Investigation on the electrode process of the Mn(II)/Mn(III) couple in redox flow battery

International Nuclear Information System (INIS)

Xue Fangqin; Wang Yongliang; Wang Wenhong; Wang Xindong

2008-01-01

The Mn(II)/Mn(III) couple has been recognized as a potential anode for redox flow batteries to take the place of the V(IV)/V(V) in all-vanadium redox battery (VRB) and the Br 2 /Br - in sodium polysulfide/bromine (PSB) because it has higher standard electrode potential. In this study, the electrochemical behavior of the Mn(II)/Mn(III) couple on carbon felt and spectral pure graphite were investigated by cyclic voltammetry, steady polarization curve, electrochemical impedance spectroscopy, transient potential-step experiment, X-ray diffraction and charge-discharge experiments. Results show that the Mn(III) disproportionation reaction phenomena is obvious on the carbon felt electrode while it is weak on the graphite electrode owing to its fewer active sites. The reaction mechanism on carbon felt was discussed in detail. The reversibility of Mn(II)/Mn(III) is best when the sulfuric acid concentration is 5 M on the graphite electrode. Performance of a RFB employing Mn(II)/Mn(III) couple as anolyte active species and V(III)/V(II) as catholyte ones was evaluated with constant-current charge-discharge tests. The average columbic efficiency is 69.4% and the voltage efficiency is 90.4% at a current density of 20 mA cm -2 . The whole energy efficiency is 62.7% close to that of the all-vanadium battery and the average discharge voltage is about 14% higher than that of an all-vanadium battery. The preliminary exploration shows that the Mn(II)/Mn(III) couple is electrochemically promising for redox flow battery

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

International Nuclear Information System (INIS)

Boland, Susan; Foster, Kevin; Leech, Donal

2009-01-01

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

Aqueous dye-sensitized solar cell electrolytes based on the ferricyanide-ferrocyanide redox couple

Energy Technology Data Exchange (ETDEWEB)

Daeneke, Torben; Spiccia, Leone [School of Chemistry and ARC Centre of Excellence for Electromaterials Science, Monash University, Victoria (Australia); Uemura, Yu.; Koumura, Nagatoshi [Research Institute for Photovoltaic Technology, National Institute of Advanced Industrial Science and Technology AIST, Ibaraki (Japan); Graduate School of Pure and Applied Sciences, University of Tsukuba, Ibaraki (Japan); Duffy, Noel W. [CSIRO Energy Technology, Clayton, VIC (Australia); Mozer, Attila J. [School of Chemistry and ARC Centre of Excellence for Electromaterials Science, University of Wollongong, NSW (Australia); Bach, Udo [Department of Materials Engineering, Monash University, Victoria (Australia)

2012-03-02

Solar energy conversion efficiencies of over 4% have been achieved in DSCs constructed with aqueous electrolytes based on the ferricyanide-ferrocyanide redox couple, thereby avoiding the use of expensive, flammable and toxic solvents. This paradigm shift was made possible by the use of a hydrophobic organic carbazole dye. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Coupling gravity, electromagnetism and space-time for space propulsion breakthroughs

Science.gov (United States)

Millis, Marc G.

1994-01-01

spaceflight would be revolutionized if it were possible to propel a spacecraft without rockets using the coupling between gravity, electromagnetism, and space-time (hence called 'space coupling propulsion'). New theories and observations about the properties of space are emerging which offer new approaches to consider this breakthrough possibility. To guide the search, evaluation, and application of these emerging possibilities, a variety of hypothetical space coupling propulsion mechanisms are presented to highlight the issues that would have to be satisfied to enable such breakthroughs. A brief introduction of the emerging opportunities is also presented.

Metabolic Control of Redox and Redox Control of Metabolism in Plants

Science.gov (United States)

Fernie, Alisdair R.

2014-01-01

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

Improved efficiency of CdS quantum dot sensitized solar cell with an organic redox couple and a polymer counter electrode

International Nuclear Information System (INIS)

Shu, Ting; Li, Xiong; Ku, Zhi-Liang; Wang, Shi; Wu, Shi; Jin, Xiao-Hong; Hu, Chun-Di

2014-01-01

Highlights: • The organic AT - /BAT and T - /T 2 redox couples were used in CdS QDSSCs. • The AT - /BAT and PEDOT are better than polysulfide electrolyte and Pt and CoS CEs. • An improved η of 1.53% was obtained with the AT - /BAT electrolyte and the PEDOT CE. • PEDOT CE deposited at high deposition charge has better electrochemical activity. • The AT - /BAT outperformed T - /T 2 electrolyte due to suppressed charge recombination. - Abstract: Quantum dot sensitized solar cells (QDSSCs) based on an organic thiolate/disulfide redox couple (C 7 H 5 N 4 S - /C 14 H 10 N 8 S 2 or C 2 H 3 N 4 S - /C 4 H 6 N 8 S 2 ) and a polymer counter electrode [poly (3, 4-ethylenedioxythiophene), PEDOT] were fabricated and their photovoltaic performance were investigated. In CdS QDSSC, the organic C 7 H 5 N 4 S - /C 14 H 10 N 8 S 2 electrolyte shows better performance than the polysulfide electrolyte, and the PEDOT counter electrode exhibits higher efficiency than that of the Pt counter electrode and the CoS counter electrode. An efficiency of 1.53% was achieved in this QDSSC. The influences of the morphology and the deposition charge of the PEDOT counter electrodes on the cell performance were also studied. Furthermore, it was found that the C 7 H 5 N 4 S - /C 14 H 10 N 8 S 2 redox couple outperformed the C 2 H 3 N 4 S - /C 4 H 6 N 8 S 2 redox couple due to reduced electron recombination

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.

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

Development and testing of a compartmentalized reaction network model for redox zones in contaminated aquifers

Science.gov (United States)

Abrams , Robert H.; Loague, Keith; Kent, Douglas B.

1998-01-01

The work reported here is the first part of a larger effort focused on efficient numerical simulation of redox zone development in contaminated aquifers. The sequential use of various electron acceptors, which is governed by the energy yield of each reaction, gives rise to redox zones. The large difference in energy yields between the various redox reactions leads to systems of equations that are extremely ill-conditioned. These equations are very difficult to solve, especially in the context of coupled fluid flow, solute transport, and geochemical simulations. We have developed a general, rational method to solve such systems where we focus on the dominant reactions, compartmentalizing them in a manner that is analogous to the redox zones that are often observed in the field. The compartmentalized approach allows us to easily solve a complex geochemical system as a function of time and energy yield, laying the foundation for our ongoing work in which we couple the reaction network, for the development of redox zones, to a model of subsurface fluid flow and solute transport. Our method (1) solves the numerical system without evoking a redox parameter, (2) improves the numerical stability of redox systems by choosing which compartment and thus which reaction network to use based upon the concentration ratios of key constituents, (3) simulates the development of redox zones as a function of time without the use of inhibition factors or switching functions, and (4) can reduce the number of transport equations that need to be solved in space and time. We show through the use of various model performance evaluation statistics that the appropriate compartment choice under different geochemical conditions leads to numerical solutions without significant error. The compartmentalized approach described here facilitates the next phase of this effort where we couple the redox zone reaction network to models of fluid flow and solute transport.

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.

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

Science.gov (United States)

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

2014-08-01

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

Polyoxometalate active charge-transfer material for mediated redox flow battery

Energy Technology Data Exchange (ETDEWEB)

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

2017-01-17

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

Substrate specificity and subcellular localization of the aldehyde-alcohol redox-coupling reaction in carp cones.

Science.gov (United States)

Sato, Shinya; Fukagawa, Takashi; Tachibanaki, Shuji; Yamano, Yumiko; Wada, Akimori; Kawamura, Satoru

2013-12-20

Our previous study suggested the presence of a novel cone-specific redox reaction that generates 11-cis-retinal from 11-cis-retinol in the carp retina. This reaction is unique in that 1) both 11-cis-retinol and all-trans-retinal were required to produce 11-cis-retinal; 2) together with 11-cis-retinal, all-trans-retinol was produced at a 1:1 ratio; and 3) the addition of enzyme cofactors such as NADP(H) was not necessary. This reaction is probably part of the reactions in a cone-specific retinoid cycle required for cone visual pigment regeneration with the use of 11-cis-retinol supplied from Müller cells. In this study, using purified carp cone membrane preparations, we first confirmed that the reaction is a redox-coupling reaction between retinals and retinols. We further examined the substrate specificity, reaction mechanism, and subcellular localization of this reaction. Oxidation was specific for 11-cis-retinol and 9-cis-retinol. In contrast, reduction showed low specificity: many aldehydes, including all-trans-, 9-cis-, 11-cis-, and 13-cis-retinals and even benzaldehyde, supported the reaction. On the basis of kinetic studies of this reaction (aldehyde-alcohol redox-coupling reaction), we found that formation of a ternary complex of a retinol, an aldehyde, and a postulated enzyme seemed to be necessary, which suggested the presence of both the retinol- and aldehyde-binding sites in this enzyme. A subcellular fractionation study showed that the activity is present almost exclusively in the cone inner segment. These results suggest the presence of an effective production mechanism of 11-cis-retinal in the cone inner segment to regenerate visual pigment.

A coupled three dimensional model of vanadium redox flow battery for flow field designs

International Nuclear Information System (INIS)

Yin, Cong; Gao, Yan; Guo, Shaoyun; Tang, Hao

2014-01-01

A 3D (three-dimensional) model of VRB (vanadium redox flow battery) with interdigitated flow channel design is proposed. Two different stack inlet designs, single-inlet and multi-inlet, are structured in the model to study the distributions of fluid pressure, electric potential, current density and overpotential during operation of VRB cell. Electrolyte flow rate and stack channel dimension are proved to be the critical factors affecting flow distribution and cell performance. The model developed in this paper can be employed to optimize both VRB stack design and system operation conditions. Further improvements of the model concerning current density and electrode properties are also suggested in the paper. - Highlights: • A coupled three-dimensional model of vanadium redox flow cell is proposed. • Interdigitated flow channels with two different manifold designs are simulated. • Manifold structure affects uniformity of distribution patterns significantly. • Increased electrolyte flow rate improves cell performance for both designs. • Decreased channel size and enlarged land width enhance cell voltage

Mn3O4 anchored on carbon nanotubes as an electrode reaction catalyst of V(IV)/V(V) couple for vanadium redox flow batteries

International Nuclear Information System (INIS)

He, Zhangxing; Dai, Lei; Liu, Suqin; Wang, Ling; Li, Chuanchang

2015-01-01

Highlights: • Mn 3 O 4 /MWCNTs (multi-walled carbon nanotubes) composite fabricated by a simple solvothermal method was developed as electrochemical catalyst of V(IV)/V(V) redox couple for vanadium redox flow batteries for the first time. • The electrocatalytic kinetics of the redox reactions of three electrocatalysts (pure Mn 3 O 4 , pure MWCNTs, Mn 3 O 4 /MWCNTs) were compared, and were in the order of Mn 3 O 4 /MWCNTs > MWCNTs > Mn 3 O 4 . • The cell using Mn 3 O 4 /MWCNTs has lower electrochemical polarization, with larger discharge capacity and energy efficiency. The average energy efficiency of the cell using Mn 3 O 4 /MWCNTs is 84.65%, 3.73% higher than that of the pristine cell. - Abstract: Mn 3 O 4 /MWCNTs (multi-walled carbon nanotubes) composite fabricated by a simple solvothermal method was developed as electrochemical catalyst of V(IV)/V(V) redox couple for vanadium redox flow batteries. The electrochemical activity of V(IV)/V(V) redox couple can be enhanced by the electrochemical catalysts (Mn 3 O 4 , MWCNTs, Mn 3 O 4 /MWCNTs), and the electrocatalytic kinetics of the redox reactions were in the order of Mn 3 O 4 /MWCNTs > MWCNTs > Mn 3 O 4 . The cell using Mn 3 O 4 /MWCNTs composite as electrochemical catalyst was assembled and the charge-discharge performance was evaluated. Compared with the pristine cell, the cell using positive graphite felt modified by Mn 3 O 4 /MWCNTs had lower electrochemical polarization, larger discharge capacity and energy efficiency. The average energy efficiency of the cell using modified positive electrode for 50 cycles was 84.65%, 3.73% higher than that of the pristine cell. The superior electrocatalytic performance of Mn 3 O 4 /MWCNTs composite was mainly due to the effective mixed conducting network, facilitating the electron transport and ion diffusion in the electrode/electrolyte interface

High-energy-density, aqueous, metal-polyiodide redox flow batteries

Science.gov (United States)

Li, Bin; Nie, Zimin; Wang, Wei; Liu, Jun; Sprenkle, Vincent L.

2017-08-29

Improved metal-based redox flow batteries (RFBs) can utilize a metal and a divalent cation of the metal (M.sup.2+) as an active redox couple for a first electrode and electrolyte, respectively, in a first half-cell. For example, the metal can be Zn. The RFBs can also utilize a second electrolyte having I.sup.-, anions of I.sub.x (for x.gtoreq.3), or both in an aqueous solution, wherein the I.sup.- and the anions of I.sub.x (for x.gtoreq.3) compose an active redox couple in a second half-cell.

Mechanical coupling and liquid exchanges in the pleural space.

Science.gov (United States)

Agostoni, E; Zocchi, L

1998-06-01

The pleural space provides the mechanical coupling between lung and chest wall: two views about this coupling are reported and discussed. Information on volume, composition, thickness, and pressure of the pleural liquid under physiologic conditions in a few species is provided. The Starling pressures of the parietal pleura filtering liquid into pleural space, and those of the visceral pleura absorbing liquid from the space are considered along with the permeability of the mesothelium. Information on the lymphatic drainage through the parietal pleura and on the solute-coupled liquid absorption from the pleural space under physiologic conditions and with various kinds of hydrothorax are provided.

Computational design of molecules for an all-quinone redox flow battery.

Science.gov (United States)

Er, Süleyman; Suh, Changwon; Marshak, Michael P; Aspuru-Guzik, Alán

2015-02-01

Inspired by the electron transfer properties of quinones in biological systems, we recently showed that quinones are also very promising electroactive materials for stationary energy storage applications. Due to the practically infinite chemical space of organic molecules, the discovery of additional quinones or other redox-active organic molecules for energy storage applications is an open field of inquiry. Here, we introduce a high-throughput computational screening approach that we applied to an accelerated study of a total of 1710 quinone (Q) and hydroquinone (QH 2 ) ( i.e. , two-electron two-proton) redox couples. We identified the promising candidates for both the negative and positive sides of organic-based aqueous flow batteries, thus enabling an all-quinone battery. To further aid the development of additional interesting electroactive small molecules we also provide emerging quantitative structure-property relationships.

Enhancing the open-circuit voltage of dye-sensitized solar cells: coadsorbents and alternative redox couples[Dissertation 4066

Energy Technology Data Exchange (ETDEWEB)

Zhang, Z.

2008-04-15

In February 2008, the oil price easily exceeded US dollar 100 per barrel due to the weak US dollar and the imbalance between the increasing demands and deficient supplies. People are paying more and more attention to seek for alternative energy sources that would suffice the modern society in the following high-oil-price era. The work in this thesis is associated with some fundamental research in one of the solutions to the energy shortage, photovoltaics. Particularly, the dye-sensitized solar cell was taken as the system where the effects of coadsorbents and alternative couples to the classic iodide/iodine redox were studied and rationalized. The first chapter was a general introduction to the photovoltaics and dye-sensitized solar cells, such as the operating principles and the characteristics of the dye cell. In Chapter 2, we specified all the experimental issues, including the chemicals, materials, film preparation, characterization techniques and data analysis. A short part was also dedicated to the basics of the photovoltaics. We studied the electronic effect of the scattering particles in our devices in Chapter 3. These particles were of 400 nm in diameter and always put on top of the nanotransparent layer to increase the light harvesting of the devices. It was found that the particles gave a small dark current but under illumination, they made a significant contribution to the total photocurrent. Photovoltage and photocurrent transient decay measurements performed under bias illumination showed that the density of electronic states of the light scattering layer was two times smaller than that of a transparent nanoparticle layer. From Chapter 4 to Chapter 7, we systematically studied the function of the coadsorbents. Application of an {omega}-guannidino carboxylic acid was found to increase the open-circuit voltage of the device by 50 mV. Coadsorbents with similar structures were then employed with an amphiphilic ruthenium sensitizer, Z-907, to scrutinize

3-D pore-scale resolved model for coupled species/charge/fluid transport in a vanadium redox flow battery

International Nuclear Information System (INIS)

Qiu Gang; Joshi, Abhijit S.; Dennison, C.R.; Knehr, K.W.; Kumbur, E.C.; Sun Ying

2012-01-01

The vanadium redox flow battery (VRFB) has emerged as a viable grid-scale energy storage technology that offers cost-effective energy storage solutions for renewable energy applications. In this paper, a novel methodology is introduced for modeling of the transport mechanisms of electrolyte flow, species and charge in the VRFB at the pore scale of the electrodes; that is, at the level where individual carbon fiber geometry and electrolyte flow are directly resolved. The detailed geometry of the electrode is obtained using X-ray computed tomography (XCT) and calibrated against experimentally determined pore-scale characteristics (e.g., pore and fiber diameter, porosity, and surface area). The processed XCT data is then used as geometry input for modeling of the electrochemical processes in the VRFB. The flow of electrolyte through the pore space is modeled using the lattice Boltzmann method (LBM) while the finite volume method (FVM) is used to solve the coupled species and charge transport and predict the performance of the VRFB under various conditions. An electrochemical model using the Butler–Volmer equations is used to provide species and charge coupling at the surfaces of the carbon fibers. Results are obtained for the cell potential distribution, as well as local concentration, overpotential and current density profiles under galvanostatic discharge conditions. The cell performance is investigated as a function of the electrolyte flow rate and external drawing current. The model developed here provides a useful tool for building the structure–property–performance relationship of VRFB electrodes.

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.

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

Science.gov (United States)

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

2017-09-01

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

A compartmentalized solute transport model for redox zones in contaminated aquifers: 1. Theory and development

Science.gov (United States)

Abrams , Robert H.; Loague, Keith

2000-01-01

This paper, the first of two parts [see Abrams and Loague, this issue], takes the compartmentalized approach for the geochemical evolution of redox zones presented by Abrams et al. [1998] and embeds it within a solute transport framework. In this paper the compartmentalized approach is generalized to facilitate the description of its incorporation into a solute transport simulator. An equivalent formulation is developed which removes any discontinuities that may occur when switching compartments. Rate‐limited redox reactions are modeled with a modified Monod relationship that allows either the organic substrate or the electron acceptor to be the rate‐limiting reactant. Thermodynamic constraints are used to inhibit lower‐energy redox reactions from occurring under infeasible geochemical conditions without imposing equilibrium on the lower‐energy reactions. The procedure used allows any redox reaction to be simulated as being kinetically limited or thermodynamically limited, depending on local geochemical conditions. Empirical reaction inhibition methods are not needed. The sequential iteration approach (SIA), a technique which allows the number of solute transport equations to be reduced, is adopted to solve the coupled geochemical/solute transport problem. When the compartmentalized approach is embedded within the SIA, with the total analytical concentration of each component as the dependent variable in the transport equation, it is possible to reduce the number of transport equations even further than with the unmodified SIA. A one‐dimensional, coupled geochemical/solute transport simulation is presented in which redox zones evolve dynamically in time and space. The compartmentalized solute transport (COMPTRAN) model described in this paper enables the development of redox zones to be simulated under both kinetic and thermodynamic constraints. The modular design of COMPTRAN facilitates the use of many different, preexisting solute transport and

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-09-24

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

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

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

DEFF Research Database (Denmark)

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

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

Redox zone II. Coupled modeling of groundwater flow, solute transport, chemical reactions and microbial processes in the Aespoe island

International Nuclear Information System (INIS)

Samper, Javier; Molinero, Jorge; Changbing Yang; Guoxiang Zhang

2003-12-01

The Redox Zone Experiment was carried out at the Aespoe HRL in order to study the redox behaviour and the hydrochemistry of an isolated vertical fracture zone disturbed by the excavation of an access tunnel. Overall results and interpretation of the Redox Zone Project were reported by Banwart et al. Later, Banwart presented a summary of the hydrochemistry of the Redox Zone Experiment. Coupled groundwater flow and reactive transport models of this experiment were carried out by Molinero who proposed a revised conceptual model for the hydrogeology of the Redox Zone Experiment which could explain simultaneously measured drawdown and salinity data. The numerical model was found useful to understand the natural system. Several conclusions were drawn about the redox conditions of recharge waters, cation exchange capacity of the fracture zone and the role of mineral phases such as pyrite, calcite, hematite and goethite. This model could reproduce the measured trends of dissolved species, except for bicarbonate and sulphate which are affected by microbially-mediated processes. In order to explore the role of microbial processes, a coupled numerical model has been constructed which accounts for water flow, reactive transport and microbial processes. The results of this model is presented in this report. This model accounts for groundwater flow and reactive transport in a manner similar to that of Molinero and extends the preliminary microbial model of Zhang by accounting for microbially-driven organic matter fermentation and organic matter oxidation. This updated microbial model considers simultaneously the fermentation of particulate organic matter by yeast and the oxidation of dissolved organic matter, a product of fermentation. Dissolved organic matter is produced by yeast and serves also as a substrate for iron-reducing bacteria. Model results reproduce the observed increase in bicarbonate and sulfaphe concentration, thus adding additional evidence for the possibility

Redox zone II. Coupled modeling of groundwater flow, solute transport, chemical reactions and microbial processes in the Aespoe island

Energy Technology Data Exchange (ETDEWEB)

Samper, Javier; Molinero, Jorge; Changbing Yang; Guoxiang Zhang [Univ. Da Coruna (Spain)

2003-12-01

The Redox Zone Experiment was carried out at the Aespoe HRL in order to study the redox behaviour and the hydrochemistry of an isolated vertical fracture zone disturbed by the excavation of an access tunnel. Overall results and interpretation of the Redox Zone Project were reported by Banwart et al. Later, Banwart presented a summary of the hydrochemistry of the Redox Zone Experiment. Coupled groundwater flow and reactive transport models of this experiment were carried out by Molinero who proposed a revised conceptual model for the hydrogeology of the Redox Zone Experiment which could explain simultaneously measured drawdown and salinity data. The numerical model was found useful to understand the natural system. Several conclusions were drawn about the redox conditions of recharge waters, cation exchange capacity of the fracture zone and the role of mineral phases such as pyrite, calcite, hematite and goethite. This model could reproduce the measured trends of dissolved species, except for bicarbonate and sulphate which are affected by microbially-mediated processes. In order to explore the role of microbial processes, a coupled numerical model has been constructed which accounts for water flow, reactive transport and microbial processes. The results of this model is presented in this report. This model accounts for groundwater flow and reactive transport in a manner similar to that of Molinero and extends the preliminary microbial model of Zhang by accounting for microbially-driven organic matter fermentation and organic matter oxidation. This updated microbial model considers simultaneously the fermentation of particulate organic matter by yeast and the oxidation of dissolved organic matter, a product of fermentation. Dissolved organic matter is produced by yeast and serves also as a substrate for iron-reducing bacteria. Model results reproduce the observed increase in bicarbonate and sulfaphe concentration, thus adding additional evidence for the possibility

Redox chemistry of americium in nitric acid media

Energy Technology Data Exchange (ETDEWEB)

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

2004-07-01

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

Redox chemistry of americium in nitric acid media

International Nuclear Information System (INIS)

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

2004-01-01

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

A rechargeable iodine-carbon battery that exploits ion intercalation and iodine redox chemistry.

Science.gov (United States)

Lu, Ke; Hu, Ziyu; Ma, Jizhen; Ma, Houyi; Dai, Liming; Zhang, Jintao

2017-09-13

Graphitic carbons have been used as conductive supports for developing rechargeable batteries. However, the classic ion intercalation in graphitic carbon has yet to be coupled with extrinsic redox reactions to develop rechargeable batteries. Herein, we demonstrate the preparation of a free-standing, flexible nitrogen and phosphorus co-doped hierarchically porous graphitic carbon for iodine loading by pyrolysis of polyaniline coated cellulose wiper. We find that heteroatoms could provide additional defect sites for encapsulating iodine while the porous carbon skeleton facilitates redox reactions of iodine and ion intercalation. The combination of ion intercalation with redox reactions of iodine allows for developing rechargeable iodine-carbon batteries free from the unsafe lithium/sodium metals, and hence eliminates the long-standing safety issue. The unique architecture of the hierarchically porous graphitic carbon with heteroatom doping not only provides suitable spaces for both iodine encapsulation and cation intercalation but also generates efficient electronic and ionic transport pathways, thus leading to enhanced performance.Carbon-based electrodes able to intercalate Li + and Na + ions have been exploited for high performing energy storage devices. Here, the authors combine the ion intercalation properties of porous graphitic carbons with the redox chemistry of iodine to produce iodine-carbon batteries with high reversible capacities.

ETL 1 kW redox flow cell

International Nuclear Information System (INIS)

Nozaki, K.; Ozawa, T.

1984-01-01

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

Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

Science.gov (United States)

Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

2015-10-01

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

A glucose bio-battery prototype based on a GDH/poly(methylene blue) bioanode and a graphite cathode with an iodide/tri-iodide redox couple.

Science.gov (United States)

Wang, Jen-Yuan; Nien, Po-Chin; Chen, Chien-Hsiao; Chen, Lin-Chi; Ho, Kuo-Chuan

2012-07-01

A glucose bio-battery prototype independent of oxygen is proposed based on a glucose dehydrogenase (GDH) bioanode and a graphite cathode with an iodide/tri-iodide redox couple. At the bioanode, a NADH electrocatalyst, poly(methylene blue) (PMB), which can be easily grown on the electrode (screen-printed carbon paste electrode, SPCE) by electrodeposition, is harnessed and engineered. We find that carboxylated multi-walled carbon nanotubes (MWCNTs) are capable of significantly increasing the deposition amount of PMB and thus enhancing the PMB's electrocatalysis of NADH oxidation and the glucose bio-battery's performance. The choice of the iodide/tri-iodide redox couple eliminates the dependence of oxygen for this bio-battery, thus enabling the bio-battery with a constant current-output feature similar to that of the solar cells. The present glucose bio-battery prototype can attain a maximum power density of 2.4 μW/cm(2) at 25 °C. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.

Space and time evolution of two nonlinearly coupled variables

International Nuclear Information System (INIS)

Obayashi, H.; Totsuji, H.; Wilhelmsson, H.

1976-12-01

The system of two coupled linear differential equations are studied assuming that the coupling terms are proportional to the product of the dependent variables, representing e.g. intensities or populations. It is furthermore assumed that these variables experience different linear dissipation or growth. The derivations account for space as well as time dependence of the variables. It is found that certain particular solutions can be obtained to this system, whereas a full solution in space and time as an initial value problem is outside the scope of the present paper. The system has a nonlinear equilibrium solution for which the nonlinear coupling terms balance the terms of linear dissipation. The case of space and time evolution of a small perturbation of the nonlinear equilibrium state, given the initial one-dimensional spatial distribution of the perturbation, is also considered in some detail. (auth.)

Analysis of redox additive-based overcharge protection for rechargeable lithium batteries

Science.gov (United States)

Narayanan, S. R.; Surampudi, S.; Attia, A. I.; Bankston, C. P.

1991-01-01

The overcharge condition in secondary lithium batteries employing redox additives for overcharge protection, has been theoretically analyzed in terms of a finite linear diffusion model. The analysis leads to expressions relating the steady-state overcharge current density and cell voltage to the concentration, diffusion coefficient, standard reduction potential of the redox couple, and interelectrode distance. The model permits the estimation of the maximum permissible overcharge rate for any chosen set of system conditions. Digital simulation of the overcharge experiment leads to numerical representation of the potential transients, and estimate of the influence of diffusion coefficient and interelectrode distance on the transient attainment of the steady state during overcharge. The model has been experimentally verified using 1,1-prime-dimethyl ferrocene as a redox additive. The analysis of the experimental results in terms of the theory allows the calculation of the diffusion coefficient and the formal potential of the redox couple. The model and the theoretical results may be exploited in the design and optimization of overcharge protection by the redox additive approach.

Recent developments in organic redox flow batteries: A critical review

Science.gov (United States)

Leung, P.; Shah, A. A.; Sanz, L.; Flox, C.; Morante, J. R.; Xu, Q.; Mohamed, M. R.; Ponce de León, C.; Walsh, F. C.

2017-08-01

Redox flow batteries (RFBs) have emerged as prime candidates for energy storage on the medium and large scales, particularly at the grid scale. The demand for versatile energy storage continues to increase as more electrical energy is generated from intermittent renewable sources. A major barrier in the way of broad deployment and deep market penetration is the use of expensive metals as the active species in the electrolytes. The use of organic redox couples in aqueous or non-aqueous electrolytes is a promising approach to reducing the overall cost in long-term, since these materials can be low-cost and abundant. The performance of such redox couples can be tuned by modifying their chemical structure. In recent years, significant developments in organic redox flow batteries has taken place, with the introduction of new groups of highly soluble organic molecules, capable of providing a cell voltage and charge capacity comparable to conventional metal-based systems. This review summarises the fundamental developments and characterization of organic redox flow batteries from both the chemistry and materials perspectives. The latest advances, future challenges and opportunities for further development are discussed.

Reply to 'Comment on kinetic modeling of microbially-driven redox chemistry of subsurface environments: coupling transport, microbial metabolism and geochemistry' by J. Griffioen

Science.gov (United States)

Hunter, K. S.; Van Cappellen, P.

2000-01-01

Our paper, 'Kinetic modeling of microbially-driven redox chemistry of subsurface environments: coupling transport, microbial metabolism and geochemistry' (Hunter et al., 1998), presents a theoretical exploration of biogeochemical reaction networks and their importance to the biogeochemistry of groundwater systems. As with any other model, the kinetic reaction-transport model developed in our paper includes only a subset of all physically, biologically and chemically relevant processes in subsurface environments. It considers aquifer systems where the primary energy source driving microbial activity is the degradation of organic matter. In addition to the primary biodegradation pathways of organic matter (i.e. respiration and fermentation), the redox chemistry of groundwaters is also affected by reactions not directly involving organic matter oxidation. We refer to the latter as secondary reactions. By including secondary redox reactions which consume reduced reaction products (e.g., Mn2+, FeS, H2S), and in the process compete with microbial heterotrophic populations for available oxidants (i.e. O2, NO3-, Mn(IV), Fe(III), SO42-), we predict spatio-temporal distributions of microbial activity which differ significantly from those of models which consider only the biodegradation reactions. That is, the secondary reactions have a significant impact on the distributions of the rates of heterotrophic and chemolithotrophic metabolic pathways. We further show that secondary redox reactions, as well as non-redox reactions, significantly influence the acid-base chemistry of groundwaters. The distributions of dissolved inorganic redox species along flowpaths, however, are similar in simulations with and without secondary reactions (see Figs. 3(b) and 7(b) in Hunter et al., 1998), indicating that very different biogeochemical reaction dynamics may lead to essentially the same chemical redox zonation of a groundwater system.

Exact Solution of Space-Time Fractional Coupled EW and Coupled MEW Equations Using Modified Kudryashov Method

International Nuclear Information System (INIS)

Raslan, K. R.; Ali, Khalid K.; EL-Danaf, Talaat S.

2017-01-01

In the present paper, we established a traveling wave solution by using modified Kudryashov method for the space-time fractional nonlinear partial differential equations. The method is used to obtain the exact solutions for different types of the space-time fractional nonlinear partial differential equations such as, the space-time fractional coupled equal width wave equation (CEWE) and the space-time fractional coupled modified equal width wave equation (CMEW), which are the important soliton equations. Both equations are reduced to ordinary differential equations by the use of fractional complex transform and properties of modified Riemann–Liouville derivative. We plot the exact solutions for these equations at different time levels. (paper)

Energy-density enhancement of carbon-nanotube-based supercapacitors with redox couple in organic electrolyte.

Science.gov (United States)

Park, Jinwoo; Kim, Byungwoo; Yoo, Young-Eun; Chung, Haegeun; Kim, Woong

2014-11-26

We demonstrate for the first time that the incorporation of a redox-active molecule in an organic electrolyte can increase the cell voltage of a supercapacitor. The redox molecule also contributes to increasing the cell capacitance by a faradaic redox reaction, and therefore the energy density of the supercapacitor can be significantly increased. More specifically, the addition of redox-active decamethylferrocene in an organic electrolyte results in an approximately 27-fold increase in the energy density of carbon-nanotube-based supercapacitors. The resulting high energy density (36.8 Wh/kg) stems from the increased cell voltage (1.1 V→2.1 V) and cell capacitance (8.3 F/g→61.3 F/g) resulting from decamethylferrocene addition. We found that the voltage increase is associated with the potential of the redox species relative to the electrochemical stability window of the supporting electrolyte. These results will be useful in identifying new electrolytes for high-energy-density supercapacitors.

Biogeochemistry of Redox at Repository Depth and Implications for the Canister

Energy Technology Data Exchange (ETDEWEB)

Bath, Adrian; Hermansson, Hans-Peter

2009-08-15

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

Biogeochemistry of Redox at Repository Depth and Implications for the Canister

International Nuclear Information System (INIS)

Bath, Adrian; Hermansson, Hans-Peter

2009-08-01

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

Kinetic modeling of microbially-driven redox chemistry of radionuclides in subsurface environments: Coupling transport, microbial metabolism and geochemistry

International Nuclear Information System (INIS)

Wang, Yifeng; Papenguth, Hans W.

2000-01-01

Microbial degradation of organic matter is a driving force in many subsurface geochemical systems, and therefore may have significant impacts on the fate of radionuclides released into subsurface environments. In this paper, the authors present a general reaction-transport model for microbial metabolism, redox chemistry, and radionuclide migration in subsurface systems. The model explicitly accounts for biomass accumulation and the coupling of radionuclide redox reactions with major biogeochemical processes. Based on the consideration that the biomass accumulation in subsurface environments is likely to achieve a quasi-steady state, they have accordingly modified the traditional microbial growth kinetic equation. They justified the use of the biogeochemical models without the explicit representation of biomass accumulation, if the interest of modeling is in the net impact of microbial reactions on geochemical processes. They then applied their model to a scenario in which an oxic water flow containing both uranium and completing organic ligands is recharged into an oxic aquifer in a carbonate formation. The model simulation shows that uranium can be reduced and therefore immobilized in the anoxic zone created by microbial degradation

Kinetic modeling of microbially-driven redox chemistry of radionuclides in subsurface environments: Coupling transport, microbial metabolism and geochemistry

Energy Technology Data Exchange (ETDEWEB)

WANG,YIFENG; PAPENGUTH,HANS W.

2000-05-04

Microbial degradation of organic matter is a driving force in many subsurface geochemical systems, and therefore may have significant impacts on the fate of radionuclides released into subsurface environments. In this paper, the authors present a general reaction-transport model for microbial metabolism, redox chemistry, and radionuclide migration in subsurface systems. The model explicitly accounts for biomass accumulation and the coupling of radionuclide redox reactions with major biogeochemical processes. Based on the consideration that the biomass accumulation in subsurface environments is likely to achieve a quasi-steady state, they have accordingly modified the traditional microbial growth kinetic equation. They justified the use of the biogeochemical models without the explicit representation of biomass accumulation, if the interest of modeling is in the net impact of microbial reactions on geochemical processes. They then applied their model to a scenario in which an oxic water flow containing both uranium and completing organic ligands is recharged into an oxic aquifer in a carbonate formation. The model simulation shows that uranium can be reduced and therefore immobilized in the anoxic zone created by microbial degradation.

Phase-space curvature in spin-orbit-coupled ultracold atomic systems

Science.gov (United States)

Armaitis, J.; Ruseckas, J.; Anisimovas, E.

2017-04-01

We consider a system with spin-orbit coupling and derive equations of motion which include the effects of Berry curvatures. We apply these equations to investigate the dynamics of particles with equal Rashba-Dresselhaus spin-orbit coupling in one dimension. In our derivation, the adiabatic transformation is performed first and leads to quantum Heisenberg equations of motion for momentum and position operators. These equations explicitly contain position-space, momentum-space, and phase-space Berry curvature terms. Subsequently, we perform the semiclassical approximation and obtain the semiclassical equations of motion. Taking the low-Berry-curvature limit results in equations that can be directly compared to previous results for the motion of wave packets. Finally, we show that in the semiclassical regime, the effective mass of the equal Rashba-Dresselhaus spin-orbit-coupled system can be viewed as a direct effect of the phase-space Berry curvature.

Dihydroxybenzene/benzoquinone-containing polymers: organic redox polymers

Energy Technology Data Exchange (ETDEWEB)

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

2000-08-01

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

Transport regimes spanning magnetization-coupling phase space

Science.gov (United States)

Baalrud, Scott D.; Daligault, Jérôme

2017-10-01

The manner in which transport properties vary over the entire parameter-space of coupling and magnetization strength is explored. Four regimes are identified based on the relative size of the gyroradius compared to other fundamental length scales: the collision mean free path, Debye length, distance of closest approach, and interparticle spacing. Molecular dynamics simulations of self-diffusion and temperature anisotropy relaxation spanning the parameter space are found to agree well with the predicted boundaries. Comparison with existing theories reveals regimes where they succeed, where they fail, and where no theory has yet been developed.

Polyarene mediators for mediated redox flow battery

Science.gov (United States)

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

2018-01-02

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

The Redox Flow System for solar photovoltaic energy storage

Science.gov (United States)

Odonnell, P.; Gahn, R. F.; Pfeiffer, W.

1976-01-01

The interfacing of a Solar Photovoltaic System and a Redox Flow System for storage was workable. The Redox Flow System, which utilizes the oxidation-reduction capability of two redox couples, in this case iron and titanium, for its storage capacity, gave a relatively constant output regardless of solar activity so that a load could be run continually day and night utilizing the sun's energy. One portion of the system was connected to a bank of solar cells to electrochemically charge the solutions, while a separate part of the system was used to electrochemically discharge the stored energy.

Investigating improvements on redox flow batteries

CSIR Research Space (South Africa)

Swartbooi, AM

2006-09-01

Full Text Available storage devices coupled to most of their applications. Lead-acid batteries have long been used as the most economical option to store electricity in many small scale applications, but lately more interest have been shown in redox flow batteries. The low...

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.

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

Directory of Open Access Journals (Sweden)

Masood Ahmad Rizvi

2015-03-01

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

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

Redox Species of Redox Flow Batteries: A Review.

Science.gov (United States)

Pan, Feng; Wang, Qing

2015-11-18

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

Redox Species of Redox Flow Batteries: A Review

Directory of Open Access Journals (Sweden)

Feng Pan

2015-11-01

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

Graphene-Nanowall-Decorated Carbon Felt with Excellent Electrochemical Activity Toward VO2+/VO2+ Couple for All Vanadium Redox Flow Battery.

Science.gov (United States)

Li, Wenyue; Zhang, Zhenyu; Tang, Yongbing; Bian, Haidong; Ng, Tsz-Wai; Zhang, Wenjun; Lee, Chun-Sing

2016-04-01

3D graphene-nanowall-decorated carbon felts (CF) are synthesized via an in situ microwave plasma enhanced chemical vapor deposition method and used as positive electrode for vanadium redox flow battery (VRFB). The carbon fibers in CF are successfully wrapped by vertically grown graphene nanowalls, which not only increase the electrode specific area, but also expose a high density of sharp graphene edges with good catalytic activities to the vanadium ions. As a result, the VRFB with this novel electrode shows three times higher reaction rate toward VO 2 + /VO 2+ redox couple and 11% increased energy efficiency over VRFB with an unmodified CF electrode. Moreover, this designed architecture shows excellent stability in the battery operation. After 100 charging-discharging cycles, the electrode not only shows no observable morphology change, it can also be reused in another battery and practical with the same performance. It is believed that this novel structure including the synthesis procedure will provide a new developing direction for the VRFB electrode.

Graphene‐Nanowall‐Decorated Carbon Felt with Excellent Electrochemical Activity Toward VO2 +/VO2+ Couple for All Vanadium Redox Flow Battery

Science.gov (United States)

Li, Wenyue; Zhang, Zhenyu; Bian, Haidong; Ng, Tsz‐Wai

2015-01-01

3D graphene‐nanowall‐decorated carbon felts (CF) are synthesized via an in situ microwave plasma enhanced chemical vapor deposition method and used as positive electrode for vanadium redox flow battery (VRFB). The carbon fibers in CF are successfully wrapped by vertically grown graphene nanowalls, which not only increase the electrode specific area, but also expose a high density of sharp graphene edges with good catalytic activities to the vanadium ions. As a result, the VRFB with this novel electrode shows three times higher reaction rate toward VO2 +/VO2+ redox couple and 11% increased energy efficiency over VRFB with an unmodified CF electrode. Moreover, this designed architecture shows excellent stability in the battery operation. After 100 charging–discharging cycles, the electrode not only shows no observable morphology change, it can also be reused in another battery and practical with the same performance. It is believed that this novel structure including the synthesis procedure will provide a new developing direction for the VRFB electrode. PMID:27774399

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

Alkynes as Allylmetal Equivalents in Redox-Triggered C–C Couplings to Primary Alcohols: (Z)-Homoallylic Alcohols via Ruthenium-Catalyzed Propargyl C–H Oxidative Addition

Science.gov (United States)

2015-01-01

The cationic ruthenium catalyst generated upon the acid–base reaction of H2Ru(CO)(PPh3)3 and 2,4,6-(2-Pr)3PhSO3H promotes the redox-triggered C–C coupling of 2-alkynes and primary alcohols to form (Z)-homoallylic alcohols with good to complete control of olefin geometry. Deuterium labeling studies, which reveal roughly equal isotopic compositions at the allylic and distal vinylic positions, along with other data, corroborate a catalytic mechanism involving ruthenium(0)-mediated allene–aldehyde oxidative coupling to form a transient oxaruthenacycle, an event that ultimately defines (Z)-olefin stereochemistry. PMID:25075434

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

Science.gov (United States)

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

2014-07-09

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

Redox-capacitor to connect electrochemistry to redox-biology.

Science.gov (United States)

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

2014-01-07

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

Electrochemical behaviour of gold and stainless steel under proton irradiation and active RedOx couples

Energy Technology Data Exchange (ETDEWEB)

Leoni, E. [Commissariat a l' Energie Atomique, DEN/DANS/DPC/SCCME, CEA-Saclay, 91191 Gif sur Yvette (France)], E-mail: elisa.leoni@polytechnique.edu; Corbel, C. [Laboratoire des Solides Irradies, Ecole Polytechnique, 91128 Palaiseau (France)], E-mail: catherine.corbel@polytechnique.fr; Cobut, V. [Laboratoire Atomes et Molecules en Astrophysique, Universite de Cergy-Pontoise, 5 Mail Gay-Lussac, Neuville/Oise, 95031 Cergy-Pontoise Cedex (France); Simon, D. [CNRS-CERI 3a rue de la Ferollerie, 45071 Cedex 2 Orleans (France); Feron, D. [Commissariat a l' Energie Atomique, DEN/DANS/DPC/SCCME, CEA-Saclay, 91191 Gif sur Yvette (France)], E-mail: Damien.FERON@cea.fr; Roy, M.; Raquet, O. [Commissariat a l' Energie Atomique, DEN/DANS/DPC/SCCME, CEA-Saclay, 91191 Gif sur Yvette (France)

2007-12-01

Model experiments are reported where proton beams delivered by the cyclotron located at CERI (CNRS-Orleans) are used for irradiating AISI 316L/water and Au/water high purity interfaces with 6 MeV protons. The free exchange potentials at the interfaces are recorded as a function of time at room temperature in situ before, under, and after proton irradiation. The evolutions are compared to those calculated for the Nernst potentials associated with the radiolytic RedOx couples. It is shown how the comparison gives evidence that five radiolytic species - O{sub 2}{center_dot}, H{sub 2}O{sub 2}, HO{sub 2}{sup -}, HO{sub 2}{center_dot} and O{sub 2}{center_dot}{sup -} exchange electrons at the Au interfaces in a range of dose rates that vary over three orders of magnitudes, i.e. 0.0048 < dr(10{sup 7} Gy h{sup -1}) < 4.8. The balance between the electron exchanges at Au interfaces is adjusted by the RedOx reactions associated with the above species. The free exchange potential reaches the same steady value for Au and AISI 316L interfaces irradiated at high doses, {>=}2.5 x 10{sup 7} Gy, (0.020 {+-} 0.025) V versus NHE. Such low values are the first ones to be reported. The HO{sub 2}{center_dot} and O{sub 2}{center_dot}{sup -} radical disproportionations play a key role and control the potential at the interfaces under 6 MeV proton flux. This role is generally mostly overlooked for gamma irradiation.

Space robots with flexible appendages: Dynamic modeling, coupling measurement, and vibration suppression

Science.gov (United States)

Meng, Deshan; Wang, Xueqian; Xu, Wenfu; Liang, Bin

2017-05-01

For a space robot with flexible appendages, vibrations of flexible structure can be easily excited during both orbit and/or attitude maneuvers of the base and the operation of the manipulators. Hence, the pose (position and attitude) of the manipulator's end-effector will greatly deviate from the desired values, and furthermore, the motion of the manipulator will trigger and exacerbate vibrations of flexible appendages. Given lack of the atmospheric damping in orbit, the vibrations will last for quite a while and cause the on-orbital tasks to fail. We derived the rigid-flexible coupling dynamics of a space robot system with flexible appendages and established a coupling model between the flexible base and the space manipulator. A specific index was defined to measure the coupling degree between the flexible motion of the appendages and the rigid motion of the end-effector. Then, we analyzed the dynamic coupling for different conditions, such as modal displacements, joint angles (manipulator configuration), and mass properties. Moreover, the coupling map was adopted and drawn to represent the coupling motion. Based on this map, a trajectory planning method was addressed to suppress structure vibration. Finally, simulation studies of typical cases were performed, which verified the proposed models and method. This work provides a theoretic basis for the system design, performance evaluation, trajectory planning, and control of such space robots.

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.

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

Science.gov (United States)

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

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

Rhodium-catalyzed redox-neutral coupling of phenidones with alkynes.

Science.gov (United States)

Fan, Zhoulong; Lu, Heng; Li, Wei; Geng, Kaijun; Zhang, Ao

2017-07-21

A switchable synthesis of N-substituted indole derivatives from phenidones via rhodium-catalyzed redox-neutral C-H activation has been achieved. In this protocol, we firstly disclosed that the reactivity of Rh(iii) catalysis could be enhanced through employing palladium acetate as an additive. Some representative features include external oxidant-free, applicable to terminal alkynes, short reaction time and operational simplicity. The utility of this method is further showcased by the economical synthesis of potent anticancer PARP-1 inhibitors.

Electrochemical redox reactions in solvated silica sol-gel glass

International Nuclear Information System (INIS)

Opallo, M.

2002-01-01

The studies of electrochemical redox reactions in solvated silica sol-gel glass were reviewed. The methodology of the experiments with emphasis on the direct preparation of the solid electrolyte and the application ultra microelectrodes was described. Generally, the level of the electrochemical signal is not much below that observed in liquid electrolyte. The current depends on time elapsed after gelation, namely the longer time, the smaller current. The differences between electrochemical behaviour of the redox couples in monoliths and thin layers were described. (author)

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

Science.gov (United States)

Tanaka, Leonardo Y; Laurindo, Francisco R M

2017-08-01

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

DataSpaces: An Interaction and Coordination Framework for Coupled Simulation Workflows

International Nuclear Information System (INIS)

Docan, Ciprian; Klasky, Scott A.; Parashar, Manish

2010-01-01

Emerging high-performance distributed computing environments are enabling new end-to-end formulations in science and engineering that involve multiple interacting processes and data-intensive application workflows. For example, current fusion simulation efforts are exploring coupled models and codes that simultaneously simulate separate application processes, such as the core and the edge turbulence, and run on different high performance computing resources. These components need to interact, at runtime, with each other and with services for data monitoring, data analysis and visualization, and data archiving. As a result, they require efficient support for dynamic and flexible couplings and interactions, which remains a challenge. This paper presents Data-Spaces, a flexible interaction and coordination substrate that addresses this challenge. DataSpaces essentially implements a semantically specialized virtual shared space abstraction that can be associatively accessed by all components and services in the application workflow. It enables live data to be extracted from running simulation components, indexes this data online, and then allows it to be monitored, queried and accessed by other components and services via the space using semantically meaningful operators. The underlying data transport is asynchronous, low-overhead and largely memory-to-memory. The design, implementation, and experimental evaluation of DataSpaces using a coupled fusion simulation workflow is presented.

Redox reaction characteristics of riboflavin: a fluorescence spectroelectrochemical analysis and density functional theory calculation.

Science.gov (United States)

Chen, Wei; Chen, Jie-Jie; Lu, Rui; Qian, Chen; Li, Wen-Wei; Yu, Han-Qing

2014-08-01

Riboflavin (RF), the primary redox active component of flavin, is involved in many redox processes in biogeochemical systems. Despite of its wide distribution and important roles in environmental remediation, its redox behaviors and reaction mechanisms in hydrophobic sites remain unclear yet. In this study, spectroelectrochemical analysis and density functional theory (DFT) calculation were integrated to explore the redox behaviors of RF in dimethyl sulfoxide (DMSO), which was used to create a hydrophobic environment. Specifically, cyclic voltafluorometry (CVF) and derivative cyclic voltafluorometry (DCVF) were employed to track the RF concentration changing profiles. It was found that the reduction contained a series of proton-coupled electron transfers dependent of potential driving force. In addition to the electron transfer-chemical reaction-electron transfer process, a disproportionation (DISP1) process was also identified to be involved in the reduction. The redox potential and free energy of each step obtained from the DFT calculations further confirmed the mechanisms proposed based on the experimental results. The combination of experimental and theoretical approaches yields a deep insight into the characteristics of RF in environmental remediation and better understanding about the proton-coupled electron transfer mechanisms. Copyright © 2014 Elsevier B.V. All rights reserved.

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

International Nuclear Information System (INIS)

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

2010-01-01

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

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.

Probing the electronic structure of redox species and direct determination of intrinsic reorganization energies of electron transfer reactions

International Nuclear Information System (INIS)

Wang, Xue-Bin; Wang, Lai-Sheng

2000-01-01

An experimental technique capable of directly determining the intrinsic reorganization energies of bimolecular electron transfer reactions is described. Appropriate solution phase redox species are prepared in the gas phase using electrospray ionization and probed using photodetachment spectroscopy. Five metal complex anions involved in the Fe 2+ -Fe 3+ redox couple are investigated and the intramolecular reorganization energies are measured directly from spectral features due to removing the most loosely bound 3d electron from the Fe(II)-complexes. The photodetachment spectra also yield electronic structure information about the Fe 2+ -Fe 3+ redox couple and provide a common electronic structure origin for the reducing capability of the Fe(II)-complexes, the most common redox reagents. (c) 2000 American Institute of Physics

First-principles molecular dynamics simulation study on electrolytes for use in redox flow battery

Science.gov (United States)

Choe, Yoong-Kee; Tsuchida, Eiji; Tokuda, Kazuya; Ootsuka, Jun; Saito, Yoshihiro; Masuno, Atsunobu; Inoue, Hiroyuki

2017-11-01

Results of first-principles molecular dynamics simulations carried out to investigate structural aspects of electrolytes for use in a redox flow battery are reported. The electrolytes studied here are aqueous sulfuric acid solutions where its property is of importance for dissolving redox couples in redox flow battery. The simulation results indicate that structural features of the acid solutions depend on the concentration of sulfuric acid. Such dependency arises from increase of proton dissociation from sulfuric acid.

Electrocatalysis in the vanadium redox flow battery and coupling the redox flow battery with the fuel cell

OpenAIRE

Britz, Anette Beata

2015-01-01

In den Redox-Fluss-Batterien (RFB) bilden die Funktionskomponenten: Elektrode, Membran und Elektrolyt die limitierenden Faktoren für die Leistung der Batterie. Als Elektrodenmaterial werden kohlenstoffbasierte Materialien verwendet. Durch geeignete Modifizierung dieser Elektroden kann die Stromdichte sowie die Energieeffizienz verbessert werden. Die richtige Wahl der Membran kann einem Kapazitätsverlust während der Lade- und Entladezyklen entgegenwirken. In dieser Arbeit wurden die Funktio...

RDH13L, an enzyme responsible for the aldehyde-alcohol redox coupling reaction (AL-OL coupling reaction) to supply 11-cis retinal in the carp cone retinoid cycle.

Science.gov (United States)

Sato, Shinya; Miyazono, Sadaharu; Tachibanaki, Shuji; Kawamura, Satoru

2015-01-30

Cone photoreceptors require effective pigment regeneration mechanisms to maintain their sensitivity in the light. Our previous studies in carp cones suggested the presence of an unconventional and very effective mechanism to produce 11-cis retinal, the necessary component in pigment regeneration. In this reaction (aldehyde-alcohol redox coupling reaction, AL-OL coupling reaction), formation of 11-cis retinal, i.e. oxidation of 11-cis retinol is coupled to reduction of an aldehyde at a 1:1 molar ratio without exogenous NADP(H) which is usually required in this kind of reaction. Here, we identified carp retinol dehydrogenase 13-like (RDH13L) as an enzyme catalyzing the AL-OL coupling reaction. RDH13L was partially purified from purified carp cones, identified as a candidate protein, and its AL-OL coupling activity was confirmed using recombinant RDH13L. We further examined the substrate specificity, subcellular localization, and expression level of RDH13L. Based on these results, we concluded that RDH13L contributes to a significant part, but not all, of the AL-OL coupling activity in carp cones. RDH13L contained tightly bound NADP(+) which presumably functions as a cofactor in the reaction. Mouse RDH14, a mouse homolog of carp RDH13L, also showed the AL-OL coupling activity. Interestingly, although carp cone membranes, carp RDH13L and mouse RDH14 all showed the coupling activity at 15-37 °C, they also showed a conventional NADP(+)-dependent 11-cis retinol oxidation activity above 25 °C without addition of aldehydes. This dual mechanism of 11-cis retinal synthesis attained by carp RDH13L and mouse RDH14 probably contribute to effective pigment regeneration in cones that function in the light. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

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.

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.

Computational design of molecules for an all-quinone redox flow battery† †Electronic supplementary information (ESI) available: The list of computationally predicted candidate quinone molecules with interesting redox properties. See DOI: 10.1039/c4sc03030c Click here for additional data file.

Science.gov (United States)

Er, Süleyman; Suh, Changwon; Marshak, Michael P.

2015-01-01

Inspired by the electron transfer properties of quinones in biological systems, we recently showed that quinones are also very promising electroactive materials for stationary energy storage applications. Due to the practically infinite chemical space of organic molecules, the discovery of additional quinones or other redox-active organic molecules for energy storage applications is an open field of inquiry. Here, we introduce a high-throughput computational screening approach that we applied to an accelerated study of a total of 1710 quinone (Q) and hydroquinone (QH2) (i.e., two-electron two-proton) redox couples. We identified the promising candidates for both the negative and positive sides of organic-based aqueous flow batteries, thus enabling an all-quinone battery. To further aid the development of additional interesting electroactive small molecules we also provide emerging quantitative structure-property relationships. PMID:29560173

1,3-Dioxolane, tetrahydrofuran, acetylacetone and dimethyl sulfoxide as solvents for non-aqueous vanadium acetylacetonate redox-flow-batteries

International Nuclear Information System (INIS)

Herr, T.; Noack, J.; Fischer, P.; Tübke, J.

2013-01-01

Highlights: • Four solvents were employed in a non-aqueous redox flow battery system. • Coulombic efficiencies of 85.9–98.5% and energy efficiencies of 26.6–43.6% were achieved. • Discharge power density was enhanced up to 0.080 mW cm −2 . • Solubility of V(acac) 3 was increased to 0.8 M compared to the acetonitrile system. -- Abstract: A non-aqueous vanadium acetylacetonate redox flow battery with different organic solvents and tetrabutylammonium hexafluorophosphate has been investigated. Cyclic voltammograms show three redox couples in 1,3-dioxolane, tetrahydrofuran, acetylacetone and two redox couples in dimethyl sulfoxide. Cell potentials between 2.21 and 2.61 V are measured, depending on the solvent used. Impedance Spectroscopy has been used to determine rate limiting step in the non-aqueous redox flow battery. Experiments in a charge–discharge test cell yielded coulombic and energy efficiencies of 85.9–98.5% and 26.6–43.6%, respectively

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 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

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.

Electronic Connection Between the Quinone and Cytochrome c Redox Pools and Its Role in Regulation of Mitochondrial Electron Transport and Redox Signaling

Science.gov (United States)

Sarewicz, Marcin; Osyczka, Artur

2015-01-01

Mitochondrial respiration, an important bioenergetic process, relies on operation of four membranous enzymatic complexes linked functionally by mobile, freely diffusible elements: quinone molecules in the membrane and water-soluble cytochromes c in the intermembrane space. One of the mitochondrial complexes, complex III (cytochrome bc1 or ubiquinol:cytochrome c oxidoreductase), provides an electronic connection between these two diffusible redox pools linking in a fully reversible manner two-electron quinone oxidation/reduction with one-electron cytochrome c reduction/oxidation. Several features of this homodimeric enzyme implicate that in addition to its well-defined function of contributing to generation of proton-motive force, cytochrome bc1 may be a physiologically important point of regulation of electron flow acting as a sensor of the redox state of mitochondria that actively responds to changes in bioenergetic conditions. These features include the following: the opposing redox reactions at quinone catalytic sites located on the opposite sides of the membrane, the inter-monomer electronic connection that functionally links four quinone binding sites of a dimer into an H-shaped electron transfer system, as well as the potential to generate superoxide and release it to the intermembrane space where it can be engaged in redox signaling pathways. Here we highlight recent advances in understanding how cytochrome bc1 may accomplish this regulatory physiological function, what is known and remains unknown about catalytic and side reactions within the quinone binding sites and electron transfers through the cofactor chains connecting those sites with the substrate redox pools. We also discuss the developed molecular mechanisms in the context of physiology of mitochondria. PMID:25540143

A domain decomposition method for analyzing a coupling between multiple acoustical spaces (L).

Science.gov (United States)

Chen, Yuehua; Jin, Guoyong; Liu, Zhigang

2017-05-01

This letter presents a domain decomposition method to predict the acoustic characteristics of an arbitrary enclosure made up of any number of sub-spaces. While the Lagrange multiplier technique usually has good performance for conditional extremum problems, the present method avoids involving extra coupling parameters and theoretically ensures the continuity conditions of both sound pressure and particle velocity at the coupling interface. Comparisons with the finite element results illustrate the accuracy and efficiency of the present predictions and the effect of coupling parameters between sub-spaces on the natural frequencies and mode shapes of the overall enclosure is revealed.

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

International Nuclear Information System (INIS)

Capdevila, H.; Vitorge, P.

1998-01-01

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

A High-Throughput Mass Spectrometry Assay Coupled with Redox Activity Testing Reduces Artifacts and False Positives in Lysine Demethylase Screening.

Science.gov (United States)

Wigle, Tim J; Swinger, Kerren K; Campbell, John E; Scholle, Michael D; Sherrill, John; Admirand, Elizabeth A; Boriack-Sjodin, P Ann; Kuntz, Kevin W; Chesworth, Richard; Moyer, Mikel P; Scott, Margaret Porter; Copeland, Robert A

2015-07-01

Demethylation of histones by lysine demethylases (KDMs) plays a critical role in controlling gene transcription. Aberrant demethylation may play a causal role in diseases such as cancer. Despite the biological significance of these enzymes, there are limited assay technologies for study of KDMs and few quality chemical probes available to interrogate their biology. In this report, we demonstrate the utility of self-assembled monolayer desorption/ionization (SAMDI) mass spectrometry for the investigation of quantitative KDM enzyme kinetics and for high-throughput screening for KDM inhibitors. SAMDI can be performed in 384-well format and rapidly allows reaction components to be purified prior to injection into a mass spectrometer, without a throughput-limiting liquid chromatography step. We developed sensitive and robust assays for KDM1A (LSD1, AOF2) and KDM4C (JMJD2C, GASC1) and screened 13,824 compounds against each enzyme. Hits were rapidly triaged using a redox assay to identify compounds that interfered with the catalytic oxidation chemistry used by the KDMs for the demethylation reaction. We find that overall this high-throughput mass spectrometry platform coupled with the elimination of redox active compounds leads to a hit rate that is manageable for follow-up work. © 2015 Society for Laboratory Automation and Screening.

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 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)

Coupled radiative gasdynamic interaction and non-equilibrium dissociation for large-scale returned space vehicles

International Nuclear Information System (INIS)

Surzhikov, S.

2012-01-01

Graphical abstract: It has been shown that different coupled vibrational dissociation models, being applied for solving coupled radiative gasdynamic problems for large size space vehicles, exert noticeable effect on radiative heating of its surface at orbital entry on high altitudes (h ⩾ 70 km). This influence decreases with decreasing the space vehicles sizes. Figure shows translational (solid lines) and vibrational (dashed lines) temperatures in shock layer with (circle markers) and without (triangles markers) radiative-gasdynamic interaction for one trajectory point of entering space vehicle. Highlights: ► Nonequilibrium dissociation processes exert effect on radiation heating of space vehicles (SV). ► The radiation gas dynamic interaction enhances this influence. ► This influence increases with increasing the SV sizes. - Abstract: Radiative aerothermodynamics of large-scale space vehicles is considered for Earth orbital entry at zero angle of attack. Brief description of used radiative gasdynamic model of physically and chemically nonequilibrium, viscous, heat conductive and radiative gas of complex chemical composition is presented. Radiation gasdynamic (RadGD) interaction in high temperature shock layer is studied by means of numerical experiment. It is shown that radiation–gasdynamic coupling for orbital space vehicles of large size is important for high altitude part of entering trajectory. It is demonstrated that the use of different models of coupled vibrational dissociation (CVD) in conditions of RadGD interaction gives rise temperature variation in shock layer and, as a result, leads to significant variation of radiative heating of space vehicle.

Cost-driven materials selection criteria for redox flow battery electrolytes

Science.gov (United States)

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

2016-10-01

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

Conductance Through a Redox System in the Coulomb Blockade Regime: Many-Particle Effects and Influence of Electronic Correlations

OpenAIRE

Tornow, Sabine; Zwicknagl, Gertrud

2009-01-01

We investigate the transport characteristics of a redox system weakly coupled to leads in the Coulomb blockade regime. The redox system comprises a donor and acceptor separated by an insulating bridge in a solution. It is modeled by a two-site extended Hubbard model which includes on-site and inter-site Coulomb interactions and the coupling to a bosonic bath. The current voltage characteristics is calculated at high temperatures using a rate equation approach. For high voltages exceeding the ...

Redox phenomena in glass melts; Les phenomenes d'oxydoreduction dans les verres d'oxyde

Energy Technology Data Exchange (ETDEWEB)

Pinet, O.; Di Nardo, Ch. [CEA Valrho, (DCC/DRRV/SCD), 30 - Marcoule (France)

2000-07-01

One of the major concerns in the glass-making industry is the control of redox mechanisms, which condition the glass properties and particularly refinement and color. The development of vitrification processes and vitreous materials for nuclear waste containment further emphasized the advantages of optimizing the glass oxidation state. The oxidation state of polyvalent species in a glass melt essentially depends on the basicity of the glass and the oxygen fugacity in the melt at a given temperature. Theoretical studies show that redox couples in glass melts can be classified according to their characteristic oxygen fugacities. This corresponds to the oxygen fugacity for which the concentrations of reduced and oxidized forms of the couple are equal. The quantity f{sub O{sub 2}}{sub char}. depends primarily on the redox couple considered, the basicity and the temperature of the glass melt. A classification of 36 redox couples is proposed here, covering a temperature range from 1085 deg C to 1500 deg C for silicate glass compositions for which the basicity can be characterized by theoretical optical basicity values [2) between 0.55 and 0.65. This classification is based on a variety of published experimental results obtained by different techniques. Figure 1 shows the satisfactory agreement obtained from these various studies. Figure 2 shows that the increase in f{sub O{sub 2}}{sub char}. with temperature in glasses with the same level of basicity ({lambda}= 0.57 {+-} 0.02) is consistent with the theory. From the characteristic oxygen fugacity values, potentiometric measurements of the oxygen fugacity in glass with an oxygen sensor allow in situ evaluation of the redox ratio. Voltammetric investigations of glasses can be used to supplement and refine the classification. The resulting Epeak values, expressed in terms of characteristic oxygen fugacity, are fully consistent with the values for other glasses of comparable basicity measured at comparable temperature

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

International Nuclear Information System (INIS)

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

2008-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-08-15

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

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...

Graphite-graphite oxide composite electrode for vanadium redox flow battery

International Nuclear Information System (INIS)

Li Wenyue; Liu Jianguo; Yan Chuanwei

2011-01-01

Highlights: → A new composite electrode is designed for vanadium redox flow battery (VRB). → The graphite oxide (GO) is used as electrode reactions catalyst. → The excellent electrode activity is attributed to the oxygen-containing groups attached on the GO surface. → A catalytic mechanism of the GO towards the redox reactions is presumed. - Abstract: A graphite/graphite oxide (GO) composite electrode for vanadium redox battery (VRB) was prepared successfully in this paper. The materials were characterized with X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The specific surface area was measured by the Brunauer-Emmett-Teller method. The redox reactions of [VO 2 ] + /[VO] 2+ and V 3+ /V 2+ were studied with cyclic voltammetry and electrochemical impedance spectroscopy. The results indicated that the electrochemical performances of the electrode were improved greatly when 3 wt% GO was added into graphite electrode. The redox peak currents of [VO 2 ] + /[VO] 2+ and V 3+ /V 2+ couples on the composite electrode were increased nearly twice as large as that on the graphite electrode, and the charge transfer resistances of the redox pairs on the composite electrode are also reduced. The enhanced electrochemical activity could be ascribed to the presence of plentiful oxygen functional groups on the basal planes and sheet edges of the GO and large specific surface areas introduced by the GO.

Pseudo-indicator behaviour of platinum electrode explored for the potentiometric estimation of non-redox systems.

Science.gov (United States)

Raashid, Syed; Chat, Oyais Ahmad; Rizvi, Masood A; Bhat, Mohsin Ahmad; Khan, Badruddin

2012-11-15

A pseudo-indicator electrode based potentiometric method for estimation of non-redox metal ions is presented. In the proposed method, nature and concentration specific impact of analyte over the redox potential of ideally polarisable Pt/pregenerated-redox-couple interface forms the basis of quantification. Utility of the method in estimation of six non-redox metal ions viz. Zn(2+), Cu(2+), Ni(2+), Cd(2+), Pb(2+), Al(3+) in the concentration range of 10(-1)-10(-3) moldm(-3), individually and as binary mixtures is also presented. Three types of potentiometric behaviours, which we ascribe to the nature specific thermodynamic and kinetic aspects of metal-EDTA binding, were observed. While Cu(2+), Ni(2+), Pb(2+) and Al(3+) were found to bind EDTA efficiently, without exchanging Fe(3+); Zn(2+) and Cd(2+) were observed to replace Fe(3+) from EDTA. In contrast, Ca(2+) and Mg(2+) were found to show no binding affinity to EDTA in the pH range employed in the present work. The proposed method was also used to explore the reversibility and the Nernestian behaviour of ferricyanide/ferrocyanide redox couple through spectroelectrochemical titration of Zn(2+) with ferrocyanide. The presented method is presaged to be a reliable and low cost future replacement for costly and delicate ion selective electrodes (ISE) in the estimation of non-redox species like Zn(2+), Cu(2+), etc. Copyright © 2012 Elsevier B.V. All rights reserved.

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...

Surface Redox Chemistry of Immobilized Nanodiamond: Effects of Particle Size and Electrochemical Environment

Science.gov (United States)

Gupta, S.; McDonald, B.; Carrizosa, S. B.

2017-07-01

The size of the diamond particle is tailored to nanoscale (nanodiamond, ND), and the ND surface is engineered targeting specific (electrochemical and biological) applications. In this work, we investigated the complex surface redox chemistry of immobilized ND layer on conductive boron-doped diamond electrode with a broad experimental parameter space such as particle size (nano versus micron), scan rate, pH (cationic/acidic versus anionic/basic), electrolyte KCl concentration (four orders of magnitude), and redox agents (neutral and ionic). We reported on the significant enhancement of ionic currents while recording reversible oxidation of neutral ferrocene methanol (FcMeOH) by almost one order of magnitude than traditional potassium ferricyanide (K3Fe(CN)6) redox agent. The current enhancement is inversely related to ND particle diameter in the following order: 1 μm << 1000 nm < 100 nm < 10 nm ≤ 5 nm < 2 nm. We attribute the current enhancement to concurrent electrocatalytic processes, i.e. the electron transfer between redox probes and electroactive surface functional (e.g. hydroxyl, carboxyl, epoxy) moieties and the electron transfer mediated by adsorbed FcMeOH+ (or Fe(CN) 6 3+ ) ions onto ND surface. The first process is pH dependent since it depends upon ND surface functionalities for which the electron transfer is coupled to proton transfer. The adsorption mediated process is observed most apparently at slower scan rates owing to self-exchange between adsorbed FcMeOH+ ions and FcMeOH redox agent molecules in diffusion-limited bulk electrolyte solution. Alternatively, it is hypothesized that the surface functionality and defect sites ( sp 2-bonded C shell and unsaturated bonds) give rise to surface electronic states with energies within the band gap (midgap states) in undoped ND. These surface states serve as electron donors (and acceptors) depending upon their bonding (and antibonding) character and, therefore, they can support electrocatalytic redox

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.

TEMPO/viologen electrochemical heterojunction for diffusion-controlled redox mediation: a highly rectifying bilayer-sandwiched device based on cross-reaction at the interface between dissimilar redox polymers.

Science.gov (United States)

Tokue, Hiroshi; Oyaizu, Kenichi; Sukegawa, Takashi; Nishide, Hiroyuki

2014-03-26

A couple of totally reversible redox-active molecules, which are different in redox potentials, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and viologen (V(2+)), were employed to give rise to a rectified redox conduction effect. Single-layer and bilayer devices were fabricated using polymers containing these sites as pendant groups per repeating unit. The devices were obtained by sandwiching the redox polymer layer(s) with indium tin oxide (ITO)/glass and Pt foil electrodes. Electrochemical measurements of the single-layer device composed of polynorbornene-bearing TEMPO (PTNB) exhibited a diffusion-limited current-voltage response based on the TEMPO(+)/TEMPO exchange reaction, which was almost equivalent to a redox gradient through the PTNB layer depending upon the thickness. The bilayer device gave rise to the current rectification because of the thermodynamically favored cross-reaction between TEMPO(+) and V(+) at the polymer/polymer interface. A current-voltage response obtained for the bilayer device demonstrated a two-step diffusion-limited current behavior as a result of the concurrent V(2+)/V(+) and V(+)/V(0) exchange reactions according to the voltage and suggested that the charge transport process through the device was most likely to be rate-determined by a redox gradient in the polymer layer. Current collection experiments revealed a charge transport balance throughout the device, as a result of the electrochemical stability and robustness of the polymers in both redox states.

An experimental and theoretical method for determination of standard electrode potential for the redox couple diphenyl sulfone/diphenyl sulfide

Science.gov (United States)

Song, Y. Z.; Wei, K. X.; Lv, J. S.

2013-12-01

DFT calculations were performed for diphenyl sulfide and diphenyl sulfone. The electrochemistry of diphenyl sulfide on the gold electrode was investigated by cyclic voltammety and the results show that standard electrode potential for redox couple diphenyl sulfone/diphenyl sulfide is 1.058 V, which is consistent with that of 1.057 calculated at B3LYP/6-31++G( d, p)-IEFPCM level. The front orbit theory and Mulliken charges of molecular explain well on the oxidation of diphenyl sulfide in oxidative desulfurization. According to equilibrium theory the experimental equilibrium constant in the oxidative desulfurization of H2O2, is 1.17 × 1048, which is consistent with the theoretical equilibrium constant is 2.18 × 1048 at B3LYP/6-31++G( d, p)-IEFPCM level.

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

Energy Technology Data Exchange (ETDEWEB)

Capdevila, H.; Vitorge, P.

1994-05-01

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

PHB Biosynthesis Counteracts Redox Stress in Herbaspirillum seropedicae

Directory of Open Access Journals (Sweden)

Marcelo B. Batista

2018-03-01

Full Text Available The ability of bacteria to produce polyhydroxyalkanoates such as poly(3-hydroxybutyrate (PHB enables provision of a carbon storage molecule that can be mobilized under demanding physiological conditions. However, the precise function of PHB in cellular metabolism has not been clearly defined. In order to determine the impact of PHB production on global physiology, we have characterized the properties of a ΔphaC1 mutant strain of the diazotrophic bacterium Herbaspirillum seropedicae. The absence of PHB in the mutant strain not only perturbs redox balance and increases oxidative stress, but also influences the activity of the redox-sensing Fnr transcription regulators, resulting in significant changes in expression of the cytochrome c-branch of the electron transport chain. The synthesis of PHB is itself dependent on the Fnr1 and Fnr3 proteins resulting in a cyclic dependency that couples synthesis of PHB with redox regulation. Transcriptional profiling of the ΔphaC1 mutant reveals that the loss of PHB synthesis affects the expression of many genes, including approximately 30% of the Fnr regulon.

PHB Biosynthesis Counteracts Redox Stress in Herbaspirillum seropedicae.

Science.gov (United States)

Batista, Marcelo B; Teixeira, Cícero S; Sfeir, Michelle Z T; Alves, Luis P S; Valdameri, Glaucio; Pedrosa, Fabio de Oliveira; Sassaki, Guilherme L; Steffens, Maria B R; de Souza, Emanuel M; Dixon, Ray; Müller-Santos, Marcelo

2018-01-01

The ability of bacteria to produce polyhydroxyalkanoates such as poly(3-hydroxybutyrate) (PHB) enables provision of a carbon storage molecule that can be mobilized under demanding physiological conditions. However, the precise function of PHB in cellular metabolism has not been clearly defined. In order to determine the impact of PHB production on global physiology, we have characterized the properties of a Δ phaC1 mutant strain of the diazotrophic bacterium Herbaspirillum seropedicae . The absence of PHB in the mutant strain not only perturbs redox balance and increases oxidative stress, but also influences the activity of the redox-sensing Fnr transcription regulators, resulting in significant changes in expression of the cytochrome c -branch of the electron transport chain. The synthesis of PHB is itself dependent on the Fnr1 and Fnr3 proteins resulting in a cyclic dependency that couples synthesis of PHB with redox regulation. Transcriptional profiling of the Δ phaC1 mutant reveals that the loss of PHB synthesis affects the expression of many genes, including approximately 30% of the Fnr regulon.

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.

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

Science.gov (United States)

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

2016-03-21

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

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 ...

Couplings

Science.gov (United States)

Stošić, Dušan; Auroux, Aline

Basic principles of calorimetry coupled with other techniques are introduced. These methods are used in heterogeneous catalysis for characterization of acidic, basic and red-ox properties of solid catalysts. Estimation of these features is achieved by monitoring the interaction of various probe molecules with the surface of such materials. Overview of gas phase, as well as liquid phase techniques is given. Special attention is devoted to coupled calorimetry-volumetry method. Furthermore, the influence of different experimental parameters on the results of these techniques is discussed, since it is known that they can significantly influence the evaluation of catalytic properties of investigated materials.

Redox-Flow-Batterie mit außenliegender Versorgungsleitung

OpenAIRE

Seipp, Thorsten; Dötsch, Christian; Berthold, Sascha

2011-01-01

A redox flow battery (1, 1') is presented and described, having at least one cell frame (4) surrounding a cell interior space (7) and having at least one supply line (2, 2') provided outside the cell frame (4) for supplying electrolyte to the cell interior space (7) and/or at least one disposal line (3, 3') provided outside the cell frame (4) for removing electrolyte from the cell interior space (4). In order to make greater degrees of freedom available in designing the cell so as to provide ...

A techno-economic comparison of ground-coupled and air-coupled heat pump system for space cooling

Energy Technology Data Exchange (ETDEWEB)

Esen, Hikmet; Esen, Mehmet [Department of Mechanical Education, Faculty of Technical Education, University of Firat, 23119 Elazig (Turkey); Inalli, Mustafa [Department of Mechanical Engineering, Faculty of Engineering, University of Firat, 23119 Elazig (Turkey)

2007-05-15

This paper reports a techno-economic comparison between a ground-coupled heat pump (GCHP) system and an air-coupled heat pump (ACHP) system. The systems connected to a test room in Firat University, Elazig (38.41{sup o}N, 39.14{sup o}E), Turkey, were designed and constructed for space cooling. The performances of the GCHP and the ACHP system were experimentally determined. The experimental results were obtained from June to September in cooling season of 2004. The average cooling performance coefficients (COP{sub sys}) of the GCHP system for horizontal ground heat exchanger (HGHE) in the different trenches, at 1 and 2m depths, were obtained to be 3.85 and 4.26, respectively and the COP{sub sys} of the ACHP system was determined to be 3.17. The test results indicate that system parameters can have an important effect on performance, and that GCHP systems are economically preferable to ACHP systems for the purpose of space cooling. (author)

Composite Sliding Mode Control for a Free-Floating Space Rigid-Flexible Coupling Manipulator System

OpenAIRE

Congqing, Wang; Pengfei, Wu; Xin, Zhou; Xiwu, Pei

2013-01-01

The flexible space manipulator is a highly nonlinear and coupled dynamic system. This paper proposes a novel composite sliding mode control to deal with the vibration suppression and trajectory tracking of a free-floating space rigid-flexible coupling manipulator with a rigid payload. First, the dynamic equations of this system are established by using Lagrange and assumed mode methods and in the meantime this dynamic modelling allows consideration of the modelling errors, the external distur...

Optimizing phonon space in the phonon-coupling model

Science.gov (United States)

Tselyaev, V.; Lyutorovich, N.; Speth, J.; Reinhard, P.-G.

2017-08-01

We present a new scheme to select the most relevant phonons in the phonon-coupling model, named here the time-blocking approximation (TBA). The new criterion, based on the phonon-nucleon coupling strengths rather than on B (E L ) values, is more selective and thus produces much smaller phonon spaces in the TBA. This is beneficial in two respects: first, it curbs the computational cost, and second, it reduces the danger of double counting in the expansion basis of the TBA. We use here the TBA in a form where the coupling strength is regularized to keep the given Hartree-Fock ground state stable. The scheme is implemented in a random-phase approximation and TBA code based on the Skyrme energy functional. We first explore carefully the cutoff dependence with the new criterion and can work out a natural (optimal) cutoff parameter. Then we use the freshly developed and tested scheme for a survey of giant resonances and low-lying collective states in six doubly magic nuclei looking also at the dependence of the results when varying the Skyrme parametrization.

Electrochemical reaction rates in a dye-sensitised solar cell - the iodide/tri-iodide redox system

DEFF Research Database (Denmark)

Bay, L.; West, K.; Winther-Jensen, B.

2006-01-01

The electrochemical reaction rate of the redox couple iodide/tri-iodide in acetonitrile is characterised by impedance spectroscopy. Different electrode materials relevant for the function of dye-sensitised solar cells (DSSC) are investigated. Preferably, the reaction with the iodide....../tri-iodide couple should be fast at the counter electrode, i.e. this electrode must have a high catalytic activity towards the redox couple, and the same reaction must be slow on the photo electrode. The catalytic activity is investigated for platinum, poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPy......), and polyaniline (PANI)-all deposited onto fluorine-doped tin oxide (FTO) glass. Both Pt and PEDOT are found to have sufficiently high catalytic activities for practical use as counter electrodes in DSSC. The reaction resistance on FTO and anatase confirmed the beneficial effect of a compact anatase layer on top...

Electrochemical reaction rates in a dye sentisised solar cell - the iodide/tri-iodide redox system

DEFF Research Database (Denmark)

Bay, Lasse; West, Keld; Winter-Jensen, Bjørn

2006-01-01

The electrochemical reaction rate of the redox couple iodide / tri-iodide in acetonitrile is characterised by impedance spectroscopy. Different electrode materials relevant for the function of dye-sensitised solar cells (DSSC) are investigated. Preferably, the reaction with the iodide / tri......-iodide couple should be fast at the counter electrode, i.e. this electrode must have a high catalytic activity towards the redox couple, and the same reaction must be slow on the photo electrode. The catalytic activity is investigated for platinum, poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPy......), and polyaniline (PANI) - all deposited onto fluorine doped tin oxide (FTO) glass. Both Pt and PEDOT are found to have sufficiently high catalytic activities for practical use as counter electrode in DSSC. The reaction resistance on FTO and anatase confirmed the beneficial effect of a compact anatase layer on top...

Oxygen-coupled Redox Regulation of the Skeletal Muscle Ryanodine Receptor/Ca2+ Release Channel (RyR1)

Science.gov (United States)

Sun, Qi-An; Wang, Benlian; Miyagi, Masaru; Hess, Douglas T.; Stamler, Jonathan S.

2013-01-01

In mammalian skeletal muscle, Ca2+ release from the sarcoplasmic reticulum (SR) through the ryanodine receptor/Ca2+-release channel RyR1 can be enhanced by S-oxidation or S-nitrosylation of separate Cys residues, which are allosterically linked. S-Oxidation of RyR1 is coupled to muscle oxygen tension (pO2) through O2-dependent production of hydrogen peroxide by SR-resident NADPH oxidase 4. In isolated SR (SR vesicles), an average of six to eight Cys thiols/RyR1 monomer are reversibly oxidized at high (21% O2) versus low pO2 (1% O2), but their identity among the 100 Cys residues/RyR1 monomer is unknown. Here we use isotope-coded affinity tag labeling and mass spectrometry (yielding 93% coverage of RyR1 Cys residues) to identify 13 Cys residues subject to pO2-coupled S-oxidation in SR vesicles. Eight additional Cys residues are oxidized at high versus low pO2 only when NADPH levels are supplemented to enhance NADPH oxidase 4 activity. pO2-sensitive Cys residues were largely non-overlapping with those identified previously as hyperreactive by administration of exogenous reagents (three of 21) or as S-nitrosylated. Cys residues subject to pO2-coupled oxidation are distributed widely within the cytoplasmic domain of RyR1 in multiple functional domains implicated in RyR1 activity-regulating interactions with the L-type Ca2+ channel (dihydropyridine receptor) and FK506-binding protein 12 as well as in “hot spot” regions containing sites of mutation implicated in malignant hyperthermia and central core disease. pO2-coupled disulfide formation was identified, whereas neither S-glutathionylated nor sulfenamide-modified Cys residues were observed. Thus, physiological redox regulation of RyR1 by endogenously generated hydrogen peroxide is exerted through dynamic disulfide formation involving multiple Cys residues. PMID:23798702

Retrieval of Au, Ag, Cu precious metals coupled with electric energy production via an unconventional coupled redox fuel cell reactor.

Science.gov (United States)

Zhang, Hui-Min; Fan, Zheng; Xu, Wei; Feng, Xiao; Wu, Zu-Cheng

2017-09-15

The recovery of heavy metals from aqueous solutions or e-wastes is of upmost importance. Retrieval of Au, Ag, and Cu with electricity generation through building an ethanol-metal coupled redox fuel cells (CRFCs) is demonstrated. The cell was uniquely assembled on PdNi/C anode the electro-oxidation of ethanol takes place to give electrons and then go through the external circuit reducing metal ions to metallic on the cathode, metals are recovered. Taking an example of removal of 100mgL -1 gold in 0.5M HAc-NaAc buffer solution as the catholyte, 2.0M ethanol in 1.0M alkaline solution as the anolyte, an open circuit voltage of 1.4V, more than 96% of gold removal efficiency in 20h, and equivalent energy production of 2.0kWhkg -1 of gold can be readily achieved in this system. When gold and copper ions coexist, it was confirmed that metallic Cu is formed on the cathodic electrode later than metallic Au formation by XPS analysis. Thus, this system can achieve step by step electrodeposition of gold and copper while the two metal ions coexisting. This work develops a new approach to retrieve valuable metals from aqueous solution or e-wastes. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Science.gov (United States)

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.

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.

Interfacial Adsorption and Redox Coupling of Li4Ti5O12 with Nanographene for High-Rate Lithium Storage.

Science.gov (United States)

Bae, Seongjun; Nam, Inho; Park, Soomin; Yoo, Young Geun; Yu, Sungju; Lee, Jong Min; Han, Jeong Woo; Yi, Jongheop

2015-08-05

Despite the many efforts to solve the problem associated with lithium storage at high rates, it is rarely achieved up until now. The design with experimental proof is reported here for the high rate of lithium storage via a core-shell structure composite comprised of a Li4Ti5O12 (LTO) core and a nanographene (NG) shell. The LTO-NG core-shell was synthesized via a first-principles understanding of the adsorption properties between LTO and NG. Interfacial reactions are considered between the two materials by a redox coupling effect. The large interfacial area between the LTO core and the NG shell resulted in a high electron-conducting path. It allowed rapid kinetics to be achieved for lithium storage and also resulted in a stable contact between LTO and NG, affording cyclic performance stability.

Kinetic investigation of vanadium (V)/(IV) redox couple on electrochemically oxidized graphite electrodes

International Nuclear Information System (INIS)

Wang, Wenjun; Wei, Zengfu; Su, Wei; Fan, Xinzhuang; Liu, Jianguo; Yan, Chuanwei; Zeng, Chaoliu

2016-01-01

Highlights: • The VO_2"+/VO"2"+ redox reaction of the electrode could be facilitated to some extent with the increasing anodic corrosion. • A real reaction kinetic equation for the oxidation of VO"2"+ on the electrochemically oxidized electrode has been firstly obtained. • The establishment of the kinetic equation is conducive to predict polarization behaviors of the electrodes in engineering application. - Abstract: The morphology, surface composition, wettability and the kinetic parameters of the electrochemically oxidized graphite electrodes obtained under different anodic polarization conditions have been examined by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), contact angle measurements, steady-state polarization and cyclic voltammetry (CV) tests, with an attempt to investigate the inherent correlation between the physicochemical properties and the kinetic characteristics for carbon electrodes used in an all-vanadium redox flow battery (VRFB). When the anodic polarization potential raises up to 1.8 V vs. SCE, the anodic corrosion of the graphite might happen and a large number of oxygen-containing functional groups generate. The VO_2"+/VO"2"+ redox reaction can be facilitated and the reaction reversibility tends to become better with the increasing anodic potential, possibly owing to the increased surface oxides and the resulting improved wettability of the electrode. Based on this, a real reaction kinetic equation for the oxidation of VO"2"+ has been obtained on the electrode polarized at 1.8 V vs. SCE and it can be also well used to predict the polarization behavior of the oxidized electrode in vanadium (IV) acidic solutions.

Plasmonic tunnel junctions for single-molecule redox chemistry.

Science.gov (United States)

de Nijs, Bart; Benz, Felix; Barrow, Steven J; Sigle, Daniel O; Chikkaraddy, Rohit; Palma, Aniello; Carnegie, Cloudy; Kamp, Marlous; Sundararaman, Ravishankar; Narang, Prineha; Scherman, Oren A; Baumberg, Jeremy J

2017-10-20

Nanoparticles attached just above a flat metallic surface can trap optical fields in the nanoscale gap. This enables local spectroscopy of a few molecules within each coupled plasmonic hotspot, with near thousand-fold enhancement of the incident fields. As a result of non-radiative relaxation pathways, the plasmons in such sub-nanometre cavities generate hot charge carriers, which can catalyse chemical reactions or induce redox processes in molecules located within the plasmonic hotspots. Here, surface-enhanced Raman spectroscopy allows us to track these hot-electron-induced chemical reduction processes in a series of different aromatic molecules. We demonstrate that by increasing the tunnelling barrier height and the dephasing strength, a transition from coherent to hopping electron transport occurs, enabling observation of redox processes in real time at the single-molecule level.

Electrochemical reverse engineering: A systems-level tool to probe the redox-based molecular communication of biology.

Science.gov (United States)

Li, Jinyang; Liu, Yi; Kim, Eunkyoung; March, John C; Bentley, William E; Payne, Gregory F

2017-04-01

The intestine is the site of digestion and forms a critical interface between the host and the outside world. This interface is composed of host epithelium and a complex microbiota which is "connected" through an extensive web of chemical and biological interactions that determine the balance between health and disease for the host. This biology and the associated chemical dialogues occur within a context of a steep oxygen gradient that provides the driving force for a variety of reduction and oxidation (redox) reactions. While some redox couples (e.g., catecholics) can spontaneously exchange electrons, many others are kinetically "insulated" (e.g., biothiols) allowing the biology to set and control their redox states far from equilibrium. It is well known that within cells, such non-equilibrated redox couples are poised to transfer electrons to perform reactions essential to immune defense (e.g., transfer from NADH to O 2 for reactive oxygen species, ROS, generation) and protection from such oxidative stresses (e.g., glutathione-based reduction of ROS). More recently, it has been recognized that some of these redox-active species (e.g., H 2 O 2 ) cross membranes and diffuse into the extracellular environment including lumen to transmit redox information that is received by atomically-specific receptors (e.g., cysteine-based sulfur switches) that regulate biological functions. Thus, redox has emerged as an important modality in the chemical signaling that occurs in the intestine and there have been emerging efforts to develop the experimental tools needed to probe this modality. We suggest that electrochemistry provides a unique tool to experimentally probe redox interactions at a systems level. Importantly, electrochemistry offers the potential to enlist the extensive theories established in signal processing in an effort to "reverse engineer" the molecular communication occurring in this complex biological system. Here, we review our efforts to develop this

Redox active polymer devices and methods of using and manufacturing the same

Science.gov (United States)

Johnson, Paul; Bautista-Martinez, Jose Antonio; Friesen, Cody; Switzer, Elise

2018-06-05

The disclosed technology relates generally to apparatus comprising conductive polymers and more particularly to tag and tag devices comprising a redox-active polymer film, and method of using and manufacturing the same. In one aspect, an apparatus includes a substrate and a conductive structure formed on the substrate which includes a layer of redox-active polymer film having mobile ions and electrons. The conductive structure further includes a first terminal and a second terminal configured to receive an electrical signal therebetween, where the layer of redox-active polymer is configured to conduct an electrical current generated by the mobile ions and the electrons in response to the electrical signal. The apparatus additionally includes a detection circuit operatively coupled to the conductive structure and configured to detect the electrical current flowing through the conductive structure.

Redox-active antibiotics control gene expression and community behavior in divergent bacteria.

Science.gov (United States)

Dietrich, Lars E P; Teal, Tracy K; Price-Whelan, Alexa; Newman, Dianne K

2008-08-29

It is thought that bacteria excrete redox-active pigments as antibiotics to inhibit competitors. In Pseudomonas aeruginosa, the endogenous antibiotic pyocyanin activates SoxR, a transcription factor conserved in Proteo- and Actinobacteria. In Escherichia coli, SoxR regulates the superoxide stress response. Bioinformatic analysis coupled with gene expression studies in P. aeruginosa and Streptomyces coelicolor revealed that the majority of SoxR regulons in bacteria lack the genes required for stress responses, despite the fact that many of these organisms still produce redox-active small molecules, which indicates that redox-active pigments play a role independent of oxidative stress. These compounds had profound effects on the structural organization of colony biofilms in both P. aeruginosa and S. coelicolor, which shows that "secondary metabolites" play important conserved roles in gene expression and development.

Space-time dependent couplings In N = 1 SUSY gauge theories: Anomalies and central functions

International Nuclear Information System (INIS)

Babington, J.; Erdmenger, J.

2005-01-01

We consider N = 1 supersymmetric gauge theories in which the couplings are allowed to be space-time dependent functions. Both the gauge and the superpotential couplings become chiral superfields. As has recently been shown, a new topological anomaly appears in models with space-time dependent gauge coupling. Here we show how this anomaly may be used to derive the NSVZ β-function in a particular, well-determined renormalisation scheme, both without and with chiral matter. Moreover we extend the topological anomaly analysis to theories coupled to a classical curved superspace background, and use it to derive an all-order expression for the central charge c, the coefficient of the Weyl tensor squared contribution to the conformal anomaly. We also comment on the implications of our results for the central charge a expected to be of relevance for a four-dimensional C-theorem. (author)

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

Enzymes as modular catalysts for redox half-reactions in H2-powered chemical synthesis: from biology to technology.

Science.gov (United States)

Reeve, Holly A; Ash, Philip A; Park, HyunSeo; Huang, Ailun; Posidias, Michalis; Tomlinson, Chloe; Lenz, Oliver; Vincent, Kylie A

2017-01-15

The present study considers the ways in which redox enzyme modules are coupled in living cells for linking reductive and oxidative half-reactions, and then reviews examples in which this concept can be exploited technologically in applications of coupled enzyme pairs. We discuss many examples in which enzymes are interfaced with electronically conductive particles to build up heterogeneous catalytic systems in an approach which could be termed synthetic biochemistry We focus on reactions involving the H + /H 2 redox couple catalysed by NiFe hydrogenase moieties in conjunction with other biocatalysed reactions to assemble systems directed towards synthesis of specialised chemicals, chemical building blocks or bio-derived fuel molecules. We review our work in which this approach is applied in designing enzyme-modified particles for H 2 -driven recycling of the nicotinamide cofactor NADH to provide a clean cofactor source for applications of NADH-dependent enzymes in chemical synthesis, presenting a combination of published and new work on these systems. We also consider related photobiocatalytic approaches for light-driven production of chemicals or H 2 as a fuel. We emphasise the techniques available for understanding detailed catalytic properties of the enzymes responsible for individual redox half-reactions, and the importance of a fundamental understanding of the enzyme characteristics in enabling effective applications of redox biocatalysis. © 2017 The Author(s).

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

Science.gov (United States)

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

2017-06-19

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

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...

Conductance through a redox system in the Coulomb blockade regime: Many-particle effects and influence of electronic correlations

Energy Technology Data Exchange (ETDEWEB)

Tornow, Sabine; Zwicknagl, Gertrud [Institut fuer Mathematische Physik, TU Braunschweig (Germany)

2010-02-15

We investigate the transport characteristics of a redox system weakly coupled to leads in the Coulomb blockade regime. The redox system comprises a donor and acceptor separated by an insulating bridge in a solution. It is modeled by a two-site extended Hubbard model which includes on-site and inter-site Coulomb interactions and the coupling to a bosonic bath. The current-voltage characteristics is calculated at high temperatures using a rate equation approach. For high voltages exceeding the Coulomb repulsion at the donor site the calculated transport characteristics exhibit pronounced deviations from the behavior expected from single-electron transport. Depending on the relative sizes of the effective on-site and inter-site Coulomb interactions on one side and the reorganization energy on the other side we find either negative differential resistance or current enhancement. Schematic view of the redox system with donor (D) and acceptor (A) coupled to the leads L and R. The electronic degrees of freedom of the DA system are coupled to the environment comprising internal vibrations and the solvent dynamics. The current is calculated as a function of the bias voltage V{sub b} and gate voltage V{sub g}. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Energy efficiency of neptunium redox battery in comparison with vanadium battery

International Nuclear Information System (INIS)

Yamamura, T.; Watanabe, N.; Shiokawa, Y.

2006-01-01

A neptunium ion possesses two isostructural and reversible redox couples (Np 3+ /Np 4+ and NpO 2 + /NpO 2 2+ ) and is therefore suitable as an active material for a redox-flow battery. Since the plastic formed carbon (PFC) is known to show the largest k values for Np(IV)/Np(III) and Np(V)/Np(VI) reactions among various carbon electrodes, a cell was constructed by using the PFC, with the circulation induced by bubbling gas through the electrolyte. In discharge experiments with a neptunium and a vanadium battery using the cell, the former showed a lower voltage loss which suggests a smaller reaction overvoltage. Because of the high radioactivity of the neptunium, it was difficult to obtain sufficient circulation required for the redox-flow battery, therefore a model for evaluating the energy efficiency of the redox-flow battery was developed. By using the known k values for neptunium and vanadium electrode reactions at PFC electrodes, the energy efficiency of the neptunium battery was calculated to be 99.1% at 70 mA cm -2 , which exceeds that of the vanadium battery by ca. 16%

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.

Changes in mitochondrial homeostasis and redox status in astronauts following long stays in space

DEFF Research Database (Denmark)

Indo, Hiroko P; Majima, Hideyuki J; Terada, Masahiro

2016-01-01

reductions in the mtRNA/nRNA ratios in both the Inflight and Postflight samples. The mtRNA/mtDNA ratios were relatively constant, except in the Postflight samples. Using the same samples, the expression of redox and signal transduction related genes, MnSOD, CuZnSOD, Nrf2, Keap1, GPx4 and Catalase was also...... examined. The results of the combined data from Preflight, Inflight and Postflight show a significant decrease in the expression of all of the redox-related genes in the samples collected Postflight, with the exception of Catalase, which show no change. This decreased expression may contribute to increased...

Concise Access to 2-Aroylbenzothiazoles by Redox Condensation Reaction between o-Halonitrobenzenes, Acetophenones, and Elemental Sulfur.

Science.gov (United States)

Nguyen, Thanh Binh; Pasturaud, Karine; Ermolenko, Ludmila; Al-Mourabit, Ali

2015-05-15

A wide range of 2-aroylbenzothiazoles 3 including some pharmacologically relevant derivatives can be obtained in high yields by simply heating o-halonitrobenzenes 1, acetophenones 2, elemental sulfur, and N-methylmorpholine. This three-component nitro methyl coupling was found to occur in an excellent atom-, step-, and redox-efficient manner in which elemental sulfur played the role of nucleophile building block and redox moderating agent to fulfill electronic requirements of the global reaction.

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

Metformin selectively targets redox control of complex I energy transduction

Directory of Open Access Journals (Sweden)

Amy R. Cameron

2018-04-01

Full Text Available Many guanide-containing drugs are antihyperglycaemic but most exhibit toxicity, to the extent that only the biguanide metformin has enjoyed sustained clinical use. Here, we have isolated unique mitochondrial redox control properties of metformin that are likely to account for this difference. In primary hepatocytes and H4IIE hepatoma cells we found that antihyperglycaemic diguanides DG5-DG10 and the biguanide phenformin were up to 1000-fold more potent than metformin on cell signalling responses, gluconeogenic promoter expression and hepatocyte glucose production. Each drug inhibited cellular oxygen consumption similarly but there were marked differences in other respects. All diguanides and phenformin but not metformin inhibited NADH oxidation in submitochondrial particles, indicative of complex I inhibition, which also corresponded closely with dehydrogenase activity in living cells measured by WST-1. Consistent with these findings, in isolated mitochondria, DG8 but not metformin caused the NADH/NAD+ couple to become more reduced over time and mitochondrial deterioration ensued, suggesting direct inhibition of complex I and mitochondrial toxicity of DG8. In contrast, metformin exerted a selective oxidation of the mitochondrial NADH/NAD+ couple, without triggering mitochondrial deterioration. Together, our results suggest that metformin suppresses energy transduction by selectively inducing a state in complex I where redox and proton transfer domains are no longer efficiently coupled. Keywords: Diabetes, Metformin, Mitochondria, NADH, NAD+

Methanesulfonic acid solution as supporting electrolyte for zinc-vanadium redox battery

International Nuclear Information System (INIS)

Tang Chao; Zhou Debi

2012-01-01

Highlights: ► Methanesulfonic acid as supporting electrolyte for V(V)/V(IV) was discussed. ► V(V)/V(IV) concentration as high as 3 mol L −1 was obtained. ► A Zn-V battery was assembled. ► The assembled Zn-V battery has good cycle performance and high cell voltage. - Abstract: The present work was performed in order to evaluate methanesulfonic acid (MSA) as electrolyte medium for V(IV)/V(V) redox couple as positive species applied in redox flow battery (RFB). V-MSA solutions containing more than 3.0 mol L −1 vanadium ions were obtained. Conductivity and viscosity of 3.0 mol L −1 V(IV)/V(V) electrolyte were determined to be 0.10 cm s −1 and 12.37 mPa s respectively. Cyclic voltammetry was conducted to investigate the electrochemical behavior of V(IV)/V(V) redox couple. The diffusion coefficients of V(IV) on Pt electrode in 1.0, 2.0 and 3.0 mol L −1 V(IV)/V(V) electrolytes determined were 3.606 × 10 −6 , 1.813 × 10 −6 and 0.5244 × 10 −6 cm 2 s −1 , respectively. A Zn-V battery was assembled with V(IV)/V(V)-MSA positive species and Zn/Zn(II)-MSA negative species. The cell voltage in charged state was 1.9–2.0 V and discharge voltage reached up to 1.7 V. The average coulombic efficiency and energy efficiency of the assembled cell were 95.85% and 63.90% respectively and it showed a good cyclic charge–discharge performance, which indicates that MSA has a promise application prospect in vanadium redox battery.

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

Treatment of graphite felt by modified Hummers method for the positive electrode of vanadium redox flow battery

International Nuclear Information System (INIS)

Wu, Xiaoxin; Xu, Hongfeng; Shen, Yang; Xu, Pengcheng; Lu, Lu; Fu, Jie; Zhao, Hong

2014-01-01

A novel and highly effective treatment based on modified Hummers method was firstly used to improve the electrochemical activity of graphite felt as the positive electrode in all-vanadium redox flow battery (VRFB). The graphite felt was treated by the modified Hummers method and characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The electrochemical performance of the prepared electrode was evaluated through cyclic voltammetry and electrochemical impedance spectroscopy. Results show that graphite felt treated by modified Hummers method exhibits excellent electrocatalytic activity and reaction rate to vanadium redox couples. In our research, the hydrogen electrode and H 2 replaced the graphite felt and V 2+ /V 3+ couple in the negative side in the VRFB performance test. The coulombic, voltage, and energy efficiencies of the VRFB with the as-prepared electrodes at 50 mA cm −2 are 95.0%, 81.3%, and 77.2%, respectively. These values are much higher than those of the cell-assembled graphite felt electrodes that were conventionally and thermally treated. The graphite felt treated by the modified Hummers method carries more hydrophilic groups, such as–OH, on its defects, which is advantageous in facilitating the redox reaction of vanadium ions, thereby improving the operation efficiency of the vanadium redox flow battery

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-10-01

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

On the effect of the Fe(2+)/Fe(3+) redox couple on oxidation of carbon in hot H3PO4

Science.gov (United States)

Dhar, H. P.; Christner, L. G.; Kush, A. K.

1986-01-01

Oxidation studies of graphite:glassy carbon composites have been carried out at 1 and 4.7 atm. pressures in conc. H3PO4 in the presence and absence of iron ions. The concentration of the acid was varied over 85-100 wt pct, and of the iron ions over 30-300 ppm; the temperature varied over 190-210 C. Unlike the effect of Fe, which has been observed to increase the corrosion of carbon in sulphuric acid, the corrosion in phosphoric acid was observed to be slightly decreased or not at all affected. This result arises because of the catalytic reduction of the oxidized surface groups of carbon by Fe(2+) ions. The catalytic reduction is possible because under the experimental conditions the redox potential of the Fe(2+)/Fe(3+) couple is lower than the open-circuit voltage of carbon.

Oncogenic IDH1 Mutations Promote Enhanced Proline Synthesis through PYCR1 to Support the Maintenance of Mitochondrial Redox Homeostasis

Directory of Open Access Journals (Sweden)

Kate E.R. Hollinshead

2018-03-01

Full Text Available Summary: Since the discovery of mutations in isocitrate dehydrogenase 1 (IDH1 in gliomas and other tumors, significant efforts have been made to gain a deeper understanding of the consequences of this oncogenic mutation. One aspect of the neomorphic function of the IDH1 R132H enzyme that has received less attention is the perturbation of cellular redox homeostasis. Here, we describe a biosynthetic pathway exhibited by cells expressing mutant IDH1. By virtue of a change in cellular redox homeostasis, IDH1-mutated cells synthesize excess glutamine-derived proline through enhanced activity of pyrroline 5-carboxylate reductase 1 (PYCR1, coupled to NADH oxidation. Enhanced proline biosynthesis partially uncouples the electron transport chain from tricarboxylic acid (TCA cycle activity through the maintenance of a lower NADH/NAD+ ratio and subsequent reduction in oxygen consumption. Thus, we have uncovered a mechanism by which tumor cell survival may be promoted in conditions associated with perturbed redox homeostasis, as occurs in IDH1-mutated glioma. : Hollinshead et al. demonstrate a role for PYCR1 in control of mitochondrial redox homeostasis. Expression of IDH1 R132H mutation leads to increased NADH-coupled proline biosynthesis, mediated by PYCR1. The resulting metabolic phenotype partially uncouples mitochondrial NADH oxidation from respiration, representing an oxygen-sparing metabolic phenotype. Keywords: glioma, IDH1, redox, metabolism, proline

Equivalence of meson scattering amplitudes in strong coupling lattice and flat space string theory

Directory of Open Access Journals (Sweden)

Adi Armoni

2018-03-01

Full Text Available We consider meson scattering in the framework of the lattice strong coupling expansion. In particular we derive an expression for the 4-point function of meson operators in the planar limit of scalar Chromodynamics. Interestingly, in the naive continuum limit the expression coincides with an independently known result, that of the worldline formalism. Moreover, it was argued by Makeenko and Olesen that (assuming confinement the resulting scattering amplitude in momentum space is the celebrated expression proposed by Veneziano several decades ago. This motivates us to also use holography in order to argue that the continuum expression for the scattering amplitude is related to the result obtained from flat space string theory. Our results hint that at strong coupling and large-Nc the naive continuum limit of the lattice formalism can be related to a flat space string theory.

Equivalence of meson scattering amplitudes in strong coupling lattice and flat space string theory

Science.gov (United States)

Armoni, Adi; Ireson, Edwin; Vadacchino, Davide

2018-03-01

We consider meson scattering in the framework of the lattice strong coupling expansion. In particular we derive an expression for the 4-point function of meson operators in the planar limit of scalar Chromodynamics. Interestingly, in the naive continuum limit the expression coincides with an independently known result, that of the worldline formalism. Moreover, it was argued by Makeenko and Olesen that (assuming confinement) the resulting scattering amplitude in momentum space is the celebrated expression proposed by Veneziano several decades ago. This motivates us to also use holography in order to argue that the continuum expression for the scattering amplitude is related to the result obtained from flat space string theory. Our results hint that at strong coupling and large-Nc the naive continuum limit of the lattice formalism can be related to a flat space string theory.

Ensemble Kalman Filtering with a Divided State-Space Strategy for Coupled Data Assimilation Problems

KAUST Repository

Luo, Xiaodong

2014-12-01

This study considers the data assimilation problem in coupled systems, which consists of two components (subsystems) interacting with each other through certain coupling terms. A straightforward way to tackle the assimilation problem in such systems is to concatenate the states of the subsystems into one augmented state vector, so that a standard ensemble Kalman filter (EnKF) can be directly applied. This work presents a divided state-space estimation strategy, in which data assimilation is carried out with respect to each individual subsystem, involving quantities from the subsystem itself and correlated quantities from other coupled subsystems. On top of the divided state-space estimation strategy, the authors also consider the possibility of running the subsystems separately. Combining these two ideas, a few variants of the EnKF are derived. The introduction of these variants is mainly inspired by the current status and challenges in coupled data assimilation problems and thus might be of interest from a practical point of view. Numerical experiments with a multiscale Lorenz 96 model are conducted to evaluate the performance of these variants against that of the conventional EnKF. In addition, specific for coupled data assimilation problems, two prototypes of extensions of the presented methods are also developed in order to achieve a trade-offbetween efficiency and accuracy.

Ensemble Kalman Filtering with a Divided State-Space Strategy for Coupled Data Assimilation Problems

KAUST Repository

Luo, Xiaodong; Hoteit, Ibrahim

2014-01-01

This study considers the data assimilation problem in coupled systems, which consists of two components (subsystems) interacting with each other through certain coupling terms. A straightforward way to tackle the assimilation problem in such systems is to concatenate the states of the subsystems into one augmented state vector, so that a standard ensemble Kalman filter (EnKF) can be directly applied. This work presents a divided state-space estimation strategy, in which data assimilation is carried out with respect to each individual subsystem, involving quantities from the subsystem itself and correlated quantities from other coupled subsystems. On top of the divided state-space estimation strategy, the authors also consider the possibility of running the subsystems separately. Combining these two ideas, a few variants of the EnKF are derived. The introduction of these variants is mainly inspired by the current status and challenges in coupled data assimilation problems and thus might be of interest from a practical point of view. Numerical experiments with a multiscale Lorenz 96 model are conducted to evaluate the performance of these variants against that of the conventional EnKF. In addition, specific for coupled data assimilation problems, two prototypes of extensions of the presented methods are also developed in order to achieve a trade-offbetween efficiency and accuracy.

Zn and Fe complexes containing a redox active macrocyclic biquinazoline ligand.

Science.gov (United States)

Banerjee, Priyabrata; Company, Anna; Weyhermüller, Thomas; Bill, Eckhard; Hess, Corinna R

2009-04-06

A series of iron and zinc complexes has been synthesized, coordinated by the macrocyclic biquinazoline ligand, 2-4:6-8-bis(3,3,4,4-tetramethyldihydropyrrolo)-10-15-(2,2'-biquinazolino)-[15]-1,3,5,8,10,14-hexaene-1,3,7,9,11,14-N(6) (Mabiq). The Mabiq ligand consists of a bipyrimidine moiety and two dihydropyrrole units. The electronic structures of the metal-Mabiq complexes have been characterized using spectroscopic and density-functional theory (DFT) computational methods. The parent zinc complex exhibits a ligand-centered reduction to generate the metal-coordinated Mabiq radical dianion, establishing the redox non-innocence of this ligand. Iron-Mabiq complexes have been isolated in three oxidation states. This redox series includes low-spin ferric and low-spin ferrous species, as well as an intermediate-spin Fe(II) compound. In the latter complex, the iron ion is antiferromagnetically coupled to a Mabiq-centered pi-radical. The results demonstrate the rich redox chemistry and electronic properties of metal complexes coordinated by the Mabiq ligand.

Redox speciation of final repository relevant elements using separation methods in combination with ICP mass spectrometry

International Nuclear Information System (INIS)

Graser, Carl-Heinrich

2015-01-01

The long-term safety assessment for nuclear waste repositories requires a detailed understanding of the chemistry of actinide elements in the geosphere. The development of advanced analytical tools is required to gain detailed insights into actinide redox speciation in a given system. The mobility of radionuclides is mostly determined by the geochemical conditions which control the redox state of radionuclides. Besides the longlived radionuclides plutonium (Pu) and neptunium (Np), which are key elements in high level nuclear waste, iron (Fe) represents a main component in natural systems controlling redox related geochemical processes. Analytical techniques for determining oxidation state distribution for redox sensitive radionuclides and other metal ions often have a lack of sensitivity. The detection limits of these methods (i.e. UV/vis, TRLFS, XANES) are in general in the range of ≥ 10 -6 mol.L -1 . As a consequence ultrasensitive new analytical techniques are required. Capillary electrophoresis (CE) and ion chromatography (IC) are powerful separation methods for metal ions. In the course of this thesis different speciation method for iron, neptunium and plutonium were optimized. With the optimized setup redox speciation analysis of these elements in different samples were done. Furthermore CE hyphenated to inductively coupled plasma sector field mass spectrometry (CE - ICP - SF - MS) was used to measure the redox speciation of Pu (III, IV, V, VI), Np (IV, V, VI) and Fe (II, III) at concentrations lower than 10 -7 mol.L -1 . CE coupling and separation parameters such as sample gas pressure, make up flow rate, capillary position, auxiliary gas flow, as well as the electrolyte system were optimized to obtain the maximum sensitivity. The methodes detection limits are 10 -12 mol.L -1 for Np and Pu. The various oxidation state species of Pu and Np in different samples were separated by application of an acetate based electrolyte system. The separation of Fe (II

Space-time coupled spectral/hp least-squares finite element formulation for the incompressible Navier-Stokes equations

International Nuclear Information System (INIS)

Pontaza, J.P.; Reddy, J.N.

2004-01-01

We consider least-squares finite element models for the numerical solution of the non-stationary Navier-Stokes equations governing viscous incompressible fluid flows. The paper presents a formulation where the effects of space and time are coupled, resulting in a true space-time least-squares minimization procedure, as opposed to a space-time decoupled formulation where a least-squares minimization procedure is performed in space at each time step. The formulation is first presented for the linear advection-diffusion equation and then extended to the Navier-Stokes equations. The formulation has no time step stability restrictions and is spectrally accurate in both space and time. To allow the use of practical C 0 element expansions in the resulting finite element model, the Navier-Stokes equations are expressed as an equivalent set of first-order equations by introducing vorticity as an additional independent variable and the least-squares method is used to develop the finite element model of the governing equations. High-order element expansions are used to construct the discrete model. The discrete model thus obtained is linearized by Newton's method, resulting in a linear system of equations with a symmetric positive definite coefficient matrix that is solved in a fully coupled manner by a preconditioned conjugate gradient method in matrix-free form. Spectral convergence of the L 2 least-squares functional and L 2 error norms in space-time is verified using a smooth solution to the two-dimensional non-stationary incompressible Navier-Stokes equations. Numerical results are presented for impulsively started lid-driven cavity flow, oscillatory lid-driven cavity flow, transient flow over a backward-facing step, and flow around a circular cylinder; the results demonstrate the predictive capability and robustness of the proposed formulation. Even though the space-time coupled formulation is emphasized, we also present the formulation and numerical results for least

Elucidating effects of cell architecture, electrode material, and solution composition on overpotentials in redox flow batteries

International Nuclear Information System (INIS)

Pezeshki, Alan M.; Sacci, Robert L.; Delnick, Frank M.; Aaron, Douglas S.; Mench, Matthew M.

2017-01-01

An improved method for quantitative measurement of the charge transfer, finite diffusion, and ohmic overpotentials in redox flow batteries using electrochemical impedance spectroscopy is presented. The use of a pulse dampener in the hydraulic circuit enables the collection of impedance spectra at low frequencies with a peristaltic pump, allowing the measurement of finite diffusion resistances at operationally relevant flow rates. This method is used to resolve the rate-limiting processes for the V 2+ /V 3+ redox couple on carbon felt and carbon paper electrodes in the vanadium redox flow battery. Carbon felt was limited by both charge transfer and ohmic resistance, while carbon paper was limited by charge transfer, finite diffusion, and ohmic resistances. The influences of vanadium concentration and flow field design also are quantified.

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.

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

Molecular imaging of in vivo redox dynamics using magnetic resonance system

International Nuclear Information System (INIS)

Utsumi, Hideo; Yasukawa, Keiji

2008-01-01

Homeostatic failure through redox systems in vivo results in abnormality in mitochondrial function, protein expression and metabolism leading to many diseases like lifestyle related ones and cancer. It is therefore important to see redox dynamics for early prevention of the diseases. This paper describes development of machines for electron spin resonance (ESR) imaging of the redox state, for Overhauser Effect MRI (OMRI), application of nitroxyl-probes and state of redox project by authors. They have developed the ESR equipments hitherto, including the latest 300 MHz one, with which images of a mouse given carbamoyl-PROXYL probe are obtained and fused with MRI images for anatomical positioning: resonator for both ESR and MRI coils has been developed for animal images. Philips OMRI machine has been able to give separate images of reduction and oxidation in animals given appropriate probe compounds, which lead to molecular imaging of redox using such probes as 14 N- and 15 N-nitroxyl radicals with different membrane permeability. Application of nitroxyl-radicals like hydroxyl-TEMPO has made it possible for the animal diseases caused by oxidative stress to be analyzed by ESR/spin probe method, and derivatization of the probe results in detection of its distribution in various cell and body areas even in nanometer-space. Authors' project concerns the development of the processing system of redox dynamics/OMRI-integrated images, of better probe complexes and application of these to actual model animals. The techniques are thought to be important in the fields of medicare and new drug development in future. (R.T.)

Corynebacterium diphtheriae methionine sulfoxide reductase a exploits a unique mycothiol redox relay mechanism.

Science.gov (United States)

Tossounian, Maria-Armineh; Pedre, Brandán; Wahni, Khadija; Erdogan, Huriye; Vertommen, Didier; Van Molle, Inge; Messens, Joris

2015-05-01

Methionine sulfoxide reductases are conserved enzymes that reduce oxidized methionines in proteins and play a pivotal role in cellular redox signaling. We have unraveled the redox relay mechanisms of methionine sulfoxide reductase A of the pathogen Corynebacterium diphtheriae (Cd-MsrA) and shown that this enzyme is coupled to two independent redox relay pathways. Steady-state kinetics combined with mass spectrometry of Cd-MsrA mutants give a view of the essential cysteine residues for catalysis. Cd-MsrA combines a nucleophilic cysteine sulfenylation reaction with an intramolecular disulfide bond cascade linked to the thioredoxin pathway. Within this cascade, the oxidative equivalents are transferred to the surface of the protein while releasing the reduced substrate. Alternatively, MsrA catalyzes methionine sulfoxide reduction linked to the mycothiol/mycoredoxin-1 pathway. After the nucleophilic cysteine sulfenylation reaction, MsrA forms a mixed disulfide with mycothiol, which is transferred via a thiol disulfide relay mechanism to a second cysteine for reduction by mycoredoxin-1. With x-ray crystallography, we visualize two essential intermediates of the thioredoxin relay mechanism and a cacodylate molecule mimicking the substrate interactions in the active site. The interplay of both redox pathways in redox signaling regulation forms the basis for further research into the oxidative stress response of this pathogen. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Ab Initio Metadynamics Study of the VO2+/VO2+ Redox Reaction Mechanism at the Graphite Edge/Water Interface.

Science.gov (United States)

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2018-06-08

Redox flow batteries (RFBs) are promising electrochemical energy storage systems, for which development is impeded by a poor understanding of redox reactions occurring at electrode/electrolyte interfaces. Even for the conventional all-vanadium RFB chemistry employing V 2+ /V 3+ and VO 2 + /VO 2+ couples, there is still no consensus about the reaction mechanism, electrode active sites, and rate-determining step. Herein, we perform Car-Parrinello molecular dynamics-based metadynamics simulations to unravel the mechanism of the VO 2 + /VO 2+ redox reaction in water at the oxygen-functionalized graphite (112̅0) edge surface serving as a representative carbon-based electrode. Our results suggest that during the battery discharge aqueous VO 2 + /VO 2+ species adsorb at the surface C-O groups as inner-sphere complexes, exhibiting faster adsorption/desorption kinetics than V 2+ /V 3+ , at least at low vanadium concentrations considered in our study. We find that this is because (i) VO 2 + /VO 2+ conversion does not involve the slow transfer of an oxygen atom, (ii) protonation of VO 2 + is spontaneous and coupled to interfacial electron transfer in acidic conditions to enable VO 2+ formation, and (iii) V 3+ found to be strongly bound to oxygen groups of the graphite surface features unfavorable desorption kinetics. In contrast, the reverse process taking place upon charging is expected to be more sluggish for the VO 2 + /VO 2+ redox couple because of both unfavorable deprotonation of the VO 2+ water ligands and adsorption/desorption kinetics.

Coupled motions direct electrons along human microsomal P450 Chains.

Directory of Open Access Journals (Sweden)

Christopher R Pudney

2011-12-01

Full Text Available Protein domain motion is often implicated in biological electron transfer, but the general significance of motion is not clear. Motion has been implicated in the transfer of electrons from human cytochrome P450 reductase (CPR to all microsomal cytochrome P450s (CYPs. Our hypothesis is that tight coupling of motion with enzyme chemistry can signal "ready and waiting" states for electron transfer from CPR to downstream CYPs and support vectorial electron transfer across complex redox chains. We developed a novel approach to study the time-dependence of dynamical change during catalysis that reports on the changing conformational states of CPR. FRET was linked to stopped-flow studies of electron transfer in CPR that contains donor-acceptor fluorophores on the enzyme surface. Open and closed states of CPR were correlated with key steps in the catalytic cycle which demonstrated how redox chemistry and NADPH binding drive successive opening and closing of the enzyme. Specifically, we provide evidence that reduction of the flavin moieties in CPR induces CPR opening, whereas ligand binding induces CPR closing. A dynamic reaction cycle was created in which CPR optimizes internal electron transfer between flavin cofactors by adopting closed states and signals "ready and waiting" conformations to partner CYP enzymes by adopting more open states. This complex, temporal control of enzyme motion is used to catalyze directional electron transfer from NADPH→FAD→FMN→heme, thereby facilitating all microsomal P450-catalysed reactions. Motions critical to the broader biological functions of CPR are tightly coupled to enzyme chemistry in the human NADPH-CPR-CYP redox chain. That redox chemistry alone is sufficient to drive functionally necessary, large-scale conformational change is remarkable. Rather than relying on stochastic conformational sampling, our study highlights a need for tight coupling of motion to enzyme chemistry to give vectorial electron

Self-consistency in the phonon space of the particle-phonon coupling model

Science.gov (United States)

Tselyaev, V.; Lyutorovich, N.; Speth, J.; Reinhard, P.-G.

2018-04-01

In the paper the nonlinear generalization of the time blocking approximation (TBA) is presented. The TBA is one of the versions of the extended random-phase approximation (RPA) developed within the Green-function method and the particle-phonon coupling model. In the generalized version of the TBA the self-consistency principle is extended onto the phonon space of the model. The numerical examples show that this nonlinear version of the TBA leads to the convergence of results with respect to enlarging the phonon space of the model.

Metabolic Dysfunction in Parkinson's Disease: Bioenergetics, Redox Homeostasis and Central Carbon Metabolism.

Science.gov (United States)

Anandhan, Annadurai; Jacome, Maria S; Lei, Shulei; Hernandez-Franco, Pablo; Pappa, Aglaia; Panayiotidis, Mihalis I; Powers, Robert; Franco, Rodrigo

2017-07-01

The loss of dopaminergic neurons in the substantia nigra pars compacta (SNpc) and the accumulation of protein inclusions (Lewy bodies) are the pathological hallmarks of Parkinson's disease (PD). PD is triggered by genetic alterations, environmental/occupational exposures and aging. However, the exact molecular mechanisms linking these PD risk factors to neuronal dysfunction are still unclear. Alterations in redox homeostasis and bioenergetics (energy failure) are thought to be central components of neurodegeneration that contribute to the impairment of important homeostatic processes in dopaminergic cells such as protein quality control mechanisms, neurotransmitter release/metabolism, axonal transport of vesicles and cell survival. Importantly, both bioenergetics and redox homeostasis are coupled to neuro-glial central carbon metabolism. We and others have recently established a link between the alterations in central carbon metabolism induced by PD risk factors, redox homeostasis and bioenergetics and their contribution to the survival/death of dopaminergic cells. In this review, we focus on the link between metabolic dysfunction, energy failure and redox imbalance in PD, making an emphasis in the contribution of central carbon (glucose) metabolism. The evidence summarized here strongly supports the consideration of PD as a disorder of cell metabolism. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

Vanadium and Chromium Redox Behavior in borosilicate Nuclear Waste Glasses

International Nuclear Information System (INIS)

McKeown, D.; Muller, I.; Gan, H.; Feng, Z.; Viragh, C.; Pegg, I.

2011-01-01

X-ray absorption spectroscopy (XAS) was used to characterize vanadium (V) and chromium (Cr) environments in low activity nuclear waste (LAW) glasses synthesized under a variety of redox conditions. V 2 O 5 was added to the melt to improve sulfur incorporation from the waste; however, at sufficiently high concentrations, V increased melt foaming, which lowered melt processing rates. Foaming may be reduced by varying the redox conditions of the melt, while small amounts of Cr are added to reduce melter refractory corrosion. Three parent glasses were studied, where CO-CO 2 mixtures were bubbled through the corresponding melt for increasing time intervals so that a series of redox-adjusted-glasses was synthesized from each parent glass. XAS data indicated that V and Cr behaviors are significantly different in these glasses with respect to the cumulative gas bubbling times: V 4+ /V total ranges from 8 to 35%, while Cr 3+ /Cr total can range from 15 to 100% and even to population distributions including Cr 2+ . As Na-content decreased, V, and especially, Cr became more reduced, when comparing equivalent glasses within a series. The Na-poor glass series show possible redox coupling between V and Cr, where V 4+ populations increase after initial bubbling, but as bubbling time increases, V 4+ populations drop to near the level of the parent glass, while Cr becomes more reduced to the point of having increasing Cr 2+ populations.

Camera memory study for large space telescope. [charge coupled devices

Science.gov (United States)

Hoffman, C. P.; Brewer, J. E.; Brager, E. A.; Farnsworth, D. L.

1975-01-01

Specifications were developed for a memory system to be used as the storage media for camera detectors on the large space telescope (LST) satellite. Detectors with limited internal storage time such as intensities charge coupled devices and silicon intensified targets are implied. The general characteristics are reported of different approaches to the memory system with comparisons made within the guidelines set forth for the LST application. Priority ordering of comparisons is on the basis of cost, reliability, power, and physical characteristics. Specific rationales are provided for the rejection of unsuitable memory technologies. A recommended technology was selected and used to establish specifications for a breadboard memory. Procurement scheduling is provided for delivery of system breadboards in 1976, prototypes in 1978, and space qualified units in 1980.

Redox equilibrium of U4+/U3+ in molten NaCl-2CsCl by UV-Vis spectrophotometry and cyclic voltammetry

International Nuclear Information System (INIS)

Nagai, Takayuki; Uehara, Akihiro; Fujii, Toshiyuki; Shirai, Osamu; Yamana, Hajimu; Sato, Nobuaki

2005-01-01

In order to investigate the redox equilibrium of uranium ions in molten NaCl-2CsCl, UV-Vis absorption spectro-photometry measurements were performed for U 4+ and U 3+ in molten NaCl-2CsCl at 923 K under simultaneous electrolytic control of their ratio. Prominent absorption bands at 480 and 570 nm were assigned to U 3+ , and their molar absorptivities were determined to be 1,260±42 and 963±32 mol -1 ·l·cm -1 respectively. From the dependence of the rest potential of the melt on the spectrophotometrically determined ratio of [U 4+ ]/[U 3+ ], the standard redox potential of the couple U 4+ /U 3+ at 923 K was determined to be -1.481±0.004 V vs. Cl 2 /Cl - . Cyclic voltammetry measurements were carried out for the couple U 4+ /U 3+ , and the results agreed well with this standard redox potential value. By the results of cyclic voltammetry, a temperature dependence of the standard redox potential was found to be -2.094+6.639 x 10 -4 T (T=823-923K). (author)

1,5-Diamido-9,10-anthraquinone, a Centrosymmetric Redox-Active Bridge with Two Coupled β-Ketiminato Chelate Functions: Symmetric and Asymmetric Diruthenium Complexes.

Science.gov (United States)

Ansari, Mohd Asif; Mandal, Abhishek; Paretzki, Alexa; Beyer, Katharina; Fiedler, Jan; Kaim, Wolfgang; Lahiri, Goutam Kumar

2016-06-06

The dinuclear complexes {(μ-H2L)[Ru(bpy)2]2}(ClO4)2 ([3](ClO4)2), {(μ-H2L)[Ru(pap)2]2}(ClO4)2 ([4](ClO4)2), and the asymmetric [(bpy)2Ru(μ-H2L)Ru(pap)2](ClO4)2 ([5](ClO4)2) were synthesized via the mononuclear species [Ru(H3L)(bpy)2]ClO4 ([1]ClO4) and [Ru(H3L)(pap)2]ClO4 ([2]ClO4), where H4L is the centrosymmetric 1,5-diamino-9,10-anthraquinone, bpy is 2,2'-bipyridine, and pap is 2-phenylazopyridine. Electrochemistry of the structurally characterized [1]ClO4, [2]ClO4, [3](ClO4)2, [4](ClO4)2, and [5](ClO4)2 reveals multistep oxidation and reduction processes, which were analyzed by electron paramagnetic resonance (EPR) of paramagnetic intermediates and by UV-vis-NIR spectro-electrochemistry. With support by time-dependent density functional theory (DFT) calculations the redox processes could be assigned. Significant results include the dimetal/bridging ligand mixed spin distribution in 3(3+) versus largely bridge-centered spin in 4(3+)-a result of the presence of Ru(II)-stabilizig pap coligands. In addition to the metal/ligand alternative for electron transfer and spin location, the dinuclear systems allow for the observation of ligand/ligand and metal/metal site differentiation within the multistep redox series. DFT-supported EPR and NIR absorption spectroscopy of the latter case revealed class II mixed-valence behavior of the oxidized asymmetric system 5(3+) with about equal contributions from a radical bridge formulation. In comparison to the analogues with the deprotonated 1,4-diaminoanthraquinone isomer the centrosymmetric H2L(2-) bridge shows anodically shifted redox potentials and weaker electronic coupling between the chelate sites.

Redox signaling in the growth and development of colonial hydroids.

Science.gov (United States)

Blackstone, Neil W

2003-02-01

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

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

Science.gov (United States)

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

2017-11-01

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

Feasibility of assessing health state by detecting redox state of human body based on Chinese medicine constitution.

Science.gov (United States)

Li, Ling-Ru; Wang, Qi; Wang, Ji; Wang, Qian-Fei; Yang, Ling-Ling; Zheng, Lu-Yu; Zhang, Yan

2016-08-01

This article discussed the feasibility of assessing health state by detecting redox state of human body. Firstly, the balance of redox state is the basis of homeostasis, and the balance ability of redox can reflflect health state of human body. Secondly, the redox state of human body is a sensitive index of multiple risk factors of health such as age, external environment and psychological factors. It participates in the occurrence and development of multiple diseases involving metabolic diseases and nervous system diseases, and can serve as a cut-in point for treatment of these diseases. Detecting the redox state of high risk people is signifificantly important for early detection and treatment of disease. The blood plasma and urine could be selected to detect, which is convenient. It is pointed that the indexes not only involve oxidation product and antioxidant enzyme but also redox couple. Chinese medicine constitution reflflects the state of body itself and the ability of adapting to external environment, which is consistent with the connotation of health. It is found that there are nine basic types of constitution in Chinese population, which provides a theoretical basis of health preservation, preventive treatment of disease and personalized treatment. With the combination of redox state detection and the Chinese medicine constitution theory, the heath state can be systemically assessed by conducting large-scale epidemiological survey with classifified detection on redox state of human body.

Redox Reactivity of Cerium Oxide Nanoparticles Induces the Formation of Disulfide Bridges in Thiol-Containing Biomolecules.

Science.gov (United States)

Rollin-Genetet, Françoise; Seidel, Caroline; Artells, Ester; Auffan, Mélanie; Thiéry, Alain; Vidaud, Claude

2015-12-21

The redox state of disulfide bonds is implicated in many redox control systems, such as the cysteine-cystine couple. Among proteins, ubiquitous cysteine-rich metallothioneins possess thiolate metal binding groups susceptible to metal exchange in detoxification processes. CeO2 NPs are commonly used in various industrial applications due to their redox properties. These redox properties that enable dual oxidation states (Ce(IV)/Ce(III)) to exist at their surface may act as oxidants for biomolecules. The interaction among metallothioneins, cysteine, and CeO2 NPs was investigated through various biophysical approaches to shed light on the potential effects of the Ce(4+)/Ce(3+) redox system on the thiol groups of these biomolecules. The possible reaction mechanisms include the formation of a disulfide bridge/Ce(III) complex resulting from the interaction between Ce(IV) and the thiol groups, leading to metal unloading from the MTs, depending on their metal content and cluster type. The formation of stable Ce(3+) disulfide complexes has been demonstrated via their fluorescence properties. This work provides the first evidence of thiol concentration-dependent catalytic oxidation mechanisms between pristine CeO2 NPs and thiol-containing biomolecules.

Elucidating effects of cell architecture, electrode material, and solution composition on overpotentials in redox flow batteries

Energy Technology Data Exchange (ETDEWEB)

Pezeshki, Alan M. [Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Sacci, Robert L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Delnick, Frank M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Aaron, Douglas S. [Univ. of Tennessee, Knoxville, TN (United States); Mench, Matthew M. [Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2017-01-16

Here, an improved method for quantitative measurement of the charge transfer, finite diffusion, and ohmic overpotentials in redox flow batteries using electrochemical impedance spectroscopy is presented. The use of a pulse dampener in the hydraulic circuit enables the collection of impedance spectra at low frequencies with a peristaltic pump, allowing the measurement of finite diffusion resistances at operationally relevant flow rates. This method is used to resolve the rate-limiting processes for the V²⁺/V³⁺ redox couple on carbon felt and carbon paper electrodes in the vanadium redox flow battery. Carbon felt was limited by both charge transfer and ohmic resistance, while carbon paper was limited by charge transfer, finite diffusion, and ohmic resistances. The influences of vanadium concentration and flow field design also are quantified.

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.

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.

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

Science.gov (United States)

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

2017-08-01

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

Extending roGFP Emission via Förster-Type Resonance Energy Transfer Relay Enables Simultaneous Dual Compartment Ratiometric Redox Imaging in Live Cells.

Science.gov (United States)

Norcross, Stevie; Trull, Keelan J; Snaider, Jordan; Doan, Sara; Tat, Kiet; Huang, Libai; Tantama, Mathew

2017-11-22

Reactive oxygen species (ROS) mediate both intercellular and intraorganellar signaling, and ROS propagate oxidative stress between cellular compartments such as mitochondria and the cytosol. Each cellular compartment contains its own sources of ROS as well as antioxidant mechanisms, which contribute to dynamic fluctuations in ROS levels that occur during signaling, metabolism, and stress. However, the coupling of redox dynamics between cellular compartments has not been well studied because of the lack of available sensors to simultaneously measure more than one subcellular compartment in the same cell. Currently, the redox-sensitive green fluorescent protein, roGFP, has been used extensively to study compartment-specific redox dynamics because it provides a quantitative ratiometric readout and it is amenable to subcellular targeting as a genetically encoded sensor. Here, we report a new family of genetically encoded fluorescent protein sensors that extend the fluorescence emission of roGFP via Förster-type resonance energy transfer to an acceptor red fluorescent protein for dual-color live-cell microscopy. We characterize the redox and optical properties of the sensor proteins, and we demonstrate that they can be used to simultaneously measure cytosolic and mitochondrial ROS in living cells. Furthermore, we use these sensors to reveal cell-to-cell heterogeneity in redox coupling between the cytosol and mitochondria when neuroblastoma cells are exposed to reductive and metabolic stresses.

Theoretical and experimental study of redox processes combined with adsorption phenomena under conditions of square-wave voltammetry

OpenAIRE

Gulaboski, Rubin

2001-01-01

Theoretical models of four electrode reactions coupled with adsorption phenomena under conditions of square-wave voltammetry are developed: simple surface redox reaction, surface catalytic reaction, cathodic stripping reaction of I order, and cathodic stripping reaction of II order.

Fundamental studies of uranium and neptunium redox flow batteries (II)

International Nuclear Information System (INIS)

Shiokawa, Y.; Yamamura, T.; Watanabe, N.

2002-01-01

The atomic power generation entails production of so-called minor actinides and accumulation of depleted uranium. The theoretical and experimental investigations are underway to transmute minor actinides for minimizing the long-term radiotoxicity and reducing the radioactive waste. The utilization, however, would be alternative means. The actinide redox couples, An(VI)/An(V) and An(IV)/An(III), have excellent properties as battery active materials. Here j the uranium and neptunium redox flow batteries for the electric power storage are discussed from the electrochemical properties of U, Np, Pu and Am [1,2]. One of the required properties for the batteries for electric power storage is high energy efficiency, which is defined by the ratio of the discharge energy to the charge energy. These energies are dependent on the rapidness of kinetics in the electrode reactions, namely the standard rate constants and also the internal resistance of the battery

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.

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

Science.gov (United States)

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

2009-01-01

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

Electrochemical Detection of Circadian Redox Rhythm in Cyanobacterial Cells via Extracellular Electron Transfer.

Science.gov (United States)

Nishio, Koichi; Pornpitra, Tunanunkul; Izawa, Seiichiro; Nishiwaki-Ohkawa, Taeko; Kato, Souichiro; Hashimoto, Kazuhito; Nakanishi, Shuji

2015-06-01

Recent research on cellular circadian rhythms suggests that the coupling of transcription-translation feedback loops and intracellular redox oscillations is essential for robust circadian timekeeping. For clarification of the molecular mechanism underlying the circadian rhythm, methods that allow for the dynamic and simultaneous detection of transcription/translation and redox oscillations in living cells are needed. Herein, we report that the cyanobacterial circadian redox rhythm can be electrochemically detected based on extracellular electron transfer (EET), a process in which intracellular electrons are exchanged with an extracellular electrode. As the EET-based method is non-destructive, concurrent detection with transcription/translation rhythm using bioluminescent reporter strains becomes possible. An EET pathway that electrochemically connected the intracellular region of cyanobacterial cells with an extracellular electrode was constructed via a newly synthesized electron mediator with cell membrane permeability. In the presence of the mediator, the open circuit potential of the culture medium exhibited temperature-compensated rhythm with approximately 24 h periodicity. Importantly, such circadian rhythm of the open circuit potential was not observed in the absence of the electron mediator, indicating that the EET process conveys the dynamic information regarding the intracellular redox state to the extracellular electrode. These findings represent the first direct demonstration of the intracellular circadian redox rhythm of cyanobacterial cells. © The Author 2015. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Novel strategy to implement active-space coupled-cluster methods

Science.gov (United States)

Rolik, Zoltán; Kállay, Mihály

2018-03-01

A new approach is presented for the efficient implementation of coupled-cluster (CC) methods including higher excitations based on a molecular orbital space partitioned into active and inactive orbitals. In the new framework, the string representation of amplitudes and intermediates is used as long as it is beneficial, but the contractions are evaluated as matrix products. Using a new diagrammatic technique, the CC equations are represented in a compact form due to the string notations we introduced. As an application of these ideas, a new automated implementation of the single-reference-based multi-reference CC equations is presented for arbitrary excitation levels. The new program can be considered as an improvement over the previous implementations in many respects; e.g., diagram contributions are evaluated by efficient vectorized subroutines. Timings for test calculations for various complete active-space problems are presented. As an application of the new code, the weak interactions in the Be dimer were studied.

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.

Nitrogen-Doped Graphene:Effects of nitrogen species on the properties of the vanadium redox flow battery

International Nuclear Information System (INIS)

Shi, Lang; Liu, Suqin; He, Zhen; Shen, Junxi

2014-01-01

Nitrogen-doped graphene nanosheets (NGS), prepared by a simple hydrothermal reaction of graphene oxide (GO) with urea as nitrogen source were studied as positive electrodes in vanadium redox flow battery (VRFB). The synthesized NGS with the nitrogen level as high as 10.12 atom% is proven to be a promising material for VRFB. The structures and electrochemical properties of the materials are investigated by scanning electron microscopy, X-ray photoelectron spectroscopy, cyclic voltammetry and electrochemical impendence spectroscopy. The results demonstrate that not only the nitrogen doping level but the nitrogen type in the NGS are significant for its catalytic activity towards the [VO] 2+ /[VO 2 ] + redox couple reaction. In more detail, among four types of nitrogen species (pyridinic-N, pyrrolic-N, quaternary-N, oxidic-N) doped into the graphene lattice, quaternary-N play mainly roles for improving the catalytic activity toward the [VO] 2+ /[VO 2 ] + couple reaction

Hybrid anodes for redox flow batteries

Science.gov (United States)

Wang, Wei; Xiao, Jie; Wei, Xiaoliang; Liu, Jun; Sprenkle, Vincent L.

2015-12-15

RFBs having solid hybrid electrodes can address at least the problems of active material consumption, electrode passivation, and metal electrode dendrite growth that can be characteristic of traditional batteries, especially those operating at high current densities. The RFBs each have a first half cell containing a first redox couple dissolved in a solution or contained in a suspension. The solution or suspension can flow from a reservoir to the first half cell. A second half cell contains the solid hybrid electrode, which has a first electrode connected to a second electrode, thereby resulting in an equipotential between the first and second electrodes. The first and second half cells are separated by a separator or membrane.

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

International Nuclear Information System (INIS)

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

2016-01-01

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

Effect of succinonitrile on electrical, structural, optical, and thermal properties of [poly(ethylene oxide)-succinonitrile]/LiI–I2 redox-couple solid polymer electrolyte

International Nuclear Information System (INIS)

Gupta, Ravindra Kumar; Rhee, Hee-Woo

2012-01-01

Effect of succinonitrile on electrical, structural, optical, and thermal properties of [poly(ethylene oxide)-succinonitrile]/LiI–I 2 redox-couple solid polymer electrolyte is reported for the first time. For the poly(ethylene oxide)-succinonitrile blend-based electrolyte electrical conductivity was noted as high as ∼3 × 10 −4 S cm −1 at 25 °C, which is an order of magnitude higher than that of pure poly(ethylene oxide)-based electrolyte. It also exhibited relatively better pseudo-activation energy (∼0.08 eV). X-ray diffractometry, polarized optical microscopy, and differential scanning calorimetry studies revealed that succinonitrile is helpful in reducing the poly(ethylene oxide) crystallinity due to its plasticizing property. FT-IR study showed significant modification of the poly(ethylene oxide) chain conformation due to the succinonitrile.

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.

Development of a redox-free Mitsunobu reaction exploiting phosphine oxides as precursors to dioxyphosphoranes.

Science.gov (United States)

Tang, Xiaoping; Chapman, Charlotte; Whiting, Matthew; Denton, Ross

2014-07-14

The development of the first redox-free protocol for the Mitsunobu reaction is described. This has been achieved by exploiting triphenylphosphine oxide--the unwanted by-product in the conventional Mitsunobu reaction--as the precursor to the active P(V) coupling reagent. Multinuclear NMR studies are consistent with hydroxyl activation via an alkoxyphosphonium salt.

Direct Solar Charging of an Organic-Inorganic, Stable, and Aqueous Alkaline Redox Flow Battery with a Hematite Photoanode.

Science.gov (United States)

Wedege, Kristina; Azevedo, João; Khataee, Amirreza; Bentien, Anders; Mendes, Adélio

2016-06-13

The intermittent nature of the sunlight and its increasing contribution to electricity generation is fostering the energy storage research. Direct solar charging of an auspicious type of redox flow battery could make solar energy directly and efficiently dispatchable. The first solar aqueous alkaline redox flow battery using low cost and environmentally safe materials is demonstrated. The electrolytes consist of the redox couples ferrocyanide and anthraquinone-2,7-disulphonate in sodium hydroxide solution, yielding a standard cell potential of 0.74 V. Photovoltage enhancement strategies are demonstrated for the ferrocyanide-hematite junction by employing an annealing treatment and growing a layer of a conductive polyaniline polymer on the electrode surface, which decreases electron-hole recombination. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Advanced screening of electrode couples

Science.gov (United States)

Giner, J. D.; Cahill, K.

1980-01-01

The chromium (Cr(3+)/Cr(2+)) redox couple (electrolyte and electrode) was investigated to determine its suitability as negative electrode for the iron (Fe(3+)/Fe(2+))-chromium (Cr(3+)/Cr(2+)) redox flow battery. Literature search and laboratory investigation established that the solubility and stability of aqueous acidic solutions of chromium(3) chloride and chromium(2) chloride are sufficient for redox battery application. Four categories of electrode materials were tested; namely, metals and metalloid materials (elements and compounds), alloys, plated materials, and Teflon-bonded materials. In all, the relative performance of 26 candidate electrode materials was evaluated on the basis of slow scan rate linear sweep voltammetry in stirred solution. No single material tested gave both acceptable anodic an acceptable cathodic performance. However, the identification of lead as a good cathodic electrocatalyst and gold as a good anodic electrocatalyst led to the invention of the lead/gold combination electrocatalyst. This type of catalyst can be fabricated in several ways and appears to offer the advantages of each metal without the disadvantages associated with their use as single materials. This lead/gold electrocatalyst was tested by NASA-Lewis Research Center in complete, flowing, redox batteries comprising a stack of several cells. A large improvement in the battery's coulombic and energy efficiency was observed.

Extracellular Redox Regulation of Intracellular Reactive Oxygen Generation, Mitochondrial Function and Lipid Turnover in Cultured Human Adipocytes.

Directory of Open Access Journals (Sweden)

Albert R Jones

Full Text Available Many tissues play an important role in metabolic homeostasis and the development of diabetes and obesity. We hypothesized that the circulating redox metabolome is a master metabolic regulatory system that impacts all organs and modulates reactive oxygen species (ROS production, lipid peroxidation, energy production and changes in lipid turnover in many cells including adipocytes.Differentiated human preadipocytes were exposed to the redox couples, lactate (L and pyruvate (P, β-hydroxybutyrate (βOHB and acetoacetate (Acoc, and the thiol-disulfides cysteine/ cystine (Cys/CySS and GSH/GSSG for 1.5-4 hours. ROS measurements were done with CM-H2DCFDA. Lipid peroxidation (LPO was assessed by a modification of the thiobarbituric acid method. Lipolysis was measured as glycerol release. Lipid synthesis was measured as 14C-glucose incorporated into lipid. Respiration was assessed using the SeaHorse XF24 analyzer and the proton leak was determined from the difference in respiration with oligomycin and antimycin A.Metabolites with increasing oxidation potentials (GSSG, CySS, Acoc increased adipocyte ROS. In contrast, P caused a decrease in ROS compared with L. Acoc also induced a significant increase in both LPO and lipid synthesis. L and Acoc increased lipolysis. βOHB increased respiration, mainly due to an increased proton leak. GSSG, when present throughout 14 days of differentiation significantly increased fat accumulation, but not when added later.We demonstrated that in human adipocytes changes in the external redox state impacted ROS production, LPO, energy efficiency, lipid handling, and differentiation. A more oxidized state generally led to increased ROS, LPO and lipid turnover and more reduction led to increased respiration and a proton leak. However, not all of the redox couples were the same suggesting compartmentalization. These data are consistent with the concept of the circulating redox metabolome as a master metabolic regulatory system.

Fiber-Coupled Wide Field of View Optical Receiver for High Speed Space Communication

Science.gov (United States)

Suddath, Shannon N.

Research groups at NASA Glenn Research Center are interested in improving data rates on the International Space Station (ISS) using a free-space optical (FSO) link. However, known flexure of the ISS structure is expected to cause misalignment of the FSO link. Passive-control designs for mitigating misalignment are under investigation, including using a fiber-bundle for improved field of view. The designs must overcome the obstacle of coupling directly to fiber, rather than a photodetector, as NASA will maintain the use of small form-factor pluggable optical transceivers (SFPs) in the ISS network. In this thesis, a bundle-based receiver capable of coupling directly to fiber is designed, simulated, and tested in lab. Two 3-lens systems were evaluated for power performance in the lab, one with a 20 mm focal length aspheric lens and the other with a 50 mm focal length aspheric lens. The maximum output power achieved was 8 muW.

Impedance aspect of charge storage at graphite and glassy carbon electrodes in potassium hexacyanoferrate (II redox active electrolyte

Directory of Open Access Journals (Sweden)

Katja Magdić

2016-04-01

Full Text Available Different types of charge storage mechanisms at unmodified graphite vs. glassy carbon electrodes in acid sulphate supporting solution containing potassium hexacyanoferrate (II redox active electrolyte, have been revealed by electrochemical impedance spectroscopy and supported by cyclic voltammetry experiments. Reversible charge transfer of Fe(CN63-/4- redox reaction detected by assessment of CVs of glassy carbon electrode, is in impedance spectra indicated by presence of bulk diffusion impedance and constant double-layer/pseudocapacitive electrode impedance compared to that measured in the pure supporting electrolyte. Some surface retention of redox species detected by assessment of CVs of graphite electrode is in impedance spectra indicated by diffusion impedance coupled in this case by diminishing of double-layer/pseudo­capacitive impedance compared to that measured in the pure supporting electrolyte. This phenomenon is ascribed to contribution of additional pseudocapacitive impedance generated by redox reaction of species confined at the electrode surface.

Wave equations on a de Sitter fiber bundle. [Semiclassical wave function, bundle space, L-S coupling

Energy Technology Data Exchange (ETDEWEB)

Drechsler, W [Max-Planck-Institut fuer Physik und Astrophysik, Muenchen (F.R. Germany)

1975-01-01

A gauge theory of strong interaction is developed based on fields defined on a fiber bundle. The structural group of the bundle is taken to be the Lsub(4,1) de Sitter group. An internal variable xi, varying in the fiber over a space-time point x, is introduced as a means to describe - with the help of a semiclassical wave function psi(x,xi) defined on the bundle space - the internal structure of extended hadrons in a framework using differential geometric techniques. Three basic nonlinear wave equations for psi(x,xi) are established which are of integro-differential type. The nonlinear coupling terms in these de Sitter gauge invariant equations represent physically a generalized spin orbit coupling or a generalized spin coupling for the motion taking place in the fiber. The motivation for using a bigger space for the definition of hadronic matter wave functions as well as the implications of this geometric approach to strong interaction physics is discussed in detail, in particular with respect to the problem of hadronic constituents. The proposed fiber bundle formalism allows a dynamical description of extended structures for hadrons without implying the necessity of introducing any constituents.

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...

Radical O-O coupling reaction in diferrate-mediated water oxidation studied using multireference wave function theory.

Science.gov (United States)

Kurashige, Yuki; Saitow, Masaaki; Chalupský, Jakub; Yanai, Takeshi

2014-06-28

The O-O (oxygen-oxygen) bond formation is widely recognized as a key step of the catalytic reaction of dioxygen evolution from water. Recently, the water oxidation catalyzed by potassium ferrate (K2FeO4) was investigated on the basis of experimental kinetic isotope effect analysis assisted by density functional calculations, revealing the intramolecular oxo-coupling mechanism within a di-iron(vi) intermediate, or diferrate [Sarma et al., J. Am. Chem. Soc., 2012, 134, 15371]. Here, we report a detailed examination of this diferrate-mediated O-O bond formation using scalable multireference electronic structure theory. High-dimensional correlated many-electron wave functions beyond the one-electron picture were computed using the ab initio density matrix renormalization group (DMRG) method along the O-O bond formation pathway. The necessity of using large active space arises from the description of complex electronic interactions and varying redox states both associated with two-center antiferromagnetic multivalent iron-oxo coupling. Dynamic correlation effects on top of the active space DMRG wave functions were additively accounted for by complete active space second-order perturbation (CASPT2) and multireference configuration interaction (MRCI) based methods, which were recently introduced by our group. These multireference methods were capable of handling the double shell effects in the extended active space treatment. The calculations with an active space of 36 electrons in 32 orbitals, which is far over conventional limitation, provide a quantitatively reliable prediction of potential energy profiles and confirmed the viability of the direct oxo coupling. The bonding nature of Fe-O and dual bonding character of O-O are discussed using natural orbitals.

Zelle und Zellstack einer Redox-Flow-Batterie

OpenAIRE

Seipp, Thorsten; Berthold, Sascha; Burfeind, Jens; Kopietz, Lukas

2015-01-01

Source: WO15007543A1 [EN] The invention illustrates and describes a cell (1) of a redox flow battery, having at least one cell frame element (2, 3, 4), a diaphragm (15) and two electrodes (5), wherein the at least one cell frame element (2, 3, 4), the diaphragm (15) and the two electrodes (5) surround two cell interior spaces (10) which are separate from one another, wherein at least four separate channels (6, 7, 8, 9) are provided in the at least one cell frame element (2, 3, 4) such that di...

A Coupled Fixed Point Theorem in Fuzzy Metric Space Satisfying ϕ-Contractive Condition

Directory of Open Access Journals (Sweden)

B. D. Pant

2013-01-01

Full Text Available The intent of this paper is to prove a coupled fixed point theorem for two pairs of compatible and subsequentially continuous (alternately subcompatible and reciprocally continuous mappings, satisfying ϕ-contractive conditions in a fuzzy metric space. We also furnish some illustrative examples to support our results.

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

Increase of nonlinear signal distortions due to linear mode coupling in space division multiplexed systems

DEFF Research Database (Denmark)

Kutluyarov, Ruslan V.; Bagmanov, Valeriy Kh; Antonov, Vyacheslav V.

2017-01-01

This paper is focused on the analysis of linear and nonlinear mode coupling in space division multiplexed (SDM) optical communications over step-index fiber in few-mode regime. Linear mode coupling is caused by the fiber imperfections, while the nonlinear coupling is caused by the Kerr......-nonlinearities. Therefore, we use the system of generalized coupled nonlinear Schrödinger equations (GCNLSE) to describe the signal propagation. We analytically show that the presence of linear mode coupling may cause increasing of the nonlinear signal distortions. For the detailed study we solve GCNLSE numerically...... for the standard step index fiber at the wavelength of 850 nm in the basis of spatial modes with helical phase front (vortex modes) and for a special kind of few-mode fiber with enlarged core, providing propagation of five spatial modes at 1550 nm. Simulation results confirm that the linear mode coupling may lead...

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

The mechanism of coupling between oxido-reduction and proton translocation in respiratory chain enzymes.

Science.gov (United States)

Papa, Sergio; Capitanio, Giuseppe; Papa, Francesco

2018-02-01

The respiratory chain of mitochondria and bacteria is made up of a set of membrane-associated enzyme complexes which catalyse sequential, stepwise transfer of reducing equivalents from substrates to oxygen and convert redox energy into a transmembrane protonmotive force (PMF) by proton translocation from a negative (N) to a positive (P) aqueous phase separated by the coupling membrane. There are three basic mechanisms by which a membrane-associated redox enzyme can generate a PMF. These are membrane anisotropic arrangement of the primary redox catalysis with: (i) vectorial electron transfer by redox metal centres from the P to the N side of the membrane; (ii) hydrogen transfer by movement of quinones across the membrane, from a reduction site at the N side to an oxidation site at the P side; (iii) a different type of mechanism based on co-operative allosteric linkage between electron transfer at the metal redox centres and transmembrane electrogenic proton translocation by apoproteins. The results of advanced experimental and theoretical analyses and in particular X-ray crystallography show that these three mechanisms contribute differently to the protonmotive activity of cytochrome c oxidase, ubiquinone-cytochrome c oxidoreductase and NADH-ubiquinone oxidoreductase of the respiratory chain. This review considers the main features, recent experimental advances and still unresolved problems in the molecular/atomic mechanism of coupling between the transfer of reducing equivalents and proton translocation in these three protonmotive redox complexes. © 2017 Cambridge Philosophical Society.

The measurement of reversible redox dependent post-translational modifications and their regulation of mitochondrial and skeletal muscle function

Directory of Open Access Journals (Sweden)

Philip A Kramer

2015-11-01

Full Text Available Mitochondrial oxidative stress is a common feature of skeletal myopathies across multiple conditions; however, the mechanism by which it contributes to skeletal muscle dysfunction remains controversial. Oxidative damage to proteins, lipids, and DNA has received the most attention, yet an important role for reversible redox post-translational modifications (PTMs in pathophysiology is emerging. The possibility that these PTMs can exert dynamic control of muscle function implicates them as a mechanism contributing to skeletal muscle dysfunction in chronic disease. Herein, we discuss the significance of thiol-based redox dependent modifications to mitochondrial, myofibrillar and excitation-contraction (EC coupling proteins with an emphasis on how these changes could alter skeletal muscle performance under chronically stressed conditions. A major barrier to a better mechanistic understanding of the role of reversible redox PTMs in muscle function is the technical challenges associated with accurately measuring the changes of site-specific redox PTMs. Here we will critically review current approaches with an emphasis on sample preparation artifacts, quantitation, and specificity. Despite these challenges, the ability to accurately quantify reversible redox PTMs is critical to understanding the mechanisms by which mitochondrial oxidative stress contributes to skeletal muscle dysfunction in chronic diseases.

The Measurement of Reversible Redox Dependent Post-translational Modifications and Their Regulation of Mitochondrial and Skeletal Muscle Function

Energy Technology Data Exchange (ETDEWEB)

Kramer, Philip A.; Duan, Jicheng; Qian, Wei-Jun; Marcinek, David J.

2015-11-25

Mitochondrial oxidative stress is a common feature of skeletal myopathies across multiple conditions; however, the mechanism by which it contributes to skeletal muscle dysfunction remains controversial. Oxidative damage to proteins, lipids, and DNA has received the most attention, yet an important role for reversible redox post-translational modifications (PTMs) in pathophysiology is emerging. The possibility that these PTMs can exert dynamic control of muscle function implicates them as a mechanism contributing to skeletal muscle dysfunction in chronic disease. Herein, we discuss the significance of thiol-based redox dependent modifications to mitochondrial, myofibrillar and excitation-contraction (EC) coupling proteins with an emphasis on how these changes could alter skeletal muscle performance under chronically stressed conditions. A major barrier to a better mechanistic understanding of the role of reversible redox PTMs in muscle function is the technical challenges associated with accurately measuring the changes of site-specific redox PTMs. Here we will critically review current approaches with an emphasis on sample preparation artifacts, quantitation, and specificity. Despite these challenges, the ability to accurately quantify reversible redox PTMs is critical to understanding the mechanisms by which mitochondrial oxidative stress contributes to skeletal muscle dysfunction in chronic diseases.

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.)

Fabrication of Freestanding Sheets of Multiwalled Carbon Nanotubes (Buckypapers) for Vanadium Redox Flow Batteries and Effects of Fabrication Variables on Electrochemical Performance

International Nuclear Information System (INIS)

Mustafa, Ibrahim; Lopez, Ivan; Younes, Hammad; Susantyoko, Rahmat Agung; Al-Rub, Rashid Abu; Almheiri, Saif

2017-01-01

Typically, multiwalled carbon nanotubes (MWCNTs) are drop-casted on the surface of the underlying carbon substrates; the outcome is a randomly distributed MWCNT layers leading to uncontrollable structure and unreproducible results. Additionally, we suspect that the electrochemical response is influenced by the primary carbon-based substrate. Herein, we propose the use of freestanding sheets of MWCNTs (buckypapers, BP electrodes) as electrode materials for vanadium redox flow batteries to directly probe the electrochemical activity of MWCNTs toward VO 2+ /VO 2 + and V 2+ /V 3+ redox couples; henceforth, eliminating the need for an underlying carbon substrate. The amount of surfactant and the sonication time used during the fabrication of BP electrodes affect their morphological characteristics and electrochemical performances. Although the electrical conductivity of BP electrodes decreases with increasing surfactant amount and increasing sonication time, the heterogeneous rate constants for both redox couples increase as these fabrication variables are increased, indicating that the performance-limiting process is not electrical conductivity but the number of active sites available for the electrochemical reaction. The standard heterogeneous rate constant of the BP electrode with the highest amount of surfactant is comparable to those of state-of-the-art electrodes. Our promising results call for more research on the potential use of BP electrodes in redox flow batteries.

The extracellular redox state modulates mitochondrial function, gluconeogenesis, and glycogen synthesis in murine hepatocytes.

Science.gov (United States)

Nocito, Laura; Kleckner, Amber S; Yoo, Elsia J; Jones Iv, Albert R; Liesa, Marc; Corkey, Barbara E

2015-01-01

Circulating redox state changes, determined by the ratio of reduced/oxidized pairs of different metabolites, have been associated with metabolic diseases. However, the pathogenic contribution of these changes and whether they modulate normal tissue function is unclear. As alterations in hepatic gluconeogenesis and glycogen metabolism are hallmarks that characterize insulin resistance and type 2 diabetes, we tested whether imposed changes in the extracellular redox state could modulate these processes. Thus, primary hepatocytes were treated with different ratios of the following physiological extracellular redox couples: β-hydroxybutyrate (βOHB)/acetoacetate (Acoc), reduced glutathione (GSH)/oxidized glutathione (GSSG), and cysteine/cystine. Exposure to a more oxidized ratio via extracellular βOHB/Acoc, GSH/GSSG, and cysteine/cystine in hepatocytes from fed mice increased intracellular hydrogen peroxide without causing oxidative damage. On the other hand, addition of more reduced ratios of extracellular βOHB/Acoc led to increased NAD(P)H and maximal mitochondrial respiratory capacity in hepatocytes. Greater βOHB/Acoc ratios were also associated with decreased β-oxidation, as expected with enhanced lipogenesis. In hepatocytes from fasted mice, a more extracellular reduced state of βOHB/Acoc led to increased alanine-stimulated gluconeogenesis and enhanced glycogen synthesis capacity from added glucose. Thus, we demonstrated for the first time that the extracellular redox state regulates the major metabolic functions of the liver and involves changes in intracellular NADH, hydrogen peroxide, and mitochondrial respiration. Because redox state in the blood can be communicated to all metabolically sensitive tissues, this work confirms the hypothesis that circulating redox state may be an important regulator of whole body metabolism and contribute to alterations associated with metabolic diseases.

The extracellular redox state modulates mitochondrial function, gluconeogenesis, and glycogen synthesis in murine hepatocytes.

Directory of Open Access Journals (Sweden)

Laura Nocito

Full Text Available Circulating redox state changes, determined by the ratio of reduced/oxidized pairs of different metabolites, have been associated with metabolic diseases. However, the pathogenic contribution of these changes and whether they modulate normal tissue function is unclear. As alterations in hepatic gluconeogenesis and glycogen metabolism are hallmarks that characterize insulin resistance and type 2 diabetes, we tested whether imposed changes in the extracellular redox state could modulate these processes. Thus, primary hepatocytes were treated with different ratios of the following physiological extracellular redox couples: β-hydroxybutyrate (βOHB/acetoacetate (Acoc, reduced glutathione (GSH/oxidized glutathione (GSSG, and cysteine/cystine. Exposure to a more oxidized ratio via extracellular βOHB/Acoc, GSH/GSSG, and cysteine/cystine in hepatocytes from fed mice increased intracellular hydrogen peroxide without causing oxidative damage. On the other hand, addition of more reduced ratios of extracellular βOHB/Acoc led to increased NAD(PH and maximal mitochondrial respiratory capacity in hepatocytes. Greater βOHB/Acoc ratios were also associated with decreased β-oxidation, as expected with enhanced lipogenesis. In hepatocytes from fasted mice, a more extracellular reduced state of βOHB/Acoc led to increased alanine-stimulated gluconeogenesis and enhanced glycogen synthesis capacity from added glucose. Thus, we demonstrated for the first time that the extracellular redox state regulates the major metabolic functions of the liver and involves changes in intracellular NADH, hydrogen peroxide, and mitochondrial respiration. Because redox state in the blood can be communicated to all metabolically sensitive tissues, this work confirms the hypothesis that circulating redox state may be an important regulator of whole body metabolism and contribute to alterations associated with metabolic diseases.

Redox-Active Antibiotics Control Gene Expression and Community Behavior in Divergent Bacteria

OpenAIRE

Dietrich, Lars E. P.; Teal, Tracy K.; Price-Whelan, Alexa; Newman, Dianne K.

2008-01-01

It is thought that bacteria excrete redox-active pigments as antibiotics to inhibit competitors. In Pseudomonas aeruginosa, the endogenous antibiotic pyocyanin activates SoxR, a transcription factor conserved in Proteo- and Actinobacteria. In Escherichia coli, SoxR regulates the superoxide stress response. Bioinformatic analysis coupled with gene expression studies in P. aeruginosa and Streptomyces coelicolor revealed that the majority of SoxR regulons in bacteria lack the genes required for ...

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.

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

Directory of Open Access Journals (Sweden)

Krishnamoorthy Arumugam

2014-04-01

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

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

International Nuclear Information System (INIS)

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

2015-01-01

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

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.

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

Science.gov (United States)

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2017-06-14

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

Electrochemical investigations of Pu(IV)/Pu(III) redox reaction using graphene modified glassy carbon electrodes and a comparison to the performance of SWCNTs modified glassy carbon electrodes

International Nuclear Information System (INIS)

Gupta, Ruma; Gamare, Jayashree; Sharma, Manoj K.; Kamat, J.V.

2016-01-01

Highlights: • First report of aqueous electrochemistry of Plutonium on graphene modified electrode. • Graphene is best electrocatalytic material for Pu(IV)/Pu(III) redox couple among the reported modifiers viz. reduced graphene oxide (rGO) and SWCNT’s. • The electrochemical reversibility of Pu(IV)/Pu(III) redox couple improves significantly on graphene modified electrode compared to previously reported rGO & SWCNTs modified electrodes • Donnan interaction between plutonium species and graphene surface offers a possibility for designing a highly sensitive sensor for plutonium • Graphene modified electrode shows higher sensitivity for the determination of plutonium compared to glassy carbon and single walled carbon nanotube modified electrode - Abstract: The work reported in this paper demonstrates for the first time that graphene modified glassy carbon electrode (Gr/GC) show remarkable electrocatalysis towards Pu(IV)/Pu(III) redox reaction and the results were compared with that of single-walled carbon nanotubes modified GC (SWCNTs/GC) and glassy carbon (GC) electrodes. Graphene catalyzes the exchange of current of the Pu(IV)/Pu(III) couple by reducing both the anodic and cathodic overpotentials. The Gr/GC electrode shows higher peak currents (i p ) and smaller peak potential separation (ΔE p ) values than the SWCNTs/GC and GC electrodes. The heterogeneous electron transfer rate constants (k s ), charge transfer coefficients (α) and the diffusion coefficients (D) involved in the electrocatalytic redox reaction were determined. Our observations show that graphene is best electrocatalytic material among both the SWCNTs and GC to study Pu(IV)/Pu(III) redox reaction.

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 ...

A Mechanistic Study of the Influence of Proton Transfer Processes on the Behavior of Thiol/Disulfide Redox Couples

National Research Council Canada - National Science Library

Shouji, Eiichi

1998-01-01

.... In order to elucidate the influence of proton transfers on these redox processes, special attention has been paid to the influence of various bases, including triethylamine, pyridine, 3-chloro...

Composition and redox control of waste glasses: Recommendation for process control limit

International Nuclear Information System (INIS)

Jantzen, C.M.; Plodinec, M.J.

1986-01-01

An electrochemical series of redox couples, originally developed for Savannah River Laboratory glass frit 131 (SRL-131) as a reference composition, has been extended to two other alkali borosilicate compositions that are candidate glasses for nuclear waste immobilization. Since no dramatic differences were ascertained in the redox chemistry of selected multivalent elements in SRL-131 versus that in Savannah River Laboratory glass frit 165 (SRL-165) and in West Valley glass number-sign 205 (WV-205), the comprehensive electrochemical series can readily be applied to a range of nuclear waste glass compositions. In order to alleviate potential problems with foaming and precipitation of insolubles during the processing of the nuclear waste in these glass melts, the [Fe 2+ ]/[Fe 3+ ] ratio of the melt should be between 0.1 and 0.5. 27 refs., 4 figs., 2 tabs

Critical rate of electrolyte circulation for preventing zinc dendrite formation in a zinc-bromine redox flow battery

Science.gov (United States)

Yang, Hyeon Sun; Park, Jong Ho; Ra, Ho Won; Jin, Chang-Soo; Yang, Jung Hoon

2016-09-01

In a zinc-bromine redox flow battery, a nonaqueous and dense polybromide phase formed because of bromide oxidation in the positive electrolyte during charging. This formation led to complicated two-phase flow on the electrode surface. The polybromide and aqueous phases led to different kinetics of the Br/Br- redox reaction; poor mixing of the two phases caused uneven redox kinetics on the electrode surface. As the Br/Br- redox reaction was coupled with the zinc deposition reaction, the uneven redox reaction on the positive electrode was accompanied by nonuniform zinc deposition and zinc dendrite formation, which degraded battery stability. A single-flow cell was operated at varying electrolyte circulation rates and current densities. Zinc dendrite formation was observed after cell disassembly following charge-discharge testing. In addition, the flow behavior in the positive compartment was observed by using a transparent version of the cell. At low rate of electrolyte circulation, the polybromide phase clearly separated from the aqueous phase and accumulated at the bottom of the flow frame. In the corresponding area on the negative electrode, a large amount of zinc dendrites was observed after charge-discharge testing. Therefore, a minimum circulation rate should be considered to avoid poor mixing of the positive electrolyte.

Transverse and longitudinal coupled bunch instabilities in trains of closely spaced bunches

International Nuclear Information System (INIS)

Thompson, K.A.; Ruth, R.D.

1989-03-01

Damping rings for the next generation of linear collider may need to contain several bunch trains within which the bunches are quire closely spaced (1 or 2 RF wavelengths). Methods are presented for studying the transverse and longitudinal coupled bunch instabilities, applicable to this problem and to other cases in which the placement of the bunches is not necessarily symmetric. 5 refs., 1 fig

Redox modulation of flavin and tyrosine determines photoinduced proton-coupled electron transfer and photoactivation of BLUF photoreceptors

NARCIS (Netherlands)

Mathes, T.; van Stokkum, I.H.M.; Stierl, M.; Kennis, J.T.M.

2012-01-01

Photoinduced electron transfer in biological systems, especially in proteins, is a highly intriguing matter. Its mechanistic details cannot be addressed by structural data obtained by crystallography alone because this provides only static information on a given redox system. In combination with

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.

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

Directory of Open Access Journals (Sweden)

Hossain eSazzad

2016-05-01

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

Adsorption behavior of redox-active suppressor additives: Combined electrochemical and STM studies

International Nuclear Information System (INIS)

Hai, N.T.M.; Huynh, T.M.T.; Fluegel, A.; Mayer, D.; Broekmann, P.

2011-01-01

Highlights: → Janus Green B and safranine are prototypical redox-active leveler additives for copper electroplating. → Their redox-transitions lie within the copper potential window. → Reduced additives are identified as active species for the leveling effect. → Electro-reduction affects in particular the central aromatic cores of the additives. - Abstract: The redox chemistry and the related surface phase behavior of Safranine (SAF) and Janus Green B (JGB) have been studied by means of cyclic voltammetry in combination with in situ Scanning Tunneling Microscopy using HOPG (Highly Oriented Pyrolytic Graphite) and single crystalline Cu(1 0 0) as model substrates, both revealing different widths of the accessible potential windows. JGB and SAF serve as prototypical heterocyclic suppressor/leveler additives that are used for the metallization of 3D-TSVs (3D Through Silicon Vias) following a classical 'leveling' concept. SAF can be considered as the reductive decomposition product of JGB that is formed at the copper/electrolyte interface upon electroplating. Both additives reveal a pronounced pH-dependent redox-chemistry with redox-transitions lying close to or even beyond the anodic limit of the copper potential window. Affected by these redox-processes are in particular the aromatic cores of those heterocycles that can be (quasi)reversibly reduced by a two electron transfer process within the potential window of copper. Therefore we identify the reduced form of those dyes as the active components for the suppressing/leveling effect in copper plating. STM data clearly shows a dye surface phase behavior that is crucially determined by its potential-dependent redox-chemistry. This will be exemplarily discussed for the SAF dye. On chloride-modified Cu(1 0 0) mono-reduced SAF forms a structurally well-defined monolayer of cationic stacking polymers. However, this coupled anion/cation layer reveals only minor suppressing capabilities with respect to the copper

Quantization of coset space σ-models coupled to two-dimensional gravity

International Nuclear Information System (INIS)

Korotkin, D.; Samtleben, H.

1996-07-01

The mathematical framework for an exact quantization of the two-dimensional coset space σ-models coupled to dilaton gravity, that arise from dimensional reduction of gravity and supergravity theories, is presented. The two-time Hamiltonian formulation is obtained, which describes the complete phase space of the model in the whole isomonodromic sector. The Dirac brackets arising from the coset constraints are calculated. Their quantization allows to relate exact solutions of the corresponding Wheeler-DeWitt equations to solutions of a modified (Coset) Knizhnik-Zamolodchikov system. On the classical level, a set of observables is identified, that is complete for essential sectors of the theory. Quantum counterparts of these observables and their algebraic structure are investigated. Their status in alternative quantization procedures is discussed, employing the link with Hamiltonian Chern-Simons theory. (orig.)

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

Two- and four-component relativistic generalized-active-space coupled cluster method: implementation and application to BiH.

Science.gov (United States)

Sørensen, Lasse K; Olsen, Jeppe; Fleig, Timo

2011-06-07

A string-based coupled-cluster method of general excitation rank and with optimal scaling which accounts for special relativity within the four-component framework is presented. The method opens the way for the treatment of multi-reference problems through an active-space inspired single-reference based state-selective expansion of the model space. The evaluation of the coupled-cluster vector function is implemented by considering contractions of elementary second-quantized operators without setting up the amplitude equations explicitly. The capabilities of the new method are demonstrated in application to the electronic ground state of the bismuth monohydride molecule. In these calculations simulated multi-reference expansions with both doubles and triples excitations into the external space as well as the regular coupled-cluster hierarchy up to full quadruples excitations are compared. The importance of atomic outer core-correlation for obtaining accurate results is shown. Comparison to the non-relativistic framework is performed throughout to illustrate the additional work of the transition to the four-component relativistic framework both in implementation and application. Furthermore, an evaluation of the highest order scaling for general-order expansions is presented. © 2011 American Institute of Physics

Redox Biology in Neurological Function, Dysfunction, and Aging.

Science.gov (United States)

Franco, Rodrigo; Vargas, Marcelo R

2018-04-23

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

Redox-dependent spatially resolved electrochemistry at graphene and graphite step edges.

Science.gov (United States)

Güell, Aleix G; Cuharuc, Anatolii S; Kim, Yang-Rae; Zhang, Guohui; Tan, Sze-yin; Ebejer, Neil; Unwin, Patrick R

2015-04-28

The electrochemical (EC) behavior of mechanically exfoliated graphene and highly oriented pyrolytic graphite (HOPG) is studied at high spatial resolution in aqueous solutions using Ru(NH3)6(3+/2+) as a redox probe whose standard potential sits close to the intrinsic Fermi level of graphene and graphite. When scanning electrochemical cell microscopy (SECCM) data are coupled with that from complementary techniques (AFM, micro-Raman) applied to the same sample area, different time-dependent EC activity between the basal planes and step edges is revealed. In contrast, other redox couples (ferrocene derivatives) whose potential is further removed from the intrinsic Fermi level of graphene and graphite show uniform and high activity (close to diffusion-control). Macroscopic voltammetric measurements in different environments reveal that the time-dependent behavior after HOPG cleavage, peculiar to Ru(NH3)6(3+/2+), is not associated particularly with any surface contaminants but is reasonably attributed to the spontaneous delamination of the HOPG with time to create partially coupled graphene layers, further supported by conductive AFM measurements. This process has a major impact on the density of states of graphene and graphite edges, particularly at the intrinsic Fermi level to which Ru(NH3)6(3+/2+) is most sensitive. Through the use of an improved voltammetric mode of SECCM, we produce movies of potential-resolved and spatially resolved HOPG activity, revealing how enhanced activity at step edges is a subtle effect for Ru(NH3)6(3+/2+). These latter studies allow us to propose a microscopic model to interpret the EC response of graphene (basal plane and edges) and aged HOPG considering the nontrivial electronic band structure.

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.

Development of a Novel Iodine-Vitamin C/Vanadium Redox Flow Battery

International Nuclear Information System (INIS)

Chen, Mei-Ling; Huang, Shu-Ling; Hsieh, Chin-Lung; Lee, Jan- Yen; Tsai, Tz-Jiun

2014-01-01

A novel (I + /I 2 )/vitamin C vs. V 4+ /V 5+ semi-vanadium redox flow battery (semi-VRFB) with iodine, vitamin C, and V 4+ /V 5+ redox couples, using multiple electrodes was investigated. The electrodes, Ni-P/carbon paper and Ni-P/TiO 2 /carbon paper, were modified by the electroless plating method and sol-gel process. The electrochemical characteristics and the performance of the semi-VRFB were verified by the cyclic voltammetry method and a charge-discharge test. This study shows modified electrodes can improve the reversibility and symmetry of the oxidation-reduction reaction of the semi-VRFB system, and effectively raise its storage ability. The coulomb efficiency of the semi-VRFB system is close to 96%, which is higher than the all-VRFB. The semi-VRFB system can reduce the amount of vanadium salt, therefore, it is not only a reduction in cost, but also has a great potential for the development of energy storage systems

Exercise redox biochemistry: Conceptual, methodological and technical recommendations

Directory of Open Access Journals (Sweden)

James N. Cobley

2017-08-01

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

Redox state, reactive oxygen species and adaptive growth in colonial hydroids.

Science.gov (United States)

Blackstone, N W

2001-06-01

Colonial metazoans often encrust surfaces over which the food supply varies in time or space. In such an environment, adaptive colony development entails adjusting the timing and spacing of feeding structures and gastrovascular connections to correspond to this variable food supply. To investigate the possibility of such adaptive growth, within-colony differential feeding experiments were carried out using the hydroid Podocoryna carnea. Indeed, such colonies strongly exhibited adaptive growth, developing dense arrays of polyps (feeding structures) and gastrovascular connections in areas that were fed relative to areas that were starved, and this effect became more consistent over time. To investigate mechanisms of signaling between the food supply and colony development, measurements were taken of metabolic parameters that have been implicated in signal transduction in other systems, particularly redox state and levels of reactive oxygen species. Utilizing fluorescence microscopy of P. carnea cells in vivo, simultaneous measurements of redox state [using NAD(P)H] and hydrogen peroxide (using 2',7'-dichlorofluorescin diacetate) were taken. Both measures focused on polyp epitheliomuscular cells, since these exhibit the greatest metabolic activity. Colonies 3-5h after feeding were relatively oxidized, with low levels of peroxide, while colonies 24h after feeding were relatively reduced, with high levels of peroxide. The functional role of polyps in feeding and generating gastrovascular flow probably produced this dichotomy. Polyps 3-5h after feeding contract maximally, and this metabolic demand probably shifts the redox state in the direction of oxidation and diminishes levels of reactive oxygen species. In contrast, 24h after feeding, polyps are quiescent, and this lack of metabolic demand probably shifts the redox state in the direction of reduction and increases levels of reactive oxygen species. Within-colony differential feeding experiments were carried out on

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

Electrochemical Single-Molecule Transistors with Optimized Gate Coupling

DEFF Research Database (Denmark)

Osorio, Henrry M.; Catarelli, Samantha; Cea, Pilar

2015-01-01

Electrochemical gating at the single molecule level of viologen molecular bridges in ionic liquids is examined. Contrary to previous data recorded in aqueous electrolytes, a clear and sharp peak in the single molecule conductance versus electrochemical potential data is obtained in ionic liquids....... These data are rationalized in terms of a two-step electrochemical model for charge transport across the redox bridge. In this model the gate coupling in the ionic liquid is found to be fully effective with a modeled gate coupling parameter, ξ, of unity. This compares to a much lower gate coupling parameter...

Redox-Active Star Molecules Incorporating the 4-Benzoylpyridinium Cation - Implications for the Charge Transfer Along Branches vs. Across the Perimeter in Dendrimer

Science.gov (United States)

Leventis, Nicholas; Yang, Jinua; Fabrizio,Even F.; Rawashdeh, Abdel-Monem M.; Oh, Woon Su; Sotiriou-Leventis, Chariklia

2004-01-01

Dendrimers are self-repeating globular branched star molecules, whose fractal structure continues to fascinate, challenge, and inspire. Functional dendrimers may incorporate redox centers, and potential applications include antennae molecules for light harvesting, sensors, mediators, and artificial biomolecules. We report the synthesis and redox properties of four star systems incorporating the 4-benzoyl-N-alkylpyridinium cation; the redox potential varies along the branches but remains constant at fixed radii. Bulk electrolysis shows that at a semi-infinite time scale all redox centers are electrochemically accessible. However, voltammetric analysis (cyclic voltammetry and differential pulse voltammetry) shows that on1y two of the three redox-active centers in the perimeter are electrochemically accessible during potential sweeps as slow as 20 mV/s and as fast as 10 V/s. On the contrary, both redox centers along branches are accessible electrochemically within the same time frame. These results are explained in terms of slow through-space charge transfer and the globular 3-D folding of the molecules and are discussed in terms of their implications on the design of efficient redox functional dendrimers.

Engineered Proteins: Redox Properties and Their Applications

Science.gov (United States)

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

2012-01-01

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

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

Czech Academy of Sciences Publication Activity Database

Heyrovská, Raji

2010-01-01

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

Simultaneous anionic and cationic redox

Science.gov (United States)

Jung, Sung-Kyun; Kang, Kisuk

2017-12-01

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

Membranes for Redox Flow Battery Applications

Science.gov (United States)

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

2012-01-01

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

Membranes for redox flow battery applications.

Science.gov (United States)

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

2012-06-19

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

Membranes for Redox Flow Battery Applications

Directory of Open Access Journals (Sweden)

Maria Skyllas-Kazacos

2012-06-01

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

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

Science.gov (United States)

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

2015-06-11

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

Environmental control of plant nuclear gene expression by chloroplast redox signals

Directory of Open Access Journals (Sweden)

Jeannette ePfalz

2012-11-01

Full Text Available Plant photosynthesis takes place in specialised cell organelles, the chloroplasts, which perform all essential steps of this process. The proteins involved in photosynthesis are encoded by genes located on the plastid and nuclear genomes. Proper function and regulation of light harvesting and energy fixation thus requires a tight coordination of the gene expression machineries in the two genetic compartments. This is achieved by a bi-directional exchange of information between nucleus and plastids. Signals emerging from plastids report the functional and developmental state of the organelle to the nucleus and initiate distinct nuclear gene expression profiles, which trigger responses that support or improve plastid functions. Recent research indicated that this signalling is absolutely essential for plant growth and development. Reduction/oxidation (redox signals from photosynthesis are key players in this information network since they do report functional disturbances in photosynthesis, the primary energy source of plants. Such disturbances are caused by environmental fluctuations for instance in illumination, temperature or water availability. These environmental changes affect the linear electron flow of photosynthesis and result in changes of the redox state of the components involved (e.g. the plastoquinone pool or coupled to it (e.g. the thioredoxin pool. Thus, the changes in redox state directly reflect the environmental impact and serve as immediate plastidial signals to the nucleus. The triggered responses range from counterbalancing reactions within the physiological range up to severe stress responses including cell death. This review focuses on physiological redox signals from photosynthetic electron transport, their relation to the environment, potential transduction pathways to the nucleus and their impact on nuclear gene expression.

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%.

Numerical studies of carbon paper-based vanadium redox flow batteries

International Nuclear Information System (INIS)

Won, Seongyeon; Oh, Kyeongmin; Ju, Hyunchul

2016-01-01

ABSTRACT: This study analyzed theoretically the effects of a carbon paper (CP)-based electrode on the performance of a vanadium redox flow battery (VRFB). Compared to conventional carbon felt-based electrode materials, the CP-based electrode showed superior characteristics in facilitating the redox reactions of VO"2"+/VO_2"+ and V"2"+/V"3"+ couples, such as better electrochemical activity and higher electronic conductivity. A three-dimensional, non-isothermal VRFB model developed in a previous study was applied to a range of single cell structures equipped with CP-based electrodes and flow channels in the current collectors. The model was then validated using the experimental data measured under the CP- and channel-based VRFB geometries. The model successfully captured the experimental trend that showed a higher discharging performance with increasing number of CP layers used for each electrode. The simulation results clearly showed that the activation overpotentials in the electrodes were reduced significantly using more CP layers, which dominated over the effects of increased mass transport limitation of vanadium ions due to the thicker electrode.

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)

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

Science.gov (United States)

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

2018-04-01

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

Thiol/disulfide redox states in signaling and sensing

Science.gov (United States)

Go, Young-Mi; Jones, Dean P.

2015-01-01

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

Reversible anionic redox chemistry in high-capacity layered-oxide electrodes

Science.gov (United States)

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.

Scleroglucan-borax hydrogel: a flexible tool for redox protein immobilization.

Science.gov (United States)

Frasconi, Marco; Rea, Sara; Matricardi, Pietro; Favero, Gabriele; Mazzei, Franco

2009-09-15

A highly stable biological film was prepared by casting an aqueous dispersion of protein and composite hydrogel obtained from the polysaccharide Scleroglucan (Sclg) and borax as a cross-linking agent. Heme proteins, such as hemoglobin (Hb), myoglobin (Mb), and horseradish peroxidase (HRP), were chosen as model proteins to investigate the immobilized system. A pair of well-defined quasi-reversible redox peaks, characteristics of the protein heme FeII/FeIII redox couples, were obtained at the Sclg-borax/proteins films on pyrolytic graphite (PG) electrodes, as a consequence of the direct electron transfer between the protein and the PG electrode. A full characterization of the electron transfer kinetic was performed by opportunely modeling data obtained from cyclic voltammetry and square wave voltammetry experiments. The efficiency of our cross-linking approach was investigated by studying the influence of different borax groups percentage in the Sclg matrix, revealing the versatility of this hydrogel in the immobilization of redox proteins. The native conformation of the three heme proteins entrapped in the hydrogel films were proved to be unchanged, reflected by the unaltered Soret adsorption band and by the catalytic activity toward hydrogen peroxide (H2O2). The main kinetic parameters, such as the apparent Michaelis-Menten constant, for the electrocatalytic reaction were also evaluated. The peculiar characteristics of Sclg-borax matrix make it possible to find wide opportunities as proteins immobilizing agent for studies of direct electrochemistry and biosensors development.

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 homeostasis: The Golden Mean of healthy living

Directory of Open Access Journals (Sweden)

Fulvio Ursini

2016-08-01

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

Exercise redox biochemistry: Conceptual, methodological and technical recommendations.

Science.gov (United States)

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

2017-08-01

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

One-pot in situ redox synthesis of hexacyanoferrate/conductive polymer hybrids as lithium-ion battery cathodes.

Science.gov (United States)

Wong, Min Hao; Zhang, Zixuan; Yang, Xianfeng; Chen, Xiaojun; Ying, Jackie Y

2015-09-14

An efficient and adaptable method is demonstrated for the synthesis of lithium hexacyanoferrate/conductive polymer hybrids for Li-ion battery cathodes. The hybrids were synthesized via a one-pot method, involving a redox-coupled reaction between pyrrole monomers and the Li3Fe(CN)6 precursor. The hybrids showed much better cyclability relative to reported Prussian Blue (PB) analogs.

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.

Delta space plot analysis of cardiovascular coupling in vasovagal syncope during orthostatic challenge.

Science.gov (United States)

Reulecke, S; Charleston-Villalobos, S; Voss, A; Gonzalez-Camarena, R; Gaitan-Gonzalez, M; Gonzalez-Hermosillo, J; Hernandez-Pacheco, G; Aljama-Corrales, T

2016-08-01

In this work, a graphical method to study cardiovascular coupling, called delta space plot analysis (DSPA), was introduced. The graphical representation is susceptible to be parameterized in shape and orientation. The usefulness of this technique was studied on cardiovascular data from patients with vasovagal syncope (VVS) and from controls. The study included 15 female patients diagnosed with VVS and 11 age-matched healthy female subjects. All subjects were enrolled in a head-up tilt (HUT) test, breathing normally, including 5 minutes of supine position (baseline) and 18 minutes of 70° orthostatic phase. The DSPA parameters were obtained at different times during the HUT test, i.e., at baseline, early (first 5 min) and late (10-15 min) orthostatic phases. In baseline there were no considerable differences between female controls and female patients. During the late orthostatic phase, parameters from DSPA showed highly significantly (p=0.000003) reduced cardiovascular coupling in patients. Findings indicated a loss of control on cardiovascular coupling in female patients susceptible to vasovagal syncope during orthostatic challenge. In addition, this study provided promising results for a new graphical method to investigate cardiovascular coupling.

Coupled Loads Analysis of the Modified NASA Barge Pegasus and Space Launch System Hardware

Science.gov (United States)

Knight, J. Brent

2015-01-01

A Coupled Loads Analysis (CLA) has been performed for barge transport of Space Launch System hardware on the recently modified NASA barge Pegasus. The barge re-design was facilitated with detailed finite element analyses by the ARMY Corps of Engineers - Marine Design Center. The Finite Element Model (FEM) utilized in the design was also used in the subject CLA. The Pegasus FEM and CLA results are presented as well as a comparison of the analysis process to that of a payload being transported to space via the Space Shuttle. Discussion of the dynamic forcing functions is included as well. The process of performing a dynamic CLA of NASA hardware during marine transport is thought to be a first and can likely support minimization of undue conservatism.

Equal-Time and Equal-Space Poisson Brackets of the N -Component Coupled NLS Equation

International Nuclear Information System (INIS)

Zhou Ru-Guang; Li Pei-Yao; Gao Yuan

2017-01-01

Two Poisson brackets for the N-component coupled nonlinear Schrödinger (NLS) equation are derived by using the variantional principle. The first one is called the equal-time Poisson bracket which does not depend on time but only on the space variable. Actually it is just the usual one describing the time evolution of system in the traditional theory of integrable Hamiltonian systems. The second one is equal-space and new. It is shown that the spatial part of Lax pair with respect to the equal-time Poisson bracket and temporal part of Lax pair with respect to the equal-space Poisson bracket share the same r-matrix formulation. These properties are similar to that of the NLS equation. (paper)

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.

Nitric oxide-releasing prodrug triggers cancer cell death through deregulation of cellular redox balance

Directory of Open Access Journals (Sweden)

Anna E. Maciag

2013-01-01

Full Text Available JS-K is a nitric oxide (NO-releasing prodrug of the O2-arylated diazeniumdiolate family that has demonstrated pronounced cytotoxicity and antitumor properties in a variety of cancer models both in vitro and in vivo. The current study of the metabolic actions of JS-K was undertaken to investigate mechanisms of its cytotoxicity. Consistent with model chemical reactions, the activating step in the metabolism of JS-K in the cell is the dearylation of the diazeniumdiolate by glutathione (GSH via a nucleophilic aromatic substitution reaction. The resulting product (CEP/NO anion spontaneously hydrolyzes, releasing two equivalents of NO. The GSH/GSSG redox couple is considered to be the major redox buffer of the cell, helping maintain a reducing environment under basal conditions. We have quantified the effects of JS-K on cellular GSH content, and show that JS-K markedly depletes GSH, due to JS-K's rapid uptake and cascading release of NO and reactive nitrogen species. The depletion of GSH results in alterations in the redox potential of the cellular environment, initiating MAPK stress signaling pathways, and inducing apoptosis. Microarray analysis confirmed signaling gene changes at the transcriptional level and revealed alteration in the expression of several genes crucial for maintenance of cellular redox homeostasis, as well as cell proliferation and survival, including MYC. Pre-treating cells with the known GSH precursor and nucleophilic reducing agent N-acetylcysteine prevented the signaling events that lead to apoptosis. These data indicate that multiplicative depletion of the reduced glutathione pool and deregulation of intracellular redox balance are important initial steps in the mechanism of JS-K's cytotoxic action.

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

Science.gov (United States)

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

2013-12-01

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

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

Science.gov (United States)

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

2014-01-01

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

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

Science.gov (United States)

Viehweger, Katrin; Geipel, Gerhard; Bernhard, Gert

2011-12-01

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

The Redox Behaviour of Randomly Dispersed Single Walled Carbon Nanotubes both in the Absence and in the Presence of Adsorbed Glucose Oxidase

Directory of Open Access Journals (Sweden)

Gareth P. Keeley

2006-12-01

Full Text Available The electrochemical behaviour of SWCNTs randomly dispersed on gold and glassy carbon electrode surfaces was characterised via cyclic voltammetry and complex impedance spectroscopy, using the ferri/ferrocyanide couple as a redox active test probe . In subsequent investigations glucose oxidase (GOx was adsorbed onto the SWCNT ensemble without apparent denaturation of the enzyme. Cyclic voltammetry and potential step chronoamperometry were used to quantify and understand the process of electron transfer between the immobilised protein redox site and the working electrode. The effect of pH on the system was also investigated. In particular, we have shown that, for the calculation of electron transfer rate constants for surface-immobilised redox systems, chronoamperometry is preferable to voltammetry, which has been the technique of choice until now.

Characterization of redox conditions in groundwater contaminant plumes

Science.gov (United States)

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

2000-10-01

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

Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries.

Science.gov (United States)

Wang, Qin-Chao; Hu, Enyuan; Pan, Yang; Xiao, Na; Hong, Fan; Fu, Zheng-Wen; Wu, Xiao-Jing; Bak, Seong-Min; Yang, Xiao-Qing; Zhou, Yong-Ning

2017-11-01

Developing sodium-ion batteries for large-scale energy storage applications is facing big challenges of the lack of high-performance cathode materials. Here, a series of new cathode materials Na 0.66 Co x Mn 0.66- x Ti 0.34 O 2 for sodium-ion batteries are designed and synthesized aiming to reduce transition metal-ion ordering, charge ordering, as well as Na + and vacancy ordering. An interesting structure change of Na 0.66 Co x Mn 0.66- x Ti 0.34 O 2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 with a P2-type layered structure delivers a reversible capacity of 120 mAh g -1 at 0.1 C. When the current density increases to 10 C, a reversible capacity of 63.2 mAh g -1 can still be obtained, indicating a promising rate capability. The low valence Co 2+ substitution results in the formation of average Mn 3.7+ valence state in Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 , effectively suppressing the Mn 3+ -induced Jahn-Teller distortion, and in turn stabilizing the layered structure. X-ray absorption spectroscopy results suggest that the charge compensation of Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 during charge/discharge is contributed by Co 2.2+ /Co 3+ and Mn 3.3+ /Mn 4+ redox couples. This is the first time that the highly reversible Co 2+ /Co 3+ redox couple is observed in P2-layered cathodes for sodium-ion batteries. This finding may open new approaches to design advanced intercalation-type cathode materials.

Membranes for Redox Flow Battery Applications

OpenAIRE

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

2012-01-01

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

Redox-flow battery of actinide complexes

International Nuclear Information System (INIS)

Yamamura, Tomoo; Shiokawa, Yoshinobu

2006-01-01

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

Redox kinetics and mechanism in silicate melts

International Nuclear Information System (INIS)

Cochain, B.

2009-12-01

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

Redox homeostasis: The Golden Mean of healthy living.

Science.gov (United States)

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

2016-08-01

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

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

Science.gov (United States)

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

2017-05-10

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

Relating hyporheic fluxes, residence times, and redox-sensitive biogeochemical processes upstream of beaver dams

Science.gov (United States)

Briggs, Martin A.; Lautz, Laura; Hare, Danielle K.

2013-01-01

Abstract. Small dams enhance the development of patchy microenvironments along stream corridors by trapping sediment and creating complex streambed morphologies. This patchiness drives intricate hyporheic flux patterns that govern the exchange of O2 and redox-sensitive solutes between the water column and the stream bed. We used multiple tracer techniques, naturally occurring and injected, to evaluate hyporheic flow dynamics and associated biogeochemical cycling and microbial reactivity around 2 beaver dams in Wyoming (USA). High-resolution fiber-optic distributed temperature sensing was used to collect temperature data over 9 vertical streambed profiles and to generate comprehensive vertical flux maps using 1-dimensional (1-D) heat-transport modeling. Coincident with these locations, vertical profiles of hyporheic water were collected every week and analyzed for dissolved O2, pH, dissolved organic C, and several conservative and redox-sensitive solutes. In addition, hyporheic and net stream aerobic microbial reactivity were analyzed with a constant-rate injection of the biologically sensitive resazurin (Raz) smart tracer. The combined results revealed a heterogeneous system with rates of downwelling hyporheic flow organized by morphologic unit and tightly coupled to the redox conditions of the subsurface. Principal component analysis was used to summarize the variability of all redox-sensitive species, and results indicated that hyporheic water varied from oxic-stream-like to anoxic-reduced in direct response to the hydrodynamic conditions and associated residence times. The anaerobic transition threshold predicted by the mean O2 Damko

Ionic properties of non-aqueous liquid and PVDF-based gel electrolytes containing a cesium thiolate/disulfide redox couple

International Nuclear Information System (INIS)

Renard, Ingrid; Li Hongmei; Marsan, Benoit

2003-01-01

Liquid electrolytes containing a cesium thiolate/disulfide redox couple, prepared from 5-mercapto-1-methyltetrazole cesium salt (CsT) and di-5-(1-methyltetrazole)disulfide (T 2 ) dissolved in several aprotic solvents and solvent mixtures, have been studied using various techniques. FTIR spectroscopy reveals that relatively strong interactions occur between the reduced species T - and DMSO or DMF while Cs + ions are very weakly coordinated to the S=O or C=O bond. It is shown that the electrolyte consisting of 1.55 mol kg -1 CsT in the solvent mixture DMSO/DMF (40/60%) exhibits the highest conductivity (1.1x10 -2 and 2.3x10 -2 S cm -1 at 23 and 80 deg. C, respectively), and that the presence of the oxidized species T 2 does not affect significantly its electrical properties up to a CsT:T 2 molar ratio of 5:1. Conductivity values as a function of salt concentration are discussed in terms of the effective number of charge carriers, taking into account the level of ionic association, and of the ionic mobility. Optically transparent gel electrolytes have been prepared by incorporation of the optimal liquid electrolyte into various amounts of poly(vinylidene fluoride) (PVDF). It is shown that ionic mobility is not much affected by the polymer concentration, suggesting that migration of ions occurs mainly through the solvent mixture surrounded by the PVDF matrix

Redox characteristics of the eukaryotic cytosol

DEFF Research Database (Denmark)

López-Mirabal, H Reynaldo; Winther, Jakob R

2007-01-01

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

Organic non-aqueous cation-based redox flow batteries

Science.gov (United States)

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

2016-03-29

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

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

Science.gov (United States)

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

2015-11-11

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

On the nature of organic and inorganic centers that bifurcate electrons, coupling exergonic and endergonic oxidation-reduction reactions.

Science.gov (United States)

Peters, John W; Beratan, David N; Schut, Gerrit J; Adams, Michael W W

2018-04-19

Bifurcating electrons to couple endergonic and exergonic electron-transfer reactions has been shown to have a key role in energy conserving redox enzymes. Bifurcating enzymes require a redox center that is capable of directing electron transport along two spatially separate pathways. Research into the nature of electron bifurcating sites indicates that one of the keys is the formation of a low potential oxidation state to satisfy the energetics required of the endergonic half reaction, indicating that any redox center (organic or inorganic) that can exist in multiple oxidation states with sufficiently separated redox potentials should be capable of electron bifurcation. In this Feature Article, we explore a paradigm for bifurcating electrons down independent high and low potential pathways, and describe redox cofactors that have been demonstrated or implicated in driving this unique biochemistry.

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

Science.gov (United States)

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

2013-01-01

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

Communication: Relativistic Fock-space coupled cluster study of small building blocks of larger uranium complexes

International Nuclear Information System (INIS)

Tecmer, Paweł; Visscher, Lucas; Severo Pereira Gomes, André; Knecht, Stefan

2014-01-01

We present a study of the electronic structure of the [UO 2 ] + , [UO 2 ] 2 + , [UO 2 ] 3 + , NUO, [NUO] + , [NUO] 2 + , [NUN] − , NUN, and [NUN] + molecules with the intermediate Hamiltonian Fock-space coupled cluster method. The accuracy of mean-field approaches based on the eXact-2-Component Hamiltonian to incorporate spin–orbit coupling and Gaunt interactions are compared to results obtained with the Dirac–Coulomb Hamiltonian. Furthermore, we assess the reliability of calculations employing approximate density functionals in describing electronic spectra and quantities useful in rationalizing Uranium (VI) species reactivity (hardness, electronegativity, and electrophilicity)

Communication: Relativistic Fock-space coupled cluster study of small building blocks of larger uranium complexes

Science.gov (United States)

Tecmer, Paweł; Severo Pereira Gomes, André; Knecht, Stefan; Visscher, Lucas

2014-07-01

We present a study of the electronic structure of the [UO2]+, [UO2]2 +, [UO2]3 +, NUO, [NUO]+, [NUO]2 +, [NUN]-, NUN, and [NUN]+ molecules with the intermediate Hamiltonian Fock-space coupled cluster method. The accuracy of mean-field approaches based on the eXact-2-Component Hamiltonian to incorporate spin-orbit coupling and Gaunt interactions are compared to results obtained with the Dirac-Coulomb Hamiltonian. Furthermore, we assess the reliability of calculations employing approximate density functionals in describing electronic spectra and quantities useful in rationalizing Uranium (VI) species reactivity (hardness, electronegativity, and electrophilicity).

Ediacaran Redox Fluctuations

Science.gov (United States)

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

2013-12-01

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

Redox interplay between mitochondria and peroxisomes

Directory of Open Access Journals (Sweden)

Celien eLismont

2015-05-01

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

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

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

2017-08-01

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

Redox properties of biscyclopentadienyl uranium(V) imido-halide complexes: a relativistic DFT study.

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Elkechai, Aziz; Kias, Farida; Talbi, Fazia; Boucekkine, Abdou

2014-06-01

Calculations of ionization energies (IE) and electron affinities (EA) of a series of biscyclopentadienyl imido-halide uranium(V) complexes Cp*2U(=N-2,6-(i)Pr2-C6H3)(X) with X =  F, Cl, Br, and I, related to the U(IV)/U(V) and U(V)/U(VI) redox systems, were carried out, for the first time, using density functional theory (DFT) in the framework of the relativistic zeroth order regular approximation (ZORA) coupled with the conductor-like screening model (COSMO) solvation approach. A very good linear correlation (R(2) =  0.993) was obtained, between calculated ionization energies at the ZORA/BP86/TZP level, and the experimental half-wave oxidation potentials E1/2. A similar linear correlation between the computed electron affinities and the electrochemical reduction U(IV)/U(III) potentials (R(2) =  0.996) is obtained. The importance of solvent effects and of spin-orbit coupling is definitively confirmed. The molecular orbital analysis underlines the crucial role played by the 5f orbitals of the central metal whereas the Nalewajski-Mrozek (N-M) bond indices explain well the bond distances variations following the redox processes. The IE variation of the complexes, i.e., IE(F) uranium charges and E1/2 in the reduction process of the U(V) species.

Redox regulation of plant development.

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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.

Short-Range Electron Transfer in Reduced Flavodoxin: Ultrafast Nonequilibrium Dynamics Coupled with Protein Fluctuations.

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Kundu, Mainak; He, Ting-Fang; Lu, Yangyi; Wang, Lijuan; Zhong, Dongping

2018-05-03

Short-range electron transfer (ET) in proteins is an ultrafast process on the similar timescales as local protein-solvent fluctuations thus the two dynamics are coupled. Here, we use semiquinone flavodoxin and systematically characterized the photoinduced redox cycle with eleven mutations of different aromatic electron donors (tryptophan and tyrosine) and local residues to change redox properties. We observed the forward and backward ET dynamics in a few picoseconds, strongly following a stretched behavior resulting from a coupling between local environment relaxations and these ET processes. We further observed the hot vibrational-state formation through charge recombination and the subsequent cooling dynamics also in a few picoseconds. Combined with the ET studies in oxidized flavodoxin, these results coherently reveal the evolution of the ET dynamics from single to stretched exponential behaviors and thus elucidate critical timescales for the coupling. The observed hot vibration-state formation is robust and should be considered in all photoinduced back ET processes in flavoproteins.

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

International Nuclear Information System (INIS)

Easwaramoorthi, S.; Natarajan, P.

2008-01-01

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

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

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Trivedi, Malav S; Deth, Richard

2014-01-01

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

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

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

2015-02-24

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

A non-aqueous all-copper redox flow battery with highly soluble active species

International Nuclear Information System (INIS)

Li, Yun; Sniekers, Jeroen; Malaquias, João; Li, Xianfeng; Schaltin, Stijn; Stappers, Linda; Binnemans, Koen; Fransaer, Jan; Vankelecom, Ivo F.J.

2017-01-01

A metal-based redox pair with acetonitrile as ligand [Cu(MeCN)_4][Tf_2N] is described for use in non-aqueous redox flow battery (RFB). The electrode kinetics of the anode and cathode are studied using cyclic voltammetry. The Cu"2"+/Cu"+ and Cu"+/Cu couples in this system yield a cell potential of 1.24 V. The diffusion coefficient for [Cu(MeCN)_4][Tf_2N] in acetonitrile is estimated to be 6.8 × 10"−"6 cm"2 s"−"1 at room temperature. The copper-acetonitrile complex has a very high solubility of 1.68 M in acetonitrile, the most widely used organic solvent for non-aqueous electrochemical applications. Hence, a maximum theoretical energy density around 28 Wh L"−"1 can be reached with the reported system. The RFB with this electrolyte shows a promising performance, with coulombic efficiencies of 87% and energy efficiencies of 44% (5 mA cm"−"2).

Room Temperature, Hybrid Sodium-Based Flow Batteries with Multi-Electron Transfer Redox Reactions

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Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; Sprenkle, Vincent L.

2015-01-01

We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volume of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multi-electron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. The critical barriers to mature this new HNFBs have also been explored. PMID:26063629

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

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

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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

Monitoring thioredoxin redox with a genetically encoded red fluorescent biosensor.

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

2017-09-01

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

Metal-Organic Frameworks as Highly Active Electrocatalysts for High-Energy Density, Aqueous Zinc-Polyiodide Redox Flow Batteries.

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Li, Bin; Liu, Jian; Nie, Zimin; Wang, Wei; Reed, David; Liu, Jun; McGrail, Pete; Sprenkle, Vincent

2016-07-13

The new aqueous zinc-polyiodide redox flow battery (RFB) system with highly soluble active materials as well as ambipolar and bifunctional designs demonstrated significantly enhanced energy density, which shows great potential to reduce RFB cost. However, the poor kinetic reversibility and electrochemical activity of the redox reaction of I3(-)/I(-) couples on graphite felts (GFs) electrode can result in low energy efficiency. Two nanoporous metal-organic frameworks (MOFs), MIL-125-NH2 and UiO-66-CH3, that have high surface areas when introduced to GF surfaces accelerated the I3(-)/I(-) redox reaction. The flow cell with MOF-modified GFs serving as a positive electrode showed higher energy efficiency than the pristine GFs; increases of about 6.4% and 2.7% occurred at the current density of 30 mA/cm(2) for MIL-125-NH2 and UiO-66-CH3, respectively. Moreover, UiO-66-CH3 is more promising due to its excellent chemical stability in the weakly acidic electrolyte. This letter highlights a way for MOFs to be used in the field of RFBs.

Mitochondrial redox biology and homeostasis in plants.

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

2007-03-01

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

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

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

2017-03-17

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

STM Studies of Spin-­Orbit Coupled Phases in Real-­ and Momentum-­Space

Energy Technology Data Exchange (ETDEWEB)

Madhavan, Vidya [Univ. of Illinois, Urbana, IL (United States)

2016-10-17

The recently discovered class of spin-orbit coupled materials with interesting topological character are fascinating both from fundamental as well as application point of view. Two striking examples are 3D topological insulators (TIs) and topological crystalline insulators (TCIs). These materials host linearly dispersing (Dirac like) surface states with an odd number of Dirac nodes and are predicted to carry a quantized half-integer value of the axion field. The non-trivial topological properties of TIs and TCIs arise from strong spin-orbit coupling leading to an inverted band structure; which also leads to the chiral spin texture in momentum space. In this project we used low temperature scanning tunneling microscopy (STM) and spectroscopy (STS) to study materials with topological phases in real- and momentum-space. We studied both single crystals and thin films of topological materials which are susceptible to being tuned by doping, strain or gating, allowing us to explore their physical properties in the most interesting regimes and set the stage for future technological applications. .

The electrochemical catalytic activity of single-walled carbon nanotubes towards VO2+/VO2+ and V3+/V2+ redox pairs for an all vanadium redox flow battery

International Nuclear Information System (INIS)

Li Wenyue; Liu Jianguo; Yan Chuanwei

2012-01-01

Highlights: ► SWCNT shows excellent electrochemical catalytic activity towards VO 2 + /VO 2+ and V 3+ /V 2+ redox couples. ► The anodic reactions are more sensitive to the surface oxygen atom content change compared with the cathodic reactions. ► The enhanced battery performance clearly demonstrated that the SWCNT is suitable to be used as an electrode catalyst for VRFB. - Abstract: Single-walled carbon nanotube (SWCNT) was used as an electrode catalyst for an all vanadium redox flow battery (VRFB). The electrochemical property of SWCNT towards VO 2 + /VO 2+ and V 3+ /V 2+ was carefully characterized by cyclic voltammetric (CV) and electrochemical impedance spectroscopy (EIS) measurements. The peak current values for these redox pairs were significantly higher on the modified glassy carbon electrode compared with those obtained on the bare electrode, suggesting the excellent electrochemical activity of the SWCNT. Moreover, it was proved that the anodic process was more dependent on the surface oxygen of the SWCNT than the cathodic process through changing its surface oxygen content. Detailed EIS analysis of different modified electrodes revealed that the charge and mass transfer processes were accelerated at the modified electrode–electrolyte interface, which could be ascribed to the large specific surface area, the surface defects and the oxygen functional groups of the SWCNT. The enhanced battery performance effectively demonstrated that the SWCNT was suitable to serve as an electrode catalyst for the VRFB.

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

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Hong, Jeehoon; Kim, Ketack

2018-04-17

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

Redox shuttles for safer lithium-ion batteries

International Nuclear Information System (INIS)

Chen, Zonghai; Qin, Yan; Amine, Khalil

2009-01-01

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

Microfluidic redox battery.

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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.

Managing the cellular redox hub in photosynthetic organisms.

Science.gov (United States)

Foyer, Christine H; Noctor, Graham

2012-02-01

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

Unusual thiol-based redox metabolism of parasitic flukes.

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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.

Redox Modulations, Antioxidants, and Neuropsychiatric Disorders

Directory of Open Access Journals (Sweden)

Erik A. Fraunberger

2016-01-01

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

Measuring intracellular redox conditions using GFP-based sensors

DEFF Research Database (Denmark)

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

2006-01-01

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

State-space modeling of the radio frequency inductively-coupled plasma generator

International Nuclear Information System (INIS)

Dewangan, Rakesh Kumar; Punjabi, Sangeeta B; Mangalvedekar, H A; Lande, B K; Joshi, N K; Barve, D N

2010-01-01

Computational fluid dynamics models of RF-ICP are useful in understanding the basic transport phenomenon in an ICP torch under a wide variety of operating conditions. However, these models lack the ability to evaluate the effects of the plasma condition on the RF generator. In this paper, simulation of an induction plasma generator has been done using state space modelling by considering inductively coupled plasma as a part of RF network .The time dependent response of the RF-ICP generator circuit to given input excitation has been computed by extracting the circuit's state-space variables and their constraint matrices. MATLAB 7.1 software has been used to solve the state equations. The values of RF coil current, frequency and plasma power has been measured experimentally also at different plate bias voltage. The simulated model is able to predict RF coil current, frequency, plasma power, overall efficiency of the generator. The simulated and measured values are in agreement with each other. This model can prove useful as a design tool for the Induction plasma generator.

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

Directory of Open Access Journals (Sweden)

Nuñez Martha

2011-05-01

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

Characterization of redox proteins using electrochemical methods

OpenAIRE

Verhagen, M.

1995-01-01

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

Nicotinamide-NAD sequence: redox process and related behavior, behavior and properties of intermediate and final products

International Nuclear Information System (INIS)

Elving, P.J.; Schmakel, C.O.; Santhanam, K.S.V.

1976-01-01

Illustrations of the application of analytical chemical techniques to the study of chemical phenomena are given. In particular, electrochemical techniques and methodology and, to a lesser extent, spectrophotometry were used to investigate the solution behavior, adsorption, redox processes including coupled chemical reactions, and allied aspects of biologically significant compounds and of their intermediate and final redox products, e.g., the behavior of the free radicals produced by initial one-electron processes. This approach is illustrated by the consideration of the behavior in aqueous and nonaqueous media of a sequence of compounds ranging from nicotinamide (3-carbamoylpyridine) to NAD + and NADP + ; the latter compounds function as coenzymes for the pyridinoproteins which are principal components in the Krebs citric acid cycle and in the electron transport chain in biological redox reactions. The discussion is presented under the following section headings: interpretation of electrochemical behavior; mechanistic patterns; kinetic aspects of charge-transfer and chemical reactions; correlation with theoretically calculated parameters; and, mechanisms of biological oxidation-reduction reactions. The use of pulse radiolysis, chronopotentiometric, and cyclic voltammetric methods in studies on free radical dimerization rates is reviewed in the discussion of the kinetic aspects of charge-transfer and chemical reactions. (188 references)

Analytically continued Fock space multi-reference coupled-cluster theory: Application to the shape resonance

International Nuclear Information System (INIS)

Pal, Sourav; Sajeev, Y.; Vaval, Nayana

2006-01-01

The Fock space multi-reference coupled-cluster (FSMRCC) method is used for the study of the shape resonance energy and width in an electron-atom/molecule collision. The procedure is based upon combining a complex absorbing potential (CAP) with FSMRCC theory. Accurate resonance parameters are obtained by solving a small non-Hermitian eigen-value problem. We study the shape resonances in e - -C 2 H 4 and e - -Mg

Studies of Redox Equilibria at Elevated Temperatures 3. Oxide/oxide and Oxide/metal Couples of Iron, Nickel, Copper, Silver. Mercury and Antimony in Aqueous Systems up to 100 deg C

Energy Technology Data Exchange (ETDEWEB)

Johansson, Karin; Johnsson, Kerstin; Lewis, Derek

1973-08-15

Redox couples formed with Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4}, FeO{sub 2}H/Fe{sub 3}O{sub 4}, NiO/Ni, Cu{sub 2}O/Cu, Ag{sub 2}O/Ag, HgO/Hg and Sb{sub 2}O{sub 3}/Sb, in borax buffer solution have been studied at temperatures up to 100 deg C. The composition and morphology of the solid phases were characterized by X-ray diffraction measurements and electron micrography. Electrodes were formed with beds of mixtures of the solids through which the electrolyte was slowly perculated, and their potentials were measured relative to the hydrogen electrode. The results show that, in weakly alkaline solutions, systems including these couples only slowly attain electrochemical equilibrium. In the case of the iron couples at 25 deg C, for example, an emf with a long-term stability within 0.1 mV is not attained until after more than eight days equilibration: At higher temperatures a stable emf is attained more rapidly. All of the electrodes except the NiO/Ni electrode seem to be reversible but only the HgO/Hg electrode and, perhaps, the Cu{sub 2}O/Cu and Ag{sub 2}O/Ag electrodes, are likely to be useful at elevated temperatures. The apparent equilibrium constants found for the electrode reactions are compared with the theoretical values

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

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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-Based Regulation of Bacterial Development and Behavior.

Science.gov (United States)

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

2017-06-20

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

Redox flow batteries having multiple electroactive elements

Energy Technology Data Exchange (ETDEWEB)

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

2018-05-01

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

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

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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.

High Electrocatalytic Activity of Vertically Aligned Single-Walled Carbon Nanotubes towards Sulfide Redox Shuttles.

Science.gov (United States)

Hao, Feng; Dong, Pei; Zhang, Jing; Zhang, Yongchang; Loya, Phillip E; Hauge, Robert H; Li, Jianbao; Lou, Jun; Lin, Hong

2012-01-01

Vertically aligned single-walled carbon nanotubes (VASWCNTs) have been successfully transferred onto transparent conducting oxide glass and implemented as efficient low-cost, platinum-free counter electrode in sulfide -mediated dye-sensitized solar cells (DSCs), featuring notably improved electrocatalytic activity toward thiolate/disulfide redox shuttle over conventional Pt counter electrodes. Impressively, device with VASWCNTs counter electrode demonstrates a high fill factor of 0.68 and power conversion efficiency up to 5.25%, which is significantly higher than 0.56 and 3.49% for that with a conventional Pt electrode. Moreover, VASWCNTs counter electrode produces a charge transfer resistance of only 21.22 Ω towards aqueous polysulfide electrolyte commonly applied in quantum dots-sensitized solar cells (QDSCs), which is several orders of magnitude lower than that of a typical Pt electrode. Therefore, VASWCNTs counter electrodes are believed to be a versatile candidate for further improvement of the power conversion efficiency of other iodine-free redox couple based DSCs and polysulfide electrolyte based QDSCs.

Genetic and biochemical investigations of the role of MamP in redox control of iron biomineralization in Magnetospirillum magneticum.

Science.gov (United States)

Jones, Stephanie R; Wilson, Tiffany D; Brown, Margaret E; Rahn-Lee, Lilah; Yu, Yi; Fredriksen, Laura L; Ozyamak, Ertan; Komeili, Arash; Chang, Michelle C Y

2015-03-31

Magnetotactic bacteria have evolved complex subcellular machinery to construct linear chains of magnetite nanocrystals that allow the host cell to sense direction. Each mixed-valent iron nanoparticle is mineralized from soluble iron within a membrane-encapsulated vesicle termed the magnetosome, which serves as a specialized compartment that regulates the iron, redox, and pH environment of the growing mineral. To dissect the biological components that control this process, we have carried out a genetic and biochemical study of proteins proposed to function in iron mineralization. In this study, we show that the redox sites of c-type cytochromes of the Magnetospirillum magneticum AMB-1 magnetosome island, MamP and MamT, are essential to their physiological function and that ablation of one or both heme motifs leads to loss of function, suggesting that their ability to carry out redox chemistry in vivo is important. We also develop a method to heterologously express fully heme-loaded MamP from AMB-1 for in vitro biochemical studies, which show that its Fe(III)-Fe(II) redox couple is set at an unusual potential (-89 ± 11 mV) compared with other related cytochromes involved in iron reduction or oxidation. Despite its low reduction potential, it remains competent to oxidize Fe(II) to Fe(III) and mineralize iron to produce mixed-valent iron oxides. Finally, in vitro mineralization experiments suggest that Mms mineral-templating peptides from AMB-1 can modulate the iron redox chemistry of MamP.

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

International Nuclear Information System (INIS)

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

2013-01-01

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

Fluxes of lactate into, from, and among gap junction-coupled astrocytes and their interaction with noradrenaline

Directory of Open Access Journals (Sweden)

Leif eHertz

2014-09-01

Full Text Available Lactate is a versatile metabolite with important roles in modulation of brain glucose utilization rate (CMRglc, diagnosis of brain-injured patients, redox- and receptor-mediated signaling, memory, and alteration of gene transcription. Neurons and astrocytes release and accumulate lactate using equilibrative monocarboxylate transporters that carry out net transmembrane transport of lactate only until intra- and extracellular levels reach equilibrium. Astrocytes have much faster lactate uptake than neurons and shuttle more lactate among gap junction-coupled astrocytes than to nearby neurons. Lactate diffusion within syncytia can provide precursors for oxidative metabolism and glutamate synthesis and facilitate its release from endfeet to perivascular space to stimulate blood flow. Lactate efflux from brain during activation underlies the large underestimation of CMRglc with labeled glucose and fall in CMRO2/CMRglc ratio. Receptor-mediated effects of lactate on locus coeruleus neurons include noradrenaline release in cerebral cortex and c-AMP-mediated stimulation of astrocytic gap junctional coupling, thereby enhancing its dispersal and release from brain. Lactate transport is essential for its multifunctional roles.

Optimization of mixed quantum-classical dynamics: Time-derivative coupling terms and selected couplings

International Nuclear Information System (INIS)

Pittner, Jiri; Lischka, Hans; Barbatti, Mario

2009-01-01

The usage of time-derivative non-adiabatic coupling terms and partially coupled time-dependent equations are investigated to accelerate non-adiabatic dynamics simulations at multireference configuration interaction (MRCI) level. The quality of the results and computational costs are compared against non-adiabatic benchmark dynamics calculations using non-adiabatic coupling vectors. In the comparison between the time-derivative couplings and coupling vectors, deviations in the adiabatic population of individual trajectories were observed in regions of rapid variation of the coupling terms. They, however, affected the average adiabatic population to only about 5%. For small multiconfiguration spaces, dynamics with time-derivative couplings are significantly faster than those with coupling vectors. This relation inverts for larger configuration spaces. The use of the partially coupled equations approach speeds up the simulations significantly while keeping the deviations in the population below few percent. Imidazole and the methaniminium cation are used as test examples

Advanced Space Vehicle Design Taking into Account Multidisciplinary Couplings and Mixed Epistemic/Aleatory Uncertainties

OpenAIRE

Balesdent , Mathieu; Brevault , Loïc; Price , Nathaniel; Defoort , Sébastien; Le Riche , Rodolphe; Kim , Nam-Ho; Haftka , Raphael T.; Bérend , Nicolas

2016-01-01

International audience; Space vehicle design is a complex process involving numerous disciplines such as aerodynamics, structure, propulsion and trajectory. These disciplines are tightly coupled and may involve antagonistic objectives that require the use of specific methodologies in order to assess trade-offs between the disciplines and to obtain the global optimal configuration. Generally, there are two ways to handle the system design. On the one hand, the design may be considered from a d...

3D imaging of the mitochondrial redox state of rat hearts under normal and fasting conditions

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He N. Xu

2014-03-01

Full Text Available The heart requires continuous ATP availability that is generated in the mitochondria. Although studies using the cell culture and perfused organ models have been carried out to investigate the biochemistry in the mitochondria in response to a change in substrate supply, mitochondrial bioenergetics of heart under normal feed or fasting conditions has not been studied at the tissue level with a sub-millimeter spatial resolution either in vivo or ex vivo. Oxidation of many food-derived metabolites to generate ATP in the mitochondria is realized through the NADH/NAD+ couple acting as a central electron carrier. We employed the Chance redox scanner — the low-temperature fluorescence scanner to image the three-dimensional (3D spatial distribution of the mitochondrial redox states in heart tissues of rats under normal feeding or an overnight starvation for 14.5 h. Multiple consecutive sections of each heart were imaged to map three redox indices, i.e., NADH, oxidized flavoproteins (Fp, including flavin adenine dinucleotide (FAD and the redox ratio NADH/Fp. The imaging results revealed the micro-heterogeneity and the spatial distribution of these redox indices. The quantitative analysis showed that in the fasted hearts the standard deviation of both NADH and Fp, i.e., SD_NADH and SD_Fp, significantly decreased with a p value of 0.032 and 0.045, respectively, indicating that the hearts become relatively more homogeneous after fasting. The fasted hearts contained 28.6% less NADH (p = 0.038. No significant change in Fp was found (p = 0.4. The NADH/Fp ratio decreased with a marginal p value (0.076. The decreased NADH in the fasted hearts is consistent with the cardiac cells' reliance of fatty acids consumption for energy metabolism when glucose becomes scarce. The experimental observation of NADH decrease induced by dietary restriction in the heart at tissue level has not been reported to our best knowledge. The Chance redox scanner demonstrated the

3D IMAGING OF THE MITOCHONDRIAL REDOX STATE OF RAT HEARTS UNDER NORMAL AND FASTING CONDITIONS.

Science.gov (United States)

Xu, He N; Zhou, Rong; Moon, Lily; Feng, Min; Li, Lin Z

2014-03-01

The heart requires continuous ATP availability that is generated in the mitochondria. Although studies using the cell culture and perfused organ models have been carried out to investigate the biochemistry in the mitochondria in response to a change in substrate supply, mitochondrial bioenergetics of heart under normal feed or fasting conditions has not been studied at the tissue level with a sub-millimeter spatial resolution either in vivo or ex vivo . Oxidation of many food-derived metabolites to generate ATP in the mitochondria is realized through the NADH/NAD + couple acting as a central electron carrier. We employed the Chance redox scanner - the low-temperature fluorescence scanner to image the three-dimensional (3D) spatial distribution of the mitochondrial redox states in heart tissues of rats under normal feeding or an overnight starvation for 14.5 h. Multiple consecutive sections of each heart were imaged to map three redox indices, i.e., NADH, oxidized flavoproteins (Fp, including flavin adenine dinucleotide (FAD)) and the redox ratio NADH/Fp. The imaging results revealed the micro-heterogeneity and the spatial distribution of these redox indices. The quantitative analysis showed that in the fasted hearts the standard deviation of both NADH and Fp, i.e., SD_NADH and SD_Fp, significantly decreased with a p value of 0.032 and 0.045, respectively, indicating that the hearts become relatively more homogeneous after fasting. The fasted hearts contained 28.6% less NADH ( p = 0.038). No significant change in Fp was found ( p = 0.4). The NADH/Fp ratio decreased with a marginal p value (0.076). The decreased NADH in the fasted hearts is consistent with the cardiac cells' reliance of fatty acids consumption for energy metabolism when glucose becomes scarce. The experimental observation of NADH decrease induced by dietary restriction in the heart at tissue level has not been reported to our best knowledge. The Chance redox scanner demonstrated the feasibility of 3D

Thermodynamic study of Eu3+/Eu2+ redox reaction in aqueous solutions at elevated temperatures and pressures by means of cyclic voltametry

International Nuclear Information System (INIS)

Bilal, B.A.

1991-01-01

The redox potential of the couple Eu 3+ /E 2+ in aqueous NaCl, NaClO 4 and Na 2 SO 4 solutions of different strength and various pH values has been determined by means of cyclic voltammetry up to 458 K and 1 kbar. In all cases reversible voltammograms were obtained. Compared to the redox potential in ClO 4 - solutions of pH 2, no significant shift was observed in Cl-solutions of the same pH, whereas a drastic shift to more negative potentials in solutions of SO 4 2- and in Cl - solutions of higher pH (pH 3-5) was obtained. This indicates a negligible complexation of Eu 3+ by means of Cl - but a strong one by means of OH - and SO 4 2- . An isothermal pressure increase up to 1 kbar led to a shift of only few mV more negative, indicating a small pressure dependence of the change of the partial molar volume (ΔV el ) accompanying the redox reaction, which results in this case only due to the different degrees of electrostriction. A more drastic shift of the redox potential (in the positive direction) results with increasing temperature. The isobaric temperature dependence of the redox potential is described by a two parameter equation which remains valid up to the saturation pressure at 458 K, due to the small pressure effect. ΔS and ΔH of the redox reaction has been determined. (orig.)

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)

Couple Support Schemata in Couples with and without Spinal Cord Injury

Science.gov (United States)

Gilad, Dvorit; Lavee, Yoav

2010-01-01

This article describes the cognitive schemata of couples' support relationships among 65 couples in which the husband had a long-term spinal cord injury and 65 couples without disability. The structure of the support relations schemata were examined by means of smallest-space analysis. Similarities between men and women in couples with and without…

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

DEFF Research Database (Denmark)

Zhang, Jingdong; Chi, Qijin; Ulstrup, Jens

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

Compartmentation of redox metabolism in malaria parasites.

Directory of Open Access Journals (Sweden)

Sebastian Kehr

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

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

DEFF Research Database (Denmark)

Heiskanen, Arto; Coman, Vasile; Kostesha, Natalie

2013-01-01

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

Redox properties of small semiconductor particles

International Nuclear Information System (INIS)

Liver, N.; Nitzan, A.

1992-01-01

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

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.

New tools for redox biology: From imaging to manipulation.

Science.gov (United States)

Bilan, Dmitry S; Belousov, Vsevolod V

2017-08-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-03-15

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

Three Redox States of Trypanosoma brucei Alternative Oxidase Identified by Infrared Spectroscopy and Electrochemistry

Science.gov (United States)

Maréchal, Amandine; Kido, Yasutoshi; Kita, Kiyoshi; Moore, Anthony L.; Rich, Peter R.

2009-01-01

Electrochemistry coupled with Fourier transform infrared (IR) spectroscopy was used to investigate the redox properties of recombinant alternative ubiquinol oxidase from Trypanosoma brucei, the organism responsible for African sleeping sickness. Stepwise reduction of the fully oxidized resting state of recombinant alternative ubiquinol oxidase revealed two distinct IR redox difference spectra. The first of these, signal 1, titrates in the reductive direction as an n = 2 Nernstian component with an apparent midpoint potential of 80 mV at pH 7.0. However, reoxidation of signal 1 in the same potential range under anaerobic conditions did not occur and only began with potentials in excess of 500 mV. Reoxidation by introduction of oxygen was also unsuccessful. Signal 1 contained clear features that can be assigned to protonation of at least one carboxylate group, further perturbations of carboxylic and histidine residues, bound ubiquinone, and a negative band at 1554 cm−1 that might arise from a radical in the fully oxidized protein. A second distinct IR redox difference spectrum, signal 2, appeared more slowly once signal 1 had been reduced. This component could be reoxidized with potentials above 100 mV. In addition, when both signals 1 and 2 were reduced, introduction of oxygen caused rapid oxidation of both components. These data are interpreted in terms of the possible active site structure and mechanism of oxygen reduction to water. PMID:19767647

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.

Contribution to the study of the redox reactions and the speciation of technetium in chloride and carbonate media

International Nuclear Information System (INIS)

Ben Said, K.

1999-11-01

Technetium is important as a long half-life multi-valent radioelement within the framework of the nuclear waste storage especially in underground geological sites. So, the safety studies require the knowledge of the redox and of the chemical properties of this element in order to model its geochemical behaviour in the environment. Our studies deal with the redox behaviour and the speciation of technetium in chloride and carbonate media. Similar natural systems possess redox potentials likely to reduce Tc(VII) into Tc(V), Tc(IV) and Tc(III). The question of the standard redox potential of the Tc(VII)Tc(IV) couple is settled in non complexing media where Tc(IV) exists as TcO 2 (s) but is still a matter of debate in complexing media. The formal potential of the Tc(VII)/Tc(IV couple has been determined by an indirect method in 1.0 M HCl media where Tc(IV) exists as chloride complexes. The species formed by dissolving K 2 TcCl 6 (s) in chloride media have been characterised by complementary techniques of speciation (UV-visible and Raman spectrometry, X-rays absorption spectroscopy and polarography). Two chemical formulae have been proposed for the chloride species of Tc(IV) in 1.0 M HCl media as hydrolyzed TcCl 6 2- : TcCl 5 (H 2 O) - or TcCl 4 (H 2 O) 2 . The chemical or electrochemical reduction of pertechnetate in carbonate media leads to amorphous oxides or carbonate complexes of Tc(IV) and/or of Tc(III). In carbonate media, the stability of the species under γ irradiation has been estimated by UV/VIS spectrophotometry: Tc(VII) is stable but reduced into Tc(IV) in the presence of formate when the carbonate complex of Tc(IV) is oxidised into Tc(VII). So the most mobile valency Tc(VII) seems to be the stable one in irradiated carbonate media. (author)

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

Science.gov (United States)

Macalady, Donald L.; Walton-Day, Katherine

2011-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-09-07

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

Contribution to the study of the redox couple Np(VI)/Np(V) in the presence of uranium(VI) in solutions of nitric acid and nitrous acid; Contribution a l'etude du comportement redox du couple Np(VI)/Np(V) en presence d'uranium VI dans les solutions constituees d'acide nitrique et d'acide nitreux

Energy Technology Data Exchange (ETDEWEB)

Arpigny, S. [CEA Marcoule, Dept. de Radiochimie et Procedes, DRP, 30 (France)

2001-07-01

The redox behavior of the Np(VI)/Np(V) couple was the subject of a spectrometric study of the Np(VI) reduction reaction in nitric acid solutions (4 to 5 M) containing variable concentrations (1.5 to 3.5 x 10{sup -3} M) of nitrous acid. A low nitrous acid concentration and a high nitric acid concentration were found to favor the stabilization of Np(VI). The stoichiometric coefficients of nitrous acid and nitric acid in the Np(VI) reduction reaction were determined thermodynamically, although only the reaction order with respect to HNO{sub 2} could be calculated from a kinetic analysis. Adding nitrate ions to a HNO{sub 3}/HNO{sub 2} solution enhanced the stability of neptunium at oxidation state +VI, but also increased the reduction rate. When uranium(VI) was added to the HNO{sub 3}/HNO{sub 2} solutions, the total quantity of neptunium at oxidation state +V (either free or as a Np(V)-U(VI) complex) remained practically unchanged, as did the Np(VI) reduction rate. The electrochemical behavior of the Np(VI)/Np(V) couple was investigated in a weak acidic medium by voltammetry with an ultra-micro-electrode (UME). The oxidation wave limiting current variation was a linear function of the Np(V) concentration when a gold UME was used, but not with a platinum UME; the reduction wave limiting current variation versus the Np(V) concentration was linear with either gold or platinum UMEs. The presence of the Np(V)-U(VI) complex in the neptunium solutions was characterized by a shift in the normal apparent potential of the Np(VI)/Np(V) couple toward anodic potentials consistent with the previously determined values of the complexation constants. (author)

Redox proteomics of tomato in response to Pseudomonas syringae infection

Science.gov (United States)

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

2015-01-01

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

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

Directory of Open Access Journals (Sweden)

Breno Pannia Espósito

2007-08-01

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

The impact of surface coverage on the kinetics of electron transfer through redox monolayers on a silicon electrode surface

International Nuclear Information System (INIS)

Ciampi, Simone; Choudhury, Moinul H.; Ahmad, Shahrul Ainliah Binti Alang; Darwish, Nadim; Brun, Anton Le; Gooding, J.Justin

2015-01-01

Graphical abstract: The impact of surface coverage on the kinetics of electron transfer through redox monolayers on a silicon electrode surface. ABSTRACT: The impact of the coverage of ferrocene moieties, attached to a silicon electrode modified via hydrosilylation of a dialkyne, on the kinetics of electron transfer between the redox species and the electrode is explored. The coverage of ferrocene is controlled by varying the coupling time between azidomethylferrocene and the distal alkyne of the monolayer via the copper assisted azide-alkyne cycloaddition reaction. All other variables in the surface preparation are maintained identical. What is observed is that the higher the surface coverage of the ferrocene moieties the faster the apparent rates of electron transfer. This surface coverage-dependent kinetic effect is attributed to electrons hopping between ferrocene moieties across the redox film toward hotspots for the electron transfer event. The origin of these hotspots is tentatively suggested to result from minor amounts of oxide on the underlying silicon surface that reduce the barrier for the electron transfer.

Symproportionation versus Disproportionation in Bromine Redox Systems

International Nuclear Information System (INIS)

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

2015-01-01

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

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

Science.gov (United States)

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

2018-02-01

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

An Excel Workbook for Identifying Redox Processes in Ground Water

Science.gov (United States)

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

2009-01-01

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

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

International Nuclear Information System (INIS)

2013-01-01

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

Electronically Induced Redox Barriers for Treatment of Groundwater

National Research Council Canada - National Science Library

Sale, Tom; Gilbert, David

2006-01-01

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

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

Science.gov (United States)

Li, Lin Z.

2012-01-01

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

Characterization of redox conditions in pollution plumes

DEFF Research Database (Denmark)

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

2000-01-01

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

Characterization of redox proteins using electrochemical methods

NARCIS (Netherlands)

Verhagen, M.

1995-01-01

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

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

Science.gov (United States)

Baier, Margarete; Dietz, Karl-Josef

2005-06-01

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

Regulation of redox reactions of chemical species (arsenic and chromium) in sediment of Marque river. From experimentation to modeling

International Nuclear Information System (INIS)

Gorny, Josselin

2015-01-01

The French national radioactive waste management agency (Andra) and the Nord-Pas de Calais (NPDC) Region aim to better understand the fate of the redox sensitive trace elements in soils and river sediments to ameliorate the management of polluted sediments and of the storage of radioactive wastes. To address this problematic, some river sediments were selected as proxies, as strong redox gradients can be observed. Two methods have been developed to study the speciation of As and Cr: (i) HPIC-ICP-MS (High Performance Ionic Performance - Inductively Coupled Plasma - Mass Spectrometry) coupling in order to separate and quantify As [As(III), As(V), DMMA V and MMAA V ] and Cr species [Cr(III) and Cr(VI)], and (ii) DGT probes (Diffusive Gradient in Thin Film) containing specific chelating binding gels to quantify As species [As(III) and total As]. These methods have been implemented to monitor the low contaminated pore waters of the Marque river during 9 months. The results demonstrated that chromium is present only under its reduced form Cr(III), which makes difficult to assess the parameters that force redox interconversions between Cr(III) and Cr(VI). Arsenic is present only under its inorganic forms: As(III), As(V), and thio-arsenical species. Seasonal changes of As speciation in the dissolved phase depends mainly of S(-II) production by sulfate-reducing bacteria, which makes the amount of dissolved S(- II) an important parameter to follow through time since the As reduction increases its mobility and toxicity. (author) [fr

Urea-assisted synthesis of AlPO4:Ce,Tb nanorods as a redox luminescence switch

International Nuclear Information System (INIS)

Yang, Wei; Hu, Juncheng

2013-01-01

AlPO 4 :Ce,Tb nanorods were synthesized by a facile hydrothermal method. The morphology of rod-like AlPO 4 was tuned by varying urea concentrations, AlPO 4 gradually changed from nanosheets to nanorods, and urea provided hydroxyl anion (OH − ) in the aqueous solution to prepare the dispersed nanorods under the hydrothermal conditions. The emission intensity of nanorods increased significantly compared to that of nanosheets. AlPO 4 :Ce,Tb nanorods provided a novel redox luminescence switch on the basis of the reversible switching of the Ce 3+ /Ce 4+ redox couple. The luminescence is quenched (off) when the system is in the oxidized form while it is restored (on) in the reduced form. The mechanism of the energy transfer and electronic transition between Ce 3+ and Tb 3+ in the AlPO 4 nanorods was also discussed. This switch has biocompatibility and low toxicity, and may have a potential application in biomedical diagnostics and analysis

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

Science.gov (United States)

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

2014-01-01

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

Analytical expression for the tunnel current through the redox-mediated tunneling contact in the case of the adiabatic electron transfer at one of the working electrodes and any possible type of the electron transfer at the other electrode.

Science.gov (United States)

Medvedev, Igor G

2017-11-21

We study the tunnel current through a one-level redox molecule immersed into the electrolyte solution for the case when the coupling of the molecule to one of the working electrodes is strong while it is arbitrary to the other electrode. Using the Feynman-Vernon influence functional theory and the perturbation expansion of the effective action of the classical oscillator coupled both to the valence level of the redox molecule and to the thermal bath representing the classical fluctuations of the polarization of the solvent, we obtain, following the canonical way, the Langevin equation for the oscillator. It is found that for the aqueous electrolyte solution, the damping and the stochastic forces which arise due to the tunnel current are much smaller than those due to the thermal bath and therefore can be neglected. We estimate the higher-order corrections to the effective action and show that the Langevin dynamics takes place in this case for arbitrary parameters of the tunneling junction under the condition of the strong coupling of the redox molecule to one of the working electrodes. Then the steady-state coordinate distribution function of the oscillator resulting from the corresponding Fokker-Planck equation is the Boltzmann distribution function which is determined by the adiabatic free energy surface arising from the mean current-induced force. It enables us to obtain the expression for the tunnel current in the case when the coupling of the redox molecule to one of the working electrodes is strong while it is arbitrary to the other electrode.

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

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

Science.gov (United States)

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

2017-11-02

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

Biorthogonal moment expansions in coupled-cluster theory: Review of key concepts and merging the renormalized and active-space coupled-cluster methods

International Nuclear Information System (INIS)

Shen Jun; Piecuch, Piotr

2012-01-01

Graphical abstract: The key ideas behind biorthogonal moment expansions in coupled-cluster theory are discussed. Methods that enable merging active-space and renormalized coupled-cluster approaches are proposed and tested. Abstract: After reviewing recent progress in the area of the development of coupled-cluster (CC) methods for quasi-degenerate electronic states that are characterized by stronger non-dynamical correlation effects, including new generations of single- and multi-reference approaches that can handle bond breaking and excited states dominated by many-electron transitions, and after discussing the key elements of the left-eigenstate completely renormalized (CR) CC and equation-of-motion (EOM) CC methods, and the underlying biorthogonal method of moments of CC (MMCC) equations [P. Piecuch, M. Włoch, J. Chem. Phys. 123 (2005) 224105; P. Piecuch, M. Włoch, J.R. Gour, A. Kinal, Chem. Phys. Lett. 418 (2006) 467; M. Włoch, M.D. Lodriguito, P. Piecuch, J.R. Gour, Mol. Phys. 104 (2006) 2149], it is argued that it is beneficial to merge the CR-CC/EOMCC and active-space CC/EOMCC [P. Piecuch, Mol. Phys. 108 (2010) 2987, and references therein] theories into a single formalism. In order to accomplish this goal, the biorthogonal MMCC theory, which provides compact many-body expansions for the differences between the full configuration interaction and CC or, in the case of excited states, EOMCC energies, obtained using conventional truncation schemes in the cluster operator T and excitation operator R μ , is generalized, so that one can correct the CC/EOMCC energies obtained with arbitrary truncations in T and R μ for the selected many-electron correlation effects of interest. The resulting moment expansions, defining the new, Flexible MMCC (Flex-MMCC) formalism, and the ensuing CC(P; Q) hierarchy, proposed in the present work, enable one to correct energies obtained in the active-space CC and EOMCC calculations, in which one selects higher many

Redox-responsive theranostic nanoplatforms based on inorganic nanomaterials.

Science.gov (United States)

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

2017-08-10

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

Space Threat Warning: Foundation for Space Superiority, Avoiding a Space Pearl Harbor

National Research Council Canada - National Science Library

Burke, Alan W

2006-01-01

... have stated the US must avoid a space Pearl Harbor. This concern is due to the idea that a decrease in the perceived threat to space assets after the demise of the Soviet Union coupled with a competition for space resources has resulted...

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

Czech Academy of Sciences Publication Activity Database

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

2015-01-01

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

Carbon Redox-Polymer-Gel Hybrid Supercapacitors

Science.gov (United States)

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

2016-01-01

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

Redox reactivity and coordination chemistry of uranium

International Nuclear Information System (INIS)

Nocton, G.

2009-09-01

The study and the understanding of actinides chemistry have important implications in the nuclear field both for the development of new actinides materials and the retreatment of the nuclear wastes. One of the major issues in that chemistry is that the actinides elements are known to undergo redox reaction and to form assemblies of different size and different topologies. In that context uranium can be a good model of the heavier radioelement because it is much less radioactive. So, this work concerns the synthesis and the study of the spectroscopy and the magnetic properties of several uranium based polymetallic assemblies synthesized by taking advantage of the redox properties and the coordination chemistry of uranium. The hydrolysis reactivity of trivalent uranium has been studied in absence of sterically hindered ligands and led to the synthesis of oxo/hydroxo uranium assemblies with different sizes by changing the starting complex or the reaction conditions. By following the same strategy, the controlled oxidation of trivalent uranium complexes led to an original azido/nitrido uranium complex. The coordination chemistry of the pentavalent uranyl polymer {[UO 2 py 5 ][KI 2 py 3 ]} n has also been studied with different ligand and in different conditions and led to several cation-cation complexes for which the stability is sufficient for studying there dismutation by proton NMR. By changing the ancillary ligands stable monomeric complexes of pentavalent uranyl complexes were also obtained. The magnetic properties of all the complexes, monomers and polymetallic complexes were studied and an antiferromagnetic coupling was observed for the cation-cation pentavalent uranyl dimer [UO 2 (dbm) 2 (K 18 C 6 )] 2 . (author)

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

Science.gov (United States)

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

2017-01-16

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

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

Science.gov (United States)

Jones, Dean P

2006-01-01

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

Kynurenine pathway metabolites and enzymes involved in redox reactions.

Science.gov (United States)

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

2017-01-01

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

Accelerated redox reaction between chromate and phenolic pollutants during freezing

Energy Technology Data Exchange (ETDEWEB)

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

2017-05-05

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

Accelerated redox reaction between chromate and phenolic pollutants during freezing

International Nuclear Information System (INIS)

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

2017-01-01

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

Organic non-aqueous cation-based redox flow batteries

Science.gov (United States)

Zhang, Lu; Huang, Jinhua; Burrell, Anthony

2018-05-08

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

Redox shuttles for overcharge protection of lithium batteries

Science.gov (United States)

Amine, Khalil; Chen, Zonghai; Wang, Qingzheng

2010-12-14

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

A multimodal optical and electrochemical device for monitoring surface reactions: redox active surfaces in porous silicon Rugate filters.

Science.gov (United States)

Ciampi, Simone; Guan, Bin; Darwish, Nadim A; Zhu, Ying; Reece, Peter J; Gooding, J Justin

2012-12-21

Herein, mesoporous silicon (PSi) is configured as a single sensing device that has dual readouts; as a photonic crystal sensor in a Rugate filter configuration, and as a high surface area porous electrode. The as-prepared PSi is chemically modified to provide it with stability in aqueous media and to allow for the subsequent coupling of chemical species, such as via Cu(I)-catalyzed cycloaddition reactions between 1-alkynes and azides ("click" reactions). The utility of the bimodal capabilities of the PSi sensor for monitoring surface coupling procedures is demonstrated by the covalent coupling of a ferrocene derivative, as well as by demonstrating ligand-exchange reactions (LER) at the PSi surface. Both types of reactions were monitored through optical reflectivity measurements, as well as electrochemically via the oxidation/reduction of the surface tethered redox species.

An unexplored role for Peroxiredoxin in exercise-induced redox signalling?

Directory of Open Access Journals (Sweden)

Alex J. Wadley

2016-08-01

Full Text Available Peroxiredoxin (PRDX is a ubiquitous oxidoreductase protein with a conserved ionised thiol that permits catalysis of hydrogen peroxide (H2O2 up to a million times faster than any thiol-containing signalling protein. The increased production of H2O2 within active tissues during exercise is thought to oxidise conserved cysteine thiols, which may in turn facilitate a wide variety of physiological adaptations. The precise mechanisms linking H2O2 with the oxidation of signalling thiol proteins (phosphates, kinases and transcription factors are unclear due to these proteins' low reactivity with H2O2 relative to abundant thiol peroxidases such as PRDX. Recent work has shown that following exposure to H2O2 in vitro, the sulfenic acid of the PRDX cysteine can form mixed disulphides with transcription factors associated with cell survival. This implicates PRDX as an ‘active’ redox relay in transmitting the oxidising equivalent of H2O2 to downstream proteins. Furthermore, under oxidative stress, PRDX can form stable oxidised dimers that can be secreted into the extracellular space, potentially acting as an extracellular ‘stress’ signal. There is extensive literature assessing non-specific markers of oxidative stress in response to exercise, however the PRDX catalytic cycle may offer a more robust approach for measuring changes in redox balance following exercise. This review discusses studies assessing PRDX-mediated cellular signalling and integrates the recent advances in redox biology with investigations that have examined the role of PRDX during exercise in humans and animals. Future studies should explore the role of PRDX as a key regulator of peroxide mediated-signal transduction during exercise in humans.

De Novo Construction of Redox Active Proteins.

Science.gov (United States)

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

2016-01-01

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

Analysis of the coupling efficiency of a tapered space receiver with a calculus mathematical model

Science.gov (United States)

Hu, Qinggui; Mu, Yining

2018-03-01

We establish a calculus mathematical model to study the coupling characteristics of tapered optical fibers in a space communications system, and obtained the coupling efficiency equation. Then, using MATLAB software, the solution was calculated. After this, the sample was produced by the mature flame-brush technique. The experiment was then performed, and the results were in accordance with the theoretical analysis. This shows that the theoretical analysis was correct and indicates that a tapered structure could improve its tolerance with misalignment. Project supported by The National Natural Science Foundation of China (grant no. 61275080); 2017 Jilin Province Science and Technology Development Plan-Science and Technology Innovation Fund for Small and Medium Enterprises (20170308029HJ); ‘thirteen five’ science and technology research project of the Department of Education of Jilin 2016 (16JK009).

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...

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

Science.gov (United States)

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

2014-01-01

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

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

Science.gov (United States)

Jones, Dean P

2016-04-01

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

NNT reverse mode of operation mediates glucose control of mitochondrial NADPH and glutathione redox state in mouse pancreatic β-cells

Directory of Open Access Journals (Sweden)

Laila R.B. Santos

2017-06-01

Full Text Available Objective: The glucose stimulation of insulin secretion (GSIS by pancreatic β-cells critically depends on increased production of metabolic coupling factors, including NADPH. Nicotinamide nucleotide transhydrogenase (NNT typically produces NADPH at the expense of NADH and ΔpH in energized mitochondria. Its spontaneous inactivation in C57BL/6J mice was previously shown to alter ATP production, Ca2+ influx, and GSIS, thereby leading to glucose intolerance. Here, we tested the role of NNT in the glucose regulation of mitochondrial NADPH and glutathione redox state and reinvestigated its role in GSIS coupling events in mouse pancreatic islets. Methods: Islets were isolated from female C57BL/6J mice (J-islets, which lack functional NNT, and genetically close C57BL/6N mice (N-islets. Wild-type mouse NNT was expressed in J-islets by adenoviral infection. Mitochondrial and cytosolic glutathione oxidation was measured with glutaredoxin 1-fused roGFP2 probes targeted or not to the mitochondrial matrix. NADPH and NADH redox state was measured biochemically. Insulin secretion and upstream coupling events were measured under dynamic or static conditions by standard procedures. Results: NNT is largely responsible for the acute glucose-induced rise in islet NADPH/NADP+ ratio and decrease in mitochondrial glutathione oxidation, with a small impact on cytosolic glutathione. However, contrary to current views on NNT in β-cells, these effects resulted from a glucose-dependent reduction in NADPH consumption by NNT reverse mode of operation, rather than from a stimulation of its forward mode of operation. Accordingly, the lack of NNT in J-islets decreased their sensitivity to exogenous H2O2 at non-stimulating glucose. Surprisingly, the lack of NNT did not alter the glucose-stimulation of Ca2+ influx and upstream mitochondrial events, but it markedly reduced both phases of GSIS by altering Ca2+-induced exocytosis and its metabolic amplification. Conclusion: These

Redox signaling in acute pancreatitis

Science.gov (United States)

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

2015-01-01

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

Redox signaling in acute pancreatitis

Directory of Open Access Journals (Sweden)

Salvador Pérez

2015-08-01

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

Biogeochemical Barriers: Redox Behavior of Metals and Metalloids

Science.gov (United States)

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-01-01

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

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

Science.gov (United States)

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

2017-06-24

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

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.

Redox processes in radiation biology and cancer

International Nuclear Information System (INIS)

Greenstock, C.L.

1981-01-01

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

Differential alkylation-based redox proteomics - Lessons learnt

DEFF Research Database (Denmark)

Wojdyla, Katarzyna; Rogowska-Wrzesinska, Adelina

2015-01-01

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

Development of redox stable, multifunctional substrates for anode supported SOFCS

DEFF Research Database (Denmark)

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

2017-01-01

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

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

Science.gov (United States)

Korkina, Liudmila

2016-01-01

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

Formation of Exceptionally Weak C–C Bonds by Metal-Templated Pinacol Coupling

NARCIS (Netherlands)

Folkertsma, Emma; Benthem, Sanne H.; Witteman, Léon; Van Slagmaat, Christian A. M. R.; Lutz, Martin; Klein Gebbink, Robertus J.m.; Moret, Marc-etienne

2017-01-01

The ability of the bis(imidazolyl)ketone ligand BMdiPhIK (bis(1-methyl-4,5-diphenylimidazolyl)ketone) to function as a redox active ligand has been investigated. The reduction of [M(BMdiPhIK)Cl2] (M = Fe and Zn) complexes resulted in a pinacol-type coupling to form dinuclear complexes featuring very

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.)

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

Directory of Open Access Journals (Sweden)

He N. Xu

2014-03-01

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

Characterization of Redox properties of humic materials

International Nuclear Information System (INIS)

Choppin, G.R.

1995-01-01

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

High Performance Redox Flow Batteries: An Analysis of the Upper Performance Limits of Flow Batteries Using Non-aqueous Solvents

International Nuclear Information System (INIS)

Sun, C.-N.; Mench, M.M.; Zawodzinski, T.A.

2017-01-01

Redox Flow Batteries (RFBs) are a promising technology for grid-scale electrochemical energy storage. In this work, we use a recently achieved high-performance flow battery performance curve as a basis to assess the maximum achievable performance of a RFB employing non-aqueous solutions as active materials. First we show high performance in a vanadium redox flow battery (VRFB), specifically a limiting situation in which the cell losses are ohmic in nature and derive from electrolyte conductance. Based on that case, we analyze the analogous limiting behavior of non-aqueous (NA) systems using a series of calculations assuming similar ohmic losses, scaled by the relative electrolyte resistances, with a higher voltage redox couple assumed for the NA battery. The results indicate that the NA battery performance is limited by the low electrolyte conductivity to a fraction of the performance of the VRFB. Given the narrow window in which the NARFB offers advantages, even for the most generous limiting assumptions related to performance while ignoring the numerous other disadvantageous aspects of these systems, we conclude that this technology is unlikely under present circumstances to provide practical large-scale energy storage solutions.

Optimal control of coupled parabolic-hyperbolic non-autonomous PDEs: infinite-dimensional state-space approach

Science.gov (United States)

Aksikas, I.; Moghadam, A. Alizadeh; Forbes, J. F.

2018-04-01

This paper deals with the design of an optimal state-feedback linear-quadratic (LQ) controller for a system of coupled parabolic-hypebolic non-autonomous partial differential equations (PDEs). The infinite-dimensional state space representation and the corresponding operator Riccati differential equation are used to solve the control problem. Dynamical properties of the coupled system of interest are analysed to guarantee the existence and uniqueness of the solution of the LQ-optimal control problem and also to guarantee the exponential stability of the closed-loop system. Thanks to the eigenvalues and eigenfunctions of the parabolic operator and also the fact that the hyperbolic-associated operator Riccati differential equation can be converted to a scalar Riccati PDE, an algorithm to solve the LQ control problem has been presented. The results are applied to a non-isothermal packed-bed catalytic reactor. The LQ optimal controller designed in the early portion of the paper is implemented for the original non-linear model. Numerical simulations are performed to show the controller performances.

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.

Characterization of the surface redox process of adsorbed morin at glassy carbon electrodes

International Nuclear Information System (INIS)

Tesio, Alvaro Yamil; Granero, Adrian Marcelo; Fernandez, Hector; Zon, Maria Alicia

2011-01-01

The thermodynamic and kinetics of the adsorption of morin (MOR) on glassy carbon (GC) electrodes in 0.2 mol dm -3 phosphate buffer solutions (PBS, pH 7.00) was studied by both cyclic (CV) and square wave (SWV) voltammetries. The Frumkin adsorption isotherm was the best to describe the specific interaction of MOR with GC electrodes. The SWV allowed to characterize the thermodynamic and kinetics of surface quasi-reversible redox couple of MOR, using the combination of the 'quasi-reversible maximum' and the 'splitting of SW net peaks' methods. Average values obtained for the formal potential and the anodic transfer coefficient were (0.27 ± 0.02) V and (0.59 ± 0.09), respectively. Moreover, a value of formal rate constant (k s ) of 87 s -1 for the overall two-electron redox process was calculated. The SWV was also employed to generate calibration curves, which were linear in the range MOR bulk concentration (c MOR *) from 1.27 x 10 -7 to 2.50 x 10 -5 mol dm -3 . The lowest concentration experimentally measured for a signal to noise ratio of 3:1 was 1.25 x 10 -8 mol dm -3 (3 ppb).

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-05-15

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

A study of redox kinetic in silicate melt

International Nuclear Information System (INIS)

Magnien, V.

2005-12-01

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

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

Le reazioni redox: un pasticcio concettuale?

Directory of Open Access Journals (Sweden)

Elena Ghibaudi

2015-10-01

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

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

International Nuclear Information System (INIS)

Kravchenko, T.A.

1986-01-01

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

Molecular Orbital Principles of Oxygen-Redox Battery Electrodes.

Science.gov (United States)

Okubo, Masashi; Yamada, Atsuo

2017-10-25

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

Synthesis and characterization of redox-active ferric nontronite

Energy Technology Data Exchange (ETDEWEB)

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

2017-10-01

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

Fast and stable redox reactions of MnO2/CNT hybrid electrodes for dynamically stretchable pseudocapacitors

Science.gov (United States)

Gu, Taoli; Wei, Bingqing

2015-07-01

Pseudocapacitors, which are energy storage devices that take advantage of redox reactions to store electricity, have a different charge storage mechanism compared to lithium-ion batteries (LIBs) and electric double-layer capacitors (EDLCs), and they could realize further gains if they were used as stretchable power sources. The realization of dynamically stretchable pseudocapacitors and understanding of the underlying fundamentals of their mechanical-electrochemical relationship have become indispensable. We report herein the electrochemical performance of dynamically stretchable pseudocapacitors using buckled MnO2/CNT hybrid electrodes. The extremely small relaxation time constant of less than 0.15 s indicates a fast redox reaction at the MnO2/CNT hybrid electrodes, securing a stable electrochemical performance for the dynamically stretchable pseudocapacitors. This finding and the fundamental understanding gained from the pseudo-capacitive behavior coupled with mechanical deformation under a dynamic stretching mode would provide guidance to further improve their overall performance including a higher power density than LIBs, a higher energy density than EDLCs, and a long-life cycling stability. Most importantly, these results will potentially accelerate the applications of stretchable pseudocapacitors for flexible and biomedical electronics.Pseudocapacitors, which are energy storage devices that take advantage of redox reactions to store electricity, have a different charge storage mechanism compared to lithium-ion batteries (LIBs) and electric double-layer capacitors (EDLCs), and they could realize further gains if they were used as stretchable power sources. The realization of dynamically stretchable pseudocapacitors and understanding of the underlying fundamentals of their mechanical-electrochemical relationship have become indispensable. We report herein the electrochemical performance of dynamically stretchable pseudocapacitors using buckled MnO2/CNT hybrid

Anticancer Activity of Metal Complexes: Involvement of Redox Processes

Science.gov (United States)

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

2012-01-01

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

Robust independent modal space control of a coupled nano-positioning piezo-stage

Science.gov (United States)

Zhu, Wei; Yang, Fufeng; Rui, Xiaoting

2018-06-01

In order to accurately control a coupled 3-DOF nano-positioning piezo-stage, this paper designs a hybrid controller. In this controller, a hysteresis observer based on a Bouc-Wen model is established to compensate the hysteresis nonlinearity of the piezoelectric actuator first. Compared to hysteresis compensations using Preisach model and Prandt-Ishlinskii model, the compensation method using the hysteresis observer is computationally lighter. Then, based on the proposed dynamics model, by constructing the modal filter, a robust H∞ independent modal space controller is designed and utilized to decouple the piezo-stage and deal with the unmodeled dynamics, disturbance, and hysteresis compensation error. The effectiveness of the proposed controller is demonstrated experimentally. The experimental results show that the proposed controller can significantly achieve the high-precision positioning.

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

Science.gov (United States)

Brandriet, Alexandra R.; Bretz, Stacey Lowery

2014-01-01

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

Time evolution of dissolved oxygen and redox conditions in a HLW repository

International Nuclear Information System (INIS)

Wersin, P.; Spahiu, K.; Bruno, J.

1994-02-01

The evolution of oxygen in a HLW repository has been studied using presently available geochemical background information. The important processes affecting oxygen migration in the near-field include diffusion and oxidation of pyrite and dissolved Fe(II). The evaluation of time scales of oxygen decrease is carried out with 1. an analytical approach involving the coupling of diffusion and chemical reaction, 2. a numerical geochemical approach involving the application of a newly developed diffusion-extended version of the STEADYQL code. Both approaches yield consistent rates of oxygen decrease and indicate that oxidation of pyrite impurities in the clay is the dominant process. The results obtained fRom geochemical modelling are interpreted in terms of evolution of redox conditions. Moreover, a sensitivity analysis of the major geochemical and physical parameters is performed. These results indicate that the uncertainties associated with reactive pyrite surface area impose the overall uncertainties of prediction of time scales. Thus, the obtained time of decrease to 1% of initial O 2 concentrations range between 7 and 290 years. The elapsed time at which the transition to anoxic conditions occurs is estimated to be within the same time range. Additional experimental information on redox sensitive impurities in the envisioned buffer and backfill material would further constrain the evaluated time scales. 41 refs

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

Science.gov (United States)

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

2013-03-14

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

Electrochemical redox processes involving soluble cerium species

International Nuclear Information System (INIS)

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

2016-01-01

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

Are bioassays useful tools to assess redox processes and biodegradation?

DEFF Research Database (Denmark)

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

2002-01-01

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

Gamma oscillations and spontaneous network activity in the hippocampus are highly sensitive to decreases in pO2 and concomitant changes in mitochondrial redox state.

Science.gov (United States)

Huchzermeyer, Christine; Albus, Klaus; Gabriel, Hans-Jürgen; Otáhal, Jakub; Taubenberger, Nando; Heinemann, Uwe; Kovács, Richard; Kann, Oliver

2008-01-30

Gamma oscillations have been implicated in higher cognitive processes and might critically depend on proper mitochondrial function. Using electrophysiology, oxygen sensor microelectrode, and imaging techniques, we investigated the interactions of neuronal activity, interstitial pO2, and mitochondrial redox state [NAD(P)H and FAD (flavin adenine dinucleotide) fluorescence] in the CA3 subfield of organotypic hippocampal slice cultures. We find that gamma oscillations and spontaneous network activity decrease significantly at pO2 levels that do not affect neuronal population responses as elicited by moderate electrical stimuli. Moreover, pO2 and mitochondrial redox states are tightly coupled, and electrical stimuli reveal transient alterations of redox responses when pO2 decreases within the normoxic range. Finally, evoked redox responses are distinct in somatic and synaptic neuronal compartments and show different sensitivity to changes in pO2. We conclude that the threshold of interstitial pO2 for robust CA3 network activities and required mitochondrial function is clearly above the "critical" value, which causes spreading depression as a result of generalized energy failure. Our study highlights the importance of a functional understanding of mitochondria and their implications on activities of individual neurons and neuronal networks.

Thiol Redox Transitions in Cell Signaling: a Lesson from N-Acetylcysteine