The Role of Human Aldo-Keto Reductases (AKRs in the Metabolic Activation and Detoxication of Polycyclic Aromatic Hydrocarbons: Interconversion of PAH-catechols and PAH o-Quinones

Directory of Open Access Journals (Sweden)

Li eZhang

2012-11-01

Full Text Available Polycyclic aromatic hydrocarbons (PAH are ubiquitous environmental pollutants. They are procarcinogens requiring metabolic activation to elicit their deleterious effects. Aldo-keto reductases (AKR catalyze the oxidation of proximate carcinogenic PAH trans-dihydrodiols to yield electrophilic and redox-active PAH o-quiniones. AKRs are also found to be capable of reducing PAH o-quinones to form PAH catechols. The interconversion of o-quinones and catechols results in the redox cycling of PAH o-quinones to give rise to the generation of reactive oxygen species and subsequent oxidative DNA damage. On the other hand, PAH catechols can be intercepted through phase II metabolism by which PAH o-quinones could be detoxified and eliminated. The aim of the present review is to summarize the role of human AKRs in the metabolic activation/detoxication of PAH and the relevance of phase II conjugation reactions to human lung carcinogenesis.

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.

Role of thiol homeostasis and adenine nucleotide metabolism in the protective effects of fructose in quinone-induced cytotoxicity in rat hepatocytes

NARCIS (Netherlands)

Toxopeus, C.; van Holsteijn, I.; de Winther, M. P.; van den Dobbelsteen, D.; Horbach, G. J.; Blaauboer, B. J.; Noordhoek, J.

1994-01-01

Freshly-isolated rat hepatocytes were exposed in glucose (15 mM) or fructose (5 mM) medium to menadione (2-methyl-1,4-naphthoquinone) (85 microM) or 1,4-naphthoquinone (NQ) (50 microM). Menadione and NQ are closely related quinones and have an approximately equal potential to induce redox cycling.

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 ...

Electrically Reversible Redox-Switchable Polydopamine Films for Regulating Cell Behavior

International Nuclear Information System (INIS)

Tan, Guoxin; Liu, Yan; Wu, Yuxuan; Ouyang, Kongyou; Zhou, Lei; Yu, Peng; Liao, Jinwen; Ning, Chengyun

2017-01-01

Highlights: • The phenolic/quinone groups on polydopamine can redox-switchable reversible under electrical stimulation. • The quinone groups on PDA (oxidized PDA) enhanced cell spreading and proliferation. • The phenolic groups on PDA (reduced PDA) induced cell differentiation. - Abstract: Switchable surfaces that respond to external stimuli are important for regulating cell behavior. The results herein suggest that the redox process of polydopamine (PDA) is a switching reaction between oxidized polydopamine and reduced polydopamine, involving an interconversion of coupled two-proton (2H + ) and two-electron (2e − ) processes. The redox-switchable reversible surface potential arising from the potential-tunable redox reaction of the phenolic and quinone groups on PDA on titanium induced both cell adhesion and spreading. In vitro experiments demonstrated that the quinone groups on PDA greatly enhanced pre-osteoblasts MC3T3-E1 cell spreading and proliferation. Phenolic groups enhanced the induction of differentiation. The proposed methodology may allow further investigation of switchable surfaces for biological and medical applications.

The level of menadione redox-cycling in pancreatic β-cells is proportional to the glucose concentration: Role of NADH and consequences for insulin secretion

Energy Technology Data Exchange (ETDEWEB)

Heart, Emma [Cellular Dynamics Program, Marine Biological Laboratory, Woods Hole, MA, 02543 (United States); Palo, Meridith; Womack, Trayce [Department of Science, United States Coast Guard Academy, New London, CT, 06320 (United States); Smith, Peter J.S. [Cellular Dynamics Program, Marine Biological Laboratory, Woods Hole, MA, 02543 (United States); Institute for Life Sciences, University of Southampton (United Kingdom); Gray, Joshua P., E-mail: Joshua.p.gray@uscga.edu [Cellular Dynamics Program, Marine Biological Laboratory, Woods Hole, MA, 02543 (United States); Department of Science, United States Coast Guard Academy, New London, CT, 06320 (United States)

2012-01-15

Pancreatic β-cells release insulin in response to elevation of glucose from basal (4–7 mM) to stimulatory (8–16 mM) levels. Metabolism of glucose by the β-cell results in the production of low levels of reactive oxygen intermediates (ROI), such as hydrogen peroxide (H{sub 2}O{sub 2}), a newly recognized coupling factor linking glucose metabolism to insulin secretion. However, high and toxic levels of H{sub 2}O{sub 2} inhibit insulin secretion. Menadione, which produces H{sub 2}O{sub 2} via redox cycling mechanism in a dose-dependent manner, was investigated for its effect on β-cell metabolism and insulin secretion in INS-1 832/13, a rat β-cell insulinoma cell line, and primary rodent islets. Menadione-dependent redox cycling and resulting H{sub 2}O{sub 2} production under stimulatory glucose exceeded several-fold those reached at basal glucose. This was paralleled by a differential effect of menadione (0.1–10 μM) on insulin secretion, which was enhanced at basal, but inhibited at stimulatory glucose. Redox cycling of menadione and H{sub 2}O{sub 2} formation was dependent on glycolytically-derived NADH, as inhibition of glycolysis and application of non-glycogenic insulin secretagogues did not support redox cycling. In addition, activity of plasma membrane electron transport, a system dependent in part on glycolytically-derived NADH, was also inhibited by menadione. Menadione-dependent redox cycling was sensitive to the NQO1 inhibitor dicoumarol and the flavoprotein inhibitor diphenylene iodonium, suggesting a role for NQO1 and other oxidoreductases in this process. These data may explain the apparent dichotomy between the stimulatory and inhibitory effects of H{sub 2}O{sub 2} and menadione on insulin secretion. -- Highlights: ► Menadione stimulation or inhibition of insulin secretion is dependent upon applied glucose levels. ► Menadione-dependent H{sub 2}O{sub 2} production is proportional to applied glucose levels. ► Quinone-mediated redox cycling

The level of menadione redox-cycling in pancreatic β-cells is proportional to the glucose concentration: Role of NADH and consequences for insulin secretion

International Nuclear Information System (INIS)

Heart, Emma; Palo, Meridith; Womack, Trayce; Smith, Peter J.S.; Gray, Joshua P.

2012-01-01

Pancreatic β-cells release insulin in response to elevation of glucose from basal (4–7 mM) to stimulatory (8–16 mM) levels. Metabolism of glucose by the β-cell results in the production of low levels of reactive oxygen intermediates (ROI), such as hydrogen peroxide (H 2 O 2 ), a newly recognized coupling factor linking glucose metabolism to insulin secretion. However, high and toxic levels of H 2 O 2 inhibit insulin secretion. Menadione, which produces H 2 O 2 via redox cycling mechanism in a dose-dependent manner, was investigated for its effect on β-cell metabolism and insulin secretion in INS-1 832/13, a rat β-cell insulinoma cell line, and primary rodent islets. Menadione-dependent redox cycling and resulting H 2 O 2 production under stimulatory glucose exceeded several-fold those reached at basal glucose. This was paralleled by a differential effect of menadione (0.1–10 μM) on insulin secretion, which was enhanced at basal, but inhibited at stimulatory glucose. Redox cycling of menadione and H 2 O 2 formation was dependent on glycolytically-derived NADH, as inhibition of glycolysis and application of non-glycogenic insulin secretagogues did not support redox cycling. In addition, activity of plasma membrane electron transport, a system dependent in part on glycolytically-derived NADH, was also inhibited by menadione. Menadione-dependent redox cycling was sensitive to the NQO1 inhibitor dicoumarol and the flavoprotein inhibitor diphenylene iodonium, suggesting a role for NQO1 and other oxidoreductases in this process. These data may explain the apparent dichotomy between the stimulatory and inhibitory effects of H 2 O 2 and menadione on insulin secretion. -- Highlights: ► Menadione stimulation or inhibition of insulin secretion is dependent upon applied glucose levels. ► Menadione-dependent H 2 O 2 production is proportional to applied glucose levels. ► Quinone-mediated redox cycling is dependent on glycolysis

Energetic change of the primary quinone in photosynthetic reaction center. Mutation, delayed fluorescence and model calculations (Theses of the Ph.D. dissertation)

International Nuclear Information System (INIS)

Rinyu, L.

2007-01-01

Complete text of publication follows. Photosynthesis is one of the basic metabolic processes of living organisms. Photosynthesizing species (bacteria, algae and higher class plants) convert the energy of light into other forms of free energy (redox potential, electro- chemical potential of ions and protons and phosphate-potential) which are directly suit- able either to cover the energy need of the vital processes of the cell or to storage. In reaction center (RC) protein of photo- synthetic bacteria, electron transfer is initiated upon light excitation from the excited bacteriochlorophyll dimer (P) to the secondary quinone (Q B ) via bacteriopheophytine (Bph) and the primary quinone (Q A ). In Rhodobacter sphaeroides purple bacteria, both quinones are ubiquinone-10, but due to the different protein environment, their electrochemical properties is highly different. Whereas Q A makes one-electron chemistry, Q B can be doubly reduced to form hydroquinone, Q B H 2 by uptake of two protons. Q B H 2 subsequently leaves the RC and is replaced by an oxidized quinone from to membrane pool. The semiquinones are important intermediates in the quinone reduction cycle of the RC. The redox midpoint potentials of the Q/Q - redox pairs (E m ) are also different: the Q A /Q A - has 60 mV more negative potential than the Q B /Q B - couple (pH 8) to make the (interquinone) electron transfer favorable. For fine tuning of the midpoint redox potentials of the quinones, the protein assures appropriate steric and electrostatic environment. The most important aim of this study was the design and production of reaction center mutants in the binding pocket of the primary quinone to investigate the effect of the amino acids of the protein and lipids of the membrane on the thermodynamics of the primary quinone. The first priority was the determination of the absolute free energy gap between the P* and the P + Q A - states in wild type and mutant reaction centers by comparison of the

The metabolism and toxicity of quinones, quinonimines, quinone methides, and quinone-thioethers.

Science.gov (United States)

Monks, Terrence J; Jones, Douglas C

2002-08-01

Quinones are ubiquitous in nature and constitute an important class of naturally occurring compounds found in plants, fungi and bacteria. Human exposure to quinones therefore occurs via the diet, but also clinically or via airborne pollutants. For example, the quinones of polycyclic aromatic hydrocarbons are prevalent as environmental contaminants and provide a major source of current human exposure to quinones. The inevitable human exposure to quinones, and the inherent reactivity of quinones, has stimulated substantial research on the chemistry and toxicology of these compounds. From a toxicological perspective, quinones possess two principal chemical properties that confer their reactivity in biological systems. Quinones are oxidants and electrophiles, and the relative contribution of these properties to quinone toxicity is influenced by chemical structure, in particular substituent effects. Modification to the quinone nucleus also influences quinone metabolism. This review will therefore focus on the differences in structure and metabolism of quinones, and how such differences influence quinone toxicology. Specific examples will be discussed to illustrate the diverse manner by which quinones interact with biological systems to initiate and propagate a toxic response.

Enhanced biotic and abiotic transformation of Cr(vi) by quinone-reducing bacteria/dissolved organic matter/Fe(iii) in anaerobic environment.

Science.gov (United States)

Huang, Bin; Gu, Lipeng; He, Huan; Xu, Zhixiang; Pan, Xuejun

2016-09-14

This study investigated the simultaneous transformation of Cr(vi) via a closely coupled biotic and abiotic pathway in an anaerobic system of quinone-reducing bacteria/dissolved organic matters (DOM)/Fe(iii). Batch studies were conducted with quinone-reducing bacteria to assess the influences of sodium formate (NaFc), electron shuttling compounds (DOM) and the Fe(iii) on Cr(vi) reduction rates as these chemical species are likely to be present in the environment during in situ bioremediation. Results indicated that the concentration of sodium formate and anthraquinone-2-sodium sulfonate (AQS) had apparently an effect on Cr(vi) reduction. The fastest decrease in rate for incubation supplemented with 5 mM sodium formate and 0.8 mM AQS showed that Fe(iii)/DOM significantly promoted the reduction of Cr(vi). Presumably due to the presence of more easily utilizable sodium formate, DOM and Fe(iii) have indirect Cr(vi) reduction capability. The coexisting cycles of Fe(ii)/Fe(iii) and DOM(ox)/DOM(red) exhibited a higher redox function than the individual cycle, and their abiotic coupling action can significantly enhance Cr(vi) reduction by quinone-reducing bacteria.

Redox regulation of the Calvin-Benson cycle: something old, something new

Directory of Open Access Journals (Sweden)

Laure eMichelet

2013-11-01

Full Text Available Reversible redox post-translational modifications such as oxido-reduction of disulfide bonds, S-nitrosylation and S-glutathionylation, play a prominent role in the regulation of cell metabolism and signaling in all organisms. These modifications are mainly controlled by members of the thioredoxin and glutaredoxin families. Early studies in photosynthetic organisms have identified the Calvin-Benson cycle, the photosynthetic pathway responsible for carbon assimilation, as a redox regulated process. Indeed, 4 out of 11 enzymes of the cycle were shown to have a low activity in the dark and to be activated in the light through thioredoxin-dependent reduction of regulatory disulfide bonds. The underlying molecular mechanisms were extensively studied at the biochemical and structural level. Unexpectedly, recent biochemical and proteomic studies have suggested that all enzymes of the cycle and several associated regulatory proteins may undergo redox regulation through multiple redox post-translational modifications including glutathionylation and nitrosylation. The aim of this review is to detail the well-established mechanisms of redox regulation of Calvin-Benson cycle enzymes as well as the most recent reports indicating that this pathway is tightly controlled by multiple interconnected redox post-translational modifications. This redox control is likely allowing fine tuning of the Calvin-Benson cycle required for adaptation to varying environmental conditions, especially during responses to biotic and abiotic stresses.

Dimensional behavior of Ni-YSZ composites during redox cycling

DEFF Research Database (Denmark)

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

2009-01-01

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

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

Menadione enhances oxyradical formation in earthworm extracts: vulnerability of earthworms to quinone toxicity

International Nuclear Information System (INIS)

Osman, A.M.; Besten, P.J. den; Noort, P.C.M. van

2003-01-01

NAD(P)H-cytochrome c reductase activities have been determined in the earthworms, L. rubellus and A. chlorotica, extracts. Menadione (0.35 mM, maximum concentration tested) was found to stimulate the rates of NADPH- and NADH-dependent cytochrome c reduction by three- and twofold, respectively. Superoxide dismutase (SOD) inhibited completely this menadione-mediated stimulation, suggesting that ·O 2 - is involved in the redox cycling of menadione. However, SOD had no effect on the basal activity (activity in the absence of quinone) in the case of NADH-dependent cytochrome c reduction, whereas it partially inhibited the basal activity of NADPH-cytochrome c reduction. This indicates direct electron transfer in the former case and the formation of superoxide anion in the latter. DT-diaphorase, measured as the dicumarol-inhibitable part of menadione reductase activity, was not detectable in the earthworms' extracts. In contrast, it was found that DT-diaphorase represents about 70% of the menadione reductase activities in the freshwater mussel, Dreissena polymorpha. The results of this work suggest that earthworms, compared with mussels, could be more vulnerable to oxidative stress from quinones due to lack, or very low level of DT-diaphorase, an enzyme considered to play a significant role in the detoxification of quinones. On the contrary, mussels have efficient DT-diaphorase, which catalyzes two-electron reduction of menadione directly to hydroquinone, thus circumventing the formation of semiquinone

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.

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

Redox Changes During the Cell Cycle in the Embryonic Root Meristem of Arabidopsis thaliana.

Science.gov (United States)

de Simone, Ambra; Hubbard, Rachel; de la Torre, Natanael Viñegra; Velappan, Yazhini; Wilson, Michael; Considine, Michael J; Soppe, Wim J J; Foyer, Christine H

2017-12-20

The aim of this study was to characterize redox changes in the nuclei and cytosol occurring during the mitotic cell cycle in the embryonic roots of germinating Arabidopsis seedlings, and to determine how redox cycling was modified in mutants with a decreased capacity for ascorbate synthesis. Using an in vivo reduction-oxidation (redox) reporter (roGFP2), we show that transient oxidation of the cytosol and the nuclei occurred at G1 in the synchronized dividing cells of the Arabidopsis root apical meristem, with reduction at G2 and mitosis. This redox cycle was absent from low ascorbate mutants in which nuclei were significantly more oxidized than controls. The cell cycle-dependent increase in nuclear size was impaired in the ascorbate-deficient mutants, which had fewer cells per unit area in the root proliferation zone. The transcript profile of the dry seeds and size of the imbibed seeds was strongly influenced by low ascorbate but germination, dormancy release and seed aging characteristics were unaffected. These data demonstrate the presence of a redox cycle within the plant cell cycle and that the redox state of the nuclei is an important factor in cell cycle progression. Controlled oxidation is a key feature of the early stages of the plant cell cycle. However, sustained mild oxidation restricts nuclear functions and impairs progression through the cell cycle leading to fewer cells in the root apical meristem. Antioxid. Redox Signal. 27, 1505-1519.

Respiratory quinones in Archaea: phylogenetic distribution and application as biomarkers in the marine environment.

Science.gov (United States)

Elling, Felix J; Becker, Kevin W; Könneke, Martin; Schröder, Jan M; Kellermann, Matthias Y; Thomm, Michael; Hinrichs, Kai-Uwe

2016-02-01

The distribution of respiratory quinone electron carriers among cultivated organisms provides clues on both the taxonomy of their producers and the redox processes these are mediating. Our study of the quinone inventories of 25 archaeal species belonging to the phyla Eury-, Cren- and Thaumarchaeota facilitates their use as chemotaxonomic markers for ecologically important archaeal clades. Saturated and monounsaturated menaquinones with six isoprenoid units forming the alkyl chain may serve as chemotaxonomic markers for Thaumarchaeota. Other diagnostic biomarkers are thiophene-bearing quinones for Sulfolobales and methanophenazines as functional quinone analogues of the Methanosarcinales. The ubiquity of saturated menaquinones in the Archaea in comparison to Bacteria suggests that these compounds may represent an ancestral and diagnostic feature of the Archaea. Overlap between quinone compositions of distinct thermophilic and halophilic archaea and bacteria may indicate lateral gene transfer. The biomarker potential of thaumarchaeal quinones was exemplarily demonstrated on a water column profile of the Black Sea. Both, thaumarchaeal quinones and membrane lipids showed similar distributions with maxima at the chemocline. Quinone distributions indicate that Thaumarchaeota dominate respiratory activity at a narrow interval in the chemocline, while they contribute only 9% to the microbial biomass at this depth, as determined by membrane lipid analysis. © 2015 Society for Applied Microbiology and John Wiley & Sons Ltd.

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

Science.gov (United States)

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

2016-01-01

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

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

Science.gov (United States)

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

2016-12-01

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

Redox cycles of vitamin E: Hydrolysis and ascorbic acid dependent reduction of 8a-(alkyldioxy)tocopherones

International Nuclear Information System (INIS)

Liebler, D.C.; Kaysen, K.L.; Kennedy, T.A.

1989-01-01

Oxidation of the biological antioxidant α-tocopherol (vitamin E; TH) by peroxyl radicals yields 8a-(alkyldioxy)tocopherones, which either may hydrolyze to α-tocopheryl quinone (TQ) or may be reduced by ascorbic acid to regenerate TH. To define the chemistry of this putative two-electron TH redox cycle, we studied the hydrolysis and reduction of 8a-[(2,4-dimethyl-1-nitrilopent-2-yl)dioxyl]tocopherone (1) in acetonitrile/buffer mixtures and in phospholipid liposomes. TQ formation in acetonitrile/buffer mixtures, which was monitored spectrophotometrically, declined with increasing pH and could not be detected above pH 4. The rate of TQ formation from 1 first increased with time and then decreased in a first-order terminal phase. Rearrangement of 8a-hydroxy-α-tocopherone (2) to TQ displayed first-order kinetics identical with the terminal phase for TQ formation from 1. Both rate constants increased with decreasing pH. Hydrolysis of 1 in acetonitrile/H 2 18 O yielded [ 18 O]TQ. These observations suggest that 1 loses the 8a-(alkyldioxy) moiety to produce the tocopherone cation (T + ), which hydrolyzes to 2, the TQ-forming intermediate. Incubation of either 1 or 2 with ascorbic acid in acetonitrile/buffer yielded TH. Reduction of both 1 and 2 decreased with increasing pH. In phosphatidylcholine liposomes at pH 7, approximately 10% of the T + generated from 1 was reduced to TH by 5 mM ascorbic acid. The results collectively demonstrate that T + is the ascorbic acid reducible intermediate in a two-electron TH redox cycle, a process that probably would require biocatalysis to proceed in biological membranes

Bioinspired aerobic oxidation of secondary amines and nitrogen heterocycles with a bifunctional quinone catalyst.

Science.gov (United States)

Wendlandt, Alison E; Stahl, Shannon S

2014-01-08

Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here we report a novel bioinspired quinone catalyst system consisting of 1,10-phenanthroline-5,6-dione/ZnI2 that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts.

Menadione enhances oxyradical formation in earthworm extracts: vulnerability of earthworms to quinone toxicity

Energy Technology Data Exchange (ETDEWEB)

Osman, A.M.; Besten, P.J. den; Noort, P.C.M. van

2003-10-08

NAD(P)H-cytochrome c reductase activities have been determined in the earthworms, L. rubellus and A. chlorotica, extracts. Menadione (0.35 mM, maximum concentration tested) was found to stimulate the rates of NADPH- and NADH-dependent cytochrome c reduction by three- and twofold, respectively. Superoxide dismutase (SOD) inhibited completely this menadione-mediated stimulation, suggesting that {center_dot}O{sub 2}{sup -} is involved in the redox cycling of menadione. However, SOD had no effect on the basal activity (activity in the absence of quinone) in the case of NADH-dependent cytochrome c reduction, whereas it partially inhibited the basal activity of NADPH-cytochrome c reduction. This indicates direct electron transfer in the former case and the formation of superoxide anion in the latter. DT-diaphorase, measured as the dicumarol-inhibitable part of menadione reductase activity, was not detectable in the earthworms' extracts. In contrast, it was found that DT-diaphorase represents about 70% of the menadione reductase activities in the freshwater mussel, Dreissena polymorpha. The results of this work suggest that earthworms, compared with mussels, could be more vulnerable to oxidative stress from quinones due to lack, or very low level of DT-diaphorase, an enzyme considered to play a significant role in the detoxification of quinones. On the contrary, mussels have efficient DT-diaphorase, which catalyzes two-electron reduction of menadione directly to hydroquinone, thus circumventing the formation of semiquinone.

TCA Cycle Defects and Cancer: When Metabolism Tunes Redox State.

Science.gov (United States)

Cardaci, Simone; Ciriolo, Maria Rosa

2012-01-01

Inborn defects of the tricarboxylic acid (TCA) cycle enzymes have been known for more than twenty years. Until recently, only recessive mutations were described which, although resulted in severe multisystem syndromes, did not predispose to cancer onset. In the last ten years, a causal role in carcinogenesis has been documented for inherited and acquired alterations in three TCA cycle enzymes, succinate dehydrogenase (SDH), fumarate hydratase (FH), and isocitrate dehydrogenase (IDH), pointing towards metabolic alterations as the underlying hallmark of cancer. This paper summarizes the neoplastic alterations of the TCA cycle enzymes focusing on the generation of pseudohypoxic phenotype and the alteration of epigenetic homeostasis as the main tumor-promoting effects of the TCA cycle affecting defects. Moreover, we debate on the ability of these mutations to affect cellular redox state and to promote carcinogenesis by impacting on redox biology.

TCA Cycle Defects and Cancer: When Metabolism Tunes Redox State

Directory of Open Access Journals (Sweden)

Simone Cardaci

2012-01-01

Full Text Available Inborn defects of the tricarboxylic acid (TCA cycle enzymes have been known for more than twenty years. Until recently, only recessive mutations were described which, although resulted in severe multisystem syndromes, did not predispose to cancer onset. In the last ten years, a causal role in carcinogenesis has been documented for inherited and acquired alterations in three TCA cycle enzymes, succinate dehydrogenase (SDH, fumarate hydratase (FH, and isocitrate dehydrogenase (IDH, pointing towards metabolic alterations as the underlying hallmark of cancer. This paper summarizes the neoplastic alterations of the TCA cycle enzymes focusing on the generation of pseudohypoxic phenotype and the alteration of epigenetic homeostasis as the main tumor-promoting effects of the TCA cycle affecting defects. Moreover, we debate on the ability of these mutations to affect cellular redox state and to promote carcinogenesis by impacting on redox biology.

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.

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

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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.

NQO1-dependent redox cycling of idebenone: effects on cellular redox potential and energy levels.

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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.

High-capacity aqueous zinc batteries using sustainable quinone electrodes

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Zhao, Qing; Huang, Weiwei; Luo, Zhiqiang; Liu, Luojia; Lu, Yong; Li, Yixin; Li, Lin; Hu, Jinyan; Ma, Hua; Chen, Jun

2018-01-01

Quinones, which are ubiquitous in nature, can act as sustainable and green electrode materials but face dissolution in organic electrolytes, resulting in fast fading of capacity and short cycle life. We report that quinone electrodes, especially calix[4]quinone (C4Q) in rechargeable metal zinc batteries coupled with a cation-selective membrane using an aqueous electrolyte, exhibit a high capacity of 335 mA h g−1 with an energy efficiency of 93% at 20 mA g−1 and a long life of 1000 cycles with a capacity retention of 87% at 500 mA g−1. The pouch zinc batteries with a respective depth of discharge of 89% (C4Q) and 49% (zinc anode) can deliver an energy density of 220 Wh kg−1 by mass of both a C4Q cathode and a theoretical Zn anode. We also develop an electrostatic potential computing method to demonstrate that carbonyl groups are active centers of electrochemistry. Moreover, the structural evolution and dissolution behavior of active materials during discharge and charge processes are investigated by operando spectral techniques such as IR, Raman, and ultraviolet-visible spectroscopies. Our results show that batteries using quinone cathodes and metal anodes in aqueous electrolyte are reliable approaches for mass energy storage. PMID:29511734

Dicumarol inhibition of NADPH:quinone oxidoreductase induces growth inhibition of pancreatic cancer via a superoxide-mediated mechanism.

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Cullen, Joseph J; Hinkhouse, Marilyn M; Grady, Matthew; Gaut, Andrew W; Liu, Jingru; Zhang, Yu Ping; Weydert, Christine J Darby; Domann, Frederick E; Oberley, Larry W

2003-09-01

NADPH:quinone oxidoreductase (NQO(1)), a homodimeric, ubiquitous, flavoprotein, catalyzes the two-electron reduction of quinones to hydroquinones. This reaction prevents the one-electron reduction of quinones by cytochrome P450 reductase and other flavoproteins that would result in oxidative cycling with generation of superoxide (O(2)(.-)). NQO(1) gene regulation may be up-regulated in some tumors to accommodate the needs of rapidly metabolizing cells to regenerate NAD(+). We hypothesized that pancreatic cancer cells would exhibit high levels of this enzyme, and inhibiting it would suppress the malignant phenotype. Reverse transcription-PCR, Western blots, and activity assays demonstrated that NQO(1) was up-regulated in the pancreatic cancer cell lines tested but present in very low amounts in the normal human pancreas. To determine whether inhibition of NQO(1) would alter the malignant phenotype, MIA PaCa-2 pancreatic cancer cells were treated with a selective inhibitor of NQO(1), dicumarol. Dicumarol increased intracellular production of O(2)(.-), as measured by hydroethidine staining, and inhibited cell growth. Both of these effects were blunted with infection of an adenoviral vector containing the cDNA for manganese superoxide dismutase. Dicumarol also inhibited cell growth, plating efficiency, and growth in soft agar. We conclude that inhibition of NQO(1) increases intracellular O(2)(.-) production and inhibits the in vitro malignant phenotype of pancreatic cancer. These mechanisms suggest that altering the intracellular redox environment of pancreatic cancer cells may inhibit growth and delineate a potential strategy directed against pancreatic cancer.

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

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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.

Modification of quinone electrochemistry by the proteins in the biological electron transfer chains: examples from photosynthetic reaction centers

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Gunner, M. R.; Madeo, Jennifer; Zhu, Zhenyu

2009-01-01

Quinones such as ubiquinone are the lipid soluble electron and proton carriers in the membranes of mitochondria, chloroplasts and oxygenic bacteria. Quinones undergo controlled redox reactions bound to specific sites in integral membrane proteins such as the cytochrome bc1 oxidoreductase. The quinone reactions in bacterial photosynthesis are amongst the best characterized, presenting a model to understand how proteins modulate cofactor chemistry. The free energy of ubiquinone redox reactions in aqueous solution and in the QA and QB sites of the bacterial photosynthetic reaction centers (RCs) are compared. In the primary QA site ubiquinone is reduced only to the anionic semiquinone (Q•−) while in the secondary QB site the product is the doubly reduced, doubly protonated quinol (QH2). The ways in which the protein modifies the relative energy of each reduced and protonated intermediate are described. For example, the protein stabilizes Q•− while destabilizing Q= relative to aqueous solution through electrostatic interactions. In addition, kinetic and thermodynamic mechanisms for stabilizing the intermediate semiquinones are compared. Evidence for the protein sequestering anionic compounds by slowing both on and off rates as well as by binding the anion more tightly is reviewed. PMID:18979192

Quinones: reactions with hemoglobin, effects within erythrocytes and potential for antimalarial development

International Nuclear Information System (INIS)

Denny, B.J.

1986-01-01

The focus of this research was to characterize the interactions of some simple quinone like compounds with purified hemoglobin and to study the effects of these compounds within erythrocytes. It is proposed that these sorts of agents can have an antimalarial effect. The simplest compounds chosen for study were benzoquinone, methylquinone (toluquinone) and hydroquinone. When 14 C-quinone was reacted with purified hemoglobin (Hb) there was rapid binding of the first two moles of substrate per Hb molecule. An unusual property of the modified Hb's is that in the presence of a redox sensitive agent such as cytochrome c they are capable of generating superoxide anions. Within erythrocytes, quinone and toluquinone which differ only by a single methyl group have completely different effects. Toluquinone causes the cells to hemolyse and the effect was enhanced when the erythrocyte superoxide dismutase was inhibited; the effect was diminished when scavengers of activated oxygen such as histidine, mannitol and vital E were present. Benzoquinone on the other hand did not cause the cells to hemolyse and instead appeared to protect the cells from certain hemolytic stresses. Growth of malaria parasites in erythrocytes has been shown to be inhibited by activated forms of oxygen, also some quinone like agents in the past have been shown to inhibit the parasite's metabolism. An initial experiment with erythrocytes infected with malaria parasites showed that quinone and toluquinone could both inhibit the growth rate of parasites

An assessment of the role of redox cycling in mediating the toxicity of paraquat and nitrofurantoin

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Adam, A.; Cohen, G.M. (Univ. of London (England)); Smith, L.L. (Imperial Chemical Industries plc, Cheshire (England))

1990-04-01

The abilities of paraquat, diquat, and nitrofurantoin to undergo cyclic oxidation and reduction with rat microsomal systems have been assessed and compared to that of the potent redox cycler, menadione. Diquat and menadione were found to be potent redox cyclers with comparable abilities to elicit a nonstoichiometric increase in both the consumption of O{sub 2} and the oxidation of NADPH, compared to the amounts of substrate added. In contrast, paraquat and nitrofurantoin redox cycled poorly, being an order of magnitude less potent than either diquat or menadione. This was reflected in kinetic studies using lung and liver microsomes. In order to assess redox cycling of the substrates in an intact lung system, the O{sub 2} consumption of rat lung slices was measured in the presence of all four compounds. A small increase in lung slice O{sub 2} uptake was observed with paraquat in the first 2.5 hr of incubation, possibly because of redox cycling of a high intracellular concentration of paraquat resulting from active accumulation into target cells. This stimulation in O{sub 2} uptake was no longer observed when slices were incubated for a longer period or with higher paraquat concentrations (10{sup {minus}4}M), possibly because of toxic effects in target cells. These results together with the poor ability to redox cycle with microsomes and the absence of a specific uptake system highlight the problem of associating redox cycling and oxidative stress in the mechanism of nitrofurantoin toxicity.

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

Garlic protects the glutathione redox cycle in irradiated rats

International Nuclear Information System (INIS)

Abu-Ghadeer, A.R.M.; Osman, S.A.A.; Abbady, M.M.

1999-01-01

The aim of the present study is to evaluate the possible radioprotective role of garlic oil on the glutathione redox cycle (GSH, GSH-Px, GR and G6-PD) in blood and tissues (liver, spleen and intestine) of irradiated rats. Garlic oil was orally administered to rats (100 mg/Kg- b.w.) for 7 days before exposure to a fractionated of whole body gamma irradiation up to 9 Gy (3 Gy X 3 at 2 days intervals) and during the whole period of irradiation. The data showed that radiation exposure caused significant inhibition of the biochemical parameters in blood and tissue of irradiated rats all over the investigation periods (3,7 and 15 days). Garlic oil ameliorated the decrease in the tested parameters with noticeable effect on the 15 Th. day after radiation exposure. It is concluded that garlic oil could control the radiation induced changes in the glutathione redox cycle and provided some radioprotective effect

Microfluidic sensor for ultra high redox cycling amplification for highly selective electrochemical measurements

NARCIS (Netherlands)

Odijk, Mathieu; Straver, Martin; Olthuis, Wouter; van den Berg, Albert

2011-01-01

In this contribution a SU8/glass-based microfluidic sensor is described with two closely spaced parallel electrodes for highly selective measurements using the redox cycling (RC) effect. Using this sensor, a RC amplification of ~2000x is measured using the ferrocyanide redox couple, which is much

Immunomodulatory Effects of Diterpene Quinone Derivatives from the Roots of Horminum pyrenaicum in Human PBMC

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K. Becker

2018-01-01

Full Text Available Several phytochemicals were shown to interfere with redox biology in the human system. Moreover, redox biochemistry is crucially involved in the orchestration of immunological cascades. When screening for immunomodulatory compounds, the two interferon gamma- (IFN-γ- dependent immunometabolic pathways of tryptophan breakdown via indoleamine 2,3-dioxygenase-1 (IDO-1 and neopterin formation by GTP-cyclohydrolase 1 (GTP-CH-I represent prominent targets, as IFN-γ-related signaling is strongly sensitive to oxidative triggers. Herein, the analysis of these pathway activities in human peripheral mononuclear cells was successfully applied in a bioactivity-guided fractionation strategy to screen for anti-inflammatory substances contained in the root of Horminum (H. pyrenaicum L. (syn. Dragon’s mouth, the only representative of the monophyletic genus Horminum. Four abietane diterpene quinone derivatives (horminone, 7-O-acetylhorminone, inuroyleanol and its 15,16-dehydro-derivative, a novel natural product, two nor-abietane diterpene quinones (agastaquinone and 3-deoxyagastaquinone and two abeo 18 (4 → 3 abietane diterpene quinones (agastol and its 15,16-dehydro-derivative could be identified. These compounds were able to dose-dependently suppress the above mentioned pathways with different potency. Beside the description of new active compounds, this study demonstrates the feasibility of integrating IDO-1 and GTP-CH-I activity in the search for novel anti-inflammatory compounds, which can then be directed towards a more detailed mode of action analysis.

Quinone exchange at the A{sub 1} site in photosystem I [PSI

Energy Technology Data Exchange (ETDEWEB)

Barkoff, A.; Brunkan, N.; Snyder, S.W.; Ostafin, A.; Werst, M.; Thurnauer, M.C. [Argonne National Lab., IL (United States); Biggins, J. [Brown Univ., Providence, RI (United States)

1995-12-31

Quinones play an essential role in light-induced electron transport in photosynthetic reaction centers (RC). Study of quinone binding within the protein matrix of the RC is a focal point of understanding the biological optimization of photosynthesis. In plant and cyanobacterial PSI, phylloquinone (K{sub 1}) is believed to be the secondary electron acceptor, A{sub 1}, similar to Q{sub a} in the purple bacterial RC. Photoinduced electron transfer is initiated by reduction of the electron acceptor (A{sub 0}), a chlorophyll species, by the photoexcited primary donor *P{sub 700}. A{sub 1} acts as a transient redox intermediate between A{sub 0} and the iron-sulfur centers (FeS). We have examined the characteristic PSI electron spin polarized (ESP) electron paramagnetic resonance (EPR) signal as a marker of the interacting radical pairs developed during electron transfer.

The inhibition mechanisms of quinones and phenols present in wood for the vinyl polymerization

International Nuclear Information System (INIS)

Nobashi, Kenzo; Yokota, Tokuo

1977-01-01

The inhibitory effects and mechanisms of the quinones and phenols present in wood for the vinyl polymerization initiated with γ-rays and other initiation systems were investigated. The results obtained are summarized as follows; (1) Although phenolic compounds like isotaxiresinol inhibit the γ-ray initiated polymerization of methyl methacrylate (MMA) under the presence of air, they have no inhibitory effects in vacuo. On the other hand, o-benzoquinone and mansonones show strong inhibitory or retarding effects in vacuo. These facts indicate that oxygen may be important for the phenols to inhibit the vinyl polymerization. (2) It is shown qualitatively that there is a relationship between the strength of inhibitory action of quinones and their normal redox potentials. (3) PMMA produced under the presence of o-benzoquinone is found to include the fraction having extremely large chain length based on gel permeation chromatogram. (4) Based on the reaction products of orthoquinones and azobisisobutyronitrile, which was assumed as a model of polymer radicals, the inhibition reaction with polymer chain radical is concluded to take place upon the oxygen atoms of the quinones. (auth.)

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

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

2016-03-21

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

Measuring protection of aromatic wine thiols from oxidation by competitive reactions vs wine preservatives with ortho-quinones.

Science.gov (United States)

Nikolantonaki, Maria; Magiatis, Prokopios; Waterhouse, Andrew L

2014-11-15

Quinones are central intermediates in wine oxidation that can degrade the quality of wine by reactions with varietal thiols, such as 3-sulfanylhexanol, decreasing desirable aroma. Protection by wine preservatives (sulphur dioxide, glutathione, ascorbic acid and model tannin, phloroglucinol) was assessed by competitive sacrificial reactions with 4-methyl-1,2-benzoquinone, quantifying products and ratios by HPLC-UV-MS. Regioselectivity was assessed by product isolation and identification by NMR spectroscopy. Nucleophilic addition reactions compete with two electron reduction of quinones by sulphur dioxide or ascorbic acid, and both routes serve as effective quenching pathways, but minor secondary products from coupled redox reactions between the products and reactants are also observed. The wine preservatives were all highly reactive and thus all very protective against 3-sulfanylhexanol loss to the quinone, but showed only additive antioxidant effects. Confirmation of these reaction rates and pathways in wine is needed to assess the actual protective action of each tested preservative. Copyright © 2014 Elsevier Ltd. All rights reserved.

Structure activity study on the quinone/quinone methide chemistry of flavonoids

NARCIS (Netherlands)

Awad, H.M.; Boersma, M.G.; Boeren, S.; Bladeren, van P.J.; Vervoort, J.; Rietjens, I.M.C.M.

2001-01-01

A structure-activity study on the quinone/quinone methide chemistry of a series of 3',4'-dihydroxyflavonoids was performed. Using the glutathione trapping method followed by HPLC, 1H NMR, MALDI-TOF, and LC/MS analysis to identify the glutathionyl adducts, the chemical behavior of the

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.

Electrocoagulation of Quinone Pigments

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Duang Buddhasukh

2006-07-01

Full Text Available Some representative quinones, viz. one naphthoquinone (plumbagin and five anthraquinones (alizarin, purpurin, chrysazin, emodin, and anthrarufin, were subjected to electrocoagulation. It was found that the rate and extent of coagulation of these compounds appears to correlate with the number and relative position of their phenolic substituent groups, and that all of the coagulated quinones could be recovered. Attempts were then made to electrochemically isolate three quinones, namely plumbagin, morindone and erythrolaccin, from natural sources.

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

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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.

Quinone-Catalyzed Selective Oxidation of Organic Molecules

Science.gov (United States)

Wendlandt, Alison E.

2016-01-01

Lead In Quinones are common stoichiometric reagents in organic chemistry. High potential para-quinones, such as DDQ and chloranil, are widely used and typically promote hydride abstraction. In recent years, many catalytic applications of these methods have been achieved by using transition metals, electrochemistry or O2 to regenerate the oxidized quinone in situ. Complementary studies have led to the development of a different class of quinones that resemble the ortho-quinone cofactors in Copper Amine Oxidases and mediate efficient and selective aerobic and/or electrochemical dehydrogenation of amines. The latter reactions typically proceed via electrophilic transamination and/or addition-elimination reaction mechanisms, rather than hydride abstraction pathways. The collective observations show that the quinone structure has a significant influence on the reaction mechanism and have important implications for the development of new quinone reagents and quinone-catalyzed transformations. PMID:26530485

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.

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.

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.

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

Energy Technology Data Exchange (ETDEWEB)

Huynh, Mioy T.; Anson, Colin W.; Cavell, Andrew C.; Stahl, Shannon S.; Hammes-Schiffer, Sharon

2016-11-10

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

Solar fuel processing efficiency for ceria redox cycling using alternative oxygen partial pressure reduction methods

International Nuclear Information System (INIS)

Lin, Meng; Haussener, Sophia

2015-01-01

Solar-driven non-stoichiometric thermochemical redox cycling of ceria for the conversion of solar energy into fuels shows promise in achieving high solar-to-fuel efficiency. This efficiency is significantly affected by the operating conditions, e.g. redox temperatures, reduction and oxidation pressures, solar irradiation concentration, or heat recovery effectiveness. We present a thermodynamic analysis of five redox cycle designs to investigate the effects of working conditions on the fuel production. We focused on the influence of approaches to reduce the partial pressure of oxygen in the reduction step, namely by mechanical approaches (sweep gassing or vacuum pumping), chemical approaches (chemical scavenger), and combinations thereof. The results indicated that the sweep gas schemes work more efficient at non-isothermal than isothermal conditions, and efficient gas phase heat recovery and sweep gas recycling was important to ensure efficient fuel processing. The vacuum pump scheme achieved best efficiencies at isothermal conditions, and at non-isothermal conditions heat recovery was less essential. The use of oxygen scavengers combined with sweep gas and vacuum pump schemes further increased the system efficiency. The present work can be used to predict the performance of solar-driven non-stoichiometric redox cycles and further offers quantifiable guidelines for system design and operation. - Highlights: • A thermodynamic analysis was conducted for ceria-based thermochemical cycles. • Five novel cycle designs and various operating conditions were proposed and investigated. • Pressure reduction method affects optimal operating conditions for maximized efficiency. • Chemical oxygen scavenger proves to be promising in further increasing efficiency. • Formulation of quantifiable design guidelines for economical competitive solar fuel processing

UV-Vis spectrophotometry of quinone flow battery electrolyte for in situ monitoring and improved electrochemical modeling of potential and quinhydrone formation.

Science.gov (United States)

Tong, Liuchuan; Chen, Qing; Wong, Andrew A; Gómez-Bombarelli, Rafael; Aspuru-Guzik, Alán; Gordon, Roy G; Aziz, Michael J

2017-12-06

Quinone-based aqueous flow batteries provide a potential opportunity for large-scale, low-cost energy storage due to their composition from earth abundant elements, high aqueous solubility, reversible redox kinetics and their chemical tunability such as reduction potential. In an operating flow battery utilizing 9,10-anthraquinone-2,7-disulfonic acid, the aggregation of an oxidized quinone and a reduced hydroquinone to form a quinhydrone dimer causes significant variations from ideal solution behavior and of optical absorption from the Beer-Lambert law. We utilize in situ UV-Vis spectrophotometry to establish (a), quinone, hydroquinone and quinhydrone molar attenuation profiles and (b), an equilibrium constant for formation of the quinhydrone dimer (K QHQ ) ∼ 80 M -1 . We use the molar optical attenuation profiles to identify the total molecular concentration and state of charge at arbitrary mixtures of quinone and hydroquinone. We report density functional theory calculations to support the quinhydrone UV-Vis measurements and to provide insight into the dimerization conformations. We instrument a quinone-bromine flow battery with a Pd-H reference electrode in order to demonstrate how complexation in both the negative (quinone) and positive (bromine) electrolytes directly impacts measured half-cell and full-cell voltages. This work shows how accounting for electrolyte complexation improves the accuracy of electrochemical modeling of flow battery electrolytes.

Ceria-based electrospun fibers for renewable fuel production via two-step thermal redox cycles for carbon dioxide splitting.

Science.gov (United States)

Gibbons, William T; Venstrom, Luke J; De Smith, Robert M; Davidson, Jane H; Jackson, Gregory S

2014-07-21

Zirconium-doped ceria (Ce(1-x)Zr(x)O2) was synthesized through a controlled electrospinning process as a promising approach to cost-effective, sinter-resistant material structures for high-temperature, solar-driven thermochemical redox cycles. To approximate a two-step redox cycle for solar fuel production, fibrous Ce(1-x)Zr(x)O2 with relatively low levels of Zr-doping (0 rates of O2 release during reduction and CO production during reoxidation and by assessing post-cycling fiber crystallite sizes and surface areas. Sintering increases with reduction temperature but occurs primarily along the fiber axes. Even after 108 redox cycles with reduction at 1400 °C and oxidation with CO2 at 800 °C, the fibers maintain their structure with surface areas of ∼0.3 m(2) g(-1), higher than those observed in the literature for other ceria-based structures operating at similarly high temperature conditions. Total CO production and peak production rate stabilize above 3.0 mL g(-1) and 13.0 mL min(-1) g(-1), respectively. The results show the potential for electrospun oxides as sinter-resistant material structures with adequate surface area to support rapid CO2 splitting in solar thermochemical redox cycles.

The role of quinone reductase (NQO1) and quinone chemistry in quercetin cytotoxicity

NARCIS (Netherlands)

Gliszczynska-Swiglo, A.; Woude, van der H.; Haan, de L.H.J.; Tyrakowska, B.; Aarts, J.M.M.J.G.; Rietjens, I.M.C.M.

2003-01-01

The effects of quercetin on viability and proliferation of Chinese Hamster Ovary (CHO) cells and CHO cells overexpressing human quinone reductase (CHO+NQO1) were studied to investigate the involvement of the pro-oxidant quinone chemistry of quercetin. The toxicity of menadione was significantly

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

Science.gov (United States)

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

2013-06-01

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

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....

Study of dimensional changes during redox cycling of oxygen carrier materials for chemical looping combustion

NARCIS (Netherlands)

Fossdal, A.; Darell, O.; Lambert, A.; Schols, E.; Comte, E.; Leenman, R.N.; Blom, R.

2015-01-01

Dimensional and phase changes of four candidate oxygen carrier materials for chemical looping combustion are investigated by dilatometry and high-temperature X-ray diffraction during four redox cycles. NiO/Ni2AlO4 does not exhibit significant dimensional changes during cycling, and it is shown that

A strategy for selective detection based on interferent depleting and redox cycling using the plane-recessed microdisk array electrodes

International Nuclear Information System (INIS)

Zhu Feng; Yan Jiawei; Lu Miao; Zhou Yongliang; Yang Yang; Mao Bingwei

2011-01-01

Highlights: → A novel strategy based on a combination of interferent depleting and redox cycling is proposed for the plane-recessed microdisk array electrodes. → The strategy break up the restriction of selectively detecting a species that exhibits reversible reaction in a mixture with one that exhibits an irreversible reaction. → The electrodes enhance the current signal by redox cycling. → The electrodes can work regardless of the reversibility of interfering species. - Abstract: The fabrication, characterization and application of the plane-recessed microdisk array electrodes for selective detection are demonstrated. The electrodes, fabricated by lithographic microfabrication technology, are composed of a planar film electrode and a 32 x 32 recessed microdisk array electrode. Different from commonly used redox cycling operating mode for array configurations such as interdigitated array electrodes, a novel strategy based on a combination of interferent depleting and redox cycling is proposed for the electrodes with an appropriate configuration. The planar film electrode (the plane electrode) is used to deplete the interferent in the diffusion layer. The recessed microdisk array electrode (the microdisk array), locating within the diffusion layer of the plane electrode, works for detecting the target analyte in the interferent-depleted diffusion layer. In addition, the microdisk array overcomes the disadvantage of low current signal for a single microelectrode. Moreover, the current signal of the target analyte that undergoes reversible electron transfer can be enhanced due to the redox cycling between the plane electrode and the microdisk array. Based on the above working principle, the plane-recessed microdisk array electrodes break up the restriction of selectively detecting a species that exhibits reversible reaction in a mixture with one that exhibits an irreversible reaction, which is a limitation of single redox cycling operating mode. The

A copper-induced quinone degradation pathway provides protection against combined copper/quinone stress in Lactococcus lactis IL1403.

Science.gov (United States)

Mancini, Stefano; Abicht, Helge K; Gonskikh, Yulia; Solioz, Marc

2015-02-01

Quinones are ubiquitous in the environment. They occur naturally but are also in widespread use in human and industrial activities. Quinones alone are relatively benign to bacteria, but in combination with copper, they become toxic by a mechanism that leads to intracellular thiol depletion. Here, it was shown that the yahCD-yaiAB operon of Lactococcus lactis IL1403 provides resistance to combined copper/quinone stress. The operon is under the control of CopR, which also regulates expression of the copRZA copper resistance operon as well as other L. lactis genes. Expression of the yahCD-yaiAB operon is induced by copper but not by quinones. Two of the proteins encoded by the operon appear to play key roles in alleviating quinone/copper stress: YaiB is a flavoprotein that converts p-benzoquinones to less toxic hydroquinones, using reduced nicotinamide adenine dinucleotide phosphate (NADPH) as reductant; YaiA is a hydroquinone dioxygenase that converts hydroquinone putatively to 4-hydroxymuconic semialdehyde in an oxygen-consuming reaction. Hydroquinone and methylhydroquinone are both substrates of YaiA. Deletion of yaiB causes increased sensitivity of L. lactis to quinones and complete growth arrest under combined quinone and copper stress. Copper induction of the yahCD-yaiAB operon offers protection to copper/quinone toxicity and could provide a growth advantage to L. lactis in some environments. © 2014 John Wiley & Sons Ltd.

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-10-01

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

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Protection of myocytes against free radical-induced damage by accelerated turnover of the glutathione redox cycle

NARCIS (Netherlands)

Le, C. T.; Hollaar, L.; van der Valk, E. J.; Franken, N. A.; van Ravels, F. J.; Wondergem, J.; van der Laarse, A.

1995-01-01

The primary defence mechanism of myocytes against peroxides and peroxide-derived peroxyl and alkoxyl radicals is the glutathione redox cycle. The purpose of the present study was to increase the turnover rate of this cycle by stimulating the glutathione peroxidase catalysed reaction (2GSH-->GSSG),

In situ redox cycle of a nickel–YSZ fuel cell anode in an environmental transmission electron microscope

DEFF Research Database (Denmark)

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

2010-01-01

triggers the reduction reaction. During Ni reoxidation, the creation of a porous structure, due to mass transport, accounts for the redox instability of the Ni-based anode. Both the expansion of NiO during a redox cycle and the presence of stress in the yttria-stabilized zirconia grains are observed......Environmental transmission electron microscopy is used in combination with density functional theory calculations to study the redox stability of a nickel/yttria-stabilized zirconia solid oxide fuel cell anode. The results reveal that the transfer of oxygen from NiO to yttria-stabilized zirconia...... directly. Besides providing an understanding of the Ni–YSZ anode redox degradation, the observations are used to propose an alternative anode design for improved redox tolerance....

Metal-free aqueous redox capacitor via proton rocking-chair system in an organic-based couple

Science.gov (United States)

Tomai, Takaaki; Mitani, Satoshi; Komatsu, Daiki; Kawaguchi, Yuji; Honma, Itaru

2014-01-01

Safe and inexpensive energy storage devices with long cycle lifetimes and high power and energy densities are mandatory for the development of electrical power grids that connect with renewable energy sources. In this study, we demonstrated metal-free aqueous redox capacitors using couples comprising low-molecular-weight organic compounds. In addition to the electric double layer formation, proton insertion/extraction reactions between a couple consisting of inexpensive quinones/hydroquinones contributed to the energy storage. This energy storage mechanism, in which protons are shuttled back and forth between two electrodes upon charge and discharge, can be regarded as a proton rocking-chair system. The fabricated capacitor showed a large capacity (>20 Wh/kg), even in the applied potential range between 0–1 V, and high power capability (>5 A/g). The support of the organic compounds in nanoporous carbon facilitated the efficient use of the organic compounds with a lifetime of thousands of cycles. PMID:24395117

Integrating a dual-silicon photoelectrochemical cell into a redox flow battery for unassisted photocharging

DEFF Research Database (Denmark)

Liao, Shichao; Zong, Xu; Seger, Brian

2016-01-01

Solar rechargeable flow cells (SRFCs) provide an attractive approach for in situ capture and storage of intermittent solar energy via photoelectrochemical regeneration of discharged redox species for electricity generation. However, overall SFRC performance is restricted by inefficient photoelect......Solar rechargeable flow cells (SRFCs) provide an attractive approach for in situ capture and storage of intermittent solar energy via photoelectrochemical regeneration of discharged redox species for electricity generation. However, overall SFRC performance is restricted by inefficient...... photoelectrochemical reactions. Here we report an efficient SRFC based on a dual-silicon photoelectrochemical cell and a quinone/bromine redox flow battery for in situ solar energy conversion and storage. Using narrow bandgap silicon for efficient photon collection and fast redox couples for rapid interface charge...

Exogenous quinones inhibit photosynthetic electron transfer in Chloroflexus aurantiacus by specific quenching of the excited bacteriochlorophyll c antenna

DEFF Research Database (Denmark)

Frigaard, N-U; Tokita, S; Matsuura, K

1999-01-01

In the photosynthetic green filamentous bacterium Chloroflexus aurantiacus, excitation energy is transferred from a large bacteriochlorophyll (BChl) c antenna via smaller BChl a antennas to the reaction center. The effects of substituted 1,4-naphthoquinones on BChl c and BChl a fluorescence and o...... antenna. Our results provide a model system for studying the redox-dependent antenna quenching in green sulfur bacteria because the antennas in these bacteria inherently exhibit a sensitivity to O(2) similar to the quinone-supplemented cells of Cfx. aurantiacus....... and on flash-induced cytochrome c oxidation were studied in whole cells under aerobic conditions. BChl c fluorescence in a cell suspension with 5.4 microM BChl c was quenched to 50% by addition of 0.6 microM shikonin ((R)-2-(1-hydroxy-4-methyl-3-pentenyl)-5,8-dihydroxy-1, 4-naphthoquinone), 0.9 microM 5......-hydroxy-1,4-naphthoquinone, or 4 microM 2-acetyl-3-methyl-1,4-naphthoquinone. Between 25 and 100 times higher quinone concentrations were needed to quench BChl a fluorescence to a similar extent. These quinones also efficiently inhibited flash-induced cytochrome c oxidation when BChl c was excited...

Fe-phyllosilicate redox cycling organisms from a redox transition zone in Hanford 300 Area sediments

Directory of Open Access Journals (Sweden)

Jason eBenzine

2013-12-01

Full Text Available Microorganisms capable of reducing or oxidizing structural iron (Fe in Fe-bearing phyllosilicate minerals were enriched and isolated from a subsurface redox transition zone at the Hanford 300 Area site in eastern Washington, USA. Both conventional and in situ i-chip enrichment strategies were employed. One Fe(III-reducing Geobacter (G. bremensis strain R1, Deltaproteobacteria and six Fe(II phyllosilicate-oxidizing isolates from the Alphaproteobacteria (Bradyrhizobium japonicum strains 22, is5, and in8p8, Betaproteobacteria (Cupriavidus necator strain A5-1, Dechloromonas agitata strain is5, and Actinobacteria (Nocardioides sp. strain in31 were recovered. The G. bremensis isolate grew by oxidizing acetate with the oxidized form of NAu-2 smectite as the electron acceptor. The Fe(II-oxidizers grew by oxidation of chemically reduced smectite as the energy source with nitrate as the electron acceptor. The Bradyrhizobium isolates could also carry out aerobic oxidation of biotite. This is the first report of the recovery of a Fe(II-oxidizing Nocardioides, and to date only one other Fe(II-oxidizing Bradyrhizobium is known. The 16S rRNA gene sequences of the isolates were similar to ones found in clone libraries from Hanford 300 sediments and groundwater, suggesting that such organisms may be present and active in situ. Whole genome sequencing of the isolates is underway, the results of which will enable comparative genomic analysis of mechanisms of extracellular phyllosilicate Fe redox metabolism, and facilitate development of techniques to detect the presence and expression of genes associated with microbial phyllosilicate Fe redox cycling in sediments.

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

DEFF Research Database (Denmark)

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

2017-01-01

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

Perylene-Based All-Organic Redox Battery with Excellent Cycling Stability.

Science.gov (United States)

Iordache, Adriana; Delhorbe, Virginie; Bardet, Michel; Dubois, Lionel; Gutel, Thibaut; Picard, Lionel

2016-09-07

Organic materials derived from biomass can constitute a viable option as replacements for inorganic materials in lithium-ion battery electrodes owing to their low production costs, recyclability, and structural diversity. Among them, conjugated carbonyls have become the most promising type of organic electrode material as they present high theoretical capacity, fast reaction kinetics, and quasi-infinite structural diversity. In this letter, we report a new perylene-based all-organic redox battery comprising two aromatic conjugated carbonyl electrode materials, the prelithiated tetra-lithium perylene-3,4,9,10-tetracarboxylate (PTCLi6) as negative electrode material and the poly(N-n-hexyl-3,4,9,10-perylene tetracarboxylic)imide (PTCI) as positive electrode material. The resulting battery shows promising long-term cycling stability up to 200 cycles. In view of the enhanced cycling performances, the two organic materials studied herein are proposed as suitable candidates for the development of new all-organic lithium-ion batteries.

Isolation of phyllosilicate-iron redox cycling microorganisms from an illite-smectite rich hydromorphic soil.

Science.gov (United States)

Shelobolina, Evgenya; Konishi, Hiromi; Xu, Huifang; Benzine, Jason; Xiong, Mai Yia; Wu, Tao; Blöthe, Marco; Roden, Eric

2012-01-01

The biogeochemistry of phyllosilicate-Fe redox cycling was studied in a Phalaris arundinacea (reed canary grass) dominated redoximorphic soil from Shovelers Sink, a small glacial depression near Madison, WI. The clay size fraction of Shovelers Sink soil accounts for 16% of the dry weight of the soil, yet contributes 74% of total Fe. The dominant mineral in the clay size fraction is mixed layer illite-smectite, and in contrast to many other soils and sediments, Fe(III) oxides are present in low abundance. We examined the Fe biogeochemistry of Shovelers Sink soils, estimated the abundance of Fe redox cycling microorganisms, and isolated in pure culture representative phyllosilicate-Fe oxidizing and reducing organisms. The abundance of phyllosilicate-Fe reducing and oxidizing organisms was low compared to culturable aerobic heterotrophs. Both direct isolation and dilution-to-extinction approaches using structural Fe(II) in Bancroft biotite as a Fe(II) source, and O(2) as the electron acceptor, resulted in recovery of common rhizosphere organisms including Bradyrhizobium spp. and strains of Cupriavidus necator and Ralstonia solanacearum. In addition to oxidizing biotite and soluble Fe(II) with O(2), each of these isolates was able to oxidize Fe(II) in reduced NAu-2 smectite with [Formula: see text] as the electron acceptor. Oxidized NAu-2 smectite or amorphous Fe(III) oxide served as electron acceptors for enrichment and isolation of Fe(III)-reducing microorganisms, resulting in recovery of a strain related to Geobacter toluenoxydans. The ability of the recovered microorganisms to cycle phyllosilicate-Fe was verified in an experiment with native Shovelers Sink clay. This study confirms that Fe in the native Shovelers Sink clay is readily available for microbial redox transformation and can be cycled by the Fe(III)-reducing and Fe(II)-oxidizing microorganisms recovered from the soil.

Isolation of Phyllosilicate–Iron Redox Cycling Microorganisms from an Illite–Smectite Rich Hydromorphic Soil

Science.gov (United States)

Shelobolina, Evgenya; Konishi, Hiromi; Xu, Huifang; Benzine, Jason; Xiong, Mai Yia; Wu, Tao; Blöthe, Marco; Roden, Eric

2012-01-01

The biogeochemistry of phyllosilicate–Fe redox cycling was studied in a Phalaris arundinacea (reed canary grass) dominated redoximorphic soil from Shovelers Sink, a small glacial depression near Madison, WI. The clay size fraction of Shovelers Sink soil accounts for 16% of the dry weight of the soil, yet contributes 74% of total Fe. The dominant mineral in the clay size fraction is mixed layer illite–smectite, and in contrast to many other soils and sediments, Fe(III) oxides are present in low abundance. We examined the Fe biogeochemistry of Shovelers Sink soils, estimated the abundance of Fe redox cycling microorganisms, and isolated in pure culture representative phyllosilicate–Fe oxidizing and reducing organisms. The abundance of phyllosilicate–Fe reducing and oxidizing organisms was low compared to culturable aerobic heterotrophs. Both direct isolation and dilution-to-extinction approaches using structural Fe(II) in Bancroft biotite as a Fe(II) source, and O2 as the electron acceptor, resulted in recovery of common rhizosphere organisms including Bradyrhizobium spp. and strains of Cupriavidus necator and Ralstonia solanacearum. In addition to oxidizing biotite and soluble Fe(II) with O2, each of these isolates was able to oxidize Fe(II) in reduced NAu-2 smectite with NO3- as the electron acceptor. Oxidized NAu-2 smectite or amorphous Fe(III) oxide served as electron acceptors for enrichment and isolation of Fe(III)-reducing microorganisms, resulting in recovery of a strain related to Geobacter toluenoxydans. The ability of the recovered microorganisms to cycle phyllosilicate–Fe was verified in an experiment with native Shovelers Sink clay. This study confirms that Fe in the native Shovelers Sink clay is readily available for microbial redox transformation and can be cycled by the Fe(III)-reducing and Fe(II)-oxidizing microorganisms recovered from the soil. PMID:22493596

Disruption of Pyridine Nucleotide Redox Status During Oxidative Challenge at Normal and Low-Glucose States: Implications for Cellular Adenosine Triphosphate, Mitochondrial Respiratory Activity, and Reducing Capacity in Colon Epithelial Cells

Science.gov (United States)

Circu, Magdalena L.; Maloney, Ronald E.

2011-01-01

Abstract We recently demonstrated that menadione (MQ), a redox cycling quinone, mediated the loss of mitochondrial glutathione/glutathione disulfide redox balance. In this study, we showed that MQ significantly disrupted cellular pyridine nucleotide (NAD+/NADH, NADP+/NADPH) redox balance that compromised cellular ATP, mitochondrial respiratory activity, and NADPH-dependent reducing capacity in colonic epithelial cells, a scenario that was exaggerated by low glucose. In the cytosol, MQ induced NAD+ loss concurrent with increased NADP+ and NAD kinase activity, but decreased NADPH. In the mitochondria, NADH loss occurred in conjunction with increased nicotinamide nucleotide transhydrogenase activity and NADP+, and decreased NADPH. These results are consistent with cytosolic NAD+-to-NADP+ and mitochondrial NADH-to-NADPH shifts, but compromised NADPH availability. Thus, despite the sacrifice of NAD+/NADH in favor of NADPH generation, steady-state NADPH levels were not maintained during MQ challenge. Impairments of cellular bioenergetics were evidenced by ATP losses and increased mitochondrial O2 dependence of pyridine nucleotide oxidation–reduction; half-maximal oxidation (P50) was 10-fold higher in low glucose, which was lowered by glutamate or succinate supplementation. This exaggerated O2 dependence is consistent with increased O2 diversion to nonmitochondrial O2 consumption by MQ-semiquinone redox cycling secondary to decreased NADPH-dependent MQ detoxication at low glucose, a situation that was corrected by glucose-sparing mitochondrial substrates. Antioxid. Redox Signal. 14, 2151–2162. PMID:21083422

Quinones in aerobic and anaerobic mitochondria

NARCIS (Netherlands)

van der Klei, S.A.

2009-01-01

Ubiquinone (UQ), also known as coenzyme Q, is a ubiquitous quinone and is known to have several functions. One of these functions is electron carrier in the mitochondrial electron transport chain of aerobically functioning bacteria and eukaryotes. In contrast to this aerobically functioning quinone,

[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.

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

The role of copper and oxalate in the redox cycling of iron in atmospheric waters

Science.gov (United States)

Sedlak, David L.; Hoigné, Jürg

During daytime, the redox cycling of dissolved iron compounds in atmospheric waters, and the related in-cloud transformations of photooxidants, are affected by reactions of Fe and Cu with hydroperoxy (HO 2) and superoxide (O 2-) radicals and the photoreduction of Fe(III)-oxalato complexes. We have investigated several of the important chemical reactions in this redox cycle, through laboratory simulation of the system, using γ-radiation to produce HO 2/O 2-. At concentrations comparable to those measured in atmospheric waters, the redox cycling of Fe was dramatically affected by the presence of oxalate and trace concentrations of Cu. At concentrations more than a hundred times lower than Fe, Cu consumed most of the HO 2/O 2-, and cycled between the Cu(II) and Cu(I) forms. Cu + reacted with FeOH 2+ to produce Fe(II) and Cu(II), with a second order rate constant of approximately 3 × 10 7 M -1s -1. The presence of oxalate resulted in the formation of Fe(III)-oxalato complexes that were essentially unreactive with HO 2/O 2-. Only at high oxalate concentrations was the Fe(II)C 2O 4 complex also formed, and it reacted relatively rapidly with hydrogen peroxide ( k = (3.1 ± 0.6) × 10 4 M -1s -1). Simulations incorporating measurements for other redox mechanisms, including oxidation by ozone, indicate that, during daytime, Fe should be found mostly in the ferrous oxidation state, and that reactions of FeOH 2+ with Cu(I) and HO 2/O 2-, and to a lesser degree, the photolysis of Fe(III)-oxalato complexes, are important mechanisms of Fe reduction in atmospheric waters. The catalytic effect of Cu(II)/Cu(I) and Fe(III)/Fe(II) should also significantly increase the sink function of the atmospheric liquid phase for HO 2 present in a cloud. A simple kinetic model for the reactions of Fe, Cu and HO 2/O 2-, accurately predicted the changes in Fe oxidation states that occurred when authentic fogwater samples were exposed to HO 2/O 2-.

Ni-YSZ solid oxide fuel cell anode behavior upon redox cycling based on electrical characterization

DEFF Research Database (Denmark)

Klemensø, Trine; Mogensen, Mogens Bjerg

2007-01-01

Nickel (Ni)—yttria-stabilized zirconia (YSZ) cermets are a prevalent material used for solid oxide fuel cells. The cermet degrades upon redox cycling. The degradation is related to microstructural changes, but knowledge of the mechanisms has been limited. Direct current conductivity measurements...

Long-Cycling Aqueous Organic Redox Flow Battery (AORFB) toward Sustainable and Safe Energy Storage.

Science.gov (United States)

Hu, Bo; DeBruler, Camden; Rhodes, Zayn; Liu, T Leo

2017-01-25

Redox flow batteries (RFBs) are a viable technology to store renewable energy in the form of electricity that can be supplied to electricity grids. However, widespread implementation of traditional RFBs, such as vanadium and Zn-Br 2 RFBs, is limited due to a number of challenges related to materials, including low abundance and high costs of redox-active metals, expensive separators, active material crossover, and corrosive and hazardous electrolytes. To address these challenges, we demonstrate a neutral aqueous organic redox flow battery (AORFB) technology utilizing a newly designed cathode electrolyte containing a highly water-soluble ferrocene molecule. Specifically, water-soluble (ferrocenylmethyl)trimethylammonium chloride (FcNCl, 4.0 M in H 2 O, 107.2 Ah/L, and 3.0 M in 2.0 NaCl, 80.4 Ah/L) and N 1 -ferrocenylmethyl-N 1 ,N 1 ,N 2 ,N 2 ,N 2 -pentamethylpropane-1,2-diaminium dibromide, (FcN 2 Br 2 , 3.1 M in H 2 O, 83.1 Ah/L, and 2.0 M in 2.0 M NaCl, 53.5 Ah/L) were synthesized through structural decoration of hydrophobic ferrocene with synergetic hydrophilic functionalities including an ammonium cation group and a halide anion. When paired with methyl viologen (MV) as an anolyte, resulting FcNCl/MV and FcN 2 Br 2 /MV AORFBs were operated in noncorrosive neutral NaCl supporting electrolytes using a low-cost anion-exchange membrane. These ferrocene/MV AORFBs are characterized as having high theoretical energy density (45.5 Wh/L) and excellent cycling performance from 40 to 100 mA/cm 2 . Notably, the FcNCl/MV AORFBs (demonstrated at 7.0 and 9.9 Wh/L) exhibited unprecedented long cycling performance, 700 cycles at 60 mA/cm 2 with 99.99% capacity retention per cycle, and delivered power density up to 125 mW/cm 2 . These AORFBs are built from earth-abundant elements and are environmentally benign, thus representing a promising choice for sustainable and safe energy storage.

Ni-YSZ solid oxide fuel cell anode behavior upon redox cycling based on electrical characterization

DEFF Research Database (Denmark)

Klemensø, Trine; Mogensen, Mogens Bjerg

2006-01-01

Ni-YSZ cermets are a prevalent material used for solid oxide fuel cells. However, the cermet degrades upon redox cycling. The degradation is related to microstructural changes, but knowledge of the mechanisms has been limited. DC conductivity measurements were performed on cermets and cermets...

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

Role of the NAD(P)H quinone oxidoreductase NQR and the cytochrome b AIR12 in controlling superoxide generation at the plasma membrane.

Science.gov (United States)

Biniek, Catherine; Heyno, Eiri; Kruk, Jerzy; Sparla, Francesca; Trost, Paolo; Krieger-Liszkay, Anja

2017-04-01

The quinone reductase NQR and the b-type cytochrome AIR12 of the plasma membrane are important for the control of reactive oxygen species in the apoplast. AIR12 and NQR are two proteins attached to the plant plasma membrane which may be important for generating and controlling levels of reactive oxygen species in the apoplast. AIR12 (Auxin Induced in Root culture) is a single gene of Arabidopsis that codes for a mono-heme cytochrome b. The NADPH quinone oxidoreductase NQR is a two-electron-transferring flavoenzyme that contributes to the generation of O 2 •- in isolated plasma membranes. A. thaliana double knockout plants of both NQR and AIR12 generated more O 2 •- and germinated faster than the single mutant affected in AIR12. To test whether NQR and AIR12 are able to interact functionally, recombinant purified proteins were added to plasma membranes isolated from soybean hypocotyls. In vitro NADH-dependent O 2 •- production at the plasma membrane in the presence of NQR was reduced upon addition of AIR12. Electron donation from semi-reduced menadione to AIR12 was shown to take place. Biochemical analysis showed that purified plasma membrane from soybean hypocotyls or roots contained phylloquinone and menaquinone-4 as redox carriers. This is the first report on the occurrence of menaquinone-4 in eukaryotic photosynthetic organisms. We propose that NQR and AIR12 interact via the quinone, allowing an electron transfer from cytosolic NAD(P)H to apoplastic monodehydroascorbate and control thereby the level of reactive oxygen production and the redox state of the apoplast.

Polychlorinated biphenyl quinone induces oxidative DNA damage and repair responses: The activations of NHEJ, BER and NER via ATM-p53 signaling axis

Energy Technology Data Exchange (ETDEWEB)

Dong, Hui; Shi, Qiong; Song, Xiufang; Fu, Juanli; Hu, Lihua; Xu, Demei; Su, Chuanyang; Xia, Xiaomin; Song, Erqun; Song, Yang, E-mail: songyangwenrong@hotmail.com

2015-07-01

Our previous studies demonstrated that polychlorinated biphenyl (PCB) quinone induced oxidative DNA damage in HepG2 cells. To promote genomic integrity, DNA damage response (DDR) coordinates cell-cycle transitions, DNA repair and apoptosis. PCB quinone-induced cell cycle arrest and apoptosis have been documented, however, whether PCB quinone insult induce DNA repair signaling is still unknown. In this study, we identified the activation of DDR and corresponding signaling events in HepG2 cells upon the exposure to a synthetic PCB quinone, PCB29-pQ. Our data illustrated that PCB29-pQ induces the phosphorylation of p53, which was mediated by ataxia telangiectasia mutated (ATM) protein kinase. The observed phosphorylated histone H2AX (γ-H2AX) foci and the elevation of 8-hydroxy-2′-deoxyguanosine (8-OHdG) indicated that DDR was stimulated by PCB29-pQ treatment. Additionally, we found PCB29-pQ activates non-homologous end joining (NHEJ), base excision repair (BER) and nucleotide excision repair (NER) signalings. However, these repair pathways are not error-free processes and aberrant repair of DNA damage may cause the potential risk of carcinogenesis and mutagenesis. - Highlights: • Polychlorinated biphenyl quinone induces oxidative DNA damage in HepG2 cells. • The elevation of γ-H2AX and 8-OHdG indicates the activation of DNA damage response. • ATM-p53 signaling acts as the DNA damage sensor and effector. • Polychlorinated biphenyl quinone activates NHEJ, BER and NER signalings.

Beyond the Fe-P-redox connection: preferential regeneration of phosphorus from organic matter as a key control on Baltic Sea nutrient cycles

NARCIS (Netherlands)

Jilbert, T.; Slomp, C.P.; Gustafsson, B.G.; Boer, W.

2011-01-01

Patterns of regeneration and burial of phosphorus (P) in the Baltic Sea are strongly dependent on redox conditions. Redox varies spatially along water depth gradients and temporally in response to the seasonal cycle and multidecadal hydrographic variability. Alongside the welldocumented link

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

Protein covalent modification by biologically active quinones

Directory of Open Access Journals (Sweden)

MIROSLAV J. GASIC

2004-11-01

Full Text Available The avarone/avarol quinone/hydroquinone couple shows considerable antitumor activity. In this work, covalent modification of b-lactoglobulin by avarone and its derivatives as well as by the synthetic steroidal quinone 2,5(10-estradiene-1,4,17-trione and its derivatives were studied. The techniques for studying chemical modification of b-lactoglobulin by quinones were: UV/Vis spectrophotometry, SDS PAGE and isoelectrofocusing. SDS PAGE results suggest that polymerization of the protein occurs. It could be seen that the protein of 18 kD gives the bands of 20 kD, 36 kD, 40 kD, 45 kD, 64 kD and 128 kD depending on modification agent. The shift of the pI of the protein (5.4 upon modification toward lower values (from pI 5.0 to 5.3 indicated that lysine amino groups are the principal site of the reaction of b-lactoglobulin with the quinones.

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.

The effects of protein crowding in bacterial photosynthetic membranes on the flow of quinone redox species between the photochemical reaction center and the ubiquinol-cytochrome c2 oxidoreductase.

Science.gov (United States)

Woronowicz, Kamil; Sha, Daniel; Frese, Raoul N; Sturgis, James N; Nanda, Vikas; Niederman, Robert A

2011-08-01

Atomic force microscopy (AFM) of the native architecture of the intracytoplasmic membrane (ICM) of a variety of species of purple photosynthetic bacteria, obtained at submolecular resolution, shows a tightly packed arrangement of light harvesting (LH) and reaction center (RC) complexes. Since there are no unattributed structures or gaps with space sufficient for the cytochrome bc(1) or ATPase complexes, they are localized in membrane domains distinct from the flat regions imaged by AFM. This has generated a renewed interest in possible long-range pathways for lateral diffusion of UQ redox species that functionally link the RC and the bc(1) complexes. Recent proposals to account for UQ flow in the membrane bilayer are reviewed, along with new experimental evidence provided from an analysis of intrinsic near-IR fluorescence emission that has served to test these hypotheses. The results suggest that different mechanism of UQ flow exist between species such as Rhodobacter sphaeroides, with a highly organized arrangement of LH and RC complexes and fast RC electron transfer turnover, and Phaeospirillum molischianum with a more random organization and slower RC turnover. It is concluded that packing density of the peripheral LH2 antenna in the Rba. sphaeroides ICM imposes constraints that significantly slow the diffusion of UQ redox species between the RC and cytochrome bc(1) complex, while in Phs. molischianum, the crowding of the ICM with LH3 has little effect upon UQ diffusion. This supports the proposal that in this type of ICM, a network of RC-LH1 core complexes observed in AFM provides a pathway for long-range quinone diffusion that is unaffected by differences in LH complex composition or organization.

Regulation of expression of Na+ -translocating NADH:quinone oxidoreductase genes in Vibrio harveyi and Klebsiella pneumoniae.

Science.gov (United States)

Fadeeva, Maria S; Yakovtseva, Evgenia A; Belevich, Galina A; Bertsova, Yulia V; Bogachev, Alexander V

2007-10-01

The expression of genes encoding sodium-translocating NADH:quinone oxidoreductase (Na(+)-NQR) was studied in the marine bacterium Vibrio harveyi and in the enterobacterium Klebsiella pneumoniae. It has been shown that such parameters as NaCl concentration, pH value, and presence of an uncoupler in the growth media do not influence significantly the level of nqr expression. However, nqr expression depends on the growth substrates used by these bacteria. Na(+)-NQR is highly repressed in V. harveyi during anaerobic growth, and nqr expression is modulated by electron acceptors and values of their redox potentials. The latter effect was shown to be independent of the ArcAB regulatory system.

Role of sulfur redox cycling on arsenic mobilization in aquifers of Datong Basin, northern China

International Nuclear Information System (INIS)

Pi, Kunfu; Wang, Yanxin; Xie, Xianjun; Ma, Teng; Su, Chunli; Liu, Yaqing

2017-01-01

Sulfur redox cycling potentially exerts important influences on arsenic (As) fate in shallow groundwater systems. Hydrochemical and sediment geochemical analysis combined with thermodynamic modeling study were conducted at Datong Basin to elaborate the effects of sulfur redox cycling on As speciation and mobilization under a strongly reducing environment. Dissolved As and sulfide concentration in 32 groundwater samples with depths of 19–40 m below the land surface varied from 8 to 2700 μg/L and from <5 to 490 μg/L, respectively, while dissolved Fe(II) was relatively low ranging from <20 to 280 μg/L. The apparent co-increase in dissolved sulfide and As concentration, especially for samples with As content larger than 500 μg/L, indicates that sulfidogenesis may significantly contribute to the mobilization of As via sulfide-induced reduction of both As-bearing Fe(III) oxide minerals and As(V). Thermodynamic calculations indicate that groundwater As might be also thiolated in the presence of high-level sulfide, particularly to a large extent for As(V) speciation, instead of sequestration by As-sulfide precipitates. Results of sequential extraction and scanning electron microscopy array on sediments indicate the presence of Fe(II) sulfide mineral phases and an appreciable amount of co-existent As in the sediments, suggesting the precipitation of Fe(II) sulfides can restrict the build-up of dissolved Fe(II) and sequester As from groundwater, but not strongly enough, thereby lowering down As to a moderate level of about 500 μg/L. Thus, redox processes involving As, S and Fe species under sulfidic conditions as observed in Datong Basin not only facilitate the enrichment of As(III) species and As(V) potentially existing as thiolated species, but also the depletion of Fe(II) concentration in groundwater due to Fe(II) sulfide formation. - Highlights: • Effects of sulfur redox cycling on As enrichment were clarified in Datong. • Co-increase in aqueous As and

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.)

The level of menadione redox-cycling in pancreatic β-cells is proportional to the glucose concentration: role of NADH and consequences for insulin secretion.

Science.gov (United States)

Heart, Emma; Palo, Meridith; Womack, Trayce; Smith, Peter J S; Gray, Joshua P

2012-01-15

Pancreatic β-cells release insulin in response to elevation of glucose from basal (4-7mM) to stimulatory (8-16mM) levels. Metabolism of glucose by the β-cell results in the production of low levels of reactive oxygen intermediates (ROI), such as hydrogen peroxide (H(2)O(2)), a newly recognized coupling factor linking glucose metabolism to insulin secretion. However, high and toxic levels of H(2)O(2) inhibit insulin secretion. Menadione, which produces H(2)O(2) via redox cycling mechanism in a dose-dependent manner, was investigated for its effect on β-cell metabolism and insulin secretion in INS-1 832/13, a rat β-cell insulinoma cell line, and primary rodent islets. Menadione-dependent redox cycling and resulting H(2)O(2) production under stimulatory glucose exceeded several-fold those reached at basal glucose. This was paralleled by a differential effect of menadione (0.1-10μM) on insulin secretion, which was enhanced at basal, but inhibited at stimulatory glucose. Redox cycling of menadione and H(2)O(2) formation was dependent on glycolytically-derived NADH, as inhibition of glycolysis and application of non-glycogenic insulin secretagogues did not support redox cycling. In addition, activity of plasma membrane electron transport, a system dependent in part on glycolytically-derived NADH, was also inhibited by menadione. Menadione-dependent redox cycling was sensitive to the NQO1 inhibitor dicoumarol and the flavoprotein inhibitor diphenylene iodonium, suggesting a role for NQO1 and other oxidoreductases in this process. These data may explain the apparent dichotomy between the stimulatory and inhibitory effects of H(2)O(2) and menadione on insulin secretion. Published by Elsevier Inc.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-06-10

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

Supercritical Fluid Extraction of Quinones from Compost for Microbial Community Analysis

Directory of Open Access Journals (Sweden)

Ni Luh Gede Ratna Juliasih

2015-01-01

Full Text Available Supercritical fluid extraction (SFE was used to extract quinones from compost to monitor the microbial community dynamics during composting. The 0.3 g of dried compost was extracted using 3 mL min−1 of carbon dioxide (90% and methanol (10% at 45°C and 25 MPa for a 30 min extraction time. The extracted quinones were analysed using ultra performance liquid chromatography (UPLC with 0.3 mL min−1 of methanol mobile phase for a 50 min chromatographic run time. A comparable detected amount of quinones was obtained using the developed method and an organic solvent extraction method, being 36.06 μmol kg−1 and 34.54 μmol kg−1, respectively. Significantly low value of dissimilarity index (D between the two methods (0.05 indicated that the quinone profile obtained by both methods was considered identical. The developed method was then applied to determine the maturity of the compost by monitoring the change of quinone during composting. The UQ-9 and MK-7 were predominant quinones in the initial stage of composting. The diversity of quinone became more complex during the cooling and maturation stages. This study showed that SFE had successfully extracted quinones from a complex matrix with simplification and rapidity of the analysis that is beneficial for routine analysis.

Beyond the Fe-P-redox connection: preferential regeneration of phosphorus from organic matter as a key control on Baltic Sea nutriënt cycles

NARCIS (Netherlands)

Jilbert, T.; Slomp, C.P.; Gustafsson, B.G.; Boer, W.

2011-01-01

Patterns of regeneration and burial of phosphorus (P) in the Baltic Sea are strongly dependent on redox conditions. Redox varies spatially along water depth gradients and temporally in response to the seasonal cycle and multidecadal hydrographic variability. Alongside the well-documented link

A novel mitochondria-targeted two-photon fluorescent probe for dynamic and reversible detection of the redox cycles between peroxynitrite and glutathione.

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Sun, Chunlong; Du, Wen; Wang, Peng; Wu, Yang; Wang, Baoqin; Wang, Jun; Xie, Wenjun

2017-12-16

Redox homeostasis is important for maintenance of normal physiological functions within cells. Redox state of cells is primarily a consequence of precise balance between levels of reducing equivalents and reactive oxygen species. Redox homeostasis between peroxynitrite (ONOO - ) and glutathione (GSH) is closely associated with physiological and pathological processes, such as prolonged relaxation in vascular tissues and smooth muscle preparations, attenuation of hepatic necrosis, and activation of matrix metalloproteinase-2. We report a two-photon fluorescent probe (TP-Se) based on water-soluble carbazole-based compound, which integrates with organic selenium, to monitor changes in ONOO - /GSH levels in cells. This probe can reversibly respond to ONOO - and GSH and exhibits high selectivity, sensitivity, and mitochondrial targeting. The probe was successfully applied to visualize changes in redox cycles during ONOO - outbreak and antioxidant GSH repair in cells. The probe will lead to significant development on redox events involved in cellular redox regulation. Copyright © 2017 Elsevier Inc. All rights reserved.

Carbons, ionic liquids and quinones for electrochemical capacitors

Directory of Open Access Journals (Sweden)

Raul eDiaz

2016-04-01

Full Text Available Carbons are the main electrode materials used in electrochemical capacitors, which are electrochemical energy storage devices with high power densities and long cycling lifetimes. However, increasing their energy density will improve their potential for commercial implementation. In this regard, the use of high surface area carbons and high voltage electrolytes are well known strategies to increase the attainable energy density, and lately ionic liquids have been explored as promising alternatives to current state of the art acetonitrile-based electrolytes. Also, in terms of safety and sustainability ionic liquids are attractive electrolyte materials for electrochemical capacitors. In addition, it has been shown that the matching of the carbon pore size with the electrolyte ion size further increases the attainable electric double layer (EDL capacitance and energy density.The use of pseudocapacitive reactions can significantly increase the attainable energy density, and quinonic-based materials offer a potentially sustainable and cost effective research avenue for both the electrode and the electrolyte. This perspective will provide an overview of the current state of the art research on electrochemical capacitors based on combinations of carbons, ionic liquids and quinonic compounds, highlighting performances and challenges and discussing possible future research avenues. In this regard, current interest is mainly focused on strategies which may ultimately lead to commercially competitive sustainable high performance electrochemical capacitors for different applications including those requiring mechanical flexibility and biocompatibility.

Profiling quinones in ambient air samples collected from the Athabasca region (Canada).

Science.gov (United States)

Wnorowski, Andrzej; Charland, Jean-Pierre

2017-12-01

This paper presents new findings on polycyclic aromatic hydrocarbon oxidation products-quinones that were collected in ambient air samples in the proximity of oil sands exploration. Quinones were characterized for their diurnal concentration variability, phase partitioning, and molecular size distribution. Gas-phase (GP) and particle-phase (PM) ambient air samples were collected separately in the summer; a lower quinone content was observed in the PM samples from continuous 24-h sampling than from combined 12-h sampling (day and night). The daytime/nocturnal samples demonstrated that nighttime conditions led to lower concentrations and some quinones not being detected. The highest quinone levels were associated with wind directions originating from oil sands exploration sites. The statistical correlation with primary pollutants directly emitted from oil sands industrial activities indicated that the bulk of the detected quinones did not originate directly from primary emission sources and that quinone formation paralleled a reduction in primary source NO x levels. This suggests a secondary chemical transformation of primary pollutants as the origin of the determined quinones. Measurements of 19 quinones included five that have not previously been reported in ambient air or in Standard Reference Material 1649a/1649b and seven that have not been previously measured in ambient air in the underivatized form. This is the first paper to report on quinone characterization in secondary organic aerosols originating from oil sands activities, to distinguish chrysenequinone and anthraquinone positional isomers in ambient air, and to report the requirement of daylight conditions for benzo[a]pyrenequinone and naphthacenequinone to be present in ambient air. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.

Removal of bisphenol derivatives through quinone oxidation by polyphenol oxidase and subsequent quinone adsorption on chitosan in the heterogeneous system.

Science.gov (United States)

Kimura, Yuji; Takahashi, Ayumi; Kashiwada, Ayumi; Yamada, Kazunori

2015-01-01

In this study, the combined use of a biopolymer chitosan and an oxidoreductase polyphenol oxidase (PPO) was systematically investigated for the removal of bisphenol derivatives from aqueous medium. The process parameters, such as the pH value, temperature, and PPO concentration, were estimated to conduct the enzymatic quinone oxidation of bisphenol derivatives by as little enzyme as possible. Bisphenol derivatives effectively underwent PPO-catalysed quinone oxidation without H2O2 unlike other oxidoreductases, such as peroxidase and tyrosinase, and the optimum conditions were determined to be pH 7.0 and 40°C for bisphenol B, bisphenol E, bisphenol O, and bisphenol Z; pH 7.0 and 30°C for bisphenol C and bisphenol F; and pH 8.0 and 40°C for bisphenol T. They were completely removed through adsorption of enzymatically generated quinone derivatives on chitosan beads or chitosan powders. Quinone adsorption on chitosan beads or chitosan powders in the heterogeneous system was found to be a more effective procedure than generation of aggregates in the homogeneous system with chitosan solution. The removal time was shortened by increasing the amount of chitosan beads or decreasing the size of the chitosan powders.

Measuring the Bioenergetic Effects of 1,2-Naphthoquinone Exposure on Human Lung Macrophages Using Seahorse Extracellular Flux Analyses

Science.gov (United States)

Exposure to ambient particulate matter (PM) is one of the leading causes of morbidity and mortality in humans. Quinones are organic PM components that induce inflammatory responses through redox cycling and electrophilic attack. 1,2-naphthoquinone (1,2-NQ) has previously been sho...

Efficiency of two-step solar thermochemical non-stoichiometric redox cycles with heat recovery

International Nuclear Information System (INIS)

Lapp, J.; Davidson, J.H.; Lipiński, W.

2012-01-01

Improvements in the effectiveness of solid phase heat recovery and in the thermodynamic properties of metal oxides are the most important paths to achieving unprecedented thermal efficiencies of 10% and higher in non-stoichiometric solar redox reactors. In this paper, the impact of solid and gas phase heat recovery on the efficiency of a non-stoichiometric cerium dioxide-based H 2 O/CO 2 splitting cycle realized in a solar-driven reactor are evaluated in a parametric thermodynamic analysis. Application of solid phase heat recovery to the cycling metal oxide allows for lower reduction zone operating temperatures, simplifying reactor design. An optimum temperature for metal oxide reduction results from two competing phenomena as the reduction temperature is increased: increasing re-radiation losses from the reactor aperture and decreasing heat loss due to imperfect solid phase heat recovery. Additionally, solid phase heat recovery increases the efficiency gains made possible by gas phase heat recovery. -- Highlights: ► Both solid and gas phase heat recovery are essential to achieve high thermal efficiency in non-stoichiometric ceria-based solar redox reactors. ► Solid phase heat recovery allows for lower reduction temperatures and increases the gains made possible by gas phase heat recovery. ► The optimum reduction temperature increases with increasing concentration ratio and decreasing solid phase heat recovery effectiveness. ► Even moderate levels of heat recovery dramatically improve reactor efficiency from 3.5% to 16%.

Bioinspired organocatalytic aerobic C-H oxidation of amines with an ortho-quinone catalyst.

Science.gov (United States)

Qin, Yan; Zhang, Long; Lv, Jian; Luo, Sanzhong; Cheng, Jin-Pei

2015-03-20

A simple bioinspired ortho-quinone catalyst for the aerobic oxidative dehydrogenation of amines to imines is reported. Without any metal cocatalysts, the identified optimal ortho-quinone catalyst enables the oxidations of α-branched primary amines and cyclic secondary amines. Mechanistic studies have disclosed the origins of different performances of ortho-quinone vs para-quinone in biomimetic amine oxidations.

Oxidation of atenolol, propranolol, carbamazepine and clofibric acid by a biological Fenton-like system mediated by the white-rot fungus Trametes versicolor.

Science.gov (United States)

Marco-Urrea, Ernest; Radjenović, Jelena; Caminal, Gloria; Petrović, Mira; Vicent, Teresa; Barceló, Damià

2010-01-01

Biological advanced oxidation of the pharmaceuticals clofibric acid (CA), carbamazepine (CBZP), atenolol (ATL) and propranolol (PPL) is reported for the first time. Extracellular oxidizing species were produced through a quinone redox cycling mechanism catalyzed by an intracellular quinone reductase and any of the ligninolytic enzymes of Trametes versicolor after addition of the lignin-derived quinone 2,6-dimethoxy-1,4-benzoquinone (DBQ) and Fe(3+)-oxalate in the medium. Time-course experiments with approximately 10mg L(-1) of initial pharmaceutical concentration resulted in percent degradations above 80% after 6h of incubation. Oxidation of pharmaceuticals was only observed under DBQ redox cycling conditions. A similar degradation pattern was observed when CBZP was added at the environmentally relevant concentration of 50 microg L(-1). Depletion of DBQ due to the attack of oxidizing agents was assumed to be the main limiting factor of pharmaceutical degradation. The main degradation products, that resulted to be pharmaceutical hydroxylated derivatives, were structurally elucidated. The detected 4- and 7-hydroxycarbamazepine intermediates of CBZP degradation were not reported to date. Total disappearance of intermediates was observed in all the experiments at the end of the incubation period. (c) 2009 Elsevier Ltd. All rights reserved.

Integrating a dual-silicon photoelectrochemical cell into a redox flow battery for unassisted photocharging.

Science.gov (United States)

Liao, Shichao; Zong, Xu; Seger, Brian; Pedersen, Thomas; Yao, Tingting; Ding, Chunmei; Shi, Jingying; Chen, Jian; Li, Can

2016-05-04

Solar rechargeable flow cells (SRFCs) provide an attractive approach for in situ capture and storage of intermittent solar energy via photoelectrochemical regeneration of discharged redox species for electricity generation. However, overall SFRC performance is restricted by inefficient photoelectrochemical reactions. Here we report an efficient SRFC based on a dual-silicon photoelectrochemical cell and a quinone/bromine redox flow battery for in situ solar energy conversion and storage. Using narrow bandgap silicon for efficient photon collection and fast redox couples for rapid interface charge injection, our device shows an optimal solar-to-chemical conversion efficiency of ∼5.9% and an overall photon-chemical-electricity energy conversion efficiency of ∼3.2%, which, to our knowledge, outperforms previously reported SRFCs. The proposed SRFC can be self-photocharged to 0.8 V and delivers a discharge capacity of 730 mAh l(-1). Our work may guide future designs for highly efficient solar rechargeable devices.

Electrochemical Reduction of Quinones in Different Media: A Review

Directory of Open Access Journals (Sweden)

Partha Sarathi Guin

2011-01-01

Full Text Available The electron transfer reactions involving quinones, hydroquinones, and catechols are very important in many areas of chemistry, especially in biological systems. The therapeutic efficiency as well as toxicity of anthracycline anticancer drugs, a class of anthraquinones, is governed by their electrochemical properties. Other quinones serve as important functional moiety in various biological systems like electron-proton carriers in the respiratory chain and their involvement in photosynthetic electron flow systems. The present paper summarizes literatures on the reduction of quinones in different solvents under various conditions using different electrochemical methods. The influence of different reaction conditions including pH of the media, nature of supporting electrolytes, nature of other additives, intramolecular or intermolecular hydrogen bonding, ion pair formation, polarity of the solvents, stabilization of the semiquinone and quinone dianion, catalytic property, and adsorption at the electrode surface, are discussed and relationships between reaction conditions and products formed have been presented.

The NQO1 bioactivatable drug, β-lapachone, alters the redox state of NQO1+ pancreatic cancer cells, causing perturbation in central carbon metabolism.

Science.gov (United States)

Silvers, Molly A; Deja, Stanislaw; Singh, Naveen; Egnatchik, Robert A; Sudderth, Jessica; Luo, Xiuquan; Beg, Muhammad S; Burgess, Shawn C; DeBerardinis, Ralph J; Boothman, David A; Merritt, Matthew E

2017-11-03

Many cancer treatments, such as those for managing recalcitrant tumors like pancreatic ductal adenocarcinoma, cause off-target toxicities in normal, healthy tissue, highlighting the need for more tumor-selective chemotherapies. β-Lapachone is bioactivated by NAD(P)H:quinone oxidoreductase 1 (NQO1). This enzyme exhibits elevated expression in most solid cancers and therefore is a potential cancer-specific target. β-Lapachone's therapeutic efficacy partially stems from the drug's induction of a futile NQO1-mediated redox cycle that causes high levels of superoxide and then peroxide formation, which damages DNA and causes hyperactivation of poly(ADP-ribose) polymerase, resulting in extensive NAD + /ATP depletion. However, the effects of this drug on energy metabolism due to NAD + depletion were never described. The futile redox cycle rapidly consumes O 2 , rendering standard assays of Krebs cycle turnover unusable. In this study, a multimodal analysis, including metabolic imaging using hyperpolarized pyruvate, points to reduced oxidative flux due to NAD + depletion after β-lapachone treatment of NQO1+ human pancreatic cancer cells. NAD + -sensitive pathways, such as glycolysis, flux through lactate dehydrogenase, and the citric acid cycle (as inferred by flux through pyruvate dehydrogenase), were down-regulated by β-lapachone treatment. Changes in flux through these pathways should generate biomarkers useful for in vivo dose responses of β-lapachone treatment in humans, avoiding toxic side effects. Targeting the enzymes in these pathways for therapeutic treatment may have the potential to synergize with β-lapachone treatment, creating unique NQO1-selective combinatorial therapies for specific cancers. These findings warrant future studies of intermediary metabolism in patients treated with β-lapachone. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Theoretical aspects of several successive two-step redox mechanisms in protein-film cyclic staircase voltammetry

International Nuclear Information System (INIS)

Gulaboski, Rubin; Kokoškarova, Pavlinka; Mitrev, Saša

2012-01-01

Highlights: ► Theoretical models for 2e− successive mechanisms are considered. ► The models are compatible for various metal-containing redox proteins. ► Diagnostic criteria are provided to recognize the particular redox mechanism. - Abstract: Protein-film voltammetry (PFV) is a versatile tool designed to provide insight into the enzymes physiological functions by studying the redox properties of various oxido-reductases with suitable voltammetric technique. The determination of the thermodynamic and kinetic parameters relevant to protein's physiological properties is achieved via methodologies established from theoretical considerations of various mechanisms in PFV. So far, the majority of the mathematical models in PFV have been developed for redox proteins undergoing a single-step electron transfer reactions. However, there are many oxido-reductases containing quinone moieties or polyvalent ions of transition metals like Mo, Mn, W, Fe or Co as redox centers, whose redox chemistry can be described only via mathematical models considering successive two-step electron transformation. In this work we consider theoretically the protein-film redox mechanisms of the EE (Electrochemical–Electrochemical), ECE (Electrochemical–Chemical–Electrochemical), and EECat (Electrochemical–Electrochemical–Catalytic) systems under conditions of cyclic staircase voltammetry. We also propose methodologies to determine the kinetics of electron transfer steps by all considered mechanisms. The experimentalists working with PFV can get large benefits from the simulated voltammograms given in this work.

Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase*

Science.gov (United States)

Mishanina, Tatiana V.; Yadav, Pramod K.; Ballou, David P.; Banerjee, Ruma

2015-01-01

The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be −123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation. PMID:26318450

Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase.

Science.gov (United States)

Mishanina, Tatiana V; Yadav, Pramod K; Ballou, David P; Banerjee, Ruma

2015-10-09

The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be -123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Enhanced microbial decolorization of methyl red with oxidized carbon fiber as redox mediator

Energy Technology Data Exchange (ETDEWEB)

Emilia Rios-Del Toro, E. [División de Ciencias Ambientales, Instituto Potosino de Investigación Científica y Tecnológica (IPICyT), Camino a la Presa San José 2055, Col. Lomas 4a Sección, San Luis Potosí, SLP 78216 (Mexico); Celis, Lourdes B. [División de Geociencias Aplicadas, Instituto Potosino de Investigación Científica y Tecnológica (IPICyT), Camino a la Presa San José 2055, Col. Lomas 4a Sección, San Luis Potosí, SLP 78216 (Mexico); Cervantes, Francisco J. [División de Ciencias Ambientales, Instituto Potosino de Investigación Científica y Tecnológica (IPICyT), Camino a la Presa San José 2055, Col. Lomas 4a Sección, San Luis Potosí, SLP 78216 (Mexico); Rangel-Mendez, J. Rene, E-mail: rene@ipicyt.edu.mx [División de Ciencias Ambientales, Instituto Potosino de Investigación Científica y Tecnológica (IPICyT), Camino a la Presa San José 2055, Col. Lomas 4a Sección, San Luis Potosí, SLP 78216 (Mexico)

2013-09-15

Highlights: • Activated carbon fibers (ACFs) act as redox mediator. • Electron accepting capacity increased with oxidation time of ACF. •ACFs increased 8-fold the reduction of methyl red in biological assays. •Biofilm formed on the ACFs partly blocked their redox mediator capacity. -- Abstract: The anaerobic degradation of azo dyes under anaerobic conditions is possible but at a slow rate. Redox mediators (quinones, activated carbon) are used to improve the reduction rate. The aim of this work was to use activated carbon fiber (ACF) as a redox mediator for the anaerobic reduction of the azo dye methyl red. ACF was chemically modified with 8 M HNO{sub 3} to increase its redox-mediating capacity and used in chemical and anaerobic biological batch assays for the reduction of methyl red. ACF increased its redox-mediating capacity up to 3-fold in chemical assays; in biological assays ACF increased the reduction rate up to 8-fold compared to controls without ACF. However, since the ACF served as support for biomass, a biofilm formed on the fiber significantly reduced its redox-mediating capacity; substrate consumption suggested that the electron transport from ACF to methyl red was the rate-limiting step in the process. These results are the first evidence of the role of ACF as a redox mediator in the reductive decolorization of methyl red, in addition to the effect of biofilm attached to ACF on methyl red reduction. Due to the versatile characteristics of ACF and its redox-mediating capacity, carbon fibers could be used in biological wastewater treatment systems to accelerate the reductive transformation of pollutants commonly found in industrial effluents.

Enhanced microbial decolorization of methyl red with oxidized carbon fiber as redox mediator

International Nuclear Information System (INIS)

Emilia Rios-Del Toro, E.; Celis, Lourdes B.; Cervantes, Francisco J.; Rangel-Mendez, J. Rene

2013-01-01

Highlights: • Activated carbon fibers (ACFs) act as redox mediator. • Electron accepting capacity increased with oxidation time of ACF. •ACFs increased 8-fold the reduction of methyl red in biological assays. •Biofilm formed on the ACFs partly blocked their redox mediator capacity. -- Abstract: The anaerobic degradation of azo dyes under anaerobic conditions is possible but at a slow rate. Redox mediators (quinones, activated carbon) are used to improve the reduction rate. The aim of this work was to use activated carbon fiber (ACF) as a redox mediator for the anaerobic reduction of the azo dye methyl red. ACF was chemically modified with 8 M HNO 3 to increase its redox-mediating capacity and used in chemical and anaerobic biological batch assays for the reduction of methyl red. ACF increased its redox-mediating capacity up to 3-fold in chemical assays; in biological assays ACF increased the reduction rate up to 8-fold compared to controls without ACF. However, since the ACF served as support for biomass, a biofilm formed on the fiber significantly reduced its redox-mediating capacity; substrate consumption suggested that the electron transport from ACF to methyl red was the rate-limiting step in the process. These results are the first evidence of the role of ACF as a redox mediator in the reductive decolorization of methyl red, in addition to the effect of biofilm attached to ACF on methyl red reduction. Due to the versatile characteristics of ACF and its redox-mediating capacity, carbon fibers could be used in biological wastewater treatment systems to accelerate the reductive transformation of pollutants commonly found in industrial effluents

Cranberry extract-enriched diets increase NAD(P)H:quinone oxidoreductase and catalase activities in obese but not in nonobese mice.

Science.gov (United States)

Boušová, Iva; Bártíková, Hana; Matoušková, Petra; Lněničková, Kateřina; Zappe, Lukáš; Valentová, Kateřina; Szotáková, Barbora; Martin, Jan; Skálová, Lenka

2015-10-01

Consumption of antioxidant-enriched diets is 1 method of addressing obesity, which is associated with chronic oxidative stress and changes in the activity/expression of various enzymes. In this study, we hypothesized that the modulation of antioxidant enzymes and redox status through a cranberry extract (CBE)-enriched diet would differ between obese and nonobese mice. The CBE used in this study was obtained from the American cranberry (Vaccinium macrocarpon, Ericaceae), a popular constituent of dietary supplements that is a particularly rich source of (poly)phenols and has strong antioxidant properties. The present study was designed to test and compare the in vivo effects of 28-day consumption of a CBE-enriched diet (2%) on the antioxidant status of nonobese mice and mice with monosodium glutamate-induced obesity. Plasma, erythrocytes, liver, and small intestine were studied concurrently to obtain more complex information. The specific activities, protein, and messenger RNA expression levels of antioxidant enzymes as well as the levels of malondialdehyde and thiol (SH) groups were analyzed. Cranberry extract treatment increased the SH group content in plasma and the glutathione S-transferase activity in the erythrocytes of the obese and nonobese mice. In addition, in the obese animals, the CBE treatment reduced the malondialdehyde content in erythrocytes and increased quinone oxidoreductase (liver) and catalase (erythrocytes and small intestine) activities. The elevation of hepatic quinone oxidoreductase activity was accompanied by an increase in the corresponding messenger RNA levels. The effects of CBE on the activity of antioxidant enzymes and redox status were more pronounced in the obese mice compared with the nonobese mice. Copyright © 2015 Elsevier Inc. All rights reserved.

Redox imbalance and mitochondrial abnormalities in the diabetic lung.

Science.gov (United States)

Wu, Jinzi; Jin, Zhen; Yan, Liang-Jun

2017-04-01

Although the lung is one of the least studied organs in diabetes, increasing evidence indicates that it is an inevitable target of diabetic complications. Nevertheless, the underlying biochemical mechanisms of lung injury in diabetes remain largely unexplored. Given that redox imbalance, oxidative stress, and mitochondrial dysfunction have been implicated in diabetic tissue injury, we set out to investigate mechanisms of lung injury in diabetes. The objective of this study was to evaluate NADH/NAD + redox status, oxidative stress, and mitochondrial abnormalities in the diabetic lung. Using STZ induced diabetes in rat as a model, we measured redox-imbalance related parameters including aldose reductase activity, level of poly ADP ribose polymerase (PAPR-1), NAD + content, NADPH content, reduced form of glutathione (GSH), and glucose 6-phophate dehydrogenase (G6PD) activity. For assessment of mitochondrial abnormalities in the diabetic lung, we measured the activities of mitochondrial electron transport chain complexes I to IV and complex V as well as dihydrolipoamide dehydrogenase (DLDH) content and activity. We also measured the protein content of NAD + dependent enzymes such as sirtuin3 (sirt3) and NAD(P)H: quinone oxidoreductase 1 (NQO1). Our results demonstrate that NADH/NAD + redox imbalance occurs in the diabetic lung. This redox imbalance upregulates the activities of complexes I to IV, but not complex V; and this upregulation is likely the source of increased mitochondrial ROS production, oxidative stress, and cell death in the diabetic lung. These results, together with the findings that the protein contents of DLDH, sirt3, and NQO1 all are decreased in the diabetic lung, demonstrate that redox imbalance, mitochondrial abnormality, and oxidative stress contribute to lung injury in diabetes. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

The study of redox mechanism of dobutamine at different pH media by electrochemical and in situ spectroelectrochemical methods

International Nuclear Information System (INIS)

Yang Gongjun; Xu Jingjuan; Chen Hongyuan

2004-01-01

Based on the comprehensive analyses of the experimental results of the electrochemical methods, in situ UV-Vis absorption spectra, in situ electron spin resonance (ESR), and attenuated total-internal reflection (ATR) as well as the calculation of UV-Vis absorption data by PM3 Semi-Empirical method, a reaction mechanism for the redox processes of dobutamine was presented. When the anodic sweep is carried out, dobutamine firstly undergoes a free radical reaction with one-electron and one-proton to form semi-quinone free radicals, which will continuously convert to its corresponding quinone form by further electrochemical oxidation reaction. The formed quinone cannot only undergo a cyclization process by chemical reaction to produce a new compound, which can be reduced at more negative potential, but also be reduced to form dobutamine again when subsequent cathodic sweep is followed. The cyclization rate is depended upon pH values, and it increases with the increase of pH. In neutral medium, the corresponding oxidation form of the cyclization reaction product is easy to convert to melanin

On-column reduction of catecholamine quinones in stainless steel columns during liquid chromatography.

Science.gov (United States)

Xu, R; Huang, X; Kramer, K J; Hawley, M D

1995-10-10

The chromatographic behavior of quinones derived from the oxidation of dopamine and N-acetyldopamine has been studied using liquid chromatography (LC) with both a diode array detector and an electrochemical detector that has parallel dual working electrodes. When stainless steel columns are used, an anodic peak for the oxidation of the catecholamine is observed at the same retention time as a cathodic peak for the reduction of the catecholamine quinone. In addition, the anodic peak exhibits a tail that extends to a second anodic peak for the catecholamine. The latter peak occurs at the normal retention time of the catecholamine. The origin of this phenomenon has been studied and metallic iron in the stainless steel components of the LC system has been found to reduce the quinones to their corresponding catecholamines. The simultaneous appearance of a cathodic peak for the reduction of catecholamine quinone and an anodic peak for the oxidation of the corresponding catecholamine occurs when metallic iron in the exit frit reduces some of the quinones as the latter exits the column. This phenomenon is designated as the "concurrent anodic-cathodic response." It is also observed for quinones of of 3,4-dihydroxybenzoic acid and probably occurs with o- or p-quinones of other dihydroxyphenyl compounds. The use of nonferrous components in LC systems is recommended to eliminate possible on-column reduction of quinones.

In situ observations of microstructural changes in SOFC anodes during redox cycling

DEFF Research Database (Denmark)

Klemensø, Trine; Appel, C. C.; Mogensen, Mogens Bjerg

2006-01-01

The anode-supported solid oxide fuel cell (SOFC) degrades when the anode is subjected to redox cycling. The degradation has qualitatively been related to microstructural changes in the nickel-yttria stabilized zirconia anode of the tested cells. In this work, the microstructural changes were...... observed in situ using environmental scanning electron microscopy. In the reduced state, a dynamic rounding of the nickel particles occurred. The oxide growth upon re-oxidation depended on the oxidation kinetics. During rapid oxidation, the NiO particles divided into 2-4 particles, which grew...... into the surrounding voids. For slower oxidation, an external oxide layer was seen to develop around the individual particles. (c) 2006 The Electrochemical Society....

The reactivity of Fe(II) associated with goethite formed during short redox cycles toward Cr(VI) reduction under oxic conditions

Energy Technology Data Exchange (ETDEWEB)

Tomaszewski, Elizabeth J.; Lee, Seungyeol; Rudolph, Jared; Xu, Huifang; Ginder-Vogel, Matthew (UW)

2017-08-01

Chromium (Cr) is a toxic metal that causes a myriad of health problems and enters the environment as a result of anthropogenic activities and/or natural processes. The toxicity and solubility of chromium is linked to its oxidation state; Cr(III) is poorly soluble and relatively nontoxic, while Cr(VI) is soluble and a known carcinogen. Solid Fe(II) in iron-bearing minerals, such as pyrite, magnetite, and green rusts, reduce the oxidation state of chromium, reducing its toxicity and mobility. However, these minerals are not the only potential sources of solid-associated Fe(II) available for Cr(VI) reduction. For example, ferric (Fe(III)) (hydr)oxides, such as goethite or hematite, can have Fe(II) in the solid without phase transformation; however, the reactivity of Fe(II) within Fe(III) (hydr)oxides with contaminants, has not been previously investigated. Here, we cyclically react goethite with dissolved Fe(II) followed by dissolved O2, leading to the formation of reactive Fe(II) associated with goethite. In separate reactors, the reactivity of this Fe(II) is probed under oxic conditions, by exposure to chromate (CrO42 -) after either one, two, three or four redox cycles. Cr is not present during redox cycling; rather, it is introduced to a subset of the solid after each oxidation half-cycle. Analysis of X-ray absorption near edge structure (XANES) spectra reveals that the extent of Cr(VI) reduction to Cr(III) depends not only on solid Fe(II) content but also surface area and mean size of ordered crystalline domains, determined by BET surface area analysis and X-ray diffraction (XRD), respectively. Shell-by-shell fitting of the extended X-ray absorption fine structure (EXAFS) spectra demonstrates chromium forms both single and double corner sharing complexes on the surface of goethite, in addition to sorbed Cr(III) species. Finally, transmission electron microscope (TEM) imaging and X-ray energy-dispersive spectroscopy (EDS) illustrate that Cr preferentially

Redox cycling-based amplifying electrochemical sensor for in situ clozapine antipsychotic treatment monitoring

International Nuclear Information System (INIS)

Ben-Yoav, Hadar; Winkler, Thomas E.; Kim, Eunkyoung; Chocron, Sheryl E.; Kelly, Deanna L.; Payne, Gregory F.; Ghodssi, Reza

2014-01-01

Highlights: • A new concept for clozapine in situ sensing with minimal pre-treatment procedures. • A catechol-chitosan redox cycling system amplifies clozapine oxidation current. • The modified amplifier signal is 3 times greater than the unmodified system. • Differentiation between clozapine and its metabolite norclozapine has been shown. • The sensor has the capability to detect clozapine in human serum. - Abstract: Schizophrenia is a lifelong mental disorder with few recent advances in treatment. Clozapine is the most effective antipsychotic for schizophrenia treatment. However, it remains underutilized since frequent blood draws are required to monitor adverse side effects, and maintain clozapine concentrations in a therapeutic range. Micro-system technology utilized towards real-time monitoring of efficacy and safety will enable personalized medicine and better use of this medication. Although work has been reported on clozapine detection using its electrochemical oxidation, no in situ monitoring of clozapine has been described. In this work, we present a new concept for clozapine in situ sensing based on amplifying its oxidation current. Specifically, we use a biofabricated catechol-modified chitosan redox cycling system to provide a significant amplification of the generated oxidizing current of clozapine through a continuous cycle of clozapine reduction followed by re-oxidation. The amplified signal has improved the signal-to-noise ratio and provided the required limit-of-detection and dynamic range for clinical applications with minimal pre-treatment procedures. The sensor reports on the functionality and sensitivity of clozapine detection between 0.1 and 10 μg/mL. The signal generated by clozapine using the catechol-modified chitosan amplifier has shown to be 3 times greater than the unmodified system. The sensor has the ability to differentiate between clozapine and its metabolite norclozapine, as well as the feasibility to detect clozapine in

Pyridine nucleotide cycling and control of intracellular redox state in relation to poly (ADP-ribose) polymerase activity and nuclear localization of glutathione during exponential growth of Arabidopsis cells in culture.

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Pellny, Till K; Locato, Vittoria; Vivancos, Pedro Diaz; Markovic, Jelena; De Gara, Laura; Pallardó, Federico V; Foyer, Christine H

2009-05-01

Pyridine nucleotides, ascorbate and glutathione are major redox metabolites in plant cells, with specific roles in cellular redox homeostasis and the regulation of the cell cycle. However, the regulation of these metabolite pools during exponential growth and their precise functions in the cell cycle remain to be characterized. The present analysis of the abundance of ascorbate, glutathione, and pyridine nucleotides during exponential growth of Arabidopsis cells in culture provides evidence for the differential regulation of each of these redox pools. Ascorbate was most abundant early in the growth cycle, but glutathione was low at this point. The cellular ascorbate to dehydroascorbate and reduced glutathione (GSH) to glutathione disulphide ratios were high and constant but the pyridine nucleotide pools were largely oxidized over the period of exponential growth and only became more reduced once growth had ceased. The glutathione pool increased in parallel with poly (ADP-ribose) polymerase (PARP) activities and with increases in the abundance of PARP1 and PARP2 mRNAs at a time of high cell cycle activity as indicated by transcriptome information. Marked changes in the intracellular partitioning of GSH between the cytoplasm and nucleus were observed. Extension of the exponential growth phase by dilution or changing the media led to increases in the glutathione and nicotinamide adenine dinucleotide, oxidized form (NAD)-plus-nicotinamide adenine dinucleotide, reduced form (NADH) pools and to higher NAD/NADH ratios but the nicotinamide adenine dinucleotide phosphate, oxidized form (NADP)-plus-nicotinamide adenine dinucleotide phosphate, reduced form (NADPH) pool sizes, and NAPD/NADPH ratios were much less affected. The ascorbate, glutathione, and pyridine nucleotide pools and PARP activity decreased before the exponential growth phase ended. We conclude that there are marked changes in intracellular redox state during the growth cycle but that redox homeostasis is

Capacitance enhancement of polyaniline coated curved-graphene supercapacitors in a redox-active electrolyte

Science.gov (United States)

Chen, Wei; Rakhi, R. B.; Alshareef, H. N.

2013-05-01

We show, for the first time, a redox-active electrolyte in combination with a polyaniline-coated curved graphene active material to achieve significant enhancement in the capacitance (36-92% increase) compared to supercapacitors that lack the redox-active contribution from the electrolyte. The supercapacitors based on the redox-active electrolyte also exhibit excellent rate capability and very long cycling performance (>50 000 cycles).We show, for the first time, a redox-active electrolyte in combination with a polyaniline-coated curved graphene active material to achieve significant enhancement in the capacitance (36-92% increase) compared to supercapacitors that lack the redox-active contribution from the electrolyte. The supercapacitors based on the redox-active electrolyte also exhibit excellent rate capability and very long cycling performance (>50 000 cycles). Electronic supplementary information (ESI) available: Experimental section, supporting figures including SEM, TEM, XPS, BET, CV and CD curves and a summary table of capacitance. See DOI: 10.1039/c3nr00773a

Identification of quinone imine containing glutathione conjugates of diclofenac in rat bile.

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Waldon, Daniel J; Teffera, Yohannes; Colletti, Adria E; Liu, Jingzhou; Zurcher, Danielle; Copeland, Katrina W; Zhao, Zhiyang

2010-12-20

High-resolution accurate MS with an LTQ-Orbitrap was used to identify quinone imine metabolites derived from the 5-hydroxy (5-OH) and 4 prime-hydroxy (4'-OH) glutathione conjugates of diclofenac in rat bile. The initial quinone imine metabolites formed by oxidation of diclofenac have been postulated to be reactive intermediates potentially involved in diclofenac-mediated hepatotoxicity; while these metabolites could be formed using in vitro systems, they have never been detected in vivo. This report describes the identification of secondary quinone imine metabolites derived from 5-OH and 4'-OH diclofenac glutathione conjugates in rat bile. To verify the proposed structures, the diclofenac quinone imine GSH conjugate standards were prepared synthetically and enzymatically. The novel metabolite peaks displayed the identical retention times, accurate mass MS/MS spectra, and the fragmentation patterns as the corresponding authentic standards. The formation of these secondary quinone metabolites occurs only under conditions where bile salt homeostasis was experimentally altered. Standard practice in biliary excretion experiments using bile duct-cannulated rats includes infusion of taurocholic acid and/or other bile acids to replace those lost due to continuous collection of bile; for this experiment, the rats received no replacement bile acid infusion. High-resolution accurate mass spectrometry data and comparison with chemically and enzymatically prepared quinone imines of diclofenac glutathione conjugates support the identification of these metabolites. A mechanism for the formation of these reactive quinone imine containing glutathione conjugates of diclofenac is proposed.

The effect of cycling on the nanoscale morphology and redox properties of poly[2,2′-bithiophene

International Nuclear Information System (INIS)

O’Neil, K.D.; Smith, A.; Forristal, T.A.; Semenikhin, O.A.

2013-01-01

The changes in the redox behavior and nanoscale morphology of poly[2,2′-bithiophene] deposited onto highly oriented pyrolytic graphite substrates upon repeated doping–undoping were studied. It was shown that repeated cycling resulted in very particular changes in the voltammetric response of the polymer films as well as their nanoscale morphology. Specifically, when the cycling was performed to relatively low anodic potentials, the overall doping–undoping charge did not change; however, the shape of voltammograms was consistently changing showing broadening of the voltammograms and reducing of the doping peak height in the anodic scan, as well as broadening and deterioration of the undoping peak in the reverse scan. Furthermore, a remarkable feature was observed that all voltammogram traces intersected at several characteristic potentials producing quasi-isosbestic points. With an increase in the anodic scan potential limit, the overall doping–undoping charge starts to decrease showing irreversible degradation of the polymer; however, the general pattern of the peak broadening could be still observed. Atomic force microscopic (AFM) studies of the polymer films cycled to various anodic limits showed that repeated cycling resulted in a gradual decrease in the degree of crystallinity, as revealed by AFM phase imaging, and an increase in the degree of disorder. Coupled with the changes in the redox behavior, these findings suggested the formation of more flexible and open polymer nanostructure that enables easier penetration of the dopant ions and solvent. However, at the same time, an increase in the degree of disorder reduced the interchain interactions and inhibited the formation of extended electronic states delocalized across neighboring polymer chains. This occurred at first without irreversible degradation of the polymer and a decrease in the overall doping–undoping charge. Cycling to higher anodic potentials resulted in irreversible degradation

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

Production of quinones by in vitro cultures of Dionaea and Streptocarpus species

OpenAIRE

Nestor, Cora

2006-01-01

Quinones are a class of oxygen-containing secondary metabolites found chiefly in higher plants, fungi, bacteria and restricted in the animal kingdom to arthropods and echinoderms (Thompson 1971). In the plant, quinones, especially naphthoquinones, have been shown to function in allelopathy (juglone; Binder et al 1989), plant-insect interactions and plant-plant interactions (plumbagin; Kubo et al 1986, 1998, Spencer et al 1986, Ganapaty et al 2004). These quinones also have significant in vitr...

Quinones from Heliotropium ovalifolium.

Science.gov (United States)

Guntern, A; Ioset, J R; Queiroz, E F; Foggin, C M; Hostettmann, K

2001-10-01

Two new benzoquinones, heliotropinones A and B, have been isolated from the aerial parts of Heliotropium ovalifolium. Their structures were elucidated by spectrometric methods including high resolution electrospray ionization (ESI-HR), EI mass spectrometry, 1H, 13C and 2D NMR experiments. The two quinones demonstrated antifungal activities against Cladosporium cucumerinum and Candida albicans as well as antibacterial activity against Bacillus subtilis.

Efficient cycles for carbon capture CLC power plants based on thermally balanced redox reactors

KAUST Repository

Iloeje, Chukwunwike

2015-10-01

© 2015 Elsevier Ltd. The rotary reactor differs from most alternative chemical looping combustion (CLC) reactor designs because it maintains near-thermal equilibrium between the two stages of the redox process by thermally coupling channels undergoing oxidation and reduction. An earlier study showed that this thermal coupling between the oxidation and reduction reactors increases the efficiency by up to 2% points when implemented in a regenerative Brayton cycle. The present study extends this analysis to alternative CLC cycles with the objective of identifying optimal configurations and design tradeoffs. Results show that the increased efficiency from reactor thermal coupling applies only to cycles that are capable of exploiting the increased availability in the reduction reactor exhaust. Thus, in addition to the regenerative cycle, the combined CLC cycle and the combined-regenerative CLC cycle are suitable for integration with the rotary reactor. Parametric studies are used to compare the sensitivity of the different cycle efficiencies to parameters like pressure ratio, turbine inlet temperature, carrier-gas fraction and purge steam generation. One of the key conclusions from this analysis is that while the optimal efficiency for regenerative CLC cycle was the highest of the three (56% at 3. bars, 1200. °C), the combined-regenerative cycle offers a trade-off that combines a reasonably high efficiency (about 54% at 12. bars, 1200. °C) with much lower gas volumetric flow rate and consequently, smaller reactor size. Unlike the other two cycles, the optimal compressor pressure ratio for the regenerative cycle is weakly dependent on the design turbine inlet temperature. For the regenerative and combined regenerative cycles, steam production in the regenerator below 2× fuel flow rate improves exhaust recovery and consequently, the overall system efficiency. Also, given that the fuel side regenerator flow is unbalanced, it is more efficient to generate steam from the

Catalytic asymmetric diels-alder reaction of quinone imine ketals: a site-divergent approach.

Science.gov (United States)

Hashimoto, Takuya; Nakatsu, Hiroki; Maruoka, Keiji

2015-04-07

The catalytic asymmetric Diels-Alder reaction of quinone imine ketals with diene carbamates catalyzed by axially chiral dicarboxylic acids is reported herein. A variety of primary and secondary alkyl-substituted quinone derivatives which have not been applied in previous asymmetric quinone Diels-Alder reactions could be employed using this method. More importantly, we succeeded in developing a strategy to divert the reaction site in unsymmetrical 3-alkyl quinone imine ketals from the inherently favored unsubstituted C=C bond to the disfavored alkyl-substituted C=C bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Long-term litter decomposition controlled by manganese redox cycling.

Science.gov (United States)

Keiluweit, Marco; Nico, Peter; Harmon, Mark E; Mao, Jingdong; Pett-Ridge, Jennifer; Kleber, Markus

2015-09-22

Litter decomposition is a keystone ecosystem process impacting nutrient cycling and productivity, soil properties, and the terrestrial carbon (C) balance, but the factors regulating decomposition rate are still poorly understood. Traditional models assume that the rate is controlled by litter quality, relying on parameters such as lignin content as predictors. However, a strong correlation has been observed between the manganese (Mn) content of litter and decomposition rates across a variety of forest ecosystems. Here, we show that long-term litter decomposition in forest ecosystems is tightly coupled to Mn redox cycling. Over 7 years of litter decomposition, microbial transformation of litter was paralleled by variations in Mn oxidation state and concentration. A detailed chemical imaging analysis of the litter revealed that fungi recruit and redistribute unreactive Mn(2+) provided by fresh plant litter to produce oxidative Mn(3+) species at sites of active decay, with Mn eventually accumulating as insoluble Mn(3+/4+) oxides. Formation of reactive Mn(3+) species coincided with the generation of aromatic oxidation products, providing direct proof of the previously posited role of Mn(3+)-based oxidizers in the breakdown of litter. Our results suggest that the litter-decomposing machinery at our coniferous forest site depends on the ability of plants and microbes to supply, accumulate, and regenerate short-lived Mn(3+) species in the litter layer. This observation indicates that biogeochemical constraints on bioavailability, mobility, and reactivity of Mn in the plant-soil system may have a profound impact on litter decomposition rates.

Chemical modification of b-lactoglobulin by quinones

Directory of Open Access Journals (Sweden)

DUSAN SLADIC

2003-05-01

Full Text Available The avarone/avarol quinone/hydroquinone couple, as well as their derivatives show considerable antitumor activity. In this work, covalent modifications of b-lactoglobulin, isolated from cow milk, by avarone, its model compound 2-tert-butyl-1,4-benzoquinone, and several of their alkylthio derivatives were studied. The techniques applied for assaying the modifications were: UV/VIS spectrophotometry, SDS PAGE and isoelectrofocusing. The results of the SDS PAGE suggest that polymerisation of the protein occurs. The shift of the pI of the protein upon modification toward lower values indicates that lysine amino groups are the principal site of the reaction of b-lactoglobulin with the quinones.

The regioselectivity of glutathione adduct formation with flavonoid quinone methides is pH-dependent

NARCIS (Netherlands)

Awad, H.M.; Boersma, M.G.; Boeren, S.; Vervoort, J.; Bladeren, van P.J.; Rietjens, I.M.C.M.

2002-01-01

In the present study, the formation of glutathionyl adducts from a series of 3',4'-dihydroxy flavonoid o-quinone/p-quinone methides was investigated with special emphasis on the regioselectivity of the glutathione addition as a function of pH. The flavonoid o-quinones were generated using

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.

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.

Redox Stable Anodes for Solid Oxide Fuel Cells

Directory of Open Access Journals (Sweden)

Guoliang eXiao

2014-06-01

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

Role of Quinone Reductase 2 in the Antimalarial Properties of Indolone-Type Derivatives

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Laure-Estelle Cassagnes

2017-01-01

Full Text Available Indolone-N-oxides have antiplasmodial properties against Plasmodium falciparum at the erythrocytic stage, with IC50 values in the nanomolar range. The mechanism of action of indolone derivatives involves the production of free radicals, which follows their bioreduction by an unknown mechanism. In this study, we hypothesized that human quinone reductase 2 (hQR2, known to act as a flavin redox switch upon binding to the broadly used antimalarial chloroquine, could be involved in the activity of the redox-active indolone derivatives. Therefore, we investigated the role of hQR2 in the reduction of indolone derivatives. We analyzed the interaction between hQR2 and several indolone-type derivatives by examining enzymatic kinetics, the substrate/protein complex structure with X-ray diffraction analysis, and the production of free radicals with electron paramagnetic resonance. The reduction of each compound in cells overexpressing hQR2 was compared to its reduction in naïve cells. This process could be inhibited by the specific hQR2 inhibitor, S29434. These results confirmed that the anti-malarial activity of indolone-type derivatives was linked to their ability to serve as hQR2 substrates and not as hQR2 inhibitors as reported for chloroquine, leading to the possibility that substrate of hQR2 could be considered as a new avenue for the design of new antimalarial compounds.

Dimethylfumarate induces cell cycle arrest and apoptosis via regulating intracellular redox systems in HeLa cells.

Science.gov (United States)

Han, Guocan; Zhou, Qiang

2016-12-01

Dimethylfumarate (DMF) is cytotoxic to several kinds of cells and serves as an anti-tumor drug. This study was designed to investigate the effects and underlying mechanism of DMF on cervical cancer cells. HeLa cells were cultured and treated with 0, 50, 100, 150, and 200 μM DMF, respectively. After 24 h, cell growth was evaluated using Cell Counting Kit-8 (CCK-8) assay and the cell cycle was examined using flow cytometry. In addition, cell apoptosis was detected by Annexin V/propidium iodide (PI) staining and the expressions of caspase-3 and poly-ADP-ribose polymerase (PARP) were detected using western blotting. The redox-related factors were then assessed. Furthermore, all of the indicators were detected in HeLa cells after combined treatment of DMF and N-acetyl-L-cysteine (NAC, an oxygen-free radical scavenger). The cell number and cell growth of HeLa were obviously inhibited by DMF in a dose-dependent manner, as the cell cycle was arrested at G0/G1 phase (P HeLa cells were markedly increased, and the expression levels of caspase-3 and PARP were significantly increased in a DMF concentration-dependent way (P cell proliferation and apoptosis of HeLa cells was mainly related to the intracellular redox systems by depletion of intracellular GSH.

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.

Akt1 intramitochondrial cycling is a crucial step in the redox modulation of cell cycle progression.

Directory of Open Access Journals (Sweden)

Valeria Gabriela Antico Arciuch

2009-10-01

Full Text Available Akt is a serine/threonine kinase involved in cell proliferation, apoptosis, and glucose metabolism. Akt is differentially activated by growth factors and oxidative stress by sequential phosphorylation of Ser(473 by mTORC2 and Thr(308 by PDK1. On these bases, we investigated the mechanistic connection of H(2O(2 yield, mitochondrial activation of Akt1 and cell cycle progression in NIH/3T3 cell line with confocal microscopy, in vivo imaging, and directed mutagenesis. We demonstrate that modulation by H(2O(2 entails the entrance of cytosolic P-Akt1 Ser(473 to mitochondria, where it is further phosphorylated at Thr(308 by constitutive PDK1. Phosphorylation of Thr(308 in mitochondria determines Akt1 passage to nuclei and triggers genomic post-translational mechanisms for cell proliferation. At high H(2O(2, Akt1-PDK1 association is disrupted and P-Akt1 Ser(473 accumulates in mitochondria in detriment to nuclear translocation; accordingly, Akt1 T308A is retained in mitochondria. Low Akt1 activity increases cytochrome c release to cytosol leading to apoptosis. As assessed by mass spectra, differential H(2O(2 effects on Akt1-PDK interaction depend on the selective oxidation of Cys(310 to sulfenic or cysteic acids. These results indicate that Akt1 intramitochondrial-cycling is central for redox modulation of cell fate.

New light on a dark subject: On the use of fluorescence data to deduce redox states of natural organic matter (NOM)

Science.gov (United States)

Macalady, Donald L.; Walton-Day, Katherine

2009-01-01

This paper reports the use of excitation-emission matrix fluorescence spectroscopy (EEMS), parallel factor statistical analysis (PARAFAC), and oxidation-reduction experiments to examine the effect of redox conditions on PARAFAC model results for aqueous samples rich in natural organic matter. Fifty-four aqueous samples from 11 different geographic locations and two plant extracts were analyzed untreated and after chemical treatments or irradiation were used in attempts to change the redox status of the natural organic matter. The EEMS spectra were generated and modeled using a PARAFAC package developed by Cory and McKnight (2005). The PARAFAC model output was examined for consistency with previously reported relations and with changes expected to occur upon experimental oxidation and reduction of aqueous samples. Results indicate the implied fraction of total sample fluorescence attributed to quinone-like moieties was consistent (0.64 to 0.78) and greater than that observed by Cory and McKnight (2005). The fraction of the quinone-like moieties that was reduced (the reducing index, RI) showed relatively little variation (0.46 to 0.71) despite attempts to alter the redox status of the natural organic matter. The RI changed little after reducing samples using zinc metal, oxidizing at high pH with air, or irradiating with a Xenon lamp. Our results, however, are consistent with the correlations between the fluorescence indices (FI) of samples and the ratio of PARAFAC fitting parameters suggested by Cory and McKnight (2005), though we used samples with a much narrower range of FI values.

Interaction of quinones with three pyrimidine bases: A laser flash photolysis study

Energy Technology Data Exchange (ETDEWEB)

Bose, Adity [Chemical Sciences Division, Saha Institute of Nuclear Physics, 1/AF Bidhannagar, Kolkata 700064 (India); Basu, Samita, E-mail: samita.basu@saha.ac.i [Chemical Sciences Division, Saha Institute of Nuclear Physics, 1/AF Bidhannagar, Kolkata 700064 (India)

2009-11-15

The interaction between three different pyrimidine bases, uracil (U), cytosine (C) and thymine (T) and two quinones, 2-methyl-1,4-naphthoquinone or menadione (MQ) and 9,10-anthraquinone (AQ) have been studied using laser flash photolysis technique in organic homogeneous medium. The three pyrimidines have revealed a difference in their extent of reactivity towards the quinones, which has been attributed to their structural difference. Our works have revealed that the difference in structural dimension of the quinones is also responsible for affecting the reactivity of these pyrimidines in homogeneous medium.

Interaction of quinones with three pyrimidine bases: A laser flash photolysis study

International Nuclear Information System (INIS)

Bose, Adity; Basu, Samita

2009-01-01

The interaction between three different pyrimidine bases, uracil (U), cytosine (C) and thymine (T) and two quinones, 2-methyl-1,4-naphthoquinone or menadione (MQ) and 9,10-anthraquinone (AQ) have been studied using laser flash photolysis technique in organic homogeneous medium. The three pyrimidines have revealed a difference in their extent of reactivity towards the quinones, which has been attributed to their structural difference. Our works have revealed that the difference in structural dimension of the quinones is also responsible for affecting the reactivity of these pyrimidines in homogeneous medium.

Powering Lithium-Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts.

Science.gov (United States)

Yuan, Zhe; Peng, Hong-Jie; Hou, Ting-Zheng; Huang, Jia-Qi; Chen, Cheng-Meng; Wang, Dai-Wei; Cheng, Xin-Bing; Wei, Fei; Zhang, Qiang

2016-01-13

Lithium-sulfur (Li-S) battery system is endowed with tremendous energy density, resulting from the complex sulfur electrochemistry involving multielectron redox reactions and phase transformations. Originated from the slow redox kinetics of polysulfide intermediates, the flood of polysulfides in the batteries during cycling induced low sulfur utilization, severe polarization, low energy efficiency, deteriorated polysulfide shuttle, and short cycling life. Herein, sulfiphilic cobalt disulfide (CoS2) was incorporated into carbon/sulfur cathodes, introducing strong interaction between lithium polysulfides and CoS2 under working conditions. The interfaces between CoS2 and electrolyte served as strong adsorption and activation sites for polar polysulfides and therefore accelerated redox reactions of polysulfides. The high polysulfide reactivity not only guaranteed effective polarization mitigation and promoted energy efficiency by 10% but also promised high discharge capacity and stable cycling performance during 2000 cycles. A slow capacity decay rate of 0.034%/cycle at 2.0 C and a high initial capacity of 1368 mAh g(-1) at 0.5 C were achieved. Since the propelling redox reaction is not limited to Li-S system, we foresee the reported strategy herein can be applied in other high-power devices through the systems with controllable redox reactions.

Antitrypanosomal isoflavan quinones from Abrus precatorius

CSIR Research Space (South Africa)

Hata, Y

2014-03-01

Full Text Available Fitoterapia Vol. 93, pp 81-87 Antitrypanosomal isoflavan quinones from Abrus precatorius Yoshie Hata a,d, Samad Nejad Ebrahimi a,e, Maria De Mieri a, Stefanie Zimmermann a, Tsholofelo Mokoka c, Dashnie Naidoo c, Gerda Fouche c, Vinesh Maharaj c...

Hexamethoxylated Monocarbonyl Analogues of Curcumin Cause G2/M Cell Cycle Arrest in NCI-H460 Cells via Michael Acceptor-Dependent Redox Intervention.

Science.gov (United States)

Li, Yan; Zhang, Li-Ping; Dai, Fang; Yan, Wen-Jing; Wang, Hai-Bo; Tu, Zhi-Shan; Zhou, Bo

2015-09-09

Curcumin, derived from the dietary spice turmeric, holds promise for cancer prevention. This prompts much interest in investigating the action mechanisms of curcumin and its analogues. Two symmetrical hexamethoxy-diarylpentadienones (1 and 2) as cucumin analogues were reported to possess significantly enhanced cytotoxicity compared with the parent molecule. However, the detailed mechanisms remain unclear. In this study, compounds 1 and 2 were identified as the G2/M cell cycle arrest agents to mediate the cytotoxicity toward NCI-H460 cells via Michael acceptor-dependent redox intervention. Compared with curcumin, they could more easily induce a burst of reactive oxygen species (ROS) and collapse of the redox buffering system. One possible reason is that they could more effectively target intracellular TrxR to convert this antioxidant enzyme into a ROS promoter. Additionally, they caused up-regulation of p53 and p21 and down-regulation of redox-sensitive Cdc25C along with cyclin B1/Cdk1 in a Michael acceptor- and ROS-dependent fashion. Interestingly, in comparison with compound 2, compound 1 displayed a relatively weak ability to generate ROS but increased cell cycle arrest activity and cytotoxicity probably due to its Michael acceptor-dependent microtubule-destabilizing effect and greater GST-inhibitory activity, as well as its enhanced cellular uptake. This work provides useful information for understanding Michael acceptor-dependent and redox-mediated cytotoxic mechanisms of curcumin and its active analogues.

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

Science.gov (United States)

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

2018-02-01

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

Novel organic redox catalyst for the electroreduction of oxygen to hydrogen peroxide

International Nuclear Information System (INIS)

Wang, Andrew; Bonakdarpour, Arman; Wilkinson, David P.; Gyenge, Előd

2012-01-01

The organic redox catalysis of O 2 electroreduction to H 2 O 2 in acidic media has been investigated using several quinone and riboflavin catalysts supported on Vulcan XC72 carbon. The synthesis of a novel riboflavinyl–anthraquinone 2-carboxylate ester (RF–AQ) is reported. The activity and selectivity of organic redox catalysts (riboflavin, anthraquinone derivatives and riboflavinyl–anthraquinone 2-carboxylate ester) for the electrosynthesis of H 2 O 2 were investigated by the rotating ring-disk electrode (RRDE) method and potentiostatic electrolysis. Electrodes with 10 wt% RF–AQ loading on Vulcan XC-72 showed excellent electrocatalytic activity toward the two-electron oxygen reduction coupled with very good catalyst layer stability. The reaction mechanism for the organic redox catalysis by RF–AQ is discussed. Electroreduction of O 2 dissolved in 0.5 M H 2 SO 4 under potentiostatic conditions (0.1 V vs. RHE) at 21 °C using the composite RF–AQ/Vulcan XC72 catalyst (total loading 2.5 mg cm −2 ) deposited on unteflonated Toray ® carbon paper, generated H 2 O 2 with an initial rate of 21 μmol h −1 cm geo −2 and a stable current efficiency of 70%.

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

Science.gov (United States)

Sahoo, S. K.; Jin, H.

2017-12-01

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

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

Science.gov (United States)

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

2015-10-01

Parathion, a widely used organophosphate insecticide, is considered a high priority chemical threat. Parathion toxicity is dependent on its metabolism by the cytochrome P450 system to paraoxon (diethyl 4-nitrophenyl phosphate), a cytotoxic metabolite. As an effective inhibitor of cholinesterases, paraoxon causes the accumulation of acetylcholine in synapses and overstimulation of nicotinic and muscarinic cholinergic receptors, leading to characteristic signs of organophosphate poisoning. Inhibition of parathion metabolism to paraoxon represents a potential approach to counter parathion toxicity. Herein, we demonstrate that menadione (methyl-1,4-naphthoquinone, vitamin K3) is a potent inhibitor of cytochrome P450-mediated metabolism of parathion. Menadione is active in redox cycling, a reaction mediated by NADPH-cytochrome P450 reductase that preferentially uses electrons from NADPH at the expense of their supply to the P450s. Using human recombinant CYP 1A2, 2B6, 3A4 and human liver microsomes, menadione was found to inhibit the formation of paraoxon from parathion. Administration of menadione bisulfite (40mg/kg, ip) to rats also reduced parathion-induced inhibition of brain cholinesterase activity, as well as parathion-induced tremors and the progression of other signs and symptoms of parathion poisoning. These data suggest that redox cycling compounds, such as menadione, have the potential to effectively mitigate the toxicity of organophosphorus pesticides including parathion which require cytochrome P450-mediated activation. Copyright © 2015 Elsevier Inc. All rights reserved.

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-09-25

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

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

Science.gov (United States)

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

2017-11-01

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

A metal-free organic-inorganic aqueous flow battery

Energy Technology Data Exchange (ETDEWEB)

Huskinson, B; Marshak, MP; Suh, C; Er, S; Gerhardt, MR; Galvin, CJ; Chen, XD; Aspuru-Guzik, A; Gordon, RG; Aziz, MJ

2014-01-08

As the fraction of electricity generation from intermittent renewable sources-such as solar or wind-grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output(1,2). In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form(3-5). Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts(6,7). Here we describe a class of energy storage materials that exploits the favourable chemical and electro-chemical properties of a family of molecules known as quinones. The example we demonstrate is ametal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br-2/Br- redox couple, yields a peak galvanic power density exceeding 0.6 W cm(-2) at 1.3 A cm(-2). Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals(8). This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of p-aromatic redox-active organic molecules instead of redox-active metals

Trinuclear ruthenium dioxolene complexes based on the bridging ligand hexahydroxytriphenylene: electrochemistry, spectroscopy, and near-infrared electrochromic behaviour associated with a reversible seven-membered redox chain.

Science.gov (United States)

Grange, Christopher S; Meijer, Anthony J H M; Ward, Michael D

2010-01-07

The trinuclear complexes [{(R2bipy)2Ru}3(mu3-HHTP)](PF6)3 [1(PF6)3, R = H; 2(PF6)3, R = 4-tBu] contain three {Ru(R2bipy)2}2+ fragments connected to the triangular tris-chelating ligand hexahydroxytriphenylene (H6HHTP). This bridging ligand contains three dioxolene-type binding sites, each of which can reversibly convert between dianionic catecholate (cat), monoanionic semiquinone (sq) or neutral quinone (q) redox states. The bridging ligand as a whole can therefore exist in seven different redox states from fully reduced [cat,cat,cat]6- through to fully oxidised, neutral [q,q,q]. Cyclic voltammetry of 1(PF6)3 in MeCN reveals six redox processes of which the three at more positive potentials (the sq/q couples) are reversible but the three at more negative potentials (the sq/cat couples) are irreversible with distorted wave shapes due to the insolubility of the reduced forms of the complex. In contrast, the more soluble complex 2(PF6)3 displays six reversible one-electron redox processes making all components of a seven-membered redox chain accessible. UV/Vis/NIR spectro-electrochemical studies reveal rich spectroscopic behaviour, with--in particular--very intense transitions in the near-IR region in many of the oxidation states associated with Ru(II)-->(dioxolene) MLCT and bridging ligand centred pi-pi* transitions. TDDFT calculations were used to analyse the electronic spectra in all seven oxidation states; the calculated spectra generally show very good agreement with experiment, which has allowed a fairly complete assignment of the low-energy transitions. The strong electrochromism of the complexes in the near-IR region has formed the basis of an optical window in which a thin film of 1(PF6)3 or 2(PF6)3 on a conductive glass surface can be reversibly and rapidly switched between redox states that alternate between strongly absorbing or near-transparent at 1100 nm, with--for 2(PF6)3--the switching being stable and reversible in water over thousands of cycles.

Redox non-innocent ligands: versatile new tools to control catalytic reactions

NARCIS (Netherlands)

Lyaskovskyy, V.; de Bruin, B.

2012-01-01

In this (tutorial overview) perspective we highlight the use of "redox non-innocent" ligands in catalysis. Two main types of reactivity in which the redox non-innocent ligand is involved can be specified: (A) The redox active ligand participates in the catalytic cycle only by accepting/donating

Editing disulphide bonds: error correction using redox currencies.

Science.gov (United States)

Ito, Koreaki

2010-01-01

The disulphide bond-introducing enzyme of bacteria, DsbA, sometimes oxidizes non-native cysteine pairs. DsbC should rearrange the resulting incorrect disulphide bonds into those with correct connectivity. DsbA and DsbC receive oxidizing and reducing equivalents, respectively, from respective redox components (quinones and NADPH) of the cell. Two mechanisms of disulphide bond rearrangement have been proposed. In the redox-neutral 'shuffling' mechanism, the nucleophilic cysteine in the DsbC active site forms a mixed disulphide with a substrate and induces disulphide shuffling within the substrate part of the enzyme-substrate complex, followed by resolution into a reduced enzyme and a disulphide-rearranged substrate. In the 'reduction-oxidation' mechanism, DsbC reduces those substrates with wrong disulphides so that DsbA can oxidize them again. In this issue of Molecular Microbiology, Berkmen and his collaborators show that a disulphide reductase, TrxP, from an anaerobic bacterium can substitute for DsbC in Escherichia coli. They propose that the reduction-oxidation mechanism of disulphide rearrangement can indeed operate in vivo. An implication of this work is that correcting errors in disulphide bonds can be coupled to cellular metabolism and is conceptually similar to the proofreading processes observed with numerous synthesis and maturation reactions of biological macromolecules.

TEMPOL increases NAD+ and improves redox imbalance in obese mice

Directory of Open Access Journals (Sweden)

Mayumi Yamato

2016-08-01

Full Text Available Continuous energy conversion is controlled by reduction–oxidation (redox processes. NAD+ and NADH represent an important redox couple in energy metabolism. 4-Hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPOL is a redox-cycling nitroxide that promotes the scavenging of several reactive oxygen species (ROS and is reduced to hydroxylamine by NADH. TEMPOL is also involved in NAD+ production in the ascorbic acid–glutathione redox cycle. We utilized the chemical properties of TEMPOL to investigate the effects of antioxidants and NAD+/NADH modulators on the metabolic imbalance in obese mice. Increases in the NAD+/NADH ratio by TEMPOL ameliorated the metabolic imbalance when combined with a dietary intervention, changing from a high-fat diet to a normal diet. Plasma levels of the superoxide marker dihydroethidium were higher in mice receiving the dietary intervention compared with a control diet, but were normalized with TEMPOL consumption. These findings provide novel insights into redox regulation in obesity.

Capacitance enhancement of polyaniline coated curved-graphene supercapacitors in a redox-active electrolyte

KAUST Repository

Chen, Wei

2013-01-01

We show, for the first time, a redox-active electrolyte in combination with a polyaniline-coated curved graphene active material to achieve significant enhancement in the capacitance (36-92% increase) compared to supercapacitors that lack the redox-active contribution from the electrolyte. The supercapacitors based on the redox-active electrolyte also exhibit excellent rate capability and very long cycling performance (>50 000 cycles). This journal is © The Royal Society of Chemistry.

The use of polybenzimidazole membranes in vanadium redox flow batteries leading to increased coulombic efficiency and cycling performance

International Nuclear Information System (INIS)

Zhou, X.L.; Zhao, T.S.; An, L.; Wei, L.; Zhang, C.

2015-01-01

An issue with conventional vanadium redox flow batteries (VRFB) with Nafion membranes is the crossover of vanadium ions, resulting in low coulombic efficiency and rapid decay in capacity. In this work, a VRFB with a polybenzimidazole (PBI) membrane is tested and compared with the Nafion system. Results show that the PBI-based VRFB exhibits a substantially higher coulombic efficiency of up to 99% at current densities ranging from 20 mA cm −2 to 80 mA cm −2 . More importantly, it is demonstrated that the PBI-based VRFB has a capacity decay rate of as low as 0.3% per cycle, which is four times lower than that of the Nafion system (1.3% per cycle). The improved coulombic efficiency and cycling performance are attributed to the low crossover of vanadium ions through the PBI membrane

A novel iron-lead redox flow battery for large-scale energy storage

Science.gov (United States)

Zeng, Y. K.; Zhao, T. S.; Zhou, X. L.; Wei, L.; Ren, Y. X.

2017-04-01

The redox flow battery (RFB) is one of the most promising large-scale energy storage technologies for the massive utilization of intermittent renewables especially wind and solar energy. This work presents a novel redox flow battery that utilizes inexpensive and abundant Fe(II)/Fe(III) and Pb/Pb(II) redox couples as redox materials. Experimental results show that both the Fe(II)/Fe(III) and Pb/Pb(II) redox couples have fast electrochemical kinetics in methanesulfonic acid, and that the coulombic efficiency and energy efficiency of the battery are, respectively, as high as 96.2% and 86.2% at 40 mA cm-2. Furthermore, the battery exhibits stable performance in terms of efficiencies and discharge capacities during the cycle test. The inexpensive redox materials, fast electrochemical kinetics and stable cycle performance make the present battery a promising candidate for large-scale energy storage applications.

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.

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.

The influence of presumable radioprotectors on vitamin E redox system in irradiated rat tissues

International Nuclear Information System (INIS)

Paranich, A.V.; Pochernyaeva, V.F.; Dubinskaya, G.M.; Mishchinko, V.P.; Mironova, N.G.; Gugalo, V.P.; Nazarets, V.V.

1993-01-01

In experiments with mature Wistar male rats under irradiation by dose of 5 Gy the effect of emoxypine, citomedine and echinacea purpurea on the content of liposoluble vitamin A, carotene, vitamin E and its metabolites (quinone and oxidized tocopherol) in blood plasma, spleen, liver and testes was studied. It was shown the drugs under study mobilized the internal reserves of these vitamins and promoted effective functioning of vitamin E redox system. Mechanisms of their action are different. The drugs might be used as radioprotectors, but they exhaust the reserves of the liposoluble vitamins. Therefore they should be used in a combination with vitamin preparations

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

Science.gov (United States)

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

2014-11-15

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

A redox-flow battery with an alloxazine-based organic electrolyte

Science.gov (United States)

Lin, Kaixiang; Gómez-Bombarelli, Rafael; Beh, Eugene S.; Tong, Liuchuan; Chen, Qing; Valle, Alvaro; Aspuru-Guzik, Alán; Aziz, Michael J.; Gordon, Roy G.

2016-09-01

Redox-flow batteries (RFBs) can store large amounts of electrical energy from variable sources, such as solar and wind. Recently, redox-active organic molecules in aqueous RFBs have drawn substantial attention due to their rapid kinetics and low membrane crossover rates. Drawing inspiration from nature, here we report a high-performance aqueous RFB utilizing an organic redox compound, alloxazine, which is a tautomer of the isoalloxazine backbone of vitamin B2. It can be synthesized in high yield at room temperature by single-step coupling of inexpensive o-phenylenediamine derivatives and alloxan. The highly alkaline-soluble alloxazine 7/8-carboxylic acid produces a RFB exhibiting open-circuit voltage approaching 1.2 V and current efficiency and capacity retention exceeding 99.7% and 99.98% per cycle, respectively. Theoretical studies indicate that structural modification of alloxazine with electron-donating groups should allow further increases in battery voltage. As an aza-aromatic molecule that undergoes reversible redox cycling in aqueous electrolyte, alloxazine represents a class of radical-free redox-active organics for use in large-scale energy storage.

Influence of Oxygen and Nitrate on Fe (Hydr)oxide Mineral Transformation and Soil Microbial Communities during Redox Cycling.

Science.gov (United States)

Mejia, Jacqueline; Roden, Eric E; Ginder-Vogel, Matthew

2016-04-05

Oscillations between reducing and oxidizing conditions are observed at the interface of anaerobic/oxic and anaerobic/anoxic environments, and are often stimulated by an alternating flux of electron donors (e.g., organic carbon) and electron acceptors (e.g., O2 and NO3(-)). In iron (Fe) rich soils and sediments, these oscillations may stimulate the growth of both Fe-reducing bacteria (FeRB) and Fe-oxidizing bacteria (FeOB), and their metabolism may induce cycling between Fe(II) and Fe(III), promoting the transformation of Fe (hydr)oxide minerals. Here, we examine the mineralogical evolution of lepidocrocite and ferrihydrite, and the adaptation of a natural microbial community to alternating Fe-reducing (anaerobic with addition of glucose) and Fe-oxidizing (with addition of nitrate or air) conditions. The growth of FeRB (e.g., Geobacter) is stimulated under anaerobic conditions in the presence of glucose. However, the abundance of these organisms depends on the availability of Fe(III) (hydr)oxides. Redox cycling with nitrate results in decreased Fe(II) oxidation thereby decreasing the availability of Fe(III) for FeRB. Additionally, magnetite is detected as the main product of both lepidocrocite and ferrihydrite reduction. In contrast, introduction of air results in increased Fe(II) oxidation, increasing the availability of Fe(III) and the abundance of Geobacter. In the lepidocrocite reactors, Fe(II) oxidation by dissolved O2 promotes the formation of ferrihydrite and lepidocrocite, whereas in the ferrihydrite reactors we observe a decrease in magnetite stoichiometry (e.g., oxidation). Understanding Fe (hydr)oxide transformation under environmentally relevant redox cycling conditions provides insight into nutrient availability and transport, contaminant mobility, and microbial metabolism in soils and sediments.

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

DEFF Research Database (Denmark)

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

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

Catechol-chitosan redox capacitor for added amplification in electrochemical immunoanalysis.

Science.gov (United States)

Yan, Kun; Liu, Yi; Guan, Yongguang; Bhokisham, Narendranath; Tsao, Chen-Yu; Kim, Eunkyoung; Shi, Xiao-Wen; Wang, Qin; Bentley, William E; Payne, Gregory F

2018-05-22

Antibodies are common recognition elements for molecular detection but often the signals generated by their stoichiometric binding must be amplified to enhance sensitivity. Here, we report that an electrode coated with a catechol-chitosan redox capacitor can amplify the electrochemical signal generated from an alkaline phosphatase (AP) linked immunoassay. Specifically, the AP product p-aminophenol (PAP) undergoes redox-cycling in the redox capacitor to generate amplified oxidation currents. We estimate an 8-fold amplification associated with this redox-cycling in the capacitor (compared to detection by a bare electrode). Importantly, this capacitor-based amplification is generic and can be coupled to existing amplification approaches based on enzyme-linked catalysis or magnetic nanoparticle-based collection/concentration. Thus, the capacitor should enhance sensitivities in conventional immunoassays and also provide chemical to electrical signal transduction for emerging applications in molecular communication. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

The importance of kinetics and redox in the biogeochemical cycling of iron in the surface ocean.

Directory of Open Access Journals (Sweden)

Peter L. Croot

2012-06-01

Full Text Available It is now well established that Iron (Fe is a limiting element in many regions of the open ocean. Our current understanding of the key processes which control iron distribution in the open ocean have been largely based on thermodynamic measurements performed under the assumption of equilibrium conditions. Using this equilibrium approach, researchers have been able to detect and quantify organic complexing ligands in seawater and examine their role in increasing the overall solubility of iron. Our current knowledge about iron bioavailability to phytoplankton and bacteria is also based heavily on carefully controlled laboratory studies where it is assumed the chemical species are in equilibrium in line with the free ion association model (FIAM and/or its successor the biotic ligand model (BLM. Similarly most field work on Fe biogeochemistry generally consists of a single profile which is in essence a ‘snap-shot’ in time of the system under investigation. However it is well known that the surface ocean is an extremely dynamic environment and it is unlikely if thermodynamic equilibrium between all the iron species present is ever truly achieved. In sunlit waters this is mostly due to the daily passage of the sun across the sky leading to photoredox processes which alter Fe speciation by cycling between redox states and between inorganic and organic species. Episodic deposition events, are also important perturbations to iron cycling as they bring new iron to the system altering the equilibrium between species and phases. Over the last 20 years the mesoscale iron enrichment experiments (e.g. IronEx I /II, SOIREE, EisenEx, SOFeX, EIFeX, SAGE, SEEDS and SERIES I /II and the FeCycle (I/II experiments have provided the first insights into processes altering iron speciation and distribution which occur over temporal scales of days to weeks. Here we utilize new field data collected in the open ocean on the redox and complexation kinetics of iron in the

Ocean acidification affects redox-balance and ion-homeostasis in the life-cycle stages of Emiliania huxleyi.

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Sebastian D Rokitta

Full Text Available Ocean Acidification (OA has been shown to affect photosynthesis and calcification in the coccolithophore Emiliania huxleyi, a cosmopolitan calcifier that significantly contributes to the regulation of the biological carbon pumps. Its non-calcifying, haploid life-cycle stage was found to be relatively unaffected by OA with respect to biomass production. Deeper insights into physiological key processes and their dependence on environmental factors are lacking, but are required to understand and possibly estimate the dynamics of carbon cycling in present and future oceans. Therefore, calcifying diploid and non-calcifying haploid cells were acclimated to present and future CO(2 partial pressures (pCO(2; 38.5 Pa vs. 101.3 Pa CO(2 under low and high light (50 vs. 300 µmol photons m(-2 s(-1. Comparative microarray-based transcriptome profiling was used to screen for the underlying cellular processes and allowed to follow up interpretations derived from physiological data. In the diplont, the observed increases in biomass production under OA are likely caused by stimulated production of glycoconjugates and lipids. The observed lowered calcification under OA can be attributed to impaired signal-transduction and ion-transport. The haplont utilizes distinct genes and metabolic pathways, reflecting the stage-specific usage of certain portions of the genome. With respect to functionality and energy-dependence, however, the transcriptomic OA-responses resemble those of the diplont. In both life-cycle stages, OA affects the cellular redox-state as a master regulator and thereby causes a metabolic shift from oxidative towards reductive pathways, which involves a reconstellation of carbon flux networks within and across compartments. Whereas signal transduction and ion-homeostasis appear equally OA-sensitive under both light intensities, the effects on carbon metabolism and light physiology are clearly modulated by light availability. These interactive effects

Ocean acidification affects redox-balance and ion-homeostasis in the life-cycle stages of Emiliania huxleyi.

Science.gov (United States)

Rokitta, Sebastian D; John, Uwe; Rost, Björn

2012-01-01

Ocean Acidification (OA) has been shown to affect photosynthesis and calcification in the coccolithophore Emiliania huxleyi, a cosmopolitan calcifier that significantly contributes to the regulation of the biological carbon pumps. Its non-calcifying, haploid life-cycle stage was found to be relatively unaffected by OA with respect to biomass production. Deeper insights into physiological key processes and their dependence on environmental factors are lacking, but are required to understand and possibly estimate the dynamics of carbon cycling in present and future oceans. Therefore, calcifying diploid and non-calcifying haploid cells were acclimated to present and future CO(2) partial pressures (pCO(2); 38.5 Pa vs. 101.3 Pa CO(2)) under low and high light (50 vs. 300 µmol photons m(-2) s(-1)). Comparative microarray-based transcriptome profiling was used to screen for the underlying cellular processes and allowed to follow up interpretations derived from physiological data. In the diplont, the observed increases in biomass production under OA are likely caused by stimulated production of glycoconjugates and lipids. The observed lowered calcification under OA can be attributed to impaired signal-transduction and ion-transport. The haplont utilizes distinct genes and metabolic pathways, reflecting the stage-specific usage of certain portions of the genome. With respect to functionality and energy-dependence, however, the transcriptomic OA-responses resemble those of the diplont. In both life-cycle stages, OA affects the cellular redox-state as a master regulator and thereby causes a metabolic shift from oxidative towards reductive pathways, which involves a reconstellation of carbon flux networks within and across compartments. Whereas signal transduction and ion-homeostasis appear equally OA-sensitive under both light intensities, the effects on carbon metabolism and light physiology are clearly modulated by light availability. These interactive effects can be

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

Science.gov (United States)

Hong, Jeehoon; Kim, Ketack

2018-04-17

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

Beyond the Fe-P-redox connection: preferential regeneration of phosphorus from organic matter as a key control on Baltic Sea nutrient cycles

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T. Jilbert

2011-06-01

Full Text Available Patterns of regeneration and burial of phosphorus (P in the Baltic Sea are strongly dependent on redox conditions. Redox varies spatially along water depth gradients and temporally in response to the seasonal cycle and multidecadal hydrographic variability. Alongside the well-documented link between iron oxyhydroxide dissolution and release of P from Baltic Sea sediments, we show that preferential remineralization of P with respect to carbon (C and nitrogen (N during degradation of organic matter plays a key role in determining the surplus of bioavailable P in the water column. Preferential remineralization of P takes place both in the water column and upper sediments and its rate is shown to be redox-dependent, increasing as reducing conditions become more severe at greater water-depth in the deep basins. Existing Redfield-based biogeochemical models of the Baltic may therefore underestimate the imbalance between N and P availability for primary production, and hence the vulnerability of the Baltic to sustained eutrophication via the fixation of atmospheric N. However, burial of organic P is also shown to increase during multidecadal intervals of expanded hypoxia, due to higher net burial rates of organic matter around the margins of the deep basins. Such intervals may be characterized by basin-scale acceleration of all fluxes within the P cycle, including productivity, regeneration and burial, sustained by the relative accessibility of the water column P pool beneath a shallow halocline.

Enhanced bio-decolorization of azo dyes by co-immobilized quinone-reducing consortium and anthraquinone

DEFF Research Database (Denmark)

Su, YY; Zhang, Yifeng; Wang, J

2009-01-01

In the present study, the accelerating effect of co-immobilized anthraquinone and quinone-reducing consortium was investigated in the bio-decolorization process. The anthraquinone and quinone-reducing consortium were co-immobilized by entrapment in calcium alginate. The co-immobilized beads...

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

X-ray structural studies of quinone reductase 2 nanomolar range inhibitors

Energy Technology Data Exchange (ETDEWEB)

Pegan, Scott D.; Sturdy, Megan; Ferry, Gilles; Delagrange, Philippe; Boutin, Jean A.; Mesecar, Andrew D. (IdRS); (Purdue); (Colorado); (UIC)

2011-09-06

Quinone reductase 2 (QR2) is one of two members comprising the mammalian quinone reductase family of enzymes responsible for performing FAD mediated reductions of quinone substrates. In contrast to quinone reductase 1 (QR1) which uses NAD(P)H as its co-substrate, QR2 utilizes a rare group of hydride donors, N-methyl or N-ribosyl nicotinamide. Several studies have linked QR2 to the generation of quinone free radicals, several neuronal degenerative diseases, and cancer. QR2 has been also identified as the third melatonin receptor (MT3) through in cellulo and in vitro inhibition of QR2 by traditional MT3 ligands, and through recent X-ray structures of human QR2 (hQR2) in complex with melatonin and 2-iodomelatonin. Several MT3 specific ligands have been developed that exhibit both potent in cellulo inhibition of hQR2 nanomolar, affinity for MT3. The potency of these ligands suggest their use as molecular probes for hQR2. However, no definitive correlation between traditionally obtained MT3 ligand affinity and hQR2 inhibition exists limiting our understanding of how these ligands are accommodated in the hQR2 active site. To obtain a clearer relationship between the structures of developed MT3 ligands and their inhibitory properties, in cellulo and in vitro IC{sub 50} values were determined for a representative set of MT3 ligands (MCA-NAT, 2-I-MCANAT, prazosin, S26695, S32797, and S29434). Furthermore, X-ray structures for each of these ligands in complex with hQR2 were determined allowing for a structural evaluation of the binding modes of these ligands in relation to the potency of MT3 ligands.

Rhodium-catalyzed C-H bond activation for the synthesis of quinonoid compounds: Significant Anti-Trypanosoma cruzi activities and electrochemical studies of functionalized quinones.

Science.gov (United States)

Jardim, Guilherme A M; Silva, Thaissa L; Goulart, Marilia O F; de Simone, Carlos A; Barbosa, Juliana M C; Salomão, Kelly; de Castro, Solange L; Bower, John F; da Silva Júnior, Eufrânio N

2017-08-18

Thirty four halogen and selenium-containing quinones, synthesized by rhodium-catalyzed C-H bond activation and palladium-catalyzed cross-coupling reactions, were evaluated against bloodstream trypomastigotes of T. cruzi. We have identified fifteen compounds with IC 50 /24 h values of less than 2 μM. Electrochemical studies on A-ring functionalized naphthoquinones were also performed aiming to correlate redox properties with trypanocidal activity. For instance, (E)-5-styryl-1,4-naphthoquinone 59 and 5,8-diiodo-1,4-naphthoquinone 3, which are around fifty fold more active than the standard drug benznidazole, are potential derivatives for further investigation. These compounds represent powerful new agents useful in Chagas disease therapy. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

1,4-Naphthoquinones: From Oxidative Damage to Cellular and Inter-Cellular Signaling

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Lars-Oliver Klotz

2014-09-01

Full Text Available Naphthoquinones may cause oxidative stress in exposed cells and, therefore, affect redox signaling. Here, contributions of redox cycling and alkylating properties of quinones (both natural and synthetic, such as plumbagin, juglone, lawsone, menadione, methoxy-naphthoquinones, and others to cellular and inter-cellular signaling processes are discussed: (i naphthoquinone-induced Nrf2-dependent modulation of gene expression and its potentially beneficial outcome; (ii the modulation of receptor tyrosine kinases, such as the epidermal growth factor receptor by naphthoquinones, resulting in altered gap junctional intercellular communication. Generation of reactive oxygen species and modulation of redox signaling are properties of naphthoquinones that render them interesting leads for the development of novel compounds of potential use in various therapeutic settings.

Cytotoxicity from coupled redox cycling of autoxidizing xenobiotics and metals: a selective critical review and commentary on work-in-progress

Energy Technology Data Exchange (ETDEWEB)

Borg, D C; Schaich, K M

1984-01-01

A comprehensive reaction schema for oxidative cytotoxicity is presented, integrating known chemical mechanisms of oxygen radical reactions and observed pathophysiology. The key features of the schema are the coupling of (1) redox cycling of autoxidizable substrates to form the equilibrium pair of superoxide anion (O/sub 2//sup -/)/and its conjugate acid, perhydroxyl radical (HO/sub 2/.); (2) hydrogen peroxide (H/sub 2/O/sub 2/) generation via O/sub 2//sup -/ dimutation; (3) catalytic redox cycling of metals reducing H/sub 2/O/sub 2/ to reactive hydroxyl radicals (OH.); (4) direct reaction of OH. with target molecules, including critical cell macromolecules and polyunsaturated lipids in membranes; (5) transfer of oxidative potential from initial to distant sites via H/sub 2/O/sub 2/ and O/sub 2/-/HO/sub 2/ diffusion, lipid free radical chain peroxidations in membranes, and migration of non-radical lipid oxidation products; and (6) cytotoxic damage at those distant sites mediated by reaction of lipid radical species and other lipid oxidation products with critical target molecules (proteins, DNA, etc.). Although there is a broad consensus of agreement within the cognizant research community concerning many aspects of this schema, there exists considerable controversy and/or misconception about several important issues. Critical analyses of four presently controversial points are presented.

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

KAUST Repository

Giovannitti, Alexander

2018-02-23

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

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

KAUST Repository

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

2018-01-01

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

Redox-mediated bypass of restriction point via skipping of G1pm

Directory of Open Access Journals (Sweden)

Greene James J

2006-07-01

Full Text Available Abstract Background It is well known that cancer cells bypass the restriction point, R, and undergo uncontrolled cell proliferation. Hypothesis and evidence We suggest here that fibrosarcoma cells enter G1ps directly from M, skipping G1pm, hence bypassing R, in response to redox modulation. Evidence is presented from the published literature that demonstrate a shortening of the cycle period of transformed fibroblasts (SV-3T3 compared to the nontransformed 3T3 fibroblasts, corresponding to the duration of G1pm in the 3T3 fibroblasts. Evidence is also presented that demonstrate that redox modulation can induce the CUA-4 fibroblasts to bypass R, resulting in a cycle period closely corresponding to the cycle period of fibrosarcoma cells (HT1080. Conclusion The evidence supports our hypothesis that a low internal redox potential can cause fibrosarcoma cells to skip the G1pm phase of the cell cycle.

Effects of juglone and lawsone on oxidative stress in maize coleoptile cells treated with IAA.

Science.gov (United States)

Kurtyka, Renata; Pokora, Wojciech; Tukaj, Zbigniew; Karcz, Waldemar

2016-01-01

Naphthoquinones are secondary metabolites widely distributed in nature and produced by bacteria, fungi and higher plants. Their biological activity may result from induction of oxidative stress, caused by redox cycling or direct interaction with cellular macromolecules, in which quinones act as electrophiles. The redox homeostasis is known as one of factors involved in auxin-mediated plant growth regulation. To date, however, little is known about the crosstalk between reactive oxygen species (ROS) produced by quinones and the plant growth hormone auxin (IAA). In this study, redox cycling properties of two naphthoquinones, juglone (5-hydroxy-1,4-naphthoquinone) and lawsone (2-hydroxy-1,4-naphthoquinone), were compared in experiments performed on maize coleoptile segments incubated with or without the addition of IAA. It was found that lawsone was much more effective than juglone in increasing both H 2 O 2 production and the activity of antioxidative enzymes (SOD, POX and CAT) in coleoptile cells, regardless of the presence of IAA. An increase in the activity of Cu/Zn-SOD isoenzymes induced by both naphthoquinones suggests that juglone- and lawsone-generated H 2 O 2 was primarily produced in the cytosolic and cell wall spaces. The cell potential to neutralize hydrogen peroxide, determined by POX and CAT activity, pointed to activity of catalase as the main enzymatic mechanism responsible for degradation of H 2 O 2 Therefore, we assumed that generation of H 2 O 2 , induced more efficiently by LW than JG, was the major factor accounting for differences in the toxicity of naphthoquinones in maize coleoptiles. The role of auxin in the process appeared negligible. Moreover, the results suggested that oxidative stress imposed by JG and LW was one of mechanisms of allelopathic action of the studied quinones in plants. © The Authors 2016. Published by Oxford University Press on behalf of the Annals of Botany Company.

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.

Role of glutathione redox cycle and catalase in defense against oxidative stress induced by endosulfan in adrenocortical cells of rainbow trout (Oncorhynchus mykiss)

International Nuclear Information System (INIS)

Dorval, J.; Hontela, A.

2003-01-01

The role of antioxidants in maintaining the functional integrity of adrenocortical cells during in vitro exposure to endosulfan, an organochlorine pesticide, was investigated in rainbow trout (Oncorhynchus mykiss). Aminotriazole (ATA), an inhibitor of catalase (CAT), L-buthionine sulfoximine (L-BSO), an inhibitor of glutathione (GSH) synthesis, and N-acetyl cysteine (NAC), a glutathione precursor, were used to investigate the role of CAT and GSH redox cycle in protection against the adrenal toxicity of endosulfan, a pesticide that impairs cell viability (LC 50 366 μM) and cortisol secretion (EC 50 19 μM) in a concentration-related manner. Pretreatment with ATA and L-BSO enhanced the toxicity of endosulfan (LC 50 and EC 50 , respectively, 302 and 2.6 μM with ATA, 346 and 3.1 μM with L-BSO), while pretreatment with NAC had no significant effect on cell viability and increased the EC 50 of endosulfan to 51 μM. CAT activity was significantly reduced following exposure to endosulfan when cells were pretreated with ATA. Pretreatment with L-BSO significantly decreased glutathione peroxidase (GPx) activity and reduced glutathione (GSH) levels in a concentration-related manner following exposure to endosulfan, while GSH levels were significantly higher in NAC pretreated cells compared to untreated cells. Finally, pretreatment with ATA and L-BSO increased, while pretreatment with NAC decreased, lipid hydroperoxides (LOOH) levels. CAT, GPx, and GSH were identified as important antioxidants in maintaining the function and integrity of rainbow trout adrenocortical cells and ATA, L-BSO, and NAC were identified as effective modulators of CAT and GSH redox cycle. Moreover, this study suggests that the glutathione redox cycle may be more efficient than catalase in protecting adrenocortical cells against endosulfan-induced oxidative stress

A biomimetic redox flow battery based on flavin mononucleotide.

Science.gov (United States)

Orita, Akihiro; Verde, Michael G; Sakai, Masanori; Meng, Ying Shirley

2016-10-21

The versatility in design of redox flow batteries makes them apt to efficiently store energy in large-scale applications at low cost. The discovery of inexpensive organic electroactive materials for use in aqueous flow battery electrolytes is highly attractive, but is thus far limited. Here we report on a flow battery using an aqueous electrolyte based on the sodium salt of flavin mononucleotide. Flavins are highly versatile electroactive molecules, which catalyse a multitude of redox reactions in biological systems. We use nicotinamide (vitamin B3) as a hydrotropic agent to enhance the water solubility of flavin mononucleotide. A redox flow battery using flavin mononucleotide negative and ferrocyanide positive electrolytes in strong base shows stable cycling performance, with over 99% capacity retention over the course of 100 cycles. We hypothesize that this is enabled due to the oxidized and reduced forms of FMN-Na being stabilized by resonance structures.

A biomimetic redox flow battery based on flavin mononucleotide

Science.gov (United States)

Orita, Akihiro; Verde, Michael G.; Sakai, Masanori; Meng, Ying Shirley

2016-10-01

The versatility in design of redox flow batteries makes them apt to efficiently store energy in large-scale applications at low cost. The discovery of inexpensive organic electroactive materials for use in aqueous flow battery electrolytes is highly attractive, but is thus far limited. Here we report on a flow battery using an aqueous electrolyte based on the sodium salt of flavin mononucleotide. Flavins are highly versatile electroactive molecules, which catalyse a multitude of redox reactions in biological systems. We use nicotinamide (vitamin B3) as a hydrotropic agent to enhance the water solubility of flavin mononucleotide. A redox flow battery using flavin mononucleotide negative and ferrocyanide positive electrolytes in strong base shows stable cycling performance, with over 99% capacity retention over the course of 100 cycles. We hypothesize that this is enabled due to the oxidized and reduced forms of FMN-Na being stabilized by resonance structures.

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

Preliminary X-ray crystallographic analysis of sulfide:quinone oxidoreductase from Acidithiobacillus ferrooxidans

International Nuclear Information System (INIS)

Zhang, Yanfei; Cherney, Maia M.; Solomonson, Matthew; Liu, Jianshe; James, Michael N. G.; Weiner, Joel H.

2009-01-01

The sulfide:quinone oxidoreductase from A. ferrooxidans ATCC 23270 was overexpressed in E. coli and purified. Crystallization and preliminarily X-ray crystallographic analysis were performed for the recombinant enzyme. The gene product of open reading frame AFE-1293 from Acidithiobacillus ferrooxidans ATCC 23270 is annotated as encoding a sulfide:quinone oxidoreductase, an enzyme that catalyses electron transfer from sulfide to quinone. Following overexpression in Escherichia coli, the enzyme was purified and crystallized using the hanging-drop vapour-diffusion method. The native crystals belonged to the tetragonal space group P4 2 2 1 2, with unit-cell parameters a = b = 131.7, c = 208.8 Å, and diffracted to 2.3 Å resolution. Preliminary crystallographic analysis indicated the presence of a dimer in the asymmetric unit, with an extreme value of the Matthews coefficient (V M ) of 4.53 Å 3 Da −1 and a solvent content of 72.9%

Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery.

Science.gov (United States)

Wei, Xiaoliang; Xu, Wu; Huang, Jinhua; Zhang, Lu; Walter, Eric; Lawrence, Chad; Vijayakumar, M; Henderson, Wesley A; Liu, Tianbiao; Cosimbescu, Lelia; Li, Bin; Sprenkle, Vincent; Wang, Wei

2015-07-20

Nonaqueous redox flow batteries hold the promise of achieving higher energy density because of the broader voltage window than aqueous systems, but their current performance is limited by low redox material concentration, cell efficiency, cycling stability, and current density. We report a new nonaqueous all-organic flow battery based on high concentrations of redox materials, which shows significant, comprehensive improvement in flow battery performance. A mechanistic electron spin resonance study reveals that the choice of supporting electrolytes greatly affects the chemical stability of the charged radical species especially the negative side radical anion, which dominates the cycling stability of these flow cells. This finding not only increases our fundamental understanding of performance degradation in flow batteries using radical-based redox species, but also offers insights toward rational electrolyte optimization for improving the cycling stability of these flow batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mass transport enhancement in redox flow batteries with corrugated fluidic networks

Science.gov (United States)

Lisboa, Kleber Marques; Marschewski, Julian; Ebejer, Neil; Ruch, Patrick; Cotta, Renato Machado; Michel, Bruno; Poulikakos, Dimos

2017-08-01

We propose a facile, novel concept of mass transfer enhancement in flow batteries based on electrolyte guidance in rationally designed corrugated channel systems. The proposed fluidic networks employ periodic throttling of the flow to optimally deflect the electrolytes into the porous electrode, targeting enhancement of the electrolyte-electrode interaction. Theoretical analysis is conducted with channels in the form of trapezoidal waves, confirming and detailing the mass transport enhancement mechanism. In dilute concentration experiments with an alkaline quinone redox chemistry, a scaling of the limiting current with Re0.74 is identified, which compares favourably against the Re0.33 scaling typical of diffusion-limited laminar processes. Experimental IR-corrected polarization curves are presented for high concentration conditions, and a significant performance improvement is observed with the narrowing of the nozzles. The adverse effects of periodic throttling on the pumping power are compared with the benefits in terms of power density, and an improvement of up to 102% in net power density is obtained in comparison with the flow-by case employing straight parallel channels. The proposed novel concept of corrugated fluidic networks comes with facile fabrication and contributes to the improvement of the transport characteristics and overall performance of redox flow battery systems.

Redox oscillation impact on natural and engineered biogeochemical systems: chemical resilience and implications for contaminant mobility

Energy Technology Data Exchange (ETDEWEB)

Charlet, Laurent [ISTerre, University of Grenoble, B.P. 53X, 38041 Grenoble (France); Institut Universitaire de France, Paris (France); Markelova, Ekaterina [ISTerre, University of Grenoble, B.P. 53X, 38041 Grenoble (France); Department of Earth and Environmental Sciences, University of Waterloo, Waterloo, ON N2L3G1 4 (Canada); Parsons, Chris; Couture, Raoul-Marie [Department of Earth and Environmental Sciences, University of Waterloo, Waterloo, ON N2L3G1 4 (Canada); Made, Benoit [Andra / DRD-TR, Direction Recherche et Developpement, 1-7 rue Jean Monnet, 92298 Chatenay-Malabry cedex (France)

2013-07-01

Many geochemical systems fluctuate regularly from oxic to anoxic conditions (flooded soils and nuclear waste surface repositories, for instance). In these conditions many inorganic contaminants including Sb, Se, Cr, As, and U are highly sensitive to changes in redox conditions. These oscillations may result in changes to their speciation, toxicity, and mobility. We demonstrate through the combination of redox-stat batch-reactor experiments 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{sub d} values for a range of redox sensitive contaminants. These results demonstrate that naturally occurring redox oscillations may result in long-term immobilization of contaminants in the solid phase in addition to short-term variations in mobility. (authors)

Changes in redox properties of humic acids upon sorption to alumina

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Subdiaga, Edisson; Orsetti, Silvia; Jindal, Sharmishta; Haderlein, Stefan B.

2016-04-01

1. Introduction A prominent role of Natural Organic Matter (NOM) in biogeochemical processes is its ability to act as an electron shuttle, accelerating rates between a bulk electron donor and an acceptor. The underlying processes are reversible redox reactions of quinone moieties.1 This shuttling effect has been studied in two major areas: transformation of redox active pollutants and microbial respiration.2-3 Previous studies primarily compared effects in the presence or absence of NOM without addressing the redox properties of NOM nor its speciation. The interaction between humic acids (HA) and minerals might change properties and reactivity of organic matter. Specifically, we investigate whether changes in the redox properties of a HA occur upon sorption to redox inactive minerals. Since fractionation and conformational rearrangements of NOM moieties upon sorption are likely to happen, the redox properties of the NOM fractions upon sorption might differ as well. 2. Materials and methods Elliot Soil Humic Acid (ESHA), Pahokee Peat Humic Acid (PPHA) and Suwannee River Humic Acid (SRHA) were used as received from IHSS. Aluminum oxide (Al2O3) was suspended in 0.1M KCl. Sorption was studied at pH 7.0 in duplicate batch experiments for several HA/Al2O3 ratios. For the suspension (mineral + sorbed HA, plus dissolved HA), the filtrate (0.45μm) and the HA stock solution, the electron donating and accepting capacities (EDC and EAC) were determined following established procedures.4 3. Results All studied HA-Al2O3 systems showed similar behavior with regard to changes in redox properties. There was a significant increase in the EDC of the whole suspension compared to the stock solutions and the non-sorbed HA in the filtrate (up to 300% for PPHA). This effect was more pronounced with increasing amounts of sorbed HA in the suspension. Although ESHA had the highest sorption capacity on Al2O3 (~ 6 times higher than PPHA & SRHA), it showed the smallest changes in redox

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

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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.

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

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

2018-04-01

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

Unusual thiol-based redox metabolism of parasitic flukes.

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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.

Cyanide as a copper and quinone-directed inhibitor of amine oxidases from pea seedlings ( Pisum sativum) and Arthrobacter globiformis: evidence for both copper coordination and cyanohydrin derivatization of the quinone cofactor.

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Shepard, Eric M; Juda, Gregory A; Ling, Ke-Qing; Sayre, Lawrence M; Dooley, David M

2004-04-01

The interactions of cyanide with two copper-containing amine oxidases (CuAOs) from pea seedlings (PSAO) and the soil bacterium Arthrobacter globiformis (AGAO) have been investigated by spectroscopic and kinetic techniques. Previously, we rationalized the effects of azide and cyanide for several CuAOs in terms of copper coordination by these exogenous ligands and their effects on the internal redox equilibrium TPQ(amr)-Cu(II) right harpoon over left harpoon TPQ(sq)-Cu(I). The mechanism of cyanide inhibition was proposed to occur through complexation to Cu(I), thereby directly competing with O(2) for reoxidation of TPQ. Although cyanide readily and reversibly reacts with quinones, no direct spectroscopic evidence for cyanohydrin derivatization of TPQ has been previously documented for CuAOs. This work describes the first direct spectroscopic evidence, using both model and enzyme systems, for cyanohydrin derivatization of TPQ. K(d) values for Cu(II)-CN(-) and Cu(I)-CN(-), as well as the K(i) for cyanide inhibition versus substrate amine, are reported for PSAO and AGAO. In spite of cyanohydrin derivatization of the TPQ cofactor in these enzymes, the uncompetitive inhibition of amine oxidation is determined to arise almost exclusively through CN(-) complexation of Cu(I).

The impact of oscillating redox conditions: Arsenic immobilisation in contaminated calcareous floodplain soils

International Nuclear Information System (INIS)

Parsons, Christopher T.; Couture, Raoul-Marie; Omoregie, Enoma O.; Bardelli, Fabrizio; Greneche, Jean-Marc; Roman-Ross, Gabriela; Charlet, Laurent

2013-01-01

Arsenic contamination of floodplain soils is extensive and additional fresh arsenic inputs to the pedosphere from human activities are ongoing. We investigate the cumulative effects of repetitive soil redox cycles, which occur naturally during flooding and draining, on a calcareous fluvisol, the native microbial community and arsenic mobility following a simulated contamination event. We show through bioreactor experiments, spectroscopic techniques and modelling that repetitive redox cycling can decrease arsenic mobility during reducing conditions by up to 45%. Phylogenetic and functional analyses of the microbial community indicate that iron cycling is a key driver of observed changes to solution chemistry. We discuss probable mechanisms responsible for the arsenic immobilisation observed in-situ. The proposed mechanisms include, decreased heterotrophic iron reduction due to the depletion of labile particulate organic matter (POM), increases to the proportion of co-precipitated vs. aqueous or sorbed arsenic with α-FeOOH/Fe(OH) 3 and potential precipitation of amorphous ferric arsenate. Highlights: •Oscillating redox conditions and heterotrophic metabolism are implemented in PHREEQC. •Depletion of labile organic matter limits iron reduction and arsenic release. •Amorphous FeAsO 4 ∙2H 2 O precipitation potentially limits arsenic mobility during redox cycling. •Water fluctuating zones may naturally attenuate arsenic liberation during flooding. -- We demonstrate through batch experiments, spectroscopy and modelling that repetitive cycles of oxidation and reduction decrease arsenic mobility in soils during subsequent reducing conditions

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

Compartmentation of redox metabolism in malaria parasites.

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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.

Quinone-Enriched Gold Nanoparticles in Bioelectrochemistry and Charge Storage

DEFF Research Database (Denmark)

Wagner, Michal; Qvortrup, Katrine; Tanner, David Ackland

for merging gold nanoparticles with resultant anthraquinones include one-pot microwave assisted synthesis or after-mixing of separately prepared gold nanoparticles with selected compounds. The quinone-enriched gold nanoparticles can be transferred onto different electrode surfaces, thus enabling facile...

Oxygen control of nif gene expression in Klebsiella pneumoniae depends on NifL reduction at the cytoplasmic membrane by electrons derived from the reduced quinone pool.

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Grabbe, Roman; Schmitz, Ruth A

2003-04-01

In Klebsiella pneumoniae, the flavoprotein, NifL regulates NifA mediated transcriptional activation of the N2-fixation (nif) genes in response to molecular O2 and ammonium. We investigated the influence of membrane-bound oxidoreductases on nif-regulation by biochemical analysis of purified NifL and by monitoring NifA-mediated expression of nifH'-'lacZ reporter fusions in different mutant backgrounds. NifL-bound FAD-cofactor was reduced by NADH only in the presence of a redox-mediator or inside-out vesicles derived from anaerobically grown K. pneumoniae cells, indicating that in vivo NifL is reduced by electrons derived from membrane-bound oxidoreductases of the anaerobic respiratory chain. This mechanism is further supported by three lines of evidence: First, K. pneumoniae strains carrying null mutations of fdnG or nuoCD showed significantly reduced nif-induction under derepressing conditions, indicating that NifL inhibition of NifA was not relieved in the absence of formate dehydrogenase-N or NADH:ubiquinone oxidoreductase. The same effect was observed in a heterologous Escherichia coli system carrying a ndh null allele (coding for NADH dehydrogenaseII). Second, studying nif-induction in K. pneumoniae revealed that during anaerobic growth in glycerol, under nitrogen-limitation, the presence of the terminal electron acceptor nitrate resulted in a significant decrease of nif-induction. The final line of evidence is that reduced quinone derivatives, dimethylnaphthoquinol and menadiol, are able to transfer electrons to the FAD-moiety of purified NifL. On the basis of these data, we postulate that under anaerobic and nitrogen-limited conditions, NifL inhibition of NifA activity is relieved by reduction of the FAD-cofactor by electrons derived from the reduced quinone pool, generated by anaerobic respiration, that favours membrane association of NifL. We further hypothesize that the quinol/quinone ratio is important for providing the signal to NifL.

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

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

2017-06-24

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

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Redox Species of Redox Flow Batteries: A Review.

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Pan, Feng; Wang, Qing

2015-11-18

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

Redox Species of Redox Flow Batteries: A Review

Directory of Open Access Journals (Sweden)

Feng Pan

2015-11-01

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

Identification of Carotenoids and Isoprenoid Quinones from Asaia lannensis and Asaia bogorensis

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Hubert Antolak

2017-09-01

Full Text Available The aim of the study was to identify and quantitatively assess of carotenoids and isoprenoid quinones biosynthesized by six different strains of acetic acid bacteria, belonging to genus Asaia, that are common beverage-spoiling bacteria in Europe. Bacterial cultures were conducted in a laboratory liquid culture minimal medium with 2% sucrose. Carotenoids and isoprenoid quinones were investigated using UHPLC-DAD-ESI-MS analysis. In general, tested strains of Asaia spp. were able to produce 10 carotenoids and 3 isoprenoid quinones: menaquinone-7, menaquinone-8, and ubiquinone-10. The main identified carotenoids in Asaia lannensis strains were phytofluene, neurosporene, α-carotene, while for Asaia bogorensis, neurosporene, canthaxanthin, and zeaxanthin were noted. What is more, tested Asaia spp. were able to produce myxoxanthophyll, which has so far been identified primarily in cyanobacteria. The results show that A. lannensis are characterized by statistically higher concentrations of produced carotenoids, as well as a greater variety of these compounds. We have noted that carotenoids were not only accumulated by bacterial cells, but also some strains of A. lannensis produced extracellular carotenoids.

Post-translational modifications near the quinone binding site of mammalian complex I.

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Carroll, Joe; Ding, Shujing; Fearnley, Ian M; Walker, John E

2013-08-23

Complex I (NADH:ubiquinone oxidoreductase) in mammalian mitochondria is an L-shaped assembly of 44 protein subunits with one arm buried in the inner membrane of the mitochondrion and the orthogonal arm protruding about 100 Å into the matrix. The protruding arm contains the binding sites for NADH, the primary acceptor of electrons flavin mononucleotide (FMN), and a chain of seven iron-sulfur clusters that carries the electrons one at a time from FMN to a coenzyme Q molecule bound in the vicinity of the junction between the two arms. In the structure of the closely related bacterial enzyme from Thermus thermophilus, the quinone is thought to bind in a tunnel that spans the interface between the two arms, with the quinone head group close to the terminal iron-sulfur cluster, N2. The tail of the bound quinone is thought to extend from the tunnel into the lipid bilayer. In the mammalian enzyme, it is likely that this tunnel involves three of the subunits of the complex, ND1, PSST, and the 49-kDa subunit. An arginine residue in the 49-kDa subunit is symmetrically dimethylated on the ω-N(G) and ω-N(G') nitrogen atoms of the guanidino group and is likely to be close to cluster N2 and to influence its properties. Another arginine residue in the PSST subunit is hydroxylated and probably lies near to the quinone. Both modifications are conserved in mammalian enzymes, and the former is additionally conserved in Pichia pastoris and Paracoccus denitrificans, suggesting that they are functionally significant.

The mechanism behind redox instability of anodes in high-temperature SOFCs

DEFF Research Database (Denmark)

Klemensø, Trine; Chung, Charissa; Larsen, Peter Halvor

2005-01-01

Bulk expansion of the anode upon oxidation is considered to be responsible for the lack of redox stability in high-temperature solid oxide fuel cells (SOFCs). The bulk expansion of nickel-yttria stabilized zirconia (YSZ) anode materials was measured by dilatometry as a function of sample geometry......, ceramic component, temperature, and temperature cycling. The strength of the ceramic network and the degree of Ni redistribution appeared to be key parameters of the redox behavior. A model of the redox mechanism in nickel-YSZ anodes was developed based on the dilatometry data and macro...

High-energy redox-flow batteries with hybrid metal foam electrodes.

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Park, Min-Sik; Lee, Nam-Jin; Lee, Seung-Wook; Kim, Ki Jae; Oh, Duk-Jin; Kim, Young-Jun

2014-07-09

A nonaqueous redox-flow battery employing [Co(bpy)3](+/2+) and [Fe(bpy)3](2+/3+) redox couples is proposed for use in large-scale energy-storage applications. We successfully demonstrate a redox-flow battery with a practical operating voltage of over 2.1 V and an energy efficiency of 85% through a rational cell design. By utilizing carbon-coated Ni-FeCrAl and Cu metal foam electrodes, the electrochemical reactivity and stability of the nonaqueous redox-flow battery can be considerably enhanced. Our approach intoduces a more efficient conversion of chemical energy into electrical energy and enhances long-term cell durability. The cell exhibits an outstanding cyclic performance of more than 300 cycles without any significant loss of energy efficiency. Considering the increasing demands for efficient energy storage, our achievement provides insight into a possible development pathway for nonaqueous redox-flow batteries with high energy densities.

Toxicity to sea urchin egg development of the quinone fraction obtained from Auxemma oncocalyx

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Costa-Lotufo L.V.

2002-01-01

Full Text Available Auxemma oncocalyx Taub. belongs to the Boraginaceae family and is native to the Brazilian northeast where it is known as "pau-branco". We investigated the ability of the water soluble fraction isolated from the heartwood of A. oncocalyx to inhibit sea urchin egg development. This fraction contains about 80% oncocalyxone A (quinone fraction, a compound known to possess strong cytotoxic and antitumor activities. In fact, the quinone fraction inhibited cleavage in a dose-dependent manner [IC50 of 18.4 (12.4-27.2 µg/ml, N = 6], and destroyed the embryos in the blastula stage [IC50 of 16.2 (13.7-19.2 µg/ml, N = 6]. We suggest that this activity is due to the presence of oncocalyxone A. In fact, these quinones present in A. oncocalyx extract have strong toxicity related to their antimitotic activity.

Redox-capacitor to connect electrochemistry to redox-biology.

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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.

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

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

2014-01-01

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

Photo-bleaching of polymer discoloration caused by quinone methides

Czech Academy of Sciences Publication Activity Database

Pospíšil, Jan; Nešpůrek, Stanislav; Zweifel, H.; Kuthan, J.

2002-01-01

Roč. 78, č. 2 (2002), s. 251-255 ISSN 0141-3910 R&D Projects: GA AV ČR IAA1050901 Institutional research plan: CEZ:AV0Z4050913 Keywords : quinone methide * photo- bleaching * polymer discoloration Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.145, year: 2002

Analysis of redox relationships in the plant cell cycle: determinations of ascorbate, glutathione and poly (ADPribose)polymerase (PARP) in plant cell cultures.

Science.gov (United States)

Foyer, Christine H; Pellny, Till K; Locato, Vittoria; De Gara, Laura

2008-01-01

Reactive oxygen species (ROS) and low molecular weight antioxidants, such as glutathione and ascorbate, are powerful signaling molecules that participate in the control of plant growth and development, and modulate progression through the mitotic cell cycle. Enhanced reactive oxygen species accumulation or low levels of ascorbate or glutathione cause the cell cycle to arrest and halt progression especially through the G1 checkpoint. Plant cell suspension cultures have proved to be particularly useful tools for the study of cell cycle regulation. Here we provide effective and accurate methods for the measurement of changes in the cellular ascorbate and glutathione pools and the activities of related enzymes such poly (ADP-ribose) polymerase during mitosis and cell expansion, particularly in cell suspension cultures. These methods can be used in studies seeking to improve current understanding of the roles of redox controls on cell division and cell expansion.

Accessible reactive surface area and abiotic redox reactivity of iron oxyhydroxides in acidic brines

Science.gov (United States)

Strehlau, Jennifer H.; Toner, Brandy M.; Arnold, William A.; Penn, R. Lee

2017-01-01

The reactivity of iron oxyhydroxide nanoparticles in low pH and high ionic strength solutions was quantified to assess abiotic contributions to oxidation-reduction chemistry in acidic brine environments, such as mine groundwater seepage, lakes in Western Australia, and acid mine drainage settings, which are of global interest for their environmental impacts and unique geomicrobiology. Factors expected to influence accessible and reactive surface area, including Fe(II) adsorption and aggregate size, were measured as a function of pH and CaCl2 concentration and related to the kinetics of redox reactions in aqueous suspensions of synthetic goethite (α-FeOOH), akaganeite (β-FeOOH), and ferrihydrite (Fe10O14(OH)2) nanoparticles. Aqueous conditions and iron oxyhydroxides were chosen based on characterization of natural iron-rich mine microbial mats located in Soudan Underground Mine State Park, Minnesota, USA. Quinone species were used as redox sensors because they are well-defined probes and are present in natural organic matter. Fe(II) adsorption to the iron oxyhydroxide mineral surfaces from aqueous solution was measurable only at pH values above 4 and either decreased or was not affected by CaCl2 concentration. Concentrations at or above 0.020 M CaCl2 in acetate buffer (pH 4.5) induced particle aggregation. Assessment of Fe(II) adsorption and particle aggregation in acidic brine suggested that accessible reactive surface area may be limited in acidic brines. This was supported by observations of decreasing benzoquinone reduction rate by adsorbed Fe(II) at high CaCl2 concentration. In contrast, the hydroquinone oxidation rate increased at high CaCl2 concentrations, which may be due to suppressed adsorption of Fe(II) generated by the reaction. Results suggest that iron geochemical cycling in acidic brine environments will be substantially different than for iron oxyhydroxides in low-saline waters with circumneutral pH. These findings have implications for acidic

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

Chemistry of superoxide radical in seawater: CDOM associated sink of superoxide in coastal waters

Energy Technology Data Exchange (ETDEWEB)

Goldstone, J.V.; Voelker, B.M.

2000-03-15

Colored dissolved organic matter (CDOM) and humic substances contain a nonmetallic redox-cycling component capable of catalyzing superoxide (O{sub 2}{sup {minus}}) dismutation. First-order rate coefficients (k{sub pseudo}) measured for this O{sub 2}{sup {minus}} sink in a number of coastal and Chesapeake Bay water samples range up to 1.4s{sup {minus}1}, comparable in magnitude to catalyzed dismutation by Cu species. A significant (r{sup 2}=0.73) correlation is observed between k{sub pseudo} and the optical absorption and salinity of individual coastal water samples, suggesting an association with non-marine-derived CDOM. The activity of this sink is not changed by acidification or boiling of samples but is removed by photooxidation, indicating that it is an organic compound, but that it is neither enzymatic nor likely to consist of tightly bound metals. The stoichiometry of hydrogen peroxide formation from O{sub 2}{sup {minus}} decay indicates that this sink is capable of a redox cycle catalyzing the dismutation of O{sub 2}{sup {minus}}. This CDOM sink combined with the organic copper sink previously described will produce a steady-state superoxide concentration in coastal waters that is 100--1000-fold lower than that predicted from bimolecular dismutation alone. Catalyzed O{sub 2}{sup {minus}} decay was also observed in a variety of humic and fulvic acid samples, possibly occurring through quinone functionalities. Although the presence of quinone moieties in humic and fulvic acids has been demonstrated, there do not appear to be good correlations between several measures of quinone content and the O{sub 2}{sup {minus}} dismutation rates of these samples.

Influence of iron redox cycling on organo-mineral associations in Arctic tundra soil

Science.gov (United States)

Herndon, Elizabeth; AlBashaireh, Amineh; Singer, David; Roy Chowdhury, Taniya; Gu, Baohua; Graham, David

2017-06-01

Arctic tundra stores large quantities of soil organic matter under varying redox conditions. As the climate warms, these carbon reservoirs are susceptible to increased rates of decomposition and release to the atmosphere as the greenhouse gases carbon dioxide (CO2) and methane (CH4). Geochemical interactions between soil organic matter and minerals influence decomposition in many environments but remain poorly understood in Arctic tundra systems and are not considered in decomposition models. The accumulation of iron (Fe) oxyhydroxides and organo-iron precipitates at redox interfaces may be particularly important for carbon cycling given that ferric iron [Fe(III)] species can enhance decomposition by serving as terminal electron acceptors in anoxic soils or inhibit microbial decomposition by binding organic molecules. Here, we examine chemical properties of solid-phase Fe and organic matter in organic and mineral horizons within the seasonally thawed active layer of Arctic tundra on the North Slope of Alaska. Spectroscopic techniques, including micro-X-ray fluorescence (μXRF) mapping, micro-X-ray absorption near-edge structure (μXANES) spectroscopy, and Fourier transform infrared spectroscopy (FTIR), were coupled with chemical sequential extractions and physical density fractionations to evaluate the spatial distribution and speciation of Fe-bearing phases and associated organic matter in soils. Organic horizons were enriched in poorly crystalline and crystalline iron oxides, and approximately 60% of total Fe stored in organic horizons was calculated to derive from upward translocation from anoxic mineral horizons. Ferrihydrite and goethite were present as coatings on mineral grains and plant debris, and in aggregates with clays and particulate organic matter. Minor amounts of ferrous iron [Fe(II)] were present in iron sulfides (i.e., pyrite and greigite) in mineral horizon soils and iron phosphates (vivianite) in organic horizons. Concentrations of organic

Soluble and stable zethrenebis(dicarboximide) and its quinone

KAUST Repository

Sun, Zhe

2010-10-15

Soluble and stable zethrenebis(dicarboximide) (1) was synthesized by an in situ Stille cross coupling/transannular cyclization reaction. 1 showed largely improved photostability and solubility compared with the very unstable zethrene and it also exhibited far-red absorption and emission with high photoluminescence quantum yield. Bromination of 1 with NBS/DMF gave its quinone form 2 via an unusual pathway. © 2010 American Chemical Society.

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

International Nuclear Information System (INIS)

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

2009-01-01

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

New Supercapacitors Based on the Synergetic Redox Effect between Electrode and Electrolyte

Directory of Open Access Journals (Sweden)

You Zhang

2016-08-01

Full Text Available Redox electrolytes can provide significant enhancement of capacitance for supercapacitors. However, more important promotion comes from the synergetic effect and matching between the electrode and electrolyte. Herein, we report a novel electrochemical system consisted of a polyanilline/carbon nanotube composite redox electrode and a hydroquinone (HQ redox electrolyte, which exhibits a specific capacitance of 7926 F/g in a three-electrode system when the concentration of HQ in H2SO4 aqueous electrolyte is 2 mol/L, and the maximum energy density of 114 Wh/kg in two-electrode symmetric configuration. Moreover, the specific capacitance retention of 96% after 1000 galvanostatic charge/discharge cycles proves an excellent cyclic stability. These ultrahigh performances of the supercapacitor are attributed to the synergistic effect both in redox polyanilline-based electrolyte and the redox hydroquinone electrode.

Highly sensitive and label-free electrochemical detection of microRNAs based on triple signal amplification of multifunctional gold nanoparticles, enzymes and redox-cycling reaction.

Science.gov (United States)

Liu, Lin; Xia, Ning; Liu, Huiping; Kang, Xiaojing; Liu, Xiaoshuan; Xue, Chan; He, Xiaoling

2014-03-15

MicroRNAs (miRNAs) are believed to be important for cancer diagnosis and prognosis, serving as reliable molecular biomarkers. In this work, we presented a label-free and highly sensitive electrochemical genosensor for miRNAs detection with the triple signal amplification of gold nanoparticles (AuNPs), alkaline phosphatase (ALP) and p-aminophenol (p-AP) redox cycling. The label-free strategy is based on the difference in the structures of RNA and DNA. Specifically, miRNAs were first captured by the pre-immobilized DNA probes on a gold electrode. Next, the cis-diol group of ribose sugar at the end of the miRNAs chain allowed 3-aminophenylboronic acid (APBA)/biotin-modified multifunctional AuNPs (denoted as APBA-biotin-AuNPs) to be attached through the formation of a boronate ester covalent bond, which facilitated the capture of streptavidin-conjugated alkaline phosphatase (SA-ALP) via the biotin-streptavidin interaction. After the addition of the 4-aminophenylphosphate (p-APP) substrate, the enzymatic conversion from p-APP to p-AP occurred. The resulting p-AP could be cycled by a chemical reducing reagent after its electro-oxidization on the electrode (known as p-AP redox cycling), thus enabling an increase in the anodic current. As a result, the current increased linearly with the miRNAs concentration over a range of 10 fM-5 pM, and a detection limit of 3 fM was achieved. We believe that this work will be valuable for the design of new types of label-free and sensitive electrochemical biosensors. © 2013 Published by Elsevier B.V.

Redox Cycling, pH Dependence, and Ligand Effects of Mn(III) in Oxalate Decarboxylase from Bacillus subtilis.

Science.gov (United States)

Twahir, Umar T; Ozarowski, Andrew; Angerhofer, Alexander

2016-11-29

This contribution describes electron paramagnetic resonance (EPR) experiments on Mn(III) in oxalate decarboxylase of Bacillus subtilis, an interesting enzyme that catalyzes the redox-neutral dissociation of oxalate into formate and carbon dioxide. Chemical redox cycling provides strong evidence that both Mn centers can be oxidized, although the N-terminal Mn(II) appears to have the lower reduction potential and is most likely the carrier of the +3 oxidation state under moderate oxidative conditions, in agreement with the general view that it represents the active site. Significantly, Mn(III) was observed in untreated OxDC in succinate and acetate buffers, while it could not be directly observed in citrate buffer. Quantitative analysis showed that up to 16% of the EPR-visible Mn is in the +3 oxidation state at low pH in the presence of succinate buffer. The fine structure and hyperfine structure parameters of Mn(III) are affected by small carboxylate ligands that can enter the active site and have been recorded for formate, acetate, and succinate. The results from a previous report [Zhu, W., et al. (2016) Biochemistry 55, 429-434] could therefore be reinterpreted as evidence of formate-bound Mn(III) after the enzyme is allowed to turn over oxalate. The pH dependence of the Mn(III) EPR signal compares very well with that of enzymatic activity, providing strong evidence that the catalytic reaction of oxalate decarboxylase is driven by Mn(III), which is generated in the presence of dioxygen.

Studies on the mechanism of quinone action on hormonal regulation of metabolism in the rat liver

International Nuclear Information System (INIS)

Cheng, E.Y.

1989-01-01

The mechanism of quinone actions in liver cell metabolism had been investigated using menadione as a model compound. Previous reports suggested that quinones and free radicals could produce perturbations in cellular calcium homeostasis. Since calcium plays an important role in the regulation of cellular metabolic processes, then regulation of cytosolic calcium concentrations, and thus of cellular metabolism, by calcium-mobilizing hormones such as phenylephrine and vasopressin could possibly be modified by quinones such as menadione. Methods used to approach this hypothesis included the assay for activation of glycogen phosphorylase, an indirect index of calcium mobilization; the determination of calcium mobilization with 45 Ca efflux exchange and with fluorescent calcium indicator fura-2; and the measurement of phosphatidylinositides, an important link in the membrane-associated receptor-mediated signal transduction mechanism

Polyoxovanadate-alkoxide clusters as multi-electron charge carriers for symmetric non-aqueous redox flow batteries.

Science.gov (United States)

VanGelder, L E; Kosswattaarachchi, A M; Forrestel, P L; Cook, T R; Matson, E M

2018-02-14

Non-aqueous redox flow batteries have emerged as promising systems for large-capacity, reversible energy storage, capable of meeting the variable demands of the electrical grid. Here, we investigate the potential for a series of Lindqvist polyoxovanadate-alkoxide (POV-alkoxide) clusters, [V 6 O 7 (OR) 12 ] (R = CH 3 , C 2 H 5 ), to serve as the electroactive species for a symmetric, non-aqueous redox flow battery. We demonstrate that the physical and electrochemical properties of these POV-alkoxides make them suitable for applications in redox flow batteries, as well as the ability for ligand modification at the bridging alkoxide moieties to yield significant improvements in cluster stability during charge-discharge cycling. Indeed, the metal-oxide core remains intact upon deep charge-discharge cycling, enabling extremely high coulombic efficiencies (∼97%) with minimal overpotential losses (∼0.3 V). Furthermore, the bulky POV-alkoxide demonstrates significant resistance to deleterious crossover, which will lead to improved lifetime and efficiency in a redox flow battery.

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

International Nuclear Information System (INIS)

Ksepko, Ewelina; Babiński, Piotr; Nalbandian, Lori

2017-01-01

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

A biomimetic high-capacity phenazine-based anolyte for aqueous organic redox flow batteries

Science.gov (United States)

Hollas, Aaron; Wei, Xiaoliang; Murugesan, Vijayakumar; Nie, Zimin; Li, Bin; Reed, David; Liu, Jun; Sprenkle, Vincent; Wang, Wei

2018-06-01

Aqueous soluble organic (ASO) redox-active materials have recently attracted significant attention as alternatives to traditional transition metal ions in redox flow batteries (RFB). However, reported reversible capacities of ASO are often substantially lower than their theoretical values based on the reported maximum solubilities. Here, we describe a phenazine-based ASO compound with an exceptionally high reversible capacity that exceeds 90% of its theoretical value. By strategically modifying the phenazine molecular structure, we demonstrate an increased solubility from near-zero with pristine phenazine to as much as 1.8 M while also shifting its redox potential by more than 400 mV. An RFB based on a phenazine derivative (7,8-dihydroxyphenazine-2-sulfonic acid) at its near-saturation concentration exhibits an operating voltage of 1.4 V with a reversible anolyte capacity of 67 Ah l-1 and a capacity retention of 99.98% per cycle over 500 cycles.

Comparative evaluation of the acceptor properties of quinone derivatized polypyridinic ligands

Energy Technology Data Exchange (ETDEWEB)

Norambuena, Ester [Departamento de Quimica, Facultad de Ciencias Basicas, Universidad Metropolitana de Ciencias de la Educacion, Santiago (Chile); Olea-Azar, Claudio [Facultad de Ciencias Quimicas y Farmaceuticas, Universidad de Chile, Santiago (Chile); Delgadillo, Alvaro [Departamento de Quimica, Facultad de Ciencias, Universidad de La Serena, Casilla 599, La Serena (Chile); Barrera, Mauricio [Facultad de Quimica, Pontificia Universidad Catolica de Chile, Casilla 306, Santiago (Chile); Loeb, Barbara, E-mail: bloeb@puc.cl [Facultad de Quimica, Pontificia Universidad Catolica de Chile, Casilla 306, Santiago (Chile)

2009-05-18

The reduction properties of four acceptor polipyridyl ligands modified with quinones were studied by different experimental methods, as cyclic voltammetry and ESR spectroscopy, and by theoretical calculations. ESR spectra for the reduced ligands show different patterns among them, suggesting that the quinone moiety plays an important role in the delocalization of the received electron. The hyperfine coupling constants calculated for the magnetic nucleus were in good agreement with experimental data. The results were additionally interpreted with the help of two theoretical predictors: the electrophilicity index and the Fukui function obtained through the spin density. The results suggest that 12,17-dihydronaphtho-[2,3-h]dipyrido[3,2-a:2',3'-c]-phenazine-12,17-dione, Aqphen, shows the most promising behavior to be employed as an acceptor ligand in complexes with potential application in NLO devices.

Comparative evaluation of the acceptor properties of quinone derivatized polypyridinic ligands

International Nuclear Information System (INIS)

Norambuena, Ester; Olea-Azar, Claudio; Delgadillo, Alvaro; Barrera, Mauricio; Loeb, Barbara

2009-01-01

The reduction properties of four acceptor polipyridyl ligands modified with quinones were studied by different experimental methods, as cyclic voltammetry and ESR spectroscopy, and by theoretical calculations. ESR spectra for the reduced ligands show different patterns among them, suggesting that the quinone moiety plays an important role in the delocalization of the received electron. The hyperfine coupling constants calculated for the magnetic nucleus were in good agreement with experimental data. The results were additionally interpreted with the help of two theoretical predictors: the electrophilicity index and the Fukui function obtained through the spin density. The results suggest that 12,17-dihydronaphtho-[2,3-h]dipyrido[3,2-a:2',3'-c]-phenazine-12,17-dione, Aqphen, shows the most promising behavior to be employed as an acceptor ligand in complexes with potential application in NLO devices.

An antibacterial ortho-quinone diterpenoid and its derivatives from Caryopteris mongolica.

Science.gov (United States)

Saruul, Erdenebileg; Murata, Toshihiro; Selenge, Erdenechimeg; Sasaki, Kenroh; Yoshizaki, Fumihiko; Batkhuu, Javzan

2015-06-15

To identify antibacterial components in traditional Mongolian medicinal plant Caryopteris mongolica, an ortho-quinone abietane caryopteron A (1) and three its derivatives caryopteron B-D (2-4) were isolated from the roots of the plant together with three known abietanes demethylcryptojaponol (5), 6α-hydroxydemethyl cryptojaponol (6), and 14-deoxycoleon U (7). The chemical structures of these abietane derivatives were elucidated on the basis of spectroscopic data. Compounds 1-4 had C-13 methylcyclopropane substructures, and 2-4 had a hexanedioic anhydride ring C instead of ortho-quinone in 1. The stereochemistry of these compound was assumed from NOE spectra and ECD Cotton effects. Compounds 1 and 5-7 showed antibacterial activities against the Gram-positive bacteria Staphylococcus aureus, Staphylococcus epidermidis, Enterococcus faecalis, and Micrococcus luteus, being 1 the more potent. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

Intermittent fasting results in tissue-specific changes in bioenergetics and redox state.

Science.gov (United States)

Chausse, Bruno; Vieira-Lara, Marcel A; Sanchez, Angélica B; Medeiros, Marisa H G; Kowaltowski, Alicia J

2015-01-01

Intermittent fasting (IF) is a dietary intervention often used as an alternative to caloric restriction (CR) and characterized by 24 hour cycles alternating ad libitum feeding and fasting. Although the consequences of CR are well studied, the effects of IF on redox status are not. Here, we address the effects of IF on redox state markers in different tissues in order to uncover how changes in feeding frequency alter redox balance in rats. IF rats displayed lower body mass due to decreased energy conversion efficiency. Livers in IF rats presented increased mitochondrial respiratory capacity and enhanced levels of protein carbonyls. Surprisingly, IF animals also presented an increase in oxidative damage in the brain that was not related to changes in mitochondrial bioenergetics. Conversely, IF promoted a substantial protection against oxidative damage in the heart. No difference in mitochondrial bioenergetics or redox homeostasis was observed in skeletal muscles of IF animals. Overall, IF affects redox balance in a tissue-specific manner, leading to redox imbalance in the liver and brain and protection against oxidative damage in the heart.

Intermittent fasting results in tissue-specific changes in bioenergetics and redox state.

Directory of Open Access Journals (Sweden)

Bruno Chausse

Full Text Available Intermittent fasting (IF is a dietary intervention often used as an alternative to caloric restriction (CR and characterized by 24 hour cycles alternating ad libitum feeding and fasting. Although the consequences of CR are well studied, the effects of IF on redox status are not. Here, we address the effects of IF on redox state markers in different tissues in order to uncover how changes in feeding frequency alter redox balance in rats. IF rats displayed lower body mass due to decreased energy conversion efficiency. Livers in IF rats presented increased mitochondrial respiratory capacity and enhanced levels of protein carbonyls. Surprisingly, IF animals also presented an increase in oxidative damage in the brain that was not related to changes in mitochondrial bioenergetics. Conversely, IF promoted a substantial protection against oxidative damage in the heart. No difference in mitochondrial bioenergetics or redox homeostasis was observed in skeletal muscles of IF animals. Overall, IF affects redox balance in a tissue-specific manner, leading to redox imbalance in the liver and brain and protection against oxidative damage in the heart.

Effects of commonly consumed fruit juices and carbohydrates on redox status and anticancer biomarkers in female rats

DEFF Research Database (Denmark)

Breinholt, Vibeke M.; Nielsen, Salka E.; Knuthsen, Pia

2003-01-01

/kg of diet. However, no effects were observed on hepatic glutathione S-transferase or quinone reductase activities, plasma redox status, or the activity of red blood cell antioxidant enzymes. Overall, the results of the present study suggest that commonly consumed fruit juices can alter lipid and protein......Administration of apple juice, black currant juice, ora 1:1 combination of the two juices significantly decreased the level of the lipid peroxidation biomarker malondialdehyde in plasma of female rats, whereas the protein oxidation biomarker 2-amino-adipic semialdehyde, was significantly increased...... following administration of orange juice, black currant juice, or the 1: 1 combination of apple and black currant juice. A significant increase in 2-amino-adipic semialdehyde was also observed in control rats given sucrose, fructose, and glucose in the drinking water at concentrations approximating...

A simple method to fabricate electrochemical sensor systems with predictable high-redox amplification

NARCIS (Netherlands)

Straver, M.G.; Odijk, Mathieu; Olthuis, Wouter; van den Berg, Albert

2012-01-01

In this paper an easy to fabricate SU8/glass-based microfluidic sensor is described with two closely spaced parallel electrodes for highly selective measurements using the redox cycling effect. By varying the length of the microfluidic entrance channel, a diffusion barrier is created for non-cycling

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African Journals Online (AJOL)

The electrochemical properties of quinones make them a promising class of compounds to be utilized as active matter in secondary batteries. Quinones incorporated in carbon paste electrodes. (CPE) have been frequently employed to investigate their electrochemical behavior [1,2,3]. The redox couple ...

Splitting CO2 with a ceria‐based redox cycle in a solar‐driven thermogravimetric analyzer

Science.gov (United States)

Takacs, M.; Ackermann, S.; Bonk, A.; Neises‐von Puttkamer, M.; Haueter, Ph.; Scheffe, J. R.; Vogt, U. F.

2016-01-01

Thermochemical splitting of CO2 via a ceria‐based redox cycle was performed in a solar‐driven thermogravimetric analyzer. Overall reaction rates, including heat and mass transport, were determined under concentrated irradiation mimicking realistic operation of solar reactors. Reticulated porous ceramic (RPC) structures and fibers made of undoped and Zr4+‐doped CeO2, were endothermally reduced under radiative fluxes of 1280 suns in the temperature range 1200–1950 K and subsequently re‐oxidized with CO2 at 950–1400 K. Rapid and uniform heating was observed for 8 ppi ceria RPC with mm‐sized porosity due to its low optical thickness and volumetric radiative absorption, while ceria fibers with μm‐sized porosity performed poorly due to its opacity to incident irradiation. The 10 ppi RPC exhibited higher fuel yield because of its higher sample density. Zr4+‐doped ceria showed increasing reduction extents with dopant concentration but decreasing specific CO yield due to unfavorable oxidation thermodynamics and slower kinetics. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1263–1271, 2017 PMID:28405030

Splitting CO2 with a ceria-based redox cycle in a solar-driven thermogravimetric analyzer.

Science.gov (United States)

Takacs, M; Ackermann, S; Bonk, A; Neises-von Puttkamer, M; Haueter, Ph; Scheffe, J R; Vogt, U F; Steinfeld, A

2017-04-01

Thermochemical splitting of CO 2 via a ceria-based redox cycle was performed in a solar-driven thermogravimetric analyzer. Overall reaction rates, including heat and mass transport, were determined under concentrated irradiation mimicking realistic operation of solar reactors. Reticulated porous ceramic (RPC) structures and fibers made of undoped and Zr 4+ -doped CeO 2 , were endothermally reduced under radiative fluxes of 1280 suns in the temperature range 1200-1950 K and subsequently re-oxidized with CO 2 at 950-1400 K. Rapid and uniform heating was observed for 8 ppi ceria RPC with mm-sized porosity due to its low optical thickness and volumetric radiative absorption, while ceria fibers with μm-sized porosity performed poorly due to its opacity to incident irradiation. The 10 ppi RPC exhibited higher fuel yield because of its higher sample density. Zr 4+ -doped ceria showed increasing reduction extents with dopant concentration but decreasing specific CO yield due to unfavorable oxidation thermodynamics and slower kinetics. © 2016 American Institute of Chemical Engineers , 63: 1263-1271, 2017.

Fundamentally Addressing Bromine Storage through Reversible Solid-State Confinement in Porous Carbon Electrodes: Design of a High-Performance Dual-Redox Electrochemical Capacitor.

Science.gov (United States)

Yoo, Seung Joon; Evanko, Brian; Wang, Xingfeng; Romelczyk, Monica; Taylor, Aidan; Ji, Xiulei; Boettcher, Shannon W; Stucky, Galen D

2017-07-26

Research in electric double-layer capacitors (EDLCs) and rechargeable batteries is converging to target systems that have battery-level energy density and capacitor-level cycling stability and power density. This research direction has been facilitated by the use of redox-active electrolytes that add faradaic charge storage to increase energy density of the EDLCs. Aqueous redox-enhanced electrochemical capacitors (redox ECs) have, however, performed poorly due to cross-diffusion of soluble redox couples, reduced cycle life, and low operating voltages. In this manuscript, we propose that these challenges can be simultaneously met by mechanistically designing a liquid-to-solid phase transition of oxidized catholyte (or reduced anolyte) with confinement in the pores of electrodes. Here we demonstrate the realization of this approach with the use of bromide catholyte and tetrabutylammonium cation that induces reversible solid-state complexation of Br 2 /Br 3 - . This mechanism solves the inherent cross-diffusion issue of redox ECs and has the added benefit of greatly stabilizing the reactive bromine generated during charging. Based on this new mechanistic insight on the utilization of solid-state bromine storage in redox ECs, we developed a dual-redox EC consisting of a bromide catholyte and an ethyl viologen anolyte with the addition of tetrabutylammonium bromide. In comparison to aqueous and organic electric double-layer capacitors, this system enhances energy by factors of ca. 11 and 3.5, respectively, with a specific energy of ∼64 W·h/kg at 1 A/g, a maximum power density >3 kW/kg, and cycling stability over 7000 cycles.

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)

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)

Quinone-fused porphyrins as contrast agents for photoacoustic imaging

KAUST Repository

Banala, Srinivas

2017-06-27

Photoacoustic (PA) imaging is an emerging non-invasive diagnostic modality with many potential clinical applications in oncology, rheumatology and the cardiovascular field. For this purpose, there is a high demand for exogenous contrast agents with high absorption coefficients in the optical window for tissue imaging, i.e. the near infrared (NIR) range between 680 and 950 nm. We herein report the photoacoustic properties of quinone-fused porphyrins inserted with different transition metals as new highly promising candidates. These dyes exhibit intense NIR absorption, a lack of fluorescence emission, and PA sensitivity in concentrations below 3 nmol mL. In this context, the highest PA signal was obtained with a Zn(ii) inserted dye. Furthermore, this dye was stable in blood serum and free thiol solution and exhibited negligible cell toxicity. Additionally, the Zn(ii) probe could be detected with an up to 3.2 fold higher PA intensity compared to the clinically most commonly used PA agent, ICG. Thus, further exploration of the \\'quinone-fusing\\' approach to other chromophores may be an efficient way to generate highly potent PA agents that do not fluoresce and shift their absorption into the NIR range.

Redox electrodes comprised of polymer-modified carbon nanomaterials

Science.gov (United States)

Roberts, Mark; Emmett, Robert; Karakaya, Mehmet; Podila, Ramakrishna; Rao, Apparao; Clemson Physics Team; Clemson Chemical Engineering Team

2013-03-01

A shift in how we generate and use electricity requires new energy storage materials and systems compatible with hybrid electric transportation and the integration of renewable energy sources. Supercapacitors provide a solution to these needs by combining the high power, rapid switching, and exceptional cycle life of a capacitor with the high energy density of a battery. Our research brings together nanotechnology and materials chemistry to address the limitations of electrode materials. Paper electrodes fabricated with various forms of carbon nanomaterials, such as nanotubes, are modified with redox-polymers to increase the electrode's energy density while maintaining rapid discharge rates. In these systems, the carbon nanomaterials provide the high surface area, electrical conductivity, nanoscale and porosity, while the redox polymers provide a mechanism for charge storage through Faradaic charge transfer. The design of redox polymers and their incorporation into nanomaterial electrodes will be discussed with a focus on enabling high power and high energy density electrodes.

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

International Nuclear Information System (INIS)

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

2014-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-12-15

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

Monitoring of BHT-quinone and BHT-CHO in the gas of capsules of Asclepias physocarpa.

Science.gov (United States)

Ma, Bing-Ji; Peng, Hua; Liu, Ji-Kai

2006-01-01

Three volatile components, namely benzoic acid ethyl ester (1), 2,6-di-tert-butyl-p-benzoquinone (BHT-quinone) (2), and 3,5-di-tert-butyl-4-hydroxybenzaldehyde (BHT-CHO) (3), were detected from the gas in the capsules of Asclepias physocarpa by means of GC/MS analysis. BHT-quinone and BHT-CHO as organic pollutants are the degradation products of the antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT). Ground water, lake water and/or rain water are a source of BHT metabolites in the plant Asclepias physocarpa.

A Hierarchically Porous Hypercrosslinked and Novel Quinone based Stable Organic Polymer Electrode for Lithium-Ion Batteries

International Nuclear Information System (INIS)

Ahmad, Aziz; Meng, Qinghai; Melhi, Saad; Mao, Lijuan; Zhang, Miao; Han, Bao-Hang; Lu, Kun; Wei, Zhixiang

2017-01-01

Highlights: •A novel hypercrosslinked Poly-Pillar[5]quinone (Poly-P5Q) polymer has been prepared and applied as electrode material in Li-ion batteries. •The novel synthetic route of Poly-P5Q was introduced by the oxidation of Poly-Dimethoxypillar[5]arene. •A Friedel-Crafts reaction was employed to prepare a novel Poly-P5Q as organic cathode material for lithium-ion batteries. -- Abstract: In the recent years, organic electrode materials have attracted tremendous attention and becoming promising electrode candidates for the green and sustainable lithium-ion batteries. A novel hypercrosslinked Poly-Pillar[5]quinone (Poly-P5Q) polymer was prepared and applied as electrode material in Li-ion batteries. Poly-P5Q is the oxidized form of Poly-Dimethoxypillar[5]arene (Poly-DMP5A) which was obtained from the condensation of dimethoxypillar[5]arene and formaldehyde dimethyl acetal using Friedel-Crafts reaction. The prepared materials were characterized by 13 C solid state NMR, FTIR, SEM, EDX and TGA analysis. The Poly-P5Q cathode showed an initial discharge capacity up to 105 mAh g −1 whereas it retained 82.3% of its initial discharge capacity after 100 charge-discharge cycles at a current speed of 100 mA g −1 in the potential window between 1.75 to 3.25 V. In future, research in this direction will provide great insight for the development of novel polymers from various small organic molecules as a stable and high performance electrode materials for green lithium-ion batteries.

A High-Current, Stable Nonaqueous Organic Redox Flow Battery

Energy Technology Data Exchange (ETDEWEB)

Wei, Xiaoliang; Duan, Wentao; Huang, Jinhua; Zhang, Lu; Li, Bin; Reed, David; Xu, Wu; Sprenkle, Vincent; Wang, Wei

2016-10-14

Nonaqueous redox flow batteries are promising in pursuit of high-energy storage systems owing to the broad voltage window, but currently are facing key challenges such as poor cycling stability and lack of suitable membranes. Here we report a new nonaqueous all-organic flow chemistry that demonstrates an outstanding cell cycling stability primarily because of high chemical persistency of the organic radical redox species and their good compatibility with the supporting electrolyte. A feasibility study shows that Daramic® and Celgard® porous separators can lead to high cell conductivity in flow cells thus producing remarkable cell efficiency and material utilization even at high current operations. This result suggests that the thickness and pore size are the key performance-determining factors for porous separators. With the greatly improved flow cell performance, this new flow system largely addresses the above mentioned challenges and the findings may greatly expedite the development of durable nonaqueous flow batteries.

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)

Electrochemical redox processes involving soluble cerium species

International Nuclear Information System (INIS)

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

2016-01-01

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

All three quinone species play distinct roles in ensuring optimal growth under aerobic and fermentative conditions in E. coli K12

Science.gov (United States)

Nitzschke, Annika

2018-01-01

The electron transport chain of E. coli contains three different quinone species, ubiquinone (UQ), menaquinone (MK) and demethylmenaquinone (DMK). The content and ratio of the different quinone species vary depending on the external conditions. To study the function of the different quinone species in more detail, strains with deletions preventing UQ synthesis, as well as MK and/or DMK synthesis were cultured under aerobic and anaerobic conditions. The strains were characterized with respect to growth and product synthesis. As quinones are also involved in the control of ArcB/A activity, we analyzed the phosphorylation state of the response regulator as well as the expression of selected genes.The data show reduced aerobic growth coupled to lactate production in the mutants defective in ubiquinone synthesis. This confirms the current assumption that ubiquinone is the main quinone under aerobic growth conditions. In the UQ mutant strains the amount of MK and DMK is significantly elevated. The strain synthesizing only DMK is less affected in growth than the strain synthesizing MK as well as DMK. An inhibitory effect of MK on aerobic growth due to increased oxidative stress is postulated.Under fermentative growth conditions the mutant synthesizing only UQ is severely impaired in growth. Obviously, UQ is not able to replace MK and DMK during anaerobic growth. Mutations affecting quinone synthesis have an impact on ArcA phosphorylation only under anaerobic conditions. ArcA phosphorylation is reduced in strains synthesizing only MK or MK plus DMK. PMID:29614086

A comparative study of all-vanadium and iron-chromium redox flow batteries for large-scale energy storage

Science.gov (United States)

Zeng, Y. K.; Zhao, T. S.; An, L.; Zhou, X. L.; Wei, L.

2015-12-01

The promise of redox flow batteries (RFBs) utilizing soluble redox couples, such as all vanadium ions as well as iron and chromium ions, is becoming increasingly recognized for large-scale energy storage of renewables such as wind and solar, owing to their unique advantages including scalability, intrinsic safety, and long cycle life. An ongoing question associated with these two RFBs is determining whether the vanadium redox flow battery (VRFB) or iron-chromium redox flow battery (ICRFB) is more suitable and competitive for large-scale energy storage. To address this concern, a comparative study has been conducted for the two types of battery based on their charge-discharge performance, cycle performance, and capital cost. It is found that: i) the two batteries have similar energy efficiencies at high current densities; ii) the ICRFB exhibits a higher capacity decay rate than does the VRFB; and iii) the ICRFB is much less expensive in capital costs when operated at high power densities or at large capacities.

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...

Quenching of bacteriochlorophyll fluorescence in chlorosomes from Chloroflexus aurantiacus by exogenous quinones

DEFF Research Database (Denmark)

Tokita, S; Frigaard, N-U; Hirota, M

2000-01-01

The quenching of bacteriochlorophyll (BChl) c fluorescence in chlorosomes isolated from Chloroflexus aurantiacus was examined by the addition of various benzoquinones, naphthoquinones (NQ), and anthraquinones (AQ). Many quinones showed strong quenching in the micromolar or submicromolar range. Th...

Bursting in the Belousov-Zhabotinsky Reaction added with Phenol in a Batch Reactor

Energy Technology Data Exchange (ETDEWEB)

Cadena, Ariel; Agreda, Jesus, E-mail: jaagredab@unal.edu.co [Departamento de Quimica, Facultad de Ciencias, Universidad Nacional de Colombia, Bogota (Colombia); Barragan, Daniel [Escuela de Quimica, Facultad de Ciencias, Universidad Nacional de Colombia, Medellin (Colombia)

2013-12-01

The classic Belousov-Zhabotinski reaction was modified by adding phenol as a second organic substrate that kinetically competes with the malonic acid in the reduction of Ce{sup 4+} to Ce{sup 3+} and in the removal of molecular bromine of the reaction mixture. The oscillating reaction of two substrates exhibited burst firing and an oscillatory period of long duration. Analysis of experimental data shows an increasing of the bursting phenomenon, with a greater spiking in the burst firing and with a longer quiescent state, as a function of the initial phenol concentration increase. It was hypothesized that the bursting phenomenon can be explained introducing a redox cycle between the reduced phenolic species (hydroxyphenols) and the oxidized ones (quinones). The hypothesis was experimentally and numerically tested and from the results it is possible to conclude that the bursting phenomenon exhibited by the oscillating reaction of two substrates is mainly driven by a p-di-hydroxy-benzene/p-benzoquinone redox cycle (author)

Bursting in the Belousov-Zhabotinsky Reaction added with Phenol in a Batch Reactor

International Nuclear Information System (INIS)

Cadena, Ariel; Agreda, Jesus; Barragan, Daniel

2013-01-01

The classic Belousov-Zhabotinski reaction was modified by adding phenol as a second organic substrate that kinetically competes with the malonic acid in the reduction of Ce 4+ to Ce 3+ and in the removal of molecular bromine of the reaction mixture. The oscillating reaction of two substrates exhibited burst firing and an oscillatory period of long duration. Analysis of experimental data shows an increasing of the bursting phenomenon, with a greater spiking in the burst firing and with a longer quiescent state, as a function of the initial phenol concentration increase. It was hypothesized that the bursting phenomenon can be explained introducing a redox cycle between the reduced phenolic species (hydroxyphenols) and the oxidized ones (quinones). The hypothesis was experimentally and numerically tested and from the results it is possible to conclude that the bursting phenomenon exhibited by the oscillating reaction of two substrates is mainly driven by a p-di-hydroxy-benzene/p-benzoquinone redox cycle (author)

Effects of oxygen radical scavengers on the inactivation of SS phi X174 DNA by the semi-quinone free radical of the antitumor agent etoposide

NARCIS (Netherlands)

van Maanen, M.J.; Mans, D.R.A.; Lafleur, M.V.M.; Van Schaik, M A; de Vries, J; Vermeulen, N P; Retèl, J.; Lankelma, J

1990-01-01

We have studied the effects of oxygen radical scavengers on the inactivation of ss phi X174 DNA by the semi-quinone free radical of the antitumor agent etoposide (VP 16-213), which was generated from the ortho-quinone of etoposide at pH greater than or equal to 7.4. A semi-quinone free radical of

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

Geomicrobiological redox cycling of the transuranic element neptunium.

Science.gov (United States)

Law, Gareth T W; Geissler, Andrea; Lloyd, Jonathan R; Livens, Francis R; Boothman, Christopher; Begg, James D C; Denecke, Melissa A; Rothe, Jörg; Dardenne, Kathy; Burke, Ian T; Charnock, John M; Morris, Katherine

2010-12-01

Microbial processes can affect the environmental behavior of redox sensitive radionuclides, and understanding these reactions is essential for the safe management of radioactive wastes. Neptunium, an alpha-emitting transuranic element, is of particular importance because of its long half-life, high radiotoxicity, and relatively high solubility as Np(V)O(2)(+) under oxic conditions. Here, we describe experiments to explore the biogeochemistry of Np where Np(V) was added to oxic sediment microcosms with indigenous microorganisms and anaerobically incubated. Enhanced Np removal to sediments occurred during microbially mediated metal reduction, and X-ray absorption spectroscopy showed this was due to reduction to poorly soluble Np(IV) on solids. In subsequent reoxidation experiments, sediment-associated Np(IV) was somewhat resistant to oxidative remobilization. These results demonstrate the influence of microbial processes on Np solubility and highlight the critical importance of radionuclide biogeochemistry in nuclear legacy management.

Interaction between heavy metals and thiol-linked redox reactions in germination.

Science.gov (United States)

Smiri, M; Chaoui, A; Ferjani, E E

2010-09-15

Thioredoxin (TRX) proteins perform important biological functions in cells by changing the redox state of proteins via dithiol disulfide exchange. Several systems are able to control the activity, stability, and correct folding of enzymes through dithiol/disulfide isomerization reactions including the enzyme protein disulfide-isomerase, the glutathione-dependent glutaredoxin system, and the thioredoxin systems. Plants have devised sophisticated mechanisms to cope with biotic and abiotic stresses imposed by their environment. Among these mechanisms, those collectively referred to as redox reactions induced by endogenous systems. This is of agronomical importance since a better knowledge of the involved mechanisms can offer novel means for crop protection. In the plant life cycle, the seed and seedling stages are key developmental stages conditioning the final yield of crops. Both are very sensitive to heavy metal stress. Plant redox reactions are principally studied on adult plant organs and there is only very scarce informations about the onset of redox regulation at the level of seed germination. In the here presented study, we discussed the importance of redox proteins in plant cell metabolism and defence. Special focus is given to TRX, which are involved in detoxification of ROS and also to their targets.

Redox pioneer:Professor Christine Helen Foyer.

Science.gov (United States)

Del Río, Luis A

2011-10-15

Dr. Christine Foyer (B.Sc. 1974; Ph.D. 1977) is recognized here as a Redox Pioneer because she has published an article on redox biology that has been cited more than 1000 times, 4 other articles that have been cited more than 500 times, and a further 32 articles that have been each cited more than 100 times. During her Ph.D. at the Kings College, University of London, United Kingdom, Dr. Foyer discovered that ascorbate and glutathione and enzymes linking NADPH, glutathione, and ascorbate are localized in isolated chloroplast preparations. These observations pioneered the discovery of the ascorbate-glutathione cycle, now known as Foyer-Halliwell-Asada pathway after the names of the three major contributors, a crucial mechanism for H(2)O(2) metabolism in both animals and plants. Dr. Foyer has made a very significant contribution to our current understanding of the crucial roles of ascorbate and glutathione in redox biology, particularly in relation to photosynthesis, respiration, and chloroplast and mitochondrial redox signaling networks. "My view is that science…is compulsive and you have to keep with it all the time and not get despondent when things do not work well. Being passionate about science is what carries you through the hard times so that it isn't so much work, as a hobby that you do for a living. It is the thrill of achieving a better understanding and finding real pleasure in putting new ideas together, explaining data and passing on knowledge that keeps you going no matter what!" --Prof. Christine Helen Foyer.

Hydrologic control on redox and nitrogen dynamics in a peatland soil.

Science.gov (United States)

Rubol, Simonetta; Silver, Whendee L; Bellin, Alberto

2012-08-15

Soils are a dominant source of nitrous oxide (N(2)O), a potent greenhouse gas. However, the complexity of the drivers of N(2)O production and emissions has hindered our ability to predict the magnitude and spatial dynamics of N(2)O fluxes. Soil moisture can be considered a key driver because it influences oxygen (O(2)) supply, which feeds back on N(2)O sources (nitrification versus denitrification) and sinks (reduction to dinitrogen). Soil water content is directly linked to O(2) and redox potential, which regulate microbial metabolism and chemical transformations in the environment. Despite its importance, only a few laboratory studies have addressed the effects of hydrological transient dynamics on nitrogen (N) cycling in the vadose zone. To further investigate these aspects, we performed a long term experiment in a 1.5 m depth soil column supplemented by chamber experiments. With this experiment, we aimed to investigate how soil moisture dynamics influence redox sensitive N cycling in a peatland soil. As expected, increased soil moisture lowered O(2) concentrations and redox potential in the soil. The decline was more severe for prolonged saturated conditions than for short events and at deep than at the soil surface. Gaseous and dissolved N(2)O, dissolved nitrate (NO(3)(-)) and ammonium (NH(4)(+)) changed considerably along the soil column profile following trends in soil O(2) and redox potential. Hot spots of N(2)O concentrations corresponded to high variability in soil O(2) in the upper and lower parts of the column. Results from chamber experiments confirmed high NO(3)(-) reduction potential in soils, particularly from the bottom of the column. Under our experimental conditions, we identified a close coupling of soil O(2) and N(2)O dynamics, both of which lagged behind soil moisture changes. These results highlight the relationship among soil hydrologic properties, redox potential and N cycling, and suggest that models working at a daily scale need to

Chloride supporting electrolytes for all-vanadium redox flow batteries.

Science.gov (United States)

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

2011-10-28

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

High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries.

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Hendriks, Koen H; Robinson, Sophia G; Braten, Miles N; Sevov, Christo S; Helms, Brett A; Sigman, Matthew S; Minteer, Shelley D; Sanford, Melanie S

2018-02-28

Nonaqueous redox flow batteries (NRFBs) represent an attractive technology for energy storage from intermittent renewable sources. In these batteries, electrical energy is stored in and extracted from electrolyte solutions of redox-active molecules (termed catholytes and anolytes) that are passed through an electrochemical flow cell. To avoid battery self-discharge, the anolyte and catholyte solutions must be separated by a membrane in the flow cell. This membrane prevents crossover of the redox active molecules, while simultaneously allowing facile transport of charge-balancing ions. A key unmet challenge for the field is the design of redox-active molecule/membrane pairs that enable effective electrolyte separation while maintaining optimal battery properties. Herein, we demonstrate the development of oligomeric catholytes based on tris(dialkylamino)cyclopropenium (CP) salts that are specifically tailored for pairing with size-exclusion membranes composed of polymers of intrinsic microporosity (PIMs). Systematic studies were conducted to evaluate the impact of oligomer size/structure on properties that are crucial for flow battery performance, including cycling stability, charge capacity, solubility, electron transfer kinetics, and crossover rates. These studies have led to the identification of a CP-derived tetramer in which these properties are all comparable, or significantly improved, relative to the monomeric counterpart. Finally, a proof-of-concept flow battery is demonstrated by pairing this tetrameric catholyte with a PIM membrane. After 6 days of cycling, no crossover is detected, demonstrating the promise of this approach. These studies provide a template for the future design of other redox-active oligomers for this application.

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

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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.

Molecular Materials for Nonaqueous Flow Batteries with a High Coulombic Efficiency and Stable Cycling.

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Milton, Margarita; Cheng, Qian; Yang, Yuan; Nuckolls, Colin; Hernández Sánchez, Raúl; Sisto, Thomas J

2017-12-13

This manuscript presents a working redox battery in organic media that possesses remarkable cycling stability. The redox molecules have a solubility over 1 mol electrons/liter, and a cell with 0.4 M electron concentration is demonstrated with steady performance >450 cycles (>74 days). Such a concentration is among the highest values reported in redox flow batteries with organic electrolytes. The average Coulombic efficiency of this cell during cycling is 99.868%. The stability of the cell approaches the level necessary for a long lifetime nonaqueous redox flow battery. For the membrane, we employ a low cost size exclusion cellulose membrane. With this membrane, we couple the preparation of nanoscale macromolecular electrolytes to successfully avoid active material crossover. We show that this cellulose-based membrane can support high voltages in excess of 3 V and extreme temperatures (-20 to 110 °C). These extremes in temperature and voltage are not possible with aqueous systems. Most importantly, the nanoscale macromolecular platforms we present here for our electrolytes can be readily tuned through derivatization to realize the promise of organic redox flow batteries.

The binding of quinone to the photosynthetic reaction centers: kinetics and thermodynamics of reactions occurring at the QB-site in zwitterionic and anionic liposomes.

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Mavelli, Fabio; Trotta, Massimo; Ciriaco, Fulvio; Agostiano, Angela; Giotta, Livia; Italiano, Francesca; Milano, Francesco

2014-07-01

Liposomes represent a versatile biomimetic environment for studying the interaction between integral membrane proteins and hydrophobic ligands. In this paper, the quinone binding to the QB-site of the photosynthetic reaction centers (RC) from Rhodobacter sphaeroides has been investigated in liposomes prepared with either the zwitterionic phosphatidylcholine (PC) or the negatively charged phosphatidylglycerol (PG) to highlight the role of the different phospholipid polar heads. Quinone binding (K Q) and interquinone electron transfer (L AB) equilibrium constants in the two type of liposomes were obtained by charge recombination reaction of QB-depleted RC in the presence of increasing amounts of ubiquinone-10 over the temperature interval 6-35 °C. The kinetic of the charge recombination reactions has been fitted by numerically solving the ordinary differential equations set associated with a detailed kinetic scheme involving electron transfer reactions coupled with quinone release and uptake. The entire set of traces at each temperature was accurately fitted using the sole quinone release constants (both in a neutral and a charge separated state) as adjustable parameters. The temperature dependence of the quinone exchange rate at the QB-site was, hence, obtained. It was found that the quinone exchange regime was always fast for PC while it switched from slow to fast in PG as the temperature rose above 20 °C. A new method was introduced in this paper for the evaluation of constant K Q using the area underneath the charge recombination traces as the indicator of the amount of quinone bound to the QB-site.

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

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

2016-11-23

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

Quinones are growth factors for the human gut microbiota.

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Fenn, Kathrin; Strandwitz, Philip; Stewart, Eric J; Dimise, Eric; Rubin, Sarah; Gurubacharya, Shreya; Clardy, Jon; Lewis, Kim

2017-12-20

The human gut microbiome has been linked to numerous components of health and disease. However, approximately 25% of the bacterial species in the gut remain uncultured, which limits our ability to properly understand, and exploit, the human microbiome. Previously, we found that growing environmental bacteria in situ in a diffusion chamber enables growth of uncultured species, suggesting the existence of growth factors in the natural environment not found in traditional cultivation media. One source of growth factors proved to be neighboring bacteria, and by using co-culture, we isolated previously uncultured organisms from the marine environment and identified siderophores as a major class of bacterial growth factors. Here, we employ similar co-culture techniques to grow bacteria from the human gut microbiome and identify novel growth factors. By testing dependence of slow-growing colonies on faster-growing neighboring bacteria in a co-culture assay, eight taxonomically diverse pairs of bacteria were identified, in which an "induced" isolate formed a gradient of growth around a cultivatable "helper." This set included two novel species Faecalibacterium sp. KLE1255-belonging to the anti-inflammatory Faecalibacterium genus-and Sutterella sp. KLE1607. While multiple helper strains were identified, Escherichia coli was also capable of promoting growth of all induced isolates. Screening a knockout library of E. coli showed that a menaquinone biosynthesis pathway was required for growth induction of Faecalibacterium sp. KLE1255 and other induced isolates. Purified menaquinones induced growth of 7/8 of the isolated strains, quinone specificity profiles for individual bacteria were identified, and genome analysis suggests an incomplete menaquinone biosynthetic capability yet the presence of anaerobic terminal reductases in the induced strains, indicating an ability to respire anaerobically. Our data show that menaquinones are a major class of growth factors for bacteria

Ocean redox change at the Permian-Triassic mass extinction

DEFF Research Database (Denmark)

Ruhl, Micha; Bjerrum, Christian J.; Canfield, Donald Eugene

2013-01-01

Earth’s history is marked by multiple events of ocean anoxia developing along continental margins and po¬tentially into the open ocean realm. These events of¬ten coincide with the emplacement of large igneous provinces (LIPs) on continents, major perturbations of global geochemical cycles and mar...... these oceanographic changes to similar observations for the Triassic-Jurassic mass extinction and discuss environmental forcing, poten¬tially inherent to major volcanic events and leading to global environmental change and extinction...... ocean redox change over the largest mass extinction event in Earth history, at the Permian-Tri¬assic boundary (at ~252 Ma). This event is marked by a major perturbation in the global exogenic carbon cycle (and associated major negative carbon isotope excursion (CIE)), likely initiated by carbon...... (anoxic but not euxinic) coinciding with the main extinction event. Molybdenum enrichments, often indicative for freely available sulfide in the water-column, only occur dur¬ing the second phase of euxinia. This pattern of ocean redox-change in Svalbard direct¬ly reflects similar trends in Greenland...

Metabolic Control of Redox and Redox Control of Metabolism in Plants

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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

The SAMHD1 dNTP Triphosphohydrolase Is Controlled by a Redox Switch.

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Mauney, Christopher H; Rogers, LeAnn C; Harris, Reuben S; Daniel, Larry W; Devarie-Baez, Nelmi O; Wu, Hanzhi; Furdui, Cristina M; Poole, Leslie B; Perrino, Fred W; Hollis, Thomas

2017-12-01

Proliferative signaling involves reversible posttranslational oxidation of proteins. However, relatively few molecular targets of these modifications have been identified. We investigate the role of protein oxidation in regulation of SAMHD1 catalysis. Here we report that SAMHD1 is a major target for redox regulation of nucleotide metabolism and cell cycle control. SAMHD1 is a triphosphate hydrolase, whose function involves regulation of deoxynucleotide triphosphate pools. We demonstrate that the redox state of SAMHD1 regulates its catalytic activity. We have identified three cysteine residues that constitute an intrachain disulfide bond "redox switch" that reversibly inhibits protein tetramerization and catalysis. We show that proliferative signals lead to SAMHD1 oxidation in cells and oxidized SAMHD1 is localized outside of the nucleus. Innovation and Conclusions: SAMHD1 catalytic activity is reversibly regulated by protein oxidation. These data identify a previously unknown mechanism for regulation of nucleotide metabolism by SAMHD1. Antioxid. Redox Signal. 27, 1317-1331.

Flowable Conducting Particle Networks in Redox-Active Electrolytes for Grid Energy Storage

Energy Technology Data Exchange (ETDEWEB)

Hatzell, K. B.; Boota, M.; Kumbur, E. C.; Gogotsi, Y.

2015-01-01

This study reports a new hybrid approach toward achieving high volumetric energy and power densities in an electrochemical flow capacitor for grid energy storage. The electrochemical flow capacitor suffers from high self-discharge and low energy density because charge storage is limited to the available surface area (electric double layer charge storage). Here, we examine two carbon materials as conducting particles in a flow battery electrolyte containing the VO2+/VO2+ redox couple. Highly porous activated carbon spheres (CSs) and multi-walled carbon nanotubes (MWCNTs) are investigated as conducting particle networks that facilitate both faradaic and electric double layer charge storage. Charge storage contributions (electric double layer and faradaic) are distinguished for flow-electrodes composed of MWCNTs and activated CSs. A MWCNT flow-electrode based in a redox-active electrolyte containing the VO2+/VO2+ redox couple demonstrates 18% less self-discharge, 10 X more energy density, and 20 X greater power densities (at 20 mV s-1) than one based on a non-redox active electrolyte. Furthermore, a MWCNT redox-active flow electrode demonstrates 80% capacitance retention, and >95% coulombic efficiency over 100 cycles, indicating the feasibility of utilizing conducting networks with redox chemistries for grid energy storage.

Carbon-free Solid Dispersion LiCoO2 Redox Couple Characterization and Electrochemical Evaluation for All Solid Dispersion Redox Flow Batteries

International Nuclear Information System (INIS)

Qi, Zhaoxiang; Liu, Aaron L.; Koenig, Gary M.

2017-01-01

Highlights: • LiCoO 2 particles can be cycled in carbon-free and binder-free coin cells. • A carbon-free LiCoO 2 suspension is electrochemically oxidized and reduced. • Comparable size LiCoO 2 and Li 4 Ti 5 O 12 suspensions have similar rheological properties. • First demonstration of redox couples with solid suspensions for both electrodes. - Abstract: Semi-solid flow batteries have been reported to have among the highest energy densities for redox flow batteries, however, they rely on percolated carbon networks which increase the electrolyte viscosity significantly. We report the first demonstration of carbon-free redox flow couples comprised of dispersed lithium-ion battery active material suspensions, with sub-micrometer LiCoO 2 (LCO) particles at the cathode and Li 4 Ti 5 O 12 (LTO) particles at the anode. Both electrochemical and rheological properties of the LCO suspensions are reported and compared to previous reports for LTO dispersed electrochemical redox couples. An LTO anode and LCO cathode full cell was constructed and reversible electrochemical redox reaction of the dispersed particles was successfully demonstrated. This carbon-free dispersed lithium-ion active material full cell provides a proof-of-concept for a system that lies between the relatively high viscosity semi-solid flow cells with percolated carbon networks and the relatively low energy density conventional flow cells comprised of dissolved transition metals, providing a system for future study of the trade-off between energy density and viscosity for electrochemical flow cells that rely on solid active materials.

Quinone methides tethered to naphthalene diimides as selective G-quadruplex alkylating agents.

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Di Antonio, Marco; Doria, Filippo; Richter, Sara N; Bertipaglia, Carolina; Mella, Mariella; Sissi, Claudia; Palumbo, Manlio; Freccero, Mauro

2009-09-16

We have developed novel G-quadruplex (G-4) ligand/alkylating hybrid structures, tethering the naphthalene diimide moiety to quaternary ammonium salts of Mannich bases, as quinone-methide precursors, activatable by mild thermal digestion (40 degrees C). The bis-substituted naphthalene diimides were efficiently synthesized, and their reactivity as activatable bis-alkylating agents was investigated in the presence of thiols and amines in aqueous buffered solutions. The electrophilic intermediate, quinone-methide, involved in the alkylation process was trapped, in the presence of ethyl vinyl ether, in a hetero Diels-Alder [4 + 2] cycloaddition reaction, yielding a substituted 2-ethoxychroman. The DNA recognition and alkylation properties of these new derivatives were investigated by gel electrophoresis, circular dichroism, and enzymatic assays. The alkylation process occurred preferentially on the G-4 structure in comparison to other DNA conformations. By dissecting reversible recognition and alkylation events, we found that the reversible process is a prerequisite to DNA alkylation, which in turn reinforces the G-quadruplex structural rearrangement.

A high-energy-density redox flow battery based on zinc/polyhalide chemistry.

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Zhang, Liqun; Lai, Qinzhi; Zhang, Jianlu; Zhang, Huamin

2012-05-01

Zn and the Art of Battery Development: A zinc/polyhalide redox flow battery employs Br(-) /ClBr(2-) and Zn/Zn(2+) redox couples in its positive and negative half-cells, respectively. The performance of the battery is evaluated by charge-discharge cycling tests and reveals a high energy efficiency of 81%, based on a Coulombic efficiency of 96% and voltage efficiency of 84%. The new battery technology can provide high performance and energy density at an acceptable cost. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bimolecular Rate Constants for FAD-Dependent Glucose Dehydrogenase from Aspergillus terreus and Organic Electron Acceptors.

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Tsuruoka, Nozomu; Sadakane, Takuya; Hayashi, Rika; Tsujimura, Seiya

2017-03-10

The flavin adenine dinucleotide-dependent glucose dehydrogenase (FAD-GDH) from Aspergillus species require suitable redox mediators to transfer electrons from the enzyme to the electrode surface for the application of bioelectrical devices. Although several mediators for FAD-GDH are already in use, they are still far from optimum in view of potential, kinetics, sustainability, and cost-effectiveness. Herein, we investigated the efficiency of various phenothiazines and quinones in the electrochemical oxidation of FAD-GDH from Aspergillus terreus . At pH 7.0, the logarithm of the bimolecular oxidation rate constants appeared to depend on the redox potentials of all the mediators tested. Notably, the rate constant of each molecule for FAD-GDH was approximately 2.5 orders of magnitude higher than that for glucose oxidase from Aspergillus sp. The results suggest that the electron transfer kinetics is mainly determined by the formal potential of the mediator, the driving force of electron transfer, and the electron transfer distance between the redox active site of the mediator and the FAD, affected by the steric or chemical interactions. Higher k ₂ values were found for ortho-quinones than for para-quinones in the reactions with FAD-GDH and glucose oxidase, which was likely due to less steric hindrance in the active site in the case of the ortho-quinones.

Bimolecular Rate Constants for FAD-Dependent Glucose Dehydrogenase from Aspergillus terreus and Organic Electron Acceptors

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Nozomu Tsuruoka

2017-03-01

Full Text Available The flavin adenine dinucleotide-dependent glucose dehydrogenase (FAD-GDH from Aspergillus species require suitable redox mediators to transfer electrons from the enzyme to the electrode surface for the application of bioelectrical devices. Although several mediators for FAD-GDH are already in use, they are still far from optimum in view of potential, kinetics, sustainability, and cost-effectiveness. Herein, we investigated the efficiency of various phenothiazines and quinones in the electrochemical oxidation of FAD-GDH from Aspergillus terreus. At pH 7.0, the logarithm of the bimolecular oxidation rate constants appeared to depend on the redox potentials of all the mediators tested. Notably, the rate constant of each molecule for FAD-GDH was approximately 2.5 orders of magnitude higher than that for glucose oxidase from Aspergillus sp. The results suggest that the electron transfer kinetics is mainly determined by the formal potential of the mediator, the driving force of electron transfer, and the electron transfer distance between the redox active site of the mediator and the FAD, affected by the steric or chemical interactions. Higher k2 values were found for ortho-quinones than for para-quinones in the reactions with FAD-GDH and glucose oxidase, which was likely due to less steric hindrance in the active site in the case of the ortho-quinones.

Enzyme-Initiated Quinone-Chitosan Conjugation Chemistry: Toward A General in Situ Strategy for High-Throughput Photoelectrochemical Enzymatic Bioanalysis.

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Wang, Guang-Li; Yuan, Fang; Gu, Tiantian; Dong, Yuming; Wang, Qian; Zhao, Wei-Wei

2018-02-06

Herein we report a general and novel strategy for high-throughput photoelectrochemical (PEC) enzymatic bioanalysis on the basis of enzyme-initiated quinone-chitosan conjugation chemistry (QCCC). Specifically, the strategy was illustrated by using a model quinones-generating oxidase of tyrosinase (Tyr) to catalytically produce 1,2-bezoquinone or its derivative, which can easily and selectively be conjugated onto the surface of the chitosan deposited PbS/NiO/FTO photocathode via the QCCC. Upon illumination, the covalently attached quinones could act as electron acceptors of PbS quantum dots (QDs), improving the photocurrent generation and thus allowing the elegant probing of Tyr activity. Enzyme cascades, such as alkaline phosphatase (ALP)/Tyr and β-galactosidase (Gal)/Tyr, were further introduced into the system for the successful probing of the corresponding targets. This work features not only the first use of QCCC in PEC bioanalysis but also the separation of enzymatic reaction from the photoelectrode as well as the direct signal recording in a split-type protocol, which enables quite convenient and high-throughput detection as compared to previous formats. More importantly, by using numerous other oxidoreductases that involve quinones as reactants/products, this protocol could serve as a common basis for the development of a new class of QCCC-based PEC enzymatic bioanalysis and further extended for general enzyme-labeled PEC bioanalysis of versatile targets.

Structural and functional investigation of flavin binding center of the NqrC subunit of sodium-translocating NADH:quinone oxidoreductase from Vibrio harveyi.

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Valentin Borshchevskiy

Full Text Available Na+-translocating NADH:quinone oxidoreductase (NQR is a redox-driven sodium pump operating in the respiratory chain of various bacteria, including pathogenic species. The enzyme has a unique set of redox active prosthetic groups, which includes two covalently bound flavin mononucleotide (FMN residues attached to threonine residues in subunits NqrB and NqrC. The reason of FMN covalent bonding in the subunits has not been established yet. In the current work, binding of free FMN to the apo-form of NqrC from Vibrio harveyi was studied showing very low affinity of NqrC to FMN in the absence of its covalent bonding. To study structural aspects of flavin binding in NqrC, its holo-form was crystallized and its 3D structure was solved at 1.56 Å resolution. It was found that the isoalloxazine moiety of the FMN residue is buried in a hydrophobic cavity and that its pyrimidine ring is squeezed between hydrophobic amino acid residues while its benzene ring is extended from the protein surroundings. This structure of the flavin-binding pocket appears to provide flexibility of the benzene ring, which can help the FMN residue to take the bended conformation and thus to stabilize the one-electron reduced form of the prosthetic group. These properties may also lead to relatively weak noncovalent binding of the flavin. This fact along with periplasmic location of the FMN-binding domains in the vast majority of NqrC-like proteins may explain the necessity of the covalent bonding of this prosthetic group to prevent its loss to the external medium.

Influence of Iron Speciation on Redox Cycling and Reactivity with Persistent Organic Contaminants

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Kim, Dongwook

2009-01-01

Although a number of past studies have been aimed at characterizing iron's redox properties in aqueous systems and its contribution to natural attenuation processes of groundwater contaminants, many questions remain. It is especially important to understand the molecular properties that control the reactivity of both Fe[superscript II] and…

Lignin decomposition and microbial community in paddy soils: effects of alternating redox conditions

Science.gov (United States)

Cerli, Chiara; Liu, Qin; Hanke, Alexander; Kaiser, Klaus; Kalbitz, Karsten

2013-04-01

Paddy soils are characterised by interchanging cycles of anaerobic and aerobic conditions. Such fluctuations cause continuous changes in soil solution chemistry as well as in the composition and physiological responses of the microbial community. Temporary deficiency in oxygen creates conditions favourable to facultative or obligates anaerobic bacteria, while aerobic communities can thrive in the period of water absence. These alterations can strongly affect soil processes, in particular organic matter (OM) accumulation and mineralization. In submerged soils, lignin generally constitutes a major portion of the total OM because of hampered degradation under anoxic conditions. The alternating redox cycles resulting from paddy soil management might promote both degradation and preservation of lignin, affecting the overall composition and reactivity of total and dissolved OM. We sampled soils subjected to cycles of anoxic (rice growing period) and oxic (harvest and growth of other crops) conditions since 700 and 2000 years. We incubated suspended Ap material, sampled from the two paddy plus two corresponding non-paddy control soils under oxic and anoxic condition, for 3 months, interrupted by a short period of three weeks (from day 21 to day 43) with reversed redox conditions. At each sampling time (day 2, 21, 42, 63, 84), we determined lignin-derived phenols (by CuO oxidation) as well as phospholipids fatty acids contents and composition. We aimed to highlight changes in lignin decomposition as related to the potential rapid changes in microbial community composition. Since the studied paddy soils had a long history of wet rice cultivation, the microbial community should be well adapted to interchanging oxic and anoxic cycles, therefore fully expressing its activity at both conditions. In non-paddy soil changes in redox conditions caused modification of quantity and composition of the microbial community. On the contrary, in well-established paddy soils the microbial

An Inverse Electron Demand Azo-Diels-Alder Reaction of o-Quinone Methides and Imino Ethers: Synthesis of Benzocondensed 1,3-Oxazines.

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Osipov, Dmitry V; Osyanin, Vitaly A; Khaysanova, Guzel' D; Masterova, Elvira R; Krasnikov, Pavel E; Klimochkin, Yuri N

2018-04-20

We have studied the reactions of o-quinone methide precursors with imino ethers. The reaction provides a versatile route to substituted 1,3-benzoxazines. The proposed reaction mechanism involves the generation of the o-quinone methide intermediates, imino-Diels-Alder reaction, and elimination. This cascade process is a rare example of the participation of imino ethers as dienophiles.

Chemical proprieties of the iron-quinone complex in mutated reaction centers of Rb. sphaeroides

International Nuclear Information System (INIS)

Hałas, Agnieszka; Derrien, Valerie; Sebban, Pierre; Matlak, Krzysztof; Korecki, Józef; Kruk, Jerzy; Burda, Kvĕtoslava

2012-01-01

We investigated type II bacterial photosynthetic reaction centers, which contain a quinone - iron complex (Q A -Fe-Q B ) on their acceptor side. Under physiological conditions it was observed mainly in a reduced high spin state but its low spin ferrous states were also observed. Therefore, it was suggested that it might regulate the dynamical properties of the iron–quinone complex and the protonation and deprotonation events in its neighbourhood. In order to get insight into the molecular mechanism of the NHFe low spin state formation, we preformed Mössbauer studies of a wild type of Rb. sphaeroides and its two mutated forms. Our Mössbauer measurements show that the hydrophobicity of the Q A binding site can be crucial for stabilization of the high spin ferrous state of NHFe.

Are the reactions of quinones on graphite adiabatic?

International Nuclear Information System (INIS)

Luque, N.B.; Schmickler, W.

2013-01-01

Outer sphere electron transfer reactions on pure metal electrodes are often adiabatic and hence independent of the electrode material. Since it is not clear, whether adiabatic electron transfer can also occur on a semi-metal like graphite, we have re-investigated experimental data presented in a recent communication by Nissim et al. [Chemical Communications 48 (2012) 3294] on the reactions of quinones on graphite. We have supplemented their work by DFT calculations and conclude, that these reactions are indeed adiabatic. This contradicts the assertion of Nissim et al. that the rates are proportional to the density of states at the Fermi level

Glutathione Redox Control of Asthma: From Molecular Mechanisms to Therapeutic Opportunities

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Jones, Dean P.; Brown, Lou Ann S.

2012-01-01

Abstract Asthma is a chronic inflammatory disorder of the airways associated with airway hyper-responsiveness and airflow limitation in response to specific triggers. Whereas inflammation is important for tissue regeneration and wound healing, the profound and sustained inflammatory response associated with asthma may result in airway remodeling that involves smooth muscle hypertrophy, epithelial goblet-cell hyperplasia, and permanent deposition of airway extracellular matrix proteins. Although the specific mechanisms responsible for asthma are still being unraveled, free radicals such as reactive oxygen species and reactive nitrogen species are important mediators of airway tissue damage that are increased in subjects with asthma. There is also a growing body of literature implicating disturbances in oxidation/reduction (redox) reactions and impaired antioxidant defenses as a risk factor for asthma development and asthma severity. Ultimately, these redox-related perturbations result in a vicious cycle of airway inflammation and injury that is not always amenable to current asthma therapy, particularly in cases of severe asthma. This review will discuss disruptions of redox signaling and control in asthma with a focus on the thiol, glutathione, and reduced (thiol) form (GSH). First, GSH synthesis, GSH distribution, and GSH function and homeostasis are discussed. We then review the literature related to GSH redox balance in health and asthma, with an emphasis on human studies. Finally, therapeutic opportunities to restore the GSH redox balance in subjects with asthma are discussed. Antioxid. Redox Signal. 17, 375–408. PMID:22304503

Whole cell Deinococcus radiodurans ameliorates salt stress in Indian mustard through pyrroloquinoline quinone

International Nuclear Information System (INIS)

Srivastava, A.K.; Jadhav, P.; Suprasanna, P.; Rajpurohit, Y.S.; Misra, H.S.

2015-01-01

Salinity stress is considered as one of the major abiotic stresses limiting crop productivity. A variety of symbiotic and non-symbiotic bacteria are currently being used worldwide with the aim to boost built-in defense system in plants. Deinococcus radiodurans is a highly desiccation and radiation tolerant bacterium which synthesizes PQQ (pyrroloquinoline quinone) that has been shown to have a versatile role in crop productivity and as a general stress response regulator in bacteria and mammals. PQQ also acts as scavenger of reactive oxygen species and hence, can module redox signaling, one of the major regulator of stress tolerance in plants. In view of this, present research was conducted to evaluate the potential of whole cell D. radiodurans for ameliorating salt stress in plants. The soil colonization with wild-type cells led to partial amelioration of salt stress. The PQQ mutant showed an intermediate phenotype between wild-type seedlings and those grown on non-colonized soils which confirmed that the effects are largely associated with PQQ. The differential phenotype was also correlated with ROS level and ABA accumulation. The flame photometry data showed that there was no significant reduction in water soluble Na + level in control plant and those treated with either wild-type or PQQ mutant. Further, the elevated levels of antioxidant enzymes and reduced ascorbate in the plants treated with bacterial cells indicated its positive role in oxidative stress management. Although, the exact molecular basis to these effects is yet to be understood, present findings support the use of whole cell D. radiodurans for managing the growth and productivity of Indian mustard in salt affected fields. (author)

A novel and high-effective redox-mediated gel polymer electrolyte for supercapacitor

International Nuclear Information System (INIS)

Ma, Guofu; Feng, Enke; Sun, Kanjun; Peng, Hui; Li, Jiajia; Lei, Ziqiang

2014-01-01

Graphical abstract: - Highlights: • Alkali and P-phenylenediamine doped polyvinyl alcohol gel electrolyte is prepared. • The PVA-KOH-PPD gel electrolyte can also be used as separator. • The introduction of PPD increases the ionic conductivity of electrolyte. • The supercapacitor exhibits flexible and high energy density. - Abstract: A supercapacitor utilize a novel redox-mediated gel polymer (PVA-KOH-PPD) as electrolyte and separator, and activated carbon as electrodes is assembled. The PVA-KOH-PPD gel polymer as potential electrolyte for supercapacitor is investigated by cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy techniques. It is found that the supercapacitor exhibits high ionic conductivity (25 mS cm −1 ), large electrode specific capacitance (611 F g −1 ) and high energy density (82.56 Wh kg −1 ). The high performance is attributed to the addition of quick redox reactions at the electrolyte|electrode interface as PPD undergoes a two-proton/two-electron reduction and oxidation during cycling. Furthermore, the supercapacitor with PVA-KOH-PPD gel polymer shows excellent charge-discharge stability, after 1000 charge-discharge cycles, the supercapacitor still retains a high electrode specific capacitance of 470 F g −1 . It is believed that the idea using redox mediator has a good prospect for improving the performances of supercapacitors

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...

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

High-energy density nonaqueous all redox flow lithium battery enabled with a polymeric membrane.

Science.gov (United States)

Jia, Chuankun; Pan, Feng; Zhu, Yun Guang; Huang, Qizhao; Lu, Li; Wang, Qing

2015-11-01

Redox flow batteries (RFBs) are considered one of the most promising large-scale energy storage technologies. However, conventional RFBs suffer from low energy density due to the low solubility of the active materials in electrolyte. On the basis of the redox targeting reactions of battery materials, the redox flow lithium battery (RFLB) demonstrated in this report presents a disruptive approach to drastically enhancing the energy density of flow batteries. With LiFePO4 and TiO2 as the cathodic and anodic Li storage materials, respectively, the tank energy density of RFLB could reach ~500 watt-hours per liter (50% porosity), which is 10 times higher than that of a vanadium redox flow battery. The cell exhibits good electrochemical performance under a prolonged cycling test. Our prototype RFLB full cell paves the way toward the development of a new generation of flow batteries for large-scale energy storage.

High–energy density nonaqueous all redox flow lithium battery enabled with a polymeric membrane

Science.gov (United States)

Jia, Chuankun; Pan, Feng; Zhu, Yun Guang; Huang, Qizhao; Lu, Li; Wang, Qing

2015-01-01

Redox flow batteries (RFBs) are considered one of the most promising large-scale energy storage technologies. However, conventional RFBs suffer from low energy density due to the low solubility of the active materials in electrolyte. On the basis of the redox targeting reactions of battery materials, the redox flow lithium battery (RFLB) demonstrated in this report presents a disruptive approach to drastically enhancing the energy density of flow batteries. With LiFePO4 and TiO2 as the cathodic and anodic Li storage materials, respectively, the tank energy density of RFLB could reach ~500 watt-hours per liter (50% porosity), which is 10 times higher than that of a vanadium redox flow battery. The cell exhibits good electrochemical performance under a prolonged cycling test. Our prototype RFLB full cell paves the way toward the development of a new generation of flow batteries for large-scale energy storage. PMID:26702440

Investigation of Iron Oxide Morphology in a Cyclic Redox Water Splitting Process for Hydrogen Generation

Directory of Open Access Journals (Sweden)

Michael M. Bobek

2012-10-01

Full Text Available A solar fuels generation research program is focused on hydrogen production by means of reactive metal water splitting in a cyclic iron-based redox process. Iron-based oxides are explored as an intermediary reactive material to dissociate water molecules at significantly reduced thermal energies. With a goal of studying the resulting oxide chemistry and morphology, chemical assistance via CO is used to complete the redox cycle. In order to exploit the unique characteristics of highly reactive materials at the solar reactor scale, a monolithic laboratory scale reactor has been designed to explore the redox cycle at temperatures ranging from 675 to 875 K. Using high resolution scanning electron microscope (SEM and electron dispersive X-ray spectroscopy (EDS, the oxide morphology and the oxide state are quantified, including spatial distributions. These images show the change of the oxide layers directly after oxidation and after reduction. The findings show a significant non-stoichiometric O/Fe gradient in the atomic ratio following oxidation, which is consistent with a previous kinetics model, and a relatively constant, non-stoichiometric O/Fe atomic ratio following reduction.

The geochemical record of the ancient nitrogen cycle, nitrogen isotopes, and metal cofactors.

Science.gov (United States)

Godfrey, Linda V; Glass, Jennifer B

2011-01-01

The nitrogen (N) cycle is the only global biogeochemical cycle that is driven by biological functions involving the interaction of many microorganisms. The N cycle has evolved over geological time and its interaction with the oxygen cycle has had profound effects on the evolution and timing of Earth's atmosphere oxygenation (Falkowski and Godfrey, 2008). Almost every enzyme that microorganisms use to manipulate N contains redox-sensitive metals. Bioavailability of these metals has changed through time as a function of varying redox conditions, and likely influenced the biological underpinnings of the N cycle. It is possible to construct a record through geological time using N isotopes and metal concentrations in sediments to determine when the different stages of the N cycle evolved and the role metal availability played in the development of key enzymes. The same techniques are applicable to understanding the operation and changes in the N cycle through geological time. However, N and many of the redox-sensitive metals in some of their oxidation states are mobile and the isotopic composition or distribution can be altered by subsequent processes leading to erroneous conclusions. This chapter reviews the enzymology and metal cofactors of the N cycle and describes proper utilization of methods used to reconstruct evolution of the N cycle through time. Copyright © 2011 Elsevier Inc. All rights reserved.

Solid state oxidation of phenols to quinones with sodium perborate on wet montmorillonite K10

Energy Technology Data Exchange (ETDEWEB)

Hashemi, Mohammed M.; Eftekhari-Sis, Bagher; Khalili, Behzad; Karimi-Jaberi, Zahed [Sharif University of Technology, Tehran (Iran, Islamic Republic of). Dept. of Chemistry]. E-mail: mhashemi@sharif.edu

2005-09-15

Phenols were oxidized to quinones using sodium perborate (SPB) on wet montmorillonite as oxidant. The reaction was carried out at ambient temperature on the solid phase under solvent free conditions. (author)

Solid state oxidation of phenols to quinones with sodium perborate on wet montmorillonite K10

International Nuclear Information System (INIS)

Hashemi, Mohammed M.; Eftekhari-Sis, Bagher; Khalili, Behzad; Karimi-Jaberi, Zahed

2005-01-01

Phenols were oxidized to quinones using sodium perborate (SPB) on wet montmorillonite as oxidant. The reaction was carried out at ambient temperature on the solid phase under solvent free conditions. (author)

A prototype hybrid 7π quinone-fused 1,3,2-dithiazolyl radical.

Science.gov (United States)

Decken, A; Mailman, A; Passmore, J; Rautiainen, J M; Scherer, W; Scheidt, E-W

2011-01-28

Reaction of 1,4-naphthoquinone and SNSMF(6) (M = As, Sb) in SO(2) solution in a 1 : 2 molar ratio led to the naphthoquinone fused 1,3,2-dithiazolylium salts, 3MF(6) quantitatively by multinuclear NMR (87% isolated yield of 3SbF(6)) via the cycloaddition and oxidative dehydrogenation chemistry of SNS(+) with formation of NH(4)SbF(6) and S(8). The product 3SbF(6) was fully characterized by IR, Raman, multinuclear {(1)H, (13)C, (14)N} NMR, elemental analysis, cyclic voltammetry and single crystal X-ray crystallography. The reduction of 3SbF(6) with ferrocene (Cp(2)Fe) in refluxing acetonitrile (CH(3)CN) led to the first isolation of a fused quinone-thiazyl radical, 3˙ in 73% yield. The prototype hybrid quinone-thiazyl radical 3˙ was fully characterized by IR, Raman microscopy, EI-MS, elemental analysis, solution and solid state EPR, magnetic susceptibility (2-370 K) and was found to form π*-π* dimers in the solid state as determined by single crystal X-ray crystallography. Furthermore, the thermal decomposition of 3˙ led to a novel quinone-fused 1,2,3,4-tetrathiine, 10 (x = 2) and the known 1,2,5-thiadiazole, 11. The energetics of the cycloadditon and oxidative dehydrogenation chemistry of SNS(+) and 1,4-naphthoquinone leading to 3SbF(6) were estimated in the gas phase and SO(2) solution by DFT calculations (PBE0/6-311G(d)) and lattice enthalpies obtained by the volume based thermodynamic (VBT) approach in the solid state. The gas phase ion energetics (ionization potential (IP) and electron affinity (EA)) of 3˙ are compared to related 1,3,2- and 1,2,3-dithiazolyl radicals.

A physiological threshold for protection against menadione toxicity by human NAD(P)H : quinone oxidoreductase (NQO1) in Chinese hamster ovary (CHO) cells

NARCIS (Netherlands)

Haan, de L.H.J.; Boerboom, A.M.J.F.; Rietjens, I.M.C.M.; Capelle, van D.; Ruijter, de A.J.M.; Jaiswal, A.K.; Aarts, J.M.M.J.G.

2002-01-01

NAD(P)H:quinone oxidoreductase 1 (NQO1) has often been suggested to be involved in cancer prevention by means of detoxification of electrophilic quinones. In the present study, a series of Chinese hamster ovary (CHO) cell lines expressing various elevated levels of human NQO1 were generated by

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

Quinones as dienophiles in the Diels-Alder reaction: history and applications in total synthesis.

Science.gov (United States)

Nawrat, Christopher C; Moody, Christopher J

2014-02-17

In the canon of reactions available to the organic chemist engaged in total synthesis, the Diels-Alder reaction is among the most powerful and well understood. Its ability to rapidly generate molecular complexity through the simultaneous formation of two carbon-carbon bonds is almost unrivalled, and this is reflected in the great number of reported applications of this reaction. Historically, the use of quinones as dienophiles is highly significant, being the very first example investigated by Diels and Alder. Herein, we review the application of the Diels-Alder reaction of quinones in the total synthesis of natural products. The highlighted examples span some 60 years from the landmark syntheses of morphine (1952) and reserpine (1956) by Gates and Woodward, respectively, through to the present day examples, such as the tetracyclines. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

H32, a non-quinone sulfone analog of vitamin K3, inhibits human hepatoma cell growth by inhibiting Cdc25 and activating ERK.

Science.gov (United States)

Kar, Siddhartha; Wang, Meifang; Ham, Seung Wook; Carr, Brian I

2006-10-01

We previously synthesized a K-vitamin derivative, Cpd 5, which was a potent growth inhibitor of human tumor cells, including Hep3B hepatoma cells. However, being a quinone compound, Cpd 5 has the potential for generating toxic reactive oxygen species (ROS). We therefore synthesized a nonquinone sulfone derivative, H32, which has a sufone group substituting the quinone. The IC50 of H32 for Hep3B cells was found to be 2.5 microM, which was 2.5 and 3.2 times more potent than Cpd 5 and vitamin K3 respectively. It induced apoptosis in Hep3B cells but did not generate ROS when compared to Cpd 5. Interestingly, under similar culture conditions, normal rat hepatocytes were 14-fold more and 7-fold more resistant to the growth inhibitory effects of H32 than Hep3B and PLC/PRF5 cells respectively. H32 preferentially inhibited the activities of the cell cycle controlling Cdc25A phosphatase likely by binding to its catalytic cysteine. As a consequence, it induced inhibitory tyrosine phosphorylation of the Cdc25 substrate kinases Cdk2 and Cdk4 in Hep3B cells and the cells undergo an arrest in the G1 phase of the cell cycle. H32 also induced persistent phosphorylation of the MAPK protein ERK1/2, but marginal JNK1/2 and p38 phosphorylation. The ERK inhibitor U0126, added at least 30 min prior to H32, antagonized the growth inhibition induced by H32. However, the JNK and p38 inhibitors, JNKI-II and SB203580, were not able to antagonize H32 induced growth inhibition. Thus, H32 differentially inhibited growth of normal and liver tumor cells by preferentially inhibiting the actions of Cdc25 phosphatases and inducing persistent ERK phosphorylation.

Production, purification and detergent exchange of isotopically labeled Bacillussubtilis cytochrome b₅₅₈ (SdhC).

Science.gov (United States)

Baureder, Michael; Hederstedt, Lars

2011-11-01

Cytochrome b₅₅₈ of the gram-positive bacterium Bacillussubtilis is the membrane anchor subunit of the succinate:quinone oxidoreductase of the citric acid cycle. The cytochrome consists of the SdhC polypeptide (202 residues) and two protoheme IX groups that function in transmembrane electron transfer to menaquinone. The general structure of the cytochrome is known from extensive experimental studies and by comparison to Wolinellasuccinogenes fumarate reductase for which the X-ray crystal structure has been determined. Solution state NMR can potentially be used to identify the quinone binding site(s) and study, e.g. redox-linked, dynamics of cytochrome b₅₅₈. In this work we present an efficient procedure for the isolation of preparative amounts of isotopically labeled B. subtilis cytochrome b₅₅₈ produced in Escherichia coli. We have also evaluated several detergents suitable for NMR for their effectiveness in maintaining the cytochrome solubilized and intact for days at room temperature. Copyright © 2011 Elsevier Inc. All rights reserved.

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

Electrochemistry of potentially bioreductive alkylating quinones. Part 3. Quantitative structure-electrochemistry relationships of aziridinylquinones

NARCIS (Netherlands)

Driebergen, R.J.; Moret, E.E.; Janssen, L.H.M.; Blauw, J.S.; Holthuis, J.J.M.; Postma kelder, S.J.; Verboom, Willem; Reinhoudt, David; van der Linden, W.E.

1992-01-01

The concept of bioreductive alkylation as a mechanism of action of aziridinylquinoid anticancer agents has been investigated by the use of electrochemical techniques. Properly substituted aziridinylquinones are activated by an electrochemical step (reduction of the quinone function), followed by

Antiproliferative effects of phenylaminonaphthoquinones are increased by ascorbate and associated with the appearance of a senescent phenotype in human bladder cancer cells

International Nuclear Information System (INIS)

Felipe, K.B.; Benites, J.; Glorieux, C.; Sid, B.; Valenzuela, M.; Kviecinski, M.R.; Pedrosa, R.C.; Valderrama, J.A.; Levêque, Ph.; Gallez, B.; Verrax, J.; Buc Calderon, P.

2013-01-01

Highlights: •Phenylaminonaphthoquinones are redox cyclers able to form ROS. •Phenylaminonaphthoquinones plus ascorbate inhibit T24 cell growth. •Phenylaminonaphthoquinones plus ascorbate lead to necrotic-like cell death. •Phenylaminonaphthoquinones plus ascorbate impair cell cycle and affect MAPKs. •Phenylaminonaphthoquinones plus ascorbate induce a senescent cancer cell phenotype. -- Abstract: Quinone-containing molecules have been developed against cancer mainly for their redox cycling ability leading to reactive oxygen species (ROS) formation. We have previously shown that donor-acceptor phenylaminonaphthoquinones are biologically active against a panel of cancer cells. In this report, we explored the mechanisms involved in cancer cell growth inhibition caused by two phenylaminonaphthoquinones, namely Q7 and Q9, with or without ascorbate (ASC). The results show that Q7 and Q9 are both redox cyclers able to form ROS, which strongly inhibit the proliferation of T24 cells. Q9 was a better redox cycler than Q7 because of marked stabilization of the semiquinone radical species arising from its reduction by ascorbate. Indeed, ASC dramatically enhances the inhibitory effect of Q9 on cell proliferation. Q9 plus ASC impairs the cell cycle, causing a decrease in the number of cells in the G2/M phase without involving other cell cycle regulating key proteins. Moreover, Q9 plus ASC influences the MAPK signaling pathways, provoking the appearance of a senescent cancer cell phenotype and ultimately leading to necrotic-like cell death. Because cellular senescence limits the replicative capacity of cells, our results suggest that induction of senescence may be exploited as a basis for new approaches to cancer therapy

Hydrologic control on redox and nitrogen dynamics in a peatland soil

International Nuclear Information System (INIS)

Rubol, Simonetta; Silver, Whendee L.; Bellin, Alberto

2012-01-01

Soils are a dominant source of nitrous oxide (N 2 O), a potent greenhouse gas. However, the complexity of the drivers of N 2 O production and emissions has hindered our ability to predict the magnitude and spatial dynamics of N 2 O fluxes. Soil moisture can be considered a key driver because it influences oxygen (O 2 ) supply, which feeds back on N 2 O sources (nitrification versus denitrification) and sinks (reduction to dinitrogen). Soil water content is directly linked to O 2 and redox potential, which regulate microbial metabolism and chemical transformations in the environment. Despite its importance, only a few laboratory studies have addressed the effects of hydrological transient dynamics on nitrogen (N) cycling in the vadose zone. To further investigate these aspects, we performed a long term experiment in a 1.5 m depth soil column supplemented by chamber experiments. With this experiment, we aimed to investigate how soil moisture dynamics influence redox sensitive N cycling in a peatland soil. As expected, increased soil moisture lowered O 2 concentrations and redox potential in the soil. The decline was more severe for prolonged saturated conditions than for short events and at deep than at the soil surface. Gaseous and dissolved N 2 O, dissolved nitrate (NO 3 − ) and ammonium (NH 4 + ) changed considerably along the soil column profile following trends in soil O 2 and redox potential. Hot spots of N 2 O concentrations corresponded to high variability in soil O 2 in the upper and lower parts of the column. Results from chamber experiments confirmed high NO 3 − reduction potential in soils, particularly from the bottom of the column. Under our experimental conditions, we identified a close coupling of soil O 2 and N 2 O dynamics, both of which lagged behind soil moisture changes. These results highlight the relationship among soil hydrologic properties, redox potential and N cycling, and suggest that models working at a daily scale need to consider

Comparison of calculated and experimental isotope edited FTIR difference spectra for purple bacterial photosynthetic reaction centers with different quinones incorporated into the QA binding site.

Directory of Open Access Journals (Sweden)

Nan eZhao

2013-08-01

Full Text Available Previously we have shown that ONIOM type (QM/MM calculations can be used to simulate isotope edited FTIR difference spectra for neutral ubiquinone in the QA binding site in Rhodobacter sphaeroides photosynthetic reaction centers. Here we considerably extend upon this previous work by calculating isotope edited FTIR difference spectra for reaction centers with a variety of unlabeled and 18O labeled foreign quinones incorporated into the QA binding site. Isotope edited spectra were calculated for reaction centers with 2,3-dimethoxy-5,6-dimethyl-1,4-benzoquinone (MQ0, 2,3,5,6-tetramethyl-1,4-benzoquinone (duroquinone, DQ, and 2,3-dimethyl-l,4-naphthoquinone (DMNQ incorporated, and compared to corresponding experimental spectra. The calculated and experimental spectra agree well, further demonstrating the utility and applicability of our ONIOM approach for calculating the vibrational properties of pigments in protein binding sites.The normal modes that contribute to the bands in the calculated spectra, their composition, frequency and intensity, and how these quantities are modified upon 18O labeling, are presented. This computed information leads to a new and more detailed understanding/interpretation of the experimental FTIR difference spectra. Hydrogen bonding to the carbonyl groups of the incorporated quinones is shown to be relatively weak. It is also shown that there is some asymmetry in hydrogen bonding, accounting for 10-13 cm-1 separation in the frequencies of the carbonyl vibrational modes of the incorporated quinones. The extent of asymmetry H-bonding could only be established by considering the spectra for various types of quinones incorporated into the QA binding site. The quinones listed above are tail-less. Spectra were also calculated for reaction centers with corresponding tail containing quinones incorporated, and it is found that replacement of the quinone methyl group by a phytyl or prenyl chain does not alter ONIOM calculated s

In vivo relevance of two critical levels for NAD(P)H:quinone oxidoreductase (NQO1)-mediated cellular protection against electrophile toxicity found in vitro

NARCIS (Netherlands)

Haan, de L.H.J.; Pot, G.K.; Aarts, J.M.M.J.G.; Rietjens, I.M.C.M.; Alink, G.M.

2006-01-01

NAD(P)H:quinone oxidoreductase (NQO1)-mediated detoxification of quinones is suggested to be involved in cancer prevention. In the present study, using transfected CHO cells, it was demonstrated that the relation between NQO1 activity and the resulting protection against the cytotoxicity of

Atmospheric Distribution of PAHs and Quinones in the Gas and PM1 Phases in the Guadalajara Metropolitan Area, Mexico: Sources and Health Risk

Directory of Open Access Journals (Sweden)

Valeria Ojeda-Castillo

2018-04-01

Full Text Available Polycyclic aromatic hydrocarbons (PAHs and quinones in the gas phase and as submicron particles raise concerns due to their potentially carcinogenic and mutagenic properties. The majority of existing studies have investigated the formation of quinones, but it is also important to consider both the primary and secondary sources to estimate their contributions. The objectives of this study were to characterize PAHs and quinones in the gas and particulate matter (PM1 phases in order to identify phase distributions, sources, and cancer risk at two urban monitoring sites in the Guadalajara Metropolitan Area (GMA in Mexico. The simultaneous gas and PM1 phases samples were analyzed using a gas chromatography–mass spectrometer. The lifetime lung cancer risk (LCR due to PAH exposure was calculated to be 1.7 × 10−3, higher than the recommended risk value of 10−6, indicating a potential health hazard. Correlations between parent PAHs, criteria pollutants, and meteorological parameters suggest that primary sources are the main contributors to the Σ8 Quinones concentrations in PM1, while the secondary formation of 5,12-naphthacenequinone and 9,10-anthraquinone may contribute less to the observed concentration of quinones. Additionally, naphthalene, acenaphthene, fluorene, phenanthrene, and anthracene in PM1, suggest photochemical degradation into unidentified species. Further research is needed to determine how these compounds are formed.

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

Science.gov (United States)

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

2015-02-13

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

Redox Regulation of Mitochondrial Function

Science.gov (United States)

Handy, Diane E.

2012-01-01

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

A nuclear glutathione cycle within the cell cycle.

Science.gov (United States)

Diaz Vivancos, Pedro; Wolff, Tonja; Markovic, Jelena; Pallardó, Federico V; Foyer, Christine H

2010-10-15

The complex antioxidant network of plant and animal cells has the thiol tripeptide GSH at its centre to buffer ROS (reactive oxygen species) and facilitate cellular redox signalling which controls growth, development and defence. GSH is found in nearly every compartment of the cell, including the nucleus. Transport between the different intracellular compartments is pivotal to the regulation of cell proliferation. GSH co-localizes with nuclear DNA at the early stages of proliferation in plant and animal cells. Moreover, GSH recruitment and sequestration in the nucleus during the G1- and S-phases of the cell cycle has a profound impact on cellular redox homoeostasis and on gene expression. For example, the abundance of transcripts encoding stress and defence proteins is decreased when GSH is sequestered in the nucleus. The functions of GSHn (nuclear GSH) are considered in the present review in the context of whole-cell redox homoeostasis and signalling, as well as potential mechanisms for GSH transport into the nucleus. We also discuss the possible role of GSHn as a regulator of nuclear proteins such as histones and PARP [poly(ADP-ribose) polymerase] that control genetic and epigenetic events. In this way, a high level of GSH in the nucleus may not only have an immediate effect on gene expression patterns, but also contribute to how cells retain a memory of the cellular redox environment that is transferred through generations.

Electrolyte for stable cycling of high-energy lithium sulfur redox flow batteries

Science.gov (United States)

Xiao, Jie; Liu, Jun; Pan, Huilin; Henderson, Wesley A.

2018-04-24

A device comprising: a lithium sulfur redox flow battery comprising an electrolyte composition comprising: (i) a dissolved Li2Sx electroactive salt, wherein x.gtoreq.4; (ii) a solvent selected from dimethyl sulfoxide, tetrahydrofuran, or a mixture thereof; and (iii) a supporting salt at a concentration of at least 2 M, as measured by moles of supporting salt divided by the volume of the solvent without considering the volume change of the electrolyte after dissolving the supporting salt.

Thermochemical storage for CSP via redox structured reactors/heat exchangers: The RESTRUCTURE project

Science.gov (United States)

Karagiannakis, George; Pagkoura, Chrysoula; Konstandopoulos, Athanasios G.; Tescari, Stefania; Singh, Abhishek; Roeb, Martin; Lange, Matthias; Marcher, Johnny; Jové, Aleix; Prieto, Cristina; Rattenbury, Michael; Chasiotis, Andreas

2017-06-01

The present work provides an overview of activities performed in the framework of the EU-funded collaborative project RESTRUCTURE, the main goal of which was to develop and validate a compact structured reactor/heat exchanger for thermochemical storage driven by 2-step high temperature redox metal oxide cycles. The starting point of development path included redox materials qualification via both theoretical and lab-scale experimental studies. Most favorable compositions were cobalt oxide/alumina composites. Preparation of small-scale structured bodies included various approaches, ranging from perforated pellets to more sophisticated honeycomb geometries, fabricated by extrusion and coating. Proof-of-concept of the proposed novel reactor/heat exchanger was successfully validated in small-scale structures and the next step included scaling up of redox honeycombs production. Significant challenges were identified for the case of extruded full-size bodies and the final qualified approach related to preparation of cordierite substrates coated with cobalt oxide. The successful experimental evaluation of the pilot reactor/heat exchanger system constructed motivated the preliminary techno-economic evaluation of the proposed novel thermochemical energy storage concept. Taking into account experimental results, available technologies and standard design aspects a model for a 70.5 MWe CSP plant was defined. Estimated LCOE costs were calculated to be in the range of reference values for Combined Cycle Power Plants operated by natural gas. One of main cost contributors was the storage system itself, partially due to relatively high cost of cobalt oxide. This highlighted the need to identify less costly and equally efficient to cobalt oxide redox materials.

Hydrogen production via thermochemical water-splitting by lithium redox reaction

International Nuclear Information System (INIS)

Nakamura, Naoya; Miyaoka, Hiroki; Ichikawa, Takayuki; Kojima, Yoshitsugu

2013-01-01

Highlights: •Hydrogen production via water-splitting by lithium redox reactions possibly proceeds below 800 °C. •Entropy control by using nonequilibrium technique successfully reduces the reaction temperature. •The operating temperature should be further reduced by optimizing the nonequilibrium condition to control the cycle. -- Abstracts: Hydrogen production via thermochemical water-splitting by lithium redox reactions was investigated as energy conversion technique. The reaction system consists of three reactions, which are hydrogen generation by the reaction of lithium and lithium hydroxide, metal separation by thermolysis of lithium oxide, and oxygen generation by hydrolysis of lithium peroxide. The hydrogen generation reaction completed at 500 °C. The metal separation reaction is thermodynamically difficult because it requires about 3400 °C in equilibrium condition. However, it was indicated from experimental results that the reaction temperature was drastically reduced to 800 °C by using nonequilibrium technique. The hydrolysis reaction was exothermic reaction, and completed by heating up to 300 °C. Therefore, it was expected that the water-splitting by lithium redox reactions was possibly operated below 800 °C under nonequilibrium condition

Ursolic Acid-enriched herba cynomorii extract induces mitochondrial uncoupling and glutathione redox cycling through mitochondrial reactive oxygen species generation: protection against menadione cytotoxicity in h9c2 cells.

Science.gov (United States)

Chen, Jihang; Wong, Hoi Shan; Ko, Kam Ming

2014-01-27

Herba Cynomorii (Cynomorium songaricum Rupr., Cynomoriaceae) is one of the most commonly used 'Yang-invigorating' tonic herbs in Traditional Chinese Medicine (TCM). An earlier study in our laboratory has demonstrated that HCY2, an ursolic acid-enriched fraction derived from Herba Cynomorii, increased mitochondrial ATP generation capacity (ATP-GC) and induced mitochondrial uncoupling as well as a cellular glutathione response, thereby protecting against oxidant injury in H9c2 cells. In this study, we demonstrated that pre-incubation of H9c2 cells with HCY2 increased mitochondrial reactive oxygen species (ROS) generation in these cells, which is likely an event secondary to the stimulation of the mitochondrial electron transport chain. The suppression of mitochondrial ROS by the antioxidant dimethylthiourea abrogated the HCY2-induced enhancement of mitochondrial uncoupling and glutathione reductase (GR)-mediated glutathione redox cycling, and also protected against menadione-induced cytotoxicity. Studies using specific inhibitors of uncoupling protein and GR suggested that the HCY2-induced mitochondrial uncoupling and glutathione redox cycling play a determining role in the cytoprotection against menadione-induced oxidant injury in H9c2 cells. Experimental evidence obtained thus far supports the causal role of HCY2-induced mitochondrial ROS production in eliciting mitochondrial uncoupling and glutathione antioxidant responses, which offer cytoprotection against oxidant injury in H9c2 cells.

Selective Alkylation of C-Rich Bulge Motifs in Nucleic Acids by Quinone Methide Derivatives.

Science.gov (United States)

Lönnberg, Tuomas; Hutchinson, Mark; Rokita, Steven

2015-09-07

A quinone methide precursor featuring a bis-cyclen anchoring moiety has been synthesized and its capacity to alkylate oligonucleotide targets quantified in the presence and absence of divalent metal ions (Zn(2+) , Ni(2+) and Cd(2+) ). The oligonucleotides were designed for testing the sequence and secondary structure specificity of the reaction. Gel electrophoretic analysis revealed predominant alkylation of C-rich bulges, regardless of the presence of divalent metal ions or even the bis-cyclen anchor. This C-selectivity appears to be an intrinsic property of the quinone methide electrophile as reflected by its reaction with an equimolar mixture of the 2'-deoxynucleosides. Only dA-N1 and dC-N3 alkylation products were detected initially and only the dC adduct persisted for detection under conditions of the gel electrophoretic analysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced performance of ultracapacitors using redox additive-based electrolytes

Science.gov (United States)

Jain, Dharmendra; Kanungo, Jitendra; Tripathi, S. K.

2018-05-01

Different concentrations of potassium iodide (KI) as redox additive had been added to 1 M sulfuric acid (H2SO4) electrolyte with an aim of enhancing the capacitance and energy density of ultracapacitors via redox reactions at the interfaces of electrode-electrolyte. Ultracapacitors were fabricated using chemically treated activated carbon as electrode with H2SO4 and H2SO4-KI as an electrolyte. The electrochemical performances of fabricated supercapacitors were investigated by impedance spectroscopy, cyclic voltammetry and charge-discharge techniques. The maximum capacitance ` C' was observed with redox additives-based electrolyte system comprising 1 M H2SO4-0.3 M KI (1072 F g- 1), which is very much higher than conventional 1 M H2SO4 (61.3 F g- 1) aqueous electrolyte-based ultracapacitors. It corresponds to an energy density of 20.49 Wh kg- 1 at 2.1 A g- 1 for redox additive-based electrolyte, which is six times higher as compared to that of pristine electrolyte (1 M H2SO4) having energy density of only 3.36 Wh kg- 1. The temperature dependence behavior of fabricated cell was also analyzed, which shows increasing pattern in its capacitance values in a temperature range of 5-70 °C. Under cyclic stability test, redox electrolyte-based system shows almost 100% capacitance retention up to 5000 cycles and even more. For comparison, ultracapacitors based on polymer gel electrolyte polyvinyl alcohol (PVA) (10 wt%)—{H2SO4 (1 M)-KI (0.3 M)} (90 wt%) have been fabricated and characterized with the same electrode materials.

Prevention of redox shuttle using electropolymerized polypyrrole film in a lithium-oxygen battery

Science.gov (United States)

Togasaki, Norihiro; Shibamura, Ryuji; Naruse, Takuya; Momma, Toshiyuki; Osaka, Tetsuya

2018-04-01

Among the recent advancements in lithium-oxygen (Li-O2) chemistries, redox mediators (RMs) have been revealed to play a significant role in decreasing overpotential on charging and in improving cycling performance. However, an intrinsic problem is redox shuttle of RMs, which leads to degraded RM utilization and induces the accumulation of discharge products on the cathode surface; this remains a significant issue in the current battery cell configuration (Li anode/separator/cathode). To address this detrimental problem, herein we propose a novel Li-O2 cell incorporating a freestanding electropolymerized polypyrrole (PPy) film for the restriction of the redox-shuttle phenomenon of lithium iodide (Li anode/separator/PPy film/cathode). In this study, a PPy film, which is prepared through oxidative electropolymerization using an ionic liquid of 1-methyl-1-butylpyrrolidinium mixed with pyrrole and lithium bis(trifluoromethanesulfonyl)imide, is introduced between the cathode and the separator. From the charge-discharge voltage profile, it is confirmed that the PPy film suppresses the diffusion of the oxidized I3- to the Li anode, while allowing Li ion transport. Secondary scanning electron microscope measurements confirm that the chemical reactions between I3- and Li2O2 are facilitated by the presence of the PPy film because I3- remains near the cathode surface during the charging process. As a result, the cycling performance in the Li-O2 cells with PPy film exhibits a cycling life four times as long as that of the Li-O2 cells without PPy film.

Prevention of redox shuttle using electropolymerized polypyrrole film in a lithium–oxygen battery

Directory of Open Access Journals (Sweden)

Norihiro Togasaki

2018-04-01

Full Text Available Among the recent advancements in lithium–oxygen (Li–O2 chemistries, redox mediators (RMs have been revealed to play a significant role in decreasing overpotential on charging and in improving cycling performance. However, an intrinsic problem is redox shuttle of RMs, which leads to degraded RM utilization and induces the accumulation of discharge products on the cathode surface; this remains a significant issue in the current battery cell configuration (Li anode/separator/cathode. To address this detrimental problem, herein we propose a novel Li–O2 cell incorporating a freestanding electropolymerized polypyrrole (PPy film for the restriction of the redox-shuttle phenomenon of lithium iodide (Li anode/separator/PPy film/cathode. In this study, a PPy film, which is prepared through oxidative electropolymerization using an ionic liquid of 1-methyl-1-butylpyrrolidinium mixed with pyrrole and lithium bis(trifluoromethanesulfonylimide, is introduced between the cathode and the separator. From the charge–discharge voltage profile, it is confirmed that the PPy film suppresses the diffusion of the oxidized I3− to the Li anode, while allowing Li ion transport. Secondary scanning electron microscope measurements confirm that the chemical reactions between I3− and Li2O2 are facilitated by the presence of the PPy film because I3− remains near the cathode surface during the charging process. As a result, the cycling performance in the Li–O2 cells with PPy film exhibits a cycling life four times as long as that of the Li–O2 cells without PPy film.

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

Porphyrin-Based Symmetric Redox-Flow Batteries towards Cold-Climate Energy Storage.

Science.gov (United States)

Ma, Ting; Pan, Zeng; Miao, Licheng; Chen, Chengcheng; Han, Mo; Shang, Zhenfeng; Chen, Jun

2018-03-12

Electrochemical energy storage with redox-flow batteries (RFBs) under subzero temperature is of great significance for the use of renewable energy in cold regions. However, RFBs are generally used above 10 °C. Herein we present non-aqueous organic RFBs based on 5,10,15,20-tetraphenylporphyrin (H 2 TPP) as a bipolar redox-active material (anode: [H 2 TPP] 2- /H 2 TPP, cathode: H 2 TPP/[H 2 TPP] 2+ ) and a Y-zeolite-poly(vinylidene fluoride) (Y-PVDF) ion-selective membrane with high ionic conductivity as a separator. The constructed RFBs exhibit a high volumetric capacity of 8.72 Ah L -1 with a high voltage of 2.83 V and excellent cycling stability (capacity retention exceeding 99.98 % per cycle) in the temperature range between 20 and -40 °C. Our study highlights principles for the design of RFBs that operate at low temperatures, thus offering a promising approach to electrochemical energy storage under cold-climate conditions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Mapping the diatom redox-sensitive proteome provides insight into response to nitrogen stress in the marine environment.

Science.gov (United States)

Rosenwasser, Shilo; Graff van Creveld, Shiri; Schatz, Daniella; Malitsky, Sergey; Tzfadia, Oren; Aharoni, Asaph; Levin, Yishai; Gabashvili, Alexandra; Feldmesser, Ester; Vardi, Assaf

2014-02-18

Diatoms are ubiquitous marine photosynthetic eukaryotes responsible for approximately 20% of global photosynthesis. Little is known about the redox-based mechanisms that mediate diatom sensing and acclimation to environmental stress. Here we used a quantitative mass spectrometry-based approach to elucidate the redox-sensitive signaling network (redoxome) mediating the response of diatoms to oxidative stress. We quantified the degree of oxidation of 3,845 cysteines in the Phaeodactylum tricornutum proteome and identified approximately 300 redox-sensitive proteins. Intriguingly, we found redox-sensitive thiols in numerous enzymes composing the nitrogen assimilation pathway and the recently discovered diatom urea cycle. In agreement with this finding, the flux from nitrate into glutamine and glutamate, measured by the incorporation of (15)N, was strongly inhibited under oxidative stress conditions. Furthermore, by targeting the redox-sensitive GFP sensor to various subcellular localizations, we mapped organelle-specific oxidation patterns in response to variations in nitrogen quota and quality. We propose that redox regulation of nitrogen metabolism allows rapid metabolic plasticity to ensure cellular homeostasis, and thus is essential for the ecological success of diatoms in the marine ecosystem.

Electrolyte for stable cycling of high-energy lithium sulfur redox flow batteries

Energy Technology Data Exchange (ETDEWEB)

Xiao, Jie; Liu, Jun; Pan, Huilin; Henderson, Wesley A.

2018-04-24

A device comprising: a lithium sulfur redox flow battery comprising an electrolyte composition comprising: (i) a dissolved Li₂S_x electroactive salt, wherein x.gtoreq.4; (ii) a solvent selected from dimethyl sulfoxide, tetrahydrofuran, or a mixture thereof; and (iii) a supporting salt at a concentration of at least 2 M, as measured by moles of supporting salt divided by the volume of the solvent without considering the volume change of the electrolyte after dissolving the supporting salt.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

Science.gov (United States)

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-07-18

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

Energy Technology Data Exchange (ETDEWEB)

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-11-07

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

A mathematical model for the iron/chromium redox battery

Science.gov (United States)

Fedkiw, P. S.; Watts, R. W.

1984-01-01

A mathematical model has been developed to describe the isothermal operation of a single anode-separator-cathode unit cell in a redox-flow battery and has been applied to the NASA iron/chromium system. The model, based on porous electrode theory, incorporates redox kinetics, mass transfer, and ohmic effects as well as the parasitic hydrogen reaction which occurs in the chromium electrode. A numerical parameter study was carried out to predict cell performance to aid in the rational design, scale-up, and operation of the flow battery. The calculations demonstrate: (1) an optimum electrode thickness and electrolyte flow rate exist; (2) the amount of hydrogen evolved and, hence, cycle faradaic efficiency, can be affected by cell geometry, flow rate, and charging procedure; (3) countercurrent flow results in enhanced cell performance over cocurrent flow; and (4) elevated temperature operation enhances cell performance.

Beneficial synergistic effects of microdose lithium with pyrroloquinoline quinone in an Alzheimer's disease mouse model.

Science.gov (United States)

Zhao, Lei; Gong, Neng; Liu, Meng; Pan, Xiaoli; Sang, Shaoming; Sun, Xiaojing; Yu, Zhe; Fang, Qi; Zhao, Na; Fei, Guoqiang; Jin, Lirong; Zhong, Chunjiu; Xu, Tianle

2014-12-01

Alzheimer's disease (AD) is a complicated, neurodegenerative disorder involving multifactorial pathogeneses and still lacks effective clinical treatment. Recent studies show that lithium exerts disease-modifying effects against AD. However, the intolerant side effects at conventional effective dosage limit the clinical use of lithium in treating AD. To explore a novel AD treatment strategy with microdose lithium, we designed and synthesized a new chemical, tri-lithium pyrroloquinoline quinone (Li3PQQ), to study the synergistic effects of low-dose lithium and pyrroloquinoline quinone, a native compound with powerful antioxidation and mitochondrial amelioration. The results showed that Li3PQQ at a relative low dose (6 and 12 mg/kg) exhibited more powerful effects in restoring the impairment of learning and memory, facilitating hippocampal long-term potentiation, and reducing cerebral amyloid deposition and phosphorylated tau level in APP/PS1 transgenic mice than that of lithium chloride at both low and high dose (5 and 100 mg/kg). We further found that Li3PQQ inhibited the activity of glycogen synthase kinase-3 and increased the activity of β-amyloid-binding alcohol dehydrogenase, which might underlie the beneficial effects of Li3PQQ on APP/PS1 transgenic mice. Our study demonstrated the efficacy of a novel AD therapeutic strategy targeting at multiple disease-causing mechanisms through the synergistic effects of microdose lithium and pyrroloquinoline quinone. Copyright © 2014 Elsevier Inc. All rights reserved.

Curvature and Strength of Ni-YSZ Solid Oxide Half-Cells After Redox Treatments

DEFF Research Database (Denmark)

Faes, Antonin; Frandsen, Henrik Lund; Pihlatie, Mikko

2010-01-01

One of the main drawbacks of anode-supported solid oxide fuel cell technology is the limited capability to withstand reduction and oxidation (“RedOx”) of the Ni phase. This study compares the effect of RedOx cycles on curvature and strength of half-cells, composed of a nickel-yttria-stabilized-zi......One of the main drawbacks of anode-supported solid oxide fuel cell technology is the limited capability to withstand reduction and oxidation (“RedOx”) of the Ni phase. This study compares the effect of RedOx cycles on curvature and strength of half-cells, composed of a nickel...... it is calculated analytically from the force. In this calculation the thermal stresses are estimated from the curvature of the half-cell. For each treatment, more than 30 samples are tested. About 20 ball-on-ring samples are laser cut from one original 12×12 cm2 half-cell. Curvature and porosity are measured...

A low-cost iron-cadmium redox flow battery for large-scale energy storage

Science.gov (United States)

Zeng, Y. K.; Zhao, T. S.; Zhou, X. L.; Wei, L.; Jiang, H. R.

2016-10-01

The redox flow battery (RFB) is one of the most promising large-scale energy storage technologies that offer a potential solution to the intermittency of renewable sources such as wind and solar. The prerequisite for widespread utilization of RFBs is low capital cost. In this work, an iron-cadmium redox flow battery (Fe/Cd RFB) with a premixed iron and cadmium solution is developed and tested. It is demonstrated that the coulombic efficiency and energy efficiency of the Fe/Cd RFB reach 98.7% and 80.2% at 120 mA cm-2, respectively. The Fe/Cd RFB exhibits stable efficiencies with capacity retention of 99.87% per cycle during the cycle test. Moreover, the Fe/Cd RFB is estimated to have a low capital cost of 108 kWh-1 for 8-h energy storage. Intrinsically low-cost active materials, high cell performance and excellent capacity retention equip the Fe/Cd RFB to be a promising solution for large-scale energy storage systems.

Hydrologic control on redox and nitrogen dynamics in a peatland soil

Energy Technology Data Exchange (ETDEWEB)

Rubol, Simonetta, E-mail: rubols@ing.unitn.it [Dipartimento di Ingegneria Civile ed Ambientale, Universita di Trento, Via Mesiano 77, I 38123 Trento (Italy); Silver, Whendee L. [Department of Environmental Science, Policy, and Management, 130 Mulford Hall, University of California, Berkeley, CA, 94720 (United States); Bellin, Alberto [Dipartimento di Ingegneria Civile ed Ambientale, Universita di Trento, Via Mesiano 77, I 38123 Trento (Italy)

2012-08-15

Soils are a dominant source of nitrous oxide (N{sub 2}O), a potent greenhouse gas. However, the complexity of the drivers of N{sub 2}O production and emissions has hindered our ability to predict the magnitude and spatial dynamics of N{sub 2}O fluxes. Soil moisture can be considered a key driver because it influences oxygen (O{sub 2}) supply, which feeds back on N{sub 2}O sources (nitrification versus denitrification) and sinks (reduction to dinitrogen). Soil water content is directly linked to O{sub 2} and redox potential, which regulate microbial metabolism and chemical transformations in the environment. Despite its importance, only a few laboratory studies have addressed the effects of hydrological transient dynamics on nitrogen (N) cycling in the vadose zone. To further investigate these aspects, we performed a long term experiment in a 1.5 m depth soil column supplemented by chamber experiments. With this experiment, we aimed to investigate how soil moisture dynamics influence redox sensitive N cycling in a peatland soil. As expected, increased soil moisture lowered O{sub 2} concentrations and redox potential in the soil. The decline was more severe for prolonged saturated conditions than for short events and at deep than at the soil surface. Gaseous and dissolved N{sub 2}O, dissolved nitrate (NO{sub 3}{sup -}) and ammonium (NH{sub 4}{sup +}) changed considerably along the soil column profile following trends in soil O{sub 2} and redox potential. Hot spots of N{sub 2}O concentrations corresponded to high variability in soil O{sub 2} in the upper and lower parts of the column. Results from chamber experiments confirmed high NO{sub 3}{sup -} reduction potential in soils, particularly from the bottom of the column. Under our experimental conditions, we identified a close coupling of soil O{sub 2} and N{sub 2}O dynamics, both of which lagged behind soil moisture changes. These results highlight the relationship among soil hydrologic properties, redox potential

Electrochemical analysis in a liposome suspension using lapachol as a hydrophobic electro active species.

Science.gov (United States)

Okumura, Noriko; Wakamatsu, Shiori; Uno, Bunji

2014-01-01

This study demonstrated that the electro-chemical analysis of hydrophobic quinones can be performed in liposome suspension systems. We prepared and analyzed liposome suspensions containing lapachol, which is a quinone-based anti-tumor activity compound. In this suspension system, a simple one redox couple of lapachol is observed. These results are quite different from those obtained in organic solvents. In addition, the pH dependence of redox behaviors of lapachol could be observed in multilamellar vesicle (MLV) suspension system. This MLV suspension system method may approximate the electrochemical behavior of hydrophobic compounds in aqueous conditions. A benefit of this liposome suspension system for electrochemical analysis is that it enables to observe water-insoluble compounds without using organic solvents.

Organic Acids: The Pools of Fixed Carbon Involved in Redox Regulation and Energy Balance in Higher Plants

Directory of Open Access Journals (Sweden)

Abir U Igamberdiev

2016-07-01

Full Text Available Organic acids are synthesized in plants as a result of the incomplete oxidation of photosynthetic products and represent the stored pools of fixed carbon accumulated due to different transient times of conversion of carbon compounds in metabolic pathways. When redox level in the cell increases, e.g., in conditions of active photosynthesis, the tricarboxylic acid (TCA cycle in mitochondria is transformed to a partial cycle supplying citrate for the synthesis of 2-oxoglutarate and glutamate (citrate valve, while malate is accumulated and participates in the redox balance in different cell compartments (via malate valve. This results in malate and citrate frequently being the most accumulated acids in plants. However, the intensity of reactions linked to the conversion of these compounds can cause preferential accumulation of other organic acids, e.g., fumarate or isocitrate, in higher concentrations than malate and citrate. The secondary reactions, associated with the central metabolic pathways, in particularly with the TCA cycle, result in accumulation of other organic acids that are derived from the intermediates of the cycle. They form the additional pools of fixed carbon and stabilize the TCA cycle. Trans-aconitate is formed from citrate or cis-aconitate, accumulation of hydroxycitrate can be linked to metabolism of 2-oxoglutarate, while 4-hydroxy-2-oxoglutarate can be formed from pyruvate and glyoxylate. Glyoxylate, a product of either glycolate oxidase or isocitrate lyase, can be converted to oxalate. Malonate is accumulated at high concentrations in legume plants. Organic acids play a role in plants in providing redox equilibrium, supporting ionic gradients on membranes, and acidification of the extracellular medium.

Electron transfer pathways in microbial oxygen biocathodes

Energy Technology Data Exchange (ETDEWEB)

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

2010-01-01

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

Iron Redox Dynamics in Humid Tropical Forest Soils: Carbon Stabilization vs. Degradation?

Science.gov (United States)

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

2015-12-01

Most terrestrial soils exhibit a patchwork of oxygen (O2) availability that varies over spatial scales of microsites to catenas to landscapes, and over temporal scales of minutes to seasons. Oxygen fluctuations often drive microbial iron (Fe) reduction and abiotic/biotic Fe oxidation at the microsite scale, contributing to anaerobic carbon (C) mineralization and changes in soil physical and chemical characteristics, especially the dissolution and precipitation of short-range ordered Fe phases thought to stabilize C. Thus, O2 fluctuations and Fe redox cycling may have multiple nuanced and opposing impacts on different soil C pools, illustrated by recent findings from Fe-rich Oxisols and Ultisols in the Luquillo Experimental Forest, Puerto Rico. Spatial patterns in surface soil C stocks at the landscape scale correlated strongly (R2 = 0.98) with concentrations of reduced Fe (Fe(II)), reflecting constitutive differences in reducing conditions within and among sites that promote C accumulation in mineral soil horizons. Similarly, turnover times of a decadal-cycling pool of mineral-associated organic matter increased with Fe(II) across a catena, possibly reflecting the role of anaerobic microsites in long-term C stabilization. However, two different indices of short-range order Fe showed highly significant opposing relationships (positive and negative) with spatial variation in soil C concentrations, possibly reflecting a dual role of Fe in driving C stabilization via co-precipitation, and C solubilization and loss following dissimilatory Fe reduction. Consistent with the field data, laboratory incubations demonstrated that redox fluctuations can increase the contribution of biochemically recalcitrant C (lignin) to soil respiration, whereas addition of short-range order Fe dramatically suppressed lignin mineralization but had no impact on bulk soil respiration. Thus, understanding spatial and temporal patterns of Fe redox cycling may provide insight into explaining the

Exposure to 9,10-phenanthrenequinone accelerates malignant progression of lung cancer cells through up-regulation of aldo-keto reductase 1B10

International Nuclear Information System (INIS)

Matsunaga, Toshiyuki; Morikawa, Yoshifumi; Haga, Mariko; Endo, Satoshi; Soda, Midori; Yamamura, Keiko; El-Kabbani, Ossama; Tajima, Kazuo; Ikari, Akira; Hara, Akira

2014-01-01

Inhalation of 9,10-phenanthrenequinone (9,10-PQ), a major quinone in diesel exhaust, exerts fatal damage against a variety of cells involved in respiratory function. Here, we show that treatment with high concentrations of 9,10-PQ evokes apoptosis of lung cancer A549 cells through production of reactive oxygen species (ROS). In contrast, 9,10-PQ at its concentrations of 2 and 5 μM elevated the potentials for proliferation, invasion, metastasis and tumorigenesis, all of which were almost completely inhibited by addition of an antioxidant N-acetyl-L-cysteine, inferring a crucial role of ROS in the overgrowth and malignant progression of lung cancer cells. Comparison of mRNA expression levels of six aldo-keto reductases (AKRs) in the 9,10-PQ-treated cells advocated up-regulation of AKR1B10 as a major cause contributing to the lung cancer malignancy. In support of this, the elevation of invasive, metastatic and tumorigenic activities in the 9,10-PQ-treated cells was significantly abolished by the addition of a selective AKR1B10 inhibitor oleanolic acid. Intriguingly, zymographic and real-time PCR analyses revealed remarkable increases in secretion and expression, respectively, of matrix metalloproteinase 2 during the 9,10-PQ treatment, and suggested that the AKR1B10 up-regulation and resultant activation of mitogen-activated protein kinase cascade are predominant mechanisms underlying the metalloproteinase induction. In addition, HPLC analysis and cytochrome c reduction assay in in vitro 9,10-PQ reduction by AKR1B10 demonstrated that the enzyme catalyzes redox-cycling of this quinone, by which ROS are produced. Collectively, these results suggest that AKR1B10 is a key regulator involved in overgrowth and malignant progression of the lung cancer cells through ROS production due to 9,10-PQ redox-cycling. - Highlights: • 9,10-PQ promotes invasion, metastasis and tumorigenicity in lung cancer cells. • The 9,10-PQ-elicited promotion is possibly due to AKR1B10 up

Exposure to 9,10-phenanthrenequinone accelerates malignant progression of lung cancer cells through up-regulation of aldo-keto reductase 1B10

Energy Technology Data Exchange (ETDEWEB)

Matsunaga, Toshiyuki, E-mail: matsunagat@gifu-pu.ac.jp [Laboratory of Biochemistry, Gifu Pharmaceutical University, Gifu 501-1196 (Japan); Morikawa, Yoshifumi; Haga, Mariko; Endo, Satoshi [Laboratory of Biochemistry, Gifu Pharmaceutical University, Gifu 501-1196 (Japan); Soda, Midori; Yamamura, Keiko [Laboratory of Clinical Pharmacy, School of Pharmacy, Aichi Gakuin University, Nagoya 464-8650 (Japan); El-Kabbani, Ossama [Monash Institute of Pharmaceutical Sciences, Monash University, Victoria 3052 (Australia); Tajima, Kazuo [Faculty of Pharmaceutical Sciences, Hokuriku University, Kanazawa 920-1181 (Japan); Ikari, Akira [Laboratory of Biochemistry, Gifu Pharmaceutical University, Gifu 501-1196 (Japan); Hara, Akira [Faculty of Engineering, Gifu University, Gifu 501-1193 (Japan)

2014-07-15

Inhalation of 9,10-phenanthrenequinone (9,10-PQ), a major quinone in diesel exhaust, exerts fatal damage against a variety of cells involved in respiratory function. Here, we show that treatment with high concentrations of 9,10-PQ evokes apoptosis of lung cancer A549 cells through production of reactive oxygen species (ROS). In contrast, 9,10-PQ at its concentrations of 2 and 5 μM elevated the potentials for proliferation, invasion, metastasis and tumorigenesis, all of which were almost completely inhibited by addition of an antioxidant N-acetyl-L-cysteine, inferring a crucial role of ROS in the overgrowth and malignant progression of lung cancer cells. Comparison of mRNA expression levels of six aldo-keto reductases (AKRs) in the 9,10-PQ-treated cells advocated up-regulation of AKR1B10 as a major cause contributing to the lung cancer malignancy. In support of this, the elevation of invasive, metastatic and tumorigenic activities in the 9,10-PQ-treated cells was significantly abolished by the addition of a selective AKR1B10 inhibitor oleanolic acid. Intriguingly, zymographic and real-time PCR analyses revealed remarkable increases in secretion and expression, respectively, of matrix metalloproteinase 2 during the 9,10-PQ treatment, and suggested that the AKR1B10 up-regulation and resultant activation of mitogen-activated protein kinase cascade are predominant mechanisms underlying the metalloproteinase induction. In addition, HPLC analysis and cytochrome c reduction assay in in vitro 9,10-PQ reduction by AKR1B10 demonstrated that the enzyme catalyzes redox-cycling of this quinone, by which ROS are produced. Collectively, these results suggest that AKR1B10 is a key regulator involved in overgrowth and malignant progression of the lung cancer cells through ROS production due to 9,10-PQ redox-cycling. - Highlights: • 9,10-PQ promotes invasion, metastasis and tumorigenicity in lung cancer cells. • The 9,10-PQ-elicited promotion is possibly due to AKR1B10 up

Self-assembling graphene-anthraquinone-2-sulphonate supramolecular nanostructures with enhanced energy density for supercapacitors

Science.gov (United States)

Gao, Lifang; Gan, Shiyu; Li, Hongyan; Han, Dongxue; Li, Fenghua; Bao, Yu; Niu, Li

2017-07-01

Boosting the energy density of capacitive energy storage devices remains a crucial issue for facilitating applications. Herein, we report a graphene-anthraquinone supramolecular nanostructure by self-assembly for supercapacitors. The sulfonated anthraquinone exhibits high water solubility, a π-conjugated structure and redox active features, which not only serve as a spacer to interact with and stabilize graphene but also introduce extra pseudocapacitance contributions. The formed nest-like three-dimensional (3D) nanostructure with further hydrothermal treatment enhances the accessibility of ion transfer and exposes the redox-active quinone groups in the electrolytes. A fabricated all-solid-state flexible symmetric device delivers a high specific capacitance of 398.5 F g-1 at 1 A g-1 (1.5 times higher than graphene), superior energy density (52.24 Wh kg-1 at about 1 kW kg-1) and good stability (82% capacitance retention after 10 000 cycles).

Identification of a lactate-quinone oxidoreductase (Lqo in staphylococcus aureus that is essential for virulence

Directory of Open Access Journals (Sweden)

James R Fuller

2011-12-01

Full Text Available Staphylococcus aureus is an important human pathogen commonly infecting nearly every host tissue. The ability of S. aureus to resist innate immunity is critical to its success as a pathogen, including its propensity to grow in the presence of host nitric oxide (NO·. Upon exogenous NO· exposure, S. aureus immediately excretes copious amounts of L-lactate to maintain redox balance. However, after prolonged NO·-exposure, S. aureus reassimilates L-lactate specifically and in this work, we identify the enzyme responsible for this L-lactate consumption as a L-lactate-quinone oxidoreductase (Lqo, SACOL2623. Originally annotated as Mqo2 and thought to oxidize malate, we show that this enzyme exhibits no affinity for malate but reacts specifically with L-lactate (KM = ~330 µM. In addition to its requirement for reassimilation of L-lactate during NO·-stress, Lqo is also critical to respiratory growth on L-lactate as a sole carbon source. Moreover, ∆lqo mutants exhibit attenuation in a murine model of sepsis, particularly in their ability to cause myocarditis. Interestingly, this cardiac-specific attenuation is completely abrogated in mice unable to synthesize inflammatory NO· (iNOS-/-. We demonstrate that S. aureus NO·-resistance is highly dependent on the availability of a glycolytic carbon sources. However, S. aureus can utilize the combination of peptides and L-lactate as carbon sources during NO·-stress in an Lqo-dependent fashion. Murine cardiac tissue has markedly high levels of L-lactate in comparison to renal or hepatic tissue consistent with the NO·-dependent requirement for Lqo in S. aureus myocarditis. Thus, Lqo provides S. aureus with yet another means of replicating in the presence of host NO·.

Mechanisms of action of quinone-containing alkylating agents: DNA alkylation by aziridinylquinones.

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Hargreaves, R H; Hartley, J A; Butler, J

2000-11-01

Aziridinyl quinones can be activated by cellular reductases eg. DT-diaphorase and cytochrome P450 reductase to form highly reactive DNA alkylating agents. The mechanisms by which this activation and alkylation take place are many and varied. Using clinically relevant and experimental agents this review will describe many of these mechanisms. The agents discussed are Mitomycin C, EO9 and analogues, diaziridinylbenzoquinones and the pyrrolo[1, 2-alpha]benzimidazolequinones.

4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl as a model organic redox active compound for nonaqueous flow batteries

Science.gov (United States)

Milshtein, Jarrod D.; Barton, John L.; Darling, Robert M.; Brushett, Fikile R.

2016-09-01

Nonaqueous redox flow batteries (NAqRFBs) that utilize redox active organic molecules are an emerging energy storage concept with the possibility of meeting grid storage requirements. Sporadic and uneven advances in molecular discovery and development, however, have stymied efforts to quantify the performance characteristics of nonaqueous redox electrolytes and flow cells. A need exists for archetypal redox couples, with well-defined electrochemical properties, high solubility in relevant electrolytes, and broad availability, to serve as probe molecules. This work investigates the 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl (AcNH-TEMPO) redox pair for such an application. We report the physicochemical and electrochemical properties of the reduced and oxidized compounds at dilute concentrations for electroanalysis, as well as moderate-to-high concentrations for RFB applications. Changes in conductivity, viscosity, and UV-vis absorbance as a function of state-of-charge are quantified. Cyclic voltammetry investigates the redox potential, reversibility, and diffusion coefficients of dilute solutions, while symmetric flow cell cycling determines the stability of the AcNH-TEMPO redox pair over long experiment times. Finally, single electrolyte flow cell studies demonstrate the utility of this redox couple as a platform chemistry for benchmarking NAqRFB performance.

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

Interactions between magnetite and humic substances: redox reactions and dissolution processes.

Science.gov (United States)

Sundman, Anneli; Byrne, James M; Bauer, Iris; Menguy, Nicolas; Kappler, Andreas

2017-10-19

Humic substances (HS) are redox-active compounds that are ubiquitous in the environment and can serve as electron shuttles during microbial Fe(III) reduction thus reducing a variety of Fe(III) minerals. However, not much is known about redox reactions between HS and the mixed-valent mineral magnetite (Fe 3 O 4 ) that can potentially lead to changes in Fe(II)/Fe(III) stoichiometry and even dissolve the magnetite. To address this knowledge gap, we incubated non-reduced (native) and reduced HS with four types of magnetite that varied in particle size and solid-phase Fe(II)/Fe(III) stoichiometry. We followed dissolved and solid-phase Fe(II) and Fe(III) concentrations over time to quantify redox reactions between HS and magnetite. Magnetite redox reactions and dissolution processes with HS varied depending on the initial magnetite and HS properties. The interaction between biogenic magnetite and reduced HS resulted in dissolution of the solid magnetite mineral, as well as an overall reduction of the magnetite. In contrast, a slight oxidation and no dissolution was observed when native and reduced HS interacted with 500 nm magnetite. This variability in the solubility and electron accepting and donating capacity of the different types of magnetite is likely an effect of differences in their reduction potential that is correlated to the magnetite Fe(II)/Fe(III) stoichiometry, particle size, and crystallinity. Our study suggests that redox-active HS play an important role for Fe redox speciation within minerals such as magnetite and thereby influence the reactivity of these Fe minerals and their role in biogeochemical Fe cycling. Furthermore, such processes are also likely to have an effect on the fate of other elements bound to the surface of Fe minerals.

Redox flow batteries. Already an alternative storage solution for hybrid PV mini-grids?

Energy Technology Data Exchange (ETDEWEB)

Vetter, Matthias; Dennenmoser, Martin; Schwunk, Simon; Smolinka, Tom [Fraunhofer Institute for Solar Energy Systems (ISE), Freiburg (Germany); Doetsch, Christian; Berthold, Sascha [Fraunhofer Institute for Environmental, Safety and Energy Technology (UMSICHT), Oberhausen (Germany); Tuebke, Jens; Noack, Jens [Fraunhofer Institute for Chemical Technology (ICT), Karlsruhe (Germany)

2010-07-01

Due to the flexible scalability of the power to energy ratio redox flow batteries are a suitable solution for quite a lot of decentralized applications. E.g. the autonomy time of a stand-alone system or mini-grid can be raised by increasing the tank size of the redox flow battery. In this paper the test site ''Rappenecker Hof'' in the black forest is used as an example for simulation based life cycle cost analyses of a vanadium redox flow battery integrated in an autonomous hybrid PV system. Two cases with lead acid batteries are considered as benchmarks for economic viability of the redox flow battery solution in such applications. At the moment a 1 KW / 6 kWh system for decentralized solutions is developed and will be installed in the ''Solarhaus'' in Freiburg. The main results of the cell stack and system design as well as performance data are presented. Furthermore simulation models and the model based development of the ''Smart Redox flow Control'' are described. For the optimized integration of the storage unit in the energy system a communication interface for exchanging data with the supervisory energy management system is introduced. On this basis a SOC forecast according to a given demand profile can be determined. (orig.)

Tannin-Metal Interactions in Soils: An Incubation-Extraction Approach in Hill-Land Environments

Science.gov (United States)

Gonzalez, J. M.; Halvorson, J. J.

2007-12-01

Tannins, plant polyphenols known to react with proteins, metals and soil organic matter, are commonly found in the vegetation growing in Appalachian hill-lands. Establishing silvopastoral grazing systems in these environments is a means for improving productivity however the fate of tannins in soils and, in particular, the effect on solubility/mobility of metals in soils is poorly understood. Soils from forest and pasture systems were sampled from two depths, treated with tannic acid or related phenolic compounds, and analyzed for metals in solution. The amount of Mn and Ca detected in solution varied among the different phenolic treatments, highest for gallic acid, and was also influenced by depth and land use. As expected, the Ca content in solution was correlated with the electrical conductivity (EC) and the Mn content was correlated with the redox potential in solution. Interestingly, the EC was also correlated with both Mn content and redox potential. The higher Ca content found in solution may result from the low pH of the phenolic compounds. The higher Mn in solution may result from the redox reaction of Mn (IV) oxides with the phenolic compounds, producing soluble Mn2+ and quinones. These quinones are very reactive compounds that can self-polymerize and/or copolymerize with other biomolecules, such as amino-containing compounds and carbohydrates, to form humic-like substances. Successful management of silvopastures, requires an understanding of factors that affect the quality and quantity of plant secondary compounds like tannins entering soil not only to increase forage productivity but also to enhance formation/stabilization of soil organic matter to increase nutrient cycling and reduce the toxicity risk of some metals such as Mn.

Selenium electrochemistry. Applications in the nuclear fuel cycle

Energy Technology Data Exchange (ETDEWEB)

Maslennikov, A.; Peretroukhine, V. [Russian Academy of Sciences, Moscow (Russian Federation). Inst. of Physical Chemistry; David, F. [Centre National de la Recherche Scientifique (CNRS), 91 - Orsay (France); Lecomte, M. [CEA Centre d' Etudes de la Valle du Rhone, 30 - Marcoule (France). Direction du Cycle du Combustible

1999-07-01

Modern state of selenium electrochemistry is reviewed in respect of the application of electrochemical methods for the study of the behavior of this element and its quantitative analysis in the solutions of nuclear fuel cycle. The review includes the data on the redox potentials of Se in aqueous solutions, and the data on Se redox reactions, occurring at mercury and solid electrodes. Analysis of the available literature data shows that the inverse stripping voltammetry technique for trace Se concentration and determination seems to be the most promising in application for the Se determination in PUREX solutions and in radioactive wastes. The adaptation of the ISV technique for the trace Se concentration and determination in the solutions of the nuclear fuel cycle is indicated as the most prospective goal of the future experimental study. (author)

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.

Highly stable pyridinium-functionalized cross-linked anion exchange membranes for all vanadium redox flow batteries

Science.gov (United States)

Zeng, L.; Zhao, T. S.; Wei, L.; Zeng, Y. K.; Zhang, Z. H.

2016-11-01

It has recently been demonstrated that the use of anion exchange membranes (AEMs) in vanadium redox flow batteries (VRFBs) can reduce the migration of vanadium ions through the membrane due to the Donnan exclusion effect among the positively charged functional groups and vanadium ions. However, AEMs are plagued by low chemical stability in harsh chemical environments. Here we propose and fabricate a pyridinium-functionalized cross-linked AEM for VRFBs. The pyridinium-functionalized bromomethylated poly (2,6-dimethyl-1,4-phenylene oxide) exhibits a superior chemical stability as a result of the strengthened internal cross-linking networks and the chemical inertness of the polymer backbone. Therefore, the membrane exhibits littler decay in a harsh environment for 20 days during the course of an ex situ immersion test. A cycling test also demonstrates that the VRFB assembled with the membrane enable to retain 80% of the initial discharge capacity over 537 cycles with a capacity decay rate of 0.037% cycle-1. Meanwhile, the membrane also shows a low vanadium permeability and a reasonably high conductivity in supporting electrolytes. Hence, all the measurements and performance tests reported in this work suggest that the membrane is a promising AEM for redox flow batteries to achieve excellent cycling stability and superior cell performance.

The roles of anion and solvent transport during the redox switching process at a poly(butyl viologen) film studied by an EQCM

Energy Technology Data Exchange (ETDEWEB)

Hsu, Chih-Yu.; Liao, Chun-Hao [Department of Chemical Engineering, National Taiwan University, Taipei 10617 (China); Ho, Kuo-Chuan [Department of Chemical Engineering, National Taiwan University, Taipei 10617 (China); Institute of Polymer Science and Engineering, National Taiwan University, Taipei 10617 (China)

2008-02-15

In this study, three electrolytes (KCl, LiCl, and KNO{sub 3}, each at 0.5 M in aqueous solution) were chosen to study the ion and solvent effect on the redox performance of poly(butyl viologen) (PBV) thin-films between its di-cation and radical-cation state, which is referred as its first redox couple. Before considering the role of ionic transport on the redox process, the exchange between ferrocyanide and anion should be completed. Since the deposition solution of PBV contains potassium ferrocyanide, the residual ferrocyanides inside the films would be exchanged by smaller anions from the bulk solution during the redox reaction of PBV. From cyclic voltammetry (CV) and electrochemical quartz crystal microbalance (EQCM) results, the exchange was almost complete around 50 cycles when scanning the potential within its first redox range. After completion of the exchange process, the transfer would reach a steady state. At 50 cycles, the EQCM results suggested that the transport involves anions and water only for both being extracted upon reduction and being inserted upon oxidation. Therefore, we could obtain the molar fluxes of Cl{sup -}, NO{sub 3}{sup -}, and water. Besides, the average numbers of accompanying water were calculated to be about 24.8 per Cl{sup -} and 14.2 per NO{sub 3}{sup -} upon redox switching process. The instantaneous water to anion molar ratios at any potential were also obtained for Cl{sup -} and NO{sub 3}{sup -}. (author)

Reaction-based small-molecule fluorescent probes for dynamic detection of ROS and transient redox changes in living cells and small animals.

Science.gov (United States)

Lü, Rui

2017-09-01

Dynamic detection of transient redox changes in living cells and animals has broad implications for human health and disease diagnosis, because intracellular redox homeostasis regulated by reactive oxygen species (ROS) plays important role in cell functions, normal physiological functions and some serious human diseases (e.g., cancer, Alzheimer's disease, diabetes, etc.) usually have close relationship with the intracellular redox status. Small-molecule ROS-responsive fluorescent probes can act as powerful tools for dynamic detection of ROS and redox changes in living cells and animals through fluorescence imaging techniques; and great advances have been achieved recently in the design and synthesis of small-molecule ROS-responsive fluorescent probes. This article highlights up-to-date achievements in designing and using the reaction-based small-molecule fluorescent probes (with high sensitivity and selectivity to ROS and redox cycles) in the dynamic detection of ROS and transient redox changes in living cells and animals through fluorescence imaging. Copyright © 2017. Published by Elsevier Ltd.

Measurement of the Structure and Molecular Dynamics of Ionic Solutions for Redox Flow Battery

Science.gov (United States)

Li, Zhixia; Robertson, Lily; Moore, Jeffery; Zhang, Yang

Redox flow battery (RFB) is a promising electrical energy storage technology with great potential to finally realize alternative energy sources for the next-generation vehicles and at grid scales. The design of RFB is unique as the power scales separately from the energy capacity. The latter depends on the size of storage tanks and the concentration of the active materials. Redox-active organic molecules are excellent candidates with high synthetic tunability for both redox properties as well as, importantly, solubility. However, upon increasing concentrations, the flow cell has less cycling stability and more capacity fade. Further, after charging the battery, the viscosity increases while the ionic conductivity decreases, and thus the cell becomes overall ineffective. To understand the mechanism of the increased viscosity, we performed differential scanning calorimetry, wide and small angle X-rays scattering, and quasi-elastic neutron scattering measurements. Herein, we will present the measurement results and relative analysis.

Brassinosteroid-induced CO2 assimilation is associated with increased stability of redox-sensitive photosynthetic enzymes in the chloroplasts in cucumber plants

International Nuclear Information System (INIS)

Jiang, Yu Ping; Cheng, Fei; Zhou, Yan Hong; Xia, Xiao Jian; Mao, Wei Hua; Shi, Kai; Chen, Zhi Xiang; Yu, Jing Quan

2012-01-01

Highlights: ► Activity of certain Calvin cycle enzymes and CO 2 assimilation are induced by BRs. ► BRs upregulate the activity of the ascorbate–glutathione cycle in the chloroplasts. ► BRs increase the chloroplast thiol reduction state. ► A BR-induced reducing environment increases the stability of photosynthetic enzymes. -- Abstract: Brassinosteroids (BRs) play important roles in plant growth, development, photosynthesis and stress tolerance; however, the mechanism underlying BR-enhanced photosynthesis is currently unclear. Here, we provide evidence that an increase in the BR level increased the quantum yield of PSII, activities of Rubisco activase (RCA) and fructose-1,6-bisphosphatase (FBPase), and CO 2 assimilation. BRs upregulated the transcript levels of genes and activity of enzymes involved in the ascorbate–glutathione cycle in the chloroplasts, leading to an increased ratio of reduced (GSH) to oxidized (GSSG) glutathione in the chloroplasts. An increased GSH/GSSG ratio protected RCA from proteolytic digestion and increased the stability of redox-sensitive enzymes in the chloroplasts. These results strongly suggest that BRs are capable of regulating the glutathione redox state in the chloroplasts through the activation of the ascorbate–glutathione cycle. The resulting increase in the chloroplast thiol reduction state promotes CO 2 assimilation, at least in part, by enhancing the stability and activity of redox-sensitive photosynthetic enzymes through post-translational modifications.

Plant cytoplasmic GAPDH: redox post-translational modifications and moonlighting properties

Directory of Open Access Journals (Sweden)

Mirko eZaffagnini

2013-11-01

Full Text Available Glyceraldehyde-3-phosphate dehydrogenase (GAPDH is a ubiquitous enzyme involved in glycolysis and shown, particularly in animal cells, to play additional roles in several unrelated non-metabolic processes such as control of gene expression and apoptosis. This functional versatility is regulated, in part at least, by redox post-translational modifications that alter GAPDH catalytic activity and influence the subcellular localization of the enzyme. In spite of the well established moonlighting (multifunctional properties of animal GAPDH, little is known about non-metabolic roles of GAPDH in plants. Plant cells contain several GAPDH isoforms with different catalytic and regulatory properties, located both in the cytoplasm and in plastids, and participating in glycolysis and the Calvin-Benson cycle. A general feature of all GAPDH proteins is the presence of an acidic catalytic cysteine in the active site that is overly sensitive to oxidative modifications, including glutathionylation and S-nitrosylation. In Arabidopsis, oxidatively-modified cytoplasmic GAPDH has been successfully used as a tool to investigate the role of reduced glutathione, thioredoxins and glutaredoxins in the control of different types of redox post-translational modifications. Oxidative modifications inhibit GAPDH activity, but might enable additional functions in plant cells. Mounting evidence support the concept that plant cytoplasmic GAPDH may fulfill alternative, non-metabolic functions that are triggered by redox post-translational modifications of the protein under stress conditions. The aim of this review is to detail the molecular mechanisms underlying the redox regulation of plant cytoplasmic GAPDH in the light of its crystal structure, and to provide a brief inventory of the well known redox-dependent multi-facetted properties of animal GAPDH, together with the emerging roles of oxidatively-modified GAPDH in stress signaling pathways in plants.

Critical transport issues for improving the performance of aqueous redox flow batteries

Science.gov (United States)

Zhou, X. L.; Zhao, T. S.; An, L.; Zeng, Y. K.; Wei, L.

2017-01-01

As the fraction of electricity generated from intermittent renewable sources (such as solar and wind) grows, developing reliable energy storage technologies to store electrical energy in large scale is of increasing importance. Redox flow batteries are now enjoying a renaissance and regarded as a leading technology in providing a well-balanced solution for current daunting challenges. In this article, state-of-the-art studies of the complex multicomponent transport phenomena in aqueous redox flow batteries, with a special emphasis on all-vanadium redox flow batteries, are reviewed and summarized. Rather than elaborating on the details of previous experimental and numerical investigations, this article highlights: i) the key transport issues in each battery's component that need to be tackled so that the rate capability and cycling stability of flow batteries can be significantly improved, ii) the basic mechanisms that control the active species/ion/electron transport behaviors in each battery's component, and iii) the key experimental and numerical findings regarding the correlations between the multicomponent transport processes and battery performance.

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

Science.gov (United States)

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

2016-04-01

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

Engineering redox balance through cofactor systems.

Science.gov (United States)

Chen, Xiulai; Li, Shubo; Liu, Liming

2014-06-01

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

Reversible multi-electron redox chemistry of π-conjugated N-containing heteroaromatic molecule-based organic cathodes

Science.gov (United States)

Peng, Chengxin; Ning, Guo-Hong; Su, Jie; Zhong, Guiming; Tang, Wei; Tian, Bingbing; Su, Chenliang; Yu, Dingyi; Zu, Lianhai; Yang, Jinhu; Ng, Man-Fai; Hu, Yong-Sheng; Yang, Yong; Armand, Michel; Loh, Kian Ping

2017-07-01

Even though organic molecules with well-designed functional groups can be programmed to have high electron density per unit mass, their poor electrical conductivity and low cycle stability limit their applications in batteries. Here we report a facile synthesis of π-conjugated quinoxaline-based heteroaromatic molecules (3Q) by condensation of cyclic carbonyl molecules with o-phenylenediamine. 3Q features a number of electron-deficient pyrazine sites, where multiple redox reactions take place. When hybridized with graphene and coupled with an ether-based electrolyte, an organic cathode based on 3Q molecules displays a discharge capacity of 395 mAh g-1 at 400 mA g-1 (1C) in the voltage range of 1.2-3.9 V and a nearly 70% capacity retention after 10,000 cycles at 8 A g-1. It also exhibits a capacity of 222 mAh g-1 at 20C, which corresponds to 60% of the initial specific capacity. Our results offer evidence that heteroaromatic molecules with multiple redox sites are promising in developing high-energy-density, long-cycle-life organic rechargeable batteries.

Redox regulation of photosynthetic gene expression.

Science.gov (United States)

Queval, Guillaume; Foyer, Christine H

2012-12-19

Redox chemistry and redox regulation are central to the operation of photosynthesis and respiration. However, the roles of different oxidants and antioxidants in the regulation of photosynthetic or respiratory gene expression remain poorly understood. Leaf transcriptome profiles of a range of Arabidopsis thaliana genotypes that are deficient in either hydrogen peroxide processing enzymes or in low molecular weight antioxidant were therefore compared to determine how different antioxidant systems that process hydrogen peroxide influence transcripts encoding proteins targeted to the chloroplasts or mitochondria. Less than 10 per cent overlap was observed in the transcriptome patterns of leaves that are deficient in either photorespiratory (catalase (cat)2) or chloroplastic (thylakoid ascorbate peroxidase (tapx)) hydrogen peroxide processing. Transcripts encoding photosystem II (PSII) repair cycle components were lower in glutathione-deficient leaves, as were the thylakoid NAD(P)H (nicotinamide adenine dinucleotide (phosphate)) dehydrogenases (NDH) mRNAs. Some thylakoid NDH mRNAs were also less abundant in tAPX-deficient and ascorbate-deficient leaves. Transcripts encoding the external and internal respiratory NDHs were increased by low glutathione and low ascorbate. Regulation of transcripts encoding specific components of the photosynthetic and respiratory electron transport chains by hydrogen peroxide, ascorbate and glutathione may serve to balance non-cyclic and cyclic electron flow pathways in relation to oxidant production and reductant availability.

Quinones from plants of northeastern Brazil: structural diversity, chemical transformations, NMR data and biological activities.

Science.gov (United States)

Lemos, Telma L G; Monte, Francisco J Q; Santos, Allana Kellen L; Fonseca, Aluisio M; Santos, Hélcio S; Oliveira, Mailcar F; Costa, Sonia M O; Pessoa, Otilia D L; Braz-Filho, Raimundo

2007-05-20

The present review focus in quinones found in species of Brazilian northeastern Capraria biflora, Lippia sidoides, Lippia microphylla and Tabebuia serratifolia. The review cover ethnopharmacological aspects including photography of species, chemical structure feature, NMR datea and biological properties. Chemical transformations of lapachol to form enamine derivatives and biological activities are discussed.

Performance of a vanadium redox flow battery with tubular cell design

Science.gov (United States)

Ressel, Simon; Laube, Armin; Fischer, Simon; Chica, Antonio; Flower, Thomas; Struckmann, Thorsten

2017-07-01

We present a vanadium redox flow battery with a tubular cell design which shall lead to a reduction of cell manufacturing costs and the realization of cell stacks with reduced shunt current losses. Charge/discharge cycling and polarization curve measurements are performed to characterize the single test cell performance. A maximum current density of 70 mAcm-2 and power density of 142 Wl-1 (per cell volume) is achieved and Ohmic overpotential is identified as the dominant portion of the total cell overpotential. Cycling displays Coulomb efficiencies of ≈95% and energy efficiencies of ≈55%. During 113 h of operation a stable Ohmic cell resistance is observed.

Dissecting Redox Biology Using Fluorescent Protein Sensors.

Science.gov (United States)

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

2016-05-01

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

Redox Buffer Strength

Science.gov (United States)

de Levie, Robert

1999-04-01

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

3D Graphene-Ni Foam as an Advanced Electrode for High-Performance Nonaqueous Redox Flow Batteries.

Science.gov (United States)

Lee, Kyubin; Lee, Jungkuk; Kwon, Kyoung Woo; Park, Min-Sik; Hwang, Jin-Ha; Kim, Ki Jae

2017-07-12

Electrodes composed of multilayered graphene grown on a metal foam (GMF) were prepared by directly growing multilayer graphene sheets on a three-dimensional (3D) Ni-foam substrate via a self-catalyzing chemical vapor deposition process. The multilayer graphene sheets are successfully grown on the Ni-foam substrate surface, maintaining the unique 3D macroporous structure of the Ni foam. The potential use of GMF electrodes in nonaqueous redox flow batteries (RFBs) is carefully examined using [Co(bpy) 3 ] +/2+ and [Fe(bpy) 3 ] 2+/3+ redox couples. The GMF electrodes display a much improved electrochemical activity and enhanced kinetics toward the [Co(bpy) 3 ] +/2+ (anolyte) and [Fe(bpy) 3 ] 2+/3+ (catholyte) redox couples, compared with the bare Ni metal foam electrodes, suggesting that the 2D graphene sheets having lots of interdomain defects provide sufficient reaction sites and secure electric-conduction pathways. Consequently, a nonaqueous RFB cell assembled with GMF electrodes exhibits high Coulombic and voltage efficiencies of 87.2 and 90.9%, respectively, at the first cycle. This performance can be maintained up to the 50th cycle without significant efficiency loss. Moreover, the importance of a rational electrode design for improving electrochemical performance is addressed.

Redox non-innocent bis(2,6-diimine-pyridine) ligand-iron complexes as anolytes for flow battery applications.

Science.gov (United States)

Duarte, Gabriel M; Braun, Jason D; Giesbrecht, Patrick K; Herbert, David E

2017-12-21

Diiminepyridines are a well-known class of "non-innocent" ligands that confer additional redox activity to coordination complexes beyond metal-centred oxidation/reduction. Here, we demonstrate that metal coordination complexes (MCCs) of diiminepyridine (DIP) ligands with iron are suitable anolytes for redox-flow battery applications, with enhanced capacitance and stability compared with bipyridine analogs, and access to storage of up to 1.6 electron equivalents. Substitution of the ligand is shown to be a key factor in the cycling stability and performance of MCCs based on DIP ligands, opening the door to further optimization.

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.

Faradic redox active material of Cu7S4 nanowires with a high conductance for flexible solid state supercapacitors

Science.gov (United States)

Javed, Muhammad Sufyan; Dai, Shuge; Wang, Mingjun; Xi, Yi; Lang, Qiang; Guo, Donglin; Hu, Chenguo

2015-08-01

The exploration of high Faradic redox active materials with the advantages of low cost and low toxicity has been attracting great attention for producing high energy storage supercapacitors. Here, the high Faradic redox active material of Cu7S4-NWs coated on a carbon fiber fabric (CFF) is directly used as a binder-free electrode for a high performance flexible solid state supercapacitor. The Cu7S4-NW-CFF supercapacitor exhibits excellent electrochemical performance such as a high specific capacitance of 400 F g-1 at the scan rate of 10 mV s-1 and a high energy density of 35 Wh kg-1 at a power density of 200 W kg-1, with the advantages of a light weight, high flexibility and long term cycling stability by retaining 95% after 5000 charge-discharge cycles at a constant current of 10 mA. The high Faradic redox activity and high conductance behavior of the Cu7S4-NWs result in a high pseudocapacitive performance with a relatively high specific energy and specific power. Such a new type of pseudocapacitive material of Cu7S4-NWs with its low cost is very promising for actual application in supercapacitors.The exploration of high Faradic redox active materials with the advantages of low cost and low toxicity has been attracting great attention for producing high energy storage supercapacitors. Here, the high Faradic redox active material of Cu7S4-NWs coated on a carbon fiber fabric (CFF) is directly used as a binder-free electrode for a high performance flexible solid state supercapacitor. The Cu7S4-NW-CFF supercapacitor exhibits excellent electrochemical performance such as a high specific capacitance of 400 F g-1 at the scan rate of 10 mV s-1 and a high energy density of 35 Wh kg-1 at a power density of 200 W kg-1, with the advantages of a light weight, high flexibility and long term cycling stability by retaining 95% after 5000 charge-discharge cycles at a constant current of 10 mA. The high Faradic redox activity and high conductance behavior of the Cu7S4-NWs result in

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

Science.gov (United States)

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

2014-03-01

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

A 3.5 V lithium-iodine hybrid redox battery with vertically aligned carbon nanotube current collector.

Science.gov (United States)

Zhao, Yu; Hong, Misun; Bonnet Mercier, Nadège; Yu, Guihua; Choi, Hee Cheul; Byon, Hye Ryung

2014-02-12

A lithium-iodine (Li-I2) cell using the triiodide/iodide (I3(-)/I(-)) redox couple in an aqueous cathode has superior gravimetric and volumetric energy densities (∼ 330 W h kg(-1) and ∼ 650 W h L(-1), respectively, from saturated I2 in an aqueous cathode) to the reported aqueous Li-ion batteries and aqueous cathode-type batteries, which provides an opportunity to construct cost-effective and high-performance energy storage. To apply this I3(-)/I(-) aqueous cathode for a portable and compact 3.5 V battery, unlike for grid-scale storage as general target of redox flow batteries, we use a three-dimensional and millimeter thick carbon nanotube current collector for the I3(-)/I(-) redox reaction, which can shorten the diffusion length of the redox couple and provide rapid electron transport. These endeavors allow the Li-I2 battery to enlarge its specific capacity, cycling retention, and maintain a stable potential, thereby demonstrating a promising candidate for an environmentally benign and reusable portable battery.

The lightest organic radical cation for charge storage in redox flow batteries.

Science.gov (United States)

Huang, Jinhua; Pan, Baofei; Duan, Wentao; Wei, Xiaoliang; Assary, Rajeev S; Su, Liang; Brushett, Fikile R; Cheng, Lei; Liao, Chen; Ferrandon, Magali S; Wang, Wei; Zhang, Zhengcheng; Burrell, Anthony K; Curtiss, Larry A; Shkrob, Ilya A; Moore, Jeffrey S; Zhang, Lu

2016-08-25

In advanced electrical grids of the future, electrochemically rechargeable fluids of high energy density will capture the power generated from intermittent sources like solar and wind. To meet this outstanding technological demand there is a need to understand the fundamental limits and interplay of electrochemical potential, stability, and solubility in low-weight redox-active molecules. By generating a combinatorial set of 1,4-dimethoxybenzene derivatives with different arrangements of substituents, we discovered a minimalistic structure that combines exceptional long-term stability in its oxidized form and a record-breaking intrinsic capacity of 161 mAh/g. The nonaqueous redox flow battery has been demonstrated that uses this molecule as a catholyte material and operated stably for 100 charge/discharge cycles. The observed stability trends are rationalized by mechanistic considerations of the reaction pathways.

Enhancing Specific Energy and Power in Asymmetric Supercapacitors - A Synergetic Strategy based on the Use of Redox Additive Electrolytes

Science.gov (United States)

Singh, Arvinder; Chandra, Amreesh

2016-01-01

The strategy of using redox additive electrolyte in combination with multiwall carbon nanotubes/metal oxide composites leads to a substantial improvements in the specific energy and power of asymmetric supercapacitors (ASCs). When the pure electrolyte is optimally modified with a redox additive viz., KI, ~105% increase in the specific energy is obtained with good cyclic stability over 3,000 charge-discharge cycles and ~14.7% capacitance fade. This increase is a direct consequence of the iodine/iodide redox pairs that strongly modifies the faradaic and non-faradaic type reactions occurring on the surface of the electrodes. Contrary to what is shown in few earlier reports, it is established that indiscriminate increase in the concentration of redox additives will leads to performance loss. Suitable explanations are given based on theoretical laws. The specific energy or power values being reported in the fabricated ASCs are comparable or higher than those reported in ASCs based on toxic acetonitrile or expensive ionic liquids. The paper shows that the use of redox additive is economically favorable strategy for obtaining cost effective and environmentally friendly ASCs. PMID:27184260

Electrochemical studies of redox probes in self-organized lyotropic ...

Indian Academy of Sciences (India)

Administrator

quinone|hydroquinone, methyl viologen and ferrocenemethanol probes in a lyotropic hexagonal columnar phase (H1 phase) using cyclic voltammetry and electrochemical impedance ..... hydrogen bond of hydroquinone during oxidation is.

Energize Electrochemical Double Layer Capacitor by Introducing an Ambipolar Organic Redox Radical in Electrolyte.

Science.gov (United States)

Wang, Yonggang; Hu, Lintong; Zhang, Yue; Shi, Chao; Guo, Kai; Zhai, Tianyou; Li, Huiqiao

2018-05-24

Carbon based electrochemical double layer capacitors (EDLCs) generally exhibit high power and long life, but low energy density/capacitance. Pore/morphology optimization and pseudocapacitive materials modification of carbon materials have been used to improve electrode capacitance, but leading to the consumption of tap density, conductivity and stability. Introducing soluble redox mediators into electrolyte is a promising alternative to improve the capacitance of electrode. However, it is difficult to find one redox mediator that can provide additional capacitance for both positive and negative electrodes simultaneously. Here, an ambipolar organic radical, 2, 2, 6, 6-tetramethylpiperidinyloxyl (TEMPO) is first introduced to the electrolyte, which can substantially contribute additional pseudocapacitance by oxidation at the positive electrode and reduction at the negative electrode simultaneously. The EDLC with TEMPO mediator delivers an energy density as high as 51 Wh kg-1, 2.4 times of the capacitor without TEMPO, and a long cycle stability over 4000 cycles. The achieved results potentially point a new way to improve the energy density of EDLCs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficiency improvement of an all-vanadium redox flow battery by harvesting low-grade heat

Science.gov (United States)

Reynard, Danick; Dennison, C. R.; Battistel, Alberto; Girault, Hubert H.

2018-06-01

Redox flow batteries (RFBs) are rugged systems, which can withstand several thousand cycles and last many years. However, they suffer from low energy density, low power density, and low efficiency. Integrating a Thermally Regenerative Electrochemical Cycle (TREC) into the RFB, it is possible to mitigate some of these drawbacks. The TREC takes advantage of the temperature dependence of the cell voltage to convert heat directly into electrical energy. Here, the performance increase of a TREC-RFB is investigated using two kinds of all-vanadium electrolyte chemistries: one containing a typical concentration of sulfuric acid and one containing a large excess of hydrochloric acid. The results show that the energy density of the system was increased by 1.3Wh L-1 and 0.8Wh L-1, respectively and the overall energy efficiency also increased by 9 and 5 percentage points, respectively. The integration of the heat exchangers necessary to change the battery temperature is readily facilitated by the design of the redox flow battery, which already utilizes fluid circulation loops.

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...

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

KAUST Repository

Liu, Pei

2014-01-28

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

Iron traps terrestrially derived dissolved organic matter at redox interfaces

Science.gov (United States)

Riedel, Thomas; Zak, Dominik; Biester, Harald; Dittmar, Thorsten

2013-01-01

Reactive iron and organic carbon are intimately associated in soils and sediments. However, to date, the organic compounds involved are uncharacterized on the molecular level. At redox interfaces in peatlands, where the biogeochemical cycles of iron and dissolved organic matter (DOM) are coupled, this issue can readily be studied. We found that precipitation of iron hydroxides at the oxic surface layer of two rewetted fens removed a large fraction of DOM via coagulation. On aeration of anoxic fen pore waters, >90% of dissolved iron and 27 ± 7% (mean ± SD) of dissolved organic carbon were rapidly (within 24 h) removed. Using ultra-high-resolution MS, we show that vascular plant-derived aromatic and pyrogenic compounds were preferentially retained, whereas the majority of carboxyl-rich aliphatic acids remained in solution. We propose that redox interfaces, which are ubiquitous in marine and terrestrial settings, are selective yet intermediate barriers that limit the flux of land-derived DOM to oceanic waters. PMID:23733946

pH-Dependent Regulation of the Relaxation Rate of the Radical Anion of the Secondary Quinone Electron Acceptor QB in Photosystem II As Revealed by Fourier Transform Infrared Spectroscopy.

Science.gov (United States)

Nozawa, Yosuke; Noguchi, Takumi

2018-05-15

Photosystem II (PSII) is a protein complex that performs water oxidation using light energy during photosynthesis. In PSII, electrons abstracted from water are eventually transferred to the secondary quinone electron acceptor, Q B , and upon double reduction, Q B is converted to quinol by binding two protons. Thus, excess electron transfer in PSII increases the pH of the stroma. In this study, to investigate the pH-dependent regulation of the electron flow in PSII, we have estimated the relaxation rate of the Q B - radical anion in the pH region between 5 and 8 by direct monitoring of its population using light-induced Fourier transform infrared difference spectroscopy. The decay of Q B - by charge recombination with the S 2 state of the water oxidation center in PSII membranes was shown to be accelerated at higher pH, whereas that of Q A - examined in the presence of a herbicide was virtually unaffected at pH ≤7.5 and slightly slowed at pH 8. These observations were consistent with the previous studies that included rather indirect monitoring of the Q B - and Q A - decays using fluorescence detection. The accelerated relaxation of Q B - was explained by the shift of a redox equilibrium between Q A - and Q B - to the Q A - side due to the decrease in the redox potential of Q B at higher pH, which is induced by deprotonation of a single amino acid residue near Q B . It is proposed that this pH-dependent Q B - relaxation is one of the mechanisms of electron flow regulation in PSII for its photoprotection.

On the activation of Pt/Al2O3 catalysts in HC-SCR by sintering. Determination of redox-active sites using Multitrack

International Nuclear Information System (INIS)

Vaccaro, A.R.; Mul, G.; Moulijn, J.A.; Perez-Ramirez, J.

2003-01-01

A highly dispersed Pt/Al 2 O 3 catalyst was used for the selective catalytic reduction of NO x using propene (HC-SCR). Contact with the reaction gas mixture led to a significant activation of the catalyst at temperatures above 523K. According to CO chemisorption data and HRTEM analysis, Pt particles on the activated catalyst had sintered. The redox behavior of the fresh and sintered catalysts was investigated using Multitrack, a TAP-like pulse reactor. If Pt particles on the catalyst are highly dispersed (average size below =2nm), only a small part (=10%) of the total number of Pt surface sites as determined by CO chemisorption (Pt surf ) participates in H 2 /O 2 redox cycles (Pt surf,redox ) in Multitrack conditions. For a sintered catalyst, with an average particle size of 2.7nm, the number of Pt surf and Pt surf,redox sites are in good agreement. Similar results were obtained for both catalysts using NO as the oxidant. The low number of Pt surf,redox sites on highly dispersed Pt/Al 2 O 3 is explained by the presence of a kinetically more stable-probably ionic-form of Pt-O bonds on all surface sites of the smaller Pt particles, including corner, edge and terrace sites. When the average particle size shifts to =2.7nm, the kinetic stability of all Pt-O bonds is collectively decreased, enabling the participation of all Pt surface sites in the redox cycles. A linear correlation between the NO x conversion in HC-SCR, and the amount of Pt surf,redox was found. This suggests that redox-active Pt sites are necessary for catalytic activity. In addition, the correlation could be significantly improved by assuming that Pt surf,terrace sites of the particles larger than 2.7nm are mainly responsible for HC-SCR activity in steady state conditions. Implications of these results for the pathway of HC-SCR over Pt catalysts are discussed

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.

Biofabricated film with enzymatic and redox-capacitor functionalities to harvest and store electrons

International Nuclear Information System (INIS)

Liba, Benjamin D; Kim, Eunkyoung; Martin, Alexandra N; Liu Yi; Bentley, William E; Payne, Gregory F

2013-01-01

Exciting opportunities in bioelectronics will be facilitated by materials that can bridge the chemical logic of biology and the digital logic of electronics. Here we report the fabrication of a dual functional hydrogel film that can harvest electrons from its chemical environment and store these electrons by switching the film's redox-state. The hydrogel scaffold was formed by the anodic deposition of the aminopolysaccharide chitosan. Electron-harvesting function was conferred by co-depositing the enzyme glucose dehydrogenase (GDH) with chitosan. GDH catalyzes the transfer of electrons from glucose to the soluble redox-shuttle NADP + . Electron-storage function was conferred by the redox-active food phenolic chlorogenic acid (CA) that was enzymatically grafted to the chitosan scaffold using tyrosinase. The grafted CA undergoes redox-cycling reactions with NADPH resulting in the net transfer of electrons to the film where they are stored in the reduced state of CA. The individual and dual functionalities of these films were demonstrated experimentally. There are three general conclusions from this proof-of-concept study. First, enzymatically-grafted catecholic moieties confer redox-capacitor function to the chitosan scaffold. Second, biological materials (i.e. chitosan and CA) and mechanisms (i.e. tyrosinase-mediated grafting) allow the reagentless fabrication of functional films that should be environmentally-friendly, safe and potentially even edible. Finally, the film's ability to mediate the transfer of electrons from a biological metabolite to an electrode suggests an approach to bridge the chemical logic of biology with the digital logic of electronics. (paper)

A study of tiron in aqueous solutions for redox flow battery application

International Nuclear Information System (INIS)

Xu Yan; Wen Yuehua; Cheng Jie; Cao Gaoping; Yang Yusheng

2010-01-01

In this study, the electrochemical behavior of tiron in aqueous solutions and the influence of pH were investigated. A change of pH mainly produces the following results. In acidic solutions of pH below 4, the electrode reaction of tiron exhibits a simple process at a relatively high potential with a favorable quasi-reversibility. The tiron redox reaction exhibits fast electrode kinetics and a diffusion-controlled process. In solutions of pH above 4, the electrode reaction of tiron tends to be complicated. Thus, acidic aqueous solutions of pH below 4 are favorable for the tiron as active species of a redox flow battery (RFB). Constant-current electrolysis shows that a part of capacity is irreversible and the structure of tiron is changed for the first electrolysis, which may result from an ECE process for the tiron electro-oxidation. Thus, the tiron needs an activation process for the application of a RFB. Average coulombic and energy efficiencies of the tiron/Pb battery are 93 and 82%, respectively, showing that self-discharge is small during the short-term cycling. The preliminary exploration shows that the tiron is electrochemically promising for redox flow battery application.

A highly reversible anthraquinone-based anolyte for alkaline aqueous redox flow batteries

Science.gov (United States)

Cao, Jianyu; Tao, Meng; Chen, Hongping; Xu, Juan; Chen, Zhidong

2018-05-01

The development of electroactive organic materials for use in aqueous redox flow battery (RFB) electrolytes is highly attractive because of their structural flexibility, low cost and sustainability. Here, we report on a highly reversible anthraquinone-based anolyte (1,8-dihydroxyanthraquinone, 1,8-DHAQ) for alkaline aqueous RFB applications. Electrochemical measurements reveal the substituent position of hydroxyl groups for DHAQ isomers has a significant impact on the redox potential, electrochemical reversibility and water-solubility. 1,8-DHAQ shows the highest redox reversibility and rapidest mass diffusion among five isomeric DHAQs. The alkaline aqueous RFB using 1,8-DHAQ as the anolyte and potassium ferrocyanide as the catholyte yields open-circuit voltage approaching 1.1 V and current efficiency and capacity retention exceeding 99.3% and 99.88% per cycle, respectively. This aqueous RFB produces a maximum power density of 152 mW cm-2 at 100% SOC and 45 °C. Choline hydroxide was used as a hydrotropic agent to enhance the water-solubility of 1,8-DHAQ. 1,8-DHAQ has a maximum solubility of 3 M in 1 M KOH with 4 M choline hydroxide.

An FeIII Azamacrocyclic Complex as a pH-Tunable Catholyte and Anolyte for Redox-Flow Battery Applications.

Science.gov (United States)

Tsitovich, Pavel B; Kosswattaarachchi, Anjula M; Crawley, Matthew R; Tittiris, Timothy Y; Cook, Timothy R; Morrow, Janet R

2017-11-02

A reversible Fe 3+ /Fe 2+ redox couple of an azamacrocyclic complex is evaluated as an electrolyte with a pH-tunable potential range for aqueous redox-flow batteries (RFBs). The Fe III complex is formed by 1,4,7-triazacyclononane (TACN) appended with three 2-methyl-imidazole donors, denoted as Fe(Tim). This complex exhibits pH-sensitive redox couples that span E 1/2 (Fe 3+ /Fe 2+ )=317 to -270 mV vs. NHE at pH 3.3 and pH 12.8, respectively. The 590 mV shift in potential and kinetic inertness are driven by ionization of the imidazoles at various pH values. The Fe 3+ /Fe 2+ redox is proton-coupled at alkaline conditions, and bulk electrolysis is non-destructive. The electrolyte demonstrates high charge/discharge capacities at both acidic and alkaline conditions throughout 100 cycles. Given its tunable redox, fast electrochemical kinetics, exceptional stability/cyclability, this complex is promising for the design of aqueous RFB catholytes and anolytes that utilize the earth-abundant element iron. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new class of solid oxide metal-air redox batteries for advanced stationary energy storage

Science.gov (United States)

Zhao, Xuan

Cost-effective and large-scale energy storage technologies are a key enabler of grid modernization. Among energy storage technologies currently being researched, developed and deployed, rechargeable batteries are unique and important that can offer a myriad of advantages over the conventional large scale siting- and geography- constrained pumped-hydro and compressed-air energy storage systems. However, current rechargeable batteries still need many breakthroughs in material optimization and system design to become commercially viable for stationary energy storage. This PhD research project investigates the energy storage characteristics of a new class of rechargeable solid oxide metal-air redox batteries (SOMARBs) that combines a regenerative solid oxide fuel cell (RSOFC) and hydrogen chemical-looping component. The RSOFC serves as the "electrical functioning unit", alternating between the fuel cell and electrolysis mode to realize discharge and charge cycles, respectively, while the hydrogen chemical-looping component functions as an energy storage unit (ESU), performing electrical-chemical energy conversion in situ via a H2/H2O-mediated metal/metal oxide redox reaction. One of the distinctive features of the new battery from conventional storage batteries is the ESU that is physically separated from the electrodes of RSOFC, allowing it to freely expand and contract without impacting the mechanical integrity of the entire battery structure. This feature also allows an easy switch in the chemistry of this battery. The materials selection for ESU is critical to energy capacity, round-trip efficiency and cost effectiveness of the new battery. Me-MeOx redox couples with favorable thermodynamics and kinetics are highly preferable. The preliminary theoretical analysis suggests that Fe-based redox couples can be a promising candidate for operating at both high and low temperatures. Therefore, the Fe-based redox-couple systems have been selected as the baseline for this

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.)

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.

Environmental Risk of Metal Mining Contaminated River Bank Sediment at Redox-Transitional Zones

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Sarah F. L. Lynch

2014-01-01

Full Text Available Diffuse metal pollution from mining impacted sediment is widely recognised as a potential source of contamination to river systems and may significantly hinder the achievement of European Union Water Framework Directive objectives. Redox-transitional zones that form along metal contaminated river banks as a result of flood and drought cycles could cause biogeochemical changes that alter the behaviour of polyvalent metals iron and manganese and anions such as sulphur. Trace metals are often partitioned with iron, manganese and sulphur minerals in mining-contaminated sediment, therefore the dissolution and precipitation of these minerals may influence the mobility of potentially toxic trace metals. Research indicates that freshly precipitated metal oxides and sulphides may be more “reactive” (more adsorbent and prone to dissolution when conditions change than older crystalline forms. Fluctuations at the oxic-anoxic interface brought about through changes in the frequency and duration of flood and drought episodes may therefore influence the reactivity of secondary minerals that form in the sediment and the flux of dissolved trace metal release. UK climate change models predict longer dry periods for some regions, interspersed with higher magnitude flood events. If we are to fully comprehend the future environmental risk these climate change events pose to mining impacted river systems it is recommended that research efforts focus on identifying the primary controls on trace metal release at the oxic-anoxic interface for flood and drought cycles of different duration and frequency. This paper critically reviews the literature regarding biogeochemical processes that occur at different temporal scales during oxic, reducing and dry periods and focuses on how iron and sulphur based minerals may alter in form and reactivity and influence the mobility of trace metal contaminants. It is clear that changes in redox potential can alter the composition

Imaging dynamic redox processes with genetically encoded probes.

Science.gov (United States)

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

2014-08-01

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

Brassinosteroid-induced CO{sub 2} assimilation is associated with increased stability of redox-sensitive photosynthetic enzymes in the chloroplasts in cucumber plants

Energy Technology Data Exchange (ETDEWEB)

Jiang, Yu Ping; Cheng, Fei; Zhou, Yan Hong; Xia, Xiao Jian; Mao, Wei Hua; Shi, Kai [Department of Horticulture, Zijingang Campus, Zhejiang University, Yuhangtang Road 866, Hangzhou 310058 (China); Chen, Zhi Xiang [Department of Horticulture, Zijingang Campus, Zhejiang University, Yuhangtang Road 866, Hangzhou 310058 (China); Department of Botany and Plant Pathology, Purdue University, West Lafayette, IN 47907-2054 (United States); Yu, Jing Quan, E-mail: jqyu@zju.edu.cn [Department of Horticulture, Zijingang Campus, Zhejiang University, Yuhangtang Road 866, Hangzhou 310058 (China); Key Laboratory of Horticultural Plants Growth, Development and Quality Improvement, Ministry of Agriculture of China, Yuhangtang Road 866, Hangzhou 310058 (China)

2012-09-28

Highlights: Black-Right-Pointing-Pointer Activity of certain Calvin cycle enzymes and CO{sub 2} assimilation are induced by BRs. Black-Right-Pointing-Pointer BRs upregulate the activity of the ascorbate-glutathione cycle in the chloroplasts. Black-Right-Pointing-Pointer BRs increase the chloroplast thiol reduction state. Black-Right-Pointing-Pointer A BR-induced reducing environment increases the stability of photosynthetic enzymes. -- Abstract: Brassinosteroids (BRs) play important roles in plant growth, development, photosynthesis and stress tolerance; however, the mechanism underlying BR-enhanced photosynthesis is currently unclear. Here, we provide evidence that an increase in the BR level increased the quantum yield of PSII, activities of Rubisco activase (RCA) and fructose-1,6-bisphosphatase (FBPase), and CO{sub 2} assimilation. BRs upregulated the transcript levels of genes and activity of enzymes involved in the ascorbate-glutathione cycle in the chloroplasts, leading to an increased ratio of reduced (GSH) to oxidized (GSSG) glutathione in the chloroplasts. An increased GSH/GSSG ratio protected RCA from proteolytic digestion and increased the stability of redox-sensitive enzymes in the chloroplasts. These results strongly suggest that BRs are capable of regulating the glutathione redox state in the chloroplasts through the activation of the ascorbate-glutathione cycle. The resulting increase in the chloroplast thiol reduction state promotes CO{sub 2} assimilation, at least in part, by enhancing the stability and activity of redox-sensitive photosynthetic enzymes through post-translational modifications.

Redox Reaction in Silicate Melts Monitored by ''Static'' In-Situ Fe K-Edge XANES up to 1180 deg. C

International Nuclear Information System (INIS)

Wilke, Max; Partzsch, Georg M.; Welter, Edmund; Farges, Francois

2007-01-01

A new experimental setup to measure in-situ kinetics of redox reactions in silicate melts is presented. To study the progress of the Fe-redox reaction, the variation of the signal is recorded at an energy, where the difference between the spectra of the oxidized and reduced Fe in the melt is largest (''static XANES''). To control the redox conditions, the gas atmosphere could be changed between to types of gases using computer-controlled valves (N2:H2 and air, respectively). In this way, a number of reduction/oxidation cycles can be monitored in-situ and continuously. Applied at the Fe K-edge in molten silicates, we obtained a set of high quality data, which includes the very first steps of the redox reaction. An Avrami-type equation is used to investigate rate-controlling parameters for the iron oxidation/reduction kinetics for two melts (basaltic and Na trisilicate) for temperatures up to 1180 deg. C

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

OpenAIRE

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

2017-01-01

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

Proliferation and differentiation of Trypanosoma cruzi inside its vector have a new trigger: redox status.

Directory of Open Access Journals (Sweden)

Natália P Nogueira

Full Text Available Trypanosoma cruzi proliferate and differentiate inside different compartments of triatomines gut that is the first environment encountered by T. cruzi. Due to its complex life cycle, the parasite is constantly exposed to reactive oxygen species (ROS. We tested the influence of the pro-oxidant molecules H2O2 and the superoxide generator, Paraquat, as well as, metabolism products of the vector, with distinct redox status, in the proliferation and metacyclogenesis. These molecules are heme, hemozoin and urate. We also tested the antioxidants NAC and GSH. Heme induced the proliferation of epimastigotes and impaired the metacyclogenesis. β-hematin, did not affect epimastigote proliferation but decreased parasite differentiation. Conversely, we show that urate, GSH and NAC dramatically impaired epimastigote proliferation and during metacyclogenesis, NAC and urate induced a significant increment of trypomastigotes and decreased the percentage of epimastigotes. We also quantified the parasite loads in the anterior and posterior midguts and in the rectum of the vector by qPCR. The treatment with the antioxidants increased the parasite loads in all midgut sections analyzed. In vivo, the group of vectors fed with reduced molecules showed an increment of trypomastigotes and decreased epimastigotes when analyzed by differential counting. Heme stimulated proliferation by increasing the cell number in the S and G2/M phases, whereas NAC arrested epimastigotes in G1 phase. NAC greatly increased the percentage of trypomastigotes. Taken together, these data show a shift in the triatomine gut microenvironment caused by the redox status may also influence T. cruzi biology inside the vector. In this scenario, oxidants act to turn on epimastigote proliferation while antioxidants seem to switch the cycle towards metacyclogenesis. This is a new insight that defines a key role for redox metabolism in governing the parasitic life cycle.

Redox poly[Ni(saldMp)] modified activated carbon electrode in electrochemical supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Gao Fei [Department of Physical Chemistry, University of Science and Technology Beijing, 30 Xueyuan Road, Haidian District, Beijing 100083 (China); Li Jianling, E-mail: lijianling@ustb.edu.c [Department of Physical Chemistry, University of Science and Technology Beijing, 30 Xueyuan Road, Haidian District, Beijing 100083 (China); Zhang Yakun; Wang Xindong [Department of Physical Chemistry, University of Science and Technology Beijing, 30 Xueyuan Road, Haidian District, Beijing 100083 (China); Kang Feiyu [Department of Material Science and Engineering, Tsinghua University, Beijing 100083 (China)

2010-08-01

The complex (2,2-dimethyl-1,3-propanediaminebis(salicylideneaminato))-nickel(II), [Ni(saldMp)], was oxidatively electropolymerized on activated carbon (AC) electrode in acetonitrile solution. The poly[Ni(saldMp)] presented an incomplete coated film on the surface of carbon particles of AC electrode by field emission scanning electron microscopy. The electrochemical behaviors of poly[Ni(saldMp)] modified activated carbon (PAC) electrode were evaluated in different potential ranges by cyclic voltammetry. Counterions and solvent swelling mainly occurred up to 0.6 V for PAC electrode by the comparison of D{sup 1/2}C values calculated from chronoamperometry experiments. Both the Ohmic resistance and Faraday resistance of PAC electrode gradually approached to those of AC electrode when its potential was ranging from 1.2 V to 0.0 V. Galvanostatic charge/discharge experiments indicated that both the specific capacitance and energy density were effectively improved by the reversible redox reaction of poly[Ni(saldMp)] film under the high current density up to 10 mA cm{sup -2} for AC electrode. The specific capacitance of PAC electrode decreased during the first 50 cycles but thereafter it remained constant for the next 200 cycles. This study showed the redox polymer may be an attractive material in supercapacitors.

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.

Application of a redox gradostat reactor for assessing rhizosphere microorganism activity on lambda-cyhalothrin.

Science.gov (United States)

Peacock, T J; Mikell, A T; Moore, M T; Smith, S

2014-03-01

Bacterial activity on pesticides can lead to decreased toxicity or persistence in aquatic systems. Rhizosphere activity is difficult to measure in situ. To mimic rhizosphere properties of the soft rush, Juncus effusus, a single-stage gradostat reactor was developed to study cycling of lambda-cyhalothrin by rhizobacteria and the effects of Fe(III) and citrate, both common in wetland soil, on lambda-cyhalothrin degradation. Redox gradient changes, greater than ± 10 mV, were apparent within days 5-15 both in the presence and absence of ferric citrate. Through the production of a redox gradient (p < 0.05) by rhizobacteria and the ability to measure pesticide loss over time (p < 0.05), reactors were useful in expanding knowledge on this active environment.

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

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Hossain eSazzad

2016-05-01

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

Influence of iron redox cycling on organo-mineral associations in arctic tundra soils

Science.gov (United States)

Herndon, E.; AlBashaireh, A.; Duroe, K.; Singer, D. M.

2016-12-01

Geochemical interactions between soil organic matter and minerals influence decomposition in many environments but remain poorly understood in arctic tundra systems. In tundra soils that are periodically to persistently saturated, the accumulation of iron oxyhydroxides and organo-iron precipitates at redox interfaces may inhibit decomposition by binding organic molecules and protecting them from microbial degradation. Here, we couple synchrotron-source spectroscopic techniques with chemical sequential extractions and physical density fractionations to evaluate the spatial distribution and speciation of Fe-bearing phases and associated organic matter in organic and mineral horizons of the seasonally thawed active layer in tundra soils from northern Alaska. Mineral-associated organic matter comprised 63 ± 9% of soil organic carbon stored in the active layer of ice wedge polygons. Ferrous iron produced in anoxic mineral horizons diffused upwards and precipitated as poorly-crystalline oxyhydroxides and organic-bound Fe(III) in the organic horizons. Ferrihydrite and goethite were present as coatings on mineral grains and plant debris and in aggregates with clays and particulate organic matter. Organic matter released through acid-dissolution of iron oxides may represent a small pool of readily-degradable organic molecules temporarily stabilized by sorption to iron oxyhydroxide surfaces, while larger quantities of particulate organic carbon and humic-like substances may be physically protected from decomposition by Fe-oxide coatings and aggregation. We conclude that formation of poorly-crystalline and crystalline iron oxides at redox interfaces contributes to mineral protection of organic matter through sorption, aggregation, and co-precipitation reactions. Further study of organo-mineral associations is necessary to determine the net impact of mineral-stabilization on carbon storage in rapidly warming arctic ecosystems.

Journal of Biosciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Keywords. Antioxidant; biofertilizer and biocontrol agent; biosensor; pharmacological agent; protein kinase inducer; pyrroloquinoline-quinone. Abstract. Pyrroloquinoline-quinine (PQQ) was initially characterized as a redox cofactor for membrane-bound dehydrogenases in the bacterial system. Subsequently, PQQ was ...

Calcium mobilization by quinones and other free radical generating systems in rat hepatocytes

International Nuclear Information System (INIS)

Chen, E.C.; Chan, T.M.

1987-01-01

Using isolated rat hepatocytes, sublethal concentrations of quinones and other free radical generating systems were used to test the role of extracellular calcium (Ca) in activating glycogen phosphorylase and intracellular Ca mobilization. The α-agonist phenylephrine (Phe) was used for comparison. The EC50's were: Phe = 2.6 x 10 -7 M, menadione (K 3 ) = 4.5 x 10 -5 M, dicumarol = 2 x 10 -5 M. In normal Ca buffer, activation by K 3 was slower than Phe, being maximal at 2' but more sustained. Dicumarol and tert-butyl hydroperoxide (t-BH) activated phosphorylase similarly. The xanthine-xanthine oxidase (X-XO) system stimulated activation similar to K 3 . Dicumarol greatly augmented phosphorylase activation by K 3 but had no effect on Phe action. Depletion of extracellular Ca abolished Phe action, markedly diminished t-BH and dicumarol, but had no effect on K 3 or X-XO activation of phosphorylase. Ca efflux exchange measured in 45 Ca preloaded cells were stimulated equally by Phe, K 3 , dicumarol, or K 3 + dicumarol in the presence of extracellular Ca. Absence of extracellular Ca abolished Phe effect but minimally affected stimulation by K 3 or K 3 + dicumarol. These data suggest that activation of glycogen phosphorylase by sublethal doses of quinones may not reflect the degree and the mechanism of intracellular Ca mobilization

The role of certain infauna and vascular plants in the mediation of redox reactions in marine sediments

Science.gov (United States)

Hines, Mark E.

1992-01-01

The mechanisms by which certain animals and plants affect redox processes in sediments was examined by studying three environments: (1) subtidal sediments dominated by the deposit-feeding polychaete Heteromastus filiformis; (2) a saltmarsh inhabited by the tall form of Spartina alterniflora; and (3) tropical carbonate sediments inhabited by three species of seagrasses. S-35-sulfide production rates were compared to pool sizes of dissolved sulfide and dissolved iron. In all of the sediments studied, rates of sulfide reduction were enhanced by macroorganisms while the rate of turnover of dissolved sulfide increased. The polychaete enhanced microbial activity and redox cycling primarily by subducting particles of organic matter and oxidized iron during sediment reworking. The Spartina species enhanced anaerobic activity by transporting primarily dissolved organic matter and oxidants. Although the final result of both animal and plant activities was the enhancement of sub-surface cycling of sulfur and iron, decreased dissolved sulfide and increased dissolved iron concentrations, the mechanisms which produced these results differed dramatically.

Enzymology and ecology of the nitrogen cycle.

Science.gov (United States)

Martínez-Espinosa, Rosa María; Cole, Jeffrey A; Richardson, David J; Watmough, Nicholas J

2011-01-01

The nitrogen cycle describes the processes through which nitrogen is converted between its various chemical forms. These transformations involve both biological and abiotic redox processes. The principal processes involved in the nitrogen cycle are nitrogen fixation, nitrification, nitrate assimilation, respiratory reduction of nitrate to ammonia, anaerobic ammonia oxidation (anammox) and denitrification. All of these are carried out by micro-organisms, including bacteria, archaea and some specialized fungi. In the present article, we provide a brief introduction to both the biochemical and ecological aspects of these processes and consider how human activity over the last 100 years has changed the historic balance of the global nitrogen cycle.

Redox and Non-Redox Mechanism of In Vitro Cyclooxygenase Inhibition by Natural Quinones

Czech Academy of Sciences Publication Activity Database

Landa, Přemysl; Kutil, Zsófia; Tremml, V.; Vuorien, A.; Malík, J.; Dvořáková, Marcela; Maršík, Petr; Kokoška, L.; Přibylová, Marie; Schuster, D.; Vaněk, Tomáš

2012-01-01

Roč. 78, č. 4 (2012), s. 326-333 ISSN 0032-0943 R&D Projects: GA ČR GP525/09/P528; GA MŠk ME08070 Grant - others:GA ČR(CZ) GA525/08/1179 Program:GA Institutional research plan: CEZ:AV0Z50380511 Keywords : inflammation * prostaglandin synthase * structure-activity relationship Subject RIV: GM - Food Processing Impact factor: 2.348, year: 2012

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

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

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

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

Improved radical stability of viologen anolytes in aqueous organic redox flow batteries.

Science.gov (United States)

Hu, Bo; Tang, Yijie; Luo, Jian; Grove, Grant; Guo, Yisong; Liu, T Leo

2018-05-09

A high voltage (1.38 V) total organic aqueous redox flow battery is reported using 1,1'-bis[3-(trimethylammonio)propyl]-4,4'-bipyridinium tetrachloride ((NPr)2V) as an anolyte and 4-trimethylammonium-TEMPO chloride (NMe-TEMPO) as a catholyte. The exceptional radical stability of [(NPr)2V]+˙ enabled the flow battery in achieving 97.48% capacity retention for 500 cycles and a power density of 128.2 mW cm-2.

Impact on the Fe redox cycling of organic ligands released by Synechococcus PCC 7002, under different iron fertilization scenarios. Modeling approach

Science.gov (United States)

Samperio-Ramos, Guillermo; González-Dávila, Melchor; Santana-Casiano, J. Magdalena

2018-06-01

The kinetics of Fe redox transformations are of crucial importance in determining the bioavailability of iron, due to inorganic Fe(II) and Fe weakly organic complexes being the most easily assimilated species by phytoplankton. The role played by the natural organic ligands excreted by the cyanobacteria Synecococcus PCC 7002 on the iron redox chemistry was studied at different stages of growth, considering changes in the organic exudation of the cyanobacteria, associated with growth under two different scenarios of iron availability. The oxidation/reduction processes of iron were studied at nanomolar levels and under different physicochemical conditions of pH (7.2- 8.2), temperature (5- 35 °C) and salinity (10- 37). The presence of natural organic exudates of Synechococcus affected the redox behavior of iron. A pH-dependent and photo-induced Fe(III) reduction process was detected in the presence of exudates produced under Fe-Low conditions. Photolytic reactions also modified the reactivity of those exudates with respect to Fe(II), increasing its lifetime in seawater. Without light mediated processes, organic ligands excreted under iron deficient conditions intensified the Fe(II) oxidation at pH redox constants between iron and the major ligands present in solution. Two organic type ligands for the exudates of Synechococcus PCC 7002, with different iron-chelation properties were included in the model. The Fe(II) speciation was radically affected when organic ligands were considered. The individual contributions to the overall Fe(II) oxidation rate demonstrated that these organic ligands played a key role in the oxidation process, although their contributions were dependent on the prescribed iron conditions. The study, therefore, suggests that the variability in the composition and nature of organic exudates released, due to iron availability conditions, might determine the redox behaviour of iron in seawater.

Redox Biology in Neurological Function, Dysfunction, and Aging.

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Franco, Rodrigo; Vargas, Marcelo R

2018-04-23

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

Exercise redox biochemistry: Conceptual, methodological and technical recommendations

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James N. Cobley

2017-08-01

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

Analytical redox reactions and redox potentials of tungsten and its concomitants

Energy Technology Data Exchange (ETDEWEB)

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

1985-01-01

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

Analytical redox reactions and redox potentials of tungsten and its concomitants

International Nuclear Information System (INIS)

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

1985-01-01

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

All-Fullerene-Based Cells for Nonaqueous Redox Flow Batteries.

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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.

Quinone-dependent D-lactate dehydrogenase Dld (Cg1027 is essential for growth of Corynebacterium glutamicum on D-lactate

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Oikawa Tadao

2010-12-01

Full Text Available Abstract Background Corynebacterium glutamicum is able to grow with lactate as sole or combined carbon and energy source. Quinone-dependent L-lactate dehydrogenase LldD is known to be essential for utilization of L-lactate by C. glutamicum. D-lactate also serves as sole carbon source for C. glutamicum ATCC 13032. Results Here, the gene cg1027 was shown to encode the quinone-dependent D-lactate dehydrogenase (Dld by enzymatic analysis of the protein purified from recombinant E. coli. The absorption spectrum of purified Dld indicated the presence of FAD as bound cofactor. Inactivation of dld resulted in the loss of the ability to grow with D-lactate, which could be restored by plasmid-borne expression of dld. Heterologous expression of dld from C. glutamicum ATCC 13032 in C. efficiens enabled this species to grow with D-lactate as sole carbon source. Homologs of dld of C. glutamicum ATCC 13032 are not encoded in the sequenced genomes of other corynebacteria and mycobacteria. However, the dld locus of C. glutamicum ATCC 13032 shares 2367 bp of 2372 bp identical nucleotides with the dld locus of Propionibacterium freudenreichii subsp. shermanii, a bacterium used in Swiss-type cheese making. Both loci are flanked by insertion sequences of the same family suggesting a possible event of horizontal gene transfer. Conclusions Cg1067 encodes quinone-dependent D-lactate dehydrogenase Dld of Corynebacterium glutamicum. Dld is essential for growth with D-lactate as sole carbon source. The genomic region of dld likely has been acquired by horizontal gene transfer.

Engineered Proteins: Redox Properties and Their Applications

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

2012-01-01

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

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

Czech Academy of Sciences Publication Activity Database

Heyrovská, Raji

2010-01-01

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

Simultaneous anionic and cationic redox

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Jung, Sung-Kyun; Kang, Kisuk

2017-12-01

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

Membranes for Redox Flow Battery Applications

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

2012-01-01

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

Membranes for redox flow battery applications.

Science.gov (United States)

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

2012-06-19

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

Membranes for Redox Flow Battery Applications

Directory of Open Access Journals (Sweden)

Maria Skyllas-Kazacos

2012-06-01

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

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

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

2015-06-11

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

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

International Nuclear Information System (INIS)

Huang Qizhao; Wang Qing

2016-01-01

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

Thiol/disulfide redox states in signaling and sensing

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Go, Young-Mi; Jones, Dean P.

2015-01-01

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

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.

Reversible anionic redox chemistry in high-capacity layered-oxide electrodes

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Sathiya, M.; Rousse, G.; Ramesha, K.; Laisa, C. P.; Vezin, H.; Sougrati, M. T.; Doublet, M.-L.; Foix, D.; Gonbeau, D.; Walker, W.; Prakash, A. S.; Ben Hassine, M.; Dupont, L.; Tarascon, J.-M.

2013-09-01

Li-ion batteries have contributed to the commercial success of portable electronics and may soon dominate the electric transportation market provided that major scientific advances including new materials and concepts are developed. Classical positive electrodes for Li-ion technology operate mainly through an insertion-deinsertion redox process involving cationic species. However, this mechanism is insufficient to account for the high capacities exhibited by the new generation of Li-rich (Li1+xNiyCozMn(1-x-y-z)O2) layered oxides that present unusual Li reactivity. In an attempt to overcome both the inherent composition and the structural complexity of this class of oxides, we have designed structurally related Li2Ru1-ySnyO3 materials that have a single redox cation and exhibit sustainable reversible capacities as high as 230 mA h g-1. Moreover, they present good cycling behaviour with no signs of voltage decay and a small irreversible capacity. We also unambiguously show, on the basis of an arsenal of characterization techniques, that the reactivity of these high-capacity materials towards Li entails cumulative cationic (Mn+→M(n+1)+) and anionic (O2-→O22-) reversible redox processes, owing to the d-sp hybridization associated with a reductive coupling mechanism. Because Li2MO3 is a large family of compounds, this study opens the door to the exploration of a vast number of high-capacity materials.

Advanced oxidation of benzene, toluene, ethylbenzene and xylene isomers (BTEX) by Trametes versicolor.

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Aranda, Elisabet; Marco-Urrea, Ernest; Caminal, Gloria; Arias, María E; García-Romera, Inmaculada; Guillén, Francisco

2010-09-15

Advanced oxidation of benzene, toluene, ethylbenzene, and o-, m-, and p-xylene (BTEX) by the extracellular hydroxyl radicals (*OH) generated by the white-rot fungus Trametes versicolor is for the first time demonstrated. The production of *OH was induced by incubating the fungus with 2,6-dimethoxy-1,4-benzoquinone (DBQ) and Fe3+-EDTA. Under these conditions, *OH were generated through DBQ redox cycling catalyzed by quinone reductase and laccase. The capability of T. versicolor growing in malt extract medium to produce *OH by this mechanism was shown during primary and secondary metabolism, and was quantitatively modulated by the replacement of EDTA by oxalate and Mn2+ addition to DBQ incubations. Oxidation of BTEX was observed only under *OH induction conditions. *OH involvement was inferred from the high correlation observed between the rates at which they were produced under different DBQ redox cycling conditions and those of benzene removal, and the production of phenol as a typical hydroxylation product of *OH attack on benzene. All the BTEX compounds (500 microM) were oxidized at a similar rate, reaching an average of 71% degradation in 6 h samples. After this time oxidation stopped due to O2 depletion in the closed vials used in the incubations. Copyright 2010 Elsevier B.V. All rights reserved.

Vitamin E and vitamin E-quinone levels in red blood cells and plasma of newborn infants and their mothers.

Science.gov (United States)

Jain, S K; Wise, R; Bocchini, J J

1996-02-01

Vitamin E is a physiological antioxidant and protects cell membranes from oxidative damage. This study has determined whether vitamin E level in RBC of newborns has any relationship with its level in their mothers. We have also examined levels of vitamin E and vitamin E-quinone, an oxidized product of vitamin E, in paired samples of red blood cells (RBC) and plasma of newborns and their mothers. Blood was collected from 26 mothers and their full-term placental cords at delivery. Vitamin E and vitamin E-quinone levels were determined in RBC and plasma by HPLC. Newborn-plasma had significantly lower vitamin E levels compared with maternal-plasma both when expressed as nmole/ml (5.5+/-0.4 vs 26.1+/-1.1, p = 0.0001) or nmole/mumole total lipids (1.9+/-0.1 vs 2.6+/-0.1, p = 0.0001). Vitamin E level in the newborn-RBC was similar to that of maternal-RBC when expressed as nmole/ml packed cells (2.77+/-0.14 vs 2.95+/-0.13), but was significantly lower when expressed as nmole/mumole total lipids (0.56+/-0.03 vs 0.64+/-0.04, p = 0.03) from that of maternal-RBC. Vitamin E-quinone levels are significantly elevated in newborns compared with their mothers both in RBC (29.4+/-2.1 vs 24.1+/-1.2, p = 0.04) and plasma (39.9+/-5.3 vs 25.3+/-4.2, p = 0.006) when expressed as nmole/mmole total lipids but not when expressed as nmole/ml. There was a significant correlation of vitamin E between newborn-plasma and newborn-RBC (r = 0.65, p = 0.0002 for nmole per ml packed RBC;r = 0.63, p = 0.0007 for nmole per mumole total lipids). The relationship between maternal plasma and newborn plasma was significant when vitamin E was normalized with nmole/mumole total lipid (r = 0.54, p = 0.007 but not when expressed as nmole/ml (r = 0.09, p = 0.64). However, vitamin E in the RBC of maternal and newborn had significant correlation when expressed as per ml packed cells (r = 0.61, p = 0.001) and per total lipid (r = 0.46, p = 0.02). There was no relationship of vitamin E-quinone levels between RBC and