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Sample records for redox couple based

  1. 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.

  2. Coupling photocatalysis and redox biocatalysis toward biocatalyzed artificial photosynthesis.

    Science.gov (United States)

    Lee, Sahng Ha; Kim, Jae Hong; Park, Chan Beum

    2013-04-02

    In green plants, solar-energy utilization is accomplished through a cascade of photoinduced electron transfer, which remains a target model for realizing artificial photosynthesis. We introduce the concept of biocatalyzed artificial photosynthesis through coupling redox biocatalysis with photocatalysis to mimic natural photosynthesis based on visible-light-driven regeneration of enzyme cofactors. Key design principles for reaction components, such as electron donors, photosensitizers, and electron mediators, are described for artificial photosynthesis involving biocatalytic assemblies. Recent research outcomes that serve as a proof of the concept are summarized and current issues are discussed to provide a future perspective. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2017-07-28

    The nicotinamide adenine dinucleotide (NAD(+))/reduced NAD(+) (NADH) and NADP(+)/reduced NADP(+) (NADPH) redox couples are essential for maintaining cellular redox homeostasis and for modulating numerous biological events, including cellular metabolism. Deficiency or imbalance of these two redox couples has been associated with many pathological disorders. Recent Advances: Newly identified biosynthetic enzymes and newly developed genetically encoded biosensors enable us to understand better how cells maintain compartmentalized NAD(H) and NADP(H) pools. The concept of redox stress (oxidative and reductive stress) reflected by changes in NAD(H)/NADP(H) has increasingly gained attention. The emerging roles of NAD(+)-consuming proteins in regulating cellular redox and metabolic homeostasis are active research topics. The biosynthesis and distribution of cellular NAD(H) and NADP(H) are highly compartmentalized. It is critical to understand how cells maintain the steady levels of these redox couple pools to ensure their normal functions and simultaneously avoid inducing redox stress. In addition, it is essential to understand how NAD(H)- and NADP(H)-utilizing enzymes interact with other signaling pathways, such as those regulated by hypoxia-inducible factor, to maintain cellular redox homeostasis and energy metabolism. Additional studies are needed to investigate the inter-relationships among compartmentalized NAD(H)/NADP(H) pools and how these two dinucleotide redox couples collaboratively regulate cellular redox states and cellular metabolism under normal and pathological conditions. Furthermore, recent studies suggest the utility of using pharmacological interventions or nutrient-based bioactive NAD(+) precursors as therapeutic interventions for metabolic diseases. Thus, a better understanding of the cellular functions of NAD(H) and NADP(H) may facilitate efforts to address a host of pathological disorders effectively. Antioxid. Redox Signal. 00, 000-000.

  4. Eosin Yellowish Dye-Sensitized ZnO Nanostructure-Based Solar Cells Employing Solid PEO Redox Couple Electrolyte

    Directory of Open Access Journals (Sweden)

    S. S. Kanmani

    2012-01-01

    Full Text Available ZnO nanostructures are synthesized by low-temperature methods, and they possess polycrystalline hexagonal wurtzite structure with preferential c-axial growth. Morphological study by SEM shows the presence of ~30 nm sized spherical-shaped ZnO nanoparticle, the branched flower-like ZnO composed of many nanorods (length: 1.2 to 4.2 μm and diameter: 0.3 to 0.4 μm, and ~50 nm diameter of individual ZnO nanorods. Reduction in photoemission intensity of nanorods infers the decrease in electron-hole recombination rate, which offers better photovoltaic performance. The dye-sensitized solar cell (DSSC based on ZnO nanorods sensitized with Eosin yellowish dye exhibits a maximum optimal energy conversion efficiency of 0.163% compared to that of nanoparticles and nanoflowers, due to better dye loading and direct conduction pathway for electron transport.

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

    Science.gov (United States)

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

    2018-01-01

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

  6. A carbon-free lithium-ion solid dispersion redox couple with low viscosity for redox flow batteries

    Science.gov (United States)

    Qi, Zhaoxiang; Koenig, Gary M.

    2016-08-01

    A new type of non-aqueous redox couple without carbon additives for flow batteries is proposed and the target anolyte chemistry is demonstrated. The so-called ;Solid Dispersion Redox Couple; incorporates solid electroactive materials dispersed in organic lithium-ion battery electrolyte as its flowing suspension. In this work, a unique and systematic characterization approach has been used to study the flow battery redox couple in half cell demonstrations relative to a lithium electrode. An electrolyte laden with Li4Ti5O12 (LTO) has been characterized in multiple specially designed lithium half cell configurations. The flow battery redox couple described in this report has relatively low viscosity, especially in comparison to other flow batteries with solid active materials. The lack of carbon additive allows characterization of the electrochemical properties of the electroactive material in flow without the complication of conductive additives and unambiguous observation of the electrorheological coupling in these dispersed particle systems.

  7. Non-corrosive, non-absorbing organic redox couple for dye-sensitized solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Li, Dongmei; Li, Hong; Luo, Yanhong; Li, Kexin; Meng, Qingbo; Chen, Liquan [Beijing Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China); Armand, Michel [LRCS, CNRS UMR-6007, Universite de Picardie Jules, Verne Amiens (France)

    2010-10-08

    A new colorless electrolyte containing an organic redox couple, tetramethylthiourea (TMTU) and its oxidized dimer tetramethylformaminium disulfide dication ([TMFDS]{sup 2+}), is applied to dye-sensitized solar cells (DSCs). Advantages of this redox couple include its non-corrosive nature, low cost, and easy handling. More impressively, it operates well with carbon electrodes. The DSCs fabricated with a lab-made HCS-CB carbon counter-electrode can present up to 3.1% power conversion efficiency under AM 1.5 illumination of 100 mW.cm{sup -2} and 4.5% under weaker light intensities. This result distinctly outperforms the identical DSCs with a Pt electrode. Corrosive experiments reveal that Al and stainless steel (SS) sheets are stable in the[TMFDS]{sup 2+}/TMTU-based electrolyte. Its electrochemical impedance spectrum (EIS) is used to evaluate the influence of different counter-electrodes on the cell performance, and preliminary investigations reveal that carbon electrodes with large surface areas and ideal corrosion-inertness toward the sulfur-containing[TMFDS]{sup 2+}/TMTU redox couple exhibit promise for application in iodine-free DSCs. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  8. Electrochemical Polymerization of Iron(III) Polypyridyl Complexes through C-C Coupling of Redox Non-innocent Phenolato Ligands.

    Science.gov (United States)

    Unjaroen, Duenpen; Swart, Marcel; Browne, Wesley R

    2017-01-03

    Phenolato moieties impart redox flexibility to metal complexes due their accessible (oxidative) redox chemistry and have been proposed as functional ligand moieties in redox non-innocent ligand based transition metal catalysis. Here, the electro- and spectroelectrochemistry of phenolato based μ-oxo-diiron(III) complexes [(L 1 )Fe(μ-O)Fe(L 1 )] 2+ (1) and [(L 2 )Fe(μ-O)Fe(L 2 )] 2+ (2), where L 1 = 2-(((di(pyridin-2-yl)methyl)(pyridin-2-ylmethyl)amino)methyl)phenol and L 2 = 3,5-di-tert-butyl-2-(((di(pyridin-2-yl)methyl)(pyridin-2-ylmethyl)amino)methyl)phenol, is described. The electrochemical oxidation of 1 in dichloromethane results in aryl C-C coupling of phenoxyl radical ligand moieties to form tetra nuclear complexes, which undergo subsequent oxidation to form iron(III) phenolato based polymers (poly-1). The coupling is blocked by placing tert-butyl groups at para and ortho positions of phenol units (i.e., 2). Poly-1 shows two fully reversible redox processes in monomer free solution. Assignment of species observed during the electrochemical and chemical {(NH 4 ) 2 [Ce IV (NO 3 ) 6 ]} oxidation of 1 in acetonitrile is made by comparison with the UV-vis-NIR absorption and resonance micro-Raman spectroelectrochemistry of poly-1, and by DFT calculations, which confirms that oxidative coupling occurs in acetonitrile also. However, in contrast to that observed in dichloromethane, in acetonitrile, the oligomers formed are degraded in terms of a loss of the Fe(III)-O-Fe(III) bridge by protonation. The oxidative redox behavior of 1 and 2 is, therefore, dominated by the formation and reactivity of Fe(III) bound phenoxyl radicals, which considerably holds implications in regard to the design of phenolato based complexes for oxidation catalysis.

  9. The chemical biology of the persulfide (RSSH)/perthiyl (RSS·) redox couple and possible role in biological redox signaling.

    Science.gov (United States)

    Bianco, Christopher L; Chavez, Tyler A; Sosa, Victor; Saund, Simran S; Nguyen, Q Nhu N; Tantillo, Dean J; Ichimura, Andrew S; Toscano, John P; Fukuto, Jon M

    2016-12-01

    The recent finding that hydropersulfides (RSSH) are biologically prevalent in mammalian systems has prompted further investigation of their chemical properties in order to provide a basis for understanding their potential functions, if any. Hydropersulfides have been touted as hyper-reactive thiol-like species that possess increased nucleophilicity and reducing capabilities compared to their thiol counterparts. Herein, using persulfide generating model systems, the ability of RSSH species to act as one-electron reductants has been examined. Not unexpectedly, RSSH is relatively easily oxidized, compared to thiols, by weak oxidants to generate the perthiyl radical (RSS·). Somewhat surprisingly, however, RSS· was found to be stable in the presence of both O2 and NO and only appears to dimerize. Thus, the RSSH/RSS· redox couple is readily accessible under biological conditions and since dimerization of RSS· may be a rare event due to low concentrations and/or sequestration within a protein, it is speculated that the general lack of reactivity of individual RSS· species may allow this couple to be utilized as a redox component in biological systems. Copyright © 2016 Elsevier Inc. All rights reserved.

  10. Chronoamperometry-Based Redox Cycling for Application to Immunoassays.

    Science.gov (United States)

    Lee, Ga-Yeon; Park, Jun-Hee; Chang, Young Wook; Cho, Sungbo; Kang, Min-Jung; Pyun, Jae-Chul

    2018-01-26

    In this work, the chronoamperometry-based redox cycling of 3,3',5,5'-tetramethylbenzidine (TMB) was performed by using interdigitated electrode (IDE). The signal was obtained from two sequential chronoamperometric profiles: (1) with the generator at the oxidative potential of TMB and the collector at the reductive potential of TMB, and (2) with the generator at the reductive potential of TMB and the collector at the oxidative potential of TMB. The chronoamperometry-based redox cycling (dual mode) showed a sensitivity of 1.49 μA/OD, and the redox cycling efficiency was estimated to be 94% (n = 10). The sensitivities of conventional redox cycling with the same interdigitated electrode and chronoamperometry using a single working electrode (single mode) were estimated to be 0.67 μA/OD and 0.18 μA/OD, respectively. These results showed that the chronoamperometry-based redox cycling (dual mode) could be more effectively used to quantify the oxidized TMB than other amperometric methods. The chronoamperometry-based redox cycling (dual mode) was applied to immunoassays using a commercial ELISA kit for medical diagnosis of the human hepatitis B virus surface antigen (hHBsAg). Finally, the chronoamperometry-based redox cycling (dual mode) provided more than a 10-fold higher sensitivity than conventional chronoamperometry using a single working electrode (single mode) when applied to a commercial ELISA kit for medical diagnosis of hHBsAg.

  11. 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...

  12. Self-induced redox cycling coupled luminescence on nanopore recessed disk-multiscale bipolar electrodes.

    Science.gov (United States)

    Ma, Chaoxiong; Zaino Iii, Lawrence P; Bohn, Paul W

    2015-05-01

    We present a new configuration for coupling fluorescence microscopy and voltammetry using self-induced redox cycling for ultrasensitive electrochemical measurements. An array of nanopores, each supporting a recessed disk electrode separated by 100 nm in depth from a planar multiscale bipolar top electrode, was fabricated using multilayer deposition, nanosphere lithography, and reactive-ion etching. Self-induced redox cycling was induced on the disk electrode producing ∼30× current amplification, which was independently confirmed by measuring induced electrogenerated chemiluminescence from Ru(bpy)32/3+/tri-n-propylamine on the floating bipolar electrode. In this design, redox cycling occurs between the recessed disk and the top planar portion of a macroscopic thin film bipolar electrode in each nanopore. Electron transfer also occurs on a remote (mm-distance) portion of the planar bipolar electrode to maintain electroneutrality. This couples the electrochemical reactions of the target redox pair in the nanopore array with a reporter, such as a potential-switchable fluorescent indicator, in the cell at the distal end of the bipolar electrode. Oxidation or reduction of reversible analytes on the disk electrodes were accompanied by reduction or oxidation, respectively, on the nanopore portion of the bipolar electrode and then monitored by the accompanying oxidation of dihydroresorufin or reduction of resorufin at the remote end of the bipolar electrode, respectively. In both cases, changes in fluorescence intensity were triggered by the reaction of the target couple on the disk electrode, while recovery was largely governed by diffusion of the fluorescent indicator. Reduction of 1 nM of Ru(NH3)63+ on the nanoelectrode array was detected by monitoring the fluorescence intensity of resorufin, demonstrating high sensitivity fluorescence-mediated electrochemical sensing coupled to self-induced redox cycling.

  13. High-performance rechargeable lithium-iodine batteries using triiodide/iodide redox couples in an aqueous cathode.

    Science.gov (United States)

    Zhao, Yu; Wang, Lina; Byon, Hye Ryung

    2013-01-01

    Development of promising battery systems is being intensified to fulfil the needs of long-driving-ranged electric vehicles. The successful candidates for new generation batteries should have higher energy densities than those of currently used batteries and reasonable rechargeability. Here we report that aqueous lithium-iodine batteries based on the triiodide/iodide redox reaction show a high battery performance. By using iodine transformed to triiodide in an aqueous iodide, an aqueous cathode involving the triiodide/iodide redox reaction in a stable potential window avoiding water electrolysis is demonstrated for lithium-iodine batteries. The high solubility of triiodide/iodide redox couples results in an energy density of ~ 0.33 kWh kg(-1), approximately twice that of lithium-ion batteries. The reversible redox reaction without the formation of resistive solid products promotes rechargeability, demonstrating 100 cycles with negligible capacity fading. A low cost, non-flammable and heavy-metal-free aqueous cathode can contribute to the feasibility of scale-up of lithium-iodine batteries for practical energy storage.

  14. Electrochemical Polymerization of Iron(III) Polypyridyl Complexes through C-C Coupling of Redox Non-innocent Phenolato Ligands

    NARCIS (Netherlands)

    Unjaroen, Duenpen; Swart, Marcel; Browne, Wesley R

    2017-01-01

    Phenolato moieties impart redox flexibility to metal complexes due their accessible (oxidative) redox chemistry and have been proposed as functional ligand moieties in redox non-innocent ligand based transition metal catalysis. Here, the electro-and spectroelectrochemistry of phenolato based

  15. Redox equilibria of iron oxides in aqueous-based magnetite dispersions: effect of pH and redox potential.

    Science.gov (United States)

    Pang, Suh Cem; Chin, Suk Fun; Anderson, Marc A

    2007-07-01

    The effect of pH and redox potential on the redox equilibria of iron oxides in aqueous-based magnetite dispersions was investigated. The ionic activities of each dissolved iron species in equilibrium with magnetite nanoparticles were determined and contoured within the Eh-pH framework of a composite stability diagram. Both standard redox potentials and equilibrium constants for all major iron oxide redox equilibria in magnetite dispersions were found to differ from values reported for noncolloidal systems. The "triple point" position of redox equilibrium among Fe(II) ions, magnetite, and hematite shifted to a higher standard redox potential and an equilibrium constant which was several orders of magnitude higher. The predominant area of magnetite stability was enlarged to cover a wider range of both pH and redox potentials as compared to that of a noncolloidal magnetite system.

  16. Green fluorescent protein-based monitoring of endoplasmic reticulum redox poise.

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    Birk, Julia; Ramming, Thomas; Odermatt, Alex; Appenzeller-Herzog, Christian

    2013-01-01

    Pathological endoplasmic reticulum (ER) stress is tightly linked to the accumulation of reactive oxidants, which can be both upstream and downstream of ER stress. Accordingly, detrimental intracellular stress signals are amplified through establishment of a vicious cycle. An increasing number of human diseases are characterized by tissue atrophy in response to ER stress and oxidative injury. Experimental monitoring of stress-induced, time-resolved changes in ER reduction-oxidation (redox) states is therefore important. Organelle-specific examination of redox changes has been facilitated by the advent of genetically encoded, fluorescent probes, which can be targeted to different subcellular locations by means of specific amino acid extensions. These probes include redox-sensitive green fluorescent proteins (roGFPs) and the yellow fluorescent protein-based redox biosensor HyPer. In the case of roGFPs, variants with known specificity toward defined redox couples are now available. Here, we review the experimental framework to measure ER redox changes using ER-targeted fluorescent biosensors. Advantages and drawbacks of plate-reader and microscopy-based measurements are discussed, and the power of these techniques demonstrated in the context of selected cell culture models for ER stress.

  17. Green fluorescent protein-based monitoring of endoplasmic reticulum redox poise

    Directory of Open Access Journals (Sweden)

    Julia eBirk

    2013-06-01

    Full Text Available Pathological endoplasmic reticulum (ER stress is tightly linked to the accumulation of reactive oxidants, which can be both upstream and downstream of ER stress. Accordingly, detrimental intracellular stress signals are amplified through establishment of a vicious cycle. An increasing number of human diseases are characterized by tissue atrophy in response to ER stress and oxidative injury. Experimental monitoring of stress-induced, time-resolved changes in ER reduction-oxidation (redox states is therefore important. Organelle-specific examination of redox changes has been facilitated by the advent of genetically encoded, fluorescent probes, which can be targeted to different subcellular locations by means of specific amino acid extensions. These probes include redox-sensitive green fluorescent proteins (roGFPs and the yellow fluorescent protein-based redox biosensor HyPer. In the case of roGFPs, variants with known specificity towards defined redox couples are now available. Here, we review the experimental framework to measure ER redox changes using ER-targeted fluorescent biosensors. Advantages and drawbacks of plate-reader- and microscopy-based measurements are discussed, and the power of these techniques demonstrated in the context of selected cell culture models for ER stress.

  18. Aptamer-based Nanosensors: Juglone as an Attached-Redox Molecule for Detection of Codeine

    Directory of Open Access Journals (Sweden)

    Ayuob Aghanejad

    2011-06-01

    Full Text Available Introduction: Among several biosensing approaches, electrochemical-based procedures have been described as one of the most common and useful methods for sensing because of their simplicity, sensitivity, accuracy, and low cost. The electroactive species, which called redox, play a main role in the electrochemical-based approaches. Of several redox molecules used for electrochemical experiments, ferrocene is one of the commonly used redox molecules. However, instability of ferrocenium ion in the chloride containing solutions appeared to be weakness of this redox molecule limiting its utilization. Methods: In the current study, Juglone was attached (using EDC/NHS coupling method to the 3'-amino-modified terminus of the immobilized specific aptamer of codeine, which was successfully used in a cyclic electrochemical voltammetry procedure. Results: The cyclic voltammogram peak of aptamer-attached Juglone was observed in the potential range of +0.4 to +0.9 V and the fabricated aptamer-based sensor was used for detection of different concentrations of codeine in the phosphate buffer 0.1 M solution containing 2 M NaCl. Conclusion: Based on these findings, it can be suggested that the new aptamer-attached Juglone could be considered as an effective alternative redox molecule in particular with oligonucleotide-based sensing systems.

  19. Ferrocyanide-Ferricyanide Redox Couple Induced Electrochemiluminescence Amplification of Carbon Dots for Ultrasensitive Sensing of Glutathione.

    Science.gov (United States)

    Niu, Wen-Jun; Zhu, Rong-Hui; Cosnier, Serge; Zhang, Xue-Ji; Shan, Dan

    2015-11-03

    Here we report a novel solid-state ECL sensor for ultrasensitive sensing of glutathione (GSH) based on ferrocyanide-ferricyanide redox couple (Fe(CN)6(3-/4-)) induced electrochemiluminescence (ECL) amplification of carbon dots (C-dots). The electropolymerization of C-dots and (11-pyrrolyl-1-yl-undecyl) triethylammonium tetrafluoroborate (A2) enabled immobilization of the hydrophilic C-dots on the surface of glassy carbon electrode (GCE) perfectly, while the excellent conductivity of polypyrrole was exploited to accelerate electron transfer between them. The Fe(CN)6(3-/4-) can expeditiously convert the C-dots and S2O8(2-) to C-dot(•-) and SO4(•-), respectively. High yields of the excited state C-dots (C-dots*) were obtained, and a ∼10-fold ECL amplification was realized. The C-dots* obtained through the recombination of electron-injected and hole-injected processes may be impeded due to the interference of GSH to K2S2O8. Therefore, the constructed sensor for GSH showed a detection limit down to 54.3 nM (S/N = 3) and a wide linear range from 0.1-1.0 μM with a correlation coefficient of 0.997.

  20. Differential alkylation-based redox proteomics - Lessons learnt

    DEFF Research Database (Denmark)

    Wojdyla, Katarzyna; Rogowska-Wrzesinska, Adelina

    2015-01-01

    -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......, including the amount of starting material required for analysis. The results of this meta-analysis are the core of this review, complemented by issues related to biological models and sample preparation in redox proteomics, including conditions for free thiol blocking and labelling of target cysteine...

  1. A biomimetic redox flow battery based on flavin mononucleotide

    Science.gov (United States)

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

    2016-10-01

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

  2. Electrochemical aptasensor of cellular prion protein based on modified polypyrrole with redox dendrimers.

    Science.gov (United States)

    Miodek, A; Castillo, G; Hianik, T; Korri-Youssoufi, H

    2014-06-15

    This work consists of the development of an electrochemical aptasensor based on polyprrole modified with redox dendrimers, able to detect human cellular prions PrP(C) with high sensitivity. The gold surface was modified by conductive polypyrrole film coupled to polyamidoamine dendrimers of fourth generation (PAMAM G4) and ferrocenyl group as redox marker. The aptamers were immobilized on the surface via biotin/streptavidin chemistry. Electrochemical signal was detected by ferrocenyl group incorporated between dendrimers and aptamers layers. We demonstrated that the interaction between aptamer and prion protein led to variation in electrochemical signal of the ferrocenyl group. The kinetics parameters (diffusion coefficient D and heterogeneous constant transfer ket) calculated from electrochemical signals demonstrate that the variation in redox signal results from the lower diffusion process of ions during redox reaction after prion interaction due to bulk effect of larger protein. The association of redox dendrimers with conducting polypyrrole leads to high sensitivity of PrP(C) determination with detection limit of 0.8 pM, which is three orders of magnitude lower, compared to flat ferrocene-functionalized polypyrrole. Detection of PrP(C) in spiked blood plasma has been achieved and demonstrated a recovery up to 90%. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. 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.

  4. Structure-redox-relaxivity relationships for redox responsive manganese-based magnetic resonance imaging probes.

    Science.gov (United States)

    Gale, Eric M; Mukherjee, Shreya; Liu, Cynthia; Loving, Galen S; Caravan, Peter

    2014-10-06

    A library of 10 Mn-containing complexes capable of switching reversibly between the Mn(II) and Mn(III) oxidation states was prepared and evaluated for potential usage as MRI reporters of tissue redox activity. We synthesized N-(2-hydroxybenzyl)-N,N',N'-ethylenediaminetriacetic acid (HBET) and N-(2-hydroxybenzyl-N,N',N'-trans-1,2-cyclohexylenediaminetriacetic acid (CyHBET) ligands functionalized (-H, -OMe, -NO2) at the 5-position of the aromatic ring. The Mn(II) complexes of all ligands and the Mn(III) complexes of the 5-H and 5-NO2 functionalized ligands were synthesized and isolated, but the Mn(III) complexes with the 5-OMe functionalized ligands were unstable. (1)H relaxivity of the 10 isolable complexes was measured at pH 7.4 and 37 °C, 1.4 T. Thermodynamic stability, pH-dependent complex speciation, hydration state, water exchange kinetics of the Mn(II) complexes, and pseudo-first order reduction kinetics of the Mn(III) complexes were studied using a combination of pH-potentiometry, UV-vis spectroscopy, and (1)H and (17)O NMR measurements. The effects of ligand structural and electronic modifications on the Mn(II/III) redox couple were studied by cyclic voltammetry. The Mn(II) complexes are potent relaxation agents as compared to the corresponding Mn(III) species with [Mn(II)(CyHBET)(H2O)](2-) exhibiting a 7.5-fold higher relaxivity (3.3 mM(-1) s(-1)) than the oxidized form (0.4 mM(-1) s(-1)). At pH 7.4, Mn(II) exists as a mixture of fully deprotonated (ML) and monoprotonated (HML) complexes and Mn(II) complex stability decreases as the ligands become more electron-releasing (pMn for 10 μM [Mn(II)(CyHBET-R')(H2O)](2-) decreases from 7.6 to 6.2 as R' goes from -NO2 to -OMe, respectively). HML speciation increases as the electron-releasing nature of the phenolato-O donor increases. The presence of a water coligand is maintained upon conversion from HML to ML, but the water exchange rate of ML is faster by up to 2 orders of magnitude (k(ex)(310) for H

  5. Entropic and Enthalpic Contributions to the Solvent Dependence of the Thermodynamics of Transition-Metal Redox Couples II. Couples Containing Ammine and Ethylenediamine Ligands.

    Science.gov (United States)

    1981-01-08

    cy --T -, 0 (-I &j 1 1 EN cn - Notes to Table I1 A = Free energy of t ransfer of redox coupl1 ,’.(At;0 )s-w (kca l. mol1-i) from water to rc...Transition-Metal Amine Complexes, Ion Transfer Energies , Reaction Entropivs, 1 Dimethylsulfoxide, N-N-dimethylformamide, N-methylformamide, Formami1...Des f wat -S 3 transfer free energy ()i each redox couple from water to the nonaqueous solvents A(AG s ,ere made from the solvent dependence of E at

  6. Combination of redox capacity and double layer capacitance in composite electrodes through immobilization of an organic redox couple on carbon black

    Energy Technology Data Exchange (ETDEWEB)

    Leitner, K.W.; Gollas, B.; Winter, M.; Besenhard, J.O. [Graz University of Technology (Austria). Institute for Chemical Technology of Inorganic Materials

    2004-11-15

    Carbon electrodes have been modified with 2-nitro-1-naphthol with the aim of producing composite supercapacitor electrodes, which make use of both the electric double layer (EDL) capacitance of high surface area carbon and the redox capacity (pseudocapacitance) of the organic compound. In situ FTIR and cyclic voltammetric data confirm literature reports of the reduction of 2-nitro-1-naphthol to 2-amino-1-naphthol and the subsequent oxidation of the o-aminonaphthol to the corresponding o-naphthaquinoneimine in aqueous acidic media. The measurements also show that the quinoneimine is not stable and hydrolized in sulphuric acid electrolyte to 1,2-naphthaquinone. The chemically highly reversible o-naphthaquinone/o-naphthahydroquinone couple remains immobilized on the carbon electrodes during redox cycling. The organic redox couple contributes a capacity of 35 mA h g{sup -1} of the bare carbon to the overall charge storage capability of the composite electrode. Surprisingly, it does not affect the capacitance of the electric double layer of the carbon. During 1000 charge/discharge cycles, the pseudocapacitance decreases by less than 20% in a normal large-volume electrochemical cell. Electrochemical impedance measurements show that the full capacity of the electrode is accessible at frequencies below 0.1 Hz. (author)

  7. Redox flow batteries based on supporting solutions containing chloride

    Energy Technology Data Exchange (ETDEWEB)

    Li, Liyu; Kim, Soowhan; Yang, Zhenguo; Wang, Wei; Nie, Zimin; Chen, Baowei; Zhang, Jianlu; Xia, Guanguang

    2017-11-14

    Redox flow battery systems having a supporting solution that contains Cl.sup.- ions can exhibit improved performance and characteristics. Furthermore, a supporting solution having mixed SO.sub.4.sup.2- and Cl.sup.- ions can provide increased energy density and improved stability and solubility of one or more of the ionic species in the catholyte and/or anolyte. According to one example, a vanadium-based redox flow battery system is characterized by an anolyte having V.sup.2+ and V.sup.3+ in a supporting solution and a catholyte having V.sup.4+ and V.sup.5+ in a supporting solution. The supporting solution can contain Cl.sup.- ions or a mixture of SO.sub.4.sup.2- and Cl.sup.- ions.

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

    Science.gov (United States)

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

    2009-01-01

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

  9. Are free radicals involved in thiol-based redox signaling?

    Science.gov (United States)

    Winterbourn, Christine C

    2015-03-01

    Cells respond to many stimuli by transmitting signals through redox-regulated pathways. It is generally accepted that in many instances signal transduction is via reversible oxidation of thiol proteins, although there is uncertainty about the specific redox transformations involved. The prevailing view is that thiol oxidation occurs by a two electron mechanism, most commonly involving hydrogen peroxide. Free radicals, on the other hand, are considered as damaging species and not generally regarded as important in cell signaling. This paper examines whether it is justified to dismiss radicals or whether they could have a signaling role. Although there is no direct evidence that radicals are involved in transmitting thiol-based redox signals, evidence is presented that they are generated in cells when these signaling pathways are activated. Radicals produce the same thiol oxidation products as two electron oxidants, although by a different mechanism, and at this point radical-mediated pathways should not be dismissed. There are unresolved issues about how radical mechanisms could achieve sufficient selectivity, but this could be possible through colocalization of radical-generating and signal-transducing proteins. Colocalization is also likely to be important for nonradical signaling mechanisms and identification of such associations should be a priority for advancing the field. Copyright © 2014 Elsevier Inc. All rights reserved.

  10. Optical and electronic coupling of the redox copper Azurin on ITO-coated quartz substrate.

    Science.gov (United States)

    Bizzarri, A R; Andolfi, L; Taranta, M; Cannistraro, S

    2008-10-15

    We have investigated the hybrid system constituted by the redox copper protein Azurin integrated with the semiconductor indium tin oxide (ITO) coated on quartz substrate. The system appears to be a good candidate for bio-sensing and bio-optoelectronics applications, especially due to the coupling between the optical and electron transfer features of Azurin with the conductive properties and optical transparency of ITO. The optical, morphological and electrical properties of the system have been investigated by combining optical absorption and transmission, steady-state fluorescence, resonance Raman spectroscopy and scanning probe microscopies. We found that Azurin molecules are firmly anchored on ITO and retain their structural and optical features underlying the physiological electron transfer activity. Scanning tunnelling spectroscopy evidenced a good electric coupling between the protein molecules and the substrate and a concomitant modulation of the ITO semiconductor properties upon deposition of Azurin. Some interplay between the conduction and valence bands of ITO and the electronic levels of Azurin is therefore suggested. These results are of a significant relevance in the perspective of developing bio-nanodevices able to process both optical and electrical signals, in conjugation also with the biorecognition capability of the protein molecules.

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

    DEFF Research Database (Denmark)

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

    , that there is a connection between extracellular and intracellular redox [2], whereas others oppose this view [3]. In general however, these experiments lack insight into the dynamics, complex network of reactions and transportation through cell membrane of redox. Therefore, current experimental results reveal......Research suggests that cellular redox environment could affect the phenotype and function of cells through a complex reaction network[1]. In cells, redox status is mainly regulated by several redox couples, such as Glutathione/glutathione disulfide (GSH/GSSG), Cysteine/ Cystine (CYS...... but a snapshot, or average of true dynamics. What is more, it can be more complex if the dynamics of redox in different intracellular compartments is included [4]. Furthermore, heterogeneous spatial and temporal distribution of reactants and enzymes, diffusion rate and import direction of chemical source [5...

  12. 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.

  13. Amperometric biosensors for glucose, lactate, and glycolate based on oxidases and redox-modified siloxane polymers

    Energy Technology Data Exchange (ETDEWEB)

    Hale, P.D.; Inagaki, Toru; Lee, Hung Sui; Skotheim, T.A.; Karan, Hiroko I.; Okamoto, Yoshi (Brookhaven National Lab., Upton, NY (USA); Medgar Evers Coll., Brooklyn, NY (USA). Div. of Natural Science and Mathematics; Polytechnic Univ., Brooklyn, NY (USA). Dept. of Chemistry)

    1989-01-01

    Amperometric biosensors based on flavin-containing oxidases undergo several steps which produce a measurable current that is related to the concentration of substrate. In the initial step, the substrate converts the oxidized flavin adenine dinucleotide (FAD) or flavin mononucleotide (FMN) into the reduced form (FADH{sub 2} or FMNH{sub 2}). Because these cofactors are located well within the enzyme molecule, direct electron transfer to the surface of a conventional electrode does not occur to a measurable degree. A common method of facilitating this electron transfer is to introduce oxygen into the system because it is the natural acceptor for the oxidases; the oxygen is reduced by the FADH{sub 2} or FMNH{sub 2} to hydrogen peroxide, which can then be detected electrochemically. The major drawback to this approach is the fact that oxidation of hydrogen peroxide requires a large overpotential, thus making these sensors susceptible to interference from electroactive species. To lower the necessary applied potential, several non-physiological redox couples have been employed to shuttle electrons between the flavin moieties and the electrode. For example, sensors based on the ferrocene/ferricinium redox couple and on electrodes consisting of conducting salts such as TTF-TCNQ (tetrathiafulvalene-tetracyanoquinodimethane) have previously been reported. Electron relays have also been attached directly to the enzyme molecule to facilitate electron transfer. More recently, these studies have been extended to include systems where the mediating redox species are covalently attached to polymers such as poly(pyrrole), poly(vinylpyridine), and poly(siloxane). The present paper describes the development of amperometric biosensors based on flavin-containing enzymes and this latter family of polymeric mediators. 9 refs., 5 figs.

  14. Self-powered denitration of landfill leachate through ammonia/nitrate coupled redox fuel cell reactor.

    Science.gov (United States)

    Zhang, Huimin; Xu, Wei; Feng, Daolun; Liu, Zhanmeng; Wu, Zucheng

    2016-03-01

    In order to explore the feasibility of energy-free denitrifying N-rich wastewater, a self-powered device was uniquely assembled, in which ammonia/nitrate coupled redox fuel cell (CRFC) reactor was served as removing nitrogen and harvesting electric energy simultaneously. Ammonia is oxidized at anodic compartment and nitrate is reduced at cathodic compartment spontaneously by electrocatalysis. In 7.14 mM ammonia+0.2M KOH anolyte and 4.29 mM KNO3+0.1M H2SO4 catholyte, the nitrate removal efficiency was 46.9% after 18 h. Meanwhile, a maximum power density of 170 mW m(-2) was achieved when applying Pd/C cathode. When NH4Cl/nitrate and ammonia/nitrite CRFCs were tested, 26.2% N-NH4Cl and 91.4% N-NO2(-) were removed respectively. Nitrogen removal efficiency for real leachate at the same initial NH3-N concentration is 22.9% and nitrification of ammonia in leachate can be used as nitrate source. This work demonstrated a new way for N-rich wastewater remediation with electricity generation. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. Design, Mechanism of Action, Bioavailability and Therapeutic Effects of Mn Porphyrin-based Redox Modulators

    Science.gov (United States)

    Tovmasyan, Artak; Sheng, Huaxin; Weitner, Tin; Arulpragasam, Amanda; Lu, Miaomiao; Warner, David S.; Vujaskovic, Zeljko; Spasojevic, Ivan; Batinic-Haberle, Ines

    2013-01-01

    Based on aqueous redox chemistry and simple in vivo models of oxidative stress, Escherichia coli and Streptomyces cerevisiae, the cationic Mn(III) N-substituted pyridylporphyrins (MnPs) have been identified as the most potent cellular redox modulators within the porphyrin class of drugs; their efficacy in animal models of diseases that have oxidative stress in common, is based on their high ability to catalytically remove superoxide (O2•−), peroxynitrite, carbonate anion radical (CO3•−), hypochlorous acid (HClO), nitric oxide (NO), lipid peroxyl and alkoxyl radicals, thus suppressing the primary oxidative event. While doing so MnPs could couple with cellular reductants and redox-active proteins. Reactive species are widely accepted as regulators of cellular transcriptional activity: minute, nanomolar levels are essential for normal cell function, while submicromolar or micromolar levels impose oxidative stress, which is evidenced in increased inflammatory and immune responses. By removing reactive species, MnPs affect redox-based cellular transcriptional activity and consequently secondary oxidative stress, and in turn inflammatory processes. The equal ability to reduce and oxidize superoxide during the dismutation process and recently accumulated results suggest that pro-oxidative actions of MnPs may also contribute to their therapeutic effects. All our data identify the superoxide dismutase (SOD)-like activity (estimated by log kca(O2•−) as a good measure for the therapeutic efficacy of MnPs. Their accumulation in mitochondria and their ability to cross the blood brain barrier contribute to their remarkable efficacy. We summarize herein the therapeutic effects of MnPs in cancer, central nervous system injuries, diabetes, their radioprotective action and potential for imaging. Few of the most potent modulators of cellular redox-based pathways, MnTE-2-PyP5+, MnTDE-2-ImP5+, MnTnHex-2-PyP5+ and MnTnBuOE-2-PyP5+ are under preclinical and clinical

  16. Redox Proteomics

    OpenAIRE

    Butterfield, D. Allan; Dalle-Donne, Isabella

    2012-01-01

    Proteins are major targets of reactive oxygen and nitrogen species (ROS/RNS) and numerous post-translational, reversible or irreversible modifications have been characterized, which may lead to a change in the structure and/or function of the oxidized protein. Redox proteomics is an increasingly emerging branch of proteomics aimed at identifying and quantifying redox-based changes within the proteome both in redox signaling and under oxidative stress conditions. Correlation between protein ox...

  17. Redox-active polypyrrole: toward polymer-based batteries

    Energy Technology Data Exchange (ETDEWEB)

    Song, H.K. [Division of Engineering, Brown University, Providence, RI 02912 (United States); Palmore, G.T.R. [Division of Engineering, Brown University, Providence, RI 02912 (United States); Department of Molecular Pharmacology, Physiology, and Biotechnology, Brown University, Providence, RI 02912 (United States)

    2006-07-04

    An energy-storage device consisting of polypyrrole (pPy) doped with indigo carmine (IC) and 2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonate) (ABTS) has been fabricated. These redox-active conducting polymers form the basis of a battery that depends on the faradaic reactions of the redox-active dopants, and performs better than conventional batteries and ultracapacitors at high power density. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

  18. Redox active materials for metal compound based hybrid electrochemical energy storage: a perspective view

    Science.gov (United States)

    Nguyen, Tuyen; Montemor, M. Fátima

    2017-11-01

    Metal compound based hybrid electrochemical energy storage (HEES) is currently emerging as a highly promising solution to provide enhanced storage capacity and high power performance. Properties of metal compound based redox active electrodes, including chemical composition, morphology, crystal structure and conductivity govern the performance of storage devices. In this perspective, we highlight the recent advances on HEES and discuss possible strategies to explore further the electrochemical response and to improve the storage performance. Redox active binders and redox active electrolytes, operating together with metal compound based electrodes, to provide additional charge storage will also be discussed.

  19. Testing and improving the redox stability of Ni-based solid oxide fuel cells

    DEFF Research Database (Denmark)

    Pihlatie, Mikko; Ramos, Tania; Kaiser, Andreas

    2009-01-01

    Despite active development, solid oxide fuel cells (SOFCs) based on Ni-YSZ anodes still suffer from thermomechanical instability under conditions where the anode side is exposed to oxidising conditions at high temperature. In the first part of the paper, structures and solutions, which could...... improve the redox stability of Ni-YSZ anode supported SOFC's in terms of dimensional and mechanical stability are reported. Porosity is identified as a major microstructural parameter linked to the dimensional and structural stability during redox cycling. The cumulative redox strain (CRS) after three...... isothermal redox cycles at 850 °C increases by a factor of more than 20 when the as-sintered porosity of the composites is reduced from 34 to 9%. The effect of reduction and redox cycling on the Ni-YSZ anode are discussed in light of electrochemical measurements using impedance spectroscopy on symmetric...

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

    Directory of Open Access Journals (Sweden)

    Malav Suchin Trivedi

    2015-01-01

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

  1. Towards the Application of Structure-Property Relationship Modeling in Materials Science: Predicting the Seebeck Coefficient for Ionic Liquid/Redox Couple Systems.

    Science.gov (United States)

    Sosnowska, Anita; Barycki, Maciej; Gajewicz, Agnieszka; Bobrowski, Maciej; Freza, Sylwia; Skurski, Piotr; Uhl, Stefanie; Laux, Edith; Journot, Tony; Jeandupeux, Laure; Keppner, Herbert; Puzyn, Tomasz

    2016-06-03

    This work focuses on determining the influence of both ionic-liquid (IL) type and redox couple concentration on Seebeck coefficient values of such a system. The quantitative structure-property relationship (QSPR) and read-across techniques are proposed as methods to identify structural features of ILs (mixed with LiI/I2 redox couple), which have the most influence on the Seebeck coefficient (Se ) values of the system. ILs consisting of small, symmetric cations and anions with high values of vertical electron binding energy are recognized as those with the highest values of Se . In addition, the QSPR model enables the values of Se to be predicted for each IL that belongs to the applicability domain of the model. The influence of the redox-couple concentration on values of Se is also quantitatively described. Thus, it is possible to calculate how the value of Se will change with changing redox-couple concentration. The presence of the LiI/I2 redox couple in lower concentrations increases the values of Se , as expected. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Redox cycling-based immunoassay for detection of carcinogenic embryonic antigen.

    Science.gov (United States)

    Lee, Ga-Yeon; Park, Jun-Hee; Chang, Young Wook; Cho, Sungbo; Kang, Min-Jung; Pyun, Jae-Chul

    2017-06-08

    Redox cycling based on an interdigitated electrode (IDE) was used as a highly sensitive immunoassay for carcinogenic embryonic antigen (CEA) through the quantification of 3,3',5,5'-tetramethylbenzidine (TMB). For the redox cycling process, one pair of interdigitated finger electrodes was used as the first working electrode (generator) for cyclic voltammetry of TMB, and another pair of interdigitated finger electrodes was used as the second working electrode (collector) for sequential application of potentials for reduction and oxidation of TMB. The reduction (and oxidation) products of TMB at the collector were supplied to the generator, and following sequential oxidization (and reduction) at the generator, again supplied to the collector. Such redox recycling processes between the generator and collector allowed signal amplification. In this work, the influences of the following factors on the redox cycling of TMB were analyzed: (1) the redox potential at the collector, (2) the gap between the interdigitated finger electrodes, and (3) the scan rate of the generator. The redox potential and electrode gap influences were simulated with COMSOL software and compared with empirical results. At the optimum redox potentials and electrode gap, redox cycling was estimated to be five-fold more sensitive for the quantification of TMB than conventional cyclic voltammetry using one pair of interdigitated finger electrodes as the working electrode. Finally, redox cycling was applied to a commercial immunoassay for CEA, and the sensitivity of redox cycling was three-fold higher than that of conventional cyclic voltammetry using a single set of interdigitated finger electrodes as the working electrode. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Electrochemical biosensor based on immobilized enzymes and redox polymers

    Science.gov (United States)

    Skotheim, Terje A.; Okamoto, Yoshiyuki; Hale, Paul D.

    1992-01-01

    The present invention relates to an electrochemical enzyme biosensor for use in liquid mixtures of components for detecting the presence of, or measuring the amount of, one or more select components. The enzyme electrode of the present invention is comprised of an enzyme, an artificial redox compound covalently bound to a flexible polymer backbone and an electron collector.

  4. 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.

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

    Science.gov (United States)

    Trivedi, Malav S; Deth, Richard

    2014-01-01

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

  6. 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

  7. Redox characterization of semiconductors based on electrochemical measurements combined with UV-Vis diffuse reflectance spectroscopy.

    Science.gov (United States)

    Świętek, Elżbieta; Pilarczyk, Kacper; Derdzińska, Justyna; Szaciłowski, Konrad; Macyk, Wojciech

    2013-09-14

    Several techniques can be applied to characterize redox properties of wide bandgap semiconductors, however some of them are of limited use. In this paper we propose a new modification of the old spectroelectrochemical method developed two decades ago. A procedure based on measurements of the reflectance changes as a function of potential applied to the electrode coated with the studied material appears to be a very convenient tool for characterizing redox properties of semiconductors, forming either transparent or opaque films at a platinum electrode. A discussion on the measured redox parameters of semiconductor films concludes with a definition of a new term, the absorption onset potential of the material.

  8. Enzyme Biosensor Based on an Electropolymerized Osmium Redox Polymer

    Science.gov (United States)

    Tsujimoto, Masaki; Maruyama, Kenichi; Mishima, Yuji; Motonaka, Junko

    Electrochemical polymerizations of metal complex as electron mediator in aqueous solution have been developed. The metal complexes as electron mediator of biosensor for practical application have a rapid electron transfer rate, a chemical stability, and an accessible manipulation. The electro-polymerized redox polymer relatively decreased the enzyme and catalytic activity, although these could be treated in organic solvent. In this work, the water-soluble osmium complex-modified pyrrole derivatives with long, flexible spacer chain were synthesized. The electro-polymerized redox polymer was generally produced by potential sweep copolymerization (-400 mV -/+1200 mV (vs. Ag|AgCl(sat.KCl))) of water-soluble osmium complex-modified pyrrole monomer and glucose oxidase (GOD) on the top of a Pt electrode in aqueous solution. With the electro-polymerized osmium redox polymer modified electrode, calibration graphs for measurements of glucose and the effect of concomitant compounds, dissolved oxygen and the lifetimes of the sensor were electrochemistry examined, respectively. Under optimal conditions, the response of the sensors was in the concentration ranges of 0.6 mM-100 mM for glucose.

  9. Cysteine-based redox regulation and signalling in plants

    Directory of Open Access Journals (Sweden)

    Jérémy eCouturier

    2013-04-01

    Full Text Available Living organisms are subjected to oxidative stress conditions which are characterized by the production of reactive oxygen (ROS, nitrogen (RNS and sulfur (RSS species. In plants as in other organisms, many of these compounds have a dual function as they damage different types of macromolecules but they also likely fulfil an important role as secondary messengers. Owing to the reactivity of their thiol groups, some protein cysteine residues are particularly prone to oxidation by these molecules. In the past years, besides their recognized catalytic and regulatory functions, the modification of cysteine thiol group was increasingly viewed as either protective or redox signalling mechanisms. The most physiologically relevant reversible redox post-translational modifications (PTMs are disulfide bonds, sulfenic acids, S-glutathionylated adducts, S-nitrosothiols and to a lesser extent S-sulfenylamides, thiosulfinates and S-persulfides. These redox PTMs are mostly controlled by two oxidoreductase families, thioredoxins and glutaredoxins. This review focuses on recent advances highlighting the variety and physiological roles of these PTMs and the proteomic strategies used for their detection.

  10. Genetically encoded fluorescent redox sensors.

    Science.gov (United States)

    Lukyanov, Konstantin A; Belousov, Vsevolod V

    2014-02-01

    Life is a constant flow of electrons via redox couples. Redox reactions determine many if not all major cellular functions. Until recently, redox processes remained hidden from direct observation in living systems due to the lack of adequate methodology. Over the last years, imaging tools including small molecule probes and genetically encoded sensors appeared, which provided, for the first time, an opportunity to visualize and, in some cases, quantify redox reactions in live cells. Genetically encoded fluorescent redox probes, such as HyPer, rxYFP and roGFPs, have been used in several models, ranging from cultured cells to transgenic animals, and now enough information has been collected to highlight advantages and pitfalls of these probes. In this review, we describe the main types of genetically encoded redox probes, their essential properties, advantages and disadvantages. We also provide an overview of the most important, in our opinion, results obtained using these probes. Finally, we discuss redox-dependent photoconversions of GFP and other prospective directions in redox probe development. Fluorescent protein-based redox probes have important advantages such as high specificity, possibility of transgenesis and fine subcellular targeting. For proper selection of a redox sensor for a particular model, it is important to understand that HyPer and roGFP2-Orp1 are the probes for H2O2, whereas roGFP1/2, rxYFP and roGFP2-Grx1 are the probes for GSH/GSSG redox state. Possible pH changes should be carefully controlled in experiments with HyPer and rxYFP. Genetically encoded redox probes are the only instruments allowing real-time monitoring of reactive oxygen species and thiol redox state in living cells and tissues. We believe that in the near future the palette of FP-based redox probes will be expanded to red and far-red parts of the spectrum and to other important reactive species such as NO, O2 and superoxide. This article is part of a Special Issue entitled

  11. Electrokinetics of the amphifunctional metal/electrolyte solution interface in the presence of a redox couple

    NARCIS (Netherlands)

    Duval, J.F.L.

    2004-01-01

    Double layers (DL) at amphifunctionally electrified interfaces, such as that of an oxidized metal in an aqueous electrolyte solution, arise from coupling between ionic and electronic surface-charging processes. The electronic component enters the double-layer formation in the well-known situation

  12. A Step-by-Step Design Methodology for a Base Case Vanadium Redox-Flow Battery

    Science.gov (United States)

    Moore, Mark; Counce, Robert M.; Watson, Jack S.; Zawodzinski, Thomas A.; Kamath, Haresh

    2012-01-01

    The purpose of this work is to develop an evolutionary procedure to be used by Chemical Engineering students for the base-case design of a Vanadium Redox-Flow Battery. The design methodology is based on the work of Douglas (1985) and provides a profitability analysis at each decision level so that more profitable alternatives and directions can be…

  13. Oxidation of butane to butanol coupled to electrochemical redox reaction of NAD+/NADH.

    Science.gov (United States)

    Kang, Hye Sun; Na, Byung Kwan; Park, Doo Hyun

    2007-08-01

    A crude cell extract from a butane-utilizing bacterium, Alcaligenes sp., catalyzed the oxidation of butane to butanol coupled to NADH. A graphite electrode modified with Neutral Red (NR-electrode) catalyzed the reduction of NAD(+) to NADH. About 4.9 mM butanol was produced from 50% n-butane/O(2) mixture through the combined reactions of the crude enzyme and the NR-electrode in 250 ml reactor for 3 h.

  14. Redox proteomics.

    Science.gov (United States)

    Butterfield, D Allan; Dalle-Donne, Isabella

    2012-12-01

    Proteins are major targets of reactive oxygen and nitrogen species (ROS/RNS) and numerous post-translational, reversible or irreversible modifications have been characterized, which may lead to a change in the structure and/or function of the oxidized protein. Redox proteomics is an increasingly emerging branch of proteomics aimed at identifying and quantifying redox-based changes within the proteome both in redox signaling and under oxidative stress conditions. Correlation between protein oxidation and human disease is widely accepted, although elucidating cause and effect remains a challenge. Increasing biomedical data have provided compelling evidences for the involvement of perturbations in redox homeostasis in a large number of pathophysiological conditions and aging. Research toward a better understanding of the molecular mechanisms of a disease together with identification of specific targets of oxidative damage is urgently required. This is the power and potential of redox proteomics. In the last few years, combined proteomics, mass spectrometry (MS), and affinity chemistry-based methodologies have contributed in a significant way to provide a better understanding of protein oxidative modifications occurring in various biological specimens under different physiological and pathological conditions. Hence, this Forum on Redox Proteomics is timely. Original and review articles are presented on various subjects ranging from redox proteomics studies of oxidatively modified brain proteins in Alzheimer disease and animal models of Alzheimer and Parkinson disease, to potential new biomarker discovery paradigm for human disease, to chronic kidney disease, to protein nitration in aging and age-related neurodegenerative disorders, electrophile-responsive proteomes of special relevance to diseases involving mitochondrial alterations, to cardiovascular physiology and pathology.

  15. 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.

  16. Novel low temperature, low energy and high efficiency pretreatment technology for large wood chips with a redox couple catalyst.

    Science.gov (United States)

    Gogoi, Parikshit; Zhang, Zhe; Geng, Zhishuai; Liu, Wei; Hu, Weize; Deng, Yulin

    2018-01-23

    Pretreatment of lignocellulosic biomass plays a vital role in the conversion of cellulosic biomass to bioethanol, specially for softwoods and hardwoods. Although many pretreatment technologies have been reported so far, but barely a few pretreatment methods can handle large sized wood chips directly. To improve the efficiency of this pretreatment all the existing technologies need to grind wood into small particles, which is an extreme energy consuming process. Herein, for the first time, we report a simple, effective and low temperature (~100 oC) process for pretreatment of hardwood (HW) and softwood (SW) chips directly by using a catalytic system of FeCl3/NaNO3 redox couple (FCSNRC). The pretreatment experiments were systematically conducted and a conversion of 71.53% and 70.66% of cellulose to sugar could be obtained even large sized hard and softwood chips being directly used. The novel method reported here overcame one of the critical barriers in biomass to biofuel conversion and both grinding and thermal energies can be significantly reduced. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2017-07-01

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

  18. Polymer-based protein engineering grown ferrocene-containing redox polymers improve current generation in an enzymatic biofuel cell.

    Science.gov (United States)

    Campbell, Alan S; Murata, Hironobu; Carmali, Sheiliza; Matyjaszewski, Krzysztof; Islam, Mohammad F; Russell, Alan J

    2016-12-15

    Enzymatic biofuel cells (EBFCs) are capable of generating electricity from physiologically present fuels making them promising power sources for the future of implantable devices. The potential application of such systems is limited, however, by inefficient current generation. Polymer-based protein engineering (PBPE) offers a unique method to tailor enzyme function through tunable modification of the enzyme surface with functional polymers. In this study, we report on the modification of glucose oxidase (GOX) with ferrocene-containing redox polymers to increase current generation efficiency in an enzyme-modified anode. Poly(N-(3-dimethyl(ferrocenyl)methylammonium bromide)propyl acrylamide) (pFcAc) was grown from covalently attached, water-soluble initiator molecules on the surface of GOX in a "grafting-from" approach using atom transfer radical polymerization (ATRP). The covalently-coupled ferrocene-containing polymers on the enzyme surface promoted the effective "wiring" of the GOX active site to an external electrode. The resulting GOX-pFcAc conjugates generated over an order of magnitude increase in current generation efficiency and a 4-fold increase in maximum EBFC power density (≈1.7µWcm(-2)) with similar open circuit voltage (0.27V) compared to native GOX when physically adsorbed onto paddle-shaped electrodes made up of electrospun polyacrylonitrile fibers coated with gold nanoparticles and multi-wall carbon nanotubes. The formation of electroactive enzyme-redox polymer conjugates using PBPE represents a powerful new tool for the improvement of mediated enzyme-based bioelectronics without the need for free redox mediators or anode/cathode compartmentalization. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

  19. Redox Species-Based Electrolytes for Advanced Rechargeable Lithium Ion Batteries

    KAUST Repository

    Ming, Jun

    2016-08-15

    Seeking high-capacity cathodes has become an intensive effort in lithium ion battery research; however, the low energy density still remains a major issue for sustainable handheld devices and vehicles. Herein, we present a new strategy of integrating a redox species-based electrolyte in batteries to boost their performance. Taking the olivine LiFePO4-based battery as an example, the incorporation of redox species (i.e., polysulfide of Li2S8) in the electrolyte results in much lower polarization and superior stability, where the dissociated Li+/Sx2– can significantly speed up the lithium diffusion. More importantly, the presence of the S82–/S2– redox reaction further contributes extra capacity, making a completely new LiFePO4/Li2Sx hybrid battery with a high energy density of 1124 Wh kgcathode–1 and a capacity of 442 mAh gcathode–1. The marriage of appropriate redox species in an electrolyte for a rechargeable battery is an efficient and scalable approach for obtaining higher energy density storage devices.

  20. Carbon nanofiber modified with osmium based redox polymer for glucose sensing

    Directory of Open Access Journals (Sweden)

    Amos Mugweru

    2017-12-01

    Full Text Available Electrochemical detection of glucose was performed on carbon nanofibers containing an osmium based redox polymer and using glucose oxidase enzyme. Redox polymer assembled on the nanofibers provided a more stable support that preserved enzyme activity and promoted the electrical communication to the glassy carbon electrode. The morphologies, structures, and electrochemical behavior of the redox polymer modified nanofibers were characterized by scanning electron microscope, energy dispersive spectrometer and voltammetry. The glucose oxidase showed excellent communication with redox polymer as observed with the increased activity toward glucose. Both cyclic voltammetry and amperometry showed a linear response with glucose concentration.  The linear range for glucose determination was from 1 to 12 mM with a relatively high sensitivity of 0.20±0.01 μA mM−1 for glucose oxidase in carbon nanofibers and 0.10±0.01 μA mM−1 without carbon nanofibers. The apparent Michaelis–Menten constant (Km for glucose oxidase with carbon nanofibers was 0.99 mM. On the other hand, the Km value for the glucose oxidase without the nanofibers was 4.90 mM.

  1. The fate of phenothiazine-based redox shuttles in lithium-ion batteries.

    Science.gov (United States)

    Casselman, Matthew D; Kaur, Aman Preet; Narayana, Kishore Anand; Elliott, Corrine F; Risko, Chad; Odom, Susan A

    2015-03-14

    The stability and reactivity of the multiple oxidation states of aromatic compounds are critical to the performance of these species as additives and electrolytes in energy-storage applications. Both for the overcharge mitigation in ion-intercalation batteries and as electroactive species in redox flow batteries, neutral, radical-cation, and radical-anion species may be present during charging and discharging processes. Despite the wide range of compounds evaluated for both applications, the progress identifying stable materials has been slow, limited perhaps by the overall lack of analysis of the failure mechanism when a material is utilized in an energy-storage device. In this study, we examined the reactivity of phenothiazine derivatives, which have found interest as redox shuttles in lithium-ion battery applications. We explored the products of the reactions of neutral compounds in battery electrolytes and the products of radical cation formation using bulk electrolysis and coin cell cycling. Following the failure of each cell, the electrolytes were characterized to identify redox shuttle decomposition products. Based on these results, a set of decomposition mechanisms is proposed and further explored using experimental and theoretical approaches. The results highlight the necessity to fully characterize and understand the chemical degradation mechanisms of the redox species in order to develop new generations of electroactive materials.

  2. Comparing Isomeric Tridentate Carbazole-Based Click Ligands: Metal Complexes and Redox Chemistry.

    Science.gov (United States)

    Pryjomska-Ray, Iweta; Zornik, Denise; Pätzel, Michael; Krause, Konstantin B; Grubert, Lutz; Braun-Cula, Beatrice; Hecht, Stefan; Limberg, Christian

    2017-12-19

    Two novel bis(triazolyl)carbazole ligands Hbtc1 (3,6-di(tert-butyl)-1,8-bis[(1-(3,5-di(tert-butyl)phenyl)-1,2,3-triazol-4-yl)]-9H-carbazole) and Hbtc2 (3,6-di(tert-butyl)-1,8-bis[(4-(3,5-di(tert-butyl)phenyl)-1,2,3-triazol-1-yl)]-9H-carbazole), differing in the regiochemistry of triazole attachment, have been synthesized by Cu-catalyzed azide-alkyne cycloaddition, the so-called "click-reactions". Metalation with Ru, Zn, and Ni precursors led to the formation of M(btc)2 complexes (M=Ru, Zn, Ni), with two deprotonated ligands coordinating to the metal center in tridentate fashion, forming almost perfectly octahedral coordination spheres. The redox properties of M(btc)2 complexes have been investigated by cyclic voltammetry, UV/Vis spectroscopy, spectroelectrochemistry, and chemically. The CV of the ruthenium complexes revealed three quasi-reversible one-electron oxidation processes, one assigned as the RuII/III couple and two originating from ligand-based oxidations. The CVs of both Zn and Ni complexes contained only two oxidation waves corresponding to the oxidation of the two ligands. The oxidation potentials of complexes derived from Hbtc1 ligands were found to be 300-400 mV lower than those of the corresponding complexes derived from Hbtc2, reflecting the significant difference in donation through the N(2) or N(3) atom of the triazole moiety. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Copper(I)/NO(g) Reductive Coupling Producing a trans-Hyponitrite Bridged Dicopper(II) Complex: Redox Reversal Giving Copper(I)/NO(g) Disproportionation.

    Science.gov (United States)

    Wijeratne, Gayan B; Hematian, Shabnam; Siegler, Maxime A; Karlin, Kenneth D

    2017-09-27

    A copper complex, [Cu(I)(tmpa)(MeCN)](+), effectively reductively couples NO(g) at RT in methanol (MeOH), giving a structurally characterized hyponitrito-dicopper(II) adduct. Hydrogen-bonding from MeOH is critical for the hyponitrite complex formation and stabilization. This complex exhibits the reverse redox process in aprotic solvents, giving Cu(I) + NO(g), leading to Cu(I)-mediated NO(g)-disproportionation. The relationship of this chemistry to biological iron and/or copper mediated NO(g) reductive coupling to give N2O(g) is discussed.

  4. 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.

  5. Redox Flow Batteries, a Review

    OpenAIRE

    Weber, Adam Z.

    2013-01-01

    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.

  6. Carbon-Dot-Based Nanosensors for the Detection of Intracellular Redox State.

    Science.gov (United States)

    Liu, Ye; Tian, Ye; Tian, Yefei; Wang, Yajun; Yang, Wuli

    2015-11-25

    Carbon-dot-based nanosensors are prepared through sequentially assembling a polymer/carbon dot multilayer shell on mesoporous silica nanoparticles with different crosslinking densities of disulfide bonds; they can be utilized to evaluate the gluthathione (GSH) concentration. In vitro cell assays demonstrate the feasibility of using such nanosensors in evaluating the intracellular redox state of different cells. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Role of the triiodide/iodide redox couple in dye regeneration in p-type dye-sensitized solar cells.

    Science.gov (United States)

    Gibson, Elizabeth A; Le Pleux, Loïc; Fortage, Jérôme; Pellegrin, Yann; Blart, Errol; Odobel, Fabrice; Hagfeldt, Anders; Boschloo, Gerrit

    2012-04-17

    A series of perylene dyes with different optical and electronic properties have been used as photosensitizers in NiO-based p-type dye-sensitized solar cells. A key target is to develop dyes that absorb light in the red to near-infrared region of the solar spectrum in order to match photoanodes optically in tandem devices; however, the photocurrent produced was found to decrease dramatically as the absorption maxima of the dye used was varied from 517 to 565 nm and varied strongly with the electrolyte solvent (acetonitrile, propionitrile, or propylene carbonate). To determine the limitations of the energy properties of the dye molecules and to provide guidelines for future sensitizer design, we have determined the redox potentials of the diiodide radical intermediate involved in the charge-transfer reactions in different solvents using photomodulated voltammetry. E°(I(3)(-)/I(2)(•-)) (V vs Fe(Cp)(2)(+/0)) = -0.64 for propylene carbonate, -0.82 for acetonitrile, and -0.87 for propionitrile. Inefficient regeneration of the sensitizer appears to be the efficiency-limiting step in the device, and the values presented here will be used to design more efficient dyes, with more cathodic reduction potentials, for photocathodes in tandem dye-sensitized solar cells. © 2012 American Chemical Society

  8. Solar Thermochemical Hydrogen Production via Terbium Oxide Based Redox Reactions

    Directory of Open Access Journals (Sweden)

    Rahul Bhosale

    2016-01-01

    Full Text Available The computational thermodynamic modeling of the terbium oxide based two-step solar thermochemical water splitting (Tb-WS cycle is reported. The 1st step of the Tb-WS cycle involves thermal reduction of TbO2 into Tb and O2, whereas the 2nd step corresponds to the production of H2 through Tb oxidation by water splitting reaction. Equilibrium compositions associated with the thermal reduction and water splitting steps were determined via HSC simulations. Influence of oxygen partial pressure in the inert gas on thermal reduction of TbO2 and effect of water splitting temperature (TL on Gibbs free energy related to the H2 production step were examined in detail. The cycle (ηcycle and solar-to-fuel energy conversion (ηsolar-to-fuel efficiency of the Tb-WS cycle were determined by performing the second-law thermodynamic analysis. Results obtained indicate that ηcycle and ηsolar-to-fuel increase with the decrease in oxygen partial pressure in the inert flushing gas and thermal reduction temperature (TH. It was also realized that the recuperation of the heat released by the water splitting reactor and quench unit further enhances the solar reactor efficiency. At TH=2280 K, by applying 60% heat recuperation, maximum ηcycle of 39.0% and ηsolar-to-fuel of 47.1% for the Tb-WS cycle can be attained.

  9. Heterogeneous Kinetics of Metal- and Ligand-Based Redox Reactions within Adsorbed Monolayers.

    Science.gov (United States)

    Forster, Robert J.

    1996-05-22

    Dense monolayers of [Os(bpy)(2)py(p3p)](2+), where bpy is 2,2'-bipyridyl, py is pyridine, and p3p is 4,4'-trimethylenedipyridine, have been formed by spontaneous adsorption onto clean platinum microelectrodes. Three well-defined waves, corresponding to osmium- and bipyridyl-based redox reactions, are observed in cyclic voltammetry of these monolayers, where the supporting electrolyte is tetrabutylammonium tetrafluoroborate (TBABF(4)) dissolved in acetonitrile. These reactions correspond to the charge states 3+/2+, 2+/1+, and 1+/0, respectively. Chronoamperometry, conducted on a microsecond time scale, has been used to measure the heterogeneous electron transfer rate constant, k/s(-1), for all three redox processes. For concentrations of TBABF(4) above 0.1 M, heterogeneous electron transfer is characterized by a single unimolecular rate constant. Standard heterogeneous electron transfer rate constants, k degrees, have been evaluated by extrapolating Tafel plots of ln k vs overpotential, eta, to zero driving force to yield values of (4.8 +/- 0.3) x 10(4) s(-1), (2.5 +/- 0.2) x 10(5) s(-1), and (3.3 +/- 0.3) x 10(4) s(-1) for k degrees (3+/2+), k degrees (2+/1+), and k degrees (1+/0), respectively. For large values of eta, these Tafel plots are curved for all three redox reactions, and while those corresponding to metal-based electron transfer are asymmetric with respect to eta, those corresponding to ligand-based reactions are symmetric. Temperature-resolved measurements of k reveal that the electrochemical activation enthalpy, DeltaH(), decreases from 43.1 +/- 2.8 kJ mol(-1) for the 3+/2+ reaction to 25.8 +/- 1.9 kJ mol(-1) for the 1+/0 process. Probing the temperature dependence of the formal potential gives the reaction entropy, DeltaS(rc) degrees. The reaction entropy depends on the state of charge of the monolayer with values of 212 +/- 18, 119 +/- 9, and 41 +/- 5 J mol(-1) K(-1) being observed for the 3+/2+, 2+/1+, and 1+/0, redox transformations, respectively

  10. Improving the Thermochemical Energy Storage Performance of the Mn2 O3 /Mn3 O4 Redox Couple by the Incorporation of Iron.

    Science.gov (United States)

    Carrillo, Alfonso J; Serrano, David P; Pizarro, Patricia; Coronado, Juan M

    2015-06-08

    Redox cycles of manganese oxides (Mn2 O3 /Mn3 O4 ) are a promising alternative for thermochemical heat storage systems coupled to concentrated solar power plants as manganese oxides are abundant and inexpensive materials. Although their cyclability for such a purpose has been proved, sintering processes, related to the high-temperature conditions at which charge-discharge cycles are performed, generally cause a cycle-to-cycle decrease in the oxidation rate of Mn3 O4 . To guarantee proper operation, both reactions should present stable reaction rates. In this study, it has been demonstrated that the incorporation of Fe, which is also an abundant material, into the manganese oxides improves the redox performance of this system by increasing the heat storage density, narrowing the redox thermal hysteresis, and, above all, stabilizing and enhancing the oxidation rate over long-term operation, which counteracts the negative effects caused by sintering, although its presence is not avoided. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Bottom RedOx Model (BROM v.1.1): a coupled benthic-pelagic model for simulation of water and sediment biogeochemistry

    Science.gov (United States)

    Yakushev, Evgeniy V.; Protsenko, Elizaveta A.; Bruggeman, Jorn; Wallhead, Philip; Pakhomova, Svetlana V.; Yakubov, Shamil Kh.; Bellerby, Richard G. J.; Couture, Raoul-Marie

    2017-02-01

    Interactions between seawater and benthic systems play an important role in global biogeochemical cycling. Benthic fluxes of some chemical elements (e.g., C, N, P, O, Si, Fe, Mn, S) alter the redox state and marine carbonate system (i.e., pH and carbonate saturation state), which in turn modulate the functioning of benthic and pelagic ecosystems. The redox state of the near-bottom layer in many regions can change with time, responding to the supply of organic matter, physical regime, and coastal discharge. We developed a model (BROM) to represent key biogeochemical processes in the water and sediments and to simulate changes occurring in the bottom boundary layer. BROM consists of a transport module (BROM-transport) and several biogeochemical modules that are fully compatible with the Framework for the Aquatic Biogeochemical Models, allowing independent coupling to hydrophysical models in 1-D, 2-D, or 3-D. We demonstrate that BROM is capable of simulating the seasonality in production and mineralization of organic matter as well as the mixing that leads to variations in redox conditions. BROM can be used for analyzing and interpreting data on sediment-water exchange, and for simulating the consequences of forcings such as climate change, external nutrient loading, ocean acidification, carbon storage leakage, and point-source metal pollution.

  12. Polyarene mediators for mediated redox flow battery

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Minimizing energy losses in dye-sensitized solar cells using coordination compounds as alternative redox mediators coupled with appropriate organic dyes

    Energy Technology Data Exchange (ETDEWEB)

    Stergiopoulos, Thomas; Falaras, Polycarpos [Institute of Physical Chemistry, NCSR Demokritos, 153 10, Aghia Paraskevi Attikis, Athens (Greece)

    2012-06-15

    To further boost the efficiency of dye-sensitized solar cells, a correct evaluation of the real limitations of this type of solar cell should be conducted. From a simple analysis of the photovoltaic data found in the literature, it is evident that the V{sub oc} decrease, through energy losses, seems to be the most crucial factor diminishing the overall system efficiency. In particular, losses arising from the regeneration of the dye by the iodide/triiodide redox mediator are huge. The most convenient manner to recuperate these losses is the use of alternative redox mediators with more positive redox potentials than that of the iodide-based shuttle. Among various types of redox active compounds, ferrocene/ferrocenium, Cu{sup +/2+}, and Co{sup 2+/3+} complexes are found to be the most effective in solar cells and the obtained efficiencies of more than 12% clearly show that a breakthrough is close, paving revolutionary roads towards making new records. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. The Redox Chemistry of Rainwater

    Science.gov (United States)

    Willey, J. D.; Mullaugh, K. M.; Kieber, R. J.; Avery, B.; Mead, R. N.

    2011-12-01

    Oxidation-reduction processes affect the chemical speciation of many inorganic and organic species in rainwater. The presence and concentrations of certain reactive radicals is also critically dependent upon redox chemistry. There are many oxidants and reductants in rainwater, and hence many competing redox reactions. Measurement of both halves of a redox couple can yield important information about rainwater pe- (-log electron activity) and also identify relevant oxidants and reductants for that particular redox speciation. Several redox couples have been measured in rainwater in Wilmington, NC, USA, as well as at other locations. There are at least three relevant oxidant-reductant couples in rainwater rather than a unique pe-. Mn redox speciation responds to the molecular oxygen-water couple (pe- = 15.9 for rainwater in contact with air and pH of 4.7). Fe, Hg and the nitrate-nitrite-ammonium system appear to be controlled by the molecular oxygen-hydrogen peroxide couple, with hydrogen peroxide acting as a reductant (pe- = 9.2). Cu responds to superoxide as a reductant with molecular oxygen as an oxidant (pe- = 2.7). Direct Pt electrode measurements of redox potential in rainwater consistently yield lower redox potentials than predicted by the molecular oxygen-water couple, indicating the redox chemistry of rainwater is more complex and rainwater is less oxidizing than previously thought.

  15. Cysteine perthiosulfenic acid (Cys-SSOH): A novel intermediate in thiol-based redox signaling?

    Science.gov (United States)

    Heppner, David E; Hristova, Milena; Ida, Tomoaki; Mijuskovic, Ana; Dustin, Christopher M; Bogdándi, Virág; Fukuto, Jon M; Dick, Tobias P; Nagy, Péter; Li, Jianing; Akaike, Takaaki; van der Vliet, Albert

    2017-10-09

    The reversible oxidation of protein cysteine residues (Cys-SH) is a key reaction in cellular redox signaling involving initial formation of sulfenic acids (Cys-SOH), which are commonly detected using selective dimedone-based probes. Here, we report that significant portions of dimedone-tagged proteins are susceptible to cleavage by DTT reflecting the presence of perthiosulfenic acid species (Cys-SSOH) due to similar oxidation of hydropersulfides (Cys-SSH), since Cys-S-dimedone adducts are stable toward DTT. Combined studies using molecular modeling, mass spectrometry, and cell-based experiments indicate that Cys-SSH are readily oxidized to Cys-SSOH, which forms stable adducts with dimedone-based probes. We additionally confirm the presence of Cys-SSH within protein tyrosine kinases such as EGFR, and their apparent oxidation to Cys-SSOH in response NADPH oxidase activation, suggesting that such Cys-SSH oxidation may represent a novel, as yet uncharacterized, event in redox-based signaling. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

  16. Strategic Coupling Based on Natural Resources

    DEFF Research Database (Denmark)

    Hauge, Mads Martinus

    and challenges that derive from such a resource-based strategic coupling. The thesis explores the nature and implications of the resource-based industrialization of the MRD Region through three entry points. The first explores the path of the industrialization and the role of natural resources in this process......The topic of this thesis is the resourced-based industrialization of the Mekong River Delta (MRD) Region of Vietnam. It shows how a region is linked with the world market and how settlements and living conditions are being transformed as part of a globalized regional development. A modular theory......, an established concept within the GPN framework that explores and explains how local assets are molded to complement the needs of the global market. However, existing applications of the notion of strategic coupling do not cover the situation in which a resource-based economy is coupled with the world market...

  17. Mechanisms and applications of redox-sensitive GFP-based H2O2 probes.

    Science.gov (United States)

    Roma, Leticia Prates; Deponte, Marcel; Riemer, Jan; Morgan, Bruce

    2017-11-21

    Genetically encoded H2O2 sensors, based upon fusions between thiol peroxidases and redox-sensitive green fluorescent protein 2 (roGFP2) have dramatically broadened the available 'toolbox' for monitoring cellular H2O2 changes. Recent advances: Recently developed peroxiredoxin-based probes such as roGFP2-Tsa2∆CR offer considerably improved H2O2-sensitivity compared to previously available genetically encoded sensors and now permit dynamic, real-time, monitoring of changes in endogenous H2O2 levels. The correct understanding and interpretation of probe read-outs is crucial for their meaningful use. We discuss probe mechanisms, potential pitfalls and best practices for application and interpretation of probe responses and highlight where gaps in our knowledge remain. The full potential of the newly available sensors remains far from being fully realized and exploited. We discuss how the ability to monitor basal H2O2 levels in real-time now allows us to re-visit long held ideas in redox biology such as the response to ischemia-reperfusion and hypoxia-induced ROS production. Furthermore, recently proposed circadian cycles of peroxiredoxin hyperoxidation might now be rigorously tested. Beyond their application as H2O2 probes, roGFP2-based H2O2 sensors hold exciting potential for studying thiol peroxidase mechanisms, inactivation properties and the impact of post-translational modifications, in vivo.

  18. Characterization of quinone derived protein adducts and their selective identification using redox cycling based chemiluminescence assay.

    Science.gov (United States)

    Elgawish, Mohamed Saleh; Kishikawa, Naoya; Ohyama, Kaname; Kuroda, Naotaka

    2015-07-17

    The cytotoxic mechanism of many quinones has been correlated to covalent modification of cellular proteins. However, the identification of relevant proteins targets is essential but challenging goals. To better understand the quinones cytotoxic mechanism, human serum albumin (HSA) was incubated in vitro with different concentration of menadione (MQ). In this respect, the initial nucleophilic addition of proteins to quinone converts the conjugates to redox-cycling quinoproteins with altered conformation and secondary structure and extended life span than the short lived, free quinones. The conjugation of MQ with nucleophilic sites likewise, free cysteine as well as ɛ-amino group of lysine residue of HSA has been found to be in concentration dependent manner. The conventional methods for modified proteins identification in complex mixtures are complicated and time consuming. Herein, we describe a highly selective, sensitive, simple, and fast strategy for quinoproteins identification. The suggested strategy exploited the unique redox-cycling capability of quinoproteins in presence of a reductant, dithiothreitol (DTT), to generate reactive oxygen species (ROS) that gave sufficient chemiluminescence (CL) when mixed with luminol. The CL approach is highly selective and sensitive to detect the quinoproteins in ten-fold molar excess of native proteins without adduct enrichment. The approach was also coupled with gel filtration chromatography (GFC) and used to identify adducts in complex mixture of proteins in vitro as well as in rat plasma after MQ administration. Albumin was identified as the main protein in human and rat plasma forming adduct with MQ. Overall, the identification of quinoproteins will encourage further studies of toxicological impact of quinones on human health. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Chemical and structural indicators for large redox potentials in Fe-based positive electrode materials.

    Science.gov (United States)

    Melot, Brent C; Scanlon, David O; Reynaud, Marine; Rousse, Gwenaëlle; Chotard, Jean-Noël; Henry, Marc; Tarascon, Jean-Marie

    2014-07-23

    Li-ion batteries have enabled a revolution in the way portable consumer-electronics are powered and will play an important role as large-scale electrochemical storage applications like electric vehicles and grid-storage are developed. The ability to identify and design promising new positive insertion electrodes will be vital in continuing to push Li-ion technology to its fullest potential. Utilizing a combination of computational tools and structural analysis, we report new indicators which will facilitate the recognition of phases with the desired redox potential. Most importantly of these, we find there is a strong correlation between the presence of Li ions sitting in close-proximity to the redox center of polyanionic phases and the open circuit voltage in Fe-based cathodes. This common structural feature suggests that the bonding associated with Li may have a secondary inductive effect which increases the ionic character of Fe bonds beyond what is typically expected based purely on arguments of electronegativity associated with the polyanionic group. This correlation is supported by ab initio calculations which show the Bader charge increases (reflecting an increased ionicity) in a nearly linear fashion with the experimental cell potentials. These features are demonstrated to be consistent across a wide variety of compositions and structures and should help to facilitate the design of new, high-potential, and environmentally sustainable insertion electrodes.

  20. Multifunctional Metal-Organic Frameworks Based on Redox-Active Rhenium Octahedral Clusters.

    Science.gov (United States)

    Litvinova, Yulia M; Gayfulin, Yakov M; Kovalenko, Konstantin A; Samsonenko, Denis G; van Leusen, Jan; Korolkov, Ilya V; Fedin, Vladimir P; Mironov, Yuri V

    2018-02-05

    The redox-active rhenium octahedral cluster unit [Re 6 Se 8 (CN) 6 ] 4- was combined with Gd 3+ ions and dicarboxylate linkers in novel types of metal-organic frameworks (MOFs) that display a set of functional properties. The hydrolytically stable complexes [{Gd(H 2 O) 3 } 2 (L)Re 6 Se 8 (CN) 6 ]·nH 2 O (1, L = furan-2,5-dicarboxylate, fdc; 2, L = thiophene-2,5-dicarboxylate, tdc) exhibit a 3D framework of trigonal symmetry where 1D chains of [{Gd(H 2 O) 3 } 2 (L)] 4+ are connected by [Re 6 Se 8 (CN) 6 ] 4- clusters. Frameworks contain spacious channels filled with H 2 O. Solvent molecules can be easily removed under vacuum to produce permanently porous solids with high volumetric CO 2 uptake and remarkable CO 2 /N 2 selectivity at room temperature. The frameworks demonstrate an ability for reversible redox transformations of the cluster fragment. The orange powders of compounds 1 and 2 react with Br 2 , yielding dark-green powders of [{Gd(H 2 O) 3 } 2 (L)Re 6 Se 8 (CN) 6 ]Br·nH 2 O (3, L = fdc; 4, L = tdc). Compounds 3 and 4 are isostructural with 1 and 2 and also have permanently porous frameworks but display different optical, magnetic, and sorption properties. In particular, oxidation of the cluster fragment "switches off" its luminescence in the red region, and the incorporation of Br - leads to a decrease of the solvent-accessible volume in the channels of 3 and 4. Finally, the green powders of 3 and 4 can be reduced back to the orange powders of 1 and 2 by reaction with hydrazine, thus displaying a rare ability for fully reversible chemical redox transitions. Compounds 1-4 are mentioned as a new class of redox-active cluster-based MOFs with potential usage as multifunctional materials for gas separation and chemical contamination sensors.

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

    KAUST Repository

    Iloeje, Chukwunwike

    2015-10-01

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

  2. Surface and Electrochemical Properties of Polymer Brush-Based Redox Poly(Ionic Liquid).

    Science.gov (United States)

    Bui-Thi-Tuyet, Van; Trippé-Allard, Gaëlle; Ghilane, Jalal; Randriamahazaka, Hyacinthe

    2016-10-26

    Redox-active poly(ionic liquid) poly(3-(2-methacryloyloxy ethyl)-1-(N-(ferrocenylmethyl) imidazolium bis(trifluoromethylsulfonyl)imide deposited onto electrode surfaces has been prepared using surface-initiated atom transfer radical polymerization SI-ATRP. The process starts by electrochemical immobilization of initiator layer, and then methacrylate monomer carrying ferrocene and imidazolium units is polymerized in ionic liquid media via SI-ATRP process. The surfaces analyses of the polymer exhibit a well-defined polymer brushlike structure and confirm the presence of ferrocene and ionic moieties within the film. Furthermore, the electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer. The attractive electrochemical performance of these materials is further demonstrated by performing electrochemical measurement, of poly(ferrocene ionic liquid), in solvent-free electrolyte. The facile synthesis of such highly ordered electroactive materials based ionic liquid could be useful for the fabrication of nanostructured electrode suitable for performing electrochemistry in solvent free electrolyte. We also demonstrate possible applications of the poly(FcIL) as electrochemically reversible surface wettability system and as electrochemical sensor for the catalytic activity toward the oxidation of tyrosine.

  3. Sulfur-based redox alterations in long-lived Snell dwarf mice.

    Science.gov (United States)

    Vitvitsky, Victor; Martinov, Michael; Ataullakhanov, Fazoil; Miller, Richard A; Banerjee, Ruma

    2013-01-01

    Changes in sulfur-based redox metabolite profiles in multiple tissues of long-lived Snell dwarf mice were compared with age- and sex-matched controls. Plasma methionine and its oxidation products, hypotaurine and taurine, were increased in Snell dwarfs while cystine and glutathione levels were decreased, leading to an oxidative shift in the redox potential. Sexual dimorphism in renal cystathionine β-synthase (CBS) activity was observed in control mice but not in Snell dwarfs. Instead, female Snell mice exhibited ~2-fold higher CBS activity, comparable to levels seen in male Snell dwarf and in control mice. Taurine levels were significantly higher in kidney and brain of Snell dwarf versus control mice. Methionine adenosyltransferase (MAT) was higher in liver of Snell dwarfs, and the higher concentration of its product, S-adenosylmethionine, was correlated with elevated global DNA methylation status. Application of a mathematical model for methionine metabolism revealed that the metabolite perturbations in Snell dwarfs could be explained by decreased methionine transport, increased MAT and increased methyltransferase activity. Our study provides a comprehensive map of systemic differences in the sulfur network between Snell dwarfs and controls, providing the necessary foundation for assessment of nutrition-linked metabolic status in long-lived versus control animals. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  4. Artificial Enzyme-based Logic Operations to Mimic an Intracellular Enzyme-participated Redox Balance System.

    Science.gov (United States)

    Huang, Yanyan; Pu, Fang; Ren, Jinsong; Qu, Xiaogang

    2017-07-06

    Owing to the biocatalytic properties of artificial enzymes and the redox characteristic of glutathione, a colorimetric and resettable biological operation was successfully designed to mimic enzyme-participated redox balance in living systems. As one promising candidate of a natural enzyme, artificial enzyme possesses many advantages and has been used in numerous fields. Similar to natural enzymes, communications are also present between different artificial enzymes. With the assistance of four artificial enzymes, three simple biological logic gates were fabricated to help us deepen the understanding of communications between artificial enzymes. In the presence of glutathione, the system could be easily reset without any complicated procedures. We prospect that this work may push forward the exploration of communications between different artificial enzymes and the design of novel artificial enzyme-based biological gates or nanodevices. We hope that our mimic system may help us further understand the functioning of complex biological pathways in biological systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2015-03-01

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

  6. 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

  7. 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 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.

  8. 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 LiFePO4 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/cm2, and voltage efficiency of 91%. Operando X-ray absorption near-edge structure measurements were conducted to monitor the evolution of LiFePO4, which provides insightful information on the redox targeting process, critical to the device operation and optimization.

  9. 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)

  10. Effect of modification of polyacrylonitrile-based graphite felts on their performance in redox fuel cell and redox flow battery

    Science.gov (United States)

    Zhang, Yue; Qian, Guocai; Huang, Chengde; Wang, Yuxin

    2016-08-01

    The electrochemical behavior of nitrogen-doped polyacrylonitrile (PAN) -based graphite felt prepared by three pretreatment methods for the reaction of Fe3+/Fe2+ was investigated. Then the effects of three pretreatment, including doped nitrogen, heat treatment and acid treatment, on the 9,10-anthraquinone-2,7-disulphonic acid (AQDS) electrochemical reaction activity of the PAN-based graphite felt were investigated and compared. The crystal structure, the surface morphology, and surface chemical composition of the PAN-based graphite felt were characterized by X-ray diffraction, scanning electron microscopy and X-ray electron spectroscopy. The results of the electrochemical performance showed that the nitrogen content can influence the activity of PAN-based graphite felt in the reaction of Fe3+/Fe2+. Besides, the activity of PAN-based graphite felt in the AQDS electrochemical reaction was affected by the content of sbnd COOH group on the surface of graphite felt.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhu Feng [State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (China); Yan Jiawei, E-mail: jwyan@xmu.edu.cn [State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (China); Lu Miao [Pen-Tung Sah Micro-Nano Technology Research Center, Xiamen University, Xiamen, Fujian 361005 (China); Zhou Yongliang; Yang Yang; Mao Bingwei [State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (China)

    2011-10-01

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

  12. Using a Redox Modality to Connect Synthetic Biology to Electronics: Hydrogel-Based Chemo-Electro Signal Transduction for Molecular Communication.

    Science.gov (United States)

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

    2017-01-01

    A hydrogel-based dual film coating is electrofabricated for transducing bio-relevant chemical information into electronical output. The outer film has a synthetic biology construct that recognizes an external molecular signal and transduces this input into the expression of an enzyme that converts redox-inactive substrate into a redox-active intermediate, which is detected through an amplification mechanism of the inner redox-capacitor film. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. An Aqueous Redox Flow Battery Based on Neutral Alkali Metal Ferri/ferrocyanide and Polysulfide Electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Xiaoliang; Xia, Gordon; Kirby, Brent W.; Thomsen, Edwin C.; Li, Bin; Nie, Zimin; Graff, Gordon L.; Liu, Jun; Sprenkle, Vincent L.; Wang, Wei

    2015-11-13

    Aiming to explore low-cost redox flow battery systems, a novel iron-polysulfide (Fe/S) flow battery has been demonstrated in a laboratory cell. This system employs alkali metal ferri/ferrocyanide and alkali metal polysulfides as the redox electrolytes. When proper electrodes, such as pretreated graphite felts, are used, 78% energy efficiency and 99% columbic efficiency are achieved. The remarkable advantages of this system over current state-of-the-art redox flow batteries include: 1) less corrosive and relatively environmentally benign redox solutions used; 2) excellent energy and utilization efficiencies; 3) low cost for redox electrolytes and cell components. These attributes can lead to significantly reduced capital cost and make the Fe/S flow battery system a promising low-cost energy storage technology. The major drawbacks of the present cell design are relatively low power density and possible sulfur species crossover. Further work is underway to address these concerns.

  14. Synthesis and ligand-based reduction chemistry of boron difluoride complexes with redox-active formazanate ligands

    NARCIS (Netherlands)

    Chang, M. -C.; Otten, E.

    2014-01-01

    Mono(formazanate) boron difluoride complexes (LBF2), which show remarkably facile and reversible ligand-based redox-chemistry, were synthesized by transmetallation of bis(formazanate) zinc complexes with boron trifluoride. The one-electron reduction product [LBF2](-)[Cp2Co](+) and a key intermediate

  15. Assessment of the development of a battery charging infrastructure for a redox flow battery based electromobility concept; Bewertung des Aufbaus einer Ladeinfrastruktur fuer eine Redox-Flow-Batteriebasierte Elektromobilitaet

    Energy Technology Data Exchange (ETDEWEB)

    Arpad Funke, Simon; Wietschel, Martin [Fraunhofer-Institut fuer System- und Innovationsforschung (ISI), Karlsruhe (Germany). Competence Center Energietechnologien und Energiesysteme

    2012-07-01

    Apart from the high acquisition cost, the major obstacles to widespread use of electric-powered vehicles today are long battery charging times and limited mileage. Rechargeable batteries might be a solution. The publication investigates a potential infrastructure for electric-powered vehicles based on so-called redox flow batteries. Redox flow batteries are characterized in that active materials are dissolved in liquid electrolyte and are stored outside the cell. Batteries are recharged by exchanging charged electrolyte for discharged electrolyte, which can be done in fuel stations. Redox flow batteries have the drawback of low energy and power density and were hardly ever considered for mobile applications so far. A technical analysis of RFB technology identified the vanadium oxygen redox flow fuel cell (VOFC) as a promising version. It provides higher energy density than conventional redox flow batteries, but development is still in an early stage. Assuming a 'best case' scenario, a refuelling infrastructure for VOFC vehicles was developed and compared with battery-powered vehicles (BEV) and fuel cell vehicles (FVEV). It was found that electromobility based on VOFC may be a promising alternative to current electromobility concepts. (orig./AKB) [German] Neben den Anschaffungsausgaben stehen lange Ladezeiten und eine beschraenkte Reichweite dem heutigen Einsatz von Elektrofahrzeugen oft entgegen. Eine moegliche Abhilfe koennten betankbare Batterien leisten. In der vorliegenden Arbeit soll ein moeglicher Infrastrukturaufbau fuer Elektrofahrzeuge mit sogenannten Redox-Flow-Batterien untersucht werden. Redox-Flow-Batterien besitzen die Eigenschaft, dass aktive Materialien geloest in Fluessigelektrolyten ausserhalb der Zelle gespeichert werden. Dieser Aufbau ermoeglicht das Aufladen der Batterie, indem der entladene Elektrolyt durch geladenen ausgetauscht wird. Dieser Tausch kann an einer Tankstelle durchgefuehrt werden. Ein wesentlicher Nachteil von Redox

  16. Redox storage systems for solar applications

    Science.gov (United States)

    Hagedorn, N. H.; Thaller, L. H.

    1981-01-01

    It is noted that the worldwide development of solar photovoltaic and wind turbine systems to meet a range of terrestrial electrical energy requirements has underscored the need for inexpensive and reliable electrical energy storage. The NASA Redox Energy Storage System, based on soluble aqueous iron and chromium chloride redox couples, has exhibited many system-related features which for the most part are unique to this storage system. The technology advances required in the two elements (electrodes and membranes), which are the key to its technological feasibility, have been attained and system development has begun. The design, construction, and testing of a 1-kW system integrated with a solar photovoltaic array is underway to provide early demonstration of the attractive system-related features of the NASA Redox Storage System. Also demonstrated will be its versatility and compatibility with a terrestrial solar photovoltaic electric power system.

  17. Sensitive and Fast Humidity Sensor Based on A Redox Conducting Supramolecular Ionic Material for Respiration Monitoring.

    Science.gov (United States)

    Yan, Hailong; Zhang, Li; Yu, Ping; Mao, Lanqun

    2017-01-03

    Real-time monitoring of respiratory rate (RR) is highly important for human health, clinical diagnosis, and fundamental scientific research. Exhaled humidity-based RR monitoring has recently attracted increased attention because of its accuracy and portability. Here, we report a new design of an exhaled humidity sensor for the real-time monitoring of the RR based on a synthetic redox conducting supramolecular ionic material (SIM). The humidity-dependent conducting SIM is prepared by ionic self-assembly in aqueous solutions of electroactive 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and 1,10-bis(3-methylimidazolium-1-yl) decane (C10(mim)2). By taking full advantage of the high hygroscopicity and water stability arising from the ionic and hydrophobic interactions between two building blocks (i.e., ABTS and C10(mim)2), the SIM-based humidity sensor exhibits both high sensitivity (less than 0.1% relative humidity) and fast response time (∼37 ms). These excellent properties allow this humidity sensor to noninvasively monitor the RRs of not only humans but also rats that have a much faster RR and much smaller tidal volume than humans. Moreover, this sensor could also be efficiently used for the real-time monitoring of the recovery process of rats from anesthesia.

  18. Electrochemical sensors and biosensors based on redox polymer/carbon nanotube modified electrodes: a review.

    Science.gov (United States)

    Barsan, Madalina M; Ghica, M Emilia; Brett, Christopher M A

    2015-06-30

    The aim of this review is to present the contributions to the development of electrochemical sensors and biosensors based on polyphenazine or polytriphenylmethane redox polymers together with carbon nanotubes (CNT) during recent years. Phenazine polymers have been widely used in analytical applications due to their inherent charge transport properties and electrocatalytic effects. At the same time, since the first report on a CNT-based sensor, their application in the electroanalytical chemistry field has demonstrated that the unique structure and properties of CNT are ideal for the design of electrochemical (bio)sensors. We describe here that the specific combination of phenazine/triphenylmethane polymers with CNT leads to an improved performance of the resulting sensing devices, because of their complementary electrical, electrochemical and mechanical properties, and also due to synergistic effects. The preparation of polymer/CNT modified electrodes will be presented together with their electrochemical and surface characterization, with emphasis on the contribution of each component on the overall properties of the modified electrodes. Their importance in analytical chemistry is demonstrated by the numerous applications based on polymer/CNT-driven electrocatalytic effects, and their analytical performance as (bio) sensors is discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Redox speciation of iron, manganese, and copper in cerebrospinal fluid by strong cation exchange chromatography - sector field inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Solovyev, Nikolay; Vinceti, Marco; Grill, Peter; Mandrioli, Jessica; Michalke, Bernhard

    2017-06-22

    A new method of simultaneous redox speciation of iron (II/III), manganese (II/III), and copper (I/II) in cerebrospinal fluid (CSF) has been designed. For the separation of redox species strong cation exchange chromatography (SCX) with isocratic elution was employed. Species were detected using inductively coupled plasma sector field mass spectrometry (ICP-sf-MS), operating at medium resolution. The following parameters were optimized: analytical column, eluent composition and pH, CSF injection volume and dilution factor. Analytical column Dionex IonPac CS5A RFIC 4*250 mm was found to retain and separate species of interest the most effectively under the isocratic elution with a buffer, containing 50 mM ammonium citrate, 7.0 mM pyridine-2,6-dicarboxylic acid at pH = 4.2 and flow rate of 0.8 L min-1. Injection volume of 50 μL with CSF sample dilution of 1/3 (v/v) with the eluent was shown to result in minimal matrix suppression. For species identification, retention time matching with standards was used. The stability of metalloproteins (ferritin, transferrin, and ceruloplasmin) under elution conditions was evaluated. For the quantification of redox species, external calibration was employed. To avoid column contamination, a blank was run after measurement and all quantification values were blank subtracted. For recovery checks, species quantification data was verified against total content of an element, measured by dynamic reaction cell ICP-MS. Recoveries (sum of quantified species vs. total element determinations) were 82.5 ± 22% (Mn), 92 ± 11% (Fe), and 88.7 ± 12% (Cu). The method was tested using 38 real CSF samples. Limits of detection (3σ) for the CSF samples were 0.5 μg L-1, 0.6 μg L-1, and 0.8 μg L-1 for Fe, Mn, and Cu species, respectively. Retention time precision was 1-7.5% (as RSD), whereas peak area RSDs were in the range 5-11%, both depending on the species. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    DEFF Research Database (Denmark)

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

    2012-01-01

    Reversible switching of conductance using redox triggered switching of a polymer-modified electrode is demonstrated. A bifunctional monomer comprising a central electroswitchable core and two bithiophene units enables formation of a film through anodic electropolymerization. The conductivity of t...

  1. Crosslinked anion exchange membranes with primary diamine-based crosslinkers for vanadium redox flow battery application

    Science.gov (United States)

    Cha, Min Suc; Jeong, Hwan Yeop; Shin, Hee Young; Hong, Soo Hyun; Kim, Tae-Ho; Oh, Seong-Geun; Lee, Jang Yong; Hong, Young Taik

    2017-09-01

    A series of polysulfone-based crosslinked anion exchange membranes (AEMs) with primary diamine-based crosslinkers has been prepared via simple a crosslinking process as low-cost and durable membranes for vanadium redox flow batteries (VRFBs). Chloromethylated polysulfone is used as a precursor polymer for crosslinked AEMs (CAPSU-x) with different degrees of crosslinking. Among the developed AEMs, CAPSU-2.5 shows outstanding dimensional stability and anion (Cl-, SO42-, and OH-) conductivity. Moreover, CAPSU-2.5 exhibits much lower vanadium ion permeability (2.72 × 10-8 cm2 min-1) than Nafion 115 (2.88 × 10-6 cm2 min-1), which results in an excellent coulombic efficiency of 100%. The chemical and operational stabilities of the membranes have been investigated via ex situ soaking tests in 0.1 M VO2+ solution and in situ operation tests for 100 cycles, respectively. The excellent chemical, physical, and electrochemical properties of the CAPSU-2.5 membrane make it suitable for use in VRFBs.

  2. Kinetic enhancement via passive deposition of carbon-based nanomaterials in vanadium redox flow batteries

    Science.gov (United States)

    Aaron, Doug; Yeom, Sinchul; Kihm, Kenneth D.; Ashraf Gandomi, Yasser; Ertugrul, Tugrul; Mench, Matthew M.

    2017-10-01

    Addition of carbon-based nanomaterials to operating flow batteries accomplishes vanadium redox flow battery performance improvement. Initial efforts focus on addition of both pristine graphene and vacuum-filtered reduced graphene oxide (rGO) film on carbon paper supporting electrodes. While the former is unable to withstand convective flow through the porous electrode, the latter shows measurable kinetic improvement, particularly when laid on the polymer electrolyte membrane (PEM) side of the electrode; in contrast to the kinetic performance gain, a deleterious impact on mass transport is observed. Based on this tradeoff, further improvement is realized using perforated rGO films placed on the PEM side of the electrodes. Poor mass transport in the dense rGO film prompts identification of a more uniform, passive deposition method. A suspension of rGO flakes or Vulcan carbon black (XC-72R), both boasting two orders-of-magnitude greater specific surface area than that of common carbon electrodes, is added to the electrolyte reservoirs and allowed to passively deposit on the carbon paper or carbon felt supporting electrodes. For common carbon felt electrodes, addition of rGO flakes or XC-72R enables a tripling of current density at the same 80% voltage efficiency.

  3. Genetically Encoded Fluorescent Redox Probes

    Directory of Open Access Journals (Sweden)

    Hui-Wang Ai

    2013-11-01

    Full Text Available Redox processes are involved in almost every cell of the body as a consequence of aerobic life. In the past decades, redox biology has been increasingly recognized as one of the key themes in cell signaling. The progress has been accelerated by development of fluorescent probes that can monitor redox conditions and dynamics in cells and cell compartments. This short paper focuses on fluorescent redox probes that are genetically encoded, and discusses their properties, molecular mechanism, advantages and pitfalls. Our recent work on reaction-based encoded probes that are responsive to particular redox signaling molecules is also reviewed. Future challenges and directions are also commented.

  4. Genetically encoded fluorescent redox probes.

    Science.gov (United States)

    Ren, Wei; Ai, Hui-Wang

    2013-11-11

    Redox processes are involved in almost every cell of the body as a consequence of aerobic life. In the past decades, redox biology has been increasingly recognized as one of the key themes in cell signaling. The progress has been accelerated by development of fluorescent probes that can monitor redox conditions and dynamics in cells and cell compartments. This short paper focuses on fluorescent redox probes that are genetically encoded, and discusses their properties, molecular mechanism, advantages and pitfalls. Our recent work on reaction-based encoded probes that are responsive to particular redox signaling molecules is also reviewed. Future challenges and directions are also commented.

  5. Mesh-based parallel code coupling interface

    Energy Technology Data Exchange (ETDEWEB)

    Wolf, K.; Steckel, B. (eds.) [GMD - Forschungszentrum Informationstechnik GmbH, St. Augustin (DE). Inst. fuer Algorithmen und Wissenschaftliches Rechnen (SCAI)

    2001-04-01

    MpCCI (mesh-based parallel code coupling interface) is an interface for multidisciplinary simulations. It provides industrial end-users as well as commercial code-owners with the facility to combine different simulation tools in one environment. Thereby new solutions for multidisciplinary problems will be created. This opens new application dimensions for existent simulation tools. This Book of Abstracts gives a short overview about ongoing activities in industry and research - all presented at the 2{sup nd} MpCCI User Forum in February 2001 at GMD Sankt Augustin. (orig.) [German] MpCCI (mesh-based parallel code coupling interface) definiert eine Schnittstelle fuer multidisziplinaere Simulationsanwendungen. Sowohl industriellen Anwender als auch kommerziellen Softwarehersteller wird mit MpCCI die Moeglichkeit gegeben, Simulationswerkzeuge unterschiedlicher Disziplinen miteinander zu koppeln. Dadurch entstehen neue Loesungen fuer multidisziplinaere Problemstellungen und fuer etablierte Simulationswerkzeuge ergeben sich neue Anwendungsfelder. Dieses Book of Abstracts bietet einen Ueberblick ueber zur Zeit laufende Arbeiten in der Industrie und in der Forschung, praesentiert auf dem 2{sup nd} MpCCI User Forum im Februar 2001 an der GMD Sankt Augustin. (orig.)

  6. Interfacial interactions and their impact on redox-based resistive switching memories (ReRAMs)

    Science.gov (United States)

    Valov, Ilia

    2017-09-01

    Redox-based resistive switching memories are nowadays one of the most studied systems in both academia and industrial communities. These devices are scalable down to an almost atomic level and are supposed to be applicable not only for next-generation nonvolatile memories, but also for neuromorphic computing, alternative logic operations and selector devices. The main characteristic feature of these cells is their nano- to sub-nano dimension. This makes the control and especially prediction of their properties very challenging. One of the ways to achieve better understanding and to improve the control of these systems is to study and modify their interfaces. In this review, first the fundamentals will be discussed, as these are essential for understanding which factors control the nanoscale interface properties. Further, different types of interactions at the electrode/solid electrolyte interface reported for ECM- and VCM-type cells will be exemplarily shown. Finally, the strategies and different solutions used to modify the interfaces and overcome the existing problems on the way to more stable and reliable devices will be highlighted.

  7. Optimal Sizing of Vanadium Redox Flow Battery Systems for Residential Applications Based on Battery Electrochemical Characteristics

    Directory of Open Access Journals (Sweden)

    Xinan Zhang

    2016-10-01

    Full Text Available The penetration of solar photovoltaic (PV systems in residential areas contributes to the generation and usage of renewable energy. Despite its advantages, the PV system also creates problems caused by the intermittency of renewable energy. As suggested by researchers, such problems deteriorate the applicability of the PV system and have to be resolved by employing a battery energy storage system (BESS. With concern for the high investment cost, the choice of a cost-effective BESS with proper sizing is necessary. To this end, this paper proposes the employment of a vanadium redox flow battery (VRB, which possesses a long cycle life and high energy efficiency, for residential users with PV systems. It further proposes methods of computing the capital and maintenance cost of VRB systems and evaluating battery efficiency based on VRB electrochemical characteristics. Furthermore, by considering the cost and efficiency of VRB, the prevalent time-of-use electricity price, the solar feed-in tariff, the solar power profile and the user load pattern, an optimal sizing algorithm for VRB systems is proposed. Simulation studies are carried out to show the effectiveness of the proposed methods.

  8. 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.

  9. Redox-Responsive Polysulfide-Based Biodegradable Organosilica Nanoparticles for Delivery of Bioactive Agents.

    Science.gov (United States)

    Hadipour Moghaddam, Seyyed Pouya; Saikia, Jiban; Yazdimamaghani, Mostafa; Ghandehari, Hamidreza

    2017-06-28

    Design and development of silica nanoparticles (SiO2 NPs) with a controlled degradation profile promises effective drug delivery with a predetermined carrier elimination profile. In this research, we fabricated a series of redox-responsive polysulfide-based biodegradable SiO2 NPs with low polydispersity and with variations in size (average diameters of 58 ± 7, 108 ± 11, 110 ± 9, 124 ± 9, and 332 ± 6 nm), porosity, and composition (disulfide vs tetrasulfide bonds). The degradation kinetics of the nanoparticles was analyzed in the presence of 8 mM glutathione (GSH), mimicking the intracellular reducing condition. Results indicate that porosity and core composition play the predominant roles in the degradation rate of these nanoparticles. The 108 nm mesoporous disulfide-based nanoparticles showed the highest degradation rate among all the synthesized nanoparticles. Transmission electron microscopy (TEM) reveals that nonporous nanoparticles undergo surface erosion, while porous nanoparticles undergo both surface and bulk erosion under reducing environment. The cytotoxicity of these nanoparticles in RAW 264.7 macrophages was evaluated. Results show that all these nanoparticles with the IC50 values ranging from 233 ± 42 to 705 ± 17 μg mL-1 do not have cytotoxic effect in macrophages at concentrations less than 125 μg mL-1. The degradation products of these nanoparticles collected within 15 days did not show cytotoxicity in the same macrophage cell line after 24 h of incubation. In vitro doxorubicin (DOX) release was examined in 108 nm mesoporous disulfide-based nanoparticles in the absence and presence of 8 mM GSH. It was shown that drug release depends on intracellular reducing conditions. Due to their ease of synthesis and scale up, robust structure, and the ability to control size, composition, release, and elimination, biodegradable SiO2 NPs provide an alternative platform for delivery of bioactive and imaging agents.

  10. Strategic Coupling Based on Natural Resources

    DEFF Research Database (Denmark)

    Hauge, Mads Martinus

    Delta Region seeking to exploit the opportunities deriving from industrialization, and what challenges are they encountering? The third entry point examines the transformations of settlements, livelihoods and living conditions through the question, (3) How are rural spaces reshaped as global influences......The topic of this thesis is the resourced-based industrialization of the Mekong River Delta (MRD) Region of Vietnam. It shows how a region is linked with the world market and how settlements and living conditions are being transformed as part of a globalized regional development. A modular theory......, nor does it take into account the implications of a strategic coupling beyond relations between firms and regional institutions. It is imperative that the transformations of local spaces, resources and actors are examined and brought to light to gain an understanding of the possibilities...

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

    DEFF Research Database (Denmark)

    Klemensø, Trine; Mogensen, Mogens Bjerg

    2007-01-01

    Nickel (Ni)—yttria-stabilized zirconia (YSZ) cermets are a prevalent material used for solid oxide fuel cells. The cermet degrades upon redox cycling. The degradation is related to microstructural changes, but knowledge of the mechanisms has been limited. Direct current conductivity measurements...... were performed on cermets and cermets where the Ni component was removed. Measurements were carried out before, during, and after redox cycling the cermet. The cermet conductivity degraded over time due to sintering of the nickel phase. Following oxidizing events, the conductivity of the cermets...

  12. The Photochemical Oxidation of Siderite That Drove Hydrogen Based Microbial Redox Reactions in The Archean Biosphere

    Science.gov (United States)

    Kim, J. D.; Yee, N.; Falkowski, P. G.

    2012-12-01

    Hydrogen is the most abundant element in the universe and molecular hydrogen (H2) is a rich source of electron in a mildly reducing environment for microbial redox reactions, such as anoxygenic photosynthesis and methanogenesis. Subaerial volcanoes, ocean crust serpentinization and mid-ocean ridge volcanoes have been believed to be the major source of the hydrogen flux to the atmosphere. Although ferrous ion (Fe2+) photooxidation has been proposed as an alternative mechanism by which hydrogen gas was produced, ferruginous water in contact with a CO2-bearing atmosphere is supersaturated with respect to FeCO3 (siderite), thus the precipitation of siderite would have been thermodynamically favored in the Archean environment. Siderite is the critical mineral component of the oldest fossilized microbial mat. It has also been inferred as a component of chemical sedimentary protolith in the >3750 Ma Nuvvuagittuq supracrustal belt, Canada and the presence of siderite in the protolith suggests the occurrence of siderite extends to Hadean time. Analyses of photooxidation of siderite suggest a significant flux of hydrogen in the early atmosphere. Our estimate of the hydrogen production rate under Archean solar flux is approximately 50 times greater than the estimated hydrogen production rate by the volcanic activity based on a previous report (Tian et al. Science 2005). Our analyses on siderite photooxidation also suggest a mechanism by which banded iron formation (BIF) was formed. The photooxidation transforms siderite to magnetite/maghemite (spinnel iron oxide), while oxygenic oxidation of siderite leads to goethite, and subsequently to hematite (Fe3+2O3) upon dehydration. We will discuss the photochemical reaction, which was once one of the most ubiquitous photochemical reactions before the rise of oxygen in the atmosphere. Photooxidation of siderite over time by UV light From left to right: UV oxidized siderite, pristine siderite, oxidized siderite by oxygen

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

    DEFF Research Database (Denmark)

    Klemensø, Trine; Mogensen, Mogens Bjerg

    2006-01-01

    , where the Ni component was removed, before, during and after redox cycling the cermet. The cermet conductivity degraded over time due to sintering of the nickel phase. Following oxidizing events, the conductivity of the cermets improved, whereas the conductivity of the YSZ phase decreased. A model...

  14. Experimental and Computational Analysis of the Solvent-Dependent O2/Li(+)-O2(-) Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium-Oxygen Batteries.

    Science.gov (United States)

    Kwabi, David G; Bryantsev, Vyacheslav S; Batcho, Thomas P; Itkis, Daniil M; Thompson, Carl V; Shao-Horn, Yang

    2016-02-24

    Understanding and controlling the kinetics of O2 reduction in the presence of Li(+)-containing aprotic solvents, to either Li(+)-O2(-) by one-electron reduction or Li2 O2 by two-electron reduction, is instrumental to enhance the discharge voltage and capacity of aprotic Li-O2 batteries. Standard potentials of O2 /Li(+)-O2(-) and O2/O2(-) were experimentally measured and computed using a mixed cluster-continuum model of ion solvation. Increasing combined solvation of Li(+) and O2(-) was found to lower the coupling of Li(+)-O2(-) and the difference between O2/Li(+)-O2(-) and O2/O2(-) potentials. The solvation energy of Li(+) trended with donor number (DN), and varied greater than that of O2 (-) ions, which correlated with acceptor number (AN), explaining a previously reported correlation between Li(+)-O2(-) solubility and DN. These results highlight the importance of the interplay between ion-solvent and ion-ion interactions for manipulating the energetics of intermediate species produced in aprotic metal-oxygen batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Effect of Humic Acid on As Redox Transformation and Kinetic Adsorption onto Iron Oxide Based Adsorbent (IBA

    Directory of Open Access Journals (Sweden)

    Hoda Fakour

    2014-10-01

    Full Text Available Due to the importance of adsorption kinetics and redox transformation of arsenic (As during the adsorption process, the present study elucidated natural organic matter (NOM effects on As adsorption-desorption kinetics and speciation transformation. The experimental procedures were conducted by examining interactions of arsenate and arsenite with different concentrations of humic acid (HA as a model representative of NOM, in the presence of iron oxide based adsorbent (IBA, as a model solid surface in three environmentally relevant conditions, including the simultaneous adsorption of both As and HA onto IBA, HA adsorption onto As-presorbed IBA, and As adsorption onto HA-presorbed IBA. Experimental adsorption-desorption data were all fitted by original and modified Lagergren pseudo-first and -second order adsorption kinetic models, respectively. Weber’s intraparticle diffusion was also used to gain insight into the mechanisms and rate controlling steps, which the results suggested that intraparticle diffusion of As species onto IBA is the main rate-controlling step. Different concentrations of HA mediated the redox transformation of As species, with a higher oxidation ability than reduction. The overall results indicated the significant effect of organic matter on the adsorption kinetics and redox transformation of As species, and consequently, the fate, transport and mobility of As in different environmentally relevant conditions.

  16. High surface area bio-waste based carbon as a superior electrode for vanadium redox flow battery

    Science.gov (United States)

    Maharjan, Makhan; Bhattarai, Arjun; Ulaganathan, Mani; Wai, Nyunt; Oo, Moe Ohnmar; Wang, Jing-Yuan; Lim, Tuti Mariana

    2017-09-01

    Activated carbon (AC) with high surface area (1901 m2 g-1) is synthesized from low cost bio-waste orange (Citrus sinensis) peel for vanadium redox flow battery (VRB). The composition, structure and electrochemical properties of orange peel derived AC (OP-AC) are characterized by elemental analyzer, field emission-scanning electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, cyclic voltammetry (CV), and electrochemical impedance spectroscopy. CV results show that OP-AC coated bipolar plate demonstrates improved electro-catalytic activity in both positive and negative side redox couples than the pristine bipolar plate electrode and this is ascribed to the high surface area of OP-AC which provides effective electrode area and better contact between the porous electrode and bipolar plate. Consequently, the performance of VRB in a static cell shows higher energy efficiency for OP-AC electrode than the pristine electrode at all current densities tested. The results suggest the OP-AC to be a promising electrode for VRB applications and can be incorporated into making conducting plastics electrode to lower the VRB cell stack weight and cost.

  17. Importance of the Reorganization Energy Barrier in Computational Design of Porphyrin-Based Solar Cells with Cobalt-Based Redox Mediators

    DEFF Research Database (Denmark)

    Ørnsø, Kristian Baruël; Jónsson, Elvar Örn; Jacobsen, Karsten Wedel

    2015-01-01

    The shift from iodide-based redox mediators in dye-sensitized solar cells toward octahedral cobalt complexes has led to a significant increase in the efficiency. However, due to the nature of this type of complexes the driving force required for the regeneration of the dye is very high...

  18. Endogenous hydrogen sulfide enhances salt tolerance by coupling the reestablishment of redox homeostasis and preventing salt-induced K⁺ loss in seedlings of Medicago sativa.

    Science.gov (United States)

    Lai, Diwen; Mao, Yu; Zhou, Heng; Li, Feng; Wu, Mingzhu; Zhang, Jing; He, Ziyi; Cui, Weiti; Xie, Yanjie

    2014-08-01

    Despite the external application of hydrogen sulfide (H2S) conferring plant tolerance against various environmental cues, the physiological significance of l-cysteine desulfhydrase (L-DES)-associated endogenous H2S production involved in salt-stress signaling was poorly understood. To address this gap, the participation of in planta changes of H2S homeostasis involved in alfalfa salt tolerance was investigated. The increasing concentration of NaCl (from 50 to 300 mM) progressively caused the induction of total l-DES activity and the increase of endogenous H2S production. NaCl-triggered toxicity symptoms (175 mM), including seedling growth inhibition and lipid peroxidation, were alleviated by sodium hydrosulfide (NaHS; 100 μM), a H2S donor, whereas aggravated by an inhibitor of l-DES or a H2S scavenger. A weaker or negative response was observed in lower or higher dose of NaHS. Further results showed that endogenous l-DES-related H2S modulated several genes/activities of antioxidant defence enzymes, and also regulated the contents of antioxidant compounds, thus counterbalancing the NaCl-induced lipid peroxidation. Moreover, H2S maintained K(+)/Na(+) homeostasis by preventing the NaCl-triggered K(+) efflux, which might be result form the impairment of SKOR expression. Together, our findings indicated that endogenous H2S homeostasis enhance salt tolerance by coupling the reestablishment of redox balance and restraining K(+) efflux in alfalfa seedlings. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  19. Behaviorally-based couple therapies reduce emotional arousal during couple conflict

    OpenAIRE

    Baucom, Brian R.; Sheng, Elisa; Christensen, Andrew; Georgiou, Panayiotis G.; Narayanan, Shrikanth S.; Atkins, David C.

    2015-01-01

    Emotional arousal during relationship conflict is a major target for intervention in couple therapies. The current study examines changes in conflict-related emotional arousal in 104 couples that participated in a randomized clinical trial of two behaviorally-based couple therapies. Emotional arousal is measured using mean fundamental frequency of spouse’s speech, and changes in emotional arousal from pre- to post-therapy are examined using multilevel models. Overall emotional arousal, the ra...

  20. Glass Based Electrodes for the Determination of Redox Potentials in Water Samples

    Directory of Open Access Journals (Sweden)

    Frank GERLACH

    2015-01-01

    Full Text Available The state of e.g. waste and process water depending on the particular application can be characterized by quantitative analysis of its composition (e.g. heavy metal ions, nitrate or phosphate but often, at least in a complementary manner, by determinating of non-specific parameters like electrolytic conductivity or redox potential. The latter is usually measured potentiometrically using indicator electrodes of precious metals. However, their application is connected with measurement errors caused by interactions between the media and the noble metal surfaces. Specifically this problem occurs in real media that can be found in process chemistry and in waste water sector, for example. Using electron conducting glass instead of noble metal membranes in potentiometric redox electrodes solves this problem. We present possibilities for their fabrication and results from their characterization and use.

  1. Outcomes of couples with infidelity in a community-based sample of couple therapy.

    Science.gov (United States)

    Atkins, David C; Marín, Rebeca A; Lo, Tracy T Y; Klann, Notker; Hahlweg, Kurt

    2010-04-01

    Infidelity is an often cited problem for couples seeking therapy, but the research literature to date is very limited on couple therapy outcomes when infidelity is a problem. The current study is a secondary analysis of a community-based sample of couple therapy in Germany and Austria. Outcomes for 145 couples who reported infidelity as a problem in their relationship were compared with 385 couples who sought therapy for other reasons. Analyses based on hierarchical linear modeling revealed that infidelity couples were significantly more distressed and reported more depressive symptoms at the start of therapy but continued improving through the end of therapy and to 6 months posttherapy. At the follow-up assessment, infidelity couples were not statistically distinguishable from non-infidelity couples, replicating previous research. Sexual dissatisfaction did not depend on infidelity status. Although there was substantial missing data, sensitivity analyses suggested that the primary findings were not due to missing data. The current findings based on a large community sample replicated previous work from an efficacy trial and show generally optimistic results for couples in which there has been an affair. 2010 APA, all rights reserved

  2. Polyoxovanadate-Alkoxide Clusters as a Redox Reservoir for Iron.

    Science.gov (United States)

    Li, Feng; Carpenter, Stephanie H; Higgins, Robert F; Hitt, Mark G; Brennessel, William W; Ferrier, Maryline G; Cary, Samantha K; Lezama-Pacheco, Juan S; Wright, Joshua T; Stein, Benjamin W; Shores, Matthew P; Neidig, Michael L; Kozimor, Stosh A; Matson, Ellen M

    2017-06-19

    Inspired by the multielectron redox chemistry achieved using conventional organic-based redox-active ligands, we have characterized a series of iron-functionalized polyoxovanadate-alkoxide clusters in which the metal oxide scaffold functions as a three-dimensional, electron-deficient metalloligand. Four heterometallic clusters were prepared through sequential reduction, demonstrating that the metal oxide scaffold is capable of storing up to four electrons. These reduced products were characterized by cyclic voltammetry, IR, electronic absorption, and (1)H NMR spectroscopies. Moreover, Mössbauer and X-ray absorption spectroscopies suggest that the redox events involve primarily the vanadium ions, while the iron atoms remained in the 3+ oxidation state throughout the redox series. In this sense, the vanadium portion of the cluster mimics a conventional organic-based redox-active ligand bound to an iron(III) ion. Magnetic coupling within the hexanuclear cluster was characterized using SQUID magnetometry. Overall, the results suggest extensive electronic delocalization between the metal centers of the cluster core. These results demonstrate the ability of electronically flexible, reducible metal oxide supports to function as redox-active reservoirs for transition-metal centers.

  3. Seniority-based coupled cluster theory

    CERN Document Server

    Henderson, Thomas M; Stein, Tamar; Scuseria, Gustavo E

    2014-01-01

    Doubly occupied configuration interaction (DOCI) with optimized orbitals often accurately describes strong correlations while working in a Hilbert space much smaller than that needed for full configuration interaction. However, the scaling of such calculations remains combinatorial with system size. Pair coupled cluster doubles (pCCD) is very successful in reproducing DOCI energetically, but can do so with low polynomial scaling ($N^3$, disregarding the two-electron integral transformation from atomic to molecular orbitals). We show here several examples illustrating the success of pCCD in reproducing both the DOCI energy and wave function, and show how this success frequently comes about. What DOCI and pCCD lack are an effective treatment of dynamic correlations, which we here add by including higher-seniority cluster amplitudes which are excluded from pCCD. This frozen pair coupled cluster approach is comparable in cost to traditional closed-shell coupled cluster methods with results that are competitive fo...

  4. Gay male couples' attitudes toward using couples-based voluntary HIV counseling and testing.

    Science.gov (United States)

    Mitchell, Jason W

    2014-01-01

    Many men who have sex with men acquire HIV from their primary male partners while in a relationship. Studies with gay couples have demonstrated that relationship characteristics and testing behaviors are important to examine for HIV prevention. Recently, couples-based voluntary HIV counseling and testing (CVCT) has become available to male couples throughout the U.S. However, HIV-negative couples' attitudes toward using CVCT and how their relationship characteristics may affect their use of CVCT remain largely unknown. This information is particularly relevant for organizations that offer CVCT. To assess couples' attitudes, and associated factors toward using CVCT, a cross-sectional study design was used with a novel Internet-based recruitment method to collect dyadic data from a national sample of 275 HIV-negative gay couples. Multivariate multilevel modeling was used to identify factors associated with differences between and within couples about their attitudes towards using CVCT. Findings revealed that couples were "somewhat" to "very likely" to use CVCT. More positive attitudes toward using CVCT were associated with couples who had higher levels of relationship satisfaction and commitment toward their sexual agreement and among those who had at least one partner having had sex outside of the relationship. Less positive attitude toward using CVCT was associated with couples who had higher levels of trust toward their partners being dependable. Differences within couples, including age between partners, whether sex had occurred outside of the relationship, and value toward a sexual agreement also affected their attitudes toward using CVCT. Providing additional testing methods may help HIV-negative gay couples better manage their HIV risk.

  5. Decreasing redox voltage of terephthalate-based electrode material for Li-ion battery using substituent effect

    Science.gov (United States)

    Lakraychi, A. E.; Dolhem, F.; Djedaïni-Pilard, F.; Thiam, A.; Frayret, C.; Becuwe, M.

    2017-08-01

    The preparation and assessment versus lithium of a functionalized terephthalate-based as a potential new negative electrode material for Li-ion battery is presented. Inspired from molecular modelling, a decrease in redox potential is achieved through the symmetrical adjunction of electron-donating fragments (-CH3) on the aromatic ring. While the electrochemical activity of this organic material was maximized when used as nanocomposite and without any binder, the potential is furthermore lowered by 110 mV upon functionalization, consistently with predicted value gained from DFT calculations.

  6. Elucidating the effect of copper as a redox additive and dopant on the performance of a PANI based supercapacitor.

    Science.gov (United States)

    Pandey, Kavita; Yadav, Pankaj; Mukhopadhyay, Indrajit

    2015-01-14

    In this article, the effect of copper (Cu) as a redox additive and dopant on the performance of a polyaniline (PANI) based supercapacitor was thoroughly investigated. The electrochemical properties of PANI in H2SO4 and in H2SO4 + CuSO4 and Cu doped PANI in H2SO4 were studied using cyclic voltammetry (CV) and impedance spectroscopy (IS). The CV result indicates that the capacity of PANI in H2SO4 was significantly improved with the introduction of Cu(2+) ions into the electrolyte, but it appeared unstable because of underpotential deposition of copper over the PANI surface and the relatively irreversible nature of the redox reaction. However, a stable and improved performance was obtained for Cu doped PANI due to the combined effect of an increase in conductivity and the surface modification of the PANI film. For Cu doped PANI, nearly ∼2.4 and ∼1.5 fold improved interfacial capacitance was achieved compared to that of PANI (H2SO4) and PANI (H2SO4 + CuSO4) respectively. The obtained Nyquist spectra for all the configurations were analysed using an equivalent circuit to understand the fundamentals of capacitive and resistive response of the supercapacitor. The IS measurements lead to direct determination of parameters like series resistance, rate capability of electrodes, ion diffusion phenomena and interfacial capacitance. The experimental results and their analysis will have significant impact on understanding the effect of dopants and redox additives on the performance of PANI based supercapacitors and also lay the basis for designing a supercapacitor with an appropriate electrode and electrolyte material for numerous industrial and consumer applications.

  7. Thiol-based redox regulation in sexual plant reproduction: new insights and perspectives

    Directory of Open Access Journals (Sweden)

    Jose A Traverso

    2013-11-01

    Full Text Available The success of sexual reproduction in plants involves (i the proper formation of the plant gametophytes (pollen and embryo sac containing the gametes, (ii the accomplishment of specific interactions between pollen grains and the stigma, which subsequently lead to (iii the fusion of the gametes and eventually to (iv the seed setting. Owing to the lack of mobility, plants have developed specific regulatory mechanisms to control all developmental events underlying the sexual plant reproduction according to environmental challenges. Over the last decade, redox regulation and signaling have come into sight as crucial mechanisms able to manage critical stages during sexual plant reproduction. This regulation involves a complex redox network which includes reactive oxygen species (ROS, reactive nitrogen species (RNS, glutathione and other classic buffer molecules or antioxidant proteins, and some thiol/disulphide-containing proteins belonging to the thioredoxin superfamily, like glutaredoxins (GRXs or thioredoxins (TRXs. These proteins participate as critical elements not only in the switch between the mitotic to the meiotic cycle but also at further developmental stages of microsporogenesis. They are also implicated in the regulation of pollen rejection as the result of self incompatibility. In addition, they display precise space-temporal patterns of expression and are present in specific localizations like the stigmatic papillae or the mature pollen, although their functions and subcellular localizations are not clear yet. In this review we summarize insights and perspectives about the presence of thiol/disulphide-containing proteins in plant reproduction, taking into account the general context of the cell redox network.

  8. Structure–Redox–Relaxivity Relationships for Redox Responsive Manganese-Based Magnetic Resonance Imaging Probes

    OpenAIRE

    Gale, Eric M.; Mukherjee, Shreya; Liu, Cynthia; Loving, Galen S.; Caravan., Peter

    2014-01-01

    A library of 10 Mn-containing complexes capable of switching reversibly between the Mn(II) and Mn(III) oxidation states was prepared and evaluated for potential usage as MRI reporters of tissue redox activity. We synthesized N-(2-hydroxybenzyl)-N,N′,N′-ethylenediaminetriacetic acid (HBET) and N-(2-hydroxybenzyl-N,N′,N′-trans-1,2-cyclohexylenediaminetriacetic acid (CyHBET) ligands functionalized (−H, −OMe, −NO2) at the 5-position of the aromatic ring. The Mn(II) complexes of all ligands and th...

  9. Review on synthesis of ferrocene-based redox polymers and derivatives and their application in glucose sensing.

    Science.gov (United States)

    Saleem, Muhammad; Yu, Haojie; Wang, Li; Zain-ul-Abdin; Khalid, Hamad; Akram, M; Abbasi, Nasir M; Huang, Jin

    2015-05-30

    The interest in glucose biosensors persisted over many years and persistent efforts have been made to develop long term stable glucose biosensors with precision, smart analytical performance, good linearity and resistance to communal interferences. In this regard, ferrocene-based polymers and derivatives (FBPDs) for the development of glucose biosensor (GBs) as redox mediators have acquired utmost attention of the scientists, especially in the second generation biosensors, as a large number of innovative molecules have been synthesized. Most of the FBPDs are considered as active components in the development of GBs, due to their ease of modification, biocompatibility, stability, large surface area, good electrical conductivity and especially excellent redox properties. This review provides a brief description of synthesis, analytical performance and glucose sensing application of ferrocene-based dendrimers, polythiophenes, polypyrroles, polyethylenimine, chitosan and carbon nano tubes (CNTs). Moreover, the analytical performance of ferrocene-based glucose biosensors (FBGBs) is summarized and the problems associated with the construction of GBs and the future trends are discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Seniority-based coupled cluster theory

    Energy Technology Data Exchange (ETDEWEB)

    Henderson, Thomas M.; Scuseria, Gustavo E. [Department of Chemistry, Rice University, Houston, Texas 77005-1892 (United States); Department of Physics and Astronomy, Rice University, Houston, Texas 77005-1892 (United States); Bulik, Ireneusz W.; Stein, Tamar [Department of Chemistry, Rice University, Houston, Texas 77005-1892 (United States)

    2014-12-28

    Doubly occupied configuration interaction (DOCI) with optimized orbitals often accurately describes strong correlations while working in a Hilbert space much smaller than that needed for full configuration interaction. However, the scaling of such calculations remains combinatorial with system size. Pair coupled cluster doubles (pCCD) is very successful in reproducing DOCI energetically, but can do so with low polynomial scaling (N{sup 3}, disregarding the two-electron integral transformation from atomic to molecular orbitals). We show here several examples illustrating the success of pCCD in reproducing both the DOCI energy and wave function and show how this success frequently comes about. What DOCI and pCCD lack are an effective treatment of dynamic correlations, which we here add by including higher-seniority cluster amplitudes which are excluded from pCCD. This frozen pair coupled cluster approach is comparable in cost to traditional closed-shell coupled cluster methods with results that are competitive for weakly correlated systems and often superior for the description of strongly correlated systems.

  11. 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.

  12. Critical coupling with graphene-based hyperbolic metamaterials.

    Science.gov (United States)

    Xiang, Yuanjiang; Dai, Xiaoyu; Guo, Jun; Zhang, Han; Wen, Shuangchun; Tang, Dingyuan

    2014-06-27

    In order to effectively realize and control the critical coupling, a graphene-based hyperbolic metamaterial has been proposed to replace the absorbing thin film in the critically coupled resonance structure. Our calculations demonstrate that the critical coupling effect (near-perfect light absorption) can be achieved at the near-infrared wavelength by using this layered structure, while the critical coupling frequency can be tuned by varying the Fermi energy level of graphene sheets via electrostatic biasing. Moreover, we show that the critical coupling frequency can be tuned by changing the thickness of the dielectric or layer number of the graphene sheets in the unit cell of the graphene-dielectric HMM. The optimization performance has also been indicated, which may offer an opportunity towards the experimental designs of high efficient graphene based critical coupling devices.

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

    Science.gov (United States)

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

    2018-01-24

    Electrochemical energy storage with redox flow batteries (RFBs) under subzero temperature is of great significance for utilizing renewable energy in cold regions. However, RFBs are generally utilized above 10 °C. Here we present non-aqueous organic RFBs which employed 5,10,15,20-tetraphenylporphyrin (H2TPP) as a bipolar redox-active material (anode: [H2TPP]2-/H2TPP, cathode: H2TPP/[H2TPP]2+ ) and a high ionic conductive Y-zeolite-polyvinylidene fluoride (Y-PVDF) ion-selective membrane as separator. The constructed RFBs exhibit a high volumetric capacity of 8.72 Ah/L with a high voltage of 2.83 V and an excellent cycling stability (capacity retention exceeding 99.98% per cycle) in temperature range of 20~-40 °C. Our work serves as principles for designing low-temperature working RFBs, offering a promising pathway for realizing electrochemical energy storage under cold-climate conditions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Mass Transfer in Amperometric Biosensors Based on Nanocomposite Thin Films of Redox Polymers and Oxidoreductases

    Directory of Open Access Journals (Sweden)

    Aleksandr L. Simonian

    2002-03-01

    Full Text Available Mass transfer in nanocomposite hydrogel thin films consisting of alternating layers of an organometallic redox polymer (RP and oxidoreductase enzymes was investigated. Multilayer nanostructures were fabricated on gold surfaces by the deposition of an anionic self-assembled monolayer of 11-mercaptoundecanoic acid, followed by the electrostatic binding of a cationic redox polymer, poly[vinylpyridine Os(bis-bipyridine2Clco-allylamine], and an anionic oxidoreductase. Surface plasmon resonance spectroscopy, Fourier transform infrared external reflection spectroscopy (FTIR-ERS, ellipsometry and electrochemistry were employed to characterize the assembly of these nanocomposite films. Simultaneous SPR/electrochemistry enabled real time observation of the assembly of sensing components, changes in film structure with electrode potential, and the immediate, in situ electrochemical verification of substrate-dependent current upon the addition of enzyme to the multilayer structure. SPR and FTIR-ERS studies also showed no desorption of polymer or enzyme from the nanocomposite structure when stored in aqueous environment occurred over the period of three weeks, suggesting that decreasing in substrate sensitivity were due to loss of enzymatic activity rather than loss of film compounds from the nanostructure.

  15. A non-invasive assay of the plastoquinone pool redox state based on the OJIP-transient.

    Science.gov (United States)

    Tóth, Szilvia Z; Schansker, Gert; Strasser, Reto J

    2007-01-01

    The plastoquinone (PQ) pool of the photosynthetic electron transport chain becomes reduced under anaerobic conditions. Here, anaerobiosis was used as a tool to manipulate the PQ-pool redox state in darkness and to study the effects of the PQ-redox state on the Chl-a fluorescence (OJIP) kinetics in pea leaves (Pisum sativum L.). It is shown that the F(J) (fluorescence intensity at 3 ms) is linearly related to the area above the OJ-phase (first 3 ms) representing the reduction of the acceptor side of photosystem II (PSII) and F(J) is also linearly related to the area above the JI-phase (3-30 ms) that parallels the reduction of the PQ-pool. This means that F(J) depends on the availability of oxidized PQ-molecules bound to the Q(B)-site. The linear relationships between F(J) and the two areas indicate that F(J) is not sensitive to energy transfer between PSII-antennae (connectivity). It is further shown that a approximately 94% reduced PQ-pool is in equilibrium with a approximately 19% reduction of Q(A) (primary quinone acceptor of PSII). The non-linear relationship between the initial fluorescence value (F(20 micros)) and the area above the OJ-phase supports the idea that F(20 mus )is sensitive to connectivity. This is reinforced by the observation that this non-linearity can be overcome by transforming the F(20 micros)-values into [Q(A) (-)]-values. Based on the F(J)-value of the OJIP-transient, a simple method for the quantification of the redox state of the PQ-pool is proposed.

  16. Behaviorally-based couple therapies reduce emotional arousal during couple conflict.

    Science.gov (United States)

    Baucom, Brian R; Sheng, Elisa; Christensen, Andrew; Georgiou, Panayiotis G; Narayanan, Shrikanth S; Atkins, David C

    2015-09-01

    Emotional arousal during relationship conflict is a major target for intervention in couple therapies. The current study examines changes in conflict-related emotional arousal in 104 couples that participated in a randomized clinical trial of two behaviorally-based couple therapies. Emotional arousal is measured using mean fundamental frequency of spouse's speech, and changes in emotional arousal from pre-to post-therapy are examined using multilevel models. Overall emotional arousal, the rate of increase in emotional arousal at the beginning of conflict, and the duration of emotional arousal declined for all couples. Reductions in overall arousal were stronger for TBCT wives than for IBCT wives but not significantly different for IBCT and TBCT husbands. Reductions in the rate of initial arousal were larger for TBCT couples than IBCT couples. Reductions in duration were larger for IBCT couples than TBCT couples. These findings suggest that both therapies can reduce emotional arousal, but that the two therapies create different kinds of change in emotional arousal. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Novel antitrypanosomal agents based on palladium nitrofurylthiosemicarbazone complexes: DNA and redox metabolism as potential therapeutic targets.

    Science.gov (United States)

    Otero, Lucía; Vieites, Marisol; Boiani, Lucía; Denicola, Ana; Rigol, Carolina; Opazo, Lucía; Olea-Azar, Claudio; Maya, Juan Diego; Morello, Antonio; Krauth-Siegel, R Luise; Piro, Oscar E; Castellano, Eduardo; González, Mercedes; Gambino, Dinorah; Cerecetto, Hugo

    2006-06-01

    In the search for new therapeutic tools against American Trypanosomiasis palladium complexes with bioactive nitrofuran-containing thiosemicarbazones as ligands were obtained. Sixteen novel palladium (II) complexes with the formulas [PdCl2(HL)] and [Pd(L)2] were synthesized, and the crystal structure of [Pd(5-nitrofuryl-3-acroleine thiosemicarbazone)2] x 3DMSO was solved by X-ray diffraction methods. Most complexes showed higher in vitro growth inhibition activity against Trypanosoma cruzi than the standard drug Nifurtimox. In most cases, the activity of the ligand was maintained or even increased as a result of palladium complexation. In addition, the complexes' mode of antitrypanosomal action was investigated. Although the complexes showed strong DNA binding, all data strongly suggest that the main trypanocidal mechanism of action is the production of oxidative stress as a result of their bioreduction and extensive redox cycling. Moreover, the complexes were found to be irreversible inhibitors of trypanothione reductase.

  18. Performance of non-compartmentalized enzymatic biofuel cell based on buckypaper cathode and ferrocene-containing redox polymer anode

    Science.gov (United States)

    Bunte, Christine; Hussein, Laith; Urban, Gerald A.

    2014-02-01

    Novel single compartment Glucose/O2 biofuel cells (BFCs) were developed using immobilized enzymes and the mediated electron transfer (MET) approach. The bioanode was prepared through a ferrocene-containing redox polymer crosslinked in the presence of a biocatalyst on a glassy carbon support. Here, the redox polymer can physically entrap the enzyme and prevent it from leaching. Additionally it provides a biocompatible microenvironment and thus could extend the life time of enzyme. On the other side, the mediated biocathode was prepared based on bilirubin oxidase and 2,2‧-azinobis(3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS2-) system which has been physically entrapped in Nafion matrix and then adsorbed directly on a highly porous, conductive and functionalized buckypaper (fBP). Both electrodes were characterized physically and electrochemically. Employing these electrodes, the resulting BFC generates an open circuit voltage (Voc) of approximately 0.550 V and a peak power density of 26 μW cm-2 at 0.2 V at 37 °C in quiescent O2-saturated physiological buffer containing 5 mM glucose. The cell sustains a load up to 225 μA cm-2. Moreover, a high short circuit current (Isc) of 300 μA cm-2 is approached. This BFC can operate in mild conditions without using any toxic materials which makes it attractive for implantable devices.

  19. Thiol-based redox signaling in the nitrogen-fixing symbiosis

    Directory of Open Access Journals (Sweden)

    Pierre eFrendo

    2013-09-01

    Full Text Available In nitrogen poor soils legumes establish a symbiotic interaction with rhizobia that results in the formation of root nodules. These are unique plant organs where bacteria differentiate into bacteroids, which express the nitrogenase enzyme complex that reduces atmospheric N2 to ammonia. Nodule metabolism requires a tight control of the concentrations of reactive oxygen and nitrogen species (RONS so that they can perform useful signaling roles while avoiding nitro-oxidative damage. In nodules a thiol-dependent regulatory network that senses, transmits and responds to redox changes is starting to be elucidated. A combination of enzymatic, immunological, pharmacological and molecular analyses has allowed to conclude that glutathione and its legume-specific homolog, homoglutathione, are abundant in meristematic and infected cells, their spatio-temporally distribution is correlated with the corresponding (homoglutathione synthetase activities, and are crucial for nodule development and function. Glutathione is at high concentrations in the bacteroids and at moderate amounts in the mitochondria, cytosol and nuclei. Less information is available on other components of the network. The expression of multiple isoforms of glutathione peroxidases, peroxiredoxins, thioredoxins, glutaredoxins and NADPH-thioredoxin reductases has been detected in nodule cells using antibodies and proteomics. Peroxiredoxins and thioredoxins are essential to regulate and in some cases to detoxify RONS in nodules. Further research is necessary to clarify the regulation of the expression and activity of thiol redox-active proteins in response to abiotic, biotic and developmental cues, their interactions with downstream targets by disulfide-exchange reactions, and their participation in signaling cascades. The availability of mutants and transgenic lines will be crucial to facilitate systematic investigations into the function of the various proteins in the legume

  20. 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.

  1. Fluorescence spectroscopy of roGFP2-based redox probes responding to various physiologically relevant oxidant species in vitro

    Directory of Open Access Journals (Sweden)

    Alexandra Müller

    2017-04-01

    Full Text Available This article contains representative fluorescence excitation spectra of roGFP2-based probes used for ratiometric analysis of redox changes as presented in the article "Systematic in vitro assessment of responses of roGFP2-based probes to physiologically relevant oxidant species" [1]. The recombinant probes roGFP2, roGFP2-Orp1, and Grx1-roGFP2 were exposed to various oxidative and nitrosative species, including hydrogen peroxide (H2O2, aldrithiol-2 (AT-2, glutathione disulfide (GSSG, hypochlorous acid (HOCl, S-nitrosoglutathione (GSNO, peroxynitrite (ONOO−, potassium polysulfide (K2Sx, spermine NONOate (SperNO, and diethyl amino NONOate (DeaNO at different molar ratios. Fluorescence excitation spectra of the probes were recorded in the excitation wavelength range between 350 and 500 nm and for a total of 60 min. Analysis and interpretation of the data is presented in an associated article [1].

  2. An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials

    Science.gov (United States)

    Janoschka, Tobias; Martin, Norbert; Martin, Udo; Friebe, Christian; Morgenstern, Sabine; Hiller, Hannes; Hager, Martin D.; Schubert, Ulrich S.

    2015-11-01

    For renewable energy sources such as solar, wind, and hydroelectric to be effectively used in the grid of the future, flexible and scalable energy-storage solutions are necessary to mitigate output fluctuations. Redox-flow batteries (RFBs) were first built in the 1940s and are considered a promising large-scale energy-storage technology. A limited number of redox-active materials--mainly metal salts, corrosive halogens, and low-molar-mass organic compounds--have been investigated as active materials, and only a few membrane materials, such as Nafion, have been considered for RFBs. However, for systems that are intended for both domestic and large-scale use, safety and cost must be taken into account as well as energy density and capacity, particularly regarding long-term access to metal resources, which places limits on the lithium-ion-based and vanadium-based RFB development. Here we describe an affordable, safe, and scalable battery system, which uses organic polymers as the charge-storage material in combination with inexpensive dialysis membranes, which separate the anode and the cathode by the retention of the non-metallic, active (macro-molecular) species, and an aqueous sodium chloride solution as the electrolyte. This water- and polymer-based RFB has an energy density of 10 watt hours per litre, current densities of up to 100 milliamperes per square centimetre, and stable long-term cycling capability. The polymer-based RFB we present uses an environmentally benign sodium chloride solution and cheap, commercially available filter membranes instead of highly corrosive acid electrolytes and expensive membrane materials.

  3. Synchrotron-based redox behavior of chromium during weathering of ultramafic rocks in New-Caledonia

    Science.gov (United States)

    Juillot, Dr.; Fandeur, Dr.; Fritsch, Dr.; Morin, Dr.; Olivi, Dr.; Webb, Dr.; Hazemann, Dr.; Ambrosi, Dr.; Brown, Jr., Dr.

    2009-04-01

    In New-Caledonia, deep weathering of ultramafic rocks (peridotites) has lead to the development of thick lateritic regoliths where Ni, Cr, Co and Mn can exhibit concentration up to several wt%. Such a large occurrence of these potentially toxic elements can represent serious risks for the environmental quality of this ‘' biodiversity hotspot'' and actual risk assessment relies on our capacity at characterizing the natural cycling of these elements. The present study reports the results of a detailed XANES analysis on the redox chemistry of Cr along a 64 meters depth lateritic regolith developed in the ultramafic rocks of the Koniambo outcrops located on the western coast of New Caledonia. In a first step, bulk XAS data at both the Cr and Mn K-edges have been used to evidence a remarkable correlation between the occurrence of Mn(III,IV)-oxides (mainly asbolane) and that of Cr(VI), at the scale of the studied regolith (Fandeur et al., 2009a). Since Cr mainly occurs as Cr(III)-bearing silicates in the ultramafic bedrock, such a correlation strongly suggests an oxidation of the fraction of Cr(III) released upon the weathering of these silicates to Cr(VI) by the Mn(III,IV)-oxides, as already demonstrated in laboratory studies (Oze et al., 2008). In a second step, µ-XANES mapping of the Cr redox at the boundary between Mn(III,IV)-oxides and Fe(III)-oxyhydroxides (mainly goethite) allowed to depict the actual behavior of Cr(VI) after oxidation. Results indicate an association of Cr(VI) with both Mn-oxides and Fe-oxyhydroxides which suggests that, after oxidation of Cr(III) to Cr(VI) by the Mn(III,IV)-oxides, part of oxidized chromium is desorbed from these Mn-oxides and transported to the surrounding Fe-oxyhydroxides where it accumulates through sorption reactions (Fandeur et al., 2009b). Such a redox-sorption pathway has been confirmed by reacting aqueous Cr(III) with birnessite alone or with a mixture of birnessite and goethite during time-resolved laboratory

  4. Redox control of ferrocene-based complexes with systematically extended π-conjugated connectors: switchable and tailorable second order nonlinear optics.

    Science.gov (United States)

    Wang, Wen-Yong; Ma, Na-Na; Sun, Shi-Ling; Qiu, Yong-Qing

    2014-03-14

    The studies of geometrical structures, thermal stabilities, redox properties, nonlinear responses and optoelectronic properties have been carried out on a series of novel ferrocenyl (Fc) chromophores with the view of assessing their switchable and tailorable second order nonlinear optics (NLO). The use of a constant Fc donor and a 4,4'-bipyridinium acceptor and varied conjugated bridges makes it possible to systematically determine the contribution of organic connectors to chromophore nonlinear optical activities. The structures reveal that both the reduction reactions and organic connectors have a significant influence on 4,4'-bipyridinium. The potential energy surface maps along with plots of reduced density gradient mirror the thermal stabilities of the Fc-based chromophores. The first and second reductions take place preferentially at the 4,4'-bipyridinium moieties. Significantly, the reduction processes result in the molecular switches with large NLO contrast varying from zero or very small to a large value. Moreover, time-dependent density functional theory results indicate that the absorption peaks are mainly attributed to Fc to 4,4'-bipyridinium charge transfer and the mixture of intramolecular charge transfer within the two respective 4,4'-bipyridinium moieties coupled with interlayer charge transfer between the two 4,4'-bipyridinium moieties. This provides us with comprehensive information on the effect of organic connectors on the NLO properties.

  5. Advanced oxidation process based on the Cr(III)/Cr(VI) redox cycle.

    Science.gov (United States)

    Bokare, Alok D; Choi, Wonyong

    2011-11-01

    Oxidative degradation of aqueous organic pollutants, using 4-chlorophenol (4-CP) as a main model substrate, was achieved with the concurrent H(2)O(2)-mediated transformation of Cr(III) to Cr(VI). The Fenton-like oxidation of 4-CP is initiated by the reaction between the aquo-complex of Cr(III) and H(2)O(2), which generates HO(•) along with the stepwise oxidation of Cr(III) to Cr(VI). The Cr(III)/H(2)O(2) system is inactive in acidic condition, but exhibits maximum oxidative capacity at neutral and near-alkaline pH. Since we previously reported that Cr(VI) can also activate H(2)O(2) to efficiently generate HO(•), the dual role of H(2)O(2) as an oxidant of Cr(III) and a reductant of Cr(VI) can be utilized to establish a redox cycle of Cr(III)-Cr(VI)-Cr(III). As a result, HO(•) can be generated using both Cr(III)/H(2)O(2) and Cr(VI)/H(2)O(2) reactions, either concurrently or sequentially. The formation of HO(•) was confirmed by monitoring the production of p-hydroxybenzoic acid from [benzoic acid + HO(•)] as a probe reaction and by quenching the degradation of 4-CP in the presence of methanol as a HO(•) scavenger. The oxidation rate of 4-CP in the Cr(III)/H(2)O(2) solution was highly influenced by pH, which is ascribed to the hydrolysis of Cr(III)(H(2)O)(n) into Cr(III)(H(2)O)(n-m)(OH)(m) and the subsequent condensation to oligomers. The present study proposes that the Cr(III)/H(2)O(2) combined with Cr(VI)/H(2)O(2) process is a viable advanced oxidation process that operates over a wide pH range using the reusable redox cycle of Cr(III) and Cr(VI).

  6. Solvent Effects on the Electrochemical Behavior of TAPD-Based Redox-Responsive Probes for Cadmium(II

    Directory of Open Access Journals (Sweden)

    Rihab Sahli

    2014-01-01

    Full Text Available Two tetralkylated phenylenediamines (TAPD 1 and 2 have been prepared by reductive alkylation of para-dimethylaminoaniline with furfural or thiophene 2-carboxaldehyde, respectively. Their chelation ability has been evaluated as electrochemical guest-responsive chemosensors for Cd(II in acetonitrile (ACN, dimethylformamide (DMF, propylene carbonate (PC, and nitromethane (NM. The voltamperometric studies showed that these compounds are able to bind the Cd(II cation with strong affinities except in DMF. The redox features of the chemosensors changed drastically when they are bounded to Cd(II to undergo important anodic potential peak shifts comprised between ca. 500 and ca. 900 mV depending on the solvent. The addition of ∼4–10% molar triflic acid (TfOH was found to be necessary to achieve rapidly the cation chelation which is slow without the acid. The electrochemical investigations suggested the formation of 1 : 2 stoichiometry complexes [Cd(L2]2+. The results are discussed in terms of solvent effects as a competitive electron donating ligand to the cation. The reaction coupling efficiency (RCE values were determined and were also found to be solvent-dependent.

  7. Crystal Structure of Green Fluorescent Protein Clover and Design of Clover-Based Redox Sensors.

    Science.gov (United States)

    Campbell, Benjamin C; Petsko, Gregory A; Liu, Ce Feng

    2017-12-27

    We have determined the crystal structure of Clover, one of the brightest fluorescent proteins, and found that its T203H/S65G mutations relative to wild-type GFP lock the critical E222 side chain in a fixed configuration that mimics the major conformer of that in EGFP. The resulting equilibrium shift to the predominantly deprotonated chromophore increases the extinction coefficient (EC), opposes photoactivation, and is responsible for the bathochromic shift. Clover's brightness can further be attributed to a π-π stacking interaction between H203 and the chromophore. Consistent with these observations, the Clover G65S mutant reversed the equilibrium shift, dramatically decreased the EC, and made Clover photoactivatable under conditions that activated photoactivatable GFP. Using the Clover structure, we rationally engineered a non-photoactivatable redox sensor, roClover1, and determined its structure as well as that of its parental template, roClover0.1. These high-resolution structures provide deeper insights into structure-function relationships in GFPs and may aid the development of excitation-improved ratiometric biosensors. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Redox balance in elite female athletes: differences based on sport types.

    Science.gov (United States)

    Arsic, Aleksandra; Vucic, Vesna; Glibetic, Marija; Popovic, Tamara; Debeljak-Martacic, Jasmina; Cubrilo, Dejan; Ahmetovic, Zlatko; Peric, Dusan; Borozan, Suncica; Djuric, Dragan; Barudzic, Nevena; Jakovljevic, Vladimir

    2016-01-01

    The aim of the present study was to analyze changes in redox balance throughout parameters of oxidative stress and activities of antioxidant enzymes in elite female water polo (N.=15) and football players (N.=19) aged between 20 and 23. Fourteen age-matched sedentary women were also included in the study. Blood sampling was performed to measure levels of lipid peroxidation (MDA), total antioxidant status (TAS), superoxide anion radical (O2-), hydrogen peroxide (H2O2), reduced glutathione (GSH), oxidized glutathione (GSSG), nitrites, superoxide dismutase activity (SOD), catalase activity (CAT) and glutathione-peroxidase activity (GPx). Levels of MDA, TAS, GSSG and H2O2 were significantly higher in athletes than in the control women. Football players had higher levels of O2- than the other two groups. Activity of SOD was higher in water polo players when compared with the football and control groups, CAT was increased in all athletes, while GPx did not differ among groups. Therefore, prolonged intensive training markedly increases oxidative stress in women, which depends on the type of sport. Lower concentration of O2- and increased activity of SOD in water polo players compared to football players suggest that mechanisms of adaptation of antioxidative defense are related to the type of exercise.

  9. n-Dopants Based on Dimers of Benzimidazoline Radicals: Structures and Mechanism of Redox Reactions

    KAUST Repository

    Zhang, Siyuan

    2015-06-18

    Dimers of 2-substituted N,N\\'-dimethylbenzimidazoline radicals, (2-Y-DMBI)2 (Y=cyclohexyl (Cyc), ferrocenyl (Fc), ruthenocenyl (Rc)), have recently been reported as n-dopants for organic semiconductors. Here their structural and energetic characteristics are reported, along with the mechanisms by which they react with acceptors, A (PCBM, TIPS-pentacene), in solution. X-ray data and DFT calculations both indicate a longer C-C bond for (2-Cyc-DMBI)2 than (2-Fc-DMBI)2, yet DFT and ESR data show that the latter dissociates more readily due to stabilization of the radical by Fc. Depending on the energetics of dimer (D2) dissociation and of D2-to-A electron transfer, D2 reacts with A to form D+ and A- by either of two mechanisms, differing in whether the first step is endergonic dissociation or endergonic electron transfer. However, the D+/0.5D2 redox potentials-the effective reducing strengths of the dimers-vary little within the series (ca. -1.9V vs. FeCp2+/0) (Cp=cyclopentadienyl) due to cancelation of trends in the D+/0 potential and D2 dissociation energy. The implications of these findings for use of these dimers as n-dopants, and for future dopant design, are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Innovative model-based flow rate optimization for vanadium redox flow batteries

    Science.gov (United States)

    König, S.; Suriyah, M. R.; Leibfried, T.

    2016-11-01

    In this paper, an innovative approach is presented to optimize the flow rate of a 6-kW vanadium redox flow battery with realistic stack dimensions. Efficiency is derived using a multi-physics battery model and a newly proposed instantaneous efficiency determination technique. An optimization algorithm is applied to identify optimal flow rates for operation points defined by state-of-charge (SoC) and current. The proposed method is evaluated against the conventional approach of applying Faraday's first law of electrolysis, scaled to the so-called flow factor. To make a fair comparison, the flow factor is also optimized by simulating cycles with different charging/discharging currents. It is shown through the obtained results that the efficiency is increased by up to 1.2% points; in addition, discharge capacity is also increased by up to 1.0 kWh or 5.4%. Detailed loss analysis is carried out for the cycles with maximum and minimum charging/discharging currents. It is shown that the proposed method minimizes the sum of losses caused by concentration over-potential, pumping and diffusion. Furthermore, for the deployed Nafion 115 membrane, it is observed that diffusion losses increase with stack SoC. Therefore, to decrease stack SoC and lower diffusion losses, a higher flow rate during charging than during discharging is reasonable.

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

    OpenAIRE

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

    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...

  12. Liquid Redox Electrolytes for Dye-Sensitized Solar Cells

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Ze

    2012-07-01

    This thesis focuses on liquid redox electrolytes in dye-sensitized solar cells (DSCs). A liquid redox electrolyte, as one of the key constituents in DSCs, typically consists of a redox mediator, additives and a solvent. This thesis work concerns all these three aspects of liquid electrolytes, aiming through fundamental insights to enhance the photovoltaic performances of liquid DSCs. Initial attention has been paid to the iodine concentration effects in ionic liquid (IL)-based electrolytes. It has been revealed that the higher iodine concentration required in IL-based electrolytes can be attributed to both triiodide mobility associated with the high viscosity of the IL, and chemical availability of triiodide. The concept of incompletely solvated ionic liquids (ISILs) has been introduced as a new type of electrolyte solvent for DSCs. It has been found that the photovoltaic performance of ISIL-based electrolytes can even rival that of organic solvent-based electrolytes. And most strikingly, ISIL-based electrolytes provide highly stable DSC devices under light-soaking conditions, as a result of the substantially lower vapor pressure of the ISIL system. A significant synergistic effect has been observed when both guanidinium thiocyanate and N-methylbenzimidazole are employed together in an IL-based electrolyte, exhibiting an optimal overall conversion efficiency. Tetrathiafulvalene (TTF) has been investigated as an organic iodine-free redox couple in electrolytes for DSCs. An unexpected worse performance has been observed for the TTF system, albeit it possesses a particularly attractive positive redox potential. An organic, iodine-free thiolate/disulfide system has also been adopted as a redox couple in electrolytes for organic DSCs. An impressive efficiency of 6.0 % has successfully been achieved by using this thiolate/disulfide redox couple in combination with a poly (3, 4-ethylenedioxythiophene) (PEDOT) counter electrode material under full sunlight illumination (AM

  13. Targetting redox polymers as mediators for laccase oxygen reduction in a membrane-less biofuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Barriere, Frederic [Universite de Rennes I, Institut de Chimie, UMR CNRS 6510, 35042 Rennes (France); Ferry, Yvonne; Leech, Donal [Department of Chemistry, National University of Ireland, Galway (Ireland); Rochefort, Dominic [Departement de Chimie, Universite de Montreal, C.P. 6128, Succursale Centre-ville, Montreal, Que. (Canada)

    2004-03-01

    Electrodes modified with co-immobilized redox enzymes and redox polymers can be used to form membrane-less biofuel cells. In this communication, we report on our initial studies of a membrane-less biofuel cell concept using an osmium-based redox polymer for laccase-mediated reduction of oxygen coupled to glucose oxidase-mediated oxidation of glucose. We then present a thermodynamic examination of mediators of laccase oxygen reduction, and stemming from this, target two redox polymers of potential use, an osmium-based redox polymer (E{sup 0'}+0.40 V vs. Ag/AgCl) and a ruthenium-based redox polymer (E{sup 0'}+0.63 V vs. Ag/AgCl). The former shows promise for use in membrane-less biofuel cell cathodes, whilst the latter's redox potential is too high to be an effective mediator of oxygen reduction by the Trametes versicolor laccase used in this study.

  14. Highly Swellable, Dual-Responsive Hydrogels Based on PNIPAM and Redox Active Poly(ferrocenylsilane) Poly(ionic liquid)s: Synthesis, Structure, and Properties

    NARCIS (Netherlands)

    Feng, Xueling; Zhang, Kaihuan; Chen, Peng; Sui, Xiaofeng; Hempenius, Mark A.; Liedberg, Bo; Vancso, Gyula J.

    2016-01-01

    Highly swellable, dual-responsive hydrogels, consisting of thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) and redox-responsive poly(ferrocenylsilane) (PFS) based poly(ionic liquid)s (PILs) are formed by photo-polymerization. PFS chains bearing cross-linkable vinylimidazolium (VIm) side

  15. Highly Swellable, Dual-Responsive Hydrogels Based on PNIPAM and Redox Active Poly(ferrocenylsilane) Poly(ionic liquid)s : Synthesis, Structure, and Properties

    NARCIS (Netherlands)

    Feng, Xueling; Zhang, Kaihuan; Chen, Peng; Sui, Xiaofeng; Hempenius, Mark A.; Liedberg, Bo; Vancso, Gyula J.

    2016-01-01

    Highly swellable, dual-responsive hydrogels, consisting of thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) and redox-responsive poly(ferrocenylsilane) (PFS) based poly(ionic liquid)s (PILs) are formed by photo-polymerization. PFS chains bearing cross-linkable vinylimidazolium (VIm) side

  16. Analysis of coupled resonator optical waveguide gyroscope based on periodically modulated coupling and circumferences

    Science.gov (United States)

    Huang, Jie; Zhang, Hailiang; Yang, Junbo; Zhang, Jingjing; Wu, Wenjun; Chang, Shengli

    2016-12-01

    Based on periodically modulated coupling and circumferences, we developed a new structure for coupled resonator optical waveguide (CROW) gyroscopes. Its sensitivity and resolution were significantly improved. With our new structure, which overcomes the individual limitations of the previous schemes, the sensitivity and resolution of our gyroscope are higher than those with coupling-coefficient modulation alone and circumference modulation alone. The resolution of the gyroscope gradually declines with increasing resonator propagation loss; when the quality factor Q ≤ 2 ×106 , the height of the center resonance peak of the transmission band decreases by more than 90%. Fortunately, this effect can be weakened by increasing the circumference difference. We also numerically analyzed the influence of manufacturing errors on the performance of the gyroscope. We found that the fluctuations of radius have a greater influence than the fluctuations of quality factor.

  17. Management of the infertile couple: an evidence-based protocol

    Directory of Open Access Journals (Sweden)

    Kamel Remah M

    2010-03-01

    Full Text Available Abstract Background Infertility is defined as inability of a couple to conceive naturally after one year of regular unprotected sexual intercourse. It remains a major clinical and social problem, affecting perhaps one couple in six. Evaluation usually starts after 12 months; however it may be indicated earlier. The most common causes of infertility are: male factor such as sperm abnormalities, female factor such as ovulation dysfunction and tubal pathology, combined male and female factors and unexplained infertility. Objectives The aim of this study is to provide the healthcare professionals an evidence-based management protocol for infertile couples away from medical information overload. Methods A comprehensive review where the literature was searched for "Management of infertility and/or infertile couples" at library website of University of Bristol (MetaLib by using a cross-search of different medical databases besides the relevant printed medical journals and periodicals. Guidelines and recommendations were retrieved from the best evidence reviews such as that from the American College of Obstetricians and Gynaecologists (ACOG, American Society for Reproductive Medicine (ASRM, Canadian Fertility and Andrology Society (CFAS, and Royal College of Obstetricians and Gynaecologists (RCOG. Results A simple guide for the clinicians to manage the infertile couples. Conclusions The study deploys a new strategy to translate the research findings and evidence-base recommendations into a simplified focused guide to be applied on routine daily practice. It is an approach to disseminate the recommended medical care for infertile couple to the practicing clinicians.

  18. Energy transducing redox steps of the Na+-pumping NADH:quinone oxidoreductase from Vibrio cholerae.

    Science.gov (United States)

    Juárez, Oscar; Morgan, Joel E; Nilges, Mark J; Barquera, Blanca

    2010-07-13

    Na(+)-NQR is a unique respiratory enzyme that couples the free energy of electron transfer reactions to electrogenic pumping of sodium across the cell membrane. This enzyme is found in many marine and pathogenic bacteria where it plays an analogous role to the H(+)-pumping complex I. It has generally been assumed that the sodium pump of Na(+)-NQR operates on the basis of thermodynamic coupling between reduction of a single redox cofactor and the binding of sodium at a nearby site. In this study, we have defined the coupling to sodium translocation of individual steps in the redox reaction of Na(+)-NQR. Sodium uptake takes place in the reaction step in which an electron moves from the 2Fe-2S center to FMN(C), while the translocation of sodium across the membrane dielectric (and probably its release into the external medium) occurs when an electron moves from FMN(B) to riboflavin. This argues against a single-site coupling model because the redox steps that drive these two parts of the sodium pumping process do not have any redox cofactor in common. The significance of these results for the mechanism of coupling is discussed, and we proposed that Na(+)-NQR operates through a novel mechanism based on kinetic coupling, mediated by conformational changes.

  19. Redox specificity of 2-hydroxyacid-coupled NAD(+/NADH dehydrogenases: a study exploiting "reactive" arginine as a reporter of protein electrostatics.

    Directory of Open Access Journals (Sweden)

    Pooja Gupta

    Full Text Available With "reactive" arginine as a kinetic reporter, 2-hydroxyacid dehydrogenases are assessed in basis of their specialization as NAD(+-reducing or NADH-oxidizing enzymes. Specifically, M4 and H4 lactate dehydrogenases (LDHs and cytoplasmic and mitochondrial malate dehydrogenases (MDHs are compared to assess if their coenzyme specificity may involve electrostatics of cationic or neutral nicotinamide structure as the basis. The enzymes from diverse eukaryote and prokaryote sources thus are assessed in "reactivity" of functionally-critical arginine as a function of salt concentration and pH. Electrostatic calculations were performed on "reactive" arginines and found good correspondence with experiment. The reductive and oxidative LDHs and MDHs are assessed in their count over ionizable residues and in placement details of the residues in their structures as proteins. The variants found to be high or low in ΔpKa of "reactive" arginine are found to be also strong or weak cations that preferentially oxidize NADH (neutral nicotinamide structure or reduce NAD(+ (cationic nicotinamide structure. The ionized groups of protein structure may thus be important to redox specificity of the enzyme on basis of electrostatic preference for the oxidized (cationic nicotinamide or reduced (neutral nicotinamide coenzyme. Detailed comparisons of isozymes establish that the residues contributing in their redox specificity are scrambled in structure of the reductive enzyme.

  20. Redox Specificity of 2-Hydroxyacid-Coupled NAD+/NADH Dehydrogenases: A Study Exploiting “Reactive” Arginine as a Reporter of Protein Electrostatics

    Science.gov (United States)

    Durani, Susheel

    2013-01-01

    With “reactive” arginine as a kinetic reporter, 2-hydroxyacid dehydrogenases are assessed in basis of their specialization as NAD+-reducing or NADH-oxidizing enzymes. Specifically, M4 and H4 lactate dehydrogenases (LDHs) and cytoplasmic and mitochondrial malate dehydrogenases (MDHs) are compared to assess if their coenzyme specificity may involve electrostatics of cationic or neutral nicotinamide structure as the basis. The enzymes from diverse eukaryote and prokaryote sources thus are assessed in “reactivity” of functionally-critical arginine as a function of salt concentration and pH. Electrostatic calculations were performed on “reactive” arginines and found good correspondence with experiment. The reductive and oxidative LDHs and MDHs are assessed in their count over ionizable residues and in placement details of the residues in their structures as proteins. The variants found to be high or low in ΔpKa of “reactive” arginine are found to be also strong or weak cations that preferentially oxidize NADH (neutral nicotinamide structure) or reduce NAD+ (cationic nicotinamide structure). The ionized groups of protein structure may thus be important to redox specificity of the enzyme on basis of electrostatic preference for the oxidized (cationic nicotinamide) or reduced (neutral nicotinamide) coenzyme. Detailed comparisons of isozymes establish that the residues contributing in their redox specificity are scrambled in structure of the reductive enzyme. PMID:24391777

  1. Lattice-Modulated Phase Transition Coupled with Redox-Isomeric Interconversion of o-Semiquinone-Catecholato into Bis(o-semiquinonato) Cobalt Complexes.

    Science.gov (United States)

    Bubnov, Michael P; Skorodumova, Nina A; Arapova, Alla V; Smirnova, Natalia N; Samsonov, Maxim A; Fukin, Georgy K; Cherkasov, Vladimir K; Abakumov, Gleb A

    2015-08-17

    Two redox-isomeric (valence tautomeric) complexes (2,2'-bpy)Co(3,6-DBSQ)2 (1) and (1,10-phen)Co(3,6-DBSQ)2 (2) (where 2,2'-bpy = 2,2'-dipyridine; 1,10-phen = 1,10-phenanthroline; 3,6-DBSQ = 3,6-di-tert-butyl-benzosemiquinone-1,2) reveal phase transitions that accompany redox-isomeric interconversions of semiquinone-catecholato isomer into a bis-(semiquinonato) one. Phase transitions differ one from another by thermodynamic parameters (transition temperature and interval, enthalpy, and entropy). Complexes 1 and 2 have the same crystal system and space group, and they form solid solutions with any molar ratio. The number of solid solutions with the molar ratios of 2:1, 1:1, 1:2, 1:4, 1:8, and 1:16 of 1 per 2, respectively, were obtained. Product with 1:1 ratio was studied by precise calorimetry, by variable-temperature magnetic susceptibility, and by X-ray structural analysis. All solid solutions were investigated by means of differential scanning calorimetry. Each solid solution possesses phase transition whose parameters depend on its composition. Transition temperature and enthalpy gradually grow with increasing of molar fraction of 1. The diagram "enthalpy-composition" is linear, whereas phase diagram "transition temperature-composition" is the bent-up arc.

  2. 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...

  3. Monitoring Dynamic Cellular Redox Homeostasis Using Fluorescence-Switchable Graphene Quantum Dots.

    Science.gov (United States)

    Li, Nan; Than, Aung; Sun, Chencheng; Tian, Jingqi; Chen, Jie; Pu, Kanyi; Dong, Xiaochen; Chen, Peng

    2016-12-27

    Monitoring cellular redox homeostasis is critical to the understanding of many physiological functions ranging from immune reactions to metabolism, as well as to the understanding of pathological development ranging from tumorigenesis to aging. Nevertheless, there is currently a lack of appropriate probes for this ambition, which should be reversibly, sensitively, and promptly responsive to a wide range of physiological oxidants and reductants. In this work, a redox-sensitive fluorescence-switchable probe is designed based on graphene quantum dots (GQDs) functionalized with a chelated redox Fe2+/Fe3+ couple. The underlying mechanism is investigated and discussed. The high sensitivity and fast response are attributable to the fact that the GQD's photoluminescence is highly sensitive to photon-induced electron transfer because of its ultrasmall size and associated prominent quantum confinement effect. Also taking advantages of GQDs' excellent photostability, biocompatibility, and readiness for cell uptake, our reversibly tunable fluorescence probe is employed to monitor in real time the triggered dynamic change of the intracellular redox state. This addition to the limited arsenal of available redox probes shall be useful to the still poorly understood redox biology, as well as for monitoring environment or chemical processes involving redox reactions.

  4. Chemiluminescence assay for quinones based on generation of reactive oxygen species through the redox cycle of quinone.

    Science.gov (United States)

    Kishikawa, Naoya; Ohkubo, Nobuhiro; Ohyama, Kaname; Nakashima, Kenichiro; Kuroda, Naotaka

    2009-02-01

    A sensitive and selective chemiluminescence assay for the determination of quinones was developed. The method was based on generation of reactive oxygen species through the redox reaction between quinone and dithiothreitol as reductant, and then the generated reactive oxygen was detected by luminol chemiluminescence. The chemiluminescence was intense, long-lived, and proportional to quinone concentration. It is concluded that superoxide anion was involved in the proposed chemiluminescence reaction because the chemiluminescence intensity was decreased only in the presence of superoxide dismutase. Among the tested quinones, the chemiluminescence was observed from 9,10-phenanthrenequinone, 1,2-naphthoquinone, and 1,4-naphthoquinone, whereas it was not observed from 9,10-anthraquinone and 1,4-benzoquinone. The chemiluminescence property was greatly different according to the structure of quinones. The chemiluminescence was also observed for biologically important quinones such as ubiquinone. Therefore, a simple and rapid assay for ubiquinone in pharmaceutical preparation was developed based on the proposed chemiluminescence reaction. The detection limit (blank + 3SD) of ubiquinone was 0.05 microM (9 ng/assay) with an analysis time of 30 s per sample. The developed assay allowed the direct determination of ubiquinone in pharmaceutical preparation without any purification procedure.

  5. The Couples' Gender-Based Communication Questionnaire (CGCQ).

    Science.gov (United States)

    Eckstein, Daniel; Goldman, Alan

    2001-01-01

    Effective communication is a cornerstone of marital happiness. The Couples' Gender-Based Communication Questionnaire is presented as a method for identifying male-female different communication styles. Suggests that once people realize that their partners have different conversational styles, they are inclined to accept difference without blaming…

  6. Active control of light based on polarization-coupling cascading

    Science.gov (United States)

    Huo, Juan; Zheng, Yuanlin; Chen, Xianfeng

    2014-10-01

    In this letter, we proposed a novel method for optical manipulation based on polarization-coupling cascading in MgO-doped periodically poled lithium niobate crystal. Polarization-coupling cascading, a series of energy exchanges between two orthogonally polarized beams close to phase matching condition, can also lead to phase shifts, in analogy with that in cascaded second-order nonlinearities. In addition, the parameters of light such as phase, amplitude, and group velocity can be modulated by changing the relative power ratio of the incident continuous wave beams. The phase control was demonstrated by Newton's rings experiment, which was in good agreement with the theoretical prediction.

  7. An interference-free glucose biosensor based on an anionic redox polymer-mediated enzymatic oxidation of glucose.

    Science.gov (United States)

    Deng, Huimin; Shen, Wei; Gao, Zhiqiang

    2013-07-22

    Herein a novel strategy for the construction of an amperometric biosensor for highly sensitive and selective determination of glucose is described. The biosensor is made of a biocomposite membrane of glucose oxidase (GOx) and an Os(bpy)2 (bpy=2,2'-bipyridine)-based anionic redox polymer (Os-RP) mediator. The biosensor is fabricated through the co-immobilization of GOx and the Os-RP on the surface of a glassy carbon electrode by a simple one-step chemical crosslinking process. The crosslinked Os-RP/GOx composite membrane shows excellent catalytic activity toward the oxidation of glucose. Under optimal experimental conditions, a linear correlation between the oxidation current of glucose in amperometry at 0.25 V (vs. Ag/AgCl) and glucose concentration up to 10 mM with a sensitivity of 16.5 μA mM(-1) cm(-2) and a response time glucose in the presence of ascorbic acid and uric acid. The low hydrophobicity of the composite membrane also effectively retards the transport of molecular oxygen within the membrane. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    National Research Council Canada - National Science Library

    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...

  9. Energy storage device including a redox-enhanced electrolyte

    Science.gov (United States)

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

    2017-08-08

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

  10. Spectrophotometric Determination of Rifampicin in Bulk Drug and Pharmaceutical Formulations Based on Redox and Complexation Reactions

    Science.gov (United States)

    Swamy, N.; Basavaiah, K.

    2017-09-01

    Two spectrophotometric methods were developed and validated for the determination of rifampicin (RIF) in bulk form, formulations, and spiked human urine. The first method is based on the reduction of the Folin-Ciocalteu (FC) reagent by RIF to form a blue colored chromogen with λmax at 760 nm (the FCR method). In the second method, iron(III) is reduced by RIF in a neutral medium, and the resulting iron(II) is complexed with ferricyanide to form a Prussian blue peaking at 750 nm (the FFC method). Under optimum conditions, Beer's law enabled the determination of the drug in the concentration ranges 1-35 and 2.5-50 μg/mL with apparent molar absorptivities of 2.72 × 104 and 1.63×104 L/(mol × cm) for the FCR and FFC methods, respectively. The Sandell sensitivity, limits of detection (LOD), and quantification (LOQ) values were also reported for both methods. The precision of the methods, with % RSD of additives and spiked human urine without interference from endogenous substances. A statistical analysis indicated that there was no significant difference between the results obtained by the developed methods and the official method.

  11. A Coupled Simulation Architecture for Agent-Based/Geohydrological Modelling

    Science.gov (United States)

    Jaxa-Rozen, M.

    2016-12-01

    The quantitative modelling of social-ecological systems can provide useful insights into the interplay between social and environmental processes, and their impact on emergent system dynamics. However, such models should acknowledge the complexity and uncertainty of both of the underlying subsystems. For instance, the agent-based models which are increasingly popular for groundwater management studies can be made more useful by directly accounting for the hydrological processes which drive environmental outcomes. Conversely, conventional environmental models can benefit from an agent-based depiction of the feedbacks and heuristics which influence the decisions of groundwater users. From this perspective, this work describes a Python-based software architecture which couples the popular NetLogo agent-based platform with the MODFLOW/SEAWAT geohydrological modelling environment. This approach enables users to implement agent-based models in NetLogo's user-friendly platform, while benefiting from the full capabilities of MODFLOW/SEAWAT packages or reusing existing geohydrological models. The software architecture is based on the pyNetLogo connector, which provides an interface between the NetLogo agent-based modelling software and the Python programming language. This functionality is then extended and combined with Python's object-oriented features, to design a simulation architecture which couples NetLogo with MODFLOW/SEAWAT through the FloPy library (Bakker et al., 2016). The Python programming language also provides access to a range of external packages which can be used for testing and analysing the coupled models, which is illustrated for an application of Aquifer Thermal Energy Storage (ATES).

  12. Cerimetric determination of simvastatin in pharmaceuticals based on redox and complex formation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Basavaiah, K.; Devi, O.Z [University of Mysore, Manasagangotri, Mysore (India). Dept. of Chemistry]. E-mail: basavaiahk@yahoo.co.in

    2008-07-01

    Two sensitive spectrophotometric methods are described for the determination of simvastatin (SMT) in bulk drug and in tablets. The methods are based on the oxidation of SMT by a measured excess of cerium (IV) in acid medium followed by determination of unreacted oxidant by two different reaction schemes. In one procedure (method A), the residual cerium (IV) is reacted with a fixed concentration of ferroin and the increase in absorbance is measured at 510 nm. The second approach (method B) involves the reduction of the unreacted cerium (IV) with a fixed quantity of iron (II), and the resulting iron (III) is complexed with thiocyanate and the absorbance measured at 470 nm. In both methods, the amount of cerium (IV) reacted corresponds to SMT concentration. The experimental conditions for both methods were optimized. In method A, the absorbance is found to increase linearly with SMT concentration (r = 0.9995) whereas in method B, the same decreased (r = -0.9943). The systems obey Beer's law for 0.6-7.5 and 0.5-5.0 {mu}g mL{sup -1} for method A and method B, respectively. The calculated molar absorptivity values are 2.7 X 104 and 1.06 X 105 Lmol{sup -1} cm{sup -1}, respectively; and the corresponding sandel sensitivity values are 0.0153 and 0.0039 {mu}g cm{sup -2}, respectively. The limit of detection (LOD) and quantification (LOQ) are reported for both methods. Intra-day and inter-day precision, and accuracy of the methods were established as per the current ICH guidelines. The methods were successfully applied to the determination of SMT in tablets and the results were statistically compared with those of the reference method by applying the Student's t-test and F-test. No interference was observed from the common excipients added to tablets. The accuracy and validity of the methods were further ascertained by performing recovery experiments via standard addition procedure. (author)

  13. Redox-sensitive self-assembled nanoparticles based on alpha-tocopherol succinate-modified heparin for intracellular delivery of paclitaxel.

    Science.gov (United States)

    Yang, Xiaoye; Cai, Xiaoqing; Yu, Aihua; Xi, Yanwei; Zhai, Guangxi

    2017-06-15

    To remedy the problems riddled in cancer chemotherapy, such as poor solubility, low selectivity, and insufficient intra-cellular release of drugs, novel heparin-based redox-sensitive polymeric nanoparticles were developed. The amphiphilic polymer, heparin-alpha-tocopherol succinate (Hep-cys-TOS) was synthesized by grafting hydrophobic TOS to heparin using cystamine as the redox-sensitive linker, which could self-assemble into nanoparticles in phosphate buffer saline (PBS) with low critical aggregation concentration (CAC) values ranging from 0.026 to 0.093mg/mL. Paclitaxel (PTX)-loaded Hep-cys-TOS nanoparticles were prepared via a dialysis method, exhibiting a high drug-loading efficiency of 18.99%. Physicochemical properties of the optimized formulation were characterized by dynamic light scattering (DLS), transmission electron microscope (TEM) and differential scanning calorimetry (DSC). Subsequently, the redox-sensitivity of Hep-cys-TOS nanoparticles was confirmed by the changes in size distribution, morphology and appearance after dithiothreitol (DTT) treatment. Besides, the in vitro release of PTX from Hep-cys-TOS nanoparticles also exhibited a redox-triggered profile. Also, the uptake behavior and pathways of coumarin 6-loaded Hep-cys-TOS nanoparticles were investigated, suggesting the nanoparticles could be taken into MCF-7 cells in energy-dependent, caveolae-mediated and cholesterol-dependent endocytosis manners. Later, MTT assays of different PTX-free and PTX-loaded formulations revealed the desirable safety of PTX-free nanoparticles and the enhanced anti-cancer activity of PTX-loaded Hep-cys-TOS nanoparticles (IC50=0.79μg/mL). Apoptosis study indicated the redox-sensitive formulation could induce more apoptosis of MCF-7 cells than insensitive one (55.2% vs. 41.7%), showing the importance of intracellular burst release of PTX. Subsequently, the hemolytic toxicity confirmed the safety of the nanoparticles for intravenous administration. The results

  14. High-temperature thermochemical energy storage based on redox reactions using Co-Fe and Mn-Fe mixed metal oxides

    Science.gov (United States)

    André, Laurie; Abanades, Stéphane; Cassayre, Laurent

    2017-09-01

    Metal oxides are potential materials for thermochemical heat storage via reversible endothermal/exothermal redox reactions, and among them, cobalt oxide and manganese oxide are attracting attention. The synthesis of mixed oxides is considered as a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering issues, and the materials potential for thermochemical heat storage application needs to be assessed. This work proposes a study combining thermodynamic calculations and experimental measurements by simultaneous thermogravimetric analysis and calorimetry, in order to identify the impact of iron oxide addition to Co and Mn-based oxides. Fe addition decreased the redox activity and energy storage capacity of Co3O4/CoO, whereas the reaction rate, reversibility and cycling stability of Mn2O3/Mn3O4 was significantly enhanced with added Fe amounts above 15 mol%, and the energy storage capacity was slightly improved. The formation of a reactive cubic spinel explained the improved re-oxidation yield of Mn-based oxides that could be cycled between bixbyite and cubic spinel phases, whereas a low reactive tetragonal spinel phase showing poor re-oxidation was formed below 15 mol% Fe. Thermodynamic equilibrium calculations predict accurately the behavior of both systems. The possibility to identify other suitable mixed oxides becomes conceivable, by enabling the selection of transition metal additives for tuning the redox properties of mixed metal oxides destined for thermochemical energy storage applications.

  15. 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

  16. Coupled interference based rate adaptation in ad hoc networks

    CSIR Research Space (South Africa)

    Awuor, F

    2011-09-01

    Full Text Available since the channel condition is time variant [5], [6]. Hence CIN considers link adaptation based on SINR performance to derive transmit power that minimizes coupled interference in the network. In [5], an algorithm is proposed where an average value... channel condition variance for proper choice of PHY mode. In [7], rate adaptation scheme is proposed wherein nodes select the power-rate pair to maximize their utility based on the previous measured SINRs. The values of SINR employed by [5],[6] and [7...

  17. Chip-based electrochromatography coupled to ESI-MS detection.

    Science.gov (United States)

    Dietze, Claudia; Hackl, Claudia; Gerhardt, Renata; Seim, Stephan; Belder, Detlev

    2016-05-01

    In this study, we present the coupling of chip-based electrochromatography to MS using a glass chip with a monolithically integrated nanoelectrospray emitter. As separation column, an acrylate-based porous polymer monolith is implemented into the glass chip by photopolymerization. For the establishment and development of this method, we used a test mixture detectable with both fluorescence and ESI-MS. After successful evaluation of the approach with the test solutes, it was applied exemplarily for drug analysis such as high-speed separations of benzodiazepines in pharmaceuticals. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Plant redox proteomics

    DEFF Research Database (Denmark)

    Navrot, Nicolas; Finnie, Christine; Svensson, Birte

    2011-01-01

    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...... 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....... 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...

  19. Microstrip Cross-coupled Interdigital SIR Based Bandpass Filter

    Directory of Open Access Journals (Sweden)

    R. K. Maharjan

    2012-09-01

    Full Text Available A simple and compact 4.9 GHz bandpass filter for C-band applications is proposed. This paper presents a novel microstrip cross-coupled interdigital half-wavelength stepped impedance resonator (SIR based bandpass filter (BPF.The designed structure is similar to that of a combination of two parallel interdigital capacitors. The scattering parameters of the structure are measured using vector network analyzer (VNA. The self generated capacitive and inductive reactances within the interdigital resonators exhibited in a resonance frequency of 4.9 GHz. The resonant frequency and bandwidth of the capacitive cross-coupled resonator is directly optimized from the physical arrangement of the resonators. The measured insertion loss (S21 and return loss (S11 were 0.3 dB and 28 dB, respectively, at resonance frequency which were almost close to the simulation results.

  20. Redox Active Polymers as Soluble Nanomaterials for Energy Storage.

    Science.gov (United States)

    Burgess, Mark; Moore, Jeffrey S; Rodríguez-López, Joaquín

    2016-11-15

    It is an exciting time for exploring the synergism between the chemical and dimensional properties of redox nanomaterials for addressing the manifold performance demands faced by energy storage technologies. The call for widespread adoption of alternative energy sources requires the combination of emerging chemical concepts with redesigned battery formats. Our groups are interested in the development and implementation of a new strategy for nonaqueous flow batteries (NRFBs) for grid energy storage. Our motivation is to solve major challenges in NRFBs, such as the lack of membranes that simultaneously allow fast ion transport while minimizing redox active species crossover between anolyte (negative electrolyte) and catholyte (positive electrolyte) compartments. This pervasive crossover leads to deleterious capacity fade and materials underutilization. In this Account, we highlight redox active polymers (RAPs) and related polymer colloids as soluble nanoscopic energy storing units that enable the simple but powerful size-exclusion concept for NRFBs. Crossover of the redox component is suppressed by matching high molecular weight RAPs with simple and inexpensive nanoporous commercial separators. In contrast to the vast literature on the redox chemistry of electrode-confined polymer films, studies on the electrochemistry of solubilized RAPs are incipient. This is due in part to challenges in finding suitable solvents that enable systematic studies on high polymers. Here, viologen-, ferrocene- and nitrostyrene-based polymers in various formats exhibit properties that make amenable their electrochemical exploration as solution-phase redox couples. A main finding is that RAP solutions store energy efficiently and reversibly while offering chemical modularity and size versatility. Beyond the practicality toward their use in NRFBs, the fundamental electrochemistry exhibited by RAPs is fascinating, showing clear distinctions in behavior from that of small molecules. Whereas

  1. Facile Fabrication of AIE-Active Fluorescent Polymeric Nanoparticles with Ultra-Low Critical Micelle Concentration Based on Ce(IV) Redox Polymerization for Biological Imaging Applications.

    Science.gov (United States)

    Wan, Qing; Xu, Dazhuang; Mao, Liucheng; He, Ziyang; Zeng, Guangjian; Shi, Yingge; Deng, Fengjie; Liu, Meiying; Zhang, Xiaoyong; Wei, Yen

    2017-04-01

    Fluorescent polymeric nanoparticles (FPNs) with aggregation-induced emission (AIE) property have received increasing attention and possess promising biomedical application potential in the recent years. Many efforts have been devoted to the fabrication methodologies of FPNs and significant advance has been achieved. In this contribution, a novel strategy for the fabrication of AIE-active amphiphilic copolymers is reported for the first time based on the Ce(IV) redox polymerization. As an example, ene group containing AIE-active dye (named as Phe-alc) is directly grafted onto a water soluble polymer polyethylene glycol (PEG) in H2 O/THF system under low temperature. Thus-obtained amphiphilic fluorescent polymers will self-assemble into FPNs with ultra-low critical micelle concentration, ultra-brightness, and great water dispersibility. Biological evaluation results suggest that the PEG-poly(Phe-alc) possess excellent biocompatibility and can be used for tracing their behavior in cells using confocal laser scanning microscope. These features make PEG-poly(Phe-alc) FPNs promising candidates for many biomedical applications, such as cell imaging, drug delivery vehicles, and targeted tracing. More importantly, many other functional groups can also be incorporated into these AIE-active FPNs through the redox polymerization. Therefore, the redox polymerization should be a facile and effective strategy for fabrication of AIE-active FPNs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. An innovative concept of use of redox-active electrolyte in asymmetric capacitor based on MWCNTs/MnO2 and Fe2O3 thin films

    Science.gov (United States)

    Chodankar, Nilesh R.; Dubal, Deepak P.; Lokhande, Abhishek C.; Patil, Amar M.; Kim, Jin H.; Lokhande, Chandrakant D.

    2016-01-01

    In present investigation, we have prepared a nanocomposites of highly porous MnO2 spongy balls and multi-walled carbon nanotubes (MWCNTs) in thin film form and tested in novel redox-active electrolyte (K3[Fe(CN)6] doped aqueous Na2SO4) for supercapacitor application. Briefly, MWCNTs were deposited on stainless steel substrate by “dip and dry” method followed by electrodeposition of MnO2 spongy balls. Further, the supercapacitive properties of these hybrid thin films were evaluated in hybrid electrolyte ((K3[Fe(CN)6 doped aqueous Na2SO4). Thus, this is the first proof-of-design where redox-active electrolyte is applied to MWCNTs/MnO2 hybrid thin films. Impressively, the MWCNTs/MnO2 hybrid film showed a significant improvement in electrochemical performance with maximum specific capacitance of 1012 Fg−1 at 2 mA cm−2 current density in redox-active electrolyte, which is 1.5-fold higher than that of conventional electrolyte (Na2SO4). Further, asymmetric capacitor based on MWCNTs/MnO2 hybrid film as positive and Fe2O3 thin film as negative electrode was fabricated and tested in redox-active electrolytes. Strikingly, MWCNTs/MnO2//Fe2O3 asymmetric cell showed an excellent supercapacitive performance with maximum specific capacitance of 226 Fg−1 and specific energy of 54.39 Wh kg−1 at specific power of 667 Wkg−1. Strikingly, actual practical demonstration shows lightning of 567 red LEDs suggesting “ready-to sell” product for industries. PMID:27982087

  3. Microwave Diplexer Purely Based on Direct Synchronous and Asynchronous Coupling

    Directory of Open Access Journals (Sweden)

    A. O. Nwajana

    2016-06-01

    Full Text Available A diplexer realized purely based on direct coupling is presented. No cross-coupling is involved in the design process. The microwave diplexer is achieved by coupling a dual-band bandpass filter onto two individual channel filters. This design eliminates the need for employing external junctions in diplexer design, as opposed to the conventional design approach which requires separate junctions for energy distribution. A 10-pole (10th order diplexer has been successfully designed, simulated, fabricated and measured. The diplexer is composed of 2 poles from the dual-band filter, 4 poles from the Tx bandpass filter, and the remaining 4 poles from the Rx bandpass filter. The design was implemented using synchronously and asynchronously tuned microstrip square open-loop resonators. The simulation and measurement results show that an isolation of 50 dB is achieved between the diplexer Tx and Rx bands. The minimum insertion loss is 2.88 dB for the transmit band, and 2.95 dB for the receive band.

  4. TWO IDEAS OF THE REDOX REACTION: MISCONCEPTIONS AND ...

    African Journals Online (AJOL)

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    participants were not sure about this and chose the reactions ii or iii or both (that are acid-base reactions!), and delivered reasons such as: "MgO and Mg(OH)2 contain oxygen, what is absolutely necessary for redox reactions; to any redox reaction O is necessary – so choice (i) cannot be a redox reaction". These students ...

  5. Investigation of activity and selectivity of redox catalysts in oxidative ...

    African Journals Online (AJOL)

    In this study, oxidative coupling of methane on Redox catalysts in fluidized bed reactor was investigated. For this purpose, the catalyst Mn-Na2WO4/SiO2 was selected as a Redox catalyst. In order to investigate this catalyst, transient state experiments were designed and performed. Then, the different reaction conditions on ...

  6. Exploring possible reaction pathways for the o-atom transfer reactions to unsaturated substrates catalyzed by a [Ni-NO2] ↔ [Ni-NO] redox couple using DFT methods.

    Science.gov (United States)

    Tsipis, Athanassios C

    2017-07-15

    The (nitro)(N-methyldithiocarbamato)(trimethylphospane)nickel(II), [Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] complex catalyses efficiently the O-atom transfer reactions to CO and acetylene. Energetically feasible sequence of elementary steps involved in the catalytic cycle of the air oxidation of CO and acetylene are proposed promoted by the Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] ↔ Ni(NO 2 )(S 2 CNHMe)(PMe 3 ) redox couple using DFT methods both in vacuum and dichloromethane solutions. The catalytic air oxidation of HC≡CH involves formation of a five-member metallacycle intermediate, via a [3 + 2] cyclo-addition reaction of HC≡CH to the Ni-N = O moiety of the Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] complex, followed by a β H-atom migration toward the C α carbon atom of the coordinated acetylene and release of the oxidation product (ketene). The geometric and energetic reaction profile for the reversible [Ni( κN1-NO 2 )(S 2 CNHMe)(PMe 3 )] ⇌ [Ni( κO,O2-ONO)(S 2 CNHMe)(PMe 3 )] linkage isomerization has also been modeled by DFT calculations. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  7. Complex between lignin and a Ti-based coupling agent

    DEFF Research Database (Denmark)

    Rasmussen, Jonas Stensgaard; Barsberg, Søren Talbro; Felby, Claus

    2014-01-01

    -fourier transform infrared spectroscopy in combination with first principle predictions based on the density functional theory (DFT). In the infrared spectra, a new band at 1586 cm-1 was identified and the DFT predictions confirmed that the new band is because of the covalent bonds in the form of ether linkages......Durability, haptic, and optical appearance of wood are improved by coatings, which are nowadays prepared using environmentally compatible and less health-damaging materials. However, contemporary wood coatings have frequently a shortened service life compared to their traditional predecessors. New...... coating formulations would have a better performance if the adhesion to wood could be improved. In the present work, the chemical interaction between a titanium-based coupling agent, isopropyl triisostearoyl titanate (titanium agent, TA) and lignin has been studied by means of attenuated total reflectance...

  8. Identification of Coupled Map Lattice Based on Compressed Sensing

    Directory of Open Access Journals (Sweden)

    Dong Xie

    2016-01-01

    Full Text Available A novel approach for the parameter identification of coupled map lattice (CML based on compressed sensing is presented in this paper. We establish a meaningful connection between these two seemingly unrelated study topics and identify the weighted parameters using the relevant recovery algorithms in compressed sensing. Specifically, we first transform the parameter identification problem of CML into the sparse recovery problem of underdetermined linear system. In fact, compressed sensing provides a feasible method to solve underdetermined linear system if the sensing matrix satisfies some suitable conditions, such as restricted isometry property (RIP and mutual coherence. Then we give a low bound on the mutual coherence of the coefficient matrix generated by the observed values of CML and also prove that it satisfies the RIP from a theoretical point of view. If the weighted vector of each element is sparse in the CML system, our proposed approach can recover all the weighted parameters using only about M samplings, which is far less than the number of the lattice elements N. Another important and significant advantage is that if the observed data are contaminated with some types of noises, our approach is still effective. In the simulations, we mainly show the effects of coupling parameter and noise on the recovery rate.

  9. 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...

  10. Paper-Based Electrochemical Cell Coupled to Mass Spectrometry.

    Science.gov (United States)

    Liu, Yao-Min; Perry, Richard H

    2015-10-01

    On-line coupling of electrochemistry (EC) to mass spectrometry (MS) is a powerful approach for identifying intermediates and products of EC reactions in situ. In addition, EC transformations have been used to increase ionization efficiency and derivatize analytes prior to MS, improving sensitivity and chemical specificity. Recently, there has been significant interest in developing paper-based electroanalytical devices as they offer convenience, low cost, versatility, and simplicity. This report describes the development of tubular and planar paper-based electrochemical cells (P-EC) coupled to sonic spray ionization (SSI) mass spectrometry (P-EC/SSI-MS). The EC cells are composed of paper sandwiched between two mesh stainless steel electrodes. Analytes and reagents can be added directly to the paper substrate along with electrolyte, or delivered via the SSI microdroplet spray. The EC cells are decoupled from the SSI source, allowing independent control of electrical and chemical parameters. We utilized P-EC/SSI-MS to characterize various EC reactions such as oxidations of cysteine, dopamine, polycyclic aromatic hydrocarbons, and diphenyl sulfide. Our results show that P-EC/SSI-MS has the ability to increase ionization efficiency, to perform online EC transformations, and to capture intermediates of EC reactions with a response time on the order of hundreds of milliseconds. The short response time allowed detection of a deprotonated diphenyl sulfide intermediate, which experimentally confirms a previously proposed mechanism for EC oxidation of diphenyl sulfide to pseudodimer sulfonium ion. This report introduces paper-based EC/MS via development of two device configurations (tubular and planar electrodes), as well as discusses the capabilities, performance, and limitations of the technique.

  11. Oxygen cathode based on a layer-by-layer self-assembled laccase and osmium redox mediator

    Energy Technology Data Exchange (ETDEWEB)

    Szamocki, R.; Flexer, V. [INQUIMAE-DQIAyQF, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires (Argentina); Levin, L.; Forchiasin, F. [Micologia Experimental, Departamento de Biodiversidad y Biologia Experimental. Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires (Argentina); Calvo, E.J. [INQUIMAE-DQIAyQF, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires (Argentina)], E-mail: calvo@qi.fcen.uba.ar

    2009-02-28

    Trametes trogii laccase has been studied as biocatalyst for the oxygen electro-reduction in three different systems: (i) soluble laccase was studied in solution; (ii) an enzyme monolayer was tethered to a gold surface by dithiobis N-succinimidyl propionate (DTSP), with a soluble osmium pyridine-bipyridine redox mediator in both cases. The third case (iii) consisted in the sequential immobilization of laccase and the osmium complex derivatized poly(allylamine) self-assembled layer-by-layer (LbL) on mercaptopropane sulfonate modified gold to produce an all integrated and wired enzymatic oxygen cathode. The polycation was the same osmium complex covalently bound to poly-(ally-lamine) backbone (PAH-Os), the polyanion was the enzyme adsorbed from a solution of a suitable pH so that the protein carries a net negative charge. The adsorption of laccase was studied by monitoring the mass uptake with a quartz crystal microbalance and the oxygen reduction electrocatalysis was studied by linear scan voltammetry. While for the three cases, oxygen electrocatalysis mediated by the osmium complex was observed, for tethered laccase direct electron transfer in the absence of redox mediator was also apparent but no electrocatalysis for the oxygen reduction was recorded in the absence of mediator in solution. For the fully integrated LbL self-assembled laccase and redox mediator (case iii) a catalytic reduction of oxygen could be recorded at different oxygen partial pressures and different electrolyte pH. The tolerance of the reaction to methanol and chloride was also investigated.

  12. The detection of transient directional couplings based on phase synchronization

    Energy Technology Data Exchange (ETDEWEB)

    Wagner, T; Fell, J; Lehnertz, K, E-mail: twagner@uni-bonn.d [Department of Epileptology, University of Bonn, Sigmund-Freud-Strasse 25, 53127 Bonn (Germany)

    2010-05-15

    We extend recent approaches based on the concept of phase synchronization to enable the time-resolved investigation of directional relationships between coupled dynamical systems from short and transient noisy time series. For our approach, we consider an observed ensemble of a sufficiently large number of time series as multiple realizations of a process. We derive an index that quantifies the direction of transient interactions and assess its statistical significance using surrogate techniques. Analysing time series from noisy and chaotic systems, we demonstrate numerically the applicability and limitations of our approach. Our findings from an exemplary application to event-related brain activities underline the importance of our method for improving knowledge about the mechanisms underlying memory formation in humans.

  13. Event-based cluster synchronization of coupled genetic regulatory networks

    Science.gov (United States)

    Yue, Dandan; Guan, Zhi-Hong; Li, Tao; Liao, Rui-Quan; Liu, Feng; Lai, Qiang

    2017-09-01

    In this paper, the cluster synchronization of coupled genetic regulatory networks with a directed topology is studied by using the event-based strategy and pinning control. An event-triggered condition with a threshold consisting of the neighbors' discrete states at their own event time instants and a state-independent exponential decay function is proposed. The intra-cluster states information and extra-cluster states information are involved in the threshold in different ways. By using the Lyapunov function approach and the theories of matrices and inequalities, we establish the cluster synchronization criterion. It is shown that both the avoidance of continuous transmission of information and the exclusion of the Zeno behavior are ensured under the presented triggering condition. Explicit conditions on the parameters in the threshold are obtained for synchronization. The stability criterion of a single GRN is also given under the reduced triggering condition. Numerical examples are provided to validate the theoretical results.

  14. Enhanced photosynthesis and redox energy production contribute to salinity tolerance in Dunaliella as revealed by homology-based proteomics.

    Science.gov (United States)

    Liska, Adam J; Shevchenko, Andrej; Pick, Uri; Katz, Adriana

    2004-09-01

    Salinity is a major limiting factor for the proliferation of plants and inhibits central metabolic activities such as photosynthesis. The halotolerant green alga Dunaliella can adapt to hypersaline environments and is considered a model photosynthetic organism for salinity tolerance. To clarify the molecular basis for salinity tolerance, a proteomic approach has been applied for identification of salt-induced proteins in Dunaliella. Seventy-six salt-induced proteins were selected from two-dimensional gel separations of different subcellular fractions and analyzed by mass spectrometry (MS). Application of nanoelectrospray mass spectrometry, combined with sequence-similarity database-searching algorithms, MS BLAST and MultiTag, enabled identification of 80% of the salt-induced proteins. Salinity stress up-regulated key enzymes in the Calvin cycle, starch mobilization, and redox energy production; regulatory factors in protein biosynthesis and degradation; and a homolog of a bacterial Na(+)-redox transporters. The results indicate that Dunaliella responds to high salinity by enhancement of photosynthetic CO(2) assimilation and by diversion of carbon and energy resources for synthesis of glycerol, the osmotic element in Dunaliella. The ability of Dunaliella to enhance photosynthetic activity at high salinity is remarkable because, in most plants and cyanobacteria, salt stress inhibits photosynthesis. The results demonstrated the power of MS BLAST searches for the identification of proteins in organisms whose genomes are not known and paved the way for dissecting molecular mechanisms of salinity tolerance in algae and higher plants.

  15. Oxidative stress alters base excision repair pathway and increases apoptotic response in apurinic/apyrimidinic endonuclease 1/redox factor-1 haploinsufficient mice.

    Science.gov (United States)

    Unnikrishnan, Archana; Raffoul, Julian J; Patel, Hiral V; Prychitko, Thomas M; Anyangwe, Njwen; Meira, Lisiane B; Friedberg, Errol C; Cabelof, Diane C; Heydari, Ahmad R

    2009-06-01

    Apurinic/apyrimidinic endonuclease 1/redox factor-1 (APE1/Ref-1) is the redox regulator of multiple stress-inducible transcription factors, such as NF-kappaB, and the major 5'-endonuclease in base excision repair (BER). We utilized mice containing a heterozygous gene-targeted deletion of APE1/Ref-1 (Apex(+/-)) to determine the impact of APE1/Ref-1 haploinsufficiency on the processing of oxidative DNA damage induced by 2-nitropropane (2-NP) in the liver tissue of mice. APE1/Ref-1 haploinsufficiency results in a significant decline in NF-kappaB DNA-binding activity in response to oxidative stress in liver. In addition, loss of APE1/Ref-1 increases the apoptotic response to oxidative stress, in which significant increases in GADD45g expression, p53 protein stability, and caspase activity are observed. Oxidative stress displays a differential impact on monofunctional (UNG) and bifunctional (OGG1) DNA glycosylase-initiated BER in the liver of Apex(+/-) mice. APE1/Ref-1 haploinsufficiency results in a significant decline in the repair of oxidized bases (e.g., 8-OHdG), whereas removal of uracil is increased in liver nuclear extracts of mice using an in vitro BER assay. Apex(+/-) mice exposed to 2-NP displayed a significant decline in 3'-OH-containing single-strand breaks and an increase in aldehydic lesions in their liver DNA, suggesting an accumulation of repair intermediates of failed bifunctional DNA glycosylase-initiated BER.

  16. A Simple Analytical Model of Coupled Single Flow Channel over Porous Electrode in Vanadium Redox Flow Battery with Serpentine Flow Channel

    CERN Document Server

    Ke, Xinyou; Prahl, Joseph M; Savinell, Robert F

    2016-01-01

    A simple analytical model of a layered system comprised of a single passage of a serpentine flow channel and a parallel underlying porous electrode (or porous layer) is proposed. This analytical model is derived from Navier-Stokes motion in the flow channel and Darcy-Brinkman model in the porous layer. The continuities of flow velocity and normal stress are applied at the interface between the flow channel and the porous layer. The effects of the inlet volumetric flow rate, thickness of the flow channel and thickness of a typical carbon fiber paper porous layer on the volumetric flow rate within this porous layer are studied. The maximum current density based on the electrolyte volumetric flow rate is predicted, and found to be consistent with reported numerical simulation. It is found that, for a mean inlet flow velocity of 33.3 cm s-1, the analytical maximum current density is estimated to be 377 mA cm-2, which compares favorably with experimental result reported by others of ~400 mA cm-2.

  17. Manganese dioxide nanosheets-based redox/pH-responsive drug delivery system for cancer theranostic application.

    Science.gov (United States)

    Hao, Yongwei; Wang, Lei; Zhang, Bingxiang; Li, Dong; Meng, Dehui; Shi, Jinjin; Zhang, Hongling; Zhang, Zhenzhong; Zhang, Yun

    2016-01-01

    The aim of this study was to construct redox- and pH-responsive degradable manganese dioxide (MnO2) nanosheets for cancer theranostic application. The small MnO2 nanosheets were synthesized, and then functionalized by hyaluronic acid (HA), demonstrating excellent stability and tumor-targeting ability. Cisplatin (cis-diamminedichloroplatinum [CDDP]) was absorbed by the nanosheets through a physical action, which was designed as MnO2/HA/CDDP. The prepared MnO2/HA/CDDP formulation was able to efficiently deliver CDDP to tumor cells in vitro and in vivo, resulting in improved therapeutic efficiency. Subsequently, they were triggered by lower pH and higher level of reduced glutathione to generate Mn(2+), enabling magnetic resonance imaging. The smart multifunctional system combining efficient magnetic resonance imaging and chemotherapy has the potential to be used as a tumor-targeting theranostic nanomedicine.

  18. Signal-to-Noise Enhancement of a Nanospring Redox-Based Sensor by Lock-in Amplification

    Directory of Open Access Journals (Sweden)

    Pavel V. Bakharev

    2015-06-01

    Full Text Available A significant improvement of the response characteristics of a redox chemical gas sensor (chemiresistor constructed with a single ZnO coated silica nanospring has been achieved with the technique of lock-in signal amplification. The comparison of DC and analog lock-in amplifier (LIA AC measurements of the electrical sensor response to toluene vapor, at the ppm level, has been conducted. When operated in the DC detection mode, the sensor exhibits a relatively high sensitivity to the analyte vapor, as well as a low detection limit at the 10 ppm level. However, at 10 ppm the signal-to-noise ratio is 5 dB, which is less than desirable. When operated in the analog LIA mode, the signal-to-noise ratio at 10 ppm increases by 30 dB and extends the detection limit to the ppb range.

  19. Evaluating adaptation options of microcirculatory-tissue systems based on the physiological link of nutritive blood flow and redox ratio

    Science.gov (United States)

    Krupatkin, Alexander I.; Sidorov, Victor V.; Dremin, Victor V.; Dunaev, Andrey V.; Novikova, Irina N.; Zhu, Simian; Nabi, Ghulam; Litvinova, Karina S.; Baklanova, Anastasia P.; Bakshaliev, Ruslan M.; Ravcheev, Sergey A.

    2015-03-01

    Fluorescent spectroscopy (FS) is becoming more widely used in chemistry, biology, in various fields of medical technology and medicine in general. Many purulent wounds, burns and other destructive inflammatory processes are accompanied by changes in the fluorescent activity of the tissues, which occurs due to a misbalance in accumulation of natural fluorophores: FAD, NADH, lipofuscin, porphyrins, structural proteins, etc. The study of redox ratio (RR), characterizing the metabolic processes, is important in the assessment of the metabolic activity ofmicrocirculatory-tissue systems (MTS). However, one of the big problems of the FS method is still the correct interpretation of the data and the development of practical methods for its application in clinical medicine. To solve this problem and create new diagnostic criteria, we propose to evaluate the adaptive capacity of MTS using indicators of links between nutritive blood flow and redox ratio during a physiological rest and functional load (occlusion test). As is known, these parameters (RR and nutritive blood flow) characterize the metabolic activity of tissues.We have performedan experimental study of the relationship between the RR, defined by FS, and nutritive blood flow, defined by the methods of laser Doppler flowmetry. Preliminary results in the study of a complex approach to diagnosis of the state of biological tissue were obtained. A positive relationship between the nutritive blood flow in the microcirculatory channel and RR of skin tissue is observed.The speed of change of metabolism in the phase of occlusion and reperfusion and duration of phase of recovery may be the criteria for adaptive capabilities of MTS, which has practical significance for physiology and medicine.

  20. Coupling Strategies Investigation of Hybrid Atomistic-Continuum Method Based on State Variable Coupling

    Directory of Open Access Journals (Sweden)

    Qian Wang

    2017-01-01

    Full Text Available Different configurations of coupling strategies influence greatly the accuracy and convergence of the simulation results in the hybrid atomistic-continuum method. This study aims to quantitatively investigate this effect and offer the guidance on how to choose the proper configuration of coupling strategies in the hybrid atomistic-continuum method. We first propose a hybrid molecular dynamics- (MD- continuum solver in LAMMPS and OpenFOAM that exchanges state variables between the atomistic region and the continuum region and evaluate different configurations of coupling strategies using the sudden start Couette flow, aiming to find the preferable configuration that delivers better accuracy and efficiency. The major findings are as follows: (1 the C→A region plays the most important role in the overlap region and the “4-layer-1” combination achieves the best precision with a fixed width of the overlap region; (2 the data exchanging operation only needs a few sampling points closer to the occasions of interactions and decreasing the coupling exchange operations can reduce the computational load with acceptable errors; (3 the nonperiodic boundary force model with a smoothing parameter of 0.1 and a finer parameter of 20 can not only achieve the minimum disturbance near the MD-continuum interface but also keep the simulation precision.

  1. Polymer based planar coupling of self-assembled bottle microresonators

    Science.gov (United States)

    Grimaldi, I. A.; Berneschi, S.; Testa, G.; Baldini, F.; Nunzi Conti, G.; Bernini, R.

    2014-12-01

    The investigation of a simple and self-assembling method for realizing polymeric micro-bottle resonators is reported. By dispensing precise amounts of SU-8 onto a cleaved optical fiber, employed as mechanical support, bottle microcavities with different shapes and diameters are fabricated. The balancing of surface energy between glass fiber and polymeric microresonator with surface tension of SU-8 confers different shape to these microstructures. Planar single-mode SU-8 based waveguide, realized on polymethylmethacrylate, is chosen for exciting the micro-bottle resonators by evanescent wave. The reliability of the fabrication process and the shape of the bottle microcavities are investigated through optical analysis. We observe whispering gallery modes in these resonant microstructures by a robust coupling with single mode planar waveguides around 1.5 μm wavelength. The resonance spectra of micro-bottle resonators and the spectral characteristics, such as Quality-factor (Q factor) and free spectral range, are evaluated for all the realized microstructures. SU-8 micro-bottle resonators show high Q-factors up to 3.8 × 104 and present a good mechanical stability. These features make these microcavities attractive for sensing and/or lasing applications in a planar platform.

  2. Redox electrochemistry of europium fluoride complexes in an equimolar NaCl-KCl melt

    Energy Technology Data Exchange (ETDEWEB)

    Kuznetsov, S.A., E-mail: kuznet@chemy.kolasc.net.ru [Institute of Chemistry, Kola Science Centre RAS, 26 Akademgorodok., 184209 Apatity, Murmansk region (Russian Federation); Gaune-Escard, M. [Ecole Polytechnique, Mecanique Energetique, Technopole de Chateau Gombert, 5 rue Enrico Fermi, 13453 Marseille Cedex 13 (France)

    2011-07-15

    The electrochemical behavior of europium fluoride complexes was studied by different electrochemical methods at a glassy carbon electrode in the temperature range 973-1100 K in the NaCl-KCl melt. The diffusion coefficients of Eu(III) and Eu(II) were determined by linear sweep voltammetry. The standard rate constants of charge transfer for the Eu(III)/Eu(II) redox couple were found on the base cyclic voltammetry, impedance spectroscopy and chronoamperometry data. The formal standard redox potentials E{sub Eu(III)/Eu(II)}{sup *} were obtained by linear sweep and cyclic voltammetry. The electrochemical behavior of europium fluoride and europium chloride complexes in NaCl-KCl melt was compared and discussed in connection with the strength and stability of these complexes. It was shown that the formation of stronger fluoride complexes reduced values of diffusion coefficients, standard rate constants for charge transfer of the Eu(III)/Eu(II) redox couple and shifted the formal standard redox potentials to the more electronegative values.

  3. Synchrotron-based X-Ray Spectroscopy Studies for Redox-based Remediation of Lead, Zinc, and Cadmium in Mine Waste Materials.

    Science.gov (United States)

    Karna, Ranju R; Hettiarachchi, Ganga M; Newville, Matthew; Sun, ChengJun; Ma, Qing

    2016-11-01

    Several studies have examined the effect of submergence on the mobility of metals present in mine waste materials. This study examines the effect of organic carbon (OC) and sulfur (S) additions and submergence time on redox-induced biogeochemical transformations of lead (Pb), zinc (Zn), and cadmium (Cd) present in mine waste materials collected from the Tri-State mining district located in southeastern Kansas, southwestern Missouri, and northeastern Oklahoma. A completely randomized design, with a two-way treatment structure, was used for conducting a series of column experiments. Two replicates were used for each treatment combination. Effluent samples were collected at several time points, and soil samples were collected at the end of each column experiment. Because these samples are highly heterogeneous, we used a variety of synchrotron-based techniques to identify Pb, Zn, and Cd speciation at both micro- and bulk-scale. Spectroscopic analysis results from the study revealed that the addition of OC, with and without S, promoted metal-sulfide formation, whereas metal carbonates dominated in the nonamended flooded materials and in mine waste materials only amended with S. Therefore, the synergistic effect of OC and S may be more promising for managing mine waste materials disposed of in flooded subsidence mine pits instead of individual S or OC treatments. The mechanistic understanding gained in this study is also relevant for remediation of waste materials using natural or constructed wetland systems. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  4. Superposed Redox Chemistry of Fused Carbon Rings in Cyclooctatetraene-Based Organic Molecules for High-Voltage and High-Capacity Cathodes.

    Science.gov (United States)

    Zhao, Xiaolin; Qiu, Wujie; Ma, Chao; Zhao, Yingqin; Wang, Kaixue; Zhang, Wenqing; Kang, Litao; Liu, Jianjun

    2018-01-24

    Even though many organic cathodes have been developed and have made a significant improvement in energy density and reversibility, some organic materials always generate relatively low voltage and limited discharge capacity because their energy storage mechanism is solely based on redox reactions of limited functional groups [N-O, C═X (X = O, N, S)] linking to aromatic rings. Here, a series of cyclooctatetraene-based (C 8 H 8 ) organic molecules were demonstrated to have electrochemical activity of high-capacity and high-voltage from carbon rings by means of first-principles calculations and electronic structure analysis. Fused molecules of C 8 -C 4 -C 8 (C 16 H 12 ) and C 8 -C 4 -C 8 -C 4 -C 8 (C 24 H 16 ) contain, respectively, four and eight electron-deficient carbons, generating high-capacity by their multiple redox reactions. Our sodiation calculations predict that C 16 H 12 and C 24 H 16 exhibit discharge capacities of 525.3 and 357.2 mA h g -1 at the voltage change from 3.5 to 1.0 V and 3.7 to 1.3 V versus Na + /Na, respectively. Electronic structure analysis reveals that the high voltages are attributed to superposed electron stabilization mechanisms, including double-bond reformation and aromatization from carbon rings. High thermodynamic stability of these C 24 H 16 -based systems strongly suggests feasibility of experimental realization. The present work provides evidence that cyclooctatetraene-based organic molecules fused with the C 4 ring are promising in designing high-capacity and high-voltage organic rechargeable cathodes.

  5. Evidence-Based Care for Couples With Infertility.

    Science.gov (United States)

    Stevenson, Eleanor L; Hershberger, Patricia E; Bergh, Paul A

    2016-01-01

    When couples cannot achieve pregnancy, they often seek health care from medical and nursing specialists. The care the couple receives begins with a thorough assessment to determine the possible cause of infertility and to plan appropriate care to ensure the best chance for the couple to have a biological child. In this article, we provide an overview of the etiology and evaluation of infertility, the various treatment options available, and the appropriate clinical implications. Copyright © 2016 AWHONN, the Association of Women's Health, Obstetric and Neonatal Nurses. Published by Elsevier Inc. All rights reserved.

  6. Reconfigurable optical routers based on Coupled Resonator Induced Transparency resonances.

    Science.gov (United States)

    Mancinelli, M; Bettotti, P; Fedeli, J M; Pavesi, L

    2012-10-08

    The interferometric coupling of pairs of resonators in a resonator sequence generates coupled ring induced transparency (CRIT) resonances. These have quality factors an order of magnitude greater than those of single resonators. We show that it is possible to engineer CRIT resonances in tapered SCISSOR (Side Coupled Integrated Space Sequence of Resonator) to realize fast and efficient reconfigurable optical switches and routers handling several channels while keeping single channel addressing capabilities. Tapered SCISSORs are fabricated in silicon-on-insulator technology. Furthermore, tapered SCISSORs show multiple-channel switching behavior that can be exploited in DWDM applications.

  7. Biogeochemical redox processes and their impact on contaminant dynamics

    Science.gov (United States)

    Borch, Thomas; Kretzschmar, Ruben; Kappler, Andreas; Van Cappellen, Philippe; Ginder-Vogel, Matthew; Campbell, Kate M.

    2010-01-01

    Life and element cycling on Earth is directly related to electron transfer (or redox) reactions. An understanding of biogeochemical redox processes is crucial for predicting and protecting environmental health and can provide new opportunities for engineered remediation strategies. Energy can be released and stored by means of redox reactions via the oxidation of labile organic carbon or inorganic compounds (electron donors) by microorganisms coupled to the reduction of electron acceptors including humic substances, iron-bearing minerals, transition metals, metalloids, and actinides. Environmental redox processes play key roles in the formation and dissolution of mineral phases. Redox cycling of naturally occurring trace elements and their host minerals often controls the release or sequestration of inorganic contaminants. Redox processes control the chemical speciation, bioavailability, toxicity, and mobility of many major and trace elements including Fe, Mn, C, P, N, S, Cr, Cu, Co, As, Sb, Se, Hg, Tc, and U. Redox-active humic substances and mineral surfaces can catalyze the redox transformation and degradation of organic contaminants. In this review article, we highlight recent advances in our understanding of biogeochemical redox processes and their impact on contaminant fate and transport, including future research needs.

  8. A redox-flow electrochromic window.

    Science.gov (United States)

    Jennings, James R; Lim, Wei Yang; Zakeeruddin, Shaik M; Grätzel, Michael; Wang, Qing

    2015-02-04

    A low-cost electrochromic (EC) window based on a redox-flow system that does not require expensive transparent conductive oxide (TCO) substrates is introduced and demonstrated for the first time. An aqueous I3–/I– redox electrolyte is used in place of a TCO to oxidize/reduce a molecular layer of an EC triphenylamine derivative that is anchored to a mesoporous TiO2 scaffold on the inner faces of a double-paned window. The redox electrolyte is electrochemically oxidized/reduced in an external two-compartment cell and circulated through the window cavity using an inexpensive peristaltic pump, resulting in coloration or decoloration of the window due to reaction of the redox solution with the triphenylamine derivative. The absorption characteristics, coloration/decoloration times, and cycling stability of the prototype EC window are evaluated, and prospects for further development are discussed.

  9. 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.

  10. Nuclear thiol redox systems in plants.

    Science.gov (United States)

    Delorme-Hinoux, Valérie; Bangash, Sajid A K; Meyer, Andreas J; Reichheld, Jean-Philippe

    2016-02-01

    Thiol-disulfide redox regulation is essential for many cellular functions in plants. It has major roles in defense mechanisms, maintains the redox status of the cell and plays structural, with regulatory roles for many proteins. Although thiol-based redox regulation has been extensively studied in subcellular organelles such as chloroplasts, it has been much less studied in the nucleus. Thiol-disulfide redox regulation is dependent on the conserved redox proteins, glutathione/glutaredoxin (GRX) and thioredoxin (TRX) systems. We first focus on the functions of glutathione in the nucleus and discuss recent data concerning accumulation of glutathione in the nucleus. We also provide evidence that glutathione reduction is potentially active in the nucleus. Recent data suggests that the nucleus is enriched in specific GRX and TRX isoforms. We discuss the biochemical and molecular characteristics of these isoforms and focus on genetic evidences for their potential nuclear functions. Finally, we make an overview of the different thiol-based redox regulated proteins in the nucleus. These proteins are involved in various pathways including transcriptional regulation, metabolism and signaling. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  11. Non-aqueous carbon black suspensions for lithium-based redox flow batteries: rheology and simultaneous rheo-electrical behavior.

    Science.gov (United States)

    Youssry, Mohamed; Madec, Lénaïc; Soudan, Patrick; Cerbelaud, Manuella; Guyomard, Dominique; Lestriez, Bernard

    2013-09-14

    We report on the rheological and electrical properties of non-aqueous carbon black (CB) suspensions at equilibrium and under steady shear flow. The smaller the primary particle size of carbon black is, the higher the magnitude of rheological parameters and the conductivity are. The electrical percolation threshold ranges seem to coincide with the strong gel rather than the weak gel rheological threshold ones. The simultaneous measurements of electrical properties under shear flow reveal the well-known breaking-and-reforming mechanism that characterises such complex fluids. The small shear rate breaks up the network into smaller agglomerates, which in turn transform into anisometric eroded ones at very high shear rates, recovering the network conductivity. The type of carbon black, its concentration range and the flow rate range are now precisely identified for optimizing the performance of a redox flow battery. A preliminary electrochemical study for a composite anolyte (CB/Li4Ti5O12) at different charge-discharge rates and thicknesses is shown.

  12. The influence of reactive oxygen species on local redox conditions in oxygenated natural waters

    Directory of Open Access Journals (Sweden)

    Andrew Rose

    2016-11-01

    Full Text Available Redox conditions in natural waters are a fundamental control on biogeochemical processes and ultimately many ecosystem functions. While the dioxygen/water redox couple controls redox thermodynamics in oxygenated aquatic environments on geological timescales, it is kinetically inert in the extracellular environment on the much shorter timescales on which many biogeochemical processes occur. Instead, electron transfer processes on these timescales are primarily mediated by a relatively small group of trace metals and stable radicals, including the reactive oxygen species superoxide. Such processes are of critical biogeochemical importance because many of these chemical species are scarce nutrients, but may also be toxic at high concentrations. Furthermore, their bioavailability and potentially toxicity is typically strongly influenced by their redox state. In this paper, I examine to what extent redox conditions in oxygenated natural waters are expected to be reflected in the redox states of labile redox-active compounds that readily exchange electrons with the dioxygen/superoxide redox couple, and potentially with each other. Additionally, I present the hypothesis that that the relative importance of the dioxygen/superoxide and superoxide/hydrogen peroxide redox couples exerts a governing control on local redox conditions in oxygenated natural waters on biogeochemically important timescales. Given the recent discovery of widespread extracellular superoxide production by a diverse range of organisms, this suggests the existence of a fundamental mechanism for organisms to tightly regulate local redox conditions in their extracellular environment in oxygenated natural waters.

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

    Directory of Open Access Journals (Sweden)

    Masood Ahmad Rizvi

    2015-03-01

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

  14. Broadband metamaterial absorber based on coupling resistive frequency selective surface.

    Science.gov (United States)

    Sun, LiangKui; Cheng, HaiFeng; Zhou, YongJiang; Wang, Jun

    2012-02-13

    We report the design, fabrication, and measurement of a broadband metamaterial absorber, which consists of lossy frequency selective surface (FSS) and a metallic ground plane separated by a dielectric layer. The compact single unit cell of the FSS contains crisscross and fractal square patch which couple with each other. Both qualitative analysis by equivalent circuit and accurate numeric calculation show that the coupling between the crisscross and the fractal square patch can enhance the bandwidth with the reflectivity below -10dB in the frequency range of 2-18GHz by producing a third absorption null. In the end, the designed absorber was realized by experiment.

  15. Cooperative redox activation for carbon dioxide conversion.

    Science.gov (United States)

    Lian, Zhong; Nielsen, Dennis U; Lindhardt, Anders T; Daasbjerg, Kim; Skrydstrup, Troels

    2016-12-16

    A longstanding challenge in production chemistry is the development of catalytic methods for the transformation of carbon dioxide into useful chemicals. Silane and borane promoted reductions can be fined-tuned to provide a number of C1-building blocks under mild conditions, but these approaches are limited because of the production of stoichiometric waste compounds. Here we report on the conversion of CO2 with diaryldisilanes, which through cooperative redox activation generate carbon monoxide and a diaryldisiloxane that actively participate in a palladium-catalysed carbonylative Hiyama-Denmark coupling for the synthesis of an array of pharmaceutically relevant diarylketones. Thus the disilane reagent not only serves as the oxygen abstracting agent from CO2, but the silicon-containing 'waste', produced through oxygen insertion into the Si-Si bond, participates as a reagent for the transmetalation step in the carbonylative coupling. Hence this concept of cooperative redox activation opens up for new avenues in the conversion of CO2.

  16. Cooperative redox activation for carbon dioxide conversion

    Science.gov (United States)

    Lian, Zhong; Nielsen, Dennis U.; Lindhardt, Anders T.; Daasbjerg, Kim; Skrydstrup, Troels

    2016-12-01

    A longstanding challenge in production chemistry is the development of catalytic methods for the transformation of carbon dioxide into useful chemicals. Silane and borane promoted reductions can be fined-tuned to provide a number of C1-building blocks under mild conditions, but these approaches are limited because of the production of stoichiometric waste compounds. Here we report on the conversion of CO2 with diaryldisilanes, which through cooperative redox activation generate carbon monoxide and a diaryldisiloxane that actively participate in a palladium-catalysed carbonylative Hiyama-Denmark coupling for the synthesis of an array of pharmaceutically relevant diarylketones. Thus the disilane reagent not only serves as the oxygen abstracting agent from CO2, but the silicon-containing `waste', produced through oxygen insertion into the Si-Si bond, participates as a reagent for the transmetalation step in the carbonylative coupling. Hence this concept of cooperative redox activation opens up for new avenues in the conversion of CO2.

  17. The AHA Moment: Assessment of the Redox Stability of Ionic Liquids Based on Aromatic Heterocyclic Anions (AHAs) for Nuclear Separations and Electric Energy Storage.

    Science.gov (United States)

    Shkrob, Ilya A; Marin, Timothy W

    2015-11-19

    Because of their extended conjugated bond network, aromatic compounds generally have higher redox stability than less saturated compounds. We conjectured that ionic liquids (ILs) consisting of aromatic heterocyclic anions (AHAs) may exhibit improved radiation and electrochemical stability. Such properties are important in applications of these ILs as diluents in radionuclide separations and electrolytes in the electric energy storage devices. In this study, we systematically examine the redox chemistry of the AHAs. Three classes of these anions have been studied: (i) simple 5-atom ring AHAs, such as the pyrazolide and triazolides, (ii) AHAs containing an adjacent benzene ring, and (iii) AHAs containing electron-withdrawing groups that were introduced to reduce their basicity and interaction with metal ions. It is shown that fragmentation in the reduced and oxidized states of these AHAs does not generally occur, and the two main products, respectively, are the H atom adduct and the imidyl radical. The latter species occurs either as an N σ-radical or as an N π-radical, depending on the length of the N-N bond, and the state that is stabilized in the solid matrix is frequently different from that having the lowest energy in the gas phase. In some instances, the formation of the sandwich π-stack dimer radical anions has been observed. For trifluoromethylated anions, H adduct formation did not occur; instead, there was facile loss of fluoride from their fluorinated groups. The latter can be problematic in nuclear separations, but beneficial in batteries. Overall, our study suggests that AHA-based ILs are viable candidates for use as radiation-exposed diluents and electrolytes.

  18. Analysis of the organic hydroperoxide response of Chromobacterium violaceum reveals that OhrR is a cys-based redox sensor regulated by thioredoxin.

    Directory of Open Access Journals (Sweden)

    José F da Silva Neto

    Full Text Available Organic hydroperoxides are oxidants generated during bacterial-host interactions. Here, we demonstrate that the peroxidase OhrA and its negative regulator OhrR comprise a major pathway for sensing and detoxifying organic hydroperoxides in the opportunistic pathogen Chromobacterium violaceum. Initially, we found that an ohrA mutant was hypersensitive to organic hydroperoxides and that it displayed a low efficiency for decomposing these molecules. Expression of ohrA and ohrR was specifically induced by organic hydroperoxides. These genes were expressed as monocistronic transcripts and also as a bicistronic ohrR-ohrA mRNA, generating the abundantly detected ohrA mRNA and the barely detected ohrR transcript. The bicistronic transcript appears to be processed. OhrR repressed both the ohrA and ohrR genes by binding directly to inverted repeat sequences within their promoters in a redox-dependent manner. Site-directed mutagenesis of each of the four OhrR cysteine residues indicated that the conserved Cys21 is critical to organic hydroperoxide sensing, whereas Cys126 is required for disulfide bond formation. Taken together, these phenotypic, genetic and biochemical data indicate that the response of C. violaceum to organic hydroperoxides is mediated by OhrA and OhrR. Finally, we demonstrated that oxidized OhrR, inactivated by intermolecular disulfide bond formation, is specifically regenerated via thiol-disulfide exchange by thioredoxin (but not other thiol reducing agents such as glutaredoxin, glutathione and lipoamide, providing a physiological reducing system for this thiol-based redox switch.

  19. Silicon-based C–N Cross-coupling Reaction

    National Research Council Canada - National Science Library

    Shimizu, Kenta; Minami, Yasunori; Goto, Osamu; Ikehira, Hideyuki; Hiyama, Tamejiro

    2014-01-01

    Palladium-catalyzed C–N bond-forming cross-coupling reaction of N-trimethylsilylamines with aryl bromides and chlorides is found to proceed in the presence of a fluoride activator in 1,3-dimethyl-2-imidazolidinone (DMI...

  20. The Redox Potential of Hot Springs in Taiwan

    Directory of Open Access Journals (Sweden)

    Wen-Fu Chen Menghau Sung

    2009-01-01

    Full Text Available Scientists began acquiring the basic of geology, occurrence, water temperature and chemistry of hot springs in Tai wan over a century ago. However, data regarding redox potential and important redox couples still remains limited. This study explores the redox status of hot springs in Taiwan by measuring Eh in the field and by determining the concentrations of commonly found redox couples, i.e., O2/H2O, NO3 -/NH4 +, and HS-/SO4 -2. Water samples were collected at hot spring discharge pools or the heads of water wells using a pump. A total of 11 hot springs located at 9 different locations across Taiwan were surveyed.

  1. Geothermally Coupled Well-Based Compressed Air Energy Storage

    Energy Technology Data Exchange (ETDEWEB)

    Davidson, C L [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Bearden, Mark D [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Horner, Jacob A [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Appriou, Delphine [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); McGrail, B Peter [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-12-01

    . This project assessed the technical and economic feasibility of implementing geothermally coupled well-based CAES for grid-scale energy storage. Based on an evaluation of design specifications for a range of casing grades common in U.S. oil and gas fields, a 5-MW CAES project could be supported by twenty to twenty-five 5,000-foot, 7-inch wells using lower-grade casing, and as few as eight such wells for higher-end casing grades. Using this information, along with data on geothermal resources, well density, and potential future markets for energy storage systems, The Geysers geothermal field was selected to parameterize a case study to evaluate the potential match between the proven geothermal resource present at The Geysers and the field’s existing well infrastructure. Based on calculated wellbore compressed air mass, the study shows that a single average geothermal production well could provide enough geothermal energy to support a 15.4-MW (gross) power generation facility using 34 to 35 geothermal wells repurposed for compressed air storage, resulting in a simplified levelized cost of electricity (sLCOE) estimated at 11.2 ¢/kWh (Table S.1). Accounting for the power loss to the geothermal power project associated with diverting geothermal resources for air heating results in a net 2-MW decrease in generation capacity, increasing the CAES project’s sLCOE by 1.8 ¢/kWh.

  2. Geothermally Coupled Well-Based Compressed Air Energy Storage

    Energy Technology Data Exchange (ETDEWEB)

    Davidson, Casie L. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Bearden, Mark D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Horner, Jacob A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Cabe, James E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Appriou, Delphine [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); McGrail, B. Peter [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-12-20

    . This project assessed the technical and economic feasibility of implementing geothermally coupled well-based CAES for grid-scale energy storage. Based on an evaluation of design specifications for a range of casing grades common in U.S. oil and gas fields, a 5-MW CAES project could be supported by twenty to twenty-five 5,000-foot, 7-inch wells using lower-grade casing, and as few as eight such wells for higher-end casing grades. Using this information, along with data on geothermal resources, well density, and potential future markets for energy storage systems, The Geysers geothermal field was selected to parameterize a case study to evaluate the potential match between the proven geothermal resource present at The Geysers and the field’s existing well infrastructure. Based on calculated wellbore compressed air mass, the study shows that a single average geothermal production well could provide enough geothermal energy to support a 15.4-MW (gross) power generation facility using 34 to 35 geothermal wells repurposed for compressed air storage, resulting in a simplified levelized cost of electricity (sLCOE) estimated at 11.2 ¢/kWh (Table S.1). Accounting for the power loss to the geothermal power project associated with diverting geothermal resources for air heating results in a net 2-MW decrease in generation capacity, increasing the CAES project’s sLCOE by 1.8 ¢/kWh.

  3. 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.

  4. Investigation on coupling error characteristics in angular rate matching based ship deformation measurement approach

    Science.gov (United States)

    Yang, Shuai; Wu, Wei; Wang, Xingshu; Xu, Zhiguang

    2018-01-01

    The coupling error in the measurement of ship hull deformation can significantly influence the attitude accuracy of the shipborne weapons and equipments. It is therefore important to study the characteristics of the coupling error. In this paper, an comprehensive investigation on the coupling error is reported, which has a potential of deducting the coupling error in the future. Firstly, the causes and characteristics of the coupling error are analyzed theoretically based on the basic theory of measuring ship deformation. Then, simulations are conducted for verifying the correctness of the theoretical analysis. Simulation results show that the cross-correlation between dynamic flexure and ship angular motion leads to the coupling error in measuring ship deformation, and coupling error increases with the correlation value between them. All the simulation results coincide with the theoretical analysis.

  5. Synchronization-based computation through networks of coupled oscillators

    Directory of Open Access Journals (Sweden)

    Daniel eMalagarriga

    2015-08-01

    Full Text Available The mesoscopic activity of the brain is strongly dynamical, while at the sametime exhibiting remarkable computational capabilities. In order to examinehow these two features coexist, here we show that the patterns of synchronizedoscillations displayed by networks of neural mass models, representing cortical columns, can be usedas substrates for Boolean computation. Our results reveal that different logicaloperations can be implemented by the same neural mass network at different timesfollowing the dynamics of the input. The results are reproduced experimentallywith electronic circuits of coupled Chua oscillators, showing the robustness of this kind of computation to the intrinsic noise and parameter mismatch of the oscillators responsible for the functioning of the gates. We also show that theinformation-processing capabilities of coupled oscillations go beyond thesimple juxtaposition of logic gates.

  6. Commande directe de couple d’un moteur asynchrone à base de techniques intelligentes

    OpenAIRE

    GDAIM, Soufien

    2013-01-01

    Design and Experimental Implementation of DTC of an Induction Machine Based on artificial intelligence Control on FPGA; Implémentation sur FPGA de la Commande directe de couple d’un moteur asynchrone à base de techniques intelligentes

  7. Simulation of Octopus Arm Based on Coupled CPGs

    OpenAIRE

    Tian, Juan; Lu, Qiang

    2015-01-01

    The octopus arm has attracted many researchers’ interests and became a research hot spot because of its amazing features. Several dynamic models inspired by an octopus arm are presented to realize the structure with a large number of degrees of freedom. The octopus arm is made of a soft material introducing high-dimensionality, nonlinearity, and elasticity, which makes the octopus arm difficult to control. In this paper, three coupled central pattern generators (CPGs) are built and a 2-dimens...

  8. Copper Bipyridyl Redox Mediators for Dye-Sensitized Solar Cells with High Photovoltage.

    Science.gov (United States)

    Saygili, Yasemin; Söderberg, Magnus; Pellet, Norman; Giordano, Fabrizio; Cao, Yiming; Muñoz-García, Ana Belen; Zakeeruddin, Shaik M; Vlachopoulos, Nick; Pavone, Michele; Boschloo, Gerrit; Kavan, Ladislav; Moser, Jacques-E; Grätzel, Michael; Hagfeldt, Anders; Freitag, Marina

    2016-11-16

    Redox mediators play a major role determining the photocurrent and the photovoltage in dye-sensitized solar cells (DSCs). To maintain the photocurrent, the reduction of oxidized dye by the redox mediator should be significantly faster than the electron back transfer between TiO2 and the oxidized dye. The driving force for dye regeneration with the redox mediator should be sufficiently low to provide high photovoltages. With the introduction of our new copper complexes as promising redox mediators in DSCs both criteria are satisfied to enhance power conversion efficiencies. In this study, two copper bipyridyl complexes, Cu((II/I))(dmby)2TFSI2/1 (0.97 V vs SHE, dmby = 6,6'-dimethyl-2,2'-bipyridine) and Cu((II/I))(tmby)2TFSI2/1 (0.87 V vs SHE, tmby = 4,4',6,6'-tetramethyl-2,2'-bipyridine), are presented as new redox couples for DSCs. They are compared to previously reported Cu((II/I))(dmp)2TFSI2/1 (0.93 V vs SHE, dmp = bis(2,9-dimethyl-1,10-phenanthroline). Due to the small reorganization energy between Cu(I) and Cu(II) species, these copper complexes can sufficiently regenerate the oxidized dye molecules with close to unity yield at driving force potentials as low as 0.1 V. The high photovoltages of over 1.0 V were achieved by the series of copper complex based redox mediators without compromising photocurrent densities. Despite the small driving forces for dye regeneration, fast and efficient dye regeneration (2-3 μs) was observed for both complexes. As another advantage, the electron back transfer (recombination) rates were slower with Cu((II/I))(tmby)2TFSI2/1 as evidenced by longer lifetimes. The solar-to-electrical power conversion efficiencies for [Cu(tmby)2](2+/1+), [Cu(dmby)2](2+/1+), and [Cu(dmp)2](2+/1+) based electrolytes were 10.3%, 10.0%, and 10.3%, respectively, using the organic Y123 dye under 1000 W m(-2) AM1.5G illumination. The high photovoltaic performance of Cu-based redox mediators underlines the significant potential of the new redox mediators

  9. High order vector mode coupling mechanism based on mode matching method

    Science.gov (United States)

    Zhang, Zhishen; Gan, Jiulin; Heng, Xiaobo; Li, Muqiao; Li, Jiong; Xu, Shanhui; Yang, Zhongmin

    2017-06-01

    The high order vector mode (HOVM) coupling mechanism is investigated based on the mode matching method (MMM). In the case of strong HOVM coupling where the weakly guiding approximation fails, conventional coupling analysis methods become invalid due to the asynchronous coupling feature of the horizontal and vertical polarization components of HOVM. The MMM, which uses the interference of the local eigenmodes instead of the assumptive modes to simulate the light propagation, is adopted as a more efficient analysis method for investigating HOVM coupling processes, especially for strong coupling situations. The rules of the optimal coupling length, coupling efficiency, and mode purity in microfiber directional coupler are firstly quantitatively analyzed and summarized. Different from the specific input modes, some special new modes would be excited at the output through the strong HOVM coupling process. The analysis of HOVM coupling mechanism based on MMM could provide precise and accurate design guidance for HOVM directional coupler and mode converter, which are believed to be fundamental devices for multi-mode communication applications.

  10. New Challenges to Study Heterogeneity in Cancer Redox Metabolism

    Directory of Open Access Journals (Sweden)

    Rui Benfeitas

    2017-07-01

    Full Text Available Reactive oxygen species (ROS are important pathophysiological molecules involved in vital cellular processes. They are extremely harmful at high concentrations because they promote the generation of radicals and the oxidation of lipids, proteins, and nucleic acids, which can result in apoptosis. An imbalance of ROS and a disturbance of redox homeostasis are now recognized as a hallmark of complex diseases. Considering that ROS levels are significantly increased in cancer cells due to mitochondrial dysfunction, ROS metabolism has been targeted for the development of efficient treatment strategies, and antioxidants are used as potential chemotherapeutic drugs. However, initial ROS-focused clinical trials in which antioxidants were supplemented to patients provided inconsistent results, i.e., improved treatment or increased malignancy. These different outcomes may result from the highly heterogeneous redox responses of tumors in different patients. Hence, population-based treatment strategies are unsuitable and patient-tailored therapeutic approaches are required for the effective treatment of patients. Moreover, due to the crosstalk between ROS, reducing equivalents [e.g., NAD(PH] and central metabolism, which is heterogeneous in cancer, finding the best therapeutic target requires the consideration of system-wide approaches that are capable of capturing the complex alterations observed in all of the associated pathways. Systems biology and engineering approaches may be employed to overcome these challenges, together with tools developed in personalized medicine. However, ROS- and redox-based therapies have yet to be addressed by these methodologies in the context of disease treatment. Here, we review the role of ROS and their coupled redox partners in tumorigenesis. Specifically, we highlight some of the challenges in understanding the role of hydrogen peroxide (H2O2, one of the most important ROS in pathophysiology in the progression of cancer

  11. Genetically Encoded Fluorescent Redox Probes

    OpenAIRE

    Hui-Wang Ai; Wei Ren

    2013-01-01

    Redox processes are involved in almost every cell of the body as a consequence of aerobic life. In the past decades, redox biology has been increasingly recognized as one of the key themes in cell signaling. The progress has been accelerated by development of fluorescent probes that can monitor redox conditions and dynamics in cells and cell compartments. This short paper focuses on fluorescent redox probes that are genetically encoded, and discusses their properties, molecular mechanism, adv...

  12. An organic redox electrolyte to rival triiodide/iodide in dye-sensitized solar cells.

    Science.gov (United States)

    Wang, Mingkui; Chamberland, Nathalie; Breau, Livain; Moser, Jacques-E; Humphry-Baker, Robin; Marsan, Benoît; Zakeeruddin, Shaik M; Grätzel, Michael

    2010-05-01

    Dye-sensitized solar cells (DSCs) have achieved impressive conversion efficiencies for solar energy of over 11% with an electrolyte that contains triiodide/iodide as a redox couple. Although triiodide/iodide redox couples work efficiently in DSCs, they suffer from two major disadvantages: electrolytes that contain triiodide/iodide corrode electrical contacts made of silver (which reduces the options for the scale up of DSCs to module size) and triiodide partially absorbs visible light. Here, we present a new disulfide/thiolate redox couple that has negligible absorption in the visible spectral range, a very attractive feature for flexible DSCs that use transparent conductors as current collectors. Using this novel, iodide-free redox electrolyte in conjunction with a sensitized heterojunction, we achieved an unprecedented efficiency of 6.4% under standard illumination test conditions. This novel redox couple offers a viable pathway to develop efficient DSCs with attractive properties for scale up and practical applications.

  13. Electrochemical and Computational Studies on the Electrocatalytic Effect of Conducting Polymers toward the Redox Reactions of Thiadiazole-Based Thiolate Compounds

    KAUST Repository

    Rodríguez-Calero, Gabriel G.

    2010-04-08

    We have studied the electrocatalytic effects of polythiophene-based conducting polymers toward the redox reactions of the dilithium salt of the thiadiazole-based dithiol compound 2,5-dimercapto-1,3,4-thiodiazole (DMcT-2Li) via cyclic voltammetry (CV), rotating-disk electrode voltammetry, and electrochemical impedance spectroscopy (EIS). We have found that the electrocatalytic activity of the conducting polymers is strongly influenced by the potential range over which the polymers are electrically conductive (i.e., window of conductivity), which was tuned by employing different electron-donating groups at the 3- or 3,4-positions of polythiophene (PTh). Both poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-propylenedioxythiophene) (PProDOT), whose windows of conductivity exhibited a good overlap with the formal potential for the dimerization process of DMcT-2Li; E0′ d (?0.54 V versus Ag/Ag+) exhibited electrocatalytic activity toward both the oxidation and reduction processes of DMcT-2Li. On the other hand, PTh, poly(3-methylthiophene) (PMTh), and poly(3,4- dimethoxythiophene) (PDMTh), whose windows of conductivity did not overlap with E0′d, did not exhibit electrocatalytic activity. The standard charge transfer rate constants for the dimerization process of DMcT-2Li at PEDOT, PProDOT, and PDMTh film-modified glassy carbon electrodes (GCEs) were estimated to be 7.4 - 10?4, 3.2 - 10?4, and 6.9 - 10?5 cm/s while the rate constant was 6.3 - 10?5 cm/s at an unmodified GCE. Moreover, EIS studies for PEDOT, PProDOT, and PDMTh film-modified GCEs indicated the smallest charge transfer resistance for a PEDOT film and highest for a PDMTh film at E0′d, indicating that the higher the electrical conductivity of a film at E 0′d the higher the electrocatalytic activity toward the redox reactions of DMcT-2Li. These results clearly indicate that in order to accelerate the redox reactions of DMcT-2Li (and likely of other organosulfur compounds) the window of conductivity

  14. Web-Based Couple Interventions: Do They Have a Future?

    Science.gov (United States)

    Georgia, Emily J; Doss, Brian D

    To examine the current and potential future impact of formal and informal resources to enhance romantic relationships, 1,160 individuals were surveyed. When asked about resources previously utilized, participants reported that numerous forms of relationship help, including talking to a friend/coworker/family member, an individual therapist, and reading self-help materials had a larger impact than attending couple therapy. When asked about potential resources they would be likely to use in the future for relationship problems, participants indicated a strong preference for online self-help resources that included detailed feedback paired with a comprehensive, structured program. Implications for future development and dissemination are discussed.

  15. Coupled-oscillator based active-array antennas

    CERN Document Server

    Pogorzelski, Ronald J

    2012-01-01

    Describing an innovative approach to phased-array control in antenna design This book explores in detail phased-array antennas that use coupled-oscillator arrays, an arrangement featuring a remarkably simple beam steering control system and a major reduction in complexity compared with traditional methods of phased-array control. It brings together in one convenient, self-contained volume the many salient research results obtained over the past ten to fifteen years in laboratories around the world, including the California Institute of Technology's Jet Propulsion Laboratory.

  16. Magnetic coupling in Fe/(Ga,Mn)As based heterostructures

    Energy Technology Data Exchange (ETDEWEB)

    Sperl, M.; Soda, M.; Eigenmann, F.; Utz, M.; Woltersdorf, G.; Bougeard, D.; Back, C.H. [Institut fuer Experimentelle Physik, Universitaet Regensburg, D-93040 Regensburg (Germany); Torelli, P.; Panaccione, G. [Laboratorio Nazionale TASC, INFM-CNR, in Area Science Park, S.S. 14, Km 163.5, I-34012 Trieste (Italy); Polesya, S. [Department of Chemistry, Ludwig-Maximilians University Munich (Germany)

    2011-07-01

    (Ga,Mn)As is one of the most promising diluted magnetic semiconductors (DMS) for spintronics due to the compatibility with the GaAs MBE technology. Despite the promising features (Ga,Mn)As has a Curie temperature well below room temperature limiting its possible applications. One potential direction to tailor novel properties of DMS thus making integration in real devices feasible is to exploit interface effects in highly controlled heterostructures (HS). Following this route FM behaviour of Mn at room temperature in both epitaxial and non-epitaxial Fe/(Ga,Mn)As interfaces has been demonstrated. We report results obtained with Synchrotron Radiation techniques, where we were able to monitor the evolution of the magnetic coupling between Fe and Mn as a function of Mn doping, temperature and thickness. In particular, XMCD experiments show a peculiar thickness dependence of the room temperature magnetic coupling between Fe and Mn, namely a switching from antiparallel to parallel, thus opening the possibility of controlling the magnetization state of the interface.

  17. Synthesis, pH dependent photometric and electrochemical investigation, redox mechanism and biological applications of novel Schiff base and its metallic derivatives

    Science.gov (United States)

    Rauf, Abdur; Shah, Afzal; Khan, Abdul Aziz; Shah, Aamir Hassan; Abbasi, Rashda; Qureshi, Irfan Zia; Ali, Saqib

    2017-04-01

    A novel Schiff base, 1-((2, 4-dimethylphenylimino)methyl)naphthalen-2-ol abbreviated as (HL) and its four metallic complexes were synthesized and confirmed by 1H and 13C NMR, FTIR, TGA and UV-Visible spectroscopy. Schiff base was also characterized by X-ray analysis. The photometric and electrochemical responses of all the synthesized compounds were investigated in a wide pH range. Structures of the compounds were optimized computationally for the evaluation of different physico-chemical parameters. On the basis of electrochemical results the redox mechanistic pathways of the compounds were proposed. The cytotoxicity analysis on Hela cells revealed that HL and its complexes inhibit cell growth as revealed from their IC50 values (HL):106.7 μM, (L2VO): 40.66 μM, (L2Sn): 5.92 μM, (L2Zn): 42.82 and (L2Co): 107.68 μM. The compounds were tested for anti-diabetic, triglyceride, cholesterol, anti-microbial, anti-fungal and enzyme inhibition activities. The results revealed that HL and its complexes are promising new therapeutic options as these compounds exhibit strong activity against cancer cells, diabetics, fungal and microbial inhibition.

  18. New Role of Flavin as a General Acid-Base Catalyst with No Redox Function in Type 2 Isopentenyl-diphosphate Isomerase*S⃞

    Science.gov (United States)

    Unno, Hideaki; Yamashita, Satoshi; Ikeda, Yosuke; Sekiguchi, Shin-ya; Yoshida, Norie; Yoshimura, Tohru; Kusunoki, Masami; Nakayama, Toru; Nishino, Tokuzo; Hemmi, Hisashi

    2009-01-01

    Using FMN and a reducing agent such as NAD(P)H, type 2 isopentenyl-diphosphate isomerase catalyzes isomerization between isopentenyl diphosphate and dimethylallyl diphosphate, both of which are elemental units for the biosynthesis of highly diverse isoprenoid compounds. Although the flavin cofactor is expected to be integrally involved in catalysis, its exact role remains controversial. Here we report the crystal structures of the substrate-free and complex forms of type 2 isopentenyl-diphosphate isomerase from the thermoacidophilic archaeon Sulfolobus shibatae, not only in the oxidized state but also in the reduced state. Based on the active-site structures of the reduced FMN-substrate-enzyme ternary complexes, which are in the active state, and on the data from site-directed mutagenesis at highly conserved charged or polar amino acid residues around the active site, we demonstrate that only reduced FMN, not amino acid residues, can catalyze proton addition/elimination required for the isomerase reaction. This discovery is the first evidence for this long suspected, but previously unobserved, role of flavins just as a general acid-base catalyst without playing any redox roles, and thereby expands the known functions of these versatile coenzymes. PMID:19158086

  19. Synthesis, pH dependent photometric and electrochemical investigation, redox mechanism and biological applications of novel Schiff base and its metallic derivatives.

    Science.gov (United States)

    Rauf, Abdur; Shah, Afzal; Khan, Abdul Aziz; Shah, Aamir Hassan; Abbasi, Rashda; Qureshi, Irfan Zia; Ali, Saqib

    2017-04-05

    A novel Schiff base, 1-((2, 4-dimethylphenylimino)methyl)naphthalen-2-ol abbreviated as (HL) and its four metallic complexes were synthesized and confirmed by 1H and 13C NMR, FTIR, TGA and UV-Visible spectroscopy. Schiff base was also characterized by X-ray analysis. The photometric and electrochemical responses of all the synthesized compounds were investigated in a wide pH range. Structures of the compounds were optimized computationally for the evaluation of different physico-chemical parameters. On the basis of electrochemical results the redox mechanistic pathways of the compounds were proposed. The cytotoxicity analysis on Hela cells revealed that HL and its complexes inhibit cell growth as revealed from their IC50 values (HL):106.7μM, (L2VO): 40.66μM, (L2Sn): 5.92μM, (L2Zn): 42.82 and (L2Co): 107.68μM. The compounds were tested for anti-diabetic, triglyceride, cholesterol, anti-microbial, anti-fungal and enzyme inhibition activities. The results revealed that HL and its complexes are promising new therapeutic options as these compounds exhibit strong activity against cancer cells, diabetics, fungal and microbial inhibition. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Improvement of BP-Based CDMA Multiuser Detection by Spatial Coupling

    CERN Document Server

    Takeuchi, Keigo; Kawabata, Tsutomu

    2011-01-01

    Kudekar et al. proved that the belief-propagation (BP) threshold for low-density parity-check (LDPC) codes can be boosted up to the maximum-a-posteriori (MAP) threshold by spatial coupling. In this paper, spatial coupling is applied to randomly-spread code-division multiple-access (CDMA) systems in order to improve the performance of BP-based multiuser detection (MUD). Spatially-coupled CDMA systems can be regarded as multi-code CDMA systems with two transmission phases. The large-system analysis shows that spatial coupling can improve the BP performance, while there is a gap between the BP performance and the optimal performance.

  1. Electrochemistry of redox-active Mn porphyrin-based SOD mimic MnTnBuOE-2-PyP5+ - Study of Redox Species Involved in ROS/RNS Scavenging

    Directory of Open Access Journals (Sweden)

    Tin Weitner

    2014-09-01

    Full Text Available Manganese ortho tetrakis(N-n-butoxyethylpyridinium-2-ylporphyrin, MnTnBuOE-2-PyP5+, is a third-generation redox-active compound currently undergoing preclinical exploration. This work is intended to complement the already extensive research of its chemical and biological properties by a simple electrochemical study. The thermodynamic parameters related to the Mn(IV porphyrin species of MnTnBuOE-2-PyP5+ determined in this work support its observed reactivity as an efficient scavenger of peroxynitrite. The corresponding driving forces for the possible single-electron or two-electron reductions of ONOO- have been estimated as well.

  2. Optical flip-flop: Based on two-coupled mode-locked ring lasers

    NARCIS (Netherlands)

    Tangdiongga, E.; Yang, X.X.; Li, Z.; Liu, Y.S.; Lenstra, D.; Khoe, G.D.; Dorren, H.J.S.

    2005-01-01

    We report an all-optical flip-flop that is based on two coupled actively mode-locked fiber ring lasers. The lasers are coupled so that when one of the lasers lases, it quenches lasing in the other laser. The state of the flip-flop is determined by the wavelength of the laser that is currently

  3. Optimisation Design of Coupling Region Based on SOI Micro-Ring Resonator

    Directory of Open Access Journals (Sweden)

    Shubin Yan

    2014-12-01

    Full Text Available Design optimization of the coupling region is conducted in order to solve the difficulty of achieving a higher quality factor (Q for large size resonators based on silicon-on-insulator (SOI. Relations among coupling length, coupling ratio and quality factor of the optical cavities are theoretically analyzed. Resonators (R = 100 μm with different coupling styles, concentric, straight, and butterfly, are prepared by the micro-electro-mechanical-systems (MEMS process. Coupling experimental results show that micro-cavity of butterfly-coupled style obtains the narrowest (3 dB bandwidth, and the quality factor has been greatly improved. The results provide the foundation for realization of a large size, high-Q resonator, and its development and application in the integrated optical gyroscopes, filters, sensors, and other related fields.

  4. Electromagnetically induced transparency and absorption in plasmonic metasurfaces based on near-field coupling

    Energy Technology Data Exchange (ETDEWEB)

    Wan, Ming-li, E-mail: mlwan@pdsu.edu.cn [College of Electric and Information Engineering, Pingdingshan University, Pingdingshan 467000 (China); He, Jin-na [College of Electric and Information Engineering, Pingdingshan University, Pingdingshan 467000 (China); Song, Yue-li [College of Electric and Information Engineering, Pingdingshan University, Pingdingshan 467000 (China); New PV-energy Engineering Research Center, Pingdingshan University, Pingdingshan 467000 (China); Zhou, Feng-qun [College of Electric and Information Engineering, Pingdingshan University, Pingdingshan 467000 (China)

    2015-09-04

    We theoretically investigate optical properties of a plasmonic metasurface consisting of a dipolar wire as the bright antenna stacked above a quadrupolar wire as the dark antenna. It is demonstrated that by adjusting the lateral displacement between the two resonators, the spectral feature of the metasurface can be evolved from the plasmonic electromagnetically-induced transparency to electromagnetically-induced absorption. The extracted physical parameters based on the two-coupled-oscillator model reveal that the near-field coupling strength plays a key role for the transition behavior in the plasmonic metasurface. - Highlights: • We study spectral response of metamaterial in dependence on near-field coupling. • Coupled two-oscillator is adopted to explain the spectral behavior. • For weak coupling, metamaterials exhibit an EIA-like feature. • For strong coupling, metamaterials exhibit an EIT-like profile.

  5. A global hybrid coupled model based on Atmosphere-SST feedbacks

    CERN Document Server

    Cimatoribus, Andrea A; Dijkstra, Henk A

    2011-01-01

    A global hybrid coupled model is developed, with the aim of studying the effects of ocean-atmosphere feedbacks on the stability of the Atlantic meridional overturning circulation. The model includes a global ocean general circulation model and a statistical atmosphere model. The statistical atmosphere model is based on linear regressions of data from a fully coupled climate model on sea surface temperature both locally and hemispherically averaged, being the footprint of Atlantic meridional overturning variability. It provides dynamic boundary conditions to the ocean model for heat, freshwater and wind-stress. A basic but consistent representation of ocean-atmosphere feedbacks is captured in the hybrid coupled model and it is more than ten times faster than the fully coupled climate model. The hybrid coupled model reaches a steady state with a climate close to the one of the fully coupled climate model, and the two models also have a similar response (collapse) of the Atlantic meridional overturning circulati...

  6. 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.

  7. Electroactive ionic liquids based on 2,5-ditert-butyl-1,4-dimethoxybenzene and triflimide anion as redox shuttle for Li4Ti5O12/LiFePO4 lithium-ion batteries

    Science.gov (United States)

    Gélinas, Bruno; Bibienne, Thomas; Dollé, Mickael; Rochefort, Dominic

    2017-12-01

    In order to increase the solubility and oxidation potential of redox shuttles, electroactive ionic liquids (RILs) based on the modification of 1,4-dimethoxybenzene with triflimide anions were synthesized. We developed two synthetic routes to obtain these RILs in which the triflimide was either linked on the benzene ring or as a ether on 2,5-ditert-butyl-1,4-dimethoxybenzene (DDB). These RILs all have melting points below 100 °C, but above room temperature. The structural impact of electroactive anion was evaluated in this study by determining the redox potential and electrochemical stability. The electrochemical properties of these RILs were investigated by cyclic voltammetry and the diffusion coefficients were measured by double potential step chronoamperometry. The viscosity and ionic conductivity measurements of redox-active electrolyte were obtained at different temperatures and the RIL additives are shown to have a low impact on these electrolyte properties at concentrations up to 0.3 M. The charge-overcharge-discharge cycles of Li/LiFePO4 half-cells and Li4Ti5O12/LiFePO4 full cells with a 100% overcharge are presented using redox-active electrolyte (0.3 M concentration level) at 0.1 C rate. This study highlights the potential of electroactive ionic liquids as highly soluble and stable functional additives in Li-ion battery electrolytes.

  8. A directional coupling scheme for efficient coupling between Si3N4 photonic and hybrid slot-based plasmonic waveguides

    Science.gov (United States)

    Ketzaki, D.; Dabos, G.; Weeber, J. C.; Dereux, A.; Tsiokos, D.; Pleros, N.

    2017-02-01

    Slot-based plasmonic waveguides have attracted significant attention owing to their unique ability to confine light within nanometer-scale. In this context, enhanced localized light-matter interaction and control have been exploited to demonstrate novel concepts in data communication and sensing applications revealing the immense potential of plasmonic slot waveguides. However, inherent light absorption in the metallic parts included is such structures hampers the scaling of plasmonic devices and limits their application diversity. A promising solution of such issues is the use of hybrid plasmo-photonic configurations. Hybrid slot waveguides have been introduced as the means to reduce such propagation losses while maintaining their functional advantages. In addition, their co-integration with low-loss photonic waveguides can enable the development of more complex structures with acceptable overall losses. In such scenario, light needs to be efficiently transferred from the photonic to the plasmonic components and/or backwards. Based on this rationale, in this work a hybrid slot-based structure is adopted to achieve highly efficient light transfer between photonic and plasmonic slot waveguides in the near-infrared spectrum region (λ=1550 nm). This transition is realized with the aid of a directional coupling scheme. For this purpose, a Si3N4 bus waveguide (photonic branch) is located below an Aubased metallic slot (plasmonic branch) forming a hybrid waveguide element. The combined configuration, as it is shown with the aid of numerical simulations , is capable of supporting two hybrid guided modes with quasi-even and odd symmetry allowing the development of a power exchange mechanism between the two branches. In this context, a new directional coupling structure has been designed which can achieve power transmission per transition over 68% within a coupling length of the order of just several microns.

  9. Hybrid method based on embedded coupled simulation of vortex particles in grid based solution

    Science.gov (United States)

    Kornev, Nikolai

    2017-09-01

    The paper presents a novel hybrid approach developed to improve the resolution of concentrated vortices in computational fluid mechanics. The method is based on combination of a grid based and the grid free computational vortex (CVM) methods. The large scale flow structures are simulated on the grid whereas the concentrated structures are modeled using CVM. Due to this combination the advantages of both methods are strengthened whereas the disadvantages are diminished. The procedure of the separation of small concentrated vortices from the large scale ones is based on LES filtering idea. The flow dynamics is governed by two coupled transport equations taking two-way interaction between large and fine structures into account. The fine structures are mapped back to the grid if their size grows due to diffusion. Algorithmic aspects of the hybrid method are discussed. Advantages of the new approach are illustrated on some simple two dimensional canonical flows containing concentrated vortices.

  10. 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.

  11. Modes Coupling Analysis of Surface Plasmon Polaritons Based Resonance Manipulation in Infrared Metamaterial Absorber

    Science.gov (United States)

    Zhen, Guoshuai; Zhou, Peiheng; Luo, Xiaojia; Xie, Jianliang; Deng, Longjiang

    2017-04-01

    Surface plasmon polaritons (SPPs) and standing wave modes provide interesting and exotic properties for infrared metamaterial absorbers. Coupling of these modes promises further development in this field but restricted by the complexity of modes analysis. In this work, we investigate the general phenomenon of modes coupling supported by a metal (with grating)-dielectric-metal sandwich structure based on rigorous coupled-wave analysis (RCWA) method and experiment results. Through the analysis of fundamental modes, a new approach based on the boundary conditions is introduced to reveal the coupling mechanism and the corresponding resonance shifting phenomenon with simple but rigorous derivations. The strong coupling between SPPs excited on the dielectric-metal interfaces and rigorous modes of standing waves in the dielectric layer can be manipulated to improve the detection sensitivity of sensors and emissivity efficiency of infrared emitters.

  12. pH and redox dual stimulate-responsive nanocarriers based on hyaluronic acid coated mesoporous silica for targeted drug delivery.

    Science.gov (United States)

    Lin, Jian-Tao; Du, Ji-Kun; Yang, Yi-Qiu; Li, Li; Zhang, Da-Wei; Liang, Cui-Ling; Wang, Jie; Mei, Jun; Wang, Guan-Hai

    2017-12-01

    In this work, we developed a drug-conjugated nanocarrier with "zero premature release" property for actively targeted drug delivery. The pH and redox dual-responsive nanocarrier was fabricated based on hyaluronic acid (HA) modified the mesoporous silica nanoparticles (MSNs). Doxorubicin (DOX) was conjugated to MSNs via hydrazone bonds, which can be cleaved in tumor tissue (acidic conditions). To improve specific cellular uptake and stability of nanocarriers, HA was equipped with an outer shell on the nanoparticle surface via a disulfide crosslinker. Stimulus-induced release of the DOX was studied in the different pH and GSH, which showed the embedded DOX can be controlled release from MSN channels. The dual-triggered drug release system provides an efficient targeted drug delivery system into the cytosol of cancer cells. The results of flow cytometry and confocal laser scanning microscopy (CLSM) showed that the HA-functionalized DOX-conjugated nanoparticles presented much better cellular uptake and higher cytotoxicity to tumor cells. This drug delivery system has great potential for tumor-trigged drug release for cancer therapy. Copyright © 2017. Published by Elsevier B.V.

  13. Colloidal Supercapattery: Redox Ions in Electrode and Electrolyte.

    Science.gov (United States)

    Chen, Kunfeng; Xue, Dongfeng

    2017-09-11

    Redox chemistry is the cornerstone of various electrochemical energy conversion and storage systems, associated with ion diffusion process. To actualize both high energy and power density in energy storage devices, both multiple electron transfer reaction and fast ion diffusion occurred in one electrode material are prerequisite. The existence forms of redox ions can lead to different electrochemical thermodynamic and kinetic properties. Here, we introduce novel colloid system, which includes multiple varying ion forms, multi-interaction and abundant redox active sites. Unlike redox cations in solution and crystal materials, colloid system has specific reactivity-structure relationship. In the colloidal ionic electrode, the occurrence of multiple-electron redox reactions and fast ion diffusion leaded to ultrahigh specific capacitance and fast charge rate. The colloidal ionic supercapattery coupled with redox electrolyte provides a new potential technique for the comprehensive use of redox ions including cations and anions in electrode and electrolyte and a guiding design for the development of next-generation high performance energy storage devices. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. 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.

  15. Hot semiworks Redox studies

    Energy Technology Data Exchange (ETDEWEB)

    Evans, T.F.; Tomlinson, R.E.

    1954-01-27

    The separations Hot Semiworks at the Hanford Atomic Products Operation was built in order to: (1) develop optimum conditions for the economic operation of the Redox and TBP plants, (2) procure engineering design data which would allow the specification of process equipment required for new processes such as Purex, (3) provide facilities for the study of future process and engineering problems on a semiworks scale employing radioactive process solutions, and (4) provide facilities for immediate trouble shooting for urgent separations plant problems. The initial operation of this facility was designed to develop conditions for the economic operation of the Redox Plant. These studies, covering a period from November, 1952 to October, 1953, are described in this report. The Redox process is used at Hanford for the separation of uranium and plutonium from fission products and from each other. The basis of the process is the preferential extraction of uranium and plutonium nitrates from an aqueous phase of high salting strength into an organic solvent (methyl isobutyl ketone) to effect the separation from fission products. This operation is conducted continuously in columns, packed with Raschig rings, through which the phases are passed counter-currently. Uranium and plutonium are separated by converting the plutonium to a lower valence state, in which form it is preferentially extracted back into an aqueous phase of high salting strength in a second column. Uranium is then returned to an aqueous phase of low salting strength in a third column. The products are further decontaminated in similar additional cycles. A detailed description of the process is given in the Redox Technical Manual.

  16. Coupling Mechanism of the Tourism Industrial Network Based on Circular Economy

    OpenAIRE

    Han, Xinming; Zheng, Xiangjiang

    2009-01-01

    This paper summarizes the research situation of circular economy and tourism industrial network at home and abroad, introduces the concept and characteristics of tourism industrial network, and analyzes the coupling mechanism of tourism industrial network based on circular economy.

  17. Nonlinear interaction between underwater explosion bubble and structure based on fully coupled model

    Science.gov (United States)

    Zhang, A. M.; Wu, W. B.; Liu, Y. L.; Wang, Q. X.

    2017-08-01

    The interaction between an underwater explosion bubble and an elastic-plastic structure is a complex transient process, accompanying violent bubble collapsing, jet impact, penetration through the bubble, and large structural deformation. In the present study, the bubble dynamics are modeled using the boundary element method and the nonlinear transient structural response is modeled using the explicit finite element method. A new fully coupled 3D model is established through coupling the equations for the state variables of the fluid and structure and solving them as a set of coupled linear algebra equations. Based on the acceleration potential theory, the mutual dependence between the hydrodynamic load and the structural motion is decoupled. The pressure distribution in the flow field is calculated with the Bernoulli equation, where the partial derivative of the velocity potential in time is calculated using the boundary integral method to avoid numerical instabilities. To validate the present fully coupled model, the experiments of small-scale underwater explosion near a stiffened plate are carried out. High-speed imaging is used to capture the bubble behaviors and strain gauges are used to measure the strain response. The numerical results correspond well with the experimental data, in terms of bubble shapes and structural strain response. By both the loosely coupled model and the fully coupled model, the interaction between a bubble and a hollow spherical shell is studied. The bubble patterns vary with different parameters. When the fully coupled model and the loosely coupled model are advanced with the same time step, the error caused by the loosely coupled model becomes larger with the coupling effect becoming stronger. The fully coupled model is more stable than the loosely coupled model. Besides, the influences of the internal fluid on the dynamic response of the spherical shell are studied. At last, the case that the bubble interacts with an air

  18. Model-based risk analysis of coupled process steps.

    Science.gov (United States)

    Westerberg, Karin; Broberg-Hansen, Ernst; Sejergaard, Lars; Nilsson, Bernt

    2013-09-01

    A section of a biopharmaceutical manufacturing process involving the enzymatic coupling of a polymer to a therapeutic protein was characterized with regards to the process parameter sensitivity and design space. To minimize the formation of unwanted by-products in the enzymatic reaction, the substrate was added in small amounts and unreacted protein was separated using size-exclusion chromatography (SEC) and recycled to the reactor. The quality of the final recovered product was thus a result of the conditions in both the reactor and the SEC, and a design space had to be established for both processes together. This was achieved by developing mechanistic models of the reaction and SEC steps, establishing the causal links between process conditions and product quality. Model analysis was used to complement the qualitative risk assessment, and design space and critical process parameters were identified. The simulation results gave an experimental plan focusing on the "worst-case regions" in terms of product quality and yield. In this way, the experiments could be used to verify both the suggested process and the model results. This work demonstrates the necessary steps of model-assisted process analysis, from model development through experimental verification. Copyright © 2013 Wiley Periodicals, Inc.

  19. Efficient fiber-coupled single-photon sources based on quantum dots

    DEFF Research Database (Denmark)

    Daveau, Raphaël Sura

    This thesis presents the study of solid-state quantum emitters in two dierent forms. The rst part of the thesis deals with quantum dot based single-photon sources with an emphasis on ecient photon extraction into an optical ber. The second part of the thesis covers a theoretical study of optical...... refrigeration with coupled quantum wells. Many photonic quantum information processing applications would benet from a highbrightness, ber-coupled source of triggered single photons. This thesis presents a study of such sources based on quantum dots coupled to unidirectional photonic-crystal waveguide devices...

  20. Proterozoic ocean redox and biogeochemical stasis.

    Science.gov (United States)

    Reinhard, Christopher T; Planavsky, Noah J; Robbins, Leslie J; Partin, Camille A; Gill, Benjamin C; Lalonde, Stefan V; Bekker, Andrey; Konhauser, Kurt O; Lyons, Timothy W

    2013-04-02

    The partial pressure of oxygen in Earth's atmosphere has increased dramatically through time, and this increase is thought to have occurred in two rapid steps at both ends of the Proterozoic Eon (∼2.5-0.543 Ga). However, the trajectory and mechanisms of Earth's oxygenation are still poorly constrained, and little is known regarding attendant changes in ocean ventilation and seafloor redox. We have a particularly poor understanding of ocean chemistry during the mid-Proterozoic (∼1.8-0.8 Ga). Given the coupling between redox-sensitive trace element cycles and planktonic productivity, various models for mid-Proterozoic ocean chemistry imply different effects on the biogeochemical cycling of major and trace nutrients, with potential ecological constraints on emerging eukaryotic life. Here, we exploit the differing redox behavior of molybdenum and chromium to provide constraints on seafloor redox evolution by coupling a large database of sedimentary metal enrichments to a mass balance model that includes spatially variant metal burial rates. We find that the metal enrichment record implies a Proterozoic deep ocean characterized by pervasive anoxia relative to the Phanerozoic (at least ∼30-40% of modern seafloor area) but a relatively small extent of euxinic (anoxic and sulfidic) seafloor (less than ∼1-10% of modern seafloor area). Our model suggests that the oceanic Mo reservoir is extremely sensitive to perturbations in the extent of sulfidic seafloor and that the record of Mo and chromium enrichments through time is consistent with the possibility of a Mo-N colimited marine biosphere during many periods of Earth's history.

  1. 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....

  2. Cerium-based metal organic frameworks with UiO-66 architecture: synthesis, properties and redox catalytic activity.

    Science.gov (United States)

    Lammert, Martin; Wharmby, Michael T; Smolders, Simon; Bueken, Bart; Lieb, Alexandra; Lomachenko, Kirill A; Vos, Dirk De; Stock, Norbert

    2015-08-14

    A series of nine Ce(iv)-based metal organic frameworks with the UiO-66 structure containing linker molecules of different sizes and functionalities were obtained under mild synthesis conditions and short reaction times. Thermal and chemical stabilities were determined and a Ce-UiO-66-BDC/TEMPO system was successfully employed for the aerobic oxidation of benzyl alcohol.

  3. Quinonoid functionality redox properties Diiminic functionality Lewis ...

    African Journals Online (AJOL)

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    base due to the presence of the two diiminic nitrogen atoms (Scheme 1). Calderazzo et al. [2], showed that PDON reacts with Lewis acids such as TiCl4 to give N,N-coordinated derivatives, and with a low-valent organometallic compound giving a redox reaction (Scheme 2). It has to be noted that when PDON coordinates ...

  4. Study on frequency characteristics of wireless power transmission system based on magnetic coupling resonance

    Science.gov (United States)

    Liang, L. H.; Liu, Z. Z.; Hou, Y. J.; Zeng, H.; Yue, Z. K.; Cui, S.

    2017-11-01

    In order to study the frequency characteristics of the wireless energy transmission system based on the magnetic coupling resonance, a circuit model based on the magnetic coupling resonant wireless energy transmission system is established. The influence of the load on the frequency characteristics of the wireless power transmission system is analysed. The circuit coupling theory is used to derive the minimum load required to suppress frequency splitting. Simulation and experimental results verify that when the load size is lower than a certain value, the system will appear frequency splitting, increasing the load size can effectively suppress the frequency splitting phenomenon. The power regulation scheme of the wireless charging system based on magnetic coupling resonance is given. This study provides a theoretical basis for load selection and power regulation of wireless power transmission systems.

  5. Improved coupling of nanowire-based high-T c SQUID magnetometers—simulations and experiments

    Science.gov (United States)

    Xie, M.; Chukharkin, M. L.; Ruffieux, S.; Schneiderman, J. F.; Kalabukhov, A.; Arzeo, M.; Bauch, T.; Lombardi, F.; Winkler, D.

    2017-11-01

    Superconducting quantum interference devices (SQUIDs) based on high critical-temperature superconducting nanowire junctions were designed, fabricated, and characterized in terms of their potential as magnetometers for magnetoencephalography (MEG). In these devices, the high kinetic inductance of junctions and the thin film thickness (50 nm) pose special challenges in optimizing the field coupling. The high kinetic inductance also brings difficulties in reaching a low SQUID noise. To explore the technique for achieving a high field sensitivity, single-layer devices with a directly connected pickup loop and flip-chip devices with an inductively coupled flux transformer using a two-level coupling approach were fabricated and tested. Two-level coupling is an approach designed for flip-chip nanowire-based SQUIDs, in which a washer type SQUID pickup loop is introduced as an intermediate coupling level between the SQUID loop and the flux transformer input coil. The inductances and effective areas of all these devices were simulated. We found that at T = 77 K, flip-chip devices with the two-level coupling approach (coupling coefficient of 0.37) provided the best effective area of 0.46 mm2 among all the tested devices. With a flux noise level of 55 μ {{Φ }} 0 {{Hz}}-1/2, the field sensitivity level was 240 fT {{Hz}}-1/2. This sensitivity is not yet adequate for MEG applications but it is the best level ever reached for nanowire-based high-T c SQUID magnetometers.

  6. Strain Field in Ultrasmall Gold Nanoparticles Supported on Cerium-Based Mixed Oxides. Key Influence of the Support Redox State.

    Science.gov (United States)

    López-Haro, Miguel; Yoshida, Kenta; Del Río, Eloy; Pérez-Omil, José A; Boyes, Edward D; Trasobares, Susana; Zuo, Jian-Min; Gai, Pratibha L; Calvino, José J

    2016-05-03

    Using a method that combines experimental and simulated Aberration-Corrected High Resolution Electron Microscopy images with digital image processing and structure modeling, strain distribution maps within gold nanoparticles relevant to real powder type catalysts, i.e., smaller than 3 nm, and supported on a ceria-based mixed oxide have been determined. The influence of the reduction state of the support and particle size has been examined. In this respect, it has been proven that reduction even at low temperatures induces a much larger compressive strain on the first {111} planes at the interface. This increase in compression fully explains, in accordance with previous DFT calculations, the loss of CO adsorption capacity of the interface area previously reported for Au supported on ceria-based oxides.

  7. Spectrophotometric determination of lansoprazole in pharmaceuticals using bromate-bromide mixture based on redox and complexation reactions

    OpenAIRE

    Basavaiah, K.; Ramakrishna, V.; U. R. Anil Kumar; Somashekar, B. C.

    2007-01-01

    Two sensitive spectrophotometric methods are described for the determination of lansoprazole (LPZ) in bulk drug and in capsule formulation. The methods are based on the oxidation of lansoprazole by insitu generated bromine followed by determination of unreacted bromine by two different reaction schemes. In one procedure (method A), the residual bromine is treated with excess of iron (II), and the resulting iron (III) is complexed with thiocyanate and measured at 470 nm. The second approach (m...

  8. Quantum mechanical determinations of reaction mechanisms, acid base, and redox properties of nitrogen oxides and their donors.

    Science.gov (United States)

    Dutton, Andrew S; Fukuto, Jon M; Houk, K N

    2005-01-01

    This chapter reviews computational methods based on quantum mechanics and commonly used commercial programs for the exploration of chemical phenomena, particularly in the field of nitrogen oxides. Examples from the literature are then used to demonstrate the application of these methods to the chemistry and biochemistry of various nitrogen oxides. These examples include determining reaction mechanisms using computed reaction energies, predicting rates of reactions using transition state theory, and determining chemical properties such as hydration equilibria, pKa's, and reduction potentials.

  9. Integrated approach for fusion multi-physics coupled analyses based on hybrid CAD and mesh geometries

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, Yuefeng, E-mail: yuefeng.qiu@kit.edu; Lu, Lei; Fischer, Ulrich

    2015-10-15

    Highlights: • Integrated approach for neutronics, thermal and structural analyses was developed. • MCNP5/6, TRIPOLI-4 were coupled with CFX, Fluent and ANSYS Workbench. • A novel meshing approach has been proposed for describing MC geometry. - Abstract: Coupled multi-physics analyses on fusion reactor devices require high-fidelity neutronic models, and flexible, accurate data exchanging between various calculation codes. An integrated coupling approach has been developed to enable the conversion of CAD, mesh, or hybrid geometries for Monte Carlo (MC) codes MCNP5/6, TRIPOLI-4, and translation of nuclear heating data for CFD codes Fluent, CFX and structural mechanical software ANSYS Workbench. The coupling approach has been implemented based on SALOME platform with CAD modeling, mesh generation and data visualization capabilities. A novel meshing approach has been developed for generating suitable meshes for MC geometry descriptions. The coupling approach has been concluded to be reliable and efficient after verification calculations of several application cases.

  10. AUV Positioning Method Based on Tightly Coupled SINS/LBL for Underwater Acoustic Multipath Propagation.

    Science.gov (United States)

    Zhang, Tao; Shi, Hongfei; Chen, Liping; Li, Yao; Tong, Jinwu

    2016-03-11

    This paper researches an AUV (Autonomous Underwater Vehicle) positioning method based on SINS (Strapdown Inertial Navigation System)/LBL (Long Base Line) tightly coupled algorithm. This algorithm mainly includes SINS-assisted searching method of optimum slant-range of underwater acoustic propagation multipath, SINS/LBL tightly coupled model and multi-sensor information fusion algorithm. Fuzzy correlation peak problem of underwater LBL acoustic propagation multipath could be solved based on SINS positional information, thus improving LBL positional accuracy. Moreover, introduction of SINS-centered LBL locating information could compensate accumulative AUV position error effectively and regularly. Compared to loosely coupled algorithm, this tightly coupled algorithm can still provide accurate location information when there are fewer than four available hydrophones (or within the signal receiving range). Therefore, effective positional calibration area of tightly coupled system based on LBL array is wider and has higher reliability and fault tolerance than loosely coupled. It is more applicable to AUV positioning based on SINS/LBL.

  11. AUV Positioning Method Based on Tightly Coupled SINS/LBL for Underwater Acoustic Multipath Propagation

    Directory of Open Access Journals (Sweden)

    Tao Zhang

    2016-03-01

    Full Text Available This paper researches an AUV (Autonomous Underwater Vehicle positioning method based on SINS (Strapdown Inertial Navigation System/LBL (Long Base Line tightly coupled algorithm. This algorithm mainly includes SINS-assisted searching method of optimum slant-range of underwater acoustic propagation multipath, SINS/LBL tightly coupled model and multi-sensor information fusion algorithm. Fuzzy correlation peak problem of underwater LBL acoustic propagation multipath could be solved based on SINS positional information, thus improving LBL positional accuracy. Moreover, introduction of SINS-centered LBL locating information could compensate accumulative AUV position error effectively and regularly. Compared to loosely coupled algorithm, this tightly coupled algorithm can still provide accurate location information when there are fewer than four available hydrophones (or within the signal receiving range. Therefore, effective positional calibration area of tightly coupled system based on LBL array is wider and has higher reliability and fault tolerance than loosely coupled. It is more applicable to AUV positioning based on SINS/LBL.

  12. Breathing Pores on Command: Redox-Responsive Spongy Membranes from Poly(ferrocenylsilane)s

    NARCIS (Netherlands)

    Zhang, Kaihuan; Feng, Xueling; Sui, Xiaofeng; Hempenius, Mark A.; Vancso, Gyula J.

    2014-01-01

    Redox-responsive porous membranes can be readily formed by electrostatic complexation between redox active poly(ferrocenylsilane) PFS-based poly(ionic liquid)s and organic acids. Redox-induced changes on this membrane demonstrated reversible switching between more open and more closed porous

  13. Multistimuli responsive organogels based on a new gelator featuring tetrathiafulvalene and azobenzene groups: reversible tuning of the gel-sol transition by redox reactions and light irradiation.

    Science.gov (United States)

    Wang, Cheng; Chen, Qun; Sun, Fei; Zhang, Deqing; Zhang, Guanxin; Huang, Yanyan; Zhao, Rui; Zhu, Daoben

    2010-03-10

    For the development of multistimuli responsive organogels, the new organic gelator LMWG 1, featuring electroactive TTF and photoresponsive azobenzene groups, was designed and studied. By manipulating the redox state of the TTF group in LMWG 1, the gel-sol transition for organogels with the LMWG 1 can be reversibly tuned by either chemical or electrochemical oxidation/reduction reactions. Alternatively, the photoisomerization of the azobenzene group in LMWG 1 can also trigger the gel-sol transition. Therefore, organogels with LMWG 1 respond not only to thermal stimuli but also to redox reactions and light irradiation.

  14. Characteristics of the iodide/triiodide redox mediator in dye-sensitized solar cells.

    Science.gov (United States)

    Boschloo, Gerrit; Hagfeldt, Anders

    2009-11-17

    Dye-sensitized solar cells (DSCs) have gained widespread interest because of their potential for low-cost solar energy conversion. Currently, the certified record efficiency of these solar cells is 11.1%, and measurements of their durability and stability suggest lifetimes exceeding 10 years under operational conditions. The DSC is a photoelectrochemical system: a monolayer of sensitizing dye is adsorbed onto a mesoporous TiO(2) electrode, and the electrode is sandwiched together with a counter electrode. An electrolyte containing a redox couple fills the gap between the electrodes. The redox couple is a key component of the DSC. The reduced part of the couple regenerates the photo-oxidized dye. The formed oxidized species diffuses to the counter electrode, where it is reduced. The photovoltage of the device depends on the redox couple because it sets the electrochemical potential at the counter electrode. The redox couple also affects the electrochemical potential of the TiO(2) electrode through the recombination kinetics between electrons in TiO(2) and oxidized redox species. This Account focuses on the special properties of the iodide/triiodide (I(-)/I(3)(-)) redox couple in dye-sensitized solar cells. It has been the preferred redox couple since the beginning of DSC development and still yields the most stable and efficient DSCs. Overall, the iodide/triiodide couple has good solubility, does not absorb too much light, has a suitable redox potential, and provides rapid dye regeneration. But what distinguishes I(-)/I(3)(-) from most redox mediators is the very slow recombination kinetics between electrons in TiO(2) and the oxidized part of the redox couple, triiodide. Certain dyes adsorbed at TiO(2) catalyze this recombination reaction, presumably by binding iodine or triiodide. The standard potential of the iodide/triiodide redox couple is 0.35 V (versus the normal hydrogen electrode, NHE), and the oxidation potential of the standard DSC-sensitizer (Ru(dcbpy)(2

  15. New frontiers in couple-based interventions in cancer care: refining the prescription for spousal communication.

    Science.gov (United States)

    Badr, Hoda

    2017-02-01

    The diagnosis and treatment of cancer is a life-altering experience that signals profound changes in a person's life. However, most people do not experience cancer in isolation or cope alone. Despite the fact that partners (i.e. spouses, significant others) provide emotional support and play a critical role in caregiving, cancer exacts a heavy toll on them and challenges their relationship with the patient by altering established communication patterns and roles. In recognition of this, a burgeoning literature involving couple-based interventions to improve patient and partner quality of life and adaptation has emerged. However, questions remain regarding how we can improve these interventions to exact greater impact on patient and partner outcomes. A narrative review of the literature on couples' communication processes in cancer was conducted in order to describe knowledge gaps and directions for future research. Most couple-based interventions have included a communication skills training component because communication is an important process through which couples make sense of cancer, engage in social support, negotiate role changes and coordinate coping responses. However, scholars still know very little about what they should instruct couples to talk about, how often they should talk and when talking (or not talking) is beneficial (and for whom - the patient, partner, or both). In order push this field forward, we need to develop a more nuanced view of couples' communication that acknowledges that there are multiple ways to talk, different aspects of the cancer experience to talk about, and preexisting communication patterns and preferences for different couples that may influence the utility of talk. Interventions that replace the unilateral and generic prescription to talk openly about cancer with targeted questions that prompt reflection on couples' unique strengths, preexisting communication patterns and support resources may thus help bolster the impact

  16. Theory of water treatment by capacitive deionization with redox active porous electrodes.

    Science.gov (United States)

    He, Fan; Biesheuvel, P M; Bazant, Martin Z; Hatton, T Alan

    2018-01-03

    Capacitive deionization (CDI) for water treatment, which relies on the capture of charged species to sustain the electrical double layers (EDLs) established within porous electrodes under an applied electrical potential, can be enhanced by the chemical attachment of fixed charged groups to the porous electrode electrodes (ECDI). It has recently been demonstrated that further improvements in capacity and energy storage can be gained by functionalization of the electrode surfaces with redox polymers in which the charge on the electrodes can be modulated through Faradaic reactions under different cell voltages in a capacitive process that can be called "Faradaic CDI" (FaCDI). Here, we extend recent mathematical models developed for the characterization of CDI and ECDI systems to incorporate the redox mediated contributions by allowing for the variable chemical charges generated by reactions in FaCDI. The lumped model developed here assumes the spacer channel is well-mixed with uniform electrosorption in each electrode. We demonstrate that the salt adsorption performance characterization of the fixed chemical charge ECDI and variable chemical charge FaCDI materials can be unified within a common theoretical framework based on the point of zero charge (PZC) of the electrode material. In the latter case the PZC is determined by the equilibrium potentials of the redox couples immobilized on the porous electrodes. The new model is able to predict the experimentally observed enhanced and inverted performance of CDI cells, and illuminates the benefit of choosing redox active materials for water treatment applications. The deionization performance of FaCDI cells is shown to be superior to that of CDI and ECDI systems with equilibrium adsorption capacities 50-100% higher than attained with CDI systems, and at smaller cell voltages, depending on the redox potentials of the Faradaic moieties. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

    Papa, Sergio; Capitanio, Giuseppe; Papa, Francesco

    2017-06-21

    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.

  18. Strong coupling and polariton lasing in Te based microcavities embedding (Cd,Zn)Te quantum wells

    Energy Technology Data Exchange (ETDEWEB)

    Rousset, J.-G., E-mail: j-g.rousset@fuw.edu.pl; Piętka, B.; Król, M.; Mirek, R.; Lekenta, K.; Szczytko, J.; Borysiuk, J.; Suffczyński, J.; Kazimierczuk, T.; Goryca, M.; Smoleński, T.; Kossacki, P.; Nawrocki, M.; Pacuski, W. [Institute of Experimental Physics, Faculty of Physics, University of Warsaw, ul. Pasteura 5, PL-02-093 Warszawa (Poland)

    2015-11-16

    We report on properties of an optical microcavity based on (Cd,Zn,Mg)Te layers and embedding (Cd,Zn)Te quantum wells. The key point of the structure design is the lattice matching of the whole structure to MgTe, which eliminates the internal strain and allows one to embed an arbitrary number of unstrained quantum wells in the microcavity. We evidence the strong light-matter coupling regime already for the structure containing a single quantum well. Embedding four unstrained quantum wells results in further enhancement of the exciton-photon coupling and the polariton lasing in the strong coupling regime.

  19. The retiring couple – A qualitative study based on grounded theory

    Directory of Open Access Journals (Sweden)

    Sabine Buchebner-Ferstl

    2010-03-01

    Full Text Available A large proportion of retiring people live with their partners. The study The Retiring Couple – a Qualitative Study Based one Grounded Theory deals with the questions of which changes the couples have to face, how they perceive them and which coping strategies they use when they retire. The situations of eight couples and one single person were explored by means of the Grounded Theory by Glaser and Strauss (1967 and the problem-centered interviews (Witzel 1989. The explanatory model deriving from the results relies on a role-based concept. The re-organisation of the role-system (of the individual on the one hand and the couple on the other hand therefore turns out to be the basic strategy to cope with retirement.

  20. Optimization of Multiresonant Wireless Power Transfer Network Based on Generalized Coupled Matrix

    Directory of Open Access Journals (Sweden)

    Qiang Zhao

    2017-01-01

    Full Text Available Magnetic coupling resonant wireless power transfer network (MCRWPTN system can realize wireless power transfer for some electrical equipment real-time and high efficiency in a certain spatial scale, which resolves the contradiction between power transfer efficiency and the power transfer distance of the wireless power transfer. A fully coupled resonant energy transfer model for multirelay coils and ports is established. A dynamic adaptive impedance matching control based on fully coupling matrix and particle swarm optimization algorithm based on annealing is developed for the MCRWPTN. Furthermore, as an example, the network which has twenty nodes is analyzed, and the best transmission coefficient which has the highest power transfer efficiency is found using the optimization algorithm, and the coupling constraints are considered simultaneously. Finally, the effectiveness of the proposed method is proved by the simulation results.

  1. PI2 controller based coordinated control with Redox Flow Battery and Unified Power Flow Controller for improved Restoration Indices in a deregulated power system

    Directory of Open Access Journals (Sweden)

    R. Thirunavukarasu

    2016-12-01

    Full Text Available The nature of power system restoration problem involves status assessment, optimization of generation capability and load pickup. This paper proposes the evaluation of Power System Restoration Indices (PSRI based on the Automatic Generation Control (AGC assessment of interconnected power system in a deregulated environment. The PSRI are useful for system planners to prepare the power system restoration plans and to improve the efficiency of the physical operation of the power system with the increased transmission capacity in the network. The stabilization of frequency and tie-line power oscillations in an interconnected power system becomes challenging when implemented in the future competitive environment. This paper also deals with the concept of AGC in two-area reheat power system having coordinated control action with Redox Flow Battery (RFB and Unified Power Flow Controller (UPFC are capable of controlling the network performance in a very fast manner and improve power transfer limits in order to have a better restoration. In addition to that a new Proportional–Double Integral (PI2 controller is designed and implemented in AGC loop and controller parameters are optimized through Bacterial Foraging Optimization (BFO algorithm. Simulation results reveal that the proposed PI2 controller is that it has good stability during load variations, excellent transient and dynamic responses when compared with the system comprising PI controller. Moreover the AGC loop with RFB coordinated with UPFC has greatly improved the dynamic response and it reduces the control input requirements, to ensure improved PSRI in order to provide the reduced restoration time, thereby improving the system reliability.

  2. Role of a redox-based methylation switch in mRNA life cycle ( pre- & post- transcriptional maturation and protein turnover : Implications in neurological disorders

    Directory of Open Access Journals (Sweden)

    MALAV SUCHIN TRIVEDI

    2012-06-01

    Full Text Available Homeostatic synaptic scaling in response to neuronal stimulus or activation, as well as due to changes in cellular niche, is an important phenomenon for memory consolidation, retrieval, and other similar cognitive functions. Neurological disorders and cognitive disabilities in autism, Rett syndrome, schizophrenia, dementia etc., are strongly correlated to alterations in protein expression (both synaptic and cytoplasmic. This correlation suggests that efficient temporal regulation of synaptic protein expression is important for synaptic plasticity. In addition, equilibrium between mRNA processing, protein translation and protein turnover is a critical sensor/trigger for recording synaptic information, normal cognition and behavior. Thus a regulatory switch, controlling the lifespan, maturation and processing of mRNA, might influence cognition and adaptive behavior. Here, we propose a two part novel hypothesis that methylation might act as this suggested coordinating switch to critically regulate mRNA maturation at 1.The pre-transcription level, by regulating precursor-RNA (pre-RNA processing into mRNA, via other non-coding RNAs and their influence on splicing phenomenon, and 2. the post-transcription level by modulating the regulatory functions of ribonucleoproteins (RNP and RNA binding proteins (RNABP in mRNA translation, dendritic translocation as well as protein synthesis and synaptic turnover. DNA methylation changes are well recognized and highly correlated to gene expression levels as well as, learning and memory; however, RNA methylation changes are recently characterized and yet their functional implications are not established. This review article provides some insight on the intriguing consequences of changes in methylation levels on mRNA life-cycle. We also suggest that, since methylation is under the control of glutathione antioxidant levels, the redox status of neurons might be the central regulatory switch for methylation-based

  3. 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.

  4. Translation of Integrative Behavioral Couple Therapy to a web-based intervention.

    Science.gov (United States)

    Doss, Brian D; Benson, Lisa A; Georgia, Emily J; Christensen, Andrew

    2013-03-01

    Couple therapy-across a number of different theoretical approaches-has been shown to be an effective treatment for a variety of individual and relationship difficulties. Moreover, recent studies have demonstrated that the effects of several approaches last at least 2-5 years after the end of treatment. However, couple therapy has a critical limitation: most distressed couples--including those who eventually divorce--do not seek couple therapy. Thus, although we recognize there are notable advances in the treatment approaches described in this special section, we argue that traditional approaches to couple therapy need to be supplemented by alternative interventions before we can make a profound, population-level impact on relationship distress and divorce. To this end, we translated Integrative Behavioral Couple Therapy into a self-help, web-based program-www.OurRelationship.com. Through a combination of tailored feedback, filmed examples, and interactive education, the online program first helps couples identify a core problem in their relationship. The program then assists partners in coming to a new and more accurate understanding of the problem they jointly identified and subsequently brings them together in a structured conversation to share their new understandings with each other. Finally, based on this shared conceptualization, the program supports couples in making concrete changes in their relationship. In this article, we discuss the rationale for the program, describe the core components of the website, and illustrate these components with a case example. Relative advantages and disadvantages compared with traditional couple therapy are presented. © FPI, Inc.

  5. Redox-mediated decolorization of Direct Red 23 and Direct Blue 80 catalyzed by bioaffinity-based immobilized tomato (Lycopersicon esculentum) peroxidase.

    Science.gov (United States)

    Matto, Mahreen; Husain, Qayyum

    2008-10-01

    The aim of this study was to investigate the role of concanavalin A (Con A)-cellulose-bound tomato peroxidase for the decolorization of direct dyes. Cellulose was used as an inexpensive material for the preparation of bioaffinity support. Con A-cellulose-bound tomato peroxidase exhibited higher efficiency in terms of dye decolorization as compared to soluble enzyme under various experimental conditions. Both Direct Red 23 and Direct Blue 80 dyes were recalcitrant to the action of enzyme without a redox mediator. Six compounds were investigated for redox-mediating property. Immobilized peroxidase decolorized both dyes to different extent in the presence of all the used redox mediators. However, 1-hydroxybenzotriazole emerged as a potential redox mediator for tomato peroxidase catalyzed decolorization of direct dyes. These dyes were maximally decolorized at pH 6.0 and 40 degrees C by soluble and immobilized peroxidase. The absorption spectra of the untreated and treated dyes exhibited a marked difference in the absorption at various wavelengths. Immobilized tomato peroxidase showed a lower Michaelis constant than the free enzyme for both dyes. Soluble and immobilized tomato peroxidase exhibited significantly higher affinity for Direct Red 23 compared to Direct Blue 80.

  6. Redox-initiated poly(methyl methcrylate) emulsion polymerizations stabilized with block copolymers based on poly(ethylene oxide), e-caprolactone and linoleic acid

    NARCIS (Netherlands)

    Tan, B.H.; Nabuurs, Tijs; Feijen, Jan; Grijpma, Dirk W.

    2009-01-01

    A redox initiating system, consisting of t-butyl hydroperoxide (tBHPO), isoascorbic acid (iAA), and ethylenediaminetetraacetic acid ferric-sodium salt (FeEDTA) was employed in emulsion polymerizations of methyl methacrylate (MMA) at high solids contents of 30 wt % in water. The system was stabilized

  7. Redox-Initiated Poly(methyl methacrylate) Emulsion Polymerizations Stabilized with Block Copolymers Based on Methoxy-Poly(ethylene glycol), epsilon-Caprolactone, and Linoleic Acid

    NARCIS (Netherlands)

    Tan, Boonhua; Nabuurs, Tijs; Feijen, Jan; Grijpma, Dirk W.

    2009-01-01

    A redox initiating system, consisting of t-butyl hydroperoxide (tBHPO), isoascorbic acid (iAA), and ethylenediaminetetraacetic acid ferric-sodium salt (FeEDTA) was employed in emulsion polymerizations of methyl methacrylate (MMA) at high solids contents of 30 wt % in water. The system was stabilized

  8. Effects of a Randomized Couple-Based Intervention on Quality of Life of Breast Cancer Patients and Their Partners

    Science.gov (United States)

    Kayser, Karen; Feldman, Barry N.; Borstelmann, Nancy A.; Daniels, Ann A.

    2010-01-01

    The purpose of this study was to determine the effectiveness of a couple-based intervention on the quality of life (QOL) of early-stage breast cancer patients and their partners. A randomized controlled design was used to assign couples to either the hospital standard social work services (SSWS) or a couple-based intervention, the Partners in…

  9. Coupling between tsunamis and ionosphere: ground-based and space-based observation opportunities

    Science.gov (United States)

    Coisson, Pierdavide; Makela, Jonathan J.; Occhipinti, Giovanni; Astafyeva, Elvira; alam Kherani, Esfhan; Lognonne, Philippe

    2012-07-01

    Large scale phenomena as tsunamis propagating through the ocean excite gravity waves that can reach ionospheric heights. The coupling between the ground/ocean and the atmosphere up to the ionosphere opens the possibility to observe in the upper atmosphere the effects of the propagation of tsunamis. During all recent major tsunami events ionospheric waves have been observed by ground GPS networks, satellite altimeters and, recently, also by an airglow imager. During the tsunami event of 11 March 2011 an all-sky camera in Hawaii observes the Internal Gravity Waves (IGW) during about one-and-a-half hours before the arrival of the, while it was crossing the Pacific Ocean in that region. Collocated ionospheric measurements were also done with GNSS sounding and Jason satellite. We present results of assessment studies of ground-based and space-based ionospheric remote sensing for tsunami propagation monitoring. We analyze the cases of airglow imager, Over-The-Horizon (OTH) radar, GPS, radio occultation and GNSS reflectometry. We describe modeling results of IGW excited by a realistic tsunami propagation model through the ocean near Hawaii. The model includes the propagation of the gravity wave in the atmosphere, the coupling between neutral and charged particles in the ionosphere and the production of the airglow emission at 630.0 nm. Synthetic all-sky images are calculated by integration of the emission along rays from the camera location to though the airglow layer. Additional ground-based observations could be provided by (OTH) radars, which operate in High Frequency (HF) band and can be used to monitor the bottomside ionosphere. Synthetic radar measurements computed using HF numerical ray-tracing confirm the possibility to detect IGW excited by tsunamis. The large coverage of OTH radar and its sensitivity to low-altitude plasma anomalies provides a wide range of observation. Additionally, we analyze the capabilities of space-based radio occultation and GNSS

  10. The decay of Redox-stress Response Capacity is a substantive characteristic of aging: Revising the redox theory of aging.

    Science.gov (United States)

    Meng, Jiao; Lv, Zhenyu; Qiao, Xinhua; Li, Xiaopeng; Li, Yazi; Zhang, Yuying; Chen, Chang

    2017-04-01

    Aging is tightly associated with redox events. The free radical theory of aging indicates that redox imbalance may be an important factor in the aging process. Most studies about redox and aging focused on the static status of oxidative stress levels, there has been little research investigating differential responses to redox challenge during aging. In this study, we used Caenorhabditis elegans and human fibroblasts as models to compare differential responses to oxidative stress challenge in young and old individuals. In response to paraquat stress, young individuals generated more ROS and activated signaling pathways including p-ERK, p-AKT and p-AMPKα/β. After the initial response, young individuals then promoted NRF2 translocation and induced additional antioxidant enzymes and higher expression of phase II enzymes, including SOD, CAT, GPX, HO-1, GSTP-1and others, to maintain redox homeostasis. Moreover, young individuals also demonstrated a better ability to degrade damaged proteins by up-regulating the expression of chaperones and improving proteasome activity. Based on these data, we propose a new concept "Redox-stress Response Capacity (RRC)", which suggests cells or organisms are capable of generating dynamic redox responses to activate cellular signaling and maintain cellular homeostasis. The decay of RRC is the substantive characteristic of aging, which gives a new understand of the redox theory of aging. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

  11. Slice-Based Formal Specification Measures -- Mapping Coupling and Cohesion Measures to Formal Z

    Science.gov (United States)

    Bollin, Andreas

    2010-01-01

    This paper demonstrates that existing slice-based measures can reasonably be mapped to the field of state-based specification languages. By making use of Z specifications this contribution renews the idea of slice-profiles and derives coupling and cohesion measures for them. The measures are then assessed by taking a critical look at their sensitiveness in respect to modifications on the specification source. The presented study shows that slice-based coupling and cohesion measures have the potential to be used as quality indicators for specifications as they reflect the changes in the structure of a specification as accustomed from their program-related pendants.

  12. Adapting an evidence-based HIV behavioral intervention for South African couples.

    Science.gov (United States)

    Wechsberg, Wendee M; El-Bassel, Nabila; Carney, Tara; Browne, Felicia A; Myers, Bronwyn; Zule, William A

    2015-02-24

    In South Africa, heterosexual couples are at risk for HIV infection and transmission through substance use, gender-based violence and traditional gender roles, and sex risk behaviors such as having multiple partners and unsafe sex. To address these interconnected HIV risks among heterosexual couples, we used the ADAPT framework to modify an existing, efficacious women's HIV prevention intervention (the Western Cape Women's Health CoOp) to include components of an evidence-based couple's intervention from the United States (Project Connect) and components from the Men as Partners program that has been used successfully in South Africa. We conducted focus groups with men, women and couples, and obtained feedback from a long-standing Community Collaborative Board (CCB) to guide the synthesis of elements of these three interventions into a new intervention. We then piloted the adapted intervention for feasibility and acceptability. The new intervention is called the Couples' Health CoOp. This intervention targets men who use alcohol and other drugs and engage in unprotected sex, and their main female sex partners. The intervention addresses substance use, sex risk, HIV and other sexually transmitted infections, gender roles, gender-based violence, communication skills, and goal-setting activities to increase sexy (eroticize) safe-sex behaviors. The Couples' Health CoOp also includes "voices" from the focus group members to ground the intervention in the experiences of these at-risk couples. In addition, it utilizes a participant handbook that reiterates workshop content and includes homework assignments for couples to complete together to increase problem-solving skills within their relationship, and to improve their sexual relationship and help sustain HIV risk-reduction strategies. All of these adaptations were based on participants' suggestions made during formative work and pilot testing. The Couples' Health CoOp is a couple-based HIV prevention intervention that

  13. Probing electronic coupling between adenine bases in RNA strands from synchrotron radiation circular dichroism experiments

    DEFF Research Database (Denmark)

    Nielsen, Lisbeth Munksgård; Hoffmann, Søren Vrønning; Nielsen, Steen Brøndsted

    2012-01-01

    Circular dichroism spectra (176–330 nm) of RNA adenine oligomers, (rA)n (n = 1–10, 12, 15, and 20), reveal electronic coupling between two bases in short strands. The number of interacting bases in long strands is more and larger than that reported previously for the corresponding DNA strands....

  14. On the Nonlinear Behavior of the Piezoelectric Coupling on Vibration-Based Energy Harvesters

    Directory of Open Access Journals (Sweden)

    Luciana L. Silva

    2015-01-01

    Full Text Available Vibration-based energy harvesting with piezoelectric elements has an increasing importance nowadays being related to numerous potential applications. A wide range of nonlinear effects is observed in energy harvesting devices and the analysis of the power generated suggests that they have considerable influence on the results. Linear constitutive models for piezoelectric materials can provide inconsistencies on the prediction of the power output of the energy harvester, mainly close to resonant conditions. This paper investigates the effect of the nonlinear behavior of the piezoelectric coupling. A one-degree of freedom mechanical system is coupled to an electrical circuit by a piezoelectric element and different coupling models are investigated. Experimental tests available in the literature are employed as a reference establishing the best matches of the models. Subsequently, numerical simulations are carried out showing different responses of the system indicating that nonlinear piezoelectric couplings can strongly modify the system dynamics.

  15. Couple-based interventions for psychopathology: a renewed direction for the field.

    Science.gov (United States)

    Baucom, Donald H; Belus, Jennifer M; Adelman, Caroline B; Fischer, Melanie S; Paprocki, Christine

    2014-09-01

    This article provides a rationale and empirical support for providing couple-based interventions when one partner in a relationship is experiencing individual psychopathology. Several investigations indicate that relationship distress and psychopathology are associated and reciprocally influence each other, such that the existence of relationship distress predicts the development of subsequent psychopathology and vice versa. Furthermore, findings indicate that for several disorders, individual psychotherapy is less effective if the client is in a distressed relationship. Finally, even within happy relationships, partners often inadvertently behave in ways that maintain or exacerbate symptoms for the other individual. Thus, within both satisfied and distressed relationships, including the partner in a couple-based intervention provides an opportunity to use the partner and the relationship as a resource rather than a stressor for an individual experiencing some form of psychological distress. The authors propose that a promising approach to including the partner in treatment involves (a) integrating intervention principles from empirically supported interventions for individual therapy for specific disorders with (b) knowledge of how to employ relationships to promote individual and dyadic change. Based on this logic, the article includes several examples to demonstrate how couple-based interventions can be focused on a specific type of psychopathology, including encouraging empirical findings for these interventions. The article concludes with recommendations for how clinicians and researchers can adapt their knowledge of couple therapy to assist couples in which one partner is experiencing notable psychological distress or diagnosable psychopathology. © 2014 FPI, Inc.

  16. Direct electrochemistry of redox proteins

    NARCIS (Netherlands)

    Heering, H.A.

    1995-01-01

    The goal of the project was to obtain more detailed insight in interactions between redox proteins and solid electrodes and the mechanisms of electron transfer. In addition to this, the influence of the protein environment on the redox properties of the active site and the possible

  17. Fabrication LSPR sensor chip of Ag NPs and their biosensor application based on interparticle coupling

    Energy Technology Data Exchange (ETDEWEB)

    Ghodselahi, T., E-mail: t_ghodselahi@yahoo.com [Nano Mabna Iranian Inc., PO Box 1676664116, Tehran (Iran, Islamic Republic of); School of Physics, Institute for Research in Fundamental Sciences, PO Box 19395-5531, Tehran (Iran, Islamic Republic of); Neishaboorynejad, T. [School of Physics, Institute for Research in Fundamental Sciences, PO Box 19395-5531, Tehran (Iran, Islamic Republic of); Department of Physics, Central Tehran Branch, Islamic Azad University, Tehran (Iran, Islamic Republic of); Arsalani, S. [School of Physics, Institute for Research in Fundamental Sciences, PO Box 19395-5531, Tehran (Iran, Islamic Republic of); School of Medicine, Bam University of Medical Sciences, Bam (Iran, Islamic Republic of)

    2015-07-15

    Highlights: • Localized surface plasmon resonance (LSPR) sensor of silver nanoparticles on hydrogenated amorphous carbon thin film were synthetized by co-deposition of RF-sputtering and RF-PECVD. • Samples were characterized by XRD, XPS, AFM, and UV visible. • DNA primer at fM concentration was detected based on breaking of inter-particles coupling. • Dipolar plasmon of isolated Ag NPs, coupled Ag NPs plasmons, in-plane and out-plane coupling, and quadrupole plasmon modes were considered to explain biosensor properties. • The initial response, wavelength shift sensitivity, and response time of LSPR sensors were compared by morphology. - Abstract: We introduce a simple method to synthesize localized surface plasmon resonance (LSPR) sensor chip of Ag NPs on the hydrogenated amorphous carbon by co-deposition of RF-Sputtering and RF-PECVD. The X-ray photoelectron spectroscopy revealed the content of Ag and C atoms. X-ray diffraction profile and atomic force microscopy indicate that the Ag NPs have fcc crystal structure and spherical shape and by increasing deposition time, particle sizes do not vary and only Ag NPs aggregation occurs, resulting in LSPR wavelength shift. Firstly, by increasing Ag NPs content, in-plan interparticles coupling is dominant and causes redshift in LSPR. At the early stage of agglomeration, out-plane coupling occurs and in-plane coupling is reduced, resulting a blueshift in the LSPR. By further increasing of Ag NPs content, agglomeration is completed on the substrate and in-plan coupling rises, resulting significant redshift in the LSPR. Results were used to implement biosensor application of chips. Detection of DNA primer at fM concentration was achieved based on breaking interparticles coupling of Ag NPs. A significant wavelength shift sensitivity of 30 nm and a short response time of 30 min were obtained, where both of these are prerequisite for biosensor applications.

  18. 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.

  19. One electron changes everything: a multispecies copper redox shuttle for dye-sensitized solar cells.

    Energy Technology Data Exchange (ETDEWEB)

    Hoffeditz, William L.; Katz, Michael J.; Deria, Pravas; Cutsail, George E.; Pellin, Michael J.; Farha, Omar K.; Hupp, Joseph T.

    2016-02-25

    Dye-sensitized solar cells (DSCs) are an established alternative photovoltaic technology that offers numerous potential advantages in solar energy applications. However, this technology has been limited by the availability of molecular redox couples that are both noncorrosive/nontoxic and do not diminish the performance of the device. In an effort to overcome these shortcomings, a copper-containing redox shuttle derived from 1,8-bis(2'-pyridyl)-3,6-dithiaoctane (PDTO) ligand and the common DSC additive 4-tert-butylpyridine (TBP) was investigated. Electrochemical measurements, single-crystal X-ray diffraction, and absorption and electron paramagnetic resonance spectroscopies reveal that, upon removal of one metal-centered electron, PDTO-enshrouded copper ions completely shed the tetradentate PDTO ligand and replace it with four or more TBP ligands. Thus, the Cu(I) and Cu(II) forms of the electron shuttle have completely different coordination spheres and are characterized by widely differing Cu(II/I) formal potentials and reactivities for forward versus reverse electron transfer. Notably, the coordination-sphere replacement process is fully reversed upon converting Cu(II) back to Cu(I). In cells featuring an adsorbed organic dye and a nano- and mesoparticulate, TiO2-based, photoelectrode, the dual species redox shuttle system engenders performance superior to that obtained with shuttles based on the (II/I) forms of either of the coordination complexes in isolation.

  20. The redox stress hypothesis of aging.

    Science.gov (United States)

    Sohal, Rajindar S; Orr, William C

    2012-02-01

    The main objective of this review is to examine the role of endogenous reactive oxygen/nitrogen species (ROS) in the aging process. Until relatively recently, ROS were considered to be potentially toxic by-products of aerobic metabolism, which, if not eliminated, may inflict structural damage on various macromolecules. Accrual of such damage over time was postulated to be responsible for the physiological deterioration in the postreproductive phase of life and eventually the death of the organism. This "structural damage-based oxidative stress" hypothesis has received support from the age-associated increases in the rate of ROS production and the steady-state amounts of oxidized macromolecules; however, there are increasing indications that structural damage alone is insufficient to satisfactorily explain the age-associated functional losses. The level of oxidative damage accrued during aging often does not match the magnitude of functional losses. Although experimental augmentation of antioxidant defenses tends to enhance resistance to induced oxidative stress, such manipulations are generally ineffective in the extension of life span of long-lived strains of animals. More recently, in a major conceptual shift, ROS have been found to be physiologically vital for signal transduction, gene regulation, and redox regulation, among others, implying that their complete elimination would be harmful. An alternative notion, advocated here, termed the "redox stress hypothesis," proposes that aging-associated functional losses are primarily caused by a progressive pro-oxidizing shift in the redox state of the cells, which leads to the overoxidation of redox-sensitive protein thiols and the consequent disruption of the redox-regulated signaling mechanisms. Copyright © 2011 Elsevier Inc. All rights reserved.

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

    OpenAIRE

    Malav Suchin Trivedi; Richard eDeth

    2015-01-01

    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 the major epigenetic mechanism and it is one of more than 200 methylation reactions supported by methyl donor S-adenosylmethionine (SAM). The levels of SAM are controlled by cellular redox status via the folate and vitamin B12-dependent enzyme methionine synthase (MS), for example; un...

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

    OpenAIRE

    Trivedi, Malav S.; Deth, Richard

    2015-01-01

    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 o...

  3. Catalytic Coupling of Carbon Dioxide with Terpene Scaffolds: Access to Challenging Bio-Based Organic Carbonates.

    Science.gov (United States)

    Fiorani, Giulia; Stuck, Moritz; Martín, Carmen; Belmonte, Marta Martínez; Martin, Eddy; Escudero-Adán, Eduardo C; Kleij, Arjan W

    2016-06-08

    The challenging coupling of highly substituted terpene oxides and carbon dioxide into bio-based cyclic organic carbonates catalyzed by Al(aminotriphenolate) complexes is reported. Both acyclic as well as cyclic terpene oxides were used as coupling partners, showing distinct reactivity/selectivity behavior. Whereas cyclic terpene oxides showed excellent chemoselectivity towards the organic carbonate product, acyclic substrates exhibited poorer selectivities owing to concomitant epoxide rearrangement reactions and the formation of undesired oligo/polyether side products. Considering the challenging nature of these coupling reactions, the isolated yields of the targeted bio-carbonates are reasonable and in most cases in the range 50-60 %. The first crystal structures of tri-substituted terpene based cyclic carbonates are reported and their stereoconnectivity suggests that their formation proceeds through a double inversion pathway. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. 20S proteasome activity is modified via S-glutathionylation based on intracellular redox status of the yeast Saccharomyces cerevisiae: implications for the degradation of oxidized proteins.

    Science.gov (United States)

    Demasi, Marilene; Hand, Adrian; Ohara, Erina; Oliveira, Cristiano L P; Bicev, Renata N; Bertoncini, Clelia A; Netto, Luis E S

    2014-09-01

    Protein S-glutathionylation is a post-translational modification that controls many cellular pathways. Recently, we demonstrated that the α5-subunit of the 20S proteasome is S-glutathionylated in yeast cells grown to the stationary phase in rich medium containing glucose, stimulating 20S core gate opening and increasing the degradation of oxidized proteins. In the present study, we evaluated the correlation between proteasomal S-glutathionylation and the intracellular redox status. The redox status was controlled by growing yeast cells in distinct carbon sources which induced respiratory (glycerol/ethanol) or fermentative (glucose) metabolism. Cells grown under glycerol/ethanol displayed higher reductive power when compared to cells grown under glucose. When purified from cells grown in glucose, 20S proteasome α5-subunit exhibited an intense anti-glutathione labeling. A higher frequency of the open catalytic chamber gate was observed in the S-glutathionylated preparations as demonstrated by transmission electron microscopy. Therefore, cells that had been grown in glucose displayed an increased ability to degrade oxidized proteins. The results of the present study suggest that 20S proteasomal S-glutathionylation is a relevant adaptive response to oxidative stress that is capable to sense the intracellular redox environment, leading to the removal of oxidized proteins via a process that is not dependent upon ubiquitylation and ATP consumption. Copyright © 2014 Elsevier Inc. All rights reserved.

  5. Refractive Index Sensor Based on Fano Resonances in Metal-Insulator-Metal Waveguides Coupled with Resonators

    Directory of Open Access Journals (Sweden)

    Yue Tang

    2017-04-01

    Full Text Available A surface plasmon polariton refractive index sensor based on Fano resonances in metal–insulator–metal (MIM waveguides coupled with rectangular and ring resonators is proposed and numerically investigated using a finite element method. Fano resonances are observed in the transmission spectra, which result from the coupling between the narrow-band spectral response in the ring resonator and the broadband spectral response in the rectangular resonator. Results are analyzed using coupled-mode theory based on transmission line theory. The coupled mode theory is employed to explain the Fano resonance effect, and the analytical result is in good agreement with the simulation result. The results show that with an increase in the refractive index of the fill dielectric material in the slot of the system, the Fano resonance peak exhibits a remarkable red shift, and the highest value of sensitivity (S is 1125 nm/RIU, RIU means refractive index unit. Furthermore, the coupled MIM waveguide structure can be integrated with other photonic devices at the chip scale. The results can provide a guide for future applications of this structure.

  6. Analyzing Sexual Health-Related Beliefs Among Couples in Marriage Based on the Health Belief Model

    Directory of Open Access Journals (Sweden)

    Majid Barati

    2014-06-01

    Full Text Available Introduction: Sexual health is the integrity between mind, emotions, and body, and any disorder leading to discoordination, can be associated with sexual dysfunction. The aim of this study was to investigate the beliefs of couples attending marriage counseling centers toward sexual health based on the health belief model. Materials and Methods: This cross sectional descriptive study was performed on 400 couples referring to marriage counseling centers of Hamadan recruited with a random sampling method. The participants completed a self-administered questionnaire including demographic characteristics, knowledge and health belief model constructs. Data analysis was performed using SPSS-16 software, by Pearson’s coefficient correlation, independent T-test, and one-way ANOVA. Results: Couples had a moderate knowledge of sexual health. In addition, perceived susceptibility and severity of the consequences of unsafe sexual behavior among couples were not satisfactory however, perceived benefits and barriers were reported in a relatively good level. Internet and friends were the most important sources for sexual health information. Conclusion: Promoting knowledge and beliefs toward sexual health by preparing training packages based on the needs of couples and removing obstacles to have normal sexual behavior are necessary.

  7. Lag Synchronization of Memristor-Based Coupled Neural Networks via ω-Measure.

    Science.gov (United States)

    Li, Ning; Cao, Jinde

    2016-03-01

    This paper deals with the lag synchronization problem of memristor-based coupled neural networks with or without parameter mismatch using two different algorithms. Firstly, we consider the memristor-based neural networks with parameter mismatch, lag complete synchronization cannot be achieved due to parameter mismatch, the concept of lag quasi-synchronization is introduced. Based on the ω-measure method and generalized Halanay inequality, the error level is estimated, a new lag quasi-synchronization scheme is proposed to ensure that coupled memristor-based neural networks are in a state of lag synchronization with an error level. Secondly, by constructing Lyapunov functional and applying common Halanary inequality, several lag complete synchronization criteria for the memristor-based neural networks with parameter match are given, which are easy to verify. Finally, two examples are given to illustrate the effectiveness of the proposed lag quasi-synchronization or lag complete synchronization criteria, which well support theoretical results.

  8. Redox-regulated transcription in plants: Emerging concepts

    Directory of Open Access Journals (Sweden)

    Jehad Shaikhali

    2017-09-01

    Full Text Available In plants, different stimuli, both internal and external, activate production of reactive oxygen species (ROS. Photosynthesis is considered as high rate redox-metabolic process with rapid transients including light/photon capture, electron fluxes, and redox potentials that can generate ROS; thus, regulatory systems are required to minimize ROS production. Despite their potential for causing harmful oxidations, it is now accepted that redox homeostasis mechanisms that maintain the intracellular reducing environment make it possible to use ROS as powerful signaling molecules within and between cells. Redox and ROS information from the chloroplasts is a fine-tuning mechanism both inside the chloroplast and as retrograde signal to the cytosol and nucleus to control processes such as gene expression/transcription and translation. Wide repertoires of downstream target genes expression (activation/repression is regulated by transcription factors. In many cases, transcription factors function through various mechanisms that affect their subcellular localization and or activity. Some post-translational modifications (PTMs known to regulate the functional state of transcription factors are phosphorylation, acetylation, and SUMOylation, ubiquitylation and disulfide formation. Recently, oxPTMs, targeted in redox proteomics, can provide the bases to study redox regulation of low abundant nuclear proteins. This review summarizes the recent advances on how cellular redox status can regulate transcription factor activity, the implications of this regulation for plant growth and development, and by which plants respond to environmental/abiotic stresses.

  9. 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...

  10. GPCR-OKB: the G Protein Coupled Receptor Oligomer Knowledge Base.

    NARCIS (Netherlands)

    Khelashvili, G.; Dorff, K.; Shan, J.; Camacho-Artacho, M.; Skrabanek, L.; Vroling, B.; Bouvier, M.; Devi, L.A.; George, S.R.; Javitch, J.A.; Lohse, M.J.; Milligan, G.; Neubig, R.R.; Palczewski, K.; Parmentier, M.; Pin, J.P.; Vriend, G.; Campagne, F.; Filizola, M.

    2010-01-01

    SUMMARY: Rapid expansion of available data about G Protein Coupled Receptor (GPCR) dimers/oligomers over the past few years requires an effective system to organize this information electronically. Based on an ontology derived from a community dialog involving colleagues using experimental and

  11. Coupling analysis of wind turbine blades based on aeroelastics and aerodynsmics

    DEFF Research Database (Denmark)

    Wang, Xudong; Chen, Jin; Zhang, Shigiang

    2010-01-01

    The structural dynamic equations of blades were constructed for blades of wind turbines. The vibration velocity of blades and the relative flow velocity were calculated using the structural dynamics model. Based on the BEM (Blade Element Momentum) theory and traditional areodynamics, the coupling...

  12. Miniature wideband filter based on coupled-line sections and quasi-lumped element resonator

    DEFF Research Database (Denmark)

    Zhurbenko, Vitaliy; Krozer, Viktor; Meincke, Peter

    2007-01-01

    A new design of a wideband bandpass filter is proposed, based on coupled-line sections and quasi-lumped element resonator, taking advantage of the last one to introduce two transmission zeros and suppress a spurious response. The proposed filter demonstrates significantly improved characteristics...

  13. Target-based drug discovery: the emerging success of frontal affinity chromatography coupled to mass spectrometry.

    Science.gov (United States)

    Calleri, Enrica; Temporini, Caterina; Caccialanza, Gabriele; Massolini, Gabriella

    2009-06-01

    Frontal affinity chromatography coupled to mass spectrometry (FAC-MS) has been reported as a potential method for screening compound mixtures against immobilized target proteins. The potentiality of this analytical approach is described and illustrated with a number of examples based on targets of pharmaceutical interest.

  14. Filter designs based on coupled transmission line model for double split ring resonators

    DEFF Research Database (Denmark)

    Yan, Lei; Tang, Meng; Krozer, Viktor

    2012-01-01

    This work presents a systematic way to design filters based on coupled transmission line model of the microstrip rectangular double split ring resonators (DSRRs). This model allows to estimate all resonance modes of DSRR and extract the quality factors of the structure for filter synthesis purpose...

  15. 500 MHz transient digitizers based on GaAs CCds (charged coupled devices)

    Energy Technology Data Exchange (ETDEWEB)

    Bryman, D.; Cresswell, J.V.; LeNoble, M.; Poutissou, R.

    1990-06-01

    A wide bandwidth transient digitizer based on a recently produced gallium arsenide charge coupled device (CCD) is under development. The CCD's have 128 pixels and operate at 500 MHz. Initial testing of prototype modules in Experiment 787 at Brookhaven National Laboratory is reported. 8 refs., 6 figs.

  16. Coupled particle filtering : A new approach for P300-based analysis of mental fatigue

    NARCIS (Netherlands)

    Jarchi, Delaram; Sanei, Saeid; Mohseni, Hamid R.; Lorist, Monicque M.

    A new method for investigating mental fatigue based on P300 variability is presented here. In this approach a new coupled particle filtering for tracking variability of P300 subcomponents, i.e., P3a and P3b, across trials is developed. The latency, amplitude, and width of each subcomponent, as the

  17. Finite element based electrostatic-structural coupled analysis with automated mesh morphing

    Energy Technology Data Exchange (ETDEWEB)

    OWEN,STEVEN J.; ZHULIN,V.I.; OSTERGAARD,D.F.

    2000-02-29

    A co-simulation tool based on finite element principles has been developed to solve coupled electrostatic-structural problems. An automated mesh morphing algorithm has been employed to update the field mesh after structural deformation. The co-simulation tool has been successfully applied to the hysteric behavior of a MEMS switch.

  18. Fabrication of poly(methyl methacrylate) microfluidic chips by redox-initiated polymerization.

    Science.gov (United States)

    Chen, Jiang; Lin, Yuehe; Chen, Gang

    2007-08-01

    In this report, a method based on the redox-initiated polymerization of methyl methacrylate (MMA) has been developed for the rapid fabrication of poly(methyl methacrylate) (PMMA) microfluidic chips. MMA containing 2-2'-azo-bis-isobutyronitrile was allowed to prepolymerize in a water bath to form a viscous prepolymer solution that was subsequently mixed with MMA containing a redox-initiation couple of benzoyl peroxide/N,N-dimethylaniline. The dense molding solution was sandwiched between a silicon template and a piece of 1-mm-thick PMMA plate. The polymerization could complete within 50 min under ambient temperature. The images of raised microfluidic structures on the silicon template were precisely replicated into the synthesized PMMA substrate during the redox-initiated polymerization of the molding solution. The chips were subsequently assembled by the thermal bonding of the channel plates and the covers. The new fabrication approach obviates the need for special equipment and significantly simplifies the process of fabricating PMMA microdevices. The attractive performance of the novel PMMA microchips has been demonstrated in connection with contactless conductivity detection for the separation and detection of ionic species.

  19. Photothermal optomechanics in superfluid helium coupled to a fiber-based cavity

    CERN Document Server

    Kashkanova, A D; Brown, C D; Flowers-Jacobs, N E; Childress, L; Hoch, S W; Hohmann, L; Ott, K; Reichel, J; Harris, J G E

    2016-01-01

    Presented in this paper are measurements of an optomechanical device in which various acoustic modes of a sample of superfluid helium couple to a fiber-based optical cavity. In contrast with recent work on the paraxial acoustic mode confined by the cavity mirrors, we focus specifically on the acoustic modes associated with the helium surrounding the cavity. This paper provides a framework for understanding how the acoustic modes depend on device geometry. The acoustic modes are observed using the technique of optomechanically induced transparency/amplification. The optomechanical coupling to these modes is found to be predominantly photothermal.

  20. Broadband Impedance Transformer Based on Asymmetric Coupled Transmission Lines in Nonhomogeneous Medium

    DEFF Research Database (Denmark)

    Zhurbenko, Vitaliy; Krozer, Viktor; Meincke, Peter

    2007-01-01

    A new broadband quarter-wavelength impedance transformer based on an asymmetric coupled line section is presented. The bandwidth of the coupled line transformer is extended with the help of an interconnecting transmission line. An analytical model for the transformer is developed. The analysis...... of the structure reveals that a fractional bandwidth of more than 100% at –20 dB reflection level can be achieved with such a structure. An experimental transformer circuit has been designed, fabricated and tested. Theoretical and experimental results are fair agreement and confirm the established theory...

  1. A morphing approach to couple state-based peridynamics with classical continuum mechanics

    KAUST Repository

    Han, Fei

    2016-01-04

    A local/nonlocal coupling technique called the morphing method is developed to couple classical continuum mechanics with state-based peridynamics. State-based peridynamics, which enables the description of cracks that appear and propagate spontaneously, is applied to the key domain of a structure, where damage and fracture are considered to have non-negligible effects. In the rest of the structure, classical continuum mechanics is used to reduce computational costs and to simultaneously satisfy solution accuracy and boundary conditions. Both models are glued by the proposed morphing method in the transition region. The morphing method creates a balance between the stiffness tensors of classical continuum mechanics and the weighted coefficients of state-based peridynamics through the equivalent energy density of both models. Linearization of state-based peridynamics is derived by Taylor approximations based on vector operations. The discrete formulation of coupled models is also described. Two-dimensional numerical examples illustrate the validity and accuracy of the proposed technique. It is shown that the morphing method, originally developed for bond-based peridynamics, can be successfully extended to state-based peridynamics through the original developments presented here.

  2. Pinning cluster synchronization in an array of coupled neural networks under event-based mechanism.

    Science.gov (United States)

    Li, Lulu; Ho, Daniel W C; Cao, Jinde; Lu, Jianquan

    2016-04-01

    Cluster synchronization is a typical collective behavior in coupled dynamical systems, where the synchronization occurs within one group, while there is no synchronization among different groups. In this paper, under event-based mechanism, pinning cluster synchronization in an array of coupled neural networks is studied. A new event-triggered sampled-data transmission strategy, where only local and event-triggering states are utilized to update the broadcasting state of each agent, is proposed to realize cluster synchronization of the coupled neural networks. Furthermore, a self-triggered pinning cluster synchronization algorithm is proposed, and a set of iterative procedures is given to compute the event-triggered time instants. Hence, this will reduce the computational load significantly. Finally, an example is given to demonstrate the effectiveness of the theoretical results. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

  3. A description of the solar wind-magnetosphere coupling based on nonlinear filters

    Science.gov (United States)

    Vassiliadis, D.; Klimas, A. J.; Baker, D. N.; Roberts, D. A.

    1995-01-01

    A nonlinear filtering method is introduced for the study of the solar wind -- magnetosphere coupling and related to earlier linear techniques. The filters are derived from the magnetospheric state, a representation of the magnetospheric conditions in terms of a few global variables, here the auroral electrojet indices. The filters also couple to the input, a representation of the solar wind variables, here the rectified electric field. Filter-based iterative prediction of the indices has been obtained for up to 20 hours. The prediction is stable with respect to perturbations in the initial magnetospheric state; these decrease exponentially at the rate of 30/min. The performance of the method is examined for a wide range of parameters and is superior to that of other linear and nonlinear techniques. In the magnetospheric state representation the coupling is modeled as a small number of nonlinear equations under a time-dependent input.

  4. Root-MUSIC Based Angle Estimation for MIMO Radar with Unknown Mutual Coupling

    Directory of Open Access Journals (Sweden)

    Jianfeng Li

    2014-01-01

    Full Text Available Direction of arrival (DOA estimation problem for multiple-input multiple-output (MIMO radar with unknown mutual coupling is studied, and an algorithm for the DOA estimation based on root multiple signal classification (MUSIC is proposed. Firstly, according to the Toeplitz structure of the mutual coupling matrix, output data of some specified sensors are selected to eliminate the influence of the mutual coupling. Then the reduced-dimension transformation is applied to make the computation burden lower as well as obtain a Vandermonde structure of the direction matrix. Finally, Root-MUSIC can be adopted for the angle estimation. The angle estimation performance of the proposed algorithm is better than that of estimation of signal parameters via rotational invariance techniques (ESPRIT-like algorithm and MUSIC-like algorithm. Furthermore, the proposed algorithm has lower complexity than them. The simulation results verify the effectiveness of the algorithm, and the theoretical estimation error of the algorithm is also derived.

  5. Sensitivity Enhancement of Biochemical Sensors Based on Er+3 Doped Microsphere Coupled to an External Mirror

    Directory of Open Access Journals (Sweden)

    Alireza BAHRAMPOUR

    2010-09-01

    Full Text Available In this paper we proposed an active optical sensor designed based on the Er+3-doped microsphere coupled to an external mirror. The microsphere-mirror coupling causes the degeneracy splitting of the resonance frequencies. Each of resonance frequencies splits in to two different resonance frequencies .The coupling coefficient changes as a result of altering the refractive index of surrounding medium. So, the presence of bio/chemical analytes can be detected by measuring the change of laser output power, laser frequency or the difference between frequencies of the red and blue shifted modes. In the presence of mirror at least one order of magnitude sensitivity enhancement is obtained relative to the active microsphere biochemical sensors.

  6. A redox-mediated Kemp eliminase

    Science.gov (United States)

    Li, Aitao; Wang, Binju; Ilie, Adriana; Dubey, Kshatresh D.; Bange, Gert; Korendovych, Ivan V.; Shaik, Sason; Reetz, Manfred T.

    2017-03-01

    The acid/base-catalysed Kemp elimination of 5-nitro-benzisoxazole forming 2-cyano-4-nitrophenol has long served as a design platform of enzymes with non-natural reactions, providing new mechanistic insights in protein science. Here we describe an alternative concept based on redox catalysis by P450-BM3, leading to the same Kemp product via a fundamentally different mechanism. QM/MM computations show that it involves coordination of the substrate's N-atom to haem-Fe(II) with electron transfer and concomitant N-O heterolysis liberating an intermediate having a nitrogen radical moiety Fe(III)-N. and a phenoxyl anion. Product formation occurs by bond rotation and H-transfer. Two rationally chosen point mutations cause a notable increase in activity. The results shed light on the prevailing mechanistic uncertainties in human P450-catalysed metabolism of the immunomodulatory drug leflunomide, which likewise undergoes redox-mediated Kemp elimination by P450-BM3. Other isoxazole-based pharmaceuticals are probably also metabolized by a redox mechanism. Our work provides a basis for designing future artificial enzymes.

  7. Preparation of redox polymer cathodes for thin film rechargeable batteries

    Energy Technology Data Exchange (ETDEWEB)

    Skotheim, T.A.; Lee, H.S.; Okamoto, Yoshiyuki.

    1994-11-08

    The present invention relates to the manufacture of thin film solid state electrochemical devices using composite cathodes comprising a redox polymer capable of undergoing oxidation and reduction, a polymer solid electrolyte and conducting carbon. The polymeric cathode material is formed as a composite of radiation crosslinked polymer electrolytes and radiation crosslinked redox polymers based on polysiloxane backbones with attached organosulfur side groups capable of forming sulfur-sulfur bonds during electrochemical oxidation.

  8. Alternative Evaluation for the REDOX (202-S) Plutonium Loadout Hood

    Energy Technology Data Exchange (ETDEWEB)

    N. R. Kerr

    1999-09-20

    Located in the 200 Areas is the inactive 202-S Reduction Oxidation (REDOX) Facility, which is managed by the Bechtel Hanford, Inc. Surveillance/Maintenance and Transition project. This facility is contaminated from nuclear material processes related to nuclear material separation from Hanford Site facility operations. This alternative evaluation report describes the alternatives and selection criteria based on the necessary protective requirements to maintain the REDOX Plutonium Loadout Hood in a safe and stable condition awaiting a final waste response action.

  9. Fabrication LSPR sensor chip of Ag NPs and their biosensor application based on interparticle coupling

    Science.gov (United States)

    Ghodselahi, T.; Neishaboorynejad, T.; Arsalani, S.

    2015-07-01

    We introduce a simple method to synthesize localized surface plasmon resonance (LSPR) sensor chip of Ag NPs on the hydrogenated amorphous carbon by co-deposition of RF-Sputtering and RF-PECVD. The X-ray photoelectron spectroscopy revealed the content of Ag and C atoms. X-ray diffraction profile and atomic force microscopy indicate that the Ag NPs have fcc crystal structure and spherical shape and by increasing deposition time, particle sizes do not vary and only Ag NPs aggregation occurs, resulting in LSPR wavelength shift. Firstly, by increasing Ag NPs content, in-plan interparticles coupling is dominant and causes redshift in LSPR. At the early stage of agglomeration, out-plane coupling occurs and in-plane coupling is reduced, resulting a blueshift in the LSPR. By further increasing of Ag NPs content, agglomeration is completed on the substrate and in-plan coupling rises, resulting significant redshift in the LSPR. Results were used to implement biosensor application of chips. Detection of DNA primer at fM concentration was achieved based on breaking interparticles coupling of Ag NPs. A significant wavelength shift sensitivity of 30 nm and a short response time of 30 min were obtained, where both of these are prerequisite for biosensor applications.

  10. C-C Coupling on Single-Atom-Based Heterogeneous Catalyst.

    Science.gov (United States)

    Zhang, Xiaoyan; Sun, Zaicheng; Wang, Bin; Tang, Yu; Nguyen, Luan; Li, Yuting; Tao, Franklin Feng

    2018-01-24

    Compared to homogeneous catalysis, heterogeneous catalysis allows for ready separation of products from the catalyst and thus reuse of the catalyst. C-C coupling is typically performed on a molecular catalyst which is mixed with reactants in liquid phase during catalysis. This homogeneous mixing at a molecular level in the same phase makes separation of the molecular catalyst extremely challenging and costly. Here we demonstrated that a TiO 2 -based nanoparticle catalyst anchoring singly dispersed Pd atoms (Pd 1 /TiO 2 ) is selective and highly active for more than 10 Sonogashira C-C coupling reactions (R≡CH + R'X → R≡R'; X = Br, I; R' = aryl or vinyl). The coupling between iodobenzene and phenylacetylene on Pd 1 /TiO 2 exhibits a turnover rate of 51.0 diphenylacetylene molecules per anchored Pd atom per minute at 60 °C, with a low apparent activation barrier of 28.9 kJ/mol and no cost of catalyst separation. DFT calculations suggest that the single Pd atom bonded to surface lattice oxygen atoms of TiO 2 acts as a site to dissociatively chemisorb iodobenzene to generate an intermediate phenyl, which then couples with phenylacetylenyl bound to a surface oxygen atom. This coupling of phenyl adsorbed on Pd 1 and phenylacetylenyl bound to O ad of TiO 2 forms the product molecule, diphenylacetylene.

  11. Redox Properties of Free Radicals.

    Science.gov (United States)

    Neta, P.

    1981-01-01

    Describes pulse radiolysis as a useful means in studing one-electron redox potentials. This method allows the production of radicals and the determination of their concentration and rates of reaction. (CS)

  12. Integration of Social, Cultural, and Biomedical Strategies into an Existing Couple-Based Behavioral HIV/STI Prevention Intervention: Voices of Latino Male Couples.

    Science.gov (United States)

    Martinez, Omar; Wu, Elwin; Levine, Ethan C; Muñoz-Laboy, Miguel; Fernandez, M Isabel; Bass, Sarah Bauerle; Moya, Eva M; Frasca, Timothy; Chavez-Baray, Silvia; Icard, Larry D; Ovejero, Hugo; Carballo-Diéguez, Alex; Rhodes, Scott D

    2016-01-01

    Successful HIV prevention and treatment requires evidence-based approaches that combine biomedical strategies with behavioral interventions that are socially and culturally appropriate for the population or community being prioritized. Although there has been a push for a combination approach, how best to integrate different strategies into existing behavioral HIV prevention interventions remains unclear. The need to develop effective combination approaches is of particular importance for men who have sex with men (MSM), who face a disproportionately high risk of HIV acquisition. We collaborated with Latino male couples and providers to adapt Connect 'n Unite, an evidence-based intervention for Black male couples, for Latino male couples. We conducted a series of three focus groups, each with two cohorts of couples, and one focus group with providers. A purposive stratified sample of 20 couples (N = 40, divided into two cohorts) and 10 providers provided insights into how to adapt and integrate social, cultural, and biomedical approaches in a couples-based HIV/AIDS behavioral intervention. The majority (N = 37) of the couple participants had no prior knowledge of the following new biomedical strategies: non-occupational post-exposure prophylaxis (nPEP); pre-exposure prophylaxis (PrEP); and HIV self-testing kits. After they were introduced to these biomedical interventions, all participants expressed a need for information and empowerment through knowledge and awareness of these interventions. In particular, participants suggested that we provide PrEP and HIV self-testing kits by the middle or end of the intervention. Providers suggested a need to address behavioral, social and structural issues, such as language barriers; and the promotion of client-centered approaches to increase access to, adaptation of, and adherence to biomedical strategies. Corroborating what couple participants suggested, providers agreed that biomedical strategies should be offered after

  13. Integration of Social, Cultural, and Biomedical Strategies into an Existing Couple-Based Behavioral HIV/STI Prevention Intervention: Voices of Latino Male Couples.

    Directory of Open Access Journals (Sweden)

    Omar Martinez

    Full Text Available Successful HIV prevention and treatment requires evidence-based approaches that combine biomedical strategies with behavioral interventions that are socially and culturally appropriate for the population or community being prioritized. Although there has been a push for a combination approach, how best to integrate different strategies into existing behavioral HIV prevention interventions remains unclear. The need to develop effective combination approaches is of particular importance for men who have sex with men (MSM, who face a disproportionately high risk of HIV acquisition.We collaborated with Latino male couples and providers to adapt Connect 'n Unite, an evidence-based intervention for Black male couples, for Latino male couples. We conducted a series of three focus groups, each with two cohorts of couples, and one focus group with providers. A purposive stratified sample of 20 couples (N = 40, divided into two cohorts and 10 providers provided insights into how to adapt and integrate social, cultural, and biomedical approaches in a couples-based HIV/AIDS behavioral intervention.The majority (N = 37 of the couple participants had no prior knowledge of the following new biomedical strategies: non-occupational post-exposure prophylaxis (nPEP; pre-exposure prophylaxis (PrEP; and HIV self-testing kits. After they were introduced to these biomedical interventions, all participants expressed a need for information and empowerment through knowledge and awareness of these interventions. In particular, participants suggested that we provide PrEP and HIV self-testing kits by the middle or end of the intervention. Providers suggested a need to address behavioral, social and structural issues, such as language barriers; and the promotion of client-centered approaches to increase access to, adaptation of, and adherence to biomedical strategies. Corroborating what couple participants suggested, providers agreed that biomedical strategies should be

  14. Catechol-Based Hydrogel for Chemical Information Processing

    Directory of Open Access Journals (Sweden)

    Eunkyoung Kim

    2017-07-01

    Full Text Available Catechols offer diverse properties and are used in biology to perform various functions that range from adhesion (e.g., mussel proteins to neurotransmission (e.g., dopamine, and mimicking the capabilities of biological catechols have yielded important new materials (e.g., polydopamine. It is well known that catechols are also redox-active and we have observed that biomimetic catechol-modified chitosan films are redox-active and possess interesting molecular electronic properties. In particular, these films can accept, store and donate electrons, and thus offer redox-capacitor capabilities. We are enlisting these capabilities to bridge communication between biology and electronics. Specifically, we are investigating an interactive redox-probing approach to access redox-based chemical information and convert this information into an electrical modality that facilitates analysis by methods from signal processing. In this review, we describe the broad vision and then cite recent examples in which the catechol–chitosan redox-capacitor can assist in accessing and understanding chemical information. Further, this redox-capacitor can be coupled with synthetic biology to enhance the power of chemical information processing. Potentially, the progress with this biomimetic catechol–chitosan film may even help in understanding how biology uses the redox properties of catechols for redox signaling.

  15. 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

  16. 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.

  17. Pathophysiological interference with neurovascular coupling - when imaging based on hemoglobin might go blind

    Directory of Open Access Journals (Sweden)

    Ute Lindauer

    2010-10-01

    Full Text Available Assessing neuronal activity by noninvasive functional brain imaging techniques which are based on the hemodynamic response depends totally on the physiological cascade of metabolism and blood flow. At present, functional brain imaging with near infrared spectroscopy (NIRS or BOLD-fMRI is widely used in cognitive neuroscience in healthy subjects where neurovascular coupling and cerebrovascular reactivity can be assumed to be intact. Local activation studies as well as studies investigating functional connectivity between brain regions of the resting brain provide a rapidly increasing body of knowledge on brain function in humans and animals. Furthermore, functional NIRS and MRI techniques are increasingly being used in patients with severe brain diseases and this use might gain more and more importance for establishing their use in the clinical routine. However, more and more experimental evidence shows that changes in baseline physiological parameters, pharmacological interventions or disease-related vascular changes may significantly alter the normal response of blood flow and blood oxygenation and thus may lead to misinterpretation of neuronal activity. In this article we present examples of recent experimental findings on pathophysiological changes of neurovascular coupling parameters in animals and discuss their potential implications for functional imaging based on hemodynamic signals such as fNIRS or BOLD-fMRI. To enable correct interpretation of neuronal activity by vascular signals, future research needs to deepen our understanding of the basic mechanisms of neurovascular coupling and the specific characteristics of disturbed neurovascular coupling in the diseased brain.

  18. Couple-based Intervention for Depression: An Effectiveness Study in the National Health Service in England.

    Science.gov (United States)

    Baucom, Donald H; Fischer, Melanie S; Worrell, Michael; Corrie, Sarah; Belus, Jennifer M; Molyva, Efthymia; Boeding, Sara E

    2017-12-04

    This study represents an effectiveness study and service evaluation of a cognitive behavioral, couple-based treatment for depression (BCT-D) provided in London services that are part of the "Improving Access to Psychological Therapies" (IAPT) program in England. Twenty-three therapists in community clinics were trained in BCT-D during a 5-day workshop, followed by monthly group supervision for 1 year. The BCT-D treatment outcome findings are based on 63 couples in which at least one partner was depressed and elected to receive BCT-D. Eighty-five percent of couples also demonstrated relationship distress, and 49% of the nonclient partners also met caseness for depression or anxiety. Findings demonstrated a recovery rate of 57% with BCT-D, compared to 41% for all IAPT treatments for depression in London. Nonclient partners who met caseness demonstrated a 48% recovery rate with BCT-D, although they were not the focus of treatment. BCT-D was equally effective for clients regardless of the clinical status of the nonclient partner, suggesting its effectiveness in assisting both members of the couple simultaneously. Likewise, treatment was equally effective whether or not both partners reported relationship distress. The findings are promising regarding the successful application of BCT-D in routine clinical settings. © 2017 Family Process Institute.

  19. Risk of Intimate Partner Violence and Relationship Conflict Following Couple-Based HIV Prevention Counseling: Results From the Harlem River Couples Project.

    Science.gov (United States)

    McMahon, James M; Chimenti, Ruth; Trabold, Nicole; Fedor, Theresa; Mittal, Mona; Tortu, Stephanie

    2015-08-27

    Heterosexual transmission of HIV often occurs in the context of intimate sexual partnerships. There is mounting evidence that couple-based HIV prevention interventions may be more effective than individual-based interventions for promoting risk reduction within such relationships. Yet, concerns have been raised about the safety of couple-based prevention approaches, especially with regard to the risk of intimate partner violence against women. Although several international studies have examined the potential for adverse consequences associated with couple-based interventions, with inconsistent results, there is little data from U.S. studies to shed light on this issue. The current study analyzed data from a randomized trial conducted in New York City with 330 heterosexual couples to examine whether participation in couple-based or relationship-focused HIV counseling and testing (HIV-CT) interventions resulted in an increased likelihood of post-intervention breakups, relationship conflicts, or emotional, physical, or sexual abuse, compared with standard individual HIV-CT. Multinomial logistic regression was used to model the odds of experiencing change in partner violence from baseline to follow-up by treatment condition. A high prevalence of partner-perpetrated violence was reported by both male and female partners across treatment conditions, but there was no conclusive evidence of an increase in relationship dissolution or partner violence subsequent to participation in either the couple-based HIV-CT intervention or relationship-focused HIV-CT intervention compared with controls. Qualitative data collected from the same participants support this interpretation. HIV prevention interventions involving persons in primary sexual partnerships should be sensitive to relationship dynamics and the potential for conflict, and take precautions to protect the safety of both male and female participants. © The Author(s) 2015.

  20. Adiabaticity of the proton-coupled electron-transfer step in the reduction of superoxide effected by nickel-containing superoxide dismutase metallopeptide-based mimics.

    Science.gov (United States)

    Shearer, Jason; Schmitt, Jennifer C; Clewett, Heather S

    2015-04-30

    Nickel-containing superoxide dismutases (NiSODs) are bacterial metalloenzymes that catalyze the disproportionation of O2(-). These enzymes take advantage of a redox-active nickel cofactor, which cycles between the Ni(II) and Ni(III) oxidation states, to catalytically disprotorptionate O2(-). The Ni(II) center is ligated in a square planar N2S2 coordination environment, which, upon oxidation to Ni(III), becomes five-coordinate following the ligation of an axial imidazole ligand. Previous studies have suggested that metallopeptide-based mimics of NiSOD reduce O2(-) through a proton-coupled electron transfer (PCET) reaction with the electron derived from a reduced Ni(II) center and the proton from a protonated, coordinated Ni(II)-S(H(+))-Cys moiety. The current work focuses on the O2(-) reduction half-reaction of the catalytic cycle. In this study we calculate the vibronic coupling between the reactant and product diabatic surfaces using a semiclassical formalism to determine if the PCET reaction is proceeding through an adiabatic or nonadiabatic proton tunneling process. These results were then used to calculate H/D kinetic isotope effects for the PCET process. We find that as the axial imidazole ligand becomes more strongly associated with the Ni(II) center during the PCET reaction, the reaction becomes more nonadiabatic. This is reflected in the calculated H/D KIEs, which moderately increase as the reaction becomes more nonadiabatic. Furthermore, the results suggest that as the axial ligand becomes less Lewis basic the observed reaction rate constants for O2(-) reduction should become faster because the reaction becomes more adiabatic. These conclusions are in-line with experimental observations. The results thus indicate that variations in the axial donor's ability to coordinate to the nickel center of NiSOD metallopeptide-based mimics will strongly influence the fundamental nature of the O2(-) reduction process.

  1. Flight Behaviors of a Complex Projectile Using a Coupled Computational Fluid Dynamics (CFD)-based Simulation Technique: Free Motion

    Science.gov (United States)

    2015-09-01

    Projectile Using a Coupled Computational Fluid Dynamics (CFD)-based Simulation Technique: Free Motion 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM...38 vi Preface The paper “Flight Behaviors of a Complex Projectile using a Coupled CFD-based Simulation Technique: Free Motion ” was...involves coupling of CFD and rigid body dynamics (RBD) codes for the simulation of projectile free flight motion in a time-accurate manner. This

  2. Redox processes and water quality of selected principal aquifer systems

    Science.gov (United States)

    McMahon, P.B.; Chapelle, F.H.

    2008-01-01

    Reduction/oxidation (redox) conditions in 15 principal aquifer (PA) systems of the United States, and their impact on several water quality issues, were assessed from a large data base collected by the National Water-Quality Assessment Program of the USGS. The logic of these assessments was based on the observed ecological succession of electron acceptors such as dissolved oxygen, nitrate, and sulfate and threshold concentrations of these substrates needed to support active microbial metabolism. Similarly, the utilization of solid-phase electron acceptors such as Mn(IV) and Fe(III) is indicated by the production of dissolved manganese and iron. An internally consistent set of threshold concentration criteria was developed and applied to a large data set of 1692 water samples from the PAs to assess ambient redox conditions. The indicated redox conditions then were related to the occurrence of selected natural (arsenic) and anthropogenic (nitrate and volatile organic compounds) contaminants in ground water. For the natural and anthropogenic contaminants assessed in this study, considering redox conditions as defined by this framework of redox indicator species and threshold concentrations explained many water quality trends observed at a regional scale. An important finding of this study was that samples indicating mixed redox processes provide information on redox heterogeneity that is useful for assessing common water quality issues. Given the interpretive power of the redox framework and given that it is relatively inexpensive and easy to measure the chemical parameters included in the framework, those parameters should be included in routine water quality monitoring programs whenever possible.

  3. Perceived acceptability of home-based couples voluntary HIV counseling and testing in Northern Tanzania.

    Science.gov (United States)

    Njau, B; Watt, M H; Ostermann, J; Manongi, R; Sikkema, K J

    2012-01-01

    It is estimated that 5.6% of the Tanzanian population ages 15-49 are infected with HIV, but only 30% of adults have ever had an HIV test. Couples' testing has proven to increase testing coverage and introduce HIV prevention, but barriers include access to testing services and unequal gender dynamics in relationships. Innovative approaches are needed to address barriers to couple's testing and increase uptake of HIV testing. Using qualitative data collection methods, a formative study was conducted to assess the acceptability of a home-based couples counseling and testing (HBCCT) approach. Eligible study participants included married men and women, HIV-infected individuals, health care and home-based care providers, voluntary counseling and testing counselors, and community leaders. A total of 91 individuals participated in focus group discussions (FGDs) and in-depth interviews conducted between September 2009 and January 2010 in rural settings in Northern Tanzania. An HBCCT intervention appears to be broadly acceptable among participants. Benefits of HBCCT were identified in terms of access, confidentiality, and strengthening the relationship. Fears of negative consequences from knowing one's HIV status, including stigma, blame, physical abuse, or divorce, remain a concern and a potential barrier to the successful provision of the intervention. Lessons for implementation highlighted the importance of appointments for home visits, building relationships of confidence and trust between counselors and clients, and assessing and responding to a couple's readiness to undergo HIV testing. HBCCT should addresses HIV stigma, emphasize confidentiality, and improve communication skills for disclosure and decision-making among couples.

  4. Novel metamaterial based on the coupling effect of a dielectric trimer

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Jiahui; Chen, Wan, E-mail: dhtyyobdc@126.com; Lv, Bo; Wang, Zhefei

    2017-01-23

    Highlights: • Novel metamaterial based on the coupling effect of a dielectric trimer is proposed. • The phenomenon of vanishing mode is explained by the zero-sum effect. • Due to the vanishing mode, the bandwidth of the dielectric trimer has been expanded to 37%. - Abstract: In this paper, a novel periodic 2D all-dielectric metamaterial based on dielectric trimer is proposed. The electromagnetic responses are explained by the corrected equations of motion using coupled mode theory (CMT). An abnormal vanishment mode phenomenon is also discovered and explained using the zero-sum effect of magnetic dipole, by which the relative bandwidth of the metamaterial has been improved significantly compared with other structures. The presented design is easy for fabrication and can be applied in microwave region by scaling the dimensions of the cubes.

  5. Loosen Couple Workflow Mode of Lean Operator Improvement Based on Positive Feedback

    Directory of Open Access Journals (Sweden)

    Yao Li

    2013-04-01

    Full Text Available In order to promote the core competitive power for telecom operating enterprises to face market fine operation, this article compares the ECTA mode (Extension Case Transmission Mode and the LCA mode (Loosen Couple Mode, both of which are promoted by WfMC. By comparing these two modes, the suitable situations for these two modes are determined. We also carry out empirical analysis based on the customization mode of mobile phones between China telecom and mobile phone manufacturers and to expound the ascension effect of mechanism based on the agile telecom loose coupling workflow with positive feedback to the telecom enterprises. Finally, on the basis of positive feedback system, the task complexity and information transparency of LCA mode are improved, so that the semantics of public flow mode is kept unchanged and the sub workflow is optimized when modifying the sub workflow.

  6. Redox reactivity and coordination chemistry of uranium; Chimie de coordination et reactivite redox de l'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Nocton, G.

    2009-09-15

    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 {l_brace}[UO{sub 2}py{sub 5}][KI{sub 2}py{sub 3}]{r_brace}{sub 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{sub 2}(dbm){sub 2}(K{sub 18}C{sub 6})]{sub 2}. (author)

  7. Fiber-optic liquid level sensor based on coupling optical path length variation.

    Science.gov (United States)

    Nath, Pabitra; Singh, Hidam Kumarjit; Tiwari, Dhananjay; Basumatry, Tenisen

    2012-05-01

    The concept for a new and simple fiber-optic liquid level sensor is presented and experimental results are shown to demonstrate the principle. The sensing principle is based on light intensity modulation when rising and falling mode of liquid level causes coupling optical path distance variation between two optical fibers. Near continuous mode of liquid level variation could be monitored with resolution as low as 1 mm can be measured in the length scale of 25 cm.

  8. Seismic response analysis of coupled building involving MR damper and elastomeric base isolation

    Directory of Open Access Journals (Sweden)

    M.K. Shrimali

    2015-06-01

    The present study investigates the comparative performance of three proposed schemes of coupled building control involving Magnetorheological (MR damper and elastomeric base isolation, named as, Semiactive, Hybrid 1 and Hybrid 2. The results of numerical study showed that Hybrid controls are more effective in controlling the response as compared to Semiactive control. Further, influence of device parameters on control performance has been investigated through a parametric study.

  9. Water-Based Assembly and Purification of Plasmon-Coupled Gold Nanoparticle Dimers and Trimers

    Directory of Open Access Journals (Sweden)

    Sébastien Bidault

    2012-01-01

    Full Text Available We describe a simple one-pot water-based scheme to produce gold nanoparticle groupings with short interparticle spacings. This approach combines a cross-linking molecule and a hydrophilic passivation layer to control the level of induced aggregation. Suspensions of dimers and trimers are readily obtained using a single electrophoretic purification step. The final interparticle spacings allow efficient coupling of the particle plasmon modes as verified in extinction spectroscopy.

  10. Gender Inequality in the Couple Relationship and Leisure-Based Physical Exercise.

    Directory of Open Access Journals (Sweden)

    Ellen Annandale

    Full Text Available To analyse whether gender inequality in the couple relationship was related to leisure-based physical activity, after controlling for earlier physical activity and confounders.Data drawn from the Northern Swedish Cohort of all pupils in their final year of compulsory schooling in a town in the North of Sweden. The sample consisted of 772 respondents (n = 381 men, n = 391 women in the 26-year follow-up (in 2007, aged 42 who were either married or cohabiting. Ordinal regression, for men and women separately, was used to assess the association between gender inequality (measured as self-perceived equality in the couple relationship using dummy variables and a measure of exercise frequency, controlling for prior exercise frequency, socioeconomic status, the presence of children in the home, and longer than usual hours in paid work.The perception of greater gender equality in the couple relationship was associated with higher levels of physical activity for both men and women. This remained significant when the other variables were controlled for. Amongst men the confidence intervals were high.The results point to the potential of perceived gender equality in the couple relationship to counteract the general time poverty and household burden that often arises from the combination of paid work and responsibility for children and the home, especially for women. The high confidence intervals among men indicate the need for more research within the field with larger samples.

  11. Gender Inequality in the Couple Relationship and Leisure-Based Physical Exercise.

    Science.gov (United States)

    Annandale, Ellen; Hammarström, Anne

    2015-01-01

    To analyse whether gender inequality in the couple relationship was related to leisure-based physical activity, after controlling for earlier physical activity and confounders. Data drawn from the Northern Swedish Cohort of all pupils in their final year of compulsory schooling in a town in the North of Sweden. The sample consisted of 772 respondents (n = 381 men, n = 391 women) in the 26-year follow-up (in 2007, aged 42) who were either married or cohabiting. Ordinal regression, for men and women separately, was used to assess the association between gender inequality (measured as self-perceived equality in the couple relationship using dummy variables) and a measure of exercise frequency, controlling for prior exercise frequency, socioeconomic status, the presence of children in the home, and longer than usual hours in paid work. The perception of greater gender equality in the couple relationship was associated with higher levels of physical activity for both men and women. This remained significant when the other variables were controlled for. Amongst men the confidence intervals were high. The results point to the potential of perceived gender equality in the couple relationship to counteract the general time poverty and household burden that often arises from the combination of paid work and responsibility for children and the home, especially for women. The high confidence intervals among men indicate the need for more research within the field with larger samples.

  12. Sensitivity Enhancement of an Inductively Coupled Local Detector Using a HEMT-based Current Amplifier

    Science.gov (United States)

    Qian, Chunqi; Duan, Qi; Dodd, Steve; Koretsky, Alan; Murphy-Boesch, Joe

    2015-01-01

    Purpose To improve the signal transmission efficiency and sensitivity of a local detection coil that is weakly inductively coupled to a larger receive coil. Methods The resonant detection coil is connected in parallel with the gate of a HEMT transistor without impedance matching. When the drain of the transistor is capacitively shunted to ground, current amplification occurs in the resonator by feedback that transforms a capacitive impedance on the transistor’s source to a negative resistance on its gate. Results High resolution images were obtained from a mouse brain using a small, 11 mm diameter surface coil that was inductively coupled to a commercial, phased array chest coil. Although the power consumption of the amplifier was only 88 µW, 14 dB gain was obtained with excellent noise performance. Conclusion An integrated current amplifier based on a High Electron Mobility Transistor (HEMT) can enhance the sensitivity of inductively coupled local detectors when weakly coupled. This amplifier enables efficient signal transmission between customized user coils and commercial clinical coils, without the need for a specialized signal interface. PMID:26192998

  13. Selective sp3 C-H alkylation via polarity-match-based cross-coupling

    Science.gov (United States)

    Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.

    2017-07-01

    The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp3)-C(sp2) coupling, there is a growing demand for C-H alkylation reactions, wherein sp3 C-H bonds are replaced with sp3 C-alkyl groups. Here we describe a polarity-match-based selective sp3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

  14. Probe And Enhancement Of SBS Based Phonons In Infrared Fibers Using Waveguide Coupled External Radiation

    Science.gov (United States)

    Yu, Chung; Chong, Yat C.; Fong, Chee K.

    1989-06-01

    Interaction of GHz and MHz radiation with CO2 laser propagation in a silver halide fiber using sBs based phonon coupling is furthet investigated. The external signal serves to both probe and enhance laser generated sBs phonons in the fiber. Efficient coupling of microwave radiation into the fiber is accomplished by placing the fiber in a hollow metallic waveguide, designed and constructed to transmit the dominant mode in the 0.9-2.0 GHz band. MHz radiation is conveniently coupled into the fiber using the guided microwave radiation as carrier. Phonon emissions from the fiber under CO2 laser pumping are first established on a spectrum analyzer; low frequency generators ale then tuned to match these frequencies and their maximum interaction recorded. Such interactions are systematically studied by monitoring the amplitude and waveform of the reflected and transmitted laser pulse at various power levels and frequencies of the externally coupled radiation. A plot of reflected laser power versus incident laser power reveals a distinct sBs generated phonon threshold. Variouslaunch directions of the GHz and MHz radiation with respect to the direction of laser propagation are realized to verify theory governing sBs interactions. The MHz radiation and its associated phonons in the fiber are convenient tools for probing sBs related phenomenon in infrared fibers.

  15. Electrohemical properties of carbon nanotube paste electrodes modified with redox cationic dyes=Propriedades eletroquímicas de eletrodos a base de pasta de nanotubo de carbono modificados com corantes redox catiônicos

    Directory of Open Access Journals (Sweden)

    Arnaldo César Pereira

    2012-07-01

    Full Text Available The present work describes the electrochemical behavior of methylene blue and toluidine blue as electron mediators adsorbed in the multiwall carbon nanotubes paste. Based on midpoint potential and separation of cathodic and anodic peaks (ΔE, it was not observed interaction of different eletrolytes with the cationic dyes by an ion exchange reaction and, as a consequence, absence of leaching of cationic dyes to the solution phase. The kinetics of electron transfer on the surface electrode was not sufficiently fast showing a fairly resistence of carbon nanotube paste modified with the mediators. The midpoint potential and ΔE also were insentive to the pH range (4-8, confirming the protective effect of carbon nanotubes matrix, owing to strong interaction of between the latter and the nitrogen of nitrogen of cationic dyes with carbon nanotube matrix, minimizing the proton interaction under cationic dye. This result is very important for sensor/biosensor preparation, because the eletrooxidation behavior of the analyte will be only affected by its formal potencial shifting. Carbon nanotubes proved to be an efficient solid matrix for the adsorption of mediator electron in comparison to the electrochemical behavior of free cationic dyes in solution phase.O presente trabalho descreve o comportamento eletroquímico de azul de metileno e azul de toluidina como mediadores de elétrons adsorvidos em pasta de nanotubo de carbono multiparede. Com base no potencial médio e na separação de pico catódico e anódico (ΔE, não foi observada interação de diferentes eletrólitos com os corantes catiônicos por meio de reação de troca iônica e, como consequência, ausência de lixiviação dos corantes para solução. A cinética de transferência de elétron na superfície do eletrodo não foi suficientemente rápida, mostrando razoável resistência da pasta de nanotubo de carbono modificada com os mediadores. O potencial médio e ΔE também foram insens

  16. Loose Coupling of Wearable-Based INSs with Automatic Heading Evaluation

    Science.gov (United States)

    Munoz Diaz, Estefania

    2017-01-01

    Position tracking of pedestrians by means of inertial sensors is a highly explored field of research. In fact, there are already many approaches to implement inertial navigation systems (INSs). However, most of them use a single inertial measurement unit (IMU) attached to the pedestrian’s body. Since wearable-devices will be given items in the future, this work explores the implementation of an INS using two wearable-based IMUs. A loosely coupled approach is proposed to combine the outputs of wearable-based INSs. The latter are based on a pocket-mounted IMU and a foot-mounted IMU. The loosely coupled fusion combines the output of the two INSs not only when these outputs are least erroneous, but also automatically favoring the best output. This approach is named smart update. The main challenge is determining the quality of the heading estimation of each INS, which changes every time. In order to address this, a novel concept to determine the quality of the heading estimation is presented. This concept is subject to a patent application. The results show that the position error rate of the loosely coupled fusion is 10 cm/s better than either the foot INS’s or pocket INS’s error rate in 95% of the cases. PMID:29099807

  17. A Nanotechnology-Ready Computing Scheme based on a Weakly Coupled Oscillator Network

    Science.gov (United States)

    Vodenicarevic, Damir; Locatelli, Nicolas; Abreu Araujo, Flavio; Grollier, Julie; Querlioz, Damien

    2017-03-01

    With conventional transistor technologies reaching their limits, alternative computing schemes based on novel technologies are currently gaining considerable interest. Notably, promising computing approaches have proposed to leverage the complex dynamics emerging in networks of coupled oscillators based on nanotechnologies. The physical implementation of such architectures remains a true challenge, however, as most proposed ideas are not robust to nanotechnology devices’ non-idealities. In this work, we propose and investigate the implementation of an oscillator-based architecture, which can be used to carry out pattern recognition tasks, and which is tailored to the specificities of nanotechnologies. This scheme relies on a weak coupling between oscillators, and does not require a fine tuning of the coupling values. After evaluating its reliability under the severe constraints associated to nanotechnologies, we explore the scalability of such an architecture, suggesting its potential to realize pattern recognition tasks using limited resources. We show that it is robust to issues like noise, variability and oscillator non-linearity. Defining network optimization design rules, we show that nano-oscillator networks could be used for efficient cognitive processing.

  18. ZnO nanowire-based glucose biosensors with different coupling agents

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Juneui [Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Lim, Sangwoo, E-mail: swlim@yonsei.ac.kr [Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 120-749 (Korea, Republic of)

    2013-01-15

    Highlights: Black-Right-Pointing-Pointer Fabrication of ZnO nanowire-based glucose biosensors using different coupling agents. Black-Right-Pointing-Pointer Highest sensitivity for (3-aminopropyl)methyldiethoxysilane-treated biosensor. Black-Right-Pointing-Pointer Larger amount of glucose oxidase and lower electron transfer resistance for (3-aminopropyl)methyldiethoxysilane-treated biosensor. - Abstract: ZnO-nanowire-based glucose biosensors were fabricated by immobilizing glucose oxidase (GOx) onto a linker attached to ZnO nanowires. Different coupling agents were used, namely (3-aminopropyl)trimethoxysilane (APTMS), (3-aminopropyl)triethoxysilane (APTES), and (3-aminopropyl)methyldiethoxysilane (APS), to increase the affinity of GOx binding to ZnO nanowires. The amount of GOx immobilized on the ZnO nanowires, the performance, sensitivity, and Michaelis-Menten constant of each biosensor, and the electron transfer resistance through the biosensor were all measured in order to investigate the effect of the coupling agent on the ZnO nanowire-based biosensor. Among the different biosensors, the APS-treated biosensor had the highest sensitivity (17.72 {mu}A cm{sup -2} mM{sup -1}) and the lowest Michaelis-Menten constant (1.37 mM). Since APS-treated ZnO nanowires showed the largest number of C-N groups and the lowest electron transfer resistance through the biosensor, we concluded that these properties were the key factors in the performance of APS-treated glucose biosensors.

  19. A Plasmonic Temperature-Sensing Structure Based on Dual Laterally Side-Coupled Hexagonal Cavities

    Directory of Open Access Journals (Sweden)

    Yiyuan Xie

    2016-05-01

    Full Text Available A plasmonic temperature-sensing structure, based on a metal-insulator-metal (MIM waveguide with dual side-coupled hexagonal cavities, is proposed and numerically investigated by using the finite-difference time-domain (FDTD method in this paper. The numerical simulation results show that a resonance dip appears in the transmission spectrum. Moreover, the full width of half maximum (FWHM of the resonance dip can be narrowed down, and the extinction ratio can reach a maximum value by tuning the coupling distance between the waveguide and two cavities. Based on a linear relationship between the resonance dip and environment temperature, the temperature-sensing characteristics are discussed. The temperature sensitivity is influenced by the side length and the coupling distance. Furthermore, for the first time, two concepts—optical spectrum interference (OSI and misjudge rate (MR—are introduced to study the temperature-sensing resolution based on spectral interrogation. This work has some significance in the design of nanoscale optical sensors with high temperature sensitivity and a high sensing resolution.

  20. Double Position Servo Synchronous Drive System Based on Cross-Coupling Integrated Feedforward Control for Broacher

    Science.gov (United States)

    Lu, Wenqi; Ji, Kehui; Dong, Hanqing; Zhang, Jianya; Wang, Quanwu; Guo, Liang

    2017-03-01

    Synchronization errors directly deteriorate the machining accuracy of metal parts and the existed method cannot keep high synchronization precision because of external disturbances. A new double position servo synchronous driving scheme based on semi-closed-loop cross-coupling integrated feedforward control is proposed. The scheme comprises a position error cross-coupling feedforward control and a load torque identification with feedforward control. A digital integrated simulation system for the dual servo synchronous drive system is established. Using a 20 t servo broacher, performance analysis of the scheme is conducted based on this simulation system and the simulation results show that systems with traditional parallel or single control have problems when the worktable works with an unbalanced load. However, the system with proposed scheme shows good synchronous performance and positional accuracy. Broaching tests are performed and the experimental results show that the maximum dual axis synchronization error of the system is only 8 μm during acceleration and deceleration processes and the error between the actual running position and the given position is almost zero. A double position servo synchronous driving scheme is presented based on cross-coupled integrated feedforward compensation control, which can improve the synchronization precision.

  1. Mineral evolution of redox-sensitive elements

    Science.gov (United States)

    Hazen, R. M.; Sverjensky, D. A.; Grew, E. S.; Downs, R. T.; Golden, J.; Hystad, G.

    2012-12-01

    Temporal trends in Earth's near-surface mineralogy correlate with major events in geochemical, tectonic, and biological evolution. Recent compilations of age and locality information for the minerals of redox-sensitive elements Mo, Hg, W, Ni, Co, and U reveal statistically significant trends related to key events in the history of the geosphere and biosphere. Mineralization for all of these elements correlates with five intervals of supercontinent assembly, from ~2.7 Ga (Kenorland) to 300 Ma (Pangaea; see Fig. 1). Details of mineral diversity and distribution correlate with changes in near-surface geochemistry, as well as such biological innovations as oxygenic photosynthesis and the rise of the terrestrial biosphere. In addition, systematic increases in average and maximum trace concentrations of Re in molybdenite since 3.0 Ga point to enhanced oxidative weathering by subsurface fluids (Fig. 2). These trace element results, coupled with the delayed appearance of minerals of other redox sensitive elements, suggest that significant terrestrial subsurface oxidation may have postdated the Great Oxidation Event (~2.4 to 2.2 Ga) by hundreds of millions of years.he distribution of molybdenite (MoS2) through Earth history is episodic, with maxima corresponding to times of supercontinent assembly. he rhenium content of molybdenite displays a statistically significant increase over 3 billion years of Earth history. This trend reflects the increased mobility of Re in more oxidized subsurface aqueous environments.

  2. Distinct redox regulation in sub-cellular compartments in response to various stress conditions in Saccharomyces cerevisiae.

    Science.gov (United States)

    Ayer, Anita; Sanwald, Julia; Pillay, Bethany A; Meyer, Andreas J; Perrone, Gabriel G; Dawes, Ian W

    2013-01-01

    Responses to many growth and stress conditions are assumed to act via changes to the cellular redox status. However, direct measurement of pH-adjusted redox state during growth and stress has never been carried out. Organellar redox state (E GSH) was measured using the fluorescent probes roGFP2 and pHluorin in Saccharomyces cerevisiae. In particular, we investigated changes in organellar redox state in response to various growth and stress conditions to better understand the relationship between redox-, oxidative- and environmental stress response systems. E GSH values of the cytosol, mitochondrial matrix and peroxisome were determined in exponential and stationary phase in various media. These values (-340 to -350 mV) were more reducing than previously reported. Interestingly, sub-cellular redox state remained unchanged when cells were challenged with stresses previously reported to affect redox homeostasis. Only hydrogen peroxide and heat stress significantly altered organellar redox state. Hydrogen peroxide stress altered the redox state of the glutathione disulfide/glutathione couple (GSSG, 2H(+)/2GSH) and pH. Recovery from moderate hydrogen peroxide stress was most rapid in the cytosol, followed by the mitochondrial matrix, with the peroxisome the least able to recover. Conversely, the bulk of the redox shift observed during heat stress resulted from alterations in pH and not the GSSG, 2H(+)/2GSH couple. This study presents the first direct measurement of pH-adjusted redox state in sub-cellular compartments during growth and stress conditions. Redox state is distinctly regulated in organelles and data presented challenge the notion that perturbation of redox state is central in the response to many stress conditions.

  3. Distinct redox regulation in sub-cellular compartments in response to various stress conditions in Saccharomyces cerevisiae.

    Directory of Open Access Journals (Sweden)

    Anita Ayer

    Full Text Available Responses to many growth and stress conditions are assumed to act via changes to the cellular redox status. However, direct measurement of pH-adjusted redox state during growth and stress has never been carried out. Organellar redox state (E GSH was measured using the fluorescent probes roGFP2 and pHluorin in Saccharomyces cerevisiae. In particular, we investigated changes in organellar redox state in response to various growth and stress conditions to better understand the relationship between redox-, oxidative- and environmental stress response systems. E GSH values of the cytosol, mitochondrial matrix and peroxisome were determined in exponential and stationary phase in various media. These values (-340 to -350 mV were more reducing than previously reported. Interestingly, sub-cellular redox state remained unchanged when cells were challenged with stresses previously reported to affect redox homeostasis. Only hydrogen peroxide and heat stress significantly altered organellar redox state. Hydrogen peroxide stress altered the redox state of the glutathione disulfide/glutathione couple (GSSG, 2H(+/2GSH and pH. Recovery from moderate hydrogen peroxide stress was most rapid in the cytosol, followed by the mitochondrial matrix, with the peroxisome the least able to recover. Conversely, the bulk of the redox shift observed during heat stress resulted from alterations in pH and not the GSSG, 2H(+/2GSH couple. This study presents the first direct measurement of pH-adjusted redox state in sub-cellular compartments during growth and stress conditions. Redox state is distinctly regulated in organelles and data presented challenge the notion that perturbation of redox state is central in the response to many stress conditions.

  4. Molecular engineering of organic electroactive materials for redox flow batteries.

    Science.gov (United States)

    Ding, Yu; Zhang, Changkun; Zhang, Leyuan; Zhou, Yangen; Yu, Guihua

    2017-10-18

    With high scalability and independent control over energy and power, redox flow batteries (RFBs) stand out as an important large-scale energy storage system. However, the widespread application of conventional RFBs is limited by the uncompetitive performance, as well as the high cost and environmental concerns associated with the use of metal-based redox species. In consideration of advantageous features such as potentially low cost, vast molecular diversity, and highly tailorable properties, organic and organometallic molecules emerge as promising alternative electroactive species for building sustainable RFBs. This review presents a systematic molecular engineering scheme for designing these novel redox species. We provide detailed synthetic strategies for modifying the organic and organometallic redox species in terms of solubility, redox potential, and molecular size. Recent advances are then introduced covering the reaction mechanisms, specific functionalization methods, and electrochemical performances of redox species classified by their molecular structures. Finally, we conclude with an analysis of the current challenges and perspectives on future directions in this emerging research field.

  5. [Study of spectrum characteristic of humidity sensor based on series coupled two micro-ring resonators].

    Science.gov (United States)

    Guo, Shi-Liang; Hu, Chun-Hai; Li, Xin; Wang, Wen-Juan

    2014-11-01

    A novel humidity sensor of polyimide (PI) based on the series coupled two-micro-ring resonators is proposed in the present paper. The transfer function of the micro ring resonator was calculated by using the transfer matrix method and the coupled mode theory. The authors compared the output spectrum characteristics of the traditional single micro-ring and series coupled two-micro-ring with different radii. The refractive index of the PI waveguide changes with different environmental humidity and this will lead to the drift of the output spectrum of the micro-ring resonator. By detecting the drift of the output spectrum we can measure the humidity, and the sensitivity and the sensing-range of the sensor are acquired accordingly. We also analyzed the output spectrum characteristics of resonators at different humidity sensing part. The theoretical results show the good performance of humidity sensor which could be used as the optimum sensing unit when the whole structure of the series coupled two-micro-ring resonators serves as the sensing part. The sensing-range and sensitivity of the system are improved by series micro-ring resonators of different radii compared to the conventional sensor with single micro-ring resonator. The free spectral range (FSR) of resonator reaches to 0.15 μm, the sensing-range is 10% RH-80% RH, and the sensitivity is 0.001 7 μm (% RH)(-1). Series coupled two-micro-ring with different radii gives theoretical instruction for producing integrated humidity sensor with low-cost, simple structure and high sensitivity.

  6. Design of a bioelectrocatalytic electrode interface for oxygen reduction in biofuel cells based on a specifically adapted Os-complex containing redox polymer with entrapped Trametes hirsuta laccase

    Energy Technology Data Exchange (ETDEWEB)

    Ackermann, Yvonne; Guschin, Dmitrii A.; Eckhard, Kathrin; Schuhmann, Wolfgang [Analytische Chemie - Elektroanalytik and Sensorik, Ruhr-Universitaet Bochum, Universitaetsstr. 150, D-44780 Bochum (Germany); Shleev, Sergey [Biomedical Laboratory Science, Faculty of Health and Society, Malmoe University, Soedra Foerstadsgatan 101, SE-20506 Malmoe (Sweden)

    2010-05-15

    The design of the coordination shell of an Os-complex and its integration within an electrodeposition polymer enables fast electron transfer between an electrode and a polymer entrapped high-potential laccase from the basidiomycete Trametes hirsuta. The redox potential of the Os{sup 3+/2+}-centre tethered to the polymer backbone (+ 720 mV vs. NHE) is perfectly matching the potential of the enzyme (+ 780 mV vs. NHE at pH 6.5). The laccase and the Os-complex modified anodic electrodeposition polymer were simultaneously precipitated on the surface of a glassy carbon electrode by means of a pH-shift to 2.5. The modified electrode was investigated with respect to biocatalytic O{sub 2} reduction to H{sub 2}O. The proposed modified electrode has potential applications as biofuel cell cathode. (author)

  7. Studies on a vinyl ruthenium-modified squaraine dye: multiple visible/near-infrared absorbance switching through dye- and substituent-based redox processes.

    Science.gov (United States)

    Chen, Jing; Winter, Rainer F

    2012-08-20

    The bis(vinyl ruthenium)-modified squaraine dye 1 was synthesized by treatment of [RuHCl(CO)(PiPr(3) )(2) ] with bis(ethynyl)-substituted squaraine 8. Spectroscopic and electrochemical measurements on 1 and its organic precursors 6-8 were performed to study the effect of the vinyl ruthenium "substituents," particularly with respect to (poly)electrochromism. Attachment of the vinyl ruthenium moieties endows metal-organic squaraine 1 with two additional oxidation waves and lowers the first two oxidation potentials by approximately 300 mV with respect to its organic precursors. Squaraines 6, 7, 8, and 1 strongly absorb at 648, 663, 656, or 709 nm. Although organic dyes 6, 7, and 8 fluoresce, no room-temperature emission is observed for 1. The radical cations and anions of 6, 7, 8, and 1 as well as the doubly oxidized dications have been studied by IR and UV/Vis/NIR spectroelectrochemistry, and the -/0/+/2+ redox sequences were found to be reversible in each case. Our results indicate that the 1(2-/-/0/+/2+) redox system constitutes a polyelectrochromic switch in which absorption in the visible or the near-infrared range is reversibly turned off or shifted deep into the NIR. They also show that radical cation 1(.+) is an intrinsically delocalized system with only little contribution from the outer vinyl ruthenium tags to the oxidation process. Dication 1(2+) constitutes a class-II mixed-valent system with two electronically different vinyl ruthenium moieties and has an open-shell singlet electronic ground-state structure. ESR and NMR spectra of chemically prepared 1(.+) and 1(2+) corroborate these results. It has also emerged that reduction involves an orbital that is strongly delocalized across the entire squaraine π system and strongly affects the peripheral vinyl ruthenium sites. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. A thermography-based method for fatigue behavior evaluation of coupling beam damper

    Directory of Open Access Journals (Sweden)

    Zhe Zhang

    2017-04-01

    Full Text Available Under cyclic load, local fatigue damage will occur in the metal damper widely used in the shear wall. This will deteriorate the stiffness of damper and weaken the hysteresis behaviour. The present paper proposed a new and easy method to manufacture kinds of coupling beam dampers. A thermography-based experiment was used to study the energy dissipation and damage accumulation during fatigue process of the metal damper. Based on the temperature variation related to fatigue damage process, the relationship between the plastic deformation and thermal energy dissipation was quantitatively established. Besides, the relationships between the temperature increase to damage accumulation and mechanical load were analyzed systematically.

  9. A concise, efficient synthesis of sugar-based benzothiazoles through chemoselective intramolecular C-S coupling

    KAUST Repository

    Shen, Chao

    2012-01-01

    Sugar-based benzothiazoles are a new class of molecules promising for many biological applications. Here, we have synthesized a wide range of sugar-based benzothiazoles from readily accessible glycosyl thioureas by chemoselective, palladium-catalyzed C-S coupling reactions. Corroborated by theoretical calculations, a mechanistic investigation indicates that the coordination to the palladium by a pivaloyl carbonyl group and the presence of intramolecular hydrogen bonding play important roles in the efficiency and chemoselectivity of reaction. These fluorescent glycoconjugates can be observed to readily enter mammalian tumor cells and exhibit potential in vitro antitumor activity. This journal is © The Royal Society of Chemistry 2012.

  10. 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.

  11. Spontaneous Synchronization in Two Mutually Coupled Memristor-Based Chua’s Circuits: Numerical Investigations

    Directory of Open Access Journals (Sweden)

    Eleonora Bilotta

    2014-01-01

    Full Text Available Chaotic dynamics of numerous memristor-based circuits is widely reported in literature. Recently, some works have appeared which study the problem of synchronization control of these systems in a master-slave configuration. In the present paper, the spontaneous dynamic behavior of two chaotic memristor-based Chua’s circuits, mutually interacting through a coupling resistance, was studied via computer simulations in order to study possible self-organized synchronization phenomena. The used memristor is a flux controlled memristor with a cubic nonlinearity, and it can be regarded as a time-varying memductance. The memristor, in effect, retains memory of its past dynamic and any difference in the initial conditions of the two circuits results in different values of the corresponding memductances. In this sense, due to the memory effect of the memristor, even if coupled circuits have the same parameters they do not constitute two completely identical chaotic oscillators. As is known, for nonidentical chaotic systems, in addition to complete synchronizations (CS other weaker forms of synchronization which provide correlations between the signals of the two systems can also occur. Depending on initial conditions and coupling strength, both chaotic and nonchaotic synchronization are observed for the system considered in this work.

  12. High content screening for G protein-coupled receptors using cell-based protein translocation assays

    DEFF Research Database (Denmark)

    Grånäs, Charlotta; Lundholt, Betina Kerstin; Heydorn, Arne

    2005-01-01

    G protein-coupled receptors (GPCRs) have been one of the most productive classes of drug targets for several decades, and new technologies for GPCR-based discovery promise to keep this field active for years to come. While molecular screens for GPCR receptor agonist- and antagonist-based drugs...... will continue to be valuable discovery tools, the most exciting developments in the field involve cell-based assays for GPCR function. Some cell-based discovery strategies, such as the use of beta-arrestin as a surrogate marker for GPCR function, have already been reduced to practice, and have been used...... as valuable discovery tools for several years. The application of high content cell-based screening to GPCR discovery has opened up additional possibilities, such as direct tracking of GPCRs, G proteins and other signaling pathway components using intracellular translocation assays. These assays provide...

  13. The Immune Self-adjusting Contour Error Coupled Control in Machining Based on Grating Ruler Sensors

    Directory of Open Access Journals (Sweden)

    Guoyong Zhao

    2014-10-01

    Full Text Available The actual dynamic performance of each feed axis can’t match well usually, which will destroy machine tool contour accuracy seriously. The immune self-adjusting contour error coupled control method based on grating ruler sensors is developed to improve machine tool contour accuracy in the paper. Firstly, measure and convert the feed axis actual displacement into pulse signals with grating ruler sensors on each sampling period; then calculate the contour error and contour error compensation control quantity. The method combines the advantages of immune mechanism and classical Proportion Integration Differentiation (PID control algorithm. The introduced method is testified on the three-axis computer numerical control (CNC milling machine with three high precision grating ruler sensors. And the experimental results show that the proposed immune self-adjusting contour error coupled control method can improve machine tool contour accuracy remarkably.

  14. Numerical simulation of induction hardening of a cylindrical part based on multi-physics coupling

    Science.gov (United States)

    Tong, Daming; Gu, Jianfeng; Totten, George Edward

    2017-04-01

    An induction hardening process was simulated based on an electromagnetic-thermal-transformation coupled numerical model. Calculation of the microstructure fraction was introduced using a coupled electromagnetic-thermal field during heating and the temperature field of the subsequent cooling process. The isoconversional method was used to formulate the austenitization process during heating, model parameters were determined by continuous heating dilatometric curves, and JMAK and K-M equations were adopted to calculate the fraction of new phases formed during cooling. The temperature and microstructure evolution in a cylindrical part of JIS-SCM440 steel were simulated during the induction hardening process and the simulated temperature and final microstructure distribution fit well with experimental data. Simulation results also showed that the free cooling prior to spray quenching could be optimized to decrease the temperature gradient in the surface layer to avoid decomposition of austenite into non-martensite microstructure.

  15. DFT-based Green's function pathways model for prediction of bridge-mediated electronic coupling.

    Science.gov (United States)

    Berstis, Laura; Baldridge, Kim K

    2015-12-14

    A density functional theory-based Green's function pathway model is developed enabling further advancements towards the long-standing challenge of accurate yet inexpensive prediction of electron transfer rate. Electronic coupling predictions are demonstrated to within 0.1 eV of experiment for organic and biological systems of moderately large size, with modest computational expense. Benchmarking and comparisons are made across density functional type, basis set extent, and orbital localization scheme. The resulting framework is shown to be flexible and to offer quantitative prediction of both electronic coupling and tunneling pathways in covalently bound non-adiabatic donor-bridge-acceptor (D-B-A) systems. A new localized molecular orbital Green's function pathway method (LMO-GFM) adaptation enables intuitive understanding of electron tunneling in terms of through-bond and through-space interactions.

  16. Design of an Angle Detector for Laser Beams Based on Grating Coupling

    Directory of Open Access Journals (Sweden)

    Weidong Zhou

    2012-02-01

    Full Text Available A novel angle detector for laser beams is designed in this paper. It takes advantage of grating coupling to couple the incident light into a slab waveguide; and, the incident light’s angle can be determined by reading the outputs of light detectors within the waveguide. This device offers fast-responding on-chip detection of laser beam’s angle. Compared to techniques based on quadrant photodiodes or lateral effect photodiodes, the device in this paper has far greater detectable range (up to a few degrees, to be specific. Performance of the laser angle detector in this paper is demonstrated by finite-difference-time-domain simulations. Numerical results show that, the detectable angle range can be adjusted by several design parameters and can reach [−4°, 4°]. The laser beam angle detector in this paper is expected to find various applications such as ultra-fast optical interconnects.

  17. High brightness laser source based on polarization coupling of two diode lasers with asymmetric feedback

    DEFF Research Database (Denmark)

    Thestrup, B.; Chi, M.; Sass, B.

    2003-01-01

    In this letter, we show that polarization coupling and asymmetric diode-laser feedback can be used to combine two diode-laser beams with low spatial coherence into a single beam with high spatial coherence. The coupled laser source is based on two similar laser systems each consisting of a 1 mumx......200 mum broad area laser diode applied with a specially designed feedback circuit. When operating at two times threshold, 50% of the freely running system output power is obtained in a single beam with an M-2 beam quality factor of 1.6+/-0.1, whereas the M-2 values of the two freely running diode...... lasers are 29+/-1 and 34+/-1, respectively. (C) 2003 American Institute of Physics....

  18. Measuring the coupled risks: A copula-based CVaR model

    Science.gov (United States)

    He, Xubiao; Gong, Pu

    2009-01-01

    Integrated risk management for financial institutions requires an approach for aggregating risk types (such as market and credit) whose distributional shapes vary considerably. The financial institutions often ignore risks' coupling influence so as to underestimate the financial risks. We constructed a copula-based Conditional Value-at-Risk (CVaR) model for market and credit risks. This technique allows us to incorporate realistic marginal distributions that capture essential empirical features of these risks, such as skewness and fat-tails while allowing for a rich dependence structure. Finally, the numerical simulation method is used to implement the model. Our results indicate that the coupled risks for the listed company's stock maybe are undervalued if credit risk is ignored, especially for the listed company with bad credit quality.

  19. Redox ratio and optical absorption of polyvalent ions in industrial ...

    Indian Academy of Sciences (India)

    The changes in glass structure and redox ratio, (reduced ion to oxidized ion) of Mn2+–Mn3+, Cu+–Cu2+, Cr3+–Cr6+, Ni2+–Ni3+ and Co2+–Co3+ couples and optical absorption due to Mn3+, Cu2+, Cr3+, Ni2+ and Co2+ ions in industrial soda–lime–silica glass were investigated as a function of Na2O concentration in the ...

  20. Five coordinate M(II)-diphenolate [M = Zn(II), Ni(II), and Cu(II)] Schiff base complexes exhibiting metal- and ligand-based redox chemistry.

    Science.gov (United States)

    Franks, Mark; Gadzhieva, Anastasia; Ghandhi, Laura; Murrell, David; Blake, Alexander J; Davies, E Stephen; Lewis, William; Moro, Fabrizio; McMaster, Jonathan; Schröder, Martin

    2013-01-18

    Five-coordinate Zn(II), Ni(II), and Cu(II) complexes containing pentadentate N(3)O(2) Schiff base ligands [1A](2-) and [1B](2-) have been synthesized and characterized. X-ray crystallographic studies reveal five coordinate structures in which each metal ion is bound by two imine N-donors, two phenolate O-donors, and a single amine N-donor. Electron paramagnetic resonance (EPR) spectroscopic studies suggest that the N(3)O(2) coordination spheres of [Cu(1A)] and [Cu(1B)] are retained in CH(2)Cl(2) solution and solid-state superconducting quantum interference device (SQUID) magnetometric studies confirm that [Ni(1A)] and [Ni(1B)] adopt high spin (S = 1) configurations. Each complex exhibits two reversible oxidation processes between +0.05 and +0.64 V vs [Fc](+)/[Fc]. The products of one- and two-electron oxidations have been studied by UV/vis spectroelectrochemistry and by EPR spectroscopy which confirm that each oxidation process for the Zn(II) and Cu(II) complexes is ligand-based with sequential formation of mono- and bis-phenoxyl radical species. In contrast, the one-electron oxidation of the Ni(II) complexes generates Ni(III) products. This assignment is supported by spectroelectrochemical and EPR spectroscopic studies, density functional theory (DFT) calculations, and the single crystal X-ray structure of [Ni(1A)][BF(4)] which contains Ni in a five-coordinate distorted trigonal bipyramidal geometry.

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

    KAUST Repository

    Chen, Wei

    2013-01-01

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

  2. Redox Pioneer: Professor Joseph Loscalzo

    OpenAIRE

    Leopold, Jane A.

    2010-01-01

    Dr. Joseph Loscalzo (M.D., 1978; Ph.D., 1977) is recognized here as a Redox Pioneer because he has published two articles in the field of antioxidant/redox biology that have been cited more than 1,000 times and 22 articles that have been cited more than 100 times. Dr. Loscalzo is known for his seminal contributions to our understanding of the vascular biology of nitric oxide. His initial discovery that the antiplatelet effects of organic nitrates are potentiated by thiols through a mechanism ...

  3. Single-molecule spectroelectrochemical cross-correlation during redox cycling in recessed dual ring electrode zero-mode waveguides.

    Science.gov (United States)

    Han, Donghoon; Crouch, Garrison M; Fu, Kaiyu; Zaino Iii, Lawrence P; Bohn, Paul W

    2017-08-01

    The ability of zero-mode waveguides (ZMW) to guide light into subwavelength-diameter nanoapertures has been exploited for studying electron transfer dynamics in zeptoliter-volume nanopores under single-molecule occupancy conditions. In this work, we report the spectroelectrochemical detection of individual molecules of the redox-active, fluorogenic molecule flavin mononucleotide (FMN) freely diffusing in solution. Our approach is based on an array of nanopore-confined recessed dual ring electrodes, wherein repeated reduction and oxidation of a single molecule at two closely spaced annular working electrodes yields amplified electrochemical signals. We have articulated these structures with an optically transparent bottom, so that the nanopores are bifunctional, exhibiting both nanophotonic and nanoelectrochemical behaviors allowing the coupling between electron transfer and fluorescence dynamics to be studied under redox cycling conditions. We also investigated the electric field intensity in electrochemical ZMWs (E-ZMW) through finite-element simulations, and the amplification of fluorescence by redox cycling agrees well with predictions based on optical confinement effects inside the E-ZMW. Proof-of-principle experiments are conducted showing that electrochemical and fluorescence signals may be correlated to reveal single molecule fluctuations in the array population. Cross-correlation of single molecule fluctuations in amperometric response and single photon emission provides unequivocal evidence of single molecule sensitivity.

  4. Modeling of thermal coupling in VO2-based oscillatory neural networks

    Science.gov (United States)

    Velichko, Andrey; Belyaev, Maksim; Putrolaynen, Vadim; Perminov, Valentin; Pergament, Alexander

    2018-01-01

    In this study, we have demonstrated the possibility of using the thermal coupling to control the dynamics of operation of coupled VO2 oscillators. Based on the example of a 'switch-microheater' pair, we have explored the synchronization and dissynchronization modes of a single oscillator with respect to an external harmonic heat impact. The features of changes in the spectra are shown, in particular, the effect of the natural frequency attraction to the affecting signal frequency and the self-oscillation noise reduction effects at synchronization. The time constant of the temperature effect for the considered system configuration is in the range 7-140 μs, which allows operation in the oscillation frequency range of up to ∼70 kHz. A model estimate of the minimum temperature sensitivity of the switch is δTswitch ∼ 0.2 K, and the effective action radius RTC of the switch-to-switch thermal coupling is not less than 25 μm. Nevertheless, as the simulation shows, the frequency range can be significantly extended up to the values of 1-30 GHz if using nanometer-scale switches (heaters).

  5. Improving couples' quality of life through a Web-based prostate cancer education intervention.

    Science.gov (United States)

    Song, Lixin; Rini, Christine; Deal, Allison M; Nielsen, Matthew E; Chang, Hao; Kinneer, Patty; Teal, Randall; Johnson, David C; Dunn, Mary W; Mark, Barbara; Palmer, Mary H

    2015-03-01

    To evaluate the feasibility and acceptability of a newly developed web-based, couple-oriented intervention called Prostate Cancer Education and Resources for Couples (PERC). Quantitative, qualitative, mixed-methods approach. Oncology outpatient clinics at the University of North Carolina (UNC) Lineberger Comprehensive Cancer Center at UNC–Chapel Hill. 26 patients with localized prostate cancer (PCa) and their partners. Pre- and postpilot quantitative assessments and a postpilot qualitative interview were conducted. General and PCa-specific symptoms, quality of life, psychosocial factors, PERC’s ease of use, and web activities. Improvement was shown in some PCa-specific and general symptoms (small effect sizes for patients and small-to-medium effect sizes for partners), overall quality of life, and physical and social domains of quality of life for patients (small effect sizes). Web activity data indicated high PERC use. Qualitative and quantitative analyses indicated that participants found PERC easy to use and understand,as well as engaging, of high quality, and relevant. Overall, participants were satisfied with PERC and reported that PERC improved their knowledge about symptom management and communication as a couple. PERC was a feasible, acceptable method of reducing the side effects of PCa treatment–related symptoms and improving quality of life. PERC has the potential to reduce the negative impacts of symptoms and enhance quality of life for patients with localized PCa and their partners, particularly for those who live in rural areas and have limited access to post-treatment supportive care.

  6. A Cost-Effective Relative Humidity Sensor Based on Side Coupling Induction Technology.

    Science.gov (United States)

    Zhang, Yingzi; Hou, Yulong; Liu, Wenyi; Zhang, Huixin; Zhang, Yanjun; Zhang, Zhidong; Guo, Jing; Liu, Jia; Zhang, Liang; Tan, Qiu-Lin

    2017-04-25

    A intensity-modulated optical fiber relative humidity (RH) sensor based on the side coupling induction technology (SCIT) is presented and experimentally demonstrated. The agarose gel and the twisted macro-bend coupling structure are first combined for RH sensing applications. The refractive index (RI) of the agarose gel increases with the increase of the RH and is in linear proportion from 20 to 80%RH. The side coupling power, which changes directly with the RI of the agarose gel, can strip the source noise from the sensor signal and improve the signal to noise ratio substantially. The experiment results show that the sensitivity of the proposed sensor increases while the bend radius decreases. When the bend radius is 8 mm, the sensor has a linear response from 40% to 80% RH with the sensitivity of 4.23 nW/% and the limit of detection of 0.70%. A higher sensitivity of 12.49 nW/% is achieved when RH raises from 80% to 90% and the limit of detection decreases to 0.55%. Furthermore, the proposed sensor is a low-cost solution, offering advantages of good reversibility, fast response time, and compensable temperature dependence.

  7. Ensemble-based Experimental Atmospheric Reanalysis using a Global Coupled Atmosphere-Ocean GCM

    Science.gov (United States)

    Komori, N.; Enomoto, T.; Miyoshi, T.; Yamazaki, A.; Kuwano-Yoshida, A.; Taguchi, B.

    2016-02-01

    To enhance the capability of the local ensemble transform Kalman filter (LETKF) with the Atmospheric general circulation model (GCM) for the Earth Simulator (AFES), a new system has been developed by replacing AFES with the Coupled atmosphere-ocean GCM for the Earth Simulator (CFES). An initial test of the prototype of the CFES-LETKF system has been completed successfully, assimilating atmospheric observational data (NCEP PREPBUFR archived at UCAR) every 6 hours to update the atmospheric variables, whereas the oceanic variables are kept unchanged throughout the assimilation procedure. An experimental retrospective analysis-forecast cycle with the coupled system (CLERA-A) starts on August 1, 2008, and the atmospheric initial conditions (63 members) are taken from the second generation of AFES-LETKF experimental ensemble reanalysis (ALERA2). The ALERA2 analyses are also used as forcing of stand-alone 63-member ensemble simulations with the Ocean GCM for the Earth Simulator (EnOFES), from which the oceanic initial conditions for the CLERA-A are taken. The ensemble spread of SST is larger in CLERA-A than in EnOFES, suggesting positive feedback between the ocean and the atmosphere. Although SST in CLERA-A suffers from the common biases among many coupled GCMs, the ensemble spreads of air temperature and specific humidity in the lower troposphere are larger in CLERA-A than in ALERA2. Thus replacement of AFES with CFES successfully contributes to mitigate an underestimation of the ensemble spread near the surface resulting from the single boundary condition for all ensemble members and the lack of atmosphere-ocean interaction. In addition, the basin-scale structure of surface atmospheric variables over the tropical Pacific is well reconstructed from the ensemble correlation in CLERA-A but not ALERA2. This suggests that use of a coupled GCM rather than an atmospheric GCM could be important even for atmospheric reanalysis with an ensemble-based data assimilation system.

  8. Coupled agent-based and finite-element models for predicting scar structure following myocardial infarction.

    Science.gov (United States)

    Rouillard, Andrew D; Holmes, Jeffrey W

    2014-08-01

    Following myocardial infarction, damaged muscle is gradually replaced by collagenous scar tissue. The structural and mechanical properties of the scar are critical determinants of heart function, as well as the risk of serious post-infarction complications such as infarct rupture, infarct expansion, and progression to dilated heart failure. A number of therapeutic approaches currently under development aim to alter infarct mechanics in order to reduce complications, such as implantation of mechanical restraint devices, polymer injection, and peri-infarct pacing. Because mechanical stimuli regulate scar remodeling, the long-term consequences of therapies that alter infarct mechanics must be carefully considered. Computational models have the potential to greatly improve our ability to understand and predict how such therapies alter heart structure, mechanics, and function over time. Toward this end, we developed a straightforward method for coupling an agent-based model of scar formation to a finite-element model of tissue mechanics, creating a multi-scale model that captures the dynamic interplay between mechanical loading, scar deformation, and scar material properties. The agent-based component of the coupled model predicts how fibroblasts integrate local chemical, structural, and mechanical cues as they deposit and remodel collagen, while the finite-element component predicts local mechanics at any time point given the current collagen fiber structure and applied loads. We used the coupled model to explore the balance between increasing stiffness due to collagen deposition and increasing wall stress due to infarct thinning and left ventricular dilation during the normal time course of healing in myocardial infarcts, as well as the negative feedback between strain anisotropy and the structural anisotropy it promotes in healing scar. The coupled model reproduced the observed evolution of both collagen fiber structure and regional deformation following coronary

  9. Coupled Simulations, Ground-Based Experiments and Flight Experiments for Astrodynamics Research

    Science.gov (United States)

    Boyce, R.; Brown, M.; Lorrain, P.; Capon, C.; Lambert, A.; Benson, C.; Tuttle, S.; Griffin, D.

    Near-Earth satellites undergo complex and poorly understood interactions with their environment, leading to large uncertainties in predicting orbits and an associated risk of collision with other satellites and with space debris. The nature, evolution and behaviour of the growing cloud of space debris in that environment is even less well understood. Significant effort and expenditure is currently being made by governments in Australia, UK, USA, Europe and elsewhere in space surveillance and tracking, in order to mitigate the risk. However, a major gap exists with respect to the science of in-orbit behaviour. Research is underway in Australia to enable the prediction of the orbits of near-Earth space objects with order(s) of magnitude greater fidelity than currently possible. This is being achieved by coupling together the necessary parts of the puzzle - the physics of rarefied space object “aerodynamics” and the space physics and space weather that affects it - and employing our capabilities in ground-based and in-orbit experiments, ground-based observations and high performance computing to do so. As part of the effort, UNSW Canberra is investing $10M to develop a sustainable university-led program to develop and fly affordable in-orbit missions for space research. In the coming 6 years, we will fly a minimum of four cubesat missions, some in partnership with DSTO, which will include flight experiments for validating Space Situational Awareness astrodynamics simulation and observation capabilities. The flights are underpinned by ground-based experimental research employing space test chambers, advanced diagnostics, and supercomputer simulations that couple DSMC and Particle-in-Cell methods for modelling space object interactions with the ionosphere. This paper will describe the research both underway and planned, with particular emphasis on the coupled numerical/experimental/flight approach.

  10. Electrical Microengineering of Redox Enzymes

    Science.gov (United States)

    1994-03-31

    as cytochrome c, myoglobin. ferredoxin and phycocyanin ) has been studied by Kuwana, Hill, Hawkridgc. Blount, Bowden. Armstrong and their colleagues.4...shell- around their redox centers. (such as cytochrome c,A h wu w AN uv. myoglobin. ferredoxin and phycocyanin ) ha•e also shown that. e~en though these

  11. Education-based health inequalities in 18,000 Norwegian couples: the Nord-Trøndelag Health Study (HUNT).

    Science.gov (United States)

    Nilsen, Sara Marie; Bjørngaard, Johan Håkon; Ernstsen, Linda; Krokstad, Steinar; Westin, Steinar

    2012-11-19

    Education-based inequalities in health are well established, but they are usually studied from an individual perspective. However, many individuals are part of a couple. We studied education-based health inequalities from the perspective of couples where indicators of health were measured by subjective health, anxiety and depression. A sample of 35,980 women and men (17,990 couples) was derived from the Norwegian Nord-Trøndelag Health Study 1995-97 (HUNT 2). Educational data and family identification numbers were obtained from Statistics Norway. The dependent variables were subjective health (four-integer scale), anxiety (21-integer scale) and depression (21-integer scale), which were captured using the Hospital Anxiety and Depression Scale. The dependent variables were rescaled from 0 to 100 where 100 was the worst score. Cross-sectional analyses were performed using two-level linear random effect regression models. The variance attributable to the couple level was 42% for education, 16% for subjective health, 19% for anxiety and 25% for depression. A one-year increase in education relative to that of one's partner was associated with an improvement of 0.6 scale points (95% confidence interval = 0.5-0.8) in the subjective health score (within-couple coefficient). A one-year increase in a couple's average education was associated with an improvement of 1.7 scale points (95% confidence interval = 1.6-1.8) in the subjective health score (between-couple coefficient). There were no education-based differences in the anxiety or depression scores when partners were compared, whereas there were substantial education-based differences between couples in all three outcome measures. We found considerable clustering of education and health within couples, which highlighted the importance of the family environment. Our results support previous studies that report the mutual effects of spouses on education-based inequalities in health, suggesting that couples develop

  12. Impedance Based Characterization of a High-Coupled Screen Printed PZT Thick Film Unimorph Energy Harvester

    DEFF Research Database (Denmark)

    Lei, Anders; Xu, R.; Borregaard, L. M.

    2014-01-01

    parameters which, by means of the piezoelectric impedance expression, all can be determined accurately by electrical measurements. It is shown how four of five lumped parameters can be determined from a single impedance measurement scan, considerably reducing the characterization effort. The remaining...... parameter is determined from shaker measurements, and a highly accurate agreement is found between model and measurements on a unimorph MEMS-based screen printed PZT harvester. With a high coupling term K-2 Q similar or equal to 7, the harvester exhibits two optimum load points. The peak power performance...

  13. Athermalization in atomic force microscope based force spectroscopy using matched microstructure coupling.

    Science.gov (United States)

    Torun, H; Finkler, O; Degertekin, F L

    2009-07-01

    The authors describe a method for athermalization in atomic force microscope (AFM) based force spectroscopy applications using microstructures that thermomechanically match the AFM probes. The method uses a setup where the AFM probe is coupled with the matched structure and the displacements of both structures are read out simultaneously. The matched structure displaces with the AFM probe as temperature changes, thus the force applied to the sample can be kept constant without the need for a separate feedback loop for thermal drift compensation, and the differential signal can be used to cancel the shift in zero-force level of the AFM.

  14. Exploiting Flexibility in Coupled Electricity and Natural Gas Markets: A Price-Based Approach

    DEFF Research Database (Denmark)

    Ordoudis, Christos; Delikaraoglou, Stefanos; Pinson, Pierre

    2017-01-01

    Natural gas-fired power plants (NGFPPs) are considered a highly flexible component of the energy system and can facilitate the large-scale integration of intermittent renewable generation. Therefore, it is necessary to improve the coordination between electric power and natural gas systems....... Considering a market-based coupling of these systems, we introduce a decision support tool that increases market efficiency in the current setup where day-ahead and balancing markets are cleared sequentially. The proposed approach relies on the optimal adjustment of natural gas price to modify the scheduling...

  15. FEAMAC-CARES Software Coupling Development Effort for CMC Stochastic-Strength-Based Damage Simulation

    Science.gov (United States)

    Nemeth, Noel N.; Bednarcyk, Brett A.; Pineda, Evan; Arnold, Steven; Mital, Subodh; Murthy, Pappu; Walton, Owen

    2015-01-01

    Reported here is a coupling of two NASA developed codes: CARES (Ceramics Analysis and Reliability Evaluation of Structures) with the MACGMC composite material analysis code. The resulting code is called FEAMACCARES and is constructed as an Abaqus finite element analysis UMAT (user defined material). Here we describe the FEAMACCARES code and an example problem (taken from the open literature) of a laminated CMC in off-axis loading is shown. FEAMACCARES performs stochastic-strength-based damage simulation response of a CMC under multiaxial loading using elastic stiffness reduction of the failed elements.

  16. Sleep state instabilities in major depressive disorder: Detection and quantification with electrocardiogram-based cardiopulmonary coupling analysis.

    Science.gov (United States)

    Yang, Albert C; Yang, Cheng-Hung; Hong, Chen-Jee; Tsai, Shih-Jen; Kuo, Chung-Hsun; Peng, Chung-Kang; Mietus, Joseph E; Goldberger, Ary L; Thomas, Robert J

    2011-02-01

    Sleep disruption is an important aspect of major depressive disorder but lacks an objective and inexpensive means of assessment. We evaluated the utility of electrocardiogram (ECG)-based cardiopulmonary coupling analysis to quantify physiologic sleep stability in patients with major depression. Relative to controls, unmedicated depressed patients had a reduction in high-frequency coupling, an index of stable sleep, an increase in low-frequency coupling, an index of unstable sleep, and an increase in very-low-frequency coupling, an index of wakefulness/REM sleep. The medicated depressed group showed a restoration of stable sleep to a level comparable with that of the control group. ECG-based cardiopulmonary coupling analysis may provide a simple, cost-efficient point-of-care method to quantify sleep quality/stability and to objectively evaluate the severity of insomnia in patients with major depression. Copyright © 2010 Society for Psychophysiological Research.

  17. High-resolution imaging of redox signaling in live cells through an oxidation-sensitive yellow fluorescent protein

    DEFF Research Database (Denmark)

    Maulucci, Giuseppe; Labate, Valentina; Mele, Marina

    2008-01-01

    We present the application of a redox-sensitive mutant of the yellow fluorescent protein (rxYFP) to image, with elevated sensitivity and high temporal and spatial resolution, oxidative responses of eukaryotic cells to pathophysiological stimuli. The method presented, based on the ratiometric...... quantitation of the distribution of fluorescence by confocal microscopy, allows us to draw real-time "redox maps" of adherent cells and to score subtle changes in the intracellular redox state, such as those induced by overexpression of redox-active proteins. This strategy for in vivo imaging of redox...

  18. A competency-based approach to couple and family therapy supervision.

    Science.gov (United States)

    Celano, Marianne P; Smith, Chaundrissa Oyeshiku; Kaslow, Nadine J

    2010-03-01

    The competency-based movement continues to guide professional psychology. This has been highlighted through the establishment of essential foundational and functional competencies. The current paper focuses on the intervention competency domain and delineates its relevance within the field of couple and family therapy (CFT). We begin by providing an overview of 8 essential components of CFT: developing a systemic formulation, forging a systemic therapeutic alliance, understanding family-of-origin issues, reframing, managing negative interactions, building cohesion/intimacy/communication, restructuring/parenting, and understanding and applying evidence-based CFT models. We then provide a brief illustration of foundational and functional competencies essential to CFT. We conclude by addressing the CFT competency within an integrative approach to supervision and provide a case illustration that depicts this process. The relevance of establishing unique, evidence-based, theory-specific competency components is highlighted. PsycINFO Database Record (c) 2010 APA, all rights reserved

  19. ProsCan for Couples: Randomised controlled trial of a couples-based sexuality intervention for men with localised prostate cancer who receive radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Ferguson Megan

    2008-08-01

    Full Text Available Abstract Background Prostate cancer is the most common male cancer in the Western world. The most substantial long term morbidity from this cancer is sexual dysfunction with consequent adverse changes in couple and intimate relationships. Research to date has not identified an effective way to improve sexual and psychosocial adjustment for both men with prostate cancer and their partners. As well, the efficacy and cost effectiveness of peer counselling as opposed to professional models of service delivery has not yet been empirically tested. This paper presents the design of a three arm randomised controlled trial (peer vs. nurse counselling vs. usual care that will evaluate the efficacy of two couples-based sexuality interventions (ProsCan for Couples: Peer support vs. nurse counselling on men's and women's sexual and psychosocial adjustment after surgical treatment for localised prostate cancer; in addition to cost-effectiveness. Methods/design Seventy couples per condition (210 couples in total will be recruited after diagnosis and before treatment through urology private practices and hospital outpatient clinics and randomised to (1 usual care; (2 eight sessions of peer-delivered telephone support with DVD education; and (3 eight sessions of oncology nurse-delivered telephone counselling with DVD education. Two intervention sessions will be delivered before surgery and six over the six months post-surgery. The intervention will utilise a cognitive behavioural approach along with couple relationship education focussed on relationship enhancement and helping the couple to conjointly manage the stresses of cancer diagnosis and treatment. Participants will be assessed at baseline (before surgery and 3, 6 and 12 months post-surgery. Outcome measures include: sexual adjustment; unmet sexuality supportive care needs; attitudes to sexual help seeking; psychological adjustment; benefit finding and quality of life. Discussion The study will provide

  20. Redox, haem and CO in enzymatic catalysis and regulation

    Science.gov (United States)

    Ragsdale, Stephen W.; Yi, Li; Bender, Güneş; Gupta, Nirupama; Kung, Yan; Yan, Lifen; Stich, Troy A.; Doukov, Tzanko; Leichert, Lars; Jenkins, Paul M.; Bianchetti, Christopher M.; George, Simon J.; Cramer, Stephen P.; Britt, R. David; Jakob, Ursula; Martens, Jeffrey R.; Phillips, George N.; Drennan, Catherine L.

    2013-01-01

    The present paper describes general principles of redox catalysis and redox regulation in two diverse systems. The first is microbial metabolism of CO by the Wood–Ljungdahl pathway, which involves the conversion of CO or H2/CO2 into acetyl-CoA, which then serves as a source of ATP and cell carbon. The focus is on two enzymes that make and utilize CO, CODH (carbon monoxide dehydrogenase) and ACS (acetyl-CoA synthase). In this pathway, CODH converts CO2 into CO and ACS generates acetyl-CoA in a reaction involving Ni·CO, methyl-Ni and acetyl-Ni as catalytic intermediates. A 70 Å (1 Å = 0.1 nm) channel guides CO, generated at the active site of CODH, to a CO ‘cage’ near the ACS active site to sequester this reactive species and assure its rapid availability to participate in a kinetically coupled reaction with an unstable Ni(I) state that was recently trapped by photolytic, rapid kinetic and spectroscopic studies. The present paper also describes studies of two haem-regulated systems that involve a principle of metabolic regulation interlinking redox, haem and CO. Recent studies with HO2 (haem oxygenase-2), a K+ ion channel (the BK channel) and a nuclear receptor (Rev-Erb) demonstrate that this mode of regulation involves a thiol–disulfide redox switch that regulates haem binding and that gas signalling molecules (CO and NO) modulate the effect of haem. PMID:22616859

  1. The role of phosphate additive in stabilization of sulphuric-acid-based vanadium(V) electrolyte for all-vanadium redox-flow batteries

    Science.gov (United States)

    Roznyatovskaya, Nataliya V.; Roznyatovsky, Vitaly A.; Höhne, Carl-Christoph; Fühl, Matthias; Gerber, Tobias; Küttinger, Michael; Noack, Jens; Fischer, Peter; Pinkwart, Karsten; Tübke, Jens

    2017-09-01

    Catholyte in all-vanadium redox-flow battery (VRFB) which consists of vanadium salts dissolved in sulphuric acid is known to be stabilized by phosphoric acid to slow down the thermal aging at temperatures higher than 40 °C. To reveal the role of phosphoric acid, the thermally-induced aggregation is investigated using variable-temperature 51V, 31P, 17O, 1H nuclear magnetic resonance (NMR) spectroscopy and dynamic light scattering (DLS). The results indicate that the thermal stabilization of vanadium(V) electrolyte is attained by the involvement of monomeric and dimeric vanadium(V) species in the reaction with phosphoric acid which is concurrent to the formation of neutral hydroxo-aqua vanadium(V) precipitation precursor. The dimers are stabilized by counter ions due to association reaction or if such stabilization is not possible, precipitation of vanadium pentoxide is favored. The evolution of particles size distributions at 50 °C in electrolyte samples containing 1.6 M vanadium and 4.0 M total sulphate and the pathways of precipitate formation are discussed. The optimal total phosphate concentration is found to be of 0.15 M. However, the induction time is assumed to be dependent not only on the total phosphate concentrations, but also on the ratio of total vanadium(V) to sulphate concentrations.

  2. Vegetarian diets and public health: biomarker and redox connections.

    Science.gov (United States)

    Benzie, Iris F F; Wachtel-Galor, Sissi

    2010-11-15

    Vegetarian diets are rich in antioxidant phytochemicals. However, they may not act as antioxidants in vivo, and yet still have important signaling and regulatory functions. Some may act as pro-oxidants, modulating cellular redox tone and oxidizing redox sensitive sites. In this review, evidence for health benefits of vegetarian diets is presented from different perspectives: epidemiological, biomarker, evolutionary, and public health, as well as antioxidant. From the perspective of molecular connections between diet and health, evidence of a role for plasma ascorbic acid as a biomarker for future disease risk is presented. Basic concepts of redox-based cell signaling are presented, and effects of antioxidant phytochemicals on signaling, especially via redox tone, sulfur switches and the Antioxidant Response Element (ARE), are explored. Sufficient scientific evidence exists for public health policy to promote a plant-rich diet for health promotion. This does not need to wait for science to provide all the answers as to why and how. However, action and interplay of dietary antioxidants in the nonequilibrium systems that control redox balance, cell signaling, and cell function provide rich ground for research to advance understanding of orthomolecular nutrition and provide science-based evidence to advance public health in our aging population.

  3. A sensitive DNA biosensor based on a facile sulfamide coupling reaction for capture probe immobilization

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Qingxiang, E-mail: axiang236@126.com [Department of Chemistry and Environment Science, Zhangzhou Normal University, Zhangzhou 363000 (China); Ding, Yingtao; Gao, Feng [Department of Chemistry and Environment Science, Zhangzhou Normal University, Zhangzhou 363000 (China); Jiang, Shulian [Zhangzhou Product Quality Supervision and Inspection Institute, Zhangzhou 363000 (China); Zhang, Bin; Ni, Jiancong; Gao, Fei [Department of Chemistry and Environment Science, Zhangzhou Normal University, Zhangzhou 363000 (China)

    2013-07-25

    Graphical abstract: A novel DNA biosensor was fabricated through a facile sulfamide coupling reaction between probe DNA and the sulfonic dye of 1-amino-2-naphthol-4-sulfonic acid that electrodeposited on a glassy carbon electrode. -- Highlights: •A versatile sulfonic dye of ANS was electrodeposited on a GCE. •A DNA biosensor was fabricated based on a facile sulfamide coupling reaction. •High probe DNA density of 3.18 × 10{sup 13} strands cm{sup −2} was determined. •A wide linear range and a low detection limit were obtained. -- Abstract: A novel DNA biosensor was fabricated through a facile sulfamide coupling reaction. First, the versatile sulfonic dye molecule of 1-amino-2-naphthol-4-sulfonate (AN-SO{sub 3}{sup −}) was electrodeposited on the surface of a glassy carbon electrode (GCE) to form a steady and ordered AN-SO{sub 3}{sup −} layer. Then the amino-terminated capture probe was covalently grafted to the surface of SO{sub 3}{sup −}-AN deposited GCE through the sulfamide coupling reaction between the amino groups in the probe DNA and the sulfonic groups in the AN-SO{sub 3}{sup −}. The step-by-step modification process was characterized by electrochemistry and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Using Ru(NH{sub 3}){sub 6}{sup 3+} as probe, the probe density and the hybridization efficiency of the biosensor were determined to be 3.18 × 10{sup 13} strands cm{sup −2} and 86.5%, respectively. The hybridization performance of the biosensor was examined by differential pulse voltammetry using Co(phen){sub 3}{sup 3+/2+} (phen = 1,10-phenanthroline) as the indicator. The selectivity experiments showed that the biosensor presented distinguishable response after hybridization with the three-base mismatched, non-complementary and complementary sequences. Under the optimal conditions, the oxidation peak currents of Co(phen){sub 3}{sup 3+/2+} increased linearly with the logarithm values of the concentration

  4. Method for Measurement of Multi-Degrees-of-Freedom Motion Parameters Based on Polydimethylsiloxane Cross-Coupling Diffraction Gratings

    National Research Council Canada - National Science Library

    Duan, Junping; Zhu, Qiang; Qian, Kun; Guo, Hao; Zhang, Binzhen

    2017-01-01

    This work presents a multi-degrees-of-freedom motion parameter measurement method based on the use of cross-coupling diffraction gratings that were prepared on the two sides of a polydimethylsiloxane (PDMS...

  5. Communication: spin densities within a unitary group based spin-adapted open-shell coupled-cluster theory: analytic evaluation of isotropic hyperfine-coupling constants for the combinatoric open-shell coupled-cluster scheme.

    Science.gov (United States)

    Datta, Dipayan; Gauss, Jürgen

    2015-07-07

    We report analytical calculations of isotropic hyperfine-coupling constants in radicals using a spin-adapted open-shell coupled-cluster theory, namely, the unitary group based combinatoric open-shell coupled-cluster (COSCC) approach within the singles and doubles approximation. A scheme for the evaluation of the one-particle spin-density matrix required in these calculations is outlined within the spin-free formulation of the COSCC approach. In this scheme, the one-particle spin-density matrix for an open-shell state with spin S and MS = + S is expressed in terms of the one- and two-particle spin-free (charge) density matrices obtained from the Lagrangian formulation that is used for calculating the analytic first derivatives of the energy. Benchmark calculations are presented for NO, NCO, CH2CN, and two conjugated π-radicals, viz., allyl and 1-pyrrolyl in order to demonstrate the performance of the proposed scheme.

  6. Long-term litter decomposition controlled by manganese redox cycling.

    Science.gov (United States)

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

    2015-09-22

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

  7. Effect of ferrite addition above the base ferrite on the coupling factor of wireless power transfer for vehicle applications

    DEFF Research Database (Denmark)

    Batra, Tushar; Schaltz, Erik; Ahn, Seungyoung

    2015-01-01

    Power transfer capability of wireless power transfer systems is highly dependent on the magnetic design of the primary and secondary inductors and is measured quantitatively by the coupling factor. The inductors are designed by placing the coil over a ferrite base to increase the coupling factor...... and measurement results are presented for different air gaps between the coils and at different gap distances between the ferrite base and added ferrite. This paper is beneficial in improving the coupling factor while adding minimum weight to wireless power transfer system....

  8. Refractive index modulation based on excitonic effects in GaInAs-InP coupled asymmetric quantum wells

    DEFF Research Database (Denmark)

    Thirstrup, Carsten

    1995-01-01

    The effect of excitons in GaInAs-InP coupled asymmetric quantum wells on the refractive index modulation, is analyzed numerically using a model based on the effective mass approximation. It is shown that two coupled quantum wells brought in resonance by an applied electric field will, due...... to the reduction in the exciton oscillator strengths, have a modulation of the refractive index which is more than one order of magnitude larger than in a similar quantum well structure based on the quantum confined Stark effect, but with no coupling between the quantum wells. Calculations show that combining...

  9. A thin layer fiber-coupled luminescence dosimeter based on Al2O3:C

    DEFF Research Database (Denmark)

    Klein, F.A.; Greilich, Steffen; Andersen, Claus Erik

    2011-01-01

    In this paper we present a fiber-coupled luminescent Al2O3:C dosimeter probe with high spatial resolution (0.1 mm). It is based on thin layers of Al2O3:C crystal powder and a UV-cured acrylate monomer composition. The fabrication of the thin layers is described in detail. No influence of the intr......In this paper we present a fiber-coupled luminescent Al2O3:C dosimeter probe with high spatial resolution (0.1 mm). It is based on thin layers of Al2O3:C crystal powder and a UV-cured acrylate monomer composition. The fabrication of the thin layers is described in detail. No influence...... of the introduced polymer host matrix on the dosimetric properties was observed. Depth-dose measurements with the new detectors in a 142.66 MeV proton and 270.55 MeV/u carbon ion beam are presented as example applications. We used an RL protocol with saturated crystals allowing for time-effective measurements...... of the protons measured with this new detector deviated by less than 1% from the reference value. For both ion types, the stem effect contributed less than 0.8% of the RL signal....

  10. Coupling of metal-based light-harvesting antennas and electron-donor subunits: Trinuclear Ruthenium(II) complexes containing tetrathiafulvalene-substituted polypyridine ligands

    DEFF Research Database (Denmark)

    Campagna, Sebastiano; Serroni, Scolastica; Puntoriero, Fausto

    2002-01-01

    as light-harvesting antennas and the tetrathiafulvalene electron donors can induce charge separation. The absorption spectra, redox behavior, and luminescence properties (both at room temperature in acetonitrile and at 77 K in a rigid matrix of butyronitrile) of the trinuclear metal complexes have been......(mu-2,3-dpp)}(2)Ru(bpy-TTF1)](PF6)(6) (9; bpy=2,2'-bipyridine; 2,3-dpp = 2,3-bis(2'-pyridyl)pyrazine) and [{(bpy)(2)Ru(mu-2,3-dpp)}(2)Ru(bpy-TTF2)](PF6)(6) (10). These compounds can be viewed as coupled antennas and charge-separation systems, in which the multichromophoric trinuclear metal subunits act......+) (4,4'-Mebpy = 4,4'-dimethyl-2,2'-bipyridine) and [{(bpy)(2)Ru(mu-2,3-dpp)}(2)Ru(bpy)](6+). The absorption spectra and redox behavior of all the new metal compounds can be interpreted by a multicomponent approach, in which specific absorption features and redox processes can be assigned to specific...

  11. Problemas de análisis cuantitativo. Valoraciones combinadas. Mezcla de ácido brómico y ácido sulfúrico y su resolución mediante combinación de volumetría ácido-base y redox.

    OpenAIRE

    Milla González, Miguel

    2016-01-01

    En este ejercicio se combina una reacción ácido-base y otra redox para resolver una mezcla de ácido sulfúrico y ácido brómico. Deben utilizarse los factores de conversión adecuados para montar las ecuaciones estequiométricas que permitan encontrar las concentraciones de ambos ácidos en la muestra. En el ejercicio, se ajusta la reacción redox entre el bromato y el reductor Fe(II) en medio ácido. Los datos del problema son aleatorios.

  12. A novel ferrocenic copper(II) complex Salen-like, derived from 5-chloromethyl-2-hydroxyacetophenone and N-ferrocenmethylaniline: Design, spectral approach and solvent effect towards electrochemical behavior of Fc+/Fc redox couple

    OpenAIRE

    Ouennoughi, Yasmina; Karce, Houssam Eddine; Aggoun, Djouhra; Lanez, Touhami; Ruiz-Rosas, Ramiro; Bouzerafa, Brahim; Ourari, Ali; Morallon, Emilia

    2017-01-01

    This paper reports the synthesis, spectroscopic characterizations and electrochemical behavior of the obtained tetradentate copper (II)-Schiff base complex with its two wings as ferrocenylaniline moieties. This new ferrocenic derivative with two ferrocenylaniline entities surrounding the copper (II)-Salen complex (5) was synthesized by reacting N-ferrocenmethyl-N-phenyl-5-aminomethyl-2-hydroxyacetophenone (3) with one half equivalent of 1,2-diaminoethane in absolute ethanol. As for the interm...

  13. Synchronization of random bit generators based on coupled chaotic lasers and application to cryptography.

    Science.gov (United States)

    Kanter, Ido; Butkovski, Maria; Peleg, Yitzhak; Zigzag, Meital; Aviad, Yaara; Reidler, Igor; Rosenbluh, Michael; Kinzel, Wolfgang

    2010-08-16

    Random bit generators (RBGs) constitute an important tool in cryptography, stochastic simulations and secure communications. The later in particular has some difficult requirements: high generation rate of unpredictable bit strings and secure key-exchange protocols over public channels. Deterministic algorithms generate pseudo-random number sequences at high rates, however, their unpredictability is limited by the very nature of their deterministic origin. Recently, physical RBGs based on chaotic semiconductor lasers were shown to exceed Gbit/s rates. Whether secure synchronization of two high rate physical RBGs is possible remains an open question. Here we propose a method, whereby two fast RBGs based on mutually coupled chaotic lasers, are synchronized. Using information theoretic analysis we demonstrate security against a powerful computational eavesdropper, capable of noiseless amplification, where all parameters are publicly known. The method is also extended to secure synchronization of a small network of three RBGs.

  14. Autonomous quantum Maxwell's demon based on two exchange-coupled quantum dots

    Science.gov (United States)

    Ptaszyński, Krzysztof

    2018-01-01

    I study an autonomous quantum Maxwell's demon based on two exchange-coupled quantum dots attached to the spin-polarized leads. The principle of operation of the demon is based on the coherent oscillations between the spin states of the system which act as a quantum iSWAP gate. Due to the operation of the iSWAP gate, one of the dots acts as a feedback controller which blocks the transport with the bias in the other dot, thus inducing the electron pumping against the bias; this leads to the locally negative entropy production. Operation of the demon is associated with the information transfer between the dots, which is studied quantitatively by mapping the analyzed setup onto the thermodynamically equivalent auxiliary system. The calculated entropy production in a single subsystem and information flow between the subsystems are shown to obey a local form of the second law of thermodynamics, similar to the one previously derived for classical bipartite systems.

  15. A new crystal structure fragment-based pharmacophore method for G protein-coupled receptors

    DEFF Research Database (Denmark)

    Fidom, Kimberley; Isberg, Vignir; Hauser, Alexander Sebastian

    2015-01-01

    We have developed a new method for the building of pharmacophores for G protein-coupled receptors, a major drug target family. The method is a combination of the ligand- and target-based pharmacophore methods and founded on the extraction of structural fragments, interacting ligand moiety...... for new targets. A validating retrospective virtual screening of histamine H1 and H3 receptor pharmacophores yielded area-under-the-curves of 0.88 and 0.82, respectively. The fragment-based method has the unique advantage that it can be applied to targets for which no (homologous) crystal structures...... and receptor residue pairs, from crystal structure complexes. We describe the procedure to collect a library with more than 250 fragments covering 29 residue positions within the generic transmembrane binding pocket. We describe how the library fragments are recombined and inferred to build pharmacophores...

  16. An RFID-Based Manufacturing Control Framework for Loosely Coupled Distributed Manufacturing System Supporting Mass Customization

    Science.gov (United States)

    Chen, Ruey-Shun; Tsai, Yung-Shun; Tu, Arthur

    In this study we propose a manufacturing control framework based on radio-frequency identification (RFID) technology and a distributed information system to construct a mass-customization production process in a loosely coupled shop-floor control environment. On the basis of this framework, we developed RFID middleware and an integrated information system for tracking and controlling the manufacturing process flow. A bicycle manufacturer was used to demonstrate the prototype system. The findings of this study were that the proposed framework can improve the visibility and traceability of the manufacturing process as well as enhance process quality control and real-time production pedigree access. Using this framework, an enterprise can easily integrate an RFID-based system into its manufacturing environment to facilitate mass customization and a just-in-time production model.

  17. High power Raman-converter based on H2-filled inhibited coupling HC-PCF

    Science.gov (United States)

    Benoit, A.; Beaudou, B.; Debord, B.; Gerome, F.; Benabid, F.

    2017-02-01

    We report on high power Raman-converter frequency stage based on hydrogen-filled inhibited-coupling hollow-core photonic crystal fibers pumped by an Yb-fiber picosecond laser. This fiber Raman-convertor can operate in two SRS emission regimes by simply controlling the fiber length or the gas pressure. It can set to either generate favorably single laser line or to generate an extremely wide Raman comb. Based on this we demonstrate a pico-second pulse Raman source of 9.3 W average-power at 1.8 μm, and an ultra-wide Raman comb spanning over more than five octaves from UV to mid-infrared, containing around 70 laser lines.

  18. Bearing fault recognition method based on neighbourhood component analysis and coupled hidden Markov model

    Science.gov (United States)

    Zhou, Haitao; Chen, Jin; Dong, Guangming; Wang, Hongchao; Yuan, Haodong

    2016-01-01

    Due to the important role rolling element bearings play in rotating machines, condition monitoring and fault diagnosis system should be established to avoid abrupt breakage during operation. Various features from time, frequency and time-frequency domain are usually used for bearing or machinery condition monitoring. In this study, NCA-based feature extraction (FE) approach is proposed to reduce the dimensionality of original feature set and avoid the "curse of dimensionality". Furthermore, coupled hidden Markov model (CHMM) based on multichannel data acquisition is applied to diagnose bearing or machinery fault. Two case studies are presented to validate the proposed approach both in bearing fault diagnosis and fault severity classification. The experiment results show that the proposed NCA-CHMM can remove redundant information, fuse data from different channels and improve the diagnosis results.

  19. Task-based evaluation of practical lens designs for lens-coupled digital mammography systems

    Science.gov (United States)

    Chen, Liying; Foo, Leslie D.; Cortesi, Rebecca L.; Thompson, Kevin P.; Barrett, Harrison H.

    2007-03-01

    Recent developments in low-noise, large-area CCD detectors have renewed interest in radiographic systems that use a lens to couple light from a scintillation screen to a detector. The lenses for this application must have very large numerical apertures and high spatial resolution over a FOV. This paper expands on our earlier work by applying the principles of task-based assessment of image quality to development of meaningful figures of merit for the lenses. The task considered in this study is detection of a lesion in a mammogram, and the figure of merit used is the lesion detectability, expressed as a task-based signal-to-noise ratio (SNR), for a channelized Hotelling observer (CHO). As in the previous work, the statistical model accounts for the random structure in the breast, the statistical properties of the scintillation screen, the random coupling of light to the CCD, the detailed structure of the shift-variant lens point spread function (PSF), and Poisson noise of the X-ray flux. The lenses considered range from F/0.9 to F/1.2. All yield nominally the same spot size at a given field. Among the F/0.9 lenses, some of them were designed by conventional means for high resolution and some for high contrast, and the shapes of the PSF differ considerably. The results show that excessively large lens numerical apertures do not improve the task-based SNR but dramatically increase the optics fabrication cost. Contrary to common wisdom, high-contrast designs have higher task-based SNRs than high-resolution designs when the signal is small. Additionally, we constructed a merit function to successfully tune the lenses to perform equally well anywhere in the FOV.

  20. Anthraquinone with Tailored Structure for Nonaqueous Metal-Organic Redox Flow Battery

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Wei; Xu, Wu; Cosimbescu, Lelia; Choi, Daiwon; Li, Liyu; Yang, Zhenguo

    2012-06-08

    A nonaqueous, hybrid metal-organic redox flow battery based on tailored anthraquinone structure is demonstrated to have an energy efficiency of {approx}82% and a specific discharge energy density similar to aqueous redox flow batteries, which is due to the significantly improved solubility of anthraquinone in supporting electrolytes.

  1. Modelling and analysis of transient state during improved coupling procedure with the grid for DFIG based wind turbine generator

    Science.gov (United States)

    Kammoun, Soulaymen; Sallem, Souhir; Ben Ali Kammoun, Mohamed

    2017-11-01

    The aim of this study is to enhance DFIG based Wind Energy Conversion Systems (WECS) dynamics during grid coupling. In this paper, a system modelling and a starting/coupling procedure for this generator to the grid are proposed. The proposed non-linear system is a variable structure system (VSS) and has two different states, before and after coupling. So, two different state models are given to the system to analyse transient stability during the coupling. The given model represents well the transient state of the machine, through which, a behaviour assessment of the generator before, during and after connection is given based on simulation results. For this, a 300 kW DFIG based wind generation system model was simulated on the Matlab/SIMULINK environment. We judge the proposed procedure to be practical, smooth and stability improved.

  2. Sequential and base rate analysis of emotional validation and invalidation in chronic pain couples: patient gender matters.

    Science.gov (United States)

    Leong, Laura E M; Cano, Annmarie; Johansen, Ayna B

    2011-11-01

    The purpose of this study was to examine the extent to which communication patterns that foster or hinder intimacy and emotion regulation in couples were related to pain, marital satisfaction, and depression in 78 chronic pain couples attempting to problem-solve an area of disagreement in their marriage. Sequences and base rates of validation and invalidation communication patterns were almost uniformly unrelated to adjustment variables unless patient gender was taken into account. Male patient couples' reciprocal invalidation was related to worse pain, but this was not found in female patient couples. In addition, spouses' validation was related to poorer patient pain and marital satisfaction, but only in couples with a male patient. It was not only the presence or absence of invalidation and validation that mattered (base rates), but the context and timing of these events (sequences) that affected patients' adjustment. This research demonstrates that sequences of interaction behaviors that foster and hinder emotion regulation should be attended to when assessing and treating pain patients and their spouses. This article presents analyses of both sequences and base rates of chronic pain couples' communication patterns, focusing on validation and invalidation. These results may potentially improve psychosocial treatments for these couples, by addressing sequential interactions of intimacy and empathy. Copyright © 2011 American Pain Society. Published by Elsevier Inc. All rights reserved.

  3. Molecular Controls of the Oxygenation and Redox Reactions of Hemoglobin

    Science.gov (United States)

    Henkens, Robert; Alayash, Abdu I.; Banerjee, Sambuddha; Crumbliss, Alvin L.

    2013-01-01

    Abstract Significance: The broad classes of O2-binding proteins known as hemoglobins (Hbs) carry out oxygenation and redox functions that allow organisms with significantly different physiological demands to exist in a wide range of environments. This is aided by allosteric controls that modulate the protein's redox reactions as well as its O2-binding functions. Recent Advances: The controls of Hb's redox reactions can differ appreciably from the molecular controls for Hb oxygenation and come into play in elegant mechanisms for dealing with nitrosative stress, in the malarial resistance conferred by sickle cell Hb, and in the as-yet unsuccessful designs for safe and effective blood substitutes. Critical Issues: An important basic principle in consideration of Hb's redox reactions is the distinction between kinetic and thermodynamic reaction control. Clarification of these modes of control is critical to gaining an increased understanding of Hb-mediated oxidative processes and oxidative toxicity in vivo. Future Directions: This review addresses emerging concepts and some unresolved questions regarding the interplay between the oxygenation and oxidation reactions of structurally diverse Hbs, both within red blood cells and under acellular conditions. Developing methods that control Hb-mediated oxidative toxicity will be critical to the future development of Hb-based blood substitutes. Antioxid. Redox Signal. 18, 2298–2313. PMID:23198874

  4. Anionic Redox Chemistry in Polysulfide Electrode Materials for Rechargeable Batteries.

    Science.gov (United States)

    Grayfer, Ekaterina D; Pazhetnov, Egor M; Kozlova, Mariia N; Artemkina, Sofya B; Fedorov, Vladimir E

    2017-12-22

    Classical Li-ion battery technology is based on the insertion of lithium ions into cathode materials involving metal (cationic) redox reactions. However, this vision is now being reconsidered, as many new-generation electrode materials with enhanced reversible capacities operate through combined cationic and anionic (non-metal) reversible redox processes or even exclusively through anionic redox transformations. Anionic participation in the redox reactions is observed in materials with more pronounced covalency, which is less typical for oxides, but quite common for phosphides or chalcogenides. In this Concept, we would like to draw the reader's attention to this new idea, especially, as it applies to transition-metal polychalcogenides, such as FeS 2 , VS 4 , TiS 3 , NbS 3 , TiS 4 , MoS 3 , etc., in which the key role is played by the (S-S) 2- /2 S 2- redox reaction. The exploration and better understanding of the anion-driven chemistry is important for designing advanced materials for battery and other energy-related applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. A hybrid algorithm for coupling partial differential equation and compartment-based dynamics.

    Science.gov (United States)

    Harrison, Jonathan U; Yates, Christian A

    2016-09-01

    Stochastic simulation methods can be applied successfully to model exact spatio-temporally resolved reaction-diffusion systems. However, in many cases, these methods can quickly become extremely computationally intensive with increasing particle numbers. An alternative description of many of these systems can be derived in the diffusive limit as a deterministic, continuum system of partial differential equations (PDEs). Although the numerical solution of such PDEs is, in general, much more efficient than the full stochastic simulation, the deterministic continuum description is generally not valid when copy numbers are low and stochastic effects dominate. Therefore, to take advantage of the benefits of both of these types of models, each of which may be appropriate in different parts of a spatial domain, we have developed an algorithm that can be used to couple these two types of model together. This hybrid coupling algorithm uses an overlap region between the two modelling regimes. By coupling fluxes at one end of the interface and using a concentration-matching condition at the other end, we ensure that mass is appropriately transferred between PDE- and compartment-based regimes. Our methodology gives notable reductions in simulation time in comparison with using a fully stochastic model, while maintaining the important stochastic features of the system and providing detail in appropriate areas of the domain. We test our hybrid methodology robustly by applying it to several biologically motivated problems including diffusion and morphogen gradient formation. Our analysis shows that the resulting error is small, unbiased and does not grow over time. © 2016 The Authors.

  6. Functional cloning, based on azole resistance in Saccharomyces cerevisiae, and characterization of Rhizopus nigricans redox carriers that are differentially involved in the P450-dependent response to progesterone stress.

    Science.gov (United States)

    Kunic, B; Truan, G; Breskvar, K; Pompon, D

    2001-07-01

    The filamentous fungus Rhizopus nigricans responds to treatment with progesterone by inducing P450-associated redox carriers. Selection for azole resistance following expression of a cDNA library constructed with RNA from progesterone-treated R. nigricans in the yeast Saccharomyces cerevisiae led to the identification of CPR1-FL and CYB5-1 cDNAs, which code for functionally competent NADPH-cytochrome P450 reductase and cytochrome b5, respectively. The central region (CPR2-CS) of an additional reductase gene sharing 66% identity with CPR1-FL was cloned from progesterone-induced mRNA by RT-PCR, using primers based on consensus sequences. Northern analysis of the 2.1-kb transcripts revealed that, of the two cloned reductase genes, only CPR1-FL mRNA was strongly induced by progesterone; transcription of CYBS-1 and CPR2-CS mRNAs was not significantly affected. Analysis of the subcellular localization and function of the R. nigricans reductase in yeast indicated that the CPR1-FL cDNA and a derivative (CPR1-S) truncated at the first ATG codon gave rise to functionally equivalent products that were found in both cytosolic and microsomal fractions. In contrast, addition of an in-frame initiation codon at the 5' end of the CPR1-FL sequence resulted in localization of the activity mainly to the microsomes, and improved ketoconazole resistance but decreased NADPH-cytochrome c reductase activity in the host strain. These findings suggest that, of the three genes for P450-associated redox carriers investigated, only CPR1-FL is associated with the progesterone response and that its major transcript encodes a reductase that shows an unusual pattern of subcellular localization.

  7. Silicon-Nitride-based Integrated Optofluidic Biochemical Sensors using a Coupled-Resonator Optical Waveguide

    Directory of Open Access Journals (Sweden)

    Jiawei eWANG

    2015-04-01

    Full Text Available Silicon nitride (SiN is a promising material platform for integrating photonic components and microfluidic channels on a chip for label-free, optical biochemical sensing applications in the visible to near-infrared wavelengths. The chip-scale SiN-based optofluidic sensors can be compact due to a relatively high refractive index contrast between SiN and the fluidic medium, and low-cost due to the complementary metal-oxide-semiconductor (CMOS-compatible fabrication process. Here, we demonstrate SiN-based integrated optofluidic biochemical sensors using a coupled-resonator optical waveguide (CROW in the visible wavelengths. The working principle is based on imaging in the far field the out-of-plane elastic-light-scattering patterns of the CROW sensor at a fixed probe wavelength. We correlate the imaged pattern with reference patterns at the CROW eigenstates. Our sensing algorithm maps the correlation coefficients of the imaged pattern with a library of calibrated correlation coefficients to extract a minute change in the cladding refractive index. Given a calibrated CROW, our sensing mechanism in the spatial domain only requires a fixed-wavelength laser in the visible wavelengths as a light source, with the probe wavelength located within the CROW transmission band, and a silicon digital charge-coupled device (CCD / CMOS camera for recording the light scattering patterns. This is in sharp contrast with the conventional optical microcavity-based sensing methods that impose a strict requirement of spectral alignment with a high-quality cavity resonance using a wavelength-tunable laser. Our experimental results using a SiN CROW sensor with eight coupled microrings in the 680nm wavelength reveal a cladding refractive index change of ~1.3 × 10^-4 refractive index unit (RIU, with an average sensitivity of ~281 ± 271 RIU-1 and a noise-equivalent detection limit (NEDL of 1.8 ×10^-8 RIU ~ 1.0 ×10^-4 RIU across the CROW bandwidth of ~1 nm.

  8. 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.

  9. Implementing Numerical Experiments Based on the Coupled Model of Atmospheric General Circulation and Thermohaline Ocean One

    Directory of Open Access Journals (Sweden)

    V. P. Parhomenko

    2015-01-01

    Full Text Available The paper presents a realized hydrodynamic three-dimensional global climatic model, which comprises the model blocks of atmospheric general circulation, thermohaline large-scale circulation of the ocean, and sea ice evolution. Before rather strongly aggregated heat-moisturebalance model of the atmosphere for temperature and humidity of a surface layer was used as a model of the atmosphere. The atmospheric general circulation model is significantly more complicated and allows us to describe processes in the atmosphere more adequately. Functioning of a coupled climatic model is considered in conditions of the seasonal cycle of solar radiation.The paper considers a procedure for coupled calculation of the ocean model and atmospheric general circulation model. Synchronization of a number of parameters in both models is necessary for their joint action. In this regard a procedure of two-dimensional interpolation of data defined on the grids of the ocean model and atmosphere model and back is developed. A feature of this task is discrepancy of grid nodes and continental configurations in models. Coupled model-based long-term calculations for more than 400 years have shown its stable work. Calculation results and comparison with observation data are under discussion.The paper shows distribution of mean global atmosphere temperature versus time in stable conditions to demonstrate that there is inter-annual variability of atmosphere temperature at the steady state of a climate system. It presents distribution of temperature difference of the ocean surface from the observations and from the model of the ocean thermohaline circulation for January. Noticeable deviations of temperature are observed near Antarctica. Apparently, it is because of inaccurate calculation of the sea ice distribution in model. The geographical distribution of the ocean surface temperature for January with coupled calculation shows, in general, a zonal uniform structure of isolines

  10. Fully Automated Quantum-Chemistry-Based Computation of Spin-Spin-Coupled Nuclear Magnetic Resonance Spectra.

    Science.gov (United States)

    Grimme, Stefan; Bannwarth, Christoph; Dohm, Sebastian; Hansen, Andreas; Pisarek, Jana; Pracht, Philipp; Seibert, Jakob; Neese, Frank

    2017-11-13

    We present a composite procedure for the quantum-chemical computation of spin-spin-coupled 1 H NMR spectra for general, flexible molecules in solution that is based on four main steps, namely conformer/rotamer ensemble (CRE) generation by the fast tight-binding method GFN-xTB and a newly developed search algorithm, computation of the relative free energies and NMR parameters, and solving the spin Hamiltonian. In this way the NMR-specific nuclear permutation problem is solved, and the correct spin symmetries are obtained. Energies, shielding constants, and spin-spin couplings are computed at state-of-the-art DFT levels with continuum solvation. A few (in)organic and transition-metal complexes are presented, and very good, unprecedented agreement between the theoretical and experimental spectra was achieved. The approach is routinely applicable to systems with up to 100-150 atoms and may open new avenues for the detailed (conformational) structure elucidation of, for example, natural products or drug molecules. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  11. Image-Based Personalization of Cardiac Anatomy for Coupled Electromechanical Modeling.

    Science.gov (United States)

    Crozier, A; Augustin, C M; Neic, A; Prassl, A J; Holler, M; Fastl, T E; Hennemuth, A; Bredies, K; Kuehne, T; Bishop, M J; Niederer, S A; Plank, G

    2016-01-01

    Computational models of cardiac electromechanics (EM) are increasingly being applied to clinical problems, with patient-specific models being generated from high fidelity imaging and used to simulate patient physiology, pathophysiology and response to treatment. Current structured meshes are limited in their ability to fully represent the detailed anatomical data available from clinical images and capture complex and varied anatomy with limited geometric accuracy. In this paper, we review the state of the art in image-based personalization of cardiac anatomy for biophysically detailed, strongly coupled EM modeling, and present our own tools for the automatic building of anatomically and structurally accurate patient-specific models. Our method relies on using high resolution unstructured meshes for discretizing both physics, electrophysiology and mechanics, in combination with efficient, strongly scalable solvers necessary to deal with the computational load imposed by the large number of degrees of freedom of these meshes. These tools permit automated anatomical model generation and strongly coupled EM simulations at an unprecedented level of anatomical and biophysical detail.

  12. Thermochemistry of the fluoroformyloxyl radical: a computational study based on coupled cluster theory.

    Science.gov (United States)

    Breidung, Jürgen; Thiel, Walter

    2006-02-02

    The standard enthalpy of formation of FCO(2) (X (2)B(2)) was determined by a computational approach based on coupled cluster theory [CCSD(T)] with energies extrapolated to the basis-set limit, with additional corrections accounting for core-valence correlation, scalar relativity, spin-orbit coupling, and zero-point vibrational motions. Utilizing a variety of independent reaction schemes, our best estimate is Delta(f)H(o)(0)(FCO(2)) = -86.0 +/- 0.6 kcal mol(-1) [Delta(f)H(o)(298) )(FCO(2)) = -86.7 +/- 0.6 kcal mol(-1)], which is shown to be more accurate than previous theoretical and experimental values. The chosen computational procedure was also applied to HCO (X (2)A'), where we find excellent agreement with experiment, and to FCO (X (2)A'), where we recommend an improved value of Delta(f)H(o)(0)(FCO) = -42.1 +/- 0.5 kcal mol(-1) [ Delta(f)H(o)(298)(FCO) = -42.0 +/- 0.5 kcal mol(-1)]. Further theoretical results concern the C-F bond dissociation energy, electron affinity, ionization energy, first and second excitation energies in FCO(2), fluoride ion affinity of CO(2), and equilibrium geometries of the molecules treated presently. For FCO (X (2)A') we propose an improved equilibrium structure: r(e)(CF) = 132.5(2) pm, r(e)(CO) = 116.7(2) pm, and theta(e)(FCO) = 127.8(2)(o).

  13. ROI reconstruction for model-based iterative reconstruction (MBIR) via a coupled dictionary learning

    Science.gov (United States)

    Ye, Dong Hye; Srivastava, Somesh; Thibault, Jean-Baptiste; Sauer, Ken D.; Bouman, Charles A.

    2017-03-01

    Model based iterative reconstruction (MBIR) algorithms have shown significant improvement in CT image quality by increasing resolution as well as reducing noise and artifacts. In diagnostic protocols, radiologists often need the high-resolution reconstruction of a limited region of interest (ROI). This ROI reconstruction is complicated for MBIR which should reconstruct an image in a full field of view (FOV) given full sinogram measurements. Multi-resolution approaches are widely used for this ROI reconstruction of MBIR, in which the image with a full FOV is reconstructed in a low-resolution and the forward projection of non-ROI is subtracted from the original sinogram measurements for high-resolution ROI reconstruction. However, a low-resolution reconstruction of a full FOV can be susceptible to streaking and blurring artifacts and these can be propagated into the following high-resolution ROI reconstruction. To tackle this challenge, we use a coupled dictionary representation model between low- and high-resolution training dataset for artifact removal and super resolution of a low-resolution full FOV reconstruction. Experimental results on phantom data show that the restored full FOV reconstruction via a coupled dictionary learning significantly improve the image quality of high-resolution ROI reconstruction for MBIR.

  14. Coupling Inward Diffusion and Precipitation Kinetics; the Case of Nitriding Iron-Based Alloys

    Science.gov (United States)

    Jung, Minsu; Meka, Sai Ramudu; Rheingans, Bastian; Mittemeijer, Eric Jan

    2016-03-01

    A model that describes the inward diffusion of an element I into a solid substrate and the simultaneous precipitation of a compound M y I z , with M as the alloying element initially dissolved in the substrate matrix, is presented for the case of nitriding iron-based alloys. The model was developed by coupling the diffusion kinetics and the precipitation (nucleation and growth) kinetics. Additionally, the role of excess nitrogen and the kinetics of ammonia dissociation at the iron surface were incorporated into this coupled model. The model was successfully applied to the case of nitriding an Fe-2.23 at. pct V alloy; the simulation results are in good agreement with the measured data and allow for detailed understanding of the evolution of the nitride precipitates (volume fraction, number density, and size distribution) as a function of both nitriding time and depth in the specimen. The present model exposed the pronounced effects of the precipitation kinetics, of excess nitrogen, and of the surface-reaction kinetics on the overall nitriding kinetics and demonstrated a striking, nonmonotonous change with time of precipitate particle size at a distinct depth in the specimen.

  15. Enhancement of spontaneous emission in a nitride based quantum well by resonant surface plasmon coupling

    Science.gov (United States)

    Neogi, Arup; Lee, Chang-Won; Everitt, Henry; Kuroda, Takamasa; Tackeuchi, Atsushi; Yablonovitch, Eli

    2002-03-01

    The photonic density of states (DOS) and the spontaneous emission rate can be modified when emitters are coupled to a surface plasmon (SP) of a metallic film. Using time-resolved and continuous-wave photoluminescence (PL) measurements, the recombination rate in an In0.18Ga0.82N/GaN quantum well (QW) is shown to be greatly enhanced when spontaneous emission is resonantly coupled to a silver surface plasmon. The transfer of the electron-hole energy to the plasmon excitation is indicated by the decrease in the PL intensity as well as the PL decay time constants from the silvered side. The rate of enhanced spontaneous emission into the surface plasmon was as much as 92 times faster than normal QW spontaneous emission. A calculation, based on Fermi's golden rule, reveals the enhancement is very sensitive to silver thickness and indicates even greater enhancements are possible for QWs placed closer to the surface metal coating. The spontaneous emission rate into the surface plasmon is also influenced by the excitation wavelength and optical power density due to bandfilling effects.

  16. Study on coupled dynamics of ship and flooding water based on experimental and SPH methods

    Science.gov (United States)

    Cheng, H.; Zhang, A. M.; Ming, F. R.

    2017-10-01

    The present paper studies the fluid dynamics during the flooding of a damaged ship numerically and experimentally. Attention is focused on the fluid flow characteristics and the fluid-structure interactions. The Smoothed Particle Hydrodynamics (SPH) method with an improved boundary treatment is established, which is able to capture the flow behaviors effectively. Fairly good agreement is obtained between the computational and experimental results. Based on the SPH method, the simulations are carried out for the flooding of a damaged ship with different opening sizes, opening positions, and numbers of the flooding cabins. Besides, the effects of the wave are also taken into account. The fluid behaviors are described and analyzed in detail. It is found that, during the first phase of flooding, an inflow jet with a large velocity is formed, significantly influencing the inner flows and the ship responses. During the progressive flooding phase, sloshing, crushing of the free surface, wave breaking, and vortex shedding are observed which are coupled with the ship motions. In addition, some relevant conclusions are enclosed for the motion laws of the damaged ship. This work provides physical insight into the flooding of the damaged ship, which is helpful to understand the coupled dynamics of the ship and flooding water.

  17. Analysis of a triple-cavity photonic molecule based on coupled-mode theory

    Science.gov (United States)

    Yang, Chao; Hu, Yong; Jiang, Xiaoshun; Xiao, Min

    2017-03-01

    In this paper, we analyze a chain-linked triple-cavity photonic molecule (TCPM) with controllable coupling strengths between the cavities on their spectral properties and field (energy) distributions by solving eigenvalues and eigenvectors of the Hamiltonian matrix based on coupled-mode theory. Phase transition is extended from double-cavity photonic molecules (DCPMs) to TCPMs, and evolutions of the supermode frequencies and linewidths are analyzed, which have synchronous relations with the degree of coherence between adjacent optical microcavities and energy distributions in the three cavities, respectively. We develop a superposition picture for the three supermodes of the TCPM, as interferences between supermodes of sub-DCPMs. In particular, we demonstrate the abnormal properties of the central supermode in TCPMs, such as the dark state in the middle cavity and phase shift when energy is flowing between the side cavities; these are promising for information processing and remote control of energy. General properties of TCPMs are summarized and limitations on linewidths are given. Finally, we make an interesting analog to intracavity electromagnetically induced transparency in multilevel atomic systems using the flexible TCPM platform under appropriate conditions.

  18. Finite Element Analysis of Mechanical Characteristics of Dropped Eggs Based on Fluid-Solid Coupling Theory

    Directory of Open Access Journals (Sweden)

    Song Haiyan

    2017-01-01

    Full Text Available It is important to study the properties and mechanics of egg drop impacts in order to reduce egg loss during processing and logistics and to provide a basis for the protective packaging of egg products. In this paper, we present the results of our study of the effects of the structural parameters on the mechanical properties of an egg using a finite element model of the egg. Based on Fluid-Solid coupling theory, a finite element model of an egg was constructed using ADINA, a finite element calculation and analysis software package. To simplify the model, the internal fluid of the egg was considered to be a homogeneous substance. The egg drop impact was simulated by the coupling solution, and the feasibility of the model was verified by comparison with the experimental results of a drop test. In summary, the modeling scheme was shown to be feasible and the simulation results provide a theoretical basis for the optimum design of egg packaging and egg processing equipment.

  19. Spin-current-driven thermoelectric generation based on interfacial spin-orbit coupling

    Energy Technology Data Exchange (ETDEWEB)

    Yagmur, A., E-mail: ahmetyagmur@imr.tohoku.ac.jp; Iguchi, R. [Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Karube, S.; Otani, Y. [Institute for Solid State Physics, University of Tokyo, Kashiwa, Chiba 277-8581 (Japan); Center for Emergent Matter Science, RIKEN, Wako, Saitama 351-0198 (Japan); Uchida, K., E-mail: kuchida@imr.tohoku.ac.jp [Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); PRESTO, Japan Science and Technology Agency, Saitama 332-0012 (Japan); Kondou, K. [Center for Emergent Matter Science, RIKEN, Wako, Saitama 351-0198 (Japan); Kikkawa, T. [Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); WPI Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Saitoh, E. [Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); WPI Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Spin Quantum Rectification Project, ERATO, Japan Science and Technology Agency, Sendai 980-8577 (Japan); Advanced Science Research Center, Japan Atomic Energy Agency, Tokai 319-1195 (Japan)

    2016-06-13

    The longitudinal spin Seebeck effect (SSE) in Bi{sub 2}O{sub 3}/Cu/yttrium-iron-garnet (YIG) devices has been investigated. When an out-of-plane temperature gradient is applied to the Bi{sub 2}O{sub 3}/Cu/YIG device, a spin current is generated across the Cu/YIG interface via the SSE and then converted into electric voltage due to the spin–orbit coupling at the Bi{sub 2}O{sub 3}/Cu interface. The sign of the SSE voltage in the Bi{sub 2}O{sub 3}/Cu/YIG devices is opposite to that induced by the conventional inverse spin Hall effect in Pt/YIG devices. The SSE voltage in the Bi{sub 2}O{sub 3}/Cu/YIG devices disappears in the absence of the Bi{sub 2}O{sub 3} layer and its thermoelectric conversion efficiency is independent of the Cu thickness, indicating the important role of the Bi{sub 2}O{sub 3}/Cu interface. This result demonstrates that not only the bulk inverse spin Hall effect but also the spin–orbit coupling near the interface can be used for SSE-based thermoelectric generation.

  20. Passage-Based Bibliographic Coupling: An Inter-Article Similarity Measure for Biomedical Articles.

    Directory of Open Access Journals (Sweden)

    Rey-Long Liu

    Full Text Available Biomedical literature is an essential source of biomedical evidence. To translate the evidence for biomedicine study, researchers often need to carefully read multiple articles about specific biomedical issues. These articles thus need to be highly related to each other. They should share similar core contents, including research goals, methods, and findings. However, given an article r, it is challenging for search engines to retrieve highly related articles for r. In this paper, we present a technique PBC (Passage-based Bibliographic Coupling that estimates inter-article similarity by seamlessly integrating bibliographic coupling with the information collected from context passages around important out-link citations (references in each article. Empirical evaluation shows that PBC can significantly improve the retrieval of those articles that biomedical experts believe to be highly related to specific articles about gene-disease associations. PBC can thus be used to improve search engines in retrieving the highly related articles for any given article r, even when r is cited by very few (or even no articles. The contribution is essential for those researchers and text mining systems that aim at cross-validating the evidence about specific gene-disease associations.

  1. Passage-Based Bibliographic Coupling: An Inter-Article Similarity Measure for Biomedical Articles

    Science.gov (United States)

    Liu, Rey-Long

    2015-01-01

    Biomedical literature is an essential source of biomedical evidence. To translate the evidence for biomedicine study, researchers often need to carefully read multiple articles about specific biomedical issues. These articles thus need to be highly related to each other. They should share similar core contents, including research goals, methods, and findings. However, given an article r, it is challenging for search engines to retrieve highly related articles for r. In this paper, we present a technique PBC (Passage-based Bibliographic Coupling) that estimates inter-article similarity by seamlessly integrating bibliographic coupling with the information collected from context passages around important out-link citations (references) in each article. Empirical evaluation shows that PBC can significantly improve the retrieval of those articles that biomedical experts believe to be highly related to specific articles about gene-disease associations. PBC can thus be used to improve search engines in retrieving the highly related articles for any given article r, even when r is cited by very few (or even no) articles. The contribution is essential for those researchers and text mining systems that aim at cross-validating the evidence about specific gene-disease associations. PMID:26440794

  2. Passage-Based Bibliographic Coupling: An Inter-Article Similarity Measure for Biomedical Articles.

    Science.gov (United States)

    Liu, Rey-Long

    2015-01-01

    Biomedical literature is an essential source of biomedical evidence. To translate the evidence for biomedicine study, researchers often need to carefully read multiple articles about specific biomedical issues. These articles thus need to be highly related to each other. They should share similar core contents, including research goals, methods, and findings. However, given an article r, it is challenging for search engines to retrieve highly related articles for r. In this paper, we present a technique PBC (Passage-based Bibliographic Coupling) that estimates inter-article similarity by seamlessly integrating bibliographic coupling with the information collected from context passages around important out-link citations (references) in each article. Empirical evaluation shows that PBC can significantly improve the retrieval of those articles that biomedical experts believe to be highly related to specific articles about gene-disease associations. PBC can thus be used to improve search engines in retrieving the highly related articles for any given article r, even when r is cited by very few (or even no) articles. The contribution is essential for those researchers and text mining systems that aim at cross-validating the evidence about specific gene-disease associations.

  3. Interplay between cellular redox oscillations and circadian clocks.

    Science.gov (United States)

    Rey, G; Reddy, A B

    2015-09-01

    The circadian clock is a cellular timekeeping mechanism that helps organisms from bacteria to humans to organize their behaviour and physiology around the solar cycle. Current models for circadian timekeeping incorporate transcriptional/translational feedback loop mechanisms in the predominant model systems. However, recent evidence suggests that non-transcriptional oscillations such as metabolic and redox cycles may play a fundamental role in circadian timekeeping. Peroxiredoxins, an antioxidant protein family, undergo rhythmic oxidation on the circadian time scale in a variety of species, including bacteria, insects and mammals, but also in red blood cells, a naturally occurring, non-transcriptional system. The profound interconnectivity between circadian and redox pathways strongly suggests that a conserved timekeeping mechanism based on redox cycles could be integral to generating circadian rhythms. © 2015 John Wiley & Sons Ltd.

  4. 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

  5. Evolutionary Design of Low Molecular Weight Organic Anolyte Materials for Applications in Nonaqueous Redox Flow Batteries.

    Science.gov (United States)

    Sevov, Christo S; Brooner, Rachel E M; Chénard, Etienne; Assary, Rajeev S; Moore, Jeffrey S; Rodríguez-López, Joaquín; Sanford, Melanie S

    2015-11-18

    The integration of renewable energy sources into the electric grid requires low-cost energy storage systems that mediate the variable and intermittent flux of energy associated with most renewables. Nonaqueous redox-flow batteries have emerged as a promising technology for grid-scale energy storage applications. Because the cost of the system scales with mass, the electroactive materials must have a low equivalent weight (ideally 150 g/(mol·e(-)) or less), and must function with low molecular weight supporting electrolytes such as LiBF4. However, soluble anolyte materials that undergo reversible redox processes in the presence of Li-ion supports are rare. We report the evolutionary design of a series of pyridine-based anolyte materials that exhibit up to two reversible redox couples at low potentials in the presence of Li-ion supporting electrolytes. A combination of cyclic voltammetry of anolyte candidates and independent synthesis of their corresponding charged-states was performed to rapidly screen for the most promising candidates. Results of this workflow provided evidence for possible decomposition pathways of first-generation materials and guided synthetic modifications to improve the stability of anolyte materials under the targeted conditions. This iterative process led to the identification of a promising anolyte material, N-methyl 4-acetylpyridinium tetrafluoroborate. This compound is soluble in nonaqueous solvents, is prepared in a single synthetic step, has a low equivalent weight of 111 g/(mol·e(-)), and undergoes two reversible 1e(-) reductions in the presence of LiBF4 to form reduced products that are stable over days in solution.

  6. Shedding light on disulfide bond formation: engineering a redox switch in green fluorescent protein

    DEFF Research Database (Denmark)

    Østergaard, H.; Henriksen, A.; Hansen, Flemming G.

    2001-01-01

    To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease in the i......To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease...... as a structural reorganization of residues in the immediate chromophore environment. By combining this information with spectroscopic data, we propose a detailed mechanism accounting for the observed redox state-dependent fluorescence. The redox potential of the cysteine couple was found to be within...

  7. Single-molecule electron tunnelling through multiple redox levels with environmental relaxation

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens

    2004-01-01

    We present an analytical theory for electron flow through a molecule with several redox levels, enclosed between a pair of metallic electrodes. The levels can be electronic or electronic-vibrational levels. Vibrational energy spacing characterises the latter sets. The levels are further coupled...... relations at fixed electrochemical overpotential or gate voltage, and current-overpotential or current-gate voltage relations at fixed bias voltage are equivalent in the two systems. Due to the activation-less nature of the processes, electron flow between the electrodes through the molecular redox levels...... can be only achieved when the latter are located between the Fermi levels of the substrate and tip or source and drain electrodes. The redox levels can be brought into this "energy window", either by the overpotential or bias and gate voltages, or by vibrational relaxation of (a) given (set of) redox...

  8. Enhanced photovoltaic performance of nanowire dye-sensitized solar cells based on coaxial TiO2@TiO heterostructures with a cobalt(II/III) redox electrolyte.

    Science.gov (United States)

    Fan, Jiandong; Fàbrega, Cristian; Zamani, Reza R; Hao, Yan; Parra, Andres; Andreu, Teresa; Arbiol, Jordi; Boschloo, Gerrit; Hagfeldt, Anders; Morante, Joan Ramon; Cabot, Andreu

    2013-10-23

    The growth of a TiO shell at the surface of TiO2 nanowires (NWs) allowed us to improve the power conversion efficiency of NW-based dye-sensitized solar cells (DSCs) by a factor 2.5. TiO2@TiO core-shell NWs were obtained by a two-step process: First, rutile-phase TiO2 NWs were hydrothermally grown. Second, a hongquiite-phase TiO shell was electrochemically deposited at the surface of the TiO2 NWs. Bare TiO2 and heterojunction TiO2@TiO NW-based DSCs were obtained using a cobalt(II/III) redox electrolyte and LEG4 as the dye. With this electrolyte/dye combination, DSCs with outstanding Voc values above 900 mV were systematically obtained. While TiO2@TiO NW-based DSCs had slightly lower Voc values than bare TiO2 NW-based DSCs, they provided 3-fold higher photocurrents, overall reaching 2.5-fold higher power conversion efficiencies. The higher photocurrents were associated with the larger surface roughness and an enhanced charge-carrier separation/transfer at the NW/dye interface.

  9. Sulfur-based absolute quantification of proteins using isotope dilution inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Lee, Hyun-Seok; Heun Kim, Sook; Jeong, Ji-Seon; Lee, Yong-Moon; Yim, Yong-Hyeon

    2015-10-01

    An element-based reductive approach provides an effective means of realizing International System of Units (SI) traceability for high-purity biological standards. Here, we develop an absolute protein quantification method using double isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS) combined with microwave-assisted acid digestion for the first time. We validated the method and applied it to certify the candidate protein certified reference material (CRM) of human growth hormone (hGH). The concentration of hGH was determined by analysing the total amount of sulfur in hGH. Next, the size-exclusion chromatography method was used with ICP-MS to characterize and quantify sulfur-containing impurities. By subtracting the contribution of sulfur-containing impurities from the total sulfur content in the hGH CRM, we obtained a SI-traceable certification value. The quantification result obtained with the present method based on sulfur analysis was in excellent agreement with the result determined via a well-established protein quantification method based on amino acid analysis using conventional acid hydrolysis combined with an ID liquid chromatography-tandem mass spectrometry. The element-based protein quantification method developed here can be generally used for SI-traceable absolute quantification of proteins, especially pure-protein standards.

  10. Performance of human body communication-based wearable ECG with capacitive coupling electrodes.

    Science.gov (United States)

    Sakuma, Jun; Anzai, Daisuke; Wang, Jianqing

    2016-09-01

    Wearable electrocardiogram (ECG) is attracting much attention in daily healthcare applications, and human body communication (HBC) technology provides an evident advantage in making the sensing electrodes of ECG also working for transmission through the human body. In view of actual usage in daily life, however, non-contact electrodes to the human body are desirable. In this Letter, the authors discussed the ECG circuit structure in the HBC-based wearable ECG for removing the common mode noise when employing non-contact capacitive coupling electrodes. Through the comparison of experimental results, they have shown that the authors' proposed circuit structure with the third electrode directly connected to signal ground can provide an effect on common mode noise reduction similar to the usual drive-right-leg circuit, and a sufficiently good acquisition performance of ECG signals.

  11. Quality control in nerve conduction studies with coupled knowledge-based system approach.

    Science.gov (United States)

    Xiang, Y; Eisen, A; MacNeil, M; Beddoes, M P

    1992-02-01

    Contemporary equipment used for nerve conduction studies is usually capable of computerized measurement of latency, amplitude, duration, and area of nerve and muscle action potentials and resulting conduction velocities. Abnormalities can be due to technical error or disease. Identification of technical error is a major element of quality control in electromyography, and artificial intelligence could be useful for this purpose. We have developed a coupled knowledge-based prototype system (QUALICON) to assess the correctness of recording and stimulating characteristics in routine conduction studies. QUALICON extracts numeric features from CMAPs or SNAPs, which are translated into symbolic form to drive a Bayesian network. The network uses high-level knowledge to infer the quality of stimulating and recording electrode placement as well as polarity and stimulus strength making recommendations as to the likely technical error when abnormal potentials are detected. A preliminary assessment shows that QUALICON performs as well as manual assessment performed by professionals.

  12. New Spectrophotometric Method for the Assay of Sulfadiazine Drug Based on Diazotization Coupling Reaction

    Directory of Open Access Journals (Sweden)

    Al-Rufaie Mohauman Mohammad

    2016-12-01

    Full Text Available A sensitive, simple and rapid spectrophotometric procedure for the assay of trace quantities of sulfadiazine (SDZ drug as bulk and in diluted solution is characterized. The procedure depends on the diazotization reaction which is produced by coupling SDZ with (4-amino-2-hydroxy acetophenon (AHA to produce an intense colored complex spectrophotometrically determined at 410 nm. Beer’s law was applied in the range of concentration 0.5 - 15 ppm; the molar absorptivity and Sandell’s sensitivity were 2.8484 × 104 L mol-1 cm-1 and 0.008 μg cm-2 respectively. The method limit of detection (LOD was 0.443 μg mL-1 and LOQ (the method limit of quantitation was 0.249 μg mL-1. The procedure is not based on solvent extraction and the additives and excipients do not significantly influence the developed procedure.

  13. Adjoint-Based a Posteriori Error Estimation for Coupled Time-Dependent Systems

    KAUST Repository

    Asner, Liya

    2012-01-01

    We consider time-dependent parabolic problem s coupled across a common interface which we formulate using a Lagrange multiplier construction and solve by applying a monolithic solution technique. We derive an adjoint-based a posteriori error representation for a quantity of interest given by a linear functional of the solution. We establish the accuracy of our error representation formula through numerical experimentation and investigate the effect of error in the adjoint solution. Crucially, the error representation affords a distinction between temporal and spatial errors and can be used as a basis for a blockwise time-space refinement strategy. Numerical tests illustrate the efficacy of the refinement strategy by capturing the distinctive behavior of a localized traveling wave solution. The saddle point systems considered here are equivalent to those arising in the mortar finite element technique for parabolic problems. © 2012 Society for Industrial and Applied Mathematics.

  14. Bifurcation Analysis of an Electrostatically Actuated Nano-Beam Based on Modified Couple Stress Theory

    Science.gov (United States)

    Rezaei Kivi, Araz; Azizi, Saber; Norouzi, Peyman

    2017-12-01

    In this paper, the nonlinear size-dependent static and dynamic behavior of an electrostatically actuated nano-beam is investigated. A fully clamped nano-beam is considered for the modeling of the deformable electrode of the NEMS. The governing differential equation of the motion is derived using Hamiltonian principle based on couple stress theory; a non-classical theory for considering length scale effects. The nonlinear partial differential equation of the motion is discretized to a nonlinear Duffing type ODE's using Galerkin method. Static and dynamic pull-in instabilities obtained by both classical theory and MCST are compared. At the second stage of analysis, shooting technique is utilized to obtain the frequency response curve, and to capture the periodic solutions of the motion; the stability of the periodic solutions are gained by Floquet theory. The nonlinear dynamic behavior of the deformable electrode due to the AC harmonic accompanied with size dependency is investigated.

  15. Direct fiber-coupled single photon source based on a photonic crystal waveguide

    Energy Technology Data Exchange (ETDEWEB)

    Ahn, Byeong-Hyeon, E-mail: seygene@kaist.ac.kr; Lee, Chang-Min; Lim, Hee-Jin [Department of Physics, KAIST, Daejeon 305-701 (Korea, Republic of); Schlereth, Thomas W.; Kamp, Martin [Technische Physik, Physikalisches Institut and Wilhelm Conrad Röntgen-Center for Complex Material Systems, Universität Würzburg, Am Hubland, D-97074 Würzburg (Germany); Höfling, Sven [Technische Physik, Physikalisches Institut and Wilhelm Conrad Röntgen-Center for Complex Material Systems, Universität Würzburg, Am Hubland, D-97074 Würzburg (Germany); SUPA, School of Physics and Astronomy, University of St. Andrews, St. Andrews KY16 9SS (United Kingdom); Lee, Yong-Hee [Department of Physics, KAIST, Daejeon 305-701 (Korea, Republic of); Graduate School of Nanoscience and Technology (WCU), KAIST, Daejeon 305-701 (Korea, Republic of)

    2015-08-24

    A single photon source plays a key role in quantum applications such as quantum computers and quantum communications. Epitaxially grown quantum dots are one of the promising platforms to implement a good single photon source. However, it is challenging to realize an efficient single photon source based on semiconductor materials due to their high refractive index. Here we demonstrate a direct fiber coupled single photon source with high collection efficiency by employing a photonic crystal (PhC) waveguide and a tapered micro-fiber. To confirm the single photon nature, the second-order correlation function g{sup (2)}(τ) is measured with a Hanbury Brown-Twiss setup. The measured g{sup (2)}(0) value is 0.15, and we can estimate 24% direct collection efficiency from a quantum dot to the fiber.

  16. Energy-based fatigue model for shape memory alloys including thermomechanical coupling

    Science.gov (United States)

    Zhang, Yahui; Zhu, Jihong; Moumni, Ziad; Van Herpen, Alain; Zhang, Weihong

    2016-03-01

    This paper is aimed at developing a low cycle fatigue criterion for pseudoelastic shape memory alloys to take into account thermomechanical coupling. To this end, fatigue tests are carried out at different loading rates under strain control at room temperature using NiTi wires. Temperature distribution on the specimen is measured using a high speed thermal camera. Specimens are tested to failure and fatigue lifetimes of specimens are measured. Test results show that the fatigue lifetime is greatly influenced by the loading rate: as the strain rate increases, the fatigue lifetime decreases. Furthermore, it is shown that the fatigue cracks initiate when the stored energy inside the material reaches a critical value. An energy-based fatigue criterion is thus proposed as a function of the irreversible hysteresis energy of the stabilized cycle and the loading rate. Fatigue life is calculated using the proposed model. The experimental and computational results compare well.

  17. A tunable bistable device based on a coupled quantum dot-metallic nanoparticle nanosystem

    Science.gov (United States)

    Li, Jian-Bo; Liang, Shan; He, Meng-Dong; Chen, Li-Qun; Wang, Xin-Jun; Peng, Xiao-Fang

    2015-07-01

    We theoretically propose a scheme of a tunable bistable device based on a coupled semiconductor quantum dot-metal nanoparticle nanosystem in the simultaneous presence of a strong pump laser and a weak probe laser with different frequencies. The results show that it is easy to turn on or off the optical bistable effect in such system by switching the polarization direction of the pump field, and the bistability thresholds are highly sensitive to the intensity, frequency, polarization direction of the pump field, and the interparticle distance. In addition, the nonlinear absorption in the two stable states exhibits a ratio as high as 104 arising from the three-photon effect, which implies that our nanosystem can also be used as an optical memory cell.

  18. Protein A Detection Based on Quantum Dots-Antibody Bioprobe Using Fluorescence Coupled Capillary Electrophoresis

    Directory of Open Access Journals (Sweden)

    Lin Qiu

    2014-01-01

    Full Text Available In this report, fluorescence detection coupled capillary electrophoresis (CE-FL was used to detect Protein A. Antibody was first labeled with Cy5 and then mixed with quantum dots (QDs to form QDs-antibody bioprobe. Further, we observed fluorescence resonance energy transfer (FRET from QDs donor to Cy5 acceptor. The bioprobe was formed and brought QDs and Cy5 close enough to allow FRET to occur. After adding protein A, the FRET system was broken and caused the FRET signal to decrease. Thus, a new method for the determination of protein A was proposed based on the FRET signal changes. This study provides a new trail of thought for the detection of protein.

  19. Transverse mode tailoring in diode lasers based on coupled large optical cavities

    Science.gov (United States)

    Gordeev, N. Yu; Maximov, M. V.; E Zhukov, A.

    2017-08-01

    The key principles of transverse mode engineering in edge-emitting lasers with broadened waveguides based on coupled large optical cavity (CLOC) structures are presented. The CLOC laser design is shown to be an effective approach for reducing the optical loss, broadening the waveguide, and lowering the beam divergence. Having simulated the sensitivity of the CLOC design to variations in layer thicknesses and compositions we have shown its high robustness. Advanced versions of the CLOC laser structures having two extra passive waveguides have been treated and shown to effectively eliminate several transverse modes. We have considered an application of the CLOC concept for waveguides with shifted active regions aimed at reducing laser thermal and electric resistances.

  20. Plasmonic metalens based on coupled resonators for focusing of surface plasmons

    KAUST Repository

    Xu, Quan

    2016-11-29

    As an essential functionality, flexible focusing of surface plasmons (SPs) is of particular interest in nonlinear optics and highly integrated plasmonic circuitry. Here, we developed a versatile plasmonic metalens, a metasurface comprised of coupled subwavelength resonators, whose optical responses exhibit a remarkable feature of electromagnetically induced transparency (EIT). We demonstrate numerically and experimentally how a proper spatial design of the unit elements steers SPs to arbitrary foci based on the holographic principles. More specifically, we show how to control the interaction between the constituent EIT resonators to efficiently manipulate the focusing intensity of SPs. We also demonstrated that the proposed metalens is capable of achieving frequency division multiplexing. The power and simplicity of the proposed design would offer promising opportunities for practical plasmonic devices.

  1. Harmonic suppressed coupled stepped-impedance resonator based dual-band tunable bandpass filter

    Directory of Open Access Journals (Sweden)

    Amarjit Kumar

    2017-10-01

    Full Text Available In this paper, a tunable dual-band bandpass filter (BPF based on a varactor-loaded coupled stepped-impedance resonator is presented. Transmission matrices techniques are employed to explain the working concept of proposed tunable BPF. For validating the proposed concept, a hardware prototype is fabricated and characterized. As per the measured results, when the center frequency of the lower band is tuning from 2.15 to 2.40 GHz, the upper band is fixed at 4.5 GHz; and when the center frequency of the upper band is tuning from 4.5 to 4.75 GHz, the lower passband almost remains constant at 2.25 GHz. Proposed tunable filter is capable of working at higher passband frequencies. Spurious harmonic suppression up to 15 GHz is demonstrated. Center frequency of dual-passband is tunable using only two dc control voltages.

  2. Stabilization of Networked Distributed Systems with Partial and Event-Based Couplings

    Directory of Open Access Journals (Sweden)

    Sufang Zhang

    2015-01-01

    Full Text Available The stabilization problem of networked distributed systems with partial and event-based couplings is investigated. The channels, which are used to transmit different levels of information of agents, are considered. The channel matrix is introduced to indicate the work state of the channels. An event condition is designed for each channel to govern the sampling instants of the channel. Since the event conditions are separately given for different channels, the sampling instants of channels are mutually independent. To stabilize the system, the state feedback controllers are implemented in the system. The control signals also suffer from the two communication constraints. The sufficient conditions in terms of linear matrix equalities are proposed to ensure the stabilization of the controlled system. Finally, a numerical example is given to demonstrate the advantage of our results.

  3. PRESBYOPIA OPTOMETRY METHOD BASED ON DIOPTER REGULATION AND CHARGE COUPLE DEVICE IMAGING TECHNOLOGY.

    Science.gov (United States)

    Zhao, Q; Wu, X X; Zhou, J; Wang, X; Liu, R F; Gao, J

    2015-01-01

    With the development of photoelectric technology and single-chip microcomputer technology, objective optometry, also known as automatic optometry, is becoming precise. This paper proposed a presbyopia optometry method based on diopter regulation and Charge Couple Device (CCD) imaging technology and, in the meantime, designed a light path that could measure the system. This method projects a test figure to the eye ground and then the reflected image from the eye ground is detected by CCD. The image is then automatically identified by computer and the far point and near point diopters are determined to calculate lens parameter. This is a fully automatic objective optometry method which eliminates subjective factors of the tested subject. Furthermore, it can acquire the lens parameter of presbyopia accurately and quickly and can be used to measure the lens parameter of hyperopia, myopia and astigmatism.

  4. Cascade-coupled racetrack resonators based on the Vernier effect in the mid-infrared.

    Science.gov (United States)

    Troia, Benedetto; Khokhar, Ali Z; Nedeljkovic, Milos; Penades, Jordi Soler; Passaro, Vittorio M N; Mashanovich, Goran Z

    2014-10-06

    In this paper we report the experimental demonstration of racetrack resonators in silicon-on-insulator technology platform operating in the mid-infrared wavelength range of 3.7-3.8 μm. Insertion loss lower than 1 dB and extinction ratio up to 30 dB were measured for single resonators. The experimental characterization of directional couplers and bending losses in silicon rib waveguides are also reported. Furthermore, we present the design and fabrication of cascade-coupled racetrack resonators based on the Vernier effect. Experimental spectra of Vernier architectures were demonstrated for the first time in the mid-infrared with insertion loss lower than 1 dB and maximum interstitial peak suppression of 10 dB.

  5. Real-Time Imaging of the Bacillithiol Redox Potential in the Human Pathogen Staphylococcus aureus Using a Genetically Encoded Bacilliredoxin-Fused Redox Biosensor.

    Science.gov (United States)

    Loi, Vu Van; Harms, Manuela; Müller, Marret; Huyen, Nguyen Thi Thu; Hamilton, Chris J; Hochgräfe, Falko; Pané-Farré, Jan; Antelmann, Haike

    2017-05-20

    Bacillithiol (BSH) is utilized as a major thiol-redox buffer in the human pathogen Staphylococcus aureus. Under oxidative stress, BSH forms mixed disulfides with proteins, termed as S-bacillithiolation, which can be reversed by bacilliredoxins (Brx). In eukaryotes, glutaredoxin-fused roGFP2 biosensors have been applied for dynamic live imaging of the glutathione redox potential. Here, we have constructed a genetically encoded bacilliredoxin-fused redox biosensor (Brx-roGFP2) to monitor dynamic changes in the BSH redox potential in S. aureus. The Brx-roGFP2 biosensor showed a specific and rapid response to low levels of bacillithiol disulfide (BSSB) in vitro that required the active-site Cys of Brx. Dynamic live imaging in two methicillin-resistant S. aureus (MRSA) USA300 and COL strains revealed fast and dynamic responses of the Brx-roGFP2 biosensor under hypochlorite and hydrogen peroxide (H2O2) stress and constitutive oxidation of the probe in different BSH-deficient mutants. Furthermore, we found that the Brx-roGFP2 expression level and the dynamic range are higher in S. aureus COL compared with the USA300 strain. In phagocytosis assays with THP-1 macrophages, the biosensor was 87% oxidized in S. aureus COL. However, no changes in the BSH redox potential were measured after treatment with different antibiotics classes, indicating that antibiotics do not cause oxidative stress in S. aureus. Conclusion and Innovation: This Brx-roGFP2 biosensor catalyzes specific equilibration between the BSH and roGFP2 redox couples and can be applied for dynamic live imaging of redox changes in S. aureus and other BSH-producing Firmicutes. Antioxid. Redox Signal. 26, 835-848.

  6. Redox-active Crosslinkable Poly(ionic liquid)s

    NARCIS (Netherlands)

    Sui, Xiaofeng; Hempenius, Mark A.; Vancso, Gyula J.

    2012-01-01

    The synthesis of a new class of cross-linkable redox-responsive poly(ferrocenylsilane)-based poly(ionic liquid)s (PFS-PILs) is reported. PFS-PILs self-cross-link at low concentrations into nanogels or form macroscopic hydrogel networks at higher concentrations. PFS-PILs proved to be efficient

  7. Coordination and redox state-dependent structural changes of the heme-based oxygen sensor AfGcHK associated with intraprotein signal transduction

    Czech Academy of Sciences Publication Activity Database

    Stráňava, M.; Man, Petr; Skálová, Tereza; Kolenko, Petr; Bláha, J.; Fojtíková, V.; Martínek, V.; Dohnálek, Jan; Lengalová, A.; Rosůlek, Michal; Shimizu, T.; Martínková, M.

    2017-01-01

    Roč. 292, č. 51 (2017), s. 20921-20935 ISSN 0021-9258 R&D Projects: GA MŠk(CZ) LM2015043; GA MŠk(CZ) ED1.1.00/02.0109; GA MŠk(CZ) LQ1604; GA MŠk(CZ) EF16_013/0001776 Institutional support: RVO:61388971 ; RVO:86652036 Keywords : INDUCED CONFORMATIONAL-CHANGES * TRANSCRIPTION ACTIVATOR COOA * COUPLED HISTIDINE KINASE Subject RIV: CE - Biochemistry; CE - Biochemistry (BTO-N) Impact factor: 4.125, year: 2016

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

    Science.gov (United States)

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

    2015-02-01

    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.

  9. Proton-directed redox control of O-O bond activation by heme hydroperoxidase models.

    Science.gov (United States)

    Soper, Jake D; Kryatov, Sergey V; Rybak-Akimova, Elena V; Nocera, Daniel G

    2007-04-25

    Hangman metalloporphyrin complexes poise an acid-base group over a redox-active metal center and in doing so allow the "pull" effect of the secondary coordination environment of the heme cofactor of hydroperoxidase enzymes to be modeled. Stopped-flow investigations have been performed to decipher the influence of a proton-donor group on O-O bond activation. Low-temperature reactions of tetramesitylporphyrin (TMP) and Hangman iron complexes containing acid (HPX-CO2H) and methyl ester (HPX-CO2Me) functional groups with peroxyacids generate high-valent Fe=O active sites. Reactions of peroxyacids with (TMP)FeIII(OH) and methyl ester Hangman (HPX-CO2Me)FeIII(OH) give both O-O heterolysis and homolysis products, Compound I (Cpd I) and Compound II (Cpd II), respectively. However, only the former is observed when the hanging group is the acid, (HPX-CO2H)FeIII(OH), because odd-electron homolytic O-O bond cleavage is inhibited. This proton-controlled, 2e- (heterolysis) vs 1e- (homolysis) redox specificity sheds light on the exceptional catalytic performance of the Hangman metalloporphyrin complexes and provides tangible benchmarks for using proton-coupled multielectron reactions to catalyze O-O bond-breaking and bond-making reactions.

  10. Efficient fiber-coupled single-photon source based on quantum dots in a photonic-crystal waveguide.

    Science.gov (United States)

    Daveau, Raphaël S; Balram, Krishna C; Pregnolato, Tommaso; Liu, Jin; Lee, Eun H; Song, Jin D; Verma, Varun; Mirin, Richard; Nam, Sae Woo; Midolo, Leonardo; Stobbe, Søren; Srinivasan, Kartik; Lodahl, Peter

    2017-02-20

    Many photonic quantum information processing applications would benefit from a high brightness, fiber-coupled source of triggered single photons. Here, we present a fiber-coupled photonic-crystal waveguide single-photon source relying on evanescent coupling of the light field from a tapered out-coupler to an optical fiber. A two-step approach is taken where the performance of the tapered out-coupler is recorded first on an independent device containing an on-chip reflector. Reflection measurements establish that the chip-to-fiber coupling efficiency exceeds 80 %. The detailed characterization of a high-efficiency photonic-crystal waveguide extended with a tapered out-coupling section is then performed. The corresponding overall single-photon source efficiency is 10.9 % ± 2.3 %, which quantifies the success probability to prepare an exciton in the quantum dot, couple it out as a photon in the waveguide, and subsequently transfer it to the fiber. The applied out-coupling method is robust, stable over time, and broadband over several tens of nanometers, which makes it a highly promising pathway to increase the efficiency and reliability of planar chip-based single-photon sources.

  11. 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.

  12. Coupling urban event-based and catchment continuous modelling for combined sewer overflow river impact assessment

    Directory of Open Access Journals (Sweden)

    I. Andrés-Doménech

    2010-10-01

    Full Text Available Since Water Framework Directive (WFD was passed in year 2000, the conservation of water bodies in the EU must be understood in a completely different way. Regarding to combined sewer overflows (CSOs from urban drainage networks, the WFD implies that we cannot accept CSOs because of their intrinsic features, but they must be assessed for their impact on the receiving water bodies in agreement with specific environmental aims. Consequently, both, urban system and the receiving water body must be jointly analysed to evaluate the environmental impact generated on the latter. In this context, a coupled scheme is presented in this paper to assess the CSOs impact on a river system in Torrelavega (Spain. First, a urban model is developed to statistically characterise the CSOs frequency, volume and duration. The main feature of this first model is the fact of being event-based: the system is modelled with some built synthetic storms which cover adequately the probability range of the main rainfall descriptors, i.e., rainfall event volume and peak intensity. Thus, CSOs are characterised in terms of their occurrence probability. Secondly, a continuous and distributed basin model is built to assess river response at different points in the river network. This model was calibrated initially on a daily scale and downscaled later to hourly scale. The main objective of this second element of the scheme is to provide the most likely state of the receiving river when a CSO occurs. By combining results of both models, CSO and river flows are homogeneously characterised from a statistical point of view. Finally, results from both models were coupled to estimate the final concentration of some analysed pollutants (biochemical oxygen demand, BOD, and total ammonium, NH4+, within the river just after the spills.

  13. Thiolactone based coupling agents for the synthesis of poly(amide/urethane)s

    OpenAIRE

    Mommer, Stefan

    2017-01-01

    In the present thesis, three different coupling agents are synthesized, which consist each of two cycles: (i) ethylene carbonate - thiolactone, (ii) bis(thiolactone) and (iii) epoxy - thiolactone. The syntheses of each are optimized to give high yields and pure products. Each coupling agent is thoroughly investigated concerning the orthogonal reactivity of its cycles. For the ethylene carbonate thiolactone coupling agent, a one-pot procedure is established where four different building blocks...

  14. Bacteriophage-based enrichment coupled to immunochromatographic strip-based detection for the determination of Salmonella in meat and poultry.

    Science.gov (United States)

    Muldoon, Mark T; Teaney, George; Li, Jingkun; Onisk, Dale V; Stave, James W

    2007-10-01

    Immunochemical-based methods for the detection of Salmonella in food can be complicated by the presence of closely related, immunocrossreactive non-Salmonella species in the sample that may cause false-positive results. To circumvent this problem, specific bacteriophages against immunocrossreactive, non-Salmonella bacteria were used in the sample enrichment step to suppress their growth and improve the performance of an immunochromatographic strip-based detection method for Salmonella. Cross-reactive bacteria were isolated from various food sources and were characterized with a panel of Salmonella somatic O antigen-specific monoclonal antibodies. These cross-reactive bacteria were primarily Citrobacter spp. and Escherichia coli with serology shared with Salmonella serogroups B, D, and F. These bacteria were used as hosts for the isolation of specific lytic bacteriophages. When formulated with the primary enrichment, the bacteriophage cocktail significantly reduced false positives with a broadly reactive immunochromatographic test strip. This was demonstrated in both artificially and naturally contaminated meat. False positives in naturally contaminated beef samples were reduced from 32 of 115 samples tested to zero. In raw meat and poultry with a relatively high bioburden (>10(5) CFU/g), the use of the bacteriophage-based enrichment procedure gave improved recovery of Salmonella compared with the conventional culture-based reference method. This was observed when coupled to either test strip-based or selective agar-based detection. The use of specific bacteriophages for the control of immunocrossreactive and competitive microflora during the food sample enrichment step provides a new approach for enhancing the performance of both immunological- and cultural-based detection methods.

  15. Determining the sign of exchange coupling in a chromia based perpendicular exchange bias heterostructure

    Science.gov (United States)

    Singh, Uday; Street, Mike; Echtenkamp, Will; Binek, Christian; Adenwalla, Shireen

    Exchange bias arises from the coupling at the AFM/FM interface and, has been observed and studied in a wide range of systems. A key property of exchange bias systems is the sign of the coupling between the ferromagnet spins and the interfacial antiferromagnet spins, which may be aligned either ferromagnetically (parallel) or antiferromagnetically (antiparallel). Antiferromagnetic exchange coupling is known to be the generic cause of positive exchange bias. Determining the sign of exchange coupling is straight forward in system where the coupling is weak and can be overcome by Zeeman energy on field -cooling. It is, however, a challenging task when the available magnetic field is low or the magnitude of the exchange coupling is high. Here, we present a technique to determine the sign of the exchange coupling using low fields. We measure the exchange bias field as a function of ferromagnet magnetization during field cooling and the resultant behavior of the exchange bias vs. the magnetization uniquely determines the sign of the coupling. We use this to measure the sign of the exchange coupling in a Cr2O3(300 nm)/Pd(0.5 nm)/[Co(0.3 nm)/Pd(1 nm)]3 heterostructure thin film system and verify our results with the conventional high field method. This work was supported by the National Science Foundation (NSF) through Grant No. DMR-1409622 and the Nebraska Materials Research Science and Engineering Center (MRSEC) (Grant No. DMR-1420645).

  16. Investigation of the electrospun carbon web as the catalyst layer for vanadium redox flow battery

    Science.gov (United States)

    Wei, Guanjie; Fan, Xinzhuang; Liu, Jianguo; Yan, Chuanwei

    2014-12-01

    Polyacrylonitrile (PAN) carbon nonwoven web consisting of 100-200 nm ultrafine fibers has been developed by electrospinning and subsequent carbonization process at 1000 °C for different times. The surface morphology, composition, structure, and electrical conductivity of the electrospun carbon webs (ECWs) as well as their electrochemical properties toward vanadium redox couples have been characterized. With the increasing of carbonization time, the electrochemical reversibility of the vanadium redox couples on the ECW is enhanced greatly. As the carbonization time increases up to 120 min, the hydrogen evolution is facilitated while the reversibility is promoted a little bit further. The excellent performance of ECW may be attributed to the conversion of fibers carbon structure and improvement of electrical conductivity. Due to the good electrochemical activity and freestanding 3-dimensional structure, the ECW carbonized for 90 min is used as catalyst layer in vanadium redox flow battery (VRFB) and enhances the cell performance.

  17. Applications of redox polymers in biosensors

    Energy Technology Data Exchange (ETDEWEB)

    Boguslavsky, L. (Moltech Corporation, Stony Brook, NY (United States)); Hale, P.D. (Moltech Corporation, Stony Brook, NY (United States)); Geng Lin (Moltech Corporation, Stony Brook, NY (United States)); Skotheim, T.A. (Moltech Corporation, Stony Brook, NY (United States)); Lee Hongsui (Dept. of Applied Science, Brookhaven National Lab., Upton, NY (United States))

    1993-03-01

    Polymers containing covalently attached redox molecules can be highly effective electron transfer mediators for flavin adenine dinucleotide redox centers of many oxidases. Highly flexible siloxane and ethylene oxide polymers containing covalently attached ferrocene molecules are shown to be capable of mediating electron transfer between enzymes and an electrode. The construction and response of bienzyme cholesterol biosensor, acetylcholine and glucose biosensor are described and discussed. Our data showed that the flexibility, hydrophilicity of the polymer, the density of redox centers in the polymer matrices and the self-exchange reaction rate of the redox molecules control the efficiency of the electron transfer mediation. (orig.)

  18. 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.

  19. Protein resonance assignment at MAS frequencies approaching 100 kHz: a quantitative comparison of J-coupling and dipolar-coupling-based transfer methods

    Energy Technology Data Exchange (ETDEWEB)

    Penzel, Susanne; Smith, Albert A.; Agarwal, Vipin; Hunkeler, Andreas [ETH Zürich, Physical Chemistry (Switzerland); Org, Mai-Liis; Samoson, Ago, E-mail: ago.samoson@ttu.ee [Tallinn University of Technology, NMR Instituut, Tartu Teadus, Tehnomeedikum (Estonia); Böckmann, Anja, E-mail: a.bockmann@ibcp.fr [UMR 5086 CNRS/Université de Lyon 1, Institut de Biologie et Chimie des Protéines (France); Ernst, Matthias, E-mail: maer@ethz.ch; Meier, Beat H., E-mail: beme@ethz.ch [ETH Zürich, Physical Chemistry (Switzerland)

    2015-10-15

    We discuss the optimum experimental conditions to obtain assignment spectra for solid proteins at magic-angle spinning (MAS) frequencies around 100 kHz. We present a systematic examination of the MAS dependence of the amide proton T{sub 2}′ times and a site-specific comparison of T{sub 2}′ at 93 kHz versus 60 kHz MAS frequency. A quantitative analysis of transfer efficiencies of building blocks, as they are used for typical 3D experiments, was performed. To do this, we compared dipolar-coupling and J-coupling based transfer steps. The building blocks were then combined into 3D experiments for sequential resonance assignment, where we evaluated signal-to-noise ratio and information content of the different 3D spectra in order to identify the best assignment strategy. Based on this comparison, six experiments were selected to optimally assign the model protein ubiquitin, solely using spectra acquired at 93 kHz MAS. Within 3 days of instrument time, the required spectra were recorded from which the backbone resonances have been assigned to over 96 %.

  20. Prediction of Treatment Response at 5-year Follow-up in a Randomized Clinical Trial of Behaviorally Based Couple Therapies

    Science.gov (United States)

    Baucom, Brian R.; Atkins, David C.; Rowe, Lorelei Simpson; Doss, Brian D.; Christensen, Andrew

    2014-01-01

    Objective Building on earlier work examining predictors of short- and moderate-term treatment response, demographic, intrapersonal, communication, and interpersonal variables were examined as predictors of clinically significant outcomes five years after couples completed one of two behaviorally based couple therapies. Method One hundred and thirty-four couples were randomly assigned to Integrative Behavioral Couple Therapy (IBCT; Jacobson & Christensen, 1998) or Traditional Behavioral Couple Therapy (TBCT; Jacobson & Margolin, 1979) and followed for 5 years after treatment. Outcomes include clinically significant change categories of relationship satisfaction and marital status at 5-year follow-up. Optimal subsets of predictors were selected using an automated, bootstrapped selection procedure based on Bayesian Information Criterion. Results Higher levels of commitment and being married for a longer period of time were associated with decreased likelihood of divorce/separation (Odds Ratio [OR] = 1.39, p = .004; OR = 0.91, p = .015). Being married for a longer period of time was also associated with increased likelihood of positive, clinically significant change (OR = 1.12, p = .029). Finally, higher levels of wife desired closeness were associated with increased odds of positive, clinically significant change and decreased odds of divorce for moderately distressed, IBCT couples (OR = 1.16, p = 0.002; OR = 0.85, p = 0.007, respectively) whereas the opposite was true for moderately distressed, TBCT couples (OR = 0.77, p divorced and most likely to report improvements in relationship satisfaction five years after ending treatment. In addition, it appears that the impact of wives’ desired closeness depended on the type of treatment moderately distressed couple received. PMID:25265544

  1. Production of G protein-coupled receptors in an insect-based cell-free system.

    Science.gov (United States)

    Sonnabend, Andrei; Spahn, Viola; Stech, Marlitt; Zemella, Anne; Stein, Christoph; Kubick, Stefan

    2017-10-01

    The biochemical analysis of human cell membrane proteins remains a challenging task due to the difficulties in producing sufficient quantities of functional protein. G protein-coupled receptors (GPCRs) represent a main class of membrane proteins and drug targets, which are responsible for a huge number of signaling processes regulating various physiological functions in living cells. To circumvent the current bottlenecks in GPCR studies, we propose the synthesis of GPCRs in eukaryotic cell-free systems based on extracts generated from insect (Sf21) cells. Insect cell lysates harbor the fully active translational and translocational machinery allowing posttranslational modifications, such as glycosylation and phosphorylation of de novo synthesized proteins. Here, we demonstrate the production of several GPCRs in a eukaryotic cell-free system, performed within a short time and in a cost-effective manner. We were able to synthesize a variety of GPCRs ranging from 40 to 133 kDa in an insect-based cell-free system. Moreover, we have chosen the μ opioid receptor (MOR) as a model protein to analyze the ligand binding affinities of cell-free synthesized MOR in comparison to MOR expressed in a human cell line by "one-point" radioligand binding experiments. Biotechnol. Bioeng. 2017;114: 2328-2338. © 2017 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc. © 2017 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc.

  2. Enhancing the performance of starch-based wood adhesive by silane coupling agent(KH570).

    Science.gov (United States)

    Chen, Lei; Wang, Yajie; Zia-Ud-Din; Fei, Peng; Jin, Wensi; Xiong, Hanguo; Wang, Zhenjiong

    2017-11-01

    To investigate the improved performance of silane coupling agents on starch-based wood adhesive, we prepared adhesive samples using γ-Methacryloxypropyl trimethoxy silane(KH570) as a cross-linking agent.The results found that the addition of KH570 resulted in enhanced shear strength and storage stability. The addition of KH570 also promoted the thermal stability due to increase the number of covalent bonds.Furthermore, the KH570 enhanced the shear-thinning property and weakened the pseudoplastic behavior of the adhesive. The characterization of copolymers was carried out via Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD) and thermal analysis. The performing XPS analysis and morphological structures of adhesive were evaluated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). In conclusion, 6% KH570 (KH570:starch, w;w) could be used to prepare starch-based wood adhesives with superior performance and stability. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Hydro-elastic analysis of marine propellers based on a BEM-FEM coupled FSI algorithm

    Directory of Open Access Journals (Sweden)

    Lee Hyoungsuk

    2014-09-01

    Full Text Available A reliable steady/transient hydro-elastic analysis is developed for flexible (composite marine propeller blade design which deforms according to its environmental load (ship speed, revolution speed, wake distribution, etc. Hydro-elastic analysis based on CFD and FEM has been widely used in the engineering field because of its accurate results however it takes large computation time to apply early propeller design stage. Therefore the analysis based on a boundary element method-Finite Element Method (BEM-FEM Fluid-Structure Interaction (FSI is introduced for computational efficiency and accuracy. The steady FSI analysis, and its application to reverse engineering, is designed for use regarding optimum geometry and ply stack design. A time domain two-way coupled transient FSI analysis is developed by considering the hydrodynamic damping ffects of added mass due to fluid around the propeller blade. The analysis makes possible to evaluate blade strength and also enable to do risk assessment by estimating the change in performance and the deformation depending on blade position in the ship’s wake. To validate this hydro-elastic analysis methodology, published model test results of P5479 and P5475 are applied to verify the steady and the transient FSI analysis, respectively. As the results, the proposed steady and unsteady analysis methodology gives sufficient accuracy to apply flexible marine propeller design

  4. Theoretical modeling of a coupled plasmon waveguide resonance sensor based on multimode optical fiber

    Science.gov (United States)

    Liu, Kun; Xue, Meng; Jiang, Junfeng; Wang, Tao; Chang, Pengxiang; Liu, Tiegen

    2018-03-01

    A coupled plasmon waveguide resonance (CPWR) sensor based on metal/dielectric-coated step index multimode optical fiber is proposed. Theoretical simulations using the four-layer Fresnel equations based on a bi-dimensional optical fiber model were implemented on four structures: Ag-ZnO, Au-ZnO, Ag-TiO2 and Au-TiO2. By controlling the thickness of dielectric layer, we managed to manipulate the CPWR resonance wavelengths. When a CPWR resonance dip is in the short wavelength region, it is insensitive to the change of surrounding refractive index (SRI) and can be used as a reference to improve the sensing accuracy of surface plasmon resonance (SPR) mode. With the increase of the thickness of the dielectric layer, the CPWR resonance dips shift to longer wavelength and the corresponding sensitivities increase. When the 1st CPWR resonance wavelength is near 1550 nm and SRI is around 1.333, the sensitivities of four structures reach 1360.61 nm/RIU, 1375.76 nm/RIU, 1048.48 nm/RIU and 1015.15 nm/RIU, respectively. The values are close to that of the conventional SPR optical fiber sensor while the spectral bandwidths of the optical fiber CPWR sensors are narrower.

  5. Coupling Agent-Based and Groundwater Modeling to Explore Demand Management Strategies for Shared Resources

    Science.gov (United States)

    Al-Amin, S.

    2015-12-01

    Municipal water demands in growing population centers in the arid southwest US are typically met through increased groundwater withdrawals. Hydro-climatic uncertainties attributed to climate change and land use conversions may also alter demands and impact the replenishment of groundwater supply. Groundwater aquifers are not necessarily confined within municipal and management boundaries, and multiple diverse agencies may manage a shared resource in a decentralized approach, based on individual concerns and resources. The interactions among water managers, consumers, and the environment influence the performance of local management strategies and regional groundwater resources. This research couples an agent-based modeling (ABM) framework and a groundwater model to analyze the effects of different management approaches on shared groundwater resources. The ABM captures the dynamic interactions between household-level consumers and policy makers to simulate water demands under climate change and population growth uncertainties. The groundwater model is used to analyze the relative effects of management approaches on reducing demands and replenishing groundwater resources. The framework is applied for municipalities located in the Verde River Basin, Arizona that withdraw groundwater from the Verde Formation-Basin Fill-Carbonate aquifer system. Insights gained through this simulation study can be used to guide groundwater policy-making under changing hydro-climatic scenarios for a long-term planning horizon.

  6. Coupled Hidden Markov Model-Based Method for Apnea Bradycardia Detection.

    Science.gov (United States)

    Montazeri Ghahjaverestan, N; Masoudi, S; Shamsollahi, M B; Beuchee, A; Pladys, P; Ge, D; Hernandez, A I

    2016-03-01

    In this paper, we present a novel framework for the coupled hidden Markov model (CHMM), based on the forward and backward recursions and conditional probabilities, given a multidimensional observation. In the proposed framework, the interdependencies of states networks are modeled with Markovian-like transition laws that influence the evolution of hidden states in all channels. Moreover, an offline inference approach by maximum likelihood estimation is proposed for the learning procedure of model parameters. To evaluate its performance, we first apply the CHMM model to classify and detect disturbances using synthetic data generated by the FitzHugh-Nagumo model. The average sensitivity and specificity of the classification are above 93.98% and 95.38% and those of the detection reach 94.49% and 99.34%, respectively. The method is also evaluated using a clinical database composed of annotated physiological signal recordings of neonates suffering from apnea-bradycardia. Different combinations of beat-to-beat features extracted from electrocardiographic signals constitute the multidimensional observations for which the proposed CHMM model is applied, to detect each apnea bradycardia episode. The proposed approach is finally compared to other previously proposed HMM-based detection methods. Our CHMM provides the best performance on this clinical database, presenting an average sensitivity of 95.74% and specificity of 91.88% while it reduces the detection delay by -0.59 s.

  7. Hydro-elastic analysis of marine propellers based on a BEM-FEM coupled FSI algorithm

    Directory of Open Access Journals (Sweden)

    Hyoungsuk Lee

    2014-09-01

    Full Text Available A reliable steady/transient hydro-elastic analysis is developed for flexible (composite marine propeller blade design which deforms according to its environmental load (ship speed, revolution speed, wake distribution, etc. Hydro-elastic analysis based on CFD and FEM has been widely used in the engineering field because of its accurate results however it takes large computation time to apply early propeller design stage. Therefore the analysis based on a boundary element method-Finite Element Method (BEM-FEM Fluid-Structure Interaction (FSI is introduced for computational efficiency and accuracy. The steady FSI analysis, and its application to reverse engineering, is designed for use regarding optimum geometry and ply stack design. A time domain two-way coupled transient FSI analysis is developed by considering the hydrodynamic damping ffects of added mass due to fluid around the propeller blade. The analysis makes possible to evaluate blade strength and also enable to do risk assessment by estimating the change in performance and the deformation depending on blade position in the ship's wake. To validate this hydro-elastic analysis methodology, published model test results of P5479 and P5475 are applied to verify the steady and the transient FSI analysis, respectively. As the results, the proposed steady and unsteady analysis methodology gives sufficient accuracy to apply flexible marine propeller design.

  8. PSO-tuned PID controller for coupled tank system via priority-based fitness scheme

    Science.gov (United States)

    Jaafar, Hazriq Izzuan; Hussien, Sharifah Yuslinda Syed; Selamat, Nur Asmiza; Abidin, Amar Faiz Zainal; Aras, Mohd Shahrieel Mohd; Nasir, Mohamad Na'im Mohd; Bohari, Zul Hasrizal

    2015-05-01

    The industrial applications of Coupled Tank System (CTS) are widely used especially in chemical process industries. The overall process is require liquids to be pumped, stored in the tank and pumped again to another tank. Nevertheless, the level of liquid in tank need to be controlled and flow between two tanks must be regulated. This paper presents development of an optimal PID controller for controlling the desired liquid level of the CTS. Two method of Particle Swarm Optimization (PSO) algorithm will be tested in optimizing the PID controller parameters. These two methods of PSO are standard Particle Swarm Optimization (PSO) and Priority-based Fitness Scheme in Particle Swarm Optimization (PFPSO). Simulation is conducted within Matlab environment to verify the performance of the system in terms of settling time (Ts), steady state error (SSE) and overshoot (OS). It has been demonstrated that implementation of PSO via Priority-based Fitness Scheme (PFPSO) for this system is potential technique to control the desired liquid level and improve the system performances compared with standard PSO.

  9. Non-contact evaluation of milk-based products using air-coupled ultrasound

    Science.gov (United States)

    Meyer, S.; Hindle, S. A.; Sandoz, J.-P.; Gan, T. H.; Hutchins, D. A.

    2006-07-01

    An air-coupled ultrasonic technique has been developed and used to detect physicochemical changes of liquid beverages within a glass container. This made use of two wide-bandwidth capacitive transducers, combined with pulse-compression techniques. The use of a glass container to house samples enabled visual inspection, helping to verify the results of some of the ultrasonic measurements. The non-contact pulse-compression system was used to evaluate agglomeration processes in milk-based products. It is shown that the amplitude of the signal varied with time after the samples had been treated with lactic acid, thus promoting sample destabilization. Non-contact imaging was also performed to follow destabilization of samples by scanning in various directions across the container. The obtained ultrasonic images were also compared to those from a digital camera. Coagulation with glucono-delta-lactone of skim milk poured into this container could be monitored within a precision of a pH of 0.15. This rapid, non-contact and non-destructive technique has shown itself to be a feasible method for investigating the quality of milk-based beverages, and possibly other food products.

  10. INS/GNSS Tightly-Coupled Integration Using Quaternion-Based AUPF for USV.

    Science.gov (United States)

    Xia, Guoqing; Wang, Guoqing

    2016-08-02

    This paper addresses the problem of integration of Inertial Navigation System (INS) and Global Navigation Satellite System (GNSS) for the purpose of developing a low-cost, robust and highly accurate navigation system for unmanned surface vehicles (USVs). A tightly-coupled integration approach is one of the most promising architectures to fuse the GNSS data with INS measurements. However, the resulting system and measurement models turn out to be nonlinear, and the sensor stochastic measurement errors are non-Gaussian and distributed in a practical system. Particle filter (PF), one of the most theoretical attractive non-linear/non-Gaussian estimation methods, is becoming more and more attractive in navigation applications. However, the large computation burden limits its practical usage. For the purpose of reducing the computational burden without degrading the system estimation accuracy, a quaternion-based adaptive unscented particle filter (AUPF), which combines the adaptive unscented Kalman filter (AUKF) with PF, has been proposed in this paper. The unscented Kalman filter (UKF) is used in the algorithm to improve the proposal distribution and generate a posterior estimates, which specify the PF importance density function for generating particles more intelligently. In addition, the computational complexity of the filter is reduced with the avoidance of the re-sampling step. Furthermore, a residual-based covariance matching technique is used to adapt the measurement error covariance. A trajectory simulator based on a dynamic model of USV is used to test the proposed algorithm. Results show that quaternion-based AUPF can significantly improve the overall navigation accuracy and reliability.

  11. INS/GNSS Tightly-Coupled Integration Using Quaternion-Based AUPF for USV

    Directory of Open Access Journals (Sweden)

    Guoqing Xia

    2016-08-01

    Full Text Available This paper addresses the problem of integration of Inertial Navigation System (INS and Global Navigation Satellite System (GNSS for the purpose of developing a low-cost, robust and highly accurate navigation system for unmanned surface vehicles (USVs. A tightly-coupled integration approach is one of the most promising architectures to fuse the GNSS data with INS measurements. However, the resulting system and measurement models turn out to be nonlinear, and the sensor stochastic measurement errors are non-Gaussian and distributed in a practical system. Particle filter (PF, one of the most theoretical attractive non-linear/non-Gaussian estimation methods, is becoming more and more attractive in navigation applications. However, the large computation burden limits its practical usage. For the purpose of reducing the computational burden without degrading the system estimation accuracy, a quaternion-based adaptive unscented particle filter (AUPF, which combines the adaptive unscented Kalman filter (AUKF with PF, has been proposed in this paper. The unscented Kalman filter (UKF is used in the algorithm to improve the proposal distribution and generate a posterior estimates, which specify the PF importance density function for generating particles more intelligently. In addition, the computational complexity of the filter is reduced with the avoidance of the re-sampling step. Furthermore, a residual-based covariance matching technique is used to adapt the measurement error covariance. A trajectory simulator based on a dynamic model of USV is used to test the proposed algorithm. Results show that quaternion-based AUPF can significantly improve the overall navigation accuracy and reliability.

  12. Redox environment in stem and differentiated cells: A quantitative approach

    Directory of Open Access Journals (Sweden)

    O.G. Lyublinskaya

    2017-08-01

    Full Text Available Stem cells are believed to maintain a specific intracellular redox status through a combination of enhanced removal capacity and limited production of ROS. In the present study, we challenge this assumption by developing a quantitative approach for the analysis of the pro- and antioxidant ability of human embryonic stem cells in comparison with their differentiated descendants, as well as adult stem and non-stem cells. Our measurements showed that embryonic stem cells are characterized by low ROS level, low rate of extracellular hydrogen peroxide removal and low threshold for peroxide-induced cytotoxicity. However, biochemical normalization of these parameters to cell volume/protein leads to matching of normalized values in stem and differentiated cells and shows that tested in the present study cells (human embryonic stem cells and their fibroblast-like progenies, adult mesenchymal stem cells, lymphocytes, HeLa maintain similar intracellular redox status. Based on these observations, we propose to use ROS concentration averaged over the cell volume instead of ROS level as a measure of intracellular redox balance. We show that attempts to use ROS level for comparative analysis of redox status of morphologically different cells could lead to false conclusions. Methods for the assessment of ROS concentration based on flow cytometry analysis with the use of H2DCFDA dye and HyPer, genetically encoded probe for hydrogen peroxide, are discussed.

  13. Anticipating, complete and lag synchronizations in RC phase-shift network based coupled Chua's circuits without delay.

    Science.gov (United States)

    Srinivasan, K; Senthilkumar, D V; Raja Mohamed, I; Murali, K; Lakshmanan, M; Kurths, J

    2012-06-01

    We construct a new RC phase shift network based Chua's circuit, which exhibits a period-doubling bifurcation route to chaos. Using coupled versions of such a phase-shift network based Chua's oscillators, we describe a new method for achieving complete synchronization (CS), approximate lag synchronization (LS), and approximate anticipating synchronization (AS) without delay or parameter mismatch. Employing the Pecora and Carroll approach, chaos synchronization is achieved in coupled chaotic oscillators, where the drive system variables control the response system. As a result, AS or LS or CS is demonstrated without using a variable delay line both experimentally and numerically.

  14. Impacts of Satellite-Based Snow Albedo Assimilation on Offline and Coupled Land Surface Model Simulations.

    Directory of Open Access Journals (Sweden)

    Tao Wang

    Full Text Available Seasonal snow cover in the Northern Hemisphere is the largest component of the terrestrial cryosphere and plays a major role in the climate system through strong positive feedbacks related to albedo. The snow-albedo feedback is invoked as an important cause for the polar amplification of ongoing and projected climate change, and its parameterization across models is an important source of uncertainty in climate simulations. Here, instead of developing a physical snow albedo scheme, we use a direct insertion approach to assimilate satellite-based surface albedo during the snow season (hereafter as snow albedo assimilation into the land surface model ORCHIDEE (ORganizing Carbon and Hydrology In Dynamic EcosystEms and assess the influences of such assimilation on offline and coupled simulations. Our results have shown that snow albedo assimilation in both ORCHIDEE and ORCHIDEE-LMDZ (a general circulation model of Laboratoire de Météorologie Dynamique improve the simulation accuracy of mean seasonal (October throughout May snow water equivalent over the region north of 40 degrees. The sensitivity of snow water equivalent to snow albedo assimilation is more pronounced in the coupled simulation than the offline simulation since the feedback of albedo on air temperature is allowed in ORCHIDEE-LMDZ. We have also shown that simulations of air temperature at 2 meters in ORCHIDEE-LMDZ due to snow albedo assimilation are significantly improved during the spring in particular over the eastern Siberia region. This is a result of the fact that high amounts of shortwave radiation during the spring can maximize its snow albedo feedback, which is also supported by the finding that the spatial sensitivity of temperature change to albedo change is much larger during the spring than during the autumn and winter. In addition, the radiative forcing at the top of the atmosphere induced by snow albedo assimilation during the spring is estimated to be -2.50 W m-2, the

  15. Impacts of Satellite-Based Snow Albedo Assimilation on Offline and Coupled Land Surface Model Simulations.

    Science.gov (United States)

    Wang, Tao; Peng, Shushi; Krinner, Gerhard; Ryder, James; Li, Yue; Dantec-Nédélec, Sarah; Ottlé, Catherine

    2015-01-01

    Seasonal snow cover in the Northern Hemisphere is the largest component of the terrestrial cryosphere and plays a major role in the climate system through strong positive feedbacks related to albedo. The snow-albedo feedback is invoked as an important cause for the polar amplification of ongoing and projected climate change, and its parameterization across models is an important source of uncertainty in climate simulations. Here, instead of developing a physical snow albedo scheme, we use a direct insertion approach to assimilate satellite-based surface albedo during the snow season (hereafter as snow albedo assimilation) into the land surface model ORCHIDEE (ORganizing Carbon and Hydrology In Dynamic EcosystEms) and assess the influences of such assimilation on offline and coupled simulations. Our results have shown that snow albedo assimilation in both ORCHIDEE and ORCHIDEE-LMDZ (a general circulation model of Laboratoire de Météorologie Dynamique) improve the simulation accuracy of mean seasonal (October throughout May) snow water equivalent over the region north of 40 degrees. The sensitivity of snow water equivalent to snow albedo assimilation is more pronounced in the coupled simulation than the offline simulation since the feedback of albedo on air temperature is allowed in ORCHIDEE-LMDZ. We have also shown that simulations of air temperature at 2 meters in ORCHIDEE-LMDZ due to snow albedo assimilation are significantly improved during the spring in particular over the eastern Siberia region. This is a result of the fact that high amounts of shortwave radiation during the spring can maximize its snow albedo feedback, which is also supported by the finding that the spatial sensitivity of temperature change to albedo change is much larger during the spring than during the autumn and winter. In addition, the radiative forcing at the top of the atmosphere induced by snow albedo assimilation during the spring is estimated to be -2.50 W m-2, the magnitude of

  16. Ocean redox change at the Permian-Triassic mass extinction

    DEFF Research Database (Denmark)

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

    2013-01-01

    and marine (mass) ex¬tinction. The geographic and temporal extend and the intensity (ferruginous vs. euxinic) of anoxic con¬ditions is, however, strongly debated and not well constraint. This complicates understanding of close coupling between Earth’s physical, chemical and bi¬ological processes. We studied...... outgassing from the Siberian Traps. We measured redox-sensitive trace element concentrations (e.g. Mo, Cu, U) and the speciation of iron [Fe-HR/Fe-T and Fe-PY/ Fe- HR] in marine sediments from Svalbard (Festningen). We compare these data to additional, new, high-lati-tude data from eastern Greenland...

  17. Two-color optical charge-coupled-device-based pyrometer using a two-peak filter.

    Science.gov (United States)

    Fu, Tairan; Zhao, Huan; Zeng, Jun; Zhong, Maohua; Shi, Congling

    2010-12-01

    A two-color optical charge-coupled-device (CCD)-based pyrometer was developed using a multipeak interference filter with a color CCD sensor to measure multicolor signals with specified wavelengths. The effective and simple method adjusts the fixed spectrum response characteristics of a color CCD to allow improved temperature measurements. This pyrometer system not only has the advantage of traditional two-color (two-wavelength) pyrometry, but also overcomes the restrictions of color CCDs that can only be applied in waveband measurements. The measurement performance of the system using a two-peak filter (λ(1)=643 nm, λ(2)=564 nm) was evaluated by blackbody experiments. The results show that the low temperature detection limit is increased about 200 K with an increase in the sensitivity of the measured signals compared with the original system without two-peak filter [Fu, et al., Opt. Laser Technol. 42, 586 (2010)]. And the effective temperature range is also increased when T > 1233 K. The measured ratio C(R)/C(G) is monotonically relative to the temperature, which simplifies the measurements. The temperature sensitivity of 2.49 is larger and more uniform than the temperature sensitivity of 1.36 in the previous original system. Thus, the measurement performance of the new system is greatly improved. Finally, as an application, the surface temperature distribution of stainless steel sample in hot environments was determined by this new CCD-based pyrometer. The results agree well with the spectrometer-based results and further verify the applicability of the new system.

  18. Breast mass segmentation in digital mammography based on pulse coupled neural network and level set method

    Science.gov (United States)

    Xie, Weiying; Ma, Yide; Li, Yunsong

    2015-05-01

    A novel approach to mammographic image segmentation, termed as PCNN-based level set algorithm, is presented in this paper. Just as its name implies, a method based on pulse coupled neural network (PCNN) in conjunction with the variational level set method for medical image segmentation. To date, little work has been done on detecting the initial zero level set contours based on PCNN algorithm for latterly level set evolution. When all the pixels of the input image are fired by PCNN, the small pixel value will be a much more refined segmentation. In mammographic image, the breast tumor presents big pixel value. Additionally, the mammographic image with predominantly dark region, so that we firstly obtain the negative of mammographic image with predominantly dark region except the breast tumor before all the pixels of an input image are fired by PCNN. Therefore, in here, PCNN algorithm is employed to achieve mammary-specific, initial mass contour detection. After that, the initial contours are all extracted. We define the extracted contours as the initial zero level set contours for automatic mass segmentation by variational level set in mammographic image analysis. What's more, a new proposed algorithm improves external energy of variational level set method in terms of mammographic images in low contrast. In accordance with the gray scale of mass region in mammographic image is higher than the region surrounded, so the Laplace operator is used to modify external energy, which could make the bright spot becoming much brighter than the surrounded pixels in the image. A preliminary evaluation of the proposed method performs on a known public database namely MIAS, rather than synthetic images. The experimental results demonstrate that our proposed approach can potentially obtain better masses detection results in terms of sensitivity and specificity. Ultimately, this algorithm could lead to increase both sensitivity and specificity of the physicians' interpretation of

  19. A soluble-lead redox flow battery with corrugated graphite sheet and ...

    Indian Academy of Sciences (India)

    2012-08-03

    Aug 3, 2012 ... 1. Introduction. Intermittent and unpredictable nature of renewable energy from sun and wind demands them to be coupled with an energy storage system. This energy storage requirement has stimulated a renaissance in redox-flow batteries wherein energy and power are decoupled and energy more than.

  20. Large-scale energy storage. Investigating improvements of redox flow batteries

    CSIR Research Space (South Africa)

    Swartbooi, A

    2008-11-01

    Full Text Available and more sustainable energy source. One problem however lies with the intermittent nature of the solar energy source, coupled with a mismatch between generation and use. Redox flow batteries provide a means to bridge the time lag between the availability...