides a central field of 3 T in a useful volume of 1.4 m in diameter and 0.82 m gap with a completely azimuthally free acceptance of +-18 deg from the central plane. Special features of the magnet, which is otherwise of a classical pancake-type, bath-cooled design, are a relatively high average current density (2500 Amp/cm 2 ) and an elaborate support structure required by the particular force configuration within the iron structure

  16. Redox potential distribution of an organic-rich contaminated site obtained by the inversion of self-potential data

    Science.gov (United States)

    Abbas, M.; Jardani, A.; Soueid Ahmed, A.; Revil, A.; Brigaud, L.; Bégassat, Ph.; Dupont, J. P.

    2017-11-01

    Mapping the redox potential of shallow aquifers impacted by hydrocarbon contaminant plumes is important for the characterization and remediation of such contaminated sites. The redox potential of groundwater is indicative of the biodegradation of hydrocarbons and is important in delineating the shapes of contaminant plumes. The self-potential method was used to reconstruct the redox potential of groundwater associated with an organic-rich contaminant plume in northern France. The self-potential technique is a passive technique consisting in recording the electrical potential distribution at the surface of the Earth. A self-potential map is essentially the sum of two contributions, one associated with groundwater flow referred to as the electrokinetic component, and one associated with redox potential anomalies referred to as the electroredox component (thermoelectric and diffusion potentials are generally negligible). A groundwater flow model was first used to remove the electrokinetic component from the observed self-potential data. Then, a residual self-potential map was obtained. The source current density generating the residual self-potential signals is assumed to be associated with the position of the water table, an interface characterized by a change in both the electrical conductivity and the redox potential. The source current density was obtained through an inverse problem by minimizing a cost function including a data misfit contribution and a regularizer. This inversion algorithm allows the determination of the vertical and horizontal components of the source current density taking into account the electrical conductivity distribution of the saturated and non-saturated zones obtained independently by electrical resistivity tomography. The redox potential distribution was finally determined from the inverted residual source current density. A redox map was successfully built and the estimated redox potential values correlated well with in

  17. pH, redox potential and local biofilm potential microenvironments within Geobacter sulfurreducens biofilms and their roles in electron transfer.

    Science.gov (United States)

    Babauta, Jerome T; Nguyen, Hung Duc; Harrington, Timothy D; Renslow, Ryan; Beyenal, Haluk

    2012-10-01

    The limitation of pH inside electrode-respiring biofilms is a well-known concept. However, little is known about how pH and redox potential are affected by increasing current inside biofilms respiring on electrodes. Quantifying the variations in pH and redox potential with increasing current is needed to determine how electron transfer is tied to proton transfer within the biofilm. In this research, we quantified pH and redox potential variations in electrode-respiring Geobacter sulfurreducens biofilms as a function of respiration rates, measured as current. We also characterized pH and redox potential at the counter electrode. We concluded that (1) pH continued to decrease in the biofilm through different growth phases, showing that the pH is not always a limiting factor in a biofilm and (2) decreasing pH and increasing redox potential at the biofilm electrode were associated only with the biofilm, demonstrating that G. sulfurreducens biofilms respire in a unique internal environment. Redox potential inside the biofilm was also compared to the local biofilm potential measured by a graphite microelectrode, where the tip of the microelectrode was allowed to acclimatize inside the biofilm. Copyright © 2012 Wiley Periodicals, Inc.

  18. Differential regulation of tissue thiol-disulfide redox status in a murine model of peritonitis

    Directory of Open Access Journals (Sweden)

    Benton Shana M

    2012-10-01

    Full Text Available Abstract Background Glutathione (GSH/glutathione disulfide (GSSG and cysteine (Cys/cystine (CySS are major redox pools with important roles in cytoprotection. We determined the impact of septic peritonitis on thiol-disulfide redox status in mice. Methods FVB/N mice (6–12 week old; 8/group underwent laparotomy with cecal ligation and puncture (CLP or laparotomy alone (control. Sections of ileum, colon, lung and liver were obtained and GSH, GSSG, Cys and CySS concentrations determined by HPLC 24 h after laparotomy. Redox potential [Eh in millivolts (mV] of the GSH/GSSG and Cys/CySS pools was calculated using the Nernst equation. Data were analyzed by ANOVA (mean ± SE. Results GSH/GSSG Eh in ileum, colon, and liver was significantly oxidized in septic mice versus control mice (ileum: septic −202±4 versus control −228±2 mV; colon: -195±8 versus −214±1 mV; and liver: -194±3 vs. -210±1 mV, all Ph was unchanged with CLP, while liver and lung Cys/CySS Eh became significantly more reducing (liver: septic = −103±3 versus control −90±2 mV; lung: -101±5 versus −81±1 mV, each P Conclusions Septic peritonitis induced by CLP oxidizes ileal and colonic GSH/GSSG redox but Cys/CySS Eh remains unchanged in these intestinal tissues. In liver, CLP oxidizes the GSH/GSSG redox pool and CyS/CySS Eh becomes more reducing; in lung, CLP does not alter GSH/GSSG Eh, and Cys/CySS Eh is less oxidized. CLP-induced infection/inflammation differentially regulates major thiol-disulfide redox pools in this murine model.

  19. SPATIAL AND TEMPORAL PATTERN OF SOIL pH AND Eh AND THEIR IMPACT ON SOLUTE IRON CONTENT IN A WETLAND (TRANSDANUBIA, HUNGARY

    Directory of Open Access Journals (Sweden)

    SZALAI ZOLTÁN

    2008-06-01

    Full Text Available Land mosaics have direct and indirect influence on chemical reaction and redox condition of soils. The present paper deals with the relationship between some environmental factors (such as soil andvegetation patterns, micro-relief, water regime, temperature and incident solar radiation and the pH, Eh of soils and solute iron in a headwater wetland in Transdanubia, Hungary. Measurements have been taken in four different patches and along their boundaries: sedge (Carex vulpina, Carex riparia, three patches and two species, horsetail (Equisetum arvense, common nettle (Urtica dioica. Thespatial pattern of the studied parameters are influenced by the water regime, micro-topography, climatic conditions and by direct and indirect effects of vegetation. The indirect effect can be the shading, which has influence on soil temperature and on the incident solar radiation (PAR. Root respiration and excretion of organic acids appear as direct effects.. There have been measured individual pH and Eh characteristic in the studied patches. Soil Eh, pH and solute iron have shown seasonal dynamics. Higher redox potentials (increasingly oxidative conditions and higher pH values were measured between late autumn and early spring. The increasing physiological activity of plants causes lower pH and Eh and it leads to higher spatial differences. Although temperature is an essential determining factor for Eh and pH, but our results suggest it rather has indirect effectsthrough plants on wetlands.

  20. Redox protective potential of fruits and vegetables: A review

    Directory of Open Access Journals (Sweden)

    Zainab Tahir

    2015-08-01

    Full Text Available Although oxidation reactions are crucial for life, they can also be damaging to cells and tissues, causing variety of chronic ailments like, aging, cancer, autoimmune problems, cardiovascular and neurodegenerative disorders etc. Redox protective systems are present in body for general immunization against free radicals, which can be supported by antioxidants that we take in our daily diet. Natural antioxidants such as flavonoids, hydrolysable tannins, coumarins, xanthones, phenolics, terpenoids, ascorbic acid, carotenoids and proanthocyanins are found in various plant products, including fruits, leaves, seeds oils, and juices. This review gives a brief account of research reports on fruits and vegetables which provide free radical scavenging compounds to the body.

  1. 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

  2. Dynamic Reference Electrode development for redox potential measurements in fluoride molten salt at high temperature

    International Nuclear Information System (INIS)

    Durán-Klie, Gabriela; Rodrigues, Davide; Delpech, Sylvie

    2016-01-01

    Measurement of redox potential in fluoride media is a major problem due to the difficulty to design a reference electrode with high stability, high mechanical resistance and high accuracy. In the frame of molten salt reactor studies, a dynamic reference electrode (DRE) is developed to measure redox potential in fluoride molten salt at high temperature. DRE is based on the in-situ generation of a transient redox system. The choice of the redox couple corresponds to the cathodic limit of the molten salt considered. As a preliminary step, the demonstration of feasibility of generating a DRE was done in LiF-NaF-KF (46.5–11.5–42 mol%) media at 500 °C. In this salt, the reference redox system generated by coulometry at applied current is KF/K, metallic potassium being electrodeposited on a tungsten wire electrode. The validation of the DRE response and the experimental optimization parameters for DRE generation were realized by following the NiF 2 /Ni redox potential evolution as a function of NiF 2 concentration in the fused salt. The current value applied for DRE generation was optimized. It depends on the amount of metallic cations contained in the fused salt and which can be electrochemically reduced simultaneously during the DRE generation. The current corresponding to the DRE generation has to be 4 times greater than the current corresponding to the reduction of the other elements.

  3. A High Redox Potential Laccase from Pycnoporus sanguineus RP15: Potential Application for Dye Decolorization

    Directory of Open Access Journals (Sweden)

    Ana L. R. L. Zimbardi

    2016-05-01

    Full Text Available Laccase production by Pycnoporus sanguineus RP15 grown in wheat bran and corncob under solid-state fermentation was optimized by response surface methodology using a Central Composite Rotational Design. A laccase (Lacps1 was purified and characterized and the potential of the pure Lacps1 and the crude culture extract for synthetic dye decolorization was evaluated. At optimal conditions (eight days, 26 °C, 18% (w/w milled corncob, 0.8% (w/w NH4Cl and 50 mmol·L−1 CuSO4, initial moisture 4.1 mL·g−1, the laccase activity reached 138.6 ± 13.2 U·g−1. Lacps1 was a monomeric glycoprotein (67 kDa, 24% carbohydrate. Optimum pH and temperature for the oxidation of 2,2’-azino-bis(3-ethylbenzthiazoline-6-sulfonate (ABTS were 4.4 and 74.4 °C, respectively. Lacps1 was stable at pH 3.0–8.0, and after two hours at 55–60 °C, presenting high redox potential (0.747 V vs. NHE. ABTS was oxidized with an apparent affinity constant of 147.0 ± 6.4 μmol·L−1, maximum velocity of 413.4 ± 21.2 U·mg−1 and catalytic efficiency of 3140.1 ± 149.6 L·mmol−1·s−1. The maximum decolorization percentages of bromophenol blue (BPB, remazol brilliant blue R and reactive blue 4 (RB4, at 25 or 40 °C without redox mediators, reached 90%, 80% and 60%, respectively, using either pure Lacps1 or the crude extract. This is the first study of the decolorization of BPB and RB4 by a P. sanguineus laccase. The data suggested good potential for treatment of industrial dye-containing effluents.

  4. 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

  5. [On the influence of local molecular environment on the redox potential of electron transfer cofactors in bacterial photosynthetic reaction centers].

    Science.gov (United States)

    Krasil'nikov, P M; Noks, P P; Rubin, A B

    2011-01-01

    The addition of cryosolvents (glycerol, dimethylsulfoxide) to a water solution containing bacterial photosynthetic reaction centers changes the redox potential of the bacteriochlorophyll dimer, but does not affect the redox potential of the quinone primary acceptor. It has been shown that the change in redox potential can be produced by changes of the electrostatic interactions between cofactors and the local molecular environment modified by additives entered into the solution. The degree of influence of a solvent on the redox potential of various cofactors is determined by degree of availability of these cofactors for molecules of solvent, which depends on the arrangement of cofactors in the structure of reaction centers.

  6. Calculation of the redox potential of the protein azurin and some mutants

    NARCIS (Netherlands)

    van den Bosch, M; Swart, M; Snijders, JG; Berendsen, HJC; Mark, AE; Oostenbrink, C; van Gunsteren, WF; Canters, GW

    Azurin from Pseudomonas aeruginosa is a small 128-residue, copper-containing protein. Its redox potential can be modified by mutating the protein. Free-energy calculations based on classical molecular-dynamics simulations of the protein and from mutants in aqueous solution at different pH values

  7. Catalytic Efficiency of Basidiomycete Laccases: Redox Potential versus Substrate-Binding Pocket Structure

    Directory of Open Access Journals (Sweden)

    Olga A. Glazunova

    2018-04-01

    Full Text Available Laccases are copper-containing oxidases that catalyze a one-electron abstraction from various phenolic and non-phenolic compounds with concomitant reduction of molecular oxygen to water. It is well-known that laccases from various sources have different substrate specificities, but it is not completely clear what exactly provides these differences. The purpose of this work was to study the features of the substrate specificity of four laccases from basidiomycete fungi Trametes hirsuta, Coriolopsis caperata, Antrodiella faginea, and Steccherinum murashkinskyi, which have different redox potentials of the T1 copper center and a different structure of substrate-binding pockets. Enzyme activity toward 20 monophenolic substances and 4 phenolic dyes was measured spectrophotometrically. The kinetic parameters of oxidation of four lignans and lignan-like substrates were determined by monitoring of the oxygen consumption. For the oxidation of the high redox potential (>700 mV monophenolic substrates and almost all large substrates, such as phenolic dyes and lignans, the redox potential difference between the enzyme and the substrate (ΔE played the defining role. For the low redox potential monophenolic substrates, ΔE did not directly influence the laccase activity. Also, in the special cases, the structure of the large substrates, such as dyes and lignans, as well as some structural features of the laccases (flexibility of the substrate-binding pocket loops and some amino acid residues in the key positions affected the resulting catalytic efficiency.

  8. Relationship Between Redox Potential, Disinfectant, and pH in Drinking Water

    Science.gov (United States)

    This work will examine the effects of pH and oxidant type (chlorine [Cl2], oxygen [O2], hydrogen peroxide [H2O2], monochloramine [MCA], and potassium permanganate [KMnO4]) and concentration (mg/L) on the redox potential of buffered test water. Also, the effects of incrementing ir...

  9. 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

  10. Real-time quantification of subcellular H2O2 and glutathione redox potential in living cardiovascular tissues.

    Science.gov (United States)

    Panieri, Emiliano; Millia, Carlo; Santoro, Massimo M

    2017-08-01

    Detecting and measuring the dynamic redox events that occur in vivo is a prerequisite for understanding the impact of oxidants and redox events in normal and pathological conditions. These aspects are particularly relevant in cardiovascular tissues wherein alterations of the redox balance are associated with stroke, aging, and pharmacological intervention. An ambiguous aspect of redox biology is how redox events occur in subcellular organelles including mitochondria, and nuclei. Genetically-encoded Rogfp2 fluorescent probes have become powerful tools for real-time detection of redox events. These probes detect hydrogen peroxide (H 2 O 2 ) levels and glutathione redox potential (E GSH ), both with high spatiotemporal resolution. By generating novel transgenic (Tg) zebrafish lines that express compartment-specific Rogfp2-Orp1 and Grx1-Rogfp2 sensors we analyzed cytosolic, mitochondrial, and the nuclear redox state of endothelial cells and cardiomyocytes of living zebrafish embryos. We provide evidence for the usefulness of these Tg lines for pharmacological compounds screening by addressing the blocking of pentose phosphate pathways (PPP) and glutathione synthesis, thus altering subcellular redox state in vivo. Rogfp2-based transgenic zebrafish lines represent valuable tools to characterize the impact of redox changes in living tissues and offer new opportunities for studying metabolic driven antioxidant response in biomedical research. Copyright © 2017 Elsevier Inc. All rights reserved.

  11. Timing of developmental reduction in epithelial glutathione redox potential is associated with increased epithelial proliferation in the immature murine intestine.

    Science.gov (United States)

    Reid, Graham K; Berardinelli, Andrew J; Ray, Laurie; Jackson, Arena R; Neish, Andrew S; Hansen, Jason M; Denning, Patricia W

    2017-08-01

    BackgroundThe intracellular redox potential of the glutathione (GSH)/glutathione disulfide (GSSG) couple regulates cellular processes. In vitro studies indicate that a reduced GSH/GSSG redox potential favors proliferation, whereas a more oxidized redox potential favors differentiation. Intestinal growth depends upon an appropriate balance between the two. However, how the ontogeny of intestinal epithelial cellular (IEC) GSH/GSSG redox regulates these processes in the developing intestine has not been fully characterized in vivo.MethodsOntogeny of intestinal GSH redox potential and growth were measured in neonatal mice.ResultsWe show that IEC GSH/GSSG redox potential becomes increasingly reduced (primarily driven by increased GSH concentration) over the first 3 weeks of life. Increased intracellular GSH has been shown to drive proliferation through increased poly-ADP-ribose polymerase (PARP) activity. We show that increasing IEC poly-ADP-ribose chains can be measured over the first 3 weeks of life, indicating an increase in IEC PARP activity. These changes are accompanied by increased intestinal growth and IEC proliferation as assessed by villus height/crypt depth, intestinal length, and Ki67 staining.ConclusionUnderstanding how IEC GSH/GSSG redox potential is developmentally regulated may provide insight into how premature human intestinal redox states can be manipulated to optimize intestinal growth and adaptation.

  12. Draft genome sequence of four coccolithoviruses: Emiliania huxleyi virus EhV-88, EhV-201, EhV-207, and EhV-208.

    Science.gov (United States)

    Nissimov, Jozef I; Worthy, Charlotte A; Rooks, Paul; Napier, Johnathan A; Kimmance, Susan A; Henn, Matthew R; Ogata, Hiroyuki; Allen, Michael J

    2012-03-01

    The Coccolithoviridae are a group of viruses which infect the marine coccolithophorid microalga Emiliania huxleyi. The Emiliania huxleyi viruses (known as EhVs) described herein have 160- to 180-nm diameter icosahedral structures, have genomes of approximately 400 kbp, and consist of more than 450 predicted coding sequences (CDSs). Here, we describe the genomic features of four newly sequenced coccolithoviruses (EhV-88, EhV-201, EhV-207, and EhV-208) together with their draft genome sequences and their annotations, highlighting the homology and heterogeneity of these genomes to the EhV-86 model reference genome.

  13. Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

    Directory of Open Access Journals (Sweden)

    Krishnamoorthy Arumugam

    2014-04-01

    Full Text Available Applications of redox processes range over a number of scientific fields. This review article summarizes the theory behind the calculation of redox potentials in solution for species such as organic compounds, inorganic complexes, actinides, battery materials, and mineral surface-bound-species. Different computational approaches to predict and determine redox potentials of electron transitions are discussed along with their respective pros and cons for the prediction of redox potentials. Subsequently, recommendations are made for certain necessary computational settings required for accurate calculation of redox potentials. This article reviews the importance of computational parameters, such as basis sets, density functional theory (DFT functionals, and relativistic approaches and the role that physicochemical processes play on the shift of redox potentials, such as hydration or spin orbit coupling, and will aid in finding suitable combinations of approaches for different chemical and geochemical applications. Identifying cost-effective and credible computational approaches is essential to benchmark redox potential calculations against experiments. Once a good theoretical approach is found to model the chemistry and thermodynamics of the redox and electron transfer process, this knowledge can be incorporated into models of more complex reaction mechanisms that include diffusion in the solute, surface diffusion, and dehydration, to name a few. This knowledge is important to fully understand the nature of redox processes be it a geochemical process that dictates natural redox reactions or one that is being used for the optimization of a chemical process in industry. In addition, it will help identify materials that will be useful to design catalytic redox agents, to come up with materials to be used for batteries and photovoltaic processes, and to identify new and improved remediation strategies in environmental engineering, for example the

  14. 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.

  15. A new synthesis route for Os-complex modified redox polymers for potential biofuel cell applications.

    Science.gov (United States)

    Pöller, Sascha; Beyl, Yvonne; Vivekananthan, Jeevanthi; Guschin, Dmitrii A; Schuhmann, Wolfgang

    2012-10-01

    A new synthesis route for Os-complex modified redox polymers was developed. Instead of ligand exchange reactions for coordinative binding of suitable precursor Os-complexes at the polymer, Os-complexes already exhibiting the final ligand shell containing a suitable functional group were bound to the polymer via an epoxide opening reaction. By separation of the polymer synthesis from the ligand exchange reaction at the Os-complex, the modification of the same polymer backbone with different Os-complexes or the binding of the same Os-complex to a number of different polymer backbones becomes feasible. In addition, the Os-complex can be purified and characterized prior to its binding to the polymer. In order to further understand and optimize suitable enzyme/redox polymer systems concerning their potential application in biosensors or biofuel cells, a series of redox polymers was synthesized and used as immobilization matrix for Trametes hirsuta laccase. The properties of the obtained biofuel cell cathodes were compared with similar biocatalytic interfaces derived from redox polymers obtained via ligand exchange reaction of the parent Os-complex with a ligand integrated into the polymer backbone during the polymer synthesis. Copyright © 2011 Elsevier B.V. All rights reserved.

  16. Phenolic acids potentiate colistin-mediated killing of Acinetobacter baumannii by inducing redox imbalance.

    Science.gov (United States)

    Ajiboye, Taofeek O; Skiebe, Evelyn; Wilharm, Gottfried

    2018-05-01

    Phenolic acids with catechol groups are good prooxidants because of their low redox potential. In this study, we provided data showing that phenolic acids, caffeic acid, gallic acid and protocatechuic acid, enhanced colistin-mediated bacterial death by inducing redox imbalance. The minimum inhibitory concentrations of these phenolic acids against Acinetobacter baumannii AB5075 were considerably lowered for ΔsodB and ΔkatG mutants. Checkerboard assay shows synergistic interactions between colistin and phenolic acids. The phenolic acids exacerbated colistin-induced oxidative stress in A. baumannii AB5075 through increased superoxide anion generation, NAD + /NADH and ADP/ATP ratio. In parallel, the level of reduced glutathione was significantly lowered. We conclude that phenolic acids potentiate colistin-induced oxidative stress in A. baumannii AB5075 by increasing ROS generation, energy metabolism and electron transport chain activity with a concomitant decrease in glutathione. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

  17. State of charge monitoring of vanadium redox flow batteries using half cell potentials and electrolyte density

    Science.gov (United States)

    Ressel, Simon; Bill, Florian; Holtz, Lucas; Janshen, Niklas; Chica, Antonio; Flower, Thomas; Weidlich, Claudia; Struckmann, Thorsten

    2018-02-01

    The operation of vanadium redox flow batteries requires reliable in situ state of charge (SOC) monitoring. In this study, two SOC estimation approaches for the negative half cell are investigated. First, in situ open circuit potential measurements are combined with Coulomb counting in a one-step calibration of SOC and Nernst potential which doesn't need additional reference SOCs. In-sample and out-of-sample SOCs are estimated and analyzed, estimation errors ≤ 0.04 are obtained. In the second approach, temperature corrected in situ electrolyte density measurements are used for the first time in vanadium redox flow batteries for SOC estimation. In-sample and out-of-sample SOC estimation errors ≤ 0.04 demonstrate the feasibility of this approach. Both methods allow recalibration during battery operation. The actual capacity obtained from SOC calibration can be used in a state of health model.

  18. Redox Probing Study of the Potential Dependence of Charge Transport Through Li2O2

    DEFF Research Database (Denmark)

    Knudsen, Kristian Bastholm; Luntz, Alan C.; Jensen, Søren Højgaard

    2015-01-01

    -of-the-art Liion technologies and the demand placed on batteries by technologies such as electrical vehicles. Here we present a redox probing study of the charge transfer across the main deposition product lithium peroxide, Li2O2, in the Li−O2 battery using outer-sphere redox shuttles. The change in heterogeneous......In the field of energy storage devices the pursuit for cheap, high energy density, reliable secondary batteries is at the top of the agenda. The Li−O2 battery is one of the possible technologies that, in theory, should be able to close the gap, which exists between the present state...... electron transfer exchange rate as a function of the potential and the Li2O2 layer thickness (∼depth-of-discharge) was determined using electrochemical impedance spectroscopy. The attenuation of the electron transfer exchange rate with film thickness is dependent on the probing potential, providing...

  19. Reactions of copper macrocycles with antioxidants and HOCl: potential for biological redox sensing.

    Science.gov (United States)

    Sowden, Rebecca J; Trotter, Katherine D; Dunbar, Lynsey; Craig, Gemma; Erdemli, Omer; Spickett, Corinne M; Reglinski, John

    2013-02-01

    A series of simple copper N(2)S(2) macrocycles were examined for their potential as biological redox sensors, following previous characterization of their redox potentials and crystal structures. The divalent species were reduced by glutathione or ascorbate at a biologically relevant pH in aqueous buffer. A less efficient reduction was also achieved by vitamin E in DMSO. Oxidation of the corresponding univalent copper species by sodium hypochlorite resulted in only partial (~65 %) recovery of the divalent form. This was concluded to be due to competition between metal oxidation and ligand oxidation, which is believed to contribute to macrocycle demetallation. Electrospray mass spectrometry confirmed that ligand oxidation had occurred. Moreover, the macrocyclic complexes could be demetallated by incubation with EDTA and bovine serum albumin, demonstrating that they would be inappropriate for use in biological systems. The susceptibility to oxidation and demetallation was hypothesized to be due to oxidation of the secondary amines. Consequently these were modified to incorporate additional oxygen donor atoms. This modification led to greater resistance to demetallation and ligand oxidation, providing a better platform for further development of copper macrocycles as redox sensors for use in biological systems.

  20. A new approach to design safe CNTs with an understanding of redox potential.

    Science.gov (United States)

    Tsuruoka, Shuji; Cassee, Flemming R; Castranova, Vincent

    2013-09-02

    Carbon nanotubes (CNTs) are being increasingly industrialized and applied for various products. As of today, although several toxicological evaluations of CNTs have been conducted, designing safer CNTs is not practiced because reaction kinetics of CNTs with bioactive species is not fully understood. The authors propose a kinetic mechanism to establish designing safe CNTs as a new goal. According to a literature search on the behavior of CNTs and the effects of impurities, it is found that chemical reactions on CNT surface are attributed to redox reactions involving metal impurities and carbon structures at the CNT surface. A new goal is proposed to design safer CNTs using the redox potential hypothesis. The value of this hypothesis must be practically investigated and proven through the further experiments.

  1. Early-Late Heterobimetallic Complexes Linked by Phosphinoamide Ligands. Tuning Redox Potentials and Small Molecule Activation

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, Christine M. [Brandeis Univ., Waltham, MA (United States)

    2015-08-01

    Recent attention in the chemical community has been focused on the energy efficient and environmentally benign conversion of abundant small molecules (CO2, H2O, etc.) to useful liquid fuels. This project addresses these goals by examining fundamental aspects of catalyst design to ultimately access small molecule activation processes under mild conditions. Specifically, Thomas and coworkers have targetted heterobimetallic complexes that feature metal centers with vastly different electronic properties, dictated both by their respective positions on the periodic table and their coordination environment. Unlike homobimetallic complexes featuring identical or similar metals, the bonds between metals in early/late heterobimetallics are more polarized, with the more electron-rich late metal center donating electron density to the more electron-deficient early metal center. While metal-metal bonds pose an interesting strategy for storing redox equivalents and stabilizing reactive metal fragments, the polar character of metal-metal bonds in heterobimetallic complexes renders these molecules ideally poised to react with small molecule substrates via cleavage of energy-rich single and double bonds. In addition, metal-metal interactions have been shown to dramatically affect redox potentials and promote multielectron redox activity, suggesting that metal-metal interactions may provide a mechanism to tune redox potentials and access substrate reduction/activation at mild overpotentials. This research project has provided a better fundamental understanding of how interactions between transition metals can be used as a strategy to promote and/or control chemical transformations related to the clean production of fuels. While this project focused on the study of homogeneous systems, it is anticipated that the broad conclusions drawn from these investigations will be applicable to heterogeneous catalysis as well, particularly on heterogeneous processes that occur at interfaces in

  2. Thermodynamic Characterization of Iron Oxide-Aqueous Fe(2+) Redox Couples.

    Science.gov (United States)

    Gorski, Christopher A; Edwards, Rebecca; Sander, Michael; Hofstetter, Thomas B; Stewart, Sydney M

    2016-08-16

    Iron is present in virtually all terrestrial and aquatic environments, where it participates in redox reactions with surrounding metals, organic compounds, contaminants, and microorganisms. The rates and extent of these redox reactions strongly depend on the speciation of the Fe2+ and Fe3+ phases, although the underlying reasons remain unclear. In particular, numerous studies have observed that Fe2+ associated with iron oxide surfaces (i.e., oxide-associated Fe2+) often reduces oxidized contaminants much faster than aqueous Fe2+ alone. Here, we tested two hypotheses related to this observation by determining if solutions containing two commonly studied iron oxides—hematite and goethite—and aqueous Fe2+ reached thermodynamic equilibrium over the course of a day. We measured reduction potential (EH) values in solutions containing these oxides at different pH values and aqueous Fe2+ concentrations using mediated potentiometry. This analysis yielded standard reduction potential (EH0) values of 768 ± 1 mV for the aqueous Fe2+–goethite redox couple and 769 ± 2 mV for the aqueous Fe2+–hematite redox couple. These values were in excellent agreement with those calculated from existing thermodynamic data, and the data could be explained by the presence of an iron oxide lowering EH values of aqueous Fe3+/Fe2+ redox couples.

  3. Use of two-potential theory in electron-molecule scattering: Application to wide-angle e-H2 scattering at 40 eV

    International Nuclear Information System (INIS)

    Ritchie, B.

    1984-01-01

    A Green's-function approach is used to solve the Schroedinger equation in an effective potential (V 0 ), which is the sum of independent-atom static potentials. The equation for the Green's function is conveniently solved in momentum space (MS), where the MS ''potentials'' (Fourier transforms of the atom-centered potentials) have translational symmetry. The Green's function is then used to construct the solution to the Schroedinger equation for scattering in the potential V-V 0 (where V is the e-molecule static potential plus a local exchange potential) relative to scattering in V 0 . This solution is found in coordinate space using single-center expansions about the internuclear midpoint. These are more rapidly convergent for V-V 0 than for V or V 0 alone. The sum of the amplitudes for scattering in V 0 and in V-V 0 relative to V 0 then represents the amplitude for scattering from the molecule. This method is intended to combine the dynamical methods best suited for each type of potential (multicenter for V 0 and single center for V-V 0 ). It also exposes the shortcomings of the use of V 0 alone

  4. Mobility of Iron-Cyanide Complexes in a Humic Topsoil under Varying Redox Conditions

    Directory of Open Access Journals (Sweden)

    Thilo Rennert

    2009-01-01

    Full Text Available The potentially toxic Fe-CN complexes ferricyanide, [FeIII(CN6]3−, and ferrocyanide, [FeII(CN6]4−, undergo a variety of redox processes in soil, which affect their mobility. We carried out microcosm experiments with suspensions of a humic topsoil (pH 5.3; Corg 107 g kg-1 to which we added ferricyanide (20 mg l-1. We varied the redox potential (EH from −280 to 580 mV by using O2, N2 and glucose. The decrease of EH led to decreasing concentrations of Fe-CN complexes and partial reductive dissolution of (hydrous Fe and Mn oxides. The dynamics of aqueous Fe-CN concentrations was characterized by decreasing concentrations when the pH rose and the EH dropped. We attribute these dependencies to adsorption on organic surfaces, for which such a pH/EH behavior has been shown previously. Adsorption was reversible, because when the pH and EH changed into the opposite direction, desorption occurred. This study demonstrates the possible impact of soil organic matter on the fate of Fe-CN complexes in soil.

  5. One-electron transfer equilibria and redox potentials of radicals studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Meisel, D.; Czapski, G.

    1975-01-01

    The pulse radiolysis technique is utilized for measurements of the equilibrium constants for electron transfer between the durosemiquinone radical anion and oxygen, menadione, and indigodisulfonate. These equilibrium constants are in turn used for calculations of one-electron redox potentials for these systems. Each of these equilibrium constants was determined experimentally and independently and found to be self-consistent. Only for the reactions of the semiquinone radical ions with oxygen could the electron transfer reaction be followed directly. For the reactions between the various quinone-semiquinone systems substantial indirect evidence is presented that these equilibria are achieved rapidly. In those cases equilibrium constants were determined from studies of the effect of quinone concentrations on the relative yields of the semiquinones. A method for distinguishing between kinetic competition and equilibrium is outlined and its usefulness is emphasized. The DQ parallel DQ - (DQ = duroquinone) and IDS parallel IDS - (IDS = indigodisulfonate) systems were employed as reference couples as the redox potentials for those systems are either available in the literature (IDS parallel IDS - ) or may be calculated from available data (DQ parallel DQ - ). Taking E 7 1 , the redox potential for the first one-electron reduction step at pH 7, of DQ parallel DQ - as -0.235 V or of IDS parallelIDS - as -0.247 V both yield E 7 1 = -0.325 V for the O 2 parallel O 2 - system (1 atm of O 2 ) and E 2 1 = -0.20 V for the menadione system. (U.S.)

  6. The reaction of neuroglobin with potential redox protein partners cytochrome b5  and cytochrome c

    DEFF Research Database (Denmark)

    Fago, Angela; Mathews, A.J.; Moens, L.

    2006-01-01

    Previously identified, potentially neuroprotective reactions of neuroglobin require the existence of yet unknown redox partners. We show here that the reduction of ferric neuroglobin by cytochrome b5 is relatively slow (k=6×102M-1s-1 at pH 7.0) and thus is unlikely to be of physiological...... significance. In contrast, the reaction between ferrous neuroglobin and ferric cytochrome c is very rapid (k=2×107M-1s-1) with an apparent overall equilibrium constant of 1μM. Based on this data we propose that ferrous neuroglobin may well play a role in preventing apoptosis...

  7. Substituent effect on redox potential of nitrido technetium complexes with Schiff base ligand. Theoretical calculations

    International Nuclear Information System (INIS)

    Takayama, T.; Sekine, T.; Kudo, H.

    2003-01-01

    Theoretical calculations based on the density functional theory (DFT) were performed to understand the effect of substituents on the molecular and electronic structures of technetium nitrido complexes with salen type Schiff base ligands. Optimized structures of these complexes are square pyramidal. The electron density on a Tc atom of the complex with electron withdrawing substituents is lower than that of the complex with electron donating substituents. The HOMO energy is lower in the complex with electron withdrawing substituents than that in the complex with electron donating substituents. The charge on Tc atoms is a good measure that reflects the redox potential of [TcN(L)] complex. (author)

  8. Analysis of Eh Condition and Evolutional Trend of Paddy Soils in a Toposequence

    Directory of Open Access Journals (Sweden)

    javad seyedmohammadi

    2017-02-01

    Full Text Available Introduction: Paddy soils are important and the base of agriculture in Guilan province. It is necessary to recognize these soils for understanding of their limitations and optimum use. Unsaturated soil submerging is the cause of collection of chemical and electrochemical process that has significant effects on soil fertility. Eh, rH and pH are important indexes that are used to investigate oxidation and reduction condition in submerged soils and have abundant effects on activity and sorption rate of nutrients. Decrease of Eh and rH in poorly drainage of paddy soils affects availability and solubility of nutrient. Different Fe forms are used for analysis of soils evolution trend and submerging influences on changes of Fe forms. The aim of the present study was conducted to investigate the effect of redox potential changes on soil characteristics and analysis of soils evolutional trend in different physiographic units. Materials and Methods: The study area with 40000ha (at the east of Rasht city is located between 49° 31' to 49° 45' E longitude and 37° 7' to 37° 27' N latitude in North of Guilan Province, Northern Iran, in the southern coast of the Caspian sea with different water table depth. The climate of the region is very humid with the mean annual precipitation of 1293.6 mm. The mean annual temperature is 15.8°C. The soil moisture and temperature regimes are Aquic, Udicand Thermic, respectively. The parent materials are derived from river sediments. The soils formed on the plateaues and upper terraces, river alluvial plain and lowland physiographic units were classified as Inceptisols and the soils formed on coastal plain physiographic unit as Entisols. Air-dried soil samples were crushed and passed through a 2mm sieve. Particle-size distribution, organic carbon and cation exchange capacity were determined by hydrometric, wet oxidation and ammonium acetate methods, respectively. Eh by Eh electrode, total iron, free iron and amorphous

  9. Tuning the redox potential of vitamin K3 derivatives by oxidative functionalization using a Ag(i)/GO catalyst.

    Science.gov (United States)

    El-Hout, S I; Suzuki, H; El-Sheikh, S M; Hassan, H M A; Harraz, F A; Ibrahim, I A; El-Sharkawy, E A; Tsujimura, S; Holzinger, M; Nishina, Y

    2017-08-03

    We propose herein initial results to develop optimum redox mediators by the combination of computational simulation and catalytic functionalization of the core structure of vitamin K 3 . We aim to correlate the calculated energy value of the LUMO of different vitamin K 3 derivatives with their actual redox potential. For this, we optimized the catalytic alkylation of 1,4-naphthoquinones with a designed Ag(i)/GO catalyst and synthesized a series of molecules.

  10. Development of a mathematical-statistical model for the analysis of sediments redox potential: An environmental pollution index; Sviluppo di un modello matematico-statistico per l`analisi del potenziale redox dei sedimenti

    Energy Technology Data Exchange (ETDEWEB)

    Izzo, G; Rizzo, V [ENEA, Centro Ricerche Casaccia, Rome (Italy). Dip. Ambiente; Bella, A; Picci, M [Rome Univ. La Sapienza (Italy). Dip. di Statistica e Probabilita` Applicata

    1996-07-01

    This work refers different depth redox potential measurement as well as a statistical analysis in Venice lagoon sediments. A mathematical model that links redox potential and detection depth has been carried out. From this model an inversion gradient has been determined. This parameter may been considered as different lagoon areas pollution index.

  11. Synthesis and Electrochemical Study of a TCAA Derivative – A potential bipolar redox-active material

    International Nuclear Information System (INIS)

    Hagemann, Tino; Winsberg, Jan; Wild, Andreas; Schubert, Ulrich S.

    2017-01-01

    The 2,3,7,8-tetracyano-1,4,5,6,9,10-hexazaanthracene (TCAA) derivatives represent an interesting substance class for future research on organic electronic devices, such as solar cells, organic batteries or redox-flow batteries (RFBs). Because of their multivalent redox behavior they are potentially “bipolar”, usable both as cathode and anode activ charge-storage materials. Furthermore, they show a strong absorption and fluorescence behavior both in solution and solid state, rendering them a promising emitter for electroluminescence devices, like lamps or displays. In order to evaluate a TCAA for electrochemical applications the derivative 2,3,7,8-tetracyano-5,10-diphenyl-5,10-dihydrodipyrazino[2,3-b:2′,3′-e] pyrazine (2) was synthesized in two straightforward synthesis steps. The electrochemical behavior of 2 was initially determined by density functional theory (DFT) calculation and afterwards investigated via rotating disc electrode (RDE), UV–vis–NIR spectroelectrochemical as well as cyclic voltammetry (CV) measurements. It features a quasi-reversible oxidation and re-reduction at E ½ = 1.42 V vs. Fc + /Fc with a peak split of 96 mV and a quasi-reversible reduction and re-oxidation at E ½ = −1.49 V vs. Fc + /Fc with a peak split of 174 mV, which lead to a theoretical potential difference of 2.91 V.

  12. A low redox potential affects monoclonal antibody assembly and glycosylation in cell culture.

    Science.gov (United States)

    Dionne, Benjamin; Mishra, Neha; Butler, Michael

    2017-03-20

    Glycosylation and intracellular assembly of monoclonal antibodies (MAbs) is important for glycan profile consistency. To better understand how these factors may be influenced by a lower redox potential, an IgG1-producing NS0 cell line was grown in the presence of varying concentrations of dithiothreitol (DTT). Cultures were monitored for growth and culture redox potential (CRP) with glycan heterogeneity determined using a HILIC-HPLC method. Macroheterogeneity was unchanged in all conditions whereas the Galactosylation Index (GI) decreased by as much as 50% in cultures with lower CRP or higher dithiothreitol levels. This shift in GI is reflected in more agalactosylated and asialylated species being produced. The MAb assembly pathway was determined using radioactive isotope 35 S incorporated into nascent IgG1 molecules. The assembly pathway for this IgG1 was shown to progress via HC→HC 2 →HC 2 LC→HC 2 LC 2 in all conditions tested and autoradiographs highlighted that the ratio of heavy chain dimer to heavy chain monomer increased over time with increasing DTT concentrations. This increase and correspondingly lower GI values may be due to disruption of the disulfide bonds at higher levels of assembly. A change in the assembly pathway may alter the final IgG glycan pattern and lead to control mechanisms that influence glycan profiles of MAbs. Copyright © 2017. Published by Elsevier B.V.

  13. Tuning of Hemes b Equilibrium Redox Potential Is Not Required for Cross-Membrane Electron Transfer.

    Science.gov (United States)

    Pintscher, Sebastian; Kuleta, Patryk; Cieluch, Ewelina; Borek, Arkadiusz; Sarewicz, Marcin; Osyczka, Artur

    2016-03-25

    In biological energy conversion, cross-membrane electron transfer often involves an assembly of two hemesb The hemes display a large difference in redox midpoint potentials (ΔEm_b), which in several proteins is assumed to facilitate cross-membrane electron transfer and overcome a barrier of membrane potential. Here we challenge this assumption reporting on hemebligand mutants of cytochromebc1in which, for the first time in transmembrane cytochrome, one natural histidine has been replaced by lysine without loss of the native low spin type of heme iron. With these mutants we show that ΔEm_b can be markedly increased, and the redox potential of one of the hemes can stay above the level of quinone pool, or ΔEm_b can be markedly decreased to the point that two hemes are almost isopotential, yet the enzyme retains catalytically competent electron transfer between quinone binding sites and remains functionalin vivo This reveals that cytochromebc1can accommodate large changes in ΔEm_b without hampering catalysis, as long as these changes do not impose overly endergonic steps on downhill electron transfer from substrate to product. We propose that hemesbin this cytochrome and in other membranous cytochromesbact as electronic connectors for the catalytic sites with no fine tuning in ΔEm_b required for efficient cross-membrane electron transfer. We link this concept with a natural flexibility in occurrence of several thermodynamic configurations of the direction of electron flow and the direction of the gradient of potential in relation to the vector of the electric membrane potential. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  14. Effect of Redox Potential on Changing of Binding Forms of Heavy Metals in Bottom Sediments of Anzali International Wetland

    International Nuclear Information System (INIS)

    Saeedi, M.; Fakhari, M.

    2016-01-01

    Heavy metals are naturally presented in different chemical bonds within sediment. Different factors affect metals bonding in sediment. One of those factors is changing in Redox potential. Redox potential may change under oxic/anoxic conditions in the bottom sediments. In the present study the effect of redox potential on fractionation and bonding of metals within Anzali international wetland bottom sediment is investigated.Sediment samples of Anzali wetland were aerated for one month and redox potential and p H was measured at 0, 1, 7, 21, and 28th days. Subsamples of sediments at mentioned days of experiments were taken and analyzed for Cu, Zn, Ni, and Cr for deferent chemical bonds using sequential extraction analysis. Results revealed that majority of Cu were presented in the sulfidic/organic bonds while Zn was associated with Fe/Mn oxides. Nickel and Cr were mostly associated in hard residual bonds. At the end of aeration process, with increasing redox potential, 8-23% of metals were released from sediments into dissolved phase. They mainly released from sulfide/organic bonds.

  15. REDOX AND REDUCTION POTENTIALS AS PARAMETERS TO PREDICT THE DEGRADATION PATHWAY OF CHLORINATED BENZENES IN ANAEROBIC ENVIRONMENTS

    NARCIS (Netherlands)

    DOLFING, J; HARRISON, BK

    1993-01-01

    The anaerobic degradation pathway of hexachlorobenzene starts with a series of reductive dehalogenation steps. In the present paper it was evaluated whether the dehalogenation pathway observed in microbial ecosystems could be predicted by the redox potential and/or the reduction potential (the

  16. Low glutathione regulates gene expression and the redox potentials of the nucleus and cytosol in Arabidopsis thaliana.

    Science.gov (United States)

    Schnaubelt, Daniel; Queval, Guillaume; Dong, Yingping; Diaz-Vivancos, Pedro; Makgopa, Matome Eugene; Howell, Gareth; De Simone, Ambra; Bai, Juan; Hannah, Matthew A; Foyer, Christine H

    2015-02-01

    Reduced glutathione (GSH) is considered to exert a strong influence on cellular redox homeostasis and to regulate gene expression, but these processes remain poorly characterized. Severe GSH depletion specifically inhibited root meristem development, while low root GSH levels decreased lateral root densities. The redox potential of the nucleus and cytosol of Arabidopsis thaliana roots determined using roGFP probes was between -300 and -320 mV. Growth in the presence of the GSH-synthesis inhibitor buthionine sulfoximine (BSO) increased the nuclear and cytosolic redox potentials to approximately -260 mV. GSH-responsive genes including transcription factors (SPATULA, MYB15, MYB75), proteins involved in cell division, redox regulation (glutaredoxinS17, thioredoxins, ACHT5 and TH8) and auxin signalling (HECATE), were identified in the GSH-deficient root meristemless 1-1 (rml1-1) mutant, and in other GSH-synthesis mutants (rax1-1, cad2-1, pad2-1) as well as in the wild type following the addition of BSO. Inhibition of auxin transport had no effect on organ GSH levels, but exogenous auxin decreased the root GSH pool. We conclude that GSH depletion significantly increases the redox potentials of the nucleus and cytosol, and causes arrest of the cell cycle in roots but not shoots, with accompanying transcript changes linked to altered hormone responses, but not oxidative stress. © 2013 John Wiley & Sons Ltd.

  17. [Changes in the redox potential and pO2 in heat shock to Escherichia coli].

    Science.gov (United States)

    Oktiabr'skiĭ, O N; Pshenichnov, R A

    1982-01-01

    When the growing culture of Escherichia coli was subjected to a temperature above 37 degrees C, the pO2 fell abruptly at 42 degrees C; a reversible decrease in the redox potential (ROP) down to the range of negative values was detected if the growth ceased at 46 degrees C. The drop in the ROP took from 6 to 10 min, with the maximal deviation of 42.5 mV. Such changes in the pO2 and ROP were not caused by a heat shock in the stationary cultures. The change in the ROP was not due to a change in the pH and pO2 of the medium. The authors believe that the effect should be attributed to an elimination of the ionic gradients and the electrochemical gradient delta muH+.

  18. [Redox-potential of blood and consistence of energoproviding defence system in cytomegalovirus infection in pregnancy].

    Science.gov (United States)

    Dzhikiia, I V; Rizhvadze, M A; Dzhangidze, M A

    2006-05-01

    We have studied the relationship between the hypoxic change and mitochondrial redox-potential disturbances in the mechanism of pheto-placental insufficiency in pregnancy with cytomegalovirus infection (CMV), detected by the positive anti-CMV-IgG titer and more then 4-fold increase of low avid anti-CMV-IgG. It was shown, that chronic CMV infection induces production of active forms of oxygen, peroxidation of structures and concurrently damage of mitochondria with essential decrease of ATP level. Results of the study have shown the important diagnostic value of estimation of hypoxic-oxidative damage induced by CMV infection. The results also revealed important relationships between the activity of the CMV infection and intensity of mitochondrial damage. On the basis of our investigations we suggest the additional diagnostic test (the determination of citozol NADH dependent isocitratdehydrogenaze activity) to evaluate the depth of CMV induced metabolic disturbances.

  19. Tunable redox potential of nonmetal doped monolayer MoS{sub 2}: First principle calculations

    Energy Technology Data Exchange (ETDEWEB)

    Lu, S. [Center for Coordination Bond Engineering, China Jiliang University (China); Li, C., E-mail: canli1983@gmail.com [Center for Coordination Bond Engineering, China Jiliang University (China); School of Materials Science and Engineering, China Jiliang University (China); Zhao, Y.F.; Gong, Y.Y.; Niu, L.Y.; Liu, X.J. [Center for Coordination Bond Engineering, China Jiliang University (China)

    2016-10-30

    Graphical abstract: Both E{sub CBM} and E{sub VBM} values are affected by the chemical valences of dopants, which also affect the redox potentials of specimens. Compared to the pristine monolayer MoS{sub 2}, the nonmetal ions with odd chemical valences [monovalent (H{sup +}, F{sup –}, Cl{sup –}, Br{sup –} and I{sup –}), trivalent (N{sup 3–}, P{sup 3–} and As{sup 3–}) and pentavalence (B{sup 5–})] enhance the oxidation potential and reduce the reduction potential of specimens, but the nonmetal ions with even chemical valences [divalent (O{sup 2–}, Se{sup 2–} and Te{sup 2–}) and quadravalent (C{sup 4–} and Si{sup 4–})] have the opposite effects on the redox potentials. Display Omitted - Highlights: • The newly formed chemical bonds affect the electronic distribution around the dopants and the nearby Mo atoms. • Compared to pristine monolayer MoS{sub 2}, the nonmetal ions with odd (even) chemical valences enhance (reduce) the oxidation potential and reduce (enhance) the reduction potential of specimens. • The lone pair electrons in nonmetal ions with odd chemical valences extra interact with the Mo ions which reduces the E{sub CBM} and E{sub VBM} values of specimens. - Abstract: Doping is an effective method to alter the electronic behavior of materials by forming new chemical bonds and bringing bond relaxation. With this aid of first principle calculations, the crystal configuration and electronic properties of monolayer MoS{sub 2} have been modulated by the nonmetal (NM) dopants (H, B, C, N, O, F, Si, P, Cl, As, Se, Br, Te and I), and the thermodynamic stability depending on the preparation conditions (Mo-rich and S-rich conditions) were discussed. Results shown that, the NM dopants substituted preferentially for S under Mo-rich condition, the electronic distribution around the dopants and the nearby Mo atoms are changed by the new formed Mo-NM bonds and bands relaxation. Compared to pristine monolayer MoS{sub 2}, the NM ions with odd

  20. Using Electrochemical SERS to Measure the Redox Potential of Drug Molecules Bound to dsDNA—a Study of Mitoxantrone

    International Nuclear Information System (INIS)

    Meneghello, Marta; Papadopoulou, Evanthia; Ugo, Paolo; Bartlett, Philip N.

    2016-01-01

    Interaction with DNA plays an important role in the biological activity of some anticancer drug molecules. In this paper we show that electrochemical surface enhanced Raman spectroscopy at sphere segment void gold electrodes can be used as a highly sensitive technique to measure the redox potential of the anticancer drug mitoxantrone bound to dsDNA. For this system we show that we can follow the redox reaction of the bound molecule and can extract the redox potential for the molecule bound to dsDNA by deconvolution of the SER spectra recorded as a function of electrode potential. We find that mitoxantrone bound to dsDNA undergoes a 2 electron, 1 proton reduction and that the redox potential (-0.87 V vs. Ag/AgCl at pH 7.2) is shifted approximately 0.12 V cathodic of the corresponding value at a glassy carbon electrode. Our results also show that the reduced form of mitoxantrone remains bound to dsDNA and we are able to use the deconvoluted SER spectra of the reduced mitoxantrone as a function of electrode potential to follow the electrochemically driven melting of the dsDNA at more negative potentials.

  1. Redox properties of iron-bearing clays and MX-80 bentonite – Electrochemical and spectroscopic characterization

    International Nuclear Information System (INIS)

    Hofstetter, Th. B.; Sosedova, Y.; Gorski, C.; Voegelin, A.; Sander, M.

    2014-03-01

    The characterization of the redox properties of Fe-bearing minerals in the presence and absence of dissolved Fe"2"+ is of major relevance for the assessment of redox reactions in natural and engineered environments such as radioactive waste repositories. In this study, we developed an electrochemical approach based on the use of soluble organic electron transfer mediators, which enabled us to quantify the redox properties of Fe-bearing clay minerals, MX- 80 bentonite and combinations of clay minerals, Fe oxides and dissolved Fe"2"+. Using mediated electrochemical oxidation and reduction, we quantified the electron accepting and donating capacities of ferrous smectite SWa-1, Wyoming montmorillonite SWy-2 and MX-80 bentonite at pH 7.5. All structural Fe in clay minerals was redox-active in contrast to that present in other, not further defined phases of MX-80. The materials investigated were redoxactive over a very wide range of Eh-values, that is the Fe"2"+/Fe_t_o_t_a_l ratio of the minerals changed from 0 to 100 % between +600 and -600 mV (vs. SHE). Redox properties were highly path-dependent due to structural changes of the minerals as revealed from the study of native and redox-cycled clay minerals after repeated reduction and re-oxidation cycles. Irreversible alteration of the mineral structure, however, was less obvious for materials with lower total Fe content such as MX-80 bentonite and SWy-2. Systems containing native montmorillonites (SWy-2 or MX-80), goethite and dissolved Fe"2"+ were also able to buffer the reduction potential E_H between 0 and -300 mV. Regardless of their Fe oxidation state, Fe-bearing minerals are redox-active over a wide potential range and therefore very relevant as redox buffers determining the fate of redox-active radionuclides and metals in waste repositories. (authors)

  2. The effect of bicarbonate on menadione-induced redox cycling and cytotoxicity: potential involvement of the carbonate radical.

    Science.gov (United States)

    Aljuhani, Naif; Michail, Karim; Karapetyan, Zubeida; Siraki, Arno G

    2013-10-01

    We have investigated the effect of NaHCO3 on menadione redox cycling and cytotoxicity. A cell-free system utilized menadione and ascorbic acid to catalyze a redox cycle, and we utilized murine hepatoma (Hepa 1c1c7) cells for in vitro experiments. Experiments were performed using low (2 mmol/L) and physiological (25 mmol/L) levels of NaHCO3 in buffer equilibrated to physiological pH. Using oximetry, ascorbic acid oxidation, and ascorbyl radical detection, we found that menadione redox cycling was enhanced by NaHCO3. Furthermore, Hepa 1c1c7 cells treated with menadione demonstrated cytotoxicity that was significantly increased with physiological concentrations of NaHCO3 in the media, compared with low levels of NaHCO3. Interestingly, the inhibition of superoxide dismutase (SOD) with 2 different metal chelators was associated with a protective effect against menadione cytotoxicity. Using isolated protein, we found a significant increase in protein carbonyls with menadione-ascorbate-SOD with physiological NaHCO3 levels; low NaHCO3 or SOD-free reactions produced lower levels of protein carbonyls. In conclusion, these findings suggest that the hydrogen peroxide generated by menadione redox cycling together with NaHCO3-CO2 are potential substrates for SOD peroxidase activity that can lead to carbonate-radical-enhanced cytotoxicity. These findings demonstrate the importance of NaHCO3 in menadione redox cycling and cytotoxicity.

  3. Characterization of apoplast phenolics: Invitro oxidation of acetosyringone results in a rapid prolonged increase in the redox potential

    Science.gov (United States)

    In a previous study we observed that if tobacco cell suspensions were inoculated with certain bacterial strains, several hours later the redox potential of the suspensions would increase (oxidative), as much as 100 mV, and in some cases last more than an hour. To discover possible contributors to t...

  4. Fate of redox-sensitive elements in two different East-African wetland systems

    Science.gov (United States)

    Glasner, Björn; Fiedler, Sabine

    2017-04-01

    We expect that an intensified cropping alters soil pH and Eh, and negatively affects the production potential of wetlands. Therefore, we investigated the redox-conditions in combination with the fate of different redox-sensitive elements in two prototypical wetland systems that show a high potential for food production in East-Africa. While the floodplains (observed near Ifakara, Kilombero District/Tanzania) serve as major crop producing areas in the region, the Inland Valleys (observed in Namulonge, Central District/Uganda) show a high potential for future production. Both systems have been divided into three positions; the fringe near to the slope, the center near to the river and the middle in between these two positions. In order to get a better understanding of the two systems we installed continuously measuring redox-electrodes in three different positions within both systems. Additionally, the fate of mineral elements was measured using ion-exchange resins with an installation period of 3-4 months. At the Tanzanian field sites the Eh-potential shows one major dry period with moderately reducing to well drained conditions in all sampling depths (10, 30, and 50 cm below ground) in all three positions during the measuring period from March 2015 to Dec 2016. Starting with the rains the Eh-potential drops from 700 mV (in 10 and 30 cm depth) to reducing conditions at all three sites - with intermediate brakes in the middle and fringe positions, showing that there has been no rain during these periods. At the Ugandan field sites the Eh-potential shows more fluctuations during the measuring period, especially in the center position in 2015 ( 750 to -200 mV in 30 and 50 cm depth). Having just the Eh-potential from the first 30 cm below ground it is not really possible to differentiate between dry- and rainy-seasons at the sites. The fate of redox-sensitive elements (Fe, Mn, and P) does not always correlate with the overall Eh-conditions (median) of the installation

  5. A way to limit the corrosion in the Molten Salt Reactor concept: the salt redox potential control

    International Nuclear Information System (INIS)

    Gibilaro, M.; Massot, L.; Chamelot, P.

    2015-01-01

    The possibility of controlling the salt redox potential thanks to a redox buffer in the Molten Salt Fast Reactor was investigated, the goal was to limit the oxidation of the reactor structural material. Tests were performed in LiF-CaF 2 at 850 °C on two different redox couples to fix the salt potential, Eu(III)/Eu(II) and U(IV)/U(III), where the first one was used as inactive system to validate the methodology to be applied on the uranium system. A metallic reducing agent (Gd plate for Eu, and U plate for U system) was inserted in the salt, leading to a spontaneous reaction: Eu(III) and U(IV) were then reduced. Eu(III) was fully converted into Eu(II) with metallic Gd, validating the approach. On the U system, the U(IV)/U(III) ratio has to be set between 10 and 100 to limit the core material oxidation: addition of metallic U decreased the concentration ratio from the infinite to 1, showing the feasibility of the salt redox potential control with the U system

  6. Microbial redox processes in deep subsurface environments and the potential application of (perchlorate in oil reservoirs

    Directory of Open Access Journals (Sweden)

    Martin G Liebensteiner

    2014-09-01

    Full Text Available The ability of microorganisms to thrive under oxygen-free conditions in subsurface environments relies on the enzymatic reduction of oxidized elements, such as sulfate, ferric iron or CO2, coupled to the oxidation of inorganic or organic compounds. A broad phylogenetic and functional diversity of microorganisms from subsurface environments has been described using isolation-based and advanced molecular ecological techniques. The physiological groups reviewed here comprise iron-, manganese- and nitrate-reducing microorganisms. In the context of recent findings also the potential of chlorate and perchlorate [jointly termed (perchlorate] reduction in oil reservoirs will be discussed. Special attention is given to elevated temperatures that are predominant in the deep subsurface. Microbial reduction of (perchlorate is a thermodynamically favorable redox process, also at high temperature. However, knowledge about (perchlorate reduction at elevated temperatures is still scarce and restricted to members of the Firmicutes and the archaeon Archaeoglobus fulgidus. By analyzing the diversity and phylogenetic distribution of functional genes in (metagenome databases and combining this knowledge with extrapolations to earlier-made physiological observations we speculate on the potential of (perchlorate reduction in the subsurface and more precisely oil fields. In addition, the application of (perchlorate for bioremediation, souring control and microbial enhanced oil recovery are addressed.

  7. Potential Role of Amino Acid/Protein Nutrition and Exercise in Serum Albumin Redox State

    Directory of Open Access Journals (Sweden)

    Yasuaki Wada

    2017-12-01

    Full Text Available Albumin is the major protein in the serum of mammals. It is synthesized exclusively in the liver, before being secreted into the circulation. Similar to skeletal muscle protein, albumin synthesis is stimulated by dietary amino acids and proteins as well as exercise. Albumin has three isoforms based on the redox states of the free cysteine residue at position 34. The redox state of serum albumin has long been extensively investigated in terms of oxidative stress-related chronic diseases, with the redox state of serum albumin having been regarded as a marker of systemic oxidative stress. However, according to recent animal studies, the redox state of serum albumin is modulated by albumin turnover and may also reflect amino acid/protein nutritional status. Furthermore, as the redox state of serum albumin is modulated by exercise training, measuring the pre- and post-exercise redox states of serum albumin in athletes may be useful in assessing amino acid/protein nutritional status and exercise-induced oxidative stress, which are closely associated with skeletal muscle adaptive responses. This article extensively reviews serum albumin and the redox state of albumin in the context of amino acid/protein nutritional status and exercise training.

  8. The use of field redox measurements in assessing remediation of ground water containing petroleum hydrocarbons and chlorinated organic compounds

    International Nuclear Information System (INIS)

    Warner, S.D.; Gallinatti, J.D.; Honniball, J.H.

    1995-01-01

    Field measurements of the reduction-oxidation (redox) condition of ground water were used to assess the effects of in situ remediation of ground water affected by petroleum hydrocarbons and chlorinated organic compounds at multiple sites in northern California. The redox condition of ground water, traditionally measured quickly and inexpensively using a meter that measures electrode potential (Eh), is a valuable parameter by which to assess the conditions that affect the relative stability of various chemicals in ground water. Although not specific to a given redox couple measurements obtained using the traditional Eh meter give a sense of the relative tendency for a ground water to be reducing or oxidizing by providing a measurement of the system Eh. Two cases demonstrate the use of ground water Eh measurements in assessing the effects of in situ ground water remediation. In the first case, ground water affected by petroleum hydrocarbons-gasoline (TPHg), and benzene, toluene, ethylbenzene, and xylenes (BTEX) (ambient Eh of -100 to +100 millivolts [mv]) was treated by injecting hydrogen peroxide to supply oxygen to the subsurface environment and stimulate microbial activity. The second case involved remediation of ground water containing chlorinated organic compounds. In this case, a subsurface permeable ground water treatment wall containing granular iron was installed across the flow path of the affected ground water. The in situ chemical treatment, which successfully dechlorinates compounds such as trichloroethylene, 1,2-dichloroethylene, and vinyl chloride, caused reducing conditions in the ground water, which resulted in the decrease in ground water Eh from am ambient reading of about -50 mv to about -400 mv

  9. Applying the Nernst equation to simulate redox potential variations for biological nitrification and denitrification processes.

    Science.gov (United States)

    Chang, Cheng-Nan; Cheng, Hong-Bang; Chao, Allen C

    2004-03-15

    In this paper, various forms of Nernst equations have been developed based on the real stoichiometric relationship of biological nitrification and denitrification reactions. Instead of using the Nernst equation based on a one-to-one stoichiometric relation for the oxidizing and the reducing species, the basic Nernst equation is modified into slightly different forms. Each is suitable for simulating the redox potential (ORP) variation of a specific biological nitrification or denitrification process. Using the data published in the literature, the validity of these developed Nernst equations has been verified by close fits of the measured ORP data with the calculated ORP curve. The simulation results also indicate that if the biological process is simulated using an incorrect form of Nernst equation, the calculated ORP curve will not fit the measured data. Using these Nernst equations, the ORP value that corresponds to a predetermined degree of completion for the biochemical reaction can be calculated. Thus, these Nernst equations will enable a more efficient on-line control of the biological process.

  10. Redox potential tuning through differential quinone binding in the photosynthetic reaction center of Rhodobacter sphaeroides.

    Science.gov (United States)

    Vermaas, Josh V; Taguchi, Alexander T; Dikanov, Sergei A; Wraight, Colin A; Tajkhorshid, Emad

    2015-03-31

    Ubiquinone forms an integral part of the electron transport chain in cellular respiration and photosynthesis across a vast number of organisms. Prior experimental results have shown that the photosynthetic reaction center (RC) from Rhodobacter sphaeroides is only fully functional with a limited set of methoxy-bearing quinones, suggesting that specific interactions with this substituent are required to drive electron transport and the formation of quinol. The nature of these interactions has yet to be determined. Through parameterization of a CHARMM-compatible quinone force field and subsequent molecular dynamics simulations of the quinone-bound RC, we have investigated and characterized the interactions of the protein with the quinones in the Q(A) and Q(B) sites using both equilibrium simulation and thermodynamic integration. In particular, we identify a specific interaction between the 2-methoxy group of ubiquinone in the Q(B) site and the amide nitrogen of GlyL225 that we implicate in locking the orientation of the 2-methoxy group, thereby tuning the redox potential difference between the quinones occupying the Q(A) and Q(B) sites. Disruption of this interaction leads to weaker binding in a ubiquinone analogue that lacks a 2-methoxy group, a finding supported by reverse electron transfer electron paramagnetic resonance experiments of the Q(A)⁻Q(B)⁻ biradical and competitive binding assays.

  11. One electron transfer redox potentials of free radicals. I. The oxygen-superoxide system. Progress report, September 1, 1975--July 1, 1976

    International Nuclear Information System (INIS)

    Ilan, Y.A.; Czapski, G.; Meisel, D.

    1976-01-01

    The method of determination of Redox potentials of radicals, using the pulse radiolysis technique, is outlined. The method is based on the determination of equilibria constants of electron transfer reactions between the radicals and appropriate acceptors. The limitations of this technique are discussed. The redox potentials of several quinones--semi-quinones are calculated, as well as the standard redox potential of the peroxy radical. E 0 /sub O 2 /O 2 /sup -/ = -0.33 V and the redox oxidation properties of the peroxy radical in various systems and pH are discussed. The value determined for the redox potentials of O 2 /O 2 - is higher by more than 0.2 volts than earlier estimates, which has important implications on the possible role of O 2 - in biological processes of O 2 fixation

  12. Ca2+ dependence of gluconeogenesis stimulation by glucagon at different cytosolic NAD+-NADH redox potentials

    Directory of Open Access Journals (Sweden)

    Marques-da-Silva A.C.

    1997-01-01

    , stimulation caused by glucagon was much smaller than that found when Ca2+ was present. e The effects of glucagon on oxygen uptake in the presence of Ca2+ showed a parabolic relationship with the lactate to pyruvate ratios which was closely similar to that found in the case of gluconeogenesis; the only difference was that inhibition rather than stimulation of oxygen uptake was observed for a lactate to pyruvate ratio equal to 0.01; progressive stimulation was observed in the 0.1 to 100 range. f In the absence of Ca2+ the effects of glucagon on oxygen uptake were different; the dependence curve was sigmoidal at the onset, with a well-defined maximum at a lactate to pyruvate ratio equal to 1; this maximum was followed by a steady decline at higher ratios; at the ratios of 0.01 and 0.1 inhibition took place; oxygen uptake stimulation caused by glucagon was generally lower in the absence of Ca2+ except when the lactate to pyruvate ratio was equal to 1. The results of the present study demonstrate that stimulation of gluconeogenesis by glucagon depends on Ca2+. However, Ca2+ is only effective in helping gluconeogenesis stimulation by glucagon at highly negative redox potentials of the cytosolic NAD+-NADH system. The triple interdependence of glucagon-Ca2+-NAD+-NADH redox potential reveals highly complex interrelations that can only be partially understood at the present stage of knowledge

  13. Changing redox potential by controlling soil moisture and addition of inorganic oxidants to dissipate pentachlorophenol in different soils

    International Nuclear Information System (INIS)

    Lin Jiajiang; He Yan; Xu Jianming

    2012-01-01

    The potential for dissipation of pentachlorophenol (PCP) was investigated in soils from four different sites in China. These were an umbraqualf (Soil 1), a Plinthudult (Soil 2), a Haplustalf (Soil 3) and an Argiustoll (Soil 4) which were either flooded, to produce anaerobic conditions, or incubated aerobically at 60% water-holding capacity (WHC). The dissipation of PCP in Soil 1 at 60% WHC was higher than under flooded condition, while the opposite occurred in the other three soils. Under flooded conditions, the redox potential decreased significantly in Soil 1 and Soil 4, where sulphate reduction was occurred and the dissipation of PCP was statistically significant (about 96% and 98%, respectively) at the end of incubation. After addition of inorganic oxidants, dissipation of PCP was significantly inhibited by FeCl 3 , while Na 2 SO 4 and NaNO 3 had different effects, depending upon the soil type. - Highlights: ► The extent of the aerobic/anaerobic interface depends upon the soil properties. ► The dissipation of PCP was accelerated in some soils due to the soil-water interface. ► The addition of oxidants inhibited the decrease in soil redox potential. ► Most external oxidants added under flooded condition inhibited PCP dechlorination. - The addition of inorganic oxidants limited the decrease in redox potential and inhibited the reductive dechlorination of pentachlorophenol.

  14. Copper corrosion in bentonite: Studying of parameters (pH, Eh/O2) of importance for Cu corrosion

    International Nuclear Information System (INIS)

    Carlsson, T.; Muurinen, A.

    2007-06-01

    The report describes the development of methods and equipment for studying the parameters (pH, Eh/O 2 ) of importance for copper corrosion. The work involved the fabrication of electrodes for determining Eh and pH in compacted water-saturated bentonite. MX-80 and the Indian Asha 505 bentonites were used in the study. The redox-measurements were carried out by using electrodes prepared of Au and Pt wires. The pH measurements were carried out by using solid IrO x electrodes. The report describes testing of electrodes in different solutions and in bentonite. A destructive method for determining oxygen content in compacted bentonite was tested, too. The electrodes were used in measurements inside compacted bentonite with about the same density as is intended to be used in the Finnish repository for spent nuclear fuel. The results indicate that Au and Pt redox-electrodes and IrO x pH electrodes function in compacted bentonite. The oxygen measurement in bentonite seems to work, too, and can complement the Eh measurements. Eh-values in originally aerobic bentonite samples having a dry densitiy of ≤1.5 g/cm 3 , exhibit mostly a decrease during the first days, which may mainly be ascribed to the depletion of oxygen. The Eh-decrease thereafter is probably associated with redox-reactions involving other species than oxygen. In samples with a dry density of 1.8 g/cm 3 , the observed Eh-decrease is mostly slower. No significant difference between the Eh and pH measurements in MX-80 and Asha 505 could be observed. (orig.)

  15. Improving the oxidative stability of a high redox potential fungal peroxidase by rational design.

    Science.gov (United States)

    Sáez-Jiménez, Verónica; Acebes, Sandra; Guallar, Victor; Martínez, Angel T; Ruiz-Dueñas, Francisco J

    2015-01-01

    Ligninolytic peroxidases are enzymes of biotechnological interest due to their ability to oxidize high redox potential aromatic compounds, including the recalcitrant lignin polymer. However, different obstacles prevent their use in industrial and environmental applications, including low stability towards their natural oxidizing-substrate H2O2. In this work, versatile peroxidase was taken as a model ligninolytic peroxidase, its oxidative inactivation by H2O2 was studied and different strategies were evaluated with the aim of improving H2O2 stability. Oxidation of the methionine residues was produced during enzyme inactivation by H2O2 excess. Substitution of these residues, located near the heme cofactor and the catalytic tryptophan, rendered a variant with a 7.8-fold decreased oxidative inactivation rate. A second strategy consisted in mutating two residues (Thr45 and Ile103) near the catalytic distal histidine with the aim of modifying the reactivity of the enzyme with H2O2. The T45A/I103T variant showed a 2.9-fold slower reaction rate with H2O2 and 2.8-fold enhanced oxidative stability. Finally, both strategies were combined in the T45A/I103T/M152F/M262F/M265L variant, whose stability in the presence of H2O2 was improved 11.7-fold. This variant showed an increased half-life, over 30 min compared with 3.4 min of the native enzyme, under an excess of 2000 equivalents of H2O2. Interestingly, the stability improvement achieved was related with slower formation, subsequent stabilization and slower bleaching of the enzyme Compound III, a peroxidase intermediate that is not part of the catalytic cycle and leads to the inactivation of the enzyme.

  16. Improving the oxidative stability of a high redox potential fungal peroxidase by rational design.

    Directory of Open Access Journals (Sweden)

    Verónica Sáez-Jiménez

    Full Text Available Ligninolytic peroxidases are enzymes of biotechnological interest due to their ability to oxidize high redox potential aromatic compounds, including the recalcitrant lignin polymer. However, different obstacles prevent their use in industrial and environmental applications, including low stability towards their natural oxidizing-substrate H2O2. In this work, versatile peroxidase was taken as a model ligninolytic peroxidase, its oxidative inactivation by H2O2 was studied and different strategies were evaluated with the aim of improving H2O2 stability. Oxidation of the methionine residues was produced during enzyme inactivation by H2O2 excess. Substitution of these residues, located near the heme cofactor and the catalytic tryptophan, rendered a variant with a 7.8-fold decreased oxidative inactivation rate. A second strategy consisted in mutating two residues (Thr45 and Ile103 near the catalytic distal histidine with the aim of modifying the reactivity of the enzyme with H2O2. The T45A/I103T variant showed a 2.9-fold slower reaction rate with H2O2 and 2.8-fold enhanced oxidative stability. Finally, both strategies were combined in the T45A/I103T/M152F/M262F/M265L variant, whose stability in the presence of H2O2 was improved 11.7-fold. This variant showed an increased half-life, over 30 min compared with 3.4 min of the native enzyme, under an excess of 2000 equivalents of H2O2. Interestingly, the stability improvement achieved was related with slower formation, subsequent stabilization and slower bleaching of the enzyme Compound III, a peroxidase intermediate that is not part of the catalytic cycle and leads to the inactivation of the enzyme.

  17. The met axial ligand determines the redox potential in Cu-A sites

    DEFF Research Database (Denmark)

    Ledesma, G.N.; Murgida, D.H.; Ly, H.K.

    2007-01-01

    The replacement of the axial methionine ligand in a native Cu-A protein rendered a series of stable mutants with spectroscopic features of a mixed valence center. The mutations resulted in minor perturbations of the electronic structure of this site but led to significant changes in the redox pot...

  18. Redox Disrupting Potential of ToxCast™Chemicals Ranked by Activity in Mouse Embryonic Stem Cells

    Science.gov (United States)

    Little is known regarding the adverse outcome pathways responsible for developmental toxicity following exposure to chemicals. An evaluation of Toxoast™ Phase I chemicals in an adherent mouse embryonic stem cell (mESC) assay revealed a redox sensitive pathway that correlated with...

  19. REDOX DISRUPTING POTENTIAL OF TOXCAST CHEMICALS RANKED BY ACTIVITY IN MOUSE EMBRYONIC STEM CELLS

    Science.gov (United States)

    To gain insight regarding the adverse outcome pathways leading to developmental toxicity following exposure to chemicals, we evaluated ToxCast™ Phase I chemicals in an adherent mouse embryonic stem cell (mESC) assay and identified a redox sensitive pathway that correlated with al...

  20. Effect of the L499M mutation of the ascomycetous Botrytis aclada laccase on redox potential and catalytic properties

    International Nuclear Information System (INIS)

    Osipov, Evgeny; Polyakov, Konstantin; Kittl, Roman; Shleev, Sergey; Dorovatovsky, Pavel; Tikhonova, Tamara; Hann, Stephan; Ludwig, Roland; Popov, Vladimir

    2014-01-01

    The structures of the ascomycetous B. aclada laccase and its L499M T1-site mutant have been solved at 1.7 Å resolution. The mutant enzyme shows a 140 mV lower redox potential of the type 1 copper and altered kinetic behaviour. The wild type and the mutant have very similar structures, which makes it possible to relate the changes in the redox potential to the L499M mutation Laccases are members of a large family of multicopper oxidases that catalyze the oxidation of a wide range of organic and inorganic substrates accompanied by the reduction of dioxygen to water. These enzymes contain four Cu atoms per molecule organized into three sites: T1, T2 and T3. In all laccases, the T1 copper ion is coordinated by two histidines and one cysteine in the equatorial plane and is covered by the side chains of hydrophobic residues in the axial positions. The redox potential of the T1 copper ion influences the enzymatic reaction and is determined by the nature of the axial ligands and the structure of the second coordination sphere. In this work, the laccase from the ascomycete Botrytis aclada was studied, which contains conserved Ile491 and nonconserved Leu499 residues in the axial positions. The three-dimensional structures of the wild-type enzyme and the L499M mutant were determined by X-ray crystallography at 1.7 Å resolution. Crystals suitable for X-ray analysis could only be grown after deglycosylation. Both structures did not contain the T2 copper ion. The catalytic properties of the enzyme were characterized and the redox potentials of both enzyme forms were determined: E 0 = 720 and 580 mV for the wild-type enzyme and the mutant, respectively. Since the structures of the wild-type and mutant forms are very similar, the change in the redox potential can be related to the L499M mutation in the T1 site of the enzyme

  1. Very high gravity ethanol fermentation by flocculating yeast under redox potential-controlled conditions

    Directory of Open Access Journals (Sweden)

    Liu Chen-Guang

    2012-08-01

    Full Text Available Abstract Background Very high gravity (VHG fermentation using medium in excess of 250 g/L sugars for more than 15% (v ethanol can save energy consumption, not only for ethanol distillation, but also for distillage treatment; however, stuck fermentation with prolonged fermentation time and more sugars unfermented is the biggest challenge. Controlling redox potential (ORP during VHG fermentation benefits biomass accumulation and improvement of yeast cell viability that is affected by osmotic pressure and ethanol inhibition, enhancing ethanol productivity and yield, the most important techno-economic aspect of fuel ethanol production. Results Batch fermentation was performed under different ORP conditions using the flocculating yeast and media containing glucose of 201 ± 3.1, 252 ± 2.9 and 298 ± 3.8 g/L. Compared with ethanol fermentation by non-flocculating yeast, different ORP profiles were observed with the flocculating yeast due to the morphological change associated with the flocculation of yeast cells. When ORP was controlled at −100 mV, ethanol fermentation with the high gravity (HG media containing glucose of 201 ± 3.1 and 252 ± 2.9 g/L was completed at 32 and 56 h, respectively, producing 93.0 ± 1.3 and 120.0 ± 1.8 g/L ethanol, correspondingly. In contrast, there were 24.0 ± 0.4 and 17.0 ± 0.3 g/L glucose remained unfermented without ORP control. As high as 131.0 ± 1.8 g/L ethanol was produced at 72 h when ORP was controlled at −150 mV for the VHG fermentation with medium containing 298 ± 3.8 g/L glucose, since yeast cell viability was improved more significantly. Conclusions No lag phase was observed during ethanol fermentation with the flocculating yeast, and the implementation of ORP control improved ethanol productivity and yield. When ORP was controlled at −150 mV, more reducing power was available for yeast cells to survive, which in turn improved their viability and VHG

  2. Electron Pathways through Erythrocyte Plasma Membrane in Human Physiology and Pathology: Potential Redox Biomarker?

    OpenAIRE

    Matteucci, Elena; Giampietro, Ottavio

    2007-01-01

    Erythrocytes are involved in the transport of oxygen and carbon dioxide in the body. Since pH is the influential factor in the Bohr-Haldane effect, pHi is actively maintained via secondary active transports Na+/H+ exchange and HC3 -/Cl- anion exchanger. Because of the redox properties of the iron, hemoglobin generates reactive oxygen species and thus, the human erythrocyte is constantly exposed to oxidative damage. Although the adult erythrocyte lacks protein synthesis and cannot restore dama...

  3. Inhibition of glutathione biosynthesis alters compartmental redox status and the thiol proteome in organogenesis-stage rat conceptuses.

    Science.gov (United States)

    Harris, Craig; Shuster, Daniel Z; Roman Gomez, Rosaicela; Sant, Karilyn E; Reed, Matthew S; Pohl, Jan; Hansen, Jason M

    2013-10-01

    Developmental signals that control growth and differentiation are regulated by environmental factors that generate reactive oxygen species (ROS) and alter steady-state redox environments in tissues and fluids. Protein thiols are selectively oxidized and reduced in distinct spatial and temporal patterns in conjunction with changes in glutathione/glutathione disulfide (GSH/GSSG) and cysteine/cystine (Cys/CySS) redox potentials (E(h)) to regulate developmental signaling. The purpose of this study was to measure compartment-specific thiol redox status in cultured organogenesis-stage rat conceptuses and to evaluate the impact of thiol oxidation on the redox proteome. The visceral yolk sac (VYS) has the highest initial (0 h) total intracellular GSH (GSH+2GSSG) concentration (5.5 mM) and the lowest Eh (-223 mV) as determined by HPLC analysis. Total embryo (EMB) GSH concentrations ranged lower (3.2 mM) and were only slightly more oxidized than the VYS. Total GSH concentrations in yolk sac fluid (YSF) and amniotic fluid (AF) are >500-fold lower than in tissues and are highly oxidized (YSF E(h)=-121 mV and AF E(h)=-49 mV). Steady-state total Cys concentrations (Cys+2CySS) were significantly lower than GSH in tissues but were otherwise equal in VYS and EMB near 0.5 mM. On gestational day 11, total GSH and Cys concentrations in EMB and VYS increase significantly over the 6h time course while E(h) remains relatively constant. The Eh (GSH/GSSG) in YSF and AF become more reduced over time while E(h) (Cys/CySS) become more oxidized. Addition of L-buthionine-S,R-sulfoximine (BS0) to selectively inhibit GSH synthesis and mimic the effects of some GSH-depleting environmental chemicals significantly decreased VYS and EMB GSH and Cys concentrations and increased Eh over the 6h exposure period, showing a greater overall oxidation. In the YSF, BSO caused a significant increase in total Cys concentrations to 1.7 mM but did not significantly change the E(h) for Cys/CySS. A significant net

  4. Redox potential monitoring as a method to control unwanted noble metal-catalyzed hydrogen generation from formic acid treatment of simulated nuclear waste media

    International Nuclear Information System (INIS)

    King, R.B.; Bhattacharyya, N.K.

    1998-01-01

    Simulants for the Hanford Waste Vitrification Plant feed containing the major nonradioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO 3 2- , NO 3 - , and NO 2 - were used to study redox potential changes in reactions of formic acid at 90 C catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Such reactions were monitored using gas chromatography to analyze the CO 2 , H 2 , NO, and N 2 O in the gas phase and a redox electrode to follow redox potential changes as a function of time. In the initial phase of formic acid addition to nitrite-containing feed simulants, the redox potential of the reaction mixture rises typically to +400 mV relative to the Al/AgCl electrode because of the generation of the moderately strongly oxidizing nitrous acid. No H 2 production occurs at this stage of the reaction as long as free nitrous acid is present. After all of the nitrous acid has been destroyed by reduction to N 2 O and NO and disproportionation to NO/NO 3 - , the redox potential of the reaction mixture becomes more negative than the Ag/AgCl electrode. The experiments outlined in this paper suggest the feasibility of controlling the production of H 2 by limiting the amount of formic acid used and monitoring the redox potential during formic acid treatment

  5. Monolayer to MTS: using SEM, HIM, TEM and SERS to compare morphology, nanosensor uptake and redox potential in MCF7 cells

    Science.gov (United States)

    Jamieson, L. E.; Bell, A. P.; Harrison, D. J.; Campbell, C. J.

    2015-06-01

    Cellular redox potential is important for the control and regulation of a vast number of processes occurring in cells. When the fine redox potential balance within cells is disturbed it can have serious consequences such as the initiation or progression of disease. It is thought that a redox gradient develops in cancer tumours where the peripheral regions are well oxygenated and internal regions, further from vascular blood supply, become starved of oxygen and hypoxic. This makes treatment of these areas more challenging as, for example, radiotherapy relies on the presence of oxygen. Currently techniques for quantitative analysis of redox gradients are limited. Surface enhanced Raman scattering (SERS) nanosensors (NS) have been used to detect redox potential in a quantitative manner in monolayer cultured cells with many advantages over other techniques. This technique has considerable potential for use in multicellular tumour spheroids (MTS) - a three dimensional (3D) cell model which better mimics the tumour environment and gradients that develop. MTS are a more realistic model of the in vivo cellular morphology and environment and are becoming an increasingly popular in vitro model, replacing traditional monolayer culture. Imaging techniques such as transmission electron microscopy (TEM), scanning electron microscopy (SEM) and helium ion microscopy (HIM) were used to investigate differences in morphology and NS uptake in monolayer culture compared to MTS. After confirming NS uptake, the first SERS measurements revealing quantitative information on redox potential in MTS were performed.

  6. Electrochemical and AFM characterization on gold and carbon electrodes of a high redox potential laccase from Fusarium proliferatum.

    Science.gov (United States)

    González Arzola, K; Gimeno, Y; Arévalo, M C; Falcón, M A; Hernández Creus, A

    2010-08-01

    The redox potential of the T1 copper site of laccase from Fusarium proliferatum was determined by titration to be about 510 mV vs. SCE (750 mV vs. NHE), which makes it a high redox potential enzyme. Anaerobic electron transfer reactions between laccase and carbon and gold electrodes were detected, both in solution and when the enzyme was adsorbed on these surfaces. In solution, a single high-potential signal (660 mV vs. SCE) was recorded at the carbon surfaces, attributable to the T1 copper site of the enzyme. However, a well-defined oxidative process at about 660 mV and an anodic wave at 350 mV vs. SCE were recorded at the gold electrode, respectively associated with the T1 and T2 copper sites. Laccase-modified carbon electrodes behaved analogously when the enzyme was in solution, unlike laccase adsorbed on gold, which showed only a low-potential signal. Laccase molecules were successfully imaged by AFM; obtaining a thick compact stable film on Au(111), and large aggregates forming a complex network of small branches leaving voids on the HOPG surface. Laccase-modified carbon electrodes retained significant enzymatic activity, efficiently oxidising violuric acid and reducing molecular oxygen. Explanations are proposed for how protein-film organisation affects the electrode function. Copyright (c) 2009 Elsevier B.V. All rights reserved.

  7. Electron-transfer studies with a new flavin adenine dinucleotide dependent glucose dehydrogenase and osmium polymers of different redox potentials.

    Science.gov (United States)

    Zafar, Muhammad Nadeem; Wang, Xiaoju; Sygmund, Christoph; Ludwig, Roland; Leech, Dónal; Gorton, Lo

    2012-01-03

    A new extracellular flavin adenine dinucleotide (FAD)-dependent glucose dehydrogenase from Glomerella cingulata (GcGDH) was electrochemically studied as a recognition element in glucose biosensors. The redox enzyme was recombinantly produced in Pichia pastoris and homogeneously purified, and its glucose-oxidizing properties on spectrographic graphite electrodes were investigated. Six different Os polymers, the redox potentials of which ranged in a broad potential window between +15 and +489 mV versus the normal hydrogen electrode (NHE), were used to immobilize and "wire" GcGDH to the spectrographic graphite electrode's surface. The GcGDH/Os polymer modified electrodes were evaluated by chronoamperometry using flow injection analysis. The current response was investigated using a stepwisely increased applied potential. It was observed that the ratio of GcGDH/Os polymer and the overall loading of the enzyme electrode significantly affect the performance of the enzyme electrode for glucose oxidation. The best-suited Os polymer [Os(4,4'-dimethyl-2,2'-bipyridine)(2)(PVI)Cl](+) had a potential of +309 mV versus NHE, and the optimum GcGDH/Os polymer ratio was 1:2 yielding a maximum current density of 493 μA·cm(-2) at a 30 mM glucose concentration. © 2011 American Chemical Society

  8. Recognition specificity of individual EH domains of mammals and yeast

    DEFF Research Database (Denmark)

    Paoluzi, S; Castagnoli, L; Lauro, I

    1998-01-01

    by characterizing the peptide-binding preference of 11 different EH domains from mammal and yeast proteins. Ten of the eleven EH domains could bind at least some peptides containing an Asn-Pro-Phe (NPF) motif. By contrast, the first EH domain of End3p preferentially binds peptides containing an His-Thr/Ser-Phe (HT...

  9. Effects of moisture content and redox potential on in situ K d values for radioiodine in soil

    International Nuclear Information System (INIS)

    Ashworth, D.J.; Shaw, G.

    2006-01-01

    The soil solid-liquid distribution coefficient (K d ) value is of great significance in understanding and modelling the environmental behaviour of soil contaminants. For many years, the batch sorption technique has been used for the determination of such values. Here, we propose an alternative 'mini-column' approach in which somewhat more realistic soil conditions are maintained. In particular, this approach allows for determination of radionuclide K d values under realistic soil moisture contents and in a system in which time-dependent processes such as changes in redox potential can take place. Data obtained for radioactive iodine (a key radionuclide in the consideration of radioactive waste disposal) are presented and indicate that soil moisture content, particularly in conjunction with soil redox potential (through water-logging of the soil), has a marked effect on measured K d values. The results indicate the advantages and potential usefulness of the mini-column approach in assessing the environmental behaviour of radioactive, and other, soil contaminants

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

    Science.gov (United States)

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

    2018-03-01

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

  11. Effect of redox conditions on bacterial and fungal biomass and carbon dioxide production in Louisiana coastal swamp forest sediment

    International Nuclear Information System (INIS)

    Seo, Dong Cheol; DeLaune, Ronald D.

    2010-01-01

    Fungal and bacterial carbon dioxide (CO 2 ) production/emission was determined under a range of redox conditions in sediment from a Louisiana swamp forest used for wastewater treatment. Sediment was incubated in microcosms at 6 Eh levels (-200, -100, 0, + 100, + 250 and + 400 mV) covering the anaerobic range found in wetland soil and sediment. Carbon dioxide production was determined by the substrate-induced respiration (SIR) inhibition method. Cycloheximide (C 15 H 23 NO 4 ) was used as the fungal inhibitor and streptomycin (C 21 H 39 N 7 O 12 ) as the bacterial inhibitor. Under moderately reducing conditions (Eh > + 250 mV), fungi contributed more than bacteria to the CO 2 production. Under highly reducing conditions (Eh ≤ 0 mV), bacteria contributed more than fungi to the total CO 2 production. The fungi/bacteria (F/B) ratios varied between 0.71-1.16 for microbial biomass C, and 0.54-0.94 for microbial biomass N. Under moderately reducing conditions (Eh ≥ + 100 mV), the F/B ratios for microbial biomass C and N were higher than that for highly reducing conditions (Eh ≤ 0 mV). In moderately reducing conditions (Eh ≥ + 100 mV), the C/N microbial biomass ratio for fungi (C/N: 13.54-14.26) was slightly higher than for bacteria (C/N: 9.61-12.07). Under highly reducing redox conditions (Eh ≤ 0 mV), the C/N microbial biomass ratio for fungi (C/N: 10.79-12.41) was higher than for bacteria (C/N: 8.21-9.14). For bacteria and fungi, the C/N microbial biomass ratios under moderately reducing conditions were higher than that in highly reducing conditions. Fungal CO 2 production from swamp forest could be of greater ecological significance under moderately reducing sediment conditions contributing to the greenhouse effect (GHE) and the global warming potential (GWP). However, increases in coastal submergence associated with global sea level rise and resultant decrease in sediment redox potential from increased flooding would likely shift CO 2 production to bacteria

  12. Determination of redox potentials for the Watson-Crick base pairs, DNA nucleosides, and relevant nucleoside analogues.

    Science.gov (United States)

    Crespo-Hernandez, Carlos E; Close, David M; Gorb, Leonid; Leszczynski, Jerzy

    2007-05-17

    Redox potentials for the DNA nucleobases and nucleosides, various relevant nucleoside analogues, Watson-Crick base pairs, and seven organic dyes are presented based on DFT/B3LYP/6-31++G(d,p) and B3YLP/6-311+G(2df,p)//B3LYP/6-31+G* levels of calculations. The values are determined from an experimentally calibrated set of equations that correlate the vertical ionization (electron affinity) energy of 20 organic molecules with their experimental reversible oxidation (reduction) potential. Our results are in good agreement with those estimated experimentally for the DNA nucleosides in acetonitrile solutions (Seidel et al. J. Phys. Chem. 1996, 100, 5541). We have found that nucleosides with anti conformation exhibit lower oxidation potentials than the corresponding syn conformers. The lowering in the oxidation potential is due to the formation of an intramolecular hydrogen bonding interaction between the 5'-OH group of the sugar and the N3 of the purine bases or C2=O of the pyrimidine bases in the syn conformation. Pairing of adenine or guanine with its complementary pyrimidine base decreases its oxidation potential by 0.15 or 0.28 V, respectively. The calculated energy difference between the oxidation potential for the G.C base pair and that of the guanine base is in good agreement with the experimental value estimated recently (0.34 V: Caruso, T.; et al. J. Am. Chem. Soc. 2005, 127, 15040). The complete and consistent set of reversible redox values determined in this work for the DNA constituents is expected to be of considerable value to those studying charge and electronic energy transfer in DNA.

  13. Transcriptome analysis of Lactococcus lactis subsp. lactis during milk acidification as affected by dissolved oxygen and the redox potential.

    Science.gov (United States)

    Larsen, Nadja; Moslehi-Jenabian, Saloomeh; Werner, Birgit Brøsted; Jensen, Maiken Lund; Garrigues, Christel; Vogensen, Finn Kvist; Jespersen, Lene

    2016-06-02

    Performance of Lactococcus lactis as a starter culture in dairy fermentations depends on the levels of dissolved oxygen and the redox state of milk. In this study the microarray analysis was used to investigate the global gene expression of L. lactis subsp. lactis DSM20481(T) during milk acidification as affected by oxygen depletion and the decrease of redox potential. Fermentations were carried out at different initial levels of dissolved oxygen (dO2) obtained by milk sparging with oxygen (high dO2, 63%) or nitrogen (low dO2, 6%). Bacterial exposure to high initial oxygen resulted in overexpression of genes involved in detoxification of reactive oxygen species (ROS), oxidation-reduction processes, biosynthesis of trehalose and down-regulation of genes involved in purine nucleotide biosynthesis, indicating that several factors, among them trehalose and GTP, were implicated in bacterial adaptation to oxidative stress. Generally, transcriptional changes were more pronounced during fermentation of oxygen sparged milk. Genes up-regulated in response to oxygen depletion were implicated in biosynthesis and transport of pyrimidine nucleotides, branched chain amino acids and in arginine catabolic pathways; whereas genes involved in salvage of nucleotides and cysteine pathways were repressed. Expression pattern of genes involved in pyruvate metabolism indicated shifts towards mixed acid fermentation after oxygen depletion with production of specific end-products, depending on milk treatment. Differential expression of genes, involved in amino acid and pyruvate pathways, suggested that initial oxygen might influence the release of flavor compounds and, thereby, flavor development in dairy fermentations. The knowledge of molecular responses involved in adaptation of L. lactis to the shifts of redox state and pH during milk fermentations is important for the dairy industry to ensure better control of cheese production. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Redox properties of iron-bearing clays and MX-80 bentonite – Electrochemical and spectroscopic characterization

    Energy Technology Data Exchange (ETDEWEB)

    Hofstetter, Th. B.; Sosedova, Y.; Gorski, C.; Voegelin, A.; Sander, M.

    2014-03-15

    The characterization of the redox properties of Fe-bearing minerals in the presence and absence of dissolved Fe{sup 2+} is of major relevance for the assessment of redox reactions in natural and engineered environments such as radioactive waste repositories. In this study, we developed an electrochemical approach based on the use of soluble organic electron transfer mediators, which enabled us to quantify the redox properties of Fe-bearing clay minerals, MX- 80 bentonite and combinations of clay minerals, Fe oxides and dissolved Fe{sup 2+}. Using mediated electrochemical oxidation and reduction, we quantified the electron accepting and donating capacities of ferrous smectite SWa-1, Wyoming montmorillonite SWy-2 and MX-80 bentonite at pH 7.5. All structural Fe in clay minerals was redox-active in contrast to that present in other, not further defined phases of MX-80. The materials investigated were redoxactive over a very wide range of Eh-values, that is the Fe{sup 2+}/Fe{sub total} ratio of the minerals changed from 0 to 100 % between +600 and -600 mV (vs. SHE). Redox properties were highly path-dependent due to structural changes of the minerals as revealed from the study of native and redox-cycled clay minerals after repeated reduction and re-oxidation cycles. Irreversible alteration of the mineral structure, however, was less obvious for materials with lower total Fe content such as MX-80 bentonite and SWy-2. Systems containing native montmorillonites (SWy-2 or MX-80), goethite and dissolved Fe{sup 2+} were also able to buffer the reduction potential E{sub H} between 0 and -300 mV. Regardless of their Fe oxidation state, Fe-bearing minerals are redox-active over a wide potential range and therefore very relevant as redox buffers determining the fate of redox-active radionuclides and metals in waste repositories. (authors)

  15. Investigation of potential analytical methods for redox control of the vitrification process

    International Nuclear Information System (INIS)

    Goldman, D.S.

    1985-11-01

    An investigation was conducted to evaluate several analytical techniques to measure ferrous/ferric ratios in simulated and radioactive nuclear waste glasses for eventual redox control of the vitrification process. Redox control will minimize the melt foaming that occurs under highly oxidizing conditions and the metal precipitation that occurs under highly reducing conditions. The analytical method selected must have a rapid response for production problems with minimal complexity and analyst involvement. The wet-chemistry, Moessbauer spectroscopy, glass color analysis, and ion chromatography techniques were explored, with particular emphasis being placed on the Moessbauer technique. In general, all of these methods can be used for nonradioactive samples. The Moessbauer method can readily analyze glasses containing uranium and thorium. A shielded container was designed and built to analyze fully radioactive glasses with the Moessbauer spectrometer in a hot cell environment. However, analyses conducted with radioactive waste glasses containing 90 Sr and 137 Cs were unsuccessful, presumably due to background radiation problems caused by the samples. The color of glass powder can be used to analyze the ferrous/ferric ratio for low chromium glasses, but this method may not be as precise as the others. Ion chromatography was only tested on nonradioactive glasses, but this technique appears to have the required precision due to its analysis of both Fe +2 and Fe +3 and its anticipated adaptability for radioactivity samples. This development would be similar to procedures already in use for shielded inductively coupled plasma emission (ICP) spectrometry. Development of the ion chromatography method is therefore recommended; conventional wet-chemistry is recommended as a backup procedure

  16. 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.

  17. 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.

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

    Science.gov (United States)

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

    2015-02-01

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

  19. Factors controlling the redox potential of ZnCe6 in an engineered bacterioferritin photochemical 'reaction centre'.

    Science.gov (United States)

    Mahboob, Abdullah; Vassiliev, Serguei; Poddutoori, Prashanth K; van der Est, Art; Bruce, Doug

    2013-01-01

    Photosystem II (PSII) of photosynthesis has the unique ability to photochemically oxidize water. Recently an engineered bacterioferritin photochemical 'reaction centre' (BFR-RC) using a zinc chlorin pigment (ZnCe6) in place of its native heme has been shown to photo-oxidize bound manganese ions through a tyrosine residue, thus mimicking two of the key reactions on the electron donor side of PSII. To understand the mechanism of tyrosine oxidation in BFR-RCs, and explore the possibility of water oxidation in such a system we have built an atomic-level model of the BFR-RC using ONIOM methodology. We studied the influence of axial ligands and carboxyl groups on the oxidation potential of ZnCe6 using DFT theory, and finally calculated the shift of the redox potential of ZnCe6 in the BFR-RC protein using the multi-conformational molecular mechanics-Poisson-Boltzmann approach. According to our calculations, the redox potential for the first oxidation of ZnCe6 in the BRF-RC protein is only 0.57 V, too low to oxidize tyrosine. We suggest that the observed tyrosine oxidation in BRF-RC could be driven by the ZnCe6 di-cation. In order to increase the efficiency of tyrosine oxidation, and ultimately oxidize water, the first potential of ZnCe6 would have to attain a value in excess of 0.8 V. We discuss the possibilities for modifying the BFR-RC to achieve this goal.

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

    Science.gov (United States)

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

    2012-09-04

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

  1. Tuning cofactor redox potentials: the 2-methoxy dihedral angle generates a redox potential difference of >160 mV between the primary (Q(A)) and secondary (Q(B)) quinones of the bacterial photosynthetic reaction center.

    Science.gov (United States)

    Taguchi, Alexander T; Mattis, Aidas J; O'Malley, Patrick J; Dikanov, Sergei A; Wraight, Colin A

    2013-10-15

    Only quinones with a 2-methoxy group can act simultaneously as the primary (QA) and secondary (QB) electron acceptors in photosynthetic reaction centers from Rhodobacter sphaeroides. (13)C hyperfine sublevel correlation measurements of the 2-methoxy in the semiquinone states, SQA and SQB, were compared with quantum mechanics calculations of the (13)C couplings as a function of the dihedral angle. X-ray structures support dihedral angle assignments corresponding to a redox potential gap (ΔEm) between QA and QB of ~180 mV. This is consistent with the failure of a ubiquinone analogue lacking the 2-methoxy to function as QB in mutant reaction centers with a ΔEm of ≈160-195 mV.

  2. Two oxidation sites for low redox potential substrates: a directed mutagenesis, kinetic, and crystallographic study on Pleurotus eryngii versatile peroxidase.

    Science.gov (United States)

    Morales, María; Mate, María J; Romero, Antonio; Martínez, María Jesús; Martínez, Ángel T; Ruiz-Dueñas, Francisco J

    2012-11-30

    Versatile peroxidase shares with manganese peroxidase and lignin peroxidase the ability to oxidize Mn(2+) and high redox potential aromatic compounds, respectively. Moreover, it is also able to oxidize phenols (and low redox potential dyes) at two catalytic sites, as shown by biphasic kinetics. A high efficiency site (with 2,6-dimethoxyphenol and p-hydroquinone catalytic efficiencies of ∼70 and ∼700 s(-1) mM(-1), respectively) was localized at the same exposed Trp-164 responsible for high redox potential substrate oxidation (as shown by activity loss in the W164S variant). The second site, characterized by low catalytic efficiency (∼3 and ∼50 s(-1) mM(-1) for 2,6-dimethoxyphenol and p-hydroquinone, respectively) was localized at the main heme access channel. Steady-state and transient-state kinetics for oxidation of phenols and dyes at the latter site were improved when side chains of residues forming the heme channel edge were removed in single and multiple variants. Among them, the E140G/K176G, E140G/P141G/K176G, and E140G/W164S/K176G variants attained catalytic efficiencies for oxidation of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) at the heme channel similar to those of the exposed tryptophan site. The heme channel enlargement shown by x-ray diffraction of the E140G, P141G, K176G, and E140G/K176G variants would allow a better substrate accommodation near the heme, as revealed by the up to 26-fold lower K(m) values (compared with native VP). The resulting interactions were shown by the x-ray structure of the E140G-guaiacol complex, which includes two H-bonds of the substrate with Arg-43 and Pro-139 in the distal heme pocket (at the end of the heme channel) and several hydrophobic interactions with other residues and the heme cofactor.

  3. Estimation of redox potentials of Fe(III)- gallic acid complexes at different pH by spectrophotometric titration with ascorbate

    International Nuclear Information System (INIS)

    Iqbal, M.; Tasneem, Z.; Kazmi, S.A.

    1993-01-01

    Fe(III) is strongly chelated by Gallic acid. This equilibrium as well as the kinetics of reduction of the complex is strongly pH dependent. The complex was prepared in acetate buffers of pH 4.6, 5.0 and 5.6 and in Tris buffer of pH 7.0.The complex was reduced by ascorbate. The reduced absorbance was taken to be a measure of reaction. Nernst equation was then applied to determine the standard redox potentials of the complex taking the literature values of the redox potentials of ascorbate at different pH. The values of redox potentials of complex were found to be 0.197 V at pH 4.6. 0.181 V at pH 5.0 1.132 V at pH 5.6 and 0.092 V at pH 7.0. (author)

  4. 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.

  5. Bench Scale Process for Low Cost CO2 Capture Using a Phase-Changing Absorbent: Topical Report EH&S Risk Assessment

    Energy Technology Data Exchange (ETDEWEB)

    Westendorf, Tiffany; Farnum, Rachel; Perry, Robert; Herwig, Mark; Giolando, Salvatore; Green, Dianne; Morall, Donna

    2016-05-11

    GE Global Research was contracted by the Department of Energy to design and build a bench-scale process for a novel phase-changing aminosilicone-based CO2 capture solvent (award number DEFE0013687). As part of this program, a technology EH&S assessment (Subtask 5.1) has been completed for a CO2 capture system for a 550 MW coal-fired power plant. The assessment focuses on two chemicals used in the process, the aminosilicone solvent, GAP-0, and dodecylbenzenesulfonic acid (DDBSA), the GAP-0 carbamate formed upon reaction of the GAP-0 with CO2, and two potential byproducts formed in the process, GAP-0/SOx salts and amine-terminated, urea-containing silicone (also referred to as “ureas” in this report). The EH&S assessment identifies and estimates the magnitude of the potential air and water emissions and solid waste generated by the process and reviews the toxicological profiles of the chemicals associated with the process. Details regarding regulatory requirements, engineering controls, and storage and handling procedures are also provided in the following sections.

  6. Redox fronts

    International Nuclear Information System (INIS)

    Chapman, N.; McKinley, I.; Shea, M.; Smellie, J.

    1993-01-01

    This article describes the investigations of redox fronts performed at the Osamu Utsumi mine. Results obtained by modelling groups on the rate of movement of the redox fronts and on the chemical reactions involved are discussed. Some of the most important rockwater interactions which occur at redox fronts can be modelled reasonably well but the complex redox chemistry of elements like sulphur is poorly simulated. The observed enrichment of many trace elements close to the redox fronts could be of significance for high-level waste repositories, but cannot be quantified by existing models. (author) 6 figs., 1 tab

  7. Equilibrium electrode U(4)-U and redox U(4)-U(3) potentials in molten alkali metal chlorides medium

    Energy Technology Data Exchange (ETDEWEB)

    Smirnov, M V; Kudyakov, V Ya; Komarov, V E; Salyulev, A B [AN SSSR, Sverdlovsk. Inst. Ehlektrokhimii

    1979-02-01

    Conditional standard electrode potentials of uranium are determined for diluted solutions of its tetrachloride in alkali metal chloride melts (LiCl, NaCl, NaCl-KCl, KCl, RbCl and CsCl) when using U(4) ion activity coefficient values experimentally found by the tensimetric method. These potentials shift to the electronegative side at the temperature decrease and alkali cation radius increase rsub(Msup(+)) according to the empiric ratio E*U(4)-U= -3.06+6.87x10/sup -4/ T-(1.67-10/sup -4/T-0.44) 1/rsub(Msup(+)) +-0.01. The temperature dependences of formal conditional redox potentials of the U(4)-U(3) system for above melted chlorides are estimated. The E*U(4)-U(3) value also becomes more electronegative in the series LiCl, NaCl, NaCl-KCl, KCl, RbCl and CsCl. This alternation is satisfactorily described by the empiric expression E*U(4)-U(3)= -1.74+1.74x10/sup -4/T-(0.71x10/sup -4/T-0.20) 1rsub(Msup(+)) +-0.05. The calculated values Eu*(4)-U(3) are compared with those directly measured for the NaCl-KCl equimolar mixture and 3LiCl-2KCl eutectic mixture. A satisfactory confirmity has been observed.

  8. Equilibrium electrode U(4)-U and redox U(4)-U(3) potentials in molten alkali metal chlorides medium

    International Nuclear Information System (INIS)

    Smirnov, M.V.; Kudyakov, V.Ya.; Komarov, V.E.; Salyulev, A.B.

    1979-01-01

    Conditional standard electrode potentials of uranium are determined for diluted solutions of its tetrachloride in alkali metal chloride melts (LiCl, NaCl, NaCl-KCl, KCl, RbCl and CsCl) when using U(4) ion activity coefficient values experimentally found by the tensimetric method. These potentials shift to the electronegative side at the temperature decrease and alkali cation radius increase rsub(Msup(+)) according to the empiric ratio E*U(4)-U= -3.06+6.87x10 -4 T-(1.67-10 -4 T-0.44) 1/rsub(Msup(+)) +-0.01. The temperature dependences of formal conditional redox potentials of the U(4)-U(3) system for above melted chlorides are estimated. The E*U(4)-U(3) value also becomes more electronegative in the series LiCl, NaCl, NaCl-KCl, KCl, RbCl and CsCl. This alternation is satisfactorily described by the empiric expression E*U(4)-U(3)= -1.74+1.74x10 -4 T-(0.71x10 -4 T-0.20) 1rsub(Msup(+)) +-0.05. The calculated values Eu*(4)-U(3) are compared with those directly measured for the NaCl-KCl equimolar mixture and 3LiCl-2KCl eutectic mixture. A satisfactory confirmity has been observed

  9. Visualizing redox orbitals and their potentials in advanced lithium-ion battery materials using high-resolution x-ray Compton scattering.

    Science.gov (United States)

    Hafiz, Hasnain; Suzuki, Kosuke; Barbiellini, Bernardo; Orikasa, Yuki; Callewaert, Vincent; Kaprzyk, Staszek; Itou, Masayoshi; Yamamoto, Kentaro; Yamada, Ryota; Uchimoto, Yoshiharu; Sakurai, Yoshiharu; Sakurai, Hiroshi; Bansil, Arun

    2017-08-01

    Reduction-oxidation (redox) reactions are the key processes that underlie the batteries powering smartphones, laptops, and electric cars. A redox process involves transfer of electrons between two species. For example, in a lithium-ion battery, current is generated when conduction electrons from the lithium anode are transferred to the redox orbitals of the cathode material. The ability to visualize or image the redox orbitals and how these orbitals evolve under lithiation and delithiation processes is thus of great fundamental and practical interest for understanding the workings of battery materials. We show that inelastic scattering spectroscopy using high-energy x-ray photons (Compton scattering) can yield faithful momentum space images of the redox orbitals by considering lithium iron phosphate (LiFePO 4 or LFP) as an exemplar cathode battery material. Our analysis reveals a new link between voltage and the localization of transition metal 3d orbitals and provides insight into the puzzling mechanism of potential shift and how it is connected to the modification of the bond between the transition metal and oxygen atoms. Our study thus opens a novel spectroscopic pathway for improving the performance of battery materials.

  10. Rapid detection of Listeria monocytogenes in raw milk and soft cheese by a redox potential measurement based method combined with real-time PCR.

    Science.gov (United States)

    Erdősi, Orsolya; Szakmár, Katalin; Reichart, Olivér; Szili, Zsuzsanna; László, Noémi; Székely Körmöczy, Péter; Laczay, Péter

    2014-09-01

    The incidence of outbreaks of foodborne listeriosis has indicated the need for a reliable and rapid detection of the microbe in different foodstuffs. A method combining redox potential measurement and real-time polymerase chain reaction (PCR) was developed to detect Listeria monocytogenes in artificially contaminated raw milk and soft cheese. Food samples of 25 g or 25 ml were homogenised in 225 ml of Listeria Enrichment Broth (LEB) with Oxford supplement, and the redox potential measurement technique was applied. For Listeria species the measuring time was maximum 34 h. The absence of L. monocytogenes could reliably be proven by the redox potential measurement method, but Listeria innocua and Bacillus subtilis could not be differentiated from L. monocytogenes on the basis of the redox curves. The presence of L. monocytogenes had to be confirmed by real-time PCR. The combination of these two methods proved to detect < 10 cfu/g of L. monocytogenes in a cost- and time-effective manner. This method can potentially be used as an alternative to the standard nutrient method for the rapid detection of L. monocytogenes in food.

  11. Development of techniques and models for the determination of redox potentials of saline solutions; Entwicklung von Methoden und Modellen zur Bestimmung des Redoxpotentials salinarer Loesungen

    Energy Technology Data Exchange (ETDEWEB)

    Hagemann, Sven; Bischofer, Barbara; Scharge, Tina; Schoenwiese, Dagmar

    2014-03-15

    The mobility of radionuclides and heavy metals in aqueous systems depends significantly on their oxidation state. Under saline conditions the measurement of pH values and redox potential are distorted/falsified by solution-specific and hardly assessable ion diffusion effects at the reference electrode. The secure prognosis of redox properties is an essential prerequisite for the calculation of the expected heavy metal and radionuclide concentrations in case of a hypothetical solution ingress in an underground disposal facility. The evaluation of the existing data base shows that there are large uncertainties even for the solubility of widespread oxides and oxy-hydroxides like goethite or hematite. The redox properties of natural systems are determined by the solubility of metastable ferrous intermediate products like ferrihydrite, ''green rust'' or jarosite. The work is aimed to establish a consistent data base with information on these phases and ferrous solute species.

  12. Development of techniques and models for the determination of redox potentials of saline solutions; Entwicklung von Methoden und Modellen zur Bestimmung des Redoxpotentials salinarer Loesungen

    Energy Technology Data Exchange (ETDEWEB)

    Hagemann, Sven; Bischofer, Barbara; Scharge, Tina; Schoenwiese, Dagmar

    2014-03-15

    The mobility of radionuclides and heavy metals in aqueous systems depends significantly on their oxidation state. Under saline conditions the measurement of pH values and redox potential are distorted/falsified by solution-specific and hardly assessable ion diffusion effects at the reference electrode. The secure prognosis of redox properties is an essential prerequisite for the calculation of the expected heavy metal and radionuclide concentrations in case of a hypothetical solution ingress in an underground disposal facility. The evaluation of the existing data base shows that there are large uncertainties even for the solubility of widespread oxides and oxy-hydroxides like goethite or hematite. The redox properties of natural systems are determined by the solubility of metastable ferrous intermediate products like ferrihydrite, ''green rust'' or jarosite. The work is aimed to establish a consistent data base with information on these phases and ferrous solute species.

  13. Electrochemistry of cations in diopsidic melt - Determining diffusion rates and redox potentials from voltammetric curves

    Science.gov (United States)

    Colson, Russell O.; Haskin, Larry A.; Crane, Daniel

    1990-01-01

    Results are presented on determinations of reduction potentials and their temperature dependence of selected ions in diopsidic melt, by using linear sweep voltammetry. Diffusion coefficients were measured for cations of Eu, Mn, Cr, and In. Enthalpies and entropies of reduction were determined for the cations V(V), Cr(3+), Mn(2+), Mn(3+), Fe(2+), Cu(2+), Mo(VI), Sn(IV), and Eu(3+). Reduction potentials were used to study the structural state of cations in the melt.

  14. Quantum Mechanics/Molecular Mechanics Method Combined with Hybrid All-Atom and Coarse-Grained Model: Theory and Application on Redox Potential Calculations.

    Science.gov (United States)

    Shen, Lin; Yang, Weitao

    2016-04-12

    We developed a new multiresolution method that spans three levels of resolution with quantum mechanical, atomistic molecular mechanical, and coarse-grained models. The resolution-adapted all-atom and coarse-grained water model, in which an all-atom structural description of the entire system is maintained during the simulations, is combined with the ab initio quantum mechanics and molecular mechanics method. We apply this model to calculate the redox potentials of the aqueous ruthenium and iron complexes by using the fractional number of electrons approach and thermodynamic integration simulations. The redox potentials are recovered in excellent accordance with the experimental data. The speed-up of the hybrid all-atom and coarse-grained water model renders it computationally more attractive. The accuracy depends on the hybrid all-atom and coarse-grained water model used in the combined quantum mechanical and molecular mechanical method. We have used another multiresolution model, in which an atomic-level layer of water molecules around redox center is solvated in supramolecular coarse-grained waters for the redox potential calculations. Compared with the experimental data, this alternative multilayer model leads to less accurate results when used with the coarse-grained polarizable MARTINI water or big multipole water model for the coarse-grained layer.

  15. Improving Fructose Utilization and Butanol Production by Clostridium acetobutylicum via Extracellular Redox Potential Regulation and Intracellular Metabolite Analysis.

    Science.gov (United States)

    Chen, Li-Jie; Wu, You-Duo; Xue, Chuang; Bai, Feng-Wu

    2017-10-01

    Jerusalem artichoke (JA) can grow well in marginal lands with high biomass yield, and thus is a potential energy crop for biorefinery. The major biomass of JA is from tubers, which contain inulin that can be easily hydrolyzed into a mixture of fructose and glucose, but fructose utilization for producing butanol as an advanced biofuel is poor compared to glucose-based ABE fermentation by Clostridium acetobutylicum. In this article, the impact of extracellular redox potential (ORP) on the process is studied using a mixture of fructose and glucose to simulate the hydrolysate of JA tubers. When the extracellular ORP is controlled above -460 mV, 13.2 g L -1 butanol is produced from 51.0 g L -1 total sugars (40.1 g L -1 fructose and 10.9 g L -1 glucose), leading to dramatically increased butanol yield and butanol/ABE ratio of 0.26 g g -1 and 0.67, respectively. Intracellular metabolite and q-PCR analysis further indicate that intracellular ATP and NADH availabilities are significantly improved together with the fructose-specific PTS expression at the lag phase, which consequently facilitate fructose transport, metabolic shift toward solventogenesis and carbon flux redistribution for butanol biosynthesis. Therefore, the extracellular ORP control can be an effective strategy to improve butanol production from fructose-based feedstock. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Complexation Effect on Redox Potential of Iron(III)-Iron(II) Couple: A Simple Potentiometric Experiment

    Science.gov (United States)

    Rizvi, Masood Ahmad; Syed, Raashid Maqsood; Khan, Badruddin

    2011-01-01

    A titration curve with multiple inflection points results when a mixture of two or more reducing agents with sufficiently different reduction potentials are titrated. In this experiment iron(II) complexes are combined into a mixture of reducing agents and are oxidized to the corresponding iron(III) complexes. As all of the complexes involve the…

  17. 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

  18. 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

  19. In-situ Eh sensor measurement and calibration: application to seafloor observatories

    Science.gov (United States)

    Ding, K.; Seyfried, W. E.; Tan, C.

    2013-12-01

    Eh measurement is often used with manned submersible and AUV assets as an effective way to detect and locate seafloor hydrothermal activity. Eh can be fundamentally and sensitively linked to dissolved H 2 , which, in turn, serves as a key constraint on subseafloor redox reactions. Moreover, Eh is now being increasingly relied on for event detection and process monitoring efforts intrinsic to cabled seafloor observatories. Due to seawater interaction with electrochemical components fundamental to the operation of the Eh sensor, however, the quality and reliability of the measurements are often compromised by signal drift, especially when the sensor is used for long term deployment. To solve this problem, a calibration protocol was developed and added to our previously constructed pH 'calibrator'. Thus, the integrated electrochemical system now permits the combined in-situ measurement and calibration of pH and Eh of seafloor hydrothermal fluids. Key aspects of the design for this calibration system are: (1) the sensing electrodes can be kept preserved in fluid of known pH, Eh and NaCl concentration prior to use, thereby preventing deterioration of electrode response characteristics by chemical and biological activity; (2) the system consists of valves and pumps for flow control, and therefore can be operated remotely with power from the seafloor cabled observatory, or as a stand-alone device, using battery power for shorter-term deployments. In both cases, standardization with on-board fluids of known redox, pH, and NaCl activity can be activated at any time, providing enhanced reliability (3) the current development is aimed at deep sea environments, cold seeps, and hydrothermal diffuse flow fluids at the temperatures up to 100°C and depths up to 4500 m. The in-situ operation is especially well-suited for use with cabled observatory for real time intervention and event response owing to enabled power supply and two way communications. Field tests have been

  20. Enhancement of acidogenic fermentation for volatile fatty acid production from food waste: Effect of redox potential and inoculum.

    Science.gov (United States)

    Yin, Jun; Yu, Xiaoqin; Zhang, Yeer; Shen, Dongsheng; Wang, Meizhen; Long, Yuyang; Chen, Ting

    2016-09-01

    The aim of this study was to explore the effects of redox potential (ORP) and inoculum on volatile fatty acids (VFAs) production from food waste by acidogenic fermentation. Four experimental conditions with two ORP levels were tested: limited aeration conditions with ORP level of -100 to -200mV inoculating anaerobic sludge (LA+AnS) or aerobic sludge (LA+AeS), and anaerobic conditions with ORP level of -200 to -300mV inoculating anaerobic sludge with 2-bromoethanosulfophate (AN+BES) and without BES (AN). The maximal VFA yield (0.79g COD/g VS) was attained in LA+AnS reactor due to enhanced hydrolysis of substrates, especially proteins (degradation efficiency 78.3%). A higher frequency of phylum Firmicutes under limited aeration conditions (42.2-48.2%) was observed than that under anaerobic conditions (21.1%). The microbial community was more diverse in LA+AnS reactors than LA+AeS. We conclude that appropriate ORP level (from -100 to -200mV) and inoculum play essential roles in VFA production. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. In vitro neuroprotective potential of lichen metabolite fumarprotocetraric acid via intracellular redox modulation

    International Nuclear Information System (INIS)

    Fernández-Moriano, Carlos; Divakar, Pradeep Kumar; Crespo, Ana; Gómez-Serranillos, M. Pilar

    2017-01-01

    The lichen-forming fungi Cetraria islandica has been largely used in folk medicines, and it has recently showed promising in vitro antioxidant effects in glial-like cells. Current work aimed at investigating the neuroprotective potential of its major isolated secondary metabolite: the depsidone fumarprotocetraric acid (FUM). H 2 O 2 was used herein to induce oxidative stress (OS)-mediated cytotoxicity in two models of neurons and astrocytes cells (SH-SY5Y and U373-MG cell lines). We found that a pre-treatment with FUM significantly enhanced cell viability compared to H 2 O 2 -treated cells, and we selected the optimal concentrations in each model (1 and 25 μg/ml, respectively) for assessing its cytoprotective mechanisms. FUM, which exerted effective peroxyl radical scavenging effect in the chemical oxygen radical antioxidant capacity (ORAC) assay, alleviated the alterations in OS markers provoked by H 2 O 2 . It attenuated intracellular ROS formation, lipid peroxidation and GSH depletion. At mitochondrial level, FUM prevented from the dissipation of mitochondrial membrane potential and the increase in mitochondrial calcium, implying a protective role against oxidative damage in mitochondrial membrane. Similarly, FUM pre-treatment diminished H 2 O 2 -induced apoptosis, as evidenced by the reduction in caspase-3 activity and expression; inmunoblot analysis also revealed a decrease in Bax and an increase in Bcl-2 proteins levels. Furthermore, FUM up-regulated the expression of the antioxidant enzymes catalase, superoxide dismutase-1, and hemeoxigenase-1. These findings and the activation of Nrf2 binding activity in nuclear extracts suggest a plausible involvement of Nrf2 signaling pathway in the cytoprotection by FUM. In conclusion, FUM emerges as a potential drug candidate in the therapy of OS-related diseases, such as the neurodegenerative disorders. - Highlights: • FUM pre-treatment exerts significant cytoprotection against H 2 O 2 -mediated apoptosis. • ROS

  2. In vitro neuroprotective potential of lichen metabolite fumarprotocetraric acid via intracellular redox modulation

    Energy Technology Data Exchange (ETDEWEB)

    Fernández-Moriano, Carlos [Department of Pharmacology, Faculty of Pharmacy, University Complutense of Madrid, Plaza Ramón y Cajal s/n, 28040 Madrid (Spain); Divakar, Pradeep Kumar; Crespo, Ana [Department of Plant Biology II, Faculty of Pharmacy, University Complutense of Madrid, Plaza Ramón y Cajal s/n, 28040 Madrid (Spain); Gómez-Serranillos, M. Pilar, E-mail: pserra@ucm.es [Department of Pharmacology, Faculty of Pharmacy, University Complutense of Madrid, Plaza Ramón y Cajal s/n, 28040 Madrid (Spain)

    2017-02-01

    The lichen-forming fungi Cetraria islandica has been largely used in folk medicines, and it has recently showed promising in vitro antioxidant effects in glial-like cells. Current work aimed at investigating the neuroprotective potential of its major isolated secondary metabolite: the depsidone fumarprotocetraric acid (FUM). H{sub 2}O{sub 2} was used herein to induce oxidative stress (OS)-mediated cytotoxicity in two models of neurons and astrocytes cells (SH-SY5Y and U373-MG cell lines). We found that a pre-treatment with FUM significantly enhanced cell viability compared to H{sub 2}O{sub 2}-treated cells, and we selected the optimal concentrations in each model (1 and 25 μg/ml, respectively) for assessing its cytoprotective mechanisms. FUM, which exerted effective peroxyl radical scavenging effect in the chemical oxygen radical antioxidant capacity (ORAC) assay, alleviated the alterations in OS markers provoked by H{sub 2}O{sub 2}. It attenuated intracellular ROS formation, lipid peroxidation and GSH depletion. At mitochondrial level, FUM prevented from the dissipation of mitochondrial membrane potential and the increase in mitochondrial calcium, implying a protective role against oxidative damage in mitochondrial membrane. Similarly, FUM pre-treatment diminished H{sub 2}O{sub 2}-induced apoptosis, as evidenced by the reduction in caspase-3 activity and expression; inmunoblot analysis also revealed a decrease in Bax and an increase in Bcl-2 proteins levels. Furthermore, FUM up-regulated the expression of the antioxidant enzymes catalase, superoxide dismutase-1, and hemeoxigenase-1. These findings and the activation of Nrf2 binding activity in nuclear extracts suggest a plausible involvement of Nrf2 signaling pathway in the cytoprotection by FUM. In conclusion, FUM emerges as a potential drug candidate in the therapy of OS-related diseases, such as the neurodegenerative disorders. - Highlights: • FUM pre-treatment exerts significant cytoprotection against H

  3. Concrete decontamination by Electro-Hydraulic Scabbling (EHS)

    International Nuclear Information System (INIS)

    1994-11-01

    EHS is being developed for decontaminating concrete structures from radionuclides, organic substances, and hazardous metals. EHS involves the generation of powerful shock waves and intense cavitation by a strong pulsed electric discharge in a water layer at the concrete surface; high impulse pressure results in stresses which crack and peel off a concrete layer of controllable thickness. Scabbling produces contaminated debris of relatively small volume which can be easily removed, leaving clean bulk concrete. Objective of Phase I was to prove the technical feasibility of EH for controlled scabbling and decontamination of concrete. Phase I is complete

  4. Concrete decontamination by Electro-Hydraulic Scabbling (EHS)

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1994-11-01

    EHS is being developed for decontaminating concrete structures from radionuclides, organic substances, and hazardous metals. EHS involves the generation of powerful shock waves and intense cavitation by a strong pulsed electric discharge in a water layer at the concrete surface; high impulse pressure results in stresses which crack and peel off a concrete layer of controllable thickness. Scabbling produces contaminated debris of relatively small volume which can be easily removed, leaving clean bulk concrete. Objective of Phase I was to prove the technical feasibility of EH for controlled scabbling and decontamination of concrete. Phase I is complete.

  5. Conformational differences between the methoxy groups of QA and QB site ubisemiquinones in bacterial reaction centers: a key role for methoxy group orientation in modulating ubiquinone redox potential.

    Science.gov (United States)

    Taguchi, Alexander T; O'Malley, Patrick J; Wraight, Colin A; Dikanov, Sergei A

    2013-07-09

    Ubiquinone is an almost universal, membrane-associated redox mediator. Its ability to accept either one or two electrons allows it to function in critical roles in biological electron transport. The redox properties of ubiquinone in vivo are determined by its environment in the binding sites of proteins and by the dihedral angle of each methoxy group relative to the ring plane. This is an attribute unique to ubiquinone among natural quinones and could account for its widespread function with many different redox complexes. In this work, we use the photosynthetic reaction center as a model system for understanding the role of methoxy conformations in determining the redox potential of the ubiquinone/semiquinone couple. Despite the abundance of X-ray crystal structures for the reaction center, quinone site resolution has thus far been too low to provide a reliable measure of the methoxy dihedral angles of the primary and secondary quinones, QA and QB. We performed 2D ESEEM (HYSCORE) on isolated reaction centers with ubiquinones (13)C-labeled at the headgroup methyl and methoxy substituents, and have measured the (13)C isotropic and anisotropic components of the hyperfine tensors. Hyperfine couplings were compared to those derived by DFT calculations as a function of methoxy torsional angle allowing estimation of the methoxy dihedral angles for the semiquinones in the QA and QB sites. Based on this analysis, the orientation of the 2-methoxy groups are distinct in the two sites, with QB more out of plane by 20-25°. This corresponds to an ≈50 meV larger electron affinity for the QB quinone, indicating a substantial contribution to the experimental difference in redox potentials (60-75 mV) of the two quinones. The methods developed here can be readily extended to ubiquinone-binding sites in other protein complexes.

  6. Composition and Redox Potential of High-Grade Fluids: An Example from the Nilgiri Block, Southern India

    Science.gov (United States)

    Samuel, V. O.; Harlov, D. E.; Kwon, S.

    2017-12-01

    Composition and redox potential of fluids present during high-grade metamorphism exert an enormous influence on mineral textures and their regional trends within metamorphic complexes. We examine silicate, oxide, and sulfide trends in the Nilgiri Block, southern India. This terrain formed through subduction-related arc magmatic processes in the Neoarchean (ca. 2500 Ma). The Nilgiri highlands are characterized by granulite-facies metagabbro in the north, a two-pyroxene granulite transition zone, and tonalitic-granodioritic charnockites in the central and southern part. Garnet-orthopyroxene and orthopyroxene-clinopyroxene thermometry and garnet-orthopyroxene-plagioclase-quartz barometric results indicate a regional trend both in temperature ( 650 to 800 °C) and in pressure (700 to 1100 MPa) from SW to NE across the Nilgiri highlands. Regional trends are also seen in the oxide-sulfide mineralogy. The main oxide assemblage in the charnockites is rutile-ilmenite, whereas in the two-pyroxene granulites and metagabbros, hemo-ilmenite-magnetite dominates. The key sulfide mineral in the charnockites is pyrrhotite, with minor chalcopyrite. In the two-pyroxene granulites and metagabbros, the principle sulfide assemblage is pyrite +/- minor pyrrhotite. This reveals a regional oxidation trend. The metagabbros and two-pyroxene granulites are highly oxidized compared to the charnockites. Their higher oxidation state is proposed to be the result of highly oxidizing agents (probably as SO2) in low H2O activity fluids (most likely concentrated NaCl brines) during granulite-facies metamorphism of the metagabbros and two-pyroxene granulites. These agents were considerably more reducing (possibly as H2S) during granulite-facies metamorphism of the charnockites. This study emphasizes the potential role of oxidizing and reducing, low H2O activity fluids during granulite-facies metamorphism.

  7. Insights in the electronic structure and redox reaction energy in LiFePO4 battery material from an accurate Tran-Blaha modified Becke Johnson potential

    International Nuclear Information System (INIS)

    Araujo, Rafael B.; Almeida, J. de S; Ferreira da Silva, A.; Ahuja, Rajeev

    2015-01-01

    The main goals of this paper are to investigate the accuracy of the Tran-Blaha modified Becke Johnson (TB-mBJ) potential to predict the electronic structure of lithium iron phosphate and the related redox reaction energy with the lithium deintercalation process. The computed electronic structures show that the TB-mBJ method is able to partially localize Fe-3d electrons in LiFePO 4 and FePO 4 which usually is a problem for the generalized gradient approximation (GGA) due to the self interaction error. The energy band gap is also improved by the TB-mBJ calculations in comparison with the GGA results. It turned out, however, that the redox reaction energy evaluated by the TB-mBJ technique is not in good agreement with the measured one. It is speculated that this disagreement in the computed redox energy and the experimental value is due to the lack of a formal expression to evaluate the exchange and correlation energy. Therefore, the TB-mBJ is an efficient method to improve the prediction of the electronic structures coming form the standard GGA functional in LiFePO 4 and FePO 4 . However, it does not appear to have the same efficiency for evaluating the redox reaction energies for the investigated system

  8. Developments in the monitoring and control of Eh and pH conditions in hydrothermal experiments

    International Nuclear Information System (INIS)

    Myers, J.; Ulmer, G.C.; Grandstaff, D.E.; Brozdowski, R.; Danielson, M.J.; Koski, O.H.

    1984-01-01

    In the design of a high-level nuclear waste repository it is essential to obtain accurate groundwater Eh-pH data. Design considerations such as the choice of matrix for the waste form, type and dimensions of canister material, use of buffers, and type and amount of backfill would all benefit from an exact knowledge of oxidation potentials (Eh) and acidity levels (pH) of the groundwater. The Basalt Waste Isolation Project (BWIP) has initiated a research effort to develop sensors which can be mounted in autoclaves to provide constant monitoring of the Eh-pH conditions that exist during waste form/barrier material/groundwater hydrothermal interaction tests. Sensors must withstand temperatures up to 300 0 C and pressures up to 300 bars. This report considers Teflon hydrogen diffusion membranes and zirconia pH sensors. The development of these sensors represents a significant advance in the environmental monitoring of Eh and pH conditions at elevated temperatures and pressures

  9. Functions of NQO1 in Cellular Protection and CoQ10 Metabolism and its Potential Role as a Redox Sensitive Molecular Switch

    Directory of Open Access Journals (Sweden)

    David Ross

    2017-08-01

    Full Text Available NQO1 is one of the two major quinone reductases in mammalian systems. It is highly inducible and plays multiple roles in cellular adaptation to stress. A prevalent polymorphic form of NQO1 results in an absence of NQO1 protein and activity so it is important to elucidate the specific cellular functions of NQO1. Established roles of NQO1 include its ability to prevent certain quinones from one electron redox cycling but its role in quinone detoxification is dependent on the redox stability of the hydroquinone generated by two-electron reduction. Other documented roles of NQO1 include its ability to function as a component of the plasma membrane redox system generating antioxidant forms of ubiquinone and vitamin E and at high levels, as a direct superoxide reductase. Emerging roles of NQO1 include its function as an efficient intracellular generator of NAD+ for enzymes including PARP and sirtuins which has gained particular attention with respect to metabolic syndrome. NQO1 interacts with a growing list of proteins, including intrinsically disordered proteins, protecting them from 20S proteasomal degradation. The interactions of NQO1 also extend to mRNA. Recent identification of NQO1 as a mRNA binding protein have been investigated in more detail using SERPIN1A1 (which encodes the serine protease inhibitor α-1-antitrypsin as a target mRNA and indicate a role of NQO1 in control of translation of α-1-antitrypsin, an important modulator of COPD and obesity related metabolic syndrome. NQO1 undergoes structural changes and alterations in its ability to bind other proteins as a result of the cellular reduced/oxidized pyridine nucleotide ratio. This suggests NQO1 may act as a cellular redox switch potentially altering its interactions with other proteins and mRNA as a result of the prevailing redox environment.

  10. 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.

  11. A Multi-Parametric Device with Innovative Solid Electrodes for Long-Term Monitoring of pH, Redox-Potential and Conductivity in a Nuclear Waste Repository

    Directory of Open Access Journals (Sweden)

    Jordan Daoudi

    2017-06-01

    Full Text Available We present an innovative electrochemical probe for the monitoring of pH, redox potential and conductivity in near-field rocks of deep geological radioactive waste repositories. The probe is composed of a monocrystalline antimony electrode for pH sensing, four AgCl/Ag-based reference or Cl− selective electrodes, one Ag2S/Ag-based reference or S2− selective electrode, as well as four platinum electrodes, a gold electrode and a glassy-carbon electrode for redox potential measurements. Galvanostatic electrochemistry impedance spectroscopy using AgCl/Ag-based and platinum electrodes measure conductivity. The use of such a multi-parameter probe provides redundant information, based as it is on the simultaneous behaviour under identical conditions of different electrodes of the same material, as well as on that of electrodes made of different materials. This identifies the changes in physical and chemical parameters in a solution, as well as the redox reactions controlling the measured potential, both in the solution and/or at the electrode/solution interface. Understanding the electrochemical behaviour of selected materials thus is a key point of our research, as provides the basis for constructing the abacuses needed for developing robust and reliable field sensors.

  12. One electron transfer equilibria and redox potentials of radicals studies by pulse radiolysis. Progress report, September 1, 1975--July 1, 1976

    International Nuclear Information System (INIS)

    Meisel, D.; Czapski, G.

    1976-01-01

    The pulse radiolysis technique is utilized for measurements of the equilibrium constants for electron transfer between the durosemiquinone radical anion and oxygen, menadione and indigo disulfonate. These equilibrium constants are in turn used for calculations of one-electron redox potentials for these systems. Each of these equilibrium constants was determined experimentally and independently and found to be self consistent. Only for the reactions of the semiquinones with oxygen could the electron transfer reaction be followed directly. For the reactions between the various quinone/semiquinone systems substantial indirect evidence is presented that these equilibria are achieved rapidly. In those cases equilibrium constants were determined from studies of the effect of quinone concentrations on the relative yields of the semiquinones. A method for distinguishing between kinetic competition and equilibrium is outlined and its usefulness is emphasized. The DQ/DQ - (DQ = duroquinone) and IDS/IDS - (IDS = indigo disulfonate) systems were employed as reference couples as the redox potentials for those systems are either available in the literature (IDS/IDS - ) or may be calculated from available data (DQ/DQ - ). Taking E 7 1 , the redox potential for the first one-electron reduction step at pH 7, of DQ/DQ - as -0.235 volts or of IDS/IDS - as -0.125 volts, both yield E 7 1 = -0.325 V for the O 2 /O 2 - system (1 atm O 2 ) and E 7 1 = -0.20 for the menadione system

  13. A Multi-Parametric Device with Innovative Solid Electrodes for Long-Term Monitoring of pH, Redox-Potential and Conductivity in a Nuclear Waste Repository.

    Science.gov (United States)

    Daoudi, Jordan; Betelu, Stephanie; Tzedakis, Theodore; Bertrand, Johan; Ignatiadis, Ioannis

    2017-06-13

    We present an innovative electrochemical probe for the monitoring of pH, redox potential and conductivity in near-field rocks of deep geological radioactive waste repositories. The probe is composed of a monocrystalline antimony electrode for pH sensing, four AgCl/Ag-based reference or Cl - selective electrodes, one Ag₂S/Ag-based reference or S 2- selective electrode, as well as four platinum electrodes, a gold electrode and a glassy-carbon electrode for redox potential measurements. Galvanostatic electrochemistry impedance spectroscopy using AgCl/Ag-based and platinum electrodes measure conductivity. The use of such a multi-parameter probe provides redundant information, based as it is on the simultaneous behaviour under identical conditions of different electrodes of the same material, as well as on that of electrodes made of different materials. This identifies the changes in physical and chemical parameters in a solution, as well as the redox reactions controlling the measured potential, both in the solution and/or at the electrode/solution interface. Understanding the electrochemical behaviour of selected materials thus is a key point of our research, as provides the basis for constructing the abacuses needed for developing robust and reliable field sensors.

  14. 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.

  15. Experimental investigation of factors affecting the control of redox conditions within a radwaste repository

    International Nuclear Information System (INIS)

    Guppy, R.M.; Atkinson, A.

    1991-04-01

    The maximum aqueous concentration of multivalent radioelements in a radwaste repository can be estimated from the expected Eh (the oxidising or reducing tendency of the solution) and pH of the aqueous phase in the repository so long as equilibrium between all oxidising and reducing species can be guaranteed. The objective of the work reported here was to ascertain whether any significant departures from redox equilibrium are likely to arise. Technetium (VII) species were exposed under anaerobic conditions to concentrations of ferrous, hydrogen sulphide and thiosulphate species likely to be present in a repository environment to establish which species are capable of reducing aqueous Tc(VII) to a less soluble Tc(IV) solid compound. Potential catalytic solid phases and phases capable of electron exchange were also exposed to Tc(VII) species under anaerobic, aerobic and hydrogen atmospheres. We have not been able to demonstrate conclusively that mutual equilibrium was attained between technetium and iron redox couples, nor that the apparent solubility of technetium was that expected from the resulting Eh and pH of the solution, although some technetium was removed from solution. Hydrogen did not reduce Tc(VII) within the timescale of the experiments and no catalytic effects by haematite or a cementitious backfill grout for reductions involving hydrogen were observable. Magnetite removed some technetium from solution, apparently by surface reaction, under inert (argon) and reducing (hydrogen) atmospheres. Sulphides, and to a lesser extent thiosulphates, will reduce the solubility of technetium to a very low level. (author)

  16. Redox front penetration in the fractured Toki Granite, central Japan: An analogue for redox reactions and redox buffering in fractured crystalline host rocks for repositories of long-lived radioactive waste

    International Nuclear Information System (INIS)

    Yamamoto, Koshi; Yoshida, Hidekazu; Akagawa, Fuminori; Nishimoto, Shoji; Metcalfe, Richard

    2013-01-01

    Highlights: • Deep redox front developed in orogenic granitic rock have been studied. • The process was controlled by the buffering capacity of minerals. • This is an analogue of redox front penetration into HLW repositories in Japan. - Abstract: Redox buffering is one important factor to be considered when assessing the barrier function of potential host rocks for a deep geological repository for long-lived radioactive waste. If such a repository is to be sited in fractured crystalline host rock it must be demonstrated that waste will be emplaced deeper than the maximum depth to which oxidizing waters can penetrate from the earth’s surface via fractures, during the assessment timeframe (typically 1 Ma). An analogue for penetration of such oxidizing water occurs in the Cretaceous Toki Granite of central Japan. Here, a deep redox front is developed along water-conducting fractures at a depth of 210 m below the ground surface. Detailed petrographical studies and geochemical analyses were carried out on drill core specimens of this redox front. The aim was to determine the buffering processes and behavior of major and minor elements, including rare earth elements (REEs), during redox front development. The results are compared with analytical data from an oxidized zone found along shallow fractures (up to 20 m from the surface) in the same granitic rock, in order to understand differences in elemental migration according to the depth below the ground surface of redox-front formation. Geochemical analyses by XRF and ICP-MS of the oxidized zone at 210 m depth reveal clear changes in Fe(III)/Fe(II) ratios and Ca depletion across the front, while Fe concentrations vary little. In contrast, the redox front identified along shallow fractures shows strong enrichments of Fe, Mn and trace elements in the oxidized zone compared with the fresh rock matrix. The difference can be ascribed to the changing Eh and pH of groundwater as it flows downwards in the granite, due to

  17. Effect of dissolved oxygen on redox potential and milk acidification by lactic acid bacteria isolated from a DL-starter culture

    DEFF Research Database (Denmark)

    Larsen, Nadja; Werner, Birgit Brøsted; Vogensen, Finn Kvist

    2015-01-01

    potential to negative values. Kinetic parameters of the DL-starter culture were comparable with the best acidifying and reducing strains, indicating their additive effects. Acidification curves were mostly diauxic at all oxygen levels, displaying 2 maxima of acidification rate: before (aerobic maximum...... subspecies in DL-starter cultures. This knowledge is important for dairies to ensure optimized, fast, and controlled milk fermentations, leading to greater standardization of dairy products.......Milk acidification by DL-starter cultures [cultures containing Lactococcus lactis diacetylactis (D) and Leuconostoc (L) species] depends on the oxidation-reduction (redox) potential in milk; however, the mechanisms behind this effect are not completely clear. The objective of this study...

  18. 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

  19. 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.

  20. Postnatal exposure to trichloroethylene alters glutathione redox homeostasis, methylation potential, and neurotrophin expression in the mouse hippocampus

    Science.gov (United States)

    Blossom, Sarah J.; Melnyk, Stepan; Cooney, Craig A.; Gilbert, Kathleen M.; James, S. Jill

    2012-01-01

    Previous studies have shown that continuous exposure throughout gestation until the juvenile period to environmentally-relevant doses of trichloroethylene (TCE) in the drinking water of MRL+/+ mice promoted adverse behavior associated with glutathione depletion in the cerebellum indicating increased sensitivity to oxidative stress. The purpose of this study was to extend our findings and further characterize the impact of TCE exposure on redox homeostasis and biomarkers of oxidative stress in the hippocampus, a brain region prone to oxidative stress. Instead of a continuous exposure, the mice were exposed to water only or two environmentally relevant doses of TCE in the drinking water postnatally from birth until 6 weeks of age. Biomarkers of plasma metabolites in the transsulfuration pathway and the transmethylation pathway of the methionine cycle were also examined. Gene expression of neurotrophins was examined to investigate a possible relationship between oxidative stress, redox imbalance and neurotrophic factor expression with TCE exposure. Our results show that hippocampi isolated from male mice exposed to TCE showed altered glutathione redox homeostasis indicating a more oxidized state. Also observed was a significant, dose dependent increase in glutathione precursors. Plasma from the TCE treated mice showed alterations in metabolites in the transsulfuration and transmethylation pathways indicating redox imbalance and altered methylation capacity. 3-Nitrotyrosine, a biomarker of protein oxidative stress, was also significantly higher in plasma and hippocampus of TCE-exposed mice compared to controls. In contrast, expression of key neurotrophic factors in the hippocampus (BDNF, NGF, and NT-3) was significantly reduced compared to controls. Our results demonstrate that low-level postnatal and early life TCE exposure modulates neurotrophin gene expression in the mouse hippocampus and may provide a mechanism for TCE-mediated neurotoxicity. PMID:22421312

  1. Case study : Mergers and acquisitions blending EHS cultures

    Energy Technology Data Exchange (ETDEWEB)

    Shoji-Lee, L.A. [Duke Energy Gas Transmission, Vancouver, BC (Canada)

    2003-06-03

    In September 2001, Duke Energy acquired the assets of Westcoast Energy Inc. (WEI). Duke Energy's expertise lies in gas gathering, processing, transportation, storage, distribution and marketing. It also specializes in electric generation, transmission and distribution. Westcoast Energy managed a portfolio of natural gas and electric supply, delivery and trading, with international assets in Mexico, Indonesia and China. Since the acquisition of WEI, Duke Energy has adopted an Environment, Health and Safety (EHS) model that will provide assistance in the transition to dealing with different cultures. The integration is meant to identify steps to evaluate and integrate new assets into a common EHS Management System, and to identify areas of discrepancy and opportunities for synergies. This report describes the EHS Management System, with respect to compliance, assurance and performance standards for air issues, waste management, contaminated sites, emergency response, and performance indicators. tabs., figs.

  2. Entamoeba histolytica EhCP112 Dislocates and Degrades Claudin-1 and Claudin-2 at Tight Junctions of the Intestinal Epithelium

    Directory of Open Access Journals (Sweden)

    Patricia Cuellar

    2017-08-01

    Full Text Available During intestinal invasion, Entamoeba histolytica opens tight junctions (TJs reflected by transepithelial electrical resistance (TEER dropping. To explore the molecular mechanisms underlying this, we studied in vitro and in vivo the damage produced by the recombinant E. histolytica cysteine protease (rEhCP112 on TJ functions and proteins. rEhCP112 reduced TEER in Caco-2 cells in a dose- and time-dependent manner; and EhCP112-overexpressing trophozoites provoked major epithelial injury compared to control trophozoites. rEhCP112 penetrated through the intercellular space, and consequently the ion flux increased and the TJs fence function was disturbed. However, macromolecular flux was not altered. Functional in vitro assays revealed specific association of rEhCP112 with claudin-1 and claudin-2, that are both involved in regulating ion flux and fence function. Of note, rEhCP112 did not interact with occludin that is responsible for regulating macromolecular flux. Moreover, rEhCP112 degraded and delocalized claudin-1, thus affecting interepithelial adhesion. Concomitantly, expression of the leaky claudin-2 at TJ, first increased and then it was degraded. In vivo, rEhCP112 increased intestinal epithelial permeability in the mouse colon, likely due to apical erosion and claudin-1 and claudin-2 degradation. In conclusion, we provide evidence that EhCP112 causes epithelial dysfunction by specifically altering claudins at TJ. Thus, EhCP112 could be a potential target for therapeutic approaches against amoebiasis.

  3. Higher Mediterranean Diet Quality Scores and Lower Body Mass Index Are Associated with a Less-Oxidized Plasma Glutathione and Cysteine Redox Status in Adults.

    Science.gov (United States)

    Bettermann, Erika L; Hartman, Terryl J; Easley, Kirk A; Ferranti, Erin P; Jones, Dean P; Quyyumi, Arshed A; Vaccarino, Viola; Ziegler, Thomas R; Alvarez, Jessica A

    2018-02-01

    Both systemic redox status and diet quality are associated with risk outcomes in chronic disease. It is not known, however, the extent to which diet quality influences plasma thiol/disulfide redox status. The purpose of this study was to investigate the influence of diet, as measured by diet quality scores and other dietary factors, on systemic thiol/disulfide redox status. We performed a cross-sectional study of 685 working men and women (ages ≥18 y) in Atlanta, GA. Diet was assessed by 3 diet quality scores: the Alternative Healthy Eating Index (AHEI), Dietary Approaches to Stop Hypertension (DASH), and the Mediterranean Diet Score (MDS). We measured concentrations of plasma glutathione (GSH), cysteine, their associated oxidized forms [glutathione disulfide (GSSG) and cystine (CySS), respectively], and their redox potentials (EhGSSG and EhCySS) to determine thiol/disulfide redox status. Linear regression modeling was performed to assess relations between diet and plasma redox after adjustment for age, body mass index (BMI), sex, race, and history of chronic disease. MDS was positively associated with plasma GSH (β = 0.02; 95% CI: 0.003, 0.03) and total GSH (GSH + GSSG) (β = 0.02; 95% CI: 0.003, 0.03), and inversely associated with the CySS:GSH ratio (β = -0.02; 95% CI: -0.04, -0.004). There were significant independent associations between individual MDS components (dairy, vegetables, fish, and monounsaturated fat intake) and varying plasma redox indexes (P indexes and other diet factors of interest were not significantly correlated with plasma thiol and disulfide redox measures. Adherence to the Mediterranean diet was significantly associated with a favorable plasma thiol/disulfide redox profile, independent of BMI, in a generally healthy working adult population. Although longitudinal studies are warranted, these findings contribute to the feasibility of targeting a Mediterranean diet to improve plasma redox status.

  4. Bertolette Selected as EHS Champion of Safety | Poster

    Science.gov (United States)

    Dan Bertolette has been selected as the most recent NCI at Frederick Champion of Safety, as part of the Champions of Safety Program sponsored by the Environment, Health, and Safety Program (EHS). The goal of the program, which began last year, is to raise awareness and promote a culture of safety by showing NCI at Frederick staff at work in their respective workplaces, according to Terri Bray, director, EHS. “Since we have so many varied work environments here, safety often takes on a different look, according to workplace. We want to take the opportunity to show real people in real situations, to encourage safety everywhere,” Bray said.

  5. The Eh-pH Diagram and Its Advances

    Directory of Open Access Journals (Sweden)

    Hsin-Hsiung Huang

    2016-01-01

    Full Text Available Since Pourbaix presented Eh versus pH diagrams in his “Atlas of Electrochemical Equilibria in Aqueous Solution”, diagrams have become extremely popular and are now used in almost every scientific area related to aqueous chemistry. Due to advances in personal computers, such diagrams can now show effects not only of Eh and pH, but also of variables, including ligand(s, temperature and pressure. Examples from various fields are illustrated in this paper. Examples include geochemical formation, corrosion and passivation, precipitation and adsorption for water treatment and leaching and metal recovery for hydrometallurgy. Two basic methods were developed to construct an Eh-pH diagram concerning the ligand component(s. The first method calculates and draws a line between two adjacent species based on their given activities. The second method performs equilibrium calculations over an array of points (500 × 800 or higher are preferred, each representing one Eh and one pH value for the whole system, then combines areas of each dominant species for the diagram. These two methods may produce different diagrams. The fundamental theories, illustrated results, comparison and required conditions behind these two methods are presented and discussed in this paper. The Gibbs phase rule equation for an Eh-pH diagram was derived and verified from actual plots. Besides indicating the stability area of water, an Eh-pH diagram normally shows only half of an overall reaction. However, merging two or more related diagrams together reveals more clearly the possibility of the reactions involved. For instance, leaching of Au with cyanide followed by cementing Au with Zn (Merrill-Crowe process can be illustrated by combining Au-CN and Zn-CN diagrams together. A second example of the galvanic conversion of chalcopyrite can be explained by merging S, Fe–S and Cu–Fe–S diagrams. The calculation of an Eh-pH diagram can be extended easily into another dimension, such

  6. Ageing temperature effect on inclination of martensite high strength steels EhP699, EhP678, EhP679 to corrosion cracking

    International Nuclear Information System (INIS)

    Rozenfel'd, I.L.; Spiridonov, V.B.; Konradi, M.V.; Krasnorutskaya, I.B.; Fridman, V.S.

    1979-01-01

    Stated are the data permitting to judge of the role of ageing temperature in the total number of factors, determining the inclination to corrosion cracking of high strength maraging steels, which contain chromium as a main alloying element. The inclination of the EhP699, EhP678, EhP679 steels to corrosion cracking was estimated on smooth stressed specimens in 3 % NaCl solution with the use of electrochemical polarization. The tensile stress resulted from deflection; anode and cathode current density was 10 mA/cm 2 . It is shown, that resistance to corrosion cracking depends on the ageing temperature: maximum sensitivity to corrosion cracking the steels manifest at the ageing temperatures, providing for maximum strength (470-500 deg). At the ageing temperatures by 20-30 deg over the temperature of this maximum the sensitivity to corrosion cracking disappears, which may result from the loss of coherence of strengthening phase in a matrix, from particle coagulation and stress relaxation in the crack peak

  7. The equation of state of n-pentane in the atomistic model TraPPE-EH

    Science.gov (United States)

    Valeev, B. U.; Pisarev, V. V.

    2018-01-01

    In this work, we study the vapor-liquid equilibrium in n-pentane. We use the TraPPE-EH (transferable potentials for phase equilibria-explicit hydrogen) forcefield, where each hydrogen and carbon atom is considered as independent center of force. The fluid behavior was investigated with different values of density and temperature by molecular dynamics method. The n-pentane evaporation curve was calculated in the temperature range of 290 to 390 K. The densities of the coexisting phases are also calculated. The compression curve at 370 K was calculated and isothermal bulk modulus was found. The simulated properties of n-pentane are in good agreement with data from a database of the National Institute of Standards and Technology, so the TraPPE-EH model can be recommended for simulations of hydrocarbons.

  8. Changes in phosphorylation of adenosine phosphate and redox state of nicotinamide-adenine dinucleotide (phosphate) in Geobacter sulfurreducens in response to electron acceptor and anode potential variation

    KAUST Repository

    Rose, Nicholas D.; Regan, John M.

    2015-01-01

    © 2015 Elsevier B.V. Geobacter sulfurreducens is one of the dominant bacterial species found in biofilms growing on anodes in bioelectrochemical systems. The intracellular concentrations of reduced and oxidized forms of nicotinamide-adenine dinucleotide (NADH and NAD+, respectively) and nicotinamide-adenine dinucleotide phosphate (NADPH and NADP+, respectively) as well as adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP) were measured in G. sulfurreducens using fumarate, Fe(III)-citrate, or anodes poised at different potentials (110, 10, -90, and -190mV (vs. SHE)) as the electron acceptor. The ratios of CNADH/CNAD+ (0.088±0.022) and CNADPH/CNADP+ (0.268±0.098) were similar under all anode potentials tested and with Fe(III)-citrate (reduced extracellularly). Both ratios significantly increased with fumarate as the electron acceptor (0.331±0.094 for NAD and 1.96±0.37 for NADP). The adenylate energy charge (the fraction of phosphorylation in intracellular adenosine phosphates) was maintained near 0.47 under almost all conditions. Anode-growing biofilms demonstrated a significantly higher molar ratio of ATP/ADP relative to suspended cultures grown on fumarate or Fe(III)-citrate. These results provide evidence that the cellular location of reduction and not the redox potential of the electron acceptor controls the intracellular redox potential in G. sulfurreducens and that biofilm growth alters adenylate phosphorylation.

  9. Changes in phosphorylation of adenosine phosphate and redox state of nicotinamide-adenine dinucleotide (phosphate) in Geobacter sulfurreducens in response to electron acceptor and anode potential variation

    KAUST Repository

    Rose, Nicholas D.

    2015-12-01

    © 2015 Elsevier B.V. Geobacter sulfurreducens is one of the dominant bacterial species found in biofilms growing on anodes in bioelectrochemical systems. The intracellular concentrations of reduced and oxidized forms of nicotinamide-adenine dinucleotide (NADH and NAD+, respectively) and nicotinamide-adenine dinucleotide phosphate (NADPH and NADP+, respectively) as well as adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP) were measured in G. sulfurreducens using fumarate, Fe(III)-citrate, or anodes poised at different potentials (110, 10, -90, and -190mV (vs. SHE)) as the electron acceptor. The ratios of CNADH/CNAD+ (0.088±0.022) and CNADPH/CNADP+ (0.268±0.098) were similar under all anode potentials tested and with Fe(III)-citrate (reduced extracellularly). Both ratios significantly increased with fumarate as the electron acceptor (0.331±0.094 for NAD and 1.96±0.37 for NADP). The adenylate energy charge (the fraction of phosphorylation in intracellular adenosine phosphates) was maintained near 0.47 under almost all conditions. Anode-growing biofilms demonstrated a significantly higher molar ratio of ATP/ADP relative to suspended cultures grown on fumarate or Fe(III)-citrate. These results provide evidence that the cellular location of reduction and not the redox potential of the electron acceptor controls the intracellular redox potential in G. sulfurreducens and that biofilm growth alters adenylate phosphorylation.

  10. nfluence of reducing and oxidizing compounds and of the redox potential of the medium on the biomass of Scenedesmus quadricauda (Turp. Breb.

    Directory of Open Access Journals (Sweden)

    Stefan Gumiński

    2014-01-01

    Full Text Available The influence was investigated of several concentrations of the reducing agents: cysteine, glutathione, ascorbic acid, pyracatechol and of the oxidizing agents: KMnO4, K4Cr2O7 and H2O2 on the total dry weight increment and that of protein with reference to redox potential changes of the medium in Scenedesmus quadricauda cultures. The culture was run in a photothermostat. It was found that the reducing compounds had as a rule a stimulating influence under 24-h illumdnation, whereas the oxidilzing agents gave the same effect when a period of 7-h darkness was applied within 24 h.

  11. EHS Open House: Learning Lab and Life Safety | Poster

    Science.gov (United States)

    Attendees of the Environment, Health, and Safety Program’s (EHS’) Open House had a chance to learn self-defense techniques, as well as visit with vendors demonstrating the latest trends in laboratory safety. “Working with sharps in labs is inherently dangerous, so EHS proactively focused on featuring equipment that would promote safer techniques,” said Siobhan Tierney, program

  12. Proteomic analysis of the EhV-86 virion

    Directory of Open Access Journals (Sweden)

    Lilley Kathryn S

    2008-03-01

    Full Text Available Abstract Background Emiliania huxleyi virus 86 (EhV-86 is the type species of the genus Coccolithovirus within the family Phycodnaviridae. The fully sequenced 407,339 bp genome is predicted to encode 473 protein coding sequences (CDSs and is the largest Phycodnaviridae sequenced to date. The majority of EhV-86 CDSs exhibit no similarity to proteins in the public databases. Results Proteomic analysis by 1-DE and then LC-MS/MS determined that the virion of EhV-86 is composed of at least 28 proteins, 23 of which are predicted to be membrane proteins. Besides the major capsid protein, putative function can be assigned to 4 other components of the virion: two lectin proteins, a thioredoxin and a serine/threonine protein kinase. Conclusion This study represents the first steps toward the identification of the protein components that make up the EhV-86 virion. Aside from the major capsid protein, whose function in the virion is well known and defined, the nature of the other proteins suggest roles involved with viral budding, caspase activation, signalling, anti-oxidation, virus adsorption and host range determination.

  13. Classroom Behavior Patterns of EMH, LD, and EH Students.

    Science.gov (United States)

    McKinney, James D.; Forman, Susan G.

    1982-01-01

    Investigated whether classroom teachers could differentiate among educable mentally handicapped (EMH), learning disabled (LD), and emotionally handicapped (EH) students based on perceptions of classroom behavior patterns. Ratings from classroom behavior inventory scales revealed that EMH students were distinguished by low intelligence, creativity,…

  14. Critical Readiness Review EHS Water Quality and Microbiology

    Science.gov (United States)

    Woo, Cindy

    2010-01-01

    Presentation reviews the status in reference to the Environmental, Health and Safety (EHS) of the water quality and microbiology for the International Space Station. It includes information about crew training, hardware delivery, and those items that will be returned for study.

  15. The evolution of redox conditions and groundwater geochemistry in recharge-discharge environments on the Canadian Shield

    International Nuclear Information System (INIS)

    Gascoyne, M.

    1996-10-01

    Groundwater composition evolves along flow paths from recharge to discharge in response to interactions with bedrock and fracture-filling minerals, and dissolution of soluble (Cl-rich) salts in the rock matrix. The groundwater redox potential changes from oxidizing to reducing conditions due, initially, to rapid consumption of dissolved oxygen by organics in the upper ∼100 m of bedrock and, subsequently, interaction with Fe (II)-containing minerals. Measured Eh values of groundwaters at depth in the granitic Lac du Bonnet batholith indicate that biotite and chlorite control groundwater redox potential. This is supported by other geochemical characteristics such as absence of CH 4 , H 2 S, H 2 , NO 3 , low concentrations of Fe (II), and abundance of SO 4 . Further evidence of evolution of redox conditions is given by variations in U concentration ranging from up to 1000 μg/L in dilute near-surface waters to <1 μg/L in some deep, saline groundwaters. Groundwaters at about 400 m depth in a recharge area on the Lac du Bonnet batholith contain significantly more U than groundwaters further along the flow path or near surface in discharge areas. Uranium concentration is found to be a useful and sensitive indicator of redox conditions. (author)

  16. Calculation of HNO2 concentration from redox potential in HNO3-H2O system as an aid to understanding the cathodic reaction of nitric acid corrosion

    International Nuclear Information System (INIS)

    Takeuchi, Masayuki; Whillock, G.O.H.

    2002-01-01

    Nitrous acid affects the corrosion of metals such as stainless steels in nitric acid. However nitrous acid is not particularly stable in nitric acid and the analytical methods available are quite involved. Accordingly, the calculation of nitrous acid concentration from redox potential was tested in the HNO 3 -H 2 O system as a convenient in situ analysis method. The calculation process is based on Nernst's equation and the required thermodynamic data were obtained from published values. The available thermodynamic data allow calculation of nitrous acid concentration from 273K to 373K for 0%-100% HNO 3 . The redox potential was 8 kmol·m -3 HNO 3 under NO bubbling and the nitrous acid concentration was determined by a Colourimetric method. The calculated data were compared with the measured data and a good agreement was found. It was found that the corrosion potential of stainless steel is influenced by nitrous acid concentration in nitric acid solution. The calculation process is useful for in-situ analysis of nitrous acid species in HNO 3 -H 2 O system and understanding the behavior of the cathodic reaction associated with nitric acid corrosion. (author)

  17. Geochemistry of Natural Redox Fronts

    International Nuclear Information System (INIS)

    Hofmann, B.A.

    1999-05-01

    Redox fronts are important geochemical boundaries which need to be considered in safety assessment of deep repositories for radioactive waste. In most cases, selected host-rock formations will be reducing due to the presence of ferrous minerals, sulphides, etc. During construction and operation of the repository, air will be introduced into the formation. After repository closure, oxidising conditions may persist locally until all oxygen is consumed. In the case of high-level waste, radiolysis of water may provide an additional source of oxidants. Oxidising conditions within a repository are thus possible and potentially have a strong influence on the mobility of many elements. The rate of movement of redox fronts, the boundary between oxidising and reducing environments, and their influence on migrating radionuclides are thus important factors influencing repository performance. The present report is a review of elemental behaviour at natural redox fronts, based on published information and work of the author. Redox fronts are geochemically and geometrically variable manifestations of a global interface between generally oxidising geochemical milieux in contact with the atmosphere and generally reducing milieux in contact with rocks containing ferrous iron, sulphide and/or organic carbon. A classification of redox fronts based on a subdivision into continental near-surface, marine near-surface, and deep environments is proposed. The global redox interface is often located close to the surface of rocks and sediments and, sometimes, within bodies of water. Temperature conditions are close to ambient. A deeper penetration of the global redox front to depths of several kilometres is found in basins containing oxidised sediments (red beds) and in some hydrothermal circulation systems. Temperatures at such deep redox fronts may reach 200 o C. Both near-surface and deep redox fronts are sites of formation of economic deposits of redox-sensitive elements, particularly of

  18. Microprofiles of oxygen, redox potential, and pH, and microbial fermentation products in the highly alkaline gut of the saprophagous larva of Penthetria holosericea (Diptera: Bibionidae)

    KAUST Repository

    Šustr, Vladimír

    2014-08-01

    The saprophagous larvae of bibionid flies harbor bacteria in their alkaline intestinal tracts, but little is known about the contribution of the gut microbiota to the digestion of their recalcitrant diet. In this study, we measured oxygen and hydrogen partial pressure, redox potential and pH in the midgut, gastric caeca and hindgut of larvae of the bibionid fly Penthetria holosericea with Clark-type O2 and H2 microsensors, platinum redox microelectrodes, and LIX-type pH microelectrodes. The center of the midgut lumen was anoxic, whereas gastric caeca and hindgut were hypoxic. However, redox potential profiles indicated oxidizing conditions throughout the gut, with lowest values in the midgut (+20 to +60mV). Hydrogen production was not detected. The midgut was extremely alkaline (pH around 11), whereas hindgut and gastric caeca were neutral to slightly alkaline. While HPLC analysis showed high concentrations of glucose in the midgut (15mM) and gastric caeca (27mM), the concentrations of microbial fermentation products such as lactate (2-4mM), acetate (<1mM) and succinate (<0.5mM) were low in all gut regions, suggesting that the contribution of microorganisms to the digestive process, particularly in the alkaline midgut, is only of minor importance. We conclude that the digestive strategy of the saprophytic larva of P. holosericea, which feeds selectively on decomposed leaves and its own microbe-rich faeces, differs fundamentally from those of detritivorous and humivorous insects, which host a highly active, fermentative microbiota in their alkaline midgut or hindgut compartments. © 2014 Elsevier Ltd.

  19. 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.)

  20. Visualizing redox orbitals and their potentials in advanced lithium-ion battery materials using high-resolution x-ray Compton scattering

    OpenAIRE

    Hafiz, Hasnain; Suzuki, Kosuke; Barbiellini, Bernardo; Orikasa, Yuki; Callewaert, Vincent; Kaprzyk, Staszek; Itou, Masayoshi; Yamamoto, Kentaro; Yamada, Ryota; Uchimoto, Yoshiharu; Sakurai, Yoshiharu; Sakurai, Hiroshi; Bansil, Arun

    2017-01-01

    Abstract: Reduction-oxidation (redox) reactions are the key processes that underlie the batteries powering smartphones, laptops, and electric cars. A redox process involves transfer of electrons between two species. For example, in a lithium-ion battery, current is generated when conduction electrons from the lithium anode are transferred to the redox orbitals of the cathode material. The ability to visualize or image the redox orbitals and how these orbitals evolve under lithiation and delit...

  1. High-speed parallel implementation of a modified PBR algorithm on DSP-based EH topology

    Science.gov (United States)

    Rajan, K.; Patnaik, L. M.; Ramakrishna, J.

    1997-08-01

    Algebraic Reconstruction Technique (ART) is an age-old method used for solving the problem of three-dimensional (3-D) reconstruction from projections in electron microscopy and radiology. In medical applications, direct 3-D reconstruction is at the forefront of investigation. The simultaneous iterative reconstruction technique (SIRT) is an ART-type algorithm with the potential of generating in a few iterations tomographic images of a quality comparable to that of convolution backprojection (CBP) methods. Pixel-based reconstruction (PBR) is similar to SIRT reconstruction, and it has been shown that PBR algorithms give better quality pictures compared to those produced by SIRT algorithms. In this work, we propose a few modifications to the PBR algorithms. The modified algorithms are shown to give better quality pictures compared to PBR algorithms. The PBR algorithm and the modified PBR algorithms are highly compute intensive, Not many attempts have been made to reconstruct objects in the true 3-D sense because of the high computational overhead. In this study, we have developed parallel two-dimensional (2-D) and 3-D reconstruction algorithms based on modified PBR. We attempt to solve the two problems encountered by the PBR and modified PBR algorithms, i.e., the long computational time and the large memory requirements, by parallelizing the algorithm on a multiprocessor system. We investigate the possible task and data partitioning schemes by exploiting the potential parallelism in the PBR algorithm subject to minimizing the memory requirement. We have implemented an extended hypercube (EH) architecture for the high-speed execution of the 3-D reconstruction algorithm using the commercially available fast floating point digital signal processor (DSP) chips as the processing elements (PEs) and dual-port random access memories (DPR) as channels between the PEs. We discuss and compare the performances of the PBR algorithm on an IBM 6000 RISC workstation, on a Silicon

  2. Effect of an aqueous extract of Cucurbita ficifolia Bouché on the glutathione redox cycle in mice with STZ-induced diabetes.

    Science.gov (United States)

    Díaz-Flores, M; Angeles-Mejia, S; Baiza-Gutman, L A; Medina-Navarro, R; Hernández-Saavedra, D; Ortega-Camarillo, C; Roman-Ramos, R; Cruz, M; Alarcon-Aguilar, F J

    2012-10-31

    Cucurbita ficifolia is used in Mexican traditional medicine as an anti-diabetic and anti-inflammatory agent and its actions can be mediated by antioxidant mechanisms. Disturbance in the homeostasis of glutathione has been implicated in the etiology and progression of diabetes mellitus and its complications. It was evaluated, the effect of an aqueous extract of Cucurbita ficifolia on glycemia, plasma lipid peroxidation; as well as levels of reduced (GSH) and oxidized (GSSG) glutathione and activities of enzymes involved in glutathione redox cycle: glutathione peroxidase (GPx) and glutathione reductase (GR) in liver, pancreas, kidney and heart homogenates of streptozotocin-induced diabetic mice. Increased blood glucose and lipid peroxidation, together with decreased of GSH concentration, GSH/GSSG ratio and its redox potential (E(h)), and enhanced activity of GPx and GR in liver, pancreas and kidney were the salient features observed in diabetic mice. Administration of the aqueous extract of Cucurbita ficifolia to diabetic mice for 30 days, used at a dose of 200 mg/kg, resulted in a significant reduction in glycemia, polydipsia, hyperphagia and plasma lipid peroxidation. Moreover, GSH was increased in liver, pancreas and kidney, and GSSG was reduced in liver, pancreas and heart, therefore GSH/GSSG ratio and its E(h) were restored. Also, the activities involved in the glutathione cycle were decreased, reaching similar values to controls. An aqueous extract of Cucurbita ficifolia with hypoglycemic action, improve GSH redox state, increasing glutathione pool, GSH, GSH/GSSG ratio and its E(h), mechanism that can explain, at least in part, its antioxidant properties, supporting its use as an alternative treatment for the control of diabetes mellitus, and prevent the induction of complications by oxidative stress. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

  3. Phase composition of EhK 990-ID steel

    International Nuclear Information System (INIS)

    Rabinovich, A.V.; Milova, I.M.; Zaslavskij, Yu.B.; Neklyudov, I.M.; Chernyj, B.P.; Vanzha, A.F.; Zejdlits, M.P.; Kurasov, A.N.; Shmelev, Yu.S.

    1990-01-01

    The microstructure and phase composition of EhK99 steel have been investigated. It is shown that the scandium absolute concentration in solid solution of hot-deformed metal is directly proportional to their total content. It was established that the ratio between the scandium concentration in solid solution and the total content [Sc] ss/[Sc] s is not the function of the latter and constitutes (24.5±5.5) rel.%. The limiting scandium solubility in the EhK99 steel at temperature 1270 deg C was determined. It constitutes 0.07±0.005 mass%. In this paper proposed is the mechanism of intermetallide-and-second phase nucleation and growth during crystallization and homogenizing annealing. The recommendation for regimes of homogenizing annealing (1270 deg C, 12 hours) are given. It is shown that the homogenizing vacuum annealing may have an appreciable influence on the technique plasticity and production of good tubes of EhK99 steel with scandium content no more than 0.07wt%. 2 refs., 10 figs., 2 tabs

  4. Biogeochemistry of Redox at Repository Depth and Implications for the Canister

    Energy Technology Data Exchange (ETDEWEB)

    Bath, Adrian; Hermansson, Hans-Peter

    2009-08-15

    The present groundwater chemical conditions at the candidate sites for a spent nuclear fuel repository in Sweden (the Forsmark and Laxemar sites) and processes affecting its future evolution comprise essential conditions for the evaluation of barrier performance and long-term safety. This report reviews available chemical sampling information from the site investigations at the candidate sites, with a particular emphasis on redox active groundwater components and microbial populations that influence redox affecting components. Corrosion of copper canister material is the main barrier performance influence of redox conditions that is elaborated in the report. One section addresses native copper as a reasonable analogue for canister materials and another addresses the feasibility of methane hydrate ice accumulation during permafrost conditions. Such an accumulation could increase organic carbon availability in scenarios involving microbial sulphate reduction. The purpose of the project is to evaluate and describe the available knowledge and data for interpretation of geochemistry, microbiology and corrosion in safety assessment. A conclusive assessment of the sufficiency of information can, however, only be done in the future context of a full safety assessment. The authors conclude that SKB's data and models for chemical and microbial processes are adequate and reasonably coherent. The redox conditions in the repository horizon are predominantly established through the SO{sub 4}2-/HS- and Fe3+/Fe2+ redox couples. The former may exhibit a more significant buffering effect as suggested by measured Eh values, while the latter is associated with a lager capacity due to abundant Fe(II) minerals in the bedrock. Among a large numbers of groundwater features considered in geochemical equilibrium modelling, Eh, pH, temperature and concentration of dissolved sulphide comprise the most essential canister corrosion influences. Groundwater sulphide may originate from

  5. Biogeochemistry of Redox at Repository Depth and Implications for the Canister

    International Nuclear Information System (INIS)

    Bath, Adrian; Hermansson, Hans-Peter

    2009-08-01

    The present groundwater chemical conditions at the candidate sites for a spent nuclear fuel repository in Sweden (the Forsmark and Laxemar sites) and processes affecting its future evolution comprise essential conditions for the evaluation of barrier performance and long-term safety. This report reviews available chemical sampling information from the site investigations at the candidate sites, with a particular emphasis on redox active groundwater components and microbial populations that influence redox affecting components. Corrosion of copper canister material is the main barrier performance influence of redox conditions that is elaborated in the report. One section addresses native copper as a reasonable analogue for canister materials and another addresses the feasibility of methane hydrate ice accumulation during permafrost conditions. Such an accumulation could increase organic carbon availability in scenarios involving microbial sulphate reduction. The purpose of the project is to evaluate and describe the available knowledge and data for interpretation of geochemistry, microbiology and corrosion in safety assessment. A conclusive assessment of the sufficiency of information can, however, only be done in the future context of a full safety assessment. The authors conclude that SKB's data and models for chemical and microbial processes are adequate and reasonably coherent. The redox conditions in the repository horizon are predominantly established through the SO 4 2- /HS - and Fe 3+ /Fe 2+ redox couples. The former may exhibit a more significant buffering effect as suggested by measured Eh values, while the latter is associated with a lager capacity due to abundant Fe(II) minerals in the bedrock. Among a large numbers of groundwater features considered in geochemical equilibrium modelling, Eh, pH, temperature and concentration of dissolved sulphide comprise the most essential canister corrosion influences. Groundwater sulphide may originate from sulphide

  6. Oxidation of extracellular cysteine/cystine redox state in bleomycin-induced lung fibrosis.

    Science.gov (United States)

    Iyer, Smita S; Ramirez, Allan M; Ritzenthaler, Jeffrey D; Torres-Gonzalez, Edilson; Roser-Page, Susanne; Mora, Ana L; Brigham, Kenneth L; Jones, Dean P; Roman, Jesse; Rojas, Mauricio

    2009-01-01

    Several lines of evidence indicate that depletion of glutathione (GSH), a critical thiol antioxidant, is associated with the pathogenesis of idiopathic pulmonary fibrosis (IPF). However, GSH synthesis depends on the amino acid cysteine (Cys), and relatively little is known about the regulation of Cys in fibrosis. Cys and its disulfide, cystine (CySS), constitute the most abundant low-molecular weight thiol/disulfide redox couple in the plasma, and the Cys/CySS redox state (E(h) Cys/CySS) is oxidized in association with age and smoking, known risk factors for IPF. Furthermore, oxidized E(h) Cys/CySS in the culture media of lung fibroblasts stimulates proliferation and expression of transitional matrix components. The present study was undertaken to determine whether bleomycin-induced lung fibrosis is associated with a decrease in Cys and/or an oxidation of the Cys/CySS redox state and to determine whether these changes were associated with changes in E(h) GSH/glutathione disulfide (GSSG). We observed distinct effects on plasma GSH and Cys redox systems during the progression of bleomycin-induced lung injury. Plasma E(h) GSH/GSSG was selectively oxidized during the proinflammatory phase, whereas oxidation of E(h) Cys/CySS occurred at the fibrotic phase. In the epithelial lining fluid, oxidation of E(h) Cys/CySS was due to decreased food intake. Thus the data show that decreased precursor availability and enhanced oxidation of Cys each contribute to the oxidation of extracellular Cys/CySS redox state in bleomycin-induced lung fibrosis.

  7. Determination of formal redox potentials in aqueous solution of copper(II) complexes with ligands having nitrogen and oxygen donor atoms and comparison with their EPR and UV-Vis spectral features.

    Science.gov (United States)

    Tabbì, Giovanni; Giuffrida, Alessandro; Bonomo, Raffaele P

    2013-11-01

    Formal redox potentials in aqueous solution were determined for copper(II) complexes with ligands having oxygen and nitrogen as donor atoms. All the chosen copper(II) complexes have well-known stereochemistries (pseudo-octahedral, square planar, square-based pyramidal, trigonal bipyramidal or tetrahedral) as witnessed by their reported spectroscopic, EPR and UV-visible (UV-Vis) features, so that a rough correlation between the measured redox potential and the typical geometrical arrangement of the copper(II) complex could be established. Negative values have been obtained for copper(II) complexes in tetragonally elongated pseudo-octahedral geometries, when measured against Ag/AgCl reference electrode. Copper(II) complexes in tetrahedral environments (or flattened tetrahedral geometries) show positive redox potential values. There is a region, always in the field of negative redox potentials which groups the copper(II) complexes exhibiting square-based pyramidal arrangements. Therefore, it is suggested that a measurement of the formal redox potential could be of great help, when some ambiguities might appear in the interpretation of spectroscopic (EPR and UV-Vis) data. Unfortunately, when the comparison is made between copper(II) complexes in square-based pyramidal geometries and those in square planar environments (or a pseudo-octahedral) a little perturbed by an equatorial tetrahedral distortion, their redox potentials could fall in the same intermediate region. In this case spectroscopic data have to be handled with great care in order to have an answer about a copper complex geometrical characteristics. © 2013.

  8. The Eps15 C. elegans homologue EHS-1 is implicated in synaptic vesicle recycling

    DEFF Research Database (Denmark)

    Salcini, A E; Hilliard, M A; Croce, A

    2001-01-01

    implicated Eps15 in endocytosis, its function in the endocytic machinery remains unclear. Here we show that the Caenorhabditis elegans gene, zk1248.3 (ehs-1), is the orthologue of Eps15 in nematodes, and that its product, EHS-1, localizes to synaptic-rich regions. ehs-1-impaired worms showed temperature...

  9. Potentiometric chip-based multipumping flow system for the simultaneous determination of fluoride, chloride, pH, and redox potential in water samples.

    Science.gov (United States)

    Chango, Gabriela; Palacio, Edwin; Cerdà, Víctor

    2018-08-15

    A simple potentiometric chip-based multipumping flow system (MPFS) has been developed for the simultaneous determination of fluoride, chloride, pH, and redox potential in water samples. The proposed system was developed by using a poly(methyl methacrylate) chip microfluidic-conductor using the advantages of flow techniques with potentiometric detection. For this purpose, an automatic system has been designed and built by optimizing the variables involved in the process, such as: pH, ionic strength, stirring and sample volume. This system was applied successfully to water samples getting a versatile system with an analysis frequency of 12 samples per hour. Good correlation between chloride and fluoride concentration measured with ISE and ionic chromatography technique suggests satisfactory reliability of the system. Copyright © 2018 Elsevier B.V. All rights reserved.

  10. Microprofiles of oxygen, redox potential, and pH, and microbial fermentation products in the highly alkaline gut of the saprophagous larva of .i.Penthetria holosericea./i. (Diptera: Bibionidae)

    Czech Academy of Sciences Publication Activity Database

    Šustr, Vladimír; Stingl, U.; Brune, A.

    2014-01-01

    Roč. 67, August (2014), s. 64-69 ISSN 0022-1910 R&D Projects: GA AV ČR IAB6066903 Grant - others:Deutsche forschungsgemeinschaft(DE) SPP 1090 Institutional support: RVO:60077344 Keywords : dipteran larvae * gut pH * redox potential * oxygen partial pressure * hydrogen partial pressure Subject RIV: EG - Zoology Impact factor: 2.470, year: 2014

  11. 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 ...

  12. 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.

  13. Concrete decontamination by Electro-Hydraulic Scabbling (EHS). Topical report

    International Nuclear Information System (INIS)

    1996-01-01

    Electro-Hydraulic Scabbling (EHS) technology and equipment for decontaminating concrete structures from radionuclides, organic substances, and hazardous metals is being developed by Textron Systems Division (TSD). This wet scabbling technique involves the generation of powerful shock waves and intense cavitation by a strong pulsed electric discharge in a water layer at the concrete surface. The high pressure impulse results in stresses which crack and peel off a concrete layer of a controllable thickness. Scabbling produces contaminated debris of relatively small volume which can be easily removed, leaving clean bulk concrete. This new technology is being developed under Contract No. DE-AC21-93MC30164. The project objective is to develop and demonstrate a cost-efficient, rapid, controllable process to remove the surface layer of contaminated concrete while generating minimal secondary waste. The primary target of this program is uranium-contaminated concrete floors which constitute a substantial part of the contaminated area at DOE weapon facilities

  14. On implications of e/h ≠ 1

    International Nuclear Information System (INIS)

    Nodulman, L.

    1991-01-01

    There is a considerable literature of studies of compensation in calorimeters at the microscopic and macroscopic level. I doubt that the exercise described here adds any fundamental understanding to previous studies, but it can be helpful in organizing thinking. Previous attempts at motivating the expense of a compensating calorimeter for an SSC detector have tended to show that noncompensation effects get buried by cone corrections and such. A marginally significant resolution increase was found in Z/Z' study for the LOl. Despite the certainty of reinvention, I opted to study the effects of e/h ≠ 1 in dijet balance, which will undoubtedly be used to extend calibrations across boundaries and study detector jet resolution. Although this is not a physics process which could offer some requirement for what is good enough, it does allow jet resolution to be reasonably defined

  15. Redox-based epigenetic status in drug addiction: a potential contributor to gene priming and a mechanistic rationale for metabolic intervention.

    Science.gov (United States)

    Trivedi, Malav S; Deth, Richard

    2014-01-01

    Alcohol and other drugs of abuse, including psychostimulants and opioids, can induce epigenetic changes: a contributing factor for drug addiction, tolerance, and associated withdrawal symptoms. DNA methylation is a major epigenetic mechanism and it is one of more than 200 methylation reactions supported by methyl donor S-adenosylmethionine (SAM). Levels of SAM are controlled by cellular redox status via the folate and vitamin B12-dependent enzyme methionine synthase (MS). For example, under oxidative conditions MS is inhibited, diverting its substrate homocysteine (HCY) to the trans sulfuration pathway. Alcohol, dopamine, and morphine, can alter intracellular levels of glutathione (GSH)-based cellular redox status, subsequently affecting SAM levels and DNA methylation status. Here, existing evidence is presented in a coherent manner to propose a novel hypothesis implicating the involvement of redox-based epigenetic changes in drug addiction. Further, we discuss how a "gene priming" phenomenon can contribute to the maintenance of redox and methylation status homeostasis under various stimuli including drugs of abuse. Additionally, a new mechanistic rationale for the use of metabolic interventions/redox-replenishers as symptomatic treatment of alcohol and other drug addiction and associated withdrawal symptoms is also provided. Hence, the current review article strengthens the hypothesis that neuronal metabolism has a critical bidirectional coupling with epigenetic changes in drug addiction exemplified by the link between redox-based metabolic changes and resultant epigenetic consequences under the effect of drugs of abuse.

  16. Redox-based Epigenetic status in Drug Addiction: Potential mediator of drug-induced gene priming phenomenon and use of metabolic intervention for symptomatic treatment in drug addiction.

    Directory of Open Access Journals (Sweden)

    Malav Suchin Trivedi

    2015-01-01

    Full Text Available Alcohol and other drugs of abuse, including psychostimulants and opioids, can induce epigenetic changes: a contributing factor for drug addiction, tolerance and associated withdrawal symptoms. DNA methylation is the major epigenetic mechanism and it is one of more than 200 methylation reactions supported by methyl donor S-adenosylmethionine (SAM. The levels of SAM are controlled by cellular redox status via the folate and vitamin B12-dependent enzyme methionine synthase (MS, for example; under oxidative conditions MS is inhibited, diverting its substrate homocysteine (HCY to the transsulfuration pathway. Alcohol, dopamine and morphine, can alter intracellular levels of glutathione (GSH-based cellular redox status, subsequently affecting S-adenosylmethionine (SAM levels and DNA methylation status. In this discussion, we compile this and other existing evidence in a coherent manner to present a novel hypothesis implicating the involvement of redox-based epigenetic changes in drug addiction. Next, we also discuss how gene priming phenomenon can contribute to maintenance of redox and methylation status homeostasis under various stimuli including drugs of abuse. Lastly, based on our hypothesis and some preliminary evidence, we discuss a mechanistic explanation for use of metabolic interventions / redox-replenishers as symptomatic treatment of alcohol addiction and associated withdrawal symptoms. Hence, the current review article strengthens the hypothesis that neuronal metabolism has a critical bidirectional coupling with epigenetic changes in drug addiction and we support this claim via exemplifying the link between redox-based metabolic changes and resultant epigenetic consequences under the effect of drugs of abuse.

  17. Characterization of a Rab11-like GTPase, EhRab11, of Entamoeba histolytica.

    Science.gov (United States)

    McGugan, Glen C; Temesvari, Lesly A

    2003-07-01

    The Entamoeba histolytica Rab11 family of small molecular weight GTPases consists of three members, EhRab11, EhRab11B, and EhRab11C. The functions of these Rabs in Entamoeba have not been determined. Therefore, as an approach to elucidate the role of the Rab11 family of GTPases in Entamoeba, immunofluorescence microscopy was undertaken to define the subcellular localization of one member of this family, EhRab11. Under conditions of growth, EhRab11 displayed a punctate pattern in the cytoplasm of trophozoites. EhRab11 did not colocalize with markers for the Golgi apparatus, endoplasmic reticulum, pinosomes, phagosomes, or compartments formed by receptor-mediated endocytosis, suggesting that this Rab may not play a role in vesicle trafficking between these organelles. Under conditions of iron and serum starvation, EhRab11 was translocated to the periphery of the cell. The altered cellular localization was accompanied by multinucleation of the cells as well as the acquisition of detergent resistance by the cells, features that are characteristic of Entamoeba cysts. The translocation of EhRab11 to the periphery of the cell during iron and serum starvation was specific as the subcellular localizations of two other Rab GTPases, EhRab7 and EhRabA, were not altered under the same conditions. In addition, the formation of multinucleated cells by inhibition of cytokinesis was not sufficient to induce the translocation of EhRab11 to the cell periphery. Taken together, the data suggest that iron and serum starvation may induce encystation in E. histolytica and that EhRab11 may play a role in this process. Moreover, these studies are the first to describe a putative role for a Rab GTPase in encystation in Entamoeba sp.

  18. Electromagnetic hypersensitivity (EHS) in the media - a qualitative content analysis of Norwegian newspapers.

    Science.gov (United States)

    Huiberts, Ashild; Hjørnevik, Mari; Mykletun, Arnstein; Skogen, Jens C

    2013-01-01

    Electromagnetic hypersensitivity (EHS) is a condition characterized by experiencing symptoms after perceived exposure to weak electromagnetic fields (EMFs). There is substantial debate concerning the aetiology of EHS, but experimental data indicate no association between EHS and actual presence of EMFs. Newspapers play a key role in shaping peoples' understanding of health-related issues. The aim of this study was to describe the content of newspaper articles concerning aetiology and treatment of EHS. Qualitative content analysis of newspaper articles. Norwegian newspaper articles were identified using a comprehensive electronic media archive. Norwegian newspaper articles published between 1 February 2006 and 11 August 2010. Statements coded according to source of information, whether it was pro or con scientific evidence on EHS aetiology, and type of intervention presented as treatment option for EHS. Of the statements concerning EHS aetiology (n = 196), 35% (n = 69) were categorized as pro evidence, 65% (n = 127) as con evidence. Of the statements about EHS interventions assessed, 78% (n = 99) were categorized as 'radiance reduction', 4% (n = 5) as 'complementary medicine', and 18% (n = 23) as 'other'. Cognitive behavioural therapy (CBT) and psychotropic drugs were never presented as possible treatment options for EHS. The newspaper media discourse of EHS aetiology and recommended treatment interventions is much in conflict with the current evidence in the field. The majority of statements concerning aetiology convey that EHS is related to the presence of weak EMFs, and radiance reduction as the most frequently conveyed measure to reduce EHS-related symptoms.

  19. Polyalthia longifolia Methanolic Leaf Extracts (PLME) induce apoptosis, cell cycle arrest and mitochondrial potential depolarization by possibly modulating the redox status in hela cells.

    Science.gov (United States)

    Vijayarathna, Soundararajan; Oon, Chern Ein; Chen, Yeng; Kanwar, Jagat R; Sasidharan, Sreenivasan

    2017-05-01

    Medicinal plants have been accepted as a gold mine, with respect to the diversity of their phytochemicals. Many medicinal plants extracts are potential anticancer agents. Polyalthia longifolia var. angustifolia Thw. (Annonaceae) is one of the most significant native medicinal plants and is found throughout Malaysia. Hence, the present study was intended to assess the anticancer properties of P. longifolia leaf methanolic extract (PLME) and its underlying mechanisms. The Annexin V/PI flow cytometry analysis showed that PLME induces apoptosis in HeLa cells in dose-dependent manner whereas the PI flow cytometric analysis for cell cycle demonstrated the accumulation of cells at sub G0/G1, G0/G1 and G2/M phases. Investigation with JC-1 flow cytometry analysis indicated increase in mitochondria membrane potential depolarisation corresponding to increase in PLME concentrations. PLME was also shown to influence intracellular reactive oxygen species (ROS) by exerting anti-oxidant (half IC 50 ) and pro-oxidant (IC 50 and double IC 50 ) affect against HeLa cells. PLME treatment also displayed DNA damage in HeLa cells in concentration depended fashion. The proteomic profiling array exposed the expression of pro-apoptotic and anti-apoptotic proteins upon PLME treatment at IC 50 concentration in HeLa cells. Pro-apoptotic proteins; BAX, BAD, cytochrome c, caspase-3, p21, p27 and p53 were found to be significantly up-regulated while anti-apoptotic proteins; BCL-2 and BCL-w were found to be significantly down-regulated. This investigation postulated the role of p53 into mediating apoptosis, cell cycle arrest and mitochondrial potential depolarisation by modulating the redox status of HeLa cells. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  20. 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

  1. Soil Redox Dynamics Vary with Landscape Position and Hydroperiod in the Pantanal Wetland Ecosystem

    Science.gov (United States)

    Couto, E. G.; Johnson, M. S.; Pinto-jr, O.; Leite, N. K.

    2012-12-01

    The Pantanal wetland ecosystem of central South America is the largest tropical wetland complex in the world. Nevertheless, biogeochemistry in the Pantanal is quite limited. A unimodal precipitation regime averages approximately 1200 mm y-1 during the six-month rainy season, leading to seasonal flooding on much, but not all, of the landscape. We investigated the impact of landscape position and hydroperiod on soil redox potential (Eh) in four research locations in the Northern Pantanal near Poconé, Mato Grosso: two locations subject to flooding (a flooded forest and a flooded scrub forest) and two locations with infrequent surface flooding (tree islands known as cordilheiras). Redox sensors were installed at 10 cm and 30 cm depths at each of the four locations with half-hourly data recorded over all hydro-periods (dry season, rising water, flood and falling water). Here we summarize results to date in this ongoing study. Reducing conditions were observed in response to both precipitation events saturating soil from the surface downward, as well as in response to regional flooding dynamics that saturate soil from below. These are helping to guide design of a study on methane dynamics in the Pantanal wetland complex.

  2. Application of RIA of PRA, AT II and NPY in typing and therapy of EH patients

    International Nuclear Information System (INIS)

    Yang Yongqing; Wang Xiaozhou; Jiang Qinian

    2001-01-01

    Objective: To study the typing and AT II receptor inhibitor therapy for essential hypertension (EH) patients. Methods: Plasma RA, AT II and NPY levels were measured by radioimmunoassay (RIA) in 208 Patients with EH and 100 controls; plasma NPY levels were measured in 40 EH patients before and after AT II receptor inhibitor therapy. The mean coefficient of variation for intra and inter batch-assay were less than 10% and 15% respectively. Results: In 208 EH patients plasma PRA levels were increased, normal and decreased in 17.8%, 71.6% and 10.6% respectively, while in 128 EH patients Plasma AT II levels were increased, normal and decreased in 20.3%, 64.1% and 15.6% respectively. In 69 EH Plasma NPY levels were significantly higher than those in 40 control subjects. (17 grade I EH, 137.3 +- 32.6 pg/mL; 28 grade II EH, 148.5 +- 41.1 pg/mL; 24 grade III EH, 162.4 +- 42.7 pg/mL; 40 controls, 118.5 +- 30.5 pg/mL). In 40 EH patients plasma NPY levels were decreased after AT II receptor inhibitor therapy as the blood pressure decreased. Conclusion: Typing of EH patients according to levels of plasma PRA and AT II is useful in guiding treatment. AT II receptor inhibitors are indicated in those patients with increased plasma levels and NPY levels can be used for appraisal of the treatment efficacy

  3. 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....

  4. 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.

  5. 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.

  6. How can nanobiotechnology oversight advance science and industry: examples from environmental, health, and safety studies of nanoparticles (nano-EHS)

    International Nuclear Information System (INIS)

    Wang Jing; Asbach, Christof; Fissan, Heinz; Hülser, Tim; Kuhlbusch, Thomas A. J.; Thompson, Drew; Pui, David Y. H.

    2011-01-01

    Nanotechnology has great potential to transform science and industry in the fields of energy, material, environment, and medicine. At the same time, more concerns are being raised about the occupational health and safety of nanomaterials in the workplace and the implications of nanotechnology on the environment and living systems. Studies on environmental, health, and safety (EHS) issues of nanomaterials have a strong influence on public acceptance of nanotechnology and, eventually, affect its sustainability. Oversight and regulation by government agencies and non-governmental organizations (NGOs) play significant roles in ensuring responsible and environmentally friendly development of nanotechnology. The EHS studies of nanomaterials can provide data and information to help the development of regulations and guidelines. We present research results on three aspects of EHS studies: physico-chemical characterization and measurement of nanomaterials; emission, exposure, and toxicity of nanomaterials; and control and abatement of nanomaterial releases using filtration technology. Measurement of nanoparticle agglomerates using a newly developed instrument, the Universal NanoParticle Analyzer (UNPA), is discussed. Exposure measurement results for silicon nanoparticles in a pilot scale production plant are presented, as well as exposure measurement and toxicity study of carbon nanotubes (CNTs). Filtration studies of nanoparticle agglomerates are also presented as an example of emission control methods.

  7. EMP and SIMS studies on Mn/Ca and Fe/Ca systematics in benthic foraminifera from the Peruvian OMZ: a contribution to the identification of potential redox proxies and the impact of cleaning protocols

    OpenAIRE

    Glock, N.; Eisenhauer, A.; Liebetrau, V.; Wiedenbeck, M.; Hensen, C.; Nehrke, G.

    2012-01-01

    In this study we present an initial dataset of Mn/Ca and Fe/Ca ratios in tests of benthic foraminifera from the Peruvian oxygen minimum zone (OMZ) determined with SIMS. These results are a contribution to a better understanding of the proxy potential of these elemental ratios for ambient redox conditions. Foraminiferal tests are often contaminated by diagenetic coatings, like Mn rich carbonate- or Fe and Mn rich (oxyhydr)oxide coatings. Thus, it is substantial to assure that...

  8. Near-infrared heat lamp therapeutic effect on paraoxonase 1 and myeloperoxidase as potential biomarkers of redox state changes induced by γ-irradiation in albino rats.

    Science.gov (United States)

    Abdel-Magied, N; Ahmed, A G; Shedid, S M

    2018-02-01

    Infrared radiation has a potential therapeutic effect in some diseases. The aim of this study was to estimate the therapeutic role of near infrared heat lamp (NIRHL) on the variations of the activity of paraoxonase 1 (PON1) and myeloperoxidase (MPO), in relation to lipid disorders, associated with oxidative stress in rats gamma-irradiated. In addition, study the effect of the duration of NIRHL treatment. Animals were divided into six groups. The results revealed that irradiated rats treated with NIRHL 20 min/once/day showed positive modulation of PON1 and MPO linked to significant improvement of lipid disorders evidenced by lower triglycerides, low density lipoprotein cholesterol (LDL-C), oxidized low density lipoprotein cholesterol (oxLDL-C) and higher density lipoprotein cholesterol (HDL-C) as well as significant amelioration of redox state, manifested by markedly increase of glutathione (GSH) content, total antioxidant capacity (TAC) associated with a noticeable decrease of pro-inflammatory cytokines. (TNF-α, IL-1 beta and IL-6), nitric oxide (NO), nitric oxide synthase (NOs), malondialdehyde (MDA), compared to irradiated rats. The results showed also that the NIRHL treatment for 20 min/twice/day had negative effects on the previous parameters and on the behavior of rats such as itching, irritability, dyspnea and death in normal as well as, irradiated rats. In conclusion, the results in this study show that NIRHL therapy for a short time can effectively prevent the lipid disorders induced by radiation through the positive modulation mechanism of PON1 and MPO enzymes and improvement of oxidative stress. Copyright © 2018 Elsevier B.V. All rights reserved.

  9. Identification of EhTIF-IA: The putative E. histolytica orthologue of the ...

    Indian Academy of Sciences (India)

    2016-02-04

    Feb 4, 2016 ... We have identified the E. histolytica equivalent of TIF-1A (EhTIF-IA) by homology search within ..... a putative EhTIF-IA with e-value (3e−25). Comparison of .... some biogenesis is correlated with altered rates of rDNA transcription ..... ylation by CK2 facilitates rDNA transcription by promoting dissociation of ...

  10. The behaviour of long-lived redox sensitive radionuclides in soil-plant system during the process of climate change

    Energy Technology Data Exchange (ETDEWEB)

    Semioshkina, N.; Staudt, C.; Kaiser, C. [Helmhotz Zetrum Muenchen (Germany); Proehl, G. [International Atomic Energy Agency - IAEA (International Atomic Energy Agency (IAEA)); Noseck, U.; Fahrenholz, C. [Gesellschaft fuer Anlagen- und Reaktorsicherheit - GRS (Germany)

    2014-07-01

    One important aspect of climate changes for the long-term safety assessment of radioactive waste repositories is its impact on exposure pathways for humans in the future, which are dependent on the environmental characteristics mentioned. It is conceivable that effects or processes occurring during climate changes lead to an increased accumulation and/or release of radionuclides in the biosphere resulting in higher doses compared to that calculated for discrete climate states. In order to shed light on this question key processes are identified which might lead to such an increased accumulation and/or release of radionuclides. The transition from one climate to another can cause changes in the physicochemical composition of radionuclides: some of them may become more available for plant uptake and due to this, their activity concentration in the plants increases. Other radionuclides maybe stronger bound to soil and their activity concentration in plants decreases. Such changes might also cause remobilization of radionuclides from localised areas with contaminated sediments, their re-suspension and transfer to the surrounding areas. A suitable illustration of the processes related to the changes of the redox potential is the examination of a dry lake or fen bed for agricultural purposes as pasture or ameliorated pasture. In these cases the accumulation of radionuclides in the lake or fen sediment is followed by their release and increasing mobility after agricultural processing of the dry bed of lake or fen. Ploughing of the soil leads to increased supply of oxygen to previous anoxic soil layers causing an increase in redox potential. The presented model describes a scenario, where the land is initially very humid and very low Eh-values cause high sorption and accumulation of radionuclides in soil particles. Then this land is dried out, the redox potential increases and redox sensitive radionuclides change their speciation and their behaviour. Such processes might

  11. 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...

  12. Ductile fracture of two-phase welds under 77K. [Steel-EhP810, steel-EhP666, steel-08Kh18N10T, steel-EhP659-VI, steel-chP810

    Energy Technology Data Exchange (ETDEWEB)

    Yushchenko, K.A.; Voronin, S.A.; Pustovit, A.I.; Shavel' , A.V.

    The effect of the type of welding and fillers on crack resistance of welded joints high-strength steel EhP810 and its various compounds with steels EhP666, 08Kh18N10T has been studied. For the welding of steel EhP810 with steels EhP810, EhP666, 08Kh18N10T electron-beam, automatic, argon tungsten arc with non-consumable electrode with various fillers, as well as argon metal-arc welding with consumable electrode, were used. It is shown, that for a joint, made by electron-beam welding, parameters sigmasub(u), Ksub(IcJ), KCV are higher than for a joint of a similar phase structure made using filler wire EhP659-VI. It is explained by the fact, that during electron-beam welding joint metal refining takes place, which removes gases. In welded joints of chP810 steel, having joints with austenitic structure, characteristic of crack resistance Ssub(c) increases by more than 0.2 mm in contrast to two-phase joints, which conventional yield strength at 77 K exceeds 1000 MPa. It is worth mentioning, that for other classes of steels formation of two-phase structure of joint increases welded joint resistance to brittle fracture. It is possible to obtain the required structure of joint with assigned level of resistance to brittle fracture by means of the use of different fillers, optimum and welding procedure, regulating the part of the basic metal in joint content.

  13. 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

  14. Chemical Shift Assignments of the C-terminal Eps15 Homology Domain-3 EH Domain*

    Science.gov (United States)

    Caplan, Steve; Sorgen, Paul L.

    2013-01-01

    The C-terminal Eps15 homology (EH) domain 3 (EHD3) belongs to a eukaryotic family of endocytic regulatory proteins and is involved in the recycling of various receptors from the early endosome to the endocytic recycling compartment or in retrograde transport from the endosomes to the Golgi. EH domains are highly conserved in the EHD family and function as protein-protein interaction units that bind to Asn-Pro-Phe (NPF) motif-containing proteins. The EH domain of EHD1 was the first C-terminal EH domain from the EHD family to be solved by NMR. The differences observed between this domain and proteins with N-terminal EH domains helped describe a mechanism for the differential binding of NPF-containing proteins. Here, structural studies were expanded to include the EHD3 EH domain. While the EHD1 and EHD3 EH domains are highly homologous, they have different protein partners. A comparison of these structures will help determine the selectivity in protein binding between the EHD family members and lead to a better understanding of their unique roles in endocytic regulation. PMID:23754701

  15. 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

    . Because the redox potential in soil is one of the most difficult soil criteria to evaluate, different redox indicators are used: measurement of eH and dissolved O 2 , analyses of the gaseous phase for CO 2 , O 2 , N 2 , CH 4 , analyses of the main redox aqueous species (Fe(II)/Fe(III), NH 4 + /NO 2 - /NO 3 - ) and analyses of the soil's solid phase by Moessbauer spectroscopy (Fe solid speciation). In addition, microbial populations are followed by different methods (total biomass, RISA) and seleno-reductive populations are specifically isolated. The first results are presented as well as the methodological approach and the experimental designs. [1] French National Program - ACI ECCO 2004. (authors)

  16. Eh and fission product solubilities: two factors in the leaching of UO2

    International Nuclear Information System (INIS)

    Ogard, A.E.; Duffy, C.J.

    1981-01-01

    Eh was found to have a large effect on the dissolution of UO 2 in water at pH 4. As was estimated from thermodynamic data, the solubility was found to decrease as the oxygen fugacity, and therefore the Eh of the water, was decreased. Some of the rare earths and other actinides such as europium, cerium, americium, and plutonium released during the leaching of a spent fuel element behaved differently. These elements were not affected to any large extent by the variation in Eh of these experiments. It has been postulated that these elements reached their solubility limits and precipitated as the spent fuel was leached. 2 figures, 2 tables

  17. The e/h ratio of the ATLAS hadronic tile calorimeter

    International Nuclear Information System (INIS)

    Budagov, Yu.A.; Vinogradov, V.B.; Kul'chitskij, Yu.A.; Kuz'min, M.V.

    2002-01-01

    We have determined the e/h ratios of the Module-0 of the ATLAS iron-scintillator barrel hadron tile calorimeter for five values of pseudorapidity η in the range of -0.55 ≤ η ≤ -0.15 for the beam energy range from 10 to 300 GeV on the basis of the July 1999 test beam data. These e/h ratios demonstrate independence from |η| value. The mean value is e/h = 1.362 + 0.006. The results are compared with the existing experimental data and with some Monte Carlo calculations

  18. 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

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

    International Nuclear Information System (INIS)

    Cho, Hye-Ryun

    2006-01-01

    in acidic condition, the concentration of each oxidation state of Pu must be determined prior to each experiment. The solubility data are determined directly after preparation and then the redox reactions between four different plutonium oxidation states are observed at different pH and Pu concentrations as a function of time. The results indicate that the redox behavior of Pu cannot be described by disproportionation of Pu alone. Under the experimental conditions, the redox reactions of Pu seem to be divided into two groups, Pu(IV) aq <-> Pu(III) aq and Pu(IV) coll <-> Pu(V) aq <-> Pu(VI) aq . In the Pu solution containing initially only Pu(IV), the reduction of Pu(IV) to Pu(III) aq dominates rather than the oxidation to Pu(V) aq and Pu(VI) aq . The observed two groups of reactions show the dependency of pH due to the related hydrolysis and colloid formation of Pu(IV). With increasing pH, the [Pu 4+ ] decreases either through its hydrolysis and colloid formation (increase of Pu(IV) coll ) or through its reduction (increase of Pu(III) aq ). The polymer species or colloids may dissolve to Pu(V)aq through the second reaction group (increase Pu(V) aq + Pu(VI) aq ). Consequently, it is observed that with increase of pH, [Pu(IV) aq ] decreases, [Pu(III) aq ] increases, and [Pu(IV) coll ]+[Pu(V) aq ]+[Pu(VI) aq ] increases. This study is also performed under inert gas conditions in order to investigate the influence of dissolved oxygen on the oxidation of Pu(IV) (Pu(IV) coll <-> Pu(V) aq ). From the relative abundance of the Pu oxidation states, namely the couples PuO 2 2+ /PuO 2 + and PuO 2 + /Pu(IV) coll , the redox potential Eh(V) can be obtained. The respective values agree well with the measured Eh values. In order to use the redox couple Pu 4+ /Pu 3+ , one has to take into account the strong hydrolysis of Pu(IV) which sets in below pH 1. When the abundance of Pu 4+ is calculated from the amount of [Pu(IV) aq. ]=[Pu 4+ ]+ sum y=1 4 [Pu(OH) y 4-y ] by use of hydrolysis

  20. 78 FR 1853 - EH California Hydro, LLC; Notice of Preliminary Permit Application Accepted for Filing and...

    Science.gov (United States)

    2013-01-09

    ... tailrace. Applicant Contact: Mr. John R. Collins, EH California Hydro, LLC, 5425 Wisconsin Avenue, Suite 600, Chevy Chase, Maryland 20815; phone: (301) 718-4433. FERC Contact: Jim Fargo at [email protected

  1. Elementary Surveillance (ELS) and Enhanced Surveillance (EHS) Validation via Mode S Secondary Radar Surveillance

    National Research Council Canada - National Science Library

    Grappel, Robert D; Harris, Garrett S; Kozar, Mark J; Wiken, Randall T

    2008-01-01

    ...) and Enhanced Surveillance (ERS) data link applications. The intended audience for this report is an engineering staff assigned the task of implementing a monitoring system used to determine ELS and EHS compliance...

  2. Ductility and resistance to deformation of EhP975 alloy during hot plastic working

    International Nuclear Information System (INIS)

    Baturin, A.I.; Martynov, A.I.

    1982-01-01

    Results of investigations into ductility and resistance to deformation of the EhP975 most heat-resistant difficult-to-form alloy of commercial melting in 1000-1200 deg C temperature range and at deformation rates epsilon = 0.1 - 25 s - 1 are presented. It is shown that ductility of EhP975 alloy grows rather slowly with increase of temperature approximately up to 1075 deg C, then sharp growth of ductility up to the maximum at 1120-1125 deg C is observed; ductility decreases above this temperature zone. It was also established that ductility of EhP975 alloy grows with increase of preliminary deformation degree. It is marked that high temperature annealing increases ductility of EhP975 alloy in comparison with (cast state), especially noticeably at high deformation rates

  3. Penetration of hydrogen isotopes through EhI 698 alloy at high pressure and temperature

    International Nuclear Information System (INIS)

    Bystritskij, V.M.; Voznyak, Ya.; Granovskij, V.B.

    1986-01-01

    The paper deals with investigations of the process of hydrogen and deuterium penetration through the high-temperature alloy EhI-698 at a pressure up to 1 kbar and temperature up to 1050 K. Parameters of the process obey Sieverts's law and can be described by Arrenius's and Vant-Goff's equations. The obtained results lead to a conclusion that the alloy EhI-698 is good for vessels to be employed in hydrogen media

  4. 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.

  5. 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.

  6. 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...

  7. Base voltammetric characterization of phenylazide modified deoxycytidine - the potential DNA redox label enabling its post-synthetic modifications by "click-reactions"

    Czech Academy of Sciences Publication Activity Database

    Daňhel, Aleš; Trošanová, Zuzana; Balintová, Jana; Havran, Luděk; Hocek, Michal; Fojta, Miroslav

    2013-01-01

    Roč. 9, č. 1 (2013), s. 140-141 ISSN 1336-7242. [Zjazd chemikov /65./. 09.09.2013-13.09.2013, Tatranské Matliare] R&D Projects: GA ČR GBP206/12/G151; GA AV ČR(CZ) IAA400040901 Grant - others:MŠMT(CZ) CZ.1.07/2.3.00/30.0019 Institutional support: RVO:61388963 ; RVO:68081707 Keywords : DNA redox label * click-reaction Subject RIV: CC - Organic Chemistry

  8. 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.

  9. 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.

  10. E-H mode transition in low-pressure inductively coupled nitrogen-argon and oxygen-argon plasmas

    International Nuclear Information System (INIS)

    Lee, Young Wook; Lee, Hye Lan; Chung, T. H.

    2011-01-01

    This work investigates the characteristics of the E-H mode transition in low-pressure inductively coupled N 2 -Ar and O 2 -Ar discharges using rf-compensated Langmuir probe measurements and optical emission spectroscopy (OES). As the ICP power increases, the emission intensities from plasma species, the electron density, the electron temperature, and the plasma potential exhibit sudden changes. The Ar content in the gas mixture and total gas pressure have been varied in an attempt to fully characterize the plasma parameters. With these control parameters varying, the changes of the transition threshold power and the electron energy distribution function (EEDF) are explored. In N 2 -Ar and O 2 -Ar discharges at low-pressures of several millitorr, the transition thresholds are observed to decrease with Ar content and pressure. It is observed that in N 2 -Ar plasmas during the transition, the shape of the EEDF changes from an unusual distribution with a flat hole near the electron energy of 3 eV in the E mode to a Maxwellian distribution in the H mode. However, in O 2 -Ar plasmas, the EEDFs in the E mode at low Ar contents show roughly bi-Maxwellian distributions, while the EEDFs in the H mode are observed to be nearly Maxwellian. In the E and H modes of O 2 -Ar discharges, the dissociation fraction of O 2 molecules is estimated using optical emission actinometry. During the E-H mode transition, the dissociation fraction of molecules is also enhanced.

  11. Development of pyridine-containing macrocyclic copper(II) complexes: potential role in the redox modulation of oxaliplatin toxicity in human breast cells.

    Science.gov (United States)

    Fernandes, Ana S; Costa, Judite; Gaspar, Jorge; Rueff, José; Cabral, M Fátima; Cipriano, Madalena; Castro, Matilde; Oliveira, Nuno G

    2012-09-01

    The unique redox and catalytic chemistry of Cu has justified the development of novel Cu complexes for different therapeutic uses including cancer therapy. In this work, four pyridine-containing aza-macrocyclic copper(II) complexes were prepared (CuL1-CuL4) varying in ring size and/or substituents and their superoxide scavenging activity evaluated. CuL3, the most active superoxide scavenger, was further studied as a modulator of the cytotoxicity of oxaliplatin in epithelial breast MCF10A cells and in MCF7 breast cancer cells. Our results show that CuL3 enhances the therapeutic window of oxaliplatin, by both protecting non-tumour cells and increasing its cytotoxic effect in breast carcinoma cells. CuL3 is thus a promising complex to be further studied and to be used as a lead compound for the optimization of novel chemotherapy sensitizers.

  12. Production of barium molybdate and tungstate on the base of ternary reciprocal Na, Ba long Cl, EhO4 (Eh - Mo, W) systems

    International Nuclear Information System (INIS)

    Garkushin, I.K.; Sechnoj, A.I.; Dibirov, M.A.; Trunin, A.S.

    1984-01-01

    Possibilities of the syntnesis of barium molybdate and tungstate on the base of ternary reciprocal Na, Ba parallel Cl, EhO 4 (Eh=Mo, W) system state diagrams are under study. It is shown that on the basis of these reciprocal state diagrams syntnesis of not only BaO 4 but also of other suhstances is possible. Purity of obtained chemical agents is basically dependent on qualification of initial components. Synthesis temperature is decreased and time is reduced as compared to other known methods. For substance synthesis, state diagrams examination (reaction type confirmation and component crystallization fields separation from compound crystallization fields) is necessary along with the calculation of the conventional thermochemical effect

  13. Seasonal variation in tissue estrogen-2/4-hydroxylases (EH) and in vitro effects of steroids on ovarian EH activity in the catfish Heteropneustes fossilis.

    Science.gov (United States)

    Chourasia, T K; Joy, K P

    2010-12-12

    A radiometric assay was used to measure microsomal EH activity from tritiated H(2)O formed during the conversion of [2,4 (3)H] estradiol-17β into catecholestrogens in the microsomal fractions of liver, brain and ovary of the catfish Heteropneustes fossilis. The validation data show that enzyme activity increased with incubation time, and substrate and cofactor (NADPH) concentrations, elicited temperature optima of 30-37°C and pH optima of 6.8-7.8. EH activity was strongly NADPH-dependent and in its absence only 13.48% activity was recorded. Liver recorded the highest enzyme activity, followed by brain and ovary. EH activity showed a significant seasonal variation with the peak activity in spawning phase and the lowest activity in resting phase. In the ovary, the follicular layer (theca and granulosa) elicited the highest activity over that of the denuded oocytes. Modulatory effects of steroids on ovarian enzyme activity were further demonstrated. The incubation of postvitellogenic follicles with 1, 10 or 100 nM concentrations of various steroids for 24 h produced varied effects on EH activity. Progesterone and 2-hydroxyestradiol-17β elicited strong suppressive effects on enzyme activity. Estrogens (E(1), E(2) and E(3)) suppressed the activity in a concentration-dependent manner. Among the progestins tested, 17,20α-dihydroxy-4-pregnen-3-one, the isomer of 17,20β-dihydroxy-4-pregnen-3-one (a teleost maturation-inducing steroid) showed the lowest depressing effect. Among androgens, the testosterone metabolite 11-ketotestosterone (functional teleost androgen) showed a high suppressing effect. Corticosteroids elicited low activity with cortisol suppressed the activity at higher concentrations. The study will form a basis to understand the physiological role of catecholestrogens in ovarian functions. Copyright © 2010 Elsevier Inc. All rights reserved.

  14. Vegetation-induced spatial variability of soil redox properties in wetlands

    Science.gov (United States)

    Szalai, Zoltán; Jakab, Gergely; Kiss, Klaudia; Ringer, Marianna; Balázs, Réka; Zacháry, Dóra; Horváth Szabó, Kata; Perényi, Katalin

    2016-04-01

    Vegetation induced land patches may result spatial pattern of on soil Eh and pH. These spatial pattern are mainly emerged by differences of aeration and exudation of assimilates. Present paper focuses on vertical extent and temporal dynamics of these patterns in wetlands. Two study sites were selected: 1. a plain wetland on calcareous sandy parent material (Ceglédbercel, Danube-Tisza Interfluve, Hungary); 2. headwater wetland with calcareous loamy parent material (Bátaapáti, Hungary). Two vegetation patches were studied in site 1: sedgy (dominated by Carex riparia) and reedy (dominated by Phragmites australis). Three patches were studied in site2: sedgy1 (dominated by C vulpina), sedgy 2 (C. riparia); nettle-horsetail (Urtica dioica and Equisetum arvense). Boundaries between patches were studied separately. Soil redox, pH and temperature studied by automated remote controlled instruments. Three digital sensors (Ponsell) were installed in each locations: 20cm and 40cm sensors represent the solum and 100 cm sensor monitors the subsoil). Groundwater wells were installed near to triplets for soil water sampling. Soil Eh, pH and temperature values were recorded in each 10 minutes. Soil water sampling for iron and DOC were carried out during saturated periods. Spatial pattern of soil Eh is clearly caused by vegetation. We measured significant differences between Eh values of the studied patches in the solum. We did not find this kinds horizontal differences in the subsoil. Boundaries of the patches usually had more reductive soil environment than the core areas. We have found temporal dynamics of the spatial redox pattern. Differences were not so well expressed during wintertime. These spatial patterns had influence on the DOC and iron content of porewater, as well. Highest temporal dynamics of soil redox properties and porewater iron could be found in the boundaries. These observations refer to importance patchiness of vegetation on soil chemical properties in

  15. Redox potentials of PuO{sub 2}{sup 2+}/PuO{sub 2}{sup +} and Pu{sup 4+}/Pu{sup 3+} at different ionic strengths and temperatures; entropy and heat capacity; Potentiels Redox des couples PuO{sub 2}{sup 2+}/PuO{sub 2}{sup +} et Pu{sup 4+}/Pu{sup 3+} a force ionique et temperature variables. Entropie et capacite calorifique

    Energy Technology Data Exchange (ETDEWEB)

    Capdevila, H.; Vitorge, P.

    1994-05-01

    The reversible redox potentials of the Plutonium couples are measured by using cyclic voltammetry, in perchloric media at ionic strength, I from 0,5 M to 3M, and temperature, T, from 5 deg C to 65 deg C. At each T, experimental results, E(T,I), are extrapolated to I = O by applying the Specific Interaction Theory (S.I.T.) to get interaction coefficients, {Delta} is element of (T), and E(T,O) (e.g. standard potentials when T = 25 deg C). At T = 25 deg C the numerical values of the potentials of all the Pu couples are nearly the same. It is then not easy to detect a systematic error due to disproportionation or redox impurity. This can explain some discrepancy on numerical values already published. We finally propose ``recommended values`` of the reversible redox potentials. As a first approximation, the variations of these potentials seem to be quite linear versus temperature: entropy variation versus T is small. But taking into account heat capacity that is involved in the E(T,I) second order derivative, usually improves the fitting. A second order expansion of {epsilon}(T) and of the Debye Huckel term, D(T) are used to propose equations that account for simultaneous ionic strength and temperature influences on G, S, Cp, H, and lg K. These equations, in particular those modelling the ionic strength influence on {Delta}S, {Delta}Cp, and {Delta}H are first checked for published mean activity coefficients of HCI and NaCI. Small discrepancy between the numerical values of entropy changes of actinides redox couples, deduced from electrochemical and calorimetric techniques are discussed. (authors). 27 refs., 6 tabs., 10 figs.

  16. Resolving the EH6/7 level in 4H-SiC by Laplace-transform deep level transient spectroscopy

    International Nuclear Information System (INIS)

    Alfieri, G.; Kimoto, T.

    2013-01-01

    We show that Laplace transform deep level transient spectroscopy (LDLTS) is an effective technique for the separation of the overlapping emission rates of the EH 6 and EH 7 levels, which are known to constitute EH 6/7 , a mid-gap level in n-type 4H-SiC. The analysis of the electron irradiation dose, electric field dependence, and the effects of carbon interstitials injection on the emission rates of EH 6 and EH 7 shows that EH 7 is dominant over EH 6 and confirms that their nature is related to a carbon vacancy.

  17. 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.

  18. Popular Cultural Struggle of "Islamist" Identity: Ehlisünnet TV Street Interviews

    OpenAIRE

    Gürel, Halil İbrahim; Şimşek-Rathke, Leyla

    2016-01-01

    This study aims to analyse and interpret Ehlisünnet TV (Ahsen TV, with its new name) emissions focussing on some “street interviews”, “street observatory shootings” and “street interview like mise en scenes” which are named as “social experiments” by the producers. The reporters of Ehlisünnet TV seem to have regularly conducted interviews in different parts of Istanbul such as Nişantaşı, Bakırköy, Eyüp, Karagümrük or Taksim. In those interviews, they put specific focus on Islamic lifestyle, s...

  19. Secular Variation and Physical Characteristics Determination of the HADS Star EH Lib

    Science.gov (United States)

    Pena, J. H.; Villarreal, C.; Pina, D. S.; Renteria, A.; Soni, A., Guillen, J. Calderon, J.

    2017-12-01

    Physical parameters of EH Lib have been determined based on observations carried out in 2015 with photometry. They have also served, along with samples from the years 1969 and 1986, to analyse the frequency content of EH Lib with Fourier Transforms. Recent CCD observations increased the times of maximum with twelve new times which helped us study the secular variation of the period with a method based on the minimization of the standard deviation of the O-C residuals. It is concluded that there may be a long-term period change.

  20. Study on the rhythmic variation of plasma cortisol levels in patients with essential hypertension (EH) and coronary heart disease (CHD)

    International Nuclear Information System (INIS)

    Zhu Mei; Wu Guo; Li Ying

    2007-01-01

    Objective: To study the rhythmic fluctuation of plasma cortisol levels in patients with EH and CHD. Methods: Plasma cortisol levels were determined with RIA at 8Am, 4Pm and midnight in 61 patients with EH, 46 patients with CHD and 36 controls. Results: The normal rhythmic fluctuation pattern of plasma cortisol levels was retained in the EH and CHD patients. However, the levels were all significantly higher in the patients than those in the controls, especially in the midnight specimens. Conclusion: Marked elevated plasma cortisol levels were observed in patients with EH and CHD, with the normal rhythmic fluctuation pattern retained. (authors)

  1. Absolute proton hydration free energy, surface potential of water, and redox potential of the hydrogen electrode from first principles: QM/MM MD free-energy simulations of sodium and potassium hydration

    Science.gov (United States)

    Hofer, Thomas S.; Hünenberger, Philippe H.

    2018-06-01

    The absolute intrinsic hydration free energy GH+,w a t ◦ of the proton, the surface electric potential jump χwa t ◦ upon entering bulk water, and the absolute redox potential VH+,w a t ◦ of the reference hydrogen electrode are cornerstone quantities for formulating single-ion thermodynamics on absolute scales. They can be easily calculated from each other but remain fundamentally elusive, i.e., they cannot be determined experimentally without invoking some extra-thermodynamic assumption (ETA). The Born model provides a natural framework to formulate such an assumption (Born ETA), as it automatically factors out the contribution of crossing the water surface from the hydration free energy. However, this model describes the short-range solvation inaccurately and relies on the choice of arbitrary ion-size parameters. In the present study, both shortcomings are alleviated by performing first-principle calculations of the hydration free energies of the sodium (Na+) and potassium (K+) ions. The calculations rely on thermodynamic integration based on quantum-mechanical molecular-mechanical (QM/MM) molecular dynamics (MD) simulations involving the ion and 2000 water molecules. The ion and its first hydration shell are described using a correlated ab initio method, namely resolution-of-identity second-order Møller-Plesset perturbation (RIMP2). The next hydration shells are described using the extended simple point charge water model (SPC/E). The hydration free energy is first calculated at the MM level and subsequently increased by a quantization term accounting for the transformation to a QM/MM description. It is also corrected for finite-size, approximate-electrostatics, and potential-summation errors, as well as standard-state definition. These computationally intensive simulations provide accurate first-principle estimates for GH+,w a t ◦, χwa t ◦, and VH+,w a t ◦, reported with statistical errors based on a confidence interval of 99%. The values obtained

  2. 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

  3. Silver nanoparticle catalysed redox reaction: An electron relay effect

    International Nuclear Information System (INIS)

    Mallick, Kaushik; Witcomb, Mike; Scurrell, Mike

    2006-01-01

    A silver cluster shows efficient catalytic activity in a redox reaction because the cluster acts as the electron relay centre behaving alternatively as an acceptor and as a donor of electrons. An effective transfer of electrons is possible when the redox potential of the cluster is intermediate between the electron donor and electron acceptor system

  4. 1.8. Brand*, HA Badenhorst, FK 8iebrits and EH Kemm JP Hayes et ...

    African Journals Online (AJOL)

    Brand*, H.A. Badenhorst, F.K. 8iebrits and E.H. Kemm. Animal and Dairy Science Research Institute, Private Bag X2, Irene 1675, Republic of South Africa. J.P. Hayes. Department of Poultry Science, University of Stellenbosch, Stellenbosch 7600, Republic of South Africa. The experiment was conducted to compare the ...

  5. Chemical resilience of clay rich barrier materials to redox-oscillating conditions and implications for contaminant mobility

    International Nuclear Information System (INIS)

    Parsons, Chris; Rossetto, Lionel; Charlet, Laurent; Made, Benoit

    2012-01-01

    nitrate and sulphate in addition to the reductive dissolution of manganese and iron oxide minerals and an increase in CO 2 partial pressure. Whilst some authors demonstrate that such cyclic redox conditions may alter the properties of clay barrier materials due to illitisation of smectite clays (6, 7), the dynamic chemical conditions occurring during redox cycling may also result in the dissolution and re-precipitation of metal oxides, sulphides and carbonates. The balance of these minerals, even if present at sub-per cent levels as impurities has the potential to dramatically alter contaminant mobility. Many inorganic contaminants often associated with LL-LLW including Sb, Cr, As, Hg and U are also highly sensitive to changes in redox conditions which may result in changes to their speciation, toxicity and mobility (8, 9). We demonstrate through the combination of redox-stat batch-reactor experiments and thermodynamic modelling that periodic and cumulative changes to matrix mineralogy, contaminant speciation and mineral surface properties occur following periodic cycles of reduction and oxidation. These changes result in both short term (intra-cycle) and long-term (inter-cycle) changes to K d values for a range of redox sensitive contaminants associated with LL-LLW including arsenic, chromium, selenium, mercury and uranium (Table 1 and Figures 1 and 2). During a series of laboratory experiments argillaceous substrates were subjected to successive cycles of oxidising and reducing conditions with Eh oscillating between -215 and +340 mV induced via both abiotic and microbial methods. Chemically induced cycles of oxidation and reduction were achieved via a combination of gas sparging (nitrogen vs compressed air) and the addition of a synthetic reduced humic substance analogue (AH 2 DS 2- ). Microbially induced cycles of oxidation and reduction were achieved using gas sparging (nitrogen vs compressed air) to stimulate different metabolic pathways of a natively present

  6. Iron chemistry of Hawaiian rainforest soil solution: Biogeochemical implications of multiple Fe redox cycles

    Science.gov (United States)

    Thompson, A.; Chorover, J.; Chadwick, O.

    2003-12-01

    Iron (Fe)-oxides are important sorbents for nutrients, pollutants and natural organic matter (NOM). When flucutations in soil oxygen status exist, Fe can cycle through reduced and oxidized forms and thus greatly affect the aqueous conc. of nutrients and metals. We are examining the influence of oscillating oxic/anoxic conditions on Fe-oxide formation and biogeochemical processes (microbial community composition, and carbon, nutrient and trace metal availability). Our work makes use of a natural rainfall gradient ranging from 2.2 to 4.2 m mean annual precipitation (MAP) on the island of Maui, Hawaii, USA. All sites developed on a 400ky basaltic lava flow and comprise soils under similar vegetation. Solid phase Fe concentration and oxidation state vary systematically across this rainfall gradient with a sharp decrease in pedogenic Fe between 2.8 m and 3.5 m MAP that corresponds with an Eh of 330 mV (1-yr ave.). Fe isotopic composition and Fe-oxide associated rare earth elements (REE) also suggest a shift from ligand-promoted to redutive Fe dissolution with increasing rainfall. To examine the effects of multiple Fe oxidation/reduction cycles, we constructed a set of redox-stat reactors that maintain Eh values within a set range by small Eh-triggered additions of oxygen. Triplicate soil slurry reactors are subjected to redox (Eh) oscillations such that Fe is repeatedly cycled from oxidized to reduced forms. During our current experiment, we measure pH and Eh dynamics and monitor the distribution of Fe(II) and Fe(III), major ion and anion concentrations, a range of trace metals including the REE, and total organic carbon (TOC) in three Stokes-effective particle size fractions (DNA fingerprinting is used to track changes in the microbial community. Prior to implementing the rigorous sampling procedure above, we completed two preliminary reactor experiments focusing only on Fe distribution between aqueous, HCl, and oxalate extractions. These experiments illustrated (1) a

  7. 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

  8. Microbial activity in argillite waste storage cells for the deep geological disposal of French bituminous medium activity long lived nuclear waste: Impact on redox reaction kinetics and potential

    Science.gov (United States)

    Albrecht, A.; Leone, L.; Charlet, L.

    2009-04-01

    Micro-organisms are ubiquitous and display remarkable capabilities to adapt and survive in the most extreme environmental conditions. It has been recognized that microorganisms can survive in nuclear waste disposal facilities if the required major (P, N, K) and trace elements, a carbon and energy source as well as water are present. The space constraint is of particular interest as it has been shown that bacteria do not prosper in compacted clay. An evaluation of the different types of French medium and high level waste, in a clay-rich host rock storage environment at a depth between 500 and 600 m, has shown that the bituminous waste is the most likely candidate to accommodate significant microbial activity. The waste consists of a mixture of bitumen (source of bio-available organic matter and H2 as a consequence of its degradation and radiolysis) and nitrates and sulphates kept in a stainless steel container. The assumption, that microbes only have an impact on reaction kinetics needs to be reassessed in the case where nitrates and sulphates are present since both are known not to react at low temperatures without bacterial catalysis. The additional impact of both oxy-anions and their reduced species on redox conditions, radionuclide speciation and mobility gives this evaluation their particular relevance. Storage architecture proposes four primary waste containers positioned into armoured cement over packs and placed with others into the waste storage cell itself composed of a cement mantle enforcing the argillite host rock, the latter being characterized by an excavation damaged zone constricted both in space and in time and a pristine part of 60 m thickness. Bacterial activity within the waste and within the pristine argillite is disregarded because of the low water activity (biofilms are within the interface zones. A major restriction for the initial development of microbial colonies is the high pH controlled by the cement solution. Archea are able to survive

  9. 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.

  10. 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

  11. 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.

  12. 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

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

    Directory of Open Access Journals (Sweden)

    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.

  14. The redox properties of the natural iron-bearing clay mineral ferruginous smectite SWA-1: a combined electrochemical and spectroscopic study

    International Nuclear Information System (INIS)

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

    2012-01-01

    . Our results indicate that the reduction and oxidation of SWa-1 is complex and partly irreversible, implying that classically used thermodynamic relationships (i.e., the Nernst equation and Gibbs free energy) cannot be used to describe SWa-1 redox reactions. SWa-1 is redox active over a much wider potential range (approx. 1.0 V) than would be expected for a single electron transferring species (i.e., Fe 2+ /Fe 3+ ) in Nernstian system, which is attributed to redox interdependence between octahedral Fe sites. SWa-1 reduction and oxidation is also shown to be inherently thermodynamically irreversible based on oxidation and reduction paths following different Fe 2+ /Fe 3+ versus applied potential (E H ) curves depending on the initial redox state of the SWa-1. By modeling the Fe 2+ /Fe 3+ versus applied potential curves, we were able to fit apparent standard reduction potential values for native and dithionite-reduced SWa-1 that can be used in future studies. Current work is underway to determine the effect of pH on the redox properties of Fe-bearing clay minerals. Spectroscopic observations indicate that the reduction and subsequent re-oxidation of all the clay minerals studied was chemically irreversible, as indicated by the native and re-oxidized samples exhibiting differences in Moessbauer and XAS spectra. Further characterization of the Moessbauer spectra suggest that certain spectral features are indicative of the reduction potential (Eh) at which structural Fe 3+ reduction occurs. Our results point out that the complex redox behavior of Fe-bearing clay minerals must be taken into account to understand and predict the fate of radionuclides in matrices containing Fe-bearing clay minerals. The spectroscopic and electrochemical characterization of Fe-bearing clay minerals in this study also provides a means to account for these factors in future studies. Finally, we show that mediated electrochemistry offers new avenues to assess the redox properties of other redox

  15. Haplotype-based case-control study on human apurinic/apyrimidinic endonuclease 1/redox effector factor-1 gene and essential hypertension.

    Science.gov (United States)

    Naganuma, Takahiro; Nakayama, Tomohiro; Sato, Naoyuki; Fu, Zhenyan; Soma, Masayoshi; Yamaguchi, Mai; Shimodaira, Masanori; Aoi, Noriko; Usami, Ron

    2010-02-01

    Oxidative DNA damage is involved in the pathophysiology of essential hypertension (EH), which is a multifactorial disorder. Apurinic/apyrimidinic endonuclease 1/redox effector factor-1 (APE1/REF-1) is an essential endonuclease in the base excision repair pathway of oxidatively damaged DNA, in addition to having reducing properties that promote the binding of redox-sensitive transcription factors. Blood pressure in APE1/REF-1-knockout mice is reported to be significantly higher than in wild-type mice. The aim of this study was to investigate the relationship between EH and the human APE1/REF-1 gene through a haplotype-based case-control study using single-nucleotide polymorphisms (SNPs). We selected five SNPs in the human APE1/REF-1 gene (rs1760944, rs3136814, rs17111967, rs3136817, and rs1130409), and performed case-control studies in 265 EH patients and 266 age-matched normotensive (NT) subjects. rs17111967 was found to show nonheterogeneity among Japanese subjects. There were no significant differences in the overall distribution of genotypes or alleles for each SNP between EH and NT groups. In the overall distribution of the haplotype-based case-control study constructed based on rs1760944, rs3136817, and rs1130409, the frequency of the G-T-T haplotype was significantly higher in the EH group than in the NT group (2.1% vs. 0.0%, P = 0.001). Multiple logistic regression analysis also revealed significant differences for the G-T-T haplotype, even after adjustment for confounding factors (OR = 8.600, 95% CI: 1.073-68.951, P = 0.043). Based on the present results, the G-T-T haplotype appears to be a genetic marker of EH, and the APE1/REF-1 gene appears to be a susceptibility gene for EH.

  16. 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.)

  17. 76 FR 41501 - Notice of Intent To Award Affordable Care Act (ACA) Funding, EH09-907

    Science.gov (United States)

    2011-07-14

    ... network expansion and enhancement. Funding is appropriated under the Affordable Care Act (Pub. L. 111-148... Intent To Award Affordable Care Act (ACA) Funding, EH09-907 AGENCY: Centers for Disease Control and... in their FY 2011 applications submitted under funding opportunity EH09-907, ``National Environmental...

  18. Binding specificity and in vivo targets of the EH domain, a novel protein-protein interaction module

    DEFF Research Database (Denmark)

    Salcini, A E; Confalonieri, S; Doria, M

    1997-01-01

    EH is a recently identified protein-protein interaction domain found in the signal transducers Eps15 and Eps15R and several other proteins of yeast nematode. We show that EH domains from Eps15 and Eps15R bind in vitro to peptides containing an asparagine-proline-phenylalanine (NPF) motif. Direct...

  19. 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.

  20. 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

  1. 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.

  2. Effect of reducing groundwater on the retardation of redox-sensitive radionuclides

    Directory of Open Access Journals (Sweden)

    Rose TP

    2008-12-01

    Full Text Available Abstract Laboratory batch sorption experiments were used to investigate variations in the retardation behavior of redox-sensitive radionuclides. Water-rock compositions were designed to simulate subsurface conditions at the Nevada Test Site (NTS, where a suite of radionuclides were deposited as a result of underground nuclear testing. Experimental redox conditions were controlled by varying the oxygen content inside an enclosed glove box and by adding reductants into the testing solutions. Under atmospheric (oxidizing conditions, radionuclide distribution coefficients varied with the mineralogic composition of the sorbent and the water chemistry. Under reducing conditions, distribution coefficients showed marked increases for 99Tc (from 1.22 at oxidizing to 378 mL/g at mildly reducing conditions and 237Np (an increase from 4.6 to 930 mL/g in devitrified tuff, but much smaller variations in alluvium, carbonate rock, and zeolitic tuff. This effect was particularly important for 99Tc, which tends to be mobile under oxidizing conditions. A review of the literature suggests that iodine sorption should decrease under reducing conditions when I- is the predominant species; this was not consistently observed in batch tests. Overall, sorption of U to alluvium, devitrified tuff, and zeolitic tuff under atmospheric conditions was less than in the glove-box tests. However, the mildly reducing conditions achieved here were not likely to result in substantial U(VI reduction to U(IV. Sorption of Pu was not affected by the decreasing Eh conditions achieved in this study, as the predominant sorbed Pu species in all conditions was expected to be the low-solubility and strongly sorbing Pu(OH4. Depending on the aquifer lithology, the occurrence of reducing conditions along a groundwater flowpath could potentially contribute to the retardation of redox-sensitive radionuclides 99Tc and 237Np, which are commonly identified as long-term dose contributors in the risk

  3. Emerging Interaction Patterns in the Emiliania huxleyi-EhV System.

    Science.gov (United States)

    Ruiz, Eliana; Oosterhof, Monique; Sandaa, Ruth-Anne; Larsen, Aud; Pagarete, António

    2017-03-22

    Viruses are thought to be fundamental in driving microbial diversity in the oceanic planktonic realm. That role and associated emerging infection patterns remain particularly elusive for eukaryotic phytoplankton and their viruses. Here we used a vast number of strains from the model system Emiliania huxleyi /Emiliania huxleyi Virus to quantify parameters such as growth rate (µ), resistance (R), and viral production (Vp) capacities. Algal and viral abundances were monitored by flow cytometry during 72-h incubation experiments. The results pointed out higher viral production capacity in generalist EhV strains, and the virus-host infection network showed a strong co-evolution pattern between E. huxleyi and EhV populations. The existence of a trade-off between resistance and growth capacities was not confirmed.

  4. The e/h method of energy reconstruction for combined calorimeter

    International Nuclear Information System (INIS)

    Kul'chitskij, Yu.A.; Kuz'min, M.V.; Vinogradov, V.B.

    1999-01-01

    The new simple method of the energy reconstruction for a combined calorimeter, which we called the e/h method, is suggested. It uses only the known e/h ratios and the electron calibration constants and does not require the determination of any parameters by a minimization technique. The method has been tested on the basis of the 1996 test beam data of the ATLAS barrel combined calorimeter and demonstrated the correctness of the reconstruction of the mean values of energies. The obtained fractional energy resolution is [(58 ± 3)%/√E + (2.5 ± 0.3)%] O+ (1.7 ± 0.2) GeV/E. This algorithm can be used for the fast energy reconstruction in the first level trigger

  5. Electron response and e/h ratio of ATLAS barrel hadron prototype calorimeter

    International Nuclear Information System (INIS)

    Budagov, Yu.A.; Vinogradov, V.B.; Arkadov, V.V.; Karapetyan, G.V.

    1995-01-01

    The detailed information about electron response, electron energy resolution and e/h ratio as a function of incident energy E, impact point Z and incidence angle Θ of ATLAS iron-scintillator hadron prototype calorimeter with longitudinal tile configuration is presented. These results are based on electron and pion beams data of E=20, 50, 100, 150, 300 GeV at Θ=10 deg, 20 deg, 30 deg, which were obtained during test beam period in July 1995. The obtained calibration constant is used for muon response converting from pC to GeV. The results are compared with existing experimental data and with some Monte Carlo calculations. For some E, Θ, Z values the compensation (e/h=1) is observed. 23 refs., 18 figs., 9 tabs

  6. 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.

  7. At the European Hybrid Spectrometer (EHS) for the experiment NA27

    CERN Multimedia

    1983-01-01

    The photo shows a downstream section of the EHS. Interactions take place some 15 m behind the Intermediate Gamma Detector (IGD, blue)in the Lexan Bubble Chamber (LEBC). Ahead of IGD sits ISIS (photo 8107533X). Leaving IGD the interaction products then traverse a magnet M2 and a 12-m long gas Forward Cerenkov (FC) counter (partially seen at bottom, right). See Nucl. Instrum. Methods A258 (1987) 26-50.

  8. 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.

  9. Effect of metals on the lytic cycle of the coccolithovirus, EhV86.

    Directory of Open Access Journals (Sweden)

    Martha eGledhill

    2012-04-01

    Full Text Available In this study we show that metals, and in particular copper (Cu, can disrupt the lytic cycle in the Emiliania huxleyi - EhV86 host-virus system. Numbers of virus particles produced per E. huxleyi cell and E. huxleyi lysis rates were reduced by Cu at total metal concentrations over 500 nM in the presence of EDTA (ethylenediaminetetraacetic acid, and 250 nM in the absence of EDTA in acute short term exposure experiments. Zinc (Zn, cadmium (Cd and cobalt (Co were not observed to affect the lysis rate of EhV86 in these experiments. The cellular glutathione (GSH content increased in virus infected cells, but not as a result of metal exposure. In contrast, the cellular content of phytochelatins (PCs increased only in response to metal exposure. The increase in gluthatione content is consistent with increases in the production of reactive oxygen species (ROS on viral infection, while increases in PC content are likely linked to metal homeostasis and indicate that metal toxicity to the host was not affected by viral infection. We propose that Cu prevents lytic production of EhV86 by interfering with virus DNA (deoxyribonucleic acid synthesis through a transcriptional block, which ultimately suppresses the formation of ROS, a biochemical response required for successful virus infection.

  10. Dietary safety assessment of genetically modified rice EH rich in β-carotene.

    Science.gov (United States)

    Wu, Yangyang; Xu, Yan; Du, Yanan; Zhao, Xiao; Hu, Ruili; Fan, Xiaorui; Ren, Fangfang; Yao, Quanhong; Peng, Rihe; Tang, Xueming; Zhao, Kai

    2017-08-01

    This 90-day study aimed to assess the dietary safety of transgenic rice EH which is rich in β-carotene. Two experimental groups of Sprague-Dawley rats were fed diets containing 45% rice flour of Zhonghua 11 rice and transgenic rice EH rich in β-carotene, respectively. The reference group was fed a diet containing standard feed nutrition. During the trial period, each rat was weighed and the food intake was recorded twice a week. Their behaviors were observed daily. In the end, blood samples were obtained from all anesthetized rats to measure the hematologic and serum chemistry indicators. Growth performance, anatomy and pathology of all organs in each group were analyzed. Although a few parameters were found to be statistically significantly different across groups, they were within the normal reference range for this breed and age of rats. Therefore, the changes were not considered to be diet related. The results revealed that the transgenic rice EH rich in β-carotene was as nutritious as Zhonghua 11 rice and showed a lack of biologically meaningful unintended effects. Copyright © 2017 Elsevier Inc. All rights reserved.

  11. Aqueous liquid redox desulfurisation

    Energy Technology Data Exchange (ETDEWEB)

    Reicher, M.; Niemiec, B.; Katona, T.

    1999-12-01

    The LO-CAT II process is an aqueous liquid redox process which uses ferric and ferrous iron catalysts to oxidise hydrogen sulfide (from sour gas) to elemental sulfur: the relevant chemical equations are given. Chelating agents keep the iron in solution. The system is described under the headings of (i) LO-CAT chemistry, (ii) design parameters, (iii) startup challenges, (iv) present situation and (v) anticipated future conditions. Further improvements to the system are anticipated.

  12. 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.

  13. A genome-wide screen in yeast identifies specific oxidative stress genes required for the maintenance of sub-cellular redox homeostasis

    NARCIS (Netherlands)

    Ayer, A.; Fellermeier, S.; Fife, C.; Li, S.S.; Smits, G.; Meyer, A.J.; Dawes, I.W.; Perrone, G.G.

    2012-01-01

    Maintenance of an optimal redox environment is critical for appropriate functioning of cellular processes and cell survival. Despite the importance of maintaining redox homeostasis, it is not clear how the optimal redox potential is sensed and set, and the processes that impact redox on a

  14. 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...

  15. 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

  16. Ciprofloxacin provokes SOS-dependent changes in respiration and membrane potential and causes alterations in the redox status of Escherichia coli.

    Science.gov (United States)

    Smirnova, Galina V; Tyulenev, Aleksey V; Muzyka, Nadezda G; Peters, Mikhail A; Oktyabrsky, Oleg N

    2017-01-01

    An in-depth understanding of the physiological response of bacteria to antibiotic-induced stress is needed for development of new approaches to combatting microbial infections. Fluoroquinolone ciprofloxacin causes phase alterations in Escherichia coli respiration and membrane potential that strongly depend on its concentration. Concentrations lower than the optimal bactericidal concentration (OBC) do not inhibit respiration during the first phase. A dose higher than the OBC provokes immediate SOS-independent inhibition of respiration and growth that can contribute to a decreased SOS response and lowered susceptibility to high concentrations of ciprofloxacin. Cells retain their metabolic activity, membrane potential and accelerated K + uptake and produce low levels of superoxide and H 2 O 2 during the first phase. The time before initiation of the second phase is inversely correlated with the ciprofloxacin concentration. The second phase is SOS-dependent and characterized by respiratory inhibition, membrane depolarization, K + and glutathione leakage and cessation of glucose consumption and may be considered as cell death. atpA, gshA and kefBkefC knockouts, which perturb fluxes of protons and K + , can modify the degree and duration of respiratory inhibition and potassium retention. Loss of K + efflux channels KefB and KefC enhances the susceptibility of E. coli to ciprofloxacin. Copyright © 2016 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

  17. 76 FR 8788 - National Nanotechnology Coordination Office; Bridging NanoEHS Research Efforts: A Joint US-EU...

    Science.gov (United States)

    2011-02-15

    ... OFFICE OF SCIENCE AND TECHNOLOGY POLICY National Nanotechnology Coordination Office; Bridging NanoEHS Research Efforts: A Joint US-EU Workshop: Public Meeting AGENCY: National Nanotechnology Coordination Office, STPO. ACTION: Notice of public meeting. SUMMARY: The National Nanotechnology Coordination...

  18. Study to establish cost projections for production of Redox chemicals

    Science.gov (United States)

    Walther, J. F.; Greco, C. C.; Rusinko, R. N.; Wadsworth, A. L., III

    1982-01-01

    A cost study of four proposed manufacturing processes for redox chemicals for the NASA REDOX Energy Storage System yielded favorable selling prices in the range $0.99 to $1.91/kg of chromic chloride, anhydrous basis, including ferrous chloride. The prices corresponded to specific energy storage costs from under $9 to $17/kWh. A refined and expanded cost analysis of the most favored process yielded a price estimate corresponding to a storage cost of $11/kWh. The findings supported the potential economic viability of the NASA REDOX system.

  19. Eh-pH diagrams of the V-H2O system at 25,60 and 1000C

    International Nuclear Information System (INIS)

    Silva, F.T. da; Ogasawara, T.; Cassa, J.C.S.

    1987-01-01

    Free energies of the formation of vanadium ions in aqueous solutions at elevated temperatures were determined. Eh-pH diagrams at 25 0 C, 60 0 C and 100 0 C at different vanadium concentrations, using microcomputers were calculated and obtained. The effects of temperature and vanadium concentration on the predominance of vanadium species were examined. The Eh-pH diagrams for the V-H 2 O system were evaluated by comparisons with experimental data. (Author) [pt

  20. A new mercury-accumulating Mucor hiemalis strain EH8 from cold sulfidic spring water biofilms.

    Science.gov (United States)

    Hoque, Enamul; Fritscher, Johannes

    2016-10-01

    Here, we report about a unique aquatic fungus Mucor hiemalisEH8 that can remove toxic ionic mercury from water by intracellular accumulation and reduction into elemental mercury (Hg 0 ). EH8 was isolated from a microbial biofilm grown in sulfidic-reducing spring water sourced at a Marching's site located downhill from hop cultivation areas with a history of mercury use. A thorough biodiversity survey and mercury-removal function analyses were undertaken in an area of about 200 km 2 in Bavaria (Germany) to find the key biofilm and microbe for mercury removal. After a systematic search using metal removal assays we identified Marching spring's biofilm out of 18 different sulfidic springs' biofilms as the only one that was capable of removing ionic Hg from water. EH8 was selected, due to its molecular biological identification as the key microorganism of this biofilm with the capability of mercury removal, and cultivated as a pure culture on solid and in liquid media to produce germinating sporangiospores. They removed 99% of mercury from water within 10-48 h after initial exposure to Hg(II). Scanning electron microscopy demonstrated occurrence of intracellular mercury in germinating sporangiospores exposed to mercury. Not only associated with intracellular components, but mercury was also found to be released and deposited as metallic-shiny nanospheres. Electron-dispersive x-ray analysis of such a nanosphere confirmed presence of mercury by the HgM α peak at 2.195 keV. Thus, a first aquatic eukaryotic microbe has been found that is able to grow even at low temperature under sulfur-reducing conditions with promising performance in mercury removal to safeguard our environment from mercury pollution. © 2016 The Authors. MicrobiologyOpen published by John Wiley & Sons Ltd.

  1. Ruthenium nanocatalysis on redox reactions.

    Science.gov (United States)

    Veerakumar, Pitchaimani; Ramdass, Arumugam; Rajagopal, Seenivasan

    2013-07-01

    Nanoparticles have generated intense interest over the past 20 years due to their high potential applications in different areas such as catalysis, sensors, nanoscale electronics, fuel and solar cells and optoelectronics. As the large fractions of metal atoms are exposed to the surface, the use of metal nanoparticles as nanocatalysts allows mild reaction conditions and high catalytic efficiency in a large number of chemical transformations. They have emerged as sustainable heterogeneous catalysts and catalyst supports alternative to conventional materials. This review focuses on the synthesis, characterization and catalytic role of ruthenium nanoparticles (RuNPs) on the redox reactions of heteroatom containing organic compounds with the green reagent H2O2, a field that has attracted immense interest among the chemical, materials and industrial communities. We intend to present a broad overview of Ru nanocatalysts for redox reactions with an emphasis on their performance, stability and reusability. The growth in the chemistry of organic sulfoxides and N-oxides during last decade was due to their importance as synthetic intermediates for the production of a wide range of chemically and biologically active molecules. Thus design of efficient methods for the synthesis of sulfoxides and N-oxides becomes important. This review concentrates on the catalysis of RuNPs on the H2O2 oxidation of organic sulfides to sulfoxides and amines to N-oxides. The deoxygenation reactions of sulfoxides to sulfides and reduction of nitro compounds to amines are fundamental reactions in both chemistry and biology. Here, we also highlight the catalysis of metal nanoparticles on the deoxygenation of sulfoxides and sulfones and reduction of nitro compounds with particular emphasis on the mechanistic aspects.

  2. Therapeutic Potential of a Prolyl Hydroxylase Inhibitor FG-4592 for Parkinson’s Diseases in Vitro and in Vivo: Regulation of Redox Biology and Mitochondrial Function

    Directory of Open Access Journals (Sweden)

    Xuan Li

    2018-04-01

    Full Text Available As the main transcription factor that regulates the cellular responses to hypoxia, Hypoxia-inducible factor-1α (HIF-1α plays an important role in the pathogenesis of Parkinson’s disease (PD. HIF-1α is normally degraded through ubiquitination after hydroxylation by prolyl hydroxylases (PHD. Emerging evidence has suggested that HIF PHD inhibitors (HIF-PHI may have neuroprotective effects on PD through increasing HIF-1α levels. However, the therapeutic benefit of HIF-PHI for PD remains poorly explored due to the lack of proper clinical compounds and understanding of the underlying molecular mechanisms. In this study, we examined the therapeutic benefit of a new HIF-PHI, FG-4592, which is currently in phase 3 clinical trials to treat anemia in patients with chronic kidney diseases (CKD in PD models. FG-4592 attenuates MPP+ -induced apoptosis and loss of tyrosine hydroxylase (TH in SH-SY5Y cells. Pretreatment with FG-4592 mitigates MPP+-induced loss of mitochondrial membrane potential (MMP, mitochondrial oxygen consumption rate (OCR, production of reactive oxygen species (ROS and ATP. Furthermore, FG-4592 counterbalances the oxidative stress through up-regulating nuclear factor erythroid 2 p45-related factor 2 (Nrf-2, heme oxygenase-1 (HO-1 and superoxide dismutase 2 (SOD2. FG-4592 treatment also induces the expression of Peroxisome proliferator-activated receptor-γ coactivator-1α (PGC-1α through increasing the phosphorylation of AMP-activated protein kinase (AMPK. In MPTP-treated mice, FG-4592 protects against MPTP-induced loss of TH-positive neurons of substantia nigra and attenuates behavioral impairments. Collectively, our study demonstrates that FG-4592 is a promising therapeutic strategy for PD through improving the mitochondrial function under oxidative stress.

  3. Heat treatment effect on the properties of the EhP767 maraging steel welded joints

    International Nuclear Information System (INIS)

    Taver, E.I.; Piskarev, M.N.; Yushchenko, K.A.; Pustovit, A.I.; Anisimova, M.S.

    1977-01-01

    Heat treatment effect on properties of welded joints of maraging 03Kh13N4K13M3T (EhP767) steel with yield strength over 150 kgs/mm 2 has been investigated. It is shown, that change in impact strength of aged joints at - 196 deg C depends on the amount of residual austenite and grain size. To stabilize 20-40 % residual austenite heat treatment regimes have been developed. Recommended are quenching at 1030-1050 deg C, sub-zero treatment and aging at 520 deg C for 16 hrs

  4. EH AND S ANALYSIS OF DYE-SENSITIZED PHOTOVOLTAIC SOLAR CELL PRODUCTION

    International Nuclear Information System (INIS)

    BOWERMAN, B.; FTHENAKIS, V.

    2001-01-01

    Photovoltaic solar cells based on a dye-sensitized nanocrystalline titanium dioxide photoelectrode have been researched and reported since the early 1990's. Commercial production of dye-sensitized photovoltaic solar cells has recently been reported in Australia. In this report, current manufacturing methods are described, and estimates are made of annual chemical use and emissions during production. Environmental, health and safety considerations for handling these materials are discussed. This preliminary EH and S evaluation of dye-sensitized titanium dioxide solar cells indicates that some precautions will be necessary to mitigate hazards that could result in worker exposure. Additional information required for a more complete assessment is identified

  5. Simulation of the WWER-440/213 maximum credible accident at the EhNITs stand

    International Nuclear Information System (INIS)

    Blinkov, V.N.; Melikhov, O.I.; Melikhov, V.I.; Davydov, M.V.; Sokolin, A.V.; Shchepetil'nikov, Eh.Yu.

    2000-01-01

    The calculations of thermohydraulic processes through the ATHLET code for determining optimal conditions for modeling the coolant leakage at the EhNITs stand by the maximum credible accident at the NPP with WWER-440/213 reactor are presented. The diameters of the nozzle at the stand, whereby the local criterion of coincidence with the data on the NPP (by the maximum flow) and integral criterion of coincidence (by the mass and energy of the coolant, effluent during 10 s) are determined in the process of parametric calculations [ru

  6. 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.

  7. Detection of the Endosomal Sorting Complex Required for Transport in Entamoeba histolytica and Characterization of the EhVps4 Protein

    Directory of Open Access Journals (Sweden)

    Israel López-Reyes

    2010-01-01

    Full Text Available Eukaryotic endocytosis involves multivesicular bodies formation, which is driven by endosomal sorting complexes required for transport (ESCRT. Here, we showed the presence and expression of homologous ESCRT genes in Entamoeba histolytica. We cloned and expressed the Ehvps4 gene, an ESCRT member, to obtain the recombinant EhVps4 and generate specific antibodies, which immunodetected EhVps4 in cytoplasm of trophozoites. Bioinformatics and biochemical studies evidenced that rEhVps4 is an ATPase, whose activity depends on the conserved E211 residue. Next, we generated trophozoites overexpressing EhVps4 and mutant EhVps4-E211Q FLAG-tagged proteins. The EhVps4-FLAG was located in cytosol and at plasma membrane, whereas the EhVps4-E211Q-FLAG was detected as abundant cytoplasmic dots in trophozoites. Erythrophagocytosis, cytopathic activity, and hepatic damage in hamsters were not improved in trophozoites overexpressing EhVps4-FLAG. In contrast, EhVps4-E211Q-FLAG protein overexpression impaired these properties. The localization of EhVps4-FLAG around ingested erythrocytes, together with our previous results, strengthens the role for EhVps4 in E. histolytica phagocytosis and virulence.

  8. EH-GC: An Efficient and Secure Architecture of Energy Harvesting Green Cloud Infrastructure

    Directory of Open Access Journals (Sweden)

    Saurabh Singh

    2017-04-01

    Full Text Available Nowadays, the high power consumption of data centers is the biggest challenge to making cloud computing greener. Many researchers are still seeking effective solutions to reduce or harvest the energy produced at data centers. To address this challenge, we propose a green cloud infrastructure which provides security and efficiency based on energy harvesting (EH-GC. The EH-GC is basically focused on harvesting the heat energy produced by data centers in the Infrastructure-as-a-Service (IaaS infrastructure. A pyroelectric material is used to generate the electric current from heat using the Olsen cycle. In order to achieve efficient green cloud computing, the architecture utilizes a genetic algorithm for proper virtual machine allocation, taking into consideration less Service Level Agreement (SLA violations. The architecture utilizes Multivariate Correlation Analysis (MCA correlation analysis based on a triangular map area generation to detect Denial of Service (DoS attacks in the data center layer of the IaaS. Finally, the experimental analysis is explained based on the energy parameter, which proves that our model is efficient and secure, and that it efficiently reuses the energy emitted from the data center.

  9. Investigating thermomechanical parameters of the EhP693VD heat resisting alloys deformation

    International Nuclear Information System (INIS)

    Garibov, G.S.; Galkin, A.M.; Ermanok, M.Z.; Trepilets, A.E.

    1975-01-01

    The purpose of the present publication consists in complex research of the deformation resistance and plastic characteristics of heat-resistant hard-to-form alloy EhP693VD at the temperatures and deformation rates peculiar for the pressing process. The test conditions are: temperature 1000 to 1200 deg C; rate of deformation 0.5, 5.0 and 25 s -1 . The curves of deformation hardening of alloy EhP693VD show that the alloy is characterized by very high values of forming resistance index Ssub(f). With the increase of the rates of deformation, the maximum of curves Ssub(f) /antiepsilon/ is shifted towards greater degrees of deformation. The increase of the temperature results in the lower deformation hardening of the alloy. The intensity of the growth of the deformation resistance with the decrease of temperature becomes higher at lower degrees of deformation. Variation of plasticity at temperatures of up to 1150 deg C correlates with the curves showing variation of the deformation resistance. At a temperature of 1200 deg C, the drop of the deformation resistance is accompanied by the intensive drop of the plastic characteristics. The planning matrices, test results and complete disperse analysis tables are given. The analysis of the obtained equations makes it possible to draw a conclusion that the rise of the test temperature and drop of the rates of deformation entail the increase of the plastic characteristics

  10. Activating mitochondrial function and haemoglobin expression with EH-201, an inducer of erythropoietin in neuronal cells, reverses memory impairment.

    Science.gov (United States)

    Horng, Lin-Yea; Hsu, Pei-Lun; Chen, Li-Wen; Tseng, Wang-Zou; Hsu, Kai-Tin; Wu, Chia-Ling; Wu, Rong-Tsun

    2015-10-01

    Memory impairment can be progressive in neurodegenerative diseases, and physiological ageing or brain injury, mitochondrial dysfunction and oxidative stress are critical components of these issues. An early clinical study has demonstrated cognitive improvement during erythropoietin treatment in patients with chronic renal failure. As erythropoietin cannot freely cross the blood-brain barrier, we tested EH-201 (2,3,5,4'-tetrahydroxystilbene-2-O-β-d-glucoside, also known as TSG), a low MW inducer of erythropoietin, for its therapeutic effects on memory impairment in models of neurodegenerative diseases, physiological ageing or brain injury. The effects of EH-201 were investigated in astrocytes and PC12 neuronal-like cells. In vivo, we used sleep-deprived (SD) mice as a stress model, amyloid-β (Aβ)-injected mice as a physiological ageing model and kainic acid (KA)-injected mice as a brain damage model to assess the therapeutic effects of EH-201. EH-201 induced expression of erythropoietin, PPAR-γ coactivator 1α (PGC-1α) and haemoglobin in astrocytes and PC12 neuronal-like cells. In vivo, EH-201 treatment restored memory impairment, as assessed by the passive avoidance test, in SD, Aβ and KA mouse models. In the hippocampus of mice given EH-201 in their diet, levels of erythropoietin, PGC-1α and haemoglobin were increased The induction of endogenous erythropoietin in neuronal cells by inducers such as EH-201 might be a therapeutic strategy for memory impairment in neurodegenerative disease, physiological ageing or traumatic brain injury. © 2015 The Authors. British Journal of Pharmacology published by John Wiley & Sons Ltd on behalf of The British Pharmacological Society.

  11. 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.

  12. 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.

  13. A protein-binding domain, EH, identified in the receptor tyrosine kinase substrate Eps15 and conserved in evolution

    DEFF Research Database (Denmark)

    Wong, W T; Schumacher, C; Salcini, A E

    1995-01-01

    In this report we structurally and functionally define a binding domain that is involved in protein association and that we have designated EH (for Eps15 homology domain). This domain was identified in the tyrosine kinase substrate Eps15 on the basis of regional conservation with several heteroge......In this report we structurally and functionally define a binding domain that is involved in protein association and that we have designated EH (for Eps15 homology domain). This domain was identified in the tyrosine kinase substrate Eps15 on the basis of regional conservation with several...... heterogeneous proteins of yeast and nematode. The EH domain spans about 70 amino acids and shows approximately 60% overall amino acid conservation. We demonstrated the ability of the EH domain to specifically bind cytosolic proteins in normal and malignant cells of mesenchymal, epithelial, and hematopoietic...... (for Eps15-related). Structural comparison of Eps15 and Eps15r defines a family of signal transducers possessing extensive networking abilities including EH-mediated binding and association with Src homology 3-containing proteins....

  14. Eh-pH diagrams for elements from Z = 40 to Z = 52: application to the Oklo natural reactor, Gabon

    Energy Technology Data Exchange (ETDEWEB)

    Brookins, D G [New Mexico Univ., Albuquerque (USA). Dept. of Geology

    1978-11-01

    Eh-pH diagrams for elements from Z = 40 (Zr) to Z = 52 (Te) have been constructed in order to comment on migration/retention of these elements at Oklo. Although data for fissiogenic amounts of some of these elements are lacking, where such data are available to agreement between predicted migration/retention based on the Eh-pH diagrams and actual measurement is excellent. Based on Eh-pH diagrams, migration (to what degree is uncertain) of Mo and Cd is predicted whereas retention of Y, Zr, Tc, Ru, Rh, Pd, Ag and Te is also predicted. An earlier report of Frejacques et al. of Tc migration is in disagreement with Eh-pH prediction, and recent (unpublished) data argue for Tc retention. In view of the agreement between prediction and observation, the possible migration of Sb and retention of In and Sn is proposed. These data again demonstrate the usefulness of Eh-pH diagrams for the Oklo fossil nuclear reactor but, more important, allow constraints to be placed on repositories for nuclear waste now under consideration.

  15. Managing EHS of PV-Related Equipment at the National Renewable Energy Laboratory: Preprint

    Energy Technology Data Exchange (ETDEWEB)

    McCuskey, T.; Nelson, B. P.

    2012-06-01

    Managing environment, health, and safety (EHS) risks at a national laboratory, or university, can be intimidating to a researcher who is focused on research results. Laboratory research and development (R&D) operations are often driven by scientists with limited engineering support and lack well-refined equipment development resources. To add to the burden for a researcher, there is a plethora of codes, standards, and regulations that govern the safe installation and operation of photovoltaic-related R&D equipment -- especially those involving hazardous production materials. To help guide the researcher through the vast list of requirements, the EHS office at NREL has taken a variety of steps. Organizationally, the office has developed hazard-specific laboratory-level procedures to govern particular activities. These procedures are a distillation of appropriate international codes, fire agencies, SEMI standards, U.S. Department of Energy orders, and other industry standards to those necessary and sufficient to govern the safe operation of a given activity. The EHS office works proactively with researchers after a concept for a new R&D capability is conceived to help guide the safe design, acquisition, installation, and operation of the equipment. It starts with a safety assessment at the early stages such that requirements are implemented to determine the level of risk and degree of complexity presented by the activity so appropriate controls can be put in place to manage the risk. As the equipment requirements and design are refined, appropriate equipment standards are applied. Before the 'to-build' specifications are finalized, a process hazard analysis is performed to ensure that no single-point failure presents an unacceptable risk. Finally, as the tool goes through construction and installation stages, reviews are performed at logical times to ensure that the requisite engineering controls and design are in place and operational. Authorization to

  16. 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.

  17. High statistics study of $\\bar{p}p$ annihilation physics at the EHS

    CERN Multimedia

    2002-01-01

    We propose to perform an experiment to study antiproton-proton annihilations at 50 GeV/c, using the EHS facility.\\\\ \\\\ We will study in detail annihilation processes in terms of the underlying quark structure, and to compare our results with the predictions of the three principal models: quark fusion, fragmentation and recombination.\\\\ \\\\ These models achieved satisfactory results for pion and non-strange resonance production but failed for strange particle production. In fact a study of the production of strange particles could lead to valuable dues in understanding the annihilation mechanisms. A possible explanation of their production is that fast gluons materialize as strange quark pairs in the annihilation process. \\\\ \\\\ We expect to obtain 35 K, well identified, annihilation events.

  18. Communication on SWIPT and EH Using Electromagnetic Behaviour for Power Allocation in Wireless Networks

    Science.gov (United States)

    Khan, Sohel Rana; Ajij, Sayyad

    2017-12-01

    This review paper focuses on the basic relations between wireless power transfer, wireless information transfer and combined phenomenon of simultaneous wireless information and power transfer. The authors reviewed and discussed electromagnetic fields behaviour (EMB) for enhancing the power allocation strategies (PAS) in energy harvesting (EH) wireless communication systems. Further, this paper presents relations between Friis transmission equation and Maxwell's equations to be used in propagation models for reduction in specific absorption rate (SAR). This paper provides a review of various methods and concepts reported in earlier works. This paper also reviews Poynting vector and power densities along with boundary conditions for antennas and human body. Finally, this paper explores the usage of electromagnetic behaviour for the possible enhancement in power saving methods for electromagnetic behaviour centered-wireless energy harvesting (EMBC-WEH). At the same time, possibilities of PAS for reduction in SAR are discussed.

  19. Elimination of ion losses in the EhGP-10-1 charge-exchange accelerator

    International Nuclear Information System (INIS)

    Fridrikh, M.

    1986-01-01

    To improve the ion transit factor in the EhGP-10-1 charge-exchange accelerator the injector ion-optical properties are studied. The injector operates at constant high voltage U a -23 kV. Using an immersion lens the negative ion energy before entering the accelerating tube is increased up to energy proportional to the conductor voltage. A single electrostatic lens provides a cross-over in the vicinity of immersion lens. By reducing the electric field gradient at the accelerating tube inlet, optimizing input electrode voltage and shifting the single lens by 0.26 m towards the accelerating tube inlet almost full beam transit is attained at all conductor voltages

  20. Conference Scene: epigenetics eh! The first formal meeting of the Canadian epigenetics community.

    Science.gov (United States)

    Underhill, Alan; Hendzel, Michael J

    2011-08-01

    In recognition of Canada's longstanding interest in epigenetics - and a particular linguistic interjection - the inaugural 'Epigenetics, Eh!' conference was held between 4-7 May 2011 in London, Ontario. The meeting struck an excellent balance between Canadian and international leaders in epigenetic research while also providing a venue to showcase up-and-coming talent. Almost without exception, presentations touched on the wide-ranging and severe consequences of epigenetic dysfunction, as well as current and emerging therapeutic opportunities. While gaining a deeper understanding of how DNA and histone modifications, together with multiple classes of ncRNAs, act to functionalize our genome, participants were also provided with a glimpse of the astounding complexity of chromatin structure, challenging existing dogma.

  1. Epigenetics, eh! A meeting summary of the Canadian Conference on Epigenetics.

    Science.gov (United States)

    Rodenhiser, David I; Bérubé, Nathalie G; Mann, Mellissa R W

    2011-10-01

    In May 2011, the Canadian Conference on Epigenetics: Epigenetics Eh! was held in London, Canada. The objectives of this conference were to showcase the breadth of epigenetic research on environment and health across Canada and to provide the catalyst to develop collaborative Canadian epigenetic research opportunities, similar to existing international epigenetic initiatives in the US and Europe. With ten platform sessions and two sessions with over 100 poster presentations, this conference featured cutting-edge epigenetic research, presented by Canadian and international principal investigators and their trainees in the field of epigenetics and chromatin dynamics. An EpigenART competition included ten artists, creating a unique opportunity for artists and scientists to interact and explore their individual interpretations of this scientific discipline. The conference provided a unique venue for a significant cross-section of Canadian epigenetic researchers from diverse disciplines to meet, interact, collaborate and strategize at the national level.

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

    OpenAIRE

    Rizvi, Masood Ahmad; Teshima, Norio; Maqsood, Syed Raashid; Akhoon, Showket Ahmad; Peerzada, Ghulam Mustafa

    2015-01-01

    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...

  3. Food Allergy Knowledge and Attitudes of Restaurant Managers and Staff: An EHS-Net Study

    Science.gov (United States)

    Radke, Taylor J.; Brown, Laura G.; Hoover, E. Rickamer; Faw, Brenda V.; Reimann, David; Wong, Melissa R.; Nicholas, David; Barkley, Jonathan; Ripley, Danny

    2016-01-01

    Dining outside of the home can be difficult for persons with food allergies who must rely on restaurant staff to properly prepare allergen-free meals. The purpose of this study was to understand and identify factors associated with food allergy knowledge and attitudes among restaurant managers, food workers, and servers. This study was conducted by the Environmental Health Specialists Network (EHS-Net), a collaborative forum of federal, state, and local environmental health specialists working to understand the environmental factors associated with food safety issues. EHS-Net personnel collected data from 278 randomly selected restaurants through interviews with restaurant managers, food workers, and servers. Results indicated that managers, food workers, and servers were generally knowledgeable and had positive attitudes about accommodating customers’ food allergies. However, we identified important gaps, such as more than 10% of managers and staff believed that a person with a food allergy can safely consume a small amount of that allergen. Managers and staff also had lower confidence in their restaurant’s ability to properly respond to a food allergy emergency. The knowledge and attitudes of all groups were higher at restaurants that had a specific person to answer food allergy questions and requests or a plan for answering questions from food allergic customers. However, food allergy training was not associated with knowledge in any of the groups but was associated with manager and server attitudes. Based on these findings, we encourage restaurants to be proactive by training staff about food allergies and creating plans and procedures to reduce the risk of a customer having a food allergic reaction. PMID:28221943

  4. Food Allergy Knowledge and Attitudes of Restaurant Managers and Staff: An EHS-Net Study.

    Science.gov (United States)

    Radke, Taylor J; Brown, Laura G; Hoover, E Rickamer; Faw, Brenda V; Reimann, David; Wong, Melissa R; Nicholas, David; Barkley, Jonathan; Ripley, Danny

    2016-09-01

    Dining outside of the home can be difficult for persons with food allergies who must rely on restaurant staff to properly prepare allergen-free meals. The purpose of this study was to understand and identify factors associated with food allergy knowledge and attitudes among restaurant managers, food workers, and servers. This study was conducted by the Environmental Health Specialists Network (EHS-Net), a collaborative forum of federal, state, and local environmental health specialists working to understand the environmental factors associated with food safety issues. EHS-Net personnel collected data from 278 randomly selected restaurants through interviews with restaurant managers, food workers, and servers. Results indicated that managers, food workers, and servers were generally knowledgeable and had positive attitudes about accommodating customers' food allergies. However, we identified important gaps, such as more than 10% of managers and staff believed that a person with a food allergy can safely consume a small amount of that allergen. Managers and staff also had lower confidence in their restaurant's ability to properly respond to a food allergy emergency. The knowledge and attitudes of all groups were higher at restaurants that had a specific person to answer food allergy questions and requests or a plan for answering questions from food allergic customers. However, food allergy training was not associated with knowledge in any of the groups but was associated with manager and server attitudes. Based on these findings, we encourage restaurants to be proactive by training staff about food allergies and creating plans and procedures to reduce the risk of a customer having a food allergic reaction.

  5. Membrane development for vanadium redox flow batteries.

    Science.gov (United States)

    Schwenzer, Birgit; Zhang, Jianlu; Kim, Soowhan; Li, Liyu; Liu, Jun; Yang, Zhenguo

    2011-10-17

    Large-scale energy storage has become the main bottleneck for increasing the percentage of renewable energy in our electricity grids. Redox flow batteries are considered to be among the best options for electricity storage in the megawatt range and large demonstration systems have already been installed. Although the full technological potential of these systems has not been reached yet, currently the main problem hindering more widespread commercialization is the high cost of redox flow batteries. Nafion, as the preferred membrane material, is responsible for about 11% of the overall cost of a 1 MW/8 MWh system. Therefore, in recent years two main membrane related research threads have emerged: 1) chemical and physical modification of Nafion membranes to optimize their properties with regard to vanadium redox flow battery (VRFB) application; and 2) replacement of the Nafion membranes with different, less expensive materials. This review summarizes the underlying basic scientific issues associated with membrane use in VRFBs and presents an overview of membrane-related research approaches aimed at improving the efficiency of VRFBs and making the technology cost-competitive. Promising research strategies and materials are identified and suggestions are provided on how materials issues could be overcome.

  6. Bifunctional redox flow battery

    International Nuclear Information System (INIS)

    Wen, Y.H.; Cheng, J.; Xun, Y.; Ma, P.H.; Yang, Y.S.

    2008-01-01

    A new bifunctional redox flow battery (BRFB) system, V(III)/V(II)-L-cystine(O 2 ), was systematically investigated by using different separators. It is shown that during charge, water transfer is significantly restricted with increasing the concentration of HBr when the Nafion 115 cation exchange membrane is employed. The same result can be obtained when the gas diffusion layer (GDL) hot-pressed separator is used. The organic electro-synthesis is directly correlated with the crossover of vanadium. When employing the anion exchange membrane, the electro-synthesis efficiency is over 96% due to a minimal crossover of vanadium. When the GDL hot-pressed separator is applied, the crossover of vanadium and water transfer are noticeably prevented and the electro-synthesis efficiency of over 99% is obtained. Those impurities such as vanadium ions and bromine can be eliminated through the purification of organic electro-synthesized products. The purified product is identified to be L-cysteic acid by IR spectrum. The BRFB shows a favorable discharge performance at a current density of 20 mA cm -2 . Best discharge performance is achieved by using the GDL hot-pressed separator. The coulombic efficiency of 87% and energy efficiency of about 58% can be obtained. The cause of major energy losses is mainly associated with the cross-contamination of anodic and cathodic active electrolytes

  7. The Analgesic Acetaminophen and the Antipsychotic Clozapine Can Each Redox-Cycle with Melanin.

    Science.gov (United States)

    Temoçin, Zülfikar; Kim, Eunkyoung; Li, Jinyang; Panzella, Lucia; Alfieri, Maria Laura; Napolitano, Alessandra; Kelly, Deanna L; Bentley, William E; Payne, Gregory F

    2017-12-20

    Melanins are ubiquitous but their complexity and insolubility has hindered characterization of their structures and functions. We are developing electrochemical reverse engineering methodologies that focus on properties and especially on redox properties. Previous studies have shown that melanins (i) are redox-active and can rapidly and repeatedly exchange electrons with diffusible oxidants and reductants, and (ii) have redox potentials in midregion of the physiological range. These properties suggest the functional activities of melanins will depend on their redox context. The brain has a complex redox context with steep local gradients in O 2 that can promote redox-cycling between melanin and diffusible redox-active chemical species. Here, we performed in vitro reverse engineering studies and report that melanins can redox-cycle with two common redox-active drugs. Experimentally, we used two melanin models: a convenient natural melanin derived from cuttlefish (Sepia melanin) and a synthetic cysteinyldopamine-dopamine core-shell model of neuromelanin. One drug, acetaminophen (APAP), has been used clinically for over a century, and recent studies suggest that low doses of APAP can protect the brain from oxidative-stress-induced toxicity and neurodegeneration, while higher doses can have toxic effects in the brain. The second drug, clozapine (CLZ), is a second generation antipsychotic with polypharmacological activities that remain incompletely understood. These in vitro observations suggest that the redox activities of drugs may be relevant to their modes-of-action, and that melanins may interact with drugs in ways that affect their activities, metabolism, and toxicities.

  8. Redox Fluctuations Increase the Contribution of Lignin to Soil Respiration

    Science.gov (United States)

    Hall, S. J.; Silver, W. L.; Timokhin, V.; Hammel, K.

    2014-12-01

    Lignin mineralization represents a critical flux in the terrestrial carbon (C) cycle, yet little is known about mechanisms and environmental factors controlling lignin breakdown in mineral soils. Hypoxia has long been thought to suppress lignin decomposition, yet variation in oxygen (O2) availability in surface soils accompanying moisture fluctuations could potentially stimulate this process by generating reactive oxygen species via coupled biotic and abiotic iron (Fe) redox cycling. Here, we tested the impact of redox fluctuations on lignin breakdown in humid tropical forest soils during ten-week laboratory incubations. We used synthetic lignins labeled with 13C in either of two positions (aromatic methoxyl and propyl Cβ) to provide highly sensitive and specific measures of lignin mineralization not previously employed in soils. Four-day redox fluctuations increased the percent contribution of methoxyl C to soil respiration, and cumulative methoxyl C mineralization was equivalent under static aerobic and fluctuating redox conditions despite lower total C mineralization in the latter treatment. Contributions of the highly stable Cβ to mineralization were also equivalent in static aerobic and fluctuating redox treatments during periods of O2 exposure, and nearly doubled in the fluctuating treatment after normalizing to cumulative O2 exposure. Oxygen fluctuations drove substantial net Fe reduction and oxidation, implying that reactive oxygen species generated during abiotic Fe oxidation likely contributed to the elevated contribution of lignin to C mineralization. Iron redox cycling provides a mechanism for lignin breakdown in soils that experience conditions unfavorable for canonical lignin-degrading organisms, and provides a potential mechanism for lignin depletion in soil organic matter during late-stage decomposition. Thus, close couplings between soil moisture, redox fluctuations, and lignin breakdown provide potential a link between climate variability and

  9. 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

  10. Rate Maximization in MIMO Decode-and-Forward Communications With an EH Relay and Possibly Imperfect CSI

    KAUST Repository

    Benkhelifa, Fatma; Salem, Ahmed Sultan; Alouini, Mohamed-Slim

    2016-01-01

    In this paper, we investigate the simultaneous wireless information and power transfer (SWIPT) in a multiple-input multiple-output (MIMO) decode-and-forward (DF) relay system where the relay is an energy harvesting (EH) multi-antenna node equipped

  11. Rate Maximization in MIMO Decode-and-Forward Communications With an EH Relay and Possibly Imperfect CSI

    KAUST Repository

    Benkhelifa, Fatma

    2016-08-29

    In this paper, we investigate the simultaneous wireless information and power transfer (SWIPT) in a multiple-input multiple-output (MIMO) decode-and-forward (DF) relay system where the relay is an energy harvesting (EH) multi-antenna node equipped with an EH receiver and an information decoding (ID) receiver. The relay harvests the energy from the radio frequency (RF) signals sent by the source and uses it to forward the signals to the destination. The main objective in this paper is to maximize the achievable transmission rate of the overall link by optimizing the source/relay precoders. First, we study an upper bound on the maximum achievable rate where we assume that the EH and ID receivers operate simultaneously and have access to the whole power of the received signals. Afterwards, we study two practical schemes, which are the power splitting (PS) and time switching (TS) schemes, where the ID and EH receivers have partial access to the power or duration of the received signals. For each scheme, we have studied the complexity and the performance comparison. In addition, we considered the case of the imperfect channel estimation error and we have observed its impact on the achievable end-to-end rate and the harvested energy at the relay. © 1972-2012 IEEE.

  12. 76 FR 41262 - Notice of Intent To Award Affordable Care Act (ACA) Funding, EH11-1103

    Science.gov (United States)

    2011-07-13

    ...,000 in ACA funding will be awarded to the grantees for network expansion and enhancement. Funding is... Intent To Award Affordable Care Act (ACA) Funding, EH11-1103 Notice of Intent to award Affordable Care Act (ACA) funding to seventeen states and local health departments to develop and implement tracking...

  13. 76 FR 41261 - Notice of Intent To Award Affordable Care Act (ACA) Funding, EH10-1003

    Science.gov (United States)

    2011-07-13

    ...): 93.070. Approximately $124,995.00 in ACA funding will be awarded to the grantee for network expansion... Intent To Award Affordable Care Act (ACA) Funding, EH10-1003 Notice of Intent to award Affordable Care Act (ACA) funding to National Association for Health Data Organizations (NAHDO) to continue with the...

  14. 76 FR 41263 - Notice of Intent To Award Affordable Care Act (ACA) Funding, EH10-1004

    Science.gov (United States)

    2011-07-13

    ... $125,000.00 in ACA funding will be awarded to the grantee for network expansion and enhancement... Intent To Award Affordable Care Act (ACA) Funding, EH10-1004 Notice of Intent to award Affordable Care Act (ACA) funding to National Association for Public Health Statistics and Information Systems...

  15. Use of Pourbaix diagrams and the eH and pH measurements in hydrometallurgy. Part 2-Applications

    International Nuclear Information System (INIS)

    Teixeira, L.A.C.

    1987-01-01

    The interpretation of Pourbaix diagrams, presenting as examples; acid lixiviation of uranium ore, iron ion removal from process solutions, lixiviation of copper ores and cyaniding of Au ores containing Cu and Fe is presented. Practical aspects on eH and pH measurement in solutions of hydrometallurgical process. (M.C.K.) [pt

  16. 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

  17. 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.

  18. Redox tuning of cytochrome b562 through facile metal porphyrin substitution

    DEFF Research Database (Denmark)

    Della Pia, Eduardo Antonio; Chi, Qijin; Elliott, Martin

    2012-01-01

    The biologically and nanotechnologically important heme protein cytochrome b562 was reconstructed with zinc and copper porphyrins, leading to significant changes in the spectral, redox and electron transfer properties. The Cu form shifts the redox potential by +300 mV and exhibits high electron t...

  19. Redox reactions in flooded uranium mines caused by natural wood degradation

    International Nuclear Information System (INIS)

    Abraham, A.; Baraniak, L.; Bernhard, G.

    2002-01-01

    Answering the question whether U(VI) and As(V) will be reduced and precipitated as U(OH) 4 and As 2 S 3 in mine water as a result of natural wood degradation. Redox equilibria were calculated, depending on the decreasing redox potential. (orig.)

  20. 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.

  1. Study of diffractive dissociation especially into strange and charmed particles with EHS

    CERN Multimedia

    2002-01-01

    The diffractive production of heavy quark-antiquark pairs leading to strangeness-antistrangeness and charm-anticharm systems is intended to be measured in this experiment. The use of the rapid cycling bubble chamber (RCBC) with a volume of 100 x 40 x 40 cm$^{3}$ and a picture taking rate of 15 Hz as vertex detector and EHS as forward spectrometer is suitable for the first step of this physics programme. Inclusive cross-sections for diffraction dissociation into $s\\bar{s}$ are lacking whereas diffractive $c\\bar{c}$ production is already better known. The gain of more insight into the mechanism of heavy quark-antiquark production, exclusive diffractive reactions with $\\pi^{0}$'s, diffractive resonance production and also the extraction of data for the double Pomeron exchange mechanism are envisaged. \\\\\\\\ This experiment will be run in two parts, the first one recording the entire unbiased sample of $pp$ and $\\pi^{-}p$ interactions, the second however using triggering for beam and high mass target diffraction di...

  2. The JRC Nanomaterials Repository: A unique facility providing representative test materials for nanoEHS research.

    Science.gov (United States)

    Totaro, Sara; Cotogno, Giulio; Rasmussen, Kirsten; Pianella, Francesca; Roncaglia, Marco; Olsson, Heidi; Riego Sintes, Juan M; Crutzen, Hugues P

    2016-11-01

    The European Commission has established a Nanomaterials Repository that hosts industrially manufactured nanomaterials that are distributed world-wide for safety testing of nanomaterials. In a first instance these materials were tested in the OECD Testing Programme. They have then also been tested in several EU funded research projects. The JRC Repository of Nanomaterials has thus developed into serving the global scientific community active in the nanoEHS (regulatory) research. The unique Repository facility is a state-of-the-art installation that allows customised sub-sampling under the safest possible conditions, with traceable final sample vials distributed world-wide for research purposes. This paper describes the design of the Repository to perform a semi-automated subsampling procedure, offering high degree of flexibility and precision in the preparation of NM vials for customers, while guaranteeing the safety of the operators, and environmental protection. The JRC nanomaterials are representative for part of the world NMs market. Their wide use world-wide facilitates the generation of comparable and reliable experimental results and datasets in (regulatory) research by the scientific community, ultimately supporting the further development of the OECD regulatory test guidelines. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

  3. 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

  4. LEW 88180, LEW 87119, and ALH 85119: New EH6, EL7, and EL4 Enstatite Chondrites

    Science.gov (United States)

    Zhang, Y.; Benoit, P. H.; Sears, D. W. G.

    1993-07-01

    The EH and EL chondrites formed in a uniquely reducing environment, containing low-Fe pyroxene, abundant metal, and a number of unusual sulphides and other minerals [1]. An important aspect of their history is that while the EL chondrites consist predominantly of metamorphosed meteorites, the EH consist primarily of little-metamorphosed meteorites (e.g., [2]), and yet EL chondrites have lower equilibrium temperatures than EH chondrite [3,4]. To help understand this observation and its implication for the history of the classes, we have been searching for new enstatite chondrites, looking especially for meteorites of previously unknown chemical-petrologic class. Using our normal INAA methods [5] and sample splits of 100-200 mg, the bulk composition of nine Antarctic enstatite chondrites and one fall were determined. The data were used to assign the meteorites to chemical classes, the Ni/Ir vs. Al/V plot (Fig. 1) being especially useful since it uses the refractory element difference between EH and EL chondrites and is insensitive to metal-silicate heterogeneity. The well-analyzed Qingzhen was included to check our method. ALH84170, ALH84206, and EET87746, which Mason described as E3, E4, and E4 were all found to be EH chondrites [6]. Our data for the three paired EL3 chondrites were discussed earlier (MAC88136, 88180, and 88184) [7,8]. LEW88180, LEW87119, and ALH85119, which Mason described as type E6, E6, and E4 respectively [6], are EH, EL, and EL; thus LEW88180 and ALH85119 appear to be the first EH6 and EL4 chondrites. The compositions of kamacite, phosphide, and niningerite-alabandite (Fig. 2) for ALH84170, ALH84206, EET87746, LEW88180, and ALH85119 are consistent with Mason's petrologic type assignments [6]. The mineral composition of LEW88180 (2.7% Si and 9.4% Ni in the kamacite, 7.8% Ni in the phosphide, and 60% FeS in the niningerite) confirms our classification of this meteorite as EH6. ALH85119 contains kamacite with 0.5% Si and 7% Ni, phosphide with 46

  5. Practical and theoretical basis for performing redox-measurements in compacted bentonite. A literature survey

    International Nuclear Information System (INIS)

    Carlsson, T.; Muurinen, A.

    2008-12-01

    This report reviews the state-of-the-art with regard to redox measurements, especially in compacted water saturated bentonite, but also in natural systems like sediments and ground waters. Both theoretical and practical aspects of redox measurements are discussed, as well as some basic concepts like terminal electron-accepting processes (TEAPs) and oxidative capacity (OXC). The problems associated with the interpretation of measured electrode potentials are treated. Despite many practical and theoretical difficulties, redox measurements continue to be carried out by researchers all over the world. The over-all conclusion from the literature survey is that fruitful redox-measurements can be performed in compacted bentonite. Irrespective of whether the measured redox potentials are absolute or not, the use of electrodes provide a valuable tool for studying, e.g., long-term changes in the pore water of compacted bentonite and/or the diffusion of oxygen into a bentonite. (orig.)

  6. Redox regulation in photosynthetic organisms: signaling, acclimation, and practical implications.

    Science.gov (United States)

    Foyer, Christine H; Noctor, Graham

    2009-04-01

    Reactive oxygen species (ROS) have multifaceted roles in the orchestration of plant gene expression and gene-product regulation. Cellular redox homeostasis is considered to be an "integrator" of information from metabolism and the environment controlling plant growth and acclimation responses, as well as cell suicide events. The different ROS forms influence gene expression in specific and sometimes antagonistic ways. Low molecular antioxidants (e.g., ascorbate, glutathione) serve not only to limit the lifetime of the ROS signals but also to participate in an extensive range of other redox signaling and regulatory functions. In contrast to the low molecular weight antioxidants, the "redox" states of components involved in photosynthesis such as plastoquinone show rapid and often transient shifts in response to changes in light and other environmental signals. Whereas both types of "redox regulation" are intimately linked through the thioredoxin, peroxiredoxin, and pyridine nucleotide pools, they also act independently of each other to achieve overall energy balance between energy-producing and energy-utilizing pathways. This review focuses on current knowledge of the pathways of redox regulation, with discussion of the somewhat juxtaposed hypotheses of "oxidative damage" versus "oxidative signaling," within the wider context of physiological function, from plant cell biology to potential applications.

  7. Liquid Quinones for Solvent-Free Redox Flow Batteries.

    Science.gov (United States)

    Shimizu, Akihiro; Takenaka, Keisuke; Handa, Naoyuki; Nokami, Toshiki; Itoh, Toshiyuki; Yoshida, Jun-Ichi

    2017-11-01

    Liquid benzoquinone and naphthoquinone having diethylene glycol monomethyl ether groups are designed and synthesized as redox active materials that dissolve supporting electrolytes. The Li-ion batteries based on the liquid quinones using LiBF 4 /PC show good performance in terms of voltage, capacity, energy efficiency, and cyclability in both static and flow modes. A battery is constructed without using intentionally added organic solvent, and its high energy density (264 W h L -1 ) demonstrates the potential of solvent-free organic redox flow batteries using liquid active materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Chemical Principles Revisited. Redox Reactions and the Electropotential Axis.

    Science.gov (United States)

    Vella, Alfred J.

    1990-01-01

    This paper suggests a nontraditional pedagogic approach to the subject of redox reactions and electrode potentials suitable for freshman chemistry. Presented is a method for the representation of galvanic cells without the introduction of the symbology and notation of conventional cell diagrams. (CW)

  9. The iodine/iodide redox couple at a platinum electrode

    NARCIS (Netherlands)

    Dane, L.M.; Janssen, L.J.J.; Hoogland, J.G.

    1968-01-01

    The I/iodide redox couple was studied on Pt in 0.5M H2SO4 by measuring the impedance as a function of frequency. From these measurements, the exchange c.d. j0 was derived according to Sluyters. The dependence of j0 on the reversible potential and the I and the iodide concns. was established. By

  10. Ab initio calculations of scattering cross sections of the three-body system (p ¯,e+,e- ) between the e-+H ¯(n =2 ) and e-+H ¯(n =3 ) thresholds

    Science.gov (United States)

    Valdes, Mateo; Dufour, Marianne; Lazauskas, Rimantas; Hervieux, Paul-Antoine

    2018-01-01

    The ab initio method based on the Faddeev-Merkuriev equations is used to calculate cross sections involving the (p ¯,e+,e-) three-body system, with an emphasis on antihydrogen formation (H ¯) via antiproton (p ¯) scattering on positronium. This system is studied in the energy range between the e-+H ¯(n =2 ) and the e-+H ¯(n =3 ) thresholds, where precisely calculated cross sections can be useful for future experiments (GBAR, AEGIS, etc.) aiming to produce antihydrogen atoms. A special treatment is developed to take into account the long-range charge-dipole interaction effect on the wave function. Emphasis is placed on the impact of Feshbach resonances and Gailitis-Damburg oscillations appearing in the vicinity of the p ¯+Ps (n =2 ) threshold.

  11. The redox-Mannich reaction.

    Science.gov (United States)

    Chen, Weijie; Seidel, Daniel

    2014-06-06

    A complement to the classic three-component Mannich reaction, the redox-Mannich reaction, utilizes the same starting materials but incorporates an isomerization step that enables the facile preparation of ring-substituted β-amino ketones. Reactions occur under relatively mild conditions and are facilitated by benzoic acid.

  12. Hybrid energy storage systems utilizing redox active organic compounds

    Science.gov (United States)

    Wang, Wei; Xu, Wu; Li, Liyu; Yang, Zhenguo

    2015-09-08

    Redox flow batteries (RFB) have attracted considerable interest due to their ability to store large amounts of power and energy. Non-aqueous energy storage systems that utilize at least some aspects of RFB systems are attractive because they can offer an expansion of the operating potential window, which can improve on the system energy and power densities. One example of such systems has a separator separating first and second electrodes. The first electrode includes a first current collector and volume containing a first active material. The second electrode includes a second current collector and volume containing a second active material. During operation, the first source provides a flow of first active material to the first volume. The first active material includes a redox active organic compound dissolved in a non-aqueous, liquid electrolyte and the second active material includes a redox active metal.

  13. Redox Conditions in Selected Principal Aquifers of the United States

    Science.gov (United States)

    McMahon, P.B.; Cowdery, T.K.; Chapelle, F.H.; Jurgens, B.C.

    2009-01-01

    Reduction/oxidation (redox) processes affect the quality of groundwater in all aquifer systems. Redox processes can alternately mobilize or immobilize potentially toxic metals associated with naturally occurring aquifer materials, contribute to the degradation or preservation of anthropogenic contami-nants, and generate undesirable byproducts, such as dissolved manganese (Mn2+), ferrous iron (Fe2+), hydrogen sulfide (H2S), and methane (CH4). Determining the kinds of redox processes that occur in an aquifer system, documenting their spatial distribution, and understanding how they affect concentrations of natural or anthropogenic contaminants are central to assessing and predicting the chemical quality of groundwater. This Fact Sheet extends the analysis of U.S. Geological Survey authors to additional principal aquifer systems by applying a framework developed by the USGS to a larger set of water-quality data from the USGS national water databases. For a detailed explanation, see the 'Introduction' in the Fact Sheet.

  14. Degree of glutathione deficiency and redox imbalance depend on subtype of mitochondrial disease and clinical status.

    Directory of Open Access Journals (Sweden)

    Gregory M Enns

    Full Text Available Mitochondrial disorders are associated with decreased energy production and redox imbalance. Glutathione plays a central role in redox signaling and protecting cells from oxidative damage. In order to understand the consequences of mitochondrial dysfunction on in vivo redox status, and to determine how this varies by mitochondrial disease subtype and clinical severity, we used a sensitive tandem mass spectrometry assay to precisely quantify whole blood reduced (GSH and oxidized (GSSG glutathione levels in a large cohort of mitochondrial disorder patients. Glutathione redox potential was calculated using the Nernst equation. Compared to healthy controls (n = 59, mitochondrial disease patients (n = 58 as a group showed significant redox imbalance (redox potential -251 mV ± 9.7, p<0.0001 with an increased level of oxidation by ∼ 9 mV compared to controls (-260 mV ± 6.4. Underlying this abnormality were significantly lower whole blood GSH levels (p = 0.0008 and GSH/GSSG ratio (p = 0.0002, and significantly higher GSSG levels (p<0.0001 in mitochondrial disease patients compared to controls. Redox potential was significantly more oxidized in all mitochondrial disease subgroups including Leigh syndrome (n = 15, electron transport chain abnormalities (n = 10, mitochondrial encephalomyopathy, lactic acidosis and stroke-like episodes (n = 8, mtDNA deletion syndrome (n = 7, mtDNA depletion syndrome (n = 7, and miscellaneous other mitochondrial disorders (n = 11. Patients hospitalized in metabolic crisis (n = 7 showed the greatest degree of redox imbalance at -242 mV ± 7. Peripheral whole blood GSH and GSSG levels are promising biomarkers of mitochondrial dysfunction, and may give insights into the contribution of oxidative stress to the pathophysiology of the various mitochondrial disorders. In particular, evaluation of redox potential may be useful in monitoring of clinical status or response to redox-modulating therapies in clinical trials.

  15. THE FIRST DISCOVERY OF PRESOLAR GRAPHITE GRAINS FROM THE HIGHLY REDUCING QINGZHEN (EH3) METEORITE

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yuchen; Lin, Yangting; Zhang, Jianchao; Hao, Jialong, E-mail: linyt@mail.iggcas.ac.cn [Key Laboratory of Earth and Planetary Physics, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029 (China)

    2016-07-10

    Presolar graphite grains have been extensively studied, but are limited in carbonaceous chondrites, particularly in Murchison (CM2) and Orgueil (CI1), which sampled materials from the oxidizing regions in the solar nebula. Here, we report the first discovery of presolar graphite grains from the Qingzhen (EH3) enstatite chondrite which formed under a highly reducing condition. Eighteen presolar graphite grains were identified by C-isotope mapping of the low-density fraction (1.75–1.85 g cm{sup 3}) from Qingzhen acid residue. Another 58 graphite spherules were found in different areas of the same sample mount using a scanning electron microscope and were classified into three morphologies, including cauliflower, onion, and cauliflower–onion. The Raman spectra of these spherules vary from ordered, disordered, and glassy to kerogen-like, suggestive of a wide range of thermal metamorphisms. NanoSIMS analysis of the C- and Si-isotopes of these graphite spherules confirmed 23 presolar grains. The other 35 graphite spherules have no significant isotopic anomalies, but they share similar morphologies and Raman spectra with the presolar ones. Another three grains were identified during NanoSIMS analysis. Of all the 44 presolar graphite grains identified, six grains show {sup 28}Si-excesses, suggestive of supernovae origins, and four grains are {sup 12}C- and {sup 29,30}Si-rich, consistent with low-metallicity asymptotic giant branch star origins. Another two graphite spherules have extremely low {sup 12}C/{sup 13}C ratios with marginal solar Si-isotopes. The morphologies, Raman spectra, and C- and Si-isotopic distributions of the presolar graphite grains from the Qingzhen enstatite chondrite are similar to those of the low-density fractions from Murchison carbonaceous chondrites. This study suggests a homogeneous distribution of presolar graphite grains in the solar nebula.

  16. THE FIRST DISCOVERY OF PRESOLAR GRAPHITE GRAINS FROM THE HIGHLY REDUCING QINGZHEN (EH3) METEORITE

    International Nuclear Information System (INIS)

    Xu, Yuchen; Lin, Yangting; Zhang, Jianchao; Hao, Jialong

    2016-01-01

    Presolar graphite grains have been extensively studied, but are limited in carbonaceous chondrites, particularly in Murchison (CM2) and Orgueil (CI1), which sampled materials from the oxidizing regions in the solar nebula. Here, we report the first discovery of presolar graphite grains from the Qingzhen (EH3) enstatite chondrite which formed under a highly reducing condition. Eighteen presolar graphite grains were identified by C-isotope mapping of the low-density fraction (1.75–1.85 g cm 3 ) from Qingzhen acid residue. Another 58 graphite spherules were found in different areas of the same sample mount using a scanning electron microscope and were classified into three morphologies, including cauliflower, onion, and cauliflower–onion. The Raman spectra of these spherules vary from ordered, disordered, and glassy to kerogen-like, suggestive of a wide range of thermal metamorphisms. NanoSIMS analysis of the C- and Si-isotopes of these graphite spherules confirmed 23 presolar grains. The other 35 graphite spherules have no significant isotopic anomalies, but they share similar morphologies and Raman spectra with the presolar ones. Another three grains were identified during NanoSIMS analysis. Of all the 44 presolar graphite grains identified, six grains show 28 Si-excesses, suggestive of supernovae origins, and four grains are 12 C- and 29,30 Si-rich, consistent with low-metallicity asymptotic giant branch star origins. Another two graphite spherules have extremely low 12 C/ 13 C ratios with marginal solar Si-isotopes. The morphologies, Raman spectra, and C- and Si-isotopic distributions of the presolar graphite grains from the Qingzhen enstatite chondrite are similar to those of the low-density fractions from Murchison carbonaceous chondrites. This study suggests a homogeneous distribution of presolar graphite grains in the solar nebula.

  17. Serum-dependent selective expression of EhTMKB1-9, a member of Entamoeba histolytica B1 family of transmembrane kinases.

    Directory of Open Access Journals (Sweden)

    Shiteshu Shrimal

    Full Text Available Entamoeba histolytica transmembrane kinases (EhTMKs can be grouped into six distinct families on the basis of motifs and sequences. Analysis of the E. histolytica genome revealed the presence of 35 EhTMKB1 members on the basis of sequence identity (>or=95%. Only six homologs were full length containing an extracellular domain, a transmembrane segment and an intracellular kinase domain. Reverse transcription followed by polymerase chain reaction (RT-PCR of the kinase domain was used to generate a library of expressed sequences. Sequencing of randomly picked clones from this library revealed that about 95% of the clones were identical with a single member, EhTMKB1-9, in proliferating cells. On serum starvation, the relative number of EhTMKB1-9 derived sequences decreased with concomitant increase in the sequences derived from another member, EhTMKB1-18. The change in their relative expression was quantified by real time PCR. Northern analysis and RNase protection assay were used to study the temporal nature of EhTMKB1-9 expression after serum replenishment of starved cells. The results showed that the expression of EhTMKB1-9 was sinusoidal. Specific transcriptional induction of EhTMKB1-9 upon serum replenishment was further confirmed by reporter gene (luciferase expression and the upstream sequence responsible for serum responsiveness was identified. EhTMKB1-9 is one of the first examples of an inducible gene in Entamoeba. The protein encoded by this member was functionally characterized. The recombinant kinase domain of EhTMKB1-9 displayed protein kinase activity. It is likely to have dual specificity as judged from its sensitivity to different kinase inhibitors. Immuno-localization showed EhTMKB1-9 to be a surface protein which decreased on serum starvation and got relocalized on serum replenishment. Cell lines expressing either EhTMKB1-9 without kinase domain, or EhTMKB1-9 antisense RNA, showed decreased cellular proliferation and target cell

  18. 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

  19. Activating mitochondrial function and haemoglobin expression with EH-201, an inducer of erythropoietin in neuronal cells, reverses memory impairment

    OpenAIRE

    Horng, Lin-Yea; Hsu, Pei-Lun; Chen, Li-Wen; Tseng, Wang-Zou; Hsu, Kai-Tin; Wu, Chia-Ling; Wu, Rong-Tsun

    2015-01-01

    Background and Purpose Memory impairment can be progressive in neurodegenerative diseases, and physiological ageing or brain injury, mitochondrial dysfunction and oxidative stress are critical components of these issues. An early clinical study has demonstrated cognitive improvement during erythropoietin treatment in patients with chronic renal failure. As erythropoietin cannot freely cross the blood?brain barrier, we tested EH-201 (2,3,5,4?-tetrahydroxystilbene-2-O-?-d-glucoside, also known ...

  20. Introduction to Nanotechnology for Defense Environment, Health & Safety (EHS) and Research Professionals in Support of the Acquisition Process

    Science.gov (United States)

    2011-03-28

    www.denix.osd.mil/MERIT Ultra fine particles ~50 1713- Ramazzini described black 197 4- First GMO lung disease mouse created by Jaenisch Diesel...exhaust Engineered NP _____ _,.? • GMO Technology 1985- Oberdorster described inhalation toxicity of Ti02 2003-lssue recognized by EPA, NIOSH...other agencies 2004- California pass broad ban on GMO products Growing Body of EHS Research Far-reaching implications or singular exceptions

  1. Biological control of fire blight in pear orchards with a formulation of Pantoea agglomerans strain Eh 24 Controle biológico de fire blight em pereiras empregando uma formulação de Pantoea agglomerans Eh 24

    Directory of Open Access Journals (Sweden)

    Hatice Özaktan

    2004-09-01

    Full Text Available Biological control by using epiphytic bacteria against Erwinia amylovora has been considered as an alternative method for controlling the disease. Talc-based formulation of Pantoea agglomerans strain Eh-24 was applied at 30% and 100% bloom on two pear orchards which were selected from different locations in the Aegean Region in Turkey. Pear orchard trials were replicated for two years (1999 and 2000 in each place. Talc-based formulation of P. agglomerans strain Eh-24 was sprayed on pear trees which were naturally infected with E. amylovora. In the orchard trials conducted in 1999 and 2000, talc-based formulation of P. agglomerans strain Eh-24 reduced the percentage of blighted blossoms on pear orchards by 63% to 76%, approximately. Copper oxychloride+maneb was less effective in reducing the incidence of blossom infection by E. amylovora in each pear orchard than the bioformulation treatment. P. agglomerans strain Eh-24 labelled with StrR+ was applied at 30% and 100% bloom to monitor the colonization and population dynamics of P. agglomerans on pear blossoms. The population size of P. agglomerans strain Eh-24 strR+ on pear blossoms increased from 2x10(4 to 1.3x10(6 cfu per blossom over 18 days.Controle biológico de Erwinia amylovora através do uso de bactérias epifíticas tem sido considerado um método alternativo para o controle de "fire blight". Uma formulação de Pantoea agglomerans Eh 24 em talco foi utilizada em pereiras a 30% e a 100% de floração, em duas plantações selecionadas na região Aegean da Turquia. Os experimentos foram repetidos duas vezes (1999 e 2000 em cada plantação. A formulação de P. agglomerans foi aspergida nas pereiras naturalmente infectadas com E. amylovora. Nos experimentos de 1999 e 2000, a redução da porcentagem de ocorrência de "fire blight" foi reduzida aproximadamente em 63% e em 76%, respectivamente. Oxicloreto de cobre + maneb foi menos eficiente na redução da infecção por E. amylovora do

  2. 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)

  3. Control of high level radioactive waste-glass melters - Part 5: Modeling of complex redox effects

    International Nuclear Information System (INIS)

    Bickford, D.F.; Choi, A.S.

    1991-01-01

    Computerized thermodynamic computations are useful in predicting the sequence and products of redox reactions and in assessing process variations. The redox state of waste-glass melters is determined by balance between the reducing potential of organic compounds in the feed, and the oxidizing potential of gases above the melt, and nitrates and polyvalent elements in the waste. Semiquantitative models predicting limitations of organic content have been developed based on crucible testing. Continuous melter test results have been compared to this improved staged-thermodynamic model of redox behavior

  4. 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.

  5. Cascade redox flow battery systems

    Science.gov (United States)

    Horne, Craig R.; Kinoshita, Kim; Hickey, Darren B.; Sha, Jay E.; Bose, Deepak

    2014-07-22

    A reduction/oxidation ("redox") flow battery system includes a series of electrochemical cells arranged in a cascade, whereby liquid electrolyte reacts in a first electrochemical cell (or group of cells) before being directed into a second cell (or group of cells) where it reacts before being directed to subsequent cells. The cascade includes 2 to n stages, each stage having one or more electrochemical cells. During a charge reaction, electrolyte entering a first stage will have a lower state-of-charge than electrolyte entering the nth stage. In some embodiments, cell components and/or characteristics may be configured based on a state-of-charge of electrolytes expected at each cascade stage. Such engineered cascades provide redox flow battery systems with higher energy efficiency over a broader range of current density than prior art arrangements.

  6. Redox front formation in an uplifting sedimentary rock sequence: An analogue for redox-controlling processes in the geosphere around deep geological repositories for radioactive waste

    International Nuclear Information System (INIS)

    Yoshida, H.; Metcalfe, R.; Yamamoto, K.; Murakami, Y.; Hoshii, D.; Kanekiyo, A.; Naganuma, T.; Hayashi, T.

    2008-01-01

    Subsurface redox fronts control the mobilization and fixation of many trace elements, including potential pollutants such as certain radionuclides. Any safety assessment for a deep geological repository for radioactive wastes needs to take into account adequately the long-term redox processes in the geosphere surrounding the repository. To build confidence in understanding these processes, a redox front in a reduced siliceous sedimentary rock distributed in an uplifting area in Japan has been studied in detail. Geochemical analyses show increased concentrations of Fe and trace elements, including rare earth elements (REEs), at the redox front, even though concentrations of reduced rock matrix constituents show little change. Detailed SEM observations revealed that fossilized microorganisms composed of amorphous granules made exclusively of Fe and Si occur in the rock's pore space. Microbial 16S rDNA analysis suggests that there is presently a zonation of different bacterial groups within the redox band, and bacterial zonation played an important role in the concentration of Fe-oxyhydroxides at the redox front. These water-rock-microbe interactions can be considered analogous to the processes occurring in the redox fronts that would develop around geological repositories for radioactive waste. Once formed, the Fe-oxyhydroxides within such a front would be preserved even after reducing conditions resume following repository closure

  7. Redox front formation in an uplifting sedimentary rock sequence: An analogue for redox-controlling processes in the geosphere around deep geological repositories for radioactive waste

    Energy Technology Data Exchange (ETDEWEB)

    Yoshida, H. [Nagoya University Museum, Material Research Section, Furocho, Nagoya 464-8602 (Japan)], E-mail: dora@num.nagoya-u.ac.jp; Metcalfe, R. [Quintessa Japan, Queen' s Tower A7-707, Minatomirai, Yokohama 220-6007 (Japan); Yamamoto, K. [Nagoya University Museum, Material Research Section, Furocho, Nagoya 464-8602 (Japan); Murakami, Y. [Japan Atomic Energy Agency (JAEA), Tono Geoscience Centre (Japan); Hoshii, D.; Kanekiyo, A.; Naganuma, T. [Hiroshima University, Higashi Hiroshima, Kagamiyama 1-4-4 (Japan); Hayashi, T. [Asahi University, Department of Dental Pharmacology, Hozumi, Gifu (Japan)

    2008-08-15

    Subsurface redox fronts control the mobilization and fixation of many trace elements, including potential pollutants such as certain radionuclides. Any safety assessment for a deep geological repository for radioactive wastes needs to take into account adequately the long-term redox processes in the geosphere surrounding the repository. To build confidence in understanding these processes, a redox front in a reduced siliceous sedimentary rock distributed in an uplifting area in Japan has been studied in detail. Geochemical analyses show increased concentrations of Fe and trace elements, including rare earth elements (REEs), at the redox front, even though concentrations of reduced rock matrix constituents show little change. Detailed SEM observations revealed that fossilized microorganisms composed of amorphous granules made exclusively of Fe and Si occur in the rock's pore space. Microbial 16S rDNA analysis suggests that there is presently a zonation of different bacterial groups within the redox band, and bacterial zonation played an important role in the concentration of Fe-oxyhydroxides at the redox front. These water-rock-microbe interactions can be considered analogous to the processes occurring in the redox fronts that would develop around geological repositories for radioactive waste. Once formed, the Fe-oxyhydroxides within such a front would be preserved even after reducing conditions resume following repository closure.

  8. 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

  9. Mycobacterium tuberculosis has diminished capacity to counteract redox stress induced by elevated levels of endogenous superoxide.

    Science.gov (United States)

    Tyagi, Priyanka; Dharmaraja, Allimuthu T; Bhaskar, Ashima; Chakrapani, Harinath; Singh, Amit

    2015-07-01

    Mycobacterium tuberculosis (Mtb) has evolved protective and detoxification mechanisms to maintain cytoplasmic redox balance in response to exogenous oxidative stress encountered inside host phagocytes. In contrast, little is known about the dynamic response of this pathogen to endogenous oxidative stress generated within Mtb. Using a noninvasive and specific biosensor of cytoplasmic redox state of Mtb, we for first time discovered a surprisingly high sensitivity of this pathogen to perturbation in redox homeostasis induced by elevated endogenous reactive oxygen species (ROS). We synthesized a series of hydroquinone-based small molecule ROS generators and found that ATD-3169 permeated mycobacteria to reliably enhance endogenous ROS including superoxide radicals. When Mtb strains including multidrug-resistant (MDR) and extensively drug-resistant (XDR) patient isolates were exposed to this compound, a dose-dependent, long-lasting, and irreversible oxidative shift in intramycobacterial redox potential was detected. Dynamic redox potential measurements revealed that Mtb had diminished capacity to restore cytoplasmic redox balance in comparison with Mycobacterium smegmatis (Msm), a fast growing nonpathogenic mycobacterial species. Accordingly, Mtb strains were extremely susceptible to inhibition by ATD-3169 but not Msm, suggesting a functional linkage between dynamic redox changes and survival. Microarray analysis showed major realignment of pathways involved in redox homeostasis, central metabolism, DNA repair, and cell wall lipid biosynthesis in response to ATD-3169, all consistent with enhanced endogenous ROS contributing to lethality induced by this compound. This work provides empirical evidence that the cytoplasmic redox poise of Mtb is uniquely sensitive to manipulation in steady-state endogenous ROS levels, thus revealing the importance of targeting intramycobacterial redox metabolism for controlling TB infection. Copyright © 2015 The Authors. Published by

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

    Directory of Open Access Journals (Sweden)

    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

  11. 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

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. Inflammatory and redox reactions in colorectal carcinogenesis.

    Science.gov (United States)

    Guina, Tina; Biasi, Fiorella; Calfapietra, Simone; Nano, Mario; Poli, Giuseppe

    2015-03-01

    It has been established that there is a relationship between chronic inflammation and cancer development. The constant colonic inflammation typical of inflammatory bowel diseases is now considered a risk factor for colorectal carcinoma (CRC) development. The inflammatory network of signaling molecules is also required during the late phases of carcinogenesis, to enable cancer cells to survive and to metastasize. Oxidative reactions are an integral part of the inflammatory response, and are generally associated with CRC development. However, when the malignant phenotype is acquired, increased oxidative status induces antioxidant defenses in cancer cells, favoring their aggressiveness. This contradictory behavior of cancer cells toward redox status is of great significance for potential anticancer therapies. This paper summarizes the essential background information relating to the molecules involved in regulating oxidative stress and inflammation during carcinogenesis. Understanding more of their function in CRC stages might provide the foundation for future developments in CRC treatment. © 2015 New York Academy of Sciences.

  17. 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.

  18. Phospholipid-binding protein EhC2A mediates calcium-dependent translocation of transcription factor URE3-BP to the plasma membrane of Entamoeba histolytica.

    Science.gov (United States)

    Moreno, Heriberto; Linford, Alicia S; Gilchrist, Carol A; Petri, William A

    2010-05-01

    The Entamoeba histolytica upstream regulatory element 3-binding protein (URE3-BP) is a transcription factor that binds DNA in a Ca(2+)-inhibitable manner. The protein is located in both the nucleus and the cytoplasm but has also been found to be enriched in the plasma membrane of amebic trophozoites. We investigated the reason for the unusual localization of URE3-BP at the amebic plasma membrane. Here we identify and characterize a 22-kDa Ca(2+)-dependent binding partner of URE3-BP, EhC2A, a novel member of the C2-domain superfamily. Immunoprecipitations of URE3-BP and EhC2A showed that the proteins interact and that such interaction was enhanced in the presence of Ca(2+). Recombinant and native EhC2A bound phospholipid liposomes in a Ca(2+)-dependent manner, with half-maximal binding occurring at 3.4 muM free Ca(2+). A direct interaction between EhC2A and URE3-BP was demonstrated by the ability of recombinant EhC2A to recruit recombinant URE3-BP to phospholipid liposomes in a Ca(2+)-dependent manner. URE3-BP and EhC2A were observed to translocate to the amebic plasma membrane upon an increase in the intracellular Ca(2+) concentration of trophozoites, as revealed by subcellular fractionation and immunofluorescent staining. Short hairpin RNA-mediated knockdown of EhC2A protein expression significantly modulated the mRNA levels of URE3-BP-regulated transcripts. Based on these results, we propose a model for EhC2A-mediated regulation of the transcriptional activities of URE3-BP via Ca(2+)-dependent anchoring of the transcription factor to the amebic plasma membrane.

  19. 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.

  20. 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.

  1. 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...

  2. Redox control of electric melters with complex feed compositions. Part I: analytical methods and models

    International Nuclear Information System (INIS)

    Bickford, D.F.; Diemer, R.B. Jr.

    1985-01-01

    The redox state of glass from electric melters with complex feed compositions is determined by balance between gases above the melt, and transition metals and organic compounds in the feed. Part I discusses experimental and computational methods of relating flowrates and other melter operating conditions to the redox state of glass, and composition of the melter offgas. Computerized thermodynamic computational methods are useful in predicting the sequence and products of redox reactions and in assessing individual process variations. Melter redox state can be predicted by combining monitoring of melter operating conditions, redox measurement of fused melter feed samples, and periodic redox measurement of product. Mossbauer spectroscopy, and other methods which measure Fe(II)/Fe(III) in glass, can be used to measure melter redox state. Part II develops preliminary operating limits for the vitrification of High-Level Radioactive Waste. Limits on reducing potential to preclude the accumulation of combustible gases, accumulation of sulfides and selenides, and degradation of melter components are the most critical. Problems associated with excessively oxidizing conditions, such as glass foaming and potential ruthenium volatility, are controlled when sufficient formic acid is added to adjust melter feed rheology

  3. Organic chemical degradation by remote study of the redox conditions

    Science.gov (United States)

    Fernandez, P. M.; Revil, A.; Binley, A. M.; Bloem, E.; French, H. K.

    2014-12-01

    Monitoring the natural (and enhanced) degradation of organic contaminants is essential for managing groundwater quality in many parts of the world. Contaminated sites often have limited access, hence non-intrusive methods for studying redox processes, which drive the degradation of organic compounds, are required. One example is the degradation of de-icing chemicals (glycols and organic salts) released to the soil near airport runways during winter. This issue has been broadly studied at Oslo airport, Gardermoen, Norway using intrusive and non-intrusive methods. Here, we report on laboratory experiments that aim to study the potential of using a self-potential, DCresistivity, and time-domain induced polarization for geochemical characterization of the degradation of Propylene Glycol (PG). PG is completely miscible in water, does not adsorb to soil particles and does not contribute to the electrical conductivity of the soil water. When the contaminant is in the unsaturated zone near the water table, the oxygen is quickly consumed and the gas exchange with the surface is insufficient to ensure aerobic degradation, which is faster than anaerobic degradation. Since biodegradation of PG is highly oxygen demanding, anaerobic pockets can exist causing iron and manganese reduction. It is hypothesised that nitrate would boost the degradation rate under such conditions. In our experiment, we study PG degradation in a sand tank. We provide the system with an electron highway to bridge zones with different redox potential. This geo-battery system is characterized by self-potential, resistivity and induced polarization anomalies. An example of preliminary results with self-potential at two different times of the experiment can be seen in the illustration. These will be supplemented with more direct information on the redox chemistry: in-situ water sampling, pH, redox potential and electrical conductivity measurements. In parallel, a series of batch experiments have been

  4. Preservation of organic matter in nontronite against iron redox cycling.

    Science.gov (United States)

    Zeng, Q.

    2015-12-01

    It is generally believed that clay minerals can protect organic matter from degradation in redox active environments, but both biotic and abiotic factors can influence the redox process and thus potentially change the clay-organic associations. However, the specific mechanisms involved in this process remain poorly understood. In this study, a model organic compound, 12-Aminolauric acid (ALA) was selected to intercalate into the structural interlayer of nontronite (an iron-rich smectite, NAu-2) to form an ALA-intercalated NAu-2 composite (ALA-NAu-2). Shawanella putrefaciens CN32 and sodium dithionite were used to reduce structural Fe(III) to Fe(II) in NAu-2 and ALA-NAu-2. The bioreduced ALA-NAu-2 was subsequently re-oxidized by air. The rates and extents of bioreduction and air re-oxidation were determined with wet chemistry methods. ALA release from ALA-NAu-2 via redox process was monitored. Mineralogical changes after iron redox cycle were investigated with X-ray diffraction, infrared spectroscopy, and scanning and transmission electron microscopy. At the beginning stage of bioreduction, S. putrefaciens CN32 reduced Fe(III) from the edges of nontronite and preferentially reduced and dissolved small and poorly crystalline particles, and released ALA, resulting a positive correlation between ALA release and iron reduction extent (80%). Because bacteria are the principal agent for mediating redox process in natural environments, our results demonstrated that the structural interlayer of smectite can serve as a potential shelter to protect organic matter from oxidation.

  5. Connecting Biology to Electronics: Molecular Communication via Redox Modality.

    Science.gov (United States)

    Liu, Yi; Li, Jinyang; Tschirhart, Tanya; Terrell, Jessica L; Kim, Eunkyoung; Tsao, Chen-Yu; Kelly, Deanna L; Bentley, William E; Payne, Gregory F

    2017-12-01

    Biology and electronics are both expert at for accessing, analyzing, and responding to information. Biology uses ions, small molecules, and macromolecules to receive, analyze, store, and transmit information, whereas electronic devices receive input in the form of electromagnetic radiation, process the information using electrons, and then transmit output as electromagnetic waves. Generating the capabilities to connect biology-electronic modalities offers exciting opportunities to shape the future of biosensors, point-of-care medicine, and wearable/implantable devices. Redox reactions offer unique opportunities for bio-device communication that spans the molecular modalities of biology and electrical modality of devices. Here, an approach to search for redox information through an interactive electrochemical probing that is analogous to sonar is adopted. The capabilities of this approach to access global chemical information as well as information of specific redox-active chemical entities are illustrated using recent examples. An example of the use of synthetic biology to recognize external molecular information, process this information through intracellular signal transduction pathways, and generate output responses that can be detected by electrical modalities is also provided. Finally, exciting results in the use of redox reactions to actuate biology are provided to illustrate that synthetic biology offers the potential to guide biological response through electrical cues. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. 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.

  7. 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

  8. Redox reactions in food fermentations

    DEFF Research Database (Denmark)

    Hansen, Egon Bech

    2018-01-01

    involves oxidative steps in the early part of the pathways whereas a multitude of different reactions are used as compensating reductions. Much of the diversity seen between food fermentations arise from the different routes and the different electron acceptors used by microorganisms to counterbalance...... and this contributes to the diversity in flavor, color, texture, and shelf life. The review concludes that these reactions are still only incompletely understood and that they represent an interesting area for fundamental research and also represent a fertile field for product development through a more conscious use...... of the redox properties of strains used to compose food cultures....

  9. Method for producing redox shuttles

    Science.gov (United States)

    Pupek, Krzysztof Z.; Dzwiniel, Trevor L.; Krumdick, Gregory K.

    2015-03-03

    A single step method for producing a redox shuttle having the formula 2,5-di-tert-butyl-1,4-phenylene tetraethyl bis(phosphate) is provided, the method comprising phosphorylating tert butyl hydroquinone with a phosphate-containing reagent. Also provided is method for producing 2,5-di-tert-butyl-1,4-phenylene tetraethyl bis(phosphate), the method comprising solubilizing tert-butyl hydroquinone and tetrabutylammonium bromide with methyltetrahydrofuran to create a mixture; heating the mixture while adding base to the mixture in an amount to turn the mixture orange; and adding diethyl chlorophosphate to the orange mixture in an amount to phosphorylate the hydroquinone.

  10. Molecular analysis of Ku redox regulation

    Directory of Open Access Journals (Sweden)

    Shatilla Andrea

    2009-08-01

    Full Text Available Abstract Background DNA double-strand breaks (DSBs can occur in response to ionizing radiation (IR, radiomimetic agents and from endogenous DNA-damaging reactive oxygen metabolites. Unrepaired or improperly repaired DSBs are potentially the most lethal form of DNA damage and can result in chromosomal translocations and contribute to the development of cancer. The principal mechanism for the repair of DSBs in humans is non-homologous end-joining (NHEJ. Ku is a key member of the NHEJ pathway and plays an important role in the recognition step when it binds to free DNA termini. Ku then stimulates the assembly and activation of other NHEJ components. DNA binding of Ku is regulated by redox conditions and evidence from our laboratory has demonstrated that Ku undergoes structural changes when oxidized that results in a reduction in DNA binding activity. The C-terminal domain and cysteine 493 of Ku80 were investigated for their contribution to redox regulation of Ku. Results We effectively removed the C-terminal domain of Ku80 generating a truncation mutant and co-expressed this variant with wild type Ku70 in an insect cell system to create a Ku70/80ΔC heterodimer. We also generated two single amino acid variants of Cys493, replacing this amino acid with either an alanine (C493A or a serine (C493S, and over-expressed the variant proteins in SF9 insect cells in complex with wild type Ku70. Neither the truncation nor the amino acid substitutions alters protein expression or stability as determined by SDS-PAGE and Western blot analysis. We show that the C493 mutations do not alter the ability of Ku to bind duplex DNA in vitro under reduced conditions while truncation of the Ku80 C-terminus slightly reduced DNA binding affinity. Diamide oxidation of cysteines was shown to inhibit DNA binding similarly for both the wild-type and all variant proteins. Interestingly, differential DNA binding activity following re-reduction was observed for the Ku70/80

  11. The knockdown of each component of the cysteine proteinase-adhesin complex of Entamoeba histolytica (EhCPADH) affects the expression of the other complex element as well as the in vitro and in vivo virulence.

    Science.gov (United States)

    Ocádiz-Ruiz, Ramón; Fonseca, Wendy; Linford, Alicia S; Yoshino, Timothy P; Orozco, Esther; Rodríguez, Mario A

    2016-01-01

    Entamoeba histolytica is the protozoan parasite causative of human amoebiasis, disease responsible for 40 000-100 000 deaths annually. The cysteine proteinase-adhesin complex of this parasite (EhCPADH) is a heterodimeric protein formed by a cysteine protease (EhCP112) and an adhesin (EhADH) that plays an important role in the cytopathic mechanism of this parasite. The coding genes for EhCP112 and EhADH are adjacent in the E. histolytica genome, suggesting that their expression may be co-regulated, but this hypothesis has not yet been confirmed. Here, we performed the knockdown of EhCP112 and EhADH using gene-specific short-hairpin RNAs (shRNA), and the effect of these knockdowns on the expression of both complex components as well as on the in vitro and in vivo virulence was analysed. Results showed that the knockdown of one of the EhCPADH components produced a simultaneous downregulation of the other protein. Accordingly, a concomitant reduction in the overall expression of the complex was observed. The downregulation of each component also produced a significant decrease in the in vitro and in vivo virulence of trophozoites. These results demonstrated that the expression of EhCP112 and EhADH is co-regulated and confirmed that the EhCPADH complex plays an important role in E. histolytica virulence.

  12. Modulation of Erythrocyte Plasma Membrane Redox System Activity by Curcumin

    Directory of Open Access Journals (Sweden)

    Prabhakar Singh

    2016-01-01

    Full Text Available Plasma membrane redox system (PMRS is an electron transport chain system ubiquitously present throughout all cell types. It transfers electron from intracellular substrates to extracellular acceptors for regulation of redox status. Curcumin, isolated from Curcuma longa, has modulatory effects on cellular physiology due to its membrane interaction ability and antioxidant potential. The present study investigates the effect of curcumin on PMRS activity of erythrocytes isolated from Wistar rats in vitro and in vivo and validated through an in silico docking simulation study using Molegro Virtual Docker (MVD. Effects of curcumin were also evaluated on level of glutathione (GSH and the oxidant potential of plasma measured in terms of plasma ferric equivalent oxidative potentials (PFEOP. Results show that curcumin significantly (p<0.01 downregulated the PMRS activity in a dose-dependent manner. Molecular docking results suggest that curcumin interacts with amino acids at the active site cavity of cytochrome b5 reductase, a key constituent of PMRS. Curcumin also increased the GSH level in erythrocytes and plasma while simultaneously decreasing the oxidant potential (PFEOP of plasma. Altered PMRS activity and redox status are associated with the pathophysiology of several health complications including aging and diabetes; hence, the above finding may explain part of the role of curcumin in health beneficial effects.

  13. 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.

  14. PHREEQC, Modeling of Geochemical Reactions, Calculation of pH, Redox Potential. PHREEQCI, Windows Interactive Version of PHREEQC. PHRQCGRF, code to create graphs from the data generated by PHREEQC

    International Nuclear Information System (INIS)

    Parkhust, David L.

    2005-01-01

    Description of program or function: PHREEQC is a computer program written in the C programming language that is designed to perform a wide variety of aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations, (2) reaction-path and advective-transport calculations involving specified irreversible reactions, mixing of solutions, mineral and gas equilibria, surface- complexation reactions, and ion-exchange reactions, and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for composition differences between waters, within specified compositional uncertainties. PHREEQC is derived from the Fortran program PHREEQE, but it has been completely rewritten in C with the addition of many new capabilities. New features include the capabilities to use redox couples to distribute redox elements among their valence states in speciation calculations; to model ion-exchange and surface-complexation reactions; to model reactions with a fixed-pressure, multicomponent gas phase (that is, a gas bubble); to calculate the mass of water in the aqueous phase during reaction and transport calculations; to keep track of the moles of minerals present in the solid phases and determine automatically the thermodynamically stable phase assemblage; to simulate advective transport in combination with PHREEQC's reaction-modeling capability; and to make inverse modeling calculations that allow for uncertainties in the analytical data. The user interface is improved through the use of a simplified approach to redox reactions, which includes explicit mole-balance equations for hydrogen and oxygen; the use of a revised input that is modular and completely free format; and the use of mineral names and standard chemical symbolism rather than index numbers. The use of C eliminates nearly all limitations on array sizes, including numbers of elements, aqueous species

  15. Electrical switching and memory phenomena observed in redox-gradient dendrimer sandwich devices

    OpenAIRE

    Li, JianChang; Blackstock, Silas C.; Szulczewski, Greg J.

    2005-01-01

    We report on the fabrication of dendrimer sandwich devices with electrical switching and memory properties. The storage media is consisted of a redox-gradient dendrimer layer sandwiched in organic barrier thin films. The dendrimer layer acts as potential well where redox-state changes and consequent electrical transitions of the embedded dendrimer molecules are expected to be effectively triggered and retained, respectively. Experimental results indicated that electrical switching could be re...

  16. Failure of the n3 scaling law in the Temkin-Poet model of e-H scattering

    International Nuclear Information System (INIS)

    Shakletron, T.; Stelbovics, A.T.

    2000-01-01

    Full text: We have carried out a study of the Temkin-Poet model of e-H scattering. This model has been of considerable interest to scattering theorists because it is a subset of the full e-H problem and has been used many times to test methods of solution of the full problem. Recently it was shown by Ihra and Macek that the ionisation cross section should be suppressed near threshold. The reason for this is that, classically, ionisation is forbidden in a small region above threshold and hence quantum mechanically we expect a manifestation of quantum mechanical tunnelling. Because the total ionisation cross section can be found using the optical theorem for total cross section and then subtracting off the discrete inelastic scattering cross sections, one might expect interesting behaviour of the inelastic cross sections. Indeed this is confirmed by our extensive numerical simulations using a solution method based on Poet's Fredholm equation of the first kind for the scattering matrix. We conclude that the cross sections fall off at a rate faster than the n 3 scaling law in a region of about 2eV below and above the ionisation threshold. The rate varies with nearness to the threshold

  17. New insights into redox regulation of stem cell self-renewal and differentiation.

    Science.gov (United States)

    Ren, Fenglian; Wang, Kui; Zhang, Tao; Jiang, Jingwen; Nice, Edouard Collins; Huang, Canhua

    2015-08-01

    Reactive oxygen species (ROS), the natural byproducts of aerobic metabolism, are precisely orchestrated to evoke diverse signaling pathways. To date, studies have focused mainly on the detrimental effects of ROS in stem cells. Recently, accumulating evidence has suggested that ROS also function as second messengers that modulate stem cell self-renewal and differentiation by regulating intricate signaling networks. Although many efforts have been made to clarify the general effects of ROS on signal transduction in stem cells, less is known about the initial and direct executors of ROS signaling, which are known as 'redox sensors'. Modifications of cysteine residues in redox sensors are of significant importance in the modulation of protein function in response to different redox conditions. Intriguingly, most key molecules in ROS signaling and cell cycle regulation (including transcriptional factors and kinases) that are crucial in the regulation of stem cell self-renewal and differentiation have the potential to be redox sensors. We highlight herein the importance of redox regulation of these key regulators in stem cell self-renewal and differentiation. Understanding the mechanisms of redox regulation in stem cell self-renewal and differentiation will open exciting new perspectives for stem cell biology. This article is part of a Special Issue entitled Redox regulation of differentiation and de-differentiation. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. 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.

  19. 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.

  20. 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...

  1. 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

  2. Redox Proteomics and Platelet Activation: Understanding the Redox Proteome to Improve Platelet Quality for Transfusion

    Science.gov (United States)

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

    2017-01-01

    Blood banks use pathogen inactivation (PI) technologies to increase the safety of platelet concentrates (PCs). The characteristics of PI-treated PCs slightly differ from those of untreated PCs, but the underlying reasons are not well understood. One possible cause is the generation of oxidative stress during the PI process. This is of great interest since reactive oxygen species (ROS) act as second messengers in platelet functions. Furthermore, there are links between protein oxidation and phosphorylation, another mechanism that is critical for cell regulation. Current research efforts focus on understanding the underlying mechanisms and identifying new target proteins. Proteomics technologies represent powerful tools for investigating signaling pathways involving ROS and post-translational modifications such as phosphorylation, while quantitative techniques enable the comparison of the platelet resting state versus the stimulated state. In particular, redox cysteine is a key player in platelet activation upon stimulation by different agonists. This review highlights the experiments that have provided insights into the roles of ROS in platelet function and the implications for platelet transfusion, and potentially in diseases such as inflammation and platelet hyperactivity. The review also describes the implication of redox mechanism in platelet storage considerations. PMID:28208668

  3. A Sustainable Redox-Flow Battery with an Aluminum-Based, Deep-Eutectic-Solvent Anolyte.

    Science.gov (United States)

    Zhang, Changkun; Ding, Yu; Zhang, Leyuan; Wang, Xuelan; Zhao, Yu; Zhang, Xiaohong; Yu, Guihua

    2017-06-19

    Nonaqueous redox-flow batteries are an emerging energy storage technology for grid storage systems, but the development of anolytes has lagged far behind that of catholytes due to the major limitations of the redox species, which exhibit relatively low solubility and inadequate redox potentials. Herein, an aluminum-based deep-eutectic-solvent is investigated as an anolyte for redox-flow batteries. The aluminum-based deep-eutectic solvent demonstrated a significantly enhanced concentration of circa 3.2 m in the anolyte and a relatively low redox potential of 2.2 V vs. Li + /Li. The electrochemical measurements highlight that a reversible volumetric capacity of 145 Ah L -1 and an energy density of 189 Wh L -1 or 165 Wh kg -1 have been achieved when coupled with a I 3 - /I - catholyte. The prototype cell has also been extended to the use of a Br 2 -based catholyte, exhibiting a higher cell voltage with a theoretical energy density of over 200 Wh L -1 . The synergy of highly abundant, dendrite-free, multi-electron-reaction aluminum anodes and environmentally benign deep-eutectic-solvent anolytes reveals great potential towards cost-effective, sustainable redox-flow batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Deep groundwater redox reactions in the Palmottu uranium deposit: The role of uranium and iron in these processes

    International Nuclear Information System (INIS)

    Bruno, J.; Cera, E.; Duro, L.; Ahonen, L.

    1996-12-01

    The reduction oxidation properties of the deep bedrock and groundwater are important geochemical factors with respect to the chemical stability of the multibarrier system, which isolates the disposed nuclear fuel from biosphere. In the report are described the results of the redox experiments carried out in the field using the natural groundwaters of Palmottu, in Nummi-Pusula, Finland. The experiments include (1) measurements of natural water redox potential values during four to eight hours continuous pumping; (2) monitoring of the redox-potential response to an artificial change of pH of the groundwater. Separate tests were made in iron and uranium-rich groundwaters, respectively. The data of the field experiments were used in the redox-modelling of the iron and uranium systems. In accordance with earlier knowledge, it was showed that dissolved iron is an important redox electrolyte in natural waters, at least at concentration levels of milligrams per liter. However, a striking observation was that in the absence of dissolved iron dissolved uranium (in concentrations of about 200 nM or more) seems to be able to give nernstian response on platinum electrode in acid/base titrations. The effective redox properties of the bedrock-groundwater system depend on the availability and reactivity of solid phases able to exchange electrons with dissolved redox electrolytes. The present results indicate that, in the bedrock/groundwater system of the Palmottu uranium mineralization, uranium minerals are important redox buffers. (orig.) (refs.)

  5. Specific Interaction between Redox Phospholipid Polymers and Plastoquinone in Photosynthetic Electron Transport Chain.

    Science.gov (United States)

    Tanaka, Kenya; Kaneko, Masahiro; Ishikawa, Masahito; Kato, Souichiro; Ito, Hidehiro; Kamachi, Toshiaki; Kamiya, Kazuhide; Nakanishi, Shuji

    2017-04-19

    Redox phospholipid polymers added in culture media are known to be capable of extracting electrons from living photosynthetic cells across bacterial cell membranes with high cytocompatibility. In the present study, we identify the intracellular redox species that transfers electrons to the polymers. The open-circuit electrochemical potential of an electrolyte containing the redox polymer and extracted thylakoid membranes shift to positive (or negative) under light irradiation, when an electron transport inhibitor specific to plastoquinone is added upstream (or downstream) in the photosynthetic electron transport chain. The same trend is also observed for a medium containing living photosynthetic cells of Synechococcus elongatus PCC7942. These results clearly indicate that the phospholipid redox polymers extract photosynthetic electrons mainly from plastoquinone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. The NASA Redox Storage System Development project, 1980

    Science.gov (United States)

    1982-12-01

    The technical accomplishments pertaining to the development of Redox systems and related technology are outlined in terms of the task elements: prototype systems development, application analyses, and supporting technology. Prototype systems development provides for a major procurement to develop an industrial capability to take the current NASA Lewis technology and go on to the design, development, and commercialization of iron-chromium Redox storage systems. Application analyses provides for the definition of application concepts and technology requirements, specific definition studies, and the identification of market sectors and their penetration potential. Supporting technology includes both in house and contractual efforts that encompass implementation of technology improvements in membranes, electrodes, reactant processing, and system design. The status of all elements is discussed.

  7. 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.

  8. 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)

  9. Converter for pulsed Bremsstrahlung generation on the basis of he linear electron accelerator EhLU-4 and the results of bipolar integrated circuits irradiation; Konvertur dlya generatsii impul`snogo tormoznogo izlucheniya na baze linejnogo uskoritelya ehlekutronov EhLU-4 i rezul`taty oblucheniya bipolyarnykh integral`nykh skhem

    Energy Technology Data Exchange (ETDEWEB)

    Korshunov, F P; Lazar` , A P; Gurinovich, N I

    1994-12-31

    Description and parameters of a converter produced on the base of EhLU-4 linear electron accelerators allowing one to obtain an intensive flux of pulsed Bremsstrahlung for radiation investigation are presented.

  10. New lab scale approaches for quantification of redox conditions

    Science.gov (United States)

    Fernandez, P. M.; Dathe, A.; Nadeem, S.; Bakken, L. R.; Bloem, E.; French, H. K.; Binley, A. M.

    2013-12-01

    Degradation of organic chemicals in the unsaturated zone is a process highly relevant for developing remediation techniques for protecting groundwater. Degradation causes changes in chemical composition of the water phase and gas releases. These changes can potentially be mapped with electrical resistivity measurements in the bulk soil and gas measurements at the soil surface. The redox potential combined with the local geological conditions determines the composition of available electron acceptors as well as microbial degradation pathways and how the soil system is affected in the long term. After oxygen and nitrate are depleted, manganese and iron should be reduced. However, in experiments conducted in the unsaturated zone at Gardermoen airport, Norway, it was found that for the degradation of the de-icing agent propylene glycol (PG), manganese and iron were preferred over nitrate as electron acceptor. A key hypothesis for the work presented is that for a designated soil, the redox potential affects gas releases and soil solution composition profoundly. As the redox potential decreases, the reactants of the degradation change and therefore the composition of the soil-water system changes. These changes can be quantified dynamically by gas measurements and changes in electrical conductivity of the pore water and electrical resistivity of the bulk soil. Batch experiments were conducted to examine whether nitrate is a preferred electron acceptor over iron and manganese oxides as described in classical redox reaction theory. Gas releases during PG and glutamate degradation were measured in a sandy pristine soil with and without nitrate under anaerobic condition during two weeks of incubation. Chemical reactions were quantified with the modelling tool ORCHESTRA. We are currently investigating whether dynamical measurements of electrical conductivity and bulk resistivity are suited to trace which electron acceptors (nitrate, manganese or iron) are being reduced. First

  11. Inhibitors of nuclease and redox activity of apurinic/apyrimidinic endonuclease 1/redox effector factor 1 (APE1/Ref-1).

    Science.gov (United States)

    Laev, Sergey S; Salakhutdinov, Nariman F; Lavrik, Olga I

    2017-05-01

    Human apurinic/apyrimidinic endonuclease 1/redox effector factor 1 (APE1/Ref-1) is a multifunctional protein which is essential in the base excision repair (BER) pathway of DNA lesions caused by oxidation and alkylation. This protein hydrolyzes DNA adjacent to the 5'-end of an apurinic/apyrimidinic (AP) site to produce a nick with a 3'-hydroxyl group and a 5'-deoxyribose phosphate moiety or activates the DNA-binding activity of certain transcription factors through its redox function. Studies have indicated a role for APE1/Ref-1 in the pathogenesis of cancer and in resistance to DNA-interactive drugs. Thus, this protein has potential as a target in cancer treatment. As a result, major efforts have been directed to identify small molecule inhibitors against APE1/Ref-1 activities. These agents have the potential to become anticancer drugs. The aim of this review is to present recent progress in studies of all published small molecule APE1/Ref-1 inhibitors. The structures and activities of APE1/Ref-1 inhibitors, that target both DNA repair and redox activities, are presented and discussed. To date, there is an urgent need for further development of the design and synthesis of APE1/Ref-1 inhibitors due to high importance of this protein target. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. 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.

  13. Physiological tolerance and stoichiometric potential of cyanobacteria for hydrocarbon fuel production

    Czech Academy of Sciences Publication Activity Database

    Kamarainen, J.; Knoop, H.; Stanford, N.; Guerrero, F.; Akhtar, M. K.; Aro, E. M.; Steuer, Ralf; Jones, P. R.

    2012-01-01

    Roč. 162, č. 1 (2012), s. 67-74 ISSN 0168-1656 Institutional support: RVO:67179843 Keywords : Cyanobacteria * Hydrocarbon * Fuel * Toxicity * Stoichiometric potential Subject RIV: EH - Ecology, Behaviour Impact factor: 3.183, year: 2012

  14. 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

  15. A molecular theory of chemically modified electrodes with self-assembled redox polyelectrolye thin films: Reversible cyclic voltammetry

    Energy Technology Data Exchange (ETDEWEB)

    Tagliazucchi, Mario; Calvo, Ernesto J. [INQUIMAE, DQIAyQF Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires (Argentina); Szleifer, Igal [Department of Biomedical Engineering, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208 (United States)

    2008-10-01

    A molecular theory of chemically modified electrodes is applied to study redox polyelectroyte modified electrodes. The molecular approach explicitly includes the size, shape, charge distribution, and conformations of all of the molecular species in the system as well as the chemical equilibria (redox and acid-base) and intermolecular interactions. An osmium pyridine-bipyridine complex covalently bound to poly(allyl-amine) backbone (PAH-Os) adsorbed onto mercapto-propane sulfonate (MPS) thiolated gold electrode is described. The potential and electrolyte composition dependent redox and nonredox capacitance can be calculated with the molecular theory in very good agreement with voltammetric experiments under reversible conditions without the use of freely adjustable parameter. Unlike existing phenomenological models the theory links the electrochemical behavior with the structure of the polymer layer. The theory predicts a highly inhomogeneous distribution of acid-base and redox states that strongly couples with the spatial arrangement of the molecular species in the nanometric redox film. (author)

  16. Protein Redox Dynamics During Light-to-Dark Transitions in Cyanobacteria and Impacts Due to Nutrient Limitation

    Directory of Open Access Journals (Sweden)

    Aaron T Wright

    2014-07-01

    Full Text Available Protein redox chemistry constitutes a major void in knowledge pertaining to photoautotrophic system regulation and signaling processes. We have employed a chemical biology approach to analyze redox sensitive proteins in live Synechococcus sp. PCC 7002 cells in both light and dark periods, and to understand how cellular redox balance is disrupted during nutrient perturbation. The present work identified 300 putative redox-sensitive proteins that are involved in the generation of reductant, macromolecule synthesis, and carbon flux through central metabolic pathways, and may be involved in cell signaling and response mechanisms. Furthermore, our research suggests that dynamic redox changes in response to specific nutrient limitations, including carbon and nitrogen limitations, contribute to the regulatory changes driven by a shift from light to dark. Taken together, these results contribute to a high-level understanding of post-translational mechanisms regulating flux distributions and suggest potential metabolic engineering targets for redirecting carbon towards biofuel precursors.

  17. A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage.

    Science.gov (United States)

    Zhao, Yu; Ding, Yu; Li, Yutao; Peng, Lele; Byon, Hye Ryung; Goodenough, John B; Yu, Guihua

    2015-11-21

    Electrical energy storage system such as secondary batteries is the principle power source for portable electronics, electric vehicles and stationary energy storage. As an emerging battery technology, Li-redox flow batteries inherit the advantageous features of modular design of conventional redox flow batteries and high voltage and energy efficiency of Li-ion batteries, showing great promise as efficient electrical energy storage system in transportation, commercial, and residential applications. The chemistry of lithium redox flow batteries with aqueous or non-aqueous electrolyte enables widened electrochemical potential window thus may provide much greater energy density and efficiency than conventional redox flow batteries based on proton chemistry. This Review summarizes the design rationale, fundamentals and characterization of Li-redox flow batteries from a chemistry and material perspective, with particular emphasis on the new chemistries and materials. The latest advances and associated challenges/opportunities are comprehensively discussed.

  18. Electron flow in multicenter enzymes: theory, applications, and consequences on the natural design of redox chains.

    Science.gov (United States)

    Léger, Christophe; Lederer, Florence; Guigliarelli, Bruno; Bertrand, Patrick

    2006-01-11

    In protein film voltammetry, a redox enzyme is directly connected to an electrode; in the presence of substrate and when the driving force provided by the electrode is appropriate, a current flow reveals the steady-state turnover. We show that, in the case of a multicenter enzyme, this signal reports on the energetics and kinetics of electron transfer (ET) along the redox chain that wires the active site to the electrode, and this provides a new strategy for studying intramolecular ET. We propose a model which takes into account all the enzyme's redox microstates, and we prove it useful to interpret data for various enzymes. Several general ideas emerge from this analysis. Considering the reversibility of ET is a requirement: the usual picture, where ET is depicted as a series of irreversible steps, is oversimplified and lacks the important features that we emphasize. We give justification to the concept of apparent reduction potential on the time scale of turnover and we explain how the value of this potential relates to the thermodynamic and kinetic properties of the system. When intramolecular ET does not limit turnover, the redox chain merely mediates the driving force provided by the electrode or the soluble redox partner, whereas when intramolecular ET is slow, the enzyme behaves as if its active active site had apparent redox properties which depend on the reduction potentials of the relays. This suggests an alternative to the idea that redox chains are optimized in terms of speed: evolutionary pressure may have resulted in slowing down intramolecular ET in order to tune the enzyme's "operating potential".

  19. Thermal detection of single e-h pairs in a biased silicon crystal detector

    Science.gov (United States)

    Romani, R. K.; Brink, P. L.; Cabrera, B.; Cherry, M.; Howarth, T.; Kurinsky, N.; Moffatt, R. A.; Partridge, R.; Ponce, F.; Pyle, M.; Tomada, A.; Yellin, S.; Yen, J. J.; Young, B. A.

    2018-01-01

    We demonstrate that individual electron-hole pairs are resolved in a 1 cm2 by 4 mm thick silicon crystal (0.93 g) operated at ˜35 mK. One side of the detector is patterned with two quasiparticle-trap-assisted electro-thermal-feedback transition edge sensor arrays held near ground potential. The other side contains a bias grid with 20% coverage. Bias potentials up to ±160 V were used in the work reported here. A fiber optic provides 650 nm (1.9 eV) photons that each produce an electron-hole (e- h+) pair in the crystal near the grid. The energy of the drifting charges is measured with a phonon sensor noise σ ˜0.09 e- h+ pair. The observed charge quantization is nearly identical for h+s or e-s transported across the crystal.

  20. Physics perspectives for a Future Circular Collider: FCC-hh/eh - Physics-Perspectives

    CERN Multimedia

    CERN. Geneva

    2017-01-01

    The lectures will briefly discuss the parameters of a Future Circular Collider, before addressing in detail the physics perspectives and the challenges for the experiments and detector systems. The main focus will be on ee and pp collisions, but opportunities for e—p physics will also be covered. The FCC physics perspectives will be presented with reference to the ongoing LHC programme, including the physics potential from future upgrades to the LHC in luminosity and possibly energy.

  1. Thermodynamic and redox properties of graphene oxides for lithium-ion battery applications: a first principles density functional theory modeling approach.

    Science.gov (United States)

    Kim, Sunghee; Kim, Ki Chul; Lee, Seung Woo; Jang, Seung Soon

    2016-07-27

    Understanding the thermodynamic stability and redox properties of oxygen functional groups on graphene is critical to systematically design stable graphene-based positive electrode materials with high potential for lithium-ion battery applications. In this work, we study the thermodynamic and redox properties of graphene functionalized with carbonyl and hydroxyl groups, and the evolution of these properties with the number, types and distribution of functional groups by employing the density functional theory method. It is found that the redox potential of the functionalized graphene is sensitive to the types, number, and distribution of oxygen functional groups. First, the carbonyl group induces higher redox potential than the hydroxyl group. Second, more carbonyl groups would result in higher redox potential. Lastly, the locally concentrated distribution of the carbonyl group is more beneficial to have higher redox potential compared to the uniformly dispersed distribution. In contrast, the distribution of the hydroxyl group does not affect the redox potential significantly. Thermodynamic investigation demonstrates that the incorporation of carbonyl groups at the edge of graphene is a promising strategy for designing thermodynamically stable positive electrode materials with high redox potentials.

  2. 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.

  3. 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

  4. 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...

  5. Profiling bacterial communities associated with sediment-based aquaculture bioremediation systems under contrasting redox regimes

    Science.gov (United States)

    Robinson, Georgina; Caldwell, Gary S.; Wade, Matthew J.; Free, Andrew; Jones, Clifford L. W.; Stead, Selina M.

    2016-12-01

    Deposit-feeding invertebrates are proposed bioremediators in microbial-driven sediment-based aquaculture effluent treatment systems. We elucidate the role of the sediment reduction-oxidation (redox) regime in structuring benthic bacterial communities, having direct implications for bioremediation potential and deposit-feeder nutrition. The sea cucumber Holothuria scabra was cultured on sediments under contrasting redox regimes; fully oxygenated (oxic) and redox stratified (oxic-anoxic). Taxonomically, metabolically and functionally distinct bacterial communities developed between the redox treatments with the oxic treatment supporting the greater diversity; redox regime and dissolved oxygen levels were the main environmental drivers. Oxic sediments were colonised by nitrifying bacteria with the potential to remediate nitrogenous wastes. Percolation of oxygenated water prevented the proliferation of anaerobic sulphate-reducing bacteria, which were prevalent in the oxic-anoxic sediments. At the predictive functional level, bacteria within the oxic treatment were enriched with genes associated with xenobiotics metabolism. Oxic sediments showed the greater bioremediation potential; however, the oxic-anoxic sediments supported a greater sea cucumber biomass. Overall, the results indicate that bacterial communities present in fully oxic sediments may enhance the metabolic capacity and bioremediation potential of deposit-feeder microbial systems. This study highlights the benefits of incorporating deposit-feeding invertebrates into effluent treatment systems, particularly when the sediment is oxygenated.

  6. Thioredoxins, Glutaredoxins, and Peroxiredoxins—Molecular Mechanisms and Health Significance: from Cofactors to Antioxidants to Redox Signaling

    Science.gov (United States)

    Hanschmann, Eva-Maria; Godoy, José Rodrigo; Berndt, Carsten; Hudemann, Christoph

    2013-01-01

    Abstract Thioredoxins (Trxs), glutaredoxins (Grxs), and peroxiredoxins (Prxs) have been characterized as electron donors, guards of the intracellular redox state, and “antioxidants”. Today, these redox catalysts are increasingly recognized for their specific role in redox signaling. The number of publications published on the functions of these proteins continues to increase exponentially. The field is experiencing an exciting transformation, from looking at a general redox homeostasis and the pathological oxidative stress model to realizing redox changes as a part of localized, rapid, specific, and reversible redox-regulated signaling events. This review summarizes the almost 50 years of research on these proteins, focusing primarily on data from vertebrates and mammals. The role of Trx fold proteins in redox signaling is discussed by looking at reaction mechanisms, reversible oxidative post-translational modifications of proteins, and characterized interaction partners. On the basis of this analysis, the specific regulatory functions are exemplified for the cellular processes of apoptosis, proliferation, and iron metabolism. The importance of Trxs, Grxs, and Prxs for human health is addressed in the second part of this review, that is, their potential impact and functions in different cell types, tissues, and various pathological conditions. Antioxid. Redox Signal. 19, 1539–1605. PMID:23397885

  7. 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

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. Redox Impact on Starch Biosynthetic Enzymes in Arabidopsis thaliana

    DEFF Research Database (Denmark)

    Skryhan, Katsiaryna

    Summary The thesis provides new insight into the influence of the plant cell redox state on the transient starch metabolism in Arabidopsis thaliana with a focus on starch biosynthetic enzymes. Two main hypotheses forms the basis of this thesis: 1) photosynthesis and starch metabolism are coordina......Summary The thesis provides new insight into the influence of the plant cell redox state on the transient starch metabolism in Arabidopsis thaliana with a focus on starch biosynthetic enzymes. Two main hypotheses forms the basis of this thesis: 1) photosynthesis and starch metabolism...... are coordinated by the redox state of the cell via post-translational modification of the starch metabolic enzymes containing redox active cysteine residues and these cysteine residues became cross-linked upon oxidation providing a conformational change leading to activity loss; 2) cysteine residues...... of chloroplast enzymes can play a role not only in enzyme activity and redox sensitivity but also in protein folding and stability upon oxidation. Several redox sensitive enzymes identified in this study can serve as potential targets to control the carbon flux to and from starch during the day and night...

  14. Model creation of moving redox reaction boundary in agarose gel electrophoresis by traditional potassium permanganate method.

    Science.gov (United States)

    Xie, Hai-Yang; Liu, Qian; Li, Jia-Hao; Fan, Liu-Yin; Cao, Cheng-Xi

    2013-02-21

    A novel moving redox reaction boundary (MRRB) model was developed for studying electrophoretic behaviors of analytes involving redox reaction on the principle of moving reaction boundary (MRB). Traditional potassium permanganate method was used to create the boundary model in agarose gel electrophoresis because of the rapid reaction rate associated with MnO(4)(-) ions and Fe(2+) ions. MRB velocity equation was proposed to describe the general functional relationship between velocity of moving redox reaction boundary (V(MRRB)) and concentration of reactant, and can be extrapolated to similar MRB techniques. Parameters affecting the redox reaction boundary were investigated in detail. Under the selected conditions, good linear relationship between boundary movement distance and time were obtained. The potential application of MRRB in electromigration redox reaction titration was performed in two different concentration levels. The precision of the V(MRRB) was studied and the relative standard deviations were below 8.1%, illustrating the good repeatability achieved in this experiment. The proposed MRRB model enriches the MRB theory and also provides a feasible realization of manual control of redox reaction process in electrophoretic analysis.

  15. 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.

  16. 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.

  17. Some redox chemistry of HPO2-. and .PO32- radicals. A pulse radiolysis study

    International Nuclear Information System (INIS)

    Packer, J.E.; Anderson, R.F.

    1990-01-01

    The HO . radical oxidises hypophosphite and phosphite anions to HPO 2 -. and . PO 3 2- respectively, but Br 2 -. and N 3 . do not. The rates of oxidation of HPO 2 -. by a series of oxidising agents of known one electron redox potentials decrease with decreasing potential while the corresponding rates for oxidation of . PO 3 2- remain close to the diffusion controlled limit. . PO 3 2- will oxidise cysteine but HPO 2 -. does not. . PO 3 2- did not oxidise ABTS, ascorbate, or the anion of the vitamin E analogue, trolox. It reduced traces of TMPD +. in TMPD rather than oxidising the substrate. The one electron redox potentials for oxidation and reduction of . PO 3 2- are calculated in light of recently published redox data on penicillamine. (author)

  18. pH and redox effects of building materials

    International Nuclear Information System (INIS)

    Van der Sloot, H.A.; Van Zomeren, A.; Meeussen, J.C.L.; De Nie, D.S.

    2007-11-01

    The application of relatively fine grained industrial slags as fill material in industrial terrains and parking lots has led to unacceptably elevated pH values and imposed reducing conditions in ground- and surface water. Based on the Dutch Building Materials Decree the materials applied were classified as category 1 materials (free use). There are no limits set to pH and redox in this regulation. In itself a lower or higher pH and a low redox potential are not necessarily critical. Only when the buffer capacity of the surroundings is exceeded, undesirable situations may develop. In this work, the release of alkaline and reducing substances has been studied to assess if regulatory controls are needed and how such controls could be implemented practically. Both pH and redox potential are unsuitable properties for this purpose as it is the buffer capacity of the releasing material and the buffer capacity of the receiving soil and water bodies that determine whether unacceptable conditions develop. As pH and redox are also affected by gas reactions (O2 and CO2), the evaluation becomes relatively complex. Using the chemical speciation-transport model ORCHESTRA, a scenario description has been developed to assess the release of alkaline and reducing species from slag by infiltration under unsaturated conditions. Proper acid neutralization and redox buffering data for the materials were determined. Based on the sophisticated model results, a simplified model description was applied to link observations to impact. Decision schemes for applications above groundwater and in surface water have been developed based on the buffer capacity and particle size distribution of the material to be used, the infiltration rate, the degree of exposure to O2 and CO2 from the atmosphere or from soil air and the dimensions of the application. This has led to a preliminary guidance on implementing rules for acceptance of materials in specific applications. The modeled release predictions

  19. Site investigation SFR. Fracture mineralogy and geochemistry of borehole sections sampled for groundwater chemistry and Eh. Results from boreholes KFR01, KFR08, KFR10, KFR19, KFR7A and KFR105

    Energy Technology Data Exchange (ETDEWEB)

    Sandstroem, Bjoern (WSP Sverige AB (Sweden)); Tullborg, Eva-Lena (Terralogica AB, Grabo (Sweden))

    2011-01-15

    This report is part of the complementary site investigations for the future expansion of SFR. The report presents the results obtained during a detailed mineralogical and geochemical study of fracture minerals in drill cores from borehole section sampled for groundwater chemistry and where downhole Eh measurements have been performed. The groundwater redox system comprises not only the water, but also the bedrock/fracture mineral system in contact with this water. It is thus important to gain knowledge of the solid phases in contact with the groundwater, i.e. the fracture minerals. The samples studied for mineralogy and geochemistry, here reported, were selected to represent the fracture surfaces in contact with the groundwater in the sampled borehole sections and will give input to the hydrogeochemical model (SFR SDM). The mineralogy was determined using SEM-EDS and XRD and the geochemistry of fracture filling material was analysed by ICP-AES and ICP-QMS. The most common fracture minerals in the samples are mixed layer clay (smectite-illite), illite, chlorite, calcite, quartz, adularia and albite. Other minerals identified in the borehole sections include laumontite, pyrite, barite, chalcopyrite, hematite, Fe-oxyhydroxide, muscovite, REE-carbonate, allanite, biotite, asphaltite, galena, sphalerite, arsenopyrite, uranium phosphate, uranium silicate, Y-Ca silicate, monazite, xenotime, harmotome and fluorite. There are no major differences between the fracture mineralogy of the investigated borehole sections from SFR and the fracture mineralogy of the Forsmark site investigation area. The four fracture mineral generations distinguished within the Forsmark site investigation are also found at SFR. However, some differences have been observed: 1) Barite and uranium minerals are more common in the SFR fractures, 2) clay minerals like mixed layer illite-smectite and illite dominates in contrast to Forsmark where corrensite is by far the most common clay mineral and, 3

  20. Site investigation SFR. Fracture mineralogy and geochemistry of borehole sections sampled for groundwater chemistry and Eh. Results from boreholes KFR01, KFR08, KFR10, KFR19, KFR7A and KFR105

    International Nuclear Information System (INIS)

    Sandstroem, Bjoern; Tullborg, Eva-Lena

    2011-01-01

    This report is part of the complementary site investigations for the future expansion of SFR. The report presents the results obtained during a detailed mineralogical and geochemical study of fracture minerals in drill cores from borehole section sampled for groundwater chemistry and where downhole Eh measurements have been performed. The groundwater redox system comprises not only the water, but also the bedrock/fracture mineral system in contact with this water. It is thus important to gain knowledge of the solid phases in contact with the groundwater, i.e. the fracture minerals. The samples studied for mineralogy and geochemistry, here reported, were selected to represent the fracture surfaces in contact with the groundwater in the sampled borehole sections and will give input to the hydrogeochemical model (SFR SDM). The mineralogy was determined using SEM-EDS and XRD and the geochemistry of fracture filling material was analysed by ICP-AES and ICP-QMS. The most common fracture minerals in the samples are mixed layer clay (smectite-illite), illite, chlorite, calcite, quartz, adularia and albite. Other minerals identified in the borehole sections include laumontite, pyrite, barite, chalcopyrite, hematite, Fe-oxyhydroxide, muscovite, REE-carbonate, allanite, biotite, asphaltite, galena, sphalerite, arsenopyrite, uranium phosphate, uranium silicate, Y-Ca silicate, monazite, xenotime, harmotome and fluorite. There are no major differences between the fracture mineralogy of the investigated borehole sections from SFR and the fracture mineralogy of the Forsmark site investigation area. The four fracture mineral generations distinguished within the Forsmark site investigation are also found at SFR. However, some differences have been observed: 1) Barite and uranium minerals are more common in the SFR fractures, 2) clay minerals like mixed layer illite-smectite and illite dominates in contrast to Forsmark where corrensite is by far the most common clay mineral and, 3

  1. 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.)

  2. Review and assessments of potential environmental, health and safety impacts of MHD technology. Final draft

    Energy Technology Data Exchange (ETDEWEB)

    1978-01-01

    The purpose of this document is to develop an environmental, health and safety (EH and S) assessment and begin a site - specific assessment of these and socio - economic impacts for the magnetohydrodynamics program of the United States Department of Energy. This assessment includes detailed scientific and technical information on the specific EH and S issues mentioned in the MHD Environmental Development Plan. A review of current literature on impact-related subjects is also included. This document addresses the coal-fired, open-cycle MHD technology and reviews and assesses potential EH and S impacts resulting from operation of commercially-installed technology.

  3. Analysis of redox additive-based overcharge protection for rechargeable lithium batteries

    Science.gov (United States)

    Narayanan, S. R.; Surampudi, S.; Attia, A. I.; Bankston, C. P.

    1991-01-01

    The overcharge condition in secondary lithium batteries employing redox additives for overcharge protection, has been theoretically analyzed in terms of a finite linear diffusion model. The analysis leads to expressions relating the steady-state overcharge current density and cell voltage to the concentration, diffusion coefficient, standard reduction potential of the redox couple, and interelectrode distance. The model permits the estimation of the maximum permissible overcharge rate for any chosen set of system conditions. Digital simulation of the overcharge experiment leads to numerical representation of the potential transients, and estimate of the influence of diffusion coefficient and interelectrode distance on the transient attainment of the steady state during overcharge. The model has been experimentally verified using 1,1-prime-dimethyl ferrocene as a redox additive. The analysis of the experimental results in terms of the theory allows the calculation of the diffusion coefficient and the formal potential of the redox couple. The model and the theoretical results may be exploited in the design and optimization of overcharge protection by the redox additive approach.

  4. Identification of EhTIF-IA: The putative E. histolytica orthologue of the human ribosomal RNA transcription initiation factor-IA.

    Science.gov (United States)

    Srivastava, Ankita; Bhattacharya, Alok; Bhattacharya, Sudha; Jhingan, Gagan Deep

    2016-03-01

    Initiation of rDNA transcription requires the assembly of a specific multi-protein complex at the rDNA promoter containing the RNA Pol I with auxiliary factors. One of these factors is known as Rrn3P in yeast and Transcription Initiation Factor IA (TIF-IA) in mammals. Rrn3p/TIF-IA serves as a bridge between RNA Pol I and the pre-initiation complex at the promoter. It is phosphorylated at multiple sites and is involved in regulation of rDNA transcription in a growth-dependent manner. In the early branching parasitic protist Entamoeba histolytica, the rRNA genes are present exclusively on circular extra chromosomal plasmids. The protein factors involved in regulation of rDNA transcription in E. histolytica are not known. We have identified the E. histolytica equivalent of TIF-1A (EhTIF-IA) by homology search within the database and was further cloned and expressed. Immuno-localization studies showed that EhTIF-IA co-localized partially with fibrillarin in the peripherally localized nucleolus. EhTIF-IA was shown to interact with the RNA Pol I-specific subunit RPA12 both in vivo and in vitro. Mass spectroscopy data identified RNA Pol I-specific subunits and other nucleolar proteins to be the interacting partners of EhTIF-IA. Our study demonstrates for the first time a conserved putative RNA Pol I transcription factor TIF-IA in E. histolytica.

  5. The dynamics processes of the soil microbecenosis to condition of radionuclides contamination under influence of agent 'Bajkal EhM-1'

    International Nuclear Information System (INIS)

    Shchur, A.V.; Vetoshkina, S.N.; Chernukha, G.A.; Shipilov, Yu.V.; Val'ko, O.V.

    2006-01-01

    Used of the preparation 'Bajkal EhM-1' influences to number of micro-organisms species in microbecenosis and it's popularity were increase. The general pool and biomass of the micro-organisms have a share in the process of the bio dynamics and transformation of an organic matter of the soil experimental plot were increase. (authors)

  6. Oxygen in human health from life to death – An approach to teaching redox biology and signaling to graduate and medical students

    Directory of Open Access Journals (Sweden)

    Margaret M. Briehl

    2015-08-01

    Full Text Available In the absence of oxygen human life is measured in minutes. In the presence of oxygen, normal metabolism generates reactive species (ROS that have the potential to cause cell injury contributing to human aging and disease. Between these extremes, organisms have developed means for sensing oxygen and ROS and regulating their cellular processes in response. Redox signaling contributes to the control of cell proliferation and death. Aberrant redox signaling underlies many human diseases. The attributes acquired by altered redox homeostasis in cancer cells illustrate this particularly well. This teaching review and the accompanying illustrations provide an introduction to redox biology and signaling aimed at instructors of graduate and medical students.

  7. Redox buffered hydrofluoric acid etchant for the reduction of galvanic attack during release etching of MEMS devices having noble material films

    Science.gov (United States)

    Hankins, Matthew G [Albuquerque, NM

    2009-10-06

    Etchant solutions comprising a redox buffer can be used during the release etch step to reduce damage to the structural layers of a MEMS device that has noble material films. A preferred redox buffer comprises a soluble thiophosphoric acid, ester, or salt that maintains the electrochemical potential of the etchant solution at a level that prevents oxidation of the structural material. Therefore, the redox buffer preferentially oxidizes in place of the structural material. The sacrificial redox buffer thereby protects the exposed structural layers while permitting the dissolution of sacrificial oxide layers during the release etch.

  8. Reverse Engineering Applied to Red Human Hair Pheomelanin Reveals Redox-Buffering as a Pro-Oxidant Mechanism

    Science.gov (United States)

    Kim, Eunkyoung; Panzella, Lucia; Micillo, Raffaella; Bentley, William E.; Napolitano, Alessandra; Payne, Gregory F.

    2015-01-01

    Pheomelanin has been implicated in the increased susceptibility to UV-induced melanoma for people with light skin and red hair. Recent studies identified a UV-independent pathway to melanoma carcinogenesis and implicated pheomelanin’s pro-oxidant properties that act through the generation of reactive oxygen species and/or the depletion of cellular antioxidants. Here, we applied an electrochemically-based reverse engineering methodology to compare the redox properties of human hair pheomelanin with model synthetic pigments and natural eumelanin. This methodology exposes the insoluble melanin samples to complex potential (voltage) inputs and measures output response characteristics to assess redox activities. The results demonstrate that both eumelanin and pheomelanin are redox-active, they can rapidly (sec-min) and repeatedly redox-cycle between oxidized and reduced states, and pheomelanin possesses a more oxidative redox potential. This study suggests that pheomelanin’s redox-based pro-oxidant activity may contribute to sustaining a chronic oxidative stress condition through a redox-buffering mechanism. PMID:26669666

  9. 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.

  10. Implication of Xenobiotic Metabolizing Enzyme gene (CYP2E1, CYP2C19, CYP2D6, mEH and NAT2 Polymorphisms in Breast Carcinoma

    Directory of Open Access Journals (Sweden)

    Gabbouj Sallouha

    2008-04-01

    Full Text Available Abstract Background Xenobiotic Metabolizing Enzymes (XMEs contribute to the detoxification of numerous cancer therapy-induced products. This study investigated the susceptibility and prognostic implications of the CYP2E1, CYP2C19, CYP2D6, mEH and NAT2 gene polymorphisms in breast carcinoma patients. Methods The authors used polymerase chain reaction and restriction enzyme digestion to characterize the variation of the CYP2E1, CYP2C19, CYP2D6, mEH and NAT2 gene in a total of 560 unrelated subjects (246 controls and 314 patients. Results The mEH (C/C mutant and the NAT2 slow acetylator genotypes were significantly associated with breast carcinoma risk (p = 0.02; p = 0.01, respectively. For NAT2 the association was more pronounced among postmenopausal patients (p = 0.006. A significant association was found between CYP2D6 (G/G wild type and breast carcinoma risk only in postmenopausal patients (p = 0.04. Association studies of genetic markers with the rates of breast carcinoma specific overall survival (OVS and the disease-free survival (DFS revealed among all breast carcinoma patients no association to DFS but significant differences in OVS only with the mEH gene polymorphisms (p = 0.02. In addition, the mEH wild genotype showed a significant association with decreased OVS in patients with axillary lymph node-negative patients (p = 0.03 and with decreasesd DFS in patients with axillary lymph node-positive patients (p = 0.001. However, the NAT2 intermediate acetylator genotype was associated with decreased DFS in axillary lymph node-negative patients. Conclusion The present study may prove that polymorphisms of some XME genes may predict the onset of breast carcinoma as well as survival after treatment.

  11. NQO1-dependent redox cycling of idebenone: effects on cellular redox potential and energy levels.

    Directory of Open Access Journals (Sweden)

    Roman H Haefeli

    Full Text Available Short-chain quinones are described as potent antioxidants and in the case of idebenone have already been under clinical investigation for the treatment of neuromuscular disorders. Due to their analogy to coenzyme Q10 (CoQ10, a long-chain quinone, they are widely regarded as a substitute for CoQ10. However, apart from their antioxidant function, this provides no clear rationale for their use in disorders with normal CoQ10 levels. Using recombinant NAD(PH:quinone oxidoreductase (NQO enzymes, we observed that contrary to CoQ10 short-chain quinones such as idebenone are good substrates for both NQO1 and NQO2. Furthermore, the reduction of short-chain quinones by NQOs enabled an antimycin A-sensitive transfer of electrons from cytosolic NAD(PH to the mitochondrial respiratory chain in both human hepatoma cells (HepG2 and freshly isolated mouse hepatocytes. Consistent with the substrate selectivity of NQOs, both idebenone and CoQ1, but not CoQ10, partially restored cellular ATP levels under conditions of impaired complex I function. The observed cytosolic-mitochondrial shuttling of idebenone and CoQ1 was also associated with reduced lactate production by cybrid cells from mitochondrial encephalomyopathy, lactic acidosis and stroke-like episodes (MELAS patients. Thus, the observed activities separate the effectiveness of short-chain quinones from the related long-chain CoQ10 and provide the rationale for the use of short-chain quinones such as idebenone for the treatment of mitochondrial disorders.

  12. Sediment phosphorus speciation and mobility under dynamic redox conditions

    Science.gov (United States)

    Parsons, Chris T.; Rezanezhad, Fereidoun; O'Connell, David W.; Van Cappellen, Philippe

    2017-07-01

    Anthropogenic nutrient enrichment has caused phosphorus (P) accumulation in many freshwater sediments, raising concerns that internal loading from legacy P may delay the recovery of aquatic ecosystems suffering from eutrophication. Benthic recycling of P strongly depends on the redox regime within surficial sediment. In many shallow environments, redox conditions tend to be highly dynamic as a result of, among others, bioturbation by macrofauna, root activity, sediment resuspension and seasonal variations in bottom-water oxygen (O2) concentrations. To gain insight into the mobility and biogeochemistry of P under fluctuating redox conditions, a suspension of sediment from a hypereutrophic freshwater marsh was exposed to alternating 7-day periods of purging with air and nitrogen gas (N2), for a total duration of 74 days, in a bioreactor system. We present comprehensive data time series of bulk aqueous- and solid-phase chemistry, solid-phase phosphorus speciation and hydrolytic enzyme activities demonstrating the mass balanced redistribution of P in sediment during redox cycling. Aqueous phosphate concentrations remained low ( ˜ 2.5 µM) under oxic conditions due to sorption to iron(III) oxyhydroxides. During anoxic periods, once nitrate was depleted, the reductive dissolution of iron(III) oxyhydroxides released P. However, only 4.5 % of the released P accumulated in solution while the rest was redistributed between the MgCl2 and NaHCO3 extractable fractions of the solid phase. Thus, under the short redox fluctuations imposed in the experiments, P remobilization to the aqueous phase remained relatively limited. Orthophosphate predominated at all times during the experiment in both the solid and aqueous phase. Combined P monoesters and diesters accounted for between 9 and 16 % of sediment particulate P. Phosphatase activities up to 2.4 mmol h-1 kg-1 indicated the potential for rapid mineralization of organic P (Po), in particular during periods of aeration when the

  13. 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.

  14. 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.

  15. Biodegradation of NSO-compounds under different redox-conditions

    DEFF Research Database (Denmark)

    Dyreborg, S.; Arvin, E.; Broholm, K.

    1997-01-01

    Laboratory experiments were carried out to investigate the potential of groundwater microorganisms to degrade selected heterocyclic aromatic compounds containing nitrogen, sulphur, or oxygen (NSO-compounds) under four redox-conditions over a period of 846 days. Eight compounds (pyrrole, 1...... anaerobic conditions, even though the microorganisms present in the anaerobic microcosms were active throughout the incubation period. A high variability in the lag period among the NSO-compounds was observed under aerobic conditions. While quinoline, indole, and carbazole were degraded with a lag period...

  16. Redox behaviour of molybdenum in aqueous medium : a potentiometric study

    International Nuclear Information System (INIS)

    Sagi, S.R.; Mohan Rao, P.R.

    1975-01-01

    The nature of the two forms; of Mo(III) cationic-aquomolybdenum(III) (green) and anionic-chloromolybdate(III) (orange-red) has been investigated using various oxidants in hydrochloric acid mdeium, the oxidation steps being detected using a potentiometric method. The two species behave differently towards the various oxidants. The green form is a better reducing agent giving large breaks in potentials during redox titrations. The existence of the intermediate oxidation states Mosup(3.5) and Mosup(4.5) reported earlier has also been confirmed. (author)

  17. Systems and methods for rebalancing redox flow battery electrolytes

    Science.gov (United States)

    Pham, Ai Quoc; Chang, On Kok

    2015-03-17

    Various methods of rebalancing electrolytes in a redox flow battery system include various systems using a catalyzed hydrogen rebalance cell configured to minimize the risk of dissolved catalyst negatively affecting flow battery performance. Some systems described herein reduce the chance of catalyst contamination of RFB electrolytes by employing a mediator solution to eliminate direct contact between the catalyzed membrane and the RFB electrolyte. Other methods use a rebalance cell chemistry that maintains the catalyzed electrode at a potential low enough to prevent the catalyst from dissolving.

  18. All-Fullerene-Based Cells for Nonaqueous Redox Flow Batteries.

    Science.gov (United States)

    Friedl, Jochen; Lebedeva, Maria A; Porfyrakis, Kyriakos; Stimming, Ulrich; Chamberlain, Thomas W

    2018-01-10

    Redox flow batteries have the potential to revolutionize our use of intermittent sustainable energy sources such as solar and wind power by storing the energy in liquid electrolytes. Our concept study utilizes a novel electrolyte system, exploiting derivatized fullerenes as both anolyte and catholyte species in a series of battery cells, including a symmetric, single species system which alleviates the common problem of membrane crossover. The prototype multielectron system, utilizing molecular based charge carriers, made from inexpensive, abundant, and sustainable materials, principally, C and Fe, demonstrates remarkable current and energy densities and promising long-term cycling stability.

  19. Comprehensive Evaluation of the Properties of Nanocrystalline Diamond Coatings Grown Using CVD with E/H Field Glow Discharge Stabilization

    Directory of Open Access Journals (Sweden)

    Iu. Nasieka

    2015-01-01

    Full Text Available The nanocrystalline diamond films (coatings were prepared using the plasma enhanced chemical vapor deposition (PECVD technique. In this method, direct current (DC glow discharge in the crossed E/H fields was used to activate the gas phase. The diamond coatings were deposited from the working gas mixture CH4/H2 with addition of nitrogen in various concentrations. It was ascertained that addition of N2 to the working gas mixture leads to reduction in the sizes of diamond grains as well as to the substantial decrease in the resistivity of the studied films. The electrophysical data are in good agreement with the changes induced by varying the N2 content in the Raman scattering spectra. The increase in the N2 concentration causes significant lowering of the crystalline diamond related peak and increase in the intensity of the peaks related to the sp2-bonded carbon. These changes in the spectra indicate significant disordering of the structure of prepared films and its uniformity in the nanodiamond film volume. With the great possibility, it is associated with a decrease in the sizes of diamond crystalline grains and tendency of NCD film to amorphization.

  20. Estimation of human percutaneous bioavailability for two novel brominated flame retardants, 2-ethylhexyl tetrabromobenzoate (EH-TBB) and bis(2-ethylhexyl) tetrabromophthalate (BEH-TEBP), using the parallelogram approach

    Science.gov (United States)

    2-ethylhexyltetrabromobenzoate (EH-TBB) and bis(2-ethylhexyl)tetrabromophthalate (BEH-TEBP) are novel brominated flame retardants (FRs). BEH-TEBP is used alone as a plasticizer or with EH-TBB in polyurethane foams; both are contaminants in the indoor and outdoor environments. In ...

  1. Electrochemical Detection of Circadian Redox Rhythm in Cyanobacterial Cells via Extracellular Electron Transfer.

    Science.gov (United States)

    Nishio, Koichi; Pornpitra, Tunanunkul; Izawa, Seiichiro; Nishiwaki-Ohkawa, Taeko; Kato, Souichiro; Hashimoto, Kazuhito; Nakanishi, Shuji

    2015-06-01

    Recent research on cellular circadian rhythms suggests that the coupling of transcription-translation feedback loops and intracellular redox oscillations is essential for robust circadian timekeeping. For clarification of the molecular mechanism underlying the circadian rhythm, methods that allow for the dynamic and simultaneous detection of transcription/translation and redox oscillations in living cells are needed. Herein, we report that the cyanobacterial circadian redox rhythm can be electrochemically detected based on extracellular electron transfer (EET), a process in which intracellular electrons are exchanged with an extracellular electrode. As the EET-based method is non-destructive, concurrent detection with transcription/translation rhythm using bioluminescent reporter strains becomes possible. An EET pathway that electrochemically connected the intracellular region of cyanobacterial cells with an extracellular electrode was constructed via a newly synthesized electron mediator with cell membrane permeability. In the presence of the mediator, the open circuit potential of the culture medium exhibited temperature-compensated rhythm with approximately 24 h periodicity. Importantly, such circadian rhythm of the open circuit potential was not observed in the absence of the electron mediator, indicating that the EET process conveys the dynamic information regarding the intracellular redox state to the extracellular electrode. These findings represent the first direct demonstration of the intracellular circadian redox rhythm of cyanobacterial cells. © The Author 2015. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  2. Review on anionic redox for high-capacity lithium- and sodium-ion batteries

    International Nuclear Information System (INIS)

    Zhao, Chenglong; Lu, Yaxiang; Hu, Yong-Sheng; Chen, Liquan; Wang, Qidi; Li, Baohua

    2017-01-01

    Rechargeable batteries, especially lithium-ion batteries, are now widely used as power sources for portable electronics and electric vehicles, but material innovations are still needed to satisfy the increasing demand for larger energy density. Recently, lithium- and sodium-rich electrode materials, including the A 2 MO 3 -family layered compounds (A  =  Li, Na; M  =  Mn 4+ , Ru 4+ , etc), have been extensively studied as potential high-capacity electrode materials for a cumulative cationic and anionic redox activity. Negatively charged oxide ions can potentially donate electrons to compensate for the absence of oxidable transition metals as a redox center to further increase the reversible capacity. Understanding and controlling the state-of-the-art anionic redox processes is pivotal for the design of advanced energy materials, highlighted in rechargeable batteries. Hence, experimental and theoretical approaches have been developed to consecutively study the diverting processes, states, and structures involved. In this review, we attempt to present a literature overview and provide insight into the reaction mechanism with respect to the anionic redox processes, proposing some opinions as target oriented. It is hoped that, through this discussion, the search for anionic redox electrode materials with high-capacity rechargeable batteries can be advanced, and practical applications realized as soon as possible. (topical review)

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

    Science.gov (United States)

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

    2014-08-01

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

  4. 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

  5. A Protocol for Electrochemical Evaluations and State of Charge Diagnostics of a Symmetric Organic Redox Flow Battery

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Wentao; Vemuri, Rama S.; Hu, Dehong; Yang, Zheng; Wei, Xiaoliang

    2017-01-01

    Redox flow batteries have been considered as one of the most promising stationary energy storage solutions for improving the reliability of the power grid and deployment of renewable energy technologies. Among the many flow battery chemistries, nonaqueous flow batteries have the potential to achieve high energy density because of the broad voltage windows of nonaqueous electrolytes. However, significant technical hurdles exist currently limiting nonaqueous flow batteries to demonstrate their full potential, such as low redox concentrations, low operating currents, under-explored battery status monitoring, etc. In an attempt to address these limitations, we report a nonaqueous flow battery based on a highly soluble, redox-active organic nitronyl nitroxide radical compound, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO). This redox materials exhibits an ambipolar electrochemical property with two reversible redox pairs that are moderately separated by a voltage gap of ~1.7 V. Therefore, PTIO can serve as both anolyte and catholyte redox materials to form a symmetric flow battery chemistry, which affords the advantages such as high effective redox concentrations and low irreversible redox material crossover. The PTIO flow battery shows decent electrochemical cyclability under cyclic voltammetry and flow cell conditions; an improved redox concentration of 0.5 M PTIO and operational current density of 20 mA cm-2 were achieved in flow cell tests. Moreover, we show that Fourier transform infrared (FTIR) spectroscopy could measure the PTIO concentrations during the PTIO flow battery cycling and offer reasonably accurate detection of the battery state of charge (SOC) as cross-validated by electron spin resonance measurements. This study suggests FTIR can be used as a reliable online SOC sensor to monitor flow battery status and ensure battery operations stringently in a safe SOC range.

  6. TEMPO/viologen electrochemical heterojunction for diffusion-controlled redox mediation: a highly rectifying bilayer-sandwiched device based on cross-reaction at the interface between dissimilar redox polymers.

    Science.gov (United States)

    Tokue, Hiroshi; Oyaizu, Kenichi; Sukegawa, Takashi; Nishide, Hiroyuki

    2014-03-26

    A couple of totally reversible redox-active molecules, which are different in redox potentials, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and viologen (V(2+)), were employed to give rise to a rectified redox conduction effect. Single-layer and bilayer devices were fabricated using polymers containing these sites as pendant groups per repeating unit. The devices were obtained by sandwiching the redox polymer layer(s) with indium tin oxide (ITO)/glass and Pt foil electrodes. Electrochemical measurements of the single-layer device composed of polynorbornene-bearing TEMPO (PTNB) exhibited a diffusion-limited current-voltage response based on the TEMPO(+)/TEMPO exchange reaction, which was almost equivalent to a redox gradient through the PTNB layer depending upon the thickness. The bilayer device gave rise to the current rectification because of the thermodynamically favored cross-reaction between TEMPO(+) and V(+) at the polymer/polymer interface. A current-voltage response obtained for the bilayer device demonstrated a two-step diffusion-limited current behavior as a result of the concurrent V(2+)/V(+) and V(+)/V(0) exchange reactions according to the voltage and suggested that the charge transport process through the device was most likely to be rate-determined by a redox gradient in the polymer layer. Current collection experiments revealed a charge transport balance throughout the device, as a result of the electrochemical stability and robustness of the polymers in both redox states.

  7. 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.

  8. Anaerobic microbial redox processes in a landfill leachate contaminated aquifer (Grindsted, Denmark)

    Science.gov (United States)

    Ludvigsen, L.; Albrechtsen, H.-J.; Heron, G.; Bjerg, P. L.; Christensen, T. H.

    1998-10-01

    The distribution of anaerobic microbial redox processes was investigated along a 305 m long transect of a shallow landfill-leachate polluted aquifer. By unamended bioassays containing sediment and groundwater, 37 samples were investigated with respect to methane production, sulfate, iron, and manganese reduction, and denitrification. Methane production was restricted to the most reduced part of the plume with rates of 0.003-0.055 nmol CH 4/g dry weight/day. Sulfate reduction was observed at rates of maximum 1.8 nmol SO 42-/g dry weight/day along with methane production in the plume, but sulfate reduction was also observed further downgradient of the landfill. Iron reduction at rates of 5-19 nmol Fe(II)/g dry weight/day was observed in only a few samples, but this may be related to a high detection limit for the iron reducing bioassay. Manganese reduction at rates of maximum 2.4 nmol Mn(II)/g dry weight/day and denitrification at rates of 0.2-37 nmol N 2O-N/g dry weight/day were observed in the less reduced part of the plume. All the redox processes were microbial processes. In many cases, several redox processes took place simultaneously, but in all samples one process dominated accounting for more than 70% of the equivalent carbon conversion. The bioassays showed that the redox zones in the plume identified from the groundwater composition (e.g. as methanogenic and sulfate reducing) locally hosted also other redox processes (e.g. iron reduction). This may have implications for the potential of the redox zone to degrade trace amounts of organic chemicals and suggests that unamended bioassays may be an important supplement to other approaches in characterizing the redox processes in an anaerobic plume.

  9. 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.

  10. Bioelectrocatalytic NAD+/NADH inter-conversion: transformation of an enzymatic fuel cell into an enzymatic redox flow battery.

    Science.gov (United States)

    Quah, Timothy; Milton, Ross D; Abdellaoui, Sofiene; Minteer, Shelley D

    2017-07-25

    Diaphorase and a benzylpropylviologen redox polymer were combined to create a bioelectrode that can both oxidize NADH and reduce NAD + . We demonstrate how bioelectrocatalytic NAD + /NADH inter-conversion can transform a glucose/O 2 enzymatic fuel cell (EFC) with an open circuit potential (OCP) of 1.1 V into an enzymatic redox flow battery (ERFB), which can be rapidly recharged by operation as an EFC.

  11. 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...

  12. 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...

  13. Sorption of redox-sensitive radionuclides to deep-sea sediments in the absence of oxygen

    International Nuclear Information System (INIS)

    Higgo, J.J.W.; Rees, L.V.C.; Cronan, D.S.; Cole, T.G.

    1986-03-01

    Sediments were recovered from the GME area of the mid-Atlantic and stored in an inert atmosphere from the time of collection Pore-water analysis showed them to be post-oxic. Sorption tests in an inert atmosphere showed that they were not sufficiently reducing to affect the distribution ratios of the redox-sensitive elements, technetium and neptunium. This may mean that previous results obtained under oxic conditions can be used in modelling. Ferrous iron was strongly sorbed onto the sediments but this iron had no effect on technetium sorption, which was negligible. Only if a large excess of Fe ++ was added so that the concentration of Fe ++ in solution exceeded 100um (Eh probably < -0.2V) was the technetium reduced and adsorption appreciable. The indications are, therefore, that ferrous iron from dissolved canisters will not increase the sorption of technetium to deep-sea sediments. Moessbauer analysis showed that a high proportion (up to 15%) of the iron in the high-carbonate turbidites was in the ferrous state but that all the iron in the clay-rich layer, containing less carbonate, was in the ferric state. This may explain the fact that, in general, neptunium is more strongly adsorbed by high-carbonate than by other types of sediment. (author)

  14. Effects of iron on arsenic speciation and redox chemistry in acid mine water

    Science.gov (United States)

    Bednar, A.J.; Garbarino, J.R.; Ranville, J.F.; Wildeman, T.R.

    2005-01-01

    Concern about arsenic is increasing throughout the world, including areas of the United States. Elevated levels of arsenic above current drinking-water regulations in ground and surface water can be the result of purely natural phenomena, but often are due to anthropogenic activities, such as mining and agriculture. The current study correlates arsenic speciation in acid mine drainage and mining-influenced water with the important water-chemistry properties Eh, pH, and iron(III) concentration. The results show that arsenic speciation is generally in equilibrium with iron chemistry in low pH AMD, which is often not the case in other natural-water matrices. High pH mine waters and groundwater do not always hold to the redox predictions as well as low pH AMD samples. The oxidation and precipitation of oxyhydroxides deplete iron from some systems, and also affect arsenite and arsenate concentrations through sorption processes. ?? 2004 Elsevier B.V. All rights reserved.

  15. Iron oxide redox chemistry and nuclear fuel disposal

    International Nuclear Information System (INIS)

    Jobe, D.J.; Lemire, R.J.; Taylor, P.

    1997-04-01

    Solubility and stability data for iron (III) oxides and aqueous Fe(II) and Fe(III) species are reviewed, and selected values are used to calculate potential-pH diagrams for the iron system at temperatures of 25 and 100 deg C, chloride activities {C1 - } = 10 -2 and 1 mol/kg, total carbonate activity {C T } = 10 -3 mol/kg, and iron(III) oxide/oxyhydroxide solubility products (25 deg C values) K sp = {Fe 3+ }{OH - } 3 = 10 -38.5 , 10 -40 and 10 -42 . The temperatures and anion concentrations bracket the range of conditions expected in a Canadian nuclear fuel waste disposal vault. The three solubility products represent a conservative upper limit, a most probable value, and a minimum credible value, respectively, for the iron oxides likely to be important in controlling redox conditions in a disposal vault for CANDU nuclear reactor fuel. Only in the first of these three cases do the calculated redox potentials significantly exceed values under which oxidative dissolution of the fuel may occur. (author)

  16. Energy-density enhancement of carbon-nanotube-based supercapacitors with redox couple in organic electrolyte.

    Science.gov (United States)

    Park, Jinwoo; Kim, Byungwoo; Yoo, Young-Eun; Chung, Haegeun; Kim, Woong

    2014-11-26

    We demonstrate for the first time that the incorporation of a redox-active molecule in an organic electrolyte can increase the cell voltage of a supercapacitor. The redox molecule also contributes to increasing the cell capacitance by a faradaic redox reaction, and therefore the energy density of the supercapacitor can be significantly increased. More specifically, the addition of redox-active decamethylferrocene in an organic electrolyte results in an approximately 27-fold increase in the energy density of carbon-nanotube-based supercapacitors. The resulting high energy density (36.8 Wh/kg) stems from the increased cell voltage (1.1 V→2.1 V) and cell capacitance (8.3 F/g→61.3 F/g) resulting from decamethylferrocene addition. We found that the voltage increase is associated with the potential of the redox species relative to the electrochemical stability window of the supporting electrolyte. These results will be useful in identifying new electrolytes for high-energy-density supercapacitors.

  17. Intracellular Redox Compartmentation and ROS-Related Communication in Regulation and Signaling.

    Science.gov (United States)

    Noctor, Graham; Foyer, Christine H

    2016-07-01

    Recent years have witnessed enormous progress in understanding redox signaling related to reactive oxygen species (ROS) in plants. The consensus view is that such signaling is intrinsic to many developmental processes and responses to the environment. ROS-related redox signaling is tightly wedded to compartmentation. Because membranes function as barriers, highly redox-active powerhouses such as chloroplasts, peroxisomes, and mitochondria may elicit specific signaling responses. However, transporter functions allow membranes also to act as bridges between compartments, and so regulated capacity to transmit redox changes across membranes influences the outcome of triggers produced at different locations. As well as ROS and other oxidizing species, antioxidants are key players that determine the extent of ROS accumulation at different sites and that may themselves act as signal transmitters. Like ROS, antioxidants can be transported across membranes. In addition, the intracellular distribution of antioxidative enzymes may be modulated to regulate or facilitate redox signaling appropriate to the conditions. Finally, there is substantial plasticity in organellar shape, with extensions such as stromules, peroxules, and matrixules playing potentially crucial roles in organelle-organelle communication. We provide an overview of the advances in subcellular compartmentation, identifying the gaps in our knowledge and discussing future developments in the area. © 2016 American Society of Plant Biologists. All Rights Reserved.

  18. Effect of the Linker in Terephthalate-Functionalized Conducting Redox Polymers

    International Nuclear Information System (INIS)

    Yang, Li; Huang, Xiao; Gogoll, Adolf; Strømme, Maria; Sjödin, Martin

    2016-01-01

    The combination of high capacity redox active pendent groups and conducting polymers, realized in conducting redox polymers (CRPs), provides materials with high charge storage capacity that are electronically conducting which makes CRPs attractive for electrical energy storage applications. In this report, six polythiophene and poly(3,4-ethylenedioxythiophene)(PEDOT)-based CRPs with a diethyl terephthalate unit covalently bound to the polymer chain by various linkers have been synthesized and characterized electrochemically. The effects of the choice of polymer backbone and of the nature of the link on the electrochemistry, and in particular the cycling stability of these polymers, are discussed. All CRPs show both the doping of the polymer backbone as well as the redox behavior of the pendent groups and the redox potential of the pendent groups in the CRPs is close to that of corresponding monomer, indicating insignificant interaction between the pendant and the polymer backbone. While all CRPs show various degrees of charge decay upon electrochemical redox conversion, the PEDOT-based CRPs show significantly improved stability compared to the polythiophene counterparts. Moreover, we show that by the right choice of link the cycling stability of diethyl terephthalate substituted PEDOT-based CRPs can be significantly improved.

  19. Characterization of PEDOT-Quinone Conducting Redox Polymers for Water Based Secondary Batteries

    International Nuclear Information System (INIS)

    Sterby, Mia; Emanuelsson, Rikard; Huang, Xiao; Gogoll, Adolf; Strømme, Maria; Sjödin, Martin

    2017-01-01

    Lithium-ion technologies show great promise to meet the demands that the transition towards renewable energy sources and the electrification of the transport sector put forward. However, concerns regarding lithium-ion batteries, including limited material resources, high energy consumption during production, and flammable electrolytes, necessitate research on alternative technologies for electrochemical energy storage. Organic materials derived from abundant building blocks and with tunable properties, together with water based electrolytes, could provide safe, inexpensive and sustainable alternatives. In this study, two conducting redox polymers based on poly(3,4-ethylenedioxythiophene) (PEDOT) and a hydroquinone pendant group have been synthesized and characterized in an acidic aqueous electrolyte. The polymers were characterized with regards to kinetics, pH dependence, and mass changes during oxidation and reduction, as well as their conductance. Both polymers show redox matching, i.e. the quinone redox reaction occurs within the potential region where the polymer is conducting, and fast redox conversion that involves proton cycling during pendant group redox conversion. These properties make the presented materials promising candidates as electrode materials for water based all-organic batteries.

  20. Optical redox imaging indices discriminate human breast cancer from normal tissues

    Science.gov (United States)

    Xu, He N.; Tchou, Julia; Feng, Min; Zhao, Huaqing; Li, Lin Z.

    2016-01-01

    Abstract. Our long-term goal was to investigate the potential of incorporating redox imaging technique as a breast cancer (BC) diagnosis component to increase the positive predictive value of suspicious imaging finding and to reduce unnecessary biopsies and overdiagnosis. We previously found that precancer and cancer tissues in animal models displayed abnormal mitochondrial redox state. We also revealed abnormal mitochondrial redox state in cancerous specimens from three BC patients. Here, we extend our study to include biopsies of 16 patients. Tissue aliquots were collected from both apparently normal and cancerous tissues from the affected cancer-bearing breasts shortly after surgical resection. All specimens were snap-frozen and scanned with the Chance redox scanner, i.e., the three-dimensional cryogenic NADH/Fp (reduced nicotinamide adenine dinucleotide/oxidized flavoproteins) fluorescence imager. We found both Fp and NADH in the cancerous tissues roughly tripled that in the normal tissues (predox ratio Fp/(NADH + Fp) was ∼27% higher in the cancerous tissues (predox ratio alone could predict cancer with reasonable sensitivity and specificity. Our findings suggest that the optical redox imaging technique can provide parameters independent of clinical factors for discriminating cancer from noncancer breast tissues in human patients. PMID:27896360

  1. Redox enzymes in the plant plasma membrane and their possible roles

    DEFF Research Database (Denmark)

    Berczi, A.; Møller, I.M.

    2000-01-01

    Purified plasma membrane (PM) vesicles from higher plants contain redox proteins with low-molecular-mass prosthetic groups such as flavins (both FMN and FAD), hemes, metals (Cu, Fe and Mn), thiol groups and possibly naphthoquinone (vitamin K-1), all of which are likely to participate in redox...... protein which has been partially purified from plant PM so far is a high-potential and ascorbate-reducible b-type cytochrome. In co-operation with vitamin K-1 and an NAD(P)H-quinone oxidoreductase, it may participate in trans-PM electron transport....

  2. In Situ Redox Manipulation Field Injection Test Report - Hanford 100-H Area

    International Nuclear Information System (INIS)

    Fruchter, J.S.; Amonette, J.E.; Cole, C.R.

    1996-11-01

    This report presents results of an In Situ Redox Manipulation (ISRM) Field Injection Withdrawal Test performed at the 100-H Area of the US. Department of Energy's (DOE's) Hanford Site in Washington State in Fiscal Year 1996 by researchers at Pacific Northwest National Laboratory (PNNL). The test is part of the overall ISRM project, the purpose of which is to determine the potential for remediating contaminated groundwater with a technology based on in situ manipulation of subsurface reduction-oxidation (redox) conditions. The ISRM technology would be used to treat subsurface contaminants in groundwater zones at DOE sites

  3. Rechargable Lithium-Air Batteries: Investigation of Redox Mediators Using DEMS

    DEFF Research Database (Denmark)

    Christensen, Mathias Kjærgård; Storm, Mie Møller; Norby, Poul

    2016-01-01

    material or electrolyte is being decomposed. This is also seen with Thermally reduced Graphene Oxide (TrGO). The graphene based cathode is interesting as it exhibits a high surface area which in turn increases capacity. Using the additive LiI, functioning as a redox mediator, the discharge curve remains...... is observed without the redox mediator [2]. This results in higher energy densities and ideally higher cyclability due to the lower over-potentials. Using DEMS we have investigated the gas evolved in the process to determine the electron to oxygen ratio using both cathode materials mentioned. As has been...

  4. Electrochemical reverse engineering: A systems-level tool to probe the redox-based molecular communication of biology.

    Science.gov (United States)

    Li, Jinyang; Liu, Yi; Kim, Eunkyoung; March, John C; Bentley, William E; Payne, Gregory F

    2017-04-01

    The intestine is the site of digestion and forms a critical interface between the host and the outside world. This interface is composed of host epithelium and a complex microbiota which is "connected" through an extensive web of chemical and biological interactions that determine the balance between health and disease for the host. This biology and the associated chemical dialogues occur within a context of a steep oxygen gradient that provides the driving force for a variety of reduction and oxidation (redox) reactions. While some redox couples (e.g., catecholics) can spontaneously exchange electrons, many others are kinetically "insulated" (e.g., biothiols) allowing the biology to set and control their redox states far from equilibrium. It is well known that within cells, such non-equilibrated redox couples are poised to transfer electrons to perform reactions essential to immune defense (e.g., transfer from NADH to O 2 for reactive oxygen species, ROS, generation) and protection from such oxidative stresses (e.g., glutathione-based reduction of ROS). More recently, it has been recognized that some of these redox-active species (e.g., H 2 O 2 ) cross membranes and diffuse into the extracellular environment including lumen to transmit redox information that is received by atomically-specific receptors (e.g., cysteine-based sulfur switches) that regulate biological functions. Thus, redox has emerged as an important modality in the chemical signaling that occurs in the intestine and there have been emerging efforts to develop the experimental tools needed to probe this modality. We suggest that electrochemistry provides a unique tool to experimentally probe redox interactions at a systems level. Importantly, electrochemistry offers the