SERS as a tool for in vitro toxicology.

PubMed

Fisher, Kate M; McLeish, Jennifer A; Jamieson, Lauren E; Jiang, Jing; Hopgood, James R; McLaughlin, Stephen; Donaldson, Ken; Campbell, Colin J

2016-06-23

Measuring markers of stress such as pH and redox potential are important when studying toxicology in in vitro models because they are markers of oxidative stress, apoptosis and viability. While surface enhanced Raman spectroscopy is ideally suited to the measurement of redox potential and pH in live cells, the time-intensive nature and perceived difficulty in signal analysis and interpretation can be a barrier to its broad uptake by the biological community. In this paper we detail the development of signal processing and analysis algorithms that allow SERS spectra to be automatically processed so that the output of the processing is a pH or redox potential value. By automating signal processing we were able to carry out a comparative evaluation of the toxicology of silver and zinc oxide nanoparticles and correlate our findings with qPCR analysis. The combination of these two analytical techniques sheds light on the differences in toxicology between these two materials from the perspective of oxidative stress.

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

PubMed Central

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

2017-01-01

We present an innovative electrochemical probe for the monitoring of pH, redox potential and conductivity in near-field rocks of deep geological radioactive waste repositories. The probe is composed of a monocrystalline antimony electrode for pH sensing, four AgCl/Ag-based reference or Cl− selective electrodes, one Ag2S/Ag-based reference or S2− selective electrode, as well as four platinum electrodes, a gold electrode and a glassy-carbon electrode for redox potential measurements. Galvanostatic electrochemistry impedance spectroscopy using AgCl/Ag-based and platinum electrodes measure conductivity. The use of such a multi-parameter probe provides redundant information, based as it is on the simultaneous behaviour under identical conditions of different electrodes of the same material, as well as on that of electrodes made of different materials. This identifies the changes in physical and chemical parameters in a solution, as well as the redox reactions controlling the measured potential, both in the solution and/or at the electrode/solution interface. Understanding the electrochemical behaviour of selected materials thus is a key point of our research, as provides the basis for constructing the abacuses needed for developing robust and reliable field sensors. PMID:28608820

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

PubMed

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

2017-06-13

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

Influence of microbial growth in the redox potential of fermented cucumbers

USDA-ARS?s Scientific Manuscript database

Commonly, pH measurements are used during the production of fermented cucumbers to indirectly monitor growth of lactic acid bacteria (LAB) and acid production. Redox potential (Eh) measurements, which are determined by the flux of electrons in a system, could serve as a more accurate tool to monitor...

The Role of Ru Redox in pH-Dependent Oxygen Evolution on Rutile Ruthenium Dioxide Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoerzinger, Kelsey A.; Rao, Reshma R.; Wang, Xiao Renshaw

Rutile RuO 2 is known to exhibit high catalytic activity for the oxygen evolution reaction (OER) and large pseudocapacitance associated with redox of surface Ru, however the mechanistic link between these properties and the role of pH is yet to be understood. Here we report that the OER activities of the (101), (001) and (111) RuO 2 surfaces were found to increase while the potential of a pseudocapacitive feature just prior to OER shifted to lower potentials (“super-Nernstian” shift) with increasing pH on the reversible hydrogen electrode (RHE) scale. This behavior is in contrast to the (100) and (110) surfacesmore » that have pH-independent Ru redox and OER activity. The link in catalytic and pseudocapacitive behavior illustrates the importance of this redox feature in generating active sites, building new mechanistic understanding of the OER.« less

Tendency for oxidation of annelid hemoglobin at alkaline pH and dissociated states probed by redox titration.

PubMed

Bispo, Jose Ailton Conceicao; Landini, Gustavo Fraga; Santos, Jose Luis Rocha; Norberto, Douglas Ricardo; Bonafe, Carlos Francisco Sampaio

2005-08-01

The redox titration of extracellular hemoglobin of Glossoscolex paulistus (Annelidea) was investigated in different pH conditions and after dissociation induced by pressure. Oxidation increased with increasing pH, as shown by the reduced amount of ferricyanide necessary for the oxidation of hemoglobin. This behavior was the opposite of that of vertebrate hemoglobins. The potential of half oxidation (E1/2) changed from -65.3 to +146.8 mV when the pH increased from 4.50 to 8.75. The functional properties indicated a reduction in the log P50 from 1.28 to 0.28 in this pH range. The dissociation at alkaline pH or induced by high pressure, confirmed by HPLC gel filtration, suggested that disassembly of the hemoglobin could be involved in the increased potential for oxidation. These results suggest that the high stability and prolonged lifetime common to invertebrate hemoglobins is related to their low tendency to oxidize at acidic pH, in contrast to vertebrate hemoglobins.

Demonstration Results of Phytoremediation of Explosives-Contaminated Groundwater Using Constructed Wetlands at the Milan Army Ammunition Plant, Milan, Tennessee Volume I (Phase II Demonstration Results).

DTIC Science & Technology

1998-12-01

influence community respiration, photosynthesis, solubility of dissolved oxygen, redox potential, biochemical reaction rates, and ensuing treatment...Conductivity 15-8 15.1.3.5 Dissolved Oxygen Concentration 15-12 15.1.3.6 Redox Potential 15-14 15.1.3.7 pH 15-16 15.1.3.8 Nutrients and Water Quality 15-19...Average Redox Potential of Wetland Waters From June 17, 6-27 1996, to September 16, 1997 Phytoremediation Demonstration Milan AAP FIGURE NUMBER

The concept of electron activity and its relation to redox potentials in aqueous geochemical systems

USGS Publications Warehouse

Thorstenson, D.C.

1984-01-01

The definition of a formal thermodynamic activity of electrons in redox reactions appears in the literature of the 1920's. The concept of pe as -log (electron activity) was introduced by Jorgensen in 1945 and popularized in the geochemical literature by Sillen, who considered pe and pH as master variables in geochemical reactions. The physical significance of the concept of electron activity was challenged as early as 1928. However, only in the last two decades have sufficient thermodynamic data become available to examine this question quantitatively. The chemical nature of hydrated electrons differs greatly from that of hydrated protons, and thermodynamic data show that hydrated electrons cannot exist at physically meaningful equilibrium concentrations under natural conditions. This has important consequences for the understanding of redox processes in natural waters. These are: (1) the analogy between pe and pH as master variables is generally carried much further than is justified; (2) a thermodynamically meaningful value of redox potential cannot be assigned to disequilibrium systems; (3) the most useful approach to the study of redox characteristics is the analysis and study of multiple redox couples in the system; and (4) for all practical purposes, thermodynamically defined redox potentials do not exist (and thus cannot be measured) in natural waters. The overall implication for natural systems is that, in terms of redox reactions, each case must be considered on an individual and detailed basis. Field studies would appear to be a mandatory part of any site-specific study; conclusions regarding redox processes cannot be based solely on electrode measurements or thermodynamic stability calculations. (USGS)

Thermodynamic properties of an emerging chemical disinfectant, peracetic acid.

PubMed

Zhang, Chiqian; Brown, Pamela J B; Hu, Zhiqiang

2018-04-15

Peracetic acid (PAA or CH 3 COOOH) is an emerging disinfectant with a low potential to form carcinogenic disinfection by-products (DBPs). Basic thermodynamic properties of PAA are, however, absent or inconsistently reported in the literature. This review aimed to summarize important thermodynamic properties of PAA, including standard Gibbs energy of formation and oxidation-reduction (redox) potential. The standard Gibbs energies of formation of CH 3 COOOH (aq) , CH 3 COOOH (g) , CH 3 COOOH (l) , and CH 3 COOO (aq) - are -299.41kJ·mol -1 , -283.02kJ·mol -1 , -276.10kJ·mol -1 , and -252.60kJ·mol -1 , respectively. The standard redox potentials of PAA are 1.748V and 1.005V vs. standard hydrogen electrode (SHE) at pH 0 and pH 14, respectively. Under biochemical standard state conditions (pH 7, 25°C, 101,325Pa), PAA has a redox potential of 1.385V vs. SHE, higher than many disinfectants. Finally, the environmental implications of the thermodynamic properties of PAA were systematically discussed. Those properties can be used to predict the physicochemical and biological behavior of aquatic systems exposed to PAA. Copyright © 2017 Elsevier B.V. All rights reserved.

Redox-mediated regulation of connexin proteins; focus on nitric oxide.

PubMed

García, Isaac E; Sánchez, Helmuth A; Martínez, Agustín D; Retamal, Mauricio A

2018-01-01

Connexins are membrane proteins that form hemichannels and gap junction channels at the plasma membrane. Through these channels connexins participate in autocrine and paracrine intercellular communication. Connexin-based channels are tightly regulated by membrane potential, phosphorylation, pH, redox potential, and divalent cations, among others, and the imbalance of this regulation have been linked to many acquired and genetic diseases. Concerning the redox potential regulation, the nitric oxide (NO) has been described as a modulator of the hemichannels and gap junction channels properties. However, how NO regulates these channels is not well understood. In this mini-review, we summarize the current knowledge about the effects of redox potential focused in NO on the trafficking, formation and functional properties of hemichannels and gap junction channels. Copyright © 2017 Elsevier B.V. All rights reserved.

n-MoSe2 photoelectrochemical halogen storage cell

NASA Astrophysics Data System (ADS)

Ang, P. G. P.; Sammells, A. F.

1982-01-01

In the study reported here, single-crystal n-MoSe2 photoanodes are investigated in a variety of halogen redox couples. The photoanode is prepared by allowing the silver epoxy cement to come into contact with the front surface of the crystal before being insulated from the redox electrolyte with paraffin wax. This photoanode is evaluated in bromine redox electrolytes in various pH ranges. In 1M HBr + 1M Br2 (pH, approximately zero), the initial open-circuit potential of the MoSe2 versus a platinum reference electrode in the same electrolyte is -130 mV in the dark and -480 mV under 200 mW/sq cm xenon illumination. It is noted that improved performance could be achieved with such crystals by subjecting them to an anodic polarization of around 1 volt from the initial resting potential, a current of about 5 mA/sq cm flowing in the dark.

Complexation Key to a pH Locked Redox Reaction

ERIC Educational Resources Information Center

Rizvi, Masood Ahmad; Dangat, Yuvraj; Shams, Tahir; Khan, Khaliquz Zaman

2016-01-01

An unfavorable pH can block a feasible electron transfer for a pH dependent redox reaction. In this experiment, a series of potentiometric titrations demonstrate the sequential loss in feasibility of iron(II) dichromate redox reaction over a pH range of 0-4. The pH at which this reaction failed to occur was termed as a pH locked reaction. The…

Redox Chemistry in Laccase-Catalyzed Oxidation of N-Hydroxy Compounds

PubMed Central

Xu, Feng; Kulys, Juozas J.; Duke, Kyle; Li, Kaichang; Krikstopaitis, Kastis; Deussen, Heinz-Josef W.; Abbate, Eric; Galinyte, Vilija; Schneider, Palle

2000-01-01

1-Hydroxybenzotriazole, violuric acid, and N-hydroxyacetanilide are three N-OH compounds capable of mediating a range of laccase-catalyzed biotransformations, such as paper pulp delignification and degradation of polycyclic hydrocarbons. The mechanism of their enzymatic oxidation was studied with seven fungal laccases. The oxidation had a bell-shaped pH-activity profile with an optimal pH ranging from 4 to 7. The oxidation rate was found to be dependent on the redox potential difference between the N-OH substrate and laccase. A laccase with a higher redox potential or an N-OH compound with a lower redox potential tended to have a higher oxidation rate. Similar to the enzymatic oxidation of phenols, phenoxazines, phenothiazines, and other redox-active compounds, an “outer-sphere” type of single-electron transfer from the substrate to laccase and proton release are speculated to be involved in the rate-limiting step for N-OH oxidation. PMID:10788380

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

PubMed

Chango, Gabriela; Palacio, Edwin; Cerdà, Víctor

2018-08-15

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

Redox polymer mediation for enzymatic biofuel cells

NASA Astrophysics Data System (ADS)

Gallaway, Joshua

Mediated biocatalytic cathodes prepared from the oxygen-reducing enzyme laccase and redox-conducting osmium hydrogels were characterized for use as cathodes in enzymatic biofuel cells. A series of osmium-based redox polymers was synthesized with redox potentials spanning the range from 0.11 V to 0.85 V (SHE), and the resulting biocatalytic electrodes were modeled to determine reaction kinetic constants using the current response, measured osmium concentration, and measured apparent electron diffusion. As in solution-phase systems, the bimolecular rate constant for mediation was found to vary greatly with mediator potential---from 250 s-1M-1 when mediator and enzyme were close in potential to 9.4 x 10 4 s-1M-1 when this overpotential was large. Optimum mediator potential for a cell operating with a non-limiting platinum anode and having no mass transport limitation from bulk solution was found to be 0.66 V (SHE). Redox polymers were synthesized under different concentrations, producing osmium variation. An increase from 6.6% to 7.2% osmium increased current response from 1.2 to 2.1 mA/cm2 for a planar film in 40°C oxygen-saturated pH 4 buffer, rotating at 900 rpm. These results translated to high surface area electrodes, nearly doubling current density to 13 mA/cm2, the highest to date for such an electrode. The typical fungal laccase from Trametes versicolor was replaced by a bacterially-expressed small laccase from Streptomyces coelicolor, resulting in biocatalytic films that reduced oxygen at increased pH, with full functionality at pH 7, producing 1.5 mA/cm 2 in planar configuration. Current response was biphasic with pH, matching the activity profile of the free enzyme in solution. The mediated enzyme electrode system was modeled with respect to apparent electron diffusion, mediator concentration, and transport of oxygen from bulk solution, all of which are to some extent controlled by design. Each factor was found to limit performance in certain circumstances. In systems relying on stagnant solution, oxygen transport was found to dominate. However, if mass transport was efficient, differences in mediator design greatly affected performance.

Antioxidative properties of hydroxycinnamic acid derivatives and a phenylpropanoid glycoside. A pulse radiolysis study

NASA Astrophysics Data System (ADS)

Lin, Weizhen; Navaratnam, Suppiah; Yao, Side; Lin, Nianyun

1998-10-01

Spectral and redox properties of the phenoxyl radicals from hydroxycinnamic acid derivatives and one selected component of phenylpropanoid glycosides, verbascoside, were studied using pulse radiolysis techniques. On the basis of the pH dependence of phenoxyl radical absorptions, the p Ka values for deprotonation of sinapic acid radical and ferulic acid radical are 4.9 and 5.2. The rate constants of one electron oxidation of those antioxidants by azide radical and bromide radical ion were determined at pH 7. The redox potentials of those antioxidants were determined as 0.59-0.71 V vs NHE at pH 7 with reference standard 4-methoxyphenol and resorcinol.

Redox reactions and weak buffering capacity lead to acidification in the Chesapeake Bay.

PubMed

Cai, Wei-Jun; Huang, Wei-Jen; Luther, George W; Pierrot, Denis; Li, Ming; Testa, Jeremy; Xue, Ming; Joesoef, Andrew; Mann, Roger; Brodeur, Jean; Xu, Yuan-Yuan; Chen, Baoshan; Hussain, Najid; Waldbusser, George G; Cornwell, Jeffrey; Kemp, W Michael

2017-08-28

The combined effects of anthropogenic and biological CO 2 inputs may lead to more rapid acidification in coastal waters compared to the open ocean. It is less clear, however, how redox reactions would contribute to acidification. Here we report estuarine acidification dynamics based on oxygen, hydrogen sulfide (H 2 S), pH, dissolved inorganic carbon and total alkalinity data from the Chesapeake Bay, where anthropogenic nutrient inputs have led to eutrophication, hypoxia and anoxia, and low pH. We show that a pH minimum occurs in mid-depths where acids are generated as a result of H 2 S oxidation in waters mixed upward from the anoxic depths. Our analyses also suggest a large synergistic effect from river-ocean mixing, global and local atmospheric CO 2 uptake, and CO 2 and acid production from respiration and other redox reactions. Together they lead to a poor acid buffering capacity, severe acidification and increased carbonate mineral dissolution in the USA's largest estuary.The potential contribution of redox reactions to acidification in coastal waters is unclear. Here, using measurements from the Chesapeake Bay, the authors show that pH minimum occurs at mid-depths where acids are produced via hydrogen sulfide oxidation in waters mixed upward from anoxic depths.

Intramolecular electron transport in quinoprotein alcohol dehydrogenase of Acetobacter methanolicus: a redox-titration study

PubMed

Frébortova; Matsushita; Arata; Adachi

1998-01-27

Quinohemoprotein-cytochrome c complex alcohol dehydrogenase (ADH) of acetic acid bacteria consists of three subunits, of which subunit I contains pyrroloquinoline quinone (PQQ) and heme c, and subunit II contains three heme c components. The PQQ and heme c components are believed to be involved in the intramolecular electron transfer from ethanol to ubiquinone. To study the intramolecular electron transfer in ADH of Acetobacter methanolicus, the redox potentials of heme c components were determined with ADH complex and the isolated subunits I and II of A. methanolicus, as well as hybrid ADH consisting of the subunit I/III complex of Gluconobacter suboxydans ADH and subunit II of A. methanolicus ADH. The redox potentials of hemes c in ADH complex were -130, 49, 188, and 188 mV at pH 7.0 and 24, 187, 190, and 255 mV at pH 4.5. In hybrid ADH, one of these heme c components was largely changed in the redox potential. Reduced ADH was fully oxidized with potassium ferricyanide, while ubiquinone oxidized the enzyme partially. The results indicate that electrons extracted from ethanol at PQQ site are transferred to ubiquinone via heme c in subunit I and two of the three hemes c in subunit II. Copyright 1998 Elsevier Science B.V.

AFM Study of Charge Transfer Between Metals Due to the Oxygen Redox Couple in Water

NASA Astrophysics Data System (ADS)

Trombley, Jeremy; Panthani, Tessie; Sankaran, Mohan; Angus, John; Kash, Kathleen

2010-03-01

The oxygen redox couple in an adsorbed water film can pin the Fermi level at the surfaces of diamond, GaN and ZnO.footnotetextV. Chakrapani, C. Pendyala, K. Kash, A. B. Anderson, M. K. Sunkara and J. C. Angus, J. Am. Chem. Soc. 130 (2008) 12944-12952, and ref. 6 therein. We report here preliminary observations of the same phenomenon at metal surfaces. A Pt-coated atomic force microscope (AFM) tip was used to take force-distance measurements on Au, Ag, and Pt surfaces placed in pH-controlled water. The work functions of these surfaces vary over ˜2eV and span the electrochemical potential range of the oxygen redox couple, which varies with pH according to the Nernst equation. Adjusting the pH of the water from 4 to 12 allowed us to change the redox potential energy from -5.42eV to -4.95eV, changing the surface charge and the associated screening charge and modulating the pull-off force. This work has relevance to AFM of many materials in air, and to contact electrification, mechanical friction, and nanoscale corona discharges.

Simulation of electron-proton coupling with a Monte Carlo method: application to cytochrome c3 using continuum electrostatics.

PubMed Central

Baptista, A M; Martel, P J; Soares, C M

1999-01-01

A new method is presented for simulating the simultaneous binding equilibrium of electrons and protons on protein molecules, which makes it possible to study the full equilibrium thermodynamics of redox and protonation processes, including electron-proton coupling. The simulations using this method reflect directly the pH and electrostatic potential of the environment, thus providing a much closer and realistic connection with experimental parameters than do usual methods. By ignoring the full binding equilibrium, calculations usually overlook the twofold effect that binding fluctuations have on the behavior of redox proteins: first, they affect the energy of the system by creating partially occupied sites; second, they affect its entropy by introducing an additional empty/occupied site disorder (here named occupational entropy). The proposed method is applied to cytochrome c3 of Desulfovibrio vulgaris Hildenborough to study its redox properties and electron-proton coupling (redox-Bohr effect), using a continuum electrostatic method based on the linear Poisson-Boltzmann equation. Unlike previous studies using other methods, the full reduction order of the four hemes at physiological pH is successfully predicted. The sites more strongly involved in the redox-Bohr effect are identified by analysis of their titration curves/surfaces and the shifts of their midpoint redox potentials and pKa values. Site-site couplings are analyzed using statistical correlations, a method much more realistic than the usual analysis based on direct interactions. The site found to be more strongly involved in the redox-Bohr effect is propionate D of heme I, in agreement with previous studies; other likely candidates are His67, the N-terminus, and propionate D of heme IV. Even though the present study is limited to equilibrium conditions, the possible role of binding fluctuations in the concerted transfer of protons and electrons under nonequilibrium conditions is also discussed. The occupational entropy contributions to midpoint redox potentials and pKa values are computed and shown to be significant. PMID:10354425

Sulfonamido tripods: tuning redox potentials via ligand modifications

PubMed Central

Lau, Nathanael; Ziller, Joseph W.

2014-01-01

A series of FeII–OH2 complexes were synthesized with ligands based on the tetradentate sulfonamido tripod N,N',N"-[2,2',2"-nitrilotris(ethane-2,1-diyl)]-tris-({R-Ph}-sulfonamido). These complexes differ by the substituent on the aryl rings and were fully characterized, including their molecular structures via X-ray diffraction methods. All the complexes were five-coordinate with trigonal bipyramidal geometry. A linear correlation was observed between the electronic effects of each ligand, given by the Hammett constants of the para-substituents, and the potential of the FeII/FeIII redox couple, which were determined using cyclic voltammetry. It was found that the range of redox potentials for the complexes spanned approximately 160 mV. PMID:25419035

Sulfonamido tripods: tuning redox potentials via ligand modifications.

PubMed

Lau, Nathanael; Ziller, Joseph W; Borovik, A S

2015-01-08

A series of Fe II -OH 2 complexes were synthesized with ligands based on the tetradentate sulfonamido tripod N , N ', N "-[2,2',2"-nitrilotris(ethane-2,1-diyl)]-tris-({R-Ph}-sulfonamido). These complexes differ by the substituent on the aryl rings and were fully characterized, including their molecular structures via X-ray diffraction methods. All the complexes were five-coordinate with trigonal bipyramidal geometry. A linear correlation was observed between the electronic effects of each ligand, given by the Hammett constants of the para -substituents, and the potential of the Fe II /Fe III redox couple, which were determined using cyclic voltammetry. It was found that the range of redox potentials for the complexes spanned approximately 160 mV.

Gold(III) biosorption and bioreduction with the brown alga Fucus vesiculosus.

PubMed

Mata, Y N; Torres, E; Blázquez, M L; Ballester, A; González, F; Muñoz, J A

2009-07-30

In this paper, the bioreduction of Au(III) to Au(0) using biomass of the brown alga Fucus vesiculosus was investigated. The recovery and reduction process took place in two stages with an optimum pH range of 4-9 with a maximum uptake obtained at pH 7. In the first stage, an induction period previous to gold reduction, the variation of pH, redox potential and gold concentration in solution was practically negligible and no color change was observed. In the second stage, the gold reduction was followed by a sharp decrease of gold concentration, pH and redox potential of solution and a color change from yellow to reddish purple. Hydroxyl groups present in the algal polysaccharides were involved in the gold bioreduction. Metallic gold was detected as microprecipitates on the biomass surface and in colloidal form as nanoparticles in the solution. Bioreduction with F. vesiculosus could be an alternative and environmentally friendly process that can be used for recovering gold from dilute hydrometallurgical solutions and leachates of electronic scraps, and for the synthesis of gold nanoparticles of different size and shape.

DFT-Supported Threshold Ionization Study of Chromium Biphenyl Complexes: Unveiling the Mechanisms of Substituent Influence on Redox Properties of Sandwich Compounds.

PubMed

Ketkov, Sergey Yu; Tzeng, Sheng-Yuan; Wu, Pei-Ying; Markin, Gennady V; Tzeng, Wen-Bih

2017-10-04

High-resolution mass-analyzed threshold ionization (MATI) spectra of (η 6 -Ph 2 ) 2 Cr and (η 6 -Ph 2 )(η 6 -PhMe)Cr demonstrate that the Ph groups work as electron donors, decreasing the ionization energy of the gas-phase bisarene complexes. In contrast to electrochemical data, a close similarity of the Ph and Me group effects on the oxidation of free sandwich molecules has been revealed. However, DFT calculations testify for the opposite shifts of the electron density caused by the Me and Ph substituents in the neutral complexes, the latter behaving as an electron-accepting fragment. On the contrary, in the bisarene cations, the Ph group becomes a stronger donor than methyl. This change provides the similar substituent effects observed with the MATI experiment. On the other hand, the well-documented opposite influence of the Me and Ph fragments on the redox potential of the (η 6 -arene) 2 Cr +/0 couple in solution appears to be a result of solvation effects but not intramolecular interactions as shown for the first time in this work. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sorption and biodegradation of six pharmaceutically active compounds under four different redox conditions.

PubMed

de Wilt, Arnoud; He, Yujie; Sutton, Nora; Langenhoff, Alette; Rijnaarts, Huub

2018-02-01

This study explored the removal of six pharmaceutically active compounds (PhACs) in lab-scale experiments with sediments under four redox conditions, namely aerobic, nitrate reducing, sulfate reducing, and methanogenic conditions using batch and column set-ups. Redox conditions were found to influence PhAC removal by sorption and biodegradation. The most optimal PhAC removal was observed at the outer ranges of the redox spectrum, i.e. either aerobic or deep anaerobic (sulfate reducing and methanogenic conditions), whereas nitrate reducing conditions were found least effective for PhACs biodegradation and sorption. For instance, sorption coefficient K d values for metoprolol in column experiments were 90, 65, 42 and 11 L/kg for sulfate reducing, methanogenic, aerobic and nitrate reducing conditions, respectively. For the same conditions K d values for propranolol were 101, 94, 55 and 55 L/kg, respectively. As expected, biodegradation efficiencies were highest under aerobic conditions, showing >99% removal of caffeine and naproxen, but no removal for propranolol and carbamazepine. The adaptive capacity of sediment was demonstrated by pre-exposure to PhACs leading to improved PhAC biodegradation. The results of this study indicate the necessity to combine diverse redox conditions, including aerobic conditions, for maximizing PhAC removal by sorption and biodegradation. Furthermore, our findings stress the need for additional treatment measures as recalcitrant PhACs are not effectively removed under any redox condition. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Effects of pH and Redox Gradients on Prebiotic Organic Synthesis and the Generation of Free Energy in Simulated Hydrothermal Systems

NASA Astrophysics Data System (ADS)

Barge, L. M.; Flores, E.; Abedian, Y.; Maltais, T.; Cameron, R.; Hermis, N.; Chin, K.; Russell, M. J.; Baum, M. M.

2017-07-01

Hydrothermal minerals in alkaline vents can promote phosphorus and organic concentration, redox reactions driven by catalytic metal sulfides, and the ambient pH and redox gradients can affect the synthesis of organics.

In situ measurements of dissolved oxygen, pH and redox potential of biocathode microenvironments using microelectrodes.

PubMed

Wang, Zejie; Deng, Huan; Chen, Lihui; Xiao, Yong; Zhao, Feng

2013-03-01

Biofilms are the core component of bioelectrochemical systems (BESs). To understand the polarization effects on biocathode performance of BES, dissolved oxygen concentrations, pHs and oxidation-reduction potentials of biofilm microenvironments were determined in situ. The results showed that lower polarization potentials resulted in the generation of larger currents and higher pH values, as well as the consumption of more oxygen. Oxidation-reduction potentials of biofilms were mainly affected by polarization potentials of the electrode rather than the concentration of dissolved oxygen or pH value, and its changes in the potentials corresponded to the electric field distribution of the electrode surface. The results demonstrated that a sufficient supply of dissolved oxygen and pH control of the biocathode are necessary to obtain optimal performance of BESs; a lower polarization potential endowed microorganisms with a higher electrochemical activity. Copyright © 2012 Elsevier Ltd. All rights reserved.

INFLUENCE OF PH AND REDOX CONDITIONS ON COPPER LEACHING

EPA Science Inventory

Leaching behavior of metals from a mineral processing waste at varying pH and redox conditions was studies. Effect of combinations of pH and Eh on leaching of copper is described. Leaching of copper was found to be dependent on both pH and Eh. Higher concentrations of Cu were ...

pH and redox-responsive mixed micelles for enhanced intracellular drug release.

PubMed

Cai, Mengtan; Zhu, Kun; Qiu, Yongbin; Liu, Xinrong; Chen, Yuanwei; Luo, Xianglin

2014-04-01

In order to prepare pH and redox sensitive micelles, amphiphilic copolymers of poly (epsilon-caprolactone)-b-poly(2-(diethylamino) ethyl methacrylate) (PCL-PDEA) and disulfide-linked poly(ethyl glycol)-poly(epsilon-caprolactone) (mPEG-SS-PCL) were synthesized. The double-sensitive micelles were prepared simply by solvent-evaporating method with the mixed two copolymers. The pH sensitivity of the mixed micelles was confirmed by the change of micelle diameter/diameter distribution measured by dynamic lighting scattering (DLS) and the redox sensitivity of the mixed micelles was testified by the change of micellar morphous observed by scanning electron microscope (SEM). In vitro drug release showed that drug-loaded mixed micelles (mass ratio 5:5) could achieve above 90% of drug release under low pH and reducing condition within 10h. Moreover, the drug-loaded mixed micelles (mass ratio 5:5) showed the largest cellular toxicity compared with other drug-loaded micelles, while blank mixed micelles exhibited no toxicity. These results meant that the mixed micelles composed by the two amphiphilic copolymers can enhance intracellular drug release. It is concluded that the newly developed mixed micelles can serve as a potential drug delivery system for anticancer drugs. Copyright © 2014 Elsevier B.V. All rights reserved.

Mitochondrial redox and pH signaling occurs in axonal and synaptic organelle clusters.

PubMed

Breckwoldt, Michael O; Armoundas, Antonis A; Aon, Miguel A; Bendszus, Martin; O'Rourke, Brian; Schwarzländer, Markus; Dick, Tobias P; Kurz, Felix T

2016-03-22

Redox switches are important mediators in neoplastic, cardiovascular and neurological disorders. We recently identified spontaneous redox signals in neurons at the single mitochondrion level where transients of glutathione oxidation go along with shortening and re-elongation of the organelle. We now have developed advanced image and signal-processing methods to re-assess and extend previously obtained data. Here we analyze redox and pH signals of entire mitochondrial populations. In total, we quantified the effects of 628 redox and pH events in 1797 mitochondria from intercostal axons and neuromuscular synapses using optical sensors (mito-Grx1-roGFP2; mito-SypHer). We show that neuronal mitochondria can undergo multiple redox cycles exhibiting markedly different signal characteristics compared to single redox events. Redox and pH events occur more often in mitochondrial clusters (medium cluster size: 34.1 ± 4.8 μm(2)). Local clusters possess higher mitochondrial densities than the rest of the axon, suggesting morphological and functional inter-mitochondrial coupling. We find that cluster formation is redox sensitive and can be blocked by the antioxidant MitoQ. In a nerve crush paradigm, mitochondrial clusters form sequentially adjacent to the lesion site and oxidation spreads between mitochondria. Our methodology combines optical bioenergetics and advanced signal processing and allows quantitative assessment of entire mitochondrial populations.

High temperature hydrothermal vent fluids in Yellowstone Lake: Observations and insights from in-situ pH and redox measurements

NASA Astrophysics Data System (ADS)

Tan, Chunyang; Cino, Christie D.; Ding, Kang; Seyfried, William E.

2017-09-01

ROV investigation of hydrothermal fluids issuing from vents on the floor of Yellowstone lake revealed temperatures in excess of 170 °C - the highest temperature yet reported for vent fluids within Yellowstone National Park (YNP). The study site is east of Stevenson Island at depth of approximately 100-125 m. In-situ pH and redox measurements of vent fluids were made using solid state sensors designed to sustain the elevated temperatures and pressures. YSZ membrane electrode with Ag/Ag2O internal element and internal pressure balanced Ag/AgCl reference electrode were used to measure pH, while a platinum electrode provided redox constraints. Lab verification of the pH sensor confirmed excellent agreement with Nernst law predictions, especially at temperatures in excess of 120 °C. In-situ pH values of between 4.2 and 4.5 were measured for the vent fluids at temperatures of 120 to 150 °C. The slightly acidic vent fluids are likely caused by CO2 enrichment in association with magmatic degassing effects that occur throughout YNP. This is consistent with results of simple model calculations and direct observation of CO2 bubbles in the immediate vicinity of the lake floor vents. Simultaneous redox measurements indicated moderate to highly reducing conditions (- 0.2 to - 0.3 V). As typical of measurements of this kind, internal and external redox disequilibria likely preclude unambiguous determination of redox controlling reactions. Redox disequilibria, however, can be expected to drive microbial metabolism and diversity in the near vent environment. Thus, the combination of in-situ pH and redox sensor deployments may ultimately provide the requisite framework to better understand the microbiology of the newly discovered hot vents on Yellowstone lake floor.

Blood tolerant laccase by directed evolution.

PubMed

Mate, Diana M; Gonzalez-Perez, David; Falk, Magnus; Kittl, Roman; Pita, Marcos; De Lacey, Antonio L; Ludwig, Roland; Shleev, Sergey; Alcalde, Miguel

2013-02-21

High-redox potential laccases are powerful biocatalysts with a wide range of applications in biotechnology. We have converted a thermostable laccase from a white-rot fungus into a blood tolerant laccase. Adapting the fitness of this laccase to the specific composition of human blood (above neutral pH, high chloride concentration) required several generations of directed evolution in a surrogate complex blood medium. Our evolved laccase was tested in both human plasma and blood, displaying catalytic activity while retaining a high redox potential at the T1 copper site. Mutations introduced in the second coordination sphere of the T1 site shifted the pH activity profile and drastically reduced the inhibitory effect of chloride. This proof of concept that laccases can be adapted to function in extreme conditions opens an array of opportunities for implantable nanobiodevices, chemical syntheses, and detoxification. Copyright © 2013 Elsevier Ltd. All rights reserved.

Tunable pH and redox-responsive drug release from curcumin conjugated γ-polyglutamic acid nanoparticles in cancer microenvironment.

PubMed

Pillarisetti, Shameer; Maya, S; Sathianarayanan, S; Jayakumar, R

2017-11-01

Tunable pH and redox responsive polymer was prepared using γ-polyglutamic acid (γ-PGA) with linker 3-mercaptopropionic acid (3-MPA) (γ-PGA_SH) via oxidation to obtain redox responsive disulfide (γ-PGA_SS) backbone and adipic acid dihydrazide (ADH) (γ-PGA_SS_ADH) with hydrazide functional group for pH responsiveness. Further curcumin (Cur) was conjugated through hydrazone bond of the γ-PGA_SS_ADH via Schiff base reaction to obtain (γ-PGA_SS_ADH_Cur). The prepared systems were characterized by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, Electrospray ionization quadrupole time-of-flight mass spectrometry (ESI-Qq-TOF-MS/MS) and Solid state nuclear magnetic resonance (SS NMR) techniques. γ-PGA_SS_ADH_Cur formed self-assembled core shell nanoparticles (NPs) in existence of stabilized aqueous medium. γ-PGA_SS_ADH_Cur NPs maintained its stability in physiological condition. NPs tunable Cur release and cytotoxicity were observed for γ-PGA_SS_ADH_Cur NPs in both acidic and redox conditions mimicking the cancer microenvironment. γ-PGA_SS_ADH_Cur NPs uptake study showed via endocytosis mechanism resulted in the lysosomal entrapment of these NPs within the cell. γ-PGA_SS_ADH_Cur NPs exhibited a dual stimuli responsive drug delivery and can be used as a smart and potential drug delivery system in cancer microenvironment. Copyright © 2017 Elsevier B.V. All rights reserved.

Carbon-Nanotube-Supported Bio-Inspired Nickel Catalyst and Its Integration in Hybrid Hydrogen/Air Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gentil, Solène; Lalaoui, Noémie; Dutta, Arnab

A biomimetic nickel bis-diphosphine complex incorporating the amino-acid arginine in the outer coordination sphere, was immobilized on modified single-wall carbon nanotubes (SWCNTs) through electrostatic interactions. The sur-face-confined catalyst is characterized by a reversible 2-electron/2-proton redox process at potentials close to the equibrium potential of the H+/H2 couple. Consequently, the functionalized redox nanomaterial exhibits reversible electrocatalytic activity for the H2/2H+ interconversion over a broad range of pH. This system exhibits catalytic bias, analogous to hydrogenases, resulting in high turnover frequencies at low overpotentials for electrocatalytic H2 oxida-tion between pH 0 and 7. This allowed integrating such bio-inspired nanomaterial together with amore » multicopper oxi-dase at the cathode side in a hybrid bioinspired/enzymatic hydrogen fuel cell. This device delivers ~2 mW cm–2 with an open-circuit voltage of 1.0 V at room temperature and pH 5, which sets a new efficiency record for a bio-related hydrogen fuel cell with base metal catalysts.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simic, M.G.; Jovanovic, S.V.

One-electron oxidation of uric acid generates the urate radical, which was studied in aqueous solution by pulse radiolysis and oxygen-uptake measurements. Acid-base properties of the uric acid radical were determined, i.e., pK{sub a1} = 3.1 {plus minus} 0.1 and pK{sub a2} = 9.5 {plus minus} 0.1. The reaction of the radical with oxygen was too slow to be measured, k < 10{sup {minus}2} dm{sup 3} mol{sup {minus}1} s{sup {minus}1}. The one-electron-redox potential vs NHE, E{sub 7} = 0.59 V, was derived from the pH dependence of the redox potential, which was fitted through the values measured at pH 7 andmore » 8.9 and those previously determined at pH 13. Rapid reactions of uric acid with oxidizing species and peroxy radicals were indicative of uric acid as a possible water-soluble physiological antioxidant. Rapid reaction of uric acid with the guanyl radical indicates that uric acid may also act as a repair agent of oxidative damage to DNA bases.« less

An FeIII Azamacrocyclic Complex as a pH-Tunable Catholyte and Anolyte for Redox-Flow Battery Applications.

PubMed

Tsitovich, Pavel B; Kosswattaarachchi, Anjula M; Crawley, Matthew R; Tittiris, Timothy Y; Cook, Timothy R; Morrow, Janet R

2017-11-02

A reversible Fe 3+ /Fe 2+ redox couple of an azamacrocyclic complex is evaluated as an electrolyte with a pH-tunable potential range for aqueous redox-flow batteries (RFBs). The Fe III complex is formed by 1,4,7-triazacyclononane (TACN) appended with three 2-methyl-imidazole donors, denoted as Fe(Tim). This complex exhibits pH-sensitive redox couples that span E 1/2 (Fe 3+ /Fe 2+ )=317 to -270 mV vs. NHE at pH 3.3 and pH 12.8, respectively. The 590 mV shift in potential and kinetic inertness are driven by ionization of the imidazoles at various pH values. The Fe 3+ /Fe 2+ redox is proton-coupled at alkaline conditions, and bulk electrolysis is non-destructive. The electrolyte demonstrates high charge/discharge capacities at both acidic and alkaline conditions throughout 100 cycles. Given its tunable redox, fast electrochemical kinetics, exceptional stability/cyclability, this complex is promising for the design of aqueous RFB catholytes and anolytes that utilize the earth-abundant element iron. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox Reactions of Phenazine Antibiotics with Ferric (Hydr)oxides and Molecular Oxygen

PubMed Central

Wang, Yun; Newman, Dianne K.

2009-01-01

Phenazines are small redox-active molecules produced by a variety of bacteria. Beyond merely serving as antibiotics, recent studies suggest that phenazines play important physiological roles, including one in iron acquisition. Here we characterize the ability of four electrochemically reduced natural phenazines—pyocyanin (PYO), phenazine-1-carboxylate (PCA), phenazine-1-carboxamide, and 1-hydroxyphenazine (1-OHPHZ)—to reductively dissolve ferrihydrite and hematite in the pH range 5–8. Generally, the reaction rate is higher for a phenazine with a lower reduction potential, with the reaction between PYO and ferrihydrite at pH 5 being an exception; the rate decreases as the pH increases; the rate is higher for poorly crystalline ferrihydrite than for highly crystalline hematite. Ferric (hydr)oxide reduction by reduced phenazines can potentially be inhibited by oxygen, where O2 competes with Fe(III) as the final oxidant. The reactivity of reduced phenazines with O2 decreases in the order: PYO > 1-OHPHZ > PCA. Strikingly, reduced PYO, which is the least reactive phenazine with ferrihydrite and hematite at pH 7, is the most reactive phenazine with O2. These results imply that different phenazines may perform different functions in environments with gradients of iron and O2. PMID:18504969

Redox potential of shallow groundwater by 1-month continuous in situ potentiometric measurements

NASA Astrophysics Data System (ADS)

Ioka, Seiichiro; Muraoka, Hirofumi; Suzuki, Yota

2017-10-01

One-month continuous in situ potentiometric measurements of redox potential (Eh) were used to investigate the dominant redox processes in the shallow groundwater (i.e., <10 m) of a Holocene aquifer, Aomori City, northern Japan. The Eh values, which were determined using a platinum electrode, were -163, -169 and -173 mV, respectively, for three monitoring campaigns. The temperatures and pH values of shallow groundwater during all three periods were approximately 12 °C and 6.6, respectively. Dissolved oxygen and sulfide ion concentrations were not detected. Chemical analyses showed that the shallow groundwater is Na-Fe-HCO3 type, and contains over 40 mg/L of Fe (the dominant cation) and over 200 mg/L of HCO3 - (the dominant anion). A good fit was found between measured Eh values and Eh values calculated using thermodynamic data of fine-grained goethite. This suggests that Fe redox system is related to the Eh values of shallow groundwater in the Aomori City aquifer.

Effects of electrolytes on redox potentials through ion pairing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bird, Matthew J.; Iyoda, Tomokazu; Bonura, Nicholas

Here, reduction potentials have been determined for two molecules, benzophenone (BzPh) and perylene (Per), effectively in the complete absence of electrolyte as well as in the presence of three different supporting electrolytes in the moderately polar solvent THF. A description of how this can be so, and qualifications, are described in the discussion section. The primary tool in this work, pulse radiolysis, measures electron transfer (ET) equilibria in solution to obtain differences in redox potentials. Voltammetry measures redox potentials by establishing ET equilibria at electrodes, but electrolytes are needed for current flow. Results here show that without electrolyte the redoxmore » potentials were 100–451 mV more negative than those with 100 mM electrolyte. These changes depended both on the molecule and the electrolyte. In THF the dominant contributor to stabilization of radical anions by electrolyte was ion pairing. An equation was derived to give changes in redox potentials when electrolyte is added in terms of ion pair dissociation constants and activity coefficients. Definite values were determined for energetics, ΔG d°, of ion pairing. Values of ΔG d° for pairs with TBA + give some doubt that it is a “weakly-coordinating cation.” Computations with DFT methods were moderately successful at describing the ion paring energies.« less

Effects of electrolytes on redox potentials through ion pairing

DOE PAGES

Bird, Matthew J.; Iyoda, Tomokazu; Bonura, Nicholas; ...

2017-09-21

Here, reduction potentials have been determined for two molecules, benzophenone (BzPh) and perylene (Per), effectively in the complete absence of electrolyte as well as in the presence of three different supporting electrolytes in the moderately polar solvent THF. A description of how this can be so, and qualifications, are described in the discussion section. The primary tool in this work, pulse radiolysis, measures electron transfer (ET) equilibria in solution to obtain differences in redox potentials. Voltammetry measures redox potentials by establishing ET equilibria at electrodes, but electrolytes are needed for current flow. Results here show that without electrolyte the redoxmore » potentials were 100–451 mV more negative than those with 100 mM electrolyte. These changes depended both on the molecule and the electrolyte. In THF the dominant contributor to stabilization of radical anions by electrolyte was ion pairing. An equation was derived to give changes in redox potentials when electrolyte is added in terms of ion pair dissociation constants and activity coefficients. Definite values were determined for energetics, ΔG d°, of ion pairing. Values of ΔG d° for pairs with TBA + give some doubt that it is a “weakly-coordinating cation.” Computations with DFT methods were moderately successful at describing the ion paring energies.« less

Mechanisms governing the leaching of soil metals as a result of disposal of olive mill wastewater on agricultural soils.

PubMed

Aharonov-Nadborny, R; Tsechansky, L; Raviv, M; Graber, E R

2018-07-15

Olive mill wastewater (OMWW) is an acidic, saline, and organic matter-rich aqueous byproduct of olive oil production that is usually disposed of by spreading on agricultural soils. This study tested whether spreading OMWW can release indigenous soil metals (Fe, Mn, Cu and Zn) through pH, redox, and DOM complexation-related mechanisms, using three agricultural soils having different textures and chemical properties, and controlled pH and redox conditions (pH5.6 or 8.4; ORP from -200 to +250mV). Comparison treatments included a solution having the same salt content and composition as OMWW but lacking OM, and deionized water (DW). In all three soils and under all pH and redox conditions, the model salt solution and DW treatments solubilized considerably fewer metal cations than did OMWW. Overall, the primary factor in metals release from the soils by OMWW was the DOM fraction. pH, redox and soil type played secondary but important roles in solubilization of the various metals. pH had a major impact on Mn leaching but no impact on Fe and Cu leaching. Conversely, redox did not affect Mn leaching, but lower redox conditions contributed to elevated release of both Fe and Cu. For the most part, released metals were sourced from water soluble, exchangeable, easily reducible, and moderately reducible soil metals pools. Fe, Mn and Cu released from the soils by OMWW featured mainly as metal-organic complexes, and OMWW generally caused Zn precipitation in the soils. Soils rich in clay and organic matter under reduced pH and low redox conditions released substantially more metal cations than did a sand-rich soil. Spreading OMWW may result in sequestration of essential micronutrients like Zn, and increased availability of other micronutrients such as Fe, Mn and Cu. Copyright © 2018 Elsevier B.V. All rights reserved.

Tracking Catalyst Redox States and Reaction Dynamics in Ni-Fe Oxyhydroxide Oxygen Evolution Reaction Electrocatalysts: The Role of Catalyst Support and Electrolyte pH.

PubMed

Görlin, Mikaela; Ferreira de Araújo, Jorge; Schmies, Henrike; Bernsmeier, Denis; Dresp, Sören; Gliech, Manuel; Jusys, Zenonas; Chernev, Petko; Kraehnert, Ralph; Dau, Holger; Strasser, Peter

2017-02-08

Ni-Fe oxyhydroxides are the most active known electrocatalysts for the oxygen evolution reaction (OER) in alkaline electrolytes and are therefore of great scientific and technological importance in the context of electrochemical energy conversion. Here we uncover, investigate, and discuss previously unaddressed effects of conductive supports and the electrolyte pH on the Ni-Fe(OOH) catalyst redox behavior and catalytic OER activity, combining in situ UV-vis spectro-electrochemistry, operando electrochemical mass spectrometry (DEMS), and in situ cryo X-ray absorption spectroscopy (XAS). Supports and pH > 13 strongly enhanced the precatalytic voltammetric charge of the Ni-Fe oxyhydroxide redox peak couple, shifted them more cathodically, and caused a 2-3-fold increase in the catalytic OER activity. Analysis of DEMS-based faradaic oxygen efficiency and electrochemical UV-vis traces consistently confirmed our voltammetric observations, evidencing both a more cathodic O 2 release and a more cathodic onset of Ni oxidation at higher pH. Using UV-vis, which can monitor the amount of oxidized Ni +3/+4 in situ, confirmed an earlier onset of the redox process at high electrolyte pH and further provided evidence of a smaller fraction of Ni +3/+4 in mixed Ni-Fe centers, confirming the unresolved paradox of a reduced metal redox activity with increasing Fe content. A nonmonotonic super-Nernstian pH dependence of the redox peaks with increasing Fe content-displaying Pourbaix slopes as steep as -120 mV/pH-suggested a two proton-one electron transfer. We explain and discuss the experimental pH effects using refined coupled (PCET) and decoupled proton transfer-electron transfer (PT/ET) schemes involving negatively charged oxygenate ligands generated at Fe centers. Together, we offer new insight into the catalytic reaction dynamics and associated catalyst redox chemistry of the most important class of alkaline OER catalysts.

Synthesis and Structural Characterization of a Series of Mn(III)-OR Complexes, Including a Water-Soluble Mn(III)-OH that Promotes Aerobic Hydrogen Atom Transfer

PubMed Central

Coggins, Michael K.; Brines, Lisa M.; Kovacs, Julie A.

2013-01-01

Hydrogen atom transfer reactions (HAT) are a class of proton-coupled electron transfer (PCET) reactions used in biology to promote substrate oxidation. The driving force for such reactions depend on both the oxidation potential of the catalyst and the pKa of the proton acceptor site. Both high-valent transition-metal oxo M(IV)=O (M= Fe, Mn) and lower-valent transition-metal hydroxo compounds M(III)–OH (M= Fe, Mn) have been shown to promote these reactions. Herein we describe the synthesis, structure and reactivity properties of a series of Mn(III)-OR compounds (R= pNO2Ph(5), Ph(6), Me(7), H(8)), some of which abstract H-atoms. The Mn(III)-OH complex 8 is water-soluble and represents a rare example of a stable mononuclear Mn(III)-OH. In water, the redox potential of 8 was found to be pH-dependent and the Pourbaix (Ep,c vs pH) diagram has a slope (52 mV/pH) that is indicative of the transfer a single proton with each electron (ie, PCET). The two compounds with the lowest oxidation potential, hydroxide and methoxide-bound 7 and 8 are found to oxidize TEMPOH, whereas the compounds with the highest oxidation potential, phenol-ligated 5 and 6, are shown to be unreactive. Hydroxide-bound 8 reacts with TEMPOH an order of magnitude faster than methoxide-bound 7. Kinetic data (kH/kD= 3.1 (8), kH/kD= 2.1 (7)) are consistent with concerted H-atom abstraction. The reactive species 8 can be aerobically regenerated in H2O, and at least 10 turnovers can be achieved without significant degradation of the “catalyst”. The linear correlation between redox potential and pH, obtained from the Pourbaix diagram, was used to calculate the BDFE= 74.0±0.5 kcal/mol for Mn(II)-OH2 in water, and in MeCN its BDFE was estimated to be (70.1 kcal/mol). The reduced protonated derivative of 8, [MnII(SMe2N4(tren))(H2O)]+ (9), was estimated to have a pKa of 21.2 in MeCN. The ability (7) and inability (5 and 6) of the other members of the series to abstract a H-atom from TEMPOH was used to estimate either an upper or lower limit to the Mn(II)-O(H)R pKa based on their experimentally determined redox potentials. The trend in pKa (21.2(R=H) > 16.2(R=Me) > 13.5(R=Ph) > 12.2(R=pNO2Ph)) is shown to oppose that of oxidation potential Ep,c (−220(R= pNO2Ph) > −300(R= Ph) > −410(R= Me) > −600(R= H) mV vs Fc+/0) for this particular series. PMID:24156315

Ionic contribution to the self-potential signals associated with a redox front.

PubMed

Revil, A; Trolard, F; Bourrié, G; Castermant, J; Jardani, A; Mendonça, C A

2009-10-13

In contaminant plumes or in the case of ore bodies, a source current density is produced at depth in response to the presence of a gradient of the redox potential. Two charge carriers can exist in such a medium: electrons and ions. Two contributions to the source current density are associated with these charge carriers (i) the gradient of the chemical potential of the ionic species and (ii) the gradient of the chemical potential of the electrons (i.e., the gradient of the redox potential). We ran a set of experiments in which a geobattery is generated using electrolysis reactions of a pore water solution containing iron. A DC power supply is used to impose a difference of electrical potential of 3 V between a working platinum electrode (anode) and an auxiliary platinum electrode (cathode). Both electrodes inserted into a tank filled with a well-calibrated sand infiltrated by a (0.01 mol L(-1) KCl+0.0035 mol L(-)(1) FeSO(4)) solution. After the direct current is turned off, we follow the pH, the redox potential, and the self-potential at several time intervals. The self-potential anomalies amount to a few tens of millivolts after the current is turned off and decreases over time. After several days, all the redox-active compounds produced initially by the electrolysis reactions are consumed through chemical reactions and the self-potential anomalies fall to zero. The resulting self-potential anomalies are shown to be much weaker than the self-potential anomalies observed in the presence of an electronic conductor in the laboratory or in the field. In the presence of a biotic or an abiotic electronic conductor, the self-potential anomalies can amount to a few hundred millivolts. These observations point out indirectly the potential role of bacteria forming biofilms in the transfer of electrons through sharp redox potential gradient in contaminant plumes that are rich in organic matter.

Redox potentials of primary electron acceptor quinone molecule (QA)- and conserved energetics of photosystem II in cyanobacteria with chlorophyll a and chlorophyll d.

PubMed

Allakhverdiev, Suleyman I; Tsuchiya, Tohru; Watabe, Kazuyuki; Kojima, Akane; Los, Dmitry A; Tomo, Tatsuya; Klimov, Vyacheslav V; Mimuro, Mamoru

2011-05-10

In a previous study, we measured the redox potential of the primary electron acceptor pheophytin (Phe) a of photosystem (PS) II in the chlorophyll d-dominated cyanobacterium Acaryochloris marina and a chlorophyll a-containing cyanobacterium, Synechocystis. We obtained the midpoint redox potential (E(m)) values of -478 mV for A. marina and -536 mV for Synechocystis. In this study, we measured the redox potentials of the primary electron acceptor quinone molecule (Q(A)), i.e., E(m)(Q(A)/Q(A)(-)), of PS II and the energy difference between [P680·Phe a(-)·Q(A)] and [P680·Phe a·Q(A)(-)], i.e., ΔG(PhQ). The E(m)(Q(A)/Q(A)(-)) of A. marina was determined to be +64 mV without the Mn cluster and was estimated to be -66 to -86 mV with a Mn-depletion shift (130-150 mV), as observed with other organisms. The E(m)(Phe a/Phe a(-)) in Synechocystis was measured to be -525 mV with the Mn cluster, which is consistent with our previous report. The Mn-depleted downshift of the potential was measured to be approximately -77 mV in Synechocystis, and this value was applied to A. marina (-478 mV); the E(m)(Phe a/Phe a(-)) was estimated to be approximately -401 mV. These values gave rise to a ΔG(PhQ) of -325 mV for A. marina and -383 mV for Synechocystis. In the two cyanobacteria, the energetics in PS II were conserved, even though the potentials of Q(A)(-) and Phe a(-) were relatively shifted depending on the special pair, indicating a common strategy for electron transfer in oxygenic photosynthetic organisms.

Redox potential of pheophytin a in photosystem II of two cyanobacteria having the different special pair chlorophylls.

PubMed

Allakhverdiev, Suleyman I; Tomo, Tatsuya; Shimada, Yuichiro; Kindo, Hayato; Nagao, Ryo; Klimov, Vyacheslav V; Mimuro, Mamoru

2010-02-23

Water oxidation by photosystem (PS) II in oxygenic photosynthetic organisms is a major source of energy on the earth, leading to the production of a stable reductant. Mechanisms generating a high oxidation potential for water oxidation have been a major focus of photosynthesis research. This potential has not been estimated directly but has been measured by the redox potential of the primary electron acceptor, pheophytin (Phe) a. However, the reported values for Phe a are still controversial. Here, we measured the redox potential of Phe a under physiological conditions (pH 7.0; 25 degrees C) in two cyanobacteria with different special pair chlorophylls (Chls): Synechocystis sp. PCC 6803, whose special pair for PS II consists of Chl a, and Acaryochloris marina MBIC 11017, whose special pair for PS II consists of Chl d. We obtained redox potentials of -536 +/- 8 mV for Synechocystis sp. PCC 6803 and -478 +/- 24 mV for A. marina on PS II complexes in the presence of 1.0 M betaine. The difference in the redox potential of Phe a between the two species closely corresponded with the difference in the light energy absorbed by Chl a versus Chl d. We estimated the potentials of the special pair of PS II to be 1.20 V and 1.18 V for Synechocystis sp. PCC 6803 (P680) and A. marina (P713), respectively. This clearly indicates conservation in the properties of water-oxidation systems in oxygenic photosynthetic organisms, irrespective of the special-pair chlorophylls.

Interaction of Triapine and related thiosemicarbazones with iron(III)/(II) and gallium(III): a comparative solution equilibrium study†

PubMed Central

Enyedy, Éva A.; Primik, Michael F.; Kowol, Christian R.; Arion, Vladimir B.; Kiss, Tamás; Keppler, Bernhard K.

2012-01-01

Stoichiometry and stability of GaIII, FeIII, FeII complexes of Triapine and five related α-N heterocyclic thiosemicarbazones with potential antitumor activity have been determined by pH-potentiometry, UV-vis spectrophotometry, 1H NMR spectroscopy, and spectrofluorimetry in aqueous solution (with 30% DMSO), together with the characterization of the proton dissociation processes. Additionally, the redox properties of the iron complexes were studied by cyclic voltammetry at various pH values. Formation of high stability bis-ligand complexes was found in all cases, which are predominant at physiological pH with FeIII/FeII, whilst only at the acidic pH range with GaIII. The results show that among the thiosemicarbazones with various substituents the N-terminal dimethylation does not exert a measurable effect on the redox potential, but has the highest impact on the stability of the complexes as well as the cytotoxicity, especially in the absence of a pyridine-NH2 group in the molecule. In addition the fluorescence properties of the ligands in aqueous solution and their changes caused by GaIII were studied. PMID:21523301

HEALTH EFFECTS AND RISK ASSESSMENT OF ARSENIC

EPA Science Inventory

Abstract - In this review, we will focus on the effects of arsenic (As) exposure from drinking water sources. The primary inorganic As species in water are arsenate (V) and/or arsenite (III); their proportions depend on the water's redox potential and pH. Many As contamination...

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

PubMed

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

2016-08-16

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

Understanding of real alternative redox partner of Streptomyces peucetius DoxA: Prediction and validation using in silico and in vitro analyses.

PubMed

Rimal, Hemraj; Lee, Seung-Won; Lee, Joo-Ho; Oh, Tae-Jin

2015-11-01

Streptomyces peucetius ATCC27952 contains the cytochrome P450 monoxygenase DoxA that is responsible for the hydroxylation of daunorubicin into doxorubicin. Although S. peucetius ATCC27952 contains several potential redox partners, the most suitable endogenous electron-transport system is still unclear; therefore, we conducted a study of potential redox partners using Accelrys Discovery Studio 3.5. Recombinant DoxA along with its redox partners from S. peucetius FDX1, FDR2, and FDX3, and the putidaredoxin and putidaredoxin reductase from Pseudomonas putida that are essential equivalents of the class I type of bacterial electron-transport system were over-expressed and purified. The successful development of an efficient redox system was achieved by an in vitro enzymatic catalysis reaction with DoxA. The optimal pH for the activation of the heme was 7.6 and the optimal temperature was 30 °C. Our findings suggest a two-fold increase of DoxA activity via the NADH → FDR2 → FDX1 → DoxA pathway for the hydroxylation of the daunorubicin, and indicate that the usage of a native redox partner may increase daunorubicin-derived doxorubicin production due to the inclusion of DoxA. Copyright © 2015 Elsevier Inc. All rights reserved.

Comparison of electrokinetic soil remediation methods using one fixed anode and approaching anodes.

PubMed

Shen, Zhemin; Chen, Xuejun; Jia, Jinping; Qu, Liya; Wang, Wenhua

2007-11-01

During the cation exchange membrane (CEM) enhanced electrokinetic (EK) soil remediation, the nearer to the anode, the higher are the H+ concentrations and the redox potentials. As both low pH and high redox potential are helpful to speed-up Cd electro-migration, soils near the anode can be quickly remedied. Usually EK process is operated with one fixed anode (FA). A novel CEM enhanced EK method with approaching anodes (AAs) is proposed to accelerate electro-migration effect. Several mesh Ti/Ru anodes were inserted as AAs in the treated soil. They were switched in turn from the anode towards the cathode. Thus high H+ ions concentrations and high redox potentials quickly migrate to the cathode. Consequently, soil remediation is accelerated and nearly 44% of energy and 40% of time can be saved. The mechanism of Cd electro-migration behavior in soils during CEM enhanced EK is described as the elution in an electrokinetically driven chromatogram.

Conditions affecting the release of phosphorus from surface lake sediments.

PubMed

Christophoridis, Christophoros; Fytianos, Konstantinos

2006-01-01

Laboratory studies were conducted to determine the effect of pH and redox conditions, as well as the effect of Fe, Mn, Ca, Al, and organic matter, on the release of ortho-phosphates in lake sediments taken from Lakes Koronia and Volvi (Northern Greece). Results were evaluated in combination with experiments to determine P fractionation in the sediment. The study revealed the major effect of redox potential and pH on the release of P from lake sediments. Both lakes showed increased release rates under reductive conditions and high pH values. The fractionation experiments revealed increased mobility of the reductive P fraction as well as of the NaOH-P fraction, indicating participation of both fractions in the overall release of sediment-bound P, depending on the prevailing environmental conditions. The results were assessed in combination with the release patterns of Fe, Mn, Ca, Al, and organic matter, enabling the identification of more specific processes of P release for each lake. The basic release patterns included the redox induced reductive dissolution of P-bearing metal oxides and the competitive exchange of phosphate anions with OH- at high pH values. The formation of an oxidized surface microlayer under oxic conditions acted as a protective film, preventing further P release from the sediments of Lake Volvi, while sediments from Lake Koronia exhibited a continuous and increased tendency to release P under various physicochemical conditions, acting as a constant source of internal P loading.

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

PubMed

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

2013-02-01

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

Chitosan-Acrylic Polymeric Nanoparticles with Dynamic Covalent Bonds. Synthesis and Stimuli Behavior.

PubMed

Palacio, Herman; Otálvaro, Felipe; Giraldo, Luis Fernando; Ponchel, Gilles; Segura-Sánchez, Freimar

2017-12-01

Drug delivery represents one of the most important research fields within the pharmaceutical industry. Different strategies are reported every day in a dynamic search for carriers with the ability to transport drugs across the body, avoiding or decreasing toxic issues and improving therapeutic activity. One of the most interesting strategies currently under research is the development of drug delivery systems sensitive to different stimuli, due to the high potential attributed to the selective delivery of the payload. In this work, a stimuli-sensitive nanocarrier was built with a bifunctional acrylic polymer, linked by imine and disulfide bonds to thiolate chitosan, the latter being a biopolymer widely known in the field of tissue engineering and drug delivery by its biodegradability and biocompatibility. These polymer nanoparticles were exposed to different changes in pH and redox potential, which are environments commonly found inside cancer cells. The results proof the ability of the nanoparticles to keep the original structure when either changes in pH or redox potential were applied individually. However, when both stimuli were applied simultaneously, a disassembly of the nanoparticles was evident. These special characteristics make these nanoparticles suitable nanocarriers with potential for the selective delivery of anticancer drugs.

Temperature- and pH-dependent effect of lactate on in vitro redox stability of red meat myoglobins.

PubMed

Nair, M N; Suman, S P; Li, S; Ramanathan, R; Mancini, R A

2014-01-01

Our objective was to evaluate the influence of lactate on in vitro redox stability and thermostability of beef, horse, pork, and sheep myoglobins. Lactate (200 mM) had no effect (P>0.05) on redox stability at physiological (pH7.4, 37°C) and meat (pH 5.6, 4°C) conditions. However, lactate increased (P<0.05) metmyoglobin formation at a condition simulating stressed live skeletal muscle (pH 6.5, 37°C). The redox stability of myoglobins at stressed live skeletal muscle and meat conditions was species-specific (P<0.05). Myoglobin thermostability at 71°C was lower (P<0.05) in the presence of lactate compared with controls and was influenced (P<0.05) by species. The results of the present study indicate that the effects of lactate on myoglobin are temperature and pH dependent. The observed lack of influence of lactate on myoglobin redox stability at meat condition suggests that the color stability of lactate-enhanced fresh meat is not due to direct interactions between the ingredient and the heme protein. © 2013.

COMPARATIVE EVALUATION OF SHORT-TERM LEACH TESTS FOR HEAVY METAL RELEASE FROM MINERAL PROCESSING WASTE

EPA Science Inventory

Evaluation of metal leaching using a single leach test such as the Toxicity Characteristic Leaching Procedure (TCLP) is often questionable. The pH, redox potential (E_h), particle size and contact time are critical variables in controlling metal stability, not accounted...

Redox characterization of the Fe(II)-catalyzed transformation of ferrihydrite to goethite

NASA Astrophysics Data System (ADS)

Jones, Adele M.; Collins, Richard N.; Waite, T. David

2017-12-01

The reduction potential of Fe(II)-Fe(III) (oxyhydr)oxide systems provides an important control on the biogeochemical cycling of redox-sensitive elements such as carbon and nitrogen as well as trace metals and organic contaminants in natural systems. As such, an in-depth understanding of the factors controlling the reduction potential of such systems is critical to predicting the likely transformation, transport and fate of these species in natural and perturbed environments. In this study the mineralogy and reduction potential of ferrihydrite suspensions at pH 6.50 and pH 7.00 were determined over the course of their Fe(II)-catalyzed transformation to lepidocrocite and goethite using X-ray absorption spectroscopy and mediated electrochemical approaches. The measured reduction potentials were compared to those of analogous Fe(II)-Fe(III) (oxyhydr)oxide suspensions reacted for 5 min containing pure ferrihydrite (Fh), lepidocrocite (L) and goethite (Gt). The reduction potentials of the pure Fe(II)-Fe(III) (oxyhydr)oxide suspensions were, respectively, +47.5, -13.5 and -122.3 mV vs. SHE at pH 6.5, and -22.9, -84.1 and -189.7 mV vs. SHE at pH 7. These values are in good agreement with reduction potentials calculated using the Nernst equation and reported thermodynamic solubility products indicating that these suspensions had reached equilibrium within 5 min. The reduction potential of the pH 6.50 Fe(II)-ferrihydrite suspension decreased from +47.4 mV to -126.4 mV over a week, and from -20.1 mV to -188.4 mV (all vs. SHE) after 24 h at pH 7. The changes in reduction potential over time matched well to those calculated from the relative proportion of each pure Fe(III) (oxyhydr)oxide present suggesting that Fe3+ activity was influenced by the mix of iron oxides present rather than the most insoluble solid species. Finally, evidence is provided that adsorbed Fe(II) has the capacity to reduce a significantly larger fraction of a reducible species than the aqueous Fe(II) species with which it is in equilibrium. As an Fe(III) (oxyhydr)oxide suspension in equilibrium with aqueous and adsorbed Fe(II) species possesses a single, unique reduction potential, this suggests that adsorbed Fe(II) is a more facile reductant than aqueous Fe(II).

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

PubMed Central

Zimbardi, Ana L. R. L.; Camargo, Priscila F.; Carli, Sibeli; Aquino Neto, Sidney; Meleiro, Luana P.; Rosa, Jose C.; De Andrade, Adalgisa R.; Jorge, João A.; Furriel, Rosa P. M.

2016-01-01

Laccase production by Pycnoporus sanguineus RP15 grown in wheat bran and corncob under solid-state fermentation was optimized by response surface methodology using a Central Composite Rotational Design. A laccase (Lacps1) was purified and characterized and the potential of the pure Lacps1 and the crude culture extract for synthetic dye decolorization was evaluated. At optimal conditions (eight days, 26 °C, 18% (w/w) milled corncob, 0.8% (w/w) NH4Cl and 50 mmol·L−1 CuSO4, initial moisture 4.1 mL·g−1), the laccase activity reached 138.6 ± 13.2 U·g−1. Lacps1 was a monomeric glycoprotein (67 kDa, 24% carbohydrate). Optimum pH and temperature for the oxidation of 2,2’-azino-bis(3-ethylbenzthiazoline-6-sulfonate) (ABTS) were 4.4 and 74.4 °C, respectively. Lacps1 was stable at pH 3.0–8.0, and after two hours at 55–60 °C, presenting high redox potential (0.747 V vs. NHE). ABTS was oxidized with an apparent affinity constant of 147.0 ± 6.4 μmol·L−1, maximum velocity of 413.4 ± 21.2 U·mg−1 and catalytic efficiency of 3140.1 ± 149.6 L·mmol−1·s−1. The maximum decolorization percentages of bromophenol blue (BPB), remazol brilliant blue R and reactive blue 4 (RB4), at 25 or 40 °C without redox mediators, reached 90%, 80% and 60%, respectively, using either pure Lacps1 or the crude extract. This is the first study of the decolorization of BPB and RB4 by a P. sanguineus laccase. The data suggested good potential for treatment of industrial dye-containing effluents. PMID:27164083

Scanning electrochemical microscopy based evaluation of influence of pH on bioelectrochemical activity of yeast cells - Saccharomyces cerevisiae.

PubMed

Ramanavicius, A; Morkvenaite-Vilkonciene, I; Kisieliute, A; Petroniene, J; Ramanaviciene, A

2017-01-01

In this research scanning electrochemical microscopy was applied for the investigation of immobilized yeast Saccharomyces cerevisiae cells. Two redox mediators based system was applied in order to increase the efficiency of charge transfer from yeast cells. 9,10-phenanthrenequinone (PQ) was applied as a lipophilic redox mediator, which has the ability to cross the cell's membrane; another redox mediator was ferricyanide, which acted as a hydrophylic electron acceptor able to transfer electrons from the PQ to the working electrode of SECM. Hill's function was applied to determine the optimal pH for this described SECM-based system. The influence of pH on cell viability could be well described by Hill's function. It was determined that at pH 6.5 the PQ has a minimal toxic influence on yeast cells, and the kinetics of metabolic processes in cells as well as electron transfer rate achieved in consecutive action of both redox mediators were appropriate to achieve optimal current signals. Copyright © 2016 Elsevier B.V. All rights reserved.

Electrochemical studies on polysorbate-20 (Tween 20)-entrapped haemoglobin and its application in a hydrogen peroxide biosensor.

PubMed

Ma, Xiang; Chen, Ting; Liu, Lifang; Li, Genxi

2005-06-01

Haemoglobin (Hb) was entrapped in polysorbate 20 and then modified on a pyrolytic graphite electrode. Electrochemical studies revealed that a pair of stable and well-defined redox peaks attributed to the direct redox reaction of Hb could be observed in a phosphate buffer solution (pH 6.0). The anodic and cathodic peaks were located at -236 and -316 mV (versus a saturated calomel reference electrode) separately. The formal potential, E0', was linearly varied with pH in the range from 3.0 to 10.0 with a slope of -48.0 mV.pH-1. Moreover, the protein was capable of catalysing the reduction of H2O2. Accordingly, an unmediated biosensor for H2O2 was prepared with a linear range from 8.0x10(-7) to 1.0x10(-3) M. This biosensor exhibited good stability, sensitivity and reproducibility.

Determining the pH of Mars from the Viking labelled release reabsorption effect

NASA Technical Reports Server (NTRS)

Plumb, Robert C.

1992-01-01

The acid-base properties and redox potentials of solids are two of the more fundamental chemical parameters characterizing a material. Knowledge of these parameters for martian regolith fines would be of considerable value in determining what specific compounds are present and making judgements on what reactions are possible.

Biogeochemical Barriers: Redox Behavior of Metals and Metalloids

EPA Science Inventory

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

Photocatalytic effect of anodic titanium oxide nanotubes on various cell culture media

NASA Astrophysics Data System (ADS)

Yu, Chun-Kang; Hu, Kan-Hung; Wang, Shing-Hoa; Hsu, Todd; Tsai, Huei-Ting; Chen, Chien-Chon; Liu, Shiu-Mei; Lin, Tai-Yuan; Chen, Chin-Hsing

2011-02-01

The use of titanium dioxide (TiO2) in photodynamic therapy for the treatment of cancer cells has been proposed following studies of cultured cancer cells. In this work, an ordered channel array of anodic titanium oxide (ATO) was fabricated by anodizing titanium foil. The ATO layer of nanotubes with diameters of 100 nm was made in NH4F electrolyte by anodization. The photocatalytic effect of ATO was examined on various culture media by ultraviolet A (UV-A) (366 nm) irradiation. After UV-A irradiation of the ATO layer, redox potential of Tris-HCl buffer (pH 7.5) and dilute acrylamide solution increased instantaneously. The redox potential of the serum-containing RPMI1640 medium also increased dramatically, while that of serum-containing MEM and DMEM media increased slightly. The UVA-induced high redox potential was correlated with the greater ability to break down plasmid DNA strands. These phenomena suggest that a culture medium, such as RPMI1640, with a greater ability to produce free radical may be associated with a stronger photocatalytic effect of ATO on cultured cancer cells reported previously.

Tetrodotoxin Blockade on Canine Cardiac L-Type Ca2+ Channels Depends on pH and Redox Potential

PubMed Central

Hegyi, Bence; Komáromi, István; Kistamás, Kornél; Ruzsnavszky, Ferenc; Váczi, Krisztina; Horváth, Balázs; Magyar, János; Bányász, Tamás; Nánási, Péter P.; Szentandrássy, Norbert

2013-01-01

Tetrodotoxin (TTX) is believed to be one of the most selective inhibitors of voltage-gated fast Na+ channels in excitable tissues. Recently, however, TTX has been shown to block L-type Ca2+ current (ICa) in canine cardiac cells. In the present study, the TTX-sensitivity of ICa was studied in isolated canine ventricular myocytes as a function of (1) channel phosphorylation, (2) extracellular pH and (3) the redox potential of the bathing medium using the whole cell voltage clamp technique. Fifty-five micromoles of TTX (IC50 value obtained under physiological conditions) caused 60% ± 2% inhibition of ICa in acidic (pH = 6.4), while only a 26% ± 2% block in alkaline (pH = 8.4) milieu. Similarly, the same concentration of TTX induced 62% ± 6% suppression of ICa in a reductant milieu (containing glutathione + ascorbic acid + dithiothreitol, 1 mM each), in contrast to the 31% ± 3% blockade obtained in the presence of a strong oxidant (100 μM H2O2). Phosphorylation of the channel protein (induced by 3 μM forskolin) failed to modify the inhibiting potency of TTX; an IC50 value of 50 ± 4 μM was found in forskolin. The results are in a good accordance with the predictions of our model, indicating that TTX binds, in fact, to the selectivity filter of cardiac L-type Ca channels. PMID:23771047

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

PubMed Central

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

2009-01-01

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

A solid-state pH sensor for nonaqueous media including ionic liquids.

PubMed

Thompson, Brianna C; Winther-Jensen, Orawan; Winther-Jensen, Bjorn; MacFarlane, Douglas R

2013-04-02

We describe a solid state electrode structure based on a biologically derived proton-active redox center, riboflavin (RFN). The redox reaction of RFN is a pH-dependent process that requires no water. The electrode was fabricated using our previously described 'stuffing' method to entrap RFN into vapor phase polymerized poly(3,4-ethylenedioxythiophene). The electrode is shown to be capable of measuring the proton activity in the form of an effective pH over a range of different water contents including nonaqueous systems and ionic liquids (ILs). This demonstrates that the entrapment of the redox center facilitates direct electron communication with the polymer. This work provides a miniaturizable system to determine pH (effective) in nonaqueous systems as well as in ionic liquids. The ability to measure pH (effective) is an important step toward the ability to customize ILs with suitable pH (effective) for catalytic reactions and biotechnology applications such as protein preservation.

Redox-linked ionization of sulredoxin, an archaeal Rieske-type [2Fe-2S] protein from Sulfolobus sp. strain 7.

PubMed

Iwasaki, T; Imai, T; Urushiyama, A; Oshima, T

1996-11-01

"Sulredoxin" of Sulfolobus sp. strain 7 is an archaeal soluble Rieske-type [2Fe-2S] protein and was initially characterized by several spectroscopic techniques (Iwasaki, T., Isogai, T., Iizuka, T. , and Oshima, T. (1995) J. Bacteriol. 177, 2576-2582). It appears to have tightly linked ionization affecting the redox properties of the protein, which is characteristic of the Rieske FeS proteins found as part of the respiratory chain. Sulredoxin had an Em(low pH) value of +188 +/- 9 mV, and the slope of pH dependence of the midpoint redox potential indicated two ionization equilibria in the oxidized form with pKa(ox1) of 6.23 +/- 0.22 and pKa(ox2) of 8.57 +/- 0.20. The absorption, CD, and resonance Raman spectra of oxidized sulredoxin are consistent with the proposed St2FeSb2Fe[N(His)]t2 core structure, and deprotonation of one of the two putative coordinated histidine imidazoles, having the pKa(ox2) of 8.57 +/- 0.20, causes a decrease in the midpoint redox potential, the change in the optical and CD spectra, and the appearance of a new Raman transition at 278 cm-1, without major structural rearrangement of the [2Fe-2S] cluster as well as the overall protein conformation. The redox-linked ionization of sulredoxin is also contributed by local changes involving another ionizable group having the pKa(ox1) of 6.23 +/- 0. 22, which is probably attributed to a certain positively charged amino acid residue that may not be a ligand by itself but located very close to the cluster. We suggest that sulredoxin provides a new tractable model of the membrane-bound homologue of the respiratory chain, the Rieske FeS proteins of the cytochrome bc1-b6f complexes.

Interior microelectrolysis oxidation of polyester wastewater and its treatment technology.

PubMed

Yang, Xiaoyi

2009-09-30

This paper has investigated the effects of interior microelectrolysis pretreatment on polyester wastewater treatment and analyzed its mechanism on COD and surfactant removal. The efficiency of interior microelectrolysis is mainly influenced by solution pH, aeration and reaction time. Contaminants can be removed not only by redox reaction and flocculation in the result of ferrous and ferric hydroxides but also by electrophoresis under electric fields created by electron flow. pH confirms the chemical states of surfactants, Fe(II)/Fe(III) ratio and the redox potential, and thus influences the effects of electrophoresis, flocculation and redox action on contaminant removal. Anaerobic and aerobic batch tests were performed to study the degradation of polyester wastewater. The results imply that interior microelectrolysis and anaerobic pretreatment are lacking of effectiveness if applied individually in treating polyester wastewater in spite of their individual advantages. The interior microelectrolysis-anaerobic-aerobic process was investigated to treat polyester wastewater with comparison with interior microelectrolysis-aerobic process and anaerobic-aerobic process. High COD removal efficiencies have been gotten by the combination of interior microelectrolysis with anaerobic technology and aerobic technology. The results also imply that only biological treatment was less effective in polyester wastewater treatment.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng

Soil organic carbon turnover to CO 2 and CH 4 is sensitive to soil redox potential and pH conditions. But, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximatelymore » describe the observed pH evolution without additional parameterization. Though Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. Furthermore, the equilibrium speciation predicts a substantial increase in CO 2 solubility as pH increases, and taking into account CO 2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO 2 production from closed microcosms can be substantially underestimated based on headspace CO 2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.« less

Biogeochemical modeling of CO2 and CH4 production in anoxic Arctic soil microcosms

NASA Astrophysics Data System (ADS)

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng; Yang, Ziming; Graham, David E.; Gu, Baohua; Painter, Scott L.; Thornton, Peter E.

2016-09-01

Soil organic carbon turnover to CO2 and CH4 is sensitive to soil redox potential and pH conditions. However, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximately describe the observed pH evolution without additional parameterization. Although Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. The equilibrium speciation predicts a substantial increase in CO2 solubility as pH increases, and taking into account CO2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO2 production from closed microcosms can be substantially underestimated based on headspace CO2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.

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

PubMed

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

2015-05-05

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

The gut microenvironment of sediment-dwelling Chironomus plumosus larvae as characterised with O2, pH, and redox microsensors.

PubMed

Stief, Peter; Eller, Gundula

2006-09-01

We devised a set-up in which microsensors can be used for characterising the gut microenvironment of aquatic macrofauna. In a small flow cell, we measured microscale gradients through dissected guts (O(2), pH, redox potential [E ( h )]), in the haemolymph (O(2)), and towards the body surface (O(2)) of Chironomus plumosus larvae. The gut microenvironment was compared with the chemical conditions in the lake sediment in which the animals reside and feed. When the dissected guts were incubated at the same nominal O(2) concentration as in haemolymph, the gut content was completely anoxic and had pH and E ( h ) values slightly lower than in the ambient sediment. When the dissected guts were artificially oxygenated, the volumetric O(2)-consumption rates of the gut content were at least 10x higher than in the sediment. Using these potential O(2)-consumption rates in a cylindrical diffusion-reaction model, it was predicted that diffusion of O(2) from the haemolymph to the gut could not oxygenate the gut content under in vivo conditions. Additionally, the potential O(2)-consumption rates were so high that the intake of dissolved O(2) along with feeding could be ruled out to oxygenate the gut content. We conclude that microorganisms present in the gut of C. plumosus cannot exhibit an aerobic metabolism. The presented microsensor technique and the data analysis are applicable to guts of other macrofauna species with cutaneous respiration.

Molecular Wiring in Smart Dressings: Opening a New Route to Monitoring Wound pH

PubMed Central

McLister, Anna; Davis, James

2015-01-01

It has been proposed that fluctuations in wound pH can give valuable insights into the healing processes in chronic wounds, but acquiring such data can be a technological challenge especially where there is little sample available. Developments in voltammetric pH sensing have opened up new avenues for the design of probes that can function in ultra-small volumes and can be inherently disposable but, as yet few can meet the demands of wound monitoring. A preliminary investigation of the pH response of a new redox wire prepared from a peptide homopolymer of tryptophan is presented and its potential applicability as a sensing material for use in smart dressings is critically discussed. PMID:27417774

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

PubMed

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

2015-03-31

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

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

PubMed

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

2013-10-01

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

Reductive Dissolution of PuO2(am): The Effect of Fe(II) and Hydroquinone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rai, Dhanpat; Gorby, Yuri A.; Fredrickson, Jim K.

2002-06-01

SYNOPIS-Reducing agents commonly present in geologic environments can increase solubility of PuO2(am), which is otherwise very insoluble, by many orders of magnitude through reduction of Pu(IV) to Pu(III). The reduction reactions involving Fe(II) and hydroquinone, hitherto unquantified under environmental pH values, were found to be relatively fast and controlled the extent of PuO2(am) dissolution: a decrease in redox potential (pe + pH) resulted in concomitant increase in PuO2(am) solubility.

Surface reaction of SnII on goethite (α-FeOOH): surface complexation, redox reaction, reductive dissolution, and phase transformation.

PubMed

Dulnee, Siriwan; Scheinost, Andreas C

2014-08-19

To elucidate the potential risk of (126)Sn migration from nuclear waste repositories, we investigated the surface reactions of Sn(II) on goethite as a function of pH and Sn(II) loading under anoxic condition with O2 level < 2 ppmv. Tin redox state and surface structure were investigated by Sn K edge X-ray absorption spectroscopy (XAS), goethite phase transformations were investigated by high-resolution transmission electron microscopy and selected area electron diffraction. The results demonstrate the rapid and complete oxidation of Sn(II) by goethite and formation of Sn(IV) (1)E and (2)C surface complexes. The contribution of (2)C complexes increases with Sn loading. The Sn(II) oxidation leads to a quantitative release of Fe(II) from goethite at low pH, and to the precipitation of magnetite at higher pH. To predict Sn sorption, we applied surface complexation modeling using the charge distribution multisite complexation approach and the XAS-derived surface complexes. Log K values of 15.5 ± 1.4 for the (1)E complex and 19.2 ± 0.6 for the (2)C complex consistently predict Sn sorption across pH 2-12 and for two different Sn loadings and confirm the strong retention of Sn(II) even under anoxic conditions.

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

PubMed

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

2016-11-29

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

Broad control of disulfide stability through microenvironmental effects and analysis in complex redox environments.

PubMed

Wu, Chuanliu; Wang, Shuo; Brülisauer, Lorine; Leroux, Jean-Christophe; Gauthier, Marc A

2013-07-08

Disulfide bonds stabilize the tertiary- and quaternary structure of proteins. In addition, they can be used to engineer redox-sensitive (bio)materials and drug-delivery systems. Many of these applications require control of the stability of the disulfide bond. It has recently been shown that the charged microenvironment of the disulfide can be used to alter their stability by ∼3 orders of magnitude in a predictable and finely tunable manner at acidic pH. The aim of this work is to extend these findings to physiological pH and to demonstrate the validity of this approach in complex redox milieu. Disulfide microenvironments were manipulated synergistically with steric hindrance herein to control disulfide bond stability over ∼3 orders of magnitude at neutral pH. Control of disulfide stability through microenvironmental effects could also be observed in complex redox buffers (including serum) and in the presence of cells. Such fine and predictable control of disulfide properties is not achievable using other existing approaches. These findings provide easily implementable and general tools for controlling the responsiveness of biomaterials and drug delivery systems toward various local endogenous redox environments.

Model predictions of realgar precipitation by reaction of As(III) with synthetic mackinawite under anoxic conditions

USGS Publications Warehouse

Gallegos, T.J.; Han, Y.-S.; Hayes, K.F.

2008-01-01

This study investigates the removal of As(III) from solution using mackinawite, a nanoparticulate reduced iron sulfide. Mackinawite suspensions (0.1-40 g/L) effectively lower initial concentrations of 1.3 ?? 10 -5 M As(III) from pH 5-10, with maximum removal occurring under acidic conditions. Based on Eh measurements, it was found that the redox state of the system depended on the mackinawite solids concentration and pH. Higher initial mackinawite concentrations and alkaline pH resulted in a more reducing redox condition. Given this, the pH edge data were modeled thermodynamically using pe (-log[e-]) as a fitting parameter and linear pe-pH relationships within the range of measured Eh values as a function of pH and mackinawite concentration. The model predicts removal of As(III) from solution by precipitation of realgar with the formation of secondary oxidation products, greigite or a mixed-valence iron oxide phase, depending on pH. This study demonstrates that mackinawite is an effective sequestration agent for As(III) and highlights the importance of incorporating redox into models describing the As-Fe-S-H2O system. ?? 2008 American Chemical Society.

pH/redox dual-sensitive dextran nanogels for enhanced intracellular drug delivery.

PubMed

Curcio, Manuela; Diaz-Gomez, Luis; Cirillo, Giuseppe; Concheiro, Angel; Iemma, Francesca; Alvarez-Lorenzo, Carmen

2017-08-01

pH/redox dual-responsive nanogels (DEX-SS) were prepared by precipitation polymerization of methacrylated dextran (DEXMA), 2-aminoethylmethacrylate (AEMA) and N,N'-bis(acryloyl)cystamine (BAC), and then loaded with methotrexate (MTX). Nanogels were spherical and exhibited homogeneous size distribution (460nm, PDI<0.30) as observed using dynamic light scattering (DLS) and scanning electron microscopy (SEM). DEX-SS were sensitive to the variations of pH and redox environment. Nanogels incubated in buffer pH 5.0 containing 10mM glutathione (GSH) synergistically increased the mean diameter and the PDI to 750nm and 0.42, respectively. In vitro release experiments were performed at pH 7.4 and 5.0 with and without GSH. The cumulative release of MTX in pH 5.0 medium with 10mMGSH was 5-fold higher than that recorded at pH 7.4 without GSH. Fibroblasts and tumor cells were used to tests the effects of blank DEX-SS and MTX@DEX-SS nanogels on cell viability. Remarkable influence of pH on nanogels internalization into HeLa cells was evidenced by means of confocal microscopy and flow cytometry. Copyright © 2017 Elsevier B.V. All rights reserved.

Redox Non-Innocence of Nitrosobenzene at Nickel

DOE PAGES

Kundu, Subrata; Stieber, S. Chantal; Ferrier, Maryline Ghislaine; ...

2016-08-22

Nitrosobenzene (PhNO) serves as a stable analogue of nitroxyl (HNO), a biologically relevant, redox-active nitric oxide derivative. Capture of nitrosobenzene at the electrondeficient β-diketiminato nickel(I) complex [ iPr 2NN F6]Ni results in reduction of the PhNO ligand to a (PhNO) ./ ⁻ species coordinated to a square planar Ni II center in [ iPr 2NN F6]Ni(η 2- ONPh). Ligand centered reduction leads to the (PhNO) -2 moiety bound to Ni II supported by XAS studies. Ultimately, systematic investigation of structure–reactivity patterns of (PhNO) ./ ⁻ and (PhNO) 2- ligands reveals parallels with superoxo (O 2) ./ ⁻ and peroxo (Omore » 2) 2- ligands, respectively, and forecasts reactivity patterns of the more transient HNO ligand.« less

Biogeochemical modeling of CO 2 and CH 4 production in anoxic Arctic soil microcosms

DOE PAGES

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng; ...

2016-09-12

Soil organic carbon turnover to CO 2 and CH 4 is sensitive to soil redox potential and pH conditions. But, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximatelymore » describe the observed pH evolution without additional parameterization. Though Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. Furthermore, the equilibrium speciation predicts a substantial increase in CO 2 solubility as pH increases, and taking into account CO 2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO 2 production from closed microcosms can be substantially underestimated based on headspace CO 2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.« less

Incorporating redox processes improves prediction of carbon and nutrient cycling and greenhouse gas emission

NASA Astrophysics Data System (ADS)

Tang, Guoping; Zheng, Jianqiu; Yang, Ziming; Graham, David; Gu, Baohua; Mayes, Melanie; Painter, Scott; Thornton, Peter

2016-04-01

Among the coupled thermal, hydrological, geochemical, and biological processes, redox processes play major roles in carbon and nutrient cycling and greenhouse gas (GHG) emission. Increasingly, mechanistic representation of redox processes is acknowledged as necessary for accurate prediction of GHG emission in the assessment of land-atmosphere interactions. Simple organic substrates, Fe reduction, microbial reactions, and the Windermere Humic Aqueous Model (WHAM) were added to a reaction network used in the land component of an Earth system model. In conjunction with this amended reaction network, various temperature response functions used in ecosystem models were assessed for their ability to describe experimental observations from incubation tests with arctic soils. Incorporation of Fe reduction reactions improves the prediction of the lag time between CO2 and CH4 accumulation. The inclusion of the WHAM model enables us to approximately simulate the initial pH drop due to organic acid accumulation and then a pH increase due to Fe reduction without parameter adjustment. The CLM4.0, CENTURY, and Ratkowsky temperature response functions better described the observations than the Q10 method, Arrhenius equation, and ROTH-C. As electron acceptors between O2 and CO2 (e.g., Fe(III), SO42-) are often involved, our results support inclusion of these redox reactions for accurate prediction of CH4 production and consumption. Ongoing work includes improving the parameterization of organic matter decomposition to produce simple organic substrates, examining the influence of redox potential on methanogenesis under thermodynamically favorable conditions, and refining temperature response representation near the freezing point by additional model-experiment iterations. We will use the model to describe observed GHG emission at arctic and tropical sites.

Application of Multivariable Analysis and FTIR-ATR Spectroscopy to the Prediction of Properties in Campeche Honey

PubMed Central

Pat, Lucio; Ali, Bassam; Guerrero, Armando; Córdova, Atl V.; Garduza, José P.

2016-01-01

Attenuated total reflectance-Fourier transform infrared spectrometry and chemometrics model was used for determination of physicochemical properties (pH, redox potential, free acidity, electrical conductivity, moisture, total soluble solids (TSS), ash, and HMF) in honey samples. The reference values of 189 honey samples of different botanical origin were determined using Association Official Analytical Chemists, (AOAC), 1990; Codex Alimentarius, 2001, International Honey Commission, 2002, methods. Multivariate calibration models were built using partial least squares (PLS) for the measurands studied. The developed models were validated using cross-validation and external validation; several statistical parameters were obtained to determine the robustness of the calibration models: (PCs) optimum number of components principal, (SECV) standard error of cross-validation, (R 2 cal) coefficient of determination of cross-validation, (SEP) standard error of validation, and (R 2 val) coefficient of determination for external validation and coefficient of variation (CV). The prediction accuracy for pH, redox potential, electrical conductivity, moisture, TSS, and ash was good, while for free acidity and HMF it was poor. The results demonstrate that attenuated total reflectance-Fourier transform infrared spectrometry is a valuable, rapid, and nondestructive tool for the quantification of physicochemical properties of honey. PMID:28070445

Estimation of palaeohydrochemical conditions using carbonate minerals

NASA Astrophysics Data System (ADS)

Amamiya, H.; Mizuno, T.; Iwatsuki, T.; Yuguchi, T.; Murakami, H.; Saito-Kokubu, Y.

2014-12-01

The long-term evolution of geochemical environment in deep underground is indispensable research subject for geological disposal of high-level radioactive waste, because the evolution of geochemical environment would impact migration behavior of radionuclides in deep underground. Many researchers have made efforts previously to elucidate the geochemical environment within the groundwater residence time based on the analysis of the actual groundwater. However, it is impossible to estimate the geochemical environment for the longer time scale than the groundwater residence time in this method. In this case, analysis of the chemical properties of secondary minerals are one of useful method to estimate the paleohydrochemical conditions (temperature, salinity, pH and redox potential). In particular, carbonate minerals would be available to infer the long-term evolution of hydrochemical for the following reasons; -it easily reaches chemical equilibrium with groundwater and precipitates in open space of water flowing path -it reflects the chemical and isotopic composition of groundwater at the time of crystallization We reviewed the previous studies on carbonate minerals and geochemical conditions in deep underground and estimated the hydrochemical characteristics of past groundwater by using carbonate minerals. As a result, it was found that temperature and salinity of the groundwater during crystallization of carbonate minerals were evaluated quantitatively. On the other hand, pH and redox potential can only be understood qualitatively. However, it is suggested that the content of heavy metal elements such as manganese, iron and uranium, and rare earth elements in the carbonate minerals are useful indicators for estimating redox potential. This study was carried out under a contract with METI (Ministry of Economy, Trade and Industry) as part of its R&D supporting program for developing geological disposal technology.

Redox potential: An indicator of site productivity in forest management

NASA Astrophysics Data System (ADS)

Sajedi, Toktam; Prescott, Cindy; Lavkulich, Les

2010-05-01

Redox potential (Eh) is an integrated soil measurement that reflects several environmental conditions in the soil associated with aeration, moisture and carbon (organic matter) dynamics. Its measurement can be related to water table fluctuations, precipitation and landscape gradients, organic matter decomposition rates, nutrient dynamics, biological diversity and plant species distribution. Redox is an excellent indicator of soil biological processes, as it is largely a reflection of microbial activities which to a large extent govern carbon dynamics and nutrient cycling. Redox thus serves as an ecological indicator of site productivity at the ecosystem scale and may be used for management purposes as its magnitude can be altered by activities such as harvesting and drainage. A threshold value of 300 mv has been documented as the critical value below which anaerobic conditions in the soil develop. However, redox measurements and its impacts on ecosystem processes such as nutrient cycling and productivity, especially in forest ecosystems, have not received the attention that this "master" variable deserves, On northern Vancouver Island, Canada, regenerating stands of western redcedar-western hemlock (CH) sites exhibit symptoms of nutrient deficiencies and slow growth, but this phenomenon does not occur on adjacent western hemlock- amabalis fir (HA) sites. We tested the hypothesis that differences in nutrient supply and distribution of plant species was caused by differences in moisture regime and redox potential. Redox potential, pH, soil aeration depth (steel rods), organic matter thickness, bulk density, soil carbon store, plant species distribution and richness were measured at five old-growth and five 10-year-old cutover blocks. Results of investigations confirmed that CH forests were wetter, had redox values lower than the critical 300mv and a shallower aerated zone, compared with adjacent regenerating HA sites. Fifty percent of the CH plots had redox values less than +300 mv in the forest floor; whereas only 15 percent of the HA plots had such low values. Composition of the forest understory species was related to soil moisture/aeration. Soil aeration was the most important soil variable influencing plant species composition, explaining 25% of the plant community variability. Eh was always greater than +300 mv in the mineral soil of old growth HA forests but below +300 mv in HA clearcuts, suggesting paludification; however it was below or at this threshold in both CH forests and clearcuts. The reduction in measured redox without a noticeable change in the watertable in HA sites suggests that harvesting HA forests shifts the ecosystem towards more anaerobic conditions more similar to CH sites. In a complimentary study, the significance of redox was assessed in a cedar swamp cutover by exploring the relationships between soil redox potential and tree growth, and mineralization of C and soil C store along a gradient of moisture caused by drainage. Drainage improved aeration in the rooting zone, expressed as redox, and above- and below ground C storage; however C mineralization measured as CO2 evolution was not affected. Tree growth was positively correlated with redox potential. Our results indicate that drainage could be a useful silvicultural practice for improving the productivity of these ecosystems and that it may be possible to improve tree growth without stimulating loss of soil C. This requires that drainage improve aeration in the rooting zone while maintaining redox levels of less than +300 mV in the bulk soil, indicating that redox measurements should be incorporated into silviculture interventions to improve productivity of these forests.

In Vivo Monitoring of pH, Redox Status, and Glutathione Using L-Band EPR for Assessment of Therapeutic Effectiveness in Solid Tumors

PubMed Central

Bobko, Andrey A.; Eubank, Timothy D.; Voorhees, Jeffrey L.; Efimova, Olga V.; Kirilyuk, Igor A.; Petryakov, Sergey; Trofimiov, Dmitrii G.; Marsh, Clay B.; Zweier, Jay L.; Grigor’ev, Igor A.; Samouilov, Alexandre; Khramtsov, Valery V.

2011-01-01

Approach for in vivo real-time assessment of tumor tissue extracellular pH (pHe), redox, and intracellular glutathione based on L-band EPR spectroscopy using dual function pH and redox nitroxide probe and disulfide nitroxide biradical, is described. These parameters were monitored in PyMT mice bearing breast cancer tumors during treatment with granulocyte macrophage colony-stimulating factor. It was observed that tumor pHe is about 0.4 pH units lower than that in normal mammary gland tissue. Treatment with granulocyte macrophage colony-stimulating factor decreased the value of pHe by 0.3 units compared with PBS control treatment. Tumor tissue reducing capacity and intracellular glutathione were elevated compared with normal mammary gland tissue. Granulocyte macrophage colony-stimulating factor treatment resulted in a decrease of the tumor tissue reducing capacity and intracellular glutathione content. In addition to spectroscopic studies, pHe mapping was performed using recently proposed variable frequency proton–electron double-resonance imaging. The pH mapping superimposed with MRI image supports probe localization in mammary gland/tumor tissue, shows high heterogeneity of tumor tissue pHe and a difference of about 0.4 pH units between average pHe values in tumor and normal mammary gland. In summary, the developed multifunctional approach allows for in vivo, noninvasive pHe, extracellular redox, and intracellular glutathione content monitoring during investigation of various therapeutic strategies for solid tumors. Magn Reson Med 000:000–000, 2011. PMID:22113626

Effect of Drying on Heavy Metal Fraction Distribution in Rice Paddy Soil

PubMed Central

Qi, Yanbing; Huang, Biao; Darilek, Jeremy Landon

2014-01-01

An understanding of how redox conditions affect soil heavy metal fractions in rice paddies is important due to its implications for heavy metal mobility and plant uptake. Rice paddy soil samples routinely undergo oxidation prior to heavy metal analysis. Fraction distribution of Cu, Pb, Ni, and Cd from paddy soil with a wide pH range was investigated. Samples were both dried according to standard protocols and also preserved under anaerobic conditions through the sampling and analysis process and heavy metals were then sequentially extracted for the exchangeable and carbonate bound fraction (acid soluble fraction), iron and manganese oxide bound fraction (reducible fraction), organic bound fraction (oxidizable fraction), and residual fraction. Fractions were affected by redox conditions across all pH ranges. Drying decreased reducible fraction of all heavy metals. Curesidual fraction, Pboxidizable fraction, Cdresidual fraction, and Niresidual fraction increased by 25%, 33%, 35%, and >60%, respectively. Pbresidual fraction, Niacid soluble fraction, and Cdoxidizable fraction decreased 33%, 25%, and 15%, respectively. Drying paddy soil prior to heavy metal analysis overestimated Pb and underestimated Cu, Ni, and Cd. In future studies, samples should be stored after injecting N2 gas to maintain the redox potential of soil prior to heavy metal analysis, and investigate the correlation between heavy metal fraction distribution under field conditions and air-dried samples. PMID:24823670

Distinct Redox Regulation in Sub-Cellular Compartments in Response to Various Stress Conditions in Saccharomyces cerevisiae

PubMed Central

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. PMID:23762325

Organic chemical degradation by remote study of the redox conditions

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Synthetic Models for Nickel-Iron Hydrogenase Featuring Redox-Active Ligands.

PubMed

Schilter, David; Gray, Danielle L; Fuller, Amy L; Rauchfuss, Thomas B

2017-05-01

The nickel-iron hydrogenase enzymes efficiently and reversibly interconvert protons, electrons, and dihydrogen. These redox proteins feature iron-sulfur clusters that relay electrons to and from their active sites. Reported here are synthetic models for nickel-iron hydrogenase featuring redox-active auxiliaries that mimic the iron-sulfur cofactors. The complexes prepared are Ni II (μ-H)Fe II Fe II species of formula [(diphosphine)Ni(dithiolate)(μ-H)Fe(CO) 2 (ferrocenylphosphine)] + or Ni II Fe I Fe II complexes [(diphosphine)Ni(dithiolate)Fe(CO) 2 (ferrocenylphosphine)] + (diphosphine = Ph 2 P(CH 2 ) 2 PPh 2 or Cy 2 P(CH 2 ) 2 PCy 2 ; dithiolate = - S(CH 2 ) 3 S - ; ferrocenylphosphine = diphenylphosphinoferrocene, diphenylphosphinomethyl(nonamethylferrocene) or 1,1'-bis(diphenylphosphino)ferrocene). The hydride species is a catalyst for hydrogen evolution, while the latter hydride-free complexes can exist in four redox states - a feature made possible by the incorporation of the ferrocenyl groups. Mixed-valent complexes of 1,1'-bis(diphenylphosphino)ferrocene have one of the phosphine groups unbound, with these species representing advanced structural models with both a redox-active moiety (the ferrocene group) and a potential proton relay (the free phosphine) proximal to a nickel-iron dithiolate.

Synthetic Models for Nickel–Iron Hydrogenase Featuring Redox-Active Ligands*

PubMed Central

Schilter, David; Gray, Danielle L.; Fuller, Amy L.; Rauchfuss, Thomas B.

2017-01-01

The nickel–iron hydrogenase enzymes efficiently and reversibly interconvert protons, electrons, and dihydrogen. These redox proteins feature iron–sulfur clusters that relay electrons to and from their active sites. Reported here are synthetic models for nickel–iron hydrogenase featuring redox-active auxiliaries that mimic the iron–sulfur cofactors. The complexes prepared are NiII(μ-H)FeIIFeII species of formula [(diphosphine)Ni(dithiolate)(μ-H)Fe(CO)2(ferrocenylphosphine)]+ or NiIIFeIFeII complexes [(diphosphine)Ni(dithiolate)Fe(CO)2(ferrocenylphosphine)]+ (diphosphine = Ph2P(CH2)2PPh2 or Cy2P(CH2)2PCy2; dithiolate = −S(CH2)3S−; ferrocenylphosphine = diphenylphosphinoferrocene, diphenylphosphinomethyl(nonamethylferrocene) or 1,1′-bis(diphenylphosphino)ferrocene). The hydride species is a catalyst for hydrogen evolution, while the latter hydride-free complexes can exist in four redox states – a feature made possible by the incorporation of the ferrocenyl groups. Mixed-valent complexes of 1,1′-bis(diphenylphosphino)ferrocene have one of the phosphine groups unbound, with these species representing advanced structural models with both a redox-active moiety (the ferrocene group) and a potential proton relay (the free phosphine) proximal to a nickel–iron dithiolate. PMID:28819328

Flow-injection analysis with electrochemical detection of reduced nicotinamide adenine dinucleotide using 2,6-dichloroindophenol as a redox coupling agent.

PubMed

Tang, H T; Hajizadeh, K; Halsall, H B; Heineman, W R

1991-01-01

The determination of reduced nicotinamide adenine dinucleotide (NADH) by electrochemical oxidation requires a more positive potential than is predicted by the formal reduction potential for the NAD+/NADH couple. This problem is alleviated by use of 2,6-dichloroindophenol (DCIP) as a redox coupling agent for NADH. The electrochemical characteristics of DCIP at the glassy carbon electrode are examined by cyclic voltammetry and hydrodynamic voltammetry. NADH is determined by reaction with DCIP to form NAD+ and DCIPH2. DCIPH2 is then quantitated by flow-injection analysis with electrochemical detection by oxidation at a detector potential of +0.25 V at pH 7. NADH is determined over a linear range of 0.5 to 200 microM and with a detection limit of 0.38 microM. The lower detection potential for DCIPH2 compared to NADH helps to minimize interference from oxidizable components in serum samples.

Electron transfer of quinone self-assembled monolayers on a gold electrode.

PubMed

Nagata, Morio; Kondo, Masaharu; Suemori, Yoshiharu; Ochiai, Tsuyoshi; Dewa, Takehisa; Ohtsuka, Toshiaki; Nango, Mamoru

2008-06-15

Dialkyl disulfide-linked naphthoquinone, (NQ-Cn-S)2, and anthraquinone, (AQ-Cn-S)2, derivatives with different spacer alkyl chains (Cn: n=2, 6, 12) were synthesized and these quinone derivatives were self-assembled on a gold electrode. The formation of self-assembled monolayers (SAMs) of these derivatives on a gold electrode was confirmed by infrared reflection-absorption spectroscopy (IR-RAS). Electron transfer between the derivatives and the gold electrode was studied by cyclic voltammetry. On the cyclic voltammogram a reversible redox reaction between quinone (Q) and hydroquinone (QH2) was clearly observed under an aqueous condition. The formal potentials for NQ and AQ derivatives were -0.48 and -0.58 V, respectively, that did not depend on the spacer length. The oxidation and reduction peak currents were strongly dependent on the spacer alkyl chain length. The redox behavior of quinone derivatives depended on the pH condition of the buffer solution. The pH dependence was in agreement with a theoretical value of E 1/2 (mV)=E'-59pH for 2H+/2e(-) process in the pH range 3-11. In the range higher than pH 11, the value was estimated with E 1/2 (mV)=E'-30pH , which may correspond to H+/2e(-) process. The tunneling barrier coefficients (beta) for NQ and AQ SAMs were determined to be 0.12 and 0.73 per methylene group (CH2), respectively. Comparison of the structures and the alkyl chain length of quinones derivatives on these electron transfers on the electrode is made.

Impact of butyric acid on butanol formation by Clostridium pasteurianum.

PubMed

Regestein, Lars; Doerr, Eric Will; Staaden, Antje; Rehmann, Lars

2015-11-01

The butanol yield of the classic fermentative acetone-butanol-ethanol (ABE) process has been enhanced in the past decades through the development of better strains and advanced process design. Nevertheless, by-product formation and the incomplete conversion of intermediates still decrease the butanol yield. This study demonstrates the potential of increasing the butanol yield from glycerol though the addition of small amounts of butyric acid. The impact of butyric acid was investigated in a 7L stirred tank reactor. The results of this study show the positive impact of butyric acid on butanol yield under pH controlled conditions and the metabolic stages were monitored via online measurement of carbon dioxide formation, pH value and redox potential. Butyric acid could significantly increase the butanol yield at low pH values if sufficient quantities of primary carbon source (glycerol) were present. Copyright © 2015 Elsevier Ltd. All rights reserved.

Redox stress in geobacilli from geothermal springs: Phenomenon and membrane-associated response mechanisms.

PubMed

Ghazaryan, Astghik; Blbulyan, Syuzanna; Poladyan, Anna; Trchounian, Armen

2015-10-01

Geobacillus toebii ArzA-8, from Armenian geothermal springs, grew well in nutrient broth. During its growth, changes in pH in opposite directions were observed depending on glucose supplementation. Accordingly, the decrease in the redox potential was determined using titanium-silicate (Eh) and platinum (Eh') electrodes: Eh decreased to -150 ± 3 mV and Eh' to -350 ± 2 mV without glucose; the decrease in these potentials was smaller with glucose. Redox stress due to an oxidizer, K3[Fe(CN)6], or a reducer, dl-dithiothreitol (DTT), inhibited bacterial growth. However, a stimulatory effect of K3[Fe(CN)6] or DTT was observed with or without glucose, respectively. With glucose, the H(+) efflux was sensitive to N,N'-dicyclohexylcarbodiimide (DCCD), an inhibitor of FoF1FOF1-ATPase and other H(+) translocation mechanisms, but the addition of an oxidizer or reducer suppressed the H(+) efflux. The ATPase activity of membrane vesicles was ~1.3-fold higher in cells grown with glucose compared with cells grown without glucose. DCCD and DTT suppressed ATPase activity in cells grown without glucose, whereas DTT stimulated FOF1-ATPase activity in cells grown with glucose. Thus, G. toebii senses redox stress; this thermophile likely presents specific membrane-associated response mechanisms involving FOF1-ATPase to overcome redox stress and survive; these mechanisms are important for adaptation to extreme environments. Copyright © 2015 Elsevier B.V. All rights reserved.

Tuning of the ionization potential of paddlewheel diruthenium(II, II) complexes with fluorine atoms on the benzoate ligands.

PubMed

Miyasaka, Hitoshi; Motokawa, Natsuko; Atsuumi, Ryo; Kamo, Hiromichi; Asai, Yuichiro; Yamashita, Masahiro

2011-01-21

A series of paddlewheel diruthenium(ii, ii) complexes with various fluorine-substituted benzoate ligands were isolated as THF adducts and structurally characterized: [Ru(2)(F(x)PhCO(2))(4)(THF)(2)] (F(x)PhCO(2)(-) = o-fluorobenzoate, o-F; m-fluorobenzoate, m-F; p-fluorobenzoate, p-F; 2,6-difluorobenzoate, 2,6-F(2); 3,4-difluorobenzoate, 3,4-F(2); 3,5-difluorobenzoate, 3,5-F(2); 2,3,4-trifluorobenzoate, 2,3,4-F(3); 2,3,6-trifluorobenzoate, 2,3,6-F(3); 2,4,5-trifluorobenzoate, 2,4,5-F(3); 2,4,6-trifluorobenzoate, 2,4,6-F(3); 3,4,5-trifluorobenzoate, 3,4,5-F(3); 2,3,4,5-tetrafluorobenzoate, 2,3,4,5-F(4); 2,3,5,6-tetrafluorobenzoate, 2,3,5,6-F(4); pentafluorobenzoate, F(5)). By adding fluorine atoms on the benzoate ligands, it was possible to tune the redox potential (E(1/2)) for [Ru(2)(II,II)]/[Ru(2)(II,III)](+) over a wide range of potentials from -40 mV to 350 mV (vs. Ag/Ag(+) in THF). 2,3,6-F(3), 2,3,4,5-F(4), 2,3,5,6-F(4) and F(5) were relatively air-stable compounds even though they are [Ru(2)(II,II)] species. The redox potential in THF was dependent on an electronic effect rather than on a structural (steric) effect of the o-F atoms, although more than one substituent in the m- and p-positions shifted E(1/2) to higher potentials in relation to the general Hammett equation. A quasi-Hammett parameter for an o-F atom (σ(o)) was estimated to be ∼0.2, and a plot of E(1/2)vs. a sum of Hammett parameters including σ(o) was linear. In addition, the HOMO energy levels, which was calculated based on atomic coordinates of solid-state structures, as well as the redox potential were affected by adding F atoms. Nevertheless, a steric contribution stabilizing their static structures in the solid state was present in addition to the electronic effect. On the basis of the electronic effect, the redox potential of these complexes is correlated to the HOMO energy level, and the electronic effect of F atoms is the main factor controlling the ionization potential of the complexes with ligands free from the rotational constraint, i.e. complexes in solution.

Oxidovanadium(IV/V) complexes as new redox mediators in dye-sensitized solar cells: a combined experimental and theoretical study.

PubMed

Apostolopoulou, Andigoni; Vlasiou, Manolis; Tziouris, Petros A; Tsiafoulis, Constantinos; Tsipis, Athanassios C; Rehder, Dieter; Kabanos, Themistoklis A; Keramidas, Anastasios D; Stathatos, Elias

2015-04-20

Corrosiveness is one of the main drawbacks of using the iodide/triiodide redox couple in dye-sensitized solar cells (DSSCs). Alternative redox couples including transition metal complexes have been investigated where surprisingly high efficiencies for the conversion of solar to electrical energy have been achieved. In this paper, we examined the development of a DSSC using an electrolyte based on square pyramidal oxidovanadium(IV/V) complexes. The oxidovanadium(IV) complex (Ph4P)2[V(IV)O(hybeb)] was combined with its oxidized analogue (Ph4P)[V(V)O(hybeb)] {where hybeb(4-) is the tetradentate diamidodiphenolate ligand [1-(2-hydroxybenzamido)-2-(2-pyridinecarboxamido)benzenato}and applied as a redox couple in the electrolyte of DSSCs. The complexes exhibit large electron exchange and transfer rates, which are evident from electron paramagnetic resonance spectroscopy and electrochemistry, rendering the oxidovanadium(IV/V) compounds suitable for redox mediators in DSSCs. The very large self-exchange rate constant offered an insight into the mechanism of the exchange reaction most likely mediated through an outer-sphere exchange mechanism. The [V(IV)O(hybeb)](2-)/[V(V)O(hybeb)](-) redox potential and the energy of highest occupied molecular orbital (HOMO) of the sensitizing dye N719 and the HOMO of [V(IV)O(hybeb)](2-) were calculated by means of density functional theory electronic structure calculation methods. The complexes were applied as a new redox mediator in DSSCs, while the cell performance was studied in terms of the concentration of the reduced and oxidized form of the complexes. These studies were performed with the commercial Ru-based sensitizer N719 absorbed on a TiO2 semiconducting film in the DSSC. Maximum energy conversion efficiencies of 2% at simulated solar light (AM 1.5; 1000 W m(-2)) with an open circuit voltage of 660 mV, a short-circuit current of 5.2 mA cm(-2), and a fill factor of 0.58 were recorded without the presence of any additives in the electrolyte.

Redox and pH Dual-Responsive Polymeric Micelles with Aggregation-Induced Emission Feature for Cellular Imaging and Chemotherapy.

PubMed

Zhuang, Weihua; Xu, Yangyang; Li, Gaocan; Hu, Jun; Ma, Boxuan; Yu, Tao; Su, Xin; Wang, Yunbing

2018-05-21

Intelligent polymeric micelles for antitumor drug delivery and tumor bioimaging have drawn a broad attention because of their reduced systemic toxicity, enhanced efficacy of drugs, and potential application of tumor diagnosis. Herein, we developed a multifunctional polymeric micelle system based on a pH and redox dual-responsive mPEG-P(TPE- co-AEMA) copolymer for stimuli-triggered drug release and aggregation-induced emission (AIE) active imaging. These mPEG-P(TPE- co-AEMA)-based micelles showed excellent biocompatibility and emission property, exhibiting great potential application for cellular imaging. Furthermore, the antitumor drug doxorubicin (DOX) could be encapsulated during self-assembly process with high loading efficiency, and a DOX-loaded micelle system with a size of 68.2 nm and narrow size distribution could be obtained. DOX-loaded micelles demonstrated great tumor suppression ability in vitro, and the dual-responsive triggered intracellular drug release could be further traced. Moreover, DOX-loaded micelles could efficiently accumulate at the tumor site because of enhanced permeability and retention effect and long circulation of micelles. Compared with free DOX, DOX-loaded micelles exhibited better antitumor effect and significantly reduced adverse effects. Given the efficient accumulation targeting to tumor tissue, dual-responsive drug release, and excellent AIE property, this polymeric micelle would be a potential candidate for cancer therapy and diagnosis.

pH controls over methanogenesis and iron reduction along soil depth profile in Arctic tundra

NASA Astrophysics Data System (ADS)

Zheng, J.; Gu, B.; Wullschleger, S. D.; Graham, D. E.

2017-12-01

Increasing soil temperature in the Arctic is expected to accelerate rates of soil organic matter decomposition. However, the magnitude of this impact is uncertain due to the many physical, chemical, and biological processes that control the decomposition pathways. Varying soil redox conditions present a key control over pathways of organic matter decomposition by diverting the flow of reductants among different electron accepting processes and further driving acid-base reactions that alter soil pH. In this study we investigated the pH controls over anaerobic carbon mineralization, methanogenesis, Fe(III) reduction and the interplay between these processes across a range of pH and redox conditions. pH manipulation experiments were conducted by incubating soils representing organic, mineral, cryoturbated transitional layers and permafrost. In the experiments we sought to understand (1) if methanogenesis or Fe(III) reduction had similar pH optima; (2) if this pH response also occurs at `upstream' fermentation process; and (3) if pH alters organo-mineral association or organic matter sorption and desorption and its availability for microbial degradation. Our preliminary results suggest that the common bell-shaped pH response curve provides a good fit for both Fe(III) reduction and methanogenesis, with optimum pH at 6.0-7.0. Exceptions to this were found in transitional layer where methanogenesis rates positively correlated with increasing pH, with maximum rates measured at pH 8.5. It is likely that the transitional layer harbors distinct groups of methanogens that prefer a high pH. Variations in the optimum pH of Fe(III) reduction and methanogenesis may play a significant role in regulating organic matter decomposition pathways and thus greenhouse gas production in thawing soils. These results support biogeochemical modeling efforts to accurately simulate organic matter decomposition under changing redox and pH conditions.

Fine Tuning of Redox Networks on Multiheme Cytochromes from Geobacter sulfurreducens Drives Physiological Electron/Proton Energy Transduction

PubMed Central

Morgado, Leonor; Dantas, Joana M.; Bruix, Marta; Londer, Yuri Y.; Salgueiro, Carlos A.

2012-01-01

The bacterium Geobacter sulfurreducens (Gs) can grow in the presence of extracellular terminal acceptors, a property that is currently explored to harvest electricity from aquatic sediments and waste organic matter into microbial fuel cells. A family composed of five triheme cytochromes (PpcA-E) was identified in Gs. These cytochromes play a crucial role by bridging the electron transfer from oxidation of cytoplasmic donors to the cell exterior and assisting the reduction of extracellular terminal acceptors. The detailed thermodynamic characterization of such proteins showed that PpcA and PpcD have an important redox-Bohr effect that might implicate these proteins in the e−/H+ coupling mechanisms to sustain cellular growth. The physiological relevance of the redox-Bohr effect in these proteins was studied by determining the fractional contribution of each individual redox-microstate at different pH values. For both proteins, oxidation progresses from a particular protonated microstate to a particular deprotonated one, over specific pH ranges. The preferred e−/H+ transfer pathway established by the selected microstates indicates that both proteins are functionally designed to couple e−/H+ transfer at the physiological pH range for cellular growth. PMID:22899897

Development and characterization of a voltammetric carbon-fiber microelectrode pH sensor.

PubMed

Makos, Monique A; Omiatek, Donna M; Ewing, Andrew G; Heien, Michael L

2010-06-15

This work describes the development and characterization of a modified carbon-fiber microelectrode sensor capable of measuring real-time physiological pH changes in biological microenvironments. The reagentless sensor was fabricated under ambient conditions from voltammetric reduction of the diazonium salt Fast Blue RR onto a carbon-fiber surface in aprotic media. Fast-scan cyclic voltammetry was used to probe redox activity of the p-quinone moiety of the surface-bound molecule as a function of pH. In vitro calibration of the sensor in solutions ranging from pH 6.5 to 8.0 resulted in a pH-dependent anodic peak potential response. Flow-injection analysis was used to characterize the modified microelectrode, revealing sensitivity to acidic and basic changes discernible to 0.005 pH units. Furthermore, the modified electrode was used to measure dynamic in vivo pH changes evoked during neurotransmitter release in the central nervous system of the microanalytical model organism Drosophila melanogaster.

Development and Characterization of a Voltammetric Carbon-fiber Microelectrode pH Sensor

PubMed Central

Makos, Monique A.; Omiatek, Donna M.; Ewing, Andrew G.; Heien, Michael L.

2010-01-01

This work describes the development and characterization of a modified carbon-fiber microelectrode sensor capable of measuring real-time physiological pH changes in biological microenvironments. The reagentless sensor was fabricated under ambient conditions from voltammetric reduction of the diazonium salt Fast Blue RR onto a carbon-fiber surface in aprotic media. Fast-scan cyclic voltammetry was used to probe redox activity of the p-quinone moiety of the surface-bound molecule as a function of pH. In vitro calibration of the sensor in solutions ranging from pH 6.5 to 8.0 resulted in a pH-dependent anodic peak potential response. Flow-injection analysis was used to characterize the modified microelectrode, revealing sensitivity to acidic and basic changes discernable to 0.005 pH units. Furthermore, the modified electrode was used to measure dynamic in vivo pH changes evoked during neurotransmitter release in the central nervous system of the microanalytical model organism Drosophila melanogaster. PMID:20380393

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

PubMed

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

2012-11-15

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

New Approach in Translational Medicine: Effects of Electrolyzed Reduced Water (ERW) on NF-κB/iNOS Pathway in U937 Cell Line under Altered Redox State

PubMed Central

Franceschelli, Sara; Gatta, Daniela Maria Pia; Pesce, Mirko; Ferrone, Alessio; Patruno, Antonia; de Lutiis, Maria Anna; Grilli, Alfredo; Felaco, Mario; Croce, Fausto; Speranza, Lorenza

2016-01-01

It is known that increased levels of reactive oxygen species (ROS) and reactive nitrogen species (RNS) can exert harmful effects, altering the cellular redox state. Electrolyzed Reduced Water (ERW) produced near the cathode during water electrolysis exhibits high pH, high concentration of dissolved hydrogen and an extremely negative redox potential. Several findings indicate that ERW had the ability of a scavenger free radical, which results from hydrogen molecules with a high reducing ability and may participate in the redox regulation of cellular function. We investigated the effect of ERW on H2O2-induced U937 damage by evaluating the modulation of redox cellular state. Western blotting and spectrophotometrical analysis showed that ERW inhibited oxidative stress by restoring the antioxidant capacity of superoxide dismutase, catalase and glutathione peroxidase. Consequently, ERW restores the ability of the glutathione reductase to supply the cell of an important endogenous antioxidant, such as GSH, reversing the inhibitory effect of H2O2 on redox balance of U937 cells. Therefore, this means a reduction of cytotoxicity induced by peroxynitrite via a downregulation of the NF-κB/iNOS pathway and could be used as an antioxidant for preventive and therapeutic application. In conclusion, ERW can protect the cellular redox balance, reducing the risk of several diseases with altered cellular homeostasis such as inflammation. PMID:27598129

Enzymatic versus nonenzymatic mechanisms for Fe(III) reduction in aquatic sediments

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.; Lonergan, D.J.

1991-01-01

The potential for nonenzymatic reduction of Fe(III) either by organic compounds or by the development of a low redox potential during microbial metabolism was compared with direct, enzymatic Fe(III) reduction by Fe(III)-reducing microorganisms. At circumneutral pH, very few organic compounds nonenzymatically reduced Fe(III). In contrast, in the presence of the appropriate Fe(IH)-reducing microorganisms, most of the organic compounds examined could be completely oxidized to carbon dioxide with the reduction of Fe(III). Even for those organic compounds that could nonenzymatically reduce Fe(III), microbial Fe(III) reduction was much more extensive. The development of a low redox potential during microbial fermentation did not result in nonenzymatic Fe(III) reduction. Model organic compounds were readily oxidized in Fe(III)-reducing aquifer sediments, but not in sterilized sediments. These results suggest that microorganisms enzymatically catalyze most of the Fe(III) reduction in the Fe(III) reduction zone of aquatic sediments and aquifers.

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

PubMed

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

2017-03-10

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

Highly Acidic Ambient Particles, Soluble Metals, and Oxidative Potential: A Link between Sulfate and Aerosol Toxicity.

PubMed

Fang, Ting; Guo, Hongyu; Zeng, Linghan; Verma, Vishal; Nenes, Athanasios; Weber, Rodney J

2017-03-07

Soluble transition metals in particulate matter (PM) can generate reactive oxygen species in vivo by redox cycling, leading to oxidative stress and adverse health effects. Most metals, such as those from roadway traffic, are emitted in an insoluble form, but must be soluble for redox cycling. Here we present the mechanism of metals dissolution by highly acidic sulfate aerosol and the effect on particle oxidative potential (OP) through analysis of size distributions. Size-segregated ambient PM were collected from a road-side and representative urban site in Atlanta, GA. Elemental and organic carbon, ions, total and water-soluble metals, and water-soluble OP were measured. Particle pH was determined with a thermodynamic model using measured ionic species. Sulfate was spatially uniform and found mainly in the fine mode, whereas total metals and mineral dust cations were highest at the road-side site and in the coarse mode, resulting in a fine mode pH < 2 and near neutral coarse mode. Soluble metals and OP peaked at the intersection of these modes demonstrating that sulfate plays a key role in producing highly acidic fine aerosols capable of dissolving primary transition metals that contribute to aerosol OP. Sulfate-driven metals dissolution may account for sulfate-health associations reported in past studies.

Bacterial community dynamics in a rumen fluid bioreactor during in-vitro cultivation.

PubMed

Zapletalová, Martina; Kašparovská, Jitka; Křížová, Ludmila; Kašparovský, Tomáš; Šerý, Omar; Lochman, Jan

2016-09-20

To study the various processes in the rumen the in vitro techniques are widely used to realize more controlled and reproducible conditions compared to in vivo experiments. Mostly, only the parameters like pH changes, volatile fatty acids content or metabolite production are monitored. In this study we examine the bacterial community dynamics of rumen fluid in course of ten day cultivation realize under standard conditions described in the literature. Whereas the pH values, total VFA content and A/P ratio in bioreactor were consistent with natural conditions in the rumen, the mean redox-potential values of -251 and -243mV were much more negative. For culture-independent assessment of bacterial community composition, the Illumina MiSeq results indicated that the community contained 292 bacterial genera. In course of ten days cultivation a significant changes in the microbial community were measured when Bacteroidetes to Firmicutes ratio changed from 3.2 to 1.2 and phyla Proteobacteria and Actinobacteria represented by genus Bifidobacterium and Olsenella significantly increased. The main responsible factor of these changes seems to be very low redox potential in bioreactor together with accumulation of simple carbohydrates in milieu as a result of limited excretion of fermented feed and absence of nutrient absorbing mechanisms. Copyright © 2016 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Glasner, Björn; Fiedler, Sabine

2017-04-01

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

pH-Dependent Regulation of the Relaxation Rate of the Radical Anion of the Secondary Quinone Electron Acceptor QB in Photosystem II As Revealed by Fourier Transform Infrared Spectroscopy.

PubMed

Nozawa, Yosuke; Noguchi, Takumi

2018-05-15

Photosystem II (PSII) is a protein complex that performs water oxidation using light energy during photosynthesis. In PSII, electrons abstracted from water are eventually transferred to the secondary quinone electron acceptor, Q B , and upon double reduction, Q B is converted to quinol by binding two protons. Thus, excess electron transfer in PSII increases the pH of the stroma. In this study, to investigate the pH-dependent regulation of the electron flow in PSII, we have estimated the relaxation rate of the Q B - radical anion in the pH region between 5 and 8 by direct monitoring of its population using light-induced Fourier transform infrared difference spectroscopy. The decay of Q B - by charge recombination with the S 2 state of the water oxidation center in PSII membranes was shown to be accelerated at higher pH, whereas that of Q A - examined in the presence of a herbicide was virtually unaffected at pH ≤7.5 and slightly slowed at pH 8. These observations were consistent with the previous studies that included rather indirect monitoring of the Q B - and Q A - decays using fluorescence detection. The accelerated relaxation of Q B - was explained by the shift of a redox equilibrium between Q A - and Q B - to the Q A - side due to the decrease in the redox potential of Q B at higher pH, which is induced by deprotonation of a single amino acid residue near Q B . It is proposed that this pH-dependent Q B - relaxation is one of the mechanisms of electron flow regulation in PSII for its photoprotection.

Hydric soils in a southeastern Oregon vernal pool

USGS Publications Warehouse

Clausnitzer, D.; Huddleston, J.H.; Horn, E.; Keller, Michael; Leet, C.

2003-01-01

Vernal pools on the High Lava Plain of the northern Great Basin become ponded in most years, but their soils exhibit weak redoximorphic features indicative of hydric conditions. We studied the hydrology, temperature, redox potentials, soil chemistry, and soil morphology of a vernal pool to determine if the soils are hydric, and to evaluate hydric soil field indicators. We collected data for 3 yr from piezometers, Pt electrodes, and thermocouples. Soil and water samples were analyzed for pH, organic C, and extractable Fe and Mn. Soils were ponded from January through April or May, but subsurface saturation was never detected. Soil temperatures 50 cm below the surface rose above 5??C by March. Clayey Bt horizons perched water and limited saturation to the upper 10 cm. Redox potentials at a 5-cm depth were often between 200 and 300 mV, indicating anaerobic conditions, but producing soluble Fe2+ concentrations <1 mg L-1. Extractable soil Fe contents indicated Fe depletion from pool surface horizons and accumulation at or near the upper Bt1 horizon. Depletions and concentrations did not satisfy the criteria of any current hydric soil indicators. We recommend development of new indicators based on acceptance of fewer, less distinct redox concentrations for recognition of a depleted A horizon, and on presence of a thin zone containing redox concentrations located in the upper part of the near-surface perching horizon.

EHPG iron(III) complexes as potential contrast contrast agents for MRI.

PubMed

Kuźnik, Nikodem; Jewuła, Paweł; Oczek, Lidia; Kozłowicz, Sylwia; Grucela, Artur; Domagała, Wojciech

2014-01-01

A series of EHPG ligands and complexes were obtained. The derivatives of choice were p-OMe, 3,4-dimethyl, p-NHAc and p-Ph substituted ones. The complexes were characterized by NMR relaxation decay (T1), EPR and cyclic voltammetry (CV). r1 Relaxivity of the Fe-EHPG-OMe, Fe-EHPG-Ph derivatives was found higher than that of Fe-EHPG. EPR measurements at liquid nitrogen temperature indicate a typical rhombohedral structure for both rac- and meso-diastereoisomers of the EHPG complexes. CV revealed the redox inactivity of the Fe-EHPG complexes at physiological conditions. Interpretation and discussion of the results is presented.

Soil microbial community composition is correlated to soil carbon processing along a boreal wetland formation gradient

USGS Publications Warehouse

Chapman, Eric; Cadillo-Quiroz, Hinsby; Childers, Daniel L.; Turetsky, Merritt R.; Waldrop, Mark P.

2017-01-01

Climate change is modifying global biogeochemical cycles. Microbial communities play an integral role in soil biogeochemical cycles; knowledge about microbial composition helps provide a mechanistic understanding of these ecosystem-level phenomena. Next generation sequencing approaches were used to investigate changes in microbial functional groups during ecosystem development, in response to climate change, in northern boreal wetlands. A gradient of wetlands that developed following permafrost degradation was used to characterize changes in the soil microbial communities that mediate C cycling: a bog representing an “undisturbed” system with intact permafrost, and a younger bog and an older bog that formed following the disturbance of permafrost thaw. Reference 16S rRNA databases and several diversity indices were used to assess structural differences among these communities, to assess relationships between soil microbial community composition and various environmental variables including redox potential and pH. Rates of potential CO2 and CH4 gas production were quantified to correlate sequence data with gas flux. The abundance of organic C degraders was highest in the youngest bog, suggesting higher rates of microbial processes, including potential CH4 production. In addition, alpha diversity was also highest in the youngest bog, which seemed to be related to a more neutral pH and a lower redox potential. These results could potentially be driven by increased niche differentiation in anaerobic soils. These results suggest that ecosystem structure, which was largely driven by changes in edaphic and plant community characteristics between the “undisturbed” permafrost bog and the two bogs formed following permafrost thaw, strongly influenced microbial function.

Electrochemistry of Cytochrome P450 BM3 in Sodium Dodecyl Sulfate Films

PubMed Central

Udit, Andrew K.; Hill, Michael G.; Gray, Harry B.

2008-01-01

Direct electrochemistry of the cytochrome P450 BM3 heme domain (BM3) was achieved by confining the protein within sodium dodecyl sulfate (SDS) films on the surface of basal-plane graphite (BPG) electrodes. Cyclic voltammetry revealed the heme FeIII/II redox couple at −330 mV (vs. Ag/AgCl, pH 7.4). Up to 10 V/s, the peak current was linear with scan rate, allowing us to treat the system as surface-confined within this regime. The standard heterogeneous rate constant determined at 10 V/s was estimated to be 10 s−1. Voltammograms obtained for the BM3-SDS-BPG system in the presence of dioxygen exhibited catalytic waves at the onset of FeIII reduction. The altered heme reduction potential of the BM3-SDS-graphite system indicates that SDS is likely bound in the enzyme active-site region. Compared to other P450-surfactant systems, we find redox potentials and electron transfer rates that differ by ~ 100 mV and > 10-fold, respectively, indicating that the nature of the surfactant environment has a significant effect on the observed heme redox properties. PMID:17129070

Acidogenic fermentation of food waste for volatile fatty acid production with co-generation of biohydrogen.

PubMed

Dahiya, Shikha; Sarkar, Omprakash; Swamy, Y V; Venkata Mohan, S

2015-04-01

Fermentation experiments were designed to elucidate the functional role of the redox microenvironment on volatile fatty acid (VFA, short chain carboxylic acid) production and co-generation of biohydrogen (H2). Higher VFA productivity was observed at pH 10 operation (6.3g/l) followed by pH 9, pH 6, pH 5, pH 7, pH 8 and pH 11 (3.5 g/l). High degree of acidification, good system buffering capacity along with co-generation of higher H2 production from food waste was also noticed at alkaline condition. Experiments illustrated the role of initial pH on carboxylic acids synthesis. Alkaline redox conditions assist solubilization of carbohydrates, protein and fats and also suppress the growth of methanogens. Among the carboxylic acids, acetate fraction was higher at alkaline condition than corresponding neutral or acidic operations. Integrated process of VFA production from waste with co-generation of H2 can be considered as a green and sustainable platform for value-addition. Copyright © 2015 Elsevier Ltd. All rights reserved.

Water-rock interaction in the magmatic-hydrothermal system of Nisyros Island (Greece)

NASA Astrophysics Data System (ADS)

Ambrosio, Michele; Doveri, Marco; Fagioli, Maria Teresa; Marini, Luigi; Principe, Claudia; Raco, Brunella

2010-04-01

In this work, we investigated the water-rock interaction processes taking place in the hydrothermal reservoir of Nisyros through both: (1) a review of the hydrothermal mineralogy encountered in the deep geothermal borehole Nisyros-2; and (2) a comparison of the analytically-derived redox potentials and acidities of fumarolic-related liquids, with those controlled by redox buffers and pH buffers, involving hydrothermal mineral phases. The propylitic zone met in the deep geothermal borehole Nisyros-2, from 950 to 1547 m (total depth), is characterised by abundant, well crystallised epidote, adularia, albite, quartz, pyrite, chlorite, and sericite-muscovite, accompanied by less abundant anhydrite, stilpnomelane, wairakite, garnet, tremolite and pyroxene. These hydrothermal minerals were produced in a comparatively wide temperature range, from 230 to 300 °C, approximately. Hydrothermal assemblages are well developed from 950 to 1360 m, whereas they are less developed below this depth, probably due to low permeability. Based on the RH values calculated for fumarolic gases and for the deep geothermal fluids of Nisyros-1 and Nisyros-2 wells, redox equilibrium with the (FeO)/(FeO 1.5) rock buffer appears to be closely attained throughout the hydrothermal reservoir of Nisyros. This conclusion may be easily reconciled with the nearly ubiquitous occurrence of anhydrite and pyrite, since RH values controlled by coexistence of anhydrite and pyrite can be achieved by gas separation. The pH of the liquids feeding the fumarolic vents of Stephanos and Polybote Micros craters was computed, by means of the EQ3 code, based on the Cl- δD relationship which is constrained by the seawater-magmatic water mixing occurring at depth in the hydrothermal-magmatic system of Nisyros. The temperature dependence of analytically-derived pH values for the reservoir liquids feeding the fumarolic vents of Stephanos and Polybote Micros craters suggests that some unspecified pH buffer fixes the acidity of these reservoir liquids at values of 4.72-4.85 and 4.88-5.23, respectively. Many of these pH values are lower than those expected for the full-equilibrium condition, although they are close to those of the reservoir liquids of Nisyros-1, 5.16, and Nisyros-2, 4.87. It is likely that this excess of acidity-producing species, chiefly CO 2, promotes release of Fe(II) and Fe(III) to the reservoir liquids through rock dissolution, permitting the attainment of redox equilibrium with the (FeO)/(FeO 1.5) rock buffer, as already suggested by the late Werner Giggenbach.

A pH and redox dual stimuli-responsive poly(amino acid) derivative for controlled drug release.

PubMed

Gong, Chu; Shan, Meng; Li, Bingqiang; Wu, Guolin

2016-10-01

A pH and redox dual stimuli-responsive poly(aspartic acid) derivative for controlled drug release was successfully developed through progressive ring-opening reactions of polysuccinimide (PSI). Polyethylene glycol (PEG) chains were grafted onto the polyaspartamide backbone via redox-responsive disulfide linkages, providing a sheddable shell for the polymeric micelles in a reductive environment. Phenyl groups were introduced into the polyaspartamide backbone via the aminolysis reaction of PSI to serve as the hydrophobic segment of micelles. The polyaspartamide scaffold was also functionalized with N-(3-aminopropyl)-imidazole to obtain the pH-responsiveness manifesting as a swelling of the core of micelles at a low pH. The polymeric micelles with a core-shell nanostructure forming in neutral media exhibited both pH and redox responsive characteristics. Doxorubicin (DOX) as a model drug was encapsulated into the core of micelles through both hydrophobic and π-π interactions between aromatic rings and the DOX-loaded polymeric micelles exhibited accelerated drug release behaviors in an acidic and reductive environment due to the swelling of hydrophobic cores and the shedding of PEG shells. Furthermore, the cytocompability of the polymer and the cytotoxicity of DOX-loaded micelles towards Hela cells under corresponding conditions were evaluated, and the endocytosis of DOX-loaded polymeric micelles and the intracellular drug release from micelles were observed. All obtained data indicated that the micelle was a promising candidate for controlled drug release. Copyright © 2016 Elsevier B.V. All rights reserved.

Sugar beet factory lime affects the mobilization of Cd, Co, Cr, Cu, Mo, Ni, Pb, and Zn under dynamic redox conditions in a contaminated floodplain soil.

PubMed

Shaheen, Sabry M; Rinklebe, Jörg

2017-01-15

The impact of sugar beet factory lime (SBFL) on the release dynamics and mobilization of toxic metals (TMs) under dynamic redox conditions in floodplain soils has not been studied up to date. Therefore, the aim of this study was to verify the scientific hypothesis that SBFL is able to immobilize Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, and Zn under different redox potentials (E H ) in a contaminated floodplain soil. For this purpose, the non-treated contaminated soil (CS) and the same soil treated with SBFL (CS+SBFL) were flooded in the laboratory using a highly sophisticated automated biogeochemical microcosm apparatus. The experiment was conducted stepwise from reducing (-13 mV) to oxidizing (+519 mV) soil conditions. Soil pH decreased under oxic conditions in CS (from 6.9 to 4.0) and in CS+SBFL (from 7.5 to 4.4). The mobilization of Cu, Cr, Pb, and Fe were lower in CS+SBFL than in CS under both reducing/neutral and oxic/acidic conditions. Those results demonstrate that SBFL is able to decrease concentrations of these elements under a wide range of redox and pH conditions. The mobilization of Cd, Co, Mn, Mo, Ni, and Zn were higher in CS+SBFL than in CS under reducing/neutral conditions; however, these concentrations showed an opposite behavior under oxic/acidic conditions and were lower in CS+SBFL than in CS. We conclude that SBFL immobilized Cu, Cr, Pb, and Fe under dynamic redox conditions and immobilized Cd, Co, Mn, Mo, Ni, and Zn under oxic acidic conditions; however, the latter elements were mobilized under reducing neutral conditions in the studied soil. Therefore, the addition of SBFL to acid floodplain soils contaminated with TMs might be an important alternative for ameliorating these soils with view to a sustainable management of these soils. Copyright © 2016 Elsevier Ltd. All rights reserved.

Heavy metals content in acid mine drainage at abandoned and active mining area

NASA Astrophysics Data System (ADS)

Hatar, Hazirah; Rahim, Sahibin Abd; Razi, Wan Mohd; Sahrani, Fathul Karim

2013-11-01

This study was conducted at former Barite Mine, Tasik Chini and former iron mine Sungai Lembing in Pahang, and also active gold mine at Lubuk Mandi, Terengganu. This study was conducted to determine heavy metals content in acid mine drainage (AMD) at the study areas. Fourteen water sampling stations within the study area were chosen for this purpose. In situ water characteristic determinations were carried out for pH, electrical conductivity (EC), redox potential (ORP) and total dissolved solid (TDS) using multi parameter YSI 556. Water samples were collected and analysed in the laboratory for sulfate, total acidity and heavy metals which follow the standard methods of APHA (1999) and HACH (2003). Heavy metals in the water samples were determined directly using Inductive Coupled Plasma Mass Spectrometry (ICP-MS). Data obtained showed a highly acidic mean of pH values with pH ranged from 2.6 ± 0.3 to 3.2 ± 0.2. Mean of electrical conductivity ranged from 0.57 ± 0.25 to 1.01 ± 0.70 mS/cm. Redox potential mean ranged from 487.40 ± 13.68 to 579.9 ± 80.46 mV. Mean of total dissolved solids (TDS) in AMD ranged from 306.50 ± 125.16 to 608.14 ± 411.64 mg/L. Mean of sulfate concentration in AMD ranged from 32.33 ± 1.41 to 207.08 ± 85.06 mg/L, whereas the mean of total acidity ranged from 69.17 ± 5.89 to 205.12 ± 170.83 mgCaCO3/L. Heavy metals content in AMD is dominated by Fe, Cu, Mn and Zn with mean concentrations range from 2.16 ± 1.61 to 36.31 ± 41.02 mg/L, 0.17 ± 0.13 to 11.06 ± 2.85 mg/L, 1.12 ± 0.65 to 7.17 ± 6.05 mg/L and 0.62 ± 0.21 to 6.56 ± 4.11 mg/L, respectively. Mean concentrations of Ni, Co, As, Cd and Pb were less than 0.21, 0.51, 0.24, 0.05 and 0.45 mg/L, respectively. Significant correlation occurred between Fe and Mn, Cu, Zn, Co and Cd. Water pH correlated negatively with all the heavy metals, whereas total acidity, sulfate, total dissolved solid, and redox potential correlated positively. The concentration of heavy metals in the AMD appeared to be influenced by acidity and the formation of Fe, Mn oxide and hydroxide.

Bacterial Fe(II) oxidation distinguished by long-range correlation in redox potential

NASA Astrophysics Data System (ADS)

Enright, Allison M. L.; Ferris, F. Grant

2016-05-01

The kinetics of bacterial Fe(II) oxidation was investigated 297 m underground at the Äspö Hard Rock Laboratory (near Oskarshamn, Sweden) under steady state groundwater flow conditions in a flow-through cell containing well-developed flocculent mats of bacteriogenic iron oxides (BIOS). Pseudo first-order rate constants of 0.004 min-1 and 0.009 min-1 were obtained for chemical and bacterial Fe(II) oxidation, respectively, based on the 104 min retention time of groundwater in the flow cell, inlet Fe(II) concentration of 21.0 ± 0.5 µm, outlet Fe(II) concentration of 8.5 ± 0.7 µm, as well as constant pH = - log H+ of 7.42 ± 0.01, dissolved O2 concentration of 0.11 ± 0.01 mg/L, and groundwater temperature of 12.4 ± 0.1°C. Redox potential was lower at the BIOS-free inlet (-135.4 ± 1.16 mV) compared to inside BIOS within the flow cell (-112.6 ± 1.91 mV), consistent with the Nernst relationship and oxidation of Fe(II) to Fe(III). Further evaluation of the redox potential time series data using detrended fluctuation analysis (DFA) revealed power law scaling in the amplitude of fluctuations over increasing intervals of time with significantly different (p < 0.01) DFA α scaling exponents of 1.89 ± 0.03 for BIOS and 1.67 ± 0.06 at the inlet. These α values not only signal the presence of long-range correlation in the redox potential time series measurements but also distinguish between the slower rate of chemical Fe(II) oxidation at the inlet and faster rate accelerated by FeOB in BIOS.

A comprehensive evaluation of the influence of air combustion and oxy-fuel combustion flue gas constituents on Hg(0) re-emission in WFGD systems.

PubMed

Ochoa-González, Raquel; Díaz-Somoano, Mercedes; Martínez-Tarazona, M Rosa

2014-07-15

This paper evaluates the influence of the main constituents of flue gases from coal combustion (CO2, O2, N2 and water vapor), in air and oxy-fuel combustion conditions on the re-emission of Hg(0) in wet scrubbers. It was observed that the concentration of water vapor does not affect the re-emission of mercury, whereas O2 and CO2 have a notable influence. High concentrations of O2 in the flue gas prevent the re-emission of Hg(0) due to the reaction of oxygen with the metals present in low oxidation states. High concentrations of CO2, which cause a decrease in the pH and the redox potential of gypsum slurries, reduce the amount of Hg(0) that is re-emitted. As a consequence, the high content of CO2 in oxy-fuel combustion may decrease the re-emission of Hg(0) due to the solubility of CO2 in the suspension and the decrease in the pH. It was also found that O2 affects the stabilization of Hg(2+) species in gypsum slurries. The results of this study confirm that the amount of metals present in limestone as well as the redox potential and pH of the slurries in wet desulphurization plants need to be strictly controlled to reduce Hg(0) re-emissions from power plants operating under oxy-fuel combustion conditions. Copyright © 2014 Elsevier B.V. All rights reserved.

A pH-activatable nanoparticle with signal-amplification capabilities for non-invasive imaging of tumour malignancy.

PubMed

Mi, Peng; Kokuryo, Daisuke; Cabral, Horacio; Wu, Hailiang; Terada, Yasuko; Saga, Tsuneo; Aoki, Ichio; Nishiyama, Nobuhiro; Kataoka, Kazunori

2016-08-01

Engineered nanoparticles that respond to pathophysiological parameters, such as pH or redox potential, have been developed as contrast agents for the magnetic resonance imaging (MRI) of tumours. However, beyond anatomic assessment, contrast agents that can sense these pathological parameters and rapidly amplify their magnetic resonance signals are desirable because they could potentially be used to monitor the biological processes of tumours and improve cancer diagnosis. Here, we report an MRI contrast agent that rapidly amplifies magnetic resonance signals in response to pH. We confined Mn(2+) within pH-sensitive calcium phosphate (CaP) nanoparticles comprising a poly(ethylene glycol) shell. At a low pH, such as in solid tumours, the CaP disintegrates and releases Mn(2+) ions. Binding to proteins increases the relaxivity of Mn(2+) and enhances the contrast. We show that these nanoparticles could rapidly and selectively brighten solid tumours, identify hypoxic regions within the tumour mass and detect invisible millimetre-sized metastatic tumours in the liver.

A pH-activatable nanoparticle with signal-amplification capabilities for non-invasive imaging of tumour malignancy

NASA Astrophysics Data System (ADS)

Mi, Peng; Kokuryo, Daisuke; Cabral, Horacio; Wu, Hailiang; Terada, Yasuko; Saga, Tsuneo; Aoki, Ichio; Nishiyama, Nobuhiro; Kataoka, Kazunori

2016-08-01

Engineered nanoparticles that respond to pathophysiological parameters, such as pH or redox potential, have been developed as contrast agents for the magnetic resonance imaging (MRI) of tumours. However, beyond anatomic assessment, contrast agents that can sense these pathological parameters and rapidly amplify their magnetic resonance signals are desirable because they could potentially be used to monitor the biological processes of tumours and improve cancer diagnosis. Here, we report an MRI contrast agent that rapidly amplifies magnetic resonance signals in response to pH. We confined Mn2+ within pH-sensitive calcium phosphate (CaP) nanoparticles comprising a poly(ethylene glycol) shell. At a low pH, such as in solid tumours, the CaP disintegrates and releases Mn2+ ions. Binding to proteins increases the relaxivity of Mn2+ and enhances the contrast. We show that these nanoparticles could rapidly and selectively brighten solid tumours, identify hypoxic regions within the tumour mass and detect invisible millimetre-sized metastatic tumours in the liver.

Guidance for Habitat Restoration Monitoring: Framework for Monitoring Plan Development and Implementation (User’s Guide)

DTIC Science & Technology

2004-08-01

release; distribution is unlimited. ENGINEERING SERVICE CENTER Port Hueneme, California 93043-4370 (This page intentionally blank.) REPORT DOCUMENTATION...responses. For example, an extended period of drought may greatly retard, set back, or even prevent establishment of a desired plant species or...Categories of Potential Chemical Monitoring Dataa Monitoring Variable Habitat Type Water Quality pH REDOX DO Salinity Freshwater wetlands S−M S–M M S–M

Munitions in the Underwater Environment: State of the Science and Knowledge Gaps

DTIC Science & Technology

2010-06-01

the Munitions Items Disposition Action System ( MIDAS ). Munitions constituents (MCs) can be identified through the known munitions type. The MIDAS and...physical damage to the casing, adjacent or touching metals, and water or substrate qualities such as temperature, pH, or Redox potential. The...environments, little is known on modeling the fate of MCs in the underwater environment. One of the anticipated problems in predicting the fate and

Polymer Electrolyte Fuel Cells Employing Heteropolyacids as Redox Mediators for Oxygen Reduction Reactions: Pt-Free Cathode Systems.

PubMed

Matsui, Toshiaki; Morikawa, Eri; Nakada, Shintaro; Okanishi, Takeou; Muroyama, Hiroki; Hirao, Yoshifumi; Takahashi, Tsuyoshi; Eguchi, Koichi

2016-07-20

In this study, the heteropolyacids of H3+xPVxMO12-xO40 (x = 0, 2, and 3) were applied as redox mediators for the oxygen reduction reaction in polymer electrolyte fuel cells, of which the cathode is free from the usage of noble metals such as Pt/C. In this system, the electrochemical reduction of heteropolyacid over the carbon cathode and the subsequent reoxidation of the partially reduced heteropolyacid by exposure to the dissolved oxygen in the regenerator are important processes for continuous power generation. Thus, the redox properties of catholytes containing these heteropolyacids were investigated in detail. The substitution quantity of V in the heteropolyacid affected the onset reduction potential as well as the reduction current density, resulting in a difference in cell performance. The chemical composition of heteropolyacid also had a significant impact on the reoxidation property. Among the three compounds, H6PV3Mo9O40 was the most suitable redox mediator. Furthermore, the pH of the catholyte was found to be the crucial factor in determining the reoxidation rate of partially reduced heteropolyacid as well as cell performance.

Stabilization of Reduced Molybdenum-Iron-Sulfur Single and Double Cubane Clusters by Cyanide Ligation

PubMed Central

Pesavento, Russell P.; Berlinguette, Curtis P.; Holm, R. H.

2008-01-01

Recent work has shown that cyanide ligation increases the redox potentials of Fe4S4 clusters, enabling the isolation of [Fe4S4(CN)4]4−, the first synthetic Fe4S4 cluster obtained in the all-ferrous oxidation state (Scott, T. A.; Berlinguette, C. P.; Holm, R. H.; Zhou, H.-C., Proc. Natl. Acad. Sci. USA 2005, 102, 9741). The generality of reduced cluster stabilization has been examined with MoFe3S4 clusters. Reaction of single cubane [(Tp)MoFe3S4(PEt3)3]1+ and edge-bridged double cubane [(Tp)2Mo2Fe6S8(PEt3)4] with cyanide in acetonitrile affords [(Tp)MoFe3S4(CN)3]2− (2) and [(Tp)2Mo2Fe6S8(CN)4]4− (5), respectively. Reduction of 2 with KC14H10 yields [(Tp)MoFe3S4(CN)3]3− (3). Clusters were isolated in ca. 70–90% yields as Et4N+ or Bu4N+ salts; Clusters 3 and 5 contain all-ferrous cores; 3 is the first [MoFe3S4]1+ cluster isolated in substance. The structures of 2 and 3 are very similar; the volume of the reduced cluster core is slightly larger (2.5%), a usual effect upon reduction of cubane-type Fe4S4 and MFe3S4 clusters. Redox potentials and 57Fe isomer shifts of [(Tp)MoFe3S4L3]2−,3 and [(Tp)2Mo2Fe6S8L4]4−,3− clusters with L = CN, PhS, halide, and PEt3 are compared. Clusters with π-donor ligands (L = halide, PhS) exhibit larger isomer shifts and lower (more negative) redox potentials while π-acceptor ligands (L = CN, PEt3) induce smaller isomer shifts and higher (less negative) redox potentials. When potentials of 3/2 and [(Tp)MoFe3S4(SPh)3]3−/2− are compared, cyanide stabilizes 3 by 270 mV vs. the reduced thiolate cluster, commensurate with the 310 mV stabilization of [Fe4S4(CN)4]4− vs. [Fe4S4(SPh)4]4− where four ligands differ. These results demonstrate the efficacy of cyanide stabilization of lower cluster oxidation states. (Tp = hydrotris(pyrazolyl)borate(1−)). PMID:17279830

Stabilization of reduced molybdenum-iron-sulfur single- and double-cubane clusters by cyanide ligation.

PubMed

Pesavento, Russell P; Berlinguette, Curtis P; Holm, R H

2007-01-22

Recent work has shown that cyanide ligation increases the redox potentials of Fe(4)S(4) clusters, enabling the isolation of [Fe(4)S(4)(CN)4]4-, the first synthetic Fe(4)S(4) cluster obtained in the all-ferrous oxidation state (Scott, T. A.; Berlinguette, C. P.; Holm, R. H.; Zhou, H.-C. Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 9741). The generality of reduced cluster stabilization has been examined with MoFe(3)S(4) clusters. Reaction of single-cubane [(Tp)MoFe(3)S(4)(PEt(3))3]1+ and edge-bridged double-cubane [(Tp)2Mo(2)Fe(6)S(8)(PEt(3))4] with cyanide in acetonitrile affords [(Tp)MoFe(3)S(4)(CN)3]2- (2) and [(Tp)2Mo(2)Fe(6)S(8)(CN)4]4- (5), respectively. Reduction of 2 with KC(14)H(10) yields [(Tp)MoFe(3)S(4)(CN)3]3- (3). Clusters were isolated in approximately 70-90% yields as Et(4)N+ or Bu(4)N+ salts; clusters 3 and 5 contain all-ferrous cores, and 3 is the first [MoFe(3)S(4)]1+ cluster isolated in substance. The structures of 2 and 3 are very similar; the volume of the reduced cluster core is slightly larger (2.5%), a usual effect upon reduction of cubane-type Fe(4)S(4) and MFe(3)S(4) clusters. Redox potentials and 57Fe isomer shifts of [(Tp)MoFe(3)S(4)L3]2-,3- and [(Tp)2Mo(2)Fe(6)S(8)L(4)]4-,3- clusters with L = CN-, PhS-, halide, and PEt3 are compared. Clusters with pi-donor ligands (L = halide, PhS) exhibit larger isomer shifts and lower (more negative) redox potentials, while pi-acceptor ligands (L = CN, PEt3) induce smaller isomer shifts and higher (less-negative) redox potentials. When the potentials of 3/2 and [(Tp)MoFe(3)S(4)(SPh)3]3-/2- are compared, cyanide stabilizes 3 by 270 mV versus the reduced thiolate cluster, commensurate with the 310 mV stabilization of [Fe(4)S(4)(CN)4]4- versus [Fe(4)S(4)(SPh)4]4- where four ligands differ. These results demonstrate the efficacy of cyanide stabilization of lower cluster oxidation states. (Tp = hydrotris(pyrazolyl)borate(1-)).

"Why not stoichiometry" versus "Stoichiometry--why not?" Part II: GATES in context with redox systems.

PubMed

Michałowska-Kaczmarczyk, Anna Maria; Asuero, Agustin G; Toporek, Marcin; Michałowski, Tadeusz

2015-01-01

Redox equilibria and titration play an important role in chemical analysis, and the formulation of an accurate mathematical description is a challenge. This article is devoted to static and (mainly) dynamic redox systems; the dynamic systems are represented by redox titrations. An overview addresses earlier approaches to static redox systems (redox diagram plots, including Pourbaix diagrams) and to titration redox systems, thereby covering a gap in the literature. After this short review, the generalized approach to electrolytic systems (GATES) is introduced, with generalized electron balance (GEB) as its inherent part within GATES/GEB. Computer simulation, performed according to GATES/GEB, enables following the changes in potential and pH of the solution, together with chemical speciation at each step of a titration, thus providing better insight into this procedure. The undeniable advantages of GATES/GEB over earlier approaches are indicated. Formulation of GEB according to two approaches (I and II) is presented on the respective examples. A general criterion distinguishing between non-redox and redox systems is presented. It is indicated that the formulation of GEB according to Approach II does not need the knowledge of oxidation degrees of particular elements; knowledge of the composition, expressed by chemical formula of the species and its charge, is sufficient for this purpose. Approach I to GEB, known also as the "short" version of GEB, is applicable if oxidation degrees for all elements of the system are known beforehand. The roles of oxidants and reductants are not ascribed to particular components forming a system and to the species thus formed. This is the complete opposite of earlier approaches to redox titrations, based on the stoichiometric redox reaction, formulated for this purpose. GEB, perceived as a law of matter conservation, is fully compatible with other (charge and concentration) balances related to the system in question. The applicability of GATES/GEB in optimization a priori of chemical analyses made with use of redox titration is indicated. The article is illustrated with many examples of static and dynamic redox systems. The related plots are obtained from calculations made according to iterative computer programs. This way, GATES/GEB enables seeing details invisible in real experiments.

Coordinated pH/redox dual-sensitive and hepatoma-targeted multifunctional polymeric micelle system for stimuli-triggered doxorubicin release: Synthesis, characterization and in vitro evaluation.

PubMed

Wang, Lele; Tian, Baocheng; Zhang, Jing; Li, Keke; Liang, Yan; Sun, Yujie; Ding, Yuanyuan; Han, Jingtian

2016-03-30

Multifunctional polymeric micelles self-assembled from a DOX-conjugated methoxypolyethylene glycols-b-poly (6-O-methacryloyl-D-galactopyranose)-disulfide bond-DOX (mPEG-b-PMAGP-SS-DOX) copolymer were prepared as an antitumor carrier for doxorubicin delivery, of which the chemical modification with disulfide bonds and hydrazone bonds allowed micelles to release doxorubicin (DOX) selectively at acidic pH and high redox conditions. The resulting micelles exhibited coordinated pH/redox dual-sensitive and hepatoma-targeted multifunction with sustaining stability in aqueous media. The multifunctional micelles showed spherical shapes with a mean diameter of 93 ± 2.08 nm, a low polydispersity index (PDI) of 0.21, a low CMC value of 0.095 mg/mL, a high drug grafting degree of 56.9% and a drug content of 39.0%. Remarkably, in vitro drug release studies clearly exhibited a pH and redox dual-sensitive drug release profile with significantly accelerated drug release treated with pH 5.0 and 10mM GSH (88.4% in 72 h) without drug burst release. The tumor proliferation assays indicated that DOX-grafted micelles, along with low cytotoxicity and well biocompatibility to normal cells up to a concentration of 10 μg/mL, inhibited the proliferation of HepG2 cells in a formulation-, time- and concentration-dependent manner in comparison with MCF-7 cells which was similar to free DOX. Anticancer activity releaved that the disulfide-modified micelles possessed much higher anti-hepatoma activity with a low IC50 value of 1.1 μg/mL following a 72 h incubation. Furthermore, the intracellular uptake tested by CLSM and FCM demonstrated that multifunctional polymeric micelles could be more efficiently taken up by HepG2 cells compared with MCF-7 cells, agreed well with MTT assays, suggesting these well-defined micelles provide a potential drug delivery system for dual-responsive controlled drug release and enhanced anti-hepatoma therapy. Copyright © 2016 Elsevier B.V. All rights reserved.

Role of Reactive Oxygen Species in Neonatal Pulmonary Vascular Disease

PubMed Central

Steinhorn, Robin H.

2014-01-01

Abstract Significance: Abnormal lung development in the perinatal period can result in severe neonatal complications, including persistent pulmonary hypertension (PH) of the newborn and bronchopulmonary dysplasia. Reactive oxygen species (ROS) play a substantive role in the development of PH associated with these diseases. ROS impair the normal pulmonary artery (PA) relaxation in response to vasodilators, and ROS are also implicated in pulmonary arterial remodeling, both of which can increase the severity of PH. Recent Advances: PA ROS levels are elevated when endogenous ROS-generating enzymes are activated and/or when endogenous ROS scavengers are inactivated. Animal models have provided valuable insights into ROS generators and scavengers that are dysregulated in different forms of neonatal PH, thus identifying potential therapeutic targets. Critical Issues: General antioxidant therapy has proved ineffective in reversing PH, suggesting that it is necessary to target specific signaling pathways for successful therapy. Future Directions: Development of novel selective pharmacologic inhibitors along with nonantioxidant therapies may improve the treatment outcomes of patients with PH, while further investigation of the underlying mechanisms may enable earlier detection of the disease. Antioxid. Redox Signal. 21, 1926–1942. PMID:24350610

Redox Control and Hydrogen Production in Sediment Caps Using Carbon Cloth Electrodes

PubMed Central

Sun, Mei; Yan, Fei; Zhang, Ruiling; Reible, Danny D.; Lowry, Gregory V.; Gregory, Kelvin B.

2010-01-01

Sediment caps that degrade contaminants can improve their ability to contain contaminants relative to sand and sorbent-amended caps, but few methods to enhance contaminant degradation in sediment caps are available. The objective of this study was to determine if, carbon electrodes emplaced within a sediment cap at poised potential could create a redox gradient and provide electron donor for the potential degradation of contaminants. In a simulated sediment cap overlying sediment from the Anacostia River (Washington, DC), electrochemically induced redox gradients were developed within 3 days and maintained over the period of the test (~100 days). Hydrogen and oxygen were produced by water electrolysis at the electrode surfaces and may serve as electron donor and acceptor for contaminant degradation. Electrochemical and geochemical factors that may influence hydrogen production were studied. Hydrogen production displayed zero order kinetics with ~75% coulombic efficiency and rates were proportional to the applied potential between 2.5V to 5V and not greatly affected by pH. Hydrogen production was promoted by increasing ionic strength and in the presence of natural organic matter. Graphite electrode-stimulated degradation of tetrachlorobenzene in a batch reactor was dependent on applied voltage and production of hydrogen to a concentration above the threshold for biological dechlorination. These findings suggest that electrochemical reactive capping can potentially be used to create “reactive” sediments caps capable of promoting chemical or biological transformations of contaminants within the cap. PMID:20879761

Elucidation of the Biological Redox Chemistry of Purines Using Electrochemical Techniques.

ERIC Educational Resources Information Center

Dryhurst, Glenn; And Others

1983-01-01

Electrochemical studies can give insights into the chemical aspects of enzymatic and in vivo redox reactions of naturally occurring organic compounds. This is illustrated by studies of the electrochemical oxidation of the purinem uric acid. The discussion is limited to information at pH 7 or greater. (JN)

Microscale geochemical gradients in Hanford 300 Area sediment biofilms and influence of uranium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Hung D.; Cao, Bin; Mishra, Bhoopesh

2012-01-01

The presence and importance of microenvironments in the subsurface at contaminated sites were suggested by previous geochemical studies. However, no direct quantitative characterization of the geochemical microenvironments had been reported. We quantitatively characterized microscale geochemical gradients (dissolved oxygen (DO), H(2), pH, and redox potential) in Hanford 300A subsurface sediment biofilms. Our results revealed significant differences in geochemical parameters across the sediment biofilm/water interface in the presence and absence of U(VI) under oxic and anoxic conditions. While the pH was relatively constant within the sediment biofilm, the redox potential and the DO and H(2) concentrations were heterogeneous at the microscale (<500-1000more » μm). We found microenvironments with high DO levels (DO hotspots) when the sediment biofilm was exposed to U(VI). On the other hand, we found hotspots (high concentrations) of H(2) under anoxic conditions both in the presence and in the absence of U(VI). The presence of anoxic microenvironments inside the sediment biofilms suggests that U(VI) reduction proceeds under bulk oxic conditions. To test this, we operated our biofilm reactor under air-saturated conditions in the presence of U(VI) and characterized U speciation in the sediment biofilm. U L(III)-edge X-ray absorption spectroscopy (XANES and EXAFS) showed that 80-85% of the U was in the U(IV) valence state.« less

Microscale geochemical gradients in Hanford 300 Area sediment biofilms and influence of uranium.

PubMed

Nguyen, Hung Duc; Cao, Bin; Mishra, Bhoopesh; Boyanov, Maxim I; Kemner, Kenneth M; Fredrickson, Jim K; Beyenal, Haluk

2012-01-01

The presence and importance of microenvironments in the subsurface at contaminated sites were suggested by previous geochemical studies. However, no direct quantitative characterization of the geochemical microenvironments had been reported. We quantitatively characterized microscale geochemical gradients (dissolved oxygen (DO), H(2), pH, and redox potential) in Hanford 300A subsurface sediment biofilms. Our results revealed significant differences in geochemical parameters across the sediment biofilm/water interface in the presence and absence of U(VI) under oxic and anoxic conditions. While the pH was relatively constant within the sediment biofilm, the redox potential and the DO and H(2) concentrations were heterogeneous at the microscale (<500-1000 μm). We found microenvironments with high DO levels (DO hotspots) when the sediment biofilm was exposed to U(VI). On the other hand, we found hotspots (high concentrations) of H(2) under anoxic conditions both in the presence and in the absence of U(VI). The presence of anoxic microenvironments inside the sediment biofilms suggests that U(VI) reduction proceeds under bulk oxic conditions. To test this, we operated our biofilm reactor under air-saturated conditions in the presence of U(VI) and characterized U speciation in the sediment biofilm. U L(III)-edge X-ray absorption spectroscopy (XANES and EXAFS) showed that 80-85% of the U was in the U(IV) valence state. Copyright © 2011 Elsevier Ltd. All rights reserved.

The impact of pH on side reactions for aqueous redox flow batteries based on nitroxyl radical compounds

NASA Astrophysics Data System (ADS)

Orita, A.; Verde, M. G.; Sakai, M.; Meng, Y. S.

2016-07-01

Electrochemical and UV-VIS measurements demonstrate that the pH value of a 4-hydroxy-2,2,6,6-tetramethyl-1-pipperidinyloxyl (TEMPOL) electrolyte significantly impacts its redox reversibility. The diffusion coefficient and kinetic rate constant of TEMPOL in neutral aqueous solution are determined and shown to be comparable to those of vanadium ions used for industrially utilized redox flow batteries (RFBs). RFBs that incorporate a TEMPOL catholyte and Zn-based anolyte have an average voltage of 1.46 V and an energy efficiency of 80.4% during the initial cycle, when subject to a constant current of 10 mA cm-2. We demonstrate several factors that significantly influence the concentration and capacity retention of TEMPOL upon cycling; namely, pH and atmospheric gases dissolved in electrolyte. We expand upon the known reactions of TEMPOL in aqueous electrolyte and propose several concepts to improve its electrochemical performance in a RFB. Controlling these factors will be the key to enable the successful implementation of this relatively inexpensive and environmentally friendly battery.

Indirect Redox Transformations of Iron, Copper, and Chromium Catalyzed by Extremely Acidophilic Bacteria

PubMed Central

Johnson, D. Barrie; Hedrich, Sabrina; Pakostova, Eva

2017-01-01

Experiments were carried out to examine redox transformations of copper and chromium by acidophilic bacteria (Acidithiobacillus, Leptospirillum, and Acidiphilium), and also of iron (III) reduction by Acidithiobacillus spp. under aerobic conditions. Reduction of iron (III) was found with all five species of Acidithiobacillus tested, grown aerobically on elemental sulfur. Cultures maintained at pH 1.0 for protracted periods displayed increasing propensity for aerobic iron (III) reduction, which was observed with cell-free culture liquors as well as those containing bacteria. At. caldus grown on hydrogen also reduced iron (III) under aerobic conditions, confirming that the unknown metabolite(s) responsible for iron (III) reduction were not (exclusively) sulfur intermediates. Reduction of copper (II) by aerobic cultures of sulfur-grown Acidithiobacillus spp. showed similar trends to iron (III) reduction in being more pronounced as culture pH declined, and occurring in both the presence and absence of cells. Cultures of Acidithiobacillus grown anaerobically on hydrogen only reduced copper (II) when iron (III) (which was also reduced) was also included; identical results were found with Acidiphilium cryptum grown micro-aerobically on glucose. Harvested biomass of hydrogen-grown At. ferridurans oxidized iron (II) but not copper (I), and copper (I) was only oxidized by growing cultures of Acidithiobacillus spp. when iron (II) was also included. The data confirmed that oxidation and reduction of copper were both mediated by acidophilic bacteria indirectly, via iron (II) and iron (III). No oxidation of chromium (III) by acidophilic bacteria was observed even when, in the case of Leptospirillum spp., the redox potential of oxidized cultures exceeded +900 mV. Cultures of At. ferridurans and A. cryptum reduced chromium (VI), though only when iron (III) was also present, confirming an indirect mechanism and contradicting an earlier report of direct chromium reduction by A. cryptum. Measurements of redox potentials of iron, copper and chromium couples in acidic, sulfate-containing liquors showed that these differed from situations where metals are not complexed by inorganic ligands, and supported the current observations of indirect copper oxido-reduction and chromium reduction mediated by acidophilic bacteria. The implications of these results for both industrial applications of acidophiles and for exobiology are discussed. PMID:28239375

Atypical protein disulfide isomerases (PDI): Comparison of the molecular and catalytic properties of poplar PDI-A and PDI-M with PDI-L1A

PubMed Central

Selles, Benjamin; Zannini, Flavien; Couturier, Jérémy; Jacquot, Jean-Pierre

2017-01-01

Protein disulfide isomerases are overwhelmingly multi-modular redox catalysts able to perform the formation, reduction or isomerisation of disulfide bonds. We present here the biochemical characterization of three different poplar PDI isoforms. PDI-A is characterized by a single catalytic Trx module, the so-called a domain, whereas PDI-L1a and PDI-M display an a-b-b’-a’ and a°-a-b organisation respectively. Their activities have been tested in vitro using purified recombinant proteins and a series of model substrates as insulin, NADPH thioredoxin reductase, NADP malate dehydrogenase (NADP-MDH), peroxiredoxins or RNase A. We demonstrated that PDI-A exhibited none of the usually reported activities, although the cysteines of the WCKHC active site signature are able to form a disulfide with a redox midpoint potential of -170 mV at pH 7.0. The fact that it is able to bind a [Fe2S2] cluster upon Escherichia coli expression and anaerobic purification might indicate that it does not have a function in dithiol-disulfide exchange reactions. The two other proteins were able to catalyze oxidation or reduction reactions, PDI-L1a being more efficient in most cases, except that it was unable to activate the non-physiological substrate NADP-MDH, in contrast to PDI-M. To further evaluate the contribution of the catalytic domains of PDI-M, the dicysteinic motifs have been independently mutated in each a domain. The results indicated that the two a domains seem interconnected and that the a° module preferentially catalyzed oxidation reactions whereas the a module catalyzed reduction reactions, in line with the respective redox potentials of -170 mV and -190 mV at pH 7.0. Overall, these in vitro results illustrate that the number and position of a and b domains influence the redox properties and substrate recognition (both electron donors and acceptors) of PDI which contributes to understand why this protein family expanded along evolution. PMID:28362814

Environmental Redox Potential and Redox Capacity Concepts Using a Simple Polarographic Experiment

NASA Astrophysics Data System (ADS)

Pidello, Alejandro

2003-01-01

The redox status of a system may be analyzed in terms of the redox potential (redox intensity component) and the size of the pool of electrons able to be transferred (redox capacity component). In single chemical systems, both terms are thermodynamically related by means of the Nernst equation, the classical redox equilibrium equation. Consequently, either the redox potential measurement or the redox capacity may be used without distinction to define the redox characteristics of these systems. However, in natural environments, which are a complex mixture of compounds undergoing redox reactions in several stages of nonequilibrium, it is difficult to establish the relationships linking redox potential and redox capacity. In this situation, as suggested by various authors, the complementary use of intensity and capacity measurements improves the characterization of the redox status of these systems. The aim of this laboratory experiment is to enable undergraduate students of applied biology (agronomy, veterinary or environmental sciences) to distinguish clearly between redox potential and redox capacity concepts through concrete results obtained in complex natural system such as soil, and to discuss the ecological significance of both concepts.

Mitochondrial Flash: Integrative Reactive Oxygen Species and pH Signals in Cell and Organelle Biology

PubMed Central

Gong, Guohua; Wang, Xianhua; Wei-LaPierre, Lan; Cheng, Heping; Dirksen, Robert

2016-01-01

Abstract Significance: Recent breakthroughs in mitochondrial research have advanced, reshaped, and revolutionized our view of the role of mitochondria in health and disease. These discoveries include the development of novel tools to probe mitochondrial biology, the molecular identification of mitochondrial functional proteins, and the emergence of new concepts and mechanisms in mitochondrial function regulation. The discovery of “mitochondrial flash” activity has provided unique insights not only into real-time visualization of individual mitochondrial redox and pH dynamics in live cells but has also advanced understanding of the excitability, autonomy, and integration of mitochondrial function in vivo. Recent Advances: The mitochondrial flash is a transient and stochastic event confined within an individual mitochondrion and is observed in a wide range of organisms from plants to Caenorhabditis elegans to mammals. As flash events involve multiple transient concurrent changes within the mitochondrion (e.g., superoxide, pH, and membrane potential), a number of different mitochondrial targeted fluorescent indicators can detect flash activity. Accumulating evidence indicates that flash events reflect integrated snapshots of an intermittent mitochondrial process arising from mitochondrial respiration chain activity associated with the transient opening of the mitochondrial permeability transition pore. Critical Issues: We review the history of flash discovery, summarize current understanding of flash biology, highlight controversies regarding the relative roles of superoxide and pH signals during a flash event, and bring forth the integration of both signals in flash genesis. Future Directions: Investigations using flash as a biomarker and establishing its role in cell signaling pathway will move the field forward. Antioxid. Redox Signal. 25, 534–549. PMID:27245241

Facile electrocatalytic redox of hemoglobin by flower-like gold nanoparticles on boron-doped diamond surface.

PubMed

Li, Mingfang; Zhao, Guohua; Geng, Rong; Hu, Huikang

2008-11-01

The flower-like gold nanoparticles together with spherical and convex polyhedron gold nanoparticles were fabricated on boron-doped diamond (BDD) surface by one-step and simple electrochemical method through easily controlling the applied potential and the concentration of HAuCl(4). The recorded X-ray diffraction (XRD) patterns confirmed that these three shapes of gold nanoparticles were dominated by different crystal facets. The cyclic voltammetric results indicated that the morphology of gold nanoparticles plays big role in their electrochemical behaviors. The direct electrochemistry of hemoglobin (Hb) was realized on all the three different shapes of nanogold-attached BDD surface without the aid of any electron mediator. In pH 4.5 acetate buffer solutions (ABS), Hb showed a pair of well defined and quasi-reversible redox peaks. However, the results obtained demonstrated that the redox peak potential, the average surface concentration of electroactive heme, and the electron transfer rates of Hb are greatly dependent upon the surface morphology of gold nanoparticles. The electron transfer rate constant of hemoglobin over flower-like nanogold/BDD electrode was more than two times higher than that over spherical and convex polyhedron nanogold. The observed differences may be ascribed to the difference in gold particle characteristics including surface roughness, exposed surface area, and crystal structure.

Redox-Active Hydrogel Polymer Electrolytes with Different pH Values for Enhancing the Energy Density of the Hybrid Solid-State Supercapacitor.

PubMed

Tang, Xiaohui; Lui, Yu Hui; Merhi, Abdul Rahman; Chen, Bolin; Ding, Shaowei; Zhang, Bowei; Hu, Shan

2017-12-27

To enhance the energy density of solid-state supercapacitors, a novel solid-state cell, made of redox-active poly(vinyl alcohol) (PVA) hydrogel electrolytes and functionalized carbon nanotube-coated cellulose paper electrodes, was investigated in this work. Briefly, acidic PVA-[BMIM]Cl-lactic acid-LiBr and neutral PVA-[BMIM]Cl-sodium acetate-LiBr hydrogel polymer electrolytes are used as catholyte and anolyte, respectively. The acidic condition of the catholyte contributes to suppression of the undesired irreversible reaction of Br - and extension of the oxygen evolution reaction potential to a higher value than that of the redox potential of Br - /Br 3 - reaction. The observed Br - /Br 3 - redox activity at the cathode contributes to enhance the cathode capacitance. The neutral condition of the anolyte helps extend the operating voltage window of the supercapacitor by introducing hydrogen evolution reaction overpotential to the anode. The electrosorption of nascent H on the negative electrode also increases the anode capacitance. As a result, the prepared solid-state hybrid supercapacitor shows a broad voltage window of 1.6 V, with a high Coulombic efficiency of 97.6% and the highest energy density of 16.3 Wh/kg with power density of 932.6 W/kg at 2 A/g obtained. After 10 000 cycles of galvanostatic charge and discharge tests at the current density of 10 A/g, it exhibits great cyclic stability with 93.4% retention of the initial capacitance. In addition, a robust capacitive performance can also be observed from the solid-state supercapacitor at different bending angles, indicating its great potential as a flexible energy storage device.

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ganguly, Sumit; Giles, Logan J.; Thomas, Kolle E.

Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF 3, H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe 2(μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]} 2O,more » and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C 4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected Fe IV-like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be Fe III-like. In conclusion, these results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.« less

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials

DOE PAGES

Ganguly, Sumit; Giles, Logan J.; Thomas, Kolle E.; ...

2017-10-06

Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF 3, H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe 2(μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]} 2O,more » and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C 4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected Fe IV-like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be Fe III-like. In conclusion, these results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.« less

Spatial patterns in salt marsh porewater dissolved organic matter over a spring-neap tidal cycle: insight to the impact of hydrodynamics on lateral carbon fluxes

NASA Astrophysics Data System (ADS)

Guimond, J. A.; Yu, X.; Duque, C.; Michael, H. A.

2016-12-01

Salt marshes are a hydrologically complex ecosystem. Tides deliver saline surface water to salt marshes via tidal creeks, and freshwater is introduced through lateral groundwater flow and vertical infiltration from precipitation. Locally, sediment heterogeneity, tides, weather, and topography introduce spatial and temporal complexities in groundwater-surface water interactions, which, in turn, can have a large impact on salt marsh biogeochemistry and the lateral fluxes of nutrients and carbon between the marsh platform and tidal creek. In this study, we investigate spatial patterns of porewater fluorescent dissolved organic matter (fDOM) and redox potential over a spring-neap tidal cycle in a mid-latitude tidal salt marsh in Dover, Delaware. Porewater samplers were used in conjunction with a peristaltic pump and YSI EXO Sonde to measure porewater fDOM, electrical conductivity, redox potential and pH from 0.5, 1.0, 1.5, 2.0, and 2.3 meters deep, as well as surface water from the creek and marsh platform. Eh was also measured continuously every 15 minutes with multi-level in-situ redox sensors at 0, 3, and 5m from the tidal creek, and water level and salinity were measured every 15 minutes continuously in 6 wells equipped with data loggers. Preliminary analyses indicate porewater salinity is dependent on the slope of the marsh platform, the elevation of the sample location, and the distance from a tidal creek. Near-creek redox analyses show tidal oscillations up to 300 mV; redox oscillations in the marsh interior show longer timescale changes. The observed redox oscillations coincide with the water level fluctuations at these locations. Therefore, lateral transport of carbon is determined by both hydrologic flow and biogeochemical processes. Results from this study provide insight into the timescales over which salt marsh hydrology impacts porewater biogeochemistry and the mechanisms controlling regional carbon cycling.

Kinetics of steel slag leaching: Batch tests and modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Windt, Laurent, E-mail: laurent.dewindt@mines-paristech.fr; Chaurand, Perrine; Rose, Jerome

2011-02-15

Reusing steel slag as an aggregate for road construction requires to characterize the leaching kinetics and metal releases. In this study, basic oxygen furnace (BOF) steel slag were subjected to batch leaching tests at liquid to solid ratios (L/S) of 10 and 100 over 30 days; the leachate chemistry being regularly sampled in time. A geochemical model of the steel slag is developed and validated from experimental data, particularly the evolution with leaching of mineralogical composition of the slag and trace element speciation. Kinetics is necessary for modeling the primary phase leaching, whereas a simple thermodynamic equilibrium approach can bemore » used for secondary phase precipitation. The proposed model simulates the kinetically-controlled dissolution (hydrolysis) of primary phases, the precipitation of secondary phases (C-S-H, hydroxide and spinel), the pH and redox conditions, and the progressive release of major elements as well as the metals Cr and V. Modeling indicates that the dilution effect of the L/S ratio is often coupled to solubility-controlled processes, which are sensitive to both the pH and the redox potential. A sensitivity analysis of kinetic uncertainties on the modeling of element releases is performed.« less

Biological durability and oxidative potential of man-made vitreous fibres as compared to crocidolite asbestos fibres.

PubMed

Hippeli, S; Dornisch, K; Wiethege, T; Gillissen, A; Müller, K M; Elstner, E F

2001-01-01

In this study we investigated relationships between redox properties and biodurability of crocidolite asbestos fibres and three different man-made vitreous fibres (MMVF): traditional stone wool fibres (MMVF 21), glass fibres (MMVF 11) and refractory ceramic fibres (RCF). Each fibre type was incubated up to 22 weeks in four different incubation media: gamble solution (GS) pH 5.0 and pH 7.4, representing blood plasma without proteins, and surfactant-like solution (SLS) pH 5.0 and pH 7.4. During incubation time aliquots of incubation mixtures were removed and analysed in a biochemical model reaction, mimicking activated phagocytes. In addition, changes of fibre morphology and chemical composition were examined using SEM- and EDX-technology. In the presence of crocidolite asbestos fibres and MMVF 21 the formation of OH*-radicals according to the Haber-Weiss sequence could be demonstrated, whereas MMVF 11 and RCF showed no reactivity. Crocidolite asbestos fibres exhibited a significant higher activity compared with the stone wool fibres at the onset of incubation. The oxidative capacities of these fibre types were shown to depend on both specific surface area and iron content. The oxidative potentials of crocidolite asbestos fibres as well as MMVF 21 were not constant during incubation over several weeks in each incubation medium. The reactivities showed sinoidal curves including reactivities much higher than those at the onset of incubation time. These irregular changes of oxidative capacity may be explained by changes of the redox state of fibre surface-complexed iron. Furthermore our results showed clear differences between incubation of fibres in GS and SLS, respectively, indicating that phospholipids play an important part in fibre dissolution behaviour and oxidative reactivity. In conclusion we suggest, that biodurability testing procedures should not exclusively concentrate on dissolution rates of fibres. They should include fibre characteristics concerning known pathogenic mechanisms to evaluate the real toxic potential of the fibre type looking at. Secondly we suggest, that phospholipids should be constituents of incubation liquids used for standardised fibre biodurability test procedures thus representing more realistic incubation conditions.

Bioinspired design of redox-active ligands for multielectron catalysis: effects of positioning pyrazine reservoirs on cobalt for electro- and photocatalytic generation of hydrogen from water† †Electronic supplementary information (ESI) available: Non-aqueous cyclic voltammetry; Levich plots and scan rate dependence of aqueous voltammetry; pH dependence of photocatalysis; computational details; and supporting figures. CCDC 1060291–1060296. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01414j Click here for additional data file. Click here for additional data file.

PubMed Central

Jurss, Jonah W.; Khnayzer, Rony S.; Panetier, Julien A.; El Roz, Karim A.; Nichols, Eva M.

2015-01-01

Mononuclear metalloenzymes in nature can function in cooperation with precisely positioned redox-active organic cofactors in order to carry out multielectron catalysis. Inspired by the finely tuned redox management of these bioinorganic systems, we present the design, synthesis, and experimental and theoretical characterization of a homologous series of cobalt complexes bearing redox-active pyrazines. These donor moieties are locked into key positions within a pentadentate ligand scaffold in order to evaluate the effects of positioning redox non-innocent ligands on hydrogen evolution catalysis. Both metal- and ligand-centered redox features are observed in organic as well as aqueous solutions over a range of pH values, and comparison with analogs bearing redox-inactive zinc(ii) allows for assignments of ligand-based redox events. Varying the geometric placement of redox non-innocent pyrazine donors on isostructural pentadentate ligand platforms results in marked effects on observed cobalt-catalyzed proton reduction activity. Electrocatalytic hydrogen evolution from weak acids in acetonitrile solution, under diffusion-limited conditions, reveals that the pyrazine donor of axial isomer 1-Co behaves as an unproductive electron sink, resulting in high overpotentials for proton reduction, whereas the equatorial pyrazine isomer complex 2-Co is significantly more active for hydrogen generation at lower voltages. Addition of a second equatorial pyrazine in complex 3-Co further minimizes overpotentials required for catalysis. The equatorial derivative 2-Co is also superior to its axial 1-Co congener for electrocatalytic and visible-light photocatalytic hydrogen generation in biologically relevant, neutral pH aqueous media. Density functional theory calculations (B3LYP-D2) indicate that the first reduction of catalyst isomers 1-Co, 2-Co, and 3-Co is largely metal-centered while the second reduction occurs at pyrazine. Taken together, the data establish that proper positioning of non-innocent pyrazine ligands on a single cobalt center is indeed critical for promoting efficient hydrogen catalysis in aqueous media, akin to optimally positioned redox-active cofactors in metalloenzymes. In a broader sense, these findings highlight the significance of electronic structure considerations in the design of effective electron–hole reservoirs for multielectron transformations. PMID:29142725

The influence of pH on the degradation of phenol and chlorophenols by potassium ferrate.

PubMed

Graham, Nigel; Jiang, Cheng-Chun; Li, Xiang-Zhong; Jiang, Jia-Qian; Ma, Jun

2004-09-01

This paper presents information concerning the influence of solution pH on the aqueous reaction between potassium ferrate and phenol and three chlorinated phenols: 4-chlorophenol (CP), 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TCP). The redox potential and aqueous stability of the ferrate ion, and the reactivity of dissociating compounds, are known to be pH dependent. Laboratory tests have been undertaken over a wide range of pH (5.8-11) and reactant concentrations (ferrate:compound molar ratios of 1:1 to 8:1). The reactivity of trichloroethylene was also investigated as a reference compound owing to its non-dissociating nature. The extent of compound degradation by ferrate was found to be highly pH dependent, and the optimal pH (maximum degradation) decreased in the order: phenol/CP, DCP, TCP; at the optimal pH the degree of degradation of these compounds was similar. The results indicate that for the group of phenol and chlorophenols studied, the presence of an increasing number of chlorine substituent atoms corresponds to an increasing reactivity of the undissociated compound, and a decreasing reactivity of the dissociated compound.

Measurement of pH micro-heterogeneity in natural cheese matrices by fluorescence lifetime imaging

PubMed Central

Burdikova, Zuzana; Svindrych, Zdenek; Pala, Jan; Hickey, Cian D.; Wilkinson, Martin G.; Panek, Jiri; Auty, Mark A. E.; Periasamy, Ammasi; Sheehan, Jeremiah J.

2015-01-01

Cheese, a product of microbial fermentation may be defined as a protein matrix entrapping fat, moisture, minerals and solutes as well as dispersed bacterial colonies. The growth and physiology of bacterial cells in these colonies may be influenced by the microenvironment around the colony, or alternatively the cells within the colony may modify the microenvironment (e.g., pH, redox potential) due to their metabolic activity. While cheese pH may be measured at macro level there remains a significant knowledge gap relating to the degree of micro-heterogeneity of pH within the cheese matrix and its relationship with microbial, enzymatic and physiochemical parameters and ultimately with cheese quality, consistency and ripening patterns. The pH of cheese samples was monitored both at macroscopic scale and at microscopic scale, using a non-destructive microscopic technique employing C-SNARF-4 and Oregon Green 488 fluorescent probes. The objectives of this work were to evaluate the suitability of these dyes for microscale pH measurements in natural cheese matrices and to enhance the sensitivity and extend the useful pH range of these probes using fluorescence lifetime imaging (FLIM). In particular, fluorescence lifetime of Oregon Green 488 proved to be sensitive probe to map pH micro heterogeneity within cheese matrices. Good agreement was observed between macroscopic scale pH measurement by FLIM and by traditional pH methods, but in addition considerable localized microheterogeneity in pH was evident within the curd matrix with pH range between 4.0 and 5.5. This technique provides significant potential to further investigate the relationship between cheese matrix physico-chemistry and bacterial metabolism during cheese manufacture and ripening. PMID:25798136

Measurement of pH micro-heterogeneity in natural cheese matrices by fluorescence lifetime imaging.

PubMed

Burdikova, Zuzana; Svindrych, Zdenek; Pala, Jan; Hickey, Cian D; Wilkinson, Martin G; Panek, Jiri; Auty, Mark A E; Periasamy, Ammasi; Sheehan, Jeremiah J

2015-01-01

Cheese, a product of microbial fermentation may be defined as a protein matrix entrapping fat, moisture, minerals and solutes as well as dispersed bacterial colonies. The growth and physiology of bacterial cells in these colonies may be influenced by the microenvironment around the colony, or alternatively the cells within the colony may modify the microenvironment (e.g., pH, redox potential) due to their metabolic activity. While cheese pH may be measured at macro level there remains a significant knowledge gap relating to the degree of micro-heterogeneity of pH within the cheese matrix and its relationship with microbial, enzymatic and physiochemical parameters and ultimately with cheese quality, consistency and ripening patterns. The pH of cheese samples was monitored both at macroscopic scale and at microscopic scale, using a non-destructive microscopic technique employing C-SNARF-4 and Oregon Green 488 fluorescent probes. The objectives of this work were to evaluate the suitability of these dyes for microscale pH measurements in natural cheese matrices and to enhance the sensitivity and extend the useful pH range of these probes using fluorescence lifetime imaging (FLIM). In particular, fluorescence lifetime of Oregon Green 488 proved to be sensitive probe to map pH micro heterogeneity within cheese matrices. Good agreement was observed between macroscopic scale pH measurement by FLIM and by traditional pH methods, but in addition considerable localized microheterogeneity in pH was evident within the curd matrix with pH range between 4.0 and 5.5. This technique provides significant potential to further investigate the relationship between cheese matrix physico-chemistry and bacterial metabolism during cheese manufacture and ripening.

Excited-state redox properties of ruthenium(II) phthalocyanine from electron-transfer quenching

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prasad, D.R.; Ferraudi, G.

1982-09-30

Electron-transfer reactions between the lowest-lying triplet state, /sup 3/..pi pi../sup */, of ruthenium (phthalocyanine)(pyridine)/sub 2/ and various nitroaromatic compounds have been studied by laser and conventional flash photolysis. Quenching rate constants determined for the oxidation of the excited state have been treated according to the Marcus-Hush theory. A self-exchange rate constant K approx. 10/sup 7/ M/sup -1/ x/sup -1/ was determined for the self-exchange reaction between the /sup 3/..pi pi../sup */ and radical cation, Ru(ph)(py)/sub 2//sup +/. Such a value indicates that the major component to the Franck-Condon reorganizational energy is the outer-sphere contribution. The photochemical properties of the phthalocyaninesmore » are discussed in terms of the redox potentials estimate for various excited states.« less

The N-Terminal Domain of Human DNA Helicase Rtel1 Contains a Redox Active Iron-Sulfur Cluster

PubMed Central

Landry, Aaron P.

2014-01-01

Human telomere length regulator Rtel1 is a superfamily II DNA helicase and is essential for maintaining proper length of telomeres in chromosomes. Here we report that the N-terminal domain of human Rtel1 (RtelN) expressed in Escherichia coli cells produces a protein that contains a redox active iron-sulfur cluster with the redox midpoint potential of −248 ± 10 mV (pH 8.0). The iron-sulfur cluster in RtelN is sensitive to hydrogen peroxide and nitric oxide, indicating that reactive oxygen/nitrogen species may modulate the DNA helicase activity of Rtel1 via modification of its iron-sulfur cluster. Purified RtelN retains a weak binding affinity for the single-stranded (ss) and double-stranded (ds) DNA in vitro. However, modification of the iron-sulfur cluster by hydrogen peroxide or nitric oxide does not significantly affect the DNA binding activity of RtelN, suggesting that the iron-sulfur cluster is not directly involved in the DNA interaction in the N-terminal domain of Rtel1. PMID:25147792

Mechanisms of redox interactions of bilirubin with copper and the effects of penicillamine.

PubMed

Božić, Bojana; Korać, Jelena; Stanković, Dalibor M; Stanić, Marina; Popović-Bijelić, Ana; Bogdanović Pristov, Jelena; Spasojević, Ivan; Bajčetić, Milica

2017-12-25

Toxic effects of unconjugated bilirubin (BR) in neonatal hyperbilirubinemia have been related to redox and/or coordinate interactions with Cu 2+ . However, the development and mechanisms of such interactions at physiological pH have not been resolved. This study shows that BR reduces Cu 2+ to Cu 1+ in 1:1 stoichiometry. Apparently, BR undergoes degradation, i.e. BR and Cu 2+ do not form stable complexes. The binding of Cu 2+ to inorganic phosphates, liposomal phosphate groups, or to chelating drug penicillamine, impedes redox interactions with BR. Cu 1+ undergoes spontaneous oxidation by O 2 resulting in hydrogen peroxide accumulation and hydroxyl radical production. In relation to this, copper and BR induced synergistic oxidative/damaging effects on erythrocytes membrane, which were alleviated by penicillamine. The production of reactive oxygen species by BR and copper represents a plausible cause of BR toxic effects and cell damage in hyperbilirubinemia. Further examination of therapeutic potentials of copper chelators in the treatment of severe neonatal hyperbilirubinemia is needed. Copyright © 2017 Elsevier B.V. All rights reserved.

Effects of rutin on the redox reactions of hemoglobin.

PubMed

Lu, Naihao; Ding, Yun; Yang, Zhen; Gao, Pingzhang

2016-08-01

Flavonoids are widely used to attenuate oxidative damage in vitro and in vivo. In this study, we investigated the influence of rutin (quercetin-3-rhamnosylglucoside) on hemoglobin (Hb)- dependent redox reactions, i.e. oxidative stability of Hb and its cytotoxic ferryl intermediate. It was found that rutin induced generation of H2O2, which in turn oxidized Hb rapidly. Meanwhile, rutin exhibited anti-oxidant effect by effectively reducing ferryl intermediate back to ferric Hb at physiological pH. In comparison with quercetin, rutin had stronger capability on reducing ferryl species while lesser pro-oxidant effect on H2O2 generation, thus it exhibited more protective effect on H2O2-induced Hb oxidation. Circular dichroism spectrum showed no significant change in the secondary structure of Hb after flavonoid addition, while molecular docking revealed different binding modes of quercetin and rutin with Hb. These results might provide new insights into the potential nutritional and physiological implications of rutin and quercetin with redox active heme proteins regarding their ani- and pro-oxidant effects. Copyright © 2016 Elsevier B.V. All rights reserved.

The N-terminal domain of human DNA helicase Rtel1 contains a redox active iron-sulfur cluster.

PubMed

Landry, Aaron P; Ding, Huangen

2014-01-01

Human telomere length regulator Rtel1 is a superfamily II DNA helicase and is essential for maintaining proper length of telomeres in chromosomes. Here we report that the N-terminal domain of human Rtel1 (RtelN) expressed in Escherichia coli cells produces a protein that contains a redox active iron-sulfur cluster with the redox midpoint potential of -248 ± 10 mV (pH 8.0). The iron-sulfur cluster in RtelN is sensitive to hydrogen peroxide and nitric oxide, indicating that reactive oxygen/nitrogen species may modulate the DNA helicase activity of Rtel1 via modification of its iron-sulfur cluster. Purified RtelN retains a weak binding affinity for the single-stranded (ss) and double-stranded (ds) DNA in vitro. However, modification of the iron-sulfur cluster by hydrogen peroxide or nitric oxide does not significantly affect the DNA binding activity of RtelN, suggesting that the iron-sulfur cluster is not directly involved in the DNA interaction in the N-terminal domain of Rtel1.

Lithium-ion batteries with intrinsic pulse overcharge protection

DOEpatents

Chen, Zonghai; Amine, Khalil

2013-02-05

The present invention relates in general to the field of lithium rechargeable batteries, and more particularly relates to the positive electrode design of lithium-ion batteries with improved high-rate pulse overcharge protection. Thus the present invention provides electrochemical devices containing a cathode comprising at least one primary positive material and at least one secondary positive material; an anode; and a non-aqueous electrolyte comprising a redox shuttle additive; wherein the redox potential of the redox shuttle additive is greater than the redox potential of the primary positive material; the redox potential of the redox shuttle additive is lower than the redox potential of the secondary positive material; and the redox shuttle additive is stable at least up to the redox potential of the secondary positive material.

Species-Specific Standard Redox Potential of Thiol-Disulfide Systems: A Key Parameter to Develop Agents against Oxidative Stress

NASA Astrophysics Data System (ADS)

Mirzahosseini, Arash; Noszál, Béla

2016-11-01

Microscopic standard redox potential, a new physico-chemical parameter was introduced and determined to quantify thiol-disulfide equilibria of biological significance. The highly composite, codependent acid-base and redox equilibria of thiols could so far be converted into pH-dependent, apparent redox potentials (E’°) only. Since the formation of stable metal-thiolate complexes precludes the direct thiol-disulfide redox potential measurements by usual electrochemical techniques, an indirect method had to be elaborated. In this work, the species-specific, pH-independent standard redox potentials of glutathione were determined primarily by comparing it to 1-methylnicotinamide, the simplest NAD+ analogue. Secondarily, the species-specific standard redox potentials of the two-electron redox transitions of cysteamine, cysteine, homocysteine, penicillamine, and ovothiol were determined using their microscopic redox equilibrium constants with glutathione. The 30 different, microscopic standard redox potential values show close correlation with the respective thiolate basicities and provide sound means for the development of potent agents against oxidative stress.

Redox Deposition of Nanoscale Metal Oxides on Carbon for Next-Generation Electrochemical Capacitors

DTIC Science & Technology

2013-01-01

Nanoscale Metal Oxides Sassin et al. Redox Deposition Approaches to Nanoscale Coatings of Metal Oxides Manganese Oxides. Permanganate (MnO4 ) is a versa...scalability of the permanganate carbon redox reaction for generating MnOx coatings that store charge.21 The initial study per- formed on planar graphite...the carbon surface from the aqueous permanganate solu- tion (pH∼5),29,35 evidenced by a sharp increase in solution pH and a decrease in solution

Enzyme electrokinetics: hydrogen evolution and oxidation by Allochromatium vinosum [NiFe]-hydrogenase.

PubMed

Léger, Christophe; Jones, Anne K; Roseboom, Winfried; Albracht, Simon P J; Armstrong, Fraser A

2002-12-31

The mechanism of catalytic hydrogen evolution and oxidation by Allochromatium vinosum [NiFe]-hydrogenase has been studied by protein film voltammetry (PFV) with the enzyme adsorbed at a pyrolytic graphite edge electrode. By analyzing the entire shapes of catalytic voltammograms, the energetics of the catalytic cycles (reduction potentials and acidity constants of the active states), including the detailed profiles of activity against pH and the sequences of proton and electron transfers, have been determined, and these are discussed with respect to the mechanism. PFV, which probes rates as a continuous function of the electrochemical potential (i.e., in the "potential domain"), is proven to be an invaluable tool for determining the redox properties of an active site in the presence of its substrate, at room temperature, and during turnover. This is especially relevant in the case of the active states of hydrogenase, since one of its substrates (the proton) is always present at significant levels in the titration medium at physiological pH values.

Water geochemistry of shallow lakes from the southeastern Pampa plain, Argentina and their implications on mollusk shells preservation.

PubMed

Cristini, Paula A; Tietze, Eleonor; De Francesco, Claudio G; Martínez, Daniel E

2017-12-15

A seasonal sampling of sediments, column and interstitial water for physico-chemical analysis were performed in littoral and open water areas in three freshwater shallow lakes (Nahuel Rucá, Las Mostazas and Los Carpinchos) from Southeastern Pampa plain, Argentina. The main objective of the present study is to evaluate how the characteristics of the depositional environments could be affecting mollusk shell preservation. These lakes are very shallow (2m) and are characterized by an extensive littoral area, dominated by the emergent macrophyte Schoenoplectus californicus, which forms a complete ring around the lake, and an open water area, in general free of vegetation. Five samples of sediments in each compartment were extracted for analysis of pH, moisture, organic matter and carbonates content using a gravity corer, while five samples from column and interstitial water were extracted for chemical analysis (pH, conductivity, major ions, minor ions and hardness). Besides, calcite and aragonite saturation indices and the redox potential were calculated for each lake. The results show the significant impact of water chemistry and redox conditions on the preservation potential of freshwater mollusk and consequently in the quality of paleonvironmental reconstruction based on the biological record from the study region. The higher concentration of organic matter and lower pH registered in the littoral area, mainly during warm months (autumn and summer), suggest worst environments for mollusk preservation, compared to open waters. Moreover, water geochemistry analysis showed aragonite and calcite indices near equilibrium or slightly subsaturated in interstitial water associated with more acid pHs, while column water is strongly oversaturated related to alkaline pHs. These results suggest that carbonate remains within sediments will be subject to dissolution affecting negatively their preservation potential. However, mollusk shells in contact with the column water are not expected to be dissolved. Copyright © 2017 Elsevier B.V. All rights reserved.

Unravelling metal mobility under complex contaminant signatures.

PubMed

de Souza Machado, Anderson Abel; Spencer, Kate L; Zarfl, Christiane; O'Shea, Francis T

2018-05-01

Metals are concerning pollutants in estuaries, where contamination can undergo significant remobilisation driven by physico-chemical forcing. Environmental concentrations of metals in estuarine sediments are often higher than natural backgrounds, but show no contiguity to potential sources. Thus, better understanding the metal mobility in estuaries is essential to improve identification of pollution sources and their accountability for environmental effects. This study aims to identify the key biogeochemical drivers of metal mobilisation on contaminated estuarine sediments through (1) evaluation of the potential mobilisation under controlled conditions, and (2) investigation of the relevance of metal mobilisation for in situ pollution levels in an area with multiple contaminant sources. Sediments from a saltmarsh adjacent to a coastal landfill, a marina, and a shipyard on the Thames Estuary (Essex, UK) were exposed in the laboratory (24h, N=96, 20°C) to water under various salinity, pH, and redox potential. Major cations, Fe(II), and trace metal concentrations were analysed in the leachate and sediment. Salinity, pH and redox had a significant effect on metal mobilisation (p<0.001), e.g. under certain conditions Fe(II) leaching was increased ~1000-fold. Measurements in situ of surface and subsurface sediment cores revealed that landfill proximity poorly explained metal spatial distribution. However, physicochemical parameters explained up to 97% of geochemically normalized metal concentrations in sediments. Organic matter and pH were dominant factors for most of the metal concentrations at the sediment surface. At subsurface, major cations (Ca, Na, Mg and K) were determinant predictors of metal concentrations. Applying the empirical model obtained in the laboratory to geochemical conditions of the studied saltmarsh it was possible to demonstrate that Fe mobilisation regulates the fate of this (and other) metal in that area. Thus, present results highlight the importance of metal mobility to control sediment pollution and estuarine fate of metals. Copyright © 2017 Elsevier B.V. All rights reserved.

Hydrologically mediated iron reduction/oxidation fluctuations and dissolved organic carbon exports in tidal wetlands

NASA Astrophysics Data System (ADS)

Guimond, J. A.; Seyfferth, A.; Michael, H. A.

2017-12-01

Salt marshes are biogeochemical hotspots where large quantities of carbon are processed and stored. High primary productivity and deposition of carbon-laden sediment enable salt marsh soils to accumulate and store organic carbon. Conversely, salt marshes can laterally export carbon from the marsh platform to the tidal channel and eventually the ocean via tidal pumping. However, carbon export studies largely focus on tidal channels, missing key physical and biogeochemical mechanisms driving the mobilization of dissolved organic carbon (DOC) within the marsh platform and limiting our understanding of and ability to predict coastal carbon dynamics. We hypothesize that iron redox dynamics mediate the mobilization/immobilization of DOC in the top 30 cm of salt marsh sediment near tidal channels. The mobilized DOC can then diffuse into the flooded surface water or be advected to tidal channels. To elucidate DOC dynamics driven by iron redox cycles, we measured porewater DOC, Fe(II), total iron, total sulfate, pH, redox potential, and electrical conductivity (EC) beside the creek, at the marsh levee, and in the marsh interior in a mid-latitude tidal salt marsh in Dover, Delaware. Samples were collected at multiple tide stages during a spring and neap tide at depths of 5-75cm. Samples were also collected from the tidal channel. Continuous Eh measurements were made using in-situ electrodes. A prior study shows that DOC and Fe(II) concentrations vary spatially across the marsh. Redox conditions near the creek are affected by tidal oscillations. High tides saturate the soil and decrease redox potential, whereas at low tide, oxygen enters the sediment and increases the Eh. This pattern is always seen in the top 7-10cm of sediment, with more constant low Eh at depth. However, during neap tides, this signal penetrates deeper. Thus, between the creek and marsh levee, hydrology mediates redox conditions. Based on porewater chemistry, if DOC mobilization can be linked to redox cycles, then hydrologic oscillations can be tied to DOC dynamics and predicted with hydrologic models. By elucidating the mechanisms driving the mobilization of DOC, we can begin to better understand, quantify, and forecast coastal carbon dynamics.

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe 3Mn-Iodosobenzene Adducts

DOE PAGES

de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz; ...

2017-03-24

In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change atmore » a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.« less

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

PubMed

de Ruiter, Graham; Carsch, Kurtis M; Gul, Sheraz; Chatterjee, Ruchira; Thompson, Niklas B; Takase, Michael K; Yano, Junko; Agapie, Theodor

2017-04-18

We report the synthesis, characterization, and reactivity of [LFe 3 (PhPz) 3 OMn( s PhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2 Fe II Mn II vs. Fe III 3 Mn II ) influence oxygen atom transfer in tetranuclear Fe 3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

First-Principles pH Theory

NASA Astrophysics Data System (ADS)

Kim, Yong-Hyun; Zhang, S. B.

2006-03-01

Despite being one of the most important macroscopic measures and a long history even before the quantum mechanics, the concept of pH has rarely been mentioned in microscopic theories, nor being incorporated computationally into first-principles theory of aqueous solutions. Here, we formulate a theory for the pH dependence of solution formation energy by introducing the proton chemical potential as the microscopic counterpart of pH in atomistic solution models. Within the theory, the general acid-base chemistry can be cast in a simple pictorial representation. We adopt density-functional molecular dynamics to demonstrate the usefulness of the method by studying a number of solution systems including water, small solute molecules such as NH3 and HCOOH, and more complex amino acids with several functional groups. For pure water, we calculated the auto- ionization constant to be 13.2 with a 95 % accuracy. For other solutes, the calculated dissociation constants, i.e., the so- called pKa, are also in reasonable agreement with experiments. Our first-principles pH theory can be readily applied to broad solution chemistry problems such as redox reactions.

Trace metal dynamics in floodplain soils of the river Elbe: a review.

PubMed

Schulz-Zunkel, Christiane; Krueger, Frank

2009-01-01

This paper reviews trace metal dynamics in floodplain soils using the Elbe floodplains in Germany as an example of extraordinary importance because of the pollution level of its sediments and soils. Trace metal dynamics are determined by processes of retention and release, which are influenced by a number of soil properties including pH value, redox potential, organic matter, type and amount of clay minerals, iron-, manganese- and aluminum-oxides. Today floodplains act as important sinks for contaminants but under changing hydraulic and geochemical conditions they may also act as sources for pollutants. In floodplains such changes may be extremes in flooding or dry periods that particularly lead to altered redox potentials and that in turn influence the pH value, the mineralization of organic matter as well as the charge of the pedogenic oxides. Such reactions may affect the bioavailability of trace metals in soils and it can be clearly seen that the bioavailability of metals is an important factor for estimating trace metal remobilization in floodplain soils. However as bioavailability is not a constant factor, there is still a lack of quantification of metal mobilization particularly on the basis of changing geochemical conditions. Moreover, mobile amounts of metals in the soil solution do not indicate to which extent remobilized metals will be transported to water bodies or plants and therefore potentially have toxicological effects. Consequently, floodplain areas still need to be taken into consideration when studying the role and behavior of sediments and soils for transporting pollutants within river systems, particularly concerning the Water Framework Directive.

Graphite Screen-Printed Electrodes Applied for the Accurate and Reagentless Sensing of pH.

PubMed

Galdino, Flávia E; Smith, Jamie P; Kwamou, Sophie I; Kampouris, Dimitrios K; Iniesta, Jesus; Smith, Graham C; Bonacin, Juliano A; Banks, Craig E

2015-12-01

A reagentless pH sensor based upon disposable and economical graphite screen-printed electrodes (GSPEs) is demonstrated for the first time. The voltammetric pH sensor utilizes GSPEs which are chemically pretreated to form surface immobilized oxygenated species that, when their redox behavior is monitored, give a Nernstian response over a large pH range (1-13). An excellent experimental correlation is observed between the voltammetric potential and pH over the entire pH range of 1-13 providing a simple approach with which to monitor solution pH. Such a linear response over this dynamic pH range is not usually expected but rather deviation from linearity is encountered at alkaline pH values; absence of this has previously been attributed to a change in the pKa value of surface immobilized groups from that of solution phase species. This non-deviation, which is observed here in the case of our facile produced reagentless pH sensor and also reported in the literature for pH sensitive compounds immobilized upon carbon electrodes/surfaces, where a linear response is observed over the entire pH range, is explained alternatively for the first time. The performance of the GSPE pH sensor is also directly compared with a glass pH probe and applied to the measurement of pH in "real" unbuffered samples where an excellent correlation between the two protocols is observed validating the proposed GSPE pH sensor.

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

PubMed Central

Li, Lin Z.

2012-01-01

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

Comparison of Eh and H2 measurements for delineating redox processes in a contaminated aquifer

USGS Publications Warehouse

Chapelle, Francis H.; Haack, Sheridan K.; Adriaens, Peter; Henry, Mark A.; Bradley, Paul M.

1996-01-01

Measurements of oxidation-reduction potential (Eh) and concentrations of dissolved hydrogen (H2) were made in a shallow groundwater system contaminated with solvents and jet fuel to delineate the zonation of redox processes. Eh measurements ranged from +69 to -158 mV in a cross section of the contaminated plume and accurately delineated oxic from anoxic groundwater. Plotting measured Eh and pH values on an equilibrium stability diagram indicated that Fe(III) reduction was the predominant redox process in the anoxic zone and did not indicate the presence of methanogenesis and sulfate reduction. In contrast, measurements of H2concentrations indicated that methanogenesis predominated in heavily contaminated sediments near the water table surface (H2 ∼ 7.0 nM) and that the methanogenic zone was surrounded by distinct sulfate-reducing (H2 ∼ 1-4 nM) and Fe(III)-reducing (H2 ∼ 0.1-0.8 nM) zones. The presence of methanogenesis, sulfate reduction, and Fe(III) reduction was confirmed by the distribution of dissolved oxygen, sulfate, Fe(II), and methane in groundwater. These results show that H2 concentrations were more useful for identifying anoxic redox processes than Ehmeasurements in this groundwater system. However, H2-based redox zone delineations are more reliable when H2 concentrations are interpreted in the context of electron-acceptor (oxygen, nitrate, sulfate) availability and the presence of final products [Fe(II), sulfide, methane] of microbial metabolism.

The Structure-Dependent Electric Release and Enhanced Oxidation of Drug in Graphene Oxide-Based Nanocarrier Loaded with Anticancer Herbal Drug Berberine.

PubMed

Yu, Danni; Ruan, Pan; Meng, Ziyuan; Zhou, Jianping

2015-08-01

The aim of the current investigation is to explore graphene oxide (GO) special electric and electrochemical properties in modulating and tuning drug delivery in tumor special environment of electrophysiology. The electric-sensitive drug release and redox behavior of GO-bearing berberine (Ber) was studied. Drug release in cell potential was applied in a designed electrode system: tumor environment was simulated at pH 6.2 with 0.1 V pulse voltage, whereas the normal was at pH 7.4 with 0.2 V. Quite different from the pH-depended profile, the electricity-triggered behavior indicated a high correlation with the carriers' structure: GO-based nanocomposite showed a burst release on its special "skin effect," whereas the PEGylated ones released slowly owing to the electroviscous effect of polymer. Cyclic voltammetry was used to investigate the redox behaviors of colloid PEGylated GO toward absorbed Ber in pH 5.8 and 7.2 solutions. After drug loading, the oxidation of Ber was enhanced in a neutral environment, whereas the enhancement of PEG-GO was in an acidic one, which means a possible increased susceptibility of their biotransformation in vivo. The studies designed in this work may help to establish a kind of carrier system for the sensitive delivery and metabolic regulation of drugs according to the different electrophysiological environment in tumor therapy. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Effects of iron on arsenic speciation and redox chemistry in acid mine water

USGS Publications Warehouse

Bednar, A.J.; Garbarino, J.R.; Ranville, J.F.; Wildeman, T.R.

2005-01-01

Concern about arsenic is increasing throughout the world, including areas of the United States. Elevated levels of arsenic above current drinking-water regulations in ground and surface water can be the result of purely natural phenomena, but often are due to anthropogenic activities, such as mining and agriculture. The current study correlates arsenic speciation in acid mine drainage and mining-influenced water with the important water-chemistry properties Eh, pH, and iron(III) concentration. The results show that arsenic speciation is generally in equilibrium with iron chemistry in low pH AMD, which is often not the case in other natural-water matrices. High pH mine waters and groundwater do not always hold to the redox predictions as well as low pH AMD samples. The oxidation and precipitation of oxyhydroxides deplete iron from some systems, and also affect arsenite and arsenate concentrations through sorption processes. ?? 2004 Elsevier B.V. All rights reserved.

A study on the selection of indigenous leaching-bacteria for effective bioleaching

NASA Astrophysics Data System (ADS)

Oh, S. J.; Cho, K. H.; Kim, B. J.; Choi, N. C.; Park, C. Y.

2012-04-01

Bioleaching technology, which is based on the ability of microorganisms to transform solid compounds into soluble and extractable valuable elements that can be recovered, has been rapidly developed in recent decades for its advantages, which include mild reaction condition, low energy consumption, simple process, low environmental impact and being suitable for low grade mine tailings and residues. The bacteria activities (survival, adaptation of toxically environments etc.) in the bioleaching technology play a key role in the solubilization of metals. The purpose of this study was to selection of optimal leaching-bacteria through changed pH and redox potential on bio-oxidation in batch experiments for successful bioleaching technology. Twenty three indigenous bacteria used throughout this study, leaching-bacteria were obtained from various geochemical conditions; bacteria inhabitation type (acid mine drainage, mine wastes leachate and sulfur hot springs) and base-metal type (sulfur, sulfide, iron and coal). Bio-oxidation experiment result was showed that 9 cycles (1 cycle - 28days) after the leaching-bacteria were inoculated to a leaching medium, pH was observed decreasing and redox potential increased. In the bacteria inhabitation type, bio-oxidation of sulfur hot springs bacteria was greater than other types (acid mine drainage and mine wastes leachate). In addition, bio-oxidation on base-metal type was appeared sulfur was greater than other types (sulfide, iron and coal). This study informs basic knowledge when bacteria apply to eco-/economic resources utilization studies including the biomining and the recycling of mine waste system.

Ion mobility based on column leaching of South African gold tailings dam with chemometric evaluation.

PubMed

Cukrowska, Ewa M; Govender, Koovila; Viljoen, Morris

2004-07-01

New column leaching experiments were designed and used as an alternative rapid screening approach to element mobility assessment. In these experiments, field-moist material was treated with an extracting solution to assess the effects of acidification on element mobility in mine tailings. The main advantage of this version of column leaching experiments with partitioned segments is that they give quick information on current element mobility in conditions closely simulating field conditions to compare with common unrepresentative air-dried, sieved samples used for column leaching experiments. Layers from the tailings dump material were sampled and packed into columns. The design of columns allows extracting leachates from each layer. The extracting solutions used were natural (pH 6.8) and acidified (pH 4.2) rainwater. Metals and anions were determined in the leachates. The concentrations of metals (Ca, Mg, Fe, Mn, Al, Cr, Ni, Co, Zn, and Cu) in sample leachates were determined using ICP OES. The most important anions (NO3-, Cl-, and SO4(2)-) were determined using the closed system izotacophoresis ITP analyser. The chemical analytical data from tailings leaching and physico-chemical data from field measurements (including pH, conductivity, redox potential, temperature) were used for chemometric evaluation of element mobility. Principal factor analysis (PFA) was used to evaluate ions mobility from different layers of tailings dump arising from varied pH and redox conditions. It was found that the results from the partitioned column leaching illustrate much better complex processes of metals mobility from tailings dump than the total column. The chemometric data analysis (PFA) proofed the differences in the various layers leachability that are arising from physico-chemical processes due to chemical composition of tailings dump deposit. Copyright 2004 Elsevier Ltd.

Effect of solvent on the electronic absorption spectral properties of some mixed β-octasubstituted Zn(II)-tetraphenylporphyrins

NASA Astrophysics Data System (ADS)

Bhyrappa, P.; Sankar, M.

2018-01-01

A series of mixed β-octasubstituted Zn(II)-porphyrins, 2,3,12,13-tetra(chloro/cyano/methyl)-5,7,8,10,15,17,18,20-octaphenylporphinato zinc(II), ZnTPP(Ph)4X4 (X = CN, Cl and CH3) have been examined by electronic absorption spectroscopy in various solvents. These Zn(II)-porphyrins exhibited varying degree of red-shift of absorption bands as high as 20-30 nm in 'B' band and 50-60 nm in longest wavelength band, 'Q(0,0)' band in polar solvents relative to that found in nonpolar solvents. The red-shift of B and Q(0,0) bands showed an unusual trend, ZnTPP(Ph)4(CN)4 > ZnTPP(Ph)4(CH3)4 > ZnTPP(Ph)4Cl4 but fails to follow an anticipated anodic shift in first porphyrin ring oxidation (vs Ag/AgCl) potential: ZnTPP(Ph)4(CN)4 (1.02 V) > ZnTPP(Ph)4Cl4 (0.74 V) > ZnTPP(Ph)4(CH3)4 (0.38 V). Such a trend suggests the combined effect of non-planarity of the macrocycle and electronic effect of the peripheral substituents. The equilibrium constants for the binding of nitrogenous bases with the Zn(II)-porphyrins showed as high as twenty fold increase for ZnTPP(Ph)4X4 (X = Br and CN) relative to ZnTPP(Ph)4(CH3)4 and follow the order: ZnTPP(Ph)4(CN)4 > ZnTPP(Ph)4Br4 > ZnTPP(Ph)4(CH3)4 ≤ ZnTPP which is approximately in line with an increase in anodic shift of their first ring redox potentials (ZnTPP(Ph)4(CN)4 (1.02 V) > ZnTPP(Ph)4Br4 (0.72 V) > ZnTPP (0.84 V) > ZnTPP(Ph)4(CH3)4) (0.38 V).

Chemolithoautotrophy in a shallow-sea hydrothermal system, Milos Island, Greece

NASA Astrophysics Data System (ADS)

Lu, G. S.; LaRowe, D.; Gilhooly, W., III; Druschel, G. K.; Fike, D. A.; Amend, J.

2017-12-01

In recent decades, numerous (hyper)thermophilic microorganisms have been isolated from hydrothermal venting systems. Although they have been shown to have the capabilities to catalyze a wide variety of reactions to gain energy, few pure cultures have been isolated from these environments. In order to more fully understand the catabolic potential of organisms living in and near hydrothermal vents, we have calculated the Gibbs energies (ΔGr) of 730 redox reactions that could be supplying energy to organisms in the shallow-sea hydrothermal sediments of Paleochori Bay, Milos Island, Greece. This analysis required in-depth geochemical data on the pore fluids and minerals in these sediments near the vent site at several depths. The geochemical profiles of Saganaki vent show steep gradients in temperature, pH, and redox-sensitive compounds resulting from the mixing of hot ( 75oC), acidic ( pH 4), chemically reduced venting fluid with colder, slightly basic and oxidized seawater. We determined values of ΔGr for 47 sediment porewater samples along a 20cm x 2m transect for metabolic reactions involving 23 inorganic H-, O-, C-, N-, S-, Fe-, Mn-, and As- bearing compounds. 379 of the reactions considered were exergonic at one or more sampling locations. The most exergonic reactions were anaerobic CO oxidation with NO2- (136 - 162 kJ/mol e-), followed by the O2/CO, NO3-/CO, and NO2-/ H2S redox pairs. ΔGr values exhibit significant variation among sites as temperature, pH and chemical concentration vary, especially concentrations of Fe2+, Mn2+, and H2S. A great diversity of energy sources are available for microbial populations to exploit: in hotter sediments, sulfide oxidation coupled to nitrite reduction yields large amounts of energy per kg of sediment, whereas aerobic S0 oxidation is more energy-yielding in cooler areas. Our results show that at Saganaki there is a substantial amount of energy available from to microorganisms from sulfur-redox reactions. 16S rRNA pyrotag sequencing data point to diverse microbial populations at Saganaki, which is consistent with our bioenergetic profile, particularly when the thermodynamic calculations are normalized per kg of venting fluid. These data suggest a complex spatial distribution of microbial physiologies that is in good agreement with predicted energy yields.

Lowering N2O emissions from soils using eucalypt biochar: the importance of redox reactions

PubMed Central

Quin, P; Joseph, S; Husson, O; Donne, S; Mitchell, D; Munroe, P; Phelan, D; Cowie, A; Van Zwieten, L

2015-01-01

Agricultural soils are the primary anthropogenic source of atmospheric nitrous oxide (N2O), contributing to global warming and depletion of stratospheric ozone. Biochar addition has shown potential to lower soil N2O emission, with the mechanisms remaining unclear. We incubated eucalypt biochar (550 °C) – 0, 1 and 5% (w/w) in Ferralsol at 3 water regimes (12, 39 and 54% WFPS) – in a soil column, following gamma irradiation. After N2O was injected at the base of the soil column, in the 0% biochar control 100% of expected injected N2O was released into headspace, declining to 67% in the 5% amendment. In a 100% biochar column at 6% WFPS, only 16% of the expected N2O was observed. X-ray photoelectron spectroscopy identified changes in surface functional groups suggesting interactions between N2O and the biochar surfaces. We have shown increases in -O-C = N /pyridine pyrrole/NH3, suggesting reactions between N2O and the carbon (C) matrix upon exposure to N2O. With increasing rates of biochar application, higher pH adjusted redox potentials were observed at the lower water contents. Evidence suggests that biochar has taken part in redox reactions reducing N2O to dinitrogen (N2), in addition to adsorption of N2O. PMID:26615820

Hydrogeochemical processes governing the origin, transport and fate of major and trace elements from mine wastes and mineralized rock to surface waters

USGS Publications Warehouse

Nordstrom, D. Kirk

2011-01-01

Mobility of potential or actual contaminants from mining and mineral processing activities depends on (1) occurrence: is the mineral source of the contaminant actually present? (2) abundance: is the mineral present in sufficient quantity to make a difference? (3) reactivity: what are the energetics, rates, and mechanisms of sorption and mineral dissolution and precipitation relative to the flow rate of the water? and (4) hydrology: what are the main flow paths for contaminated water? Estimates of relative proportions of minerals dissolved and precipitated can be made with mass-balance calculations if minerals and water compositions along a flow path are known. Combined with discharge, these mass-balance estimates quantify the actual weathering rate of pyrite mineralization in the environment and compare reasonably well with laboratory rates of pyrite oxidation except when large quantities of soluble salts and evaporated mine waters have accumulated underground. Quantitative mineralogy with trace-element compositions can substantially improve the identification of source minerals for specific trace elements through mass balances. Post-dissolution sorption and precipitation (attenuation) reactions depend on the chemical behavior of each element, solution composition and pH, aqueous speciation, temperature, and contact-time with mineral surfaces. For example, little metal attenuation occurs in waters of low pH (2, and redox-sensitive oxyanions (As, Sb, Se, Mo, Cr, V). Once dissolved, metal and metalloid concentrations are strongly affected by redox conditions and pH. Iron is the most reactive because it is rapidly oxidized by bacteria and archaea and Fe(III) hydrolyzes and precipitates at low pH (1–3) which is related directly to its first hydrolysis constant, pK1 = 2.2. Several insoluble sulfate minerals precipitate at low pH including anglesite, barite, jarosite, alunite and basaluminite. Aluminum hydrolyzes near pH 5 (pK1 = 5.0) and provides buffering and removal of Al by mineral precipitation from pH 4–5.5. Dissolved sulfate behaves conservatively because the amount removed from solution by precipitation is usually too small relative to the high concentrations in the water column and relative to the flow rate of the water.

Effect of protonation, composition and isomerism on the redox properties and electron (de)localization of classical polyoxometalates

NASA Astrophysics Data System (ADS)

López, Xavier

2017-10-01

This publication reviews some relevant features related with the redox activity of two inorganic compounds: [XM12O40]q- (Keggin structure) and [X2M18O62]q- (Wells-Dawson structure). These are two well-known specimens of the vast Polyoxometalate (POM) family, which has been the subject of extensive experimental and theoretical research owing to their unmatched properties. In particular, their redox activity focus a great deal of attention from scientists due to their prospective related applications. POMs are habitually seen as `electron sponges' since many of them accept several electrons without losing their chemical identity. This makes them excellent models to study mechanisms of electrochemical nature. Their redox properties depend on: (i) the type and number of transition metal atoms in the structure, (ii) the basicity of the first reduced species and, occasionally, of the fully oxidized species; (iii) the size of the molecule, (iv) the overall negative charge of the POM, and (v) the size of the central heteroatom. In the last years, important collaboration between the experimental and theoretical areas has been usual on the development of POM science. In the present chapter three of these synergies are highlighted: the influence of the internal heteroatom upon the redox potentials of Keggin anions; the dependence of the redox waves of Fe-substituted Wells-Dawson compounds with pH; and the role of electron delocalization and pairing in mixed-metal Mo/W Wells-Dawson compounds in their ability to accept electrons. In these three cases, a complete understanding of the problem would not have been possible without the mutual benefit of experimental and computational data.

Redox equilibria in hydroxylamine oxidoreductase. Electrostatic control of electron redistribution in multielectron oxidative processes.

PubMed

Kurnikov, Igor V; Ratner, Mark A; Pacheco, A Andrew

2005-02-15

We report results of continuum electrostatics calculations of the cofactor redox potentials, and of the titratable group pK(a) values, in hydroxylamine oxidoreductase (HAO). A picture of a sophisticated multicomponent control of electron flow in the protein emerged from the studies. First, we found that neighboring heme cofactors strongly interact electrostatically, with energies of 50-100 mV. Thus, cofactor redox potentials depend on the oxidation state of other cofactors, and cofactor redox potentials in the active (partially oxidized) enzyme differ substantially from the values obtained in electrochemical redox titration experiments. We found that, together, solvent-exposed heme 1 (having a large negative redox potential) and heme 2 (having a large positive redox potential) form a lock for electrons generated during the oxidation reaction The attachment of HAO's physiological electron transfer partner cytochrome c(554) results in a positive shift in the redox potential of heme 1, and "opens the electron gate". Electrons generated as a result of hydroxylamine oxidation travel to heme 3 and heme 8, which have redox potentials close to 0 mV versus NHE (this result is in partial disagreement with an existing experimental redox potential assignment). The closeness of hemes 3 and 8 from different enzyme subunits allows redistribution of the four electrons generated as a result of hydroxylamine oxidation, among the three enzyme subunits. For the multielectron oxidation process to be maximally efficient, the redox potentials of the electron-accepting cofactors should be roughly equal, and electrostatic interactions between extra electrons on these cofactors should be minimal. The redox potential assignments presented in the paper satisfy this general rule.

Synergistic oxygen atom transfer by ruthenium complexes with non-redox metal ions.

PubMed

Lv, Zhanao; Zheng, Wenrui; Chen, Zhuqi; Tang, Zhiming; Mo, Wanling; Yin, Guochuan

2016-07-28

Non-redox metal ions can affect the reactivity of active redox metal ions in versatile biological and heterogeneous oxidation processes; however, the intrinsic roles of these non-redox ions still remain elusive. This work demonstrates the first example of the use of non-redox metal ions as Lewis acids to sharply improve the catalytic oxygen atom transfer efficiency of a ruthenium complex bearing the classic 2,2'-bipyridine ligand. In the absence of Lewis acid, the oxidation of ruthenium(ii) complex by PhI(OAc)2 generates the Ru(iv)[double bond, length as m-dash]O species, which is very sluggish for olefin epoxidation. When Ru(bpy)2Cl2 was tested as a catalyst alone, only 21.2% of cyclooctene was converted, and the yield of 1,2-epoxycyclooctane was only 6.7%. As evidenced by electronic absorption spectra and EPR studies, both the oxidation of Ru(ii) by PhI(OAc)2 and the reduction of Ru(iv)[double bond, length as m-dash]O by olefin are kinetically slow. However, adding non-redox metal ions such as Al(iii) can sharply improve the oxygen transfer efficiency of the catalyst to 100% conversion with 89.9% yield of epoxide under identical conditions. Through various spectroscopic characterizations, an adduct of Ru(iv)[double bond, length as m-dash]O with Al(iii), Ru(iv)[double bond, length as m-dash]O/Al(iii), was proposed to serve as the active species for epoxidation, which in turn generated a Ru(iii)-O-Ru(iii) dimer as the reduced form. In particular, both the oxygen transfer from Ru(iv)[double bond, length as m-dash]O/Al(iii) to olefin and the oxidation of Ru(iii)-O-Ru(iii) back to the active Ru(iv)[double bond, length as m-dash]O/Al(iii) species in the catalytic cycle can be remarkably accelerated by adding a non-redox metal, such as Al(iii). These results have important implications for the role played by non-redox metal ions in catalytic oxidation at redox metal centers as well as for the understanding of the redox mechanism of ruthenium catalysts in the oxygen atom transfer reaction.

Middle-redox potential laccase from Ganoderma sp.: its application in improvement of feed for monogastric animals

PubMed Central

Sharma, Krishna Kant; Shrivastava, Bhuvnesh; Sastry, V. R. B.; Sehgal, Neeta; Kuhad, Ramesh Chander

2013-01-01

The variables influencing laccase production by white-rot fungus Ganoderma sp. rckk-02 were optimized employing response surface methodology. Malt extract (6.0% w/v), lignin (0.5% w/v) and pH (5.5) were found to be the most significant factors for enhanced laccase production by 7 fold (226.0 U/ml) as compared to unoptimized growth conditions (32.0 U/ml). The N-terminal sequence of laccase revealed its distinct amino acid profile (S- I- R- N- S- G), which suggested it as a novel enzyme. The Far-UV CD spectrum of the laccase showed single broad negative trough at around 213 nm, a typical signature of all β proteins. The laccase was found to fall in the range of middle redox potential laccases. Purified laccase at dosage of 2.5 Ug−1 body weight when supplemented with pelleted diet of rats, a significant improvement (p < 0.05) in nutrients digestibility without causing any elevation of blood stress enzymes was observed. PMID:23416696

Quality changes in refrigerated stored minced pork wrapped with plastic cling film and the effect of glucose supplementation.

PubMed

Del Blanco, Alba; Caro, Irma; Quinto, Emiliano J; Mateo, Javier

2017-04-01

Meat spoilage greatly depends on meat composition and storage conditions. Microbial and biochemical changes in minced pork (100-g portions) wrapped with a polyvinyl chloride film during a 4-day refrigerated storage were studied. As glucose is the first substrate used by spoilage bacteria and when it is depleted bacteria could generate undesirable volatiles, the effect of the addition of glucose to minced meat was also studied. Three treatments were used: control (C), without added glucose, and low and high glucose concentration (L and H), 150mg and 750mg of glucose in 100g of meat, respectively. Spoilage bacteria, pH, redox potential, colour, basic volatile nitrogen, glucose, organic acids, and volatiles were analyzed in both recently prepared and stored pork samples. Storage resulted in increased levels of lactic acid bacteria and glucose-derived short chain alkyl volatiles, and a decrease in redox potential and volatile aldehyde levels. The addition of glucose to meat did not affect the biochemical characteristics of stored minced pork. Copyright © 2016 Elsevier Ltd. All rights reserved.

Direct structural evidence of protein redox regulation obtained by in-cell NMR.

PubMed

Mercatelli, Eleonora; Barbieri, Letizia; Luchinat, Enrico; Banci, Lucia

2016-02-01

The redox properties of cellular environments are critical to many functional processes, and are strictly controlled in all living organisms. The glutathione-glutathione disulfide (GSH-GSSG) couple is the most abundant intracellular redox couple. A GSH redox potential can be calculated for each cellular compartment, which reflects the redox properties of that environment. This redox potential is often used to predict the redox state of a disulfide-containing protein, based on thermodynamic considerations. However, thiol-disulfide exchange reactions are often catalyzed by specific partners, and the distribution of the redox states of a protein may not correspond to the thermodynamic equilibrium with the GSH pool. Ideally, the protein redox state should be measured directly, bypassing the need to extrapolate from the GSH. Here, by in-cell NMR, we directly observe the redox state of three human proteins, Cox17, Mia40 and SOD1, in the cytoplasm of human and bacterial cells. We compare the observed distributions of redox states with those predicted by the GSH redox potential, and our results partially agree with the predictions. Discrepancies likely arise from the fact that the redox state of SOD1 is controlled by a specific partner, its copper chaperone (CCS), in a pathway which is not linked to the GSH redox potential. In principle, in-cell NMR allows determining whether redox proteins are at the equilibrium with GSH, or they are kinetically regulated. Such approach does not need assumptions on the redox potential of the environment, and provides a way to characterize each redox-regulating pathway separately. Copyright © 2015 Elsevier B.V. All rights reserved.

Polyoxometalate active charge-transfer material for mediated redox flow battery

DOEpatents

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

2017-01-17

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

The influence of redox chemistry and pH on chemically active forms of arsenic in sewage sludge-amended soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carbonell-Barrachina, A.; Jugsujinda, A.; DeLaune, R.D.

1999-07-01

Chemical fractionation procedures were used to quantify the effect of the sediment redox and pH conditions on the adsorption and solubility of arsenic (As) in municipal sewage sludge and sewage sludge-amended soil. Sludge and sludge-amended soil were incubated in microcosms in which Eh-pH conditions were controlled. Samples were sequentially extracted to determine As in various chemical forms (water soluble, exchangeable, bound to carbonates, bound to iron (Fe) and manganese (Mn) oxides, bound to insoluble organics and sulfides) and the chemically inactive fraction (mineral residues). In both sewage sludge and sludge-amended soil, As chemistry was governed by large molecular humic mattermore » and sulfides and Fe and Mn-oxides. Solubility of As remained low and constant under both aerobic and anaerobic conditions in sludge-amended soil. After dissolution of Fe and Mn-oxides, As{sup 5+} was released into sludge solution, reduced to As{sup 3+} and likely precipitated as sulfide. Therefore, an organic amendment rich in sulfur compounds, such as sewage sludge, would drastically reduce the potential risks derived from As pollution under highly anoxic conditions by precipitation of this toxic metalloid as insoluble and immobile sulfides.« less

Fabrication of an Electrochemical Sensor Based on Gold Nanoparticles/Carbon Nanotubes as Nanocomposite Materials: Determination of Myricetin in Some Drinks

PubMed Central

Hajian, Reza; Yusof, Nor Azah; Faragi, Tayebe; Shams, Nafiseh

2014-01-01

In this paper, the electrochemical behavior of myricetin on a gold nanoparticle/ethylenediamine/multi-walled carbon-nanotube modified glassy carbon electrode (AuNPs/en/MWCNTs/GCE) has been investigated. Myricetin effectively accumulated on the AuNPs/en/MWCNTs/GCE and caused a pair of irreversible redox peaks at around 0.408 V and 0.191 V (vs. Ag/AgCl) in 0.1 mol L−1 phosphate buffer solution (pH 3.5) for oxidation and reduction reactions respectively. The heights of the redox peaks were significantly higher on AuNPs/en/MWNTs/GCE compare with MWCNTs/GC and there was no peak on bare GC. The electron-transfer reaction for myricetin on the surface of electrochemical sensor was controlled by adsorption. Some parameters including pH, accumulation potential, accumulation time and scan rate have been optimized. Under the optimum conditions, anodic peak current was proportional to myricetin concentration in the dynamic range of 5.0×10−8 to 4.0×10−5 mol L−1 with the detection limit of 1.2×10−8 mol L−1. The proposed method was successfully used for the determination of myricetin content in tea and fruit juices. PMID:24809346

Redox potential tuning by redox-inactive cations in nature's water oxidizing catalyst and synthetic analogues.

PubMed

Krewald, Vera; Neese, Frank; Pantazis, Dimitrios A

2016-04-28

The redox potential of synthetic oligonuclear transition metal complexes has been shown to correlate with the Lewis acidity of a redox-inactive cation connected to the redox-active transition metals of the cluster via oxo or hydroxo bridges. Such heterometallic clusters are important cofactors in many metalloenzymes, where it is speculated that the redox-inactive constituent ion of the cluster serves to optimize its redox potential for electron transfer or catalysis. A principal example is the oxygen-evolving complex in photosystem II of natural photosynthesis, a Mn4CaO5 cofactor that oxidizes water into dioxygen, protons and electrons. Calcium is critical for catalytic function, but its precise role is not yet established. In analogy to synthetic complexes it has been suggested that Ca(2+) fine-tunes the redox potential of the manganese cluster. Here we evaluate this hypothesis by computing the relative redox potentials of substituted derivatives of the oxygen-evolving complex with the cations Sr(2+), Gd(3+), Cd(2+), Zn(2+), Mg(2+), Sc(3+), Na(+) and Y(3+) for two sequential transitions of its catalytic cycle. The theoretical approach is validated with a series of experimentally well-characterized Mn3AO4 cubane complexes that are structural mimics of the enzymatic cluster. Our results reproduce perfectly the experimentally observed correlation between the redox potential and the Lewis acidities of redox-inactive cations for the synthetic complexes. However, it is conclusively demonstrated that this correlation does not hold for the oxygen evolving complex. In the enzyme the redox potential of the cluster only responds to the charge of the redox-inactive cations and remains otherwise insensitive to their precise identity, precluding redox-tuning of the metal cluster as a primary role for Ca(2+) in biological water oxidation.

Macroscopic experimental and modeling evaluation of selenite and selenate adsorption mechanisms on gibbsite

USDA-ARS?s Scientific Manuscript database

Selenite Se(IV) and selenate Se(VI) selenium adsorption behavior was investigated on gibbsite as a function of solution pH and solution ionic strength. Adsorption of both Se redox states decreased with increasing solution pH. Electrophoretic mobility measurements showed downward shifts in point of...

Reversible Redox Activity by Ion-pH Dually Modulated Duplex Formation of i-Motif DNA with Complementary G-DNA.

PubMed

Chang, Soyoung; Kilic, Tugba; Lee, Chang Kee; Avci, Huseyin; Bae, Hojae; Oskui, Shirin Mesbah; Jung, Sung Mi; Shin, Su Ryon; Kim, Seon Jeong

2018-04-08

The unique biological features of supramolecular DNA have led to an increasing interest in biomedical applications such as biosensors. We have developed an i-motif and G-rich DNA conjugated single-walled carbon nanotube hybrid materials, which shows reversible conformational switching upon external stimuli such as pH (5 and 8) and presence of ions (Li⁺ and K⁺). We observed reversible electrochemical redox activity upon external stimuli in a quick and robust manner. Given the ease and the robustness of this method, we believe that pH- and ion-driven reversible DNA structure transformations will be utilized for future applications for developing novel biosensors.

Selective separation of iron from uranium in quantitative determination of traces of uranium by alpha spectrometry in soil/sediment sample.

PubMed

Singhal, R K; Narayanan, Usha; Karpe, Rupali; Kumar, Ajay; Ranade, A; Ramachandran, V

2009-04-01

During this work, controlled redox potential methodology was adopted for the complete separation of traces of uranium from the host matrix of mixed hydroxide of Iron. Precipitates of Fe(+2) and Fe(+3) along with other transuranic elements were obtained from acid leached solution of soil by raising the pH to 9 with 14N ammonia solution. The concentration of the uranium observed in the soil samples was 200-600 ppb, whereas in sediment samples, the concentration range was 61-400 ppb.

Plutonium Oxidation State Distribution under Aerobic and Anaerobic Subsurface Conditions for Metal-Reducing Bacteria

NASA Astrophysics Data System (ADS)

Reed, D. T.; Swanson, J.; Khaing, H.; Deo, R.; Rittmann, B.

2009-12-01

The fate and potential mobility of plutonium in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium is the near-surface contaminant of concern at several DOE sites and continues to be the contaminant of concern for the permanent disposal of nuclear waste. The mobility of plutonium is highly dependent on its redox distribution at its contamination source and along its potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. The redox distribution of plutonium in the presence of facultative metal reducing bacteria (specifically Shewanella and Geobacter species) was established in a concurrent experimental and modeling study under aerobic and anaerobic conditions. Pu(VI), although relatively soluble under oxidizing conditions at near-neutral pH, does not persist under a wide range of the oxic and anoxic conditions investigated in microbiologically active systems. Pu(V) complexes, which exhibit high chemical toxicity towards microorganisms, are relatively stable under oxic conditions but are reduced by metal reducing bacteria under anaerobic conditions. These facultative metal-reducing bacteria led to the rapid reduction of higher valent plutonium to form Pu(III/IV) species depending on nature of the starting plutonium species and chelating agents present in solution. Redox cycling of these lower oxidation states is likely a critical step in the formation of pseudo colloids that may lead to long-range subsurface transport. The CCBATCH biogeochemical model is used to explain the redox mechanisms and final speciation of the plutonium oxidation state distributions observed. These results for microbiologically active systems are interpreted in the context of their importance in defining the overall migration of plutonium in the subsurface.

Thermodynamic and redox properties of graphene oxides for lithium-ion battery applications: a first principles density functional theory modeling approach.

PubMed

Kim, Sunghee; Kim, Ki Chul; Lee, Seung Woo; Jang, Seung Soon

2016-07-27

Understanding the thermodynamic stability and redox properties of oxygen functional groups on graphene is critical to systematically design stable graphene-based positive electrode materials with high potential for lithium-ion battery applications. In this work, we study the thermodynamic and redox properties of graphene functionalized with carbonyl and hydroxyl groups, and the evolution of these properties with the number, types and distribution of functional groups by employing the density functional theory method. It is found that the redox potential of the functionalized graphene is sensitive to the types, number, and distribution of oxygen functional groups. First, the carbonyl group induces higher redox potential than the hydroxyl group. Second, more carbonyl groups would result in higher redox potential. Lastly, the locally concentrated distribution of the carbonyl group is more beneficial to have higher redox potential compared to the uniformly dispersed distribution. In contrast, the distribution of the hydroxyl group does not affect the redox potential significantly. Thermodynamic investigation demonstrates that the incorporation of carbonyl groups at the edge of graphene is a promising strategy for designing thermodynamically stable positive electrode materials with high redox potentials.

Redox-induced mobilization of copper, selenium, and zinc in deltaic soils originating from Mississippi (U.S.A.) and Nile (Egypt) River Deltas: A better understanding of biogeochemical processes for safe environmental management.

PubMed

Shaheen, Sabry M; Frohne, Tina; White, John R; DeLaune, Ron D; Rinklebe, Jörg

2017-01-15

Studies about the mobilization of potentially toxic elements (PTEs) in deltaic soils can be challenging, provide critical information on assessing the potential risk and fate of these elements and for sustainable management of these soils. The impact of redox potential (E H ), pH, iron (Fe), manganese (Mn), sulfate (SO 4 2- ), chloride (Cl - ), aliphatic dissolved organic carbon (DOC), and aromatic dissolved organic carbon (DAC) on the mobilization of copper (Cu), selenium (Se), and zinc (Zn) was studied in two soils collected from the Nile and Mississippi Rivers deltaic plains focused on increasing our understanding of the fate of these toxic elements. Soils were exposed to a range of redox conditions stepwise from reducing to oxidizing soil conditions using an automated biogeochemical microcosm apparatus. Concentrations of DOC and Fe were high under reducing conditions as compared to oxidizing conditions in both soils. The proportion of DAC in relation to DOC in solution (aromaticity) was high in the Nile Delta soil (NDS) and low in the Mississippi Delta soil (MDS) under oxidizing conditions. Mobilization of Cu was low under reducing conditions in both soils which was likely caused by sulfide precipitation and as a result of reduction of Cu 2+ to Cu 1+ . Mobilization of Se was high under low E H in both soils. Release of Se was positively correlated with DOC, Fe, Mn, and SO 4 2- in the NDS, and with Fe in the MDS. Mobilization of Zn showed negative correlations with E H and pH in the NDS while these correlations were non-significant in the MDS. The release dynamics of dissolved Zn could be governed mainly by the chemistry of Fe and Mn in the NDS and by the chemistry of Mn in the MDS. Our findings suggest that a release of Se and Zn occurs under anaerobic conditions, while aerobic conditions favor the release of Cu in both soils. In conclusion, the release of Cu, Se, and Zn under different reducing and oxidizing conditions in deltaic wetland soils should be taken into account due to increased mobilization and the potential environmental risks associated with food security in utilizing these soils for flooded agricultural and fisheries systems. Copyright © 2016 Elsevier Ltd. All rights reserved.

Optically active red-emitting Cu nanoclusters originating from complexation and redox reaction between copper(ii) and d/l-penicillamine

NASA Astrophysics Data System (ADS)

Long, Tengfei; Guo, Yanjia; Lin, Min; Yuan, Mengke; Liu, Zhongde; Huang, Chengzhi

2016-05-01

Despite a significant surge in the number of investigations into both optically active Au and Ag nanostructures, there is currently only limited knowledge about optically active Cu nanoclusters (CuNCs) and their potential applications. Here, we have succeeded in preparing a pair of optically active red-emitting CuNCs on the basis of complexation and redox reaction between copper(ii) and penicillamine (Pen) enantiomers, in which Pen serves as both a reducing agent and a stabilizing ligand. Significantly, the CuNCs feature unique aggregation induced emission (AIE) characteristics and therefore can serve as pH stimuli-responsive functional materials. Impressively, the ligand chirality plays a dramatic role for the creation of brightly emissive CuNCs, attributed to the conformation of racemic Pen being unfavorable for the electrostatic interaction, and thus suppressing the formation of cluster aggregates. In addition, the clusters display potential toward cytoplasmic staining and labelling due to the high photoluminescence (PL) quantum yields (QYs) and remarkable cellular uptake, in spite that no chirality-dependent effects in autophagy and subcellular localization are observed in the application of chiral cluster enantiomer-based cell imaging.Despite a significant surge in the number of investigations into both optically active Au and Ag nanostructures, there is currently only limited knowledge about optically active Cu nanoclusters (CuNCs) and their potential applications. Here, we have succeeded in preparing a pair of optically active red-emitting CuNCs on the basis of complexation and redox reaction between copper(ii) and penicillamine (Pen) enantiomers, in which Pen serves as both a reducing agent and a stabilizing ligand. Significantly, the CuNCs feature unique aggregation induced emission (AIE) characteristics and therefore can serve as pH stimuli-responsive functional materials. Impressively, the ligand chirality plays a dramatic role for the creation of brightly emissive CuNCs, attributed to the conformation of racemic Pen being unfavorable for the electrostatic interaction, and thus suppressing the formation of cluster aggregates. In addition, the clusters display potential toward cytoplasmic staining and labelling due to the high photoluminescence (PL) quantum yields (QYs) and remarkable cellular uptake, in spite that no chirality-dependent effects in autophagy and subcellular localization are observed in the application of chiral cluster enantiomer-based cell imaging. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01492e

On the potential of redox potential measurements for the characterization of greenhouse gas emissions - preliminary results

NASA Astrophysics Data System (ADS)

Wang, Jihuan; Bogena, Heye; Brüggemann, Nicolas

2017-04-01

Soil greenhouse gas (GHG) emissions contribute to global warming. In order to support mitigation measures against global warming it is important to understand the controlling processes of GHG emissions. Previous studies focused mainly on the paddy rice fields or wetlands showed a strong relationship between soil redox potential and GHG emission (e.g. N2O). Recent sensor developments open the possibility for the long-term monitoring of field scale soil redox potential changes. Here, we performed laboratory lysimeter experiments to investigate how changes in the redox potential, induced by changes in the water level, affect GHG emissions from agricultural soil. Under our experimental conditions, we found that N2O emissions followed closely the changes in redox potential. The dynamics of redox potential were induced by changing the water-table depth in a laboratory lysimeter. During saturated conditions we found a clear negative correlation between redox potentials and N2O emission rates N2O. After switching from saturated to unsaturated conditions, N2O emission quickly decreased. In contrast, the emissions of CO2 increased with increasing soil redox potentials. The level of N2O emission also depended on the fertilization level of the soil. We propose that redox potential measurements are a viable method for better understanding of the controlling factors of GHG emission and the development agricultural management practices to reduce such emissions.

Roles of charged residues in pH-dependent redox properties of cytochrome c3 from Desulfovibrio vulgaris Miyazaki F

PubMed Central

Yahata, Naoki; Ozawa, Kiyoshi; Tomimoto, Yusuke; Morita, Kumiko; Komori, Hirofumi; Ogata, Hideaki; Higuchi, Yoshiki; Akutsu, Hideo

2006-01-01

Complicated pH-properties of the tetraheme cytochrome c3 (cyt c3) from Desulfovibrio vulgaris Miyazaki F (DvMF) were examined by the pH titrations of 1H-15N HSQC spectra in the ferric and ferrous states. The redox-linked pKa shift for the propionate group at C13 of heme 1 was observed as the changes of the NH signals around it. This pKa shift is consistent with the redox-linked conformational alteration responsible for the cooperative reduction between hemes 1 and 2. On the other hand, large chemical shift changes caused by the protonation/deprotonation of Glu41 and/or Asp42, and His67 were redox-independent. Nevertheless, these charged residues affect the redox properties of the four hemes. Furthermore, one of interesting charged residues, Glu41, was studied by site-directed mutagenesis. E41K mutation increased the microscopic redox potentials of heme 1 by 46 and 34 mV, and heme 2 by 35 and 30 mV at the first and last reduction steps, respectively. Although global folding in the crystal structure of E41K cyt c3 is similar to that of wild type, local change was observed in 1H NMR spectrum. Glu41 is important to keep the stable conformation in the region between hemes 1 and 2, controlling the redox properties of DvMF cyt c3. In contrast, the kinetic parameters for electron transfer from DvMF [NiFe] hydrogenase were not influenced by E41K mutation. This suggests that the region between hemes 1 and 2 is not involved in the interaction with [NiFe] hydrogenase, and it supports the idea that heme 4 is the exclusive entrance gate to accept the electron in the initial reduction stage. PMID:27857559

Roles of charged residues in pH-dependent redox properties of cytochrome c3 from Desulfovibrio vulgaris Miyazaki F.

PubMed

Yahata, Naoki; Ozawa, Kiyoshi; Tomimoto, Yusuke; Morita, Kumiko; Komori, Hirofumi; Ogata, Hideaki; Higuchi, Yoshiki; Akutsu, Hideo

2006-01-01

Complicated pH-properties of the tetraheme cytochrome c 3 (cyt c 3 ) from Desulfovibrio vulgaris Miyazaki F ( Dv MF) were examined by the pH titrations of 1 H- 15 N HSQC spectra in the ferric and ferrous states. The redox-linked p K a shift for the propionate group at C13 of heme 1 was observed as the changes of the NH signals around it. This p K a shift is consistent with the redox-linked conformational alteration responsible for the cooperative reduction between hemes 1 and 2. On the other hand, large chemical shift changes caused by the protonation/deprotonation of Glu41 and/or Asp42, and His67 were redox-independent. Nevertheless, these charged residues affect the redox properties of the four hemes. Furthermore, one of interesting charged residues, Glu41, was studied by site-directed mutagenesis. E41K mutation increased the microscopic redox potentials of heme 1 by 46 and 34 mV, and heme 2 by 35 and 30 mV at the first and last reduction steps, respectively. Although global folding in the crystal structure of E41K cyt c 3 is similar to that of wild type, local change was observed in 1 H NMR spectrum. Glu41 is important to keep the stable conformation in the region between hemes 1 and 2, controlling the redox properties of Dv MF cyt c 3 . In contrast, the kinetic parameters for electron transfer from Dv MF [NiFe] hydrogenase were not influenced by E41K mutation. This suggests that the region between hemes 1 and 2 is not involved in the interaction with [NiFe] hydrogenase, and it supports the idea that heme 4 is the exclusive entrance gate to accept the electron in the initial reduction stage.

Iron Hydroxide Minerals Drive Organic and Phosphorus Chemistry in Subsurface Redox / pH Gradients

NASA Astrophysics Data System (ADS)

Flores, E.; Barge, L. M.; VanderVelde, D.; Baum, M.

2017-12-01

Iron minerals, particularly iron oxides and oxyhydroxides, are prevalent on Mars and may exist in mixed valence or even reduced states beneath the oxidized surface. Iron (II,III) hydroxides, including green rust, are reactive and potentially catalytic minerals that can absorb and concentrate charged species, while also driving chemical reactions. These minerals are highly redox-sensitive and the presence of organics and/or phosphorus species could affect their mineralogy and/or stability. Conversely, the minerals might be able to drive chemical processes such as amino acid formation, phosphorus oxyanion reactions, or could simply selectively preserve organic species via surface adsorption. In an open aqueous sediment column, soluble products of mineral-driven reactions could also diffuse to sites of different chemical conditions to react even further. We synthesized Fe-hydroxide minerals under various conditions relevant to early Earth and ancient Mars (>3.0 Gyr), anoxically and in the presence of salts likely to have been present in surface or ground waters. Using these minerals we conducted experiments to test whether iron hydroxides could promote amino acid formation, and how the reaction is affected by subsurface gradients of redox, pH, and temperature. We also tested the adsorption of organic and phosphorus species onto Fe-hydroxide minerals at different conditions within the gradients. The suite of organic or phosphorus signatures that may be found in a particular mineral system is a combination of what is synthesized there, what is preferentially concentrated / retained there, and what is preserved against degradation. Further work is needed to determine how these processes could have proceeded on Mars and what mineral-organic signatures, abiotic or otherwise, would be produced from such processes.

Rational design of Pleurotus eryngii versatile ligninolytic peroxidase for enhanced pH and thermal stability through structure-based protein engineering.

PubMed

Gao, Yu; Li, Jian-Jun; Zheng, Lanyan; Du, Yuguang

2017-11-01

Versatile peroxidase (VP) from Pleurotus eryngii is a high redox potential peroxidase. It has aroused great biotechnological interest due to its ability to oxidize a wide range of substrates, but its application is still limited due to low pH and thermal stability. Since CiP (Coprinopsis cinerea peroxidase) and PNP (peanut peroxidase) exhibited higher pH and thermal stability than VP, several motifs, which might contribute to their pH and thermal stability, were identified through structure and sequence alignment. Six VP variants incorporating the beneficial motifs were designed and constructed. Most variants were nearly completely inactivated except V1 (Variant 1) and V4. V1 showed comparable activity to WT VP against ABTS, while V4 exhibited reduced activity. V1 displayed improved pH stability than WT VP, at pH 3.0 in particular, whereas the pH stability of V4 did not change a lot. The thermal stabilities of V1 and V4 were enhanced with T50 raised by 3°C. The results demonstrated that variants containing the beneficial motifs of CiP and PNP conferred VP with improved pH and thermal stability. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Quantitative structure toxicity relationships for phenols in isolated rat hepatocytes.

PubMed

Moridani, Majid Y; Siraki, Arno; O'Brien, Peter J

2003-05-06

Quantitative structure toxicity relationship (QSTR) equations were obtained to predict and describe the cytotoxicity of 31 phenols using logLD(50) as a concentration to induce 50% cytotoxicity of isolated rat hepatocytes in 2 h and logP as octanol/water partitioning: logLD(50) (microM)=-0.588(+/-0.059)logP+4.652(+/-0.153) (n=27, r(2)=0.801, s=0.261, P<1 x 10(-9)). Hydroquinone, catechol, 4-nitrophenol, and 2,4-dinitrophenol were outliers for this equation. When the ionization constant pK(a) was considered as a contributing factor a two-parameter QSTR equation was derived: logLD(50) (microM)=-0.595(+/-0.051)logP+0.197(+/-0.029)pK(a)+2.665(+/-0.281) (n=28, r(2)=0.859, s=0.218, P<1 x 10(-6)). Using sigma+, the Brown variation of the Hammet electronic constant, as a contributing parameter, the cytotoxicity of phenols towards hepatocytes were defined by logLD(50) (microM)=-0.594(+/-0.052)logP-0.552(+/-0.085)sigma+ +4.540(+/-0.132) (n=28, r(2)=0.853, s=0.223, P<1 x 10(-6)). Replacing sigma+ with the homolytic bond dissociation energy (BDE) for (X-PhOH+PhO.-->X-PhO.+PhOH) led to logLD(50) (microM)=-0.601(+/-0.066)logP-0.040(+/-0.018)BDE+4.611(+/-0.166) (n=23, r(2)=0.827, s=0.223, P<0.05). Hydroquinone, catechol and 2-nitrophenol were outliers for the above equations. Using redox potential and logP led to a new correlation: logLD(50) (microM)=-0.529(+/-0.135)logP+2.077(+/-0.892)E(p/2)+2.806(+/-0.592) (n=15, r(2)=0.561, s=0.383, P<0.05) with 4-nitrophenol as an outlier. Our findings indicate that phenols with higher lipophilicity, BDE, or sigma+ values or with lower pK(a) and redox potential were more toxic towards hepatocytes. We also showed that a collapse of hepatocyte mitochondrial membrane potential preceded the cytotoxicity of most phenols. Our study indicates that one or a combination of mechanisms; i.e. mitochondrial uncoupling, phenoxy radicals, or phenol metabolism to quinone methides and quinones, contribute to phenol cytotoxicity towards hepatocytes depending on the phenol chemical structure.

Electrochemical behavior and pH stability of artificial salivas for corrosion tests.

PubMed

Queiroz, Gláucia Maria Oliveira de; Silva, Leandro Freitas; Ferreira, José Tarcísio Lima; Gomes, José Antônio da Cunha P; Sathler, Lúcio

2007-01-01

It is assumed that the compositions of artificial salivas are similar to that of human saliva. However, the use of solutions with different compositions in in vitro corrosion studies can lead dissimilar electrolytes to exhibit dissimilar corrosivity and electrochemical stability. This study evaluated four artificial salivas as regards pH stability with time, redox potentials and the polarization response of an inert platinum electrode. The tested solutions were: SAGF medium, Mondelli artificial saliva, UFRJ artificial saliva (prepared at the School of Pharmacy, Federal University of Rio de Janeiro, RJ, Brazil) and USP-RP artificial saliva (prepared at the School of Pharmaceutical Sciences of Ribeirão Preto, University of São Paulo, SP, Brazil). It was observed that pH variations were less than 1 unit during a 50-hour test. The SAGF medium, and the UFRJ and USP-RP solutions exhibited more oxidizing characteristics, whereas the Mondelli solution presented reducing properties. Anodic polarization revealed oxidation of the evaluated electrolytes at potentials below +600 mV SCE. It was observed that the UFRJ and USP-RP solutions presented more intense oxidation and reduction processes as compared to the Mondelli and SAGF solutions.

Pourbaix Diagrams at Elevated Temperatures A Study of Zinc and Tin

NASA Astrophysics Data System (ADS)

Palazhchenko, Olga

Metals in industrial settings such as power plants are often subjected to high temperature and pressure aqueous environments, where failure to control corrosion compromises worker and environment safety. For instance, zircaloy (1.2-1.7 wt.% Sn) fuel rods are exposed to aqueous 250-310 °C coolant in CANDU reactors. The Pourbaix (EH-pH) diagram is a plot of electrochemical potential versus pH, which shows the domains of various metal species and by inference, corrosion susceptibility. Elevated temperature data for tin +II and tin +IV species were obtained using solid-aqueous phase equilibria with the respective oxides, in a batch vessel with in-situ pH measurement. Solubilities, determined via spectroscopic techniques, were used to calculate equilibrium constants and the Gibbs energies of Sn complexes for E-pH diagram construction. The SnOH3+ and Sn(OH )-5 species were incorporated, for the first time, into the 298.15 K and 358.15 K diagrams, with novel Go values determined at 358.15 K. Key words: Pourbaix diagrams, EH-pH, elevated temperatures, solubility, equilibrium, metal oxides, hydrolysis, redox potential, pH, thermochemical data, tin, zinc, zircaloy, corrosion, passivity.

Multicomponent polymeric nanoparticles enhancing intracellular drug release in cancer cells.

PubMed

Ahmed, Arsalan; Liu, Sen; Pan, Yutong; Yuan, Shanmei; He, Jian; Hu, Yong

2014-12-10

Three kinds of amphiphilic copolymer, that is, poly(ε-caprolactone)-SS-poly(ethylene glycol) (PCL-SS-PEG), poly(ε-caprolactone)-polyethylenimine (PCL-PEI), and poly(ε-caprolactone)-polyethylenimine-folate (PCL-PEI-Fol) were synthesized and self-assembled into surface engineered hybrid nanoparticles (NPs). Morphological studies elucidated the stable, spherical, and uniform sandwich structure of the NPs. PCL-PEI and PCL-SS-PEG segments have introduced pH and reduction responsive characteristics in these NPs, while PCL-PEI-FA copolymers could provide specific targeting capability to cancer cells. The stimuli responsive capabilities of these NPs were carried out. Negative-to-positive charge reversible property, in response to the pH change, was investigated by zeta potential and nuclear magnetic resonance (NMR) measurements. The structure cleavage, due to redox gradient, was studied by dynamic light scattering (DLS) and transmission electron microscopy (TEM). These NPs showed controlled degradation, better drug release, less toxicity, and effective uptake in MCF-7 breast cancer cells. These multifunctional NPs showed promising potential in the treatment of cancer.

Mitochondrial pharmacology: electron transport chain bypass as strategies to treat mitochondrial dysfunction.

PubMed

Atamna, Hani; Mackey, Jeanette; Dhahbi, Joseph M

2012-01-01

Mitochondrial dysfunction (primary or secondary) is detrimental to intermediary metabolism. Therapeutic strategies to treat/prevent mitochondrial dysfunction could be valuable for managing metabolic and age-related disorders. Here, we review strategies proposed to treat mitochondrial impairment. We then concentrate on redox-active agents, with mild-redox potential, who shuttle electrons among specific cytosolic or mitochondrial redox-centers. We propose that specific redox agents with mild redox potential (-0.1 V; 0.1 V) improve mitochondrial function because they can readily donate or accept electrons in biological systems, thus they enhance metabolic activity and prevent reactive oxygen species (ROS) production. These agents are likely to lack toxic effects because they lack the risk of inhibiting electron transfer in redox centers. This is different from redox agents with strong negative (-0.4 V; -0.2 V) or positive (0.2 V; 0.4 V) redox potentials who alter the redox status of redox-centers (i.e., become permanently reduced or oxidized). This view has been demonstrated by testing the effect of several redox active agents on cellular senescence. Methylene blue (MB, redox potential ≅10 mV) appears to readily cycle between the oxidized and reduced forms using specific mitochondrial and cytosolic redox centers. MB is most effective in delaying cell senescence and enhancing mitochondrial function in vivo and in vitro. Mild-redox agents can alter the biochemical activity of specific mitochondrial components, which then in response alters the expression of nuclear and mitochondrial genes. We present the concept of mitochondrial electron-carrier bypass as a potential result of mild-redox agents, a method to prevent ROS production, improve mitochondrial function, and delay cellular aging. Thus, mild-redox agents may prevent/delay mitochondria-driven disorders. Copyright © 2012 International Union of Biochemistry and Molecular Biology, Inc.

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

Dechlorination of chloropicrin and 1,3-dichloropropene by hydrogen sulfide species: redox and nucleophilic substitution reactions.

PubMed

Zheng, Wei; Yates, Scott R; Papiernik, Sharon K; Guo, Mingxin; Gan, Jianying

2006-03-22

The chlorinated fumigants chloropicrin (trichloronitromethane) and 1,3-dichloropropene (1,3-D) are extensively used in agricultural production for the control of soilborne pests. The reaction of these two fumigants with hydrogen sulfide species (H2S and HS-) was examined in well-defined anoxic aqueous solutions. Chloropicrin underwent an extremely rapid redox reaction in the hydrogen sulfide solution. Transformation products indicated reductive dechlorination of chloropicrin by hydrogen sulfide species to produce dichloro- and chloronitromethane. The transformation of chloropicrin in hydrogen sulfide solution significantly increased with increasing pH, indicating that H2S is less reactive toward chloropicrin than HS- is. For both 1,3-D isomers, kinetics and transformation products analysis revealed that the reaction between 1,3-D and hydrogen sulfide species is an S(N)2 nucleophilic substitution process, in which the chlorine at C3 of 1,3-D is substituted by the sulfur nucleophile to form corresponding mercaptans. The 50% disappearance time (DT50) of 1,3-D decreased with increasing hydrogen sulfide species concentration at a constant pH. Transformation of 1,3-D was more rapid at high pH, suggesting that the reactivity of hydrogen sulfide species in the experimental system stems primarily from HS-. Because of the relatively low smell threshold values and potential environmental persistence of organic sulfur products yielded by the reaction of 1,3-D and HS-, the effects of reduced sulfide species should be considered in the development of alternative fumigation practices, especially in the integrated application of sulfur-containing fertilizers.

Organelle Redox of CF and CFTR-Corrected Airway Epithelia

PubMed Central

Schwarzer, Christian; Illek, Beate; Suh, Jung H.; Remington, S. James; Fischer, Horst; Machen, Terry E.

2014-01-01

In cystic fibrosis reduced CFTR function may alter redox properties of airway epithelial cells. Redox-sensitive GFP (roGFP1) and imaging microscopy were used to measure redox potentials of cytosol, ER, mitochondria and cell surface of cystic fibrosis nasal epithelial cells and CFTR-corrected cells. We also measured glutathione and cysteine thiol redox states in cell lysates and apical fluids to provide coverage over a range of redox potentials and environments that might be affected by CFTR. As measured with roGFP1, redox potentials at the cell surface (~ -207 ±8 mV) and in the ER (~ -217 ±1 mV) and rates of regulation of the apical fluid and ER lumen following DTT treatment were similar for CF and CFTR-corrected cells. CF and CFTR-corrected cells had similar redox potentials in mitochondria (-344 ±9 mV) and cytosol (-322 ±7 mV). Oxidation of carboxy-dichlorodihydrofluoresceindiacetate and of apical Amplex Red occurred at equal rates in CF and CFTR-corrected cells. Glutathione and cysteine redox couples in cell lysates and apical fluid were equal in CF and CFTR-corrected cells. These quantitative estimates of organelle redox potentials combined with apical and cell measurements using small molecule couples confirmed there were no differences in redox properties of CF and CFTR-corrected cells. PMID:17603939

Electron transfer catalysis with monolayer protected Au25 clusters

NASA Astrophysics Data System (ADS)

Antonello, Sabrina; Hesari, Mahdi; Polo, Federico; Maran, Flavio

2012-08-01

Au25L18 (L = S(CH2)2Ph) clusters were prepared and characterized. The resulting monodisperse clusters were reacted with bis(pentafluorobenzoyl) peroxide in dichloromethane to form Au25L18+ quantitatively. The kinetics and thermodynamics of the corresponding electron transfer (ET) reactions were characterized via electrochemistry and thermochemical calculations. Au25L18+ was used in homogeneous redox catalysis experiments with a series of sym-substituted benzoyl peroxides, including the above peroxide, bis(para-cyanobenzoyl) peroxide, dibenzoyl peroxide, and bis(para-methoxybenzoyl) peroxide. Peroxide dissociative ET was catalyzed using both the Au25L18/Au25L18- and the Au25L18+/Au25L18 redox couples as redox mediators. Simulation of the CV curves led to determination of the ET rate constant (kET) values for concerted dissociative ET to the peroxides. The ET free energy ΔG° could be estimated for all donor-acceptor combinations, leading to observation of a nice activation-driving force (log kETvs. ΔG°) relationship. Comparison with the kET obtained using a ferrocene-type donor with a formal potential similar to that of Au25L18/Au25L18- showed that the presence of the capping monolayer affects the ET rate rather significantly, which is attributed to the intrinsic nonadiabaticity of peroxide acceptors.Au25L18 (L = S(CH2)2Ph) clusters were prepared and characterized. The resulting monodisperse clusters were reacted with bis(pentafluorobenzoyl) peroxide in dichloromethane to form Au25L18+ quantitatively. The kinetics and thermodynamics of the corresponding electron transfer (ET) reactions were characterized via electrochemistry and thermochemical calculations. Au25L18+ was used in homogeneous redox catalysis experiments with a series of sym-substituted benzoyl peroxides, including the above peroxide, bis(para-cyanobenzoyl) peroxide, dibenzoyl peroxide, and bis(para-methoxybenzoyl) peroxide. Peroxide dissociative ET was catalyzed using both the Au25L18/Au25L18- and the Au25L18+/Au25L18 redox couples as redox mediators. Simulation of the CV curves led to determination of the ET rate constant (kET) values for concerted dissociative ET to the peroxides. The ET free energy ΔG° could be estimated for all donor-acceptor combinations, leading to observation of a nice activation-driving force (log kETvs. ΔG°) relationship. Comparison with the kET obtained using a ferrocene-type donor with a formal potential similar to that of Au25L18/Au25L18- showed that the presence of the capping monolayer affects the ET rate rather significantly, which is attributed to the intrinsic nonadiabaticity of peroxide acceptors. This article was submitted as part of a Themed Issue on metallic clusters. Other papers on this topic can be found in issue 14 of vol. 4 (2012). This issue can be found from the Nanoscale homepage [http://www.rsc.org/nanoscale].

A catalytic approach to estimate the redox potential of heme-peroxidases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ayala, Marcela; Roman, Rosa; Vazquez-Duhalt, Rafael

2007-06-08

The redox potential of heme-peroxidases varies according to a combination of structural components within the active site and its vicinities. For each peroxidase, this redox potential imposes a thermodynamic threshold to the range of oxidizable substrates. However, the instability of enzymatic intermediates during the catalytic cycle precludes the use of direct voltammetry to measure the redox potential of most peroxidases. Here we describe a novel approach to estimate the redox potential of peroxidases, which directly depends on the catalytic performance of the activated enzyme. Selected p-substituted phenols are used as substrates for the estimations. The results obtained with this catalyticmore » approach correlate well with the oxidative capacity predicted by the redox potential of the Fe(III)/Fe(II) couple.« less

Macroscopic experimental and modeling evaluation of selenite and selenate adsorption mechanisms on gibbsite

USDA-ARS?s Scientific Manuscript database

Selenite Se(IV) and selenate Se(VI) adsorption behavior was investigated on gibbsite as a function of solution pH and solution ionic strength. Adsorption of both Se redox states decreased with increasing solution pH. Electrophoretic mobility measurements showed downward shifts in point of zero cha...

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

PubMed

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

2017-08-01

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

Probing Aspergillus niger glucose oxidase with pentacyanoferrate(III) aza- and thia-complexes.

PubMed

Kulys, J; Tetianec, L; Ziemys, A

2006-10-01

Complexes of pentacyanoferrate(III) and biologically relevant ligands, such as pyridine, pyrazole, imidazole, histidine, and other aza- and thia-heterocycles, were synthesized. Their spectral, electrochemical properties, electron exchange constants, electronic structure parameters, and reactivity with glucose oxidase from Aspergillus niger were determined. The formation of the complexes following ammonia replacement by the ligands was associated with the appearance of a new band of absorbance in the visible spectrum. The constants of the complexes formation calculated at a ligand-pentacyanoferrate(III) concentrations ratio of 10:1, were 7.5 x 10(-5), 7.7 x 10(-5), and 1.8 x 10(-3) s(-1) for benzotriazole, benzimidazole, and aminothiazole ligands, respectively. The complexes showed quasi-reversible redox conversion at a glassy carbon electrode. The redox potential of the complexes spanned the potential range from 70 to 240 mV vs. saturated calomel electrode (SCE) at pH7.2. For most of the complexes self-exchange constants (k(11)) were similar to or larger than that of hexacyanoferrate(III) (ferricyanide). The complexes containing pyridine derivatives and thia-heterocyclic ligands held a lower value of k(11) than that of ferricyanide. All complexes reacted with reduced glucose oxidase at pH7.2. The reactivity of the complex containing pyrazole was the largest in comparison to the rest of the complexes. Correlations between the complexes' reactivity and both the free energy of reaction and k(11) shows that the reactivity of pentacyanoferrates obeys the principles of Marcus's electron transfer theory. The obtained data suggest that large negative charges of the complexes decrease their reactivity.

Instrumental methods of analysis of sulfur compounds in synfuel process streams. Quarterly technical progress report, July-September 1984

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jordan, J.; Talbott, J.

1984-01-01

Task 1. Methods development for the speciation of the polysulfides. Work on this task has been completed in December 1983 and reported accordingly in DOE/PC/40783-T13. Task 2. Methods development for the speciation of dithionite and polythionates. Work on Task 2 has been completed in June 1984 and has been reported accordingly in DOE/PC/40783-T15. Task 3. Total accounting of the sulfur balance in representative samples of synfuel process streams. A systematic and critical comparison of results, obtained in the analysis of sulfur moieties in representative samples of coal conversion process streams, revealed the following general trends. (a) In specimens of highmore » pH (9-10) and low redox potential (-0.3 to -0.4 volt versus NHE) sulfidic and polysulfidic sulfur moieties predominate. (b) In process streams of lower pH and more positive redox potential, higher oxidation states of sulfur (notably sulfate) account for most of the total sulfur present. (c) Oxidative wastewater treatment procedures by the PETC stripping process convert lower oxidation states of sulfur into thiosulfate and sulfate. In this context, remarkable similarities were observed between liquefaction and gasification process streams. However, the thiocyanate present in samples from the Grand Forks gasifier were impervious to the PETC stripping process. (d) Total sulfur contaminant levels in coal conversion process stream wastewater samples are primarily determined by the abundance of sulfur in the coal used as starting material than by the nature of the conversion process (liquefaction or gasification). 13 references.« less

Suspended particle destabilization in retained urban stormwater as a function of coagulant dosage and redox conditions.

PubMed

Sansalone, John J; Kim, Jong-Yeop

2008-02-01

Source area runoff entrains a hetero-disperse particle size distribution (PSD). When retained for clarification, larger sediment and settleable particles are mainly influenced by gravitational forces, while the suspended particles, in particular the clay-size particles, are subject to coagulation phenomena. Such phenomena occur in untreated runoff as well as runoff treated with a coagulant, albeit to differing rates and extents. Runoff PSDs and water chemistry indices including zeta potential (xi) are potentially modified during inter-event stormwater retention in best management practices (BMPs). This study examined xi of clay-size particles (<2 microm) in retained runoff, captured from an instrumented watershed, subject to batch coagulation and variable redox conditions. Separate parallel tests were also conducted with wastewater. Significant turbidity, particle mass (measured as total suspended solids (TSS)) and volume concentration (as total volume concentration (TVC)) reduction generated by alum and ferric chloride consistently occurred at a xi in the range of -15 to about -10 mV. Alum addition produced a charge reversal at dosing above 60 mg/L (18 x 10(-5)M) while ferric chloride did not reverse charge. With respect to turbidity and TSS reductions, alum outperformed ferric chloride, without the need for pH control. While xi illustrated no clear trend during aerobic retention, anoxic retention resulted in a trend for xi approaching the isoelectric point. The decrease in negative xi towards the isoelectric point appears to be a result of the coupled pH depression under reductive conditions and an increase in conductivity. Results have significant implications for BMPs that retain runoff between events.

Redox Abnormalities as a Vulnerability Phenotype for Autism and Related Alterations in CNS Development

DTIC Science & Technology

2011-10-01

the hypothesis that SJL mice would have impaired neuronal dendrite generation, as has been observed in autism . This was our prediction due to the...phenotype for Autism and related alterations in CNS development PRINCIPAL INVESTIGATOR: Mark D. Noble, Ph.D. CONTRACTING...SUBTITLE Redox abnormalities as a vulnerability phenotype for Autism 5a. CONTRACT NUMBER And related alterations in CNS development 5b. GRANT

Interaction with the Redox Cofactor MYW and Functional Role of a Mobile Arginine in Eukaryotic Catalase-Peroxidase

PubMed Central

2016-01-01

Catalase-peroxidases (KatGs) are unique bifunctional heme peroxidases with an additional posttranslationally formed redox-active Met-Tyr-Trp cofactor that is essential for catalase activity. On the basis of studies of bacterial KatGs, controversial mechanisms of hydrogen peroxide oxidation were proposed. The recent discovery of eukaryotic KatGs with differing pH optima of catalase activity now allows us to scrutinize those postulated reaction mechanisms. In our study, secreted KatG from the fungus Magnaporthe grisea (MagKatG2) was used to analyze the role of a remote KatG-typical mobile arginine that was shown to interact with the Met-Tyr-Trp adduct in a pH-dependent manner in bacterial KatGs. Here we present crystal structures of MagKatG2 at pH 3.0, 5.5, and 7.0 and investigate the mobility of Arg461 by molecular dynamics simulation. Data suggest that at pH ≥4.5 Arg461 mostly interacts with the deprotonated adduct Tyr. Elimination of Arg461 by mutation to Ala slightly increases the thermal stability but does not alter the active site architecture or the kinetics of cyanide binding. However, the variant Arg461Ala lost the wild-type-typical optimum of catalase activity at pH 5.25 (kcat = 6450 s–1) but exhibits a broad plateau between pH 4.5 and 7.5 (kcat = 270 s–1 at pH 5.5). Moreover, significant differences in the kinetics of interconversion of redox intermediates of wild-type and mutant protein mixed with either peroxyacetic acid or hydrogen peroxide are observed. These findings together with published data from bacterial KatGs allow us to propose a role of Arg461 in the H2O2 oxidation reaction of KatG. PMID:27293030

Reduced flavin: NMR investigation of N5-H exchange mechanism, estimation of ionisation constants and assessment of properties as biological catalyst.

PubMed

Macheroux, Peter; Ghisla, Sandro; Sanner, Christoph; Rüterjans, Heinz; Müller, Franz

2005-11-25

The flavin in its FMN and FAD forms is a versatile cofactor that is involved in catalysis of most disparate types of biological reactions. These include redox reactions such as dehydrogenations, activation of dioxygen, electron transfer, bioluminescence, blue light reception, photobiochemistry (as in photolyases), redox signaling etc. Recently, hitherto unrecognized types of biological reactions have been uncovered that do not involve redox shuffles, and might involve the reduced form of the flavin as a catalyst. The present work addresses properties of reduced flavin relevant in this context. N(5)-H exchange reactions of the flavin reduced form and its pH dependence were studied using the 15N-NMR-signals of 15N-enriched, reduced flavin in the pH range from 5 to 12. The chemical shifts of the N(3) and N(5) resonances are not affected to a relevant extent in this pH range. This contrasts with the multiplicity of the N(5)-resonance, which strongly depends on pH. It is a doublet between pH 8.45 and 10.25 that coalesces into a singlet at lower and higher pH values. From the line width of the 15N(5) signal the pH-dependent rate of hydrogen exchange was deduced. The multiplicity of the 15N(5) signal and the proton exchange rates are little dependent on the buffer system used. The exchange rates allow an estimation of the pKa value of N(5)-H deprotonation in reduced flavin to be >or= 20. This value imposes specific constraints for mechanisms of flavoprotein catalysis based on this process. On the other hand the pK asymptotically equal to 4 for N(5)-H protonation (to form N(5)+-H2) would be consistent with a role of N(5)-H as a base.

Do microbial exudates control EH electrode measurements?

NASA Astrophysics Data System (ADS)

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

2017-12-01

Redox electrodes are widely used as simple, inexpensive monitoring devices to rapidly measure redox potentials (EH) of waterlogged soils, sediments, and aquifers. While a variety of physicochemical and biogeochemical factors have been involved to explain measured EH values, the role of microorganisms remains comparatively understudied and uncertain. Besides catalyzing many inorganic redox reactions (e.g., nitrate reduction), microorganisms produce a variety of redox-active organic compounds (e.g., NAD+/NADH, GSSG/2GSH, FAD/FADH2), which can be released into the surrounding environment via active secretion, passive diffusion, or cell lysis. To isolate different microbial effects on EH measurements, we performed batch experiments using S. oneidensis MR-I as a model heterotrophic microorganism and flavins as example microbial exudates [1]. We monitored EH and pH along with flavin production (fluorescence measurements) during dissimilatory nitrate reduction to ammonium (DNRA). Dissolved flavins increased to 0.2 mM (riboflavin equivalent) under anoxic conditions during complete consumption of 1 mM nitrate by DNRA at pH 7.4 and 30 °C over 80 hours. The observed redox cascade from +255 to -250 mV did not follow the EH predicted for the reduction of NO3- to NO2- and NO2- to NH4+ by the Nernst equation. However, a set of separate abiotic experiments on the photoreduction of synthetic flavins (LMC, RF, FMN, and FAD, Sigma Aldrich) under the same conditions indicated that measured EH values are buffered at +270 ± 20 mV and -230 ± 50 mV when oxidized and reduced flavin species dominate, respectively. Moreover, based on the temporal changes in EH, we speculate that NO3- reduction by S. oneidensis consumes reduced flavins (i.e., NO3- accepts electrons from reduced flavins) and generates oxidized flavins, thus buffering EH at +255 mV. By contrast, NO2- reduction to NH4+ is independent of flavin speciation, which leads to the accumulation of reduced flavins in the solution and lowering of EH to -250 mV. Overall, the experiments demonstrate that microbial exudates do affect EH measurements, however, their importance in natural water-saturated systems has to be further evaluated. [1] Von Canstein, H., et al., 2008. Appl. Environ. Microbiol. 74, 615-623.

Thermodynamic stability of CoOOH and its coprecipitation with manganese

USGS Publications Warehouse

Hem, J.D.; Roberson, C.E.; Lind, Carol J.

1985-01-01

A precipitate of cobalt oxyhydroxides formed by bubbling oxygen through a dilute solution of Co(NO3)2 held at pH 9.0 and 25??C was aged for 23 months in contact with the original solution, with access to atmospheric oxygen. Co3O4 and CoOOH were identified in the precipitate by X-ray diffraction. Chemical equilibria involving these solids were evaluated by measurements of solution pH and Co2+ activities and by redox potential measurements and gave a ??GcoOOH0 of -92.3 ?? 0.5 kcal/mole. This value and other thermodynamic data show relative feasibility of hypothetical reaction steps and changes in reaction paths during automated coprecipitation titrations and subsequent aging of a precipitate that finally contained ??MnOOH, MnO2 (birnessite) and CoOOH. ?? 1985.

Two reaction pathways for transformation of high potential cytochrome b559 of PS II into the intermediate potential form.

PubMed

Kaminskaya, Olga; Shuvalov, Vladimir A; Renger, Gernot

2007-06-01

This study describes an analysis of different treatments that influence the relative content and the midpoint potential of HP Cyt b559 in PS II membrane fragments from higher plants. Two basically different types of irreversible modification effects are distinguished: the HP form of Cyt b559 is either predominantly affected when the heme group is oxidized ("O-type" effects) or when it is reduced ("R-type" effects). Transformation of HP Cyt b559 to lower potential redox forms (IP and LP forms) by the "O-type" mechanism is induced by high pH and detergent treatments. In this case the effects consist of a gradual decrease in the relative content of HP Cyt b559 while its midpoint potential remains unaffected. Transformation of HP Cyt b559 via an "R-type" mechanism is caused by a number of exogenous compounds denoted L: herbicides, ADRY reagents and tetraphenylboron. These compounds are postulated to bind to the PS II complex at a quinone binding site designated as Q(C) which interacts with Cyt b559 and is clearly not the Q(B) site. Binding of compounds L to the Q(C) site when HP Cyt b559 is oxidized gives rise to a gradual decrease in the E(m) of HP Cyt b559 with increasing concentration of L (up to 10 K(ox)(L) values) while the relative content of HP Cyt b559 is unaffected. Higher concentrations of compounds L required for their binding to Q(C) site when HP Cyt b559 is reduced (described by K(red)(L)) induce a conversion of HP Cyt b559 to lower potential redox forms ("R-type" transformation). Two reaction pathways for transitions of Cyt b559 between the different protein conformations that are responsible for the HP and IP/LP redox forms are proposed and new insights into the functional regulation of Cyt b559 via the Q(C) site are discussed.

Microbial communities acclimate to recurring changes in soil redox potential status

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeAngelis, Kristen M.; Silver, Whendee; Thompson, Andrew

Rapidly fluctuating environmental conditions can significantly stress organisms, particularly when fluctuations cross thresholds of normal physiological tolerance. Redox potential fluctuations are common in humid tropical soils, and microbial community acclimation or avoidance strategies for survival will in turn shape microbial community diversity and biogeochemistry. To assess the extent to which indigenous bacterial and archaeal communities are adapted to changing in redox potential, soils were incubated under static anoxic, static oxic or fluctuating redox potential conditions, and the standing (DNA-based) and active (RNA-based) communities and biogeochemistry were determined. Fluctuating redox potential conditions permitted simultaneous CO{sub 2} respiration, methanogenesis, N{sub 2}O productionmore » and iron reduction. Exposure to static anaerobic conditions significantly changed community composition, while 4-day redox potential fluctuations did not. Using RNA: DNA ratios as a measure of activity, 285 taxa were more active under fluctuating than static conditions, compared with three taxa that were more active under static compared with fluctuating conditions. These data suggest an indigenous microbialcommunity adapted to fluctuating redox potential.« less

Evaluation of possible physical-chemical processes that might lead to separations of actinides in ORNL waste tanks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Del Cul, G.D.; Toth, L.M.; Bond, W.D.

The concern that there might be some physical-chemical process which would lead to a separation of the poisoning actinides ({sup 232}Th, {sup 238}U) from the fissionable ones ({sup 239}Pu, {sup 235}U) in waste storage tanks at Oak Ridge National Laboratory has led to a paper study of potential separations processes involving these elements. At the relatively high pH values (>8), the actinides are normally present as precipitated hydroxides. Mechanisms that might then selectively dissolve and reprecipitate the actinides through thermal processes or additions of reagents were addressed. Although redox reactions, pH changes, and complexation reactions were all considered, only themore » last type was regarded as having any significant probability. Furthermore, only carbonate accumulation, through continual unmonitored air sparging of the tank contents, could credibly account for gross transport and separation of the actinide components. From the large amount of equilibrium data in the literature, concentration differences in Th, U, and Pu due to carbonate complexation as a function of pH have been presented to demonstrate this phenomenon. While the carbonate effect does represent a potential separations process, control of long-term air sparging and solution pH, accompanied by routine determinations of soluble carbonate concentration, should ensure that this separations process does not occur.« less

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

NASA Astrophysics Data System (ADS)

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

Experimental work was performed with the aim of evaluating the Ce 4+/Ce 3+ redox couple in sulfuric acid electrolyte for use in redox flow battery (RFB) technology. The solubility of cerium sulfates in 0.1-4.0 M sulfuric acid at 20-60 °C was studied. A synergistic effect of both sulfuric acid concentration and temperature on the solubility of cerous sulfate was observed. The solubility of cerous sulfate significantly decreased with rising concentration of sulfuric acid and rising temperature, while the solubility of ceric sulfate goes through a significant maximum at 40 °C. Redox potentials and the kinetics of the cerous/ceric redox reaction were also studied under the same temperature-concentration conditions. The redox potentials were measured using the combined redox electrode (Pt-Ag/AgCl) in equimolar Ce 4+/Ce 3+ solutions (i.e.[Ce 3+]=[Ce 4+]) in sulfuric acid electrolyte. The Ce 3+/Ce 4+ redox potentials significantly decrease (i.e. shift to more negative values) with rising sulfuric acid concentration; a small maximum is observed at 40 °C. Cyclic voltammetric experiments confirmed slow electrochemical kinetics of the Ce 3+/Ce 4+ redox reaction on carbon glassy electrodes (CGEs) in sulfuric acid solutions. The observed dependencies of solubilities, the redox potentials and the kinetics of Ce 3+/Ce 4+ redox reaction on sulfuric acid concentration are thought to be the result of inequivalent complexation of the two redox species by sulfate anions: the ceric ion is much more strongly bound to sulfate than is the cerous ion. The best temperature-concentration conditions for the RFB electrolytes appear to be 40 °C and 1 M sulfuric acid, where the relatively good solubility of both cerium species, the maximum of redox potentials, and the more or less satisfying stability of CGE s were found. Even so, the relatively low solubility of cerium salts in sulfuric acid media and slow redox kinetics of the Ce 3+/Ce 4+ redox reaction at carbon indicate that the Ce 3+/Ce 4+ may not be well suited for use in RFB technology.

Hydrochemistry indicating groundwater contamination and the potential fate of chlorohydrocarbons in combined polluted groundwater: a case study at a contamination site in North China.

PubMed

Huang, Shuang-Bing; Han, Zhan-Tao; Zhao, Long; Kong, Xiang-Ke

2015-05-01

Groundwater contamination characteristics and the potential fate of chlorohydrocarbons were investigated at a combined polluted groundwater site in North China. Groundwater chemistry and (2)D and (18)O isotope compositions indicated that high salination of groundwater was related with chemical pollution. The elevated salinity plume was consistent with the domain where typical chlorohydrocarbon contaminants occurred. The concentrations of heavy metals, oxidation-reduction potential, and pH in organic polluted areas significantly differed from those in peripheral (background) areas, indicating modified hydrochemistry possibly resulting from organic pollution. Under the presented redox conditions of groundwater, monochlorobenzene oxidation may have occurred when the trichlorohydrocarbons underwent reductive dechlorination. These findings suggested that inorganic hydrochemistry effectively indicated the occurrence of chemical contamination in groundwater and the potential fate of chlorohydrocarbons.

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

PubMed Central

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

2014-01-01

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

Comparative study of the oxidation behavior of sulfur-containing amino acids and glutathione by electrochemistry-mass spectrometry in the presence and absence of cisplatin.

PubMed

Zabel, Robert; Weber, Günther

2016-02-01

Small sulfur-containing compounds are involved in several important biochemical processes, including-but not limited to-redox regulation and drug conjugation/detoxification. While methods for stable redox pairs of such compounds (thiols/disulfides) are available, analytical data on more labile and short-lived redox intermediates are scarce, due to highly challenging analytical requirements. In this study, we employ the direct combination of reagentless electrochemical oxidation and mass spectrometric (EC-MS) identification for monitoring oxidation reactions of cysteine, N-acetylcysteine, methionine, and glutathione under simulated physiological conditions (pH 7.4, 37 °C). For the first time, all theoretically expected redox intermediates-with only one exception-are detected simultaneously and in situ, including sulfenic, sulfinic, and sulfonic acids, disulfides, thiosulfinates, thiosulfonates, and sulfoxides. By monitoring the time/potential-dependent interconversion of sulfur species, mechanistic oxidation routes are confirmed and new reactions detected, e.g., sulfenamide formation due to reaction with ammonia from the buffer. Furthermore, our results demonstrate a highly significant impact of cisplatin on the redox reactivity of sulfur species. Namely, the amount of thiol oxidation to sulfonic acid via sulfenic and sulfinic acid intermediates is diminished for glutathione in the presence of cisplatin in favor of the disulfide formation, while for N-acetylcysteine the contrary applies. N-acetylcysteine is the only ligand which displays enhanced oxidation currents upon cisplatin addition, accompanied by increased levels of thiosulfinate and thiosulfonate species. This is traced back to thiol reactivity and highlights the important role of sulfenic acid intermediates, which may function as a switch between different oxidation routes.

Phoenix's Wet Chemistry Lab

NASA Technical Reports Server (NTRS)

2008-01-01

This is an illustration of the analytical procedure of NASA's Phoenix Mars Lander's Wet Chemistry Lab (WCL) on board the Microscopy, Electrochemistry, and Conductivity Analyzer (MECA) instrument. By dissolving small amounts of soil in water, WCL can determine the pH, the abundance of minerals such as magnesium and sodium cations or chloride, bromide and sulfate anions, as well as the conductivity and redox potential.

The Phoenix Mission is led by the University of Arizona, Tucson, on behalf of NASA. Project management of the mission is by NASA's Jet Propulsion Laboratory, Pasadena, Calif. Spacecraft development is by Lockheed Martin Space Systems, Denver.

Phoenix's Wet Chemistry Lab

NASA Technical Reports Server (NTRS)

2008-01-01

This is an illustration of soil analysis on NASA's Phoenix Mars Lander's Wet Chemistry Lab (WCL) on board the Microscopy, Electrochemistry, and Conductivity Analyzer (MECA) instrument. By dissolving small amounts of soil in water, WCL will attempt to determine the pH, the abundance of minerals such as magnesium and sodium cations or chloride, bromide and sulfate anions, as well as the conductivity and redox potential.

The Phoenix Mission is led by the University of Arizona, Tucson, on behalf of NASA. Project management of the mission is by NASA's Jet Propulsion Laboratory, Pasadena, Calif. Spacecraft development is by Lockheed Martin Space Systems, Denver.

Synthesis and characterization of a material derived from 4-mercaptobenzoic acid: A novel platform for oligonucleotide immobilization.

PubMed

Alves, Rafael da Fonseca; da Silva, Amanda Gonçalves; Ferreira, Lucas Franco; Franco, Diego Leoni

2017-04-01

This paper reports the electrochemical modification of pencil carbon graphite electrodes with a polymeric material derived from 4-mercaptobenzoic acid. Acidic solutions (pH 0 and 5.02) yielded an insulating polymeric film with anionic permselective properties. Scanning Electron Microscopy (SEM) analysis showed a complete coverage of the carbon graphite electrodes with a laminar-like polymeric structure. Different characterization studies indicate that the carboxyl group remained unchanged since the absorbance peak and oxidation potential did not change with the increase in pH at the pK a accounting for the carboxyl/carboxylate redox transition. The functionalized matrix was activated using carbodiimide, succinimide and an amine-modified oligonucleotide. The immobilization and hybridization processes were successfully verified using the redox electroactive indicator methylene blue, where better electrochemical signals were obtained when compared with the traditional self-assembled monolayer system. The selectivity of the system was verified using a noncomplementary target where no significant difference in electric current was observed when compared to the system containing only the probe. The method showed a good linear correlation coefficient (r 2 =0.9915), low limit of detection (1.17nmolL -1 ), and an acceptable precision (RSD=2.75%). The proposed method is suitable for further studies using different sequences of oligonucleotides. Copyright © 2016 Elsevier B.V. All rights reserved.

Redox and pH dual-responsive mesoporous silica nanoparticles for site-specific drug delivery

NASA Astrophysics Data System (ADS)

Wang, Ying; Cui, Yu; Huang, Jiahao; Di, Donghua; Dong, Yanyan; Zhang, Xiaojing; Zhao, Qinfu; Han, Ning; Gao, Yikun; Jiang, Tongying; Wang, Siling

2015-11-01

In this paper, a mesoporous silica nanoparticles (MSN)-based redox and pH dual-responsive delivery system (MSN-SS-PAA) was developed for site-specific drug delivery, in which poly(acrylic acid) (PAA), a polyanion polymer, was grafted on the outlets of MSN via the cleavable disulfide bonds. PAA was chosen as a gatekeeper to block drugs within the mesopores of MSN mainly because PAA possesses many favorable features, such as appropriate molecular weight to block the entrances of MSNs, good biocompatibility, and ability to prolong the blood circulation time and improve the dispersing stability of MSN in physiological conditions. RhB, a fluorescent dye, was used as a model drug. In vitro release profiles indicated that RhB was markedly blocked within the mesopores in the absence of GSH or in pH 7.4 PBS; however, the release of RhB was dramatically increased after the addition of GSH or in pH 5.0 PBS. Moreover, the release of RhB was further improved in the simultaneous presence of GSH and pH 5.0 PBS. This paper provided an exploration of stimuli-responsive delivery system and the results demonstrated that MSN-SS-PAA exhibiting dual-responsive drug release property can be further considered as a promising candidate for cancer therapy.

Catalytic effect of light illumination on bioleaching of chalcopyrite.

PubMed

Zhou, Shuang; Gan, Min; Zhu, Jianyu; Li, Qian; Jie, Shiqi; Yang, Baojun; Liu, Xueduan

2015-04-01

The influence of visible light exposure on chalcopyrite bioleaching was investigated using Acidithiobacillus ferrooxidans. The results indicated, in both shake-flasks and aerated reactors with 8500-lux light, the dissolved Cu was 91.80% and 23.71% higher, respectively, than that in the controls without light. The catalytic effect was found to increase bioleaching to a certain limit, then plateaued as the initial chalcopyrite concentration increased from 2% to 4.5%. Thus a balanced mineral concentration is highly amenable to bioleaching via offering increased available active sites for light adsorption while eschewing mineral aggregation and screening effects. Using semiconducting chalcopyrite, the light facilitated the reduction of Fe(3+) to Fe(2+) as metabolic substrates for A.ferrooxidans, leading to better biomass, lower pH and redox potential, which are conducive to chalcopyrite leaching. The light exposure on iron redox cycling was further confirmed by chemical leaching tests using Fe(3+), which exhibited higher Fe(2+) levels in the light-induced system. Copyright © 2015 Elsevier Ltd. All rights reserved.

Antibiotic-induced changes in the microbiota disrupt redox dynamics in the gut

PubMed Central

Reese, Aspen T; Cho, Eugenia H; Klitzman, Bruce; Nichols, Scott P; Wisniewski, Natalie A; Villa, Max M; Durand, Heather K; Jiang, Sharon; Midani, Firas S; Nimmagadda, Sai N; O'Connell, Thomas M; Wright, Justin P; Deshusses, Marc A

2018-01-01

How host and microbial factors combine to structure gut microbial communities remains incompletely understood. Redox potential is an important environmental feature affected by both host and microbial actions. We assessed how antibiotics, which can impact host and microbial function, change redox state and how this contributes to post-antibiotic succession. We showed gut redox potential increased within hours of an antibiotic dose in mice. Host and microbial functioning changed under treatment, but shifts in redox potentials could be attributed specifically to bacterial suppression in a host-free ex vivo human gut microbiota model. Redox dynamics were linked to blooms of the bacterial family Enterobacteriaceae. Ecological succession to pre-treatment composition was associated with recovery of gut redox, but also required dispersal from unaffected gut communities. As bacterial competition for electron acceptors can be a key ecological factor structuring gut communities, these results support the potential for manipulating gut microbiota through managing bacterial respiration. PMID:29916366

Reducing capacities and redox potentials of humic substances extracted from sewage sludge.

PubMed

Yang, Zhen; Du, Mengchan; Jiang, Jie

2016-02-01

Humic substances (HS) are redox active organic materials that can be extracted from sewage sludge generated in wastewater treatment processes. Due to the poor understanding of reducing capacity, redox potentials and redox active functional groups of HS in sewage sludge, the potential contribution of sludge HS in transformation of wastewater contaminants is unclear. In the present study, the number of electrons donated or accepted by sewage sludge HS were quantified before and after reduction by iron compounds that possess different redox potentials and defined as the reducing capacity of the sewage sludge. In contrast to previous studies of soil and commercial humic acids (HA), reduced sludge HA showed a lower reducing capacity than that of native HA, which implies formation of semiquinone radicals since the semiquinone radical/hydroquinone pair has a much higher redox potential than the quinone/hydroquinone pair. It is novel that reducing capacities of sludge HA were determined in the redox potential range from -314 to 430 mV. The formation of semiquinone radicals formed during the reduction of quinone moieties in sludge HA is shown by three-dimensional excitation/emission matrix fluorescence spectroscopies information, increasing fluorescence intensities and blue-shifting of the excitation/emission peak of reduced sludge HA. Knowledge of sludge HS redox potentials and corresponding reducing capacities makes it possible to predict the transformation of redox active pollutants and facilitate manipulation and optimization of sludge loading wastewater treatment processes. Copyright © 2015 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz

In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change atmore » a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.« less

Novel thioredoxin-related transmembrane protein TMX4 has reductase activity.

PubMed

Sugiura, Yoshimi; Araki, Kazutaka; Iemura, Shun-ichiro; Natsume, Tohru; Hoseki, Jun; Nagata, Kazuhiro

2010-03-05

In the endoplasmic reticulum (ER), a number of thioredoxin (Trx) superfamily proteins are present to enable correct disulfide bond formation of secretory and membrane proteins via Trx-like domains. Here, we identified a novel transmembrane Trx-like protein 4 (TMX4), in the ER of mammalian cells. TMX4, a type I transmembrane protein, was localized to the ER and possessed a Trx-like domain that faced the ER lumen. A maleimide alkylation assay showed that a catalytic CXXC motif in the TMX4 Trx-like domain underwent changes in its redox state depending on cellular redox conditions, and, in the normal state, most of the endogenous TMX4 existed in the oxidized form. Using a purified recombinant protein containing the Trx-like domain of TMX4 (TMX4-Trx), we confirmed that this domain had reductase activity in vitro. The redox potential of this domain (-171.5 mV; 30 degrees C at pH 7.0) indicated that TMX4 could work as a reductase in the environment of the ER. TMX4 had no effect on the acceleration of ER-associated degradation. Because TMX4 interacted with calnexin and ERp57 by co-immunoprecipitation assay, the role of TMX4 may be to enable protein folding in cooperation with these proteins consisting of folding complex in the ER.

Membrane-less hybrid flow battery based on low-cost elements

NASA Astrophysics Data System (ADS)

Leung, P. K.; Martin, T.; Shah, A. A.; Mohamed, M. R.; Anderson, M. A.; Palma, J.

2017-02-01

The capital cost of conventional redox flow batteries is relatively high (>USD 200/kWh) due to the use of expensive active materials and ion-exchange membranes. This paper presents a membrane-less hybrid organic-inorganic flow battery based on the low-cost elements zinc (92.7% with the use of carbon felt electrodes. In the presence of a fully oxidized active species close to its solubility limit, dissolution of the deposited anode is relatively slow (<2.37 g h-1 cm-2) with an equivalent corrosion current density of <1.9 mA cm-2. In a parallel plate flow configuration, the resulting battery was charge-discharge cycled at 30 mA cm-2 with average coulombic and energy efficiencies of c.a. 71.8 and c.a. 42.0% over 20 cycles, respectively.

Metal(loid)s behaviour in soils amended with nano zero-valent iron as a function of pH and time.

PubMed

Vítková, Martina; Rákosová, Simona; Michálková, Zuzana; Komárek, Michael

2017-01-15

Nano zero-valent iron (nZVI) is currently investigated as a stabilising amendment for contaminated soils. The effect of pH (4-8) and time (48 and 192 h) on the behaviour of nZVI-treated Pb-Zn and As-contaminated soil samples was assessed. Additionally, soil leachates were subsequently used to study the direct interaction between soil solution components and nZVI particles in terms of mineralogical changes and contaminant retention. A typical U-shaped leaching trend as a function of pH was observed for Cd, Pb and Zn, while As was released predominantly under alkaline conditions. Oxidising conditions prevailed, so pH was the key controlling parameter rather than redox conditions. Generally, longer contact time resulted in increased soluble concentrations of metal(loid)s. However, the stabilisation effect of nZVI was only observed after the direct soil leachate-nZVI interactions, showing enhanced redox and sorption processes for the studied metals. A significant decrease of dissolved As concentrations was observed for both experimental soils, but with different efficiencies depending on neutralisation capacity, organic matter content or solid fractionation of As related to the origin of the soils. Scorodite (FeAsO 4 ·2H 2 O) was predicted as a potential solubility-controlling mineral phase for As. Sorption of metal(loid)s onto secondary Fe- and Al-(oxyhydr)oxides (predicted to precipitate at pH > 5) represents an important scavenger mechanism. Moreover, transmission electron microscopy confirmed the retention of Zn and Pb under near-neutral and alkaline conditions by newly formed Fe oxides or aluminosilicates. This study shows that the efficiency of nZVI application strongly depends not only on soil pH-Eh conditions and contaminant type, but also on the presence of organic matter and other compounds such as Al/Fe/Mn oxyhydroxides and clay minerals. Copyright © 2016 Elsevier Ltd. All rights reserved.

Steric/π-electronic insulation of the carbo-benzene ring: dramatic effects of tert-butyl vs phenyl crowns on geometric, chromophoric, redox and magnetic properties.

PubMed

Listunov, Dymytrii; Duhayon, Carine; Poater, Albert; Mazères, Serge; Saquet, Alix; Maraval, Valérie; Chauvin, Remi

2018-04-13

Hexa-tert-butyl-carbo-benzene C18tBu6 and three phenylated counterparts C18tBumPh6-m (m = 4, 2) have been synthesized. The peralkylated version (m = 6) provides experimental access to intrinsic features of the insulated C18 core independently from the influence of π-conjugated substituent. Over the series, structural, spectroscopical and electrochemical properties are compared with those of the hexaphenylated reference (m = 0). Anchoring tBu substituents at the C18 macrocycle is shown to enhance stability and solubility, and to dramatically modify UV-vis absorption and redox properties. Whereas all the carbo-benzenes reported hitherto were obtained as dark-reddish/greenish solids, crystals and solutions of C18tBu6 happen to be yellow (max = 379 nm vs 472 nm for C18Ph6). By comparison to C18Ph6, reduction of C18tBu6 remains reversible but occurs at a twice higher absolute potential (E1/2 = -1.36 V vs -0.72 V). Systematic X-ray diffraction analyses and DFT calculations show that the C18 ring symmetry is the nearest to D6h for m = 6, indicating a maximum geometrical aromaticity. According to calculated nucleus independent chemical shifts, the macrocyclic magnetic aromaticity is also found to be maximum for C18tBu6: NICS(0)=-17.2 ppm, vs -18.0±0.1 ppm for the theoretical references C18H6 and C18F6, and -13.5 ppm for C18Ph6. Accurate correlations of NICS(0) with experimental or calculated maximum UV-vis absorption wavelength max and chemical hardness =ELUMO-EHOMO are evidenced. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox and complexation chemistry of the CrVI/CrV-D-glucaric acid system.

PubMed

Mangiameli, María Florencia; González, Juan Carlos; Bellú, Sebastián; Bertoni, Fernando; Sala, Luis F

2014-06-28

When an excess of uronic acid over Cr(VI) is used, the oxidation of D-glucaric acid (Glucar) by Cr(VI) yields D-arabinaric acid, CO2 and Cr(III)-Glucar complex as final redox products. The redox reaction involves the formation of intermediate Cr(IV) and Cr(V) species. The reaction rate increases with [H(+)] and [substrate]. The experimental results indicated that Cr(IV) and Cr(V) are very reactive intermediates since their disappearance rates are much faster than Cr(VI). Cr(IV) and Cr(V) intermediates are involved in fast steps and do not accumulate in the redox reaction of the mixture Cr(VI)-Glucar. Kinetic studies show that the redox reaction between Glucar and Cr(VI) proceeds through a mechanism combining one- and two-electron pathways: Cr(VI) → Cr(IV) → Cr(II) and Cr(VI) → Cr(IV) → Cr(III). After the redox reaction, results show a slow hydrolysis of the Cr(III)-Glucar complex into [Cr(OH2)6](3+). The proposed mechanism is supported by the observation of free radicals, CrO2(2+) (superoxo-Cr(III) ion) and oxo-Cr(V)-Glucar species as reaction intermediates. The continuous-wave electron paramagnetic resonance, CW-EPR, spectra show that five-coordinate oxo-Cr(V) bischelates are formed at pH ≤ 4 with the aldaric acid bound to oxo-Cr(V) through the carboxylate and the α-OH group. A different oxo-Cr(V) species with Glucar was detected at pH 6.0. The high g(iso) value for the last species suggests a mixed coordination species, a five-coordinated oxo-Cr(V) bischelate with one molecule of Glucar acting as a bi-dentate ligand, using the 2-hydroxycarboxylate group, and a second molecule of Glucar with any vic-diolate sites. At pH 7.5 only a very weak EPR signal was observed, which may point to instability of these complexes. This behaviour contrasts with oxo-Cr(V)-uronic species, and must thus be related to the Glucar acyclic structure. In vitro, our studies on the chemistry of oxo-Cr(V)-Glucar complexes can provide information on the nature of the species that are likely to be stabilized in vivo.

Uranium behaviour in an estuary polluted by mining and industrial effluents: the Ría of Huelva (SW of Spain).

PubMed

Hierro, A; Martín, J E; Olías, M; Vaca, F; Bolivar, J P

2013-10-15

This paper describes a comprehensive study of the behaviour of U in the Ría of Huelva estuary, formed by the Tinto and Odiel rivers. This ecosystem is conditioned by two hydrochemical facts: one connected with the acid mining drainage (AMD) generated in the first section of the river basins, and another one related to the fertilizer industry located at the estuary. AMD gives a singular character to these rivers; low pH and high redox potential that keep high amounts of toxic elements and radionuclides in dissolution. Most of the data for dissolved U in estuaries indicate conservative mixing, but there are examples of non-conservative behaviour attributed to oxidation/reduction processes or solubility variations. In the Ría of Huelva estuary the U shows a non-conservative behaviour due to solubility changes produced by variations in the pH. A complete removal of riverine dissolved U is observed in a pH range of 4-6. At higher pH values, U release from suspended matter, and probably also from sediments into the dissolved phase is found. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ozonation kinetics of winery wastewater in a pilot-scale bubble column reactor.

PubMed

Lucas, Marco S; Peres, José A; Lan, Bing Yan; Li Puma, Gianluca

2009-04-01

The degradation of organic substances present in winery wastewater was studied in a pilot-scale, bubble column ozonation reactor. A steady reduction of chemical oxygen demand (COD) was observed under the action of ozone at the natural pH of the wastewater (pH 4). At alkaline and neutral pH the degradation rate was accelerated by the formation of radical species from the decomposition of ozone. Furthermore, the reaction of hydrogen peroxide (formed from natural organic matter in the wastewater) and ozone enhances the oxidation capacity of the ozonation process. The monitoring of pH, redox potential (ORP), UV absorbance (254 nm), polyphenol content and ozone consumption was correlated with the oxidation of the organic species in the water. The ozonation of winery wastewater in the bubble column was analysed in terms of a mole balance coupled with ozonation kinetics modeled by the two-film theory of mass transfer and chemical reaction. It was determined that the ozonation reaction can develop both in and across different kinetic regimes: fast, moderate and slow, depending on the experimental conditions. The dynamic change of the rate coefficient estimated by the model was correlated with changes in the water composition and oxidant species.

Acidophilic sulfur disproportionation

NASA Astrophysics Data System (ADS)

Hardisty, Dalton S.; Olyphant, Greg A.; Bell, Jonathan B.; Johnson, Adam P.; Pratt, Lisa M.

2013-07-01

Bacterial disproportionation of elemental sulfur (S0) is a well-studied metabolism and is not previously reported to occur at pH values less than 4.5. In this study, a sediment core from an abandoned-coal-mine-waste deposit in Southwest Indiana revealed sulfur isotope fractionations between S0 and pyrite (Δ34Ses-py) of up to -35‰, inferred to indicate intense recycling of S0 via bacterial disproportionation and sulfide oxidation. Additionally, the chemistry of seasonally collected pore-water profiles were found to vary, with pore-water pH ranging from 2.2 to 3.8 and observed seasonal redox shifts expressed as abrupt transitions from Fe(III) to Fe(II) dominated conditions, often controlled by fluctuating water table depths. S0 is a common product during the oxidation of pyrite, a process known to generate acidic waters during weathering and production of acid mine drainage. The H2S product of S0 disproportionation, fractionated by up to -8.6‰, is rapidly oxidized to S0 near redox gradients via reaction with Fe(III) allowing for the accumulation of isotopically light S0 that can then become subject to further sulfur disproportionation. A mass-balance model for S0 incorporating pyrite oxidation, S0 disproportionation, and S0 oxidation readily explains the range of observed Δ34Ses-py and emphasizes the necessity of seasonally varying pyrite weathering and metabolic rates, as indicated by the pore water chemistry. The findings of this research suggest that S0 disproportionation is potentially a common microbial process at a pH < 4.5 and can create large sulfur isotope fractionations, even in the absence of sulfate reduction.

Redox-activated MRI contrast agents based on lanthanide and transition metal ions.

PubMed

Tsitovich, Pavel B; Burns, Patrick J; McKay, Adam M; Morrow, Janet R

2014-04-01

The reduction/oxidation (redox) potential of tissue is tightly regulated in order to maintain normal physiological processes, but is disrupted in disease states. Thus, the development of new tools to map tissue redox potential may be clinically important for the diagnosis of diseases that lead to redox imbalances. One promising area of chemical research is the development of redox-activated probes for mapping tissue through magnetic resonance imaging (MRI). In this review, we summarize several strategies for the design of redox-responsive MRI contrast agents. Our emphasis is on both lanthanide(III) and transition metal(II/III) ion complexes that provide contrast either as T1 relaxivity MRI contrast agents or as paramagnetic chemical exchange saturation transfer (PARACEST) contrast agents. These agents are redox-triggered by a variety of chemical reactions or switches including redox-activated thiol groups, and heterocyclic groups that interact with the metal ion or influence properties of other ancillary ligands. Metal ion centered redox is an approach which is ripe for development by coordination chemists. Redox-triggered metal ion approaches have great potential for creating large differences in magnetic properties that lead to changes in contrast. An attractive feature of these agents is the ease of fine-tuning the metal ion redox potential over a biologically relevant range. Copyright © 2014 Elsevier Inc. All rights reserved.

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

PubMed

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

2011-01-01

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

Long-term leaching of photovoltaic modules

NASA Astrophysics Data System (ADS)

Nover, Jessica; Zapf-Gottwick, Renate; Feifel, Carolin; Koch, Michael; Metzger, Jörg W.; Werner, Jürgen H.

2017-08-01

Some photovoltaic module technologies use toxic materials. We report long-term leaching on photovoltaic module pieces of 5 × 5 cm2 size. The pieces are cut out from modules of the four major commercial photovoltaic technologies: crystalline and amorphous silicon, cadmium telluride as well as from copper indium gallium diselenide. To simulate different environmental conditions, leaching occurs at room temperature in three different water-based solutions with pH 3, 7, and 11. No agitation is performed to simulate more representative field conditions. After 360 days, about 1.4% of lead from crystalline silicon module pieces and 62% of cadmium from cadmium telluride module pieces are leached out in acidic solutions. The leaching depends heavily on the pH and the redox potential of the aqueous solutions and it increases with time. The leaching behavior is predictable by thermodynamic stability considerations. These predictions are in good agreement with the experimental results.

Redox electrodeposition polymers: adaptation of the redox potential of polymer-bound Os complexes for bioanalytical applications.

PubMed

Guschin, Dmitrii A; Castillo, John; Dimcheva, Nina; Schuhmann, Wolfgang

2010-10-01

The design of polymers carrying suitable ligands for coordinating Os complexes in ligand exchange reactions against labile chloro ligands is a strategy for the synthesis of redox polymers with bound Os centers which exhibit a wide variation in their redox potential. This strategy is applied to polymers with an additional variation of the properties of the polymer backbone with respect to pH-dependent solubility, monomer composition, hydrophilicity etc. A library of Os-complex-modified electrodeposition polymers was synthesized and initially tested with respect to their electron-transfer ability in combination with enzymes such as glucose oxidase, cellobiose dehydrogenase, and PQQ-dependent glucose dehydrogenase entrapped during the pH-induced deposition process. The different polymer-bound Os complexes in a library containing 50 different redox polymers allowed the statistical evaluation of the impact of an individual ligand to the overall redox potential of an Os complex. Using a simple linear regression algorithm prediction of the redox potential of Os complexes becomes feasible. Thus, a redox polymer can now be designed to optimally interact in electron-transfer reactions with a selected enzyme.

Examining the effect of altered redox conditions on deep soil organic matter stability

NASA Astrophysics Data System (ADS)

Gabriel, C.; Kellman, L. M.; Ziegler, S. E.

2013-12-01

Since subsoil horizons contribute significantly to terrestrial carbon (C) budgets, understanding the influence of disturbances such as forest harvesting on subsoil C stability is critical. Clearcut harvesting leads to changes in the soil physico-chemical environment, including altering redox conditions arising from changes in soil hydrology that increase soil saturation, soil temperature, and pH. These physico-chemical changes have the potential to alter the adsorption of soil organic matter (SOM) to minerals, particularly at depth where SOM is primarily associated with mineral phases. The objective of this study was to determine the effect of differing redox states (aerobic vs. anaerobic) and temperature upon SOM stability of forested soils representative of the Acadian Forest Region of Eastern North America. Composite soil samples through depth (0-10, 10-20, 20-35, and 35-50 cm) from a mature red spruce forest (110 years) were incubated under optimum (aerobic) or saturated (anaerobic) conditions for 1 or 4 months at two temperatures (5 and 15 C). Following incubation, soil leachate was analyzed for dissolved organic carbon (DOC), and UV-vis absorbance in order to determine soil C losses and its optical character. Specific UV-vis absorbance SUVA (254 nm) and spectral slope ratios were calculated in order to assess the composition of chromophoric dissolved organic matter (CDOM). Preliminary results from the 1 month incubation indicate that under anaerobic conditions, all depths released DOC with a higher SUVA than under aerobic conditions, with the largest change observed in the 0-10 cm depth increment. Soil incubated at 5 C produced leachate with significantly less DOC and with a lower absorbance compared to 15 C under both redox conditions. These results suggest that both temperature and redox state are important in determining the aromaticity of DOC released from soils. Spectral slope ratios revealed that a greater proportion of CDOM of lower molecular weight (MW) compounds were released from deep mineral podzolic soils when saturated (high SUVA, low spectral slope), while higher MW CDOM were released from shallow soil strata (low SUVA, high spectral slope). This is consistent with research that indicates plant-derived SOM and microbial products each dominate in shallow and deep mineral soils, respectively. These preliminary results suggest that alterations to the redox state of a forested podzolic soil may have the potential to alter the mobilization of SOM, its composition and associated soil carbon stores.

Reduction potentials of protein disulfides and catalysis of glutathionylation and deglutathionylation by glutaredoxin enzymes.

PubMed

Ukuwela, Ashwinie A; Bush, Ashley I; Wedd, Anthony G; Xiao, Zhiguang

2017-11-09

Glutaredoxins (Grxs) are a class of GSH (glutathione)-dependent thiol-disulfide oxidoreductase enzymes. They use the cellular redox buffer GSSG (glutathione disulfide)/GSH directly to catalyze these exchange reactions. Grxs feature dithiol active sites and can shuttle rapidly between three oxidation states, namely dithiol Grx(SH) 2 , mixed disulfide Grx(SH)(SSG) and oxidized disulfide Grx(SS). Each is characterized by a distinct standard reduction potential [Formula: see text] The [Formula: see text] values for the redox couple Grx(SS)/Grx(SH) 2 are available, but a recent estimate differs by over 100 mV from the literature values. No estimates are available for [Formula: see text] for the mixed disulfide couple Grx(SH)(SSG)/(Grx(SH) 2  + GSH). This work determined both [Formula: see text] and [Formula: see text] for two representative Grx enzymes, Homo sapiens HsGrx1 and Escherichia coli EcGrx1. The empirical approaches were verified rigorously to overcome the sensitivity of these redox-labile enzymes to experimental conditions. The classic method of acid 'quenching' was demonstrated to shift the thiol-disulfide redox equilibria. Both enzymes exhibit an [Formula: see text] (vs. SHE) at a pH of 7.0. Their [Formula: see text] values (-213 and -230 mV for EcGrx1 and HsGrx1, respectively) are slightly less negative than that ([Formula: see text]) of the redox buffer GSSG/2GSH. Both [Formula: see text] and [Formula: see text] vary with log [GSH], but the former more sensitively by a factor of 2. This confers dual catalytic functions to a Grx enzyme as either an oxidase at low [GSH] or as a reductase at high [GSH]. Consequently, these enzymes can participate efficiently in either glutathionylation or deglutathionylation. The catalysis is demonstrated to proceed via a monothiol ping-pong mechanism relying on a single Cys residue only in the dithiol active site. © 2017 The Author(s). Published by Portland Press Limited on behalf of the Biochemical Society.

Pediatric Cystic Fibrosis Sputum Can Be Chemically Dynamic, Anoxic, and Extremely Reduced Due to Hydrogen Sulfide Formation

PubMed Central

Cowley, Elise S.; Kopf, Sebastian H.; LaRiviere, Alejandro

2015-01-01

ABSTRACT Severe and persistent bacterial lung infections characterize cystic fibrosis (CF). While several studies have documented the microbial diversity within CF lung mucus, we know much less about the inorganic chemistry that constrains microbial metabolic processes and their distribution. We hypothesized that sputum is chemically heterogeneous both within and between patients. To test this, we measured microprofiles of oxygen and sulfide concentrations as well as pH and oxidation-reduction potentials in 48 sputum samples from 22 pediatric patients with CF. Inorganic ions were measured in 20 samples from 12 patients. In all cases, oxygen was depleted within the first few millimeters below the sputum-air interface. Apart from this steep oxycline, anoxia dominated the sputum environment. Different sputum samples exhibited a broad range of redox conditions, with either oxidizing (16 mV to 355 mV) or reducing (−300 to −107 mV) potentials. The majority of reduced samples contained hydrogen sulfide and had a low pH (2.9 to 6.5). Sulfide concentrations increased at a rate of 0.30 µM H2S/min. Nitrous oxide was detected in only one sample that also contained sulfide. Microenvironmental variability was observed both within a single patient over time and between patients. Modeling oxygen dynamics within CF mucus plugs indicates that anoxic zones vary as a function of bacterial load and mucus thickness and can occupy a significant portion of the mucus volume. Thus, aerobic respiration accounts only partially for pathogen survival in CF sputum, motivating research to identify mechanisms of survival under conditions that span fluctuating redox states, including sulfidic environments. PMID:26220964

Urban stormwater treatment by a constructed wetland: Seasonality impacts on hydraulic efficiency, physico-chemical behavior and heavy metal occurrence.

PubMed

Walaszek, M; Bois, P; Laurent, J; Lenormand, E; Wanko, A

2018-05-09

Urban stormwater affects the general quality of water bodies because of their hydraulic and pollution impacts. Stormwater discharges modify stream water flow and are reported as major source of heavy metals (HMs) in urban streams. Stormwater Constructed Wetlands (SCWs) have been built worldwide to manage stormwater before it is released into hydrosystems. In SCWs, stormwater is stored, evaporated and sometimes infiltrated. Subsequently, the HMs in stormwater can be settled, filtered and bioassimilated by microorganisms. Hence, the efficiency of SCWs in managing stormwater depends on climatic conditions, which change with season. The aim of this study was to investigate the impacts of seasonality on the performance of a 6-year-old constructed wetland made with a pond followed by a vertical flow filter. Hydraulic performance of, physico-chemical behaviour of, and HM mitigation via the SCW were evaluated using over 3 years of monitoring (2015-2017) data. Only 35% of the rain events that occurred in the studied catchment caused a discharge into the pond and 17% into the filter. The SCW was mostly supplied with stormwater in spring and summer and provided peak flow attenuation from 97 to 100% in all seasons. Variations in physico-chemical parameters (temperature, dissolved oxygen, pH, and redox potential) were caused by seasonal and dry/wet weather changes. They were greater in the pond than in the filter, which buffers these variations. The high physico-chemical variations in the pond probably had a deleterious effect on HM storage in the pond sediments. Finally, hydrologic and physico-chemical conditions (antecedent dry period length, pH, redox potential) affected the HM concentrations along the SCW. However, HM removal efficiencies were >97% in all seasons. Copyright © 2018 Elsevier B.V. All rights reserved.

Deprotonation/protonation of coordinated secondary thioamide units of pincer ruthenium complexes: modulation of voltammetric and spectroscopic characterization of the pincer complexes.

PubMed

Teratani, Takuya; Koizumi, Take-aki; Yamamoto, Takakazu; Tanaka, Koji; Kanbara, Takaki

2011-09-21

New pincer ruthenium complexes, [Ru(SCS)(tpy)]PF(6) (1) (SCS = 2,6-bis(benzylaminothiocarbonyl)phenyl), tpy = 2,2':6',2''-terpyridyl) and [Ru(SNS)(tpy)]PF(6) (2) (SNS = 2,5-bis(benzylaminothiocarbonyl)pyrrolyl), having κ(3)SCS and κ(3)SNS pincer ligands with two secondary thioamide units were synthesized by the reactions of [RuCl(3)(tpy)] with N,N'-dibenzyl-1,3-benzenedicarbothioamide (L1) and N,N'-dibenzyl-2,5-1H-pyrroledicarbothioamide (L2), respectively, and their chemical and electrochemical properties were elucidated. The structure of 1 was determined by X-ray crystallography. The complexes 1 and 2 showed a two-step deprotonation reaction by treatment with 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU), and the addition of DBU led to a shift of the metal-centered redox couples to a lower potential by 720 and 550 mV, respectively. The di-deprotonated complexes were also studied by (1)H-NMR and UV-vis spectroscopy. The addition of methanesulfonic acid (MSA) to the di-deprotonated complexes enabled the recovery of 1 and 2, indicating that the thioamide moiety underwent a reversible deprotonation-protonation process, which resulted in regulating the redox potentials of the metal center. The Pourbaix diagram of 1 revealed that 1 underwent a one-proton/one-electron transfer process in the pH range of 5.83-10.35, and a two-proton/one-electron process at a pH of over 10.35, indicating that the deprotonation/protonation process of the complexes is related to proton-coupled electron transfer (PCET). This journal is © The Royal Society of Chemistry 2011

Redox subpopulations and the risk of cancer progression: a new method for characterizing redox heterogeneity

NASA Astrophysics Data System (ADS)

Xu, He N.; Li, Lin Z.

2016-02-01

It has been shown that a malignant tumor is akin to a complex organ comprising of various cell populations including tumor cells that are genetically, metabolically and functionally different. Our redox imaging data have demonstrated intra-tumor redox heterogeneity in all mouse xenografts derived from human melanomas, breast, prostate, and colon cancers. Based on the signals of NADH and oxidized flavoproteins (Fp, including flavin adenine dinucleotide (FAD)) and their ratio, i.e., the redox ratio, which is an indicator of mitochondrial metabolic status, we have discovered several distinct redox subpopulations in xenografts of breast tumors potentially recapitulating functional/metabolic heterogeneity within the tumor. Furthermore, xenografts of breast tumors with higher metastatic potential tend to have a redox subpopulation whose redox ratio is significantly different from that of tumors with lower metastatic potential and usually have a bi-modal distribution of the redox ratio. The redox subpopulations from human breast cancer samples can also be very complex with multiple subpopulations as determined by fitting the redox ratio histograms with multi- Gaussian functions. In this report, we present a new method for identifying the redox subpopulations within individual breast tumor xenografts and human breast tissues, which may be used to differentiate between breast cancer and normal tissue and among breast cancer with different risks of progression.

Impact of pH on hydrogen oxidizing redox processes in aquifers due to gas intrusions

NASA Astrophysics Data System (ADS)

Metzgen, Adrian; Berta, Marton; Dethlefsen, Frank; Ebert, Markus; Dahmke, Andreas

2017-04-01

Hydrogen production from excess energy and its storage can help increasing the efficiency of solar and wind in the energy mix. Therefore, hydrogen needs large-scale intermediate storage independent of the intended later use as hydrogen gas or as reactant to produce methane in the Sabatier process. A possible storage solution is using the geological subsurface such as caverns built in salt deposits or aquifers that are not used for drinking water production. However, underground storage of hydrogen gas potentially leads to accidental gas leakages into near-surface potable aquifers triggering subsequent geochemical processes. These leakages pose potential risks that are currently not sufficiently understood. To close this gap in knowledge, a high-pressure laboratory column system was used to simulate a hydrogen gas intrusion into a shallow aquifer. Water and sediment were gained from a sandy Pleistocene aquifer near Neumünster, Germany. In the first stage of the experiment, 100% hydrogen gas was used to simulate dissolved hydrogen concentrations between 800 and 4000 µM by varying pH2 between 2 and 15 bars. pH values rose to between 7.9 and 10.4, partly due to stripping CO2 from the groundwater used during H2 gas addition. In a second stage, the pH was regulated in a range of 6.7 to 7.9 by using a gas mixture of 99% H2 and 1% CO2 at 5 bars of total gas pressure. Observed processes included hydrogen oxidation, sulfate reduction, acetogenesis, formate production, and methanogenesis, which were independent of the hydrogen concentration. Hydrogen oxidation and sulfate reduction showed zeroth order reaction rates and rate constants (106 to 412 µM/h and 12 to 33 µM/h, respectively) in the pH range between 8 and 10. At pH levels between 7 and 8, both reactions started out faster near the column's inflow but then seemed limited towards the columns outflow, suggesting the dependence of sulfate reduction on the pH-value. Acetogenesis dominated the pH range between 8 and 10 (first order rate constants between 0.029 and 0.036 1/h). Between pH 7 and 8, acetogenesis showed a linear trend (zeroth order rates between 3 and 5 µM/h) whereas formate production became the main process (zeroth order rates between 38 to 197 µM/h) together with methanogenesis as a minor process. The results indicated a strong dependency of the biogeochemical hydrogenotrophic redox reactions on the pH milieu. Thus, pH buffers such as dissolved or solid phase carbonates should be taken into account when predicting effects a hydrogen leakage may have on shallow aquifers. Additionally, parameters derived from the observed processes and their rates allow the design of a process based numerical model simulating a hydrogen intrusion into a shallow aquifer. Consequently the presented outcomes allow an exemplary quantification of the resulting geochemical effects. This study was carried out within the ANGUS+ project and was funded by the German Federal Ministry of Education and Research (BMBF) energy storage funding initiative.

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

Inverting Residual Self-Potential Data for Redox Potentials of Contaminant Plumes

NASA Astrophysics Data System (ADS)

Linde, N.; Revil, A.

2007-05-01

Self-potential (SP) data can be separated into a streaming potential component that is associated with pore water flow and a redox potential component, which is sensitive to differences in the redox potentials of organic-rich contaminant plumes and the surroundings. This work presents the first inversion method that uses residual SP (i.e., corrected for the streaming potential component) to invert for the redox potentials of contaminant plumes. We consider a two-layered electrical conductivity structure, where the boundary corresponds to the water table. We assume that the electrical dipole sources are associated with microbial breakdown of contaminants at the water table. This geobattery model is hypothesized to exist (1) because the water table is associated with a strong redox gradient between highly reducing conditions within the contaminated groundwater (due to biodegradation and oxygen depletion) and the oxidized vadose zone, and (2) because the microbial biofilms and precipitation of metallic particles can provide an electron conductor to complete the circuit required for the geobattery. The inverse method was applied to residual SP estimated from SP measurements collected at the ground surface in the vicinity of the Entressen landfill, South of France. The estimated redox potentials correlate well with in situ measurements (correlation coefficient is 0.93) and the estimated amplitudes of the redox potentials are similar to those measured in situ. A sensitivity analysis reveals that meaningful estimates of the redox potential can be derived even if the electrical conductivity structure is only known within an order of magnitude. These results provide further evidence that the SP method can be useful to monitor the spreading of contaminants around landfills and to evaluate the efficiency of remediation programs.

Source of Sustained Voltage Difference between the Xylem of a Potted Ficus benjamina Tree and Its Soil

PubMed Central

Love, Christopher J.; Zhang, Shuguang; Mershin, Andreas

2008-01-01

It has long been known that there is a sustained electrical potential (voltage) difference between the xylem of many plants and their surrounding soil, but the mechanism behind this voltage has remained controversial. After eliminating any extraneous capacitive or inductive couplings and ground-mediated electric current flows, we have measured sustained differences of 50–200 mV between the xylem region of a Faraday-caged, intact, potted Ficus benjamina tree and its soil, as well as between its cut branches and soils and ionic solutions standardized to various pH values. Using identical platinum electrodes, no correlation between the voltage and time of day, illumination, sap flow, electrode elevation, or ionic composition of soil was found, suggesting no direct connection to simple dissimilar-metal redox reactions or transpirational activity. Instead, a clear relationship between the voltage polarity and magnitude and the pH difference between xylem and soil was observed. We attribute these sustained voltages to a biological concentration cell likely set up by the homeostatic mechanisms of the tree. Potential applications of this finding are briefly explored. PMID:18698415

Novel insights into the bioenergetics of mixed-acid fermentation: can hydrogen and proton cycles combine to help maintain a proton motive force?

PubMed

Trchounian, Armen; Gary Sawers, R

2014-01-01

Escherichia coli possesses four [NiFe]-hydrogenases that catalyze the reversible redox reaction of 2H(+) + 2e(-) ↔ H2. These enzymes together have the potential to form a hydrogen cycle across the membrane. Their activity, operational direction, and interaction with each other depend on the fermentation substrate and particularly pH. The enzymes producing H2 are likely able to translocate protons through the membrane. Moreover, the activity of some of these enzymes is dependent on the F0 F1 -ATPase, thus linking a proton cycle with the cycling of hydrogen. These two cycles are suggested to have a primary basic role in modulating the cell's energetics during mixed-acid fermentation, particularly in response to pH. Nevertheless, the mechanisms underlying the physical interactions between these enzyme complexes, as well as how this is controlled, are still not clearly understood. Here, we present a synopsis of the potential impact of proton-hydrogen cycling in fermentative bioenergetics. © 2013 International Union of Biochemistry and Molecular Biology.

Sediment profile imaging (SPI) and micro-electrode technologies in impact assessment studies: Example from two fjords in Southern Chile used for fish farming

NASA Astrophysics Data System (ADS)

Mulsow, S.; Krieger, Y.; Kennedy, R.

2006-10-01

Two state-of-the-art techniques were used to assess the impact of organic loading from fish farming in two fjords of Southern Chile, Pillan and Reñihue Fjords. A sediment profile imaging (SPI) camera was deployed and sediment microprofiles (oxygen, H 2S, redox and pH) were measured in undisturbed sediment cores collected using a HAPS corer. Four out of seven stations in Pillan Fjord were found to be severely disturbed: SPI images showed azoic conditions (no apparent Redox Potential Discontinuity layer, no evidence of aerobic life form, presence of an uneaten fish food layer, negative OSI scores). These findings were corroborated by very high oxygen consumption rates (700-1200 mmol m - 2 day - 1 ), H 2S concentrations increasing quickly within the sediment column and redox potential decreasing towards negative values within a few mm down core. Results for Reñihue Fjord were not so straightforward. SPI images indicated that most of the stations (R3 to R7) presented well-mixed conditions (high apparent RPD layers, presence of infauna, burrows, etc.), but oxygen profiles yielded consumption rates of 230 to 490 mmol m - 2 day - 1 and organic carbon mineralization of 2.16 to 4.53 g C m - 2 day - 1 . These latter values were close to the limit of aerobic degradation of organic matter although no visible changes were recorded within the sediment column. In view of our findings, the importance of integrating multidisciplinary methodologies in impact assessment studies was discussed.

In situ crosslinked smart polypeptide nanoparticles for multistage responsive tumor-targeted drug delivery

NASA Astrophysics Data System (ADS)

Yi, Huqiang; Liu, Peng; Sheng, Nan; Gong, Ping; Ma, Yifan; Cai, Lintao

2016-03-01

Smart tumor-targeted drug delivery is crucial for improving the effect of chemotherapy and reducing the adverse effects. Here, we synthesized a smart polypeptide copolymer based on n-butylamine-poly(l-lysine)-b-poly(l-cysteine) (PLL-PLC) with functionalization of folic acid (FA) and 1,2-dicarboxylic-cyclohexene anhydride (DCA) for multistage responsive tumor-targeted drug delivery. The copolymers (FA-PLL(DCA)-PLC) spontaneously crosslinked in situ to form redox and pH dual responsive FA-PLL(DCA)-PLC nanoparticles (FD-NPs), which had a reversible zeta potential around -30 mV at pH 7.4, but switched to +15 mV at pH 5.0. Moreover, FD-NPs effectively loaded DOX with a loading capacity at 15.7 wt%. At pH 7.4, only 24.5% DOX was released within 60 h. However, at pH 5.0, the presence of 10 mM DTT dramatically accelerated DOX release with over 90% of DOX released within 10 h. Although the FD-NPs only enhanced DOX uptake in FA receptor positive (FR+) cancer cells at pH 7.4, a weak acidic condition promoted FD-NP-facilitated DOX uptake in both FR+ HeLa and FR- A549 cells, as well as significantly improving cellular binding and end/lysosomal escape. In vivo studies in a HeLa cancer model demonstrated that the charge-reversible FD-NPs delivered DOX into tumors more effectively than charge-irreversible nanoparticles. Hence, these multistage responsive FD-NPs would serve as highly efficient drug vectors for targeted cancer chemotherapy.Smart tumor-targeted drug delivery is crucial for improving the effect of chemotherapy and reducing the adverse effects. Here, we synthesized a smart polypeptide copolymer based on n-butylamine-poly(l-lysine)-b-poly(l-cysteine) (PLL-PLC) with functionalization of folic acid (FA) and 1,2-dicarboxylic-cyclohexene anhydride (DCA) for multistage responsive tumor-targeted drug delivery. The copolymers (FA-PLL(DCA)-PLC) spontaneously crosslinked in situ to form redox and pH dual responsive FA-PLL(DCA)-PLC nanoparticles (FD-NPs), which had a reversible zeta potential around -30 mV at pH 7.4, but switched to +15 mV at pH 5.0. Moreover, FD-NPs effectively loaded DOX with a loading capacity at 15.7 wt%. At pH 7.4, only 24.5% DOX was released within 60 h. However, at pH 5.0, the presence of 10 mM DTT dramatically accelerated DOX release with over 90% of DOX released within 10 h. Although the FD-NPs only enhanced DOX uptake in FA receptor positive (FR+) cancer cells at pH 7.4, a weak acidic condition promoted FD-NP-facilitated DOX uptake in both FR+ HeLa and FR- A549 cells, as well as significantly improving cellular binding and end/lysosomal escape. In vivo studies in a HeLa cancer model demonstrated that the charge-reversible FD-NPs delivered DOX into tumors more effectively than charge-irreversible nanoparticles. Hence, these multistage responsive FD-NPs would serve as highly efficient drug vectors for targeted cancer chemotherapy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07348k

Electrosorption of As(III) in aqueous solutions with activated carbon as the electrode

NASA Astrophysics Data System (ADS)

Dai, Min; Xia, Ling; Song, Shaoxian; Peng, Changsheng; Rangel-Mendez, Jose Rene; Cruz-Gaona, Roel

2018-03-01

The electrosorption of As(III) in aqueous solutions by using activated carbon (AC) as the electrode was studied in this work. This study was performed through the measurements of adsorption and desorption, Cyclic Voltammetry (CV), Electrochemical Impedance Spectroscopy (EIS) and X-ray photoelectron spectra (XPS). Three parameters, applied voltage, solution pH and initial As(III) concentration, on the electrosoprtion of As(III) were investigated. The experimental results have demonstrated that the electrosorption followed three steps: migration of As(III) to the anode, oxidation of As(III) to As(V) and accumulation of As(V) in the electric double layers of the anode. The electrodorption capacity increased with increasing applied voltage and initial As(III) concentration, whereas the effect of pH was complicated for the variation of arsenite species and the competition of OH-. The oxidation of As(III) increased with the increasing voltage and pH due to the increasing redox potential acted on As(III). The electrosorption served to reduce the toxicity of arsenic and was a promising technology for As(III) removal from water.

Mechanisms of arsenic-containing pyrite oxidation by aqueous arsenate under anoxic conditions

NASA Astrophysics Data System (ADS)

Qiu, Guohong; Gao, Tianyu; Hong, Jun; Tan, Wenfeng; Liu, Fan; Zheng, Lirong

2017-11-01

Adsorption and redox reactions occur between arsenic-containing pyrite and arsenate, which affect the migration and conversion of arsenic in soils and waters. However, the influence of arsenic incorporated in pyrite on the interaction processes is still enigmatic. In this work, arsenic-containing pyrites were hydrothermally synthesized with composition similar to naturally surface-oxidized pyrites in supergene environments. The effects of arsenic incorporation on the chemical composition and physicochemical properties were analyzed, and the interaction mechanism between arsenic-containing pyrites and aqueous arsenate was also studied within pH 3.0-11.0. Arsenic-containing pyrites with the arsenic contents of 0 (Apy0), 4.4 (Apy5) and 9.9 wt.% (Apy10) were produced in hydrothermal systems. As(III) and As(-I) respectively substituted Fe(II) and S2(-II) in the pyrite, and their relative contents respectively reached 76.6% and 17.2% in Apy5, and 91.0% and 8.0% in Apy10. Arsenic substitution resulted in a high content of Fe(III) in the form of Fe(III)sbnd S and a decrease in pyrite crystallinity. During the redox processes of arsenic-containing pyrites and arsenate, elemental S0, SO42- and goethite were formed as the main products with the adsorption of As(III,V), and As(III) was released due to the collapse of the crystal structure of pyrite and the oxidation of As(-I). Different redox mechanisms were achieved with pH increasing from 3.0 to 11.0 in the reaction system. At pH 3.0-6.0, Fe(III) contributed much to the oxidation of arsenic-containing pyrites, and arsenate and released As(III) were adsorbed on the surface of solid products. At pH 7.0-11.0, aqueous arsenate worked as the major oxidant, and its oxidation capacity increased with increasing pH. When the pH was increased from 3.0 to 7.0 and 11.0, the release ratio of incorporated arsenic from Apy10 particles increased from 34.1% to 45.0% and 56.8%, respectively. The present study facilitates a better understanding about the interaction mechanisms between arsenic-containing pyrite and arsenate in supergene environments.

A series of tetraazalene radical-bridged M2 (M = CrIII, MnII, FeII, CoII) complexes with strong magnetic exchange coupling.

PubMed

DeGayner, Jordan A; Jeon, Ie-Rang; Harris, T David

2015-11-13

The ability of tetraazalene radical bridging ligands to mediate exceptionally strong magnetic exchange coupling across a range of transition metal complexes is demonstrated. The redox-active bridging ligand N , N ', N '', N '''-tetra(2-methylphenyl)-2,5-diamino-1,4-diiminobenzoquinone ( NMePh LH 2 ) was metalated to give the series of dinuclear complexes [(TPyA) 2 M 2 ( NMePh L 2- )] 2+ (TPyA = tris(2-pyridylmethyl)amine, M = Mn II , Fe II , Co II ). Variable-temperature dc magnetic susceptibility data for these complexes reveal the presence of weak superexchange interactions between metal centers, and fits to the data provide coupling constants of J = -1.64(1) and -2.16(2) cm -1 for M = Mn II and Fe II , respectively. One-electron reduction of the complexes affords the reduced analogues [(TPyA) 2 M 2 ( NMePh L 3- ˙)] + . Following a slightly different synthetic procedure, the related complex [(TPyA) 2 CrIII2( NMePh L 3- ˙)] 3+ was obtained. X-ray diffraction, cyclic voltammetry, and Mössbauer spectroscopy indicate the presence of radical NMePh L 3- ˙ bridging ligands in these complexes. Variable-temperature dc magnetic susceptibility data of the radical-bridged species reveal the presence of strong magnetic interactions between metal centers and ligand radicals, with simulations to data providing exchange constants of J = -626(7), -157(7), -307(9), and -396(16) cm -1 for M = Cr III , Mn II , Fe II , and Co II , respectively. Moreover, the strength of magnetic exchange in the radical-bridged complexes increases linearly with decreasing M-L bond distance in the oxidized analogues. Finally, ac magnetic susceptibility measurements reveal that [(TPyA) 2 Fe 2 ( NMePh L 3- ˙)] + behaves as a single-molecule magnet with a relaxation barrier of U eff = 52(1) cm -1 . These results highlight the ability of redox-active tetraazalene bridging ligands to enable dramatic enhancement of magnetic exchange coupling upon redox chemistry and provide a rare opportunity to examine metal-radical coupling trends across a transmetallic series of complexes.

Insight into the template effect of vesicles on the laccase-catalyzed oligomerization of N-phenyl-1,4-phenylenediamine from Raman spectroscopy and cyclic voltammetry measurements

NASA Astrophysics Data System (ADS)

Ležaić, Aleksandra Janoševic; Luginbühl, Sandra; Bajuk-Bogdanović, Danica; Pašti, Igor; Kissner, Reinhard; Rakvin, Boris; Walde, Peter; Ćirić-Marjanović, Gordana

2016-08-01

We report about the first Raman spectroscopy study of a vesicle-assisted enzyme-catalyzed oligomerization reaction. The aniline dimer N-phenyl-1,4-phenylenediamine (= p-aminodiphenylamine, PADPA) was oxidized and oligomerized with Trametes versicolor laccase and dissolved O2 in the presence of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) vesicles (80-100 nm diameter) as templates. The conversion of PADPA into oligomeric products, poly(PADPA), was monitored during the reaction by in situ Raman spectroscopy. The results obtained are compared with UV/vis/NIR and EPR measurements. All three complementary methods indicate that at least some of the poly(PADPA) products, formed in the presence of AOT vesicles, resemble the conductive emeraldine salt form of polyaniline (PANI-ES). The Raman measurements also show that structural units different from those of “ordinary” PANI-ES are present too. Without vesicles PANI-ES-like products are not obtained. For the first time, the as-prepared stable poly(PADPA)-AOT vesicle suspension was used directly to coat electrodes (without product isolation) for investigating redox activities of poly(PADPA) by cyclic voltammetry (CV). CV showed that poly(PADPA) produced with vesicles is redox active not only at pH 1.1-as expected for PANI-ES-but also at pH 6.0, unlike PANI-ES and poly(PADPA) synthesized without vesicles. This extended pH range of the redox activity of poly(PADPA) is important for applications.

Insight into the template effect of vesicles on the laccase-catalyzed oligomerization of N-phenyl-1,4-phenylenediamine from Raman spectroscopy and cyclic voltammetry measurements.

PubMed

Ležaić, Aleksandra Janoševic; Luginbühl, Sandra; Bajuk-Bogdanović, Danica; Pašti, Igor; Kissner, Reinhard; Rakvin, Boris; Walde, Peter; Ćirić-Marjanović, Gordana

2016-08-26

We report about the first Raman spectroscopy study of a vesicle-assisted enzyme-catalyzed oligomerization reaction. The aniline dimer N-phenyl-1,4-phenylenediamine (= p-aminodiphenylamine, PADPA) was oxidized and oligomerized with Trametes versicolor laccase and dissolved O2 in the presence of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) vesicles (80-100 nm diameter) as templates. The conversion of PADPA into oligomeric products, poly(PADPA), was monitored during the reaction by in situ Raman spectroscopy. The results obtained are compared with UV/vis/NIR and EPR measurements. All three complementary methods indicate that at least some of the poly(PADPA) products, formed in the presence of AOT vesicles, resemble the conductive emeraldine salt form of polyaniline (PANI-ES). The Raman measurements also show that structural units different from those of "ordinary" PANI-ES are present too. Without vesicles PANI-ES-like products are not obtained. For the first time, the as-prepared stable poly(PADPA)-AOT vesicle suspension was used directly to coat electrodes (without product isolation) for investigating redox activities of poly(PADPA) by cyclic voltammetry (CV). CV showed that poly(PADPA) produced with vesicles is redox active not only at pH 1.1-as expected for PANI-ES-but also at pH 6.0, unlike PANI-ES and poly(PADPA) synthesized without vesicles. This extended pH range of the redox activity of poly(PADPA) is important for applications.

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

PubMed

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

2016-06-02

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

Theoretical determination of one-electron redox potentials for DNA bases, base pairs, and stacks.

PubMed

Paukku, Y; Hill, G

2011-05-12

Electron affinities, ionization potentials, and redox potentials for DNA bases, base pairs, and N-methylated derivatives are computed at the DFT/M06-2X/6-31++G(d,p) level of theory. Redox properties of a guanine-guanine stack model are explored as well. Reduction and oxidation potentials are in good agreement with the experimental ones. Electron affinities of base pairs were found to be negative. Methylation of canonical bases affects the ionization potentials the most. Base pair formation and base stacking lower ionization potentials by 0.3 eV. Pairing of guanine with the 5-methylcytosine does not seem to influence the redox properties of this base pair much.

Dual pH/redox responsive and CD44 receptor targeting hybrid nano-chrysalis based on new oligosaccharides of hyaluronan conjugates.

PubMed

Chen, Daquan; Dong, Xue; Qi, Mengjiao; Song, Xiaoyan; Sun, Jingfang

2017-02-10

A smart hybrid microenvironment-mediated dual pH/redox-responsive polymeric nanoparticles combined with inorganic calcium phosphate (CaP) was fabricated, which we term as armored nano-chrysalis inspired by butterfly pupa. The nano-chrysalis has an inner core composed of specially designed oligosaccharides of hyaluronan (oHA) targeting CD44 receptor. The inner core has two functions, i.e., the dual pH/redox responsive polymeric conjugate and the fluorescent curcumin-prodrug function. The prepared nano-chrysalis possessed a smaller size (102.5±4.6nm) than the unarmored nano-chrysalis (122.5±6.6nm). Interestingly, while the nano-chrysalis were stable under pH 7.4, when incubated under the tumor acidic conditions (pH 6.5) the outer CaP armor would dissolve in a pH-dependent, sustained manner. Moreover, nano-chrysalis was demonstrated to present the most effective antitumor efficacy than other formulations. This study provides a promising smart nano-carrier platform to enhance the stability, decrease the side effects, and improve the therapeutic efficacy of anticancer drugs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Application of mineral-solution equilibria to geochemical exploration for sandstone-hosted uranium deposits in two basins in west central Utah.

USGS Publications Warehouse

Miller, W.R.; Wanty, R.B.; McHugh, J.B.

1984-01-01

This study applies mineral-solution equilibrium methods to the interpretation of ground-water chemistry in evaluating the uranium potential of the Beaver and Milford basins in west central Utah. Waters were collected mainly from wells and springs at 100 sites in limited areas in the basins, and in part from mixed sources. The waters were analysed for T, pH, alkalinity, specific conductance, SO4, Cl, F, NO3, Ca, Mg, Na, K, SiO2, Zn, Cu, Mo, As, U, V, Se, Li, Fe, Mn, and Al on different fractions. A computer model (WATEQ3) was used to calculate the redox potential and the state of saturation of the waters with respect to uraninite, coffinite, realgar and arsenopyrite. Mineral saturation studies have reliably predicted the location of known (none given here) U deposits and are more diagnostic of these deposits than are concentrations of indicator elements (U, Mo, As, Se). Several areas in the basins have ground-water environments of reducing redox potential, favourable for precipitation of reduced U minerals, and some of these areas are saturated or near-saturated with respect to uraninite and coffinite. The approach shows only that the environment is favourable locally for precipitation of reduced U minerals, but thereby locates exploration targets for (modern?) sandstone-hosted U deposits.-G.J.N.

Effect of pH on film structure and electrical property of PMMA-Au composite particles prepared by redox transmetalation

NASA Astrophysics Data System (ADS)

Wu, Hong-Mao; Lin, Kuan-Ju; Yu, Yi-Hsiuan; Ho, Chan-Yuan; Wei, Ming-Hsiung; Lu, Fu-Hsing; Tseng, Wenjea J.

2014-01-01

Surface-selective deposition of gold (Au) on electroless plated poly(methyl methacrylate)-nickel (PMMA-Ni) beads was prepared chemically by a facile redox-transmetalation route in which the Ni atoms on the PMMA surface were reacted with Au precursors, i.e., chloroauric acid (HAuCl4), in water to form predominately core-shell PMMA-Au composite particles without the need of reducing agent. The Ni layer acted as a sacrificial template to facilitate the selective transmetalation deposition of a metallic Au film. When pH of the precursor solution was adjusted from 6 to 9, morphology of the Au film changed from a uniform particulate film consisting of assemblies of Au nanoparticles, to densely packed, continuous film with platelet Au crystals, and finally to isolated Au islands on the PMMA surface with a raspberry-like core-shell morphology. Uniformly dense Au coating with a thickness of about 200 nm was formed on the PMMA beads at pH of 7 to 8, which gave rise to an electrical resistivity as low as 3 × 10-2 Ω cm.

Quinonoid metal complexes: toward molecular switches.

PubMed

Dei, Andrea; Gatteschi, Dante; Sangregorio, Claudio; Sorace, Lorenzo

2004-11-01

The peculiar redox-active character of quinonoid metal complexes makes them extremely appealing to design materials of potential technological interest. We show here how the tuning of the properties of these systems can be pursued by using appropriate molecular synthetic techniques. In particular, we focus our attention on metal polyoxolene complexes exhibiting intramolecular electron transfer processes involving either the ligand and the metal ion or the two dioxolene moieties of a properly designed ligand thus inducing electronic bistability. The transition between the two metastable electronic states can be induced by different external stimuli such as temperature, pressure, light, or pH suggesting the use of these systems for molecular switches.

Simultaneous detection of refractive index and surface charges in nanolaser biosensors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Watanabe, Keisuke; Kishi, Yoji; Hachuda, Shoji

2015-01-12

The emission intensity of a GaInAsP photonic crystal nanolaser is affected by the pH of the solution, in which the nanolaser is immersed. This phenomenon can be explained by the change in the redox potential, which modifies the filling of electrons at surface states of the semiconductor and hence the nonradiative surface recombination. This phenomenon allows the nanolaser to simultaneously and independently detect the refractive index and electric charges near the surface on the basis of the variation in emission wavelength and intensity, respectively. This paper demonstrates this function through alternate deposition of charged polyelectrolytes and hybridization of deoxyribonucleic acids.

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

PubMed

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)(NCS)(2)) is 1.1 V. The driving force for reduction of oxidized dye is therefore as large as 0.75 V. This process leads to the largest internal potential loss in DSC devices. We expect that overall efficiencies above 15% might be achieved if half of this internal potential loss could be gained. The regeneration of oxidized dye with iodide leads to the formation of the diiodide radical (I(2)(-*)). The redox potential of the I(2)(-*)/I(-) couple must therefore be considered when determining the actual driving force for dye regeneration. The formed I(2)(-*) disproportionates to I(3)(-) and I(-), which leads to a large loss in potential energy.

pH- and redox-responsive nanoparticles composed of charge-reversible pullulan-based shells and disulfide-containing poly(ß-amino ester) cores for co-delivery of a gene and chemotherapeutic agent.

PubMed

Zhang, Sipei; Wang, Dan; Li, Yating; Li, Ling; Chen, Hongli; Xiong, Qingqing; Liu, Yuanyuan; Wang, Yinsong

2018-08-10

A novel pH- and redox-responsive nanoparticle system was designed based on a charge-reversible pullulan derivative (CAPL) and disulfide-containing poly(β-amino ester) (ssPBAE) for the co-delivery of a gene and chemotherapeutic agent targeting hepatoma. The end-alkene groups of ssPBAE were reacted with diethylenetriamine to form amino-modified ssPBAE (NH-ssPBAE). Methotrexate (MTX), a chemotherapy agent, was then conjugated to NH-ssPBAE via an amide bond to obtain the polymeric prodrug ssPBAE-MTX. ssPBAE-MTX exhibited a good capability for condensing genes, including plasmid DNA (pDNA) and tetramethyl rhodamine-labeled DNA (TAMRA-DNA), and almost completely condensed pDNA at the weight ratio of 5/1 to form spherical nanocomplexes with a uniform size. In a D,L-dithiothreitol solution, the ssPBAE-MTX/pDNA nanocomplexes showed rapid release of pDNA and MTX, indicating their redox-responsive capability. CAPL, a pullulan derivative containing β-carboxylic amide bond, was efficiently coated on the surfaces of ssPBAE-MTX/pDNA nanocomplexes to form polysaccharide shells, thus realizing co-loading of the gene and chemotherapeutic agent. CAPL/ssPBAE-MTX/pDNA nanoparticles displayed an obvious pH-responsive charge reversal ability due to the rupture of the β-carboxylic amide bond under the weakly acidic condition. In human hepatoma HepG2 cells, CAPL/ssPBAE-MTX/TAMRA-DNA nanoparticles were efficiently internalized via endocytosis and successfully escaped from the endo/lysosomes into the cytoplasm, and CAPL/ssPBAE-MTX/pDNA nanoparticles remarkably inhibited the cell growth. In summary, this nanoparticle system based on CAPL and ssPBAE showed great potential for combined gene/chemotherapy on hepatomas.

Gold core/ceria shell-based redox active nanozyme mimicking the biological multienzyme complex phenomenon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhagat, Stuti; Srikanth Vallabani, N. V.; Shutthanandan, Vaithiyalingam

Catalytically active individual gold (Au) and cerium oxide (CeO2) nanoparticles are well known to exhibit specific enzyme-like activities, such as natural catalase, oxidase, superoxide dismutase, and peroxidase enzymes. These activities have been maneuvered to design several biological applications such as immunoassays, glucose detection, radiation and free radical protection and tissue engineering. A functional nanozyme depicting multienzyme like properties that functions as a synthetic super enzyme has eluded the researchers in the nanoscience community for past decade. In current report, we have designed a functional multienzyme in the form of Gold (core)-CeO2 (shell) nanoparticles (Au@CeO2 CSNPs) exhibiting excellent peroxidase, catalase andmore » superoxide dismutase enzyme-like activities that are controlled simply by tuning the pH. The reaction kinetic parameters reveal that the peroxidase-like activity of this core shell nanozyme is comparable to natural HRP enzyme. Unlike peroxidase-like activity exhibited by other nanomaterials, Au@CeO2 CSNPs showed decrease in hydroxyl radical formation, suggesting that the bio catalytic reactions are performed by efficient electron transfers. A significant enzyme-like activity of this core shell nanoparticle was conserved at extreme pH (2 – 11) and temperatures (up to 90 °C), clearly suggesting the superiority over natural enzymes. Further, the utility of peroxidase-like activity of this core shell nanoparticles was extended for the detection of glucose, which showed a linear range of detection between (100 µM – 1 mM). It is hypothesized that the proximity of the redox potentials of Au+/Au and Ce (III)/Ce (IV) may result in a redox couple promoting the multienzyme activity of core shell nanoparticles. Au@CeO2 CSNPs may open new directions for development of single platform sensors in multiple biosensing applications.« less

Development of redox-sensitive red fluorescent proteins for imaging redox dynamics in cellular compartments.

PubMed

Fan, Yichong; Ai, Hui-wang

2016-04-01

We recently reported a redox-sensitive red fluorescent protein, rxRFP1, which is one of the first genetically encoded red-fluorescent probes for general redox states in living cells. As individual cellular compartments have different basal redox potentials, we hereby describe a group of rxRFP1 mutants, showing different midpoint redox potentials for detection of redox dynamics in various subcellular domains, such as mitochondria, the cell nucleus, and endoplasmic reticulum (ER). When these redox probes were expressed and subcellularly localized in human embryonic kidney (HEK) 293 T cells, they responded to membrane-permeable oxidants and reductants. In addition, a mitochondrially localized rxRFP1 mutant, Mito-rxRFP1.1, was used to detect mitochondrial oxidative stress induced by doxorubicin-a widely used cancer chemotherapy drug. Our work has expanded the fluorescent protein toolkit with new research tools for studying compartmentalized redox dynamics and oxidative stress under various pathophysiological conditions.

Definition of redox and pH influence in the AMD mine system using a fuzzy qualitative tool (Iberian Pyrite Belt, SW Spain).

PubMed

de la Torre, M L; Grande, J A; Valente, T; Perez-Ostalé, E; Santisteban, M; Aroba, J; Ramos, I

2016-03-01

Poderosa Mine is an abandoned pyrite mine, located in the Iberian Pyrite Belt which pours its acid mine drainage (AMD) waters into the Odiel river (South-West Spain). This work focuses on establishing possible reasons for interdependence between the potential redox and pH, with the load of metals and sulfates, as well as a set of variables that define the physical chemistry of the water-conductivity, temperature, TDS, and dissolved oxygen-transported by a channel from Poderosa mine affected by acid mine drainage, through the use of techniques of artificial intelligence: fuzzy logic and data mining. The sampling campaign was carried out in May of 2012. There were a total of 16 sites, the first inside the tunnel and the last at the mouth of the river Odiel, with a distance of approximately 10 m between each pair of measuring stations. While the tools of classical statistics, which are widely used in this context, prove useful for defining proximity ratios between variables based on Pearson's correlations, in addition to making it easier to handle large volumes of data and producing easier-to-understand graphs, the use of fuzzy logic tools and data mining results in better definition of the variations produced by external stimuli on the set of variables. This tool is adaptable and can be extrapolated to any system polluted by acid mine drainage using simple, intuitive reasoning.

Smart micro/nanoparticles in stimulus-responsive drug/gene delivery systems.

PubMed

Karimi, Mahdi; Ghasemi, Amir; Sahandi Zangabad, Parham; Rahighi, Reza; Moosavi Basri, S Masoud; Mirshekari, H; Amiri, M; Shafaei Pishabad, Z; Aslani, A; Bozorgomid, M; Ghosh, D; Beyzavi, A; Vaseghi, A; Aref, A R; Haghani, L; Bahrami, S; Hamblin, Michael R

2016-03-07

New achievements in the realm of nanoscience and innovative techniques of nanomedicine have moved micro/nanoparticles (MNPs) to the point of becoming actually useful for practical applications in the near future. Various differences between the extracellular and intracellular environments of cancerous and normal cells and the particular characteristics of tumors such as physicochemical properties, neovasculature, elasticity, surface electrical charge, and pH have motivated the design and fabrication of inventive "smart" MNPs for stimulus-responsive controlled drug release. These novel MNPs can be tailored to be responsive to pH variations, redox potential, enzymatic activation, thermal gradients, magnetic fields, light, and ultrasound (US), or can even be responsive to dual or multi-combinations of different stimuli. This unparalleled capability has increased their importance as site-specific controlled drug delivery systems (DDSs) and has encouraged their rapid development in recent years. An in-depth understanding of the underlying mechanisms of these DDS approaches is expected to further contribute to this groundbreaking field of nanomedicine. Smart nanocarriers in the form of MNPs that can be triggered by internal or external stimulus are summarized and discussed in the present review, including pH-sensitive peptides and polymers, redox-responsive micelles and nanogels, thermo- or magnetic-responsive nanoparticles (NPs), mechanical- or electrical-responsive MNPs, light or ultrasound-sensitive particles, and multi-responsive MNPs including dual stimuli-sensitive nanosheets of graphene. This review highlights the recent advances of smart MNPs categorized according to their activation stimulus (physical, chemical, or biological) and looks forward to future pharmaceutical applications.

Electrochemistry and electrocatalysis of hemoglobin in Nafion/nano-CaCO3 film on a new ionic liquid BPPF6 modified carbon paste electrode.

PubMed

Sun, Wei; Gao, Ruifang; Jiao, Kui

2007-05-03

Room temperature ionic liquid N-butylpyridinium hexafluorophosphate (BPPF6) was used as a binder to construct a new carbon ionic liquid electrode (CILE), which exhibited enhanced electrochemical behavior as compared with the traditional carbon paste electrode with paraffin. By using the CILE as the basal electrode, hemoglobin (Hb) was immobilized on the surface of the CILE with nano-CaCO3 and Nafion film step by step. The Hb molecule in the film kept its native structure and showed good electrochemical behavior. In pH 7.0 Britton-Robinson (B-R) buffer solution, a pair of well-defined, quasi-reversible cyclic voltammetric peaks appeared with cathodic and anodic peak potentials located at -0.444 and -0.285 V (vs SCE), respectively, and the formal potential (E degrees') was at -0.365 V, which was the characteristic of Hb Fe(III)/Fe(II) redox couples. The formal potential of Hb shifted linearly to the increase of buffer pH with a slope of -50.6 mV pH-1, indicating that one electron transferred was accompanied with one proton transportation. Ultraviolet-visible (UV-vis) and Fourier transform infrared (FT-IR) spectroscopy studies showed that Hb immobilized in the Nafion/nano-CaCO3 film still remained its native arrangement. The Hb modified electrode showed an excellent electrocatalytic behavior to the reduction of H2O2, trichloroacetic acid (TCA), and NaNO2.

SiP monolayers: New 2D structures of group IV-V compounds for visible-light photohydrolytic catalysts

NASA Astrophysics Data System (ADS)

Ma, Zhinan; Zhuang, Jibin; Zhang, Xu; Zhou, Zhen

2018-06-01

Because of graphene and phosphorene, two-dimensional (2D) layered materials of group IV and group V elements arouse great interest. However, group IV-V monolayers have not received due attention. In this work, three types of SiP monolayers were computationally designed to explore their electronic structure and optical properties. Computations confirm the stability of these monolayers, which are all indirect-bandgap semiconductors with bandgaps in the range 1.38-2.21 eV. The bandgaps straddle the redox potentials of water at pH = 0, indicating the potential of the monolayers for use as watersplitting photocatalysts. The computed optical properties demonstrate that certain monolayers of SiP 2D materials are absorbers of visible light and would serve as good candidates for optoelectronic devices.

Vegetation-induced spatial variability of soil redox properties in wetlands

NASA Astrophysics Data System (ADS)

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

2016-04-01

Vegetation induced land patches may result spatial pattern of on soil Eh and pH. These spatial pattern are mainly emerged by differences of aeration and exudation of assimilates. Present paper focuses on vertical extent and temporal dynamics of these patterns in wetlands. Two study sites were selected: 1. a plain wetland on calcareous sandy parent material (Ceglédbercel, Danube-Tisza Interfluve, Hungary); 2. headwater wetland with calcareous loamy parent material (Bátaapáti, Hungary). Two vegetation patches were studied in site 1: sedgy (dominated by Carex riparia) and reedy (dominated by Phragmites australis). Three patches were studied in site2: sedgy1 (dominated by C vulpina), sedgy 2 (C. riparia); nettle-horsetail (Urtica dioica and Equisetum arvense). Boundaries between patches were studied separately. Soil redox, pH and temperature studied by automated remote controlled instruments. Three digital sensors (Ponsell) were installed in each locations: 20cm and 40cm sensors represent the solum and 100 cm sensor monitors the subsoil). Groundwater wells were installed near to triplets for soil water sampling. Soil Eh, pH and temperature values were recorded in each 10 minutes. Soil water sampling for iron and DOC were carried out during saturated periods. Spatial pattern of soil Eh is clearly caused by vegetation. We measured significant differences between Eh values of the studied patches in the solum. We did not find this kinds horizontal differences in the subsoil. Boundaries of the patches usually had more reductive soil environment than the core areas. We have found temporal dynamics of the spatial redox pattern. Differences were not so well expressed during wintertime. These spatial patterns had influence on the DOC and iron content of porewater, as well. Highest temporal dynamics of soil redox properties and porewater iron could be found in the boundaries. These observations refer to importance patchiness of vegetation on soil chemical properties in wetlands. Authors are grateful to Hungarian Scientific research Fund (K100180)

Attenuation of landfill leachate by UK Triassic sandstone aquifer materials. 1. Fate of inorganic pollutants in laboratory columns

NASA Astrophysics Data System (ADS)

Thornton, Steven F.; Tellam, John H.; Lerner, David N.

2000-05-01

The attenuation of inorganic contaminants in acetogenic and methanogenic landfill leachate by calcareous and carbonate-deficient, oxide-rich Triassic sandstone aquifer materials from the English Midlands was examined in laboratory columns. Aqueous equilibrium speciation modelling, simple transport modelling and chemical mass balance approaches are used to evaluate the key processes and aquifer geochemical properties controlling contaminant fate. The results indicate that leachate-rock interactions are dominated by ion-exchange processes, acid-base and redox reactions and sorption/precipitation of metal species. Leachate NH 4 is attenuated by cation exchange with the aquifer sediments; however, NH 4 migration could be described with a simple model using retardation factors. Organic acids in the acetogenic leachate buffered the system pH at low levels during flushing of the calcareous aquifer material. In contrast, equilibrium with Al oxyhydroxide phases initially buffered pH (˜4.5) during flushing of the carbonate-deficient sandstone with methanogenic leachate. This led to the mobilisation of sorbed and oxide-bound heavy metals from the aquifer sediment which migrated as a concentrated pulse at the leachate front. Abiotic reductive dissolution of Mn oxyhydroxides on each aquifer material by leachate Fe 2+ maintains high concentrations of dissolved Mn and buffers the leachate inorganic redox system. This feature is analogous to the Mn-reducing zones found in leachate plumes and in the experiments provides a sink for the leachate Fe load and other heavy metals. The availability of reactive solid phase Mn oxyhydroxides limits the duration of redox buffering and Fe attenuation by these aquifer sediments. Aquifer pH and redox buffering capacity exert a fundamental influence on leachate inorganic contaminant fate in these systems. The implications for the assessment of aquifer vulnerability at landfills are discussed and simple measurements of aquifer properties which may improve the prediction of contaminant attenuation are outlined.

A dual-plate ITO-ITO generator-collector microtrench sensor: surface activation, spatial separation and suppression of irreversible oxygen and ascorbate interference.

PubMed

Hasnat, Mohammad A; Gross, Andrew J; Dale, Sara E C; Barnes, Edward O; Compton, Richard G; Marken, Frank

2014-02-07

Generator-collector electrode systems are based on two independent working electrodes with overlapping diffusion fields where chemically reversible redox processes (oxidation and reduction) are coupled to give amplified current signals. A generator-collector trench electrode system prepared from two tin-doped indium oxide (ITO) electrodes placed vis-à-vis with a 22 μm inter-electrode gap is employed here as a sensor in aqueous media. The reversible 2-electron anthraquinone-2-sulfonate redox system is demonstrated to give well-defined collector responses even in the presence of oxygen due to the irreversible nature of the oxygen reduction. For the oxidation of dopamine on ITO, novel "Piranha-activation" effects are observed and chemically reversible generator-collector feedback conditions are achieved at pH 7, by selecting a more negative collector potential, again eliminating possible oxygen interference. Finally, dopamine oxidation in the presence of ascorbate is demonstrated with the irreversible oxidation of ascorbate at the "mouth" of the trench electrode and chemically reversible oxidation of dopamine in the trench "interior". This spatial separation of chemically reversible and irreversible processes within and outside the trench is discussed as a potential in situ microscale sensing and separation tool.

Functionalized carbon nanotube based hybrid electrochemical capacitors using neutral bromide redox-active electrolyte for enhancing energy density

NASA Astrophysics Data System (ADS)

Tang, Xiaohui; Lui, Yu Hui; Chen, Bolin; Hu, Shan

2017-06-01

A hybrid electrochemical capacitor (EC) with enhanced energy density is realized by integrating functionalized carbon nanotube (FCNT) electrodes with redox-active electrolyte that has a neutral pH value (1 M Na2SO4 and 0.5 M KBr mixed aqueous solution). The negative electrode shows an electric double layer capacitor-type behavior. On the positive electrode, highly reversible Br-/Br3- redox reactions take place, presenting a battery-type behavior, which contributes to increase the capacitance of the hybrid cell. The voltage window of the whole cell is extended up to 1.5 V because of the high over-potentials of oxygen and hydrogen evolution reactions in the neutral electrolyte. Compared with raw CNT, the FCNT has better wettability in the aqueous electrolyte and contributes to increase the electric double layer capacitance of the cell. As a result, the maximum energy density of 28.3 Wh kg-1 is obtained from the hybrid EC at 0.5 A g-1 without sacrificing its power density, which is around 4 times larger than that of the electrical double layer capacitor constructed by FCNT electrodes and 1 M Na2SO4 electrolyte. Moreover, the discharge capacity retained 86.3% of its initial performance after 10000 cycles of galvanostatic charge and discharge test (10 A/g), suggesting its long life cycle even at high current loading.

High resolution microprofiling, fractionation and speciation at sediment water interfaces

NASA Astrophysics Data System (ADS)

Fabricius, Anne-Lena; Duester, Lars; Ecker, Dennis; Ternes, Thomas A.

2016-04-01

Within aquatic environments, the exchange between the sediment and the overlaying water is often driven by steep gradients of, e.g., the oxygen concentration, the redox potential or the pH value at the sediment water interface (SWI). Important transport processes at the SWI are sedimentation and resuspension of particulate matter and diffusional fluxes of dissolved substances. To gain a better understanding of the key factors and processes determining the fate of substances at the SWI, methods with a spatial high resolution are required that enable the investigation of several sediment parameters in parallel to different analytes of interest in the sediment pore water. Moreover, beside the total content, questions concerning the speciation and fractionation are of concern in studying the different (transport) processes. Due to the availability of numerous micro-sensors and -electrodes (e.g., O2, redox potential, pH value, H2S, N2O) and the development of methods for pore water sampling [1], the toolbox to study the heterogeneous and often dynamic conditions at the SWI at a sub-millimetre scale were considerably improved. Nevertheless, the methods available for pore water sampling often require the installation of the sampling devices at the sampling site and/or intensive preparation procedures that may influence the conditions at the area studied and/or the characteristics of the samples taken. By combination of a micro profiling system with a new micro filtration probe head connected to a pump and a fraction collector, a micro profiling and micro sampling system ("missy") was developed that enables for the first time a direct, automate and low invasive sampling of small volumes (<500 μL) at a spatial high resolution of a few millimetres to sub-millimetres [2]. Via the application of different sample preparation procedures followed by inductively plasma-mass spectrometry analyses, it was possible to address not only the total content of metal(loid)s, but also their fractionation (size dependent and micelle mediated) or speciation related distributions along sediment depth profiles in parallel to different sediment parameters (O2, redox and pH). Together with the results of missy-experiments, the results of different experimental approaches will be given and discussed, especially with regard to their potentials and limitations. Based on application examples it will be demonstrated how a variety of parameters can be studied in parallel with the aim to get a more holistic understanding of natural and anthropogenic caused processes that govern the fate of substances at the SWI. 1. Stockdale, A., W. Davison, and H. Zhang, Micro-scale biogeochemical heterogeneity in sediments: A review of available technology and observed evidence. Earth-Science Reviews, 2009. 92(1-2): p. 81-97. 2. Fabricius, A.-L., et al., New Microprofiling and Micro Sampling System for Water Saturated Environmental Boundary Layers. Environmental Science & Technology, 2014.

Ranking Coal Ash Materials for Their Potential to Leach Arsenic and Selenium: Relative Importance of Ash Chemistry and Site Biogeochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwartz, Grace E.; Hower, James C.; Phillips, Allison L.

The chemical composition of coal ash is highly heterogeneous and dependent on the origin of the source coal, combustion parameters, and type and configuration of air pollution control devices. This heterogeneity results in uncertainty in the evaluation of leaching potential of contaminants from coal ash. The goal of this work was to identify whether a single leaching protocol could roughly group high-leaching potential coal ash from low-leaching potential coal ash, with respect to arsenic (As) and selenium (Se). We used four different leaching tests, including the Toxicity Characteristic Leaching Protocol (TCLP), natural pH, aerobic sediment microcosms, and anaerobic sediment microcosmsmore » on 10 different coal ash materials, including fly ash, lime-treated ash, and flue gas desulfurization materials. Leaching tests showed promise in categorizing high and low-leaching potential ash materials, indicating that a single point test could act as a first screening measure to identify high-risk ash materials. However, the amount of contaminant leached varied widely across tests, reflecting the importance of ambient conditions (pH, redox state) on leaching. These results demonstrate that on-site geochemical conditions play a critical role in As and Se mobilization from coal ash, underscoring the need to develop a situation-based risk assessment framework for contamination by coal ash pollutants.« less

Ranking Coal Ash Materials for Their Potential to Leach Arsenic and Selenium: Relative Importance of Ash Chemistry and Site Biogeochemistry

DOE PAGES

Schwartz, Grace E.; Hower, James C.; Phillips, Allison L.; ...

2018-01-23

The chemical composition of coal ash is highly heterogeneous and dependent on the origin of the source coal, combustion parameters, and type and configuration of air pollution control devices. This heterogeneity results in uncertainty in the evaluation of leaching potential of contaminants from coal ash. The goal of this work was to identify whether a single leaching protocol could roughly group high-leaching potential coal ash from low-leaching potential coal ash, with respect to arsenic (As) and selenium (Se). We used four different leaching tests, including the Toxicity Characteristic Leaching Protocol (TCLP), natural pH, aerobic sediment microcosms, and anaerobic sediment microcosmsmore » on 10 different coal ash materials, including fly ash, lime-treated ash, and flue gas desulfurization materials. Leaching tests showed promise in categorizing high and low-leaching potential ash materials, indicating that a single point test could act as a first screening measure to identify high-risk ash materials. However, the amount of contaminant leached varied widely across tests, reflecting the importance of ambient conditions (pH, redox state) on leaching. These results demonstrate that on-site geochemical conditions play a critical role in As and Se mobilization from coal ash, underscoring the need to develop a situation-based risk assessment framework for contamination by coal ash pollutants.« less

Development of Field Guidance for Assessing Feasibility of Intrinsic Bioremediation to Restore Petroleum-Contaminated Soils

DTIC Science & Technology

1994-09-01

Biodegradation, whether aerobic or anaerobic. is an oxidation-reduction or redox reaction . Microbes utilize the redox energy potential from the... redox reaction of organic contaminants and electron acceptors resulting in products such as carbon dioxide and water. According to the figure shown...electron acceptors in the intrinsic bioremediation oxidation/reduction reactions . Redox potentials are from Stumm and Morgan as reported by Bouwer

Thiol Redox and pKa Properties of Mycothiol, the Predominant Low-Molecular-Weight Thiol Cofactor in the Actinomycetes.

PubMed

Sharma, Sunil V; Van Laer, Koen; Messens, Joris; Hamilton, Chris J

2016-09-15

The thiol pKa and standard redox potential of mycothiol, the major low-molecular-weight thiol cofactor in the actinomycetes, are reported. The measured standard redox potential reveals substantial discrepancies in one or more of the other previously measured intracellular parameters that are relevant to mycothiol redox biochemistry. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Geothrix fermentans Secretes Two Different Redox-Active Compounds To Utilize Electron Acceptors across a Wide Range of Redox Potentials

PubMed Central

Mehta-Kolte, Misha G.

2012-01-01

The current understanding of dissimilatory metal reduction is based primarily on isolates from the proteobacterial genera Geobacter and Shewanella. However, environments undergoing active Fe(III) reduction often harbor less-well-studied phyla that are equally abundant. In this work, electrochemical techniques were used to analyze respiratory electron transfer by the only known Fe(III)-reducing representative of the Acidobacteria, Geothrix fermentans. In contrast to previously characterized metal-reducing bacteria, which typically reach maximal rates of respiration at electron acceptor potentials of 0 V versus standard hydrogen electrode (SHE), G. fermentans required potentials as high as 0.55 V to respire at its maximum rate. In addition, G. fermentans secreted two different soluble redox-active electron shuttles with separate redox potentials (−0.2 V and 0.3 V). The compound with the lower midpoint potential, responsible for 20 to 30% of electron transfer activity, was riboflavin. The behavior of the higher-potential compound was consistent with hydrophilic UV-fluorescent molecules previously found in G. fermentans supernatants. Both electron shuttles were also produced when cultures were grown with Fe(III), but not when fumarate was the electron acceptor. This study reveals that Geothrix is able to take advantage of higher-redox-potential environments, demonstrates that secretion of flavin-based shuttles is not confined to Shewanella, and points to the existence of high-potential-redox-active compounds involved in extracellular electron transfer. Based on differences between the respiratory strategies of Geothrix and Geobacter, these two groups of bacteria could exist in distinctive environmental niches defined by redox potential. PMID:22843516

Doxorubicin Delivery Using pH and Redox Dual-Responsive Hollow Nanocapsules with a Cationic Electrostatic Barrier

PubMed Central

Teranishi, Ryoma; Matsuki, Ryota; Yuba, Eiji; Harada, Atsushi; Kono, Kenji

2016-01-01

For the delivery of doxorubicin (DOX), pH and redox dual responsive hollow nanocapsules were prepared through the stabilization of polymer vesicles, which spontaneously formed from polyamidoamine dendron-poly(l-lysine) (PAMAM dendron-PLL), by the introduction of disulfide (SS) bonds between PLLs. The SS-bonded nanocapsules exhibited a very slow release of DOX under an extracellular environment because the cationic PLL membrane acted as an electrostatic barrier against the protonated DOX molecules. However, increasing the glutathione concentration to the intracellular level facilitated the immediate release of DOX through the collapse of nanocapsules by the spontaneous cleavage of SS bonds. SS-bonded nanocapsules also escaped from the endosome by the buffering effect of PAMAM dendrons, and DOX delivery into the cytoplasm was achieved. Furthermore, DOX molecules delivered by SS-bonded nanocapsules exhibited an effective in vitro anticancer effect to HeLa cells. PMID:28042818

Dynamics of Chromium(VI) Removal from Drinking Water by Iron Electrocoagulation.

PubMed

Pan, Chao; Troyer, Lyndsay D; Catalano, Jeffrey G; Giammar, Daniel E

2016-12-20

The potential for new U.S. regulations for Cr(VI) in drinking water have spurred strong interests in improving technologies for Cr(VI) removal. This study examined iron electrocoagulation for Cr(VI) removal at conditions directly relevant to drinking water treatment. Cr(VI) is chemically reduced to less soluble Cr(III) species by the Fe(II) produced from an iron anode, and XANES spectra indicate that the Cr is entirely Cr(III) in solid-phases produced in electrocoagulation. The dynamics of Cr(VI) removal in electrocoagulation at pH 6 and pH 8 at both oxic and anoxic conditions can be described by a new model that incorporates Fe(II) release from the anode and heterogeneous and homogeneous reduction of Cr(VI) by Fe(II). Heterogeneous Cr(VI) reduction by adsorbed Fe(II) was critical to interpreting Cr(VI) removal at pH 6, and the Fe- and Cr-containing EC product was found to catalyze the redox reaction. Dissolved oxygen (DO) did not observably inhibit Cr(VI) removal because Fe(II) reacts with DO more slowly than it does with Cr(VI), and Cr(VI) removal was faster at higher pH. Even in the presence of common groundwater solutes, iron electrocoagulation lowered Cr(VI) concentrations to levels well below California's 10 μg/L.

Redox and Chemical Activities of the Hemes in the Sulfur Oxidation Pathway Enzyme SoxAX*

PubMed Central

Bradley, Justin M.; Marritt, Sophie J.; Kihlken, Margaret A.; Haynes, Kate; Hemmings, Andrew M.; Berks, Ben C.; Cheesman, Myles R.; Butt, Julea N.

2012-01-01

SoxAX enzymes couple disulfide bond formation to the reduction of cytochrome c in the first step of the phylogenetically widespread Sox microbial sulfur oxidation pathway. Rhodovulum sulfidophilum SoxAX contains three hemes. An electrochemical cell compatible with magnetic circular dichroism at near infrared wavelengths has been developed to resolve redox and chemical properties of the SoxAX hemes. In combination with potentiometric titrations monitored by electronic absorbance and EPR, this method defines midpoint potentials (Em) at pH 7.0 of approximately +210, −340, and −400 mV for the His/Met, His/Cys−, and active site His/CysS−-ligated heme, respectively. Exposing SoxAX to S2O42−, a substrate analog with Em ∼−450 mV, but not Eu(II) complexed with diethylene triamine pentaacetic acid (Em ∼−1140 mV), allows cyanide to displace the cysteine persulfide (CysS−) ligand to the active site heme. This provides the first evidence for the dissociation of CysS− that has been proposed as a key event in SoxAX catalysis. PMID:23060437

In vitro susceptibility of thioredoxins and glutathione to redox modification and aging-related changes in skeletal muscle

PubMed Central

Dimauro, Ivan; Pearson, Timothy; Caporossi, Daniela; Jackson, Malcolm J.

2012-01-01

Thioredoxins (Trx's) regulate redox signaling and are localized to various cellular compartments. Specific redox-regulated pathways for adaptation of skeletal muscle to contractions are attenuated during aging, but little is known about the roles of Trx's in regulating these pathways. This study investigated the susceptibility of Trx1 and Trx2 in skeletal muscle to oxidation and reduction in vitro and the effects of aging and contractions on Trx1, Trx2, and thioredoxin reductase (TrxR) 1 and 2 contents and nuclear and cytosolic Trx1 and mitochondrial Trx2 redox potentials in vivo. The proportions of cytosolic and nuclear Trx1 and mitochondrial Trx2 in the oxidized or reduced forms were analyzed using redox Western blotting. In myotubes, the mean redox potentials were nuclear Trx1, −251 mV; cytosolic Trx1, −242 mV; mitochondrial Trx2, −346 mV, data supporting the occurrence of differing redox potentials between cell compartments. Exogenous treatment of myoblasts and myotubes with hydrogen peroxide or dithiothreitol modified glutathione redox status and nuclear and cytosolic Trx1, but mitochondrial Trx2 was unchanged. Tibialis anterior muscles from young and old mice were exposed to isometric muscle contractions in vivo. Aging increased muscle contents of Trx1, Trx2, and TrxR2, but neither aging nor endogenous ROS generated during contractions modified Trx redox potentials, although oxidation of glutathione and other thiols occurred. We conclude that glutathione redox couples in skeletal muscle are more susceptible to oxidation than Trx and that Trx proteins are upregulated during aging, but do not appear to modulate redox-regulated adaptations to contractions that fail during aging. PMID:23022873

Review of the inorganic geochemistry of peats and peatland waters

NASA Astrophysics Data System (ADS)

Shotyk, William

1988-06-01

The major floristic and geochemical differences between bogs, fens, and swamps are summarized, and the most common peat types described. This is followed by a critical, historical review of the literature. The methods used to measure the pH of peatland (mire) waters are examined, and the pH range of various peatland types is reported. In addition, horizontal and vertical pH variations are illustrated, and factors affecting the pH of these waters reviewed. The cause of the low pH of surface waters of Sphagnum bogs (approximately pH 4) is critically investigated, and the relative importance of dissolved CO 2 and other inorganic acids, and organic acids to the low pH is assessed. Cation exchange on the surfaces of Sphagnum mosses is found to be a relatively unimportant acidification mechanism, but important to the chemical ecology of the plants. The redox chemistry of mire waters is described in terms of the geochemistry of such redox indicators as O 2, CO 2, CH 4, CO, H 2, H 2S, SO 42-, native Cu, and siderite (FeCO 3). Published studies of Eh in peatlands are cited, and the problems of Eh measurement and interpretation are explored. The chemical composition of mire waters (major and trace metals, and nonmetallic species) is examined, and factors affecting their composition reported. The abundance and distribution of mineral matter in peats is described, and the occurrence and formation of minerals of Fe (pyrite and other sulphides, siderite, vivianite), Cu (chalcopyrite, native Cu, covellite) and Zn (smithsonite and wurtzite) investigated. The abundance and distribution of major elements (Si, Al, Na, K, Mg, Ca) and trace metals (Ni, V, Cr, Fe, Mn, Cu, U, Zn, Pb) is described, and factors affecting their solubility examined.

Revision of iron(III)-citrate speciation in aqueous solution. Voltammetric and spectrophotometric studies.

PubMed

Vukosav, Petra; Mlakar, Marina; Tomišić, Vladislav

2012-10-01

A detailed study of iron (III)-citrate speciation in aqueous solution (θ=25°C, I(c)=0.7 mol L(-1)) was carried out by voltammetric and UV-vis spectrophotometric measurements and the obtained data were used for reconciled characterization of iron (III)-citrate complexes. Four different redox processes were registered in the voltammograms: at 0.1 V (pH=5.5) which corresponded to the reduction of iron(III)-monocitrate species (Fe:cit=1:1), at about -0.1 V (pH=5.5) that was related to the reduction of FeL(2)(5-), FeL(2)H(4-) and FeL(2)H(2)(3-) complexes, at -0.28 V (pH=5.5) which corresponded to the reduction of polynuclear iron(III)-citrate complex(es), and at -0.4V (pH=7.5) which was probably a consequence of Fe(cit)(2)(OH)(x) species reduction. Reversible redox process at -0.1 V allowed for the determination of iron(III)-citrate species and their stability constants by analyzing E(p) vs. pH and E(p) vs. [L(4-)] dependence. The UV-vis spectra recorded at varied pH revealed four different spectrally active species: FeLH (logβ=25.69), FeL(2)H(2)(3-) (log β=48.06), FeL(2)H(4-) (log β=44.60), and FeL(2)(5-) (log β=38.85). The stability constants obtained by spectrophotometry were in agreement with those determined electrochemically. The UV-vis spectra recorded at various citrate concentrations (pH=2.0) supported the results of spectrophotometric-potentiometric titration. Copyright © 2012 Elsevier B.V. All rights reserved.

Dependence of particle concentration effect on pH and redox for arsenic removal by FeS-coated sand under anoxic conditions.

PubMed

Han, Young-Soo; Demond, Avery H; Gallegos, Tanya J; Hayes, Kim F

2015-09-01

FeS has been recognized as a good scavenger for arsenic under anoxic conditions. To create a suitable adsorbent for flow-through reactors such as permeable reactive barriers, it has been suggested that this material may be coated onto sand. However, previous work on FeS-coated sand has focused on batch reactors, while flow-through reactors usually have higher solid-solution ratios. To ascertain whether differences in the solid-solution ratio (SSR) are important in this system, batch sorption experiments were conducted as a function of pH using As(III) and FeS-coated sands at various solid-solution ratios. The results showed little variation in the distribution coefficient with SSR at pH 7 and 9. However, at pH 5, the results showed lower values of the distribution coefficient at lower SSRs, the reverse of typically reported SSR effects. Measured pe values showed a dependence on SSR, which, when coupled with chemical modeling of the Fe-As-S-H2O system, suggested a change in the removal mechanism with SSR, from adsorption to a reduced Fe(II) oxyhydroxide phase (represented by Fe2(OH)5) to precipitation as As2S3 or AsS. On the other hand, at pH 7 and 9, arsenite adsorption is the most probable removal mechanism regardless of the pe. Thus, this study identified variations in pH and redox conditions, and the removal mechanisms that these parameters govern, as the reason for the apparent SSR effect. Copyright © 2014 Elsevier Ltd. All rights reserved.

Role of multiple substrates (spent mushroom compost, ochre, steel slag, and limestone) in passive remediation of metal-containing acid mine drainage.

PubMed

Molahid, Verma Loretta M; Mohd Kusin, Faradiella; Madzin, Zafira

2018-01-12

The potential of selected materials in treating metal-rich acid mine drainage (AMD) has been investigated in a series of batch experiment. The efficiencies of both single and mixed substrates under two conditions i.e. low- and high-concentration solutions containing heavy metals were evaluated. Synthetic metal-containing AMD was used in the experiments treated using spent mushroom compost (SMC), ochre, steel slag (SS), and limestone. Different ratios of treatment materials were incorporated in the substrate mix and were tested in an anoxic condition. In the batch test, physicochemical parameters (pH, redox potential, total dissolved solids, conductivity, and Ca concentration) and heavy metals (Fe, Mn, Pb, Zn, and Al) were analysed. The mixed substrates have shown satisfactory performance in increasing pH with increasing Ca concentration and removing metals. It has been found that SS and ochre played an important role in the treatment of AMD. The results showed that the mixed substrates SM1 (i.e. 10% SMC mixed with 20% ochre, 30% steel slag, and 40% limestone) and SM2 (i.e. 20% SMC mixed with 30% ochre, 40% steel slag, and 10% limestone) were effective in increasing the pH from as low as 3.5-8.09, and removing heavy metals with more than 90% removal efficiencies.

Insight into the template effect of vesicles on the laccase-catalyzed oligomerization of N-phenyl-1,4-phenylenediamine from Raman spectroscopy and cyclic voltammetry measurements

PubMed Central

Ležaić, Aleksandra Janoševic; Luginbühl, Sandra; Bajuk-Bogdanović, Danica; Pašti, Igor; Kissner, Reinhard; Rakvin, Boris; Walde, Peter; Ćirić-Marjanović, Gordana

2016-01-01

We report about the first Raman spectroscopy study of a vesicle-assisted enzyme-catalyzed oligomerization reaction. The aniline dimer N-phenyl-1,4-phenylenediamine (= p-aminodiphenylamine, PADPA) was oxidized and oligomerized with Trametes versicolor laccase and dissolved O2 in the presence of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) vesicles (80–100 nm diameter) as templates. The conversion of PADPA into oligomeric products, poly(PADPA), was monitored during the reaction by in situ Raman spectroscopy. The results obtained are compared with UV/vis/NIR and EPR measurements. All three complementary methods indicate that at least some of the poly(PADPA) products, formed in the presence of AOT vesicles, resemble the conductive emeraldine salt form of polyaniline (PANI-ES). The Raman measurements also show that structural units different from those of “ordinary” PANI-ES are present too. Without vesicles PANI-ES-like products are not obtained. For the first time, the as-prepared stable poly(PADPA)-AOT vesicle suspension was used directly to coat electrodes (without product isolation) for investigating redox activities of poly(PADPA) by cyclic voltammetry (CV). CV showed that poly(PADPA) produced with vesicles is redox active not only at pH 1.1–as expected for PANI-ES–but also at pH 6.0, unlike PANI-ES and poly(PADPA) synthesized without vesicles. This extended pH range of the redox activity of poly(PADPA) is important for applications. PMID:27561552

Electrochemical Properties of Boron-Doped Fullerene Derivatives for Lithium-Ion Battery Applications.

PubMed

Sood, Parveen; Kim, Ki Chul; Jang, Seung Soon

2018-03-19

The high electron affinity of fullerene C 60 coupled with the rich chemistry of carbon makes it a promising material for cathode applications in lithium-ion batteries. Since boron has one electron less than carbon, the presence of boron on C 60 cages is expected to generate electron deficiency in C 60 , and thereby to enhance its electron affinity. By using density functional theory (DFT), we studied the redox potentials and electronic properties of C 60 and C 59 B. We have found that doping C 60 with one boron atom results in a substantial increase in redox potential from 2.462 V to 3.709 V, which was attributed to the formation of an open shell system. We also investigated the redox and electronic properties of C 59 B functionalized with various redox-active oxygen containing functional groups (OCFGs). For the combination of functionalization with OCFGs and boron doping, it is found that the enhancement of redox potential is reduced, which is mainly attributed to the open shell structure being changed to a closed-shell one. Nevertheless, the redox potentials are still higher than that of pristine C 60 . From the observation that the lowest unoccupied molecular orbital of closed-shell OCFG- functionalized C 59 B is correlated well with the redox potential, it was confirmed that the spin state is crucial to be considered to understand the relationship between electronic structure and redox properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

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

Accelerated redox reaction between chromate and phenolic pollutants during freezing.

PubMed

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

2017-05-05

The redox reaction between 4-chlorophenol (4-CP) and chromate (Cr(VI)) (i.e., the simultaneous oxidation of 4-CP by Cr(VI) and reduction of Cr(VI) by 4-CP) in ice (i.e., at -20°C) was compared with the corresponding reaction in water (i.e., at 25°C). The redox conversion of 4-CP/Cr(VI), which was negligible in water, was significantly accelerated in ice. This accelerated redox conversion of 4-CP/Cr(VI) in ice is ascribed to the freeze concentration effect occurring during freezing, which excludes solutes (i.e., 4-CP and Cr(VI)) and protons from the ice crystals and subsequently concentrates them in the liquid brine. The concentrations of Cr(VI) and protons in the liquid brine were confirmed by measuring the optical image and the UV-vis absorption spectra of cresol red (CR) as a pH indicator of frozen solution. The redox conversion of 4-CP/Cr(VI) was observed in water when the concentrations of 4-CP/protons or Cr(VI)/protons increased by 100/1000-fold. These results corroborate the freeze concentration effect as the reason for the accelerated redox conversion of 4-CP/Cr(VI) in ice. The redox conversion of various phenolic pollutants/Cr(VI) and 4-CP/Cr(VI) in real wastewater was successfully achieved in ice, which verifies the environmental relevance and importance of freezing-accelerated redox conversion of phenolic pollutants/Cr(VI) in cold regions. Copyright © 2017 Elsevier B.V. All rights reserved.

Mechanisms involved in phosphorus mobility at sediment/water interface under redox oscillations in dam-reservoir context

NASA Astrophysics Data System (ADS)

Rapin, Anne; Grybos, Malgorzata; Rabiet, Marion; Kestens, Tim; Mourier, Brice; Deluchat, Veronique

2017-04-01

The construction of dams, in response to the growing human demand of water and electricity, leads to the perturbation of several natural biogeochemical cycles, including phosphorus (P). Given its high affinity for solid phases, P tends to accumulate with the sediments in dam-reservoirs. Since the sedimentary P may contribute to water eutrophication, attention should be paid to better understand the parameters, conditions and mechanisms controlling the release of P at the sediment/water interface in such a system. The mobility of P at sediment/water interface closely depends on bio-physico-chemical conditions (redox potential, pH, temperature). Champsanglard dam-reservoir (19.5 m height; 55 ha; Creuse, France) was constructed in 1982 and is annually subject to bathing bans caused by the development of cyanobacteria, although the surface water is classified by the EU Water Framework Directive as being of medium quality regarding total dissolved P. The sediments accumulated in this reservoir are relatively rich in P (1.81 ± 0.22 mgP/gDW), in the silt-sand fraction and characterized by high organic matter content (21 ± 0.1 %). The development of temporary anoxia during summer in hypolimnion and P distribution in the sediments (66% of P associated with amorphous Mn/Fe-oxy-hydroxydes) highlight the importance of the redox potential variation on P mobility. In this context, incubation experiments were conducted to evaluate the role of alternation between aerobic and anaerobic conditions on P sediment mobility. Surface sediments (Φ<2 mm) were incubated with a synthetic solution simulating the chemistry of Champsanglard reservoir water and submitted to two successive aerated and non-aerated phases. Physico-chemical composition (pH, Eh, P-PO43-, FeII, Mn, NO3-, SO42- and dissolved organic carbon (DOC)) and organic matter aromaticity (SUVA254) of the supernatant were monitored all along the incubation. The results showed that the development of anaerobic conditions (decrease of redox potential, NO3- and SO42- and increase of FeII and Mn concentrations) during the two non-aerated phases induces the release of P to the solution. However, during the second anaerobic phase, a higher release of 57 % P- PO43- was observed (8.7 ± 0.5 mgP/L for the second phase to 6.4 ± 0.5 mgP/L for the first one). During the first anaerobic phase, P-PO43- dynamic was correlated with the release of FeII and Mn suggesting that the reductive dissolution of Mn/Fe-oxy-hydroxydes was the main mechanism controlling the P mobility. However, in the second anaerobic phase, Mn and FeII concentrations were much lower (respectively of 24 % and 56 %) than in the first anaerobic phase. SUVA254 index showed that organic compounds released in the first cycle were less aromatic than in the second cycle and exhibited the geochemical characteristics of microbial metabolites (in opposition to humic substances in the second cycle). According to Pan et al. (2016), aromatic organic matter could limit reductive dissolution of Fe-oxyhydroxydes and involve competition for P sorption sites. This experiment highlighted that organic matter quality plays together with Mn/Fe-oxy-hydroxydes an important role in P mobility at sediment/water interface in dam-reservoirs. Keywords: Phosphorus; Sediment; Redox-oscillations; Dam reservoir; Mechanisms

Profiling Redox and Energy Coenzymes in Whole Blood, Tissue and Cells Using NMR Spectroscopy.

PubMed

Gowda, G A Nagana

2018-05-14

Coenzymes of cellular redox reactions and cellular energy, as well as antioxidants mediate biochemical reactions fundamental to the functioning of all living cells. Conventional analysis methods lack the opportunity to evaluate these important redox and energy coenzymes and antioxidants in a single step. Major coenzymes include redox coenzymes: NAD⁺ (oxidized nicotinamide adenine dinucleotide), NADH (reduced nicotinamide adenine dinucleotide), NADP⁺ (oxidized nicotinamide adenine dinucleotide phosphate) and NADPH (reduced nicotinamide adenine dinucleotide phosphate); energy coenzymes: ATP (adenosine triphosphate), ADP (adenosine diphosphate) and AMP (adenosine monophosphate); and antioxidants: GSSG (oxidized glutathione) and GSH (reduced glutathione). We show here that a simple ¹H NMR experiment can measure these coenzymes and antioxidants in tissue and whole blood apart from a vast pool of other metabolites. In addition, focused on the goal of identification of coenzymes in subcellular fractions, we demonstrate analysis of coenzymes in the cytoplasm using breast cancer cells. Owing to their unstable nature, or low concentrations, most of the coenzymes either evade detection or lose their integrity when established sample preparation and analysis methods are used. To overcome this challenge, here we describe the development of new methods to detect these molecules without affecting the integrity of other metabolites. We used an array of 1D and 2D NMR methods, chemical shift databases, pH measurements and spiking with authentic compounds to establish the identity of peaks for the coenzymes and antioxidants in NMR spectra. Interestingly, while none of the coenzymes and antioxidants were detected in plasma, they were abundant in whole blood. Considering that the coenzymes and antioxidants represent a sensitive measure of human health and risk for numerous diseases, the presented NMR methods to measure them in one step potentially open new opportunities in the metabolomics field.

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

NASA Technical Reports Server (NTRS)

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

2004-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

Tumor pHe-triggered charge-reversal and redox-responsive nanoparticles for docetaxel delivery in hepatocellular carcinoma treatment

NASA Astrophysics Data System (ADS)

Chen, Fengqian; Zhang, Jinming; Wang, Lu; Wang, Yitao; Chen, Meiwan

2015-09-01

The insufficient cellular uptake of nanocarriers and their slow drug release have become major obstacles for achieving satisfactory anticancer outcomes in nano-medicine therapy. Because of the slightly acidic extracellular environment (pHe ~ 6.5) and a higher glutathione (GSH) concentration (approximately 10 mM) in tumor tissue/cells, we firstly designed a novel d-α-tocopheryl polyethylene glycol 1000-poly(β-amino ester) block copolymer containing disulfide linkages (TPSS). TPSS nanoparticles (NPs) with pH- and redox-sensitive behaviors were developed for on-demand delivery of docetaxel (DTX) in hepatocellular carcinoma. DTX/TPSS NPs exhibited sensitive surface charge reversal from -47.6 +/- 2.5 mV to +22.5 +/- 3.2 mV when the pH decreased from 7.4 to 6.5, to simulate the pHe. Meanwhile, anabatic drug release of DTX/TPSS NPs was observed in PBS buffer (pH 6.5, 10 mM GSH). Due to the synergism between the pHe-triggered charge reversal and the redox-triggered drug release, enhanced drug uptake and anticancer efficacy were observed in HepG2 and SMMC 7721 cells treated with DTX/TPSS NPs. The positively charged NPs exhibited a stronger inhibitory effect on cell proliferation, promoted cell cycle arrest in the G2/M phase, and increased the rate of apoptosis. More importantly, based on the higher tumor accumulation of TPSS vehicles in vivo, a significant suppression of tumor growth, but without side-effects, was observed when DTX/TPSS NPs were injected intravenously into HepG2 xenograft tumor-bearing mice. Collectively, these results demonstrate that the newly developed dual-functional TPSS copolymer may be utilized as a drug delivery system for anticancer therapy.The insufficient cellular uptake of nanocarriers and their slow drug release have become major obstacles for achieving satisfactory anticancer outcomes in nano-medicine therapy. Because of the slightly acidic extracellular environment (pHe ~ 6.5) and a higher glutathione (GSH) concentration (approximately 10 mM) in tumor tissue/cells, we firstly designed a novel d-α-tocopheryl polyethylene glycol 1000-poly(β-amino ester) block copolymer containing disulfide linkages (TPSS). TPSS nanoparticles (NPs) with pH- and redox-sensitive behaviors were developed for on-demand delivery of docetaxel (DTX) in hepatocellular carcinoma. DTX/TPSS NPs exhibited sensitive surface charge reversal from -47.6 +/- 2.5 mV to +22.5 +/- 3.2 mV when the pH decreased from 7.4 to 6.5, to simulate the pHe. Meanwhile, anabatic drug release of DTX/TPSS NPs was observed in PBS buffer (pH 6.5, 10 mM GSH). Due to the synergism between the pHe-triggered charge reversal and the redox-triggered drug release, enhanced drug uptake and anticancer efficacy were observed in HepG2 and SMMC 7721 cells treated with DTX/TPSS NPs. The positively charged NPs exhibited a stronger inhibitory effect on cell proliferation, promoted cell cycle arrest in the G2/M phase, and increased the rate of apoptosis. More importantly, based on the higher tumor accumulation of TPSS vehicles in vivo, a significant suppression of tumor growth, but without side-effects, was observed when DTX/TPSS NPs were injected intravenously into HepG2 xenograft tumor-bearing mice. Collectively, these results demonstrate that the newly developed dual-functional TPSS copolymer may be utilized as a drug delivery system for anticancer therapy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04612b

Redox signaling in acute pancreatitis

PubMed Central

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

Host-pathogen redox dynamics modulate Mycobacterium tuberculosis pathogenesis.

PubMed

Pacl, Hayden T; Reddy, Vineel P; Saini, Vikram; Chinta, Krishna C; Steyn, Adrie J C

2018-07-01

Mycobacterium tuberculosis (Mtb), the causative agent of tuberculosis, encounters variable and hostile environments within the host. A major component of these hostile conditions is reductive and oxidative stresses induced by factors modified by the host immune response, such as oxygen tension, NO or CO gases, reactive oxygen and nitrogen intermediates, the availability of different carbon sources and changes in pH. It is therefore essential for Mtb to continuously monitor and appropriately respond to the microenvironment. To this end, Mtb has developed various redox-sensitive systems capable of monitoring its intracellular redox environment and coordinating a response essential for virulence. Various aspects of Mtb physiology are regulated by these systems, including drug susceptibility, secretion systems, energy metabolism and dormancy. While great progress has been made in understanding the mechanisms and pathways that govern the response of Mtb to the host's redox environment, many questions in this area remain unanswered. The answers to these questions are promising avenues for addressing the tuberculosis crisis.

Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti=NAd (Ad = adamantyl)

DOE PAGES

Heins, Spencer P.; Wolczanski, Peter T.; Cundari, Thomas R.; ...

2017-03-06

Application of the diamide, diimine {–CH=N(1,2-C 6H 4)N(2,6- iPr 2-C 6H 3)} 2 m ((dadi) m) ligand to titanium provided adducts (dadi)TiL x (1-L x; L x = THF, PMe 2Ph, (CNMe) 2), which possess the redox formulation [(dadi) 4-]Ti(IV)L x, and 22 πe - (4n + 2). Related complexes containing titanium-ligand multiple bonds, (dadi)Ti=X (2=X; X = O, NAd), exhibit a different dadi redox state, [(dadi) 2-]Ti(IV)X, consistent with 20 πe - (4n). The Redox Non-Innocence (RNI) displayed by dadi m impedes binding by CO, and permits catalytic conversion of AdN 3 + CO to AdNCO + N 2.more » Kinetics measurements support carbonylation of 2=NAd as the rate determining step. Finally, structural and computational evidence for the observed RNI is provided.« less

Control of electron transfer in the cytochrome system of mitochondria by pH, transmembrane pH gradient and electrical potential. The cytochromes b-c segment.

PubMed

Papa, S; Lorusso, M; Izzo, G; Capuano, F

1981-02-15

1. A study is presented of the effects of pH, transmembrane pH gradient and electrical potential on oxidoreductions of b and c cytochromes in ox heart mitochondria and 'inside-out' submitochondrial particles. 2. Kinetic analysis shows that, in mitochondria at neutral pH, there is a restraint on the aerobic oxidation of cytochrome b566 with respect to cytochrome b562. Valinomycin plus K+ accelerates cytochrome b566 oxidation and retards net oxidation of cytochrome b562. At alkaline pH the rate of cytochrome b566 oxidation approaches that of cytochrome b562 and the effects of valinomycin on b cytochromes are impaired. 3. At slightly acidic pH, oxygenation of antimycin-supplemented mitochondria causes rapid reduction of cytochrome b566 and small delayed reduction of cytochrome b562. Valinomycin or a pH increase in the medium promote reduction of cytochrome b562 and decrease net reduction of cytochrome b566. 4. Addition of valinomycin to mitochondria and submitochondrial particles in the respiring steady state causes, at pH values around neutrality, preferential oxidation of cytochrome b566 with respect to cytochrome b562. The differential effect of valinomycin on oxidation of cytochromes b566 and b562 is enhanced by substitution of 1H2O of the medium with 2H2O and tends to disappear as the pH of the medium is raised to alkaline values. 5. Nigericin addition in the aerobic steady state causes, both in mitochondria and submitochondrial particles, preferential oxidation of cytochrome b562 with respect to cytochrome b566. This is accompanied by c cytochrome oxidation in mitochondria but c cytochrome reduction in submitochondrial particles. 6. In mitochondria as well as in submitochondrial particles, the aerobic transmembrane potential (delta psi) does not change by raising the pH of the external medium from neutrality to alkalinity. The transmembrane pH gradient (delta pH) on the other hand, decrease slightly. 7. The results presented provide evidence that the delta psi component of the aerobic delta microH+ (the sum of the proton chemical and electrical activities) exerts a pH-dependent constraint on forward electron flow from cytochrome b566 to cytochrome b562. This effect is explained as a consequence of anisotropic location of cytochromes b566 and b562 in the membrane and the pH-dependence of the redox function of these cytochromes. Transmembrane delta pH, on the other hand, exerts control on electron flow from cytochrome b562 to c cytochromes.

Real-Time Imaging of the Bacillithiol Redox Potential in the Human Pathogen Staphylococcus aureus Using a Genetically Encoded Bacilliredoxin-Fused Redox Biosensor.

PubMed

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 (H 2 O 2 ) 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.

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

PubMed

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

2013-11-01

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

Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl reduction studied by titration and XAFS

NASA Astrophysics Data System (ADS)

Boyanov, Maxim I.; O'Loughlin, Edward J.; Roden, Eric E.; Fein, Jeremy B.; Kemner, Kenneth M.

2007-04-01

The chemical reduction of U(VI) by Fe(II) is a potentially important pathway for immobilization of uranium in subsurface environments. Although the presence of surfaces has been shown to catalyze the reaction between Fe(II) and U(VI) aqueous species, the mechanism(s) responsible for the enhanced reactivity remain ambiguous. To gain further insight into the U-Fe redox process at a complexing, non-conducting surface that is relevant to common organic phases in the environment, we studied suspensions containing combinations of 0.1 mM U(VI), 1.0 mM Fe(II), and 4.2 g/L carboxyl-functionalized polystyrene microspheres. Acid-base titrations were used to monitor protolytic reactions, and Fe K-edge and U L-edge X-ray absorption fine structure spectroscopy was used to determine the valence and atomic environment of the adsorbed Fe and U species. In the Fe + surface carboxyl system, a transition from monomeric to oligomeric Fe(II) surface species was observed between pH 7.5 and pH 8.4. In the U + surface carboxyl system, the U(VI) cation was adsorbed as a mononuclear uranyl-carboxyl complex at both pH 7.5 and 8.4. In the ternary U + Fe + surface carboxyl system, U(VI) was not reduced by the solvated or adsorbed Fe(II) at pH 7.5 over a 4-month period, whereas complete and rapid reduction to U(IV) nanoparticles occurred at pH 8.4. The U(IV) product reoxidized rapidly upon exposure to air, but it was stable over a 4-month period under anoxic conditions. Fe atoms were found in the local environment of the reduced U(IV) atoms at a distance of 3.56 Å. The U(IV)-Fe coordination is consistent with an inner-sphere electron transfer mechanism between the redox centers and involvement of Fe(II) atoms in both steps of the reduction from U(VI) to U(IV). The inability of Fe(II) to reduce U(VI) in solution and at pH 7.5 in the U + Fe + carboxyl system is explained by the formation of a transient, "dead-end" U(V)-Fe(III) complex that blocks the U(V) disproportionation pathway after the first electron transfer. The increased reactivity at pH 8.4 relative to pH 7.5 is explained by the reaction of U(VI) with an Fe(II) oligomer, whereby the bonds between Fe atoms facilitate the transfer of a second electron to the hypothetical U(V)-Fe(III) intermediate. We discuss how this mechanism may explain the commonly observed higher efficiency of uranyl reduction by adsorbed or structural Fe(II) relative to aqueous Fe(II).

Electrochemical behavior of meso-substituted iron porphyrins in alkaline aqueous media

NASA Astrophysics Data System (ADS)

Berezina, N. M.; Bazanov, M. I.; Maksimova, A. A.; Semeikin, A. S.

2017-12-01

The effect meso-substitution in iron porphyrin complexes has on their redox behavior in alkaline aqueous solutions is studied via cyclic voltammetry. The voltammetric features of the reduction of iron pyridylporphyrins suggest that the sites of electron transfer lie at the ligand, the metal ion, and the pyridyl moieties. The electron transfer reactions between the different forms of these compounds, including the oxygen reduction reaction they mediate, are outlined to show the sequence and potential ranges in which they occur in alkaline aqueous media. Under our experimental conditions, the iron porphyrins exist as μ-oxo dimmers whose activity for the electrocatalytic reduction of oxygen displays a considerable dependence on the nature of the substitutents and nitrogen isomerization (for pyridylporphyrins) and grows in the order (Fe( ms-Ph)4P)2O, (Fe[ ms-(Py-3)Ph3]P)2O, (Fe[ ms-(Py-4)4]P)2O, and (Fe[ ms-(Py-3)4]P)2O.

Characterization of cellulolytic enzyme system of Schizophyllum commune mutant and evaluation of its efficiency on biomass hydrolysis.

PubMed

Sornlake, Warasirin; Rattanaphanjak, Phatcharamon; Champreda, Verawat; Eurwilaichitr, Lily; Kittisenachai, Suthathip; Roytrakul, Sittiruk; Fujii, Tatsuya; Inoue, Hiroyuki

2017-07-01

Schizophyllum commune is a basidiomycete equipped with an efficient cellulolytic enzyme system capable of growth on decaying woods. In this study, production of lignocellulose-degrading enzymes from S. commune mutant G-135 (SC-Cel) on various cellulosic substrates was examined. The highest cellulase activities including CMCase, FPase, and β-glucosidase were obtained on Avicel-PH101 while a wider range of enzymes attacking non-cellulosic polysaccharides and lignin were found when grown on alkaline-pretreated biomass. Proteomic analysis of SC-Cel also revealed a complex enzyme system comprising seven glycosyl hydrolase families with an accessory carbohydrate esterase, polysaccharide lyase, and auxiliary redox enzymes. SC-Cel obtained on Avicel-PH101 effectively hydrolyzed all agricultural residues with the maximum glucan conversion of 98.0% using corn cobs with an enzyme dosage of 5 FPU/g-biomass. The work showed potential of SC-Cel on hydrolysis of various herbaceous biomass with enhanced efficiency by addition external β-xylosidase.

Development of an activated carbon-packed microbial bioelectrochemical system for azo dye degradation.

PubMed

Cardenas-Robles, Arely; Martinez, Eduardo; Rendon-Alcantar, Idelfonso; Frontana, Carlos; Gonzalez-Gutierrez, Linda

2013-01-01

A microbial bioelectrochemical reactor (BER) was employed for the degradation of azo dyes without the use of an external electron donor, using activated carbon (GAC) as a redox mediator. Contribution of pH values, open circuit potential (OCP), dye concentration and applied current were individually studied. A batch system and an upflow fixed bed bioreactor were built for analyzing the effect of the applied current on biodegradation of the azo dye Reactive Red 272. The presence of GAC (20% w/v) regulated both pH and OCP values in solution and led to a removal efficiency of 98%. Cyclic voltammetry results indicate a dependence of the electron transfer mechanism with the concentration of the azo compound. With these results, a continuous flow reactor operating with J=0.045 mA cm(-2), led to removal rates of 95% (± 3.5%) in a half-residence time of 1 hour. Copyright © 2012 Elsevier Ltd. All rights reserved.

Electroactive Film of Myoglobin Incorporated in a 3D-porous Calcium Alginate Film with Polyvinyl Alcohol, Glycerin and Gelatin.

PubMed

Zheng, Xueqin; Sun, Hong; Hou, Shifeng

2015-01-01

In this work, an electroactive porous Mb-CA's composite film was fabricated by incorporating myoglobin (Mb) in a three-dimension (3D) porous calcium alginate (CA) film with polyvinyl alcohol, glycerol, and gelatin. The porous Mb-CA's film modified electrodes exhibited a pair of well-defined, quasi-reversible cyclic voltammetric (CV) peaks at about -0.37 V vs. SCE in pH 7.0 buffers, characteristic of Mb heme Fe((III))/Fe((II)) redox couples. The electrochemical parameters, such as formal potentials (E(o')) and apparent heterogeneous electron-transfer rate constants (ks), were estimated by square-wave voltammetry with nonlinear regression analysis. The porous CA's composite film could form hydrogel in aqueous solution. The positions of the Soret absorbance band suggest that Mb in the CA's composite film kept its native states in the medium pH range. Hydrogen peroxide, oxygen, and nitrite were electrochemically catalyzed by the Mb-CA's composite film with significant lowering of the reduction overpotential.

Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides

DOE PAGES

Gent, William E.; Lim, Kipil; Liang, Yufeng; ...

2017-12-01

© 2017 The Author(s). Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li 1.17-x Ni 0.21 Co 0.08 Mn 0.54 O 2 , these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by >more » 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.« less

Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gent, William E.; Lim, Kipil; Liang, Yufeng

© 2017 The Author(s). Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li 1.17-x Ni 0.21 Co 0.08 Mn 0.54 O 2 , these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by >more » 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.« less

Efficacy of β-lactam/β-lactamase inhibitor combination is linked to WhiB4-mediated changes in redox physiology of Mycobacterium tuberculosis.

PubMed

Mishra, Saurabh; Shukla, Prashant; Bhaskar, Ashima; Anand, Kushi; Baloni, Priyanka; Jha, Rajiv Kumar; Mohan, Abhilash; Rajmani, Raju S; Nagaraja, Valakunja; Chandra, Nagasuma; Singh, Amit

2017-05-26

Mycobacterium tuberculosis ( Mtb ) expresses a broad-spectrum β-lactamase (BlaC) that mediates resistance to one of the highly effective antibacterials, β-lactams. Nonetheless, β-lactams showed mycobactericidal activity in combination with β-lactamase inhibitor, clavulanate (Clav). However, the mechanistic aspects of how Mtb responds to β-lactams such as Amoxicillin in combination with Clav (referred as Augmentin [AG]) are not clear. Here, we identified cytoplasmic redox potential and intracellular redox sensor, WhiB4, as key determinants of mycobacterial resistance against AG. Using computer-based, biochemical, redox-biosensor, and genetic strategies, we uncovered a functional linkage between specific determinants of β-lactam resistance (e.g. β-lactamase) and redox potential in Mtb . We also describe the role of WhiB4 in coordinating the activity of β-lactamase in a redox-dependent manner to tolerate AG. Disruption of WhiB4 enhances AG tolerance, whereas overexpression potentiates AG activity against drug-resistant Mtb . Our findings suggest that AG can be exploited to diminish drug-resistance in Mtb through redox-based interventions.

Fluorescence Lifetime Imaging Microscopy (FLIM) of quantum dots in living cells

NASA Astrophysics Data System (ADS)

Nadeau, Jay; Carlini, Lina

2013-02-01

Fluorescence lifetime imaging microscopy (FLIM) is an emerging imaging technique that can indicate environmental factors such as pH and redox potential by the effect of these factors on the fluorescence lifetimes of fluorophores. Semiconductor quantum dots (QDs) are highly sensitive to environment and so are ideal for use in FLIM, although certain experimental parameters must be carefully considered for QD imaging to account for their long lifetimes and two-photon behavior. We image the uptake of three types of QDs in cultured fibroblasts and show some preliminary results on the effects of endosomes and lysosomes on QD lifetimes. These results indicate the feasibility of FLIM for studies using QDs in live cells.

Effect of H+ ion activity and Ca2+ on the toxicity of metals in the environment.

PubMed Central

Hutchinson, T C; Collins, F W

1978-01-01

The role of acidity in determining and restricting plant distribution and performance is discussed. In soils especially, a key effect of H+ ion concentration is on the solubility of potentially toxic heavy metals such as aluminum, managenese, zinc, iron, copper, and nickel. Al has been reported from many studies since the 1920's as the key determining toxic factor in acid soils. Some acid-tolerant species have been shown to be especially tolerant of Al, and mechanisms of tolerance have been suggested. Mn is also a commonly toxic factor at soil pH less than 5.0. Calcium has been shown to alleviate Mn toxicity. Low pH soils are also generally low in Ca, K, Na, and P; all essential major elements for plant growth. In lakes and marine situations acidic waters are uncommon as the waters are buffered. Calcium is again ameliorative of metal toxicities. The pH, redox, and valency state are critical in determining nutrient availability and metal speciation. Recent increases in the H+ ion content of precipitation have caused increased acidities of freshwater lakes in Scandinavia and eastern North America, which have depleted biota, including fish populations. PMID:31277

Chemically grafted polymeric filters for chemical sensors: Hyperbranched poly(acrylic acid) films incorporating {Beta}-cyclodextrin receptors and amine-functionalized filter layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dermody, D.L.; Peez, R.F.; Bergbreiter, D.E.

1999-02-02

The authors report a new molecular-filter approach for enhancing the selectivity of chemical sensors. Specifically, they describe electrochemical sensors prepared from Au electrodes coated with {beta}-cyclodextrin-functionalized, hyperbranched poly(acrylic acid)(PAA) films capped with a chemically grafted, ultrathin polyamine layer. The hyperbranched PAA film is a highly functionalized framework for covalently binding the {beta}-cyclodextrin molecular receptors. The thin, grafted polyamine overlayer acts as a pH-sensitive molecular filter that selectively passes suitably charged analytes. Poly(amidoamine) dendrimers or poly-D-lysine is used as 10--15-nm-thick filter layers. The results show that at low pH, when the polyamines are fully protonated, positively charged redox probe molecules, suchmore » as benzyl viologen (BV), do not permeate the filter layer. However, at high pH, when the filter layer is uncharged, BV penetrates the filter layer and is reduced at the electrode. The opposite pH dependence is observed for negatively charged redox molecules such as anthraquinone-2-sulfonate (AQS). Both BV and AQS specifically interact with the {beta}-cyclodextrin receptors underlying the polyamine filter layers.« less

Hexanuclear gold(I) phosphide complexes as platforms for multiple redox-active ferrocenyl units.

PubMed

Lee, Terence Kwok-Ming; Cheng, Eddie Chung-Chin; Zhu, Nianyong; Yam, Vivian Wing-Wah

2014-01-03

The synthesis, X-ray crystal structures, electrochemical, and spectroscopic studies of a series of hexanuclear gold(I) μ(3)-ferrocenylmethylphosphido complexes stabilized by bridging phosphine ligands, [Au(6)(P-P)(n)(Fc-CH(2)-P)(2)][PF(6)](2) (n=3, P-P=dppm (bis(diphenylphosphino)methane) (1), dppe (1,2-bis(diphenylphosphino)ethane) (2), dppp (1,3-bis(diphenylphosphino)propane) (3), Ph(2)PN(C(3)H(7))-PPh(2) (4), Ph(2)PN(Ph-CH(3)-p)PPh(2) (5), dppf (1,1′-bis(diphenylphosphino)ferrocene) (6); n=2, P-P=dpepp (bis(2-diphenylphosphinoethyl)phenylphosphine) (7)), as platforms for multiple redox-active ferrocenyl units, are reported. The investigation of the structural changes of the clusters has been probed by introducing different bridging phosphine ligands. This class of gold(I) μ(3)-ferrocenylmethylphosphido complexes has been found to exhibit one reversible oxidation couple, suggestive of the absence of electronic communication between the ferrocene units through the Au(6)P(2) cluster core, providing an understanding of the electronic properties of the hexanuclear Au(I) cluster linkage. The present complexes also serve as an ideal system for the design of multi-electron reservoir and molecular battery systems.

Manufacture and application of RuO2 solid-state metal-oxide pH sensor to common beverages.

PubMed

Lonsdale, W; Wajrak, M; Alameh, K

2018-04-01

A new reproducible solid-state metal-oxide pH sensor for beverage quality monitoring is developed and characterised. The working electrode of the developed pH sensor is based on the use of laser-etched sputter-deposited RuO 2 on Al 2 O 3 substrate, modified with thin layers of sputter-deposited Ta 2 O 5 and drop-cast Nafion for minimisation of redox interference. The reference electrode is manufactured by further modifying a working electrode with a porous polyvinyl butyral layer loaded with fumed SiO 2 . The developed pH sensor shows excellent performance when applied to a selection of beverage samples, with a measured accuracy within 0.08 pH of a commercial glass pH sensor. Copyright © 2017 Elsevier B.V. All rights reserved.

Reverse Engineering Applied to Red Human Hair Pheomelanin Reveals Redox-Buffering as a Pro-Oxidant Mechanism

PubMed Central

Kim, Eunkyoung; Panzella, Lucia; Micillo, Raffaella; Bentley, William E.; Napolitano, Alessandra; Payne, Gregory F.

2015-01-01

Pheomelanin has been implicated in the increased susceptibility to UV-induced melanoma for people with light skin and red hair. Recent studies identified a UV-independent pathway to melanoma carcinogenesis and implicated pheomelanin’s pro-oxidant properties that act through the generation of reactive oxygen species and/or the depletion of cellular antioxidants. Here, we applied an electrochemically-based reverse engineering methodology to compare the redox properties of human hair pheomelanin with model synthetic pigments and natural eumelanin. This methodology exposes the insoluble melanin samples to complex potential (voltage) inputs and measures output response characteristics to assess redox activities. The results demonstrate that both eumelanin and pheomelanin are redox-active, they can rapidly (sec-min) and repeatedly redox-cycle between oxidized and reduced states, and pheomelanin possesses a more oxidative redox potential. This study suggests that pheomelanin’s redox-based pro-oxidant activity may contribute to sustaining a chronic oxidative stress condition through a redox-buffering mechanism. PMID:26669666

Reverse Engineering Applied to Red Human Hair Pheomelanin Reveals Redox-Buffering as a Pro-Oxidant Mechanism.

PubMed

Kim, Eunkyoung; Panzella, Lucia; Micillo, Raffaella; Bentley, William E; Napolitano, Alessandra; Payne, Gregory F

2015-12-16

Pheomelanin has been implicated in the increased susceptibility to UV-induced melanoma for people with light skin and red hair. Recent studies identified a UV-independent pathway to melanoma carcinogenesis and implicated pheomelanin's pro-oxidant properties that act through the generation of reactive oxygen species and/or the depletion of cellular antioxidants. Here, we applied an electrochemically-based reverse engineering methodology to compare the redox properties of human hair pheomelanin with model synthetic pigments and natural eumelanin. This methodology exposes the insoluble melanin samples to complex potential (voltage) inputs and measures output response characteristics to assess redox activities. The results demonstrate that both eumelanin and pheomelanin are redox-active, they can rapidly (sec-min) and repeatedly redox-cycle between oxidized and reduced states, and pheomelanin possesses a more oxidative redox potential. This study suggests that pheomelanin's redox-based pro-oxidant activity may contribute to sustaining a chronic oxidative stress condition through a redox-buffering mechanism.

Regulatory mechanisms of thiol-based redox sensors: lessons learned from structural studies on prokaryotic redox sensors.

PubMed

Lee, Sang Jae; Kim, Dong-Gyun; Lee, Kyu-Yeon; Koo, Ji Sung; Lee, Bong-Jin

2018-05-17

Oxidative stresses, such as reactive oxygen species, reactive electrophilic species, reactive nitrogen species, and reactive chlorine species, can damage cellular components, leading to cellular malfunction and death. In response to oxidative stress, bacteria have evolved redox-responsive sensors that enable them to simultaneously monitor and eradicate potential oxidative stress. Specifically, redox-sensing transcription regulators react to oxidative stress by means of modifying the thiol groups of cysteine residues, functioning as part of an efficient survival mechanism for many bacteria. In general, oxidative molecules can induce changes in the three-dimensional structures of redox sensors, which, in turn, affects the transcription of specific genes in detoxification pathways and defense mechanisms. Moreover, pathogenic bacteria utilize these redox sensors for adaptation and to evade subsequent oxidative attacks from host immune defense. For this reason, the redox sensors of pathogenic bacteria are potential antibiotic targets. Understanding the regulatory mechanisms of thiol-based redox sensors in bacteria will provide insight and knowledge into the discovery of new antibiotics.

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

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

Paraquat-Melanin Redox-Cycling: Evidence from Electrochemical Reverse Engineering.

PubMed

Kim, Eunkyoung; Leverage, W Taylor; Liu, Yi; Panzella, Lucia; Alfieri, Maria Laura; Napolitano, Alessandra; Bentley, William E; Payne, Gregory F

2016-08-17

Parkinson's disease is a neurodegenerative disorder associated with oxidative stress and the death of melanin-containing neurons of the substantia nigra. Epidemiological evidence links exposure to the pesticide paraquat (PQ) to Parkinson's disease, and this link has been explained by a redox cycling mechanism that induces oxidative stress. Here, we used a novel electrochemistry-based reverse engineering methodology to test the hypothesis that PQ can undergo reductive redox cycling with melanin. In this method, (i) an insoluble natural melanin (from Sepia melanin) and a synthetic model melanin (having a cysteinyldopamine-melanin core and dopamine-melanin shell) were entrapped in a nonconducting hydrogel film adjacent to an electrode, (ii) the film-coated electrode was immersed in solutions containing PQ (putative redox cycling reductant) and a redox cycling oxidant (ferrocene dimethanol), (iii) sequences of input potentials (i.e., voltages) were imposed to the underlying electrode to systematically engage reductive and oxidative redox cycling, and (iv) output response currents were analyzed for signatures of redox cycling. The response characteristics of the PQ-melanin systems to various input potential sequences support the hypothesis that PQ can directly donate electrons to melanin. This observation of PQ-melanin redox interactions demonstrates an association between two components that have been individually linked to oxidative stress and Parkinson's disease. Potentially, melanin's redox activity could be an important component in understanding the etiology of neurological disorders such as Parkinson's disease.

Pyruvate dehydrogenase complex and nicotinamide nucleotide transhydrogenase constitute an energy consuming redox circuit

PubMed Central

Fisher-Wellman, Kelsey H.; Lin, Chien-Te; Ryan, Terence E.; Reese, Lauren R.; Gilliam, Laura A. A.; Cathey, Brook L.; Lark, Daniel S.; Smith, Cody D.; Muoio, Deborah M.; Neufer, P. Darrell

2015-01-01

SUMMARY Cellular proteins rely on reversible redox reactions to establish and maintain biological structure and function. How redox catabolic (NAD+:NADH) and anabolic (NADP+:NADPH) processes integrate during metabolism to maintain cellular redox homeostasis however is unknown. The present work identifies a continuously cycling, mitochondrial membrane potential-dependent redox circuit between the pyruvate dehydrogenase complex (PDHC) and nicotinamide nucleotide transhydrogenase (NNT). PDHC is shown to produce H2O2 in relation to reducing pressure within the complex. The H2O2 produced however is effectively masked by a continuously cycling redox circuit that links, via glutathione/thioredoxin, to NNT, which catalyzes the regeneration of NADPH from NADH at the expense of the mitochondrial membrane potential. The net effect is an automatic fine tuning of NNT-mediated energy expenditure to metabolic balance at the level of PDHC. In mitochondria, genetic or pharmacological disruptions in the PDHC-NNT redox circuit negate counterbalance changes in energy expenditure. At the whole animal level, mice lacking functional NNT (C57BL/6J) are characterized by lower energy expenditure rates, consistent with their well known susceptibility to diet-induced obesity. These findings suggest the integration of redox sensing of metabolic balance with compensatory changes in energy expenditure provides a potential mechanism by which cellular redox homeostasis is maintained and body weight is defended during periods of positive and negative energy balance. PMID:25643703

Biological and Environmental Transformations of Copper-Based Nanomaterials

PubMed Central

Wang, Zhongying; Von Dem Bussche, Annette; Kabadi, Pranita K.; Kane, Agnes B.; Hurt, Robert H.

2013-01-01

Copper-based nanoparticles are an important class of materials with applications as catalysts, conductive inks, and antimicrobial agents. Environmental and safety issues are particularly important for copper-based nanomaterials because of their potential large-scale use and their high redox activity and toxicity reported from in vitro studies. Elemental nanocopper oxidizes readily upon atmospheric exposure during storage and use, so copper oxides are highly relevant phases to consider in studies of environmental and health impacts. Here we show that copper oxide nanoparticles undergo profound chemical transformations under conditions relevant to living systems and the natural environment. Copper oxide nanoparticle (CuO-NP) dissolution occurs at lysosomal pH (4-5), but not at neutral pH in pure water. Despite the near-neutral pH of cell culture medium, CuO-NPs undergo significant dissolution in media over time scales relevant to toxicity testing due to ligand-assisted ion release, in which amino acid complexation is an important contributor. Electron paramagnetic resonance (EPR) spectroscopy shows that dissolved copper in association with CuO-NPs are the primary redox-active species. CuO-NPs also undergo sulfidation by a dissolution-reprecipitation mechanism, and the new sulfide surfaces act as catalysts for sulfide oxidation. Copper sulfide NPs are found to be much less cytotoxic than CuO NPs, which is consistent with the very low solubility of CuS. Despite this low solubility of CuS, EPR studies show that sulfidated CuO continues to generate some ROS activity due to the release of free copper by H2O2 oxidation during the Fenton-chemistry-based EPR assay. While sulfidation can serve as a natural detoxification process for nanosilver and other chalcophile metals, our results suggest that sulfidation may not fully and permanently detoxify copper in biological or environmental compartments that contain reactive oxygen species. PMID:24032665

(+/-)-catechin: chemical weapon, antioxidant, or stress regulator?

PubMed

Chobot, Vladimir; Huber, Christoph; Trettenhahn, Guenter; Hadacek, Franz

2009-08-01

(+/-)-Catechin is a flavan-3-ol that occurs in the organs of many plant species, especially fruits. Health-beneficial effects have been studied extensively, and notable toxic effects have not been found. In contrast, (+/-)-catechin has been implicated as a 'chemical weapon' that is exuded by the roots of Centaurea stoebe, an invasive knapweed of northern America. Recently, this hypothesis has been rejected based on (+/-)-catechin's low phytotoxicity, instability at pH levels higher than 5, and poor recovery from soil. In the current study, (+/-)-catechin did not inhibit the development of white and black mustard to an extent that was comparable to the highly phytotoxic juglone, a naphthoquinone that is allegedly responsible for the allelopathy of the walnut tree. At high stress levels, caused by sub-lethal methanol concentrations in the medium, and a 12 h photoperiod, (+/-)-catechin even attenuated growth retardation. A similar effect was observed when (+/-)-catechin was assayed for brine shrimp mortality. Higher concentrations reduced the mortality caused by toxic concentrations of methanol. Further, when (+/-)-catechin was tested in variants of the deoxyribose degradation assay, it was an efficient scavenger of reactive oxygen species (ROS) when they were present in higher concentrations. This antioxidant effect was enhanced when iron was chelated directly by (+/-)-catechin. Conversely, if iron was chelated to EDTA, pro-oxidative effects were demonstrated at higher concentrations; in this case (+/-)-catechin reduced molecular oxygen and iron to reagents required by the Fenton reaction to produce hydroxyl radicals. A comparison of cyclic voltammograms of (+/-)-catechin with the phytotoxic naphthoquinone juglone indicated similar redox-cycling properties for both compounds although juglone required lower electrochemical potentials to enter redox reactions. In buffer solutions, (+/-)-catechin remained stable at pH 3.6 (vacuole) and decomposed at pH 7.4 (cytoplasm) after 24 h. The results support the recent rejection of the hypothesis that (+/-)-catechin may serve as a 'chemical weapon' for invasive plants. Instead, accumulation and exudation of (+/-)-catechin may help plants survive periods of stress.

Ground Water Redox Zonation near La Pine, Oregon: Relation to River Position within the Aquifer-Riparian Zone Continuum

USGS Publications Warehouse

Hinkle, Stephen R.; Morgan, David S.; Orzol, Leonard L.; Polette, Danial J.

2007-01-01

Increasing residential development since in the 1960s has lead to increases in nitrate concentrations in shallow ground water in parts of the 247 square mile study area near La Pine, Oregon. Denitrification is the dominant nitrate-removal process that occurs in suboxic ground water, and suboxic ground water serves as a barrier to transport of most nitrate in the aquifer. Oxic ground water, on the other hand, represents a potential pathway for nitrate transport from terrestrial recharge areas to the Deschutes and Little Deschutes Rivers. The effects of present and potential future discharge of ground-water nitrate into the nitrogen-limited Deschutes and Little Deschutes Rivers are not known. However, additions of nitrogen to nitrogen-limited rivers can lead to increases in primary productivity which, in turn, can increase the magnitudes of dissolved oxygen and pH swings in river water. An understanding of the distribution of oxic ground water in the near-river environment could facilitate understanding the vulnerability of these rivers and could be a useful tool for management of these rivers. In this study, transects of temporary wells were installed in sub-river sediments beneath the Deschutes and Little Deschutes Rivers near La Pine to characterize near-river reduction/oxidation (redox) conditions near the ends of ground-water flow paths. Samples from transects installed near the center of the riparian zone or flood plain were consistently suboxic. Where transects were near edges of riparian zones, most ground-water samples also were suboxic. Oxic ground water (other than hyporheic water) was uncommon, and was only detected near the outside edge of some meander bends. This pattern of occurrence likely reflects geochemical controls throughout the aquifer as well as geochemical processes in the microbiologically active riparian zone near the end of ground-water flow paths. Younger, typically less reduced ground water generally enters near-river environments through peripheral zones, whereas older, typically more reduced ground water tends to discharge closer to the center of the river corridor. Such distributions of redox state reflect ground-water movement and geochemical evolution at the aquifer-scale. Redox state of ground water undergoes additional modification as ground water nears discharge points in or adjacent to rivers, where riparian zone processes can be important. Lateral erosion of river systems away from the center of the flood plain can decrease or even eliminate interactions between ground water and reducing riparian zone sediments. Thus, ground water redox patterns in near-river sediments appear to reflect the position of a river within the riparian zone/aquifer continuum. Spatial heterogeneity of redox conditions near the river/aquifer boundary (that is, near the riverbed) makes it difficult to extrapolate transect-scale findings to a precise delineation of the oxic-suboxic boundary in the near-river environment of the entire study area. However, the understanding of relations between near-river redox state and proximity to riparian zone edges provides a basis for applying these results to the study-area scale, and could help guide management efforts such as nitrogen-reduction actions or establishment of Total Maximum Daily Load criteria. Coupling the ground-water redox-based understanding of river vulnerability with ground-water particle-tracking-based characterization of connections between upgradient recharge areas and receiving rivers demonstrates one means of linking effects of potential nitrate loads at the beginning of ground-water flow paths with river vulnerability.

Ferrocene functionalized graphene based electrode for the electro-Fenton oxidation of ciprofloxacin.

PubMed

Divyapriya, Govindaraj; Nambi, Indumathi; Senthilnathan, Jaganathan

2018-05-26

Ferrocene functionalized graphene based graphite felt electrode was firstly investigated for heterogeneous electro-Fenton oxidation of ciprofloxacin in neutral pH condition. Electrochemical reduction of Ferrocene functionalized graphene oxide (Fc-ErGO) was performed by cyclic voltammetry technique. At neutral pH condition, Fc-ErGO electrode (0.035 min ─1 ) exhibited ∼3 times and ∼9 times higher removal rates in comparison with plane ErGO (0.010 min ─1 ) and plane graphite felt (0.004 min ─1 ) electrodes respectively. The effect of pH and applied potential were studied for the degradation of ciprofloxacin in Fc-ErGO based electrode. Higher removal rate was observed at acidic pH (0.222 min ─1 ), whereas alkaline pH showed lower removal efficiency (0.014 min ─1 ). > 99% removal of ciprofloxacin was achieved with in 15 min and 120 min of reactions period at pH 3.0 and pH 7.0, respectively. H 2 O 2 generation was found to be high in plane ErGO electrode system in all of the pH conditions. Owing to the high redox ability of ferrocene, Fc-ErGO electrode generated high concentration of OH radicals (426 μM pH 3.0; 247 μM pH 7.0; 210 μM pH 9.0) than ErGO and plane graphite felt electrodes; The electrode reusability study was performed to understand the electrode stability. There was no significant change in removal efficiency even after the 5th cycle of reusability study at both acidic and neutral conditions. The possible mechanism of oxidation in Fc-ErGO based electro-Fenton process was also proposed based on the continuous monitoring of H 2 O 2 and OH radicals generated in the system. Copyright © 2018. Published by Elsevier Ltd.

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

NASA Technical Reports Server (NTRS)

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.

Smart micro/nanoparticles in stimulus-responsive drug/gene delivery systems

PubMed Central

Karimi, Mahdi; Ghasemi, Amir; Zangabad, Parham Sahandi; Rahighi, Reza; Moosavi Basri, S. Masoud; Mirshekari, H.; Amiri, M.; Pishabad, Z. Shafaei; Aslani, A.; Bozorgomid, M.; Ghosh, D.; Beyzavi, A.; Vaseghi, A.; Aref, A. R.; Haghani, L.; Bahrami, S.; Hamblin, Michael R.

2016-01-01

New achievements in the realm of nanoscience and innovative techniques of nanomedicine have moved micro/nanoparticles (MNPs) to the point of becoming actually useful for practical applications in the near future. Various differences between the extracellular and intracellular environments of cancerous and normal cells and the particular characteristics of tumors such as physicochemical properties, neovasculature, elasticity, surface electrical charge, and pH have motivated the design and fabrication of inventive “smart” MNPs for stimulus-responsive controlled drug release. These novel MNPs can be tailored to be responsive to pH variations, redox potential, enzymatic activation, thermal gradients, magnetic fields, light, and ultrasound (US), or can even be responsive to dual or multi-combinations of different stimuli. This unparalleled capability has increased their importance as site-specific controlled drug delivery systems (DDSs) and has encouraged their rapid development in recent years. An in-depth understanding of the underlying mechanisms of these DDS approaches is expected to further contribute to this groundbreaking field of nanomedicine. Smart nanocarriers in the form of MNPs that can be triggered by internal or external stimulus are summarized and discussed in the present review, including pH-sensitive peptides and polymers, redox-responsive micelles and nanogels, thermo- or magnetic-responsive nanoparticles (NPs), mechanical- or electrical-responsive MNPs, light or ultrasound-sensitive particles, and multi-responsive MNPs including dual stimuli-sensitive nanosheets of graphene. This review highlights the recent advances of smart MNPs categorized according to their activation stimulus (physical, chemical, or biological) and looks forward to future pharmaceutical applications. PMID:26776487

Novel reductive-reductive mode electrochemical detection of Rohypnol following liquid chromatography and its determination in coffee.

PubMed

Honeychurch, Kevin C; Davidson, Gwen M; Brown, Emma; Hart, John P

2015-01-01

Rohypnol (flunitrazepam) has been successfully determined in coffee by high performance liquid chromatography dual electrode detection (LC-DED) in the dual reductive mode. Initial studies were performed to optimise the chromatographic conditions and these were found to be 50% acetonitrile, 50% 50 mM pH 2.0 phosphate buffer at a flow rate of 0.75 mL min(-1), employing a Hypersil C18, 5 μm, 250 mm × 4.6 mm column. Cyclic voltammetric studies were made to ascertain the redox behaviour of Rohypnol at a glassy carbon electrode over the pH range 2-12. Hydrodynamic voltammetry was used to optimise the applied potential at the generator and detector cells; these were identified to be -2.4 V and +0.8 V for the redox mode and -2.4 V and -0.1 V for the dual reductive mode respectively. A linear range of 0.5-100 μg mL(-1), with a detection limit of 20 ng mL(-1) was obtained for the dual reductive mode. Further studies were then performed to identify the optimum conditions required for the LC-DED determination of Rohypnol in beverage samples. A convenient and rapid method for the determination of Rohypnol in beverage samples was developed using a simple sample pre-treatment procedure. A recovery of 95.5% was achieved for a sample of white coffee fortified at 9.6 μg mL(-1) Rohypnol. Copyright © 2014 Elsevier B.V. All rights reserved.

[Comparative studies on the action of chlorine and ozone on polioviruses in the reprocessing of drinking water in Essen (author's transl)].

PubMed

Thraenhart, O; Kuwert, E

1975-07-01

The present study was performed in order to evaluate comparatively the inactivation of polio virus type I strains (wild type and attenuated) by means of chlorine and ozone. Polio virus type I was chosen with regard to its epidemiological behaviour and high stability in drinking-water and sewage lines. In view of the lack of propagation techniques, hepatitis viruses A and B, unfortunately, could not be used for these experiments. The experiments were done under laboratory conditions only, and not in the water recovery plant because of hygienic reasons. Defined quantities of disinfectants were examined for their virus-inactivating effect in water without redox-potential (double-distilled water), water with low defined redox-potential (double-distilled water + KOH), previously chlorinated water with a residual chlorine content of 0.03 mg chlorine per liter (tap water) and water with a high redox-potential (well water from the drinking-water plant). Time-course studies were performed, both with chlorine and ozone, in order to evaluate the characteristics of the inactivation procedure. The experimental conditions chosen varied from experiment to experiment to obtain relevant conclusions for the practice. On the basis of our results, and taking into account the quantitative differences in effect, chlorine and ozone principially can be considered equivalent in their action of virus-disinfection. Both, the initial rate and the kinetics of virus disinfection are really identical. Both disinfectants are dependant on the condition of the water (redox-potential, pH etc.) to a great extent in their efficacy. Therefore, a decision of whether or not ozone should substitute for chlorine for the drinking-water supply in Essen cannot be drawn on the basis of virological experiments. This decision, then, depends more or less on other questions - such as relative costs and practicability of the ozonization on a large technical scale. The safety risk and technical reliability of the ozonization process is of particular significance. In the present condition of the Essen reservoir water, a good virus disinfection can be expected already with 1.0 to 1.5 mg ozone/liter (dissolved!); such a concentration guarantees very little residual ozone and, thus, makes then this procedure technically feasible. Continuous checking of the redox-potential and the amount of the ozone added is necessary. With regard to a continuous supply of ozone, the dependence on current supply must be guaranteed. Ozonization of water, probably by the cleavage of humic acid, promotes bacterial recontamination of the drinking-water in the city taps(Stalder und Klosterkötter, 45). Therefore only a combined pre-ozonization with subsequent chlorination would guarantee, both, safety and improvement of the cosmetical conditions of the drinking-water. Such a combination would be feasible with highly reduced amounts of ozone and chlorine.

A fuel-cell-assisted iron redox process for simultaneous sulfur recovery and electricity production from synthetic sulfide wastewater.

PubMed

Zhai, Lin-Feng; Song, Wei; Tong, Zhong-Hua; Sun, Min

2012-12-01

Sulfide present in wastewaters and waste gases should be removed due to its toxicity, corrosivity, and malodorous property. Development of effective, stable, and feasible methods for sulfur recovery from sulfide attains a double objective of waste minimization and resource recovery. Here we report a novel fuel-cell-assisted iron redox (FC-IR) process for simultaneously recovering sulfur and electricity from synthetic sulfide wastewater. The FC-IR system consists of an oxidizing reactor where sulfide is oxidized to elemental sulfur by Fe(III), and a fuel cell where Fe(III) is regenerated from Fe(II) concomitantly with electricity producing. The oxidation of sulfide by Fe(III) is significantly dependent on solution pH. Increasing the pH from 0.88 to 1.96 accelerates the oxidation of sulfide, however, lowers the purity of the produced elemental sulfur. The performance of fuel cell is also a strong function of solution pH. Fe(II) is completely oxidized to Fe(III) when the fuel cell is operated at a pH above 6.0, whereas only partially oxidized below pH 6.0. At pH 6.0, the highest columbic efficiency of 75.7% is achieved and electricity production maintains for the longest time of 106 h. Coupling operation of the FC-IR system obtains sulfide removal efficiency of 99.90%, sulfur recovery efficiency of 78.6 ± 8.3%, and columbic efficiency of 58.6 ± 1.6%, respectively. These results suggest that the FC-IR process is a promising tool to recover sulfur and energy from sulfide. Copyright © 2012 Elsevier B.V. All rights reserved.

Thermodynamic and kinetic data for adduct formation, cis-trans isomerization and redox reactions of ML4 complexes: a case study with rhodium- and iridium-tropp complexes in d8, d9 and d10 valence electron configurations (tropp=dibenzotropylidene phosphanes).

PubMed

Breher, Frank; Rüegger, Heinz; Mlakar, Marina; Rudolph, Manfred; Deblon, Stephan; Schönberg, Hartmut; Boulmaâz, Souad; Thomaier, Jörg; Grützmacher, Hansjörg

2004-02-06

The formation of adducts of the square-planar 16-electron complexes trans-[M(tropp(ph))(2)](+) and cis-[M(tropp(ph))(2)](+) (M=Rh, Ir; tropp(Ph)=5-diphenylphosphanyldibenzo[a,d]cycloheptene) with acetonitrile (acn) and Cl(-), and the redox chemistry of these complexes was investigated by various physical methods (NMR and UV-visible spectroscopy, square-wave voltammetry), in order to obtain some fundamental thermodynamic and kinetic data for these systems. A trans/cis isomerization cannot be detected for [M(tropp(ph))(2)](+) in non-coordinating solvents. However, both isomers are connected through equilibria of the type trans-[M(tropp(ph))(2)](+)+L<==>[ML(tropp(ph))(2)](n)<==>cis-[M(tropp(ph))(2)](+)+L, involving five-coordinate intermediates [ML(tropp(ph))(2)](n) (L=acn, n=+1; L=Cl(-), n=0). Values for K(d) (K(f)), that is, the dissociation (formation) equilibrium constant, and k(d) (k(f)), that is, the dissociation (formation) rate constant, were obtained. The formation reactions are fast, especially with the trans isomers (k(f)>1x10(5) m(-1) s(-1)). The reaction with the sterically more hindered cis isomers is at least one order of magnitude slower. The stability of the five-coordinate complexes [ML(tropp(ph))(2)](n) increases with Ir>Rh and Cl(-)>acn. The dissociation reaction has a pronounced influence on the square-wave (SW) voltammograms of trans/cis-[Ir(tropp(ph))(2)](+). With the help of the thermodynamic and kinetic data independently determined by other physical means, these reactions could be simulated and allowed the setting up of a reaction sequence. Examination of the data obtained showed that the trans/cis isomerization is a process with a low activation barrier for the four-coordinate 17-electron complexes [M(tropp(ph))(2)](0) and especially that a disproportionation reaction 2 trans/cis-[M(tropp(ph))(2)](0)-->[M(tropp(ph))(2)](+)+[M(tropp(ph))(2)](-) may be sufficiently fast to mask the true reactivity of the paramagnetic species, which are probably less reactive than their diamagnetic equilibrium partners.

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

PubMed

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

2018-04-19

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

Mechanisms of Hop Inhibition Include the Transmembrane Redox Reaction▿

PubMed Central

Behr, Jürgen; Vogel, Rudi F.

2010-01-01

In this work, a novel mechanistic model of hop inhibition beyond the proton ionophore action toward (beer spoiling) bacteria was developed. Investigations were performed with model systems using cyclic voltammetry for the determination of redox processes/conditions in connection with growth challenges with hop-sensitive and -resistant Lactobacillus brevis strains in the presence of oxidants. Cyclic voltammetry identified a transmembrane redox reaction of hop compounds at low pH (common in beer) and in the presence of manganese (present in millimolar levels in lactic acid bacteria). The antibacterial action of hop compounds could be extended from the described proton ionophore activity, lowering the intracellular pH, to pronounced redox reactivity, causing cellular oxidative damage. Accordingly, a correlation between the resistance of L. brevis strains to a sole oxidant to their resistance to hop could not be expected and was not detected. However, in connection with our recent study concerning hop ionophore properties and the resistance of hop-sensitive and -tolerant L. brevis strains toward proton ionophores (J. Behr and R. F. Vogel, J. Agric. Food Chem. 57:6074-6081, 2009), we suggest that both ionophore and oxidant resistance are required for survival under hop stress conditions and confirmed this correlation according to the novel mechanistic model. In consequence, the expression of several published hop resistance mechanisms involved in manganese binding/transport and intracellular redox balance, as well as that of proteins involved in oxidative stress under “highly reducing” conditions (cf. anaerobic cultivation and “antioxidative” hop compounds in the growth medium), is now comprehensible. Accordingly, hop resistance as a multifactorial dynamic property at least implies distinct resistance levels against two different mechanisms of hop inhibition, namely, proton ionophore-induced and oxidative stress-induced mechanisms. Beyond this specific model of hop inhibition, these investigations provide general insight on the role of electrophysiology and ion homeostasis in bacterial stress responses to membrane-active drugs. PMID:19880646

An electrochemical series of redox couples in silicate melts - A review and applications to geochemistry

NASA Technical Reports Server (NTRS)

Schreiber, Henry D.

1987-01-01

An electrochemical series for redox couples in a glass-forming oxide melt is developed. This series is a quantitative numerical scale of reference reduction potentials of the redox couples in a silicate melt that is a model for basaltic magmas. The redox couples are ordered in terms of their reference reduction potentials; the order appears to be relatively independent of the exact melt composition and temperature. Thus, upon calibration to a desired composition, oxygen fugacity, and temperature, this electrochemical series can provide estimates of redox state proportions in basaltic magmas on different planetary bodies. The geochemical electrochemical series can also be used to understand the interrelationship of the redox state of the magma and the presence of volatile species such as oxygen, water, sulfur gases, and carbon gases.

Mutual interactions of redox couples via electron exchange in silicate melts - Models for geochemical melt systems

NASA Technical Reports Server (NTRS)

Schreiber, Henry D.; Merkel, Robert C., Jr.; Schreiber, V. Lea; Balazs, G. Bryan

1987-01-01

The mutual interactions via electron exchange of redox couples in glass-forming melts were investigated both theoretically and experimentally. A thermodynamic approach for considering the mutual interactions leads to conclusion that the degree of mutual interaction in the melt should be proportional in part to the difference in relative reduction potentials of the interacting redox couples. Experimental studies verify this conclusion for numerous redox couples in several composition/temperature/oxygen fugacity regimes. Geochemical systems simultaneously possess many potentially multivalent elements; the stabilized redox states in the resulting magmas can be explained in part by mutual interactions and by redox buffering through the central Fe(III)- Fe(II) couples in the melts. The significance of these results for basaltic magmas of the earth, moon, and meteorites is addressed.

Studying the relationship between redox and cell growth using quantitative phase imaging (Conference Presentation)

NASA Astrophysics Data System (ADS)

Sridharan, Shamira; Leslie, Matthew T.; Bapst, Natalya; Smith, John; Gaskins, H. Rex; Popescu, Gabriel

2016-03-01

Quantitative phase imaging has been used in the past to study the dry mass of cells and study cell growth under various treatment conditions. However, the relationship between cellular redox and growth rates has not yet been studied in this context. This study employed the recombinant Glrx-roGFP2 redox biosensor targeted to the mitochondrial matrix or cytosolic compartments of A549 lung epithelial carcinoma cells. The Glrx-roGFP2s biosensor consists of a modified GFP protein containing internal cysteine residues sensitive to the local redox environment. The formation/dissolution of sulfide bridges contorts the internal chromophore, dictating corresponding changes in florescence emission that provide direct measures of the local redox potential. Combining 2-channel florescent imaging of the redox sensor with quantitative phase imaging allowed observation of redox homeostasis alongside measurements of cellular mass during full cycles of cellular division. The results indicate that mitochondrial redox showed a stronger inverse correlation with cell growth than cytoplasmic redox states; although redox changes are restricted to a 5% range. We are now studying the relationship between mitochondrial redox and cell growth in an isogenic series of breast cell lines built upon the MCF-10A genetic background that vary both in malignancy and metastatic potential.

Comparative evaluation of short-term leach tests for heavy metal release from mineral processing waste

USGS Publications Warehouse

Al-Abed, S. R.; Hageman, P.L.; Jegadeesan, G.; Madhavan, N.; Allen, D.

2006-01-01

Evaluation of metal leaching using a single leach test such as the Toxicity Characteristic Leaching Procedure (TCLP) is often questionable. The pH, redox potential (Eh), particle size and contact time are critical variables in controlling metal stability, not accounted for in the TCLP. This paper compares the leaching behavior of metals in mineral processing waste via short-term extraction tests such as TCLP, Field Leach Test (FLT) used by USGS and deionized water extraction tests. Variation in the extracted amounts was attributed to the use of different particle sizes, extraction fluid and contact time. In the controlled pH experiments, maximum metal extraction was obtained at acidic pH for cationic heavy metals such as Cu, Pb and Zn, while desorption of Se from the waste resulted in high extract concentrations in the alkaline region. Precipitation of iron, caused by a pH increase, probably resulted in co-precipitation and immobilization of Cu, Pb and Zn in the alkaline pH region. A sequential extraction procedure was performed on the original waste and the solid residue from the Eh-pH experiments to determine the chemical speciation and distribution of the heavy metals. In the as-received waste, Cu existed predominantly in water soluble or sulfidic phases, with no binding to carbonates or iron oxides. Similar characteristics were observed for Pb and Zn, while Se existed mostly associated with iron oxides or sulfides. Adsorption/co-precipitation of Cu, Se and Pb on precipitated iron hydroxides was observed in the experimental solid residues, resulting in metal immobilization above pH 7.

Control of oxidation-reduction potential during Cheddar cheese ripening and its effect on the production of volatile flavour compounds.

PubMed

Caldeo, Veronica; Hannon, John A; Hickey, Dara-Kate; Waldron, Dave; Wilkinson, Martin G; Beresford, Thomas P; McSweeney, Paul L H

2016-11-01

In cheese, a negative oxidation-reduction (redox) potential is required for the stability of aroma, especially that associated with volatile sulphur compounds. To control the redox potential during ripening, redox agents were added to the salted curd of Cheddar cheese before pressing. The control cheese contained only salt, while different oxidising or reducing agents were added with the NaCl to the experimental cheeses. KIO3 (at 0·05, 0·1 and 1%, w/w) was used as the oxidising agent while cysteine (at 2%, w/w) and Na2S2O4 (at 0·05 and 0·1%, w/w) were used as reducing agents. During ripening the redox potential of the cheeses made with the reducing agents did not differ significantly from the control cheese (E h ≈ -120 mV) while the cheeses made with 0·1 and 0·05% KIO3 had a significantly higher and positive redox potential in the first month of ripening. Cheese made with 1% KIO3 had positive values of redox potential throughout ripening but no starter lactic acid bacteria survived in this cheese; however, numbers of starter organisms in all other cheeses were similar. Principal component analysis (PCA) of the volatile compounds clearly separated the cheeses made with the reducing agents from cheeses made with the oxidising agents at 2 month of ripening. Cheeses with reducing agents were characterized by the presence of sulphur compounds whereas cheeses made with KIO3 were characterized mainly by aldehydes. At 6 month of ripening, separation by PCA was less evident. These findings support the hypothesis that redox potential could be controlled during ripening and that this parameter has an influence on the development of cheese flavour.

Integrated self-assembling drug delivery system possessing dual responsive and active targeting for orthotopic ovarian cancer theranostics.

PubMed

Lin, Chun-Jui; Kuan, Chen-Hsiang; Wang, Li-Wen; Wu, Hsi-Chin; Chen, Yunching; Chang, Chien-Wen; Huang, Rih-Yang; Wang, Tzu-Wei

2016-06-01

Ovarian cancers are the leading cause for mortality among gynecologic malignancies with five-year survival rate less than 30%. The purpose of this study is to develop a redox and pH-sensitive self-assembling hyaluronic acid nanoparticle with active targeting peptide for anticancer drug delivery. Anti-cancer drug is grafted onto hyaluronic acid (HA) via cis-aconityl linkage and disulfide bond to possess pH sensitivity and redox property, respectively. This conjugate is amphiphilic and can self-assemble into nanoparticle (NP) in aqueous solution. The results show that the nanoconjugate is successfully developed and the grafting ratio of cystamine (cys) is 17.8% with drug loading amount about 6.2% calculated by (1)H NMR spectra. The particle size is approximately 229.0 nm using dynamic light scatting measurement, and the morphology of nanoparticles is observed as spherical shape by transmission electron microscope. The pH and redox sensitivities are evaluated by changing either pH value or concentration of dithiothreitol in the medium. It is proved that the drug carrier is capable of achieving sustained controlled release of anti-cancer drug to 95% within 150 h. The intracellular uptake is observed by fluorescent microscope and the images show that conjugating luteinizing hormone-releasing hormone (LHRH) peptide can enhance specific uptake of nanoparticles by OVCAR-3 cancer cells; thus, resulting in inhibitory cell growth to less than 20% in 72 h in vitro. Orthotopic ovarian tumor model is also established to evaluate the therapeutic and diagnostic efficacy using non-invasive in vivo imaging system. The representative results demonstrate that LHRH-conjugated NPs possess a preferable tumor imaging capability and an excellent antitumor ability to almost 30% of original size in 20 days. Copyright © 2016 Elsevier Ltd. All rights reserved.

Phenazines and Other Redox-Active Antibiotics Promote Microbial Mineral Reduction

PubMed Central

Hernandez, Maria E.; Kappler, Andreas; Newman, Dianne K.

2004-01-01

Natural products with important therapeutic properties are known to be produced by a variety of soil bacteria, yet the ecological function of these compounds is not well understood. Here we show that phenazines and other redox-active antibiotics can promote microbial mineral reduction. Pseudomonas chlororaphis PCL1391, a root isolate that produces phenazine-1-carboxamide (PCN), is able to reductively dissolve poorly crystalline iron and manganese oxides, whereas a strain carrying a mutation in one of the phenazine-biosynthetic genes (phzB) is not; the addition of purified PCN restores this ability to the mutant strain. The small amount of PCN produced relative to the large amount of ferric iron reduced in cultures of P. chlororaphis implies that PCN is recycled multiple times; moreover, poorly crystalline iron (hydr)oxide can be reduced abiotically by reduced PCN. This ability suggests that PCN functions as an electron shuttle rather than an iron chelator, a finding that is consistent with the observation that dissolved ferric iron is undetectable in culture fluids. Multiple phenazines and the glycopeptidic antibiotic bleomycin can also stimulate mineral reduction by the dissimilatory iron-reducing bacterium Shewanella oneidensis MR1. Because diverse bacterial strains that cannot grow on iron can reduce phenazines, and because thermodynamic calculations suggest that phenazines have lower redox potentials than those of poorly crystalline iron (hydr)oxides in a range of relevant environmental pH (5 to 9), we suggest that natural products like phenazines may promote microbial mineral reduction in the environment. PMID:14766572

Measurement of europium (III)/europium (II) couple in fluoride molten salt for redox control in a molten salt reactor concept

NASA Astrophysics Data System (ADS)

Guo, Shaoqiang; Shay, Nikolas; Wang, Yafei; Zhou, Wentao; Zhang, Jinsuo

2017-12-01

The fluoride molten salt such as FLiNaK and FLiBe is one of the coolant candidates for the next generation nuclear reactor concepts, for example, the fluoride salt cooled high temperature reactor (FHR). For mitigating corrosion of structural materials in molten fluoride salt, the redox condition of the salts needs to be monitored and controlled. This study investigates the feasibility of applying the Eu3+/Eu2+ couple for redox control. Cyclic voltammetry measurements of the Eu3+/Eu2+ couple were able to obtain the concentrations ratio of Eu3+/Eu2+ in the melt. Additionally, the formal standard potential of Eu3+/Eu2+ was characterized over the FHR's operating temperatures allowing for the application of the Nernst equation to establish a Eu3+/Eu2+ concentration ratio below 0.05 to prevent corrosion of candidate structural materials. A platinum quasi-reference electrode with potential calibrated by potassium reduction potential is shown as reliable for the redox potential measurement. These results show that the Eu3+/Eu2+ couple is a feasible redox buffering agent to control the redox condition in molten fluoride salts.

Depth distribution of abiotic drivers of N mineralization and methane emission from a continuously and intermittently flooded Bangladeshi paddy soil

NASA Astrophysics Data System (ADS)

Akter, Masuda; Kader, Md. Abdul; Pierreux, Sofie; Boeckx, Pascal; Kamal, Ahammad Mostafa; Sleutel, Steven

2016-04-01

Water-saving irrigation such as AWD may significantly alter depth profiles of moisture content, pH, Eh and soil microbial activity. Modelling the effect of irrigation management on soil N mineralization, therefore requires detailed insight into depth distribution of these variables and dissolved organic carbon (DOC), and evolution of electron acceptors. We set up a field experiment at Bangladesh Agricultural University from January to May' 2015. The cultivated rice variety (BRRI dhan28) was grown under continuous flooding (CF) and alternate wetting and drying (AWD) management, with 120 kg N ha-1(N120) or without (N0)N fertilizer application. We measured soil mineral N and plant N uptake to evaluate N mineralization. CH4 emissions were monitored with timely gas sample collection and GC-analysis. Soil Eh at four depths and temperature at two depths were monitored continuously by Eh/T°-probes connected to a HYPNOS III data logger (MVH, The Netherlands). Simultaneously, soil solution from three depths were sampled with rhizon samplers to track DOC, Fe and Mn in solution. Over the growing season soil and air temperature increased by 8°C, and soil pH stayed near neutral (6.7 to 7.8). In all depths of AWD and CF, Eh dropped sharply to methanic conditions within 21 days after transplanting (DAT). Low redox-potential continued until 77DAT in all cases, except in the puddle layers under AWD, where redox raised to -200mV during drainage. Fe and Mn in soil solution increased gradually over the growing season, indicating continued reductive dissolution of Fe and Mn (hydro-)oxides. DOC increased continuously as well in all depths. Besides to release of DOC bound to pedogenic oxides upon their reductive dissolution, higher plant and soil microbial activity with increasing soil temperature (till 28°C) through the growing season explains the increasing DOC levels. Increasing methanogenic activity as indicated by the high CH4 emissions at 70-84DAT under both CF and AWD is logically linked. The elevated redox potential in puddle layer depth increments during AWD drainage events, significantly (p<0.01) declined the cumulative CH4 emission by 47% when compared to CF management. Moreover, seasonal CH4 emissions in N-fertilized fields (N120) decreased by 29 and 8% under CF and AWD, respectively relative to the control (N0), possibly due to promotion of methanotrophs, which were N-limited in N0. Mostly, mineral N content in N120 plots of AWD and CF exceeded contents in the N0 fields. Contrary to CH4 emission, irrigation management did not affect evolutions of pH, Fe, Mn and DOC in soil solution. Likewise, soil exchangeable N content evolution was unaffected and followed zero-order kinetics (N120: R2=0.53 to 0.81; N0: R2=0.12 to 0.48). Our results generally indicate that in Northern Bangladesh's Boro season, evolutions in paddy soil solution chemistry and CH4 emission are strongly depending on course soil temperature and only secondarily on irrigation management. Whether temperature steers microbial activity and methanogenesis directly or via concomitant plant activity and exudation is not known. Key words: Redox, CH4, emission, mineralization, Fe, Mn, DOC, water management

Marine environmental impact assessment of abalone, Haliotis discus hannai, cage farm in Wan-do, Republic of Korea

NASA Astrophysics Data System (ADS)

Oh, Hyun-Taik; Jung, Rae-Hong; Cho, Yoon-Sik; Hwang, Dong-Woon; Yi, Yong-Min

2015-12-01

To assess the marine environmental impacts of abalone, Haliotis discus hannai, cage farms in Wan-do, we monitored the benthic environment on top of the sediment underneath cage farm stations and reference stations. We applied two methods for this assessment. One was the A- and B-investigation of the MOM system (Modeling-On fish farm-Monitoring) developed in Norway. The other was a general environmental monitoring method which is widely used. In this study, we found benthic animals in all samples that belonged to condition 1 which were based on group 1(presence of macrofauna) of the B-investigation method. The values of redox potential (group 2-pH, redox potential) in all samples were above +65 mV belonging to condition 1. Based on sensory results (group 3-gas, color, odor, thickness of deposits), five out of seven experiment samples showed condition 1 while stations 2 and 7 showed condition 2, which have been cultured for 10 years in semi-closed waters. As group 2 takes precedence over group 3, the level of the conditions for B-investigation results consequently showed condition 1 in all stations. We found that pollutants and trace metals in the sediment underneath cage farms were lower than the pollution standard. This led us to conclude that the environmental impacts of the cage farms in this study were not significant.

Imposed glutathione-mediated redox switch modulates the tobacco wound-induced protein kinase and salicylic acid-induced protein kinase activation state and impacts on defence against Pseudomonas syringae

PubMed Central

Matern, Sanja; Peskan-Berghoefer, Tatjana; Gromes, Roland; Kiesel, Rebecca Vazquez; Rausch, Thomas

2015-01-01

The role of the redox-active tripeptide glutathione in plant defence against pathogens has been studied extensively; however, the impact of changes in cellular glutathione redox potential on signalling processes during defence reactions has remained elusive. This study explored the impact of elevated glutathione content on the cytosolic redox potential and on early defence signalling at the level of mitogen-activated protein kinases (MAPKs), as well as on subsequent defence reactions, including changes in salicylic acid (SA) content, pathogenesis-related gene expression, callose depositions, and the hypersensitive response. Wild-type (WT) Nicotiana tabacum L. and transgenic high-glutathione lines (HGL) were transformed with the cytosol-targeted sensor GRX1-roGFP2 to monitor the cytosolic redox state. Surprisingly, HGLs displayed an oxidative shift in their cytosolic redox potential and an activation of the tobacco MAPKs wound-induced protein kinase (WIPK) and SA-induced protein kinase (SIPK). This activation occurred in the absence of any change in free SA content, but was accompanied by constitutively increased expression of several defence genes. Similarly, rapid activation of MAPKs could be induced in WT tobacco by exposure to either reduced or oxidized glutathione. When HGL plants were challenged with adapted or non-adapted Pseudomonas syringae pathovars, the cytosolic redox shift was further amplified and the defence response was markedly increased, showing a priming effect for SA and callose; however, the initial and transient hyperactivation of MAPK signalling was attenuated in HGLs. The results suggest that, in tobacco, MAPK and SA signalling may operate independently, both possibly being modulated by the glutathione redox potential. Possible mechanisms for redox-mediated MAPK activation are discussed. PMID:25628332

Efficacy of β-lactam/β-lactamase inhibitor combination is linked to WhiB4-mediated changes in redox physiology of Mycobacterium tuberculosis

PubMed Central

Mishra, Saurabh; Shukla, Prashant; Bhaskar, Ashima; Anand, Kushi; Baloni, Priyanka; Jha, Rajiv Kumar; Mohan, Abhilash; Rajmani, Raju S; Nagaraja, Valakunja; Chandra, Nagasuma; Singh, Amit

2017-01-01

Mycobacterium tuberculosis (Mtb) expresses a broad-spectrum β-lactamase (BlaC) that mediates resistance to one of the highly effective antibacterials, β-lactams. Nonetheless, β-lactams showed mycobactericidal activity in combination with β-lactamase inhibitor, clavulanate (Clav). However, the mechanistic aspects of how Mtb responds to β-lactams such as Amoxicillin in combination with Clav (referred as Augmentin [AG]) are not clear. Here, we identified cytoplasmic redox potential and intracellular redox sensor, WhiB4, as key determinants of mycobacterial resistance against AG. Using computer-based, biochemical, redox-biosensor, and genetic strategies, we uncovered a functional linkage between specific determinants of β-lactam resistance (e.g. β-lactamase) and redox potential in Mtb. We also describe the role of WhiB4 in coordinating the activity of β-lactamase in a redox-dependent manner to tolerate AG. Disruption of WhiB4 enhances AG tolerance, whereas overexpression potentiates AG activity against drug-resistant Mtb. Our findings suggest that AG can be exploited to diminish drug-resistance in Mtb through redox-based interventions. DOI: http://dx.doi.org/10.7554/eLife.25624.001 PMID:28548640

A microbiological survey of Montserrat Island hydrothermal biotopes.

PubMed

Atkinson, T; Cairns, S; Cowan, D A; Danson, M J; Hough, D W; Johnson, D B; Norris, P R; Raven, N; Robinson, C; Robson, R; Sharp, R J

2000-10-01

In March 1996, a survey of hydrothermal sites on the island of Montserrat was carried out. Six sites (Galway's Soufrière. Gages Upper and Lower Soufrières, Hot Water Pond, Hot River, and Tar River Soufrière) were mapped and sampled for chemical, ATP, and microbial analyses. The hydrothermal Soufrière sites on the slopes of the active Chances Peak volcano exhibited temperatures up to almost 100 degrees C and were generally either mildly acidic at pH 5-7 or strongly acidic at pH 1.5-3, but with some hot streams and pools of low redox potential at pH 7-8. Hot Water Pond sites, comprising a series of heated pools near the western shoreline of the island. were neutral and saline, consistent with subsurface heating of entrained seawater. Biological activity shown by ATP analyses was greatest in near-neutral pH samples and generally decreased as acidity increased. A variety of heterotrophic and chemolithotrophic thermophilic organisms were isolated or observed in enrichment cultures. Most of the bacteria that were obtained in pure culture were familiar acidophiles and neutrophiles, but novel, iron-oxidizing species of Sulfobacillus were revealed. These species included the first mesophilic iron-oxidizing Sulfobacillus strains to be isolated and a strain with a higher maximum growth temperature (65 degrees C) than the previously described moderately thermophilic Sulfobacillus species.

Rapid and Automated Analytical Methods for Redox Species Based on Potentiometric Flow Injection Analysis Using Potential Buffers

PubMed Central

Ohura, Hiroki; Imato, Toshihiko

2011-01-01

Two analytical methods, which prove the utility of a potentiometric flow injection technique for determining various redox species, based on the use of some redox potential buffers, are reviewed. The first is a potentiometric flow injection method in which a redox couple such as Fe(III)-Fe(II), Fe(CN)6 3−-Fe(CN)(CN)6 4−, and bromide-bromine and a redox electrode or a combined platinum-bromide ion selective electrode are used. The analytical principle and advantages of the method are discussed, and several examples of its application are reported. Another example is a highly sensitive potentiometric flow injection method, in which a large transient potential change due to bromine or chlorine as an intermediate, generated during the reaction of the oxidative species with an Fe(III)-Fe(II) potential buffer containing bromide or chloride, is utilized. The analytical principle and details of the proposed method are described, and examples of several applications are described. The determination of trace amounts of hydrazine, based on the detection of a transient change in potential caused by the reaction with a Ce(IV)-Ce(III) potential buffer, is also described. PMID:21584280

David W. Mulder, Ph.D. | NREL

Science.gov Websites

an emphasis on identifying unique structure-functions relationships and molecular determinates of exploring structure-function relationships of redox metalloenzymes Designated Area Representative of the ]-hydrogenase H-cluster assembly revealed in the structure of HydAΔEFG" Nature (2010) Illustration labeled

Calvin A. Henard | NREL

Science.gov Websites

years of postdoctoral training at the University of Texas Medical Branch in Galveston, Texas, evaluating transcriptional regulation Redox signaling Education Ph.D., Microbiology, University of Colorado Anschutz Medical Postdoctoral Scholar, University of Texas Medical Branch, 2012-2014 Graduate Student Fellow, University of

Engineering Redox Potential of Lithium Clusters for Electrode Material in Lithium-Ion Batteries

DOE PAGES

Kushwaha, Anoop Kumar; Sahoo, Mihir Ranjan; Nanda, Jagjit; ...

2017-07-01

Low negative electrode potential and high reactivity makes lithium (Li) ideal candidate for obtaining highest possible energy density among other materials. Here, we show a novel route with which the overall electrode potential could significantly be enhanced through selection of cluster size. In using first principles density functional theory and continuum dielectric model, we studied free energy and redox potential as well as investigated relative stability of Li n (n ≤ 8) clusters in both gas phase and solution. We found that Li 3 has the lowest negative redox potential (thereby highest overall electrode potential) suggesting that cluster based approachmore » could provide a novel way of engineering the next generation battery technology. The microscopic origin of Li 3 cluster’s superior performance is related to two major factors: gas phase ionization and difference between solvation free energy for neutral and positive ion. Taken together, our study provides insight into the engineering of redox potential in battery and could stimulate further work in this direction.« less

Engineering Redox Potential of Lithium Clusters for Electrode Material in Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kushwaha, Anoop Kumar; Sahoo, Mihir Ranjan; Nanda, Jagjit

Low negative electrode potential and high reactivity makes lithium (Li) ideal candidate for obtaining highest possible energy density among other materials. Here, we show a novel route with which the overall electrode potential could significantly be enhanced through selection of cluster size. In using first principles density functional theory and continuum dielectric model, we studied free energy and redox potential as well as investigated relative stability of Li n (n ≤ 8) clusters in both gas phase and solution. We found that Li 3 has the lowest negative redox potential (thereby highest overall electrode potential) suggesting that cluster based approachmore » could provide a novel way of engineering the next generation battery technology. The microscopic origin of Li 3 cluster’s superior performance is related to two major factors: gas phase ionization and difference between solvation free energy for neutral and positive ion. Taken together, our study provides insight into the engineering of redox potential in battery and could stimulate further work in this direction.« less

Redox Bulk Energy Storage System Study, Volume 1

NASA Technical Reports Server (NTRS)

Ciprios, G.; Erskine, W., Jr.; Grimes, P. G.

1977-01-01

Opportunities were found for electrochemical energy storage devices in the U.S. electric utility industry. Application requirements for these devices were defined, including techno-economic factors. A new device, the Redox storage battery was analyzed. The Redox battery features a decoupling of energy storage and power conversion functions. General computer methods were developed to simulate Redox system operations. These studies showed that the Redox system is potentially attractive if certain performance goals can be achieved. Pathways for reducing the cost of the Redox system were identified.

Dioxygen Reactivity of Biomimetic Fe(II) Complexes with Noninnocent Catecholate, o-Aminophenolate, and o-Phenylenediamine Ligands

PubMed Central

2015-01-01

This study describes the O2 reactivity of a series of high-spin mononuclear Fe(II) complexes each containing the facially coordinating tris(4,5-diphenyl-1-methylimidazol-2-yl)phosphine (Ph2TIP) ligand and one of the following bidentate, redox-active ligands: 4-tert-butylcatecholate (tBuCatH–), 4,6-di-tert-butyl-2-aminophenolate (tBu2APH–), or 4-tert-butyl-1,2-phenylenediamine (tBuPDA). The preparation and X-ray structural characterization of [Fe2+(Ph2TIP)(tBuCatH)]OTf, [3]OTf and [Fe2+(Ph2TIP)(tBuPDA)](OTf)2, [4](OTf)2 are described here, whereas [Fe2+(Ph2TIP)(tBu2APH)]OTf, [2]OTf was reported in our previous paper [Bittner et al., Chem.—Eur. J.2013,19, 9686–9698]. These complexes mimic the substrate-bound active sites of nonheme iron dioxygenases, which catalyze the oxidative ring-cleavage of aromatic substrates like catechols and aminophenols. Each complex is oxidized in the presence of O2, and the geometric and electronic structures of the resulting complexes were examined with spectroscopic (absorption, EPR, Mössbauer, resonance Raman) and density functional theory (DFT) methods. Complex [3]OTf reacts rapidly with O2 to yield the ferric-catecholate species [Fe3+(Ph2TIP)(tBuCat)]+ (3ox), which undergoes further oxidation to generate an extradiol cleavage product. In contrast, complex [4]2+ experiences a two-electron (2e–), ligand-based oxidation to give [Fe2+(Ph2TIP)(tBuDIBQ)]2+ (4ox), where DIBQ is o-diiminobenzoquinone. The reaction of [2]+ with O2 is also a 2e– process, yet in this case both the Fe center and tBu2AP ligand are oxidized; the resulting complex (2ox) is best described as [Fe3+(Ph2TIP)(tBu2ISQ)]+, where ISQ is o-iminobenzosemiquinone. Thus, the oxidized complexes display a remarkable continuum of electronic structures ranging from [Fe3+(L2–)]+ (3ox) to [Fe3+(L•–)]2+ (2ox) to [Fe2+(L0)]2+ (4ox). Notably, the O2 reaction rates vary by a factor of 105 across the series, following the order [3]+ > [2]+ > [4]2+, even though the complexes have similar structures and Fe3+/2+ redox potentials. To account for the kinetic data, we examined the relative abilities of the title complexes to bind O2 and participate in H-atom transfer reactions. We conclude that the trend in O2 reactivity can be rationalized by accounting for the role of proton transfer(s) in the overall reaction. PMID:24697567

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

PubMed Central

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

2012-01-01

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

Sensor systems for bacterial reactors: A new flavin-phenol composite film for the in situ voltammetric measurement of pH.

PubMed

Casimero, Charnete; McConville, Aaron; Fearon, John-Joe; Lawrence, Clare L; Taylor, Charlotte M; Smith, Robert B; Davis, James

2018-10-16

Monitoring pH within microbial reactors has become an important requirement across a host of applications ranging from the production of functional foods (probiotics) to biofuel cell systems. An inexpensive and scalable composite sensor capable of monitoring the pH within the demanding environments posed by microbial reactors has been developed. A custom designed flavin derivative bearing an electropolymerisable phenol monomer was used to create a redox film sensitive to pH but free from the interferences that can impede conventional pH systems. The film was integrated within a composite carbon-fibre-polymer laminate and was shown to exhibit Nernstian behaviour (55 mV/pH) with minimal drift and robust enough to operate within batch reactors. Copyright © 2018 Elsevier B.V. All rights reserved.

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

PubMed

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

2017-08-01

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

Single-layer MnO2 nanosheets for sensitive and selective detection of glutathione by a colorimetric method

NASA Astrophysics Data System (ADS)

Di, Weihua; Zhang, Xiang; Qin, Weiping

2017-04-01

The rapid, sensitive and selective detection of glutathione (GSH) is of great importance in the biological systems. In this work, a template-free and one-step method was used to synthesize the single-layer MnO2 nanosheets via a redox reaction. The resulting product was characterized by XRD, TEM, FTIR, XPS and UV-vis absorption. The addition of GSH results in the change of solution color depth owing to the occurrence of a redox reaction between MnO2 and GSH, enabling colorimetric detection of GSH. At a pH of 3.6, the proposed sensor gives a linear calibration over a GSH concentration range of 10-100 μM, with a rapid response of less than 2 min and a low detection limit of 0.5 μM. The relative standard deviation for seven repeated determinations of GSH is lower than 5.6%. Furthermore, the chemical response of the synthesized MnO2 nanosheets toward GSH is selective. Owing to the advantages with good water solubility, rapid response, high sensitivity, good biocompatibility and operation simplicity, this two-dimensional MnO2-based sensing material might be potential for detecting GSH in biological applications.

Pigments for natural dye-sensitized solar cells from in vitro grown shoot cultures

NASA Astrophysics Data System (ADS)

Di Bari, Chiara; Forni, Cinzia; Di Carlo, Aldo; Barrajón-Catalán, Enrique; Micol, Vicente; Teoli, Federico; Nota, Paolo; Matteocci, Fabio; Frattarelli, Andrea; Caboni, Emilia; Lucioli, Simona

2017-04-01

In vitro grown shoots cultures (Prunus salicina × Prunus persica), elicited by methyl jasmonate (MJ), are reported here for the first time to prepare a natural dye for dye-sensitized solar cells (DSSC). Redox properties of the dye, its photostability, and light absorption properties suggested it as a candidate as natural photosensitizers for TiO2 photoelectrodes. Redox properties of the dye influence the DSSC production of photocurrent, thus three antioxidant assays were performed in order to characterize the antioxidant potential of this dye. The dye exhibited a high antioxidant activity in all the assays performed. Photostability assay revealed that the dye was quite stable to light. The power conversion efficiency that we obtained (0.53%) was comparable to the data by other authors with anthocyanins-based dyes from in vivo grown plants. Finally, we compared the dye with the partially purified one as photosensitizer in DSSC. The results indicated that the raw pigment from in vitro shoot cultures of P. salicina × P. persica elicited with MJ can be proposed without the needing of any other chemicals, thermal or purification process, or pH adjustments, as a dye for natural sensitized solar cells.

Gold core/Ceria shell-based redox active nanozyme mimicking the biological multienzyme complex phenomenon

DOE PAGES

Bhagat, Stuti; Srikanth Vallabani, NV; Shutthanandan, Vaithiyalingam; ...

2017-12-02

Catalytically active individual gold (Au) and cerium oxide (CeO 2) nanoparticles (NPs) are well known to exhibit specific enzyme-like activities, such as natural catalase, oxidase, superoxide dismutase, and peroxidase enzymes. Our activities have been maneuvered to design several biological applications such as immunoassays, glucose detection, radiation and free radical protection and tissue engineering. In biological systems, multienzyme complexes are involved in catalyzing important reactions of essential metabolic processes such as respiration, biomolecule synthesis, and photosynthesis. It is well known that metabolic processes linked with multienzyme complexes offer several advantages over reactions catalyzed by individual enzymes. A functional nanozyme depicting multienzymemore » like properties has eluded the researchers in the nanoscience community for the past few decades. Here, we have designed a functional multienzyme in the form of Gold (core)-CeO 2 (shell) nanoparticles (Au/CeO 2 CSNPs) exhibiting excellent peroxidase, catalase, and superoxide dismutase enzyme-like activities that are controlled simply by tuning the pH. The reaction kinetic parameters reveal that the peroxidase-like activity of this core-shell nanozyme is comparable to natural horseradish peroxidase (HRP) enzyme. Unlike peroxidase-like activity exhibited by other nanomaterials, Au/CeO 2 CSNPs showed a decrease in hydroxyl radical formation, suggesting that the biocatalytic reactions are performed by efficient electron transfers. A significant enzyme-like activity of this core-shell nanoparticle was conserved at extreme pH (2 – 11) and temperatures (up to 90 °C), clearly suggesting the superiority over natural enzymes. Further, the utility of peroxidase-like activity of this core-shell nanoparticles was extended for the detection of glucose, which showed a linear range of detection between (100 µM – 1 mM). It is hypothesized that the proximity of the redox potentials of Au+/Au and Ce (III)/Ce (IV) may result in a redox couple promoting the multienzyme activity of core-shell nanoparticles. Au/CeO 2 CSNPs may open new directions for development of single platform sensors in multiple biosensing applications.« less

The Microbial Ferrous Wheel in a Neutral pH Groundwater Seep

PubMed Central

Roden, Eric E.; McBeth, Joyce M.; Blöthe, Marco; Percak-Dennett, Elizabeth M.; Fleming, Emily J.; Holyoke, Rebecca R.; Luther, George W.; Emerson, David; Schieber, Juergen

2012-01-01

Evidence for microbial Fe redox cycling was documented in a circumneutral pH groundwater seep near Bloomington, Indiana. Geochemical and microbiological analyses were conducted at two sites, a semi-consolidated microbial mat and a floating puffball structure. In situ voltammetric microelectrode measurements revealed steep opposing gradients of O2 and Fe(II) at both sites, similar to other groundwater seep and sedimentary environments known to support microbial Fe redox cycling. The puffball structure showed an abrupt increase in dissolved Fe(II) just at its surface (∼5 cm depth), suggesting an internal Fe(II) source coupled to active Fe(III) reduction. Most probable number enumerations detected microaerophilic Fe(II)-oxidizing bacteria (FeOB) and dissimilatory Fe(III)-reducing bacteria (FeRB) at densities of 102 to 105 cells mL−1 in samples from both sites. In vitro Fe(III) reduction experiments revealed the potential for immediate reduction (no lag period) of native Fe(III) oxides. Conventional full-length 16S rRNA gene clone libraries were compared with high throughput barcode sequencing of the V1, V4, or V6 variable regions of 16S rRNA genes in order to evaluate the extent to which new sequencing approaches could provide enhanced insight into the composition of Fe redox cycling microbial community structure. The composition of the clone libraries suggested a lithotroph-dominated microbial community centered around taxa related to known FeOB (e.g., Gallionella, Sideroxydans, Aquabacterium). Sequences related to recognized FeRB (e.g., Rhodoferax, Aeromonas, Geobacter, Desulfovibrio) were also well-represented. Overall, sequences related to known FeOB and FeRB accounted for 88 and 59% of total clone sequences in the mat and puffball libraries, respectively. Taxa identified in the barcode libraries showed partial overlap with the clone libraries, but were not always consistent across different variable regions and sequencing platforms. However, the barcode libraries provided confirmation of key clone library results (e.g., the predominance of Betaproteobacteria) and an expanded view of lithotrophic microbial community composition. PMID:22783228

Gold core/Ceria shell-based redox active nanozyme mimicking the biological multienzyme complex phenomenon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhagat, Stuti; Srikanth Vallabani, NV; Shutthanandan, Vaithiyalingam

Catalytically active individual gold (Au) and cerium oxide (CeO 2) nanoparticles (NPs) are well known to exhibit specific enzyme-like activities, such as natural catalase, oxidase, superoxide dismutase, and peroxidase enzymes. Our activities have been maneuvered to design several biological applications such as immunoassays, glucose detection, radiation and free radical protection and tissue engineering. In biological systems, multienzyme complexes are involved in catalyzing important reactions of essential metabolic processes such as respiration, biomolecule synthesis, and photosynthesis. It is well known that metabolic processes linked with multienzyme complexes offer several advantages over reactions catalyzed by individual enzymes. A functional nanozyme depicting multienzymemore » like properties has eluded the researchers in the nanoscience community for the past few decades. Here, we have designed a functional multienzyme in the form of Gold (core)-CeO 2 (shell) nanoparticles (Au/CeO 2 CSNPs) exhibiting excellent peroxidase, catalase, and superoxide dismutase enzyme-like activities that are controlled simply by tuning the pH. The reaction kinetic parameters reveal that the peroxidase-like activity of this core-shell nanozyme is comparable to natural horseradish peroxidase (HRP) enzyme. Unlike peroxidase-like activity exhibited by other nanomaterials, Au/CeO 2 CSNPs showed a decrease in hydroxyl radical formation, suggesting that the biocatalytic reactions are performed by efficient electron transfers. A significant enzyme-like activity of this core-shell nanoparticle was conserved at extreme pH (2 – 11) and temperatures (up to 90 °C), clearly suggesting the superiority over natural enzymes. Further, the utility of peroxidase-like activity of this core-shell nanoparticles was extended for the detection of glucose, which showed a linear range of detection between (100 µM – 1 mM). It is hypothesized that the proximity of the redox potentials of Au+/Au and Ce (III)/Ce (IV) may result in a redox couple promoting the multienzyme activity of core-shell nanoparticles. Au/CeO 2 CSNPs may open new directions for development of single platform sensors in multiple biosensing applications.« less

Dissection of the mechanism of manganese porphyrin-catalyzed chlorine dioxide generation.

PubMed

Umile, Thomas P; Wang, Dong; Groves, John T

2011-10-17

Chlorine dioxide, an industrially important biocide and bleach, is produced rapidly and efficiently from chlorite ion in the presence of water-soluble, manganese porphyrins and porphyrazines at neutral pH under mild conditions. The electron-deficient manganese(III) tetra-(N,N-dimethyl)imidazolium porphyrin (MnTDMImP), tetra-(N,N-dimethyl)benzimidazolium (MnTDMBImP) porphyrin, and manganese(III) tetra-N-methyl-2,3-pyridinoporphyrazine (MnTM23PyPz) were found to be the most efficient catalysts for this process. The more typical manganese tetra-4-N-methylpyridiumporphyrin (Mn-4-TMPyP) was much less effective. Rates for the best catalysts were in the range of 0.24-32 TO/s with MnTM23PyPz being the fastest. The kinetics of reactions of the various ClO(x) species (e.g., chlorite ion, hypochlorous acid, and chlorine dioxide) with authentic oxomanganese(IV) and dioxomanganese(V)MnTDMImP intermediates were studied by stopped-flow spectroscopy. Rate-limiting oxidation of the manganese(III) catalyst by chlorite ion via oxygen atom transfer is proposed to afford a trans-dioxomanganese(V) intermediate. Both trans-dioxomanganese(V)TDMImP and oxoaqua-manganese(IV)TDMImP oxidize chlorite ion by 1-electron, generating the product chlorine dioxide with bimolecular rate constants of 6.30 × 10(3) M(-1) s(-1) and 3.13 × 10(3) M(-1) s(-1), respectively, at pH 6.8. Chlorine dioxide was able to oxidize manganese(III)TDMImP to oxomanganese(IV) at a similar rate, establishing a redox steady-state equilibrium under turnover conditions. Hypochlorous acid (HOCl) produced during turnover was found to rapidly and reversibly react with manganese(III)TDMImP to give dioxoMn(V)TDMImP and chloride ion. The measured equilibrium constant for this reaction (K(eq) = 2.2 at pH 5.1) afforded a value for the oxoMn(V)/Mn(III) redox couple under catalytic conditions (E' = 1.35 V vs NHE). In subsequent processes, chlorine dioxide reacts with both oxomanganese(V) and oxomanganese(IV)TDMImP to afford chlorate ion. Kinetic simulations of the proposed mechanism using experimentally measured rate constants were in agreement with observed chlorine dioxide growth and decay curves, measured chlorate yields, and the oxoMn(IV)/Mn(III) redox potential (1.03 V vs NHE). This acid-free catalysis could form the basis for a new process to make ClO(2).

H2O2 dynamics in the malaria parasite Plasmodium falciparum

PubMed Central

Rahbari, Mahsa; Bogeski, Ivan

2017-01-01

Hydrogen peroxide is an important antimicrobial agent but is also crucially involved in redox signaling and pathogen-host cell interactions. As a basis for systematically investigating intracellular H2O2 dynamics and regulation in living malaria parasites, we established the genetically encoded fluorescent H2O2 sensors roGFP2-Orp1 and HyPer-3 in Plasmodium falciparum. Both ratiometric redox probes as well as the pH control SypHer were expressed in the cytosol of blood-stage parasites. Both redox sensors showed reproducible sensitivity towards H2O2 in the lower micromolar range in vitro and in the parasites. Due to the pH sensitivity of HyPer-3, we used parasites expressing roGFP2-Orp1 for evaluation of short-, medium-, and long-term effects of antimalarial drugs on H2O2 levels and detoxification in Plasmodium. None of the quinolines or artemisinins tested had detectable direct effects on the H2O2 homeostasis at pharmacologically relevant concentrations. However, pre-treatment of the cells with antimalarial drugs or heat shock led to a higher tolerance towards exogenous H2O2. The systematic evaluation and comparison of the two genetically encoded cytosolic H2O2 probes in malaria parasites provides a basis for studying parasite-host cell interactions or drug effects with spatio-temporal resolution while preserving cell integrity. PMID:28369083

Automated measurement and monitoring of bioprocesses: key elements of the M(3)C strategy.

PubMed

Sonnleitner, Bernhard

2013-01-01

The state-of-routine monitoring items established in the bioprocess industry as well as some important state-of-the-art methods are briefly described and the potential pitfalls discussed. Among those are physical and chemical variables such as temperature, pressure, weight, volume, mass and volumetric flow rates, pH, redox potential, gas partial pressures in the liquid and molar fractions in the gas phase, infrared spectral analysis of the liquid phase, and calorimetry over an entire reactor. Classical as well as new optical versions are addressed. Biomass and bio-activity monitoring (as opposed to "measurement") via turbidity, permittivity, in situ microscopy, and fluorescence are critically analyzed. Some new(er) instrumental analytical tools, interfaced to bioprocesses, are explained. Among those are chromatographic methods, mass spectrometry, flow and sequential injection analyses, field flow fractionation, capillary electrophoresis, and flow cytometry. This chapter surveys the principles of monitoring rather than compiling instruments.

Understanding of the mode of action of Fe(III)-EDDHA as iron chlorosis corrector based on its photochemical and redox behavior.

PubMed

Gómez-Gallego, Mar; Pellico, Daniel; Ramírez-López, Pedro; Mancheño, María J; Romano, Santiago; de la Torre, María C; Sierra, Miguel A

2005-10-07

The very low reduction potential of the chelate Fe(III)-EDDHA (EDDHA = ethylenediamine N,N'-bis(2-hydroxy)phenylacetic acid) makes it unreactive in photochemically or chemically induced electron transfer processes. The lack of reactivity of this complex toward light invalidates photodegradation as an alternative mechanism for environmental elimination. However, in spite of its low reduction potential, the biological reduction of Fe(III)-EDDHA is very effective. Based on electrochemical measurements, it is proposed that Fe(III)-EDDHA itself is not the substrate of the enzyme ferric chelate reductase. Likely, at the more acidic pH in the vicinity of the roots, the ferric chelate in a closed form (FeL-) could generate a vacant coordination site that leads to an open hexacoordinate species (FeHL) where the reduction of the metal by the enzyme takes place.

Biodegradable polyurethane micelles with pH and reduction responsive properties for intracellular drug delivery.

PubMed

Guan, Yayuan; Su, Yuling; Zhao, Lili; Meng, Fancui; Wang, Quanxin; Yao, Yongchao; Luo, Jianbin

2017-06-01

Polyurethane micelles with disulfide linkage located at the interface of hydrophilic shell and hydrophobic core (PU-SS-I) have been shown enhanced drug release profiles. However, the payloads could not be released completely. The occurrence of aggregation of hydrophobic cores upon shedding hydrophilic PEG coronas was considered as the reason for the incomplete release. To verify the above hypothesis and to develop a new polyurethane based micelles with dual stimuli respond properties and controllable location of pH and reduction responsive groups in the PU main chains, a tertiary amine was incorporated into the hydrophobic core PU-SS-I, which resulted polyurethane with both reduction and pH sensitive properties (PU-SS-N). Biodegradable polyurethane with only disulfide linkages located between the hydrophilic PEG segment and the hydrophobic PCL segments (PU-SS-I) and polyurethane with only pH sensitive tertiary amine at the hydrophobic core (PU-N-C) were used as comparisons. Paclitaxel (PTX) was chosen as mode hydrophobic drug to evaluate the loading and redox triggered release profiles of the PU micelles. It was demonstrated that PU-SS-N micelles disassembled instantly at the presence of 10mM GSH and at an acidic environment (pH=5.5), which resulted the nearly complete release (~90%) of the payloads within 48h, while about ~70% PTX was released from PU-SS-I and PU-SS-N micelles at neutral environment (pH=7.4) with the presence of 10mM GSH. The rapid and complete redox and pH stimuli release properties of the PU-SS-N nanocarrier will be a promising anticancer drug delivery system to ensure sufficient drug concentration to kill the cancer cells and to prevent the emergency of MDR. The in vitro cytotoxicity and cell uptake of the PTX-loaded micelles was also assessed in H460 and HepG2 cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Redox Species of Redox Flow Batteries: A Review.

PubMed

Pan, Feng; Wang, Qing

2015-11-18

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

Effects of redox-active interlayer anions on the oxygen evolution reactivity of NiFe-layered double hydroxide nanosheets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Daojin; Cai, Zhao; Bi, Yongmin

Nickel-iron layered double hydroxide (NiFe-LDH) nanosheets have shown optimal oxygen evolution reaction (OER) performance; however, the role of the intercalated ions in the OER activity remains unclear. In this work, we show that the activity of the NiFe-LDHs can be tailored by the intercalated anions with different redox potentials. The intercalation of anions with low redox potential (high reducing ability), such as hypophosphites, leads to NiFe-LDHs with low OER overpotential of 240 mV and a small Tafel slope of 36.9 mV/dec, whereas NiFe-LDHs intercalated with anions of high redox potential (low reducing ability), such as fluorion, show a high overpotentialmore » of 370 mV and a Tafel slope of 80.8 mV/dec. The OER activity shows a surprising linear correlation with the standard redox potential. Density functional theory calculations and X-ray photoelectron spectroscopy analysis indicate that the intercalated anions alter the electronic structure of metal atoms which exposed at the surface. Anions with low standard redox potential and strong reducing ability transfer more electrons to the hydroxide layers. Finally, this increases the electron density of the surface metal sites and stabilizes their high-valence states, whose formation is known as the critical step prior to the OER process.« less

Effects of redox-active interlayer anions on the oxygen evolution reactivity of NiFe-layered double hydroxide nanosheets

DOE PAGES

Zhou, Daojin; Cai, Zhao; Bi, Yongmin; ...

2018-02-02

Nickel-iron layered double hydroxide (NiFe-LDH) nanosheets have shown optimal oxygen evolution reaction (OER) performance; however, the role of the intercalated ions in the OER activity remains unclear. In this work, we show that the activity of the NiFe-LDHs can be tailored by the intercalated anions with different redox potentials. The intercalation of anions with low redox potential (high reducing ability), such as hypophosphites, leads to NiFe-LDHs with low OER overpotential of 240 mV and a small Tafel slope of 36.9 mV/dec, whereas NiFe-LDHs intercalated with anions of high redox potential (low reducing ability), such as fluorion, show a high overpotentialmore » of 370 mV and a Tafel slope of 80.8 mV/dec. The OER activity shows a surprising linear correlation with the standard redox potential. Density functional theory calculations and X-ray photoelectron spectroscopy analysis indicate that the intercalated anions alter the electronic structure of metal atoms which exposed at the surface. Anions with low standard redox potential and strong reducing ability transfer more electrons to the hydroxide layers. Finally, this increases the electron density of the surface metal sites and stabilizes their high-valence states, whose formation is known as the critical step prior to the OER process.« less

Redox-Active Star Molecules Incorporating the 4-Benzolypyridinium Cation: Implications for the Charge Transfer Efficiency Along Branches versus Across the Perimeter in Dendrimers

NASA Technical Reports Server (NTRS)

Yang, Jin-Hua; Rawashdeh, Abdel Monem M.; Oh, Woon Su; Sotiriou-Leventis, Chariklia; Leventis, Nicholas

2003-01-01

We report the redox properties of four star systems incorporating the 4-benzoyl-N-alkylpyridinium cation; the redox potential varies along the branches, but remains constant at fixed radii. Voltammetric analysis (cyclic voltammetry and differential pulse voltammetry) shows that only two of the three redox-active centers in the perimeter are electrochemically accessible during potential sweeps as slow as 20 mV/s and as fast as 10 V/s. On the contrary, both redox centers of a branch are accessible electrochemically within the same time frame. These results are discussed in terms of slow through-space charge transfer and the globular 3-D folding of the molecules.

Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 NAd (Ad = adamantyl).

PubMed

Heins, Spencer P; Wolczanski, Peter T; Cundari, Thomas R; MacMillan, Samantha N

2017-05-01

Application of the diamide, diimine {-CHN(1,2-C 6 H 4 )N(2,6- i Pr 2 -C 6 H 3 )} 2 m ((dadi) m ) ligand to titanium provided adducts (dadi)TiL x ( 1 -L x ; L x = THF, PMe 2 Ph, (CNMe) 2 ), which possess the redox formulation [(dadi) 4- ]Ti(iv)L x , and 22 πe - (4 n + 2). Related complexes containing titanium-ligand multiple bonds, (dadi)TiX ( 2 X; X = O, NAd), exhibit a different dadi redox state, [(dadi) 2- ]Ti(iv)X, consistent with 20 πe - (4 n ). The Redox Non-Innocence (RNI) displayed by dadi m impedes binding by CO, and permits catalytic conversion of AdN 3 + CO to AdNCO + N 2 . Kinetics measurements support carbonylation of 2 NAd as the rate determining step. Structural and computational evidence for the observed RNI is provided.

Can microbes mediate nano-transformation?

NASA Astrophysics Data System (ADS)

Prasad, K.; Jha, Anal K.; Prasad, Kamlesh; Kulkarni, A. R.

2010-10-01

A green low-cost and reproducible microbe ( Lactobacillus) and baker's yeast ( Saccharomyces cerevisiae) mediated biosynthesis of metallic and oxide nanoparticles are reported. Silver and copper oxide nanoparticles are synthesized using Lactobacillus sp. and Saccharomyces cerevisiae. The synthesis is performed akin to room temperature in the laboratory ambience. X-ray and transmission electron microscopy analyses are performed to ascertain the formation of metallic and oxide nanoparticles. Individual nanoparticles having the dimensions of 2-6 nm (metallic) and 10-20 nm (oxide) are found. A possible mechanism involved for the synthesis of metallic and oxide nanoparticles has also been proposed in which pH as well as the partial pressure of gaseous hydrogen (r-H2) or redox potential of the culture solution seem to play an important role in the process.

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

PubMed

Tanaka, Leonardo Y; Laurindo, Francisco R M

2017-08-01

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

A redox-based mechanism for nitric oxide-induced inhibition of DNA synthesis in human vascular smooth muscle cells

PubMed Central

Bundy, Ruth E; Marczin, Nándor; Chester, Adrian H; Yacoub, Magdi

2000-01-01

The current study explored potential redox mechanisms of nitric oxide (NO)-induced inhibition of DNA synthesis in cultured human and rat aortic smooth muscle cells.Exposure to S-nitrosothiols, DETA-NONOate and NO itself inhibited ongoing DNA synthesis and S phase progression in a concentration-dependent manner, as measured by thymidine incorporation and flow cytometry. Inhibition by NO donors occurred by release of NO, as detected by chemiluminescence and judged by the effects of NO scavengers, haemoglobin and cPTIO.Co-incubation with redox compounds, N-acetyl-L-cysteine, glutathione and L-ascorbic acid prevented NO inhibition of DNA synthesis. These observations suggest that redox agents may alternatively attenuate NO bioactivity extracellularly, interfere with intracellular actions of NO on the DNA synthesis machinery or restore DNA synthesis after established inhibition by NO.Recovery of DNA synthesis after inhibition by NO was similar with and without redox agents suggesting that augmented restoration of DNA synthesis is an unlikely mechanism to explain redox regulation.Study of extracellular interactions revealed that all redox agents potentiated S-nitrosothiol decomposition and NO release.Examination of intracellular NO bioactivity showed that as opposed to attenuation of NO inhibition of DNA synthesis by redox agents, there was no inhibition (potentiation in the presence of ascorbic acid) of soluble guanylate cyclase (sGC) activation judged by cyclic GMP accumulation in rat cells.These data provide evidence that NO-induced inhibition of ongoing DNA synthesis is sensitive to redox environment. Redox processes might protect the DNA synthesis machinery from inhibition by NO, in the setting of augmented liberation of biologically active NO from NO donors. PMID:10742309

Pd-catalyzed versus uncatalyzed, PhI(OAc)2-mediated cyclization reactions of N6-([1,1'-biaryl]-2-yl)adenine nucleosides.

PubMed

Satishkumar, Sakilam; Poudapally, Suresh; Vuram, Prasanna K; Gurram, Venkateshwarlu; Pottabathini, Narender; Sebastian, Dellamol; Yang, Lijia; Pradhan, Padmanava; Lakshman, Mahesh K

2017-11-09

In this work we have assessed reactions of N 6 -([1,1'-biaryl]-2-yl)adenine nucleosides with Pd(OAc) 2 and PhI(OAc) 2 , via a Pd II /Pd IV redox cycle. The substrates are readily obtained by Pd/Xantphos-catalyzed reaction of adenine nucleosides with 2-bromo-1,1'-biaryls. In PhMe, the N 6 -biarylyl nucleosides gave C6-carbazolyl nucleoside analogues by C-N bond formation with the exocyclic N 6 nitrogen atom. In the solvent screening for the Pd-catalyzed reactions, an uncatalyzed process was found to be operational. It was observed that the carbazolyl products could also be obtained in the absence of a metal catalyst by reaction with PhI(OAc) 2 in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP). Thus, under Pd catalysis and in HFIP, reactions proceed to provide carbazolyl nucleoside analogues, with some differences. If reactions of N 6 -biarylyl nucleoside substrates were conducted in MeCN, formation of aryl benzimidazopurinyl nucleoside derivatives was observed in many cases by C-N bond formation with the N 1 ring nitrogen atom of the purine (carbazole and benzimidazole isomers are readily separated by chromatography). Whereas Pd II /Pd IV redox is responsible for carbazole formation under the metal-catalyzed conditions, in HFIP and MeCN radical cations and/or nitrenium ions can be intermediates. An extensive set of radical inhibition experiments was conducted and the data are presented.

Microbial reduction of iodate

USGS Publications Warehouse

Councell, T.B.; Landa, E.R.; Lovley, D.R.

1997-01-01

The different oxidation species of iodine have markedly different sorption properties. Hence, changes in iodine redox states can greatly affect the mobility of iodine in the environment. Although a major microbial role has been suggested in the past to account for these redox changes, little has been done to elucidate the responsible microorganisms or the mechanisms involved. In the work presented here, direct microbial reduction of iodate was demonstrated with anaerobic cell suspensions of the sulfate reducing bacterium Desulfovibrio desulfuricans which reduced 96% of an initial 100 ??M iodate to iodide at pH 7 in 30 mM NaHCO3 buffer, whereas anaerobic cell suspensions of the dissimilatory Fe(III)-reducing bacterium Shewanella putrefaciens were unable to reduce iodate in 30 mM NaHCO3 buffer (pH 7). Both D. desulfuricans and S. putrefaciens were able to reduce iodate at pH 7 in 10 mM HEPES buffer. Both soluble ferrous iron and sulfide, as well as iron monosulfide (FeS) were shown to abiologically reduce iodate to iodide. These results indicate that ferric iron and/or sulfate reducing bacteria are capable of mediating both direct, enzymatic, as well as abiotic reduction of iodate in natural anaerobic environments. These microbially mediated reactions may be important factors in the fate and transport of 129I in natural systems.

Influence of Oxalate on Ni Fate during Fe(II)-Catalyzed Recrystallization of Hematite and Goethite.

PubMed

Flynn, Elaine D; Catalano, Jeffrey G

2018-06-05

During biogeochemical iron cycling at redox interfaces, dissolved Fe(II) induces the recrystallization of Fe(III) oxides. Oxalate and other organic acids promote dissolution of these minerals and may also induce recrystallization. These processes may redistribute trace metals among the mineral bulk, mineral surface, and aqueous solution. However, the impact of interactions among organic acids, dissolved Fe(II), and iron oxide minerals on trace metal fate in such systems is unclear. The present study thus explores the effect of oxalate on Ni release from and incorporation into hematite and goethite in the absence and presence of Fe(II). When Ni is initially structurally incorporated into the iron oxides, both oxalate and dissolved Fe(II) promote the release of Ni to aqueous solution. When both species are present, their effects on Ni release are synergistic at pH 7 but inhibitory at pH 4, indicating that cooperative and competitive interactions vary with pH. In contrast, oxalate suppresses Ni incorporation into goethite and hematite during Fe(II)-induced recrystallization, decreasing the proportion of Ni substituting in a mineral structure by up to 36%. These observations suggest that at redox interfaces oxalate largely enhances trace metal mobility. In such settings, oxalate, and likely other organic acids, may thus enhance micronutrient availability and inhibit contaminant sequestration.

Profiling bacterial communities associated with sediment-based aquaculture bioremediation systems under contrasting redox regimes

NASA Astrophysics Data System (ADS)

Robinson, Georgina; Caldwell, Gary S.; Wade, Matthew J.; Free, Andrew; Jones, Clifford L. W.; Stead, Selina M.

2016-12-01

Deposit-feeding invertebrates are proposed bioremediators in microbial-driven sediment-based aquaculture effluent treatment systems. We elucidate the role of the sediment reduction-oxidation (redox) regime in structuring benthic bacterial communities, having direct implications for bioremediation potential and deposit-feeder nutrition. The sea cucumber Holothuria scabra was cultured on sediments under contrasting redox regimes; fully oxygenated (oxic) and redox stratified (oxic-anoxic). Taxonomically, metabolically and functionally distinct bacterial communities developed between the redox treatments with the oxic treatment supporting the greater diversity; redox regime and dissolved oxygen levels were the main environmental drivers. Oxic sediments were colonised by nitrifying bacteria with the potential to remediate nitrogenous wastes. Percolation of oxygenated water prevented the proliferation of anaerobic sulphate-reducing bacteria, which were prevalent in the oxic-anoxic sediments. At the predictive functional level, bacteria within the oxic treatment were enriched with genes associated with xenobiotics metabolism. Oxic sediments showed the greater bioremediation potential; however, the oxic-anoxic sediments supported a greater sea cucumber biomass. Overall, the results indicate that bacterial communities present in fully oxic sediments may enhance the metabolic capacity and bioremediation potential of deposit-feeder microbial systems. This study highlights the benefits of incorporating deposit-feeding invertebrates into effluent treatment systems, particularly when the sediment is oxygenated.

Profiling bacterial communities associated with sediment-based aquaculture bioremediation systems under contrasting redox regimes

PubMed Central

Robinson, Georgina; Caldwell, Gary S.; Wade, Matthew J.; Free, Andrew; Jones, Clifford L. W.; Stead, Selina M.

2016-01-01

Deposit-feeding invertebrates are proposed bioremediators in microbial-driven sediment-based aquaculture effluent treatment systems. We elucidate the role of the sediment reduction-oxidation (redox) regime in structuring benthic bacterial communities, having direct implications for bioremediation potential and deposit-feeder nutrition. The sea cucumber Holothuria scabra was cultured on sediments under contrasting redox regimes; fully oxygenated (oxic) and redox stratified (oxic-anoxic). Taxonomically, metabolically and functionally distinct bacterial communities developed between the redox treatments with the oxic treatment supporting the greater diversity; redox regime and dissolved oxygen levels were the main environmental drivers. Oxic sediments were colonised by nitrifying bacteria with the potential to remediate nitrogenous wastes. Percolation of oxygenated water prevented the proliferation of anaerobic sulphate-reducing bacteria, which were prevalent in the oxic-anoxic sediments. At the predictive functional level, bacteria within the oxic treatment were enriched with genes associated with xenobiotics metabolism. Oxic sediments showed the greater bioremediation potential; however, the oxic-anoxic sediments supported a greater sea cucumber biomass. Overall, the results indicate that bacterial communities present in fully oxic sediments may enhance the metabolic capacity and bioremediation potential of deposit-feeder microbial systems. This study highlights the benefits of incorporating deposit-feeding invertebrates into effluent treatment systems, particularly when the sediment is oxygenated. PMID:27941918

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heins, Spencer P.; Wolczanski, Peter T.; Cundari, Thomas R.

Application of the diamide, diimine {–CH=N(1,2-C 6H 4)N(2,6- iPr 2-C 6H 3)} 2 m ((dadi) m) ligand to titanium provided adducts (dadi)TiL x (1-L x; L x = THF, PMe 2Ph, (CNMe) 2), which possess the redox formulation [(dadi) 4-]Ti(IV)L x, and 22 πe - (4n + 2). Related complexes containing titanium-ligand multiple bonds, (dadi)Ti=X (2=X; X = O, NAd), exhibit a different dadi redox state, [(dadi) 2-]Ti(IV)X, consistent with 20 πe - (4n). The Redox Non-Innocence (RNI) displayed by dadi m impedes binding by CO, and permits catalytic conversion of AdN 3 + CO to AdNCO + N 2.more » Kinetics measurements support carbonylation of 2=NAd as the rate determining step. Finally, structural and computational evidence for the observed RNI is provided.« less

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

PubMed

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

2014-09-01

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

Role of tartaric and malic acids in wine oxidation.

PubMed

Danilewicz, John C

2014-06-04

Tartaric acid determines the reduction potential of the Fe(III)/Fe(II) redox couple. Therefore, it is proposed that it determines the ability of Fe to catalyze wine oxidation. The importance of tartaric acid was demonstrated by comparing the aerial oxidation of 4-methylcatechol (4-MeC) in model wine made up with tartaric and acetic acids at pH 3.6. Acetic acid, as a weaker Fe(III) ligand, should raise the reduction potential of the Fe couple. 4-MeC was oxidized in both systems, but the mechanisms were found to differ. Fe(II) readily reduced oxygen in tartrate model wine, but Fe(III) alone failed to oxidize the catechol, requiring sulfite assistance. In acetate model wine the reverse was found to operate. These observations should have broad application to model systems designed to study the oxidative process in foods and other beverages. Consideration should be given to the reduction potential of metal couples by the inclusion of appropriate ligands.

[The relationship between oxidized form glutathione, coenzyme II and carotid artery atherosclerosis].

PubMed

Huang, Yan-sheng; Wang, Shu-ren; Zhi, Yan-fang; Xu, Bo-shi; Sun, Lin; Wu, Yu; Lu, Jian-min; Dai, Fu-min

2006-06-01

To explore the relationship between plasma redox status and atherosclerosis. IVUS was performed in common carotid in the neck of 167 patients with heart diseases. Patients were divided into three groups: plaque-forming group (A, n = 79), intima-thickening group (B, n = 52) and control group (C, n = 36). Plasma glutathione (reduced form GSH and oxidized form GSSG), nicotinamide adenine dinucleotide phosphate (reduced form NADPH and oxidized form NADP(+)), oxidized low density lipoprotein (ox-LDL) and malondialdehyde (MDA) were measured in all patients. The GSH/GSSG and NADPH/NADP(+) redox potential were calculated according to Nernst equation, and correlation analysis performed. GSH and GSH/GSSG gradually reduced and GSH/GSSG redox potential gradually increased in proportion to the thickening of artery intima (from Group C to Group A, P < 0.05). Similar but milder results were shown for NADPH and NADPH/NADP(+) redox status. The products of oxidative stress ox-LDL and MDA also increased significantly (P < 0.05) in proportion to the thickening of artery intima. GSH/GSSG redox potential is positively correlated to ox-LDL (P < 0.05). The redox status shifted to oxidizing direction in proportion to the intima thickness. The imbalance of plasma redox status deviating to oxidation might be implicated in oxidized injury of lipid, intima thickening and atherosclerosis progress.

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

PubMed

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

2017-06-19

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

Developmental changes in the levels and redox potentials of main hemolymph thiols/disulfides in the Jamaican field cricket Gryllus assimilis.

PubMed

Sadowska-Bartosz, Izabela; Furmaniak, Paulina; Bieszczad-Bedrejczuk, Edyta; Bartosz, Grzegorz; Głowacki, Rafał

2017-01-01

Main thiols and disulfides were determined in the hemolymph of the Jamaican field cricket Gryllus assimilis at various developmental stages. On the basis of these data, redox potentials of the glutathione, cysteine and homocysteine redox systems were calculated. The concentrations of all thiols studied decreased during development (at a stage of 6 molts) with respect to young crickets, and increased again in adult insects. Redox potentials of the glutathione and cysteine systems increased from values of -131.0±5.6 mV and -86.9±17.1 mV, respectively in young crickets to -58.0±3.6 mV and -36.1±4.2 mV, respectively, at the stage of 6 molts and decreased to values of -110.4±24.8 mV and -66.3±12.2 mV, respectively, in adult insects. Redox potentials of the glutathione and cysteine systems in the hemolymph of young and adult insects were similar to those reported for human plasma.

Effects of Concrete Channels on Stream Biogeochemistry, Maryland Coastal Plain

NASA Astrophysics Data System (ADS)

Prestegaard, K. L.; Gilbert, L.; Phemister, K.

2005-05-01

In the 1950's and 60's, extensive networks of cement-lined channels were built in suburban watersheds near Washington, D.C. to convey storm water to downstream locations. These cement-lined stream channels limit interactions between surface and groundwater and they provide sources of alkalinity in Maryland Coastal Plain watersheds that normally have low alkalinity. This project was designed to 1) compare base flow water chemistry in headwater reaches of urban and non-urban streams, and 2) to evaluate downstream changes in water chemistry in channelized urban streams in comparison with non-urban reference streams. During a drought year, headwater streams in both urban and non-urban sites had significant concentrations of Fe(II) that were discharged from groundwater sources and rapidly oxidized by iron-oxidizing bacteria. During a wet year, the concentrations of Fe(II) were higher in headwater urban streams than in the non-urban streams. This suggests that impervious surfaces in headwater urban watersheds prevent the recharge of oxygen-rich waters during storm events, which maintains iron-rich groundwater discharge to the stream. Downstream changes in water chemistry are prominent in cement-lined urban channels because they are associated with distinctive microbial communities. The headwater zones of channelized streams are dominated by iron-ozidizing bacteria, that are replaced downstream by manganese-oxidizing zones, and replaced further downstream by biofilms dominated by photosynthesizing cyanobacteria. The reaches dominated by cyanobacteria exhibit diurnal changes in pH due to uptake of CO2 for photosynthesis. Diurnal changes range from 7.5 to 8.8 in the summer months to 7.0 to 7.5 in the cooler months, indicating both the impact of photosynthesis and the additional source of alkalinity provided by concrete. The dissolved oxygen, pH, and other characteristics of tributaries dominated by cyanobacteria are similar to the water chemistry characteristics observed in much larger urban river channels further downstream. These downstream redox zonations, microbial habitats, and pH characteristics observed in channelized tributaries are very different from non-urban watersheds in the Maryland Coastal Plain, which have pH values less than 7 and do not have the prominent redox zonations and associated microbial habitats. These downstream changes in redox chemistry and pH in urban stream channels have implications for the transport and retention of heavy metals in urban streams.

Iron and aluminum solid phase dynamics and carbon storage across a water balance gradient in volcanic soils

NASA Astrophysics Data System (ADS)

Bateman, J. B.; Fendorf, S. E.; Vitousek, P.

2017-12-01

Iron (Fe) and Aluminum (Al) are major components of volcanic soils, and strongly influence the stability of soil carbon (C). The stability of Fe and Al phases is dictated by the redox conditions and pH of soils, respectively. The water balance of a soil, defined as annual precipitation minus evapotranspiration, ultimately controls pH and redox conditions. Consequently, we hypothesize that water balance influences Fe/Al solid phase dynamics in volcanic soils when the climatic regime has persisted on timescales of 20 ky. To test this hypothesis, we collected soils from a naturally occurring water balance gradient on the windward side of Mauna Kea Volcano in Hawaii, across which water balance ranges from -1270 mm/y to +2000 mm/y. Sampling included complete soil profiles, and 30 cm surface soil samples. We determined the solid phases of Fe/Al with selective extractions and total C via combustion. Extracted Fe/Al were then partitioned into operational pools: organically bound, amorphous, crystalline, primary mineral, primary glass, and residual. All soils in the study were acidic, with pH between 3.4 and 6.4. Soil C varied considerably across the gradient, from <1% C to >15% C by weight. Across sites, soil pH, Fe in primary minerals and glasses, and residual Al are negatively correlated with water balance, while soil C, organic Fe and Al, and crystalline Fe correlated positively with water balance. Organically bound Al increases linearly with water balance, while organically bound Fe is uncorrelated with water balance in soils where water balance is negative and is positively correlated with water balance in wetter sites. These results show that soils developing from the same parent material, though under different water balance regimes, range from lightly weathered ash deposits with little C accumulation in the driest regions, to heavily weathered soils composed of crystalline Fe, organic matter, and organically bound Fe/Al in the wettest regions. Al appears to be the primary stabilizer for organic matter in many of these soils, though Fe plays a role when both water availability and soil C are high. The pattern of organic Fe/Al indicate that pH is a stronger controller on C storage in these soils when water balance is low or negative, and that redox reactions become increasingly important as water balance becomes more positive.

Sedimentary reservoir oxidation during geologic CO2 sequestration

NASA Astrophysics Data System (ADS)

Lammers, Laura N.; Brown, Gordon E.; Bird, Dennis K.; Thomas, Randal B.; Johnson, Natalie C.; Rosenbauer, Robert J.; Maher, Katharine

2015-04-01

Injection of carbon dioxide into subsurface geologic reservoirs during geologic carbon sequestration (GCS) introduces an oxidizing supercritical CO2 phase into a subsurface geologic environment that is typically reducing. The resulting redox disequilibrium provides the chemical potential for the reduction of CO2 to lower free energy organic species. However, redox reactions involving carbon typically require the presence of a catalyst. Iron oxide minerals, including magnetite, are known to catalyze oxidation and reduction reactions of C-bearing species. If the redox conditions in the reservoir are modified by redox transformations involving CO2, such changes could also affect mineral stability, leading to dissolution and precipitation reactions and alteration of the long-term fate of CO2 in GCS reservoirs. We present experimental evidence that reservoirs with reducing redox conditions are favorable environments for the relatively rapid abiotic reduction of CO2 to organic molecules. In these experiments, an aqueous suspension of magnetite nanoparticles was reacted with supercritical CO2 under pressure and temperature conditions relevant to GCS in sedimentary reservoirs (95-210 °C and ∼100 bars of CO2). Hydrogen production was observed in several experiments, likely caused by Fe(II) oxidation either at the surface of magnetite or in the aqueous phase. Heating of the Fe(II)-rich system resulted in elevated PH2 and conditions favorable for the reduction of CO2 to acetic acid. Implications of these results for the long-term fate of CO2 in field-scale systems were explored using reaction path modeling of CO2 injection into reservoirs containing Fe(II)-bearing primary silicate minerals, with kinetic parameters for CO2 reduction obtained experimentally. The results of these calculations suggest that the reaction of CO2 with reservoir constituents will occur in two primary stages (1) equilibration of CO2 with organic acids resulting in mineral-fluid disequilibrium, and (2) gradual dissolution of primary minerals promoting significant CO2 reduction through the release of Fe(II). The reduction of CO2 is identified as a new trapping mechanism that could significantly enhance the long-term stability of GCS reservoirs. Identification of reservoir characteristics that promote CO2 redox transformations could be used as an additional factor in screening geologic reservoirs for GCS.

Iron-sulfide redox flow batteries

DOEpatents

Xia, Guanguang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

2016-06-14

Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

Iron-sulfide redox flow batteries

DOEpatents

Xia, Guan-Guang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

2013-12-17

Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

Electron flow in multicenter enzymes: theory, applications, and consequences on the natural design of redox chains.

PubMed

Léger, Christophe; Lederer, Florence; Guigliarelli, Bruno; Bertrand, Patrick

2006-01-11

In protein film voltammetry, a redox enzyme is directly connected to an electrode; in the presence of substrate and when the driving force provided by the electrode is appropriate, a current flow reveals the steady-state turnover. We show that, in the case of a multicenter enzyme, this signal reports on the energetics and kinetics of electron transfer (ET) along the redox chain that wires the active site to the electrode, and this provides a new strategy for studying intramolecular ET. We propose a model which takes into account all the enzyme's redox microstates, and we prove it useful to interpret data for various enzymes. Several general ideas emerge from this analysis. Considering the reversibility of ET is a requirement: the usual picture, where ET is depicted as a series of irreversible steps, is oversimplified and lacks the important features that we emphasize. We give justification to the concept of apparent reduction potential on the time scale of turnover and we explain how the value of this potential relates to the thermodynamic and kinetic properties of the system. When intramolecular ET does not limit turnover, the redox chain merely mediates the driving force provided by the electrode or the soluble redox partner, whereas when intramolecular ET is slow, the enzyme behaves as if its active active site had apparent redox properties which depend on the reduction potentials of the relays. This suggests an alternative to the idea that redox chains are optimized in terms of speed: evolutionary pressure may have resulted in slowing down intramolecular ET in order to tune the enzyme's "operating potential".

Impact of glutathione supplementation of parenteral nutrition on hepatic methionine adenosyltransferase activity.

PubMed

Elremaly, Wesam; Mohamed, Ibrahim; Rouleau, Thérèse; Lavoie, Jean-Claude

2016-08-01

The oxidation of the methionine adenosyltransferase (MAT) by the combined impact of peroxides contaminating parenteral nutrition (PN) and oxidized redox potential of glutathione is suspected to explain its inhibition observed in animals. A modification of MAT activity is suspected to be at origin of the PN-associated liver disease as observed in newborns. We hypothesized that the correction of redox potential of glutathione by adding glutathione in PN protects the MAT activity. To investigate whether the addition of glutathione to PN can reverse the inhibition of MAT observed in animal on PN. Three days old guinea pigs received through a jugular vein catheter 2 series of solutions. First with methionine supplement, (1) Sham (no infusion); (2) PN: amino acids, dextrose, lipids and vitamins; (3) PN-GSSG: PN+10μM GSSG. Second without methionine, (4) D: dextrose; (5) D+180μM ascorbylperoxide; (6) D+350μM H2O2. Four days later, liver was sampled for determination of redox potential of glutathione and MAT activity in the presence or absence of 1mM DTT. Data were compared by ANOVA, p<0.05. MAT activity was 45±4% lower in animal infused with PN and 23±7% with peroxides generated in PN. The inhibition by peroxides was associated with oxidized redox potential and was reversible by DTT. Correction of redox potential (PN+GSSG) or DTT was without effect on the inhibition of MAT by PN. The slope of the linear relation between MAT activity and redox potential was two fold lower in animal infused with PN than in others groups. The present study suggests that prevention of peroxide generation in PN and/or correction of the redox potential by adding glutathione in PN are not sufficient, at least in newborn guinea pigs, to restore normal MAT activity. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Thiol-based Redox Proteins in Brassica napus Guard Cell Abscisic Acid and Methyl Jasmonate Signaling

PubMed Central

Zhu, Mengmeng; Zhu, Ning; Song, Wen-yuan; Harmon, Alice C.; Assmann, Sarah M.; Chen, Sixue

2014-01-01

SUMMARY Reversibly oxidized cysteine sulfhydryl groups serve as redox sensors or targets of redox sensing that are important in different physiological processes. Little is known, however, about redox sensitive proteins in guard cells and how they function in stomatal signaling. In this study, Brassica napus guard cell proteins altered by redox in response to abscisic acid (ABA) or methyl jasmonate (MeJA) were identified by complementary proteomics approaches, saturation differential in-gel electrophoresis (DIGE) and isotope-coded affinity tag (ICAT). In total, 65 and 118 potential redox responsive proteins were identified in ABA and MeJA treated guard cells, respectively. All the proteins contain at least one cysteine, and over half of them are predicted to form intra-molecular disulfide bonds. Most of the proteins fall into the functional groups of energy, stress and defense, and metabolism. Based on the peptide sequences identified by mass spectrometry, 30 proteins were common to ABA and MeJA treated samples. A total of 44 cysteines was mapped in all the identified proteins, and their levels of redox sensitivity were quantified. Two of the proteins, a SNRK2 kinase and an isopropylmalate dehydrogenase were confirmed to be redox regulated and involved in stomatal movement. This study creates an inventory of potential redox switches, and highlights a protein redox regulatory mechanism in guard cell ABA and MeJA signal transduction. PMID:24580573

Influence of the solution pH in the 6-mercaptopurine self-assembled monolayer (6MP-SAM) on a Au(111) single-crystal electrode.

PubMed

Madueño, Rafael; García-Raya, Daniel; Viudez, Alfonso J; Sevilla, José M; Pineda, Teresa; Blázquez, Manuel

2007-10-23

Self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) have been prepared on a Au(111) single-crystal electrode by immersion of the metal surface in a 100 microM 6MP and 0.01 M HClO4 solution. The 6MP-SAM Au(111) single-crystal electrodes were transferred to the cell and allowed to equilibrate with the different aqueous working solutions before the electrochemical experiments. The influence of the solution pH was studied by cyclic voltammetry, double layer capacitance curves, and electrochemical impedance spectroscopy. The electrochemical behavior of the 6MP-SAM in acetic acid at pH 4 presents important differences in comparison to that obtained in 0.1 M KOH solutions. Cyclic voltammograms for the reductive desorption process in acid medium are broad and show some features that can be explained by a phase transition between a chemisorbed and a physisorbed state of the 6MP molecules. The low solubility of these molecules in acid medium could explain this phenomenon and the readsorption of the complete monolayer when the potential is scanned in the positive direction. The variation of the double-layer capacitance values in the potential range of monolayer stability with the pH suggests that the acid-base chemistry of the 6MP molecules is playing a role. This fact has been studied by following the variations of the electron-transfer rate constant of the highly charged redox probes as are Fe(CN)(6)-3/-4 and Ru(NH3)(6)+3/+2 as a function of solution pH. The apparent surface pKa value for the 6MP-SAM (pKa approximately 8) is explained by the total conversion of the different 6MP tautomers that exist in solution to the thiol species in the adsorbed state.

Remediation of groundwater contaminated with arsenic through enhanced natural attenuation: Batch and column studies.

PubMed

Hafeznezami, Saeedreza; Zimmer-Faust, Amity G; Jun, Dukwoo; Rugh, Megyn B; Haro, Heather L; Park, Austin; Suh, Jae; Najm, Tina; Reynolds, Matthew D; Davis, James A; Parhizkar, Tarannom; Jay, Jennifer A

2017-10-01

Batch and column laboratory experiments were conducted on natural sediment and groundwater samples from a contaminated site in Maine, USA with the aim of lowering the dissolved arsenate [As(V)] concentrations through chemical enhancement of natural attenuation capacity. In batch factorial experiments, two levels of treatment for three parameters (pH, Ca, and Fe) were studied at different levels of phosphate to evaluate their impact on As(V) solubility. Results illustrated that lowering pH, adding Ca, and adding Fe significantly increased the sorption capacity of sediments. Overall, Fe amendment had the highest individual impact on As(V) levels. To provide further evidence for the positive impact of Ca on As(V) adsorption, isotherm experiments were conducted at three different levels of Ca concentrations. A consistent increase in adsorption capacity (26-37%) of sediments was observed with the addition of Ca. The observed favorable effect of Ca on As(V) adsorption is likely caused by an increase in the surface positive charges due to surface accumulation of Ca 2+ ions. Column experiments were conducted by flowing contaminated groundwater with elevated pH, As(V), and phosphate through both uncontaminated and contaminated sediments. Potential in-situ remediation scenarios were simulated by adding a chemical amendment feed to the columns injecting Fe(II) or Ca as well as simultaneous pH adjustment. Results showed a temporary and limited decrease in As(V) concentrations under the Ca treatment (39-41%) and higher levels of attenuation in Fe(II) treated columns (50-91%) but only after a certain number of pore volumes (18-20). This study illustrates the importance of considering geochemical parameters including pH, redox potential, presence of competing ions, and sediment chemical and physical characteristics when considering enhancing the natural attenuation capacity of sediments to mitigate As contamination in natural systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Emission and distribution of phosphine in paddy fields and its relationship with greenhouse gases.

PubMed

Chen, Weiyi; Niu, Xiaojun; An, Shaorong; Sheng, Hong; Tang, Zhenghua; Yang, Zhiquan; Gu, Xiaohong

2017-12-01

Phosphine (PH 3 ), as a gaseous phosphide, plays an important role in the phosphorus cycle in ecosystems. In this study, the emission and distribution of phosphine, carbon dioxide (CO 2 ) and methane (CH 4 ) in paddy fields were investigated to speculate the future potential impacts of enhanced greenhouse effect on phosphorus cycle involved in phosphine by the method of Pearson correlation analysis and multiple linear regression analysis. During the whole period of rice growth, there was a significant positive correlation between CO 2 emission flux and PH 3 emission flux (r=0.592, p=0.026, n=14). Similarly, a significant positive correlation of emission flux was also observed between CH 4 and PH 3 (r=0.563, p=0.036, n=14). The linear regression relationship was determined as [PH 3 ] flux =0.007[CO 2 ] flux +0.063[CH 4 ] flux -4.638. No significant differences were observed for all values of matrix-bound phosphine (MBP), soil carbon dioxide (SCO 2 ), and soil methane (SCH 4 ) in paddy soils. However, there was a significant positive correlation between MBP and SCO 2 at heading, flowering and ripening stage. The correlation coefficients were 0.909, 0.890 and 0.827, respectively. In vertical distribution, MBP had the analogical variation trend with SCO 2 and SCH 4 . Through Pearson correlation analysis and multiple stepwise linear regression analysis, pH, redox potential (Eh), total phosphorus (TP) and acid phosphatase (ACP) were identified as the principal factors affecting MBP levels, with correlative rankings of Eh>pH>TP>ACP. The multiple stepwise regression model ([MBP]=0.456∗[ACP]+0.235∗[TP]-1.458∗[Eh]-36.547∗[pH]+352.298) was obtained. The findings in this study hold great reference values to the global biogeochemical cycling of phosphorus in the future. Copyright © 2017 Elsevier B.V. All rights reserved.

Potential impacts of leakage from deep CO2 geosequestration on overlying freshwater aquifers.

PubMed

Little, Mark G; Jackson, Robert B

2010-12-01

Carbon Capture and Storage may use deep saline aquifers for CO(2) sequestration, but small CO(2) leakage could pose a risk to overlying fresh groundwater. We performed laboratory incubations of CO(2) infiltration under oxidizing conditions for >300 days on samples from four freshwater aquifers to 1) understand how CO(2) leakage affects freshwater quality; 2) develop selection criteria for deep sequestration sites based on inorganic metal contamination caused by CO(2) leaks to shallow aquifers; and 3) identify geochemical signatures for early detection criteria. After exposure to CO(2), water pH declines of 1-2 units were apparent in all aquifer samples. CO(2) caused concentrations of the alkali and alkaline earths and manganese, cobalt, nickel, and iron to increase by more than 2 orders of magnitude. Potentially dangerous uranium and barium increased throughout the entire experiment in some samples. Solid-phase metal mobility, carbonate buffering capacity, and redox state in the shallow overlying aquifers influence the impact of CO(2) leakage and should be considered when selecting deep geosequestration sites. Manganese, iron, calcium, and pH could be used as geochemical markers of a CO(2) leak, as their concentrations increase within 2 weeks of exposure to CO(2).

Electrochemical evidence on the molten globule conformation of cytochrome c.

PubMed

Pineda, T; Sevilla, J M; Román, A J; Blázquez, M

1997-12-05

To explore a new approach for characterizing the molten globule conformation, cyclic voltammetric studies of salt induced transitions at acidic pH of cyt c have been carried out. The use of modified electrodes has made the observation of direct electrochemistry in native cyt c possible. However, most of these electrodes do not show reversible responses at acidic pH, due to the fact that, for this system, a deprotonated electrode surface is needed. In these studies, we have used a 6-mercaptopurine and cysteine-modified gold electrodes which are effective for direct rapid electron transfer to cyt c, even in acid solutions. The change in the absorption bands of cyt c are used to monitor the conformational states and, hence, to compare the voltammetric results. Under the experimental conditions where the A state of cyt c is obtained, a reversible voltammetric signal is observed. The midpoint peak potentials are found to be very close to the formal potential of native cyt c. Results are discussed in terms of a cooperative two-state transition between the acid unfolded and the globular acidic states of cyt c. This finding establishes, for the first time, the similarity of both the native and the molten globule-like conformations in terms of its redox properties.

Effect of Palygorskite Clay, Fertilizers, and Lime on the Degradation of Oil Products in Oligotrophic Peat Soil under Laboratory Experimental Conditions

NASA Astrophysics Data System (ADS)

Tolpeshta, I. I.; Erkenova, M. I.

2018-02-01

The effect of native palygorskite clay and that modified with dodecyltrimethylammonium chloride on the degradation of oil products in an oligotrophic peat soil under complete flooding at the application of lime and mineral fertilizers has been studied under laboratory conditions. It has been shown that the incubation of oil-contaminated soil with unmodified clay and fertilizers at the application of lime under complete flooding with water affects the dynamics of pH and Eh and slows the development of reducing conditions compared to the use of clay without fertilizers. The addition of organoclay under similar conditions favors the formation of potential-determining system with a high redox capacity, which is capable of retaining the potential on a level of 100-200 mV at pH ˜ 7 for two months. It has been found that, under the experimental conditions, unmodified and modified clay, which has no toxic effect on the bacterial complex, does not increase the biodegradation efficiency of oil products in the oligotrophic peat soil compared to the experimental treatments without clay addition. Possible reasons for no positive effect of palygorskite clay on the biodegradation rate of oil products under experimental conditions have been analyzed.

Diel variation of selenium and arsenic in a wetland of the Great Salt Lake, Utah

USGS Publications Warehouse

Dicataldo, G.; Johnson, W.P.; Naftz, D.L.; Hayes, D.F.; Moellmer, W.O.; Miller, T.

2011-01-01

Diel (24-h) changes in Se and As concentrations in a freshwater wetland pond bordering the Great Salt Lake (GSL) were examined. Selenium concentrations (filtered and unfiltered) changed on a diel basis, i.e., were depleted during early morning and enriched during daytime over August 17-18. During the May 24-25, 2006 and September 29-30 diel studies, no significant 24-h trends were observed in Se concentrations compared to August, which showed daily maximums up to 59% greater than the daily minimum. Both filtered and unfiltered As concentrations also varied on a diel cycle, with increased concentrations during early morning and decreased concentrations during daytime. Filtered As concentrations increased 110% during the May 24-25, 2006 diel study. Selenium varied in phase with pH, dissolved O2 (DO), and water temperature (Tw) whereas As varied opposite to Se, pH, DO and Tw. Changes in pH, DO and Tw showed a direct linear correlation (r=0.74, 0.75, and 0.55, respectively) to filtered Se. Also pH, DO and Tw were inversely correlated to filtered As concentration (r=-0.88, -0.87, and -0.84, respectively). Equilibrium geochemical speciation and sorption models were used to examine the potential oxidation state changes in Se and As, and sorption and desorption reactions corresponding to the observed 24-h variations in pe and pH. In this wetland it was postulated that diel Se variation was driven by sorption and desorption due to photosynthesis-induced changes in pH and redox conditions. Diel variations of As were hypothesized to be linked to pH-driven sorption and desorption as well as co-precipitation and co-dissolution with mineral phases of Mn. ?? 2010 Elsevier Ltd.

Simple electro-assisted immobilization of ciprofloxacin on carbon nanotube modified electrodes: its selective hydrogen peroxide electrocatalysis.

PubMed

Sornambikai, Sundaram; Kumar, Annamalai Senthil

2014-09-01

Ciprofloxacin (Cf) is a synthetic fourth generation fluoroquinolone class antibiotic used for the treatment of gram-positive, gram-negative and mycobacterium species infections. Electrochemical characteristic of the Cf antibiotic on carbon nanotube modified glassy carbon electrode (GCE/CNT) in pH 7 phosphate buffer solution has been investigated. Electrochemically oxidized radical byproduct of the Cf drug, which is formed as intermediate, gets immobilized on the GCE/CNT (GCE/Cf@CNT) and showed stable and well defined surface confined redox peak at -0.220 V versus Ag/AgCl. Control electrochemical experiment with unmodified GCE failed to show any such immobilization and redox features. Physicochemical characterizations of the Cf@CNT by transmission electron microscope, scanning electron microscope, infrared spectroscopy, UV-Vis and gas chromatography coupled mass spectroscopic analyses of Cf@CNT collectively revealed presence of native form of the Cf antibiotic molecule onto the CNT. The interaction between the Cf molecule and the CNT tubes are revealed from the decreased intensity in the Raman spectrum. The GCE/Cf@CNT showed excellent electrocatalytic response to hydrogen peroxide reduction reaction in pH 7 phosphate buffer solution. Amperometric i-t analysis for the detection of H2O2 showed a current linearity plot upto [H2O2] = 200 μM at an applied potential - 0.1 V versus Ag/AgCl with a current sensitivity value 678 μA mM(-1) cm(-2). No interferences were noticed with ascorbic acid, uric acid, cysteine and nitrite. The present study can be highly helpful to understand the interaction between the Cf and H2O2 in physiological systems and for the removal of Cf from the antibiotic polluted water samples especially in the aquaculture and agricultural systems.

Characterization of the free energy dependence of an interprotein electron transfer reaction by variation of pH and site-directed mutagenesis.

PubMed

Dow, Brian A; Davidson, Victor L

2015-10-01

The interprotein electron transfer (ET) reactions of the cupredoxin amicyanin, which mediates ET from the tryptophan tryptophylquinone (TTQ) cofactor of methylamine dehydrogenase to cytochrome c-551i have been extensively studied. However, it was not possible to perform certain key experiments in that native system. This study examines the ET reaction from reduced amicyanin to an alternative electron acceptor, the diheme protein MauG. It was possible to vary the ΔG° for this ET reaction by simply changing pH to determine the dependence of kET on ΔG°. A P94A mutation of amicyanin significantly altered its oxidation-reduction midpoint potential value. It was not possible to study the ET from reduced P94A amicyanin to cytochrome c-551i in the native system because that reaction was kinetically coupled. However, the reaction from reduced P94A amicyanin to MauG was a true ET reaction and it was possible to determine values of reorganization energy (λ) and electronic coupling for the reactions of this variant as well as native amicyanin. Comparison of the λ values associated with the ET reactions between amicyanin and the TTQ of methylamine dehydrogenase, the diheme center of MauG and the single heme of cytochrome c-551i, provides insight into the factors that dictate the λ values for the respective reactions. These results demonstrate how study of ET reactions with alternative redox partner proteins can complement and enhance our understanding of the reactions with the natural redox partners, and further our understanding of mechanisms of protein ET reactions. Copyright © 2015 Elsevier B.V. All rights reserved.

Copper complexes as a source of redox active MRI contrast agents.

PubMed

Dunbar, Lynsey; Sowden, Rebecca J; Trotter, Katherine D; Taylor, Michelle K; Smith, David; Kennedy, Alan R; Reglinski, John; Spickett, Corinne M

2015-10-01

The study reports an advance in designing copper-based redox sensing MRI contrast agents. Although the data demonstrate that copper(II) complexes are not able to compete with lanthanoids species in terms of contrast, the redox-dependent switch between diamagnetic copper(I) and paramagnetic copper(II) yields a novel redox-sensitive contrast moiety with potential for reversibility.

Imaging Redox State in Mouse Muscles of Different Ages.

PubMed

Moon, Lily; Frederick, David W; Baur, Joseph A; Li, Lin Z

2017-01-01

Aging is the greatest risk factor for many diseases. Intracellular concentrations of nicotinamide adenine dinucleotide (NAD + ) and the NAD + -coupled redox state have been proposed to moderate many aging-related processes, yet the specific mechanisms remain unclear. The concentration of NAD + falls with age in skeletal muscle, yet there is no consensus on whether aging will increase or decrease the redox potential of NAD + /NADH. Oxidized flavin groups (Fp) (e.g. FAD, i.e., flavin adenine dinucleotide, contained in flavoproteins) and NADH are intrinsic fluorescent indicators of oxidation and reduction status of tissue, respectively. The redox ratio, i.e., the ratio of Fp to NADH, may be a surrogate indicator of the NAD + /NADH redox potential. In this study we used the Chance redox scanner (NADH/Fp fluorescence imaging at low temperature) to investigate the effect of aging on the redox state of mitochondria in skeletal muscles. The results showed that there are borderline significant differences in nominal concentrations of Fp and NADH, but not in the redox ratio s when comparing 3.5-month and 13-month old muscles of mice (n = 6). It may be necessary to increase the number of muscle samples and study mice of more advanced age.

Minimizing analyte electrolysis in electrospray ionization mass spectrometry using a redox buffer coated emitter electrode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peintler-Krivan, Emese; Van Berkel, Gary J; Kertesz, Vilmos

2010-01-01

An emitter electrode with an electroactive poly(pyrrole) (PPy) polymer film coating was constructed for use in electrospray ionization mass spectrometry (ESI-MS). The PPy film acted as a surface-attached redox buffer limiting the interfacial potential of the emitter electrode. While extensive oxidation of selected analytes (reserpine and amodiaquine) was observed in positive ion mode ESI using a bare metal (gold) emitter electrode, the oxidation was suppressed for these same analytes when using the PPy-coated electrode. A semi-quantitative relationship between the rate of oxidation observed and the interfacial potential of the emitter electrode was shown. The redox buffer capacity, and therefore themore » lifetime of the redox buffering effect, correlated with the oxidation potential of the analyte and with the magnitude of the film charge capacity. Online reduction of the PPy polymer layer using negative ion mode ESI between analyte injections was shown to successfully restore the redox buffering capacity of the polymer film to its initial state.« less

Correlation between pH dependence of O2 evolution and sensitivity of Mn cations in the oxygen-evolving complex to exogenous reductants.

PubMed

Semin, Boris K; Davletshina, Lira N; Rubin, Andrei B

2015-08-01

Effects of pH, Ca(2+), and Cl(-) ions on the extraction of Mn cations from oxygen-evolving complex (OEC) in Ca-depleted photosystem II (PSII(-Ca)) by exogenous reductants hydroquinone (H2Q) and H2O2 were studied. Two of 4 Mn cations are released by H2Q and H2O2 at pHs 5.7, 6.5, and 7.5, and their extraction does not depend on the presence of Ca(2+) and Cl(-) ions. One of Mn cations ("resistant" Mn cation) cannot be extracted by H2Q and H2O2 at any pH. Extraction of 4th Mn ion ("flexible" Mn cation) is sensitive to pH, Ca(2+), and Cl(-). This Mn cation is released by reductants at pH 6.5 but not at pHs 5.7 and 7.5. A pH dependence curve of the oxygen-evolving activity in PSII(-Ca) membranes (in the presence of exogenous Ca(2+)) has a bell-shaped form with the maximum at pH 6.5. Thus, the increase in the resistance of flexible Mn cation in OEC to the action of reductants at acidic and alkaline pHs coincides with the decrease in oxygen evolution activity at these pHs. Exogenous Ca(2+) protects the extraction of flexible Mn cation at pH 6.5. High concentration of Cl(-) anions (100 mM) shifts the pH optimum of oxygen evolution to alkaline region (around pH 7.5), while the pH of flexible Mn extraction is also shifted to alkaline pH. This result suggests that flexible Mn cation plays a key role in the water-splitting reaction. The obtained results also demonstrate that only one Mn cation in Mn4 cluster is under strong control of calcium. The change in the flexible Mn cation resistance to exogenous reductants in the presence of Ca(2+) suggests that Ca(2+) can control the redox potential of this cation.

Imposed glutathione-mediated redox switch modulates the tobacco wound-induced protein kinase and salicylic acid-induced protein kinase activation state and impacts on defence against Pseudomonas syringae.

PubMed

Matern, Sanja; Peskan-Berghoefer, Tatjana; Gromes, Roland; Kiesel, Rebecca Vazquez; Rausch, Thomas

2015-04-01

The role of the redox-active tripeptide glutathione in plant defence against pathogens has been studied extensively; however, the impact of changes in cellular glutathione redox potential on signalling processes during defence reactions has remained elusive. This study explored the impact of elevated glutathione content on the cytosolic redox potential and on early defence signalling at the level of mitogen-activated protein kinases (MAPKs), as well as on subsequent defence reactions, including changes in salicylic acid (SA) content, pathogenesis-related gene expression, callose depositions, and the hypersensitive response. Wild-type (WT) Nicotiana tabacum L. and transgenic high-glutathione lines (HGL) were transformed with the cytosol-targeted sensor GRX1-roGFP2 to monitor the cytosolic redox state. Surprisingly, HGLs displayed an oxidative shift in their cytosolic redox potential and an activation of the tobacco MAPKs wound-induced protein kinase (WIPK) and SA-induced protein kinase (SIPK). This activation occurred in the absence of any change in free SA content, but was accompanied by constitutively increased expression of several defence genes. Similarly, rapid activation of MAPKs could be induced in WT tobacco by exposure to either reduced or oxidized glutathione. When HGL plants were challenged with adapted or non-adapted Pseudomonas syringae pathovars, the cytosolic redox shift was further amplified and the defence response was markedly increased, showing a priming effect for SA and callose; however, the initial and transient hyperactivation of MAPK signalling was attenuated in HGLs. The results suggest that, in tobacco, MAPK and SA signalling may operate independently, both possibly being modulated by the glutathione redox potential. Possible mechanisms for redox-mediated MAPK activation are discussed. © The Author 2015. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Impact on the Fe redox cycling of organic ligands released by Synechococcus PCC 7002, under different iron fertilization scenarios. Modeling approach

NASA Astrophysics Data System (ADS)

Samperio-Ramos, Guillermo; González-Dávila, Melchor; Santana-Casiano, J. Magdalena

2018-06-01

The kinetics of Fe redox transformations are of crucial importance in determining the bioavailability of iron, due to inorganic Fe(II) and Fe weakly organic complexes being the most easily assimilated species by phytoplankton. The role played by the natural organic ligands excreted by the cyanobacteria Synecococcus PCC 7002 on the iron redox chemistry was studied at different stages of growth, considering changes in the organic exudation of the cyanobacteria, associated with growth under two different scenarios of iron availability. The oxidation/reduction processes of iron were studied at nanomolar levels and under different physicochemical conditions of pH (7.2- 8.2), temperature (5- 35 °C) and salinity (10- 37). The presence of natural organic exudates of Synechococcus affected the redox behavior of iron. A pH-dependent and photo-induced Fe(III) reduction process was detected in the presence of exudates produced under Fe-Low conditions. Photolytic reactions also modified the reactivity of those exudates with respect to Fe(II), increasing its lifetime in seawater. Without light mediated processes, organic ligands excreted under iron deficient conditions intensified the Fe(II) oxidation at pH < 7.5. The organic exudates released under High-Fe conditions retarded the Fe(II) oxidation rate, as a function of DOC produced. The changes in the apparent oxidation rate were fitted to polynomial functions for both of the Fe-scenarios considered. A kinetic modeling approach to describe the speciation and the contribution of individual Fe(II) species to the overall oxidation rate was applied, considering the experimental data and delimiting the equilibrium and redox constants between iron and the major ligands present in solution. Two organic type ligands for the exudates of Synechococcus PCC 7002, with different iron-chelation properties were included in the model. The Fe(II) speciation was radically affected when organic ligands were considered. The individual contributions to the overall Fe(II) oxidation rate demonstrated that these organic ligands played a key role in the oxidation process, although their contributions were dependent on the prescribed iron conditions. The study, therefore, suggests that the variability in the composition and nature of organic exudates released, due to iron availability conditions, might determine the redox behaviour of iron in seawater.

Boosting water oxidation layer-by-layer.

PubMed

Hidalgo-Acosta, Jonnathan C; Scanlon, Micheál D; Méndez, Manuel A; Amstutz, Véronique; Vrubel, Heron; Opallo, Marcin; Girault, Hubert H

2016-04-07

Electrocatalysis of water oxidation was achieved using fluorinated tin oxide (FTO) electrodes modified with layer-by-layer deposited films consisting of bilayers of negatively charged citrate-stabilized IrO2 NPs and positively charged poly(diallyldimethylammonium chloride) (PDDA) polymer. The IrO2 NP surface coverage can be fine-tuned by controlling the number of bilayers. The IrO2 NP films were amorphous, with the NPs therein being well-dispersed and retaining their as-synthesized shape and sizes. UV/vis spectroscopic and spectro-electrochemical studies confirmed that the total surface coverage and electrochemically addressable surface coverage of IrO2 NPs increased linearly with the number of bilayers up to 10 bilayers. The voltammetry of the modified electrode was that of hydrous iridium oxide films (HIROFs) with an observed super-Nernstian pH response of the Ir(III)/Ir(IV) and Ir(IV)-Ir(IV)/Ir(IV)-Ir(V) redox transitions and Nernstian shift of the oxygen evolution onset potential. The overpotential of the oxygen evolution reaction (OER) was essentially pH independent, varying only from 0.22 V to 0.28 V (at a current density of 0.1 mA cm(-2)), moving from acidic to alkaline conditions. Bulk electrolysis experiments revealed that the IrO2/PDDA films were stable and adherent under acidic and neutral conditions but degraded in alkaline solutions. Oxygen was evolved with Faradaic efficiencies approaching 100% under acidic (pH 1) and neutral (pH 7) conditions, and 88% in alkaline solutions (pH 13). This layer-by-layer approach forms the basis of future large-scale OER electrode development using ink-jet printing technology.

Perturbation of the quinone-binding site of complex II alters the electronic properties of the proximal [3Fe-4S] iron-sulfur cluster.

PubMed

Ruprecht, Jonathan; Iwata, So; Rothery, Richard A; Weiner, Joel H; Maklashina, Elena; Cecchini, Gary

2011-04-08

Succinate-ubiquinone oxidoreductase (SQR) and menaquinol-fumarate oxidoreductase (QFR) from Escherichia coli are members of the complex II family of enzymes. SQR and QFR catalyze similar reactions with quinones; however, SQR preferentially reacts with higher potential ubiquinones, and QFR preferentially reacts with lower potential naphthoquinones. Both enzymes have a single functional quinone-binding site proximal to a [3Fe-4S] iron-sulfur cluster. A difference between SQR and QFR is that the redox potential of the [3Fe-4S] cluster in SQR is 140 mV higher than that found in QFR. This may reflect the character of the different quinones with which the two enzymes preferentially react. To investigate how the environment around the [3Fe-4S] cluster affects its redox properties and catalysis with quinones, a conserved amino acid proximal to the cluster was mutated in both enzymes. It was found that substitution of SdhB His-207 by threonine (as found in QFR) resulted in a 70-mV lowering of the redox potential of the cluster as measured by EPR. The converse substitution in QFR raised the redox potential of the cluster. X-ray structural analysis suggests that placing a charged residue near the [3Fe-4S] cluster is a primary reason for the alteration in redox potential with the hydrogen bonding environment having a lesser effect. Steady state enzyme kinetic characterization of the mutant enzymes shows that the redox properties of the [3Fe-4S] cluster have only a minor effect on catalysis.

The fairytale of the GSSG/GSH redox potential.

PubMed

Flohé, Leopold

2013-05-01

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

Beneficial Use of Drilling Waste - A Wetland Restoration Technology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pioneer Natural Resources

1999-07-01

The results obtained thus far are promising with regard to the low toxicity of restored drill cuttings (particularly the Cameron substrate) with increasing levels of salinity. Water extraction, acid digestion, and interstitial water samples from the restored drill cuttings, as well as redox potential, soil pH and interstitial nitrate/ammonium concentrations, and the photosynthetic response, have been determined for the baseline fresh water condition (June-August 1998), at 9ppt (September-November 1998), at 18ppt (December-February 1998,1999), and at 27ppt (currently underway). Salinities will be brought to full-strength seawater (36ppt) on May 24, 1999. The Cameron drill cuttings are remarkably similar to dredge spoil,more » which is currently being used as a wetland creation substrate. The few elements that were extracted into the interstitial water were primarily cations (Ca, K, Mg) and were not elevated to a level that would pose a threat to wetlands productivity. Swaco drill cuttings remained high in aluminum with concomitant high pH, which likely resulted in limited plant productivity through hindered nutrient uptake.« less

Efficient Self-Assembly of mPEG End-Capped Porous Silica as a Redox-Sensitive Nanocarrier for Controlled Doxorubicin Delivery.

PubMed

Nguyen, Anh Khoa; Nguyen, Thi Hiep; Bao, Bui Quoc; Bach, Long Giang; Nguyen, Dai Hai

2018-01-01

Porous nanosilica (PNS) has been regarded as a promising candidate for controlled delivery of anticancer drugs. Unmodified PNS-based nanocarriers, however, showed a burst release of encapsulated drugs, which may limit their clinical uses. In this report, PNS was surface conjugated with adamantylamine (ADA) via disulfide bridges (-SS-), PNS-SS-ADA, which was further modified with cyclodextrin-poly(ethylene glycol) methyl ether conjugate (CD-mPEG) to form a core@shell structure PNS-SS-ADA@CD-mPEG for redox triggered delivery of doxorubicin (DOX), DOX/PNS-SS-ADA@CD-mPEG. The prepared PNS-SS-ADA@CD-mPEG nanoparticles were spherical in shape with an average diameter of 55.5 ± 3.05 nm, a little larger than their parentally PNS nanocarriers, at 49.6 ± 2.56 nm. In addition, these nanoparticles possessed high drug loading capacity, at 79.2 ± 3.2%, for controlled release. The release of DOX from DOX/PNS-SS-ADA@CD-mPEG nanoparticles was controlled and prolonged up to 120 h in PBS medium (pH 7.4), compared to less than 40 h under reducing condition of 5 mM DTT. Notably, the PNS-SS-ADA@CD-mPEG was a biocompatible nanocarrier, and the toxicity of DOX was dramatically reduced after loading drugs into the porous core. This redox-sensitive PNS-SS-ADA@CD-mPEG nanoparticle could be considered a potential candidate with high drug loading capacity and a lower risk of systemic toxicity.

Redox Conversion of Chromium(VI) and Arsenic(III) with the Intermediates of Chromium(V) and Arsenic(IV) via AuPd/CNTs Electrocatalysis in Acid Aqueous Solution.

PubMed

Sun, Meng; Zhang, Gong; Qin, Yinghua; Cao, Meijuan; Liu, Yang; Li, Jinghong; Qu, Jiuhui; Liu, Huijuan

2015-08-04

Simultaneous reduction of Cr(VI) to Cr(III) and oxidation of As(III) to As(V) is a promising pretreatment process for the removal of chromium and arsenic from acid aqueous solution. In this work, the synergistic redox conversion of Cr(VI) and As(III) was efficiently achieved in a three-dimensional electrocatalytic reactor with synthesized AuPd/CNTs particles as electrocatalysts. The AuPd/CNTs facilitated the exposure of active Pd{111} facets and possessed an approximate two-electron-transfer pathway of oxygen reduction with the highly efficient formation of H2O2 as end product, resulting in the electrocatalytic reduction of 97.2 ± 2.4% of Cr(VI) and oxidation of 95.7 ± 4% of As(III). The electrocatalytic reduction of Cr(VI) was significantly accelerated prior to the electrocatalytic oxidation of As(III), and the effectiveness of Cr(VI)/As(III) conversion was favored at increased currents from 20 to 150 mA, decreased initial pH from 7 to 1 and concentrations of Cr(VI) and As(III) ranging from 50 to 1 mg/L. The crucial intermediates of Cr(V) and As(IV) and active free radicals HO(•) and O2(•-) were found for the first time, whose roles in the control of Cr(VI)/As(III) redox conversion were proposed. Finally, the potential applicability of AuPd/CNTs was revealed by their stability in electrocatalytic conversion over 10 cycles.

Combination of ORP and pH sensors in tow-yo studies to map redox and acid-base anomalies in seawater due to hydrothermal activity in shallow areas

NASA Astrophysics Data System (ADS)

Santana-Casiano, J. M.; González-Dávila, M.; Fraile-Nuez, E.; Santana-González, C.; Baker, E. T.; Resing, J. A.; Walker, S. L.

2016-12-01

The detection of activity from low-temperature hydrothermal vents, where the increase in temperature is not evident, requires the utilization of alternative sensors that respond to emissions of certain chemical species. The character of both reduced and acid fluids in the volcanic emissions in the El Hierro submarine volcano allowed us to detect anomalies related with changes in the chemical potential and the proton concentration using ORP and pH sensors, respectively. Tow-yos with these sensors provided the approximate locations of the emissions plotting δ(ORP)/δt and ΔpH versus the latitude or longitude. The ORP sensor responds very quickly to the presence of reduced chemicals in the water column. The magnitude of this change is examined by the time derivative of ORP, δ(ORP)/δt. For pH changes, ΔpH, the mean pH for each depth at a reference station in an area not affected by the vent emission is subtracted from each point measured near the volcanic edifice. The submarine volcano of El Hierro, in its degasification stage, provided an excellent opportunity to apply CTD-pH-ORP tow-yo methodology and to study the effect of CO2 emission on the seawater carbonate system, the global carbon flux, and local ocean acidification. Detailed surveys of the volcanic edifice were carried out during VULCANO 0314 and VULCANA0615 cruises using several CTD-pH-ORP tow-yo studies, localizing the redox and acidic changes, which were used to obtain surface maps of anomalies. CTD-pH-ORP yo-yo studies were also conducted that included discrete sampling for carbonate system parameters and total dissolved Fe(II), TDFe(II). The inputs of CO2 along multiple sections combined with measurements of oceanic currents produced an estimated volcanic CO2 flux = 6.0 105 ± 1.1 105 kg d-1and increases the acidity above the volcano by 20%. From the yo-yo studies important anomalies in both pHT and TDFe(II) were observed. The increased TDFe(II) concentrations and the low associated pHT values may be acting as an important fertilization event in the seawater around the volcano at the Island of El Hierro providing optimal conditions for the regeneration of the area.

In situ potential distribution measurement in an all-vanadium flow battery.

PubMed

Liu, Qinghua; Turhan, Ahmet; Zawodzinski, Thomas A; Mench, Matthew M

2013-07-18

An experimental method for measurement of local redox potential within multilayer electrodes was developed and applied to all-vanadium redox flow batteries (VRFBs). Through-plane measurement at the positive side reveals several important phenomena including potential distribution, concentration distribution of active species and the predominant reaction location within the porous carbon electrodes.

Irrigation with oxygen-nanobubble water can reduce methane emission and arsenic dissolution in a flooded rice paddy

NASA Astrophysics Data System (ADS)

Minamikawa, Kazunori; Takahashi, Masayoshi; Makino, Tomoyuki; Tago, Kanako; Hayatsu, Masahito

2015-08-01

A remarkable feature of nanobubbles (<10-6 m in diameter) is their long lifetime in water. Supplying oxygen-nanobubbles (NBs) to continuously flooded paddy soil may retard the development of reductive conditions, thereby reducing the emission of methane (CH4), a potent greenhouse gas, and dissolution of arsenic, an environmental load. We tested this hypothesis by performing a pot experiment and measuring redox-related variables. The NBs were introduced into control water (with properties similar to those of river water) using a commercially available generator. Rice (Oryza sativa L.) growth did not differ between plants irrigated with NB water and those irrigated with control water, but NB water significantly (p < 0.05) reduced cumulative CH4 emission during the rice-growing season by 21%. The amounts of iron, manganese, and arsenic that leached into the drainage water before full rice heading were also reduced by the NB water. Regardless of the water type, weekly-measured CH4 flux was linearly correlated with the leached iron concentration during the rice-growing season (r = 0.74, p < 0.001). At the end of the experiment, the NB water significantly lowered the soil pH in the 0-5 cm layer, probably because of the raised redox potential. The population of methanogenic Archaea (mcrA copy number) in the 0-5 cm layer was significantly increased by the NB water, but we found no correlation between the mcrA copy number and the cumulative CH4 emission (r = -0.08, p = 0.85). In pots without rice plants, soil reduction was not enhanced, regardless of the water type. The results indicate that NB water reduced CH4 emission and arsenic dissolution through an oxidative shift of the redox conditions in the flooded soil. We propose the use of NB water as a tool for controlling redox conditions in flooded paddy soils.

ELECTROCHEMICAL DEGRADATION OF ORGANIC CONTAMINANTS IN WATER AND SEDIMENTS

EPA Science Inventory

Electrochemical degradation (ECD) utilizes high redox potential at the anode and low redox potential at the cathode to oxidize and/or reduce organic and inorganic contaminants. EDC of Trichloroethylene (TCE), although theoretically possible, has not been experimentally proven. Th...

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

PubMed

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

2015-07-01

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

The role of extremophile in the redox reaction of Fe and As relating with the formation of secondary phase mineral in extreme environment, Norris Geyser Basin, Yellowstone National Park, USA

NASA Astrophysics Data System (ADS)

Koo, T. H.; Kim, J. Y.; Park, K. R.; Jung, D. H.; Geesey, G. G.; Kim, J. W.

2015-12-01

Redox reaction associated with microbial elemental respiration is a ubiquitous process in sediments and suspended particles at various temperatures or pH/Eh conditions. Particularly, changes in elemental redox states (structural or dissolved elemental form) induced by microbial respiration result in the unexpected biogeochemical reactions in the light of biotic/abiotic mineralization. The objective of the present study is, therefore to investigate the secondary phase mineralization through a-/biogeochemical Fe and As redox cycling in the acido-hyperhtermal Norris Geyser Basin (NGB) in Yellowstone National Park, USA, typical of the extreme condition. X-ray diffraction, scanning electron microscope with energy dispersive x-ray spectroscopy, X-ray absorption near edge structure, inductively coupled plasma-atomic emission spectrometer and liquid chromatography with ICP-mass spectroscopy with filtrated supernatant were performed for the mineralogical and hydro-geochemical analysis. The clay slurry collected from the active hot-spring of the NGB area (pH=3.5 and Temperature=78 ℃) was incubated with ("enrichment") or without the growth medium ("natural"). The control was prepared in the same condition except adding the glutaraldehyde to eliminate the microbial activity. The secondary phase mineral formation of the oxidative phase of Fe and As, and K identified as 'Pharmacosiderite' only appeared in the enrichment set suggesting a role of extremophiles in the mineral formation. The considerable population of Fe-oxidizer (Metallosphera yellowstonensis MK-1) and As-oxidizer (Sulfurihydrogenibium sp.) was measured by phylogenetic analysis in the present study area. The inhibition of As-oxidation in the low pH conditions was reported in the previous study, however the As-redox reaction was observed and consequently, precipitated the Pharmacosiderite only in the enrichment set suggesting a biotic mineralization. The present study collectively suggests that the microbial activity may bypass the chemical or thermodynamical reaction barriers and promote the secondary phase mineral formation through the elemental respiration. The possible biotic/abiotic mechanism or process in mineral alteration/formation in extreme environment will be discussed.

Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox

NASA Astrophysics Data System (ADS)

Zhan, Chun; Yao, Zhenpeng; Lu, Jun; Ma, Lu; Maroni, Victor A.; Li, Liang; Lee, Eungje; Alp, Esen E.; Wu, Tianpin; Wen, Jianguo; Ren, Yang; Johnson, Christopher; Thackeray, Michael M.; Chan, Maria K. Y.; Wolverton, Chris; Amine, Khalil

2017-12-01

Anionic redox reactions in cathodes of lithium-ion batteries are allowing opportunities to double or even triple the energy density. However, it is still challenging to develop a cathode, especially with Earth-abundant elements, that enables anionic redox activity for real-world applications, primarily due to limited strategies to intercept the oxygenates from further irreversible oxidation to O2 gas. Here we report simultaneous iron and oxygen redox activity in a Li-rich anti-fluorite Li5FeO4 electrode. During the removal of the first two Li ions, the oxidation potential of O2- is lowered to approximately 3.5 V versus Li+/Li0, at which potential the cationic oxidation occurs concurrently. These anionic and cationic redox reactions show high reversibility without any obvious O2 gas release. Moreover, this study provides an insightful guide to designing high-capacity cathodes with reversible oxygen redox activity by simply introducing oxygen ions that are exclusively coordinated by Li+.

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

PubMed

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

2017-11-01

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

Determination of the “NiOOH” charge and discharge mechanisms at ideal activity

DOE PAGES

Merrill, Matthew; Worsley, Marcus; Wittstock, Arne; ...

2014-01-24

Here, optimization of electrodeposition conditions produced Ni(OH) 2 deposits chargeable up to 1.84 ± 0.02 e – per Ni on and the resulting nickel oxide/hydroxide active material could subsequently deliver 1.58 ± 0.02 e – per Ni ion (462 mA h/g) over a potential range <0.2 V. The ability of the “NiOOH” active material to deliver an approximately ideal charge and discharge facilitated a coulometric and thermodynamic analysis through which the charge/discharge mechanisms were determined from known enthalpies of formation. The (dis)charge states were confirmed with in situ Raman spectroscopy. The mechanisms were additionally evaluated with respect to pH andmore » potential dependence, charge quantities, hysteresis, and fluoride ion partial inhibition of the charge mechanism. The results indicate that the “NiOOH” (dis)charges as a solid-state system with mechanisms consistent with known nickel and oxygen redox reactions. A defect chemistry mechanism known for the LiNiO 2 system also occurs for “NiOOH” to cause both high activity and hysteresis. Similar to other cation insertion nickel oxides, the activity of the “NiOOH” mechanism is predominantly due to oxygen redox activity and does not involve the Ni4 + oxidation state. The “NiOOH” was produced from cathodic electrodeposition of Ni(OH) 2 from nickel nitrate solutions onto highly oriented pyrolytic graphite at ideal electrodeposition current efficiencies and the deposition mechanism was also characterized.« less

A simple biofuel cell cathode with human red blood cells as electrocatalysts for oxygen reduction reaction.

PubMed

Ayato, Yusuke; Sakurai, Kenichiro; Fukunaga, Saori; Suganuma, Takuya; Yamagiwa, Kiyofumi; Shiroishi, Hidenobu; Kuwano, Jun

2014-05-15

A red blood cell (RBC) from human exhibited direct electron transfer (DET) activity on a bare indium tin oxide (ITO) electrode. A formal potential of -0.152 V vs. a silver-silver chloride saturated potassium chloride (Ag|AgCl|KCl(satd.)) was estimated for the human RBC (type AB) from a pair of redox peaks at around 0.089 and -0.215 V (vs. Ag|AgCl|KCl(satd.)) on cyclic voltammetric (CV) measurements in a phosphate buffered saline (PBS; 39 mM; pH 7.4) solution. The results agreed well with those of a redox couple for iron-bearing heme groups in hemoglobin molecules (HbFe(II)/HbFe(III)) on the bare ITO electrodes, indicated that DET active species were hemoglobin (Hb) molecules encapsulated by a phospholipid bilayer membrane of the human RBC. The quantity of electrochemically active Hb in the human RBC was estimated to be 30 pmol cm(-2). In addition, the human RBC exhibited oxygen reduction reaction (ORR) activity in the dioxygen (O2) saturated PBS solution at the negative potential from ca. -0.15 V (vs. Ag|AgCl|KCl(satd.)). A single cell test proved that a biofuel cell (BFC) with an O2|RBC|ITO cathode showed the open-circuit voltage (OCV) of ca. 0.43 V and the maximum power density of ca. 0.68 μW cm(-2). © 2013 Published by Elsevier B.V.

Structural studies on Desulfovibrio gigas cytochrome c3 by two-dimensional 1H-nuclear-magnetic-resonance spectroscopy.

PubMed Central

Piçarra-Pereira, M A; Turner, D L; LeGall, J; Xavier, A V

1993-01-01

Several aromatic amino acid residues and haem resonances in the fully reduced form of Desulfovibrio gigas cytochrome c3 are assigned, using two-dimensional 1H n.m.r., on the basis of the interactions between the protons of the aromatic amino acids and the haem protons as well as the intrahaem distances known from the X-ray structure [Kissinger (1989) Ph.D. Thesis, Washington State University]. The interhaem interactions observed in the n.m.r. spectra are in full agreement with the D. gigas X-ray structure and also with the n.m.r. data from Desulfovibrio vulgaris (Hildenborough) [Turner, Salgueiro, LeGall and Xavier (1992) Eur. J. Biochem. 210, 931-936]. The good correlation between the calculated ring-current shifts and the observed chemical shifts strongly supports the present assignments. Observation of the two-dimensional nuclear-Overhauser-enhancement spectra of the protein in the reduced, intermediate and fully oxidized stages led to the ordering of the haems in terms of their midpoint redox potentials and their identification in the X-ray structure. The first haem to oxidize is haem I, followed by haems II, III and IV, numbered according to the Cys ligand positions in the amino acid sequences [Mathews (1985) Prog. Biophys. Mol. Biol. 54, 1-56]. Although the haem core architecture is the same for the different Desulfovibrio cytochromes c3, the order of redox potentials is different. PMID:8397514

Electrolysis-driven bioremediation of crude oil-contaminated marine sediments.

PubMed

Bellagamba, Marco; Cruz Viggi, Carolina; Ademollo, Nicoletta; Rossetti, Simona; Aulenta, Federico

2017-09-25

Bioremediation is an effective technology to tackle crude oil spill disasters, which takes advantage of the capacity of naturally occurring microorganisms to degrade petroleum hydrocarbons under a range of environmental conditions. The enzymatic process of breaking down oil is usually more rapid in the presence of oxygen. However, in contaminated sediments, oxygen levels are typically too low to sustain the rapid and complete biodegradation of buried hydrocarbons. Here, we explored the possibility to electrochemically manipulate the redox potential of a crude oil-contaminated marine sediment in order to establish, in situ, conditions that are conducive to contaminants biodegradation by autochthonous microbial communities. The proposed approach is based on the exploitation of low-voltage (2V) seawater electrolysis to drive oxygen generation (while minimizing chlorine evolution) on Dimensionally Stable Anodes (DSA) placed within the contaminated sediment. Results, based on a laboratory scale setup with chronically polluted sediments spiked with crude oil, showed an increased redox potential and a decreased pH in the vicinity of the anode of 'electrified' treatments, consistent with the occurrence of oxygen generation. Accordingly, hydrocarbons biodegradation was substantially accelerated (up to 3-times) compared to 'non-electrified' controls, while sulfate reduction was severely inhibited. Intermittent application of electrolysis proved to be an effective strategy to minimize the energy requirements of the process, without adversely affecting degradation performance. Taken as a whole, this study suggests that electrolysis-driven bioremediation could be a sustainable technology for the management of contaminated sediments. Copyright © 2016 Elsevier B.V. All rights reserved.

Engineered Proteins: Redox Properties and Their Applications

PubMed Central

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

2012-01-01

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

Thiol-based redox proteins in abscisic acid and methyl jasmonate signaling in Brassica napus guard cells.

PubMed

Zhu, Mengmeng; Zhu, Ning; Song, Wen-yuan; Harmon, Alice C; Assmann, Sarah M; Chen, Sixue

2014-05-01

Reversibly oxidized cysteine sulfhydryl groups serve as redox sensors or targets of redox sensing that are important in various physiological processes. However, little is known about redox-sensitive proteins in guard cells and how they function in stomatal signaling. In this study, Brassica napus guard-cell proteins altered by redox in response to abscisic acid (ABA) or methyl jasmonate (MeJA) were identified by complementary proteomics approaches, saturation differential in-gel electrophoresis and isotope-coded affinity tagging. In total, 65 and 118 potential redox-responsive proteins were identified in ABA- and MeJA-treated guard cells, respectively. All the proteins contain at least one cysteine, and over half of them are predicted to form intra-molecular disulfide bonds. Most of the proteins fall into the functional groups of 'energy', 'stress and defense' and 'metabolism'. Based on the peptide sequences identified by mass spectrometry, 30 proteins were common to ABA- and MeJA-treated samples. A total of 44 cysteines were mapped in the identified proteins, and their levels of redox sensitivity were quantified. Two of the proteins, a sucrose non-fermenting 1-related protein kinase and an isopropylmalate dehydrogenase, were confirmed to be redox-regulated and involved in stomatal movement. This study creates an inventory of potential redox switches, and highlights a protein redox regulatory mechanism in ABA and MeJA signal transduction in guard cells. © 2014 The Authors The Plant Journal © 2014 John Wiley & Sons Ltd.

Novel Redox-Responsive Amphiphilic Copolymer Micelles for Drug Delivery: Synthesis and Characterization.

PubMed

Bae, Jungeun; Maurya, Abhijeet; Shariat-Madar, Zia; Murthy, S Narasimha; Jo, Seongbong

2015-11-01

A novel redox-responsive amphiphilic polymer was synthesized with bioreductive trimethyl-locked quinone propionic acid for a potential triggered drug delivery application. The aim of this study was to synthesize and characterize the redox-responsive amphiphilic block copolymer micelles containing pendant bioreductive quinone propionic acid (QPA) switches. The redox-responsive hydrophobic block (polyQPA), synthesized from QPA-serinol and adipoyl chloride, was end-capped with methoxy poly(ethylene glycol) of molecular weight 750 (mPEG750) to achieve a redox-responsive amphiphilic block copolymer, polyQPA-mPEG750. PolyQPA-mPEG750 was able to self-assemble as micelles to show a critical micelle concentration (CMC) of 0.039% w/v (0.39 mg/ml, 0.107 mM) determined by a dye solubilization method using 1,6-diphenyl-1,3,5-hexatriene (DPH) in phosphate-buffered saline (PBS). The mean diameter of polymeric micelles was found to be 27.50 nm (PI = 0.064) by dynamic light scattering. Furthermore, redox-triggered destabilization of the polymeric micelles was confirmed by (1)H-NMR spectroscopy and particle size measurements in a simulated redox state. PolyQPA-mPEG750 underwent triggered reduction to shed pendant redox-responsive QPA groups and its polymeric micelles were swollen to be dissembled in the presence of a reducing agent, thereby enabling the release of loaded model drug, paclitaxel. The redox-responsive polyQPA-mPEG750 polymer micelles would be useful as a drug delivery system allowing triggered drug release in an altered redox state such as tumor microenvironments with an altered redox potential and/or redox enzyme upregulation.

Pyruvate dehydrogenase complex and nicotinamide nucleotide transhydrogenase constitute an energy-consuming redox circuit.

PubMed

Fisher-Wellman, Kelsey H; Lin, Chien-Te; Ryan, Terence E; Reese, Lauren R; Gilliam, Laura A A; Cathey, Brook L; Lark, Daniel S; Smith, Cody D; Muoio, Deborah M; Neufer, P Darrell

2015-04-15

Cellular proteins rely on reversible redox reactions to establish and maintain biological structure and function. How redox catabolic (NAD+/NADH) and anabolic (NADP+/NADPH) processes integrate during metabolism to maintain cellular redox homoeostasis, however, is unknown. The present work identifies a continuously cycling mitochondrial membrane potential (ΔΨm)-dependent redox circuit between the pyruvate dehydrogenase complex (PDHC) and nicotinamide nucleotide transhydrogenase (NNT). PDHC is shown to produce H2O2 in relation to reducing pressure within the complex. The H2O2 produced, however, is effectively masked by a continuously cycling redox circuit that links, via glutathione/thioredoxin, to NNT, which catalyses the regeneration of NADPH from NADH at the expense of ΔΨm. The net effect is an automatic fine-tuning of NNT-mediated energy expenditure to metabolic balance at the level of PDHC. In mitochondria, genetic or pharmacological disruptions in the PDHC-NNT redox circuit negate counterbalance changes in energy expenditure. At the whole animal level, mice lacking functional NNT (C57BL/6J) are characterized by lower energy-expenditure rates, consistent with their well-known susceptibility to diet-induced obesity. These findings suggest the integration of redox sensing of metabolic balance with compensatory changes in energy expenditure provides a potential mechanism by which cellular redox homoeostasis is maintained and body weight is defended during periods of positive and negative energy balance.

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

PubMed

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

2012-09-04

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

EFFECT OF PH AND REDOX CONDITIONS ON DESTABILIZATION OF MINING WASTES CONTAINING MERCURY

EPA Science Inventory

Clear Lake in Northern California has received inputs of mercury mining wastes from the Sulfur Bank Mercury Mine. About 1.2M tons of Hg-contaminated overburden and mine tailings were distributed over a 50-ha surface area due to mining operations from 1865-1957. The SBMM ws placed...

Reactions of metal ions at surfaces of hydrous iron oxide

USGS Publications Warehouse

Hem, J.D.

1977-01-01

Cu, Ag and Cr concentrations in natural water may be lowered by mild chemical reduction involving ferric hydroxide-ferrous ion redox processes. V and Mo solubilities may be controlled by precipitation of ferrous vanadate or molybdate. Concentrations as low as 10-8.00 or 10-9.00 M are readily attainable for all these metals in oxygen-depleted systems that are relatively rich in Fe. Deposition of manganese oxides such as Mn3O4 can be catalyzed in oxygenated water by coupling to ferrous-ferric redox reactions. Once formed, these oxides may disproportionate, giving Mn4+ oxides. This reaction produces strongly oxidizing conditions at manganese oxide surfaces. The solubility of As is significantly influenced by ferric iron only at low pH. Spinel structures such as chromite or ferrites of Cu, Ni, and Zn, are very stable and if locally developed on ferric hydroxide surfaces could bring about solubilities much below 10-9.00 M for divalent metals near neutral pH. Solubilities calculated from thermodynamic data are shown graphically and compared with observed concentrations in some natural systems. ?? 1977.

Transport of oxaliplatin species in water-saturated natural soil.

PubMed

Goykhman, Natalia; Dror, Ishai; Berkowitz, Brian

2018-06-05

This study reports the transport characteristics of the organometallic anticancer compound oxaliplatin and its derivatives in natural soil-water environments. Although pharmaceuticals and their derivatives have for many years been detected in water resources, and linked to toxicological impacts on ecological systems, their transport in soil and groundwater is not fully understood. Specifically, studies that describe transport of organometallic pharmaceuticals in porous media are rare, and the transport characteristics of platinum complexes have received little attention. Oxaliplatin transport was studied in sand, as a function of two added natural chelators (citrate and humic acid), and in soil, under four continuously monitored, environmentally-relevant redox conditions: oxic, nitrate reducing, iron reducing and methanogenic. In sand, oxaliplatin species retention was about 7%, and affected only mildly by added citrate, and by humic acid under buffered pH. Transport with unbuffered humic acid was affected significantly by pH variations, and exhibited strong retention at pH < 8. In soil, unexpectedly similar breakthrough patterns of oxaliplatin species were found for all redox conditions, exhibiting linear, reversible retention of 79-87%. The strongest retention was observed under iron reducing conditions, whereas the weakest retention was under oxic conditions. Increased cation activity appears to promote weaker sorption. The results indicate that soil composition is the leading factor affecting oxaliplatin species mobility and fate in the soil-water environment, followed by the weaker factors of redox conditions and cation activities. Copyright © 2018 Elsevier Ltd. All rights reserved.

Oxidative stress, thiols, and redox profiles.

PubMed

Harris, Craig; Hansen, Jason M

2012-01-01

Oxidative stress has been recognized as a contributing factor in the toxicity of a large number of developmental toxicants. Traditional definitions of oxidative stress state that a shift in the balance between reduced and oxidized biomolecules within cells, in favor of the latter, result in changes that are deleterious to vital cell functions and can culminate in malformations and death. The glutathione (GSH)/glutathione disulfide (GSSG) redox couple has been the traditional marker of choice for characterization of oxidative stress because of its high concentrations and direct roles as antioxidant and cellular protectant. Steady state depletion of GSH through conjugation, oxidation, or export has often been reported as the sole criteria for invoking oxidative stress and a myriad of associated deleterious consequences. Numerous other, mostly qualitative, observations have also been reported to suggest oxidative stress has occurred but it is not always clear how well they reflect the state of a cell or its functions. Our emerging understanding of redox signaling and the roles of reactive oxygen species (ROS), thiols, oxidant molecules, and cellular antioxidants, all acting as second messengers, has prompted a redefinition of oxidative stress based on changes in the real posttranslational protein thiol modifications that are central to redox regulation and control. Thiol-based redox couples such as GSH/GSSG, cysteine/cystine (cys/cySS), thioredoxin-reduced/thioredoxin-oxidized (TRX(red)/TRX(ox)) form independent signaling nodes that selectively regulate developmental events and are closely linked to changes in intracellular redox potentials. Accurate assessment of the consequences of increased free radicals in developing conceptuses should best be made using a battery of measurements including the quantitative assessment of intracellular redox potential, ROS, redox status of biomolecules, and induced changes in specific redox signaling nodes. Methods are presented for a determination of ROS production, soluble thiol oxidation, redox potential, and a proteomic approach to evaluate the thiol oxidation state of specific proteins.

Constraining Habitable Environments on Mars by Quantifying Available Geochemical Energy

NASA Astrophysics Data System (ADS)

Tierney, L. L.; Jakosky, B. M.

2009-12-01

The search for life on Mars includes the availability of liquid water, access to biogenic elements and an energy source. In the past, when water was more abundant on Mars, a source of energy may have been the limiting factor for potential life. Energy, either from photosynthesis or chemosynthesis, is required in order to drive metabolism. Potential martian organisms most likely took advantage of chemosynthetic reactions at and below the surface. Terrestrial chemolithoautotrophs, for example, thrive off of chemical disequilibrium that exists in many environments and use inorganic redox (reduction-oxidation) reactions to drive metabolism and create cellular biomass. The chemical disequilibrium of six different martian environments were modeled in this study and analyzed incorporating a range of water and rock compositions, water:rock mass ratios, atmospheric fugacities, pH, and temperatures. All of these models can be applied to specific sites on Mars including environments similar to Meridiani Planum and Gusev Crater. Both a mass transfer geochemical model of groundwater-basalt interaction and a mixing model of groundwater-hydrothermal fluid interaction were used to estimate hypothetical martian fluid compositions that results from mixing over the entire reaction path. By determining the overall Gibbs free energy yields for redox reactions in the H-O-C-S-Fe-Mn system, the amount of geochemical energy that was available for potential chemolithoautotrophic microorganisms was quantified and the amount of biomass that could have been sustained was estimated. The quantity of biomass that can be formed and supported within a system depends on energy availability, thus sites that have higher levels and fluxes of energy have greater potential to support life. Results show that iron- and sulfur-oxidation reactions would have been the most favorable redox reactions in aqueous systems where groundwater and rock interacted at or near the surface. These types of reactions could have supported between 0.05 and 1.0 grams (dry weight) of biomass per mole of iron or sulfur. The hydrothermal environments would have had numerous redox reactions in the H-O-C-S-Fe-Mn system that could have provided sufficient metabolic energy for potential microorganisms. Methanotrophy, for example, provides the greatest amount of energy at ~760 kJ per mole of methane, which is equivalent to 0.6 grams (dry weight) of biomass. Additional results show that varying the amount of CO2 in the martian atmosphere or adjusting the water:rock ratios has little effect on the resulting Gibbs free energies. The martian values that are reported for available free energy in this study are similar to values that have been calculated for terrestrial systems in hydrothermal settings in which life is known to be abundant. In summary, the models indicate that martian aqueous environments were likely to have been habitable at a wide range of conditions when liquid water was more abundant and would have been able to supply a large amount of energy for potential organisms.

The Redox Potentials of n-type Colloidal Semiconductor Nanocrystals

NASA Astrophysics Data System (ADS)

Carroll, Gerard Michael

This thesis presents investigations for two related fields of semiconductor electrochemistry: redox potential determination of colloidal semiconductor nanocrystals, and mechanistic analysis of photoelectrochemical water oxidation with electrocatalyst modified mesostructured hematite photoanodes. Adapting electrochemical techniques to colloidal semiconductor nanocrystals (SC NC) is a long-standing challenge for this class of materials. Subject to a variety of complications, standard voltammetric techniques are not as straight forward for SC NCs as they are for small molecules. As a result, researchers have developed creative ways to side step these complications by coupling electrochemistry with NC spectroscopy. Chapter 1 discusses the fundamental electronic and spectroscopic properties of SC NCs at different redox states. We present a brief review of some of the notable studies employing SC NC spectroelectrochemistry that provide the theoretical and experimental context for the following chapters. Chapter 2 presents an investigation on NC redox potentials of photochemically reduced colloidal ZnO NCs using a solvated redox-indicator method. In the one electron limit, conduction band electrons show evidence of quantum confinement, but at higher electron concentrations, the NC Fermi-level becomes dependent on the electron density across all NC sizes. Chapter 3 outlines a poteniometric method for monitoring the NC redox potentials in situ. NC redox potentials for ZnO and CdSe are measured, and as predicted from these measurements, spontaneous electron transfer from CdSe to ZnO is demonstrated. Chapter 4 details the impact of the surface of CdSe NCs on the NC redox potentials. We find that the ratio of Cd2+:Se2- on the surface of CdSe NCs changes both the NC band edge potentials, as well as the maximum electron density achievable by photochemical reduction. These changes are proposed to arise from interfacial dipoles when CdSe has a Se2-rich surface. Chapters 5 and 6 examine the mechanistic pathways of solar water oxidation on Co-Pi modified alpha-Fe2O3 photoanodes. A rate constant analysis of water oxidation and electron-hole recombination paired with the identification of surface-morphology-dependent current-voltage characteristics reveal new insights into the role of the semiconductor/electrocatalyst interface on the overall solar water oxidation efficiency. These findings reconcile disparate observations from previous studies.

Unveiling the Structural Basis That Regulates the Energy Transduction Properties within a Family of Triheme Cytochromes from Geobacter sulfurreducens

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dantas, Joana M.; Simões, Telma; Morgado, Leonor

A family of triheme cytochromes from Geobacter sulfurreducens plays an important role in extracellular electron transfer. In addition to their role in electron transfer pathways, two members of this family (PpcA and PpcD) were also found to be able to couple e(-)/H+ transfer through the redox Bohr effect observed in the physiological pH range, a feature not observed for cytochromes PpcB and PpcE. In attempting to understand the molecular control of the redox Bohr effect in this family of cytochromes, which is highly homologous both in amino acid sequence and structures, it was observed that residue 6 is a conservedmore » leucine in PpcA and PpcD, whereas in the other two characterized members (PpcB and PpcE) the equivalent residue is a phenylalanine. To determine the role of this residue located close to the redox Bohr center, we replaced Leu(6) in PpcA with Phe and determined the redox properties of the mutant, as well as its solution structure in the fully reduced state. In contrast with the native form, the mutant PpcAL6F is not able to couple the e(-)/H+ pathway. We carried out the reverse mutation in PpcB and PpcE (i.e., replacing Phe(6) in these two proteins by leucine) and the mutated proteins showed an increased redox Bohr effect. The results clearly establish the role of residue 6 in the control of the redox Bohr effect in this family of cytochromes, a feature that could enable the rational design of G. sulfurreducens strains that carry mutant cytochromes with an optimal redox Bohr effect that would be suitable for various biotechnological applications.« less

Platinum(II) 1,10-phenanthroline complexes of acetylides containing redox-active groups.

PubMed

Siemeling, Ulrich; Bausch, Kirstin; Fink, Heinrich; Bruhn, Clemens; Baldus, Marc; Angerstein, Brigitta; Plessow, Regina; Brockhinke, Andreas

2005-07-21

The new diimine ligand 3,8-di-n-pentyl-4,7-di(phenylethynyl)-1,10-phenanthroline (1) was used for the synthesis of a range of Pt(II) complexes, viz.[Pt(1)Cl2], [Pt(1)(C triple bond C-Ph)2], [Pt(1)(C triple bond C-Fc)2] and [Pt(1)(C triple bond C-p-C6H4-C triple bond C-Fc)2](Fc = ferrocenyl). Crystal structure analyses were performed for [Pt(1)Cl2] and [Pt(1)(C triple bond C-Ph)2] and revealed that the di(acetylide)pi-tweezer of the latter binds a molecule of chloroform through C-H...pi hydrogen bonds. The redox and optical properties of 1 and its complexes were investigated by (spectro-)electrochemistry, UV-Vis and luminescence spectroscopy, and an energy level diagram was derived for [Pt(1)(C triple bond C-Fc)2] and related compounds on the basis of the data collected. The ferrocenyl-substituted Pt(II) complexes are donor-sensitiser assemblies. Intramolecular quenching of the photoexcited Pt(II) diimine unit leads to very short luminescence lifetimes for [Pt(1)(C triple bond C-p-C(6)H(4)-C triple bond C-Fc)2](2 ns) and [Pt(1)(C triple bond C-Fc)2](0.3 ns), as opposed to [Pt(1)(C triple bond C-Ph)2](0.7 micros). Excimer formation has been observed for [Pt(1)(C triple bond C-Ph)(2)] at room temperature in dichloromethane and at low temperatures in frozen glassy dichloromethane and 2-methyltetrahydrofuran solution, but not in the solid state.

Dynamic groundwater flows and geochemistry in a sandy nearshore aquifer over a wave event

NASA Astrophysics Data System (ADS)

Malott, Spencer; O'Carroll, Denis M.; Robinson, Clare E.

2016-07-01

Dynamic coastal forcing influences the transport of pollutants in nearshore aquifers and their ultimate flux to coastal waters. In this study, field data are presented that show, for the first time, the influence of a period of intensified wave conditions (wave event) on nearshore groundwater flows and geochemistry in a sandy beach. Field measurements at a freshwater beach allow wave effects to be quantified without other complex forcing that are present along marine shorelines (e.g., tides). Pressure transducer data obtained over an isolated wave event reveal the development of transient groundwater flow recirculations. The groundwater flows were simulated in FEFLOW using a phase-averaged wave setup approach to represent waves acting on the sediment-water interface. Comparison of measured and simulated data indicates that consideration of wave setup alone is able to adequately capture wave-induced perturbations in groundwater flows. While prior studies have shown sharp pH and redox spatial zonations in nearshore aquifers, this study reveals rapid temporal variations in conductivity, pH, and redox (ORP) in shallow sediments (up to 0.5 m depth) in response to varying wave conditions. Comparison of head gradients with calculated conductivity and pH mixing ratios indicates the controlling effect of the wave-induced water exchange and flows in driving the observed geochemical dynamics. While we are not able to conclusively determine the extent to which temporal variations are caused by conservative mixing versus reactive processes, the pH and ORP variations observed will have significant implications for the fate of reactive pollutants discharging through sandy nearshore aquifers.

Electronegativity and redox reactions.

PubMed

Miranda-Quintana, Ramón Alain; Martínez González, Marco; Ayers, Paul W

2016-08-10

Using the maximum hardness principle, we show that the oxidation potential of a molecule increases as its electronegativity increases and also increases as its electronegativity in its oxidized state increases. This insight can be used to construct a linear free energy relation for the oxidation potential, which we train on a set of 31 organic redox couples and test on a set of 10 different redox reactions. Better results are obtained when the electronegativity of the oxidized/reduced reagents are adjusted to account for the reagents' interaction with their chemical environment.

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

PubMed

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

2017-08-03

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

Theoretical and experimental prediction of the redox potentials of metallocene compounds

NASA Astrophysics Data System (ADS)

Li, Ya-Ping; Liu, Hai-Bo; Liu, Tao; Yu, Zhang-Yu

2017-11-01

The standard redox electrode potential ( E°) values of metallocene compounds are obtained theoretically with density functional theory (DFT) method at B3LYP/6-311++G( d, p) level and experimentally with cyclic voltammetry (CV). The theoretical E° values of metallocene compounds are in good agreement with experimental ones. We investigate the substituent effects on the redox properties of metallocene compounds. Among the four metallocene compounds, the E° values is largest for titanocene dichloride and smallest for ferrocene.

Transition-Metal Mixing and Redox Potentials in Li x (M 1–y M' y )PO 4 (M, M' = Mn, Fe, Ni) Olivine Materials from First-Principles Calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Snydacker, David H.; Wolverton, Chris

The performance of olivine cathode materials can be improved using core/shell structures such as LiMnPO 4/LiFePO 4 and LiMnPO 4/LiNiPO 4. We use density functional theory to calculate the energetics, phase stability, and voltages of transition-metal mixing for a series of olivine phosphate materials. For LiMn 1–yFe yPO 4, LiFe 1–yNi yPO 4, and LiMn 1–yNi yPO 4, we find phase-separating tendencies with (mean-field) maximum miscibility gap temperatures of 120, 320, and 760 K respectively. At room temperature, we find that Mn is completely miscible in LiFePO 4, whereas Mn solubility in LiNiPO 4 is just 0.3%. Therefore, we suggestmore » that core/shell LiMnPO 4/LiNiPO 4 particles could be more effective at containing Mn in the particle core and limiting Mn dissolution into the electrolyte relative to LiMnPO 4/LiFePO 4 particles. We calculate shifts in redox potentials for dilute transition metals, M, substituted into Li xM'PO 4 host materials. Unmixed Li xMnPO 4 exhibits a redox potential of 4.0 V, but we find that dilute Mn in a LiNiPO 4 shell exhibits a redox potential of 4.3 V and therefore remains redox inactive at lower cathode potentials. We find that strain plays a large role in the redox potentials of some mixed systems (Li xMn 1–yFe yPO 4) but not others (Li xMn 1–yNi yPO 4).« less

Photocatalytic degradation of model textile dyes in wastewater using ZnO as semiconductor catalyst.

PubMed

Chakrabarti, Sampa; Dutta, Binay K

2004-08-30

Semiconductor photocatalysis often leads to partial or complete mineralization of organic pollutants. Upon irradiation with UV/visible light, semiconductors catalyze redox reactions in presence of air/O2 and water. Here, the potential of a common semiconductor, ZnO, has been explored as an effective catalyst for the photodegradation of two model dyes: Methylene Blue and Eosin Y. A 16 W lamp was the source of UV-radiation in a batch reactor. The effects of process parameters like, catalyst loading, initial dye concentration, airflow rate, UV-radiation intensity, and pH on the extent of photo degradation have been investigated. Substantial reduction of COD, besides removal of colour, was also achieved. A rate equation for the degradation based on Langmuir-Hinshelwood model has been proposed.

Benzoisothiazolone Organo/Copper-Cocatalyzed Redox Dehydrative Construction of Amides and Peptides from Carboxylic Acids using (EtO)3P as the Reductant and O2 in Air as the Terminal Oxidant.

PubMed

Liebeskind, Lanny S; Gangireddy, Pavankumar; Lindale, Matthew G

2016-06-01

Carboxylic acids and amine/amino acid reactants can be converted to amides and peptides at neutral pH within 5-36 h at 50 °C using catalytic quantities of a redox-active benzoisothiazolone and a copper complex. These catalytic "oxidation-reduction condensation" reactions are carried out open to dry air using O2 as the terminal oxidant and a slight excess of triethyl phosphite as the reductant. Triethyl phosphate is the easily removed byproduct. These simple-to-run catalytic reactions provide practical and economical procedures for the acylative construction of C-N bonds.

Changes in microbial communities along redox gradients in polygonized Arctic wet tundra soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lipson, David A.; Raab, Theodore K.; Parker, Melanie

2015-08-01

Summary This study investigated how microbial community structure and diversity varied with depth and topography in ice wedge polygons of wet tundra of the Arctic Coastal Plain in northern Alaska and what soil variables explain these patterns. We observed strong changes in community structure and diversity with depth, and more subtle changes between areas of high and low topography, with the largest differences apparent near the soil surface. These patterns are most strongly correlated with redox gradients (measured using the ratio of reduced Fe to total Fe in acid extracts as a proxy): conditions grew more reducing with depth andmore » were most oxidized in shallow regions of polygon rims. Organic matter and pH also changed with depth and topography but were less effective predictors of the microbial community structure and relative abundance of specific taxa. Of all other measured variables, lactic acid concentration was the best, in combination with redox, for describing the microbial community. We conclude that redox conditions are the dominant force in shaping microbial communities in this landscape. Oxygen and other electron acceptors allowed for the greatest diversity of microbes: at depth the community was reduced to a simpler core of anaerobes,« less

Evidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides

DOE PAGES

Klet, Rachel C.; Kaphan, David M.; Liu, Cong; ...

2018-04-09

The chemical and electronic interactions of organometallic species with metal oxide support materials are of fundamental importance for the development of new classes of catalytic materials. Chemisorption of Cp*(PMe 3)IrMe 2 on sulfated alumina (SA) and sulfated zirconia (SZ) led to an unexpected redox mechanism for deuteration of the ancillary Cp* ligand. Evidence for this oxidative mechanism was provided by studying the analogous homogeneous reactivity of the organometallic precursors toward trityl cation ([Ph 3C] +), a Lewis acid known to effect formal hydride abstraction by one-electron oxidation followed by hydrogen abstraction. Organometallic deuterium incorporation was found to be correlated withmore » surface sulfate concentration as well as the extent of dehydration under thermal activation conditions of SA and SZ supports. Surface sulfate concentration dependence, in conjunction with a computational study of surface electron affinity, indicates an electron-deficient pyrosulfate species as the redox-active moiety. Furthermore, these results provide further evidence for the ability of sulfated metal oxides to participate in redox chemistry not only toward organometallic complexes but also in the larger context of their application as catalysts for the transformation of light alkanes.« less

Evidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klet, Rachel C.; Kaphan, David M.; Liu, Cong

The chemical and electronic interactions of organometallic species with metal oxide support materials are of fundamental importance for the development of new classes of catalytic materials. Chemisorption of Cp*(PMe 3)IrMe 2 on sulfated alumina (SA) and sulfated zirconia (SZ) led to an unexpected redox mechanism for deuteration of the ancillary Cp* ligand. Evidence for this oxidative mechanism was provided by studying the analogous homogeneous reactivity of the organometallic precursors toward trityl cation ([Ph 3C] +), a Lewis acid known to effect formal hydride abstraction by one-electron oxidation followed by hydrogen abstraction. Organometallic deuterium incorporation was found to be correlated withmore » surface sulfate concentration as well as the extent of dehydration under thermal activation conditions of SA and SZ supports. Surface sulfate concentration dependence, in conjunction with a computational study of surface electron affinity, indicates an electron-deficient pyrosulfate species as the redox-active moiety. Furthermore, these results provide further evidence for the ability of sulfated metal oxides to participate in redox chemistry not only toward organometallic complexes but also in the larger context of their application as catalysts for the transformation of light alkanes.« less

Hydroquinone-Mediated Redox Cycling of Iron and Concomitant Oxidation of Hydroquinone in Oxic Waters under Acidic Conditions: Comparison with Iron-Natural Organic Matter Interactions.

PubMed

Jiang, Chao; Garg, Shikha; Waite, T David

2015-12-15

Interactions of 1,4-hydroquinone with soluble iron species over a pH range of 3-5 in the air-saturated and partially deoxygenated solution are examined here. Our results show that 1,4-hydroquinone reduces Fe(III) in acidic conditions, generating semiquinone radicals (Q(•-)) that can oxidize Fe(II) back to Fe(III). The oxidation rate of Fe(II) by Q(•-)increases with increase in pH due to the speciation change of Q(•-) with its deprotonated form (Q(•-)) oxidizing Fe(II) more rapidly than the protonated form (HQ(•)). Although the oxygenation of Fe(II) is negligible at pH < 5, O2 still plays an important role in iron redox transformation by rapidly oxidizing Q(•-) to form benzoquinone (Q). A kinetic model is developed to describe the transformation of quinone and iron under all experimental conditions. The results obtained here are compared with those obtained in our previous studies of iron-Suwannee River fulvic acid (SRFA) interactions in acidic solutions and support the hypothesis that hydroquinone moieties can reduce Fe(III) in natural waters. However, the semiquinone radicals generated in pure hydroquinone solution are rapidly oxidized by dioxygen, while the semiquinone radicals generated in SRFA solution are resistant to oxidation by dioxygen, with the result that steady-state semiquinone concentrations in SRFA solutions are 2-3 orders of magnitude greater than in solutions of 1,4-hydroquinone. As a result, semiquinone moieties in SRFA play a much more important role in iron redox transformations than is the case in solutions of simple quinones such as 1,4-hydroquinone. This difference in the steady-state concentration of semiquinone species has a dramatic effect on the cycling of iron between the +II and +III oxidation states, with iron turnover frequencies in solutions containing SRFA being 10-20 times higher than those observed in solutions of 1,4-hydroquinone.

ELECTROCHEMICAL DECHLORINATION OF TRICHLOROETHYLENE USING GRANULAR-GRAPHITE ELECTRODES: IDENTIFICATION AND QUANTIFICATION OF DECHLORINATION PRODUCTS

EPA Science Inventory

Electrochemical degradation (ECD) utilizes high redox potential at the anode and low redox potential at the cathode to oxidize and/or reduce organic and inorganic contaminants. ECD of Trichloroethylene (TCE), although theoretically possible, has not been experimentally proven. Th...

Online monitoring of Mezcal fermentation based on redox potential measurements.

PubMed

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.

Examination of Technetium Transport Through Soils Under Contrasting Redox Conditions: Batch and Column Work

NASA Astrophysics Data System (ADS)

Dozier, R.; Montgomery, D.; Wylie, E. M.; Dogan, M.; Moysey, S. M.; Powell, B. A.; Martinez, N. E.

2015-12-01

Experiments were performed under various reducing conditions to evaluate the transport behavior of technetium-99 (99Tc) in the presence of sandy clay loam soil from the Savannah River Site (SRS) and goethite, magnetite, and iron sulfide, which were selected for their increasing reducing potential. The experiments were conducted to investigate how redox reaction equilibria and rates affect the overall mobility of 99Tc as it transitions between the mobile Tc(VII) and immobile Tc(IV). Under oxygen-rich conditions, batch sorption isotherms measured for TcO4- across the concentration range 0.5 to 50 μg/L were linear with distribution coefficients (Kd) of 0.78 mL/g or lower, with decreasing sorption for goethite, magnetite, and iron sulfide, respectively. Addition of Na2S resulted in a marked increase in apparent 99Tc sorption to the solid phase, with Kd of 43 mL/g, 35 mL/g, and 29 mL/g, following the same mineral trend as previously. The increased Kd values are possibly due to reduction of Tc(VII) to Tc(IV), resulting in the formation of TcO2(s). SRS soil batch sorption isotherms measured for TcO4- across the same concentration range were also linear, with Kd of 0.7 mL/g for unadjusted pH, 5.1 mL/g for pH of around 6, and 6.7 mL/g for pH of around 4. Kinetic batch sorption tests showed less than 10% 99Tc sorption in an oxidizing environment and greater than 95% sorption in a reducing environment, with both reactions occurring on the order of minutes. In contrast, desorption experiments initiated by transferring the samples from a reducing environment (0.1% H2(g)/99.9% N2(g)) to atmospheric conditions resulted in a slow desorption step on the order of days. Column experiments conducted with the SRS sands indicate a retardation factor of 1.17 for 99Tc under oxygen rich conditions. Additional column experiments are being conducted to evaluate 99Tc transport dependencies on transitions between oxygen rich and poor conditions.

Chemical Shuttle Additives in Lithium Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patterson, Mary

2013-03-31

The goals of this program were to discover and implement a redox shuttle that is compatible with large format lithium ion cells utilizing LiNi{sub 1/3}Mn{sub 1/3}Co{sub 1/3}O{sub 2} (NMC) cathode material and to understand the mechanism of redox shuttle action. Many redox shuttles, both commercially available and experimental, were tested and much fundamental information regarding the mechanism of redox shuttle action was discovered. In particular, studies surrounding the mechanism of the reduction of the oxidized redox shuttle at the carbon anode surface were particularly revealing. The initial redox shuttle candidate, namely 2-(pentafluorophenyl)-tetrafluoro-1,3,2-benzodioxaborole (BDB) supplied by Argonne National Laboratory (ANL, Lemont,more » Illinois), did not effectively protect cells containing NMC cathodes from overcharge. The ANL-RS2 redox shuttle molecule, namely 1,4-bis(2-methoxyethoxy)-2,5-di-tert-butyl-benzene, which is a derivative of the commercially successful redox shuttle 2,5-di-tert-butyl-1,4-dimethoxybenzene (DDB, 3M, St. Paul, Minnesota), is an effective redox shuttle for cells employing LiFePO{sub 4} (LFP) cathode material. The main advantage of ANL-RS2 over DDB is its larger solubility in electrolyte; however, ANL-RS2 is not as stable as DDB. This shuttle also may be effectively used to rebalance cells in strings that utilize LFP cathodes. The shuttle is compatible with both LTO and graphite anode materials although the cell with graphite degrades faster than the cell with LTO, possibly because of a reaction with the SEI layer. The degradation products of redox shuttle ANL-RS2 were positively identified. Commercially available redox shuttles Li{sub 2}B{sub 12}F{sub 12} (Air Products, Allentown, Pennsylvania and Showa Denko, Japan) and DDB were evaluated and were found to be stable and effective redox shuttles at low C-rates. The Li{sub 2}B{sub 12}F{sub 12} is suitable for lithium ion cells utilizing a high voltage cathode (potential that is higher than NMC) and the DDB is useful for lithium ion cells with LFP cathodes (potential that is lower than NMC). A 4.5 V class redox shuttle provided by Argonne National Laboratory was evaluated which provides a few cycles of overcharge protection for lithium ion cells containing NMC cathodes but it is not stable enough for consideration. Thus, a redox shuttle with an appropriate redox potential and sufficient chemical and electrochemical stability for commercial use in larger format lithium ion cells with NMC cathodes was not found. Molecular imprinting of the redox shuttle molecule during solid electrolyte interphase (SEI) layer formation likely contributes to the successful reduction of oxidized redox shuttle species at carbon anodes. This helps to understand how a carbon anode covered with an SEI layer, that is supposed to be electrically insulating, can reduce the oxidized form of a redox shuttle.« less

Redox active polymers and colloidal particles for flow batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gavvalapalli, Nagarjuna; Moore, Jeffrey S.; Rodriguez-Lopez, Joaquin

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

TRANSPORT AND FATE OF AMMONIUM AND ITS IMPACT ON URANIUM AND OTHER TRACE ELEMENTS AT A FORMER URANIUM MILL TAILING SITE

PubMed Central

Miao, Ziheng; Nihat, Hakan; McMillan, Andrew Lee; Brusseau, Mark L.

2013-01-01

The remediation of ammonium-containing groundwater discharged from uranium mill tailing sites is a difficult problem facing the mining industry. The Monument Valley site is a former uranium mining site in the southwest US with both ammonium and nitrate contamination of groundwater. In this study, samples collected from 14 selected wells were analyzed for major cations and anions, trace elements, and isotopic composition of ammonium and nitrate. In addition, geochemical data from the U.S. Department of Energy (DOE) database were analyzed. Results showing oxic redox conditions and correspondence of isotopic compositions of ammonium and nitrate confirmed the natural attenuation of ammonium via nitrification. Moreover, it was observed that ammonium concentration within the plume area is closely related to concentrations of uranium and a series of other trace elements including chromium, selenium, vanadium, iron, and manganese. It is hypothesized that ammonium-nitrate transformation processes influence the disposition of the trace elements through mediation of redox potential, pH, and possibly aqueous complexation and solid-phase sorption. Despite the generally relatively low concentrations of trace elements present in groundwater, their transport and fate may be influenced by remediation of ammonium or nitrate at the site. PMID:24357895

How Redox Fluctuation Shapes Microbial Community Structure and Mineral-Organic Matter Relationships in a Humid Tropical Forest Soil

NASA Astrophysics Data System (ADS)

Campbell, A.; Bhattacharyya, A.; Lin, Y.; Tfaily, M. M.; Paša-Tolić, L.; Chu, R. K.; Silver, W. L.; Nico, P. S.; Pett-Ridge, J.

2016-12-01

Wet tropical soils can alternate frequently between fully oxygenated and anaerobic conditions, constraining both the metabolism of tropical soil microorganisms, and the mineral-organic matter relationships that regulate many aspects of soil C cycling. Tropical forests are predicted to experience a 2-5°C temperature increase and substantial differences in the amount and timing of rainfall in the coming half century. Yet we have a poor understanding of how soil microbial activity and C cycling in these systems will respond to changes in environmental variability caused by climate change. Using a 44 day redox manipulation and isotope tracing experiment with soils from the Luquillo Experimental Forest, Puerto Rico, we examined patterns of tropical soil microorganisms, metabolites and soil chemistry when soils were exposed to different redox regimes - static oxic, static anoxic, high frequency redox fluctuation (4 days oxic, 4 days anoxic), or low frequency redox fluctuation (8 days oxic, 4 days anoxic). Replicate microcosms were harvested throughout the incubation to understand how changes in redox oscillation frequency altered microbial community structure and activity, organic matter turnover and fate, and soil chemistry. While gross soil respiration was highest in static oxic soils, respiration derived from added litter was highest in static anoxic soils, suggesting that decomposition of preexisting SOM was limited by O2 availability in the anoxic treatment. Microbial communities responded to shifting O2 availability in the different treatments, resulting in significant differences in DOC concentration and molecular composition (measured by FTICR-MS). DOC and Fe2+ concentrations were positively correlated for all four redox treatments, and rapidly increased following oscillation from oxic to anoxic conditions. These results, along with parallel studies of biogeochemical responses (Fe speciation, pH, P availability), suggest a highly responsive microbial and geochemical system, where the frequency of low-redox events controls exchanges of C between mineral-sorbed and aqueous pools.

Self-Assembly Assisted Fabrication of Dextran-Based Nanohydrogels with Reduction-Cleavable Junctions for Applications as Efficient Drug Delivery Systems

PubMed Central

Wang, Hao; Dai, Tingting; Zhou, Shuyan; Huang, Xiaoxiao; Li, Songying; Sun, Kang; Zhou, Guangdong; Dou, Hongjing

2017-01-01

In order to overcome the key challenge in improving both fabrication efficiency and their drug delivery capability of anti-cancer drug delivery systems (ACDDS), here polyacrylic acid (PAA) grafted dextran (Dex) nanohydrogels (NGs) with covalent crosslinked structure bearing redox sensitive disulfide crosslinking junctions (Dex-SS-PAA) were synthesized efficiently through a one-step self-assembly assisted methodology (SAA). The Dex-SS-PAA were subsequently conjugated with doxorubicin through an acid-labile hydrazone bond (Dex-SS-PAA-DOX). The in vitro drug release behavior, anti-cancer effects in vivo, and biosafety of the as-prepared acid- and redox-dual responsive biodegradable NGs were systematically investigated. The results revealed that the Dex-SS-PAA-DOX exhibited pH- and redox-controlled drug release, greatly reduced the toxicity of free DOX, while exhibiting a strong ability to inhibit the growth of MDA-MB-231 tumors. Our study demonstrated that the Dex-SS-PAA-DOX NGs are very promising candidates as ACDDS for anti-cancer therapeutics. PMID:28071743

Self-Assembly Assisted Fabrication of Dextran-Based Nanohydrogels with Reduction-Cleavable Junctions for Applications as Efficient Drug Delivery Systems

NASA Astrophysics Data System (ADS)

Wang, Hao; Dai, Tingting; Zhou, Shuyan; Huang, Xiaoxiao; Li, Songying; Sun, Kang; Zhou, Guangdong; Dou, Hongjing

2017-01-01

In order to overcome the key challenge in improving both fabrication efficiency and their drug delivery capability of anti-cancer drug delivery systems (ACDDS), here polyacrylic acid (PAA) grafted dextran (Dex) nanohydrogels (NGs) with covalent crosslinked structure bearing redox sensitive disulfide crosslinking junctions (Dex-SS-PAA) were synthesized efficiently through a one-step self-assembly assisted methodology (SAA). The Dex-SS-PAA were subsequently conjugated with doxorubicin through an acid-labile hydrazone bond (Dex-SS-PAA-DOX). The in vitro drug release behavior, anti-cancer effects in vivo, and biosafety of the as-prepared acid- and redox-dual responsive biodegradable NGs were systematically investigated. The results revealed that the Dex-SS-PAA-DOX exhibited pH- and redox-controlled drug release, greatly reduced the toxicity of free DOX, while exhibiting a strong ability to inhibit the growth of MDA-MB-231 tumors. Our study demonstrated that the Dex-SS-PAA-DOX NGs are very promising candidates as ACDDS for anti-cancer therapeutics.

Thermodynamic characterization of a tetrahaem cytochrome isolated from a facultative aerobic bacterium, Shewanella frigidimarina: a putative redox model for flavocytochrome c3.

PubMed Central

Pessanha, Miguel; Louro, Ricardo O; Correia, Ilídio J; Rothery, Emma L; Pankhurst, Kate L; Reid, Graeme A; Chapman, Stephen K; Turner, David L; Salgueiro, Carlos A

2003-01-01

The facultative aerobic bacterium Shewanella frigidimarina produces a small c-type tetrahaem cytochrome (86 residues) under anaerobic growth conditions. This protein is involved in the respiration of iron and shares 42% sequence identity with the N-terminal domain of a soluble flavocytochrome, isolated from the periplasm of the same bacterium, which also contains four c -type haem groups. The thermodynamic properties of the redox centres and of an ionizable centre in the tetrahaem cytochrome were determined using NMR and visible spectroscopy techniques. This is the first detailed thermodynamic study performed on a tetrahaem cytochrome isolated from a facultative aerobic bacterium and reveals that this protein presents unique features. The redox centres have negative and different redox potentials, which are modulated by redox interactions between the four haems (covering a range of 8-56 mV) and by redox-Bohr interactions between the haems and an ionizable centre (-4 to -36 mV) located in close proximity to haem III. All of the interactions between the five centres are clearly dominated by electrostatic effects and the microscopic reduction potential of haem III is the one most affected by the oxidation of the other haems and by the protonation state of the molecule. Altogether, this study indicates that the tetrahaem cytochrome isolated from S. frigidimarina (Sfc) has the thermodynamic properties to work as an electron wire between its redox partners. Considering the high degree of sequence identity between Sfc and the cytochrome domain of flavocytochrome c(3), the structural similarities of the haem core, and that the macroscopic potentials are also identical, the results obtained in this work are rationalized in order to put forward a putative redox model for flavocytochrome c(3). PMID:12413396

Redox Fluctuations Increase the Contribution of Lignin to Soil Respiration

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

A series of tetraazalene radical-bridged M2 (M = CrIII, MnII, FeII, CoII) complexes with strong magnetic exchange coupling† †Electronic supplementary information (ESI) available: Experimental details, UV/Vis/NIR spectra for 2–8, additional magnetic data for 4–8, crystallographic data, selected bond distances, and crystallographic information files (CIFs) for 1, 2·0.4THF, 3·2.5THF, 4·2.5THF, and 5·2.9MeCN (CCDC 1414648–1414652). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc02725j

PubMed Central

DeGayner, Jordan A.; Jeon, Ie-Rang

2015-01-01

The ability of tetraazalene radical bridging ligands to mediate exceptionally strong magnetic exchange coupling across a range of transition metal complexes is demonstrated. The redox-active bridging ligand N,N′,N′′,N′′′-tetra(2-methylphenyl)-2,5-diamino-1,4-diiminobenzoquinone (NMePhLH2) was metalated to give the series of dinuclear complexes [(TPyA)2M2(NMePhL2–)]2+ (TPyA = tris(2-pyridylmethyl)amine, M = MnII, FeII, CoII). Variable-temperature dc magnetic susceptibility data for these complexes reveal the presence of weak superexchange interactions between metal centers, and fits to the data provide coupling constants of J = –1.64(1) and –2.16(2) cm–1 for M = MnII and FeII, respectively. One-electron reduction of the complexes affords the reduced analogues [(TPyA)2M2(NMePhL3–˙)]+. Following a slightly different synthetic procedure, the related complex [(TPyA)2CrIII2(NMePhL3–˙)]3+ was obtained. X-ray diffraction, cyclic voltammetry, and Mössbauer spectroscopy indicate the presence of radical NMePhL3–˙ bridging ligands in these complexes. Variable-temperature dc magnetic susceptibility data of the radical-bridged species reveal the presence of strong magnetic interactions between metal centers and ligand radicals, with simulations to data providing exchange constants of J = –626(7), –157(7), –307(9), and –396(16) cm–1 for M = CrIII, MnII, FeII, and CoII, respectively. Moreover, the strength of magnetic exchange in the radical-bridged complexes increases linearly with decreasing M–L bond distance in the oxidized analogues. Finally, ac magnetic susceptibility measurements reveal that [(TPyA)2Fe2(NMePhL3–˙)]+ behaves as a single-molecule magnet with a relaxation barrier of Ueff = 52(1) cm–1. These results highlight the ability of redox-active tetraazalene bridging ligands to enable dramatic enhancement of magnetic exchange coupling upon redox chemistry and provide a rare opportunity to examine metal–radical coupling trends across a transmetallic series of complexes. PMID:29435213

Synthesis, characterization and electrochemistry studies of iron(III) complex with curcumin ligand.

PubMed

Özbolat, Gülüzar; Yegani, Arash Alizadeh; Tuli, Abdullah

2018-05-11

Iron overload is a serious clinical condition for humans and is a key target in drug development. The aim of this study was to investigate the coordination of iron(III) ions with curcumin ligand that may be used in the treatment of iron overload. Iron(III) complex of curcumin was synthesized and structurally characterized in its solid and solution state by FT-IR, UV-Vis, elemental analysis, and magnetic susceptibility. Electrochemical behaviour of the ligand and the complexes were examined using cyclic voltammetry. The cytotoxic activities of the ligand and the iron(III) complex were evaluated by the MTT assay. Curcumin reacted with iron in high concentrations at physiological pH at room temperature. Subsequently, a brown-red complex was formed. Data regarding magnetic susceptibility showed that the complexes with a 1:2 (metal/ligand) mole ratio had octahedral geometry. The complex showed higher anti-oxidant effect towards the cell line ECV304 at IC 50 values of 4.83 compared to curcumin. The complex exhibited very high cytotoxic activity and showed a cytotoxic effect that was much better than that of the ligand. The potentials for redox were calculated as 0.180 V and 0.350 V, respectively. The electrochemistry studies showed that Fe 3+ /Fe 2+ couple redox process occurred at low potentials. This value was within the range of compounds that are expected to show superoxide dismutase activity. This finding indicates that the iron complex is capable of removing free radicals. The observed cytotoxicity could be pursued to obtain a potential drug. Further studies investigating the use of curcumin for this purpose are needed. © 2018 John Wiley & Sons Australia, Ltd.

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

PubMed

Shen, Lin; Yang, Weitao

2016-04-12

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

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

PubMed

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

2017-09-01

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

Screening of redox couples and electrode materials

NASA Technical Reports Server (NTRS)

Giner, J.; Swette, L.; Cahill, K.

1976-01-01

Electrochemical parameters of selected redox couples that might be potentially promising for application in bulk energy storage systems were investigated. This was carried out in two phases: a broad investigation of the basic characteristics and behavior of various redox couples, followed by a more limited investigation of their electrochemical performance in a redox flow reactor configuration. In the first phase of the program, eight redox couples were evaluated under a variety of conditions in terms of their exchange current densities as measured by the rotating disk electrode procedure. The second phase of the program involved the testing of four couples in a redox reactor under flow conditions with a varity of electrode materials and structures.

Effects of redox and sulfhydryl reagents on the bioelectric properties of the giant axon of the squid.

PubMed

Huneeus-Cox, F; Fernandez, H L; Smith, B H

1966-09-01

The effects of internally and externally applied sulfhydryl reagents on the bioelectric properties of the giant axon of the squid Loligo pealeii and Dosidicus gigas were studied. Cysteine-HCl (400 mM, pH 7.3) was used to remove axoplasm from the perfusion channel. Oxidizing agents (1 to 60 mM) tended to increase the duration of the action potential and had a slow, irreversible blocking effect when perfused internally; the membrane potential was little affected. Reducing agents applied internally caused a decrease in the spike duration without affecting its height or the membrane potential, although at high concentrations there was reversible deterioration of the action potential. Both external and internal perfusion of mercaptide-forming reagents caused deterioration in the action and membrane potentials with conduction block occurring in 5 to 45 min. 2-mercaptoethanol reversed the effects. Thiol alkylating reagents, iodoacetate and iodoacetamide, were without effect. N-ethylmaleimide did, however, block. Tests with chelating agents for nonheme iron in the membrane brought about no change in the electrical parameters. The implications of the present findings with regard to the macromolecular mechanism of excitation are discussed.