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Sample records for manganese redox chemistry

  1. Possible roles of manganese redox chemistry in the sulfur cycle

    NASA Technical Reports Server (NTRS)

    Nealson, K. H.

    1985-01-01

    Sulfate reducing bacteria (SRB) are very potent MnO2 reducers by virtue of their sulfide production: H2S reacts rapidly with MnO2 to yield Mn(2), elemental sulfur, and water. In manganese rich zones, Mn cycles rapidly if sulfate is present to drive the reduction and the MnO2 precipitates and sinks into anaerobic zones. The production of sulfide (by organisms requiring organic carbon compounds) to reduce manganese oxides might act to couple the carbon and sulfur cycles in water bodies in which the two cycles are physically separated. Iron has been proposed for this provision of reducing power by (Jorgensen, 1983), but since MnS is soluble and FeS is very insoluble in water, it is equally likely that manganese rather than iron provides the electrons to the more oxidized surface layers.

  2. SPECTROSCOPIC STUDY OF SURFACE REDOX REACTIONS WITH MANGANESE OXIDES

    EPA Science Inventory

    Redox reactions involving soil minerals and materials are important processes in environmental chemistry, but unfortunately they only have been characterized in the solution phase. he lack of a suitable method has prevented investigations of the mineral surface component of redox...

  3. A redox-assisted supramolecular assembly of manganese oxide nanotube

    SciTech Connect

    Tao Li; Sun Chenggao; Fan Meilian; Huang Caijuan; Wu Hailong; Chao Zisheng . E-mail: zschao@yahoo.com; Zhai Hesheng . E-mail: hszhai@xmu.edu.cn

    2006-11-09

    In this paper, we report the hydrothermal synthesis of manganese oxide nanotube from an aqueous medium of pH 7, using KMnO{sub 4} and MnCl{sub 2} as inorganic precursors, polyoxyethylene (10) nonyl phenyl ether (TX-10) a surfactant and acetaldehyde an additive. The characterization of X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and N{sub 2} adsorption at 77 K (BET) reveals that the synthesized manganese oxide nanotube has a mesopore size of ca. 3.65 nm and a wall thickness of ca. 12 nm, with the wall being composed of microporous crystals of monoclinic manganite. The X-ray photoelectron spectroscopy (XPS) result demonstrates a decrease of the binding energy of the Mn{sup 3+} in the manganese oxide nanotube, which may be related to both the nanotubular morphology and the crystalline pore wall. A mechanism of a redox-assisted supramolecular assembly, regulated by acetaldehyde, is postulated.

  4. Long-term litter decomposition controlled by manganese redox cycling.

    PubMed

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

    2015-09-22

    Litter decomposition is a keystone ecosystem process impacting nutrient cycling and productivity, soil properties, and the terrestrial carbon (C) balance, but the factors regulating decomposition rate are still poorly understood. Traditional models assume that the rate is controlled by litter quality, relying on parameters such as lignin content as predictors. However, a strong correlation has been observed between the manganese (Mn) content of litter and decomposition rates across a variety of forest ecosystems. Here, we show that long-term litter decomposition in forest ecosystems is tightly coupled to Mn redox cycling. Over 7 years of litter decomposition, microbial transformation of litter was paralleled by variations in Mn oxidation state and concentration. A detailed chemical imaging analysis of the litter revealed that fungi recruit and redistribute unreactive Mn(2+) provided by fresh plant litter to produce oxidative Mn(3+) species at sites of active decay, with Mn eventually accumulating as insoluble Mn(3+/4+) oxides. Formation of reactive Mn(3+) species coincided with the generation of aromatic oxidation products, providing direct proof of the previously posited role of Mn(3+)-based oxidizers in the breakdown of litter. Our results suggest that the litter-decomposing machinery at our coniferous forest site depends on the ability of plants and microbes to supply, accumulate, and regenerate short-lived Mn(3+) species in the litter layer. This observation indicates that biogeochemical constraints on bioavailability, mobility, and reactivity of Mn in the plant-soil system may have a profound impact on litter decomposition rates. PMID:26372954

  5. Long-term litter decomposition controlled by manganese redox cycling

    PubMed Central

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

    2015-01-01

    Litter decomposition is a keystone ecosystem process impacting nutrient cycling and productivity, soil properties, and the terrestrial carbon (C) balance, but the factors regulating decomposition rate are still poorly understood. Traditional models assume that the rate is controlled by litter quality, relying on parameters such as lignin content as predictors. However, a strong correlation has been observed between the manganese (Mn) content of litter and decomposition rates across a variety of forest ecosystems. Here, we show that long-term litter decomposition in forest ecosystems is tightly coupled to Mn redox cycling. Over 7 years of litter decomposition, microbial transformation of litter was paralleled by variations in Mn oxidation state and concentration. A detailed chemical imaging analysis of the litter revealed that fungi recruit and redistribute unreactive Mn2+ provided by fresh plant litter to produce oxidative Mn3+ species at sites of active decay, with Mn eventually accumulating as insoluble Mn3+/4+ oxides. Formation of reactive Mn3+ species coincided with the generation of aromatic oxidation products, providing direct proof of the previously posited role of Mn3+-based oxidizers in the breakdown of litter. Our results suggest that the litter-decomposing machinery at our coniferous forest site depends on the ability of plants and microbes to supply, accumulate, and regenerate short-lived Mn3+ species in the litter layer. This observation indicates that biogeochemical constraints on bioavailability, mobility, and reactivity of Mn in the plant–soil system may have a profound impact on litter decomposition rates. PMID:26372954

  6. Photosynthetic water oxidation: insights from manganese model chemistry.

    PubMed

    Young, Karin J; Brennan, Bradley J; Tagore, Ranitendranath; Brudvig, Gary W

    2015-03-17

    Catalysts for light-driven water oxidation are a critical component for development of solar fuels technology. The multielectron redox chemistry required for this process has been successfully deployed on a global scale in natural photosynthesis by green plants and cyanobacteria using photosystem II (PSII). PSII employs a conserved, cuboidal Mn4CaOX cluster called the O2-evolving complex (OEC) that offers inspiration for artificial O2-evolution catalysts. In this Account, we describe our work on manganese model chemistry relevant to PSII, particularly the functional model [Mn(III/IV)2(terpy)2(μ-O)2(OH2)2](NO3)3 complex (terpy = 2,2';6',2″-terpyridine), a mixed-valent di-μ-oxo Mn dimer with two terminal aqua ligands. In the presence of oxo-donor oxidants such as HSO5(-), this complex evolves O2 by two pathways, one of which incorporates solvent water in an O-O bond-forming reaction. Deactivation pathways of this catalyst include comproportionation to form an inactive Mn(IV)Mn(IV) dimer and also degradation to MnO2, a consequence of ligand loss when the oxidation state of the complex is reduced to labile Mn(II) upon release of O2. The catalyst's versatility has been shown by its continued catalytic activity after direct binding to the semiconductor titanium dioxide. In addition, after binding to the surface of TiO2 via a chromophoric linker, the catalyst can be oxidized by a photoinduced electron-transfer mechanism, mimicking the natural PSII process. Model oxomanganese complexes have also aided in interpreting biophysical and computational studies on PSII. In particular, the μ-oxo exchange rates of the Mn-terpy dimer have been instrumental in establishing that the time scale for μ-oxo exchange of high-valent oxomanganese complexes with terminal water ligands is slower than O2 evolution in the natural photosynthetic system. Furthermore, computational studies on the Mn-terpy dimer and the OEC point to similar Mn(IV)-oxyl intermediates in the O-O bond

  7. Chemistry Rocks: Redox Chemistry as a Geologic Tool.

    ERIC Educational Resources Information Center

    Burns, Mary Sue

    2001-01-01

    Applies chemistry to earth science, uses rocks in chemistry laboratories, and teaches about transition metal chemistry, oxidation states, and oxidation-reduction reactions from firsthand experiences. (YDS)

  8. Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration

    PubMed Central

    Birkner, Nancy; Navrotsky, Alexandra

    2014-01-01

    Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn2O3 and Mn3O4) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings. PMID:24733903

  9. Synthesis, and characterization of low- and high-spin manganese(II) complexes of polyfunctional adipoyldihydrazone: Effect of coordination of N-donor ligands on stereo-redox chemistry

    NASA Astrophysics Data System (ADS)

    Basumatary, Debajani; Lal, Ram Ashray; Kumar, Arvind

    2015-07-01

    Manganese(II) complexes [MnII(npahH2)] (1), [MnII(npahH2)(A)2] and [MnII(npahH2)(NN)] (where A = pyridine, (2); 2-picoline, (3); 3-picoline, (4); 4-picoline, (5) and NN = 2,2‧ bipyridine, (6); 1,10-phenanthroline, (7)) have been synthesized from bis(2-hydroxy-1-naphthaldehyde)adipoyldihydrazone (npahH4) in methanol. The composition of metal complexes has been established by elemental analyses. Complexes (1) and (3) have been characterized by mass spectral data also. Structural assessments of the complexes have been based on data obtained from molar conductance, magnetic moment, electronic, electron paramagnetic resonance and infrared spectral studies. Conductivity measurements in DMSO suggest that they are non-electrolyte. Electronic spectral studies suggest a six-coordinate octahedral geometry around the manganese center in complexes (2) to (7) and square-planar geometry in complex (1). IR spectral studies reveal that the dihydrazone coordinates to the metal in keto form with an anti-cis configuration. Magnetic moment, and EPR studies suggest manganese in +2 oxidation state in all complexes with high-spin distorted octahedral stereochemistry in complexes (2-7) while low-spin square-planar stereochemistry is involved with significant metal-metal interactions in the solid state in complex (1). Cyclic voltammetric studies reveal that the metal center cycles among the MnII → MnI → Mn0 in complexes (2) to (7) and among MnII → MnI oxidation states in complex (1).

  10. Macroform and microform-induced change in redox-sensitive chemistries of river channel surface sediments

    NASA Astrophysics Data System (ADS)

    Byrne, P.; Zhang, H.; Heathwaite, A. L.; Binley, A.; Ullah, S.; Kaeser, D.; Heppell, C. M.; Lansdown, K.; Trimmer, M.

    2012-04-01

    In-stream geomorphological features such as riffle-pool sequences (macroforms) can produce steep hydraulic gradients which induce flow in and out of the riverbed - hyporheic exchange flow (HEF). The acceleration of flow over channel obstacles such as large cobbles and boulders (microforms) can create variation in surface-subsurface pressure gradients and generation of HEF. HEF in shallow surface sediments affect the transformation of redox-sensitive chemical forms and, therefore, the attenuation or release of nutrients in river systems. Here, we examine the relationship between stream geomorphological environment (microform and macroform) and concentration profiles of redox-sensitive species (nitrate, sulphate, iron, manganese) in shallow (15cm) subsurface sediments. In-situ passive samplers (diffusive equilibrium in thin films - DET) are used to obtain biogeochemical data from armoured environments at fine scale (cm) depth resolution where there is strong upwelling. The probes were deployed in a 50m reach of the River Eden, Cumbria, UK, during baseflow conditions. The experimental setup allowed for the assessment of differences in redox-sensitive chemistries between a riffle and pool environment and between smooth and rough bed surfaces in the pool. The passive sensing basis of the DET methodology provided a means for investigating how HEF systems generated at two different geomorphological scales influence the concentration and spatial patterns of redox-sensitive species. DET's capability of measuring at high spatial resolution allowed the extent of hyporheic mixing to be targeted, even though it is often limited to the top few centimetres of sediment.

  11. Redox chemistry in the phosphorus biogeochemical cycle

    PubMed Central

    Pasek, Matthew A.; Sampson, Jacqueline M.; Atlas, Zachary

    2014-01-01

    The element phosphorus (P) controls growth in many ecosystems as the limiting nutrient, where it is broadly considered to reside as pentavalent P in phosphate minerals and organic esters. Exceptions to pentavalent P include phosphine—PH3—a trace atmospheric gas, and phosphite and hypophosphite, P anions that have been detected recently in lightning strikes, eutrophic lakes, geothermal springs, and termite hindguts. Reduced oxidation state P compounds include the phosphonates, characterized by C−P bonds, which bear up to 25% of total organic dissolved phosphorus. Reduced P compounds have been considered to be rare; however, the microbial ability to use reduced P compounds as sole P sources is ubiquitous. Here we show that between 10% and 20% of dissolved P bears a redox state of less than +5 in water samples from central Florida, on average, with some samples bearing almost as much reduced P as phosphate. If the quantity of reduced P observed in the water samples from Florida studied here is broadly characteristic of similar environments on the global scale, it accounts well for the concentration of atmospheric phosphine and provides a rationale for the ubiquity of phosphite utilization genes in nature. Phosphine is generated at a quantity consistent with thermodynamic equilibrium established by the disproportionation reaction of reduced P species. Comprising 10–20% of the total dissolved P inventory in Florida environments, reduced P compounds could hence be a critical part of the phosphorus biogeochemical cycle, and in turn may impact global carbon cycling and methanogenesis. PMID:25313061

  12. Redox chemistry in the phosphorus biogeochemical cycle

    NASA Astrophysics Data System (ADS)

    Pasek, Matthew A.; Sampson, Jacqueline M.; Atlas, Zachary

    2014-10-01

    The element phosphorus (P) controls growth in many ecosystems as the limiting nutrient, where it is broadly considered to reside as pentavalent P in phosphate minerals and organic esters. Exceptions to pentavalent P include phosphine-PH3-a trace atmospheric gas, and phosphite and hypophosphite, P anions that have been detected recently in lightning strikes, eutrophic lakes, geothermal springs, and termite hindguts. Reduced oxidation state P compounds include the phosphonates, characterized by C-P bonds, which bear up to 25% of total organic dissolved phosphorus. Reduced P compounds have been considered to be rare; however, the microbial ability to use reduced P compounds as sole P sources is ubiquitous. Here we show that between 10% and 20% of dissolved P bears a redox state of less than +5 in water samples from central Florida, on average, with some samples bearing almost as much reduced P as phosphate. If the quantity of reduced P observed in the water samples from Florida studied here is broadly characteristic of similar environments on the global scale, it accounts well for the concentration of atmospheric phosphine and provides a rationale for the ubiquity of phosphite utilization genes in nature. Phosphine is generated at a quantity consistent with thermodynamic equilibrium established by the disproportionation reaction of reduced P species. Comprising 10-20% of the total dissolved P inventory in Florida environments, reduced P compounds could hence be a critical part of the phosphorus biogeochemical cycle, and in turn may impact global carbon cycling and methanogenesis.

  13. Redox reactions involving chromium, plutonium, and manganese in soils. Final report, 1 July 1978-30 September 1981

    SciTech Connect

    Amacher, M C; Baker, D E

    1982-06-01

    Although particulate movement through wind and water erosion is the most important mechanism of dispersion of Pu at the Nevada Test Site, dispersion of water-soluble species may also be occurring. However, because Pu is toxic, usually insoluble, not uniformly distributed in the soil, and can exist in four oxidation states in the environment, it is very difficult to study. Therefore, Cr reactions in soil were investigated as a possible general model for Pu reactions in soil, since it was postulated that the redox chemistries of the two elements should be similar. Chemical fractionation methods were used to determine the redox states of Pu in a Nevada Test Site soil and the amounts of Pu associated with various soil components in order to deduce possible reactions between the various Pu species and soil components so that weathering and dispersion by chemical mechanisms can be predicted. Chemical fractionation and kinetics experiments were performed to study reactions of Cr with soil, manganese oxides, and fulvic acids in order to provide information to eventually develop a qualitative, predictive model for Pu behavior in soil.

  14. Redox-inactive metal ions promoted the catalytic reactivity of non-heme manganese complexes towards oxygen atom transfer.

    PubMed

    Choe, Cholho; Yang, Ling; Lv, Zhanao; Mo, Wanling; Chen, Zhuqi; Li, Guangxin; Yin, Guochuan

    2015-05-21

    Redox-inactive metal ions can modulate the reactivity of redox-active metal ions in a variety of biological and chemical oxidations. Many synthetic models have been developed to help address the elusive roles of these redox-inactive metal ions. Using a non-heme manganese(II) complex as the model, the influence of redox-inactive metal ions as a Lewis acid on its catalytic efficiency in oxygen atom transfer was investigated. In the absence of redox-inactive metal ions, the manganese(II) catalyst is very sluggish, for example, in cyclooctene epoxidation, providing only 9.9% conversion with 4.1% yield of epoxide. However, addition of 2 equiv. of Al(3+) to the manganese(II) catalyst sharply improves the epoxidation, providing up to 97.8% conversion with 91.4% yield of epoxide. EPR studies of the manganese(II) catalyst in the presence of an oxidant reveal a 16-line hyperfine structure centered at g = 2.0, clearly indicating the formation of a mixed valent di-μ-oxo-bridged diamond core, Mn(III)-(μ-O)2-Mn(IV). The presence of a Lewis acid like Al(3+) causes the dissociation of this diamond Mn(III)-(μ-O)2-Mn(IV) core to form monomeric manganese(iv) species which is responsible for improved epoxidation efficiency. This promotional effect has also been observed in other manganese complexes bearing various non-heme ligands. The findings presented here have provided a promising strategy to explore the catalytic reactivity of some di-μ-oxo-bridged complexes by adding non-redox metal ions to in situ dissociate those dimeric cores and may also provide clues to understand the mechanism of methane monooxygenase which has a similar diiron diamond core as the intermediate. PMID:25904197

  15. Manganese superoxide dismutase (Sod2) and redox-control of signaling events that drive metastasis

    PubMed Central

    Hempel, Nadine; Carrico, Pauline M.; Melendez, J. Andres

    2013-01-01

    Manganese superoxide dismutase (Sod2) has emerged as a key enzyme with a dual role in tumorigenic progression. Early studies were primarily directed at defining the tumor suppressive function of Sod2 based on its low level expression in many tumor types. It is now commonly held that loss of Sod2 expression is likely an early event in tumor progression allowing for further propagation of the tumorigenic phenotype resulting from steady state increases in free radical production. Increases in free radical load have also been linked to defects in mitochondrial function and metastatic disease progression. It was initially believed that Sod2 loss may propagate metastatic disease progression, in reality both epidemiologic and experimental evidence indicate that Sod2 levels increase in many tumor types as they progress from early stage non-invasive disease to late stage metastatic disease. Sod2 overexpression in many instances enhances the metastatic phenotype that is reversed by efficient H2O2 scavenging. This review evaluates the many sequelae associated with increases in Sod2 that impinge on the metastatic phenotype. The ability to use Sod2 to modulate the cellular redox-environment has allowed for the identification of redox-responsive signaling events that drive malignancy, such as invasion, migration and prolonged tumor cell survival. Further studies of these redox-driven events will help in the development of targeted therapeutic strategies to efficiently restrict redox-signaling essential for malignant progression. PMID:21434856

  16. Redox-Responsive Micelles with Cores Crosslinked via Click Chemistry.

    PubMed

    Zhang, Xiaojin; Dong, Hui; Fu, Shuangli; Zhong, Zhenlin; Zhuo, Renxi

    2016-06-01

    Redox-responsive micelles with cores crosslinked via click chemistry are developed to improve the stability of polymer micelles. Amphiphilic block copolymer mPEG-b-P(DTC-ADTC) with pendant azido groups on the hydrophobic chains is synthesized by the ring-opening polymerization of 2,2-bis(azidomethyl)trimethylene carbonate (ADTC) and 2,2-dimethyltrimethylene carbonate (DTC) with monomethoxy poly(ethylene glycol) (mPEG) as an initiator. mPEG-b-P(DTC-ADTC) self-assemble to form the micelles in aqueous solution and the cores of the micelles are crosslinked via click chemistry to afford redox-responsive core-crosslinked micelles. Core-crosslinking enhances the stability of the micelles in aqueous solution and improve the drug-loading property. The redox-responsive core-crosslinked micelles can be reduced by the addition of reducing agents such as dithiothreitol (DTT), and thus release the loaded drug quickly in the presence of DTT. PMID:27150437

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

    USGS Publications Warehouse

    MacAlady, Donald L.; Walton-Day, Katherine

    2011-01-01

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

  18. Manganese

    MedlinePlus

    Manganese is a mineral that is found in several foods including nuts, legumes, seeds, tea, whole grains, and leafy green vegetables. It is ... manganese by mouth along with other vitamins and minerals can promote growth in children who have low ...

  19. Nanostructured manganese oxides as highly active water oxidation catalysts: a boost from manganese precursor chemistry.

    PubMed

    Menezes, Prashanth W; Indra, Arindam; Littlewood, Patrick; Schwarze, Michael; Göbel, Caren; Schomäcker, Reinhard; Driess, Matthias

    2014-08-01

    We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1manganese oxides including the newly formed amorphous MnOx . Both Mn2 O3 and the amorphous MnOx exhibit tremendous enhancement in oxygen evolution during photocatalysis and are much higher in comparison to so far known bioinspired manganese oxides and calcium-manganese oxides. Also, for the first time, a new approach for the representation of activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers. PMID:25044528

  20. Complexation and redox interactions between aqueous plutonium and manganese oxide interfaces

    SciTech Connect

    Shaughnessy, Dawn A.; Nitsche, Heino; Booth, Corwin H.; Shuh, David K.; Waychunas, Glenn A.; Wilson, Richard E.; Cantrell, Kirk J.; Serne, R. Jeffrey

    2001-11-01

    The sorption of Pu(VI) and Pu(V) onto manganite (MnOOH) and Hausmannite (Mn3O4) was studied at pH 5. Manganite sorbed 21-24% from a 1x10-4 M plutonium solution and the hausmannite removed between 43-66% of the plutonium. The increased sorption by hausmannite results from its larger surface area (about twice that of manganite) plus a larger number of active surface sites. X-ray absorption near-edge structure (XANES) spectra taken at the Pu LIII edge were compared to standard spectra of plutonium in single oxidation states. Based on these spectra, it appears that both manganite and hausmannite reduce the higher valent plutonium species to Pu(IV). Between 53-59% of the plutonium was present as Pu(IV) in the manganite samples while 55-61% of the plutonium complexed to the hausmannite had also been reduced to Pu(IV). The exact mechanism behind this redox interaction between the plutonium and the manganese needs to be identified.

  1. Problems in Teaching the Topic of Redox Reactions: Actions and Conceptions of Chemistry Teachers.

    ERIC Educational Resources Information Center

    De Jong, Onno; And Others

    1995-01-01

    Presents a case study of problems that can occur when teaching the topic of redox reactions to grade-11 students. Concludes that the teachers' scientific expertise is an important source of difficulties when teaching redox reactions. Discusses implications for improvement of current chemistry classroom practice and content-related teacher…

  2. Synthesis and Characterization of a Layered Manganese Oxide: Materials Chemistry for the Inorganic or Instrumental Methods Lab

    ERIC Educational Resources Information Center

    Ching, Stanton; Neupane, Ram P.; Gray, Timothy P.

    2006-01-01

    A three-week laboratory project involving synthesis and characterization of a layered manganese oxide provides an excellent vehicle for teaching important concepts of inorganic chemistry and instrumental methods related to non-molecular systems. Na-birnessite is an easily prepared manganese oxide with a 7 A interlayer spacing and Na[superscript +]…

  3. Manganese

    Integrated Risk Information System (IRIS)

    Manganese ; CASRN 7439 - 96 - 5 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

  4. Manganese

    MedlinePlus

    ... no RDAs for a nutrient, the Adequate Intake (AI) is used as a guide. The AI is the estimated amount of the nutrient that ... assumed to be adequate. The daily Adequate Intake (AI) levels for manganese are: infants birth to 6 ...

  5. PEGylated Nanoceria as Radical Scavenger with Tunable Redox Chemistry

    SciTech Connect

    Karakoti, Ajay S.; Singh, Sanjay; Kumar, Amit; Malinska, M.; Kuchibhatla, Satyanarayana V N T; Wozniak, K.; Self, William; Seal, Sudipta

    2009-10-14

    Cerium oxide nanoparticles (CNPs) have shown tremendous potential in various applications such as water gas shift catalysis, chemical mechanical planarization (CMP), solid oxide fuel cells (SOFC), solar cells4 and high temperature oxidation protection coatings1. Recently, CNPs have been demonstrated to protect biological tissues against radiation induced damage, scavenging of superoxide anions, prevention of laser induced retinal damage, reduction of spinal injury in a tissue culture model, prevention of cardiovascular myopathy, pH dependent antioxidant properties, as a tool for immunoassays as well as other inflammatory diseases2. In most biomedical applications it is speculated that nanoceria is a regenerative radical scavenger with the ability to regenerate its active 3+ oxidation state for radical scavenging. Thus far there are no reports to control the regeneration of Ce3+ oxidation state which is the most important parameter in the application of CNPs as a reliable and regenerative radical scavenger. Thus, there is an imminent need to increase the potency of CNPs to achieve higher degree of protection against reactive oxygen species (ROS), to increase the residence time of CNPs in body and to control the regeneration of 3+ oxidation state. PEG has been reported to increase the residence time of nanoparticles and proteins inside cells and provide biocompatibility3. PEGylated counterparts of the SOD enzymes have shown improved performance over non-PEGylated enzymes. Herein, we report our efforts to synthesize CNPs directly in polyethylene glycol (mol wt 600) solution and determine the effect of increasing concentration of PEG (PEG vol % as 5, 10, 20, 40, 60 and 80) on the SOD mimetic properties exhibited by nanoceria. We also report how the active Ce3+ oxidation state can be regenerated or further tuned to regenerate at faster rate. We further demonstrate the role of PEG on the redox chemistry of CNPs catalyzed by hydrogen peroxide. Several complexes of PEGs

  6. Redox processes controlling manganese fate and transport in a mountain stream.

    PubMed

    Scott, Durelle T; McKnight, Diane M; Voelker, Bettina M; Hrncir, Duane C

    2002-02-01

    The biogeochemical processes controlling the speciation and transport of manganese in a Colorado mountain stream were studied using a conservative tracer approach combined with laboratory experiments. The study stream, Lake Fork Creek, receives manganese-rich inflows from a wetland contaminated by acid mine drainage. A conservative tracer experiment was conducted on a 1300-m reach of the stream. Results indicate that manganese was progressively removed from the stream, resulting in a loss of 64 +/- 17 micromol day(-1) m(-1). Laboratory experiments using streamwater, mine effluent, and rocks from the stream showed the importance of surface-catalyzed oxidation and photoreduction on the speciation of manganese. The field and modeling results indicate that light generally promotes oxidation and removal of manganese from the stream, presumably through a photosynthetically enhanced oxidation process. Differences in Mn speciation within the stream suggest that reductive processes affect Mn speciation within the water column. These results identify the rapid oxidation and precipitation of MnOx as a dominant process within this freshwater stream. PMID:11871561

  7. Redox Models in Chemistry Textbooks for the Upper Secondary School: Friend or Foe?

    ERIC Educational Resources Information Center

    Osterlund, Lise-Lotte; Berg, Anders; Ekborg, Margareta

    2010-01-01

    We have investigated how chemistry textbooks use models of redox reactions in different subject areas, how they change models between and within the topics, and how they deal with specific learning difficulties identified in the literature. The textbooks examined were published for use in the natural science programme in Swedish upper secondary…

  8. NEW PERSPECTIVES IN AQUATIC REDOX CHEMISTRY: ABIOTIC TRANSFORMATION OF POLLUTANTS IN GROUNDWATER AND SEDIMENTS

    EPA Science Inventory

    Presented is a review of recent advances in the chemistry of abiotic redox transformations of organic pollutants in anaerobic ecosystems. he goal is to provide an indication of the state of knowledge and the remaining difficulties, rather than an exhaustive review of the existing...

  9. Limitations in determining redox chemistry in basalt groundwaters at the Hanford site

    SciTech Connect

    Dill, J.A.; Jones, T.E.; Marcy, A.D.; West, M.H.

    1986-03-01

    The oxidation-reduction (redox) chemistry of the basalt groundwater system will be an important factor governing both the design and performance of a high-level nuclear waste repository in basalt. Although the redox state of the basalt groundwater system is inherently difficult to measure, there are a number of types of measurements that provide valuable information on this subject. These measurements include concentrations of dissolved sulfide, ferrous iron, electrode redox potential, and groundwater reducing capacity. These measurements have been made on a limited basis in a number of different repository test horizons. Taken collectively, the results of these measurements suggest that both sulfide and ferrous iron play an important role in the establishment of the basalt groundwater redox condition. Thermodynamic calculations of redox potential (E/sub h/) based on these measurements are indicative of an E/sub h/ of -0.4 V. Additional measurements are proposed that will provide a more complete understanding of basalt groundwater redox conditions. The proposed measurements include a more in-depth analysis of redox active species as well as quantification of dissolved gas species such as oxygen and methane.

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

    PubMed Central

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

    2016-01-01

    The aim of this study was to construct redox- and pH-responsive degradable manganese dioxide (MnO2) nanosheets for cancer theranostic application. The small MnO2 nanosheets were synthesized, and then functionalized by hyaluronic acid (HA), demonstrating excellent stability and tumor-targeting ability. Cisplatin (cis-diamminedichloroplatinum [CDDP]) was absorbed by the nanosheets through a physical action, which was designed as MnO2/HA/CDDP. The prepared MnO2/HA/CDDP formulation was able to efficiently deliver CDDP to tumor cells in vitro and in vivo, resulting in improved therapeutic efficiency. Subsequently, they were triggered by lower pH and higher level of reduced glutathione to generate Mn2+, enabling magnetic resonance imaging. The smart multifunctional system combining efficient magnetic resonance imaging and chemotherapy has the potential to be used as a tumor-targeting theranostic nanomedicine. PMID:27199556

  11. A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage.

    PubMed

    Zhao, Yu; Ding, Yu; Li, Yutao; Peng, Lele; Byon, Hye Ryung; Goodenough, John B; Yu, Guihua

    2015-11-21

    Electrical energy storage system such as secondary batteries is the principle power source for portable electronics, electric vehicles and stationary energy storage. As an emerging battery technology, Li-redox flow batteries inherit the advantageous features of modular design of conventional redox flow batteries and high voltage and energy efficiency of Li-ion batteries, showing great promise as efficient electrical energy storage system in transportation, commercial, and residential applications. The chemistry of lithium redox flow batteries with aqueous or non-aqueous electrolyte enables widened electrochemical potential window thus may provide much greater energy density and efficiency than conventional redox flow batteries based on proton chemistry. This Review summarizes the design rationale, fundamentals and characterization of Li-redox flow batteries from a chemistry and material perspective, with particular emphasis on the new chemistries and materials. The latest advances and associated challenges/opportunities are comprehensively discussed. PMID:26265165

  12. Photochemically driven redox chemistry induces protocell membrane pearling and division.

    PubMed

    Zhu, Ting F; Adamala, Katarzyna; Zhang, Na; Szostak, Jack W

    2012-06-19

    Prior to the evolution of complex biochemical machinery, the growth and division of simple primitive cells (protocells) must have been driven by environmental factors. We have previously demonstrated two pathways for fatty acid vesicle growth in which initially spherical vesicles grow into long filamentous vesicles; division is then mediated by fluid shear forces. Here we describe a different pathway for division that is independent of external mechanical forces. We show that the illumination of filamentous fatty acid vesicles containing either a fluorescent dye in the encapsulated aqueous phase, or hydroxypyrene in the membrane, rapidly induces pearling and subsequent division in the presence of thiols. The mechanism of this photochemically driven pathway most likely involves the generation of reactive oxygen species, which oxidize thiols to disulfide-containing compounds that associate with fatty acid membranes, inducing a change in surface tension and causing pearling and subsequent division. This vesicle division pathway provides an alternative route for the emergence of early self-replicating cell-like structures, particularly in thiol-rich surface environments where UV-absorbing polycyclic aromatic hydrocarbons (PAHs) could have facilitated protocell division. The subsequent evolution of cellular metabolic processes controlling the thiol:disulfide redox state would have enabled autonomous cellular control of the timing of cell division, a major step in the origin of cellular life. PMID:22665773

  13. ROSics: chemistry and proteomics of cysteine modifications in redox biology.

    PubMed

    Kim, Hee-Jung; Ha, Sura; Lee, Hee Yoon; Lee, Kong-Joo

    2015-01-01

    Post-translational modifications (PTMs) occurring in proteins determine their functions and regulations. Proteomic tools are available to identify PTMs and have proved invaluable to expanding the inventory of these tools of nature that hold the keys to biological processes. Cysteine (Cys), the least abundant (1-2%) of amino acid residues, are unique in that they play key roles in maintaining stability of protein structure, participating in active sites of enzymes, regulating protein function and binding to metals, among others. Cys residues are major targets of reactive oxygen species (ROS), which are important mediators and modulators of various biological processes. It is therefore necessary to identify the Cys-containing ROS target proteins, as well as the sites and species of their PTMs. Cutting edge proteomic tools which have helped identify the PTMs at reactive Cys residues, have also revealed that Cys residues are modified in numerous ways. These modifications include formation of disulfide, thiosulfinate and thiosulfonate, oxidation to sulfenic, sulfinic, sulfonic acids and thiosulfonic acid, transformation to dehydroalanine (DHA) and serine, palmitoylation and farnesylation, formation of chemical adducts with glutathione, 4-hydroxynonenal and 15-deoxy PGJ2, and various other chemicals. We present here, a review of relevant ROS biology, possible chemical reactions of Cys residues and details of the proteomic strategies employed for rapid, efficient and sensitive identification of diverse and novel PTMs involving reactive Cys residues of redox-sensitive proteins. We propose a new name, "ROSics," for the science which describes the principles of mode of action of ROS at molecular levels. PMID:24916017

  14. 1: Redox chemistry of bimetallic fulvalene complexes; 2: Oligocyclopentadienyl complexes

    SciTech Connect

    Brown, D. S.

    1993-11-01

    The electrochemistry of the heterobimetallic complexes (fulvalene)WFe(CO){sub 5} (30) and (fulvalene)WRu(CO){sub 5} (31) has been investigated. Compound 30 is reduced in two one-electron processes, and this behavior was exploited synthetically to prepare a tetranuclear dimer by selective metal reduction. Complex 31 displayed a distinction between the metals upon reoxidation of the dianion, allowing the formation of a dimer by selective metal anion oxidation. The redox behavior of 30 led to an investigation of the use of electrocatalysis to effect metal-specific ligand substitution. It was found that reduction of 30 with a catalytic amount of CpFe(C{sub 6}Me{sub 6}) (97) in the presence of excess P(OMe){sub 3} or PMe{sub 3} led to the formation of the zwitterions (fulvalene)[W(CO){sub 3}{sup {minus}}][Fe(CO)PR{sub 3}{sup +}] (107, R = P(OMe){sub 3}; 108, R = PMe{sub 3}). Compound 31 also displayed unique behavior with different reducing agents, as the monosubstituted zwitterion (fulvalene)[W(CO){sub 3}{sup {minus}}][Ru(CO){sub 2}(PMe{sub 3}){sup +}] was obtained when 97 was used while the disubstituted complex (fulvalene) [W(CO){sub 3}{sup {minus}}] [Ru(CO)(PMe{sub 3}){sub 2}{sup +}] was produced when Cp*Fe(C{sub 6}Me{sub 6}) was the catalyst. Potential synthetic routes to quatercyclopentadienyl complexes were also explored. Various attempts to couple heterobimetallic fulvalene compounds proved to be unsuccessful. 138 refs.

  15. ROSICS: CHEMISTRY AND PROTEOMICS OF CYSTEINE MODIFICATIONS IN REDOX BIOLOGY

    PubMed Central

    Kim, Hee-Jung; Ha, Sura; Lee, Hee Yoon; Lee, Kong-Joo

    2015-01-01

    Post-translational modifications (PTMs) occurring in proteins determine their functions and regulations. Proteomic tools are available to identify PTMs and have proved invaluable to expanding the inventory of these tools of nature that hold the keys to biological processes. Cysteine (Cys), the least abundant (1–2%) of amino acid residues, are unique in that they play key roles in maintaining stability of protein structure, participating in active sites of enzymes, regulating protein function and binding to metals, among others. Cys residues are major targets of reactive oxygen species (ROS), which are important mediators and modulators of various biological processes. It is therefore necessary to identify the Cys-containing ROS target proteins, as well as the sites and species of their PTMs. Cutting edge proteomic tools which have helped identify the PTMs at reactive Cys residues, have also revealed that Cys residues are modified in numerous ways. These modifications include formation of disulfide, thiosulfinate and thiosulfonate, oxidation to sulfenic, sulfinic, sulfonic acids and thiosulfonic acid, transformation to dehydroalanine (DHA) and serine, palmitoylation and farnesylation, formation of chemical adducts with glutathione, 4-hydroxynonenal and 15-deoxy PGJ2, and various other chemicals. We present here, a review of relevant ROS biology, possible chemical reactions of Cys residues and details of the proteomic strategies employed for rapid, efficient and sensitive identification of diverse and novel PTMs involving reactive Cys residues of redox-sensitive proteins. We propose a new name, “ROSics,” for the science which describes the principles of mode of action of ROS at molecular levels. © 2014 The Authors. Mass Spectrometry Reviews Published by Wiley Periodicals, Inc. Rapid Commun. Mass Spec Rev 34:184–208, 2015. PMID:24916017

  16. A Mononuclear Non-Heme Manganese(IV)-Oxo Complex Binding Redox-Inactive Metal Ions

    SciTech Connect

    Chen, Junying; Lee, Yong-Min; Davis, Katherine M.; Wu, Xiujuan; Seo, Mi Sook; Cho, Kyung-Bin; Yoon, Heejung; Park, Young Jun; Fukuzumi, Shunichi; Pushkar, Yulia N.; Nam, Wonwoo

    2013-05-29

    Redox-inactive metal ions play pivotal roles in regulating the reactivities of high-valent metal–oxo species in a variety of enzymatic and chemical reactions. A mononuclear non-heme Mn(IV)–oxo complex bearing a pentadentate N5 ligand has been synthesized and used in the synthesis of a Mn(IV)–oxo complex binding scandium ions. The Mn(IV)–oxo complexes were characterized with various spectroscopic methods. The reactivities of the Mn(IV)–oxo complex are markedly influenced by binding of Sc3+ ions in oxidation reactions, such as a ~2200-fold increase in the rate of oxidation of thioanisole (i.e., oxygen atom transfer) but a ~180-fold decrease in the rate of C–H bond activation of 1,4-cyclohexadiene (i.e., hydrogen atom transfer). The present results provide the first example of a non-heme Mn(IV)–oxo complex binding redox-inactive metal ions that shows a contrasting effect of the redox-inactive metal ions on the reactivities of metal–oxo species in the oxygen atom transfer and hydrogen atom transfer reactions.

  17. Coprecipitation and redox reactions of manganese oxides with copper and nickel

    USGS Publications Warehouse

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

    1989-01-01

    Open-system, continuous-titration experiments have been done in which a slow flux of ???0.02 molar solution of Mn2+ chloride, nitrate, or perchlorate with Cu2+ or Ni2+ in lesser concentrations was introduced into an aerated reactor solution held at constant temperature and at constant pH by a pH-stat titrator that added dilute NaOH. The resulting mixtures of metal oxyhydroxides and their native solutions were aged for periods as long as 2 1/2 years. Fresh and aged precipitates were characterized by chemical analysis, oxidation state determinations, X-ray and electron diffraction, and electron microscopy. The precipitates can be described as mixtures of oxide and oxyhydroxide species, using concepts of equilibrium and nonequilibrium chemical thermodynamics. The metal-ion content of the aged precipitates in systems that contained copper is distributed among three principal components. One of these is a mixed oxide Cu2Mn3O8 in which all Mn is in the 4+ oxidation state. A major component in all precipitates is feitknechtite, ??MnOOH. These forms are supplemented by CuO or by birnessite or ramsdellite forms of MnO2 where stoichiometry and thermodynamic calculations predict them. In systems that contained nickel and manganese, identifiable components included ??MnOOH, Ni(OH)2, and the same two forms of MnO2. The oxidation number of the precipitated manganese increased during aging, and the pH of the supernatant solution decreased. The maximum Mn oxidation number observed was 3.55 in an Mn + Cu precipitate aged for 18 months. Concentrations of Cu2+ and Ni2+ generally decreased to values substantially below those predicted by oxide or hydroxide equilibrium. Scavenging effects of this type are common in natural aqueous systems. ?? 1989.

  18. Reactive iron and manganese in estuarine sediments of the Baltic Sea: Impacts of flocculation and redox shuttling

    NASA Astrophysics Data System (ADS)

    Jilbert, Tom; Tiihonen, Rosa; Myllykangas, Jukka-Pekka; Asmala, Eero; Hietanen, Susanna

    2016-04-01

    Iron (Fe) and manganese (Mn) play important roles in sedimentary carbon cycling in both freshwater and marine systems. Dissimilatory reduction of Fe and Mn oxides is known to be a major pathway of suboxic organic matter remineralization in surface sediments, while recent studies have shown that Fe and Mn oxides may be involved in the anaerobic oxidation of methane deeper in the sediment column (e.g., Egger et al., 2015). Estuaries are transitional environments, characterized by gradients of salinity and redox conditions which impact on the mobility of Fe and Mn. In turn, the distribution of Fe and Mn in estuarine sediments, and the role of the two metals in carbon cycling, is expected to be spatially heterogeneous. However, few studies have attempted to describe the sedimentary distribution of Fe and Mn in the context of processes occurring in the estuarine water column. In particular, salinity-driven flocculation and redox shuttling are two key processes whose relative impacts on sedimentary Fe and Mn have not been clearly demonstrated. In this study we investigated the coupled water column and sedimentary cycling of Fe and Mn along a 60km non-tidal estuarine transect in the Gulf of Finland, Baltic Sea. We show that riverine Fe entering the estuary as colloidal oxides associated with dissolved organic matter (DOM) is quickly flocculated and sedimented within 5 km of the river mouth, despite the shallow lateral salinity gradient. Sediments within this range are enriched in Fe (up to twice the regional average), principally in the form of crystalline Fe oxides as determined by sequential extractions. The high crystallinity implies relative maturity of the oxide mineralogy, likely due to sustained oxic conditions and long residence time in the river catchment. Despite the reducing conditions below the sediment-water interface, Fe is largely retained in the sediments close to the river mouth. In contrast, sedimentary Mn concentrations are highest in a deep silled

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

    PubMed Central

    2015-01-01

    A library of 10 Mn-containing complexes capable of switching reversibly between the Mn(II) and Mn(III) oxidation states was prepared and evaluated for potential usage as MRI reporters of tissue redox activity. We synthesized N-(2-hydroxybenzyl)-N,N′,N′-ethylenediaminetriacetic acid (HBET) and N-(2-hydroxybenzyl-N,N′,N′-trans-1,2-cyclohexylenediaminetriacetic acid (CyHBET) ligands functionalized (−H, −OMe, −NO2) at the 5-position of the aromatic ring. The Mn(II) complexes of all ligands and the Mn(III) complexes of the 5-H and 5-NO2 functionalized ligands were synthesized and isolated, but the Mn(III) complexes with the 5-OMe functionalized ligands were unstable. 1H relaxivity of the 10 isolable complexes was measured at pH 7.4 and 37 °C, 1.4 T. Thermodynamic stability, pH-dependent complex speciation, hydration state, water exchange kinetics of the Mn(II) complexes, and pseudo-first order reduction kinetics of the Mn(III) complexes were studied using a combination of pH-potentiometry, UV–vis spectroscopy, and 1H and 17O NMR measurements. The effects of ligand structural and electronic modifications on the Mn(II/III) redox couple were studied by cyclic voltammetry. The Mn(II) complexes are potent relaxation agents as compared to the corresponding Mn(III) species with [MnII(CyHBET)(H2O)]2– exhibiting a 7.5-fold higher relaxivity (3.3 mM–1 s–1) than the oxidized form (0.4 mM–1 s–1). At pH 7.4, Mn(II) exists as a mixture of fully deprotonated (ML) and monoprotonated (HML) complexes and Mn(II) complex stability decreases as the ligands become more electron-releasing (pMn for 10 μM [MnII(CyHBET–R′)(H2O)]2– decreases from 7.6 to 6.2 as R′ goes from −NO2 to −OMe, respectively). HML speciation increases as the electron-releasing nature of the phenolato-O donor increases. The presence of a water coligand is maintained upon conversion from HML to ML, but the water exchange rate of ML is faster by up to 2 orders of magnitude (kex310 for

  20. Chromium Mobilization by Microbially-Driven Iron and Manganese Redox Cycling

    NASA Astrophysics Data System (ADS)

    Garcia Arredondo, M.; Hausladen, D.; Ying, S.; Fendorf, S. E.

    2014-12-01

    Chromium, a naturally occurring contaminant, poses a significant threat to California groundwater quality when ultramafic rocks weather leaving Cr-enriched serpentine soils. Benign and of limited solubility, Cr(III) can oxidize into soluble and carcinogenic Cr(VI). Under most environmental conditions, Mn-oxides are the principal oxidant of Cr(III). Here we investigate Cr(III) oxidation by both abiotically synthesized birnessite and biogenically produced Mn-oxides. Further, we explore chromium dynamics within artificial soil aggregates composed of Cr(OH)3- and Cr0.25Fe0.75(OH)3-coated quartz grains surrounded by aerated solute flow. Abiotic aggregates contained synthetic birnessite, while biotic aggregates were inoculated with Leptothrix cholodnii, a manganese-oxidizing bacterium, and Shewanella putrefaciens, an iron-reducing bacterium. Results show aqueous Cr(VI) concentrations scaling with Cr-mineral solubility. When Leptothrix sp.-inoculated Cr(III),Fe(III)-aggregates are supplied with aqueous Mn(II), Mn-oxides precipitate in the aerobic aggregate. Cr(VI) production occurs similar to that via synthetic birnessite. With the addition of Shewanella sp., coupled biotic and abiotic processes occur causing the reduction, and subsequent immobilization, of chromium by microbial metabolites (e.g., Fe(II)). This study shows the importance of microbial community composition on chromium dynamics within diffusion-limited zones, and suggests the potential for biological immobilization of Cr even in the presence of Mn-oxidizing bacteria.

  1. NCAW feed chemistry: Effect of starting chemistry on melter offgas and iron redox

    SciTech Connect

    Smith, P.A.; Vienna, J.D.; Merz, M.D.

    1995-03-01

    The Pacific Northwest Laboratory (PNL) Vitrification Technology Development (PVTD) program has been established to develop technology to support immobilization of selected Hanford wastes. The effort of the PVTD program is directed by the U.S. Department of Energy (DOE). This report is part of the effort and focuses on the effect of starting waste chemistry on the vitrification process. The objective of the investigation was the evaluation of the effect of starting chemistry on the cold cap behavior in the vitrification of simulated neutralized current acid waste (NCAW). In addition this investigation provides an initial laboratory investigation of the cold cap and method for evaluation of alternate reductants.

  2. Iron-Manganese Redox Reactions in Endeavour Crater Rim Apron Rocks

    NASA Technical Reports Server (NTRS)

    Ming, D. W.; Mittlefehldt, D. W.; Gellert, R.; Peretyazhko, T.; Clark, B. C.; Morris, R. V.; Yen, A. S.; Arvidson, R. E.; Crumpler, L. S.; Farrand, W. H.; Grant, J. A., III; Jolliff, B. L.; Parker, T. J.; Schroder, C.

    2015-01-01

    The Mars Exploration Rover Opportunity has been exploring Noachian age rocks and outcrops on the rim of the 22 km diameter Endeavour crater since August 2011. The Cape York area is a low-lying rim of Endeavour that contains 3 distinct lithologies: 1) the stratigraphically lowest Matijevic fm of pre-impact lithology, 2) Shoemaker fm of impact breccias, and 3) the stratigraphically highest rim lithology Grasberg fm of post-impact sediments that drape the lower slopes of the rim. The sulfate-rich sediment of the Burns fm lies unconformably over the Grasberg fm. Ca-sulfate veins were discovered in Grasberg fm sediments; the sulfates precipitated from aqueous fluids flowing upward through these materials. Opportunity investigated the chemistry and morphology of outcrops in the Matijevic fm that have Fe(sup 3+)-rich smectite detected by orbital signatures returned by CRISM on MRO. Matijevic fm also contains "boxwork" fractures with chemistry consistent with an Al-rich smectite and veins that appear to be rich in Ca-sulfate. More recently on Cape Tribulation, Opportunity has characterized two S-, Mg- and Mn-rich rich rocks overturned and fractured by the rover's wheels on Cook Haven. Those rocks have been dubbed "Pinnacle Island" and "Stuart Island" and will be referred to as the "Island" rocks. The objectives of this study are to characterize the Fe and Mn contents in the Cape York materials, including the two Island rocks, and to provide a model for Mn mobilization and precipitation. Detailed geochemistry of Endeavour rim rocks is presented in a companion paper. Geochemical trends and elemental associations were obtained from data returned by the Alpha Particle X-ray Spectrometer (APXS) on Opportunity.

  3. Thioredoxin Activates MKK4-NFκB Pathway in a Redox-dependent Manner to Control Manganese Superoxide Dismutase Gene Expression in Endothelial Cells*

    PubMed Central

    Kundumani-Sridharan, Venkatesh; Subramani, Jaganathan; Das, Kumuda C.

    2015-01-01

    The mitogen-activated protein kinase kinase 4 (MKK4) is activated via phosphorylation of Ser-257 and Thr-261 by upstream MAP3Ks and activates JNK and p38 MAPKs in response to cellular stress. We show that thioredoxin (Trx), a cellular redox protein, activates MKK4 via Cys-246 and Cys-266 residues as mutation of these residues renders MKK4 insensitive to phosphorylation by MAP3Ks, TNFα, or Trx. MKK4 is activated in vitro by reduced Trx but not oxidized Trx in the absence of an upstream kinase, suggesting that autophosphorylation of this protein occurs due to reduction of Cys-246 and Cys-266 by Trx. Additionally, mutation of Cys-246 and Cys-266 resulted in loss of kinase activity suggesting that the redox state of Cys-246 and Cys-266 is a critical determinant of MKK4 activation. Trx induces manganese superoxide dismutase (MnSOD) gene transcription by activating MKK4 via redox control of Cys-246 and Cys-266, as mutation of these residues abrogates MKK4 activation and MnSOD expression. We further show that MKK4 activates NFκB for its binding to the MnSOD promoter, which leads to AP-1 dissociation followed by MnSOD transcription. Taken together, our studies show that the redox status of Cys-246 and Cys-266 in MKK4 controls its activities independent of MAP3K, demonstrating integration of the endothelial redox environment to MAPK signaling. PMID:26028649

  4. Versatile Redox Chemistry Complicates Antioxidant Capacity Assessment: Flavonoids as Milieu-Dependent Antiand Pro-Oxidants

    PubMed Central

    Chobot, Vladimir; Kubicova, Lenka; Bachmann, Gert; Hadacek, Franz

    2013-01-01

    Some antioxidants have been shown to possess additional pro-oxidant effects. Diverse methodologies exist for studying redox properties of synthetic and natural chemicals. The latter are substantial components of our diet. Exploration of their contribution to life-extending or -compromising effects is mandatory. Among reactive oxygen species (ROS), hydroxyl radical (•OH) is the most damaging species. Due to its short half-life, the assay has to contain a specific generation system. Plants synthesize flavonoids, phenolic compounds recognized as counter-agents to coronary heart disease. Their antioxidant activities are affected by their hydroxylation patterns. Moreover, in the plant, they mainly occur as glycosides. We chose three derivatives, quercetin, luteolin, and rutin, in attempts to explore their redox chemistry in contrasting hydrogen peroxide environments. Initial addition of hydrogen peroxide in high concentration or gradual development constituted a main factor affecting their redox chemical properties, especially in case of quercetin. Our study exemplifies that a combination of a chemical assay (deoxyribose degradation) with an electrochemical method (square-wave voltammetry) provides insightful data. The ambiguity of the tested flavonoids to act either as anti- or pro-oxidant may complicate categorization, but probably contributed to their evolution as components of a successful metabolic system that benefits both producer and consumer. PMID:23736691

  5. Authigenic uranium in foraminiferal coatings: A proxy for ocean redox chemistry

    NASA Astrophysics Data System (ADS)

    Boiteau, Rene; Greaves, Mervyn; Elderfield, Henry

    2012-09-01

    The rate of uranium accumulation in oceanic sediments from seawater is controlled by bottom water oxygen concentrations and organic carbon fluxes—two parameters that are linked to deep ocean storage of CO2. To investigate glacial-interglacial changes in what is known as authigenic U, we have developed a rapid method for its determination as a simple addition to a procedure for foraminiferal trace element analysis. Foraminiferal calcite acts as a low U substrate (U/Ca < 15 nmol/mol) upon which authigenic U accumulates in reducing sediments. We measured a downcore record of foraminiferal U/Ca from ODP Site 1090 in the South Atlantic and found that U/Ca ratios increase by 70-320 nmol/mol during glacial intervals. There is a significant correlation between U/Ca records of benthic and planktonic foraminiferal species and between U/Ca and bulk sediment authigenic U. These results indicate that elevated U/Ca ratios are attributable to the accumulation of authigenic U coatings in sediments. Foraminiferal Mn/Ca ratios were lower during the glacial intervals, suggesting that the observed U accumulation on the shells is not directly linked to U incorporation into secondary manganese phases. Thus, foraminiferal U/Ca ratios may provide useful information on past changes in sediment redox conditions.

  6. Distribution and chemistry of manganese, iron, and suspended particulates in Orca Basin

    NASA Astrophysics Data System (ADS)

    Trefry, John H.; Presley, Bob J.; Keeney-Kennicutt, Wendy L.; Trocine, Robert P.

    1984-06-01

    The intense halocline and redoxcline in the Orca Basin, northwest Gulf of Mexico, induce dramatic water column profiles for manganese, iron, and suspended particulates. Within a 17 m interval, the salinity of the basin water increases from 66 to ≈260 & permil and dissolved oxygen decreases to zero. Midway through this transition zone, concentrations of suspended matter peak at ≈900 μg/liter. Dissolved iron and manganese concentrations in the anoxic brine increase from oceanic values to maxima of 1.6 and 22 mg/liter, respectively. Upward migration of dissolved manganese from the brine leads to production of manganese-rich particles in the slightly oxygenated overlying water.

  7. The Basics of Thiols and Cysteines in Redox Biology and Chemistry

    PubMed Central

    Poole, Leslie B.

    2014-01-01

    Cysteine is one of the least abundant amino acids, yet it is frequently found as a highly conserved residue within functional (regulatory, catalytic or binding) sites in proteins. It is the unique chemistry of the thiol or thiolate group of cysteine that imparts functional sites with their specialized properties (e.g., nucleophilicity, high affinity metal binding, and/or ability to form disulfide bonds). Highlighted in this review are some of the basic biophysical and biochemical properties of cysteine groups and the equations that apply to them, particularly with respect to pKa and redox potential. Also summarized are the types of low molecular weight thiols present in high concentrations in most cells, as well as the ways in which modifications of cysteinyl residues can impart or regulate molecular functions important to cellular processes including signal transduction. PMID:25433365

  8. The Role of Alpha-Hemoglobin Stabilizing Protein in Redox Chemistry, Denaturation, and Hemoglobin Assembly

    PubMed Central

    Mollan, Todd L.; Yu, Xiang; Weiss, Mitchell J.

    2010-01-01

    Abstract Hemoglobin biosynthesis in erythrocyte precursors involves several steps. The correct ratios and concentrations of normal alpha (α) and beta (β) globin proteins must be expressed; apoproteins must be folded correctly; heme must be synthesized and incorporated into these globins rapidly; and the individual α and β subunits must be rapidly and correctly assembled into heterotetramers. These events occur on a large scale in vivo, and dysregulation causes serious clinical disorders such as thalassemia syndromes. Recent work has implicated a conserved erythroid protein known as Alpha-Hemoglobin Stabilizing Protein (AHSP) as a participant in these events. Current evidence suggests that AHSP enhances α subunit stability and diminishes its participation in harmful redox chemistry. There is also evidence that AHSP facilitates one or more early-stage post-translational hemoglobin biosynthetic events. In this review, recent experimental results are discussed in light of several current models describing globin subunit folding, heme uptake, assembly, and denaturation during hemoglobin synthesis. Particular attention is devoted to molecular interactions with AHSP that relate to α chain oxidation and the ability of α chains to associate with partner β chains. Antioxid. Redox Signal. 12, 219–232. PMID:19659437

  9. Redox chemistry of molybdenum in natural waters and its involvement in biological evolution

    PubMed Central

    Wang, Deli

    2012-01-01

    The transition element molybdenum (Mo) possesses diverse valances (+II to +VI), and is involved in forming cofactors in more than 60 enzymes in biology. Redox switching of the element in these enzymes catalyzes a series of metabolic reactions in both prokaryotes and eukaryotes, and the element therefore plays a fundamental role in the global carbon, nitrogen, and sulfur cycling. In the present oxygenated waters, oxidized Mo(VI) predominates thermodynamically, whilst reduced Mo species are mainly confined within specific niches including cytoplasm. Only recently has the reduced Mo(V) been separated from Mo(VI) in sulfidic mats and even in some reducing waters. Given the presence of reduced Mo(V) in contemporary anaerobic habitats, it seems that reduced Mo species were present in the ancient reducing ocean (probably under both ferruginous and sulfidic conditions), prompting the involvement of Mo in enzymes including nitrogenase and nitrate reductase. During the global transition to oxic conditions, reduced Mo species were constrained to specific anaerobic habitats, and efficient uptake systems of oxidized Mo(VI) became a selective advantage for current prokaryotic and eukaryotic cells. Some prokaryotes are still able to directly utilize reduced Mo if any exists in ambient environments. In total, this mini-review describes the redox chemistry and biogeochemistry of Mo over the Earth’s history. PMID:23267355

  10. Chemistry of manganese precipitation in Pinal Creek, Arizona, USA: A laboratory study

    USGS Publications Warehouse

    Hem, J.D.; Lind, Carol J.

    1994-01-01

    Groundwater underlying the valley of Pinal Creek downstream from Globe, Arizona, has been contaminated by low-pH metal-enriched wastewater from copper mining and ore processing at Miami, Arizona. At present, the acidity and most of the dissolved metal content, except for Mn, of the wastewater is removed by reactions with carbonate and other solids in the alluvial aquifer before the neutralized contaminated water enters the creek channel and becomes surface flow. Where flow in the creek is perennial, Mn-bearing precipitates are formed in the stream bed and in some places in the subsurface. As an aid to understanding the processes involved and explaining the mineralogy of the precipitates, closely controlled laboratory redox titration experiments were performed on samples of surface flow and groundwater taken near the head of perennial flow in the creek. The high content of dissolved Ca, Mg, Mn and COP2 species in the neutralized contaminated groundwater caused precipitation of some of the Mn as kutnahorite, (Mn, Mg)Ca(CO3)2, when the experimental system was held between pH 8.5 and 9.0 while CO2-free air was bubbled into the solution. Hausmannite and manganite also were precipitated, in somewhat lower amounts. When the concentrations of dissolved CO2 species in the groundwater sample were decreased before the experiment was started, the Mn precipitated was predominantly in the oxides hausmannite and manganite. In some of the experimental titrations clinoenstatite, (MgSiO3), was precipitated. After titrations were stopped the solutions and precipitates were allowed to stand, with limited access to the atmosphere, for several months. During this aging period the degree of oxidation of the precipitated Mn increased and in one precipitate from an experimental solution the Ca + Mn4+ oxides todorokite and takanelite were identified. These oxides also have been identified in streambed precipitates. Some of these precipitates also gave X-ray diffraction reflections for

  11. 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.

  12. Gas-phase ion/ion reactions of peptides and proteins: acid/base, redox, and covalent chemistries

    PubMed Central

    Prentice, Boone M.

    2013-01-01

    Gas-phase ion/ion reactions are emerging as useful and flexible means for the manipulation and characterization of peptide and protein biopolymers. Acid/base-like chemical reactions (i.e., proton transfer reactions) and reduction/oxidation (redox) reactions (i.e., electron transfer reactions) represent relatively mature classes of gas-phase chemical reactions. Even so, especially in regards to redox chemistry, the widespread utility of these two types of chemistries is undergoing rapid growth and development. Additionally, a relatively new class of gas-phase ion/ion transformations is emerging which involves the selective formation of functional-group-specific covalent bonds. This feature details our current work and perspective on the developments and current capabilities of these three areas of ion/ion chemistry with an eye towards possible future directions of the field. PMID:23257901

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

    SciTech Connect

    Carbonell-Barrachina, A.; Jugsujinda, A.; DeLaune, R.D.; Patrick, W.H. Jr.; Burlo, F.; Sirisukhodom, S.; Anurakpongsatorn, P.

    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 matter 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.

  14. Redox preparation of mixed-valence cobalt manganese oxide nanostructured materials: highly efficient noble metal-free electrocatalysts for sensing hydrogen peroxide

    NASA Astrophysics Data System (ADS)

    Kuo, Cheng-Chi; Lan, Wen-Jie; Chen, Chun-Hu

    2013-12-01

    High-performance hydrogen peroxide sensors provide valuable signals of biological interactions, disorders, and developing of diseases. Low-cost metal oxides are promising alternatives but suffer from low conductivity and sensing activity. Multi-component metal oxides are excellent candidates to accomplish these challenges, but the composition inhomogeneity is difficult to manage with conventional material preparation. We demonstrated redox preparation strategies to successfully synthesize highly homogeneous, noble metal-free H2O2 sensors of spinel nanostructured cobalt manganese oxides with enhanced conductivity, multiple mixed-valence features, and efficient H2O2 sensing activities. The designed redox reactions accompanied with material nucleation/formation are the key factors for compositional homogeneity. High conductivity (1.5 × 10-2 S cm-1) and H2O2 sensing activity (12 times higher than commercial Co3O4) were achieved due to the homogeneous multiple mixed-valence systems of Co(ii)/(iii) and Mn(iii)/(iv). A wide linear detection range (from 0.1 to 25 mM) with a detection limit of 15 μM was observed. Manganese species assist the formation of large surface area nanostructures, enhancing the H2O2 reduction activities, and inhibit the sensing interference. The material controls of hierarchical nanostructures, elemental compositions, porosity, and electrochemical performances are highly associated with the reaction temperatures. The temperature-dependent properties and nanostructure formation mechanisms based on a reaction rate competition are proposed.High-performance hydrogen peroxide sensors provide valuable signals of biological interactions, disorders, and developing of diseases. Low-cost metal oxides are promising alternatives but suffer from low conductivity and sensing activity. Multi-component metal oxides are excellent candidates to accomplish these challenges, but the composition inhomogeneity is difficult to manage with conventional material

  15. Comparative analysis for various redox flow batteries chemistries using a cost performance model

    NASA Astrophysics Data System (ADS)

    Crawford, Alasdair; Viswanathan, Vilayanur; Stephenson, David; Wang, Wei; Thomsen, Edwin; Reed, David; Li, Bin; Balducci, Patrick; Kintner-Meyer, Michael; Sprenkle, Vincent

    2015-10-01

    The total energy storage system cost is determined by means of a robust performance-based cost model for multiple flow battery chemistries. Systems aspects such as shunt current losses, pumping losses and various flow patterns through electrodes are accounted for. The system cost minimizing objective function determines stack design by optimizing the state of charge operating range, along with current density and current-normalized flow. The model cost estimates are validated using 2-kW stack performance data for the same size electrodes and operating conditions. Using our validated tool, it has been demonstrated that an optimized all-vanadium system has an estimated system cost of < 350 kWh-1 for 4-h application. With an anticipated decrease in component costs facilitated by economies of scale from larger production volumes, coupled with performance improvements enabled by technology development, the system cost is expected to decrease to 160 kWh-1 for a 4-h application, and to 100 kWh-1 for a 10-h application. This tool has been shared with the redox flow battery community to enable cost estimation using their stack data and guide future direction.

  16. On the Way Toward Understanding Solution Chemistry of Lithium Polysulfides for High Energy Li-S Redox Flow Batteries

    SciTech Connect

    Pan, Huilin; Wei, Xiaoliang; Henderson, Wesley A.; Shao, Yuyan; Chen, Junzheng; Bhattacharya, Priyanka; Xiao, Jie; Liu, Jun

    2015-04-27

    Lithium sulfur (Li-S) redox flow battery (RFB) is a promising candidate for high energy large-scale energy storage application due to good solubility of long-chain polysulfide species and low cost of sulfur. In this report, recent progress and new concepts for Li-S redox flow batteries are discussed with an emphasis on the fundamental understanding and control of lithium polysulfide chemistry to enable the development of liquid phase Li-S redox flow prototype cells. These differ significantly from conventional static Li-S batteries targeting for vehicle electrification. A high solubility of the different lithium polysulfides generated at different depths of discharge and states of charge is required for a flow battery in order to take full advantage of the multiple electron transitions between elemental sulfur and Li2S. A new DMSO-based electrolyte is proposed for Li-S redox flow batteries, which not only enables the high solubility of lithium polysulfide species, especially for the short-chain species, but also results in excellent cycling with a high Coulombic efficiency. The challenges and opportunities for the Li-S redox flow concept have also been discussed in depth.

  17. IMPACT OF WATER CHEMISTRY ON MANGANESE REMOVAL DURING OXIDATION/FILTRATION TREATMENT

    EPA Science Inventory

    This is a poster showing the purpose and setup of our pilot plant experiments with manganese filtration. The focus is on the differences, effectiveness, and problems with using chlorine and potassium permanganate in oxidation/filtration. The poster will show the results and findi...

  18. SERUM CHEMISTRIES OF COTURNIX JAPONICA GIVEN DIETARY MANGANESE OXIDE (MN3O4)

    EPA Science Inventory

    Plasma creatinine and inorganic phosphorus were increased in manganese oxide (Mn3O4)-treated adult male Coturnix quail, but BUN, BUN/creatinine ratio, uric acid, and total calcium were decreased. 2. Serum enzymes (alkaline phosphatase glutamic oxaloacetic transaminase, glutamic p...

  19. Groundwater phosphate dynamics in a river riparian zone: effects of hydrologic flowpaths, lithology and redox chemistry

    NASA Astrophysics Data System (ADS)

    Carlyle, G. C.; Hill, A. R.

    2001-07-01

    This study examines the influence of riparian zone hydrology, lithology and redox chemistry on groundwater phosphate dynamics. Patterns of soluble reactive phosphorus (SRP), dissolved oxygen (DO) and ferrous iron (Fe 2+) in combination with hydrologic data and sediment characteristics were studied in a forested floodplain connected to a large upland sand aquifer in an agricultural region of southern Ontario, Canada. Groundwater discharge from the upland aquifer flowed laterally beneath peat in a 2-4 m thick zone of permeable sands across the floodplain to the river. Within the sands, low SRP concentrations (<25 μg L -1) occurred in a plume of groundwater with DO concentrations >3 mg L -1 and Fe 2+ concentrations <0.2 mg L -1 which extended for a horizontal distance of 100-140 m across the riparian zone. High SRP concentrations (50-950 μg L -1) were associated with low DO and high Fe 2+ concentrations which exceeded 1 mg L -1 in buried channel sediments near the river bank. Sediment P fractionation indicated that the buried channel sediments contained a much higher pool of total P and Fe+Al-P than the sands. Groundwater SRP concentrations at the river bank were 25-80 μg L -1 compared to <10 μg L -1 in river water indicating that the floodplain was a source of SRP to the river. Areas of elevated SRP and Fe 2+ within the floodplain expanded in August when DO concentrations in groundwater were lower than in late spring or autumn. These data suggest that the microbial reduction of Fe 3+ to soluble Fe 2+ in anaerobic conditions influences groundwater SRP concentrations in the riparian zone. This study shows that well-organized patterns of groundwater SRP concentrations occur in riparian zones which reflect the interaction of hydrologic flowpaths and environments of different redox state. Internal sources of P associated with buried channel sediments can also influence subsurface SRP transport and release to streams.

  20. Mercury Redox Chemistry in Waters of the Eastern Asian Seas: From Polluted Coast to Clean Open Ocean.

    PubMed

    Ci, Zhijia; Zhang, Xiaoshan; Yin, Yongguang; Chen, Jinsheng; Wang, Shiwei

    2016-03-01

    We performed incubation experiments using seawaters from representative marine environments of the eastern Asian seas to determine the mercury (Hg) available for photoreduction (Hgr(II)), to investigate the Hg redox reaction kinetics, and to explore the effect of environmental factors and water chemistry on the Hg redox chemistry. Results show that Hgr(II) accounted for a considerable fraction of total Hg (THg) (%Hgr(II)/THg: 24.90 ± 10.55%, n = 27) and positively correlated with THg. Filtration decreased the Hgr(II) pool of waters with high suspended particulate matter (SPM). The positive linear relationships were found between pseudo-first order rate constants of gross Hg(II) photoreduction (kr) and gross Hg(0) photo-oxidation (ko) with photosynthetically active radiation (PAR). Under the condition of PAR of 1 m mol m(-2) s(-1), the kr were significantly (p < 0.05) lower than ko (kr/ko: 0.86 ± 0.22). The Hg(0) dark oxidation were significantly higher than the Hg(II) dark reduction. The Hg(II) dark reduction was positively correlated to THg, and the anaerobic condition favored the Hg(II) dark reduction. Filtration significantly influenced the Hg photoredox chemistry of waters with high SPM. UVB radiation was important for both Hg(II) photoreduction and Hg(0) photo-oxidation, and the role of other wavebands in photoinduced transformations of Hg varied with the water chemistry. PMID:26863412

  1. Electrochemical studies of iron meteorites: phosphorus redox chemistry on the early Earth

    NASA Astrophysics Data System (ADS)

    Bryant, David E.; Greenfield, David; Walshaw, Richard D.; Evans, Suzanne M.; Nimmo, Alexander E.; Smith, Caroline L.; Wang, Liming; Pasek, Matthew A.; Kee, Terence P.

    2009-01-01

    The mineral schreibersite, (Fe,Ni)3P, a ubiquitous component of iron meteorites, is known to undergo anoxic hydrolytic modification to afford a range of phosphorus oxyacids. H-phosphonic acid (H3PO3) is the principal hydrolytic product under hydrothermal conditions, as confirmed here by 31P-NMR spectroscopic studies on shavings of the Seymchan pallasite (Magadan, Russia, 1967), but in the presence of photochemical irradiation a more reduced derivative, H-phosphinic (H3PO2) acid, dominates. The significance of such lower oxidation state oxyacids of phosphorus to prebiotic chemistry upon the early Earth lies with the facts that such forms of phosphorus are considerably more soluble and chemically reactive than orthophosphate, the commonly found form of phosphorus on Earth, thus allowing nature a mechanism to circumvent the so-called Phosphate Problem. This paper describes the Galvanic corrosion of Fe3P, a hydrolytic modification pathway for schreibersite, leading again to H-phosphinic acid as the key P-containing product. We envisage this pathway to be highly significant within a meteoritic context as iron meteorites are polymetallic composites in which dissimilar metals, with different electrochemical potentials, are connected by an electrically conducting matrix. In the presence of a suitable electrolyte medium, i.e., salt water, galvanic corrosion can take place. In addition to model electrochemical studies, we also report the first application of the Kelvin technique to map surface potentials of a meteorite sample that allows the electrochemical differentiation of schreibersite inclusions within an Fe:Ni matrix. Such experiments, coupled with thermodynamic calculations, may allow us to better understand the chemical redox behaviour of meteoritic components with early Earth environments.

  2. ROLE OF MANGANESE REDUCTION/OXIDATION (REDOX) ON FOAMING AND MELT RATE IN HIGH LEVEL WASTE (HLW) MELTERS (U)

    SciTech Connect

    Jantzen, C; Michael Stone, M

    2007-03-30

    High-level nuclear waste is being immobilized at the Savannah River Site (SRS) by vitrification into borosilicate glass at the Defense Waste Processing Facility (DWPF). Control of the Reduction/Oxidation (REDOX) equilibrium in the DWPF melter is critical for processing high level liquid wastes. Foaming, cold cap roll-overs, and off-gas surges all have an impact on pouring and melt rate during processing of high-level waste (HLW) glass. All of these phenomena can impact waste throughput and attainment in Joule heated melters such as the DWPF. These phenomena are caused by gas-glass disequilibrium when components in the melter feeds convert to glass and liberate gases such as H{sub 2}O vapor (steam), CO{sub 2}, O{sub 2}, H{sub 2}, NO{sub x}, and/or N{sub 2}. During the feed-to-glass conversion in the DWPF melter, multiple types of reactions occur in the cold cap and in the melt pool that release gaseous products. The various gaseous products can cause foaming at the melt pool surface. Foaming should be avoided as much as possible because an insulative layer of foam on the melt surface retards heat transfer to the cold cap and results in low melt rates. Uncontrolled foaming can also result in a blockage of critical melter or melter off-gas components. Foaming can also increase the potential for melter pressure surges, which would then make it difficult to maintain a constant pressure differential between the DWPF melter and the pour spout. Pressure surges can cause erratic pour streams and possible pluggage of the bellows as well. For these reasons, the DWPF uses a REDOX strategy and controls the melt REDOX between 0.09 {le} Fe{sup 2+}/{summation}Fe {le} 0.33. Controlling the DWPF melter at an equilibrium of Fe{sup +2}/{summation}Fe {le} 0.33 prevents metallic and sulfide rich species from forming nodules that can accumulate on the floor of the melter. Control of foaming, due to deoxygenation of manganic species, is achieved by converting oxidized MnO{sub 2} or Mn

  3. Azide groups in higher oxidation state manganese cluster chemistry: from structural aesthetics to single-molecule magnets.

    PubMed

    Stamatatos, Theocharis C; Christou, George

    2009-04-20

    This Forum Article overviews the recent amalgamation of two long-established areas, manganese/oxo coordination cluster chemistry involving the higher Mn(II)/Mn(IV) oxidation states and transition-metal azide (N(3)(-)) chemistry. The combination of azide and alkoxide- or carboxylate-containing ligands in Mn chemistry has led to a variety of new polynuclear clusters, high-spin molecules, and single-molecule magnets, with metal nuclearities ranging from Mn(4) to Mn(32) and with ground-state spin values as large as S = 83/2. The organic bridging/chelating ligands are discussed separately as follows: (i) pyridyl alkoxides [the anions of 2-(hydroxymethyl)pyridine (hmpH), 2,6-pyridinedimethanol (pdmH(2)), and the gem-diol form of di-2-pyridyl ketone (dpkdH(2))]; (ii) non-pyridyl alkoxides [the anions of 1,1,1-tris(hydroxymethyl)ethane (thmeH(3)), triethanolamine (teaH(3)), and N-methyldiethanolamine (mdaH(2))]; (iii) other alcohols [the anions of 2,6-dihydroxymethyl-4-methylphenol (LH(3)) and Schiff bases]; (iv) pyridyl monoximes/dioximes [the anions of methyl-2-pyridyl ketone oxime (mpkoH), phenyl-2-pyridyl ketone oxime (ppkoH), and 2,6-diacetylpyridine dioxime (dapdoH(2))]; (v) non-pyridyl oximes [the anions of salicylaldoxime (saoH(2)) and its derivatives R-saoH(2)]. The large structural diversity of the resulting complexes stems from the combined ability of the azide and organic ligands to adopt a variety of ligation and bridging modes. The combined work demonstrates the synthetic novelty that arises when azide is used in conjunction with alcohol-based chelates, the aesthetic beauty of the resulting molecules, and the often fascinating magnetic properties that these compounds possess. This continues to emphasize the extensive and remarkable ability of Mn chemistry to satisfy a variety of different tastes. PMID:19364123

  4. The Application of 238U/235U as a Redox-Proxy for Past Ocean Chemistry

    NASA Astrophysics Data System (ADS)

    Andersen, M. B.; Westermann, S.; Bahniuk, A.; Vasconcelos, C.; McKenzie, J. A.; Föllmi, K. B.; Vance, D.

    2014-12-01

    The recent discovery of significant variation in 238U/235U caused by redox change at the surface Earth has led to its use to extract information on the oxygenation state of ancient oceans from marine sediments [e.g. 1]. Recent studies have focused on improving the understanding of the 238U/235U signature in modern marine carbonates [2] and black shales [3] to improve the robustness of this tracer. To further advance its use we have focused on improving our understanding of 238U/235U systematics in modern dolomite, another commonly occurring rock-type in the geological record, before turning to 238U/235U signatures in ancient sediments. The measured dolomite samples, precipitated in modern environments of coastal hypersaline lagoons in Brazil, all exhibit 238U/235U values that deviate from the seawater composition [3]. Observed values are both lighter (ca. 130 ppm; as also observed in dolomite from tidal-ponds on Bahamas [2]) and heavier (50-180 ppm). These distinct 238U/235U values for different dolomite-precipitates likely attest to the particular formation style, as well as early diagenetic processes. We use such modern settings to discuss the utility of 238U/235U in ancient sediments, the singularity of any observed 238U/235U signal, its relation to global ocean chemistry and potential diagenetic overprinting. These constraints are then used to evaluate a well-preserved marine carbonate section [4] and published black shale 238U/235U data [1], both deposited during the Oceanic Anoxic Event 2 (93 Ma). We discuss the capabilities of both the carbonate and black shale section for retaining information on the 238U/235U composition in the ocean during OAE 2. [1] Montoya-Pino et al. (2010) Geology, 38, 315-318 [2] Romaniello et al. (2013) 362, 305-316 [3] Andersen et al. (2014) EPSL, 400, 184-194 [4] Westermann et al. (2010) Cret. Res., 31, 500-514

  5. Electronic Structure of Manganese Complexes of the Redox-Non-innocent Tetrazene Ligand and Evidence for the Metal-Azide/Imido Cycloaddition Intermediate.

    PubMed

    Vaddypally, Shivaiah; McKendry, Ian G; Tomlinson, Warren; Hooper, Joseph P; Zdilla, Michael J

    2016-07-18

    The first synthetic manganese tetrazene complexes are described as a redox pair comprising anionic [Mn(N4 Ad2 )2 ](-) (1) and neutral Mn(N4 Ad2 )2 (2) complexes (N4 Ad2 =[Ad-N-N=N-N-Ad](2-) ). Compound 1 is obtained in two forms as lithium salts, one as a cationic Li2 Mn cluster, and one as a Mn-Li 1D ionic polymer. Compound 1 is electronically described as a Mn(III) center with two [N4 Ad2 ](2-) ligands. The one-electron oxidized 2 is crystalized in two morphologies, one as pure 2 and one as an acetonitrile adduct. Despite similar composition, the behavior of 2 differs in the two morphologies. Compound 2-MeCN is relatively air and temperature stable. Crystalline 2, on the other hand, exhibits a compositional, dynamic disorder wherein the tetrazene metallacycle ring-opens into a metal imide/azide complex detectable by X-ray crystallography and FTIR spectroscopy. Electronic structure of 2 was examined by EPR and XPS spectroscopies and DFT calculations, which indicate 2 is best described as a Mn(III) ion with an anion radical delocalized across the two ligands through spin-polarization effects. PMID:27339316

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

    PubMed

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

    2012-05-01

    Zn and the Art of Battery Development: A zinc/polyhalide redox flow battery employs Br(-) /ClBr(2-) and Zn/Zn(2+) redox couples in its positive and negative half-cells, respectively. The performance of the battery is evaluated by charge-discharge cycling tests and reveals a high energy efficiency of 81%, based on a Coulombic efficiency of 96% and voltage efficiency of 84%. The new battery technology can provide high performance and energy density at an acceptable cost. PMID:22262638

  7. Protein redox chemistry: post-translational cysteine modifications that regulate signal transduction and drug pharmacology

    PubMed Central

    Wani, Revati; Nagata, Asako; Murray, Brion W.

    2014-01-01

    The perception of reactive oxygen species has evolved over the past decade from agents of cellular damage to secondary messengers which modify signaling proteins in physiology and the disease state (e.g., cancer). New protein targets of specific oxidation are rapidly being identified. One emerging class of redox modification occurs to the thiol side chain of cysteine residues which can produce multiple chemically distinct alterations to the protein (e.g., sulfenic/sulfinic/sulfonic acid, disulfides). These post-translational modifications (PTM) are shown to affect the protein structure and function. Because redox-sensitive proteins can traffic between subcellular compartments that have different redox environments, cysteine oxidation enables a spatio-temporal control to signaling. Understanding ramifications of these oxidative modifications to the functions of signaling proteins is crucial for understanding cellular regulation as well as for informed-drug discovery process. The effects of EGFR oxidation of Cys797 on inhibitor pharmacology are presented to illustrate the principle. Taken together, cysteine redox PTM can impact both cell biology and drug pharmacology. PMID:25339904

  8. 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)

  9. 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

  10. Comparative analysis for various redox flow batteries chemistries using a cost performance model

    SciTech Connect

    Crawford, Aladsair J.; Viswanathan, Vilayanur V.; Stephenson, David E.; Wang, Wei; Thomsen, Edwin C.; Reed, David M.; Li, Bin; Balducci, Patrick J.; Kintner-Meyer, Michael CW; Sprenkle, Vincent L.

    2015-10-20

    A robust performance-based cost model is developed for all-vanadium, iron-vanadium and iron chromium redox flow batteries. Systems aspects such as shunt current losses, pumping losses and thermal management are accounted for. The objective function, set to minimize system cost, allows determination of stack design and operating parameters such as current density, flow rate and depth of discharge (DOD). Component costs obtained from vendors are used to calculate system costs for various time frames. A 2 kW stack data was used to estimate unit energy costs and compared with model estimates for the same size electrodes. The tool has been shared with the redox flow battery community to both validate their stack data and guide future direction.

  11. Redox chemistry of green tea polyphenols: therapeutic benefits in neurodegenerative diseases.

    PubMed

    Hügel, H M; Jackson, N

    2012-05-01

    Evidence for the medicinal and health benefits of polyphenols in green tea for the prevention of chronic diseases such as heart disease, various types of cancer and neurodegenerative diseases is advancing. Their in vivo effectiveness and molecular mechanisms are difficult to elucidate and remain a challenging task. We review the redox responsiveness and amyloid protein perturbation biophysical properties of the major green tea polyphenol constituent (-)- epigallocatechin-3-gallate [EGCG]. PMID:22303970

  12. Ionizing Radiation-Induced Responses: Where Free Radical Chemistry Meets Redox Biology and Medicine

    PubMed Central

    Hauer-Jensen, Martin

    2014-01-01

    Abstract The biological effects of ionizing radiation (IR) from environmental, medical, and man-made sources, as well as from space exploration are of broad health concern. During the last 40 years it has become evident that, in addition to short-lived free radical-mediated events initiated within microseconds of exposure and generally thought to dissipate within milliseconds, IR-induced production of reactive oxygen and nitrogen species as well as changes in redox signaling linked to disruption of metabolic processes persist long after radiation exposure. Furthermore, persistent IR-induced increases in the metabolic production of reactive oxygen and nitrogen species appear to significantly contribute to the delayed effects of IR exposure, including induction of adaptive responses at low doses as well as carcinogenesis, fibrosis, inflammation, genomic instability, and acceleration of the onset of degenerative tissue injury processes associated with aging. The ability to identify the specific metabolic mechanisms and dose–response relationships that contribute to adaptive responses as well as persistent IR-induced injury processes holds great promise for identifying novel strategies to mitigate the deleterious effects of IR exposure as well as for gathering mechanistic information critical for risk assessment. This Forum contains original and review articles authored by experts in the field of radiobiology focusing on novel mechanisms involving redox biology and metabolism that significantly contribute to the persistent biological effects seen following IR exposure. Antioxid. Redox Signal. 20, 1407–1409. PMID:24354361

  13. Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode

    PubMed Central

    Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao; Nishimura, Shin-ichi; Chung, Sai-Cheong; Kiuchi, Hisao; Harada, Yoshihisa; Kikkawa, Jun; Kobayashi, Yoshio; Okubo, Masashi; Yamada, Atsuo

    2016-01-01

    Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na1/3Ru2/3]O2 slabs delivers a capacity of 180 mAh g−1 (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g−1 (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes. PMID:27088834

  14. Redox Energy and Sulfur Chemistry in Prebiotic Polymer Synthesis and Replication

    NASA Technical Reports Server (NTRS)

    Weber, Arthur L.

    1997-01-01

    In the past year we have made significant progress in three research areas: (1) Most importantly, we discovered a new pathway of prebiotic amino acid synthesis in which formaldehyde and glycolaldehyde (substrates of the formose reaction) react with ammonia yielding alanine and homoserine in the presence of thiol catalysts. This thiol-dependent synthesis of amino acids undoubtedly occurs via amino acid thioester intermediates capable of forming peptides. This 'one-pot' reaction system operates under mild aqueous conditions, and like modern amino acid biosynthesis, uses sugar intermediates which are converted to amino acids by energy-yielding redox disproportionation. (2) Finally, in preparation for the analysis of Martian meteorite samples, we upgraded our HPLC system and developed an improved method capable of detecting a I femtomole of amino acid enantiomers. (3) We completed our analysis of the energetics of metabolism that revealed that life depends on biosynthetic processes driven by chemical energy made available by the redox disproportionation of carbon groups of sugars. We established that the favorable energy of redox disproportionation is based on the universal reduction potentials of carbon groups. We concluded that it is hard to imagine any other organic molecule besides sugars (formaldehyde oligomers) having the energy and reactivity needed to drive either modem biosynthesis or the chemical processes behind its origin.

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

    PubMed

    Sathiya, M; Rousse, G; Ramesha, K; Laisa, C P; Vezin, H; Sougrati, M T; Doublet, M-L; Foix, D; Gonbeau, D; Walker, W; Prakash, A S; Ben Hassine, M; Dupont, L; Tarascon, J-M

    2013-09-01

    Li-ion batteries have contributed to the commercial success of portable electronics and may soon dominate the electric transportation market provided that major scientific advances including new materials and concepts are developed. Classical positive electrodes for Li-ion technology operate mainly through an insertion-deinsertion redox process involving cationic species. However, this mechanism is insufficient to account for the high capacities exhibited by the new generation of Li-rich (Li(1+x)Ni(y)Co(z)Mn(1-x-y-z)O₂) layered oxides that present unusual Li reactivity. In an attempt to overcome both the inherent composition and the structural complexity of this class of oxides, we have designed structurally related Li₂Ru(1-y)Sn(y)O₃ materials that have a single redox cation and exhibit sustainable reversible capacities as high as 230 mA h g(-1). Moreover, they present good cycling behaviour with no signs of voltage decay and a small irreversible capacity. We also unambiguously show, on the basis of an arsenal of characterization techniques, that the reactivity of these high-capacity materials towards Li entails cumulative cationic (M(n+)→M((n+1)+)) and anionic (O(2-)→O₂(2-)) reversible redox processes, owing to the d-sp hybridization associated with a reductive coupling mechanism. Because Li₂MO₃ is a large family of compounds, this study opens the door to the exploration of a vast number of high-capacity materials. PMID:23852398

  16. Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode

    NASA Astrophysics Data System (ADS)

    Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao; Nishimura, Shin-Ichi; Chung, Sai-Cheong; Kiuchi, Hisao; Harada, Yoshihisa; Kikkawa, Jun; Kobayashi, Yoshio; Okubo, Masashi; Yamada, Atsuo

    2016-04-01

    Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na1/3Ru2/3]O2 slabs delivers a capacity of 180 mAh g-1 (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g-1 (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes.

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

    SciTech Connect

    Haschke, J M; Siekhaus, W J

    2009-02-11

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

  18. Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode.

    PubMed

    Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao; Nishimura, Shin-Ichi; Chung, Sai-Cheong; Kiuchi, Hisao; Harada, Yoshihisa; Kikkawa, Jun; Kobayashi, Yoshio; Okubo, Masashi; Yamada, Atsuo

    2016-01-01

    Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na1/3Ru2/3]O2 slabs delivers a capacity of 180 mAh g(-1) (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g(-1) (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes. PMID:27088834

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

    NASA Astrophysics Data System (ADS)

    Sathiya, M.; Rousse, G.; Ramesha, K.; Laisa, C. P.; Vezin, H.; Sougrati, M. T.; Doublet, M.-L.; Foix, D.; Gonbeau, D.; Walker, W.; Prakash, A. S.; Ben Hassine, M.; Dupont, L.; Tarascon, J.-M.

    2013-09-01

    Li-ion batteries have contributed to the commercial success of portable electronics and may soon dominate the electric transportation market provided that major scientific advances including new materials and concepts are developed. Classical positive electrodes for Li-ion technology operate mainly through an insertion-deinsertion redox process involving cationic species. However, this mechanism is insufficient to account for the high capacities exhibited by the new generation of Li-rich (Li1+xNiyCozMn(1-x-y-z)O2) layered oxides that present unusual Li reactivity. In an attempt to overcome both the inherent composition and the structural complexity of this class of oxides, we have designed structurally related Li2Ru1-ySnyO3 materials that have a single redox cation and exhibit sustainable reversible capacities as high as 230 mA h g-1. Moreover, they present good cycling behaviour with no signs of voltage decay and a small irreversible capacity. We also unambiguously show, on the basis of an arsenal of characterization techniques, that the reactivity of these high-capacity materials towards Li entails cumulative cationic (Mn+→M(n+1)+) and anionic (O2-→O22-) reversible redox processes, owing to the d-sp hybridization associated with a reductive coupling mechanism. Because Li2MO3 is a large family of compounds, this study opens the door to the exploration of a vast number of high-capacity materials.

  20. Storm-associated hydrodynamics drive transient solute and redox chemistry within the floodplain aquifer and hyporheic zone of a piedmont stream

    NASA Astrophysics Data System (ADS)

    Sawyer, A. H.; Kaplan, L. A.; Lazareva, O.; Michael, H. A.

    2013-12-01

    Riparian and hyporheic zones are dynamic settings where fluctuations in pore water flow influence redox-sensitive biogeochemical processes and solute transport. We instrumented a riparian-hyporheic zone transect with pressure transducers, redox probes, and pore water samplers to measure hydrology, redox potential, and water chemistry before, during and after Hurricane Sandy in October 2012. The transect spanned opposing, topographically distinct floodplains, consisting of a broad, flat western side and narrow, steep eastern side. The water table on both sides of the stream rose rapidly with rising stage and promoted continuous groundwater discharge to the stream throughout the storm hydrograph. Soil moisture and oxygen isotope data suggest that preferential recharge through macropores drove the rapid water table response. Macropore flow was also implicated in the delivery of oxygenated, carbon-rich water from the land surface into the floodplain aquifer, driving a shift in redox conditions at depth. Groundwater chemistry changed dramatically: DOC concentrations increased while nitrate and metal concentrations decreased. Greater shifts in groundwater chemistry occurred on the steep eastern side and required more time to reestablish after the storm. The eastern floodplain aquifer also drained more rapidly. Topographic variations across the floodplain transect influenced fluid flow paths and residence times that ultimately controlled the spatial and temporal dynamics of groundwater biogeochemistry. Use of paired sensors such as redox and pressure sensors can improve our understanding of hydrobiogeochemical dynamics during storms.

  1. Thermal chemistry of Mn{sub 2}(CO){sub 10} during deposition of thin manganese films on silicon oxide and on copper surfaces

    SciTech Connect

    Qin Xiangdong; Sun Huaxing; Zaera, Francisco

    2012-01-15

    The surface chemistry of dimanganese decacarbonyl on the native oxide of Si(100) wafers was characterized with the aid of x-ray photoelectron spectroscopy. Initial experiments in a small stainless-steel reactor identified a narrow range of temperatures, between approximately 445 and 465 K, in which the deposition of manganese could be achieved in a self-limiting fashion, as is desirable for atomic layer deposition. Deposition at higher temperatures leads to multilayer growth, but the extent of this Mn deposition reverses at even higher temperatures (about 625 K), and also ifhydrogen is added to the reaction mixture. Extensive decarbonylation takes place below room temperature, but limited C-O bond dissociation and carbon deposition are still seen after high exposures at 625 K. The films deposited at low ({approx}450 K) temperatures are mostly in the form of MnO, but at 625 K that converts to a manganese silicate, and upon higher doses a manganese silicide forms at the SiO{sub 2}/Si(100) interface as well. No metallic manganese could be deposited with this precursor on either silicon dioxide or copper surfaces.

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

    SciTech Connect

    WANG,YIFENG; PAPENGUTH,HANS W.

    2000-05-04

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

  3. The influence of EI-21 redox ion-exchange resins on the secondary-coolant circuit water chemistry of vehicular nuclear power installations

    NASA Astrophysics Data System (ADS)

    Moskvin, L. N.; Rakov, V. T.

    2015-06-01

    The results obtained from testing the secondary-coolant circuit water chemistry of full-scale land-based prototype bench models of vehicular nuclear power installations equipped with water-cooled water-moderated and liquid-metal reactor plants are presented. The influence of copper-containing redox ionexchange resins intended for chemically deoxygenating steam condensate on the working fluid circulation loop's water chemistry is determined. The influence of redox ion-exchange resins on the water chemistry is evaluated by generalizing an array of data obtained in the course of extended monitoring using the methods relating to physicochemical analysis of the quality of condensate-feedwater path media and the methods relating to metallographic analysis of the state of a faulty steam generator's tube system surfaces. The deoxygenating effectiveness of the normal state turbine condensate vacuum deaeration system is experimentally determined. The refusal from applying redox ion-exchange resins in the condensate polishing ion-exchange filters is formulated based on the obtained data on the adverse effect of copper-containing redox ionexchange resins on the condensate-feedwater path water chemistry and based on the data testifying a sufficient effect from using the normal state turbine condensate vacuum deaeration system. Data on long-term operation of the prototype bench model of a vehicular nuclear power installation without subjecting the turbine condensate to chemical deoxygenation are presented.

  4. Review about the manganese speciation project related to neurodegeneration: An analytical chemistry approach to increase the knowledge about manganese related parkinsonian symptoms.

    PubMed

    Michalke, Bernhard

    2016-09-01

    Neurodegenerative diseases get a growing relevance for societies. But yet the complex multi-factorial mechanisms of these diseases are not fully understood, although it is well accepted that metal ions may play a crucial role. Manganese (Mn) is a transition metal which has essential biochemical functions but from occupational exposure scenarios it appeared that Mn can cause severe neurological damage. This "two-faces"-nature of manganese initiated us to start a project on Mn-speciation, since different element species are known to exhibit different impacts on health. A summary about the step-wise developments and findings from our working group was presented during the annual conference of the German trace element society in 2015. This paper summarizes now the contribution to this conference. It is intended to provide a complete picture of the so far evolved puzzle from our studies regarding manganese, manganese speciation and metabolomics as well as Mn-related mechanisms of neural damage. Doing so, the results of the single studies are now summarized in a connected way and thus their interrelationships are demonstrated. In short terms, we found that Mn-exposure leads to an increase of low molecular weight Mn compounds, above all Mn-citrate complex, which gets even enriched across neural barriers (NB). At a Mn serum concentration between 1.5 and 1.9μg/L a carrier switch from Mn-transferrin to Mn-citrate was observed. We concluded that the Mn-citrate complex is that important Mn-carrier to NB which can be found also beyond NB in human cerebrospinal fluid (CSF) or brain of exposed rats. In brain of Mn-exposed rats manganese leads to a decreased iron (Fe) concentration, to a shift from Fe(III) to Fe(II) after long term exposure and thus to a shift toward oxidative stress. This was additionally supported by an increase of markers for oxidative stress, inflammation or lipid peroxidation at increased Mn concentration in brain extracts. Furthermore, glutamate and

  5. Surface chemistry of coated lithium manganese nickel oxide thin film cathodes studied by XPS

    SciTech Connect

    Baggetto, Loic; Dudney, Nancy J; Veith, Gabriel M

    2013-01-01

    The effect of coating high voltage LiMn1.5Ni0.5O4 spinel cathode thin films with three metal oxide thin layers is discussed. The changes in surface chemistry of the electrodes are measured by X-ray photoelectron spectroscopy. ZnO is found to decompose during the first charge whereas Al2O3 and ZrO2 are stable for more than 100 cycles. ZrO2, however, importantly limits the available Li storage capacity of the electrochemical reaction due to poorer kinetics. Al2O3 offers the best results in term of capacity retention. Upon cycling, the evidence of a signal at 75.4 eV in the Al2p binding energy spectrum indicates the partial conversion of Al2O3 into Al2O2F2. Moreover, the continuous formation of PEO , esters and LixPOyFz compounds on the surface of the electrodes is found for all coating materials.

  6. Probing the redox chemistry of titanium silicalite-1: formation of tetrahedral Ti3+ centers by reaction with triethylaluminum.

    PubMed

    Morra, Elena; Giamello, Elio; Chiesa, Mario

    2014-06-10

    Transition-metal ions with open-shell configurations hold promise in the development of novel coordination chemistry and potentially unprecedented redox catalysis. Framework-substituted Ti(3+) ions with tetrahedral coordination are generated by reductive activation of titanium silicalite-1 with triethylaluminum, an indispensable co-catalyst for heterogeneous Ziegler-Natta polymerization catalysts. Continuous-wave and pulse electron paramagnetic resonance methods are applied to unravel details on the local environment of the reduced transition metal-ions, which are shown to be part of the silica framework by detection of (29)Si hyperfine interactions. The chemical accessibility of the reduced sites is probed using ammonia as probe molecule. Evidence is found for the coordination of a single ammonia molecule. Comparison to similar systems, such as TiAlPO-5, reveals clear differences in the coordination chemistry of the reduced Ti sites in the two solids, which may be understood considering the different electronic properties of the solid frameworks. PMID:24824439

  7. Water oxidation chemistry of a synthetic dinuclear ruthenium complex containing redox-active quinone ligands.

    PubMed

    Isobe, Hiroshi; Tanaka, Koji; Shen, Jian-Ren; Yamaguchi, Kizashi

    2014-04-21

    We investigated theoretically the catalytic mechanism of electrochemical water oxidation in aqueous solution by a dinuclear ruthenium complex containing redox-active quinone ligands, [Ru2(X)(Y)(3,6-tBu2Q)2(btpyan)](m+) [X, Y = H2O, OH, O, O2; 3,6-tBu2Q = 3,6-di-tert-butyl-1,2-benzoquinone; btpyan =1,8-bis(2,2':6',2″-terpyrid-4'-yl)anthracene] (m = 2, 3, 4) (1). The reaction involves a series of electron and proton transfers to achieve redox leveling, with intervening chemical transformations in a mesh scheme, and the entire molecular structure and motion of the catalyst 1 work together to drive the catalytic cycle for water oxidation. Two substrate water molecules can bind to 1 with simultaneous loss of one or two proton(s), which allows pH-dependent variability in the proportion of substrate-bound structures and following pathways for oxidative activation of the aqua/hydroxo ligands at low thermodynamic and kinetic costs. The resulting bis-oxo intermediates then undergo endothermic O-O radical coupling between two Ru(III)-O(•) units in an anti-coplanar conformation leading to bridged μ-peroxo or μ-superoxo intermediates. The μ-superoxo species can liberate oxygen with the necessity for the preceding binding of a water molecule, which is possible only after four-electron oxidation is completed. The magnitude of catalytic current would be limited by the inherent sluggishness of the hinge-like bending motion of the bridged μ-superoxo complex that opens up the compact, hydrophobic active site of the catalyst and thereby allows water entry under dynamic conditions. On the basis of a newly proposed mechanism, we rationalize the experimentally observed behavior of electrode kinetics with respect to potential and discuss what causes a high overpotential for water oxidation by 1. PMID:24694023

  8. Soil Redox Chemistry Limitation of Selenium Concentration in Carex Species Sedges

    SciTech Connect

    Bruce J. Mincher; John Mionczynski; Patrick A. Hnilicka

    2007-09-01

    The trace element selenium (Se) is required in the production of enzymes that protect mammalian cells from oxidative damage due to the byproducts of aerobic respiration. Its deficiency in livestock results in the nutritional muscular dystrophy called white muscle disease. This especially affects juveniles in the preweaning period. Symptoms have also been reported in wild herbivores on low-Se forage, and their appearance may be episodic, suggesting temporal variations in Se uptake by plants. Here, we report variations in selenium concentrations in Carex spp. sedges used as forage by bighorn sheep (Ovis canadensis) on summer range in the Wyoming, Wind River Mountains, and correlate those variations with soil conditions that affect the bioavailability of selenium. Variations in available Se are explained based upon the known oxidation/reduction chemistry of the element. It is concluded that water-saturated, alpine soils provide conditions suitable for the reduction of Se to the unavailable, elemental form, limiting its concentration in forage plants.

  9. A Cyclic Voltammetry Experiment Illustrating Redox Potentials, Equilibrium Constants, and Substitution Reactions in Coordination Chemistry

    NASA Astrophysics Data System (ADS)

    Toma, Henrique E.; Araki, Koiti; Dovidauskas, Sergio

    2000-10-01

    We report a cyclic voltammetry experiment focusing on the [RuIII(EDTA)(H2O)]- complex and its equilibrium reaction with dimethyl sulfoxide (DMSO) in aqueous solution, yielding the [RuIII(EDTA)(kS-DMSO)]- complex. From the electrochemistry data, the formation constants for the [RuIII(EDTA)(kS-DMSO)]- and [RuII(EDTA)(kS-DMSO)]2- complexes were calculated as 2.0 mol-1 dm3 and 2.7 x 109 mol-1 dm3, respectively. The results illustrate the kinetic lability of the ruthenium(III)-EDTA complexes and the role of backbonding stabilization in ruthenium(II)-DMSO complexes. The experiment has been successfully performed in a Coordination Chemistry course, exploiting fundamental aspects of metal complexes and the applications of that important electrochemical technique.

  10. Probing the chemistry, electronic structure and redox energetics in pentavalent organometallic actinide complexes

    SciTech Connect

    Graves, Christopher R; Vaughn, Anthony E; Morris, David E; Kiplinger, Jaqueline L

    2008-01-01

    Complexes of the early actinides (Th-Pu) have gained considerable prominence in organometallic chemistry as they have been shown to undergo chemistries not observed with their transition- or lanthanide metal counterparts. Further, while bonding in f-element complexes has historically been considered to be ionic, the issue of covalence remains a subject of debate in the area of actinide science, and studies aimed at elucidating key bonding interactions with 5f-orbitals continue to garner attention. Towards this end, our interests have focused on the role that metal oxidation state plays in the structure, reactivity and spectral properties of organouranium complexes. We report our progress in the synthesis of substituted U{sup V}-imido complexes using various routes: (1) Direct oxidation of U{sup IV}-imido complexes with copper(I) salts; (2) Salt metathesis with U{sup V}-imido halides; (3) Protonolysis and insertion of an U{sup V}-imido alkyl or aryl complex with H-N{double_bond}CPh{sub 2} or N{triple_bond}C-Ph, respectively, to form a U{sup V}-imido ketimide complex. Further, we report and compare the crystallographic, electrochemical, spectroscopic and magnetic characterization of the pentavalent uranium (C{sub 5}Me{sub 5}){sub 2}U({double_bond}N-Ar)(Y) series (Y = OTf, SPh, C{triple_bond}C-Ph, NPh{sub 2}, OPh, N{double_bond}CPh{sub 2}) to further interrogate the molecular, electronic, and magnetic structures of this new class of uranium complexes.

  11. Electrochemical evidence that pyranopterin redox chemistry controls the catalysis of YedY, a mononuclear Mo enzyme.

    PubMed

    Adamson, Hope; Simonov, Alexandr N; Kierzek, Michelina; Rothery, Richard A; Weiner, Joel H; Bond, Alan M; Parkin, Alison

    2015-11-24

    A long-standing contradiction in the field of mononuclear Mo enzyme research is that small-molecule chemistry on active-site mimic compounds predicts ligand participation in the electron transfer reactions, but biochemical measurements only suggest metal-centered catalytic electron transfer. With the simultaneous measurement of substrate turnover and reversible electron transfer that is provided by Fourier-transformed alternating-current voltammetry, we show that Escherichia coli YedY is a mononuclear Mo enzyme that reconciles this conflict. In YedY, addition of three protons and three electrons to the well-characterized "as-isolated" Mo(V) oxidation state is needed to initiate the catalytic reduction of either dimethyl sulfoxide or trimethylamine N-oxide. Based on comparison with earlier studies and our UV-vis redox titration data, we assign the reversible one-proton and one-electron reduction process centered around +174 mV vs. standard hydrogen electrode at pH 7 to a Mo(V)-to-Mo(IV) conversion but ascribe the two-proton and two-electron transition occurring at negative potential to the organic pyranopterin ligand system. We predict that a dihydro-to-tetrahydro transition is needed to generate the catalytically active state of the enzyme. This is a previously unidentified mechanism, suggested by the structural simplicity of YedY, a protein in which Mo is the only metal site. PMID:26561582

  12. Electrochemical evidence that pyranopterin redox chemistry controls the catalysis of YedY, a mononuclear Mo enzyme

    PubMed Central

    Adamson, Hope; Simonov, Alexandr N.; Kierzek, Michelina; Rothery, Richard A.; Weiner, Joel H.; Bond, Alan M.

    2015-01-01

    A long-standing contradiction in the field of mononuclear Mo enzyme research is that small-molecule chemistry on active-site mimic compounds predicts ligand participation in the electron transfer reactions, but biochemical measurements only suggest metal-centered catalytic electron transfer. With the simultaneous measurement of substrate turnover and reversible electron transfer that is provided by Fourier-transformed alternating-current voltammetry, we show that Escherichia coli YedY is a mononuclear Mo enzyme that reconciles this conflict. In YedY, addition of three protons and three electrons to the well-characterized “as-isolated” Mo(V) oxidation state is needed to initiate the catalytic reduction of either dimethyl sulfoxide or trimethylamine N-oxide. Based on comparison with earlier studies and our UV-vis redox titration data, we assign the reversible one-proton and one-electron reduction process centered around +174 mV vs. standard hydrogen electrode at pH 7 to a Mo(V)-to-Mo(IV) conversion but ascribe the two-proton and two-electron transition occurring at negative potential to the organic pyranopterin ligand system. We predict that a dihydro-to-tetrahydro transition is needed to generate the catalytically active state of the enzyme. This is a previously unidentified mechanism, suggested by the structural simplicity of YedY, a protein in which Mo is the only metal site. PMID:26561582

  13. Distinct effects of oxalate versus malonate on the iron redox chemistry: Implications for the photo-Fenton reaction.

    PubMed

    Xiao, Dongxue; Guo, Yaoguang; Lou, Xiaoyi; Fang, Changling; Wang, Zhaohui; Liu, Jianshe

    2014-05-01

    The dicarboxylic acids oxalate (Oxal) and malonate (Mal) are frequently detected as the final low-molecular-weight organic acids during oxidative degradation of aromatic compounds. Here a distinct effect of Oxal versus Mal on iron-based photocatalytic technologies was reported by testing the degradation efficiency of the dye rhodamine B. The rates of dye degradation in irradiated Fe(III) solutions depended on Fe(III/II) speciation, photoreactivities of Fe complexes and reactivities of Fe(II) complexes with H2O2. Photolysis of the Fe(III)-oxalato complex was favorable due to the formation of O2-, HO2 and OH for oxidizing the dye; however, an excess of H2O2 could quench the excited state of ferrioxalate, decreasing the degradation efficiency. In contrast, activities of UV/Fe(III) in the presence of Mal were significantly diminished because Fe(III)-Mal complexes, with much lower quantum yield of Fe(II) from photoreduction, dominated Fe(III) speciation. The results provide data for an understanding of the mechanism of iron redox (photo)chemistry mediated by diacids, which will aid in selecting appropriate Fe ligands, screening photo-Fenton conditions and designing UV/Fe(III) treatability. PMID:24359921

  14. 40Ar/39Ar age and chemistry of manganese mineralization in the Moab and Lisbon fault systems, southeastern Utah

    NASA Astrophysics Data System (ADS)

    Chan, Marjorie A.; Parry, William T.; Petersen, Erich U.; Hall, Chris M.

    2001-04-01

    Diagenetic iron and manganese mineralization is associated with the Moab and Lisbon faults and is an important indicator of fluid flow in Jurassic Navajo Sandstone of southeastern Utah. Reducing brines originating from the Pennsylvanian Paradox Formation (with or without hydrocarbons) mobilized disseminated iron and manganese in the Jurassic sandstones and mixed with shallow, oxygenated groundwater to precipitate both iron and manganese mineralization. Mineralization consists of colliform and concretionary hematite, pyrolusite, and cryptomelane-hollandite that contains 1.33 2.12 wt% K. The 40Ar/39Ar dating of vacuum-encapsulated cryptomelane yields age estimates of 25 20 Ma, indicating mineralization coincident with either a Colorado Plateau uplift episode or La Sal Mountains volcanism.

  15. Computational chemistry insights in the REDOX Behaviour of Cr and W Fischer carbene complexes

    NASA Astrophysics Data System (ADS)

    Landman, Marile; Conradie, Jeanet; van Rooyen, Petrus H.

    2015-09-01

    An electrochemical study of a series of Fischer carbene complexes containing a hetero-aryl group showed that Cr and W carbenes exhibit different electrochemical behaviour. The Cr carbenes are oxidized in two one electron oxidation processes, namely Cr(0) to Cr(I) and Cr(I) to Cr(II). On the contrary, Fischer carbene complexes of tungsten are directly oxidized from W(0) to W(II). The first reduction process observed for both W- and Cr- carbenes, is a one electron process. A density functional theory (DFT) computational chemistry study of the electronic structure of the Cr- and W-carbenes, showed that the oxidation is metal based and the reduction is located on the carbene ligand. The DFT calculations further showed that the Cr(II) species is a triplet and the W(II) species a closed shell singlet. The DFT calculated energies of the HOMO and LUMO of the neutral carbenes relate linearly to the experimental oxidation and reduction potential, respectively. These mathematical relationships obtained can be used to predict experimentally measured potentials of related Fischer carbene complexes.

  16. Redox chemistry and metal-insulator transitions intertwined in a nano-porous material

    NASA Astrophysics Data System (ADS)

    Maximoff, Sergey N.; Smit, Berend

    2014-06-01

    Metal-organic frameworks are nano-porous adsorbents of relevance to gas separation and catalysis, and separation of oxygen from air is essential to diverse industrial applications. The ferrous salt of 2,5-dihydroxy-terephthalic acid, a metal-organic framework of the MOF74 family, can selectively adsorb oxygen in a manner that defies the classical picture: adsorption sites either do or do not share electrons over a long range. Here we propose, and then justify phenomenologically and computationally, a mechanism. Charge-transfer-mediated adsorption of electron acceptor oxygen molecules in the metal-organic framework, which is a quasi-one-dimensional electron-donor semiconductor, drives and is driven by quasi-one-dimensional metal-insulator-metal transitions that localize or delocalize the quasi-one-dimensional electrons. This mechanism agrees with the empirical evidence, and predicts a class of nano-porous semiconductors or metals and potential adsorbents and catalysts in which chemistry and metal-insulator-metal transitions intertwine.

  17. Probing the chemistry, electronic structure and redox energetics in organometallic pentavalent uranium complexes.

    PubMed

    Graves, Christopher R; Vaughn, Anthony E; Schelter, Eric J; Scott, Brian L; Thompson, Joe D; Morris, David E; Kiplinger, Jaqueline L

    2008-12-15

    A series of organometallic pentavalent uranium complexes of the general formula (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(Y) (Y = monoanionic, non-halide ligand) have been prepared using a variety of routes. Utilizing the direct oxidation of (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(THF) (2) with the appropriate copper(I) salt yielded the triflate (Y = OTf (OSO(2)CF(3)), 11), thiolate (Y = SPh, 12), and acetylide (Y = C[triple bond]CPh, 13) complexes, while a salt metathesis route between the U(V)-imido (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(I) (10) and various alkali salts gave the diphenylamide (Y = NPh(2), 14), aryloxide (Y = OPh, 15), alkyl (Y = Me, 16), and aryl (Y = Ph, 17) complexes. Paired with 13, the isolation of 16 and 17 shows that U(V) can support the full range of carbon anions (sp, sp(2), and sp(3)), and these are, to the best of our knowledge, the first examples of pentavalent uranium complexes with anionic carbon moieties other than carbocyclic (C(5)R(5), C(7)H(7), C(8)H(8)) ligands. Finally, both protonolysis and insertion pathways afforded the U(V)-imido ketimide complex (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(N=CPh(2)) (18). The complexes have been isolated in good yield and characterized using various combinations of (1)H NMR spectroscopy, elemental analysis, mass spectrometry, single crystal X-ray diffraction, cyclic voltammetry, UV-visible-NIR absorption spectroscopy, and magnetic susceptibility measurements. All (C(5)Me(5))(2)U(=N-Ar)(X) (X = F, Cl, Br, I) and (C(5)Me(5))(2)U(=N-Ar)(Y) complexes exhibit U(VI)/U(V) and U(V)/U(IV) redox couples by voltammetry. The potential separation between these couples remains essentially constant at approximately 1.50 V, but both processes shift in tandem in potential by approximately 700 mV across the series of X/Y ligands. No significant differences between mu(eff) values or temperature dependencies in the magnetic susceptibility were observed for these complexes regardless of the identity of the

  18. Revisiting the coordination chemistry for preparing manganese oxide nanocrystals in the presence of oleylamine and oleic acid

    NASA Astrophysics Data System (ADS)

    Zhang, Hongwei; Jing, Lihong; Zeng, Jianfeng; Hou, Yi; Li, Zhen; Gao, Mingyuan

    2014-05-01

    By pyrolyzing manganese(ii) acetate in 1-octadecene in the presence of oleylamine and oleic acid, manganese oxide nanocrystals were prepared. It was observed that both MnO and Mn3O4 nanocrystals were simultaneously formed by quickly heating the reaction mixture up to 250 °C, while a preheating procedure carried out at 100 °C led to uniform MnO nanocubes that developed into eight-arm MnO nanocrystals upon prolonged reaction. To understand the mechanisms for forming these two different kinds of manganese oxide nanocrystals, i.e., Mn3O4 and MnO, the coordination between oleic acid/oleylamine and Mn2+ was investigated. The detailed investigations suggest that Mn2+-oleylamine coordination is kinetically driven and favorable for the formation of Mn3O4 nanocrystals due to the relatively low electronegativity of N from oleylamine, while Mn2+-oleate coordination is thermodynamically driven and can prevent the central metal ion (Mn2+) from being oxidized owing to the relatively high electronegativity of O from the oleate ligand. Following these new insights, by properly balancing the coordination of oleic acid and oleylamine to Mn2+, the selective synthesis of MnO and Mn3O4 nanocrystals with uniform shapes was successfully achieved.By pyrolyzing manganese(ii) acetate in 1-octadecene in the presence of oleylamine and oleic acid, manganese oxide nanocrystals were prepared. It was observed that both MnO and Mn3O4 nanocrystals were simultaneously formed by quickly heating the reaction mixture up to 250 °C, while a preheating procedure carried out at 100 °C led to uniform MnO nanocubes that developed into eight-arm MnO nanocrystals upon prolonged reaction. To understand the mechanisms for forming these two different kinds of manganese oxide nanocrystals, i.e., Mn3O4 and MnO, the coordination between oleic acid/oleylamine and Mn2+ was investigated. The detailed investigations suggest that Mn2+-oleylamine coordination is kinetically driven and favorable for the formation of Mn3

  19. Anticorrelation between Surface and Subsurface Point Defects and the Impact on the Redox Chemistry of TiO2(110)

    SciTech Connect

    Yoon, Yeohoon; Du, Yingge; Garcia, Juan C.; Zhu, Zihua; Wang, Zhitao; Petrik, Nikolay G.; Kimmel, Gregory A.; Dohnalek, Zdenek; Henderson, Michael A.; Rousseau, Roger J.; Deskins, N. Aaron; Lyubinetsky, Igor

    2015-02-02

    Using combination of STM, DFT and SIMS, we explored the interplay and relative impact of surface vs. subsurface defects on the surface chemistry of rutile TiO2. STM results show that surface O vacancies (VO’s) are virtually absent in the vicinity of positively-charged subsurface point-defects. This observation is consistent with DFT calculations of impact of subsurface defect proximity on VO formation energy. To monitor the influence of such lateral anticorrelation on surface redox chemistry, a test reaction of the dissociative adsorption of O2 is employed, which is observed to be suppressed around them. DFT results attribute this to a perceived absence of the intrinsic (Ti) (and likely extrinsic) interstitials in the nearest subsurface layer beneath “inhibited” areas. We also postulate that the entire nearest subsurface region could be voided of any charged point-defects, whereas prevalent VO’s are largely responsible for mediation of the redox chemistry at reduced TiO2(110) surface.

  20. Redox chemistry of copper-amyloid-beta: the generation of hydroxyl radical in the presence of ascorbate is linked to redox-potentials and aggregation state.

    PubMed

    Guilloreau, Luc; Combalbert, Sarah; Sournia-Saquet, Alix; Mazarguil, Honoré; Faller, Peter

    2007-07-23

    Aggregation of the beta-amyloid peptide (Abeta) to amyloid plaques is a key event in Alzheimer's disease. According to the amyloid-cascade hypothesis, Abeta aggregates are toxic to neurons through the production of reactive oxygen species (ROS). Copper ions play an important role, because they are able to bind to Abeta and influence its aggregation properties. Moreover, Cu-Abeta is supposed to be directly involved in ROS production. To get a better understanding of these reactions, we measured the production of HO(.) and the redox potential of Cu-Abeta. The results were compared to other biological copper-peptide complexes in order to get an insight into the biological relevance. Cu-Abeta produced more HO(.) than the complex of copper with Asp-Ala-His-Lys (Cu-DAHK), but less than with Gly-His-Lys (Cu-GHK). Cyclic voltammetry revealed that the order for reduction potential is Cu-GHK>Cu-Abeta>Cu-DAHK, but for the oxidation potential the order is reversed. Thus, easier copper redox cycling correlated to higher HO(.) production. The copper complex of the form Abeta1-42 showed a HO(.) production five-times higher than that of the form Abeta1-40. Time-dependence and aggregation studies suggest that an aggregation intermediate is responsible for this increased HO(.) production. PMID:17577900

  1. Acid-base and Electrochemical Properties of Manganese meso(ortho- and meta-ethylpyridyl)porphyrins: Potentiometric, Spectrophotometric and Spectroelectrochemical Study of Protolytic and Redox Equilibria

    PubMed Central

    Weitner, Tin; Budimir, Ana; Batinić-Haberle, Ines

    2013-01-01

    The difference in electrostatics and reduction potentials between manganese ortho-tetrakis(N-ethylpyridinium-2-yl)porphyrin (MnTE-2-PyP) and manganese meta-tetrakis(N-ethylpyridinium-2-yl)porphyrin (MnTE-3-PyP) is a challenging topic, particularly because of the high likelihood for their clinical development. Hence, a detailed study of the protolytic and electrochemical speciation of MnII–IVTE-2-PyP and MnII-IVTE-3-PyP in a broad pH range has been performed using the combined spectrophotometric and potentiometric methods. The results reveal that in aqueous solutions within the pH range ~2–13 the following species exist: (H2O)MnIITE-m-PyP4+, (HO)MnIITE-m-PyP3+, (H2O)2MnIIITE-m-PyP5+, (H2O)(HO)MnIIITE-m-PyP4+, (H2O)(O=)MnIIITE-m-PyP3+, (H2O)(O=)MnIVTE-m-PyP4+ and (HO)(O=)MnIVTE-m-PyP3+ (m = 2, 3). All the protolytic equilibrium constants that include the accessible species as well as the thermodynamic parameters for each particular protolytic equilibrium have been determined. The corresponding formal reduction potentials related to the reduction of the above species and the thermodynamic parameters describing the accessible reduction couples were calculated as well. PMID:21052598

  2. FeS/S/FeS2 Redox System and Its Oxidoreductase-like Chemistry in the Iron-Sulfur World

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Yang, Bin; Qu, Youpeng; Liu, Xiaoyang; Su, Wenhui

    2011-06-01

    The iron-sulfur world (ISW) theory is an intriguing prediction regarding the origin of life on early Earth. It hypothesizes that life arose as a geochemical process from inorganic starting materials on the surface of sulfide minerals in the vicinity of deep-sea hot springs. During the last two decades, many experimental studies have been carried out on this topic, and some interesting results have been achieved. Among them, however, the processes of carbon/nitrogen fixation and biomolecular assembly on the mineral surface have received an inordinate amount of attention. To the present, an abiotic model for the oxidation-reduction of intermediates participating in metabolic pathways has been ignored. We examined the oxidation-reduction effect of a prebiotic FeS/S/FeS2 redox system on the interconversion between several pairs of ±-hydroxy acids and ±-keto acids (i.e., lactate/pyruvate, malate/oxaloacetate, and glycolate/glyoxylate). We found that, in the absence of FeS, elemental sulfur (S) oxidized ±-hydroxy acids to form corresponding keto acids only at a temperature higher than its melting point (113°C); in the presence of FeS, such reactions occurred more efficiently through a coupled reaction mechanism, even at a temperature below the phase transition point of S. On the other hand, FeS was shown to have the capacity to reversibly reduce the keto acids. Such an oxidoreductase-like chemistry of the FeS/S/FeS2 redox system suggests that it can determine the redox homeostasis of metabolic intermediates in the early evolutionary phase of life. The results provide a possible pathway for the development of primordial redox biochemistry in the iron-sulfur world.

  3. Acid-base and electrochemical properties of manganese meso(ortho- and meta-N-ethylpyridyl)porphyrins: potentiometric, spectrophotometric and spectroelectrochemical study of protolytic and redox equilibria.

    PubMed

    Weitner, Tin; Budimir, Ana; Kos, Ivan; Batinić-Haberle, Ines; Biruš, Mladen

    2010-12-28

    The difference in electrostatics and reduction potentials between manganese ortho-tetrakis(N-ethylpyridinium-2-yl)porphyrin (MnTE-2-PyP) and manganese meta-tetrakis(N-ethylpyridinium-3-yl)porphyrin (MnTE-3-PyP) is a challenging topic, particularly because of the high likelihood for their clinical development. Hence, a detailed study of the protolytic and electrochemical speciation of Mn(II-IV)TE-2-PyP and Mn(II-IV)TE-3-PyP in a broad pH range has been performed using the combined spectrophotometric and potentiometric methods. The results reveal that in aqueous solutions within the pH range ∼2-13 the following species exist: (H(2)O)Mn(II)TE-m-PyP(4+), (HO)Mn(II)TE-m-PyP(3+), (H(2)O)(2)Mn(III)TE-m-PyP(5+), (HO)(H(2)O)Mn(III)TE-m-PyP(4+), (O)(H(2)O)Mn(III)TE-m-PyP(3+), (O)(H(2)O)Mn(IV)TE-m-PyP(4+) and (O)(HO)Mn(IV)TE-m-PyP(3+) (m = 2, 3). All the protolytic equilibrium constants that include the accessible species as well as the thermodynamic parameters for each particular protolytic equilibrium have been determined. The corresponding formal reduction potentials related to the reduction of the above species and the thermodynamic parameters describing the accessible reduction couples were calculated as well. PMID:21052598

  4. Manganese mineralogy and diagenesis in the sedimentary rock record

    NASA Astrophysics Data System (ADS)

    Johnson, Jena E.; Webb, Samuel M.; Ma, Chi; Fischer, Woodward W.

    2016-01-01

    Oxidation of manganese (II) to manganese (III,IV) demands oxidants with very high redox potentials; consequently, manganese oxides are both excellent proxies for molecular oxygen and highly favorable electron acceptors when oxygen is absent. The first of these features results in manganese-enriched sedimentary rocks (manganese deposits, commonly Mn ore deposits), which generally correspond to the availability of molecular oxygen in Earth surface environments. And yet because manganese reduction is promoted by a variety of chemical species, these ancient manganese deposits are often significantly more reduced than modern environmental manganese-rich sediments. We document the impacts of manganese reduction and the mineral phases that form stable manganese deposits from seven sedimentary examples spanning from modern surface environments to rocks over 2 billion years old. Integrating redox and coordination information from synchrotron X-ray absorption spectroscopy and X-ray microprobe imaging with scanning electron microscopy and energy and wavelength-dispersive spectroscopy, we find that unlike the Mn(IV)-dominated modern manganese deposits, three manganese minerals dominate these representative ancient deposits: kutnohorite (CaMn(CO3)2), rhodochrosite (MnCO3), and braunite (Mn(III)6Mn(II)O8SiO4). Pairing these mineral and textural observations with previous studies of manganese geochemistry, we develop a paragenetic model of post-depositional manganese mineralization with kutnohorite and calcian rhodochrosite as the earliest diagenetic mineral phases, rhodochrosite and braunite forming secondarily, and later alteration forming Mn-silicates.

  5. Combined Quantum Chemistry and Photoelectron Spectroscopy Study of the Electronic Structure and Reduction Potentials of Rubredoxin Redox Site Analogues

    SciTech Connect

    Niu, Shuqiang; Wang, Xue B.; Nichols, J. A.; Wang, Lai S.; Ichiye, Toshiko

    2003-04-24

    Iron-sulfur proteins are an important class of electron carriers in a wide variety of biological reactions. Determining the intrinsic contribution of the metal site to the redox potential is crucial in understanding how the protein environment influences the overall redox properties of the Fe-S proteins. Here we combine density functional theory and coupled cluster methods with photodetachment spectroscopy to study the electronic structures and gas-phase redox potentials of the [Fe(SCH3)(4)](2-/-/0) and [Fe(SCH3)(3)](-/0) analogues of the rubredoxin redox site. The calculations show that oxidations of [Fe(SCH3)(4)](2-) and [Fe(SCH3)(4)](-) involve mainly the Fe 3d and S 3p orbitals, respectively. The calculated adiabatic and vertical detachment energies are in good agreement with the experiment for [Fe(SCH3)(3)](-) and [Fe(SCH3)(4)](-). The current results further confirm the "inverted level scheme" for the high-spin [1Fe] systems. The redox couple, [Fe(SCH3)(4)](- /2), which is the one found in rubredoxin, but cannot be accessed experimentally in the gas phase, was investigated using a thermodynamic cycle that relates it to the [Fe(SCH3)(3)](-/0) couple and the ligand association reaction, [Fe(SCH3)(3)](0/-) + SCH3- --> [Fe(SCH3)(4)](-/2-). The calculated reduction energy of [Fe(SCH3)(4)](-) (1.7 eV) compares well with the value (1.6 eV) estimated from the calculated bond energies and the experimental detachment energy of [Fe(SCH3)(3)](-). Thus, this thermodynamic cycle method can be used to estimate metal-ligand bonding energies and determine intrinsic reduction potentials from photodetachment experiments when the reduced forms are not stable in the gas phase.

  6. Environmental Controls of Biological Manganese Oxidation

    NASA Astrophysics Data System (ADS)

    Belz, A. P.; Ahn, C. C.; Nealson, K. H.

    2001-12-01

    Biological catalysis of manganese oxidation represents an important contribution to global manganese cycling; biological oxidation rates are several orders of magnitude higher than those of abiotic processes. Despite recent genetics advances, ongoing behavioral studies, and a large pool of knowledge regarding manganese chemistry, the links between biology and environmental chemistry remain unresolved. We have performed experiments on batch cultures of Leptothrix discophora SS-1 to explore the physiology of biological manganese oxidation. We have further conducted spectroscopic and microscopic studies of the mechanism as manganese proceeds from the soluble Mn2+ species to the insoluble Mn(III) and Mn(IV) phases. These investigations suggest roles for aqueous chemistry, mineralogy, and microbial physiology in controlling manganese fluxes in metal-rich environments.

  7. Long-Term Stability of Organic Carbon-Stimulated Chromate Reduction in Contaminated Soils and Its Relation to Manganese Redox Status

    SciTech Connect

    Tokunaga,T.; Wan, J.; Lanzirotti, A.; Sutton, S.; Newville, M.; Rao, W.

    2007-01-01

    In situ reduction of toxic Cr(VI) to less hazardous Cr(III) is becoming a popular strategy for remediating contaminated soils. However, the long-term stability of reduced Cr remains to be understood, especially given the common presence of Mn(III,IV) oxides that re-oxidize Cr(III). This 4.6 year laboratory study tracked Cr and Mn redox transformations in soils contaminated with Cr(VI), which were then treated with different amounts of organic carbon (OC). Changes in Cr and Mn oxidation states within soils were directly and nondestructively measured using micro-X-ray absorption near-edge structure spectroscopy. Chromate reduction was roughly first-order, and the extent of reduction was enhanced with higher OC additions. However, significant Cr(III) re-oxidation occurred in soils exposed to the highest Cr(VI) concentrations (2560 mg kg{sup -1}). Transient Cr(III) re-oxidation up to 420 mg kg{sup -1} was measured at 1.1 years after OC treatment, followed by further reduction. Chromate concentrations increased by 220 mg kg{sup -1} at the end of the study (4.6 years) in one soil. The causal role that the Mn oxidation state had in re-oxidizing Cr was supported by trends in Mn K-edge energies. These results provide strong evidence for long-term dependence of soil Cr oxidation states on balances between OC availability and Mn redox status.

  8. Layered-to-Tunnel Structure Transformation and Oxygen Redox Chemistry in LiRhO2 upon Li Extraction and Insertion.

    PubMed

    Mikhailova, Daria; Karakulina, Olesia M; Batuk, Dmitry; Hadermann, Joke; Abakumov, Artem M; Herklotz, Markus; Tsirlin, Alexander A; Oswald, Steffen; Giebeler, Lars; Schmidt, Marcus; Eckert, Jürgen; Knapp, Michael; Ehrenberg, Helmut

    2016-07-18

    Layered Li(M,Li)O2 (where M is a transition metal) ordered rock-salt-type structures are used in advanced metal-ion batteries as one of the best hosts for the reversible intercalation of Li ions. Besides the conventional redox reaction involving oxidation/reduction of the M cation upon Li extraction/insertion, creating oxygen-located holes because of the partial oxygen oxidation increases capacity while maintaining the oxidized oxygen species in the lattice through high covalency of the M-O bonding. Typical degradation mechanism of the Li(M,Li)O2 electrodes involves partially irreversible M cation migration toward the Li positions, resulting in gradual capacity/voltage fade. Here, using LiRhO2 as a model system (isostructural and isoelectronic to LiCoO2), for the first time, we demonstrate an intimate coupling between the oxygen redox and M cation migration. A formation of the oxidized oxygen species upon electrochemical Li extraction coincides with transformation of the layered Li1-xRhO2 structure into the γ-MnO2-type rutile-ramsdellite intergrowth LiyRh3O6 structure with rutile-like [1 × 1] channels along with bigger ramsdellite-like [2 × 1] tunnels through massive and concerted Rh migration toward the empty positions in the Li layers. The oxidized oxygen dimers with the O-O distances as short as 2.26 Å are stabilized in this structure via the local Rh-O configuration reminiscent to that in the μ-peroxo-μ-hydroxo Rh complexes. The LiyRh3O6 structure is remarkably stable upon electrochemical cycling illustrating that proper structural implementation of the oxidized oxygen species can open a pathway toward deliberate employment of the anion redox chemistry in high-capacity/high-voltage positive electrodes for metal-ion batteries. PMID:27367435

  9. Why did Nature choose manganese to make oxygen?

    PubMed Central

    Armstrong, Fraser A

    2007-01-01

    This paper discusses the suitability of manganese for its function in catalysing the formation of molecular oxygen from water. Manganese is an abundant element. In terms of its inherent properties, Mn has a particularly rich redox chemistry compared with other d-block elements, with several oxidizing states accessible. The most stable-state Mn2+ behaves like a Group 2 element—it is mobile, weakly complexing, easily taken up by cells and redox-inactive in simple aqueous media. Only in the presence of suitable ligands does Mn2+ become oxidized, so it provides an uncomplicated building unit for the oxygen-evolving centre (OEC). The intermediate oxidation states Mn(III) and Mn(IV) are strongly complexed by O2− and form robust mixed-valence poly-oxo clusters in which the Mn(IV)/Mn(III) ratio can be elevated, one electron at a time, accumulating oxidizing potential and capacity. The OEC is a Mn4CaOx cluster that undergoes sequential oxidations by P680+ at potentials above 1 V, ultimately to a super-oxidized level that includes one Mn(V) or a Mn(IV)-oxyl radical. The latter is powerfully oxidizing and provides the crucial ‘power stroke’ necessary to generate an O–O bond. This leaves a centre still rich in Mn(IV), ensuring a rapid follow-through to O2. PMID:17971329

  10. Chemistry Notes

    ERIC Educational Resources Information Center

    School Science Review, 1973

    1973-01-01

    Several ideas are proposed for chemistry teachers to try in their classrooms. Subjects included are polymerization of acrylate, polymerization of styrene, conductivity, pollution, preparation of chlorine, redox equations, chemiluminescence, and molecular sieves. (PS)

  11. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1981

    1981-01-01

    Describes 13 activities, experiments and demonstrations, including the preparation of iron (III) chloride, simple alpha-helix model, investigating camping gas, redox reactions of some organic compounds, a liquid crystal thermometer, and the oxidation number concept in organic chemistry. (JN)

  12. Linking Groundwater Age and Chemistry Data to Determine Redox Reaction Rates and Trends in Nitrate Concentrations in Agricultural Areas. (Invited)

    NASA Astrophysics Data System (ADS)

    Tesoriero, A. J.; Puckett, L.

    2009-12-01

    Use of industrially fixed nitrogen (N) fertilizer for agricultural purposes has increased dramatically, both in the United States (U.S.) and globally, since 1945. As a result, there has been growing concern about the consequences of increases in the amounts of anthropogenic N circulating in the atmosphere, hydrosphere, and biosphere. The U.S. Geological Survey’s National Water-Quality Assessment Program has collected groundwater samples along flow paths in more than 20 agricultural areas covering a range in hydrogeologic settings to evaluate the trends and transformations of agricultural chemicals. Historical trends in nitrogen fluxes to groundwater were evaluated by relating the recharge dates of groundwater samples, estimated using tracer (e.g., chlorofluorocarbon) concentrations, with concentrations of nitrate at the time of recharge, estimated by summing the molar concentrations of the parent compound (nitrate) and its transformation product (excess N2) in the age-dated sample. Results from this analysis indicate that median nitrate (NO3-) concentrations in recharge have increased markedly over the last 50 years: increasing from 4 mg/L (as N) in samples that recharged prior to 1983 to 7.5 mg/L (as N) in samples that recharged since 1983. Trends in nitrate concentrations in recharging groundwater were related to increases in the amount of fertilizer applied. Estimates of the portion of applied N reaching the water table ranged from 4 to 49% among the sites, with a median value of 14%. The fate of NO3- and many other groundwater contaminants is dependent on aquifer redox conditions. The reduction of oxygen is the most energetically favorable reaction that microorganisms use to oxidize organic material or other electron donors (e.g., pyrite). As a result, other reduction reactions (e.g., denitrification) affecting contaminant transport typically do not occur until most dissolved oxygen (DO) has been consumed. To improve assessments of contaminant transformations

  13. A high-resolution record of Holocene millennial-scale oscillations of surface water, foraminiferal paleoecology and sediment redox chemistry in the SE Brazilian margin

    NASA Astrophysics Data System (ADS)

    Dias, B. B.; Barbosa, C. F.; Albuquerque, A. L.; Piotrowski, A. M.

    2014-12-01

    . The 8.2kyr climatic event is reported here for the first time in South American coastal sediment records as high productivity conditions and a rapid change in porewater redox chemistry.

  14. Redox chemistry of the molecular interactions between tea catechins and human serum proteins under simulated hyperglycemic conditions.

    PubMed

    Özyurt, Hazal; Luna, Carolina; Estévez, Mario

    2016-03-01

    Carbonylation is an irreversible modification in oxidized proteins that has been directly related to a number of health disorders including Type 2 diabetes. Dietary antioxidants have been proposed to counteract the oxidative stress occurring under hyperglycemic conditions. An understanding of the nature and consequences of the molecular interactions between phytochemicals and human plasma proteins is of utmost scientific interest. Three tea catechins namely epicatechin (EC), epigallocatechin (EGC) and epigallocatechin-3-gallate (EGCG) were tested for (i) their affinity to bind to human serum albumin (HSA) and human hemoglobin (HH) and (ii) their ability to inhibit tryptophan (Trp) depletion and for the formation of specific protein carbonyls and pentosidine in the aforementioned proteins. Both proteins (20 mg mL(-1)) were allowed to react with postprandial plasmatic concentrations of the catechins (EC: 0.7 μM, EGC: 1.8 μM, and EGCG: 0.7 μM) under simulated hyperglycemic conditions (12 mM glucose/0.2 mM Fe(3+)/37 °C/10 days). The three catechins were able to inhibit Trp oxidation and protein carbonylation in both plasma proteins. Some anti-glycation properties were linked to their binding affinities. The molecular interactions reported in the present study may explain the alleged beneficial effects of tea catechins against the redox impairment linked to hyperglycemic conditions. PMID:26839039

  15. The influence of the biological pump on ocean chemistry: implications for long-term trends in marine redox chemistry, the global carbon cycle, and marine animal ecosystems.

    PubMed

    Meyer, K M; Ridgwell, A; Payne, J L

    2016-05-01

    The net export of organic matter from the surface ocean and its respiration at depth create vertical gradients in nutrient and oxygen availability that play a primary role in structuring marine ecosystems. Changes in the properties of this 'biological pump' have been hypothesized to account for important shifts in marine ecosystem structure, including the Cambrian explosion. However, the influence of variation in the behavior of the biological pump on ocean biogeochemistry remains poorly quantified, preventing any detailed exploration of how changes in the biological pump over geological time may have shaped long-term shifts in ocean chemistry, biogeochemical cycling, and ecosystem structure. Here, we use a 3-dimensional Earth system model of intermediate complexity to quantitatively explore the effects of the biological pump on marine chemistry. We find that when respiration of sinking organic matter is efficient, due to slower sinking or higher respiration rates, anoxia tends to be more prevalent and to occur in shallower waters. Consequently, the Phanerozoic trend toward less bottom-water anoxia in continental shelf settings can potentially be explained by a change in the spatial dynamics of nutrient cycling rather than by any change in the ocean phosphate inventory. The model results further suggest that the Phanerozoic decline in the prevalence ocean anoxia is, in part, a consequence of the evolution of larger phytoplankton, many of which produce mineralized tests. We hypothesize that the Phanerozoic trend toward greater animal abundance and metabolic demand was driven more by increased oxygen concentrations in shelf environments than by greater food (nutrient) availability. In fact, a lower-than-modern ocean phosphate inventory in our closed system model is unable to account for the Paleozoic prevalence of bottom-water anoxia. Overall, these model simulations suggest that the changing spatial distribution of photosynthesis and respiration in the oceans has

  16. Thermal modification of activated carbon surface chemistry improves its capacity as redox mediator for azo dye reduction.

    PubMed

    Pereira, L; Pereira, R; Pereira, M F R; van der Zee, F P; Cervantes, F J; Alves, M M

    2010-11-15

    The surface chemistry of a commercial AC (AC(0)) was selectively modified, without changing significantly its textural properties, by chemical oxidation with HNO(3) (AC(HNO3)) and O(2) (AC(O2)), and thermal treatments under H(2) (AC(H2)) or N(2) (AC(N2)) flow. The effect of modified AC on anaerobic chemical dye reduction was assayed with sulphide at different pH values 5, 7 and 9. Four dyes were tested: Acid Orange 7, Reactive Red 2, Mordant Yellow 10 and Direct Blue 71. Batch experiments with low amounts of AC (0.1 g L(-1)) demonstrated an increase of the first-order reduction rate constants, up to 9-fold, as compared with assays without AC. Optimum rates were obtained at pH 5 except for MY10, higher at pH 7. In general, rates increased with increasing the pH of point zero charge (pH(pzc)), following the trend AC(HNO3) < AC(O2) < AC(0) < AC(N2) < AC(H2). The highest reduction rate was obtained for MY10 with AC(H2) at pH 7, which corresponded to the double, as compared with non-modified AC. In a biological system using granular biomass, AC(H2) also duplicated and increase 4.5-fold the decolourisation rates of MY10 and RR2, respectively. In this last experiment, reaction rate was independent of AC concentration in the tested range 0.1-0.6 g L(-1). PMID:20800966

  17. Chemistry for Potters.

    ERIC Educational Resources Information Center

    Denio, Allen A.

    1980-01-01

    Relates pottery making to chemistry by providing chemical information about clay, its origin, composition, properties, and changes that occur during firing; also describes glaze compositions, examples of redox chemistry, salt glazing, crystalline glazes, and problems in toxicity. (CS)

  18. Chemistry Notes

    ERIC Educational Resources Information Center

    School Science Review, 1976

    1976-01-01

    Describes several chemistry projects, including solubility, formula for magnesium oxide, dissociation of dinitrogen tetroxide, use of 1-chloro-2, 4-dinitrobenzene, migration of ions, heats of neutralizations, use of pocket calculators, sonic cleaning, oxidation states of manganese, and cell potentials. Includes an extract from Chemical Age on…

  19. Manganese-oxide minerals in fractures of the Crater Flat Tuff in drill core USW G-4, Yucca Mountain, Nevada

    SciTech Connect

    Carlos, B.A.; Bish, D.L.; Chipera, S.J.

    1990-07-01

    The Crater Flat Tuff is almost entirely below the water table in drill hole USW G-4 at Yucca Mountain, Nevada. Manganese-oxide minerals from the Crater Flat Tuff in USW G-4 were studied using optical, scanning electron microscopic, electron microprobe, and x-ray powder diffraction methods to determine their distribution, mineralogy, and chemistry. Manganese-oxide minerals coat fractures in all three members of the Crater Flat Tuff (Prow Pass, Bullfrog, and Tram), but they are most abundant in fractures in the densely welded devitrified intervals of these members. The coatings are mostly of the cryptomelane/hollandite mineral group, but the chemistry of these coatings varies considerably. Some of the chemical variations, particularly the presence of calcium, sodium, and strontium, can be explained by admixture with todorokite, seen in some x-ray powder diffraction patterns. Other chemical variations, particularly between Ba and Pb, demonstrate that considerable substitution of Pb for Ba occurs in hollandite. Manganese-oxide coatings are common in the 10-m interval that produced 75% of the water pumped from USW G-4 in a flow survey in 1983. Their presence in water-producing zones suggests that manganese oxides may exert a significant chemical effect on groundwater beneath Yucca Mountain. In particular, the ability of the manganese oxides found at Yucca Mountain to be easily reduced suggests that they may affect the redox conditions of the groundwater and may oxidize dissolved or suspended species. Although the Mn oxides at Yucca Mountain have low exchange capacities, these minerals may retard the migration of some radionuclides, particularly the actinides, through scavenging and coprecipitation. 23 refs., 21 figs., 2 tabs.

  20. Differential coordination demands in Fe vs Mn water-soluble cationic metalloporphyrins translates into remarkably different aqueous redox chemistry and biology

    PubMed Central

    Tovmasyan, Artak; Weitner, Tin; Sheng, Huaxin; Lu, MiaoMiao; Rajic, Zrinka; Warner, David S.; Spasojevic, Ivan; Reboucas, Julio S.; Benov, Ludmil; Batinic-Haberle, Ines

    2013-01-01

    The different biological behavior of cationic Fe and Mn pyridylporphyrins in Escherichia coli and mouse studies prompted us to revisit and compare their chemistry. For that purpose the series of ortho and meta isomers of Fe(III) meso-tetrakis-N-alkylpyridylporphyrins, alkyl being methyl to n-octyl, were synthesized and characterized by elemental analysis, UV/vis spectroscopy, mass spectrometry, lipophilicity, protonation equilibria of axial waters, metal-centered reduction potential, E1/2 for MIIIP/MIIP redox couple (M = Fe, Mn, P=porphyrin), kcat for the catalysis of O2•− dismutation, stability towards peroxide-driven porphyrin oxidative degradation (produced in the catalysis of ascorbate oxidation by MP), ability to affect growth of SOD-deficient E. coli and toxicity to mice. Electron-deficiency of the metal site is modulated by the porphyrin ligand, which renders Fe(III) porphyrins ≥ 5 orders of magnitude more acidic than the analogous Mn(III) porphyrins, as revealed by the pKa1 of axially coordinated waters. The 5 log units difference in the acidity between the Mn and Fe sites in porphyrin translates into the predominance of tetracationic (OH)(H2O)FeP complexes relative to pentacationic (H2O)2MnP species at pH ~7.8. This is evidenced in large differences in the thermodynamic parameters - pKa of axial waters and E1/2 of MIII/MII redox couple. The presence of hydroxo ligand labilizes trans-axial water which results in higher reactivity of Fe- relative to Mn center. The differences in the catalysis of O2•− dismutation (log kcat) between Fe and Mn porphyrins is modest, 2.5-5-fold, due to predominantly outer-sphere, with partial inner-sphere character of two reaction steps. However, the rate constant for the inner-sphere H2O2-based porphyrin oxidative degradation is 18-fold larger for (OH)(H2O)FeP than for (H2O)2MnP. The in vivo consequences of the differences between the Fe- and Mn porphyrins were best demonstrated in SOD-deficient E. coli growth. Based

  1. 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

  2. Reversible Redox Chemistry and Catalytic C(sp(3))-H Amination Reactivity of a Paramagnetic Pd Complex Bearing a Redox-Active o-Aminophenol-Derived NNO Pincer Ligand.

    PubMed

    Broere, Daniël L J; van Leest, Nicolaas P; de Bruin, Bas; Siegler, Maxime A; van der Vlugt, Jarl Ivar

    2016-09-01

    The synthesis, spectroelectrochemical characterization (ultraviolet-visible and nuclear magnetic resonance), solid state structures, and computational metric parameters of three isostructural PdCl(NNO) complexes 1 [PdCl(NNO(ISQ))], 2 {[PdCl(NNO(AP))](-)}, and 5 {[PdCl(NNO(IBQ))](+)} (NNO = o-aminophenol-derived redox-active ligand with a pendant pyridine) with different NNO oxidation states are described. The reduced diamagnetic complex 2 readily reacts with halogenated solvents, including lattice solvent from crystalline pure material, as supported by spectroscopic data and density functional theory calculations. Thorough removal of chlorinated impurities allows for modest catalytic turnover in the conversion of 4-phenylbutyl azide into N-protected 2-phenylpyrrolidine, which is the first example of a palladium-catalyzed radical-type transformation facilitated by a redox-active ligand as well as the first C-H amination mediated by ligand-to-substrate single-electron transfer. PMID:27525360

  3. Heterogeneous redox conditions, arsenic mobility, and groundwater flow in a fractured-rock aquifer near a waste repository site in New Hampshire, USA

    USGS Publications Warehouse

    Harte, Philip T.; Ayotte, Joseph D.; Hoffman, Andrew; Revesz, Kinga M.; Belaval, Marcel; Lamb, Steven; Böhlke, J.K.

    2012-01-01

    Anthropogenic sources of carbon from landfill or waste leachate can promote reductive dissolution of in situ arsenic (As) and enhance the mobility of As in groundwater. Groundwater from residential-supply wells in a fractured crystalline-rock aquifer adjacent to a Superfund site in Raymond, New Hampshire, USA, showed evidence of locally enhanced As mobilization in relatively reducing (mixed oxic-anoxic to anoxic) conditions as determined by redox classification and other lines of evidence. Redox classification was determined from geochemical indicators based on threshold concentrations of dissolved oxygen (DO), nitrate (NO3-), iron (Fe2+), manganese (Mn2+), and sulfate (SO42-). Redox conditions were evaluated also based on methane (CH4), excess nitrogen gas (N2) from denitrification, the oxidation state of dissolved As speciation (As(III) and As(V)), and several stable isotope ratios. Samples from the residential-supply wells primarily exhibit mixed redox conditions, as most have long open boreholes (typically 50–100 m) that receive water from multiple discrete fractures with contrasting groundwater chemistry and redox conditions. The methods employed in this study can be used at other sites to gauge redox conditions and the potential for As mobilization in complex fractured crystalline-rock aquifers where multiple lines of evidence are likely needed to understand As occurrence, mobility, and transport.

  4. Heterogeneous redox conditions, arsenic mobility, and groundwater flow in a fractured-rock aquifer near a waste repository site in New Hampshire, USA

    NASA Astrophysics Data System (ADS)

    Harte, Philip T.; Ayotte, Joseph D.; Hoffman, Andrew; Révész, Kinga M.; Belaval, Marcel; Lamb, Steven; Böhlke, J. K.

    2012-09-01

    Anthropogenic sources of carbon from landfill or waste leachate can promote reductive dissolution of in situ arsenic (As) and enhance the mobility of As in groundwater. Groundwater from residential-supply wells in a fractured crystalline-rock aquifer adjacent to a Superfund site in Raymond, New Hampshire, USA, showed evidence of locally enhanced As mobilization in relatively reducing (mixed oxic-anoxic to anoxic) conditions as determined by redox classification and other lines of evidence. Redox classification was determined from geochemical indicators based on threshold concentrations of dissolved oxygen (DO), nitrate (NO{3/-}), iron (Fe2+), manganese (Mn2+), and sulfate (SO{4/2-}). Redox conditions were evaluated also based on methane (CH4), excess nitrogen gas (N2) from denitrification, the oxidation state of dissolved As speciation (As(III) and As(V)), and several stable isotope ratios. Samples from the residential-supply wells primarily exhibit mixed redox conditions, as most have long open boreholes (typically 50-100 m) that receive water from multiple discrete fractures with contrasting groundwater chemistry and redox conditions. The methods employed in this study can be used at other sites to gauge redox conditions and the potential for As mobilization in complex fractured crystalline-rock aquifers where multiple lines of evidence are likely needed to understand As occurrence, mobility, and transport.

  5. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1983

    1983-01-01

    Presents chemistry experiments, laboratory procedures, demonstrations, teaching suggestions, and classroom materials/activities. These include: game for teaching ionic formulas; method for balancing equations; description of useful redox series; computer programs (with listings) for water electrolysis simulation and for determining chemical…

  6. Structural and surface changes of copper modified manganese oxides

    NASA Astrophysics Data System (ADS)

    Gac, Wojciech; Słowik, Grzegorz; Zawadzki, Witold

    2016-05-01

    The structural and surface properties of manganese and copper-manganese oxides were investigated. The oxides were prepared by the redox-precipitation method. X-ray diffraction and electron microscopy studies evidenced transformation of cryptomelane-type nanoparticles with 1-D channel structure into the large MnO crystallites with regular rippled-like surface patterns under reduction conditions. The development of Cu/CuO nanorods from strongly dispersed species was evidenced. Coper-modified manganese oxides showed good catalytic performance in methanol steam reforming reaction for hydrogen production. Low selectivity to CO was observed in the wide range of temperatures.

  7. Biogeochemical effects of atmospheric oxygen concentration, phosphorus weathering, and sea-level stand on oceanic redox chemistry: Implications for greenhouse climates

    NASA Astrophysics Data System (ADS)

    Ozaki, Kazumi; Tajika, Eiichi

    2013-07-01

    Understanding the key factors influencing the global oceanic redox system is crucial to fully explaining the variations in oceanic chemical dynamics that have occurred throughout the Earth's history. In order to elucidate the mechanisms behind these variations on geological timescales, numerical sensitivity experiments were conducted with respect to the partial pressure of atmospheric molecular oxygen (pO2), the continental shelf area (Acs), and the riverine input rate of reactive phosphorus to the oceans (RP). The sensitivity experiment for atmospheric pO2 indicates that pervasive oceanic anoxia and euxinia appear when pO2<0.145 atm and <0.125 atm, respectively. These critical values of pO2 are higher than a previous estimate of ~50% PAL (present atmospheric level) due to redox-dependent phosphorus cycling. The sensitivity experiment regarding the shelf area demonstrates that changes in the shelf area during the Phanerozoic significantly affected oceanic oxygenation states by changing marine biogeochemical cycling; a large continental shelf acts as an efficient buffer against oceanic eutrophication and prevents the appearance of ocean anoxia/euxinia. We also found that an enhanced RP is an important mechanism for generation of widespread anoxia/euxinia via expansion of both the oxygen minimum zone and coastal deoxygenation, although the critical RP value depends significantly on pO2, Acs, and the redox-dependent burial efficiency of phosphorus at the sediment--water interface. Our systematic examination of the oceanic redox state under Cretaceous greenhouse climatic conditions also supports the above results.

  8. Green chemistry methods in sulfur dyeing: application of various reducing D-sugars and analysis of the importance of optimum redox potential.

    PubMed

    Blackburn, Richard S; Harvey, Anna

    2004-07-15

    The importance of sulfur dyeing of cellulosic fibers, particularly cotton, is realized economically throughout the dyeing industry. At the present time, dyeing with sulfur dyes requires the use of various auxiliaries, many of which have adverse effects on the environment. The most damaging of these is the reducing agent sodium sulfide, required to reduce the dye molecules to a water-soluble leuco form to enable adsorption and diffusion into the fiber. In this study, attempts have been made to replace the sodium sulfide used within the sulfur dyeing process with a variety of environmentally friendly reducing sugars. The redox potential of various hexose and pentose monosaccharides and reducing disaccharides was recorded and compared. Subsequently, cotton was dyed with the world's most important sulfur dye, C. I. Sulfur Black 1, using the reducing sugars under alkaline conditions, and compared to dyeings secured by employing commercial sulfide reducing agents. It was observed that reducing sugars gave comparable, and in many cases superior, color strength and wash fastness results, with respect to the commercial sulfide-based reducing agents, which still account for the vast majority of sulfur dyeing processes and that pose significant environmental concern. Employment of reducing sugars in sulfur dyeing could provide a sustainable, nontoxic, biodegradable, cost-effective alternative to sodium polysulfide and sodium hydrogen sulfide. Comparison of the redox potential of reducing sugars against the color strength of the dyeings secured demonstrated that there was an optimum redox potential of around -650 mV for maximum color strength achieved. The same redox potential also conferred the lowest color loss upon washing. These observations were attributed to reduction of the polymeric dye molecules to an optimum size for fiber affinity and diffusion into the fiber, but which would also confer maximum wash fastness upon oxidation. PMID:15298216

  9. Redox Redone.

    ERIC Educational Resources Information Center

    Petty, John T.

    1996-01-01

    Presents an extension of the change in oxidation number method that is used for balancing skeletal redox reactions in aqueous solutions. Retains most of the simplicity of the change in oxidation number method but provides the additional step-by-step process necessary for the beginner to balance an equation. (JRH)

  10. High manganese concentrations in rocks at Gale crater, Mars

    USGS Publications Warehouse

    Lanza, Nina L.; Fischer, Woodward W.; Wiens, Roger C.; Grotzinger, John; Ollila, Ann M.; Anderson, Ryan B.; Clark, Benton C.; Gellert, Ralf; Mangold, Nicolas; Maurice, Sylvestre; Le Mouélic, Stéphane; Nachon, Marion; Schmidt, Mariek E.; Berger, Jeffrey; Clegg, Samuel M.; Forni, Olivier; Hardgrove, Craig; Melikechi, Noureddine; Newsom, Horton E.; Sautter, Violaine

    2014-01-01

    The surface of Mars has long been considered a relatively oxidizing environment, an idea supported by the abundance of ferric iron phases observed there. However, compared to iron, manganese is sensitive only to high redox potential oxidants, and when concentrated in rocks, it provides a more specific redox indicator of aqueous environments. Observations from the ChemCam instrument on the Curiosity rover indicate abundances of manganese in and on some rock targets that are 1–2 orders of magnitude higher than previously observed on Mars, suggesting the presence of an as-yet unidentified manganese-rich phase. These results show that the Martian surface has at some point in time hosted much more highly oxidizing conditions than has previously been recognized.

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

    PubMed

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

    2016-04-20

    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. PMID:26762578

  12. Analysis of numerical simulations and influencing factors of seasonal manganese pollution in reservoirs.

    PubMed

    Peng, Hui; Zheng, Xilai; Chen, Lei; Wei, Yang

    2016-07-01

    Seasonal manganese pollution has become an increasingly pressing water quality issue for water supply reservoirs in recent years. Manganese is a redox-sensitive element and is released from sediment under anoxic conditions near the sediment-water interface during summer and autumn, when water temperature stratification occurs. The reservoir water temperature and water dynamic conditions directly influence the formation of manganese pollution. Numerical models are useful tools to quantitatively evaluate manganese pollution and its influencing factors. This paper presents a reservoir manganese pollution model by adding a manganese biogeochemical module to a water quality model-CE-QUAL-W2. The model is applied to the Wangjuan reservoir (Qingdao, China), which experiences manganese pollution during summer and autumn. Field data are used to verify the model, and the results show that the model can reproduce the main features of the thermal stratification and manganese distribution. The model is used to evaluate the manganese pollution process and its four influencing factors, including air temperature, water level, wind speed, and wind directions, through different simulation scenarios. The results show that all four factors can influence manganese pollution. High air temperature, high water level, and low wind speed aggravate manganese pollution, while low air temperature, low water level, and high wind speed reduce manganese pollution. Wind that travels in the opposite direction of the flow aggravates manganese pollution, while wind in the same direction as the flow reduces manganese pollution. This study provides useful information to improve our understanding of seasonal manganese pollution in reservoirs, which is important for reservoir manganese pollution warnings and control. PMID:27068892

  13. Supramolecular effects in redox chemistry. Local solvation in basket-handle iron porphyrins containing an increasing number of secondary amide groups

    SciTech Connect

    Lexa, D.; Maillard, P.; Momenteau, M.; Saveant, J.M.

    1987-03-26

    Local solvation can be created by including dipolar groups in a molecular superstructure attached to a reacting center. Changes in reactivity of the latter ensue in a manner which is reminiscent of the modulation of the reactivity of the prosthetic groups by surrounding protein chains in enzymatic systems. Quite large effects can thus be obtained as shown by an electrochemical study of two redox reactions, Fe(II) + e/sup -/ in equilibrium Fe(I)/sup -/, Fe(I)/sup -/ + e/sup -/ in equilibrium Fe(0)/sup 2 -/, in a series of basket-handle iron prophyrins including an increasing number of secondary amide groups in the chains. The local solvation which results from the electrostatic interaction between the CONH dipoles and the negatively charged porphyrin centers is shown to build up as more and more CONH groups are included and to depend upon the distance between these groups and the reacting center.

  14. Manganese laser using manganese chloride as lasant

    NASA Technical Reports Server (NTRS)

    Chen, C. J.

    1974-01-01

    A manganese vapor laser utilizing manganese chloride as a lasant has been observed and investigated. Lasing is attained by means of two consecutive electrical discharges. The maximum laser output is obtained at a vapor pressure of about 3 torr, a temperature of 680 C, and a time delay between electrical discharges of 150 microsec. The maximum energy density is 1.3 microjoule per cu cm.

  15. Blue-to-red colorimetric sensing strategy for Hg²⁺ and Ag⁺ via redox-regulated surface chemistry of gold nanoparticles.

    PubMed

    Lou, Tingting; Chen, Zhaopeng; Wang, Yunqing; Chen, Lingxin

    2011-05-01

    Here we report a "blue-to-red" colorimetric method for determination of mercury ions (Hg²⁺) and silver ions (Ag⁺) based on stabilization of gold nanoparticles (AuNPs) by redox formed metal coating in the presence of ascorbic acid (AA). AuNPs were first stabilized by Tween 20 in phosphate buffer solution with high ionic strength. In a target ion-free system, the addition of N-acetyl-L-cysteine resulted in the aggregation of Tween 20 stabilized AuNPs for mercapto ligand self-assembled on the surface of AuNPs, which induced the AuNPs to be unstable. This would lead to a color change from red to blue. By contrast, in an aqueous solution with Hg²⁺ or Ag⁺, the ions could be reduced with the aid of AA to form Hg-Au alloy or Ag coating on the surface of AuNPs. This metal coating blocked mercapto ligand assembly and AuNPs kept monodispersed after addition of N-acetyl-L-cysteine, exhibiting a red color. Therefore, taking advantage of this mechanism, a "blue-to-red" colorimetric sensing strategy could be established for Hg²⁺ and Ag⁺ detection. Compare with the commonly reported aggregation-based method ('red-to-blue'), the color change from blue to red seems more eye-sensitive, especial in low concentration of target. Moreover, selective analysis of Hg²⁺ and Ag⁺ was simply achieved by the redox nature of target ions and the application of classic ion masking agents, avoiding the design and selection of ion chelating moieties and complicated gold surface modification procedure. This method could selectively detect Hg²⁺ and Ag⁺ as low as 5 nM and 10 nM in pure water with a linear range of 5 × 10⁻⁷ to 1 × 10⁻⁵ M for Hg²⁺ and 1 × 10⁻⁶ to 8 × 10⁻⁶ M for Ag⁺, respectively. It was successfully applied to determination of Hg²⁺ and Ag⁺ in tap water and drinking water. PMID:21469714

  16. The Products of Manganese (II) Oxidation

    SciTech Connect

    Perkins, A.

    2004-09-03

    Manganese, the second most abundant transition metal in the earth's crust, exists in a number of oxidation states, among which the II, III, and IV oxidation states are of greatest environmental importance. Produced through microbial activity, manganese oxides help to mediate redox reactions with organic and inorganic compounds and help to sequester a variety of metals. The mechanism by which Manganese (II) is oxidized to Manganese (IV) is a biologically catalyzed process. There are at least three different pathways by which Mn(II) can be bacterially oxidized to Mn(IV); the first in which states that Mn(II) can be oxidized to mixed Mn(III, IV), and Mn(IV) oxides and oxyhydroxides. The second of these pathways is that Mn(II) can be directly oxidized to Mn(IV) and the last of these pathways is that Mn(II) follows an enzymatic bond with a Mn(III) intermediate in which Mn(II) oxidizes to Mn(III) and then to Mn(IV). The pathways of focus for this research are the latter two pathways.

  17. Manganese carbonates as possible biogenic relics in Archean settings

    NASA Astrophysics Data System (ADS)

    Rincón-Tomás, Blanca; Khonsari, Bahar; Mühlen, Dominik; Wickbold, Christian; Schäfer, Nadine; Hause-Reitner, Dorothea; Hoppert, Michael; Reitner, Joachim

    2016-07-01

    Carbonate minerals such as dolomite, kutnahorite or rhodochrosite are frequently, but not exclusively generated by microbial processes. In recent anoxic sediments, Mn(II)carbonate minerals (e.g. rhodochrosite, kutnahorite) derive mainly from the reduction of Mn(IV) compounds by anaerobic respiration. The formation of huge manganese-rich (carbonate) deposits requires effective manganese redox cycling in an oxygenated atmosphere. However, putative anaerobic pathways such as microbial nitrate-dependent manganese oxidation, anoxygenic photosynthesis and oxidation in ultraviolet light may facilitate manganese cycling even in an early Archean environment, without the availability of oxygen. In addition, manganese carbonates precipitate by microbially induced processes without change of the oxidation state, e.g. by pH shift. Hence, there are several ways how these minerals could have been formed biogenically and deposited in Precambrian sediments. We will summarize microbially induced manganese carbonate deposition in the presence and absence of atmospheric oxygen and we will make some considerations about the biogenic deposition of manganese carbonates in early Archean settings.

  18. Manganese uptake of imprinted polymers

    DOE Data Explorer

    Susanna Ventura

    2015-09-30

    Batch tests of manganese imprinted polymers of variable composition to assess their ability to extract lithium and manganese from synthetic brines at T=45C . Data on manganese uptake for two consecutive cycles are included.

  19. Green polymer chemistry: investigating the mechanism of radical ring-opening redox polymerization (R3P) of 3,6-dioxa-1,8-octanedithiol (DODT).

    PubMed

    Rosenthal-Kim, Emily Q; Puskas, Judit E

    2015-01-01

    The mechanism of the new Radical Ring-opening Redox Polymerization (R3P) of 3,6-dioxa-1,8-octanedithiol (DODT) by triethylamine (TEA) and dilute H2O2 was investigated. Scouting studies showed that the formation of high molecular weight polymers required a 1:2 molar ratio of DODT to TEA and of DODT to H2O2. Further investigation into the chemical composition of the organic and aqueous phases by 1H-NMR spectroscopy and mass spectrometry demonstrated that DODT is ionized by two TEA molecules (one for each thiol group) and thus transferred into the aqueous phase. The organic phase was found to have cyclic disulfide dimers, trimers and tetramers. Dissolving DODT and TEA in water before the addition of H2O2 yielded a polymer with Mn = 55,000 g/mol, in comparison with Mn = 92,000 g/mol when aqueous H2O2 was added to a DODT/TEA mixture. After polymer removal, MALDI-ToF MS analysis of the residual reaction mixtures showed only cyclic oligomers remaining. Below the LCST for TEA in water, 18.7 °C, the system yielded a stable emulsion, and only cyclic oligomers were found. Below DODT/TEA and H2O2 1:2 molar ratio mostly linear oligomers were formed, with <20% cyclic oligomers. The findings support the proposed mechanism of R3P. PMID:25871370

  20. The Redox Chemistry and Chemical Biology of H2S, Hydropersulfides and Derived Species: Implications to Their Possible Biological Activity and Utility

    PubMed Central

    Ono, Katsuhiko; Akaike, Takaake; Sawa, Tomohiro; Kumagai, Yoshito; Wink, David A.; Tantillo, Dean J.; Hobbs, Adrian J.; Nagy, Peter; Xian, Ming; Lin, Joseph; Fukuto, Jon M.

    2014-01-01

    Hydrogen sulfide (H2S) is an endogenously generated and putative signaling/effector molecule. In spite of its numerous reported functions, the chemistry by which it elicits its functions is not understood. Moreover, recent studies allude to the existence of other sulfur species besides H2S that may play critical physiological roles. Herein, the basic chemical biology of H2S as well as other related or derived species is discussed and reviewed. A particular focus of this review are the per- and poly-sulfides which are likely in equilibrium with free H2S and which may be important biological effectors themselves. PMID:25229186

  1. Implications of phosphorus redox geochemistry

    NASA Astrophysics Data System (ADS)

    Pasek, Matthew

    2015-04-01

    Phosphorus is the limiting nutrient in many environments. Until recently, redox changes to phosphorus speciation have been confined to the realm of chemical laboratories as phosphorus was considered to be synonymous with phosphate in the natural environment. The few known phosphorus species with a reduced redox state, such as phosphine gas, were considered novelties. Recent work has revealed a surprising role for low redox state organophosphorus compounds -- the phosphonates -- in biogeochemistry. Additionally, phosphite and hypophosphite (the lower oxyanions of phosphorus) have been identified from natural sources, and microbial genomics suggests these compounds may be ubiquitous in nature. Recent work from our laboratory suggests that reduced phosphorus compounds such as phosphite and hypophosphite may be ubiquitous (Pasek et al. 2014). If so, then these species maybe important in the global phosphorus biogeochemical cycle, and could influence global phosphorus sustainability. Additionally, these compounds could have been relevant on the early earth environment, priming the earth with reactive phosphorus for prebiotic chemistry. Reference: Pasek, M. A., Sampson, J. M., & Atlas, Z. (2014). Redox chemistry in the phosphorus biogeochemical cycle. Proceedings of the National Academy of Sciences, 111(43), 15468-15473.

  2. Redox sorting of carbon nanotubes.

    PubMed

    Gui, Hui; Streit, Jason K; Fagan, Jeffrey A; Hight Walker, Angela R; Zhou, Chongwu; Zheng, Ming

    2015-03-11

    This work expands the redox chemistry of single-wall carbon nanotubes (SWCNTs) by investigating its role in a number of SWCNT sorting processes. Using a polyethylene glycol (PEG)/dextran (DX) aqueous two-phase system, we show that electron-transfer between redox molecules and SWCNTs triggers reorganization of the surfactant coating layer, leading to strong modulation of nanotube partition in the two phases. While the DX phase is thermodynamically more favored by an oxidized SWCNT mixture, the mildly reducing PEG phase is able to recover SWCNTs from oxidation and extract them successively from the DX phase. Remarkably, the extraction order follows SWCNT bandgap: semiconducting nanotubes of larger bandgap first, followed by semiconducting nanotubes of smaller bandgap, then nonarmchair metallic tubes of small but nonvanishing bandgap, and finally armchair metallic nanotubes of zero bandgap. Furthermore, we show that redox-induced surfactant reorganization is a common phenomenon, affecting nanotube buoyancy in a density gradient field, affinity to polymer matrices, and solubility in organic solvents. These findings establish redox modulation of surfactant coating structures as a general mechanism for tuning a diverse range of SWCNT sorting processes and demonstrate for the first time that armchair and nonarmchair metallic SWCNTs can be separated by their differential response to redox. PMID:25719939

  3. Redox Pioneer: Professor Helmut Sies

    PubMed Central

    Radi, Rafael

    2014-01-01

    Abstract Professor Helmut Sies Dr. Helmut Sies (MD, 1967) is recognized as a Redox Pioneer, because he authored five articles on oxidative stress, lycopene, and glutathione, each of which has been cited more than 1000 times, and coauthored an article on hydroperoxide metabolism in mammalian systems cited more than 5000 times (Google Scholar). He obtained preclinical education at the University of Tübingen and the University of Munich, clinical training at Munich (MD, 1967) and Paris, and completed Habilitation at Munich (Physiological Chemistry and Physical Biochemistry, 1972). In early research, he first identified hydrogen peroxide (H2O2) as a normal aerobic metabolite and devised a method to quantify H2O2 concentration and turnover in cells. He quantified central redox systems for energy metabolism (NAD, NADP systems) and antioxidant GSH in subcellular compartments. He first described ebselen, a selenoorganic compound, as a glutathione peroxidase mimic. He contributed a fundamental discovery to the physiology of GSH, selenium nutrition, singlet oxygen biochemistry, and health benefits of dietary lycopene and cocoa flavonoids. He has published more than 600 articles, 134 of which are cited at least 100 times, and edited 28 books. His h-index is 115. During the last quarter of the 20th century and well into the 21st, he has served as a scout, trailblazer, and pioneer in redox biology. His formulation of the concept of oxidative stress stimulated and guided research in oxidants and antioxidants; his pioneering research on carotenoids and flavonoids informed nutritional strategies against cancer, cardiovascular disease, and aging; and his quantitative approach to redox biochemistry provides a foundation for modern redox systems biology. Helmut Sies is a true Redox Pioneer. Antioxid. Redox Signal. 21, 2459–2468. The joy of exploring the unknown and finding something novel and noteworthy: what a privilege! —Prof. Helmut Sies PMID:25178739

  4. Redox chemistry of Mycobacterium tuberculosis alkylhydroperoxide reductase E (AhpE): Structural and mechanistic insight into a mycoredoxin-1 independent reductive pathway of AhpE via mycothiol.

    PubMed

    Kumar, Arvind; Balakrishna, Asha Manikkoth; Nartey, Wilson; Manimekalai, Malathy Sony Subramanian; Grüber, Gerhard

    2016-08-01

    Mycobacterium tuberculosis (Mtb) has the ability to persist within the human host for a long time in a dormant stage and re-merges when the immune system is compromised. The pathogenic bacterium employs an elaborate antioxidant defence machinery composed of the mycothiol- and thioredoxin system in addition to a superoxide dismutase, a catalase, and peroxiredoxins (Prxs). Among the family of Peroxiredoxins, Mtb expresses a 1-cysteine peroxiredoxin, known as alkylhydroperoxide reductase E (MtAhpE), and defined as a potential tuberculosis drug target. The reduced MtAhpE (MtAhpE-SH) scavenges peroxides to become converted to MtAhpE-SOH. To provide continuous availability of MtAhpE-SH, MtAhpE-SOH has to become reduced. Here, we used NMR spectroscopy to delineate the reduced (MtAhpE-SH), sulphenic (MtAhpE-SOH) and sulphinic (MtAhpE-SO2H) states of MtAhpE through cysteinyl-labelling, and provide for the first time evidence of a mycothiol-dependent mechanism of MtAhpE reduction. This is confirmed by crystallographic studies, wherein MtAhpE was crystallized in the presence of mycothiol and the structure was solved at 2.43Å resolution. Combined with NMR-studies, the crystallographic structures reveal conformational changes of important residues during the catalytic cycle of MtAhpE. In addition, alterations of the overall protein in solution due to redox modulation are observed by small angle X-ray scattering (SAXS) studies. Finally, by employing SAXS and dynamic light scattering, insight is provided into the most probable physiological oligomeric state of MtAhpE necessary for activity, being also discussed in the context of concerted substrate binding inside the dimeric MtAhpE. PMID:27417938

  5. Comparison of control of Listeria by nitric oxide redox chemistry from murine macrophages and NO donors: insights into listeriocidal activity of oxidative and nitrosative stress.

    PubMed

    Ogawa, R; Pacelli, R; Espey, M G; Miranda, K M; Friedman, N; Kim, S M; Cox, G; Mitchell, J B; Wink, D A; Russo, A

    2001-02-01

    The physiological function of nitric oxide (NO) in the defense against pathogens is multifaceted. The exact chemistry by which NO combats intracellular pathogens such as Listeria monocytogenes is yet unresolved. We examined the effects of NO exposure, either delivered by NO donors or generated in situ within ANA-1 murine macrophages, on L. monocytogenes growth. Production of NO by the two NONOate compounds PAPA/NO (NH2(C3H6)(N[N(O)NO]C3H7) and DEA/NO (Na(C2H5)2N[N(O)NO]) resulted in L. monocytogenes cytostasis with minimal cytotoxicity. Reactive oxygen species generated from xanthine oxidase/hypoxanthine were neither bactericidal nor cytostatic and did not alter the action of NO. L. monocytogenes growth was also suppressed upon internalization into ANA-1 murine macrophages primed with interferon-gamma (INF-gamma) + tumor necrosis factor-alpha (TNF-alpha or INF-gamma + lipid polysaccharide (LPS). Growth suppression correlated with nitrite formation and nitrosation of 2,3-diaminonaphthalene elicited by stimulated murine macrophages. This nitrosative chemistry was not dependent upon nor mediated by interaction with reactive oxygen species (ROS), but resulted solely from NO and intermediates related to nitrosative stress. The role of nitrosation in controlling L. monocytogenes was further examined by monitoring the effects of exposure to NO on an important virulence factor, Listeriolysin O, which was inhibited under nitrosative conditions. These results suggest that nitrosative stress mediated by macrophages is an important component of the immunological arsenal in controlling L. monocytogenes infections. PMID:11165873

  6. BIOLOGICAL EFFECTS OF MANGANESE

    EPA Science Inventory

    The biological effects of manganese were studied in a town on the coast of Dalmatia in which a ferromanganese plant has been operating since before World War II. The study focused on the question of whether the exposure to manganese can cause a higher incidence of respiratory dis...

  7. Impact of nonadiabatic charge transfer on the rate of redox chemistry of carbon oxides on rutile TiO2 (110) surface

    SciTech Connect

    Yoon, Yeohoon; Wang, Yanggang; Rousseau, Roger J.; Glezakou, Vassiliki Alexandra

    2015-03-06

    We present the results of a density functional theory (DFT) within the LDA+U approximation on large models of partially reduced TiO2 (110) rutile surface to investigate the nature of charge transfer and the role of non-adiabatic effects on three prototypical redox reactions: (i) O2 adsorption (ii) CO oxidation and (iii) CO2 reduction. Charge-constrained DFT (cDFT) is used to estimate kinetic parameters for a Marcus theory rate law that accounts for adiabatic coupling effects on reaction rates. We find that for O2 adsorption, the coupling between adiabatic states is strong, leading to fast charge transfer rates. The lowest energy structures at high coverage consist of two chemisorbed O2-, one adsorbed at a VO site and the other adsorbed at an adjacent Ti5C site. For CO oxidation, however, all reactions are kinetically hindered on the ground state due to the weak adiabatic coupling at the state crossing, such that one has to overcome two kinetically unfavorable charge transfer events to drive the process (non-adiabatically) on the thermal ground state. The process can be driven by photochemical means but would result in an adsorbed radical [OCOO-] intermediate species. Similarly, CO2 reduction also proceeds via a non-adiabatic charge transfer to form an adsorbed CO2- species followed by a second non-adiabatic charge transfer to produce CO. Our analysis provides important computational guidelines for modeling these types of processes. We thank Z. Dohnalek, M. Hendersen, G. Kimmel, H. Metieu, and N. Petrik for invaluable discussions. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle. Computational resources were provided at W. R. Wiley Environmental Molecular Science Laboratory (EMSL), a national scientific user facility sponsored by the

  8. Quantifying manganese and nitrogen cycle coupling in manganese-rich, organic carbon-starved marine sediments: Examples from the Clarion-Clipperton fracture zone

    NASA Astrophysics Data System (ADS)

    Mogollón, José M.; Mewes, Konstantin; Kasten, Sabine

    2016-07-01

    Extensive deep-sea sedimentary areas are characterized by low organic carbon contents and thus harbor suboxic sedimentary environments where secondary (autotrophic) redox cycling becomes important for microbial metabolic processes. Simulation results for three stations in the Eastern Equatorial Pacific with low organic carbon content (<0.5 dry wt %) and low sedimentation rates (10-1-100 mm ky-1) show that ammonium generated during organic matter degradation may act as a reducing agent for manganese oxides below the oxic zone. Likewise, at these sedimentary depths, dissolved reduced manganese may act as a reducing agent for oxidized nitrogen species. These manganese-coupled transformations provide a suboxic conversion pathway of ammonium and nitrate to dinitrogen. These manganese-nitrogen interactions further explain the presence and production of dissolved reduced manganese (up to tens of μM concentration) in sediments with high nitrate (>20 μM) concentrations.

  9. Microbiology, Redox and Contaminat Fate in the Grindsted Landfill Leachate Plume - A Summary of 25 Years of work

    NASA Astrophysics Data System (ADS)

    Christensen, T. H.

    2001-05-01

    The contamination by leachate of the upper aquifer at the Grindsted Landfill (Denmark) stretches about 300 m downgradient from the landfill. The plume has been described with respect to water chemistry, sediment chemistry, pollutant distribution, microbial counts, PLFA and redox rates determined by unamended bioassays. This presentation summaries the findings and discusses unanswered questions. The landfill was active from 1930 to the mid 1970 and has no engineered leachate collection system. Leachate from municipal as well as from industrial waste has entered the aquifer for more than thirty years. The redox conditions change from strongly anaerobic (methanogenic, sulfate reducing, iron reducing) close to the landfill over manganese reduction and denitrification to aerobic conditions in the outskirts of the plume The redox conditions were determined from groundwater sample composition, hydrogen concentrations and sediment chemistry. The plume showed strong attenuation of aromatic compounds within the first 100 m downgradient of the landfill. Degradation experiments (batch, in-situ testers, long term field injection experiments) could not fully document degradation of all the compounds. MPN-measurements of methanogens, sulfate-reducers, iron-reducers, manganese-reducers and denitrifiers showed abundance of all groups with a slight trend with the redox conditions. PLFA measurements did not provide much insight into the microbial populations of the plume, but confirmed some previous observations. Bioassays gave estimates of the rates of the various redox processes, but showed for some samples more simultaneous redox processes. More than 25 years of work has been put into the Grindsted Landfill leachate plume. References Bjerg, P.L., Rugge, K., Cortsen, J., Nielsen, P.H. & Christensen, T.H. (1999): Degradation of aromatic and chlorinated aliphatic hydrocarbons in the anaerobic part of the Grindsted Landfill leachate plume: In situ microcosm and laboratory batch

  10. Stability Behavior and Thermodynamic States of Iron and Manganese in Sandy Soil Aquifer, Manukan Island, Malaysia

    SciTech Connect

    Lin, Chin Yik; Abdullah, Mohd. Harun; Musta, Baba; Praveena, Sarva Mangala; Aris, Ahmad Zaharin

    2011-03-15

    A total of 20 soil samples were collected from 10 boreholes constructed in the low lying area, which included ancillary samples taken from the high elevation area. Redox processes were investigated in the soil as well as groundwater in the shallow groundwater aquifer of Manukan Island, Sabah, Malaysia. Groundwater samples (n = 10) from each boreholes were also collected in the low lying area to understand the concentrations and behaviors of Fe and Mn in the dissolved state. This study strives to obtain a general understanding of the stability behaviors on Fe and Mn at the upper unsaturated and the lower-saturated soil horizons in the low lying area of Manukan Island as these elements usually play a major role in the redox chemistry of the shallow groundwater. Thermodynamic calculations using PHREEQC showed that the groundwater samples in the study area are oversaturated with respect to goethite, hematite, Fe(OH){sub 3} and undersaturated with respect to manganite and pyrochroite. Low concentrations of Fe and Mn in the groundwater might be probably due to the lack of minerals of iron and manganese oxides, which exist in the sandy aquifer. In fact, high organic matters that present in the unsaturated horizon are believed to be responsible for the high Mn content in the soil. It was observed that the soil samples collected from high elevation area (BK) comprises considerable amount of Fe in both unsaturated (6675.87 mg/kg) and saturated horizons (31440.49 mg/kg) compared to the low Fe content in the low lying area. Based on the stability diagram, the groundwater composition lies within the stability field for Mn{sup 2+} and Fe{sup 2+} under suboxic condition and very close to the FeS/Fe{sup 2+} stability boundary. This study also shows that both pH and Eh values comprise a strong negative value thus suggesting that the redox potential is inversely dependent on the changes of pH.

  11. Globally sustainable manganese metal production and use.

    PubMed

    Hagelstein, Karen

    2009-09-01

    The "cradle to grave" concept of managing chemicals and wastes has been a descriptive analogy of proper environmental stewardship since the 1970s. The concept incorporates environmentally sustainable product choices-such as metal alloys utilized steel products which civilization is dependent upon. Manganese consumption is related to the increasing production of raw steel and upgrading ferroalloys. Nonferrous applications of manganese include production of dry-cell batteries, plant fertilizer components, animal feed and colorant for bricks. The manganese ore (high grade 35% manganese) production world wide is about 6 million ton/year and electrolytic manganese metal demand is about 0.7 million ton/year. The total manganese demand is consumed globally by industries including construction (23%), machinery (14%), and transportation (11%). Manganese is recycled within scrap of iron and steel, a small amount is recycled within aluminum used beverage cans. Recycling rate is 37% and efficiency is estimated as 53% [Roskill Metals and Minerals Reports, January 13, 2005. Manganese Report: rapid rise in output caused by Chinese crude steel production. Available from: http://www.roskill.com/reports/manganese.]. Environmentally sustainable management choices include identifying raw material chemistry, utilizing clean production processes, minimizing waste generation, recycling materials, controlling occupational exposures, and collecting representative environmental data. This paper will discuss two electrolytically produced manganese metals, the metal production differences, and environmental impacts cited to date. The two electrolytic manganese processes differ due to the addition of sulfur dioxide or selenium dioxide. Adverse environmental impacts due to use of selenium dioxide methodology include increased water consumption and order of magnitude greater solid waste generation per ton of metal processed. The use of high grade manganese ores in the electrolytic process also

  12. Beginning Chemistry Can Be Relevant

    ERIC Educational Resources Information Center

    Corwin, James F.

    1971-01-01

    Reviews ways of applying laboratory work in general and analytical chemistry to supermarket products. Describes ways water and air pollution analysis can illustrate acid-base reactions, redox reactions, precipitimetry, and colorimetry. (PR)

  13. Characteristic hydrogen concentrations for various redox processes in batch study.

    PubMed

    Lu, X X; Tao, S; Bosma, T; Gerritse, J

    2001-01-01

    The dissolved hydrogen concentrations under various redox processes were investigated based on batch experiments. Chloroethenes including tetrachloroethene (PCE), cis-dichloroethene (cis-DCE) and vinylchloride (VC) were respectively used as culture substrates. For each chloroethene, a series of bottles were prepared with the additions of different electron acceptors or donors such as nitrate, manganese oxide, ferrous iron, sulfate, carbondioxide and volatile fatty acids. Hydrogen concentrations as well as redox species were measured over time to ensure the achievements of characteristic hydrogen levels in various enrichment batches. The results showed that redox processes with nitrate, manganese oxide and ferric iron as the electron acceptors exhibited hydrogen threshold values close to PCE/TCE dechlorination, whereas cis-DCE and VC dechlorinations exhibited hydrogen threshold values in the range of sulfate reduction and methanogenesis, respectively. Characteristic hydrogen concentrations for various redox processes were as follows (nM): denitrification, 0.1-0.4; manganese reduction, 0.1-2.0; iron reduction, 0.1-0.4; sulfate reduction, 1.5-4.5; methanogenesis, 2.5-24; PCE/TCE dechlorination, 0.6-0.9; eis-DCE dechlorination, 0.1-2.5; and VC dechlorination, 2-24. PMID:11688686

  14. High energy density redox flow device

    DOEpatents

    Chiang, Yet-Ming; Carter, W. Craig; Ho, Bryan Y; Duduta, Mihai; Limthongkul, Pimpa

    2014-05-13

    Redox flow devices are described in which at least one of the positive electrode or negative electrode-active materials is a semi-solid or is a condensed ion-storing electroactive material, and in which at least one of the electrode-active materials is transported to and from an assembly at which the electrochemical reaction occurs, producing electrical energy. The electronic conductivity of the semi-solid is increased by the addition of conductive particles to suspensions and/or via the surface modification of the solid in semi-solids (e.g., by coating the solid with a more electron conductive coating material to increase the power of the device). High energy density and high power redox flow devices are disclosed. The redox flow devices described herein can also include one or more inventive design features. In addition, inventive chemistries for use in redox flow devices are also described.

  15. [Function and disease in manganese].

    PubMed

    Kimura, Mieko

    2016-07-01

    Manganese is a metal that has been known named a Greek word "Magnesia" meaning magnesia nigra from Roman Empire. Manganese provide the wide range of metablic function and the multiple abnomalities from its deficiency or toxicity. In 1931, the essentiality of manganese was demonstrated with the authoritative poor growth and declined reproduction in its deficiency. Manganese deficiency has been recognized in a number of species and its signs are impaired growth, impaired reproduction, ataxia, skeletal abnormalities and disorders in lipid and carbohydrate metabolism. Manganese toxicity is also acknowledged as health hazard for animals and humans. Here manganese nutrition, metabolism and metabolic function are summarized. PMID:27455810

  16. Chemistry of soil solutions

    SciTech Connect

    Elprince, A.M.

    1986-01-01

    Designed for advanced undergraduate and graduate students and researchers, this book serves as an introduction to the field of soil chemistry and associated fields such as aquatic chemistry, geochemistry, environmental chemistry, oceanography, and public health. The volume includes discussions on the structure of adsorbed water, adsorption of inorganics, solubility, redox, solute transport, chemical modeling, and sampling and monitoring the soil solution. Important papers on these topics together with editor's comments place each of the carefully chosen papers in the proper context. Because the chemistry of soil solutions requires the knowledge of many aspects of science, introductory information is provided for each topic to cover its history of development, present knowledge, and future prospects.

  17. The Redox Code

    PubMed Central

    Jones, Dean P.

    2015-01-01

    Abstract Significance: The redox code is a set of principles that defines the positioning of the nicotinamide adenine dinucleotide (NAD, NADP) and thiol/disulfide and other redox systems as well as the thiol redox proteome in space and time in biological systems. The code is richly elaborated in an oxygen-dependent life, where activation/deactivation cycles involving O2 and H2O2 contribute to spatiotemporal organization for differentiation, development, and adaptation to the environment. Disruption of this organizational structure during oxidative stress represents a fundamental mechanism in system failure and disease. Recent Advances: Methodology in assessing components of the redox code under physiological conditions has progressed, permitting insight into spatiotemporal organization and allowing for identification of redox partners in redox proteomics and redox metabolomics. Critical Issues: Complexity of redox networks and redox regulation is being revealed step by step, yet much still needs to be learned. Future Directions: Detailed knowledge of the molecular patterns generated from the principles of the redox code under defined physiological or pathological conditions in cells and organs will contribute to understanding the redox component in health and disease. Ultimately, there will be a scientific basis to a modern redox medicine. Antioxid. Redox Signal. 23, 734–746. PMID:25891126

  18. Manganese oxide cathodes for rechargeable batteries

    NASA Astrophysics Data System (ADS)

    Im, Dongmin

    Manganese oxides are considered as promising cathodes for rechargeable batteries due to their low cost and low toxicity as well as the abundant natural resources. In this dissertation, manganese oxides have been investigated as cathodes for both rechargeable lithium and alkaline batteries. Nanostructured lithium manganese oxides designed for rechargeable lithium cells have been synthesized by reducing lithium permanganate with methanol or hydrogen in various solvents followed by firing at moderate temperatures. The samples have been characterized by wet-chemical analyses, thermal methods, spectroscopic methods, and electron microscopy. It has been found that chemical residues in the oxides such as carboxylates and hydroxyl groups, which could be controlled by varying the reaction medium, reducing agents, and additives, make a significant influence on the electrochemical properties. The Li/Mn ratio in the material has also been found to be a critical factor in determining the rechargeability of the cathodes. The optimized samples exhibit a high capacity of close to 300 mAh/g with good cyclability and charge efficiency. The high capacity with a lower discharge voltage may make these nanostructured oxides particularly attractive for lithium polymer batteries. The research on the manganese oxide cathodes for alkaline batteries is focused on an analysis of the reaction products generated during the charge/discharge processes or by some designed chemical reactions mimicking the electrochemical processes. The factors influencing the formation of Mn3O4 in the two-electron redox process of delta-MnO2 have been studied with linear sweep voltammetry combined with X-ray diffraction. The presence of bismuth, the discharge rate, and the microstructure of the electrodes are found to affect the formation of Mn3O4, which is known to be electrochemically inactive. A faster voltage sweep and a more intimate mixing of the manganese oxide and carbon in the cathode are found to suppress

  19. Mn-Ti-Zr (Manganese-Titanium-Zirconium)

    NASA Astrophysics Data System (ADS)

    Materials Science International Team MSIT

    This document is part of Subvolume C3 'Non-Ferrous Metal Systems. Part 3: Selected Soldering and Brazing Systems' of Volume 11 'Ternary Alloy Systems - Phase Diagrams, Crystallographic and Thermodynamic Data critically evaluated by MSIT®' of Landolt-Börnstein - Group IV 'Physical Chemistry'. It provides data of the ternary system Manganese-Titanium-Zirconium.

  20. Cu-Mn-Si (Copper-Manganese-Silicon)

    NASA Astrophysics Data System (ADS)

    Materials Science International Team MSIT

    This document is part of Subvolume C2 'Non-Ferrous Metal Systems. Part 2: Selected Copper Systems' of Volume 11 'Ternary Alloy Systems - Phase Diagrams, Crystallographic and Thermodynamic Data critically evaluated by MSIT®' of Landolt-Börnstein - Group IV 'Physical Chemistry'. It provides data of the ternary system Copper-Manganese-Silicon.

  1. INHALATION TOXICOLOGY OF AIRBORNE PARTICULATE MANGANESE IN RHESUS MONKEYS

    EPA Science Inventory

    Four male and four female rhesus monkeys were exposed to manganese oxide (Mn3O4) aerosol at 100 micrograms/cubic meter in an exposure chamber for periods up to 66 weeks. Three male and three female monkeys were maintained as unexposed controls. Observation and clinical chemistry ...

  2. Manganese As a Metal Accumulator

    EPA Science Inventory

    Manganese deposits in water distribution systems accumulate metals, radionuclides and oxyanions by a combination of surface complexation, adsorption and solid substitution, as well as a combination of oxidation followed by manganese reduction and sorption of the oxidized constitu...

  3. Manganese biomining: A review.

    PubMed

    Das, A P; Sukla, L B; Pradhan, N; Nayak, S

    2011-08-01

    Biomining comprises of processing and extraction of metal from their ores and concentrates using microbial techniques. Currently this is used by the mining industry to extract copper, uranium and gold from low grade ores but not for low grade manganese ore in industrial scale. The study of microbial genomes, metabolites and regulatory pathways provide novel insights to the metabolism of bioleaching microorganisms and their synergistic action during bioleaching operations. This will promote understanding of the universal regulatory responses that the biomining microbial community uses to adapt to their changing environment leading to high metal recovery. Possibility exists of findings ways to imitate the entire process during industrial manganese biomining endeavor. This paper reviews the current status of manganese biomining research operations around the world, identifies factors that drive the selection of biomining as a processing technology, describes challenges in exploiting these innovations, and concludes with a discussion of Mn biomining's future. PMID:21632238

  4. Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

    PubMed

    Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

    2015-10-01

    Vanadium redox reactions have been considered as a key factor affecting the energy efficiency of the all-vanadium redox flow batteries (VRFBs). This redox reaction determines the reaction kinetics of whole cells. However, poor kinetic reversibility and catalytic activity towards the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples on the commonly used carbon substrate limit broader applications of VRFBs. Consequently, modified carbon substrates have been extensively investigated to improve vanadium redox reactions. In this Focus Review, recent progress on metal- and carbon-based nanomaterials as an electrocatalyst for VRFBs is discussed in detail, without the intention to provide a comprehensive review on the whole components of the system. Instead, the focus is mainly placed on the redox chemistry of vanadium ions at a surface of various metals, different dimensional carbons, nitrogen-doped carbon nanostructures, and metal-carbon composites. PMID:25899910

  5. Electrochemical evaluation of manganese reducers - Recovery of Mn from Zn-Mn and Zn-C battery waste

    NASA Astrophysics Data System (ADS)

    Sobianowska-Turek, Agnieszka; Szczepaniak, Włodzimierz; Zabłocka-Malicka, Monika

    2014-12-01

    Extraction of manganese from ores or battery waste involves the use of reductive reagents for transformation of MnO2 to Mn2+ ions. There are many reducers, both organic and inorganic, described in the literature. A series of 18 reducers has been discussed in the paper and they were classified according to standard redox potential (pE = -log ae- where pE is used to express formal electron activity and ae- is formal electron activity). The experiments of manganese extraction from paramagnetic fraction of Zn-C and Zn-Mn battery waste in the laboratory scale have been described for 3 reducers of different origin. The best result was achieved with oxalic acid (75%, with the lowest redox potential) and urea (with typical redox potential) appeared inactive. Extraction supported by hydrogen peroxide resulted in moderate yield (50%). It shows that formal thermodynamic scale is only preliminary information useful for selection of possible reducers for manganese extraction resources.

  6. Water, water everywhere, and its remarkable chemistry.

    PubMed

    Barber, Jim

    2004-04-12

    Photosystem II (PSII), the multisubunit pigment-protein complex localised in the thylakoid membranes of oxygenic photosynthetic organisms, uses light energy to drive a series of remarkable reactions leading to the oxidation of water. The products of this oxidation are dioxygen, which is released to the atmosphere, and reducing equivalents destined to reduce carbon dioxide to organic molecules. The water oxidation occurs at catalytic sites composed of four manganese atoms (Mn(4)-cluster) and powered by the redox potential of an oxidised chlorophyll a molecule (P680(*+)). Gerald T (Jerry) Babcock and colleagues showed that electron/proton transfer processes from substrate water to P680(*+) involved a tyrosine residue (Y(Z)) and proposed an attractive reaction mechanism for the direct involvement of Y(Z) in the chemistry of water oxidation. The 'hydrogen-atom abstract/metalloradical' mechanism he formulated is an expression of his genius and a highlight of his many other outstanding contributions to photosynthesis research. A structural basis for Jerry's model is now being revealed by X-ray crystallography. PMID:15100024

  7. Manganese, Metallogenium, and Martian Microfossils

    NASA Technical Reports Server (NTRS)

    Stein, L. Y.; Nealson, K. H.

    1999-01-01

    Manganese could easily be considered an abundant element in the Martian regolith, assuming that the composition of martian meteorites reflects the composition of the planet. Mineralogical analyses of 5 SNC meteorites have revealed an average manganese oxide concentration of 0.48%, relative to the 0.1% concentration of manganese found in the Earth's crust. On the Earth, the accumulation of manganese oxides in oceans, soils, rocks, sedimentary ores, fresh water systems, and hydrothermal vents can be largely attributed to microbial activity. Manganese is also a required trace nutrient for most life forms and participates in many critical enzymatic reactions such as photosynthesis. The wide-spread process of bacterial manganese cycling on Earth suggests that manganese is an important element to both geology and biology. Furthermore, there is evidence that bacteria can be fossilized within manganese ores, implying that manganese beds may be good repositories for preserved biomarkers. A particular genus of bacteria, known historically as Metallogenium, can form star-shaped manganese oxide minerals (called metallogenium) through the action of manganese oxide precipitation along its surface. Fossilized structures that resemble metallogenium have been found in Precambrian sedimentary formations and in Cretaceous-Paleogene cherts. The Cretaceous-Paleogene formations are highly enriched in manganese and have concentrations of trace elements (Fe, Zn, Cu, and Co) similar to modern-day manganese oxide deposits in marine environments. The appearance of metallogenium-like fossils associated with manganese deposits suggests that bacteria may be preserved within the minerals that they form. Additional information is contained in the original extended abstract.

  8. Redox Potential of Peroxidases

    NASA Astrophysics Data System (ADS)

    Ayala, Marcela

    Redox potential of peroxidases greatly influences the range of oxidizable substrates: in principle, peroxidases may only catalyze the oxidation of substrates with lower redox potential. There is substantial information on the factors that modulate the redox potential of heme proteins. Both theoretical and experimental evidence highlight the most significant contributions arising from the interaction of heme iron with the axial ligands, as well as the electrostatic interactions surrounding the heme group. However, for different proteins, the factors contribute to different extents. Understanding the electrochemistry of heme peroxidases is fundamental in order to design enhanced biocatalysts. In this chapter, current knowledge of the forces influencing redox potential of heme peroxidases is reviewed.

  9. New lab scale approaches for quantification of redox conditions

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  10. Manganese deposits in northeastern European Russia and the Urals: Isotope geochemistry, genesis, and evolution of ore formation

    NASA Astrophysics Data System (ADS)

    Kuleshov, V. N.; Brusnitsyn, A. I.; Starikova, E. V.

    2014-09-01

    Based on new data on the lithology, mineralogy, chemistry, and isotopic composition of manganese carbonate ores and rocks at the deposits and occurrences in the Novaya Zemlya Archipelago, the Pai-Khoi, and the Urals, as well as using data from the literature, the main Phanerozoic basins of manganese deposition have been established in the geological history of Laurasia, Pangea, and Siberian paleocontinents. The formation conditions of manganese ore gradually changed from hydrothermal-sedimentary in the Middle Paleozoic to sedimentary-diagenetic in Mesozoic and Cenozoic. The ore was also formed under catagenetic conditions. Carbon of oxidized organic matter plays a substantial role in the formation of manganese carbonates.

  11. An overview of mechanisms of redox signaling

    PubMed Central

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

    2014-01-01

    A principal characteristic of redox signaling is that it involves an oxidation-reduction reaction or covalent adduct formation between the sensor signaling protein and second messenger. Non-redox signaling may involve alteration of the second messenger as in hydrolysis of GTP by G proteins, modification of the signaling protein as in farnesylation, or simple non-covalent binding of an agonist or second messenger. The chemistry of redox signaling is reviewed here. Specifically we have described how among the so-called reactive oxygen species, only hydroperoxides clearly fit the role of a second messenger. Consideration of reaction kinetics and cellular location strongly suggests that for hydroperoxides, particular protein cysteines are the targets and that the requirements for redox signaling is that these cysteines are in microenvironments in which the cysteine is ionized to the thiolate, and a proton can be donated to form a leaving group. The chemistry described here is the same as occurs in the cysteine and selenocysteine peroxidases that are generally considered the primary defense against oxidative stress. But, these same enzymes can also act as the sensors and transducer for signaling. Conditions that would allow specific signaling by peroxynitrite and superoxide are also defined. Signaling by other electrophiles, which includes lipid peroxidation products, quinones formed from polyphenols and other metabolites also involves reaction with specific protein thiolates. Again, kinetics and location are the primary determinants that provide specificity required for physiological signaling although enzymatic catalysis is not likely involved. PMID:24512843

  12. Anion Redox Chemistry in the Cobalt Free 3d Transition Metal Oxide Intercalation Electrode Li[Li0.2Ni0.2Mn0.6]O2.

    PubMed

    Luo, Kun; Roberts, Matthew R; Guerrini, Niccoló; Tapia-Ruiz, Nuria; Hao, Rong; Massel, Felix; Pickup, David M; Ramos, Silvia; Liu, Yi-Sheng; Guo, Jinghua; Chadwick, Alan V; Duda, Laurent C; Bruce, Peter G

    2016-09-01

    Conventional intercalation cathodes for lithium batteries store charge in redox reactions associated with the transition metal cations, e.g., Mn(3+/4+) in LiMn2O4, and this limits the energy storage of Li-ion batteries. Compounds such as Li[Li0.2Ni0.2Mn0.6]O2 exhibit a capacity to store charge in excess of the transition metal redox reactions. The additional capacity occurs at and above 4.5 V versus Li(+)/Li. The capacity at 4.5 V is dominated by oxidation of the O(2-) anions accounting for ∼0.43 e(-)/formula unit, with an additional 0.06 e(-)/formula unit being associated with O loss from the lattice. In contrast, the capacity above 4.5 V is mainly O loss, ∼0.08 e(-)/formula. The O redox reaction involves the formation of localized hole states on O during charge, which are located on O coordinated by (Mn(4+)/Li(+)). The results have been obtained by combining operando electrochemical mass spec on (18)O labeled Li[Li0.2Ni0.2Mn0.6]O2 with XANES, soft X-ray spectroscopy, resonant inelastic X-ray spectroscopy, and Raman spectroscopy. Finally the general features of O redox are described with discussion about the role of comparatively ionic (less covalent) 3d metal-oxygen interaction on anion redox in lithium rich cathode materials. PMID:27498756

  13. An Excel Workbook for Identifying Redox Processes in Ground Water

    USGS Publications Warehouse

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

    2009-01-01

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

  14. Anticancer Activity of Metal Complexes: Involvement of Redox Processes

    PubMed Central

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

    2012-01-01

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

  15. Redox controls UPR to control redox.

    PubMed

    Eletto, Davide; Chevet, Eric; Argon, Yair; Appenzeller-Herzog, Christian

    2014-09-01

    In many physiological contexts, intracellular reduction-oxidation (redox) conditions and the unfolded protein response (UPR) are important for the control of cell life and death decisions. UPR is triggered by the disruption of endoplasmic reticulum (ER) homeostasis, also known as ER stress. Depending on the duration and severity of the disruption, this leads to cell adaptation or demise. In this Commentary, we review reductive and oxidative activation mechanisms of the UPR, which include direct interactions of dedicated protein disulfide isomerases with ER stress sensors, protein S-nitrosylation and ER Ca(2+) efflux that is promoted by reactive oxygen species. Furthermore, we discuss how cellular oxidant and antioxidant capacities are extensively remodeled downstream of UPR signals. Aside from activation of NADPH oxidases, mitogen-activated protein kinases and transcriptional antioxidant responses, such remodeling prominently relies on ER-mitochondrial crosstalk. Specific redox cues therefore operate both as triggers and effectors of ER stress, thus enabling amplification loops. We propose that redox-based amplification loops critically contribute to the switch from adaptive to fatal UPR. PMID:25107370

  16. A Multistep Equilibria-Redox-Complexation Demonstration to Illustrate Le Chatelier's Principle.

    ERIC Educational Resources Information Center

    Berger, Tomas G.; Mellon, Edward K.

    1996-01-01

    Describes a process that can be used to illustrate a number of chemical principles including Le Chatelier's principle, redox chemistry, equilibria versus steady state situations, and solubility of species. (JRH)

  17. Redox Species of Redox Flow Batteries: A Review.

    PubMed

    Pan, Feng; Wang, Qing

    2015-01-01

    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. PMID:26593894

  18. Mineral of the month: manganese

    USGS Publications Warehouse

    Corathers, Lisa

    2005-01-01

    Manganese is one of the most important ferrous metals and one of the few for which the United States is totally dependent on imports. It is a black, brittle element predominantly used in metallurgical applications as an alloying addition, particularly in steel and cast iron production, which together provide the largest market for manganese (about 83 percent). It is also used as an alloy with nonferrous metals such as aluminum and copper. Nonmetallurgical applications of manganese include battery cathodes, soft ferrite magnets used in electronics, micronutrients found in fertilizers and animal feed, water treatment chemicals, and a colorant for bricks and ceramics.

  19. Mobility of metals over the redox boundary in Peru Basin sediments

    NASA Astrophysics Data System (ADS)

    Stummeyer, Jens; Marchig, Vesna

    Downcore variations and phase distribution of metals in the Quaternary sediments from six areas of the Peru Basin were investigated. The sediments are characterised by a 5-20 cm thick, oxic layer at the water/sediment interface formed under the influence of dissolved oxygen in the bottom water. In deeper sediment sections, suboxic conditions are found due to the degradation of organic matter. Variations in the downcore abundance of metals (e.g., Fe, Mn, Co, Ni, Cu, Zn, V, Mo, Cr) were determined by bulk chemical methods. A significant accumulation of manganese is observed at the depth of the manganese redox boundary, caused by diagenetic remobilisation under suboxic conditions and reprecipitation under oxic conditions. To investigate their phase distributions, partitioning of elements in selected samples over the sediment column was carried out in sequential leaching experiments. A comparison between the surface layer and deeper sediment layers shows a distinct change in the element distribution between operationally defined host phases (carbonates, oxy-hydroxides, detrital components). Above the redox boundary at the sediment surface, transition metals are enriched in the reducible Mn-oxide fraction. When the horizontal position of the Mn-redox boundary moves upward, influenced by naturally occurring enhancement of surface-water productivity, these elements are mobilised and available to the manganese nodule accretion process if the redox boundary reaches the level of growth of the nodules. In contrast to the naturally induced mobilisation of metals, a technical impact (e.g., mining of manganese nodules) would be a rapid event occurring under completely different redox conditions. Metals would be released into the bottom water, an oxic environment, where scavenging of dissolved metals and resedimentation takes place in relatively short periods of time. Presumably, a long-distance transport of contaminants will not happen.

  20. Manganese oxidation model for rivers

    USGS Publications Warehouse

    Hess, Glen W.; Kim, Byung R.; Roberts, Philip J.W.

    1989-01-01

    The presence of manganese in natural waters (>0.05 mg/L) degrades water-supply quality. A model was devised to predict the variation of manganese concentrations in river water released from an impoundment with the distance downstream. The model is one-dimensional and was calibrated using dissolved oxygen, biochemical oxygen demand, pH, manganese, and hydraulic data collected in the Duck River, Tennessee. The results indicated that the model can predict manganese levels under various conditions. The model was then applied to the Chattahoochee River, Georgia. Discrepancies between observed and predicted may be due to inadequate pH data, precipitation of sediment particles, unsteady flow conditions in the Chattahoochee River, inaccurate rate expressions for the low pH conditions, or their combinations.

  1. Manganese and the Evolution of Photosynthesis

    NASA Astrophysics Data System (ADS)

    Fischer, Woodward W.; Hemp, James; Johnson, Jena E.

    2015-09-01

    Oxygenic photosynthesis is the most important bioenergetic event in the history of our planet—it evolved once within the Cyanobacteria, and remained largely unchanged as it was transferred to algae and plants via endosymbiosis. Manganese plays a fundamental role in this history because it lends the critical redox behavior of the water-oxidizing complex of photosystem II. Constraints from the photoassembly of the Mn-bearing water-oxidizing complex fuel the hypothesis that Mn(II) once played a key role as an electron donor for anoxygenic photosynthesis prior to the evolution of oxygenic photosynthesis. Here we review the growing body of geological and geochemical evidence from the Archean and Paleoproterozoic sedimentary records that supports this idea and demonstrates that the oxidative branch of the Mn cycle switched on prior to the rise of oxygen. This Mn-oxidizing phototrophy hypothesis also receives support from the biological record of extant phototrophs, and can be made more explicit by leveraging constraints from structural biology and biochemistry of photosystem II in Cyanobacteria. These observations highlight that water-splitting in photosystem II evolved independently from a homodimeric ancestral type II reaction center capable of high potential photosynthesis and Mn(II) oxidation, which is required by the presence of homologous redox-active tyrosines in the modern heterodimer. The ancestral homodimer reaction center also evolved a C-terminal extension that sterically precluded standard phototrophic electron donors like cytochrome c, cupredoxins, or high-potential iron-sulfur proteins, and could only complete direct oxidation of small molecules like Mn2+, and ultimately water.

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

    ERIC Educational Resources Information Center

    Vella, Alfred J.

    1990-01-01

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

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

    PubMed

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

    2015-06-01

    Redox cycles of manganese oxides (Mn2 O3 /Mn3 O4 ) are a promising alternative for thermochemical heat storage systems coupled to concentrated solar power plants as manganese oxides are abundant and inexpensive materials. Although their cyclability for such a purpose has been proved, sintering processes, related to the high-temperature conditions at which charge-discharge cycles are performed, generally cause a cycle-to-cycle decrease in the oxidation rate of Mn3 O4 . To guarantee proper operation, both reactions should present stable reaction rates. In this study, it has been demonstrated that the incorporation of Fe, which is also an abundant material, into the manganese oxides improves the redox performance of this system by increasing the heat storage density, narrowing the redox thermal hysteresis, and, above all, stabilizing and enhancing the oxidation rate over long-term operation, which counteracts the negative effects caused by sintering, although its presence is not avoided. PMID:25925817

  4. The Expanding Landscape of the Thiol Redox Proteome.

    PubMed

    Yang, Jing; Carroll, Kate S; Liebler, Daniel C

    2016-01-01

    Cysteine occupies a unique place in protein chemistry. The nucleophilic thiol group allows cysteine to undergo a broad range of redox modifications beyond classical thiol-disulfide redox equilibria, including S-sulfenylation (-SOH), S-sulfinylation (-SO(2)H), S-sulfonylation (-SO(3)H), S-nitrosylation (-SNO), S-sulfhydration (-SSH), S-glutathionylation (-SSG), and others. Emerging evidence suggests that these post-translational modifications (PTM) are important in cellular redox regulation and protection against oxidative damage. Identification of protein targets of thiol redox modifications is crucial to understanding their roles in biology and disease. However, analysis of these highly labile and dynamic modifications poses challenges. Recent advances in the design of probes for thiol redox forms, together with innovative mass spectrometry based chemoproteomics methods make it possible to perform global, site-specific, and quantitative analyses of thiol redox modifications in complex proteomes. Here, we review chemical proteomic strategies used to expand the landscape of thiol redox modifications. PMID:26518762

  5. General Chemoselective and Redox-Responsive Ligation and Release Strategy

    PubMed Central

    2015-01-01

    We report a switchable redox click and cleave reaction strategy for conjugating and releasing a range of molecules on demand. This chemoselective redox-responsive ligation (CRRL) and release strategy is based on a redox switchable oxime linkage that is controlled by mild chemical or electrochemical redox signals and can be performed at physiological conditions without the use of a catalyst. Both conjugation and release reactions are kinetically well behaved and quantitative. The CRRL strategy is synthetically modular and easily monitored and characterized by routine analytical techniques. We demonstrate how the CRRL strategy can be used for the dynamic generation of cyclic peptides and the ligation of two different peptides that are stable but can be selectively cleaved upon changes in the redox environment. We also demonstrate a new redox based delivery of cargoes to live cells strategy via the CRRL methodology by synthesizing a FRET redox-responsive probe that is selectively activated within a cellular environment. We believe the ease of the CRRL strategy should find wide use in a range of applications in biology, tissue engineering, nanoscience, synthetic chemistry, and material science and will expand the suite of current conjugation and release strategies. PMID:24559434

  6. General chemoselective and redox-responsive ligation and release strategy.

    PubMed

    Park, Sungjin; Westcott, Nathan P; Luo, Wei; Dutta, Debjit; Yousaf, Muhammad N

    2014-03-19

    We report a switchable redox click and cleave reaction strategy for conjugating and releasing a range of molecules on demand. This chemoselective redox-responsive ligation (CRRL) and release strategy is based on a redox switchable oxime linkage that is controlled by mild chemical or electrochemical redox signals and can be performed at physiological conditions without the use of a catalyst. Both conjugation and release reactions are kinetically well behaved and quantitative. The CRRL strategy is synthetically modular and easily monitored and characterized by routine analytical techniques. We demonstrate how the CRRL strategy can be used for the dynamic generation of cyclic peptides and the ligation of two different peptides that are stable but can be selectively cleaved upon changes in the redox environment. We also demonstrate a new redox based delivery of cargoes to live cells strategy via the CRRL methodology by synthesizing a FRET redox-responsive probe that is selectively activated within a cellular environment. We believe the ease of the CRRL strategy should find wide use in a range of applications in biology, tissue engineering, nanoscience, synthetic chemistry, and material science and will expand the suite of current conjugation and release strategies. PMID:24559434

  7. Redox control of teratogenesis.

    PubMed

    Hansen, Jason M; Harris, Craig

    2013-01-01

    A number of human teratogens elicit their deleterious effects through mechanisms involving the generation of reactive oxygen species (ROS) and oxidative stress. However, classic definitions of oxidative stress do not fully coincide with basic fundamental principles of teratology. Newer definitions of oxidative stress focus on the targeted redox modification of cysteine/thiol functional groups found in the regulatory domains of critical signaling pathway proteins, suggesting that the targeted disruption of signaling through specific redox couples may account for the specificity of teratogen-induced malformations which previously could not be rationalized. Here, we review examples of teratogens that induce ROS and oxidative injury, describe oxidative stress-related teratogenic mechanisms, and provide rationale for developmental periods of sensitivity and species susceptibility. Understanding how chemicals disrupt redox status, induce oxidative stress leading to dysmorphogenesis becomes important to identify potential teratogens and develop therapeutic interventions for attenuation of harmful chemical effects in utero following exposure. PMID:23089153

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

    NASA Astrophysics Data System (ADS)

    Qi, Zhaoxiang; Koenig, Gary M.

    2016-08-01

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

  9. 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. PMID:27451962

  10. Regulating proton-coupled electron transfer for efficient water splitting by manganese oxides at neutral pH

    PubMed Central

    Yamaguchi, Akira; Inuzuka, Riko; Takashima, Toshihiro; Hayashi, Toru; Hashimoto, Kazuhito; Nakamura, Ryuhei

    2014-01-01

    Manganese oxides have been extensively investigated as model systems for the oxygen-evolving complex of photosystem II. However, most bioinspired catalysts are inefficient at neutral pH and functional similarity to the oxygen-evolving complex has been rarely achieved with manganese. Here we report the regulation of proton-coupled electron transfer involved in water oxidation by manganese oxides. Pyridine and its derivatives, which have pKa values intermediate to the water ligand bound to manganese(II) and manganese(III), are used as proton-coupled electron transfer induction reagents. The induction of concerted proton-coupled electron transfer is demonstrated by the detection of deuterium kinetic isotope effects and compliance of the reactions with the libido rule. Although proton-coupled electron transfer regulation is essential for the facial redox change of manganese in photosystem II, most manganese oxides impair these regulatory mechanisms. Thus, the present findings may provide a new design rationale for functional analogues of the oxygen-evolving complex for efficient water splitting at neutral pH. PMID:24977746

  11. Successes and Techniques Associated with Teaching the Chemistry of Radioactive Wastes.

    ERIC Educational Resources Information Center

    Williams, Donald H.

    1995-01-01

    Describes a chemistry course that is built around the topic of radioactive waste and encompasses a large number of chemistry concepts including redox, equilibrium, kinetics, nuclear energy, and the periodic chart. (JRH)

  12. Redox Regulation of Mitochondrial Function

    PubMed Central

    Handy, Diane E.

    2012-01-01

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

  13. Bog Manganese Ore: A Resource for High Manganese Steel Making

    NASA Astrophysics Data System (ADS)

    Pani, Swatirupa; Singh, Saroj K.; Mohapatra, Birendra K.

    2016-05-01

    Bog manganese ore, associated with the banded iron formation of the Iron Ore Group (IOG), occurs in large volume in northern Odisha, India. The ore is powdery, fine-grained and soft in nature with varying specific gravity (2.8-3.9 g/cm3) and high thermo-gravimetric loss, It consists of manganese (δ-MnO2, manganite, cryptomelane/romanechite with minor pyrolusite) and iron (goethite/limonite and hematite) minerals with sub-ordinate kaolinite and quartz. It shows oolitic/pisolitic to globular morphology nucleating small detritus of quartz, pyrolusite/romanechite and hematite. The ore contains around 23% Mn and 28% Fe with around 7% of combined alumina and silica. Such Mn ore has not found any use because of its sub-grade nature and high iron content, and is hence considered as waste. The ore does not respond to any physical beneficiation techniques because of the combined state of the manganese and iron phases. Attempts have been made to recover manganese and iron value from such ore through smelting. A sample along with an appropriate charge mix when processed through a plasma reactor, produced high-manganese steel alloy having 25% Mn within a very short time (<10 min). Minor Mn content from the slag was recovered through acid leaching. The aim of this study has been to recover a value-added product from the waste.

  14. Extraction of manganese from electrolytic manganese residue by bioleaching.

    PubMed

    Xin, Baoping; Chen, Bing; Duan, Ning; Zhou, Changbo

    2011-01-01

    Extraction of manganese from electrolytic manganese residues using bioleaching was investigated in this paper. The maximum extraction efficiency of Mn was 93% by sulfur-oxidizing bacteria at 4.0 g/l sulfur after bioleaching of 9days, while the maximum extraction efficiency of Mn was 81% by pyrite-leaching bacteria at 4.0 g/l pyrite. The series bioleaching first by sulfur-oxidizing bacteria and followed by pyrite-leaching bacteria evidently promoted the extraction of manganese, witnessing the maximum extraction efficiency of 98.1%. In the case of sulfur-oxidizing bacteria, the strong dissolution of bio-generated sulfuric acid resulted in extraction of soluble Mn2+, while both the Fe2+ catalyzed reduction of Mn4+ and weak acidic dissolution of Mn2+ accounted for the extraction of manganese with pyrite-leaching bacteria. The chemical simulation of bioleaching process further confirmed that the acid dissolution of Mn2+ and Fe2+ catalyzed reduction of Mn4+ were the bioleaching mechanisms involved for Mn extraction from electrolytic manganese residues. PMID:21050747

  15. Bog Manganese Ore: A Resource for High Manganese Steel Making

    NASA Astrophysics Data System (ADS)

    Pani, Swatirupa; Singh, Saroj K.; Mohapatra, Birendra K.

    2016-06-01

    Bog manganese ore, associated with the banded iron formation of the Iron Ore Group (IOG), occurs in large volume in northern Odisha, India. The ore is powdery, fine-grained and soft in nature with varying specific gravity (2.8-3.9 g/cm3) and high thermo-gravimetric loss, It consists of manganese (δ-MnO2, manganite, cryptomelane/romanechite with minor pyrolusite) and iron (goethite/limonite and hematite) minerals with sub-ordinate kaolinite and quartz. It shows oolitic/pisolitic to globular morphology nucleating small detritus of quartz, pyrolusite/romanechite and hematite. The ore contains around 23% Mn and 28% Fe with around 7% of combined alumina and silica. Such Mn ore has not found any use because of its sub-grade nature and high iron content, and is hence considered as waste. The ore does not respond to any physical beneficiation techniques because of the combined state of the manganese and iron phases. Attempts have been made to recover manganese and iron value from such ore through smelting. A sample along with an appropriate charge mix when processed through a plasma reactor, produced high-manganese steel alloy having 25% Mn within a very short time (<10 min). Minor Mn content from the slag was recovered through acid leaching. The aim of this study has been to recover a value-added product from the waste.

  16. Arsenic behavior in river sediments under redox gradient: a review.

    PubMed

    Gorny, Josselin; Billon, Gabriel; Lesven, Ludovic; Dumoulin, David; Madé, Benoît; Noiriel, Catherine

    2015-02-01

    The fate of arsenic - a redox sensitive metalloid - in surface sediments is closely linked to early diagenetic processes. The review presents the main redox mechanisms and final products of As that have been evidenced over the last years. Oxidation of organic matter and concomitant reduction of oxidants by bacterial activity result in redox transformations of As species. The evolution of the sediment reactivity will also induce secondary abiotic reactions like complexation/de-complexation, sorption, precipitation/dissolution and biotic reactions that could, for instance, lead to the detoxification of some As species. Overall, abiotic redox reactions that govern the speciation of As mostly involve manganese (hydr)-oxides and reduced sulfur species produced by the sulfate-reducing bacteria. Bacterial activity is also responsible for the inter-conversion between As(V) and As(III), as well as for the production of methylated arsenic species. In surficial sediments, sorption processes also control the fate of inorganic As(V), through the formation of inner sphere complexes with iron (hydr)-oxides, that are biologically reduced in buried sediment. Arsenic species can also be bound to organic matter, either directly to functional groups or indirectly through metal complexes. Finally, even if the role of reduced sulfur species in the cycling of arsenic in sediments has been evidenced, some of the transformations remain hypothetical and deserve further investigation. PMID:25461044

  17. Redox Flow Batteries, a Review

    SciTech Connect

    Knoxville, U. Tennessee; U. Texas Austin; U, McGill; Weber, Adam Z.; Mench, Matthew M.; Meyers, Jeremy P.; Ross, Philip N.; Gostick, Jeffrey T.; Liu, Qinghua

    2011-07-15

    Redox flow batteries are enjoying a renaissance due to their ability to store large amounts of electrical energy relatively cheaply and efficiently. In this review, we examine the components of redox flow batteries with a focus on understanding the underlying physical processes. The various transport and kinetic phenomena are discussed along with the most common redox couples.

  18. 21 CFR 582.5446 - Manganese chloride.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5446 Manganese chloride. (a) Product. Manganese chloride. (b) Conditions of use....

  19. 21 CFR 582.5461 - Manganese sulfate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5461 Manganese sulfate. (a) Product. Manganese sulfate. (b) Conditions of use....

  20. 21 CFR 582.5452 - Manganese gluconate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5452 Manganese gluconate. (a) Product. Manganese gluconate. (b) Conditions of use....

  1. 21 CFR 582.5461 - Manganese sulfate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5461 Manganese sulfate. (a) Product. Manganese sulfate. (b) Conditions of use....

  2. 21 CFR 582.5458 - Manganese hypophosphite.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5458 Manganese hypophosphite. (a) Product. Manganese hypophosphite. (b) Conditions of...

  3. 21 CFR 582.5449 - Manganese citrate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5449 Manganese citrate. (a) Product. Manganese citrate. (b) Conditions of use....

  4. 21 CFR 582.5449 - Manganese citrate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5449 Manganese citrate. (a) Product. Manganese citrate. (b) Conditions of use....

  5. 21 CFR 582.5458 - Manganese hypophosphite.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5458 Manganese hypophosphite. (a) Product. Manganese hypophosphite. (b) Conditions of...

  6. 21 CFR 582.5452 - Manganese gluconate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5452 Manganese gluconate. (a) Product. Manganese gluconate. (b) Conditions of use....

  7. Oxidative stress: a concept in redox biology and medicine

    PubMed Central

    Sies, Helmut

    2015-01-01

    “Oxidative stress” as a concept in redox biology and medicine has been formulated in 1985; at the beginning of 2015, approx. 138,000 PubMed entries show for this term. This concept has its merits and its pitfalls. Among the merits is the notion, elicited by the combined two terms of (i) aerobic metabolism as a steady-state redox balance and (ii) the associated potential strains in the balance as denoted by the term, stress, evoking biological stress responses. Current research on molecular redox switches governing oxidative stress responses is in full bloom. The fundamental importance of linking redox shifts to phosphorylation/dephosphorylation signaling is being more fully appreciated, thanks to major advances in methodology. Among the pitfalls is the fact that the underlying molecular details are to be worked out in each particular case, which is bvious for a global concept, but which is sometimes overlooked. This can lead to indiscriminate use of the term, oxidative stress, without clear relation to redox chemistry. The major role in antioxidant defense is fulfilled by antioxidant enzymes, not by small-molecule antioxidant compounds. The field of oxidative stress research embraces chemistry, biochemistry, cell biology, physiology and pathophysiology, all the way to medicine and health and disease research. PMID:25588755

  8. Sol-gel synthesis and adsorption properties of mesoporous manganese oxide

    NASA Astrophysics Data System (ADS)

    Ivanets, A. I.; Kuznetsova, T. F.; Prozorovich, V. G.

    2015-03-01

    Sol-gel synthesis of mesoporous xerogels of manganese oxide with different phase compositions has been performed. The manganese oxide sols were obtained by redox reactions of potassium permanganate with hydrogen peroxide or manganese(II) chloride in aqueous solutions. The isotherms of the low-temperature adsorption-desorption of nitrogen with manganese oxide xerogels treated at 80, 200, 400, and 600°C were measured. The samples were studied by electron microscopy and thermal and XRD analysis. The phase transformation and the changes in the adsorption and capillary-condensation properties of manganese oxide were shown to depend on the sol synthesis conditions and the temperature of the thermal treatment of the gel. The X-ray amorphous samples heated at 80°C were shown to have low values of the specific surface; at higher temperatures, the xerogel crystallized into mixed phases with various compositions and its surface area increased at 200-400°C and decreased at 600°C.

  9. Controlled Synthesis of Hollow Manganese Oxide Nanocrystals.

    PubMed

    Nam, Ki Min; Oh, Kyung Hee; Ham, Kyung-Sik

    2016-02-01

    Carbon spheres have been prepared from glucose under hydrothermal conditions to facilitate the synthesis of hollow manganese oxides. The phases of manganese oxide are controlled by changing annealing temperature of the manganese monoxide on a carbon sphere template. The particles on the carbon surface get an agglomeration and make dense oxide shell during the calcination step, which result in typical hollow structures. The electrochemical properties of hollow manganese oxides have been investigated to elucidate their relative catalytic activities. PMID:27433689

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

    PubMed

    Jones, Dean P

    2016-04-01

    When Rafael Radi and I wrote about Helmut Sies for the Redox Pioneer series, I was disappointed that the Editor restricted us to the use of "Pioneer" in the title. My view is that Helmut was always ahead of the pioneers: He was a scout discovering paths for exploration and a trailblazer developing strategies and methods for discovery. I have known him for nearly 40 years and greatly enjoyed his collegiality as well as brilliance in scientific scholarship. He made monumental contributions to 20th century physiological chemistry beginning with his first measurement of H2O2 in rat liver. While continuous H2O2 production is dogma today, the concept of H2O2 production in mammalian tissues was largely buried for half a century. He continued this leadership in research on oxidative stress, GSH, selenium, and singlet oxygen, during the timeframe when physiological chemistry and biochemistry transitioned to contemporary 21st century systems biology. His impact has been extensive in medical and health sciences, especially in nutrition, aging, toxicology and cancer. I briefly summarize my interactions with Helmut, stressing our work together on the redox code, a set of principles to link mitochondrial respiration, bioenergetics, H2O2 metabolism, redox signaling and redox proteomics into central redox theory. PMID:27095208

  11. Manganese depresses rat heart muscle respiration

    Technology Transfer Automated Retrieval System (TEKTRAN)

    It has previously been reported that moderately high dietary manganese (Mn) in combination with marginal magnesium (Mg) resulted in ultrastructural damage to heart mitochondria. Manganese may replace Mg in biological functions, including the role of enzyme cofactor. Manganese may accumulate and subs...

  12. Recent Progress in Redox Flow Battery Research and Development

    SciTech Connect

    Wang, Wei; Luo, Qingtao; Li, Bin; Wei, Xiaoliang; Li, Liyu; Yang, Zhenguo

    2013-02-20

    With the increase need to seamlessly integrate the renewable energy with the current grid which itself is evolving into a more intelligent, efficient, and capable electrical power system, it is envisioned that the energy storage system will play a more prominent role in bridging the gap between the current technology and a clean sustainable future in grid reliability and utilization. Redox flow battery technology is leading the way in this perspective in providing a well balanced approach for current challenges. Recent progress in the research and development of redox flow battery technology is reviewed here with a focus on new chemistries and systems.

  13. Redox theory of aging

    PubMed Central

    Jones, Dean P.

    2015-01-01

    Metazoan genomes encode exposure memory systems to enhance survival and reproductive potential by providing mechanisms for an individual to adjust during lifespan to environmental resources and challenges. These systems are inherently redox networks, arising during evolution of complex systems with O2 as a major determinant of bioenergetics, metabolic and structural organization, defense, and reproduction. The network structure decreases flexibility from conception onward due to differentiation and cumulative responses to environment (exposome). The redox theory of aging is that aging is a decline in plasticity of genome–exposome interaction that occurs as a consequence of execution of differentiation and exposure memory systems. This includes compromised mitochondrial and bioenergetic flexibility, impaired food utilization and metabolic homeostasis, decreased barrier and defense capabilities and loss of reproductive fidelity and fecundity. This theory accounts for hallmarks of aging, including failure to maintain oxidative or xenobiotic defenses, mitochondrial integrity, proteostasis, barrier structures, DNA repair, telomeres, immune function, metabolic regulation and regenerative capacity. PMID:25863726

  14. SEPARATING PROTOACTINIUM WITH MANGANESE DIOXIDE

    DOEpatents

    Seaborg, G.T.; Gofman, J.W.; Stoughton, R.W.

    1958-04-22

    The preparation of U/sup 235/ and an improved method for isolating Pa/ sup 233/ from foreign products present in neutronirradiated thorium is described. The method comprises forming a solution of neutron-irradiated thorium together with a manganous salt, then adding potassium permanganate to precipitate the manganese as manganese dioxide whereby protoactinium is carried down with the nnanganese dioxide dissolving the precipitate, adding a soluble zirconium salt, and adding phosphate ion to precipitate zirconium phosphate whereby protoactinium is then carried down with the zirconium phosphate to effect a further concentration.

  15. Ediacaran Redox Fluctuations

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  16. Redox regulated peroxisome homeostasis

    PubMed Central

    Wang, Xiaofeng; Li, Shuo; Liu, Yu; Ma, Changle

    2014-01-01

    Peroxisomes are ubiquitous organelles present in nearly all eukaryotic cells. Conserved functions of peroxisomes encompass beta-oxidation of fatty acids and scavenging of reactive oxygen species generated from diverse peroxisomal metabolic pathways. Peroxisome content, number, and size can change quickly in response to environmental and/or developmental cues. To achieve efficient peroxisome homeostasis, peroxisome biogenesis and degradation must be orchestrated. We review the current knowledge on redox regulated peroxisome biogenesis and degradation with an emphasis on yeasts and plants. PMID:25545794

  17. Redox regulated peroxisome homeostasis.

    PubMed

    Wang, Xiaofeng; Li, Shuo; Liu, Yu; Ma, Changle

    2015-01-01

    Peroxisomes are ubiquitous organelles present in nearly all eukaryotic cells. Conserved functions of peroxisomes encompass beta-oxidation of fatty acids and scavenging of reactive oxygen species generated from diverse peroxisomal metabolic pathways. Peroxisome content, number, and size can change quickly in response to environmental and/or developmental cues. To achieve efficient peroxisome homeostasis, peroxisome biogenesis and degradation must be orchestrated. We review the current knowledge on redox regulated peroxisome biogenesis and degradation with an emphasis on yeasts and plants. PMID:25545794

  18. Redox conditions in sediments and during sedimentation in the Ontong Java Plateau, west equatorial Pacific

    NASA Astrophysics Data System (ADS)

    Lu, Bo; Li, Tiegang; Yu, Xinke; Chang, Fengming; Nan, Qingyun

    2011-11-01

    Redox-sensitive elements in sediments, such as manganese (Mn), vanadium (V), molybdenum (Mo), and uranium (U), are promising indicators of past redox conditions during sedimentation and early diagenesis. However, in the Ontong Java Plateau, west equatorial Pacific, there are sparse datasets of redox-sensitive elements in sediment cores. Here, we present a 250 ka record of redox sensitive elements from a 460 cm gravity core at site WP7 (3°56'S, 156°E, water depth 1 800 m), which was recovered from the southwest Ontong Java Plateau during the 1993 cruise of R/V Science I of the Institute of Oceanology, Chinese Academy of Sciences (IOCAS). Relative to the Post-Archean Australian Shale (PAAS), authigenic Mn, cobalt (Co), nickel (Ni), Mo, V, U, and cadmium (Cd) were found at constantly low levels except when peaks occurred at several depth intervals. Manganese, Co, Ni, and Mo concentrations were elevated at 25-35 cm due to Mn redox cycling. The core was divided into three distinct sections, the top 0-25 cm being oxic, a suboxic section at 25-35 cm and from 35-460 cm which was anoxic. Differential authigenic enrichments of Co, Ni, Mo, V, U, and Cd at the same depth intervals were observed indicating that the enrichments happened during sedimentation or diagenesis and suffered no post settlement redox changes. Therefore, no significant changes in redox conditions during sedimentation must have happened. The water at depth on the Ontong Java Plateau during past 250 ka must have been well oxygenated, possibly resulted from the more or less continuous presence of oxygen-rich deep water like the modern Antarctic Intermediate Water (AAIW) and Antarctic Circumpolar Water (ACW); while it's slightly less oxygenated in glacial intervals, possibly due to ventilation weakening and/or the surface productivity increase.

  19. Influence of essential elements on manganese intoxication

    SciTech Connect

    Khandelwal, S.; Ashquin, M.; Tandon, S.K.

    1984-01-01

    With a view to explore the influence of essential metals in manganese intoxication, the effect of calcium, iron or zinc supplementation on the uptake of manganese and on the activity of manganese sensitive enzymes, succinic dehydrogenase and cytochrome oxidase in brain and liver of rat was investigated. The choice of the two mitochondrial enzymes was based on the fact that the mitochondria are the chief site of manganese accumulation and their activity in brain, liver and blood of rats is significantly influenced by manganese.

  20. 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.

  1. 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.

  2. Iron and manganese oxide mineralization in the Pacific

    USGS Publications Warehouse

    Hein, J.R.; Koschinsky, A.; Halbach, P.; Manheim, F. T.; Bau, M.; Kang, J.-K.; Lubick, N.

    1997-01-01

    Iron, manganese, and iron-manganese deposits occur in nearly all geomorphologic and tectonic environments in the ocean basins and form by one or more of four processes: (1) hydrogenetic precipitation from cold ambient seawater, (2) precipitation from hydrothermal fluids, (3) precipitation from sediment pore waters that have been modified from bottom water compositions by diagenetic reactions in the sediment column and (4) replacement of rocks and sediment. Iron and manganese deposits occur in five forms: nodules, crusts, cements, mounds and sediment-hosted stratabound layers. Seafloor oxides show a wide range of compositions from nearly pure iron to nearly pure manganese end members. Fe/Mn ratios vary from about 24 000 (up to 58% elemental Fe) for hydrothermal seamount ironstones to about 0.001 (up to 52% Mn) for hydrothermal stratabound manganese oxides from active volcanic arcs. Hydrogenetic Fe-Mn crusts that occur on most seamounts in the ocean basins have a mean Fe/Mn ratio of 0.7 for open-ocean seamount crusts and 1.2 for continental margin seamount crusts. Fe-Mn nodules of potential economic interest from the Clarion-Clipperton Zone have a mean Fe/Mn ratio of 0.3, whereas the mean ratio for nodules from elsewhere in the Pacific is about 0.7. Crusts are enriched in Co, Ni and Pt and nodules in Cu and Ni, and both have significant concentrations of Pb, Zn, Ba, Mo, V and other elements. In contrast, hydrothermal deposits commonly contain only minor trace metal contents, although there are many exceptions, for example, with Ni contents up to 0.66%, Cr to 1.2%, and Zn to 1.4%. Chondrite-normalized REE patterns generally show a positive Ce anomaly and abundant ??REEs for hydrogenetic and mixed hydrogenetic-diagenetic deposits, whereas the Ce anomaly is negative for hydrothermal deposits and ??REE contents are low. However, the Ce anomaly in crusts may vary from strongly positive in East Pacific crusts to slightly negative in West Pacific crusts, which may reflect

  3. Detailed Vertical and Lateral Delineation of Redox Zones in Contaminant Plumes Using Redox-Sensitive Tapes (RST)

    NASA Astrophysics Data System (ADS)

    Blum, P.; Oeste, F. D.; Melzer, R.; Martus, P.

    2006-12-01

    Innovative redox-sensitive tapes (RST) have been developed for a detailed vertical and lateral delineation of redox zones in contaminated aquifers. The RST have the potential to become an integral part of a data acquisition strategy for monitored natural attenuation (MNA). The tape material, consists of a 2 cm wide synthetic textile coated with reactive manganese dioxide minerals. The RST are submerged into existing monitoring wells for approximately one month. This time period is sufficient to allow for a reaction of the mineral coating with groundwater. The RST are aimed at investigating four different redox-zones in contaminated aquifers: Mn(II)-oxidizing, Mn(IV)-reducing, Fe(III)-reducing and sulfate-reducing. Two RST case studies are presented. The RST investigations on a coal tar contaminated site allowed for a precise lateral and vertical delineation of the contaminant plume using the existing monitoring well network. The RST investigations on a BTEX contaminated site yielded a good correlation of RST data with hydrochemical data at the wells sampled. In the majority of plume wells located 50 m downstream of the source area and beyond, Mn(IV)-reducing environment appeared to be prevailing. Comparing the RST data with hydrochemical data indicated evidence for the transport of transformation products with groundwater flow. The repeated application of the RST facilitated an assessment of the plume dynamics. No significant seasonal variation with respect to the redox zone distribution was observed within the contaminant plume. However, the assessment of the changes in redox conditions over a time period of 2.5 years showed that the iron-reducing zone is shrinking and the sulfate-reducing zone disappeared completely indicating that the contaminant plume might decrease in the near future. Thus, the application of the RST facilitated an assessment of the plume dynamics on a centimeter-scale without the necessity of pumping and treating contaminated groundwater.

  4. Quantitative measures for redox signaling.

    PubMed

    Pillay, Ché S; Eagling, Beatrice D; Driscoll, Scott R E; Rohwer, Johann M

    2016-07-01

    Redox signaling is now recognized as an important regulatory mechanism for a number of cellular processes including the antioxidant response, phosphokinase signal transduction and redox metabolism. While there has been considerable progress in identifying the cellular machinery involved in redox signaling, quantitative measures of redox signals have been lacking, limiting efforts aimed at understanding and comparing redox signaling under normoxic and pathogenic conditions. Here we have outlined some of the accepted principles for redox signaling, including the description of hydrogen peroxide as a signaling molecule and the role of kinetics in conferring specificity to these signaling events. Based on these principles, we then develop a working definition for redox signaling and review a number of quantitative methods that have been employed to describe signaling in other systems. Using computational modeling and published data, we show how time- and concentration- dependent analyses, in particular, could be used to quantitatively describe redox signaling and therefore provide important insights into the functional organization of redox networks. Finally, we consider some of the key challenges with implementing these methods. PMID:27151506

  5. Label free redox capacitive biosensing.

    PubMed

    Fernandes, Flávio C Bedatty; Góes, Márcio S; Davis, Jason J; Bueno, Paulo R

    2013-12-15

    A surface confined redox group contributes to an interfacial charging (quantifiable by redox capacitance) that can be sensitively probed by impedance derived capacitance spectroscopy. In generating mixed molecular films comprising such redox groups, together with specific recognition elements (here antibodies), this charging signal is able to sensitively transduce the recognition and binding of specific analytes. This novel transduction method, exemplified here with C-reactive protein, an important biomarker of cardiac status and general trauma, is equally applicable to any suitably prepared interfacial combination of redox reporter and receptor. The assays are label free, ultrasensitive, highly specific and accompanied by a good linear range. PMID:23896524

  6. Synthesis, characterization, optical and sensing property of manganese oxide nanoparticles

    SciTech Connect

    Manigandan, R.; Suresh, R.; Giribabu, K.; Narayanan, V.; Vijayalakshmi, L.; Stephen, A.

    2014-01-28

    Manganese oxide nanoparticles were prepared by thermal decomposition of manganese oxalate. Manganese oxalate was synthesized by reacting 1:1 mole ratio of manganese acetate and ammonium oxalate along with sodium dodecyl sulfate (SDS). The structural characterization of manganese oxalate and manganese oxide nanoparticles was analyzed by XRD. The XRD spectrum confirms the crystal structure of the manganese oxide and manganese oxalate. In addition, the average grain size, lattice parameter values were also calculated using XRD spectrum. Moreover, the diffraction peaks were broadened due to the smaller size of the particle. The band gap of manganese oxide was calculated from optical absorption, which was carried out by DRS UV-Visible spectroscopy. The morphology of manganese oxide nanoparticles was analyzed by SEM images. The FT-IR analysis confirms the formation of the manganese oxide from manganese oxalate nanoparticles. The electrochemical sensing behavior of manganese oxide nanoparticles were investigated using hydrogen peroxide by cyclic voltammetry.

  7. Biological Superoxide In Manganese Oxide Formation

    NASA Astrophysics Data System (ADS)

    Hansel, C.; Learman, D.; Zeiner, C.; Santelli, C. M.

    2011-12-01

    Manganese (Mn) oxides are among the strongest sorbents and oxidants within the environment, controlling the fate and transport of numerous elements and the degradation of recalcitrant carbon. Both bacteria and fungi mediate the oxidation of Mn(II) to Mn(III/IV) oxides but the genetic and biochemical mechanisms responsible remain poorly understood. Furthermore, the physiological basis for microbial Mn(II) oxidation remains an enigma. We have recently reported that a common marine bacterium (Roseobacter sp. AzwK-3b) oxidizes Mn(II) via reaction with extracellular superoxide (O2-) produced during exponential growth. Here we expand this superoxide-mediated Mn(II) oxidation pathway to fungi, introducing a surprising homology between prokaryotic and eukaryotic metal redox processes. For instance, Stibella aciculosa, a common soil Ascomycete filamentous fungus, precipitates Mn oxides at the base of asexual reproductive structures (synnemata) used to support conidia (Figure 1). This distribution is a consequence of localized production of superoxide (and it's dismutation product hydrogen peroxide, H2O2), leading to abiotic oxidation of Mn(II) by superoxide. Disruption of NADPH oxidase activity using the oxidoreductase inhibitor DPI leads to diminished cell differentiation and subsequent Mn(II) oxidation inhibition. Addition of Cu(II) (an effective superoxide scavenger) leads to a concentration dependent decrease in Mn oxide formation. We predict that due to the widespread production of extracellular superoxide within the fungal and likely bacterial kingdoms, biological superoxide may be an important contributor to the cycling of Mn, as well as other metals (e.g., Hg, Fe). Current and future explorations of the genes and proteins involved in superoxide production and Mn(II) oxidation will ideally lend insight into the physiological and biochemical basis for these processes.

  8. Water exchange in manganese-based water-oxidizing catalysts in photosynthetic systems: from the water-oxidizing complex in photosystem II to nano-sized manganese oxides.

    PubMed

    Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Eaton-Rye, Julian J; Tomo, Tatsuya; Nishihara, Hiroshi; Satoh, Kimiyuki; Carpentier, Robert; Shen, Jian-Ren; Allakhverdiev, Suleyman I

    2014-09-01

    The water-oxidizing complex (WOC), also known as the oxygen-evolving complex (OEC), of photosystem II in oxygenic photosynthetic organisms efficiently catalyzes water oxidation. It is, therefore, responsible for the presence of oxygen in the Earth's atmosphere. The WOC is a manganese-calcium (Mn₄CaO₅(H₂O)₄) cluster housed in a protein complex. In this review, we focus on water exchange chemistry of metal hydrates and discuss the mechanisms and factors affecting this chemical process. Further, water exchange rates for both the biological cofactor and synthetic manganese water splitting are discussed. The importance of fully unveiling the water exchange mechanism to understand the chemistry of water oxidation is also emphasized here. This article is part of a special issue entitled: photosynthesis research for sustainability: keys to produce clean energy. PMID:24685431

  9. Microbial oxidation and reduction of manganese: consequences in groundwater and applications.

    PubMed

    Gounot, A M

    1994-08-01

    In the natural environment, manganese is found as reduced soluble or adsorbed Mn(II) and insoluble Mn(III) and Mn(IV) oxides. Mn oxidation has been reported in various microorganisms. Several possible pathways, indirect or direct, have been proposed. A wider variety of Mn-reducing microorganisms, from highly aerobic to strictly anaerobic, has been described. The mechanisms of Mn reduction can be either an indirect process resulting from interactions with organic or inorganic compounds, or a direct enzymatic (electron-transfer) reaction. The role of microorganisms in Mn cycle is now well demonstrated by various methods in superficial natural environments, and research has been initiated on subsurface sediments. Observations in vivo (Rhône valley) and under in vitro suggested that bacterial activities are the main processes that promote manganese evolution and migration in shallow aquifers. After the building of hydroelectric dams, the stream of the Rhône was modified, giving rise to mud deposition on the bank. In the mud, bacteria are stimulated by the high organic content and consume oxygen. The redox potential drops. The manganese oxides previously formed under aerobic conditions are reduced and soluble manganese (Mn(II)) migrates into the aquifer. If the subsurface sediments are coarse-grained, the aquifer is well aerated, allowing the re-oxidation of Mn(II) by the oligotrophic attached bacteria in aquifer sediments. If the aquifer is confined, aeration is not sufficient for Mn-reoxidation. Mn(II) remains in a reduced state and migrates to the wells. Furthermore, the presence of organic matter in subsurface sediments results in the reduction of previously formed Mn oxides. Pseudo-amorphous manganese oxides, which were probably recently formed by bacteria, are more readily reduced than old crystalline manganese oxides. Although the concentrations of soluble manganese found in groundwaters are not toxic, it still is a problem since its oxidation results in

  10. Modeling CO2 sediment-water flux variations connected with changes of redox conditions

    NASA Astrophysics Data System (ADS)

    Yakushev, Evgeniy; Protsenko, Elizaveta

    2013-04-01

    Changes of bottom redox conditions from oxic to hypoxic, suboxic and anoxic affect rates of sediment-water fluxes of chemical parameters, i.e. oxygen, nutrient (including carbon), redox metals. Chemosynthetic organic matter production in suboxic and anoxic conditions additionally affects transformation of carbon. This work aimed in estimation of a potential influence of changes of the bottom redox conditions on the sediment -water fluxes of carbon. We use a 1-dimensional C-N-P-Si-O-S-Mn-Fe vertical transport-reaction model describing both the sediments and bottom boundary layers coupled with biogeochemical block simulating changeable redox conditions, and the carbonate system processes block. A biogeochemical block is based on ROLM (RedOx Layer Model), that was constructed to simulate basic features of the water column biogeochemical structure changes in oxic, anoxic and changeable conditions (Yakushev et al., 2007). Organic matter formation and decay, reduction and oxidation of species of nitrogen, sulfur, manganese, iron, and the transformation of phosphorus species are parameterized in the model. The model includes blocks for phytoplankton, zooplankton, aerobic autotrophic and heterotrophic bacteria and anaerobic autotrophic and heterotrophic bacteria. In this study we additionally parameterized transformation of Si and C and forms of alkalinity. We simulate changes in the bottom boundary layer pH in different redox conditions under the same leakage scenario.

  11. Molten fluoride fuel salt chemistry

    SciTech Connect

    Toth, L.M.; Del Cul, G.D.; Dai, S.; Metcalf, D.H.

    1994-09-01

    The chemistry of molten fluorides is traced from their development as fuels in the Molten Salt Reactor Experiment with important factors in their selection being discussed. Key chemical characteristics such as solubility, redox behavior, and chemical activity are explained as they relate to the behavior of molten fluoride fuel systems. Fission product behavior is described along with processing experience. Development requirements for fitting the current state of the chemistry to modern nuclear fuel system are described. It is concluded that while much is known about molten fluoride behavior, processing and recycle of the fuel components is a necessary factor if future systems are to be established.

  12. Oxidation kinetics of pentachlorophenol by manganese dioxide.

    PubMed

    Zhao, Ling; Yu, Zhiqiang; Peng, Pingán; Huang, Weilin; Feng, Shunqing; Zhou, Haiyan

    2006-11-01

    This study examined the abiotic transformation kinetics of pentachlorophenol (PCP) by manganese dioxide (MnO2) at different solution chemistry and initial concentrations of PCP and MnO2. The measured PCP transformation rates were found to be on the order of 1.07 with respect to [PCP] and 0.91 and 0.87 with respect to [MnO2] and [H+], respectively. Dissolved Mn2+ and Ca2+ as background electrolytes considerably decreased the reaction rate because of their adsorption and hence blocking of active sites on MnO2 surfaces. The dechlorination number, 0.59 chloride ions per transformed PCP after a 1-h reaction, suggests that a fraction of the transformed PCP was not dechlorinated and may be coupled directly to dimeric products. Gas chromatography/ mass spectrometry and liquid chromatography/mass spectrometry/mass spectrometry techniques were used to identify two isomeric nonachlorohydroxybiphenylethers as major products and 2,3,5,6-tetrachloro-1,4-hydroquinone and tetrachlorocatechol as minor products. Product identification suggested that the reaction may include two parallel reactions to form either dimers or 2,3,5,6-tetrachloro-1,4-hydroquinone and tetrachlorocatechol via simultaneous dehydrochlorination and hydroxylation. PMID:17089714

  13. Microbial fuel cell using anaerobic respiration as an anodic reaction and biomineralized manganese as a cathodic reactant.

    PubMed

    Rhoads, Allison; Beyenal, Haluk; Lewandowski, Zbigniew

    2005-06-15

    We have operated a microbial fuel cell in which glucose was oxidized by Klebsiella pneumoniae in the anodic compartment, and biomineralized manganese oxides, deposited by Leptothrix discophora, were electrochemically reduced in the cathodic compartment. In the anodic compartment, to facilitate the electron transfer from glucose to the graphite electrode, we added a redox mediator, 2-hydroxy-1,4-naphthoquinone. We did not add any redox mediator to the cathodic compartment because the biomineralized manganese oxides were deposited on the surface of a graphite electrode and were reduced directly by electrons from the electrode. We have demonstrated that biomineralized manganese oxides are superiorto oxygen when used as cathodic reactants in microbial fuel cells. The current density delivered by using biomineralized manganese oxides as the cathodic reactant was almost 2 orders of magnitude higher than that delivered using oxygen. Several fuel cells were operated for 500 h, reaching anodic potentials of -441.5 +/- 31 mVscE and cathodic potentials of +384.5 +/- 64 mVscE. When the electrodes were connected by a 50 Ohms resistor, the fuel cell delivered the peak power density of 126.7 +/- 31.5 mW/m2. PMID:16047807

  14. Redox flow batteries: a review

    SciTech Connect

    Weber, Adam Z.; Mench, Matthew M; Meyers, Jeremy; Ross, Philip N.; Gostick, Jeffrey T.; Liu, Qinghua

    2011-01-01

    Redox flow batteries (RFBs) are enjoying a renaissance due to their ability to store large amounts of electrical energy relatively cheaply and efficiently. In this review, we examine the components of RFBs with a focus on understanding the underlying physical processes. The various transport and kinetic phenomena are discussed along with the most common redox couples.

  15. High resolution redox potential measurements: techniques, interpretation and value

    NASA Astrophysics Data System (ADS)

    Vorenhout, Michel; van der Geest, Harm G.

    2013-04-01

    The ongoing improvement of techniques for the in situ measurement of redox potentials has led to a large number of studies on redox variability in various environments. These studies originate from a wide array of scientific disciplines, amongst which ecology (sediment biogeochemistry), environmental chemistry (degradation studies) and archaeology (in situ preservation). To gain insight in the potential applications, this paper presents three examples of studies in which a newly developed measurement technique was used in soils and where spatial and temporal variation plays an important role. The first one is a microcosm study on the effects of biota on the dynamics of redox conditions in the toplayer of aquatic sediments, showing that the presence of microbiota has a direct influence on biogeochemical parameters. The second is the study of the redox potential in the world heritage site of Bryggen (Bergen, NO) that is under threat of oxidation. The oxidation, caused by a lowered groundwater table, causes soil degradation and unstable conditions for the monumental buildings of the Medieval site. The third study shows variability in a sandy flood plain in Bangladesh, where redox processes dictate the environmental behaviour of Arsenic. This toxic metal is present in many wells used for drinking water, but shows very local variation in dissolution dynamics. In these three studies, continuous measurements of (changes in) redox conditions revealed a strong variability in these systems and consequences for the interpretation of single point measurements or low frequency sampling campaigns are discussed. In these and many other cases, the continuous measurement of the redox potential in soil media will aid in the understanding of the system under study.

  16. Manganese chlorins immobilized on silica as oxidation reaction catalysts.

    PubMed

    Castro, Kelly A D F; Pires, Sónia M G; Ribeiro, Marcos A; Simões, Mário M Q; Neves, M Graça P M S; Schreiner, Wido H; Wypych, Fernando; Cavaleiro, José A S; Nakagaki, Shirley

    2015-07-15

    Synthetic strategies that comply with the principles of green chemistry represent a challenge: they will enable chemists to conduct reactions that maximize the yield of products with commercial interest while minimizing by-products formation. The search for catalysts that promote the selective oxidation of organic compounds under mild and environmentally friendly conditions constitutes one of the most important quests of organic chemistry. In this context, metalloporphyrins and analogues are excellent catalysts for oxidative transformations under mild conditions. In fact, their reduced derivatives chlorins are also able to catalyze organic compounds oxidation effectively, although they have been still little explored. In this study, we synthesized two chlorins through porphyrin cycloaddition reactions with 1.3-dipoles and prepared the corresponding manganese chlorins (MnCHL) using adequate manganese(II) salts. These MnCHL were posteriorly immobilized on silica by following the sol-gel process and the resulting solids were characterized by powder X-ray diffraction (PXRD), UVVIS spectroscopy, FTIR, XPS, and EDS. The catalytic activity of the immobilized MnCHL was investigated in the oxidation of cyclooctene, cyclohexene and cyclohexane and the results were compared with the ones obtained under homogeneous conditions. PMID:25841060

  17. [Radiation therapy and redox imaging].

    PubMed

    Matsumoto, Ken-ichiro

    2015-01-01

    Radiation therapy kills cancer cells in part by flood of free radicals. Radiation ionizes and/or excites water molecules to create highly reactive species, i.e. free radicals and/or reactive oxygen species. Free radical chain reactions oxidize biologically important molecules and thereby disrupt their function. Tissue oxygen and/or redox status, which can influence the course of the free radical chain reaction, can affect the efficacy of radiation therapy. Prior observation of tissue oxygen and/or redox status is helpful for planning a safe and efficient course of radiation therapy. Magnetic resonance-based redox imaging techniques, which can estimate tissue redox status non-invasively, have been developed not only for diagnostic information but also for estimating the efficacy of treatment. Redox imaging is now spotlighted to achieve radiation theranostics. PMID:25948308

  18. Thiol-based redox switches.

    PubMed

    Groitl, Bastian; Jakob, Ursula

    2014-08-01

    Regulation of protein function through thiol-based redox switches plays an important role in the response and adaptation to local and global changes in the cellular levels of reactive oxygen species (ROS). Redox regulation is used by first responder proteins, such as ROS-specific transcriptional regulators, chaperones or metabolic enzymes to protect cells against mounting levels of oxidants, repair the damage and restore redox homeostasis. Redox regulation of phosphatases and kinases is used to control the activity of select eukaryotic signaling pathways, making reactive oxygen species important second messengers that regulate growth, development and differentiation. In this review we will compare different types of reversible protein thiol modifications, elaborate on their structural and functional consequences and discuss their role in oxidative stress response and ROS adaptation. This article is part of a Special Issue entitled: Thiol-Based Redox Processes. PMID:24657586

  19. [Clinical cases of occupational chronic manganese intoxication].

    PubMed

    Konstantinova, T N; Lakhman, O L; Katamanova, E V; Kartapol'tseva, N V; Meshcheriagin, V A; Rusanova, D V; Andreeva, O K

    2009-01-01

    Classic symptoms of manganese intoxication are very rarely seen nowadays. Clinic in Angarsk Research Institute for Occupational medicine and Human ecology registered two cases of stage I and II chronic manganese intoxication over 10 years among electric welders. The cases were diagnosed with consideration of long length of exposure to manganese with the ambient air level exceeding the MAC 1.5 times, the disease manifestation at middle age, high manganese level in serum and urine, characteristic neurologic symptoms in association with organic psychopathologic defects and polyneuropathy of limbs. PMID:19278189

  20. Negative impact of manganese on honeybee foraging

    PubMed Central

    Søvik, Eirik; Perry, Clint J.; LaMora, Angie; Barron, Andrew B.; Ben-Shahar, Yehuda

    2015-01-01

    Anthropogenic accumulation of metals such as manganese is a well-established health risk factor for vertebrates. By contrast, the long-term impact of these contaminants on invertebrates is mostly unknown. Here, we demonstrate that manganese ingestion alters brain biogenic amine levels in honeybees and fruit flies. Furthermore, we show that manganese exposure negatively affects foraging behaviour in the honeybee, an economically important pollinator. Our findings indicate that in addition to its direct impact on human health, the common industrial contaminant manganese might also have indirect environmental and economical impacts via the modulation of neuronal and behavioural functions in economically important insects. PMID:25808001

  1. Theoretical study of the interaction between molecular oxygen and tetraaza macrocyclic manganese complexes.

    PubMed

    Costa, Alexandre; Silva, Adilson Luís Pereira; Viana, Rommel Bezerra; Tanaka, Auro Atsushi; Varela, Jaldyr de Jesus Gomes

    2016-09-01

    Theoretical chemistry calculations using the Density Functional Theory (DFT) were carried out to understand the interaction between oxygen (O2) and MnN4 type manganese-based complexes during the formation of MnN4-O2 adducts. In order to understand how this interaction is affected by different macrocyclic ligands, O2 was bonded to manganese-porphyrin (MnP), manganese-octamethylporphyrin (MnOMP), manganese-tetraaza[14]annulene (MnTAA), manganese-dibenzo [b,i] [1, 4, 8, 11]-tetraaza [14] annulene (MnDBTAA), manganese-2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene ([(tim)Mn](2+)), and manganese-2,3,9,10-tetraphenyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene ([(ph-tim)Mn](2+)). The binding and activation of the oxygen molecule was facilitated by an increasing trend in the O-O bond lengths and a decreasing one in the O-O vibrational frequency, with preference for the O2 side-on interaction among MnN4 macrocycles. The catalytic activities of the MnN4 complexes toward the O2 binding process increased in the following order: [(ph-tim)Mn](2+) < MnP < MnOMP < MnDBTAA < MnTAA < [(tim)Mn](2+). Therefore, it was concluded that the [(tim)Mn](2+)complex was the most active for the binding and activation of molecular oxygen. PMID:27553302

  2. Redox regulation of photosynthetic gene expression

    PubMed Central

    Queval, Guillaume; Foyer, Christine H.

    2012-01-01

    Redox chemistry and redox regulation are central to the operation of photosynthesis and respiration. However, the roles of different oxidants and antioxidants in the regulation of photosynthetic or respiratory gene expression remain poorly understood. Leaf transcriptome profiles of a range of Arabidopsis thaliana genotypes that are deficient in either hydrogen peroxide processing enzymes or in low molecular weight antioxidant were therefore compared to determine how different antioxidant systems that process hydrogen peroxide influence transcripts encoding proteins targeted to the chloroplasts or mitochondria. Less than 10 per cent overlap was observed in the transcriptome patterns of leaves that are deficient in either photorespiratory (catalase (cat)2) or chloroplastic (thylakoid ascorbate peroxidase (tapx)) hydrogen peroxide processing. Transcripts encoding photosystem II (PSII) repair cycle components were lower in glutathione-deficient leaves, as were the thylakoid NAD(P)H (nicotinamide adenine dinucleotide (phosphate)) dehydrogenases (NDH) mRNAs. Some thylakoid NDH mRNAs were also less abundant in tAPX-deficient and ascorbate-deficient leaves. Transcripts encoding the external and internal respiratory NDHs were increased by low glutathione and low ascorbate. Regulation of transcripts encoding specific components of the photosynthetic and respiratory electron transport chains by hydrogen peroxide, ascorbate and glutathione may serve to balance non-cyclic and cyclic electron flow pathways in relation to oxidant production and reductant availability. PMID:23148274

  3. Hybrid ternary rice paper-manganese oxide-carbon nanotube nanocomposites for flexible supercapacitors.

    PubMed

    Jiang, Wenchao; Zhang, Kaixi; Wei, Li; Yu, Dingshan; Wei, Jun; Chen, Yuan

    2013-11-21

    Modern portable electronic devices create a strong demand for flexible energy storage devices. Paper based nanocomposites are attractive as sustainable materials for such applications. Here, we directly explored the hydroxyl chemistry of cellulose fibers to synthesize hybrid ternary nanocomposites, comprised of rice paper, single-walled carbon nanotubes (SWCNTs) and manganese oxide nanoparticles. The functional groups on cellulose fibers can react with adsorbed permanganate ions, resulting in uniform deposition of manganese oxide nanoparticles. SWCNTs coated on top of manganese oxide nanoparticles form a highly conductive network connecting individual manganese oxide particles. By using the hybrid ternary composites as electrodes, the assembled two-electrode supercapacitors demonstrated high capacitance (260.2 F g(-1)), energy (9.0 W h kg(-1)), power (59.7 kW kg(-1)), and cycle stability (12% drop after 3000 cycles). In addition, the nanocomposites show good strength and excellent mechanical flexibility, and their capacitance shows negligible changes after bending more than 100 times. These findings suggest that opportunities exist to further explore the rich chemistry of cellulose fibers for innovative energy applications. PMID:24077360

  4. Thermodynamics of Manganese Oxides at Bulk and Nanoscale: Phase Formation, Transformation, Oxidation-Reduction, and Hydration

    NASA Astrophysics Data System (ADS)

    Birkner, Nancy R.

    Natural manganese oxides are generally formed in surficial environments that are near ambient temperature and water-rich, and may be exposed to wet-dry cycles and a variety of adsorbate species that influence dramatically their level of hydration. Manganese oxide minerals are often poorly crystalline, nanophase, and hydrous. In the near-surface environment they are involved in processes that are important to life, such as water column oxygen cycling, biomineralization, and transport of minerals/nutrients through soils and water. These processes, often involving transformations among manganese oxide polymorphs, are governed by a complex interplay between thermodynamics and kinetics. Manganese oxides are also used in technology as catalysts, and for other applications. The major goal of this dissertation is to examine the energetics of bulk and nanophase manganese oxide phases as a function of particle size, composition, and surface hydration. Careful synthesis and characterization of manganese oxide phases with different surface areas provided samples for the study of enthalpies of formation by high temperature oxide melt solution calorimetry and of the energetics of water adsorption on their surfaces. These data provide a quantitative picture of phase stability and how it changes at the nanoscale. The surface energy of the hydrous surface of Mn3O4 is 0.96 +/- 0.08 J/m2, of Mn2O3 is 1.29 +/- 0.10 J/m2, and of MnO2 is 1.64 +/- 0.10 J/m2. The surface energy of the anhydrous surface of Mn3O4 is 1.62 +/- 0.08 J/m 2, of Mn2O3 is 1.77 +/- 0.10 J/m 2, and of MnO2 is 2.05 +/- 0.10 J/m2. Supporting preliminary findings (Navrotsky et al., 2010), the spinel phase (Mn3O4) has a lower surface energy (more stabilizing) than bixbyite, while the latter has a smaller surface energy than pyrolusite. These differences significantly change the positions in oxygen fugacity---temperature space of the redox couples Mn3O4-Mn2O 3 and Mn2O3-MnO2 favoring the lower surface enthalpy phase (the

  5. Redox biology of the intestine

    PubMed Central

    Circu, Magdalena L.; Aw, Tak Yee

    2011-01-01

    The intestinal tract, known for its capability for self-renew, represents the first barrier of defense between the organism and its luminal environment. The thiol/disulfide redox systems comprising the glutathione/glutathione disulfide (GSH/GSSG), cysteine/cystine (Cys/CySS) and reduced and oxidized thioredoxin (Trx/TrxSS) redox couples play important roles in preserving tissue redox homeostasis, metabolic functions, and cellular integrity. Control of the thiol-disulfide status at the luminal surface is essential for maintaining mucus fluidity and absorption of nutrients, and protection against chemical-induced oxidant injury. Within intestinal cells, these redox couples preserve an environment that supports physiological processes and orchestrates networks of enzymatic reactions against oxidative stress. In this review, we focus on the intestinal redox and antioxidant systems, their subcellular compartmentation, redox signaling and epithelial turnover, and contribution of luminal microbiota, key aspects that are relevant to understanding redox-dependent processes in gut biology with implications for degenerative digestive disorders, such as inflammation and cancer. PMID:21831010

  6. Manganese(III) binding to a pyoverdine siderophore produced by a manganese(II)-oxidizing bacterium

    NASA Astrophysics Data System (ADS)

    Parker, Dorothy L.; Sposito, Garrison; Tebo, Bradley M.

    2004-12-01

    The possible roles of siderophores (high affinity chelators of iron(III)) in the biogeochemistry of manganese remain unknown. Here we investigate the interaction of Mn(III) with a pyoverdine-type siderophore (PVD MnB1) produced by the model Mn(II)-oxidizing bacterium Pseudomonas putida strain MnB1. PVD MnB1 confirmed typical pyoverdine behavior with respect to: (a) its absorption spectrum at 350-600 nm, both in the absence and presence of Fe(III), (b) the quenching of its fluorescence by Fe(III), (c) the formation of a 1:1 complex with Fe(III), and (d) the thermodynamic stability constant of its Fe(III) complex. The Mn(III) complex of PVD MnB1 had a 1:1 Mn:pvd molar ratio, showed fluorescence quenching, and exhibited a light absorption spectrum (A max = 408-410 nm) different from that of either PVD MnB1-Fe(III) or uncomplexed PVD MnB1. Mn(III) competed strongly with Fe(III) for binding by PVD MnB1 in culture filtrates (pH 8, 4°C). Equilibration with citrate, a metal-binding ligand, did not detectably release Mn from its PVD MnB1 complex at a citrate/PVD MnB1 molar ratio of 830 (pH 8, 4°C), whereas pyrophosphate under the same conditions removed 55% of the Mn from its PVD MnB1 complex. Most of the PVD MnB1-complexed Mn was released by reaction with ascorbate, a reducing agent, or with EDTA, a ligand that is also oxidized by Mn(III). Data on the competition for binding to PVD MnB1 by Fe(III) vs. Mn(III) were used to determine a thermodynamic stability constant (nominally at 4°C) for the neutral species MnHPVD MnB1 (log K = 47.5 ± 0.5, infinite dilution reference state). This value was larger than that determined for FeHPVD MnB1 (log K = 44.6 ± 0.5). This result has important implications for the metabolism, solubility, speciation, and redox cycling of manganese, as well as for the biologic uptake of iron.

  7. Chemistry Notes

    ERIC Educational Resources Information Center

    School Science Review, 1976

    1976-01-01

    Described are eight chemistry experiments and demonstrations applicable to introductory chemistry courses. Activities include: measure of lattice enthalpy, Le Chatelier's principle, decarboxylation of soap, use of pocket calculators in pH measurement, and making nylon. (SL)

  8. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1983

    1983-01-01

    Presents background information, laboratory procedures, classroom materials/activities, and chemistry experiments. Topics include sublimation, electronegativity, electrolysis, experimental aspects of strontianite, halide test, evaluation of present and future computer programs in chemistry, formula building, care of glass/saturated calomel…

  9. ENVIRONMENTAL CHEMISTRY

    EPA Science Inventory

    Environmental chemistry is applied to estimating the exposure of ecosystems and humans to various chemical environmental stressors. Among the stressors of concern are mercury, pesticides, and arsenic. Advanced analytical chemistry techniques are used to measure these stressors ...

  10. Chemistry Notes

    ERIC Educational Resources Information Center

    School Science Review, 1972

    1972-01-01

    Thirteen ideas are presented that may be of use to chemistry teachers. Topics covered include vitamin C, industrial chemistry, electrical conductivity, electrolysis, alkali metals, vibration modes infra-red, dynamic equilibrium, and some new demonstrations in gaseous combinations. (PS)