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Sample records for cerium redox state

  1. Electrochemical redox processes involving soluble cerium species

    International Nuclear Information System (INIS)

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

    2016-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-05-15

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

  3. Using cerium anomaly as an indicator of redox reactions in constructed wetland

    Science.gov (United States)

    Liang, R.

    2013-12-01

    The study area, Chiayi County located in southern Taiwan, has highly developed livestock. The surface water has very low dissolved oxygen and high NH4. Under the situation, constructed wetland becomes the most effective and economic choice to treat the wastewater in the natural waterways. Hebao Island free surface constructed wetland started to operate in late 2006. It covers an area of 0.28 km2 and is subdivided into 3 major cells, which are sedimentation cell, 1st aeration cell with rooted plants and 2nd aeration cell with float plants. The water depth of cells ranges from 0.6 m to 1.2 m. The total hydraulic retention time is about a half day. In this study, the water samples were sequentially collected along the flow path. The results of hydrochemical analysis show that the untreated inflow water can be characterized with enriched NH4 (11 ppm), sulfate (6 ppm) and arsenic (50 ppb). The removal efficiency of NH4 in the first two cells is arsenic is still higher than the permissible limits recommended by WHO (10 ppb). The wetland operation should be tuned to take more arsenic away in the future. As demonstrated in the above, oxidation reaction is the most dominant mechanism to remove pollutants from the wastewater; therefore, dissolved oxygen is traditionally considered as an important indicator to evaluate the operation efficiency of wetland. However, it would need longer time to achieve equilibrium state of redox reaction involving dissolved oxygen due to the slower reaction rate. For example, the input water in this study has fairly high dissolved oxygen (5 ppm) but the NH4 content is still high, which indicates a non-equilibrium condition. In this study, the cerium anomaly is alternatively utilized to evaluate the water redox state. The results demonstrate that the input water has the negative cerium anomaly of -0.16. Along the flow path, the cerium negative anomaly does not change in the first two cells and dramatically becomes -0.23 in cell 3. The trend of

  4. The developments and challenges of cerium half-cell in zinc–cerium redox flow battery for energy storage

    International Nuclear Information System (INIS)

    Xie, Zhipeng; Liu, Qingchao; Chang, Zhiwen; Zhang, Xinbo

    2013-01-01

    Zinc–cerium redox flow batteries (ZCBs) are emerging as a very promising new technology with the potential to store a large amount of energy economically and efficiently, thanking to its highest thermodynamic open-circuit cell voltage among all the currently studied aqueous redox flow batteries. However, there are numerous scientific and technical challenges that must be overcome if this alluring promise is to turn into reality, from designing the battery structure, to optimizing the electrolyte compositions and elucidating the complex chemical reactions that occur during charge and discharge. This review article is the first summary of the most significant developments and challenges of cerium half-cell and the current understanding of their chemistry. We are certain that this review will be of great interest to audience over a broad range, especially in fields of energy storage, electrochemistry, and chemical engineering

  5. Redox-active cerium oxide nanoparticles protect human dermal fibroblasts from PQ-induced damage

    Directory of Open Access Journals (Sweden)

    Claudia von Montfort

    2015-04-01

    Full Text Available Recently, it has been published that cerium (Ce oxide nanoparticles (CNP; nanoceria are able to downregulate tumor invasion in cancer cell lines. Redox-active CNP exhibit both selective pro-oxidative and antioxidative properties, the first being responsible for impairment of tumor growth and invasion. A non-toxic and even protective effect of CNP in human dermal fibroblasts (HDF has already been observed. However, the effect on important parameters such as cell death, proliferation and redox state of the cells needs further clarification. Here, we present that nanoceria prevent HDF from reactive oxygen species (ROS-induced cell death and stimulate proliferation due to the antioxidative property of these particles.

  6. Sulphonated metal phthalocyanine complexes as redox indicators in micro titrations with cerium(IV) sulphate

    Energy Technology Data Exchange (ETDEWEB)

    Gowda, H S; Achar, B N [Mysore Univ. (India). Dept. of Chemistry

    1980-01-01

    Tetrasodium salts of copper(II) 4,4', 4'', 4'''-tetrasulphophthalocyanine 2-hydrate, nickel(II) 4,4', 4'', 4'''-tetrasulphophthalocyanine, nickel(II) 3,3', 3'', 3'''-tetrasulphophthalocyanine and cobalt(II) 4,4', 4'', 4'''-tetrasulphophthalocyanine 2-hydrate, and copper phthalocyanine trisulphonic acid are prepared in pure state. The molar absorptivity and formal redox potentials of the complexes are determined. The complexes are proposed as sensitive redox indicators in the micro determination of iron(II), arsenic(III), molybdenum(V), uranium(IV) and hydroquinone with 0.001-0.0005N cerium(IV) sulphate in sulphuric, hydrochloric and acetic acid media. They give sharp colour change from light turquoise blue to pale purple colour at the equivalence point. They have advantages over a few existing redox indicators.

  7. Decontamination of alpha contaminated metallic waste by cerium IV redox process

    International Nuclear Information System (INIS)

    Shah, J.G.; Dhami, P.S.; Gandhi, P.M.; Wattal, P.K.

    2012-01-01

    Decontamination of alpha contaminated metallic waste is an important aspect in the management of waste generated during dismantling and decommissioning of nuclear facilities. Present work on cerium redox process targets decontamination of alpha contaminated metallic waste till it qualifies for the non alpha waste category for disposal in near surface disposal facility. Recovery of the alpha radio nuclides and cerium from aqueous secondary waste streams was also studied deploying solvent extraction process and established. The alpha-lean secondary waste stream has been immobilised in cement based matrix for final disposal. (author)

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

    Science.gov (United States)

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

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

  9. Tuning Reactivity and Electronic Properties through Ligand Reorganization within a Cerium Heterobimetallic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, Jerome R.; Gordon, Zachary; Booth, Corwin H.; Carroll, Patrick J.; Walsh, Patrick J.; Schelter, Eric J.

    2014-06-24

    Cerium compounds have played vital roles in organic, inorganic, and materials chemistry due to their reversible redox chemistry between trivalent and tetravalent oxidation states. However, attempts to rationally access molecular cerium complexes in both oxidation states have been frustrated by unpredictable reactivity in cerium(III) oxidation chemistry. Such oxidation reactions are limited by steric saturation at the metal ion, which can result in high energy activation barriers for electron transfer. An alternative approach has been realized using a rare earth/alkali metal/1,1'-BINOLate (REMB) heterobimetallic framework, which uses redox-inactive metals within the secondary coordination sphere to control ligand reorganization. The rational syntheses of functionalized cerium(IV) products and a mechanistic examination of the role of ligand reorganization in cerium(III) oxidation are presented.

  10. Pyrazolates advance cerium chemistry: a CeIII/CeIV redox equilibrium with benzoquinone.

    Science.gov (United States)

    Werner, Daniel; Deacon, Glen B; Junk, Peter C; Anwander, Reiner

    2017-05-16

    Two stable cerium(iv) 3,5-dialkylpyrazolate complexes are presented, namely dimeric [Ce(Me 2 pz) 4 ] 2 (Me 2 pz = 3,5-dimethylpyrazolate) and monomeric Ce(tBu 2 pz) 4 (tBu 2 pz = 3,5-di-tert-butylpyrazolate) along with their trivalent counterparts [Ce(Me 2 pz) 3 ] and [Ce(tBu 2 pz) 3 ] 2 . All complexes were obtained from protonolysis reactions employing the silylamide precursors Ce[N(SiHMe 2 ) 2 ] 4 and Ce[N(SiMe 3 ) 2 ] 3 . Treatment of homoleptic Ce IV and Ce III Me 2 pz complexes with 1,4-hydroquinone (H 2 hq) or 1,4-benzoquinone (bq), respectively, ultimately gave the same trimetallic Ce III species via a cerium redox equilibrium. The Ce III complex Ce 3 (Me 2 pz) 5 (pchd) 2 (L) (pchd = 1,4-bis(3,5-dimethylpyrazol-1-yl)cyclohex-2,5-diene-1,4-diolato; L = Me 2 pzH or (thf) 2 ) results from a di-1,4-pyrazolyl attack on pre-coordinated bq. The reduction of bq by [Ce(Me 2 pz) 3 (thf)] 2 , and re-oxidation by the resulting Ce IV species was supported by UV-vis spectroscopic investigations. Comparisons with the redox-innocent complexes [Ln(Me 2 pz) 3 (thf)] 2 (Ln = La and Pr) revealed far less selective reactions with bq, giving hexametallic and octametallic rare-earth metal side products containing 2-Me 2 pz substituted hq ligands.

  11. Correlation of the oxidation state of cerium in sol-gel glasses as a function of thermal treatment via optical spectroscopy and XANES studies.

    Science.gov (United States)

    Assefa, Zerihun; Haire, R G; Caulder, D L; Shuh, D K

    2004-07-01

    Sol-gel glass matrices containing lanthanides have numerous technological applications and their formation involves several chemical facets. In the case of cerium, its ability to exist in two different oxidation states or in mixed valence state provides additional complexities for the sol-gel process. The oxidation state of cerium present during different facets of preparation of sol-gel glasses, and also as a function of the starting oxidation state of cerium added, were studied both by optical spectroscopy and X-ray absorption near-edge structures (XANES). The findings acquired by each approach were compared. The primary focus was on the redox chemistries associated with sample preparation, gelation, and thermal treatment. When Ce3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 degrees C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 degrees C and up to approximately 1000 degrees C, cerium is oxidized to its tetravalent state. In contrast, when tetravalent cerium is introduced into the sol, both the wet and room temperature-dried gels lose the yellow-brown color of the initial ceric ammonium nitrate solution. When the sol-gel is heated to 110 degrees C it turns yellowish as the cerium tends to be re-oxidized. The yellow color is believed to represent the effect of oxidation and oligomerization of the cerium-silanol units in the matrix. The luminescence properties are also affected by these changes, the details of which are reported herein.

  12. Preparation and Biocompatible Surface Modification of Redox Altered Cerium Oxide Nanoparticle Promising for Nanobiology and Medicine

    KAUST Repository

    Nanda, Himansu Sekhar

    2016-11-03

    The biocompatible surface modification of metal oxide nanoparticles via surface functionalization technique has been used as an important tool in nanotechnology and medicine. In this report, we have prepared aqueous dispersible, trivalent metal ion (samarium)-doped cerium oxide nanoparticles (SmCNPs) as model redox altered CNPs of biological relevance. SmCNP surface modified with hydrophilic biocompatible (6-{2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxy}-hexyl) triethoxysilane (MEEETES) were prepared using ammonia-induced ethylene glycol-assisted precipitation method and were characterized using a variety of complementary characterization techniques. The chemical interaction of functional moieties with the surface of doped nanoparticle was studied using powerful 13C cross polarization magic angle sample spinning nuclear magnetic resonance spectroscopy. The results demonstrated the production of the extremely small size MEEETES surface modified doped nanoparticles with significant reduction in aggregation compared to their unmodified state. Moreover, the functional moieties had strong chemical interaction with the surface of the doped nanoparticles. The biocompatible surface modification using MEEETES should also be extended to several other transition metal ion doped and co-doped CNPs for the production of aqueous dispersible redox altered CNPs that are promising for nanobiology and medicine.

  13. Preparation and Biocompatible Surface Modification of Redox Altered Cerium Oxide Nanoparticle Promising for Nanobiology and Medicine

    KAUST Repository

    Nanda, Himansu Sekhar

    2016-01-01

    The biocompatible surface modification of metal oxide nanoparticles via surface functionalization technique has been used as an important tool in nanotechnology and medicine. In this report, we have prepared aqueous dispersible, trivalent metal ion (samarium)-doped cerium oxide nanoparticles (SmCNPs) as model redox altered CNPs of biological relevance. SmCNP surface modified with hydrophilic biocompatible (6-{2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxy}-hexyl) triethoxysilane (MEEETES) were prepared using ammonia-induced ethylene glycol-assisted precipitation method and were characterized using a variety of complementary characterization techniques. The chemical interaction of functional moieties with the surface of doped nanoparticle was studied using powerful 13C cross polarization magic angle sample spinning nuclear magnetic resonance spectroscopy. The results demonstrated the production of the extremely small size MEEETES surface modified doped nanoparticles with significant reduction in aggregation compared to their unmodified state. Moreover, the functional moieties had strong chemical interaction with the surface of the doped nanoparticles. The biocompatible surface modification using MEEETES should also be extended to several other transition metal ion doped and co-doped CNPs for the production of aqueous dispersible redox altered CNPs that are promising for nanobiology and medicine.

  14. Preparation and Biocompatible Surface Modification of Redox Altered Cerium Oxide Nanoparticle Promising for Nanobiology and Medicine

    Directory of Open Access Journals (Sweden)

    Himansu Sekhar Nanda

    2016-11-01

    Full Text Available The biocompatible surface modification of metal oxide nanoparticles via surface functionalization technique has been used as an important tool in nanotechnology and medicine. In this report, we have prepared aqueous dispersible, trivalent metal ion (samarium-doped cerium oxide nanoparticles (SmCNPs as model redox altered CNPs of biological relevance. SmCNP surface modified with hydrophilic biocompatible (6-{2-[2-(2-methoxy-ethoxy-ethoxy]-ethoxy}-hexyl triethoxysilane (MEEETES were prepared using ammonia-induced ethylene glycol-assisted precipitation method and were characterized using a variety of complementary characterization techniques. The chemical interaction of functional moieties with the surface of doped nanoparticle was studied using powerful 13C cross polarization magic angle sample spinning nuclear magnetic resonance spectroscopy. The results demonstrated the production of the extremely small size MEEETES surface modified doped nanoparticles with significant reduction in aggregation compared to their unmodified state. Moreover, the functional moieties had strong chemical interaction with the surface of the doped nanoparticles. The biocompatible surface modification using MEEETES should also be extended to several other transition metal ion doped and co-doped CNPs for the production of aqueous dispersible redox altered CNPs that are promising for nanobiology and medicine.

  15. An electrochemical study on the positive electrode side of the zinc–cerium hybrid redox flow battery

    International Nuclear Information System (INIS)

    Nikiforidis, Georgios; Berlouis, Léonard; Hall, David; Hodgson, David

    2014-01-01

    Highlights: •Elevated temperatures favoured the Ce 3+/4+ reaction on the Pt, Pt–Ir and carbon substrates. •j o increased with temperature over the range 25 °C to 60 °C for all substrates. •Non-porous carbon substrates showed higher reversibility on the Ce 3+/4+ reaction. •Surface degradation of the carbon electrodes occurred due to the high positive potentials. •The Pt–Ir coatings gave the largest j o at 60 °C and appear best suited for use as the positive electrode in the Zn–Ce RFB. -- Abstract: In this study, the electrochemical behaviour of the Ce 3+/4+ redox couple in methanesulfonic acid medium on various electrode substrates was investigated as a function of temperature. Carbon composite electrodes as well as platinum and platinum iridium coated electrodes were studied for their suitability in carrying out the Ce 3+/4+ redox reaction. Cyclic voltammetry in 0.8 mol dm −3 cerium and 4.5 mol dm −3 methanesulfonic acid solution showed that elevated temperatures favoured the Ce 3+ /Ce 4+ reaction on the various platinum and platinum–iridium coated substrates as well as on carbon composite surfaces. The latter electrodes showed better kinetics than the metal coatings but deteriorated badly under the high positive potentials required for the cerium reaction. The exchange current density (j o ), obtained through Tafel extrapolation, polarisation resistance and electrochemical impedance spectroscopy measurements, increased with temperature over the range 25 °C to 60 °C. The Pt–Ir coatings gave the largest j o at 60 °C and appear best suited for use as the positive electrode in the Zn–Ce redox flow battery

  16. Electronic state of cerium-based catalysts studied by spectroscopic methods (XPS, XAS)

    International Nuclear Information System (INIS)

    Le Normand, F.; Bernhardt, P.; Hilaire, L.; Kili, K.; Maire, G.; Krill, G.

    1987-01-01

    X-ray Photoelectron Spectroscopy (XPS) of the 3d core level of cerium and X-ray Absorption Spectroscopy (XAS) of the L III absorption edge of cerium have been used to study Pd/CeO 2 , Pd-Ce/γAl 2 O 3 and Ce/γAl 2 O 3 catalysts. The oxidation state of cerium was found to decrease with decreasing amounts of cerium on the surface. It was quite close to III for very low contents of cerium (2-3%). For higher cerium contents the oxidation state was nearer to IV but differences between the two methods were found, owing to the fact that XAS is a volume sensitive probe. The oxidation state of cerium was also lower for Pd-Ce/γAl 2 O 3 than for Ce/γAl 2 O 3 , suggesting the formation of Ce III OCl, chlorine coming from the precursor salt of palladium. 15 refs.; 5 figs.; 1 table

  17. REDOX BEHAVIOR AND DIFFUSIVITY OF ANTIMONY AND CERIUM ION IN ALKALI ALKALINE EARTH SILICATE GLASS MELTS

    Directory of Open Access Journals (Sweden)

    K. D. Kim

    2010-03-01

    Full Text Available Redox behavior and diffusivity of antimony and cerium ion in alkali alkaline earth silicate CRT (Cathode Ray Tube model glass melts were studied by means of square wave voltammetry under the frequency range of 5-1000 Hz and in the temperature range of 800-1400°C. According to voltammogram, peaks due to Sb³⁺/Sb⁰ were positioned in the negative potential region while peaks due to Sb⁵⁺/Sb³⁺ and Ce⁴⁺/Ce³⁺ were found in the positive potential region. By using some equations, correlation for peak potential versus temperature and peak current versus reciprocal frequency was examined, respectively. Their correlation showed a linear relation in the applied temperature and frequency range. Based on the linear relationship, thermodynamic and kinetic properties for each redox reaction were suggested.

  18. Electrolytic technique for the chemical decontamination process with sulfuric acid-cerium (IV) for decommissioning

    International Nuclear Information System (INIS)

    Wei, Tsong-Yang; Hsieh, Jung-Chun.

    1992-01-01

    An electrolyzer with an ion-exchange membrane as the separator has been used to study the electrolytic redox reaction of Ce 4+ / Ce 3+ in sulfuric acid solution, which is a reagent for predismantling system decontamination. Influencing factors such as current density, cerium concentration, acidity, electrolyte flow rate, membrane type and electrode material were studied experimentally. The results indicate that the redox can be achieved with high conversion even as the cerium concentration is below 0.005 M. However, the current efficiency strongly depends on the cerium concentration. In addition, the acid content and the electrolyte flow rate show little influence on the redox reaction. Both cation and anion membrane are feasible for this process. Therefore, the operation conditions are widely applicable. Moreover, two different electrode materials, platinized titanium meshes and graphite, were used. The results show that the platinized titanium meshes is preferable to the graphite for higher current efficiency. (author)

  19. Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

    Energy Technology Data Exchange (ETDEWEB)

    Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Marry K.; Tyliszczak, T.; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

    2015-09-01

    Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells.

  20. A phosphate-dependent shift in redox state of cerium oxide nanoparticles and its effects on catalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Sanjay; Dosani, Talib; Karakoti, Ajay S.; Kumar, Amit; Seal, Sudipta; Self, William

    2011-10-01

    Cerium oxide nanoparticles (CeNPs) have shown promise as catalytic antioxidants in cell culture and animal models as both superoxide dismutase and catalase mimetics. The reactivity of the cerium (Ce) atoms at the surface of its oxide particle is critical to such therapeutic properties, yet little is known about the potential for a protein or small molecule corona to form on these materials in vivo. Moreover Ce atoms in these active sites have the potential to interact with small molecule anions, peptides, or sugars when administered in culture or animal models. Several nanomaterials have been shown to alter or aggregate under these conditions, rendering them less useful for biomedical applications. In this work we have studied the change in catalytic properties of CeNPs when exposed to various biologically relevant conditions in vitro. We have found that CeNPs are resistant to broad changes in pH and also not altered by incubation in cell culture medium. However to our surprise phosphate anions significantly altered the characteristics of these nanomaterials and shifted the catalytic behavior due to the binding of phosphate anions to cerium. Given the abundance of phosphate in biological systems in an inorganic form, it is likely that the action of CeNPs as a catalyst may be strongly influenced by the local concentration of phosphate in the cells and/or tissues in which it has been introduced.

  1. Determination of cerium

    International Nuclear Information System (INIS)

    Stepin, V.V.; Kurbatova, V.I.; Fedorova, N.D.

    1980-01-01

    Techniques of cerium determination in steels and alloys are developed. Amperometric method of determination which is based on Ce(4) titration by a solution of double salt of sulfuric Fe(2) and ammonium when cerium amount exceeds 0.01% is suggested. Cerium is oxidated to tetravalent state by KMnO 4 . The elements interfering with the determination (Cr, Ni etc.) are separated by means of deposition. When cerium content exceeds 0.005% in steels and alloys the determination is carried out using photometric method with arsenazo 3 in hydrochloric medium (pH 1.8-2.3). Optimum concentration is 5-50 μg [ru

  2. Fundamental aspects of regenerative cerium oxide nanoparticles and their applications in nanobiotechnology

    Science.gov (United States)

    Patil, Swanand D.

    nanoparticles reduced the cellular damages to the normal breast epithelial cell line (CRL 8798) induced by X-rays and to the Keratinocyte cell line induced by UV irradiation. Cerium oxide nanoparticles were also found to be neuroprotective to adult rat spinal cord and retinal neurons. We propose that cerium oxide nanoparticles act as free radical scavenger (via redox reactions on its surface) to decrease the ROS induced cellular damages. Additionally, UV-visible spectroscopic studies indicated that cerium oxide nanoparticles possess auto-regenerative property by switching its oxidation state between Ce3+ and Ce4+. The auto-regenerative antioxidant property of these nanoparticles appears to be a key component in all the biological applications discussed in the present study.

  3. Development of Models to Predict the Redox State of Nuclear Waste Containment Glass

    Energy Technology Data Exchange (ETDEWEB)

    Pinet, O.; Guirat, R.; Advocat, T. [Commissariat a l' Energie Atomique (CEA), Departement de Traitement et de Conditionnement des Dechets, Marcoule, BP 71171, 30207 Bagnols-sur-Ceze Cedex (France); Phalippou, J. [Universite de Montpellier II, Laboratoire des Colloides, Verres et Nanomateriaux, 34095 Montpellier Cedex 5 (France)

    2008-07-01

    Vitrification is one of the recommended immobilization routes for nuclear waste, and is currently implemented at industrial scale in several countries, notably for high-level waste. To optimize nuclear waste vitrification, research is conducted to specify suitable glass formulations and develop more effective processes. This research is based not only on experiments at laboratory or technological scale, but also on computer models. Vitrified nuclear waste often contains several multi-valent species whose oxidation state can impact the properties of the melt and of the final glass; these include iron, cerium, ruthenium, manganese, chromium and nickel. Cea is therefore also developing models to predict the final glass redox state. Given the raw materials and production conditions, the model predicts the oxygen fugacity at equilibrium in the melt. It can also estimate the ratios between the oxidation states of the multi-valent species contained in the molten glass. The oxidizing or reductive nature of the atmosphere above the glass melt is also taken into account. Unlike the models used in the conventional glass industry based on empirical methods with a limited range of application, the models proposed are based on the thermodynamic properties of the redox species contained in the waste vitrification feed stream. The thermodynamic data on which the model is based concern the relationship between the glass redox state and the oxygen fugacity in the molten glass. The model predictions were compared with oxygen fugacity measurements for some fifty glasses. The experiments carried out at laboratory and industrial scale with a cold crucible melter. The oxygen fugacity of the glass samples was measured by electrochemical methods and compared with the predicted value. The differences between the predicted and measured oxygen fugacity values were generally less than 0.5 Log unit. (authors)

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

    Science.gov (United States)

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

    2015-02-13

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

  5. Contribution to research on the metabolism of fission product. Studies on the physico-chemical state and the metabolic fate of radio-cerium solution

    International Nuclear Information System (INIS)

    Aeberhardt, A.

    1961-01-01

    This paper describes a study of the physico-chemical state of radio-cerium in dilute solutions on the tracer scale, as a function of the pH of the solution. The way in which this radioelement is transported in the blood is studied in vitro and in vivo, with reference to the ionic or colloidal state of the radio-cerium used. The distribution of cerium amongst the various components of the blood is studied by a new method of blood fractionation and by paper electrophoresis. Evidence of a cerium globulin connection is shown in the case of ionic cerium. A study of the initial distribution of radio-cerium in rats, after intravenous administration of ionic or colloidal solutions, shows considerable differences according to the physico-chemical state of the cerium injected. (author) [fr

  6. Spectrophotometric determination of cerium with methylthymol blue in the presence of oxalate and cyanide as masking agents

    Energy Technology Data Exchange (ETDEWEB)

    Cabrera-Martin, A; Izquierdo-Hornillos, R; Quejido-Cabezas, A J; Peral-Fernandez, J L [Universidad Complutense de Madrid (Spain). Facultad de Ciencias Quimicas

    1983-04-01

    The spectrophotometric determination of cerium can be carried out by several methods, which involve either the formation of complexes of cerium(III) and cerium(IV) or the oxidation of suitable reagents by cerium(IV) and further measuring the intensity of the colour of the oxidised matter. The latter methods show a lack of selectivity and low sensitivity owing to the nature of the redox reaction. The methods that involve the formation of complexes have also been shown to have low selectivity and sensitivity. However, the most useful methods are those based on the complexes of cerium(III) with Xylenol Orange and Methylthymol Blue (MTB), but they are affected by many interferences. In this work the reaction of cerium(III) with MTB in the presence of oxalate and cyanide ions was studied at pH 10.2, which improves the sensitivity and the selectivity of the determination of cerium.

  7. Implementation of a complex multi-phase equation of state for cerium and its correlation with experiment

    Energy Technology Data Exchange (ETDEWEB)

    Cherne, Frank J [Los Alamos National Laboratory; Jensen, Brian J [Los Alamos National Laboratory; Elkin, Vyacheslav M [VNIITF

    2009-01-01

    The complexity of cerium combined with its interesting material properties makes it a desirable material to examine dynamically. Characteristics such as the softening of the material before the phase change, low pressure solid-solid phase change, predicted low pressure melt boundary, and the solid-solid critical point add complexity to the construction of its equation of state. Currently, we are incorporating a feedback loop between a theoretical understanding of the material and an experimental understanding. Using a model equation of state for cerium we compare calculated wave profiles with experimental wave profiles for a number of front surface impact (cerium impacting a plated window) experiments. Using the calculated release isentrope we predict the temperature of the observed rarefaction shock. These experiments showed that the release state occurs at different magnitudes, thus allowing us to infer where dynamic {gamma} - {alpha} phase boundary is.

  8. REDOX IMAGING OF THE p53-DEPENDENT MITOCHONDRIAL REDOX STATE IN COLON CANCER EX VIVO

    Science.gov (United States)

    XU, HE N.; FENG, MIN; MOON, LILY; DOLLOFF, NATHAN; EL-DEIRY, WAFIK; LI, LIN Z.

    2015-01-01

    The mitochondrial redox state and its heterogeneity of colon cancer at tissue level have not been previously reported. Nor has how p53 regulates mitochondrial respiration been measured at (deep) tissue level, presumably due to the unavailability of the technology that has sufficient spatial resolution and tissue penetration depth. Our prior work demonstrated that the mitochondrial redox state and its intratumor heterogeneity is associated with cancer aggressiveness in human melanoma and breast cancer in mouse models, with the more metastatic tumors exhibiting localized regions of more oxidized redox state. Using the Chance redox scanner with an in-plane spatial resolution of 200 μm, we imaged the mitochondrial redox state of the wild-type p53 colon tumors (HCT116 p53 wt) and the p53-deleted colon tumors (HCT116 p53−/−) by collecting the fluorescence signals of nicotinamide adenine dinucleotide (NADH) and oxidized flavoproteins [Fp, including flavin adenine dinucleotide (FAD)] from the mouse xenografts snap-frozen at low temperature. Our results show that: (1) both tumor lines have significant degree of intratumor heterogeneity of the redox state, typically exhibiting a distinct bi-modal distribution that either correlates with the spatial core–rim pattern or the “hot/cold” oxidation-reduction patches; (2) the p53−/− group is significantly more heterogeneous in the mitochondrial redox state and has a more oxidized tumor core compared to the p53 wt group when the tumor sizes of the two groups are matched; (3) the tumor size dependence of the redox indices (such as Fp and Fp redox ratio) is significant in the p53−/− group with the larger ones being more oxidized and more heterogeneous in their redox state, particularly more oxidized in the tumor central regions; (4) the H&E staining images of tumor sections grossly correlate with the redox images. The present work is the first to reveal at the submillimeter scale the intratumor heterogeneity pattern

  9. In-situ irradiation of cerium precursors in TEM to study nanocrystal formation

    Science.gov (United States)

    Asghar, Muhammad Sajid Ali; Sabri, Mohammed Mohammed; Tian, Zijian; Möbus, Günter

    2017-09-01

    Three of the most commonly used precursor chemicals for wet-chemical nano-ceria synthesis are examined by means of direct dry electron irradiation in TEM. Transformation reactions of micron-size carbonate, chloride, and nitrate grains into nanocrystallites (internal or external) are recorded in situ. Progress of possible redox-changes of cerium is tracked by EELS. We find a straight local oxidation reaction for carbonates, but external nanorod formation by condensation in the case of chlorides, while nitrates show a multi-stage complex redox behaviour.

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

    Science.gov (United States)

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

    2015-12-21

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

  11. Effect of adduct formation on valent state of cerium in its ν-diketonates

    International Nuclear Information System (INIS)

    Spitsyn, V.I.; Martynenko, L.I.; Pechurova, N.I.; Snezhko, N.I.; Murav'eva, I.A.; Anufrieva, S.I.

    1982-01-01

    Physicochemical investigation of the system cerium (III, IV)-ν-diketone-additional ligand shows that ν-diketonate ability to adduct formation decreases in the series tenoyltrifluoro-acetonate > acetylacetonate > dibenzoylmethanate > benzoylmethanate. Adduct formation of the cerium (III, IV) ν-diketonates stabilizes cerium in trivalent condition, while oxidation degree 4+ is stable in tetrakis-ν-diketonates. The additional ligands are arranged in the series: tributhylphosphate < trioctyl-phosphineoxide < triphenylphosphineoxide < α, α'-dipyridyl < o-phenanthroline by the effect on cerium (III) stabilization in its ν-diketonates

  12. Effect of adduct formation on valent state of cerium in its. beta. -diketonates

    Energy Technology Data Exchange (ETDEWEB)

    Spitsyn, V.I.; Martynenko, L.I.; Pechurova, N.I.; Snezhko, N.I.; Murav' eva, I.A.; Anufrieva, S.I. (Moskovskij Gosudarstvennyj Univ. (USSR))

    1982-04-01

    Physicochemical investigation of the system cerium (III, IV)-..beta..-diketone-additional ligand shows that ..beta..-diketonate ability to adduct formation decreases in the series tenoyltrifluoro-acetonate > acetylacetonate > dibenzoylmethanate > benzoylmethanate. Adduct formation of the cerium (III, IV) ..beta..-diketonates stabilizes cerium in trivalent condition, while oxidation degree 4+ is stable in tetrakis-..beta..-diketonates. The additional ligands are arranged in the series: tributhylphosphate < trioctyl-phosphineoxide < triphenylphosphineoxide < ..cap alpha.., ..cap alpha..'-dipyridyl < o-phenanthroline by the effect on cerium (III) stabilization in its ..beta..-diketonates.

  13. Thiol/disulfide redox states in signaling and sensing

    Science.gov (United States)

    Go, Young-Mi; Jones, Dean P.

    2015-01-01

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

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

    Science.gov (United States)

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

    2015-05-05

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

  15. Citric complexes of trivalent cerium and berkelium

    International Nuclear Information System (INIS)

    Boulhassa, S.

    1977-01-01

    The extraction by thenoyltrifluoroacetone (TTA) in benzene of trivalent cerium, berkelium and californium, at the indicator scale, hydrolysis and complexation by citric acid of these cations are studied. The radionuclides used were 144 Ce, 249 Bk and 249 Cf respectively γ, β and α emitters. The solvent extraction technique of the elements by TTA in benzene from a perchloric medium at the ionic stength 0.1 was employed. The distribution coefficients D were measured by the γ, β or α radiometry. Cerium and berkelium, which have a comparable redox behavior, show in solution a relatively stable valency IV. Therefore the study by solvent extraction of their trivalent form required the standing up of complete reducing conditions of these elements and their stabilization in solution at the valency III. The thermodynamic data obtained for berkelium and californium contribute to understand the chemistry of these elements and permit to complete the third 'tetrad branch' of 5f elements from Cm 3+ to Es 3+ . This tetrad effect is a manifestation of thermodynamic consequence of the 'nephelauxetic effect'. As for Ce(III), the data confirm the pronounced acid property and may be show no neglected ligand effect for f 1 configuration [fr

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

    Science.gov (United States)

    Jones, Dean P

    2006-01-01

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

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

    Science.gov (United States)

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

    2016-08-01

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

  18. The use of cerium(IV) phosphate for the gravimetric determination and separation of cerium

    International Nuclear Information System (INIS)

    Masin, V.; Dolezal, J.

    1978-01-01

    A method for the gravimetric determination of cerium as Ce 3 (PO 4 ) 4 is described. Cerium can be separated from many metals in this form, as well as from permanganate and dichromate; the cerium separated can then be titrated with iron(II) solution. The method was verified for the determination of cerium in a rare earth concentrate. (Auth.)

  19. Berkelium (4) and cerium (4) extraction with tertiary amines

    International Nuclear Information System (INIS)

    Milyukova, M.S.; Malikov, D.A.; Myasoedov, B.V.

    1978-01-01

    Oxidation of indicator quantities of berkelium and cerium by a mixture of silver nitrate and ammonium persulfate in the solutions of nitric and sulfuric acid has been examined. The stability of the elements in a tetravalent state and their extraction by the solutions of ternary amines have been investigated. It has been established that berkelium and cerium oxidation under these conditions occurs under the effect of ions of divalent silver which is formed owing to oxidation of monovalent silver by peroxide sulfate ions. The following supposition has been put forward: a difference in the behaviour of tetravalent berkelium and cerium during their extraction by ternary amines is explained by their different stability in this state, but not by the formation of complex compounds with nitrate ions

  20. Reaction chemistry of cerium

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-01-01

    It is truly ironic that a synthetic organic chemist likely has far greater knowledge of the reaction chemistry of cerium(IV) than an inorganic colleague. Cerium(IV) reagents have long since been employed as oxidants in effecting a wide variety of organic transformations. Conversely, prior to the late 1980s, the number of well characterized cerium(IV) complexes did not extend past a handful of known species. Though in many other areas, interest in the molecular chemistry of the 4f-elements has undergone an explosive growth over the last twenty years, the chemistry of cerium(IV) has for the most part been overlooked. This report describes reactions of cerium complexes and structure.

  1. The effect of cerium valence states at cerium oxide nanoparticle surfaces on cell proliferation

    KAUST Repository

    Naganuma, Tamaki

    2014-05-01

    Understanding and controlling cell proliferation on biomaterial surfaces is critical for scaffold/artificial-niche design in tissue engineering. The mechanism by which underlying integrin ligates with functionalized biomaterials to induce cell proliferation is still not completely understood. In this study, poly-l-lactide (PL) scaffold surfaces were functionalized using layers of cerium oxide nanoparticles (CNPs), which have recently attracted attention for use in therapeutic application due to their catalytic ability of Ce4+ and Ce3+ sites. To isolate the influence of Ce valance states of CNPs on cell proliferation, human mesenchymal stem cells (hMSCs) and osteoblast-like cells (MG63) were cultured on the PL/CNP surfaces with dominant Ce4+ and Ce3+ regions. Despite cell type (hMSCs and MG63 cells), different surface features of Ce4+ and Ce3+ regions clearly promoted and inhibited cell spreading, migration and adhesion behavior, resulting in rapid and slow cell proliferation, respectively. Cell proliferation results of various modified CNPs with different surface charge and hydrophobicity/hydrophilicity, indicate that Ce valence states closely correlated with the specific cell morphologies and cell-material interactions that trigger cell proliferation. This finding suggests that the cell-material interactions, which influence cell proliferation, may be controlled by introduction of metal elements with different valence states onto the biomaterial surface. © 2014 Elsevier Ltd.

  2. Proteostasis and REDOX state in the heart

    Science.gov (United States)

    Christians, Elisabeth S.

    2012-01-01

    Force-generating contractile cells of the myocardium must achieve and maintain their primary function as an efficient mechanical pump over the life span of the organism. Because only half of the cardiomyocytes can be replaced during the entire human life span, the maintenance strategy elicited by cardiac cells relies on uninterrupted renewal of their components, including proteins whose specialized functions constitute this complex and sophisticated contractile apparatus. Thus cardiac proteins are continuously synthesized and degraded to ensure proteome homeostasis, also termed “proteostasis.” Once synthesized, proteins undergo additional folding, posttranslational modifications, and trafficking and/or become involved in protein-protein or protein-DNA interactions to exert their functions. This includes key transient interactions of cardiac proteins with molecular chaperones, which assist with quality control at multiple levels to prevent misfolding or to facilitate degradation. Importantly, cardiac proteome maintenance depends on the cellular environment and, in particular, the reduction-oxidation (REDOX) state, which is significantly different among cardiac organelles (e.g., mitochondria and endoplasmic reticulum). Taking into account the high metabolic activity for oxygen consumption and ATP production by mitochondria, it is a challenge for cardiac cells to maintain the REDOX state while preventing either excessive oxidative or reductive stress. A perturbed REDOX environment can affect protein handling and conformation (e.g., disulfide bonds), disrupt key structure-function relationships, and trigger a pathogenic cascade of protein aggregation, decreased cell survival, and increased organ dysfunction. This review covers current knowledge regarding the general domain of REDOX state and protein folding, specifically in cardiomyocytes under normal-healthy conditions and during disease states associated with morbidity and mortality in humans. PMID:22003057

  3. Bordoni relaxation and magnetic transformation in cerium and cerium-lanthanum alloys

    Energy Technology Data Exchange (ETDEWEB)

    Postnikov, V S; Polner, G L; Sharshakov, I M

    1975-11-01

    The internal friction in pure cerium and cerium-base alloys with 2.5 and 12 weight percent of lanthanum added at temperature ranging from 4.2 deg up to 77/sup 0/K is described. Amplitude-independent internal friction has been measured with an inverse torsion pendulum with a specimen oscillation frequency of 1-30 hz in vacuum not less than 1.10/sup -5/ torr. A temperature of the specimen has been determined with a capacitance-type sensor and a gas gage. A curve showing the dependence of internal friction upon a temperature of pure cerium has two distinct peaks; the first at 12.5/sup 0/K, the second at 45/sup 0/K. The 12.5/sup 0/K peak is accounted for by a transition of antiferromagnetic ..beta..-Ce into a paramagnetic state. The 45/sup 0/K peak is a Bordoni maximum. The paper describes an influence of additions, specimen oscillation frequency variations, deformation and annealing upon the peak behavor. Added lanthanum reduces not only a peak temperature but a height as well. Studies of the 45/sup 0/K peak have shown that its temperature location depends upon the specimen oscillation frequency. As the frequency increases the peak tends to a range of high temperatures which confirms its relaxation nature.

  4. Cerium oxalate precipitation

    International Nuclear Information System (INIS)

    Chang, T.P.

    1987-02-01

    Cerium, a nonradioactive, common stand-in for plutonium in development work, has been used to simulate several plutonium precipitation processes at the Savannah River Laboratory. There are similarities between the plutonium trifluoride and the cerium oxalate precipitations in particle size and extent of plating, but not particle morphology. The equilibrium solubility, precipitation kinetics, particle size, extent of plating, and dissolution characteristics of cerium oxalate have been investigated. Interpretations of particle size and plating based on precipitation kinetics (i.e., nucleation and crystal growth) are presented. 16 refs., 7 figs., 6 tabs

  5. Preparation of high-purity cerium nitrate

    International Nuclear Information System (INIS)

    Avila, Daniela Moraes; Silva Queiroz, Carlos Alberto da; Santos Mucillo, Eliana Navarro dos

    1995-01-01

    The preparation of high-purity cerium nitrate has been carried out Cerium oxide has been prepared by fractioned precipitation and ionic exchange techniques, using a concentrate with approximately 85% of cerium oxide from NUCLEMON as raw material. Five sequential ion-exchange columns with a retention capacity of 170 g each have been used. The ethylenediamine-tetraacetic acid (EDTA) was used as eluent. The cerium content has been determined by gravimetry and iodometry techniques. The resulting cerium oxide has a purity > 99%. This material was transformed in cerium nitrate to be used as precursor for the preparation of Zirconia-ceria ceramics by the coprecipitation technique. (author)

  6. Unusual kinetics of poly(ethylene glycol) oxidation with cerium(IV) ions in sulfuric acid medium and implications for copolymer synthesis.

    Science.gov (United States)

    Szymański, Jan K; Temprano-Coleto, Fernando; Pérez-Mercader, Juan

    2015-03-14

    The cerium(IV)-alcohol couple in an acidic medium is an example of a redox system capable of initiating free radical polymerization. When the alcohol has a polymeric nature, the outcome of such a process is a block copolymer, a member of a class of compounds possessing many useful properties. The most common polymer with a terminal -OH group is poly(ethylene glycol) (PEG); however, the detailed mechanism of its reaction with cerium(IV) remains underexplored. In this paper, we report our findings for this reaction based on spectrophotometric measurements and kinetic modeling. We find that both the reaction order and the net rate constant for the oxidation process depend strongly on the nature of the acidic medium used. In order to account for the experimental observations, we postulate that protonation of PEG decreases its affinity for some of the cerium(IV)-sulfate complexes formed in the system.

  7. Potential Role of Amino Acid/Protein Nutrition and Exercise in Serum Albumin Redox State

    Directory of Open Access Journals (Sweden)

    Yasuaki Wada

    2017-12-01

    Full Text Available Albumin is the major protein in the serum of mammals. It is synthesized exclusively in the liver, before being secreted into the circulation. Similar to skeletal muscle protein, albumin synthesis is stimulated by dietary amino acids and proteins as well as exercise. Albumin has three isoforms based on the redox states of the free cysteine residue at position 34. The redox state of serum albumin has long been extensively investigated in terms of oxidative stress-related chronic diseases, with the redox state of serum albumin having been regarded as a marker of systemic oxidative stress. However, according to recent animal studies, the redox state of serum albumin is modulated by albumin turnover and may also reflect amino acid/protein nutritional status. Furthermore, as the redox state of serum albumin is modulated by exercise training, measuring the pre- and post-exercise redox states of serum albumin in athletes may be useful in assessing amino acid/protein nutritional status and exercise-induced oxidative stress, which are closely associated with skeletal muscle adaptive responses. This article extensively reviews serum albumin and the redox state of albumin in the context of amino acid/protein nutritional status and exercise training.

  8. Glutathione redox potential in the mitochondrial intermembrane space is linked to the cytosol and impacts the Mia40 redox state

    Science.gov (United States)

    Kojer, Kerstin; Bien, Melanie; Gangel, Heike; Morgan, Bruce; Dick, Tobias P; Riemer, Jan

    2012-01-01

    Glutathione is an important mediator and regulator of cellular redox processes. Detailed knowledge of local glutathione redox potential (EGSH) dynamics is critical to understand the network of redox processes and their influence on cellular function. Using dynamic oxidant recovery assays together with EGSH-specific fluorescent reporters, we investigate the glutathione pools of the cytosol, mitochondrial matrix and intermembrane space (IMS). We demonstrate that the glutathione pools of IMS and cytosol are dynamically interconnected via porins. In contrast, no appreciable communication was observed between the glutathione pools of the IMS and matrix. By modulating redox pathways in the cytosol and IMS, we find that the cytosolic glutathione reductase system is the major determinant of EGSH in the IMS, thus explaining a steady-state EGSH in the IMS which is similar to the cytosol. Moreover, we show that the local EGSH contributes to the partially reduced redox state of the IMS oxidoreductase Mia40 in vivo. Taken together, we provide a comprehensive mechanistic picture of the IMS redox milieu and define the redox influences on Mia40 in living cells. PMID:22705944

  9. Uptake and accumulation of bulk and nanosized cerium oxide particles and ionic cerium by radish (Raphanus sativus L.).

    Science.gov (United States)

    Zhang, Weilan; Ebbs, Stephen D; Musante, Craig; White, Jason C; Gao, Cunmei; Ma, Xingmao

    2015-01-21

    The potential toxicity and accumulation of engineered nanomaterials (ENMs) in agricultural crops has become an area of great concern and intense investigation. Interestingly, although below-ground vegetables are most likely to accumulate the highest concentrations of ENMs, little work has been done investigating the potential uptake and accumulation of ENMs for this plant group. The overall objective of this study was to evaluate how different forms of cerium (bulk cerium oxide, cerium oxide nanoparticles, and the cerium ion) affected the growth of radish (Raphanus sativus L.) and accumulation of cerium in radish tissues. Ionic cerium (Ce(3+)) had a negative effect on radish growth at 10 mg CeCl3/L, whereas bulk cerium oxide (CeO2) enhanced plant biomass at the same concentration. Treatment with 10 mg/L cerium oxide nanoparticles (CeO2 NPs) had no significant effect on radish growth. Exposure to all forms of cerium resulted in the accumulation of this element in radish tissues, including the edible storage root. However, the accumulation patterns and their effect on plant growth and physiological processes varied with the characteristics of cerium. This study provides a critical frame of reference on the effects of CeO2 NPs versus their bulk and ionic counterparts on radish growth.

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

    Directory of Open Access Journals (Sweden)

    He N. Xu

    2014-03-01

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

  11. A cerium(IV)-carbon multiple bond

    Energy Technology Data Exchange (ETDEWEB)

    Gregson, Matthew; Lu, Erli; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [Nottingham Univ. (United Kingdom). School of Chemistry

    2013-12-02

    Straightforward access to a cerium(IV)-carbene complex was provided by one-electron oxidation of an anionic ''ate'' cerium(III)-carbene precursor, thereby avoiding decomposition reactions that plague oxidations of neutral cerium(III) compounds. The cerium(IV)-carbene complex is the first lanthanide(IV)-element multiple bond and involves a twofold bonding interaction of two electron pairs between cerium and carbon. [German] Auf direktem Wege zu einem Cer(IV)-Carbenkomplex gelangt man durch die Einelektronenoxidation einer anionischen Carben-Cerat(III)-Vorstufe. So werden Zersetzungsprozesse vermieden, die die Oxidation neutraler Cer(III)-Verbindungen erschweren. Der Cer(IV)-Carbenkomplex enthaelt die erste Lanthanoid(IV)-Element-Mehrfachbindung; dabei binden Cer und Kohlenstoff ueber zwei Elektronenpaare.

  12. Calcination of the cerium concentrate to be cerium oxide

    International Nuclear Information System (INIS)

    Suyanti; MV Purwani

    2016-01-01

    Calcination of the cerium concentrate to be cerium oxide has done. The cerium concentrate were obtained from the Ce making process wear KBrO_3 and without using KBrO_3. The calcination were done with a variation of time 1, 2, 3 and 4 hours with the temperature variations of 700, 800 and 900°C. The easiest calcination of Ce concentrates to be CeO_2 containing majority of Ce(OH)_4 and contains least impurities as Th(OH)_4, (NH_4)_2Y(NO_3), H_4N_5O_1_2La, H_1_2N_3NdO_1_5 and N_3O_9Sm. On the calcination of Ce concentrates process results without using KBrO_3 1, the calcination temperature 900°C was obtained CeO_2 content of 73.53% for calcination time of 4 hours, has little difference when compared with the predictions and calculation result of complete calcination was equal 73.84%. (author)

  13. Cerium and jojoba in engines?; Cerium et jojoba dans les moteurs?

    Energy Technology Data Exchange (ETDEWEB)

    Massy-Delhotel, E.

    1996-10-01

    The Belgium company CreaTel proposes a new system, called Forac, which can lead to a 10% reduction of fuel consumption in thermal engines together with a quasi-complete reduction of CO, HC, NOx pollutants and CO{sub 2} particulates emission. The system comprises a steam production device and an admission pipe with a cerium alloy whorl inside. The steam produced is mixed with the admission air and tears cerium particles from the inside of the admission pipe to the combustion chamber. The cerium particles act as a catalyst which favours the complete combustion of the fuel. The same company proposes also lubricant additives made from liquid jojoba wax which allow the reduction of pollutant emissions, fuel consumption and noise emissions of diesel engines. (J.S.)

  14. Cerium and rare earth separation process

    International Nuclear Information System (INIS)

    Martin, M.; Rollat, M.

    1986-01-01

    An aqueous solution containing cerium III and rare earths is oxidized in the anodic compartment of an electrolytic cell, cerium IV is extracted by an organic solvent, the organic phase containing Ce IV is reduced in the catodic compartment of the same electrolytic cell and cerium III is extracted in a nitric aqueous phase [fr

  15. Multifunctional cerium-based nanomaterials and methods for producing the same

    Science.gov (United States)

    O'Keefe, Matthew J.; Castano Londono, Carlos E.; Fahrenholtz, William G.

    2018-01-09

    Embodiments relate to a cerium-containing nano-coating composition, the composition including an amorphous matrix including one or more of cerium oxide, cerium hydroxide, and cerium phosphate; and crystalline regions including one or more of crystalline cerium oxide, crystalline cerium hydroxide, and crystalline cerium phosphate. The diameter of each crystalline region is less than about 50 nanometers.

  16. CHOP THERAPY INDUCED MITOCHONDRIAL REDOX STATE ALTERATION IN NON-HODGKIN'S LYMPHOMA XENOGRAFTS

    Directory of Open Access Journals (Sweden)

    H. N. XU

    2013-04-01

    Full Text Available We are interested in investigating whether cancer therapy may alter the mitochondrial redox state in cancer cells to inhibit their growth and survival. The redox state can be imaged by the redox scanner that collects the fluorescence signals from both the oxidized-flavoproteins (Fp and the reduced form of nicotinamide adenine dinucleotide (NADH in snap-frozen tissues and has been previously employed to study tumor aggressiveness and treatment responses. Here, with the redox scanner we investigated the effects of chemotherapy on mouse xenografts of a human diffuse large B-cell lymphoma cell line (DLCL2. The mice were treated with CHOP therapy, i.e., cyclophosphamide (C + hydroxydoxorubicin (H + Oncovin (O + prednisone (P with CHO administration on day 1 and prednisone administration on days 1–5. The Fp content of the treated group was significantly decreased (p = 0.033 on day 5, and the mitochondrial redox state of the treated group was slightly more reduced than that of the control group (p = 0.048. The decrease of the Fp heterogeneity (measured by the mean standard deviation had a border-line statistical significance (p = 0.071. The result suggests that the mitochondrial metabolism of lymphoma cells was slightly suppressed and the lymphomas became less aggressive after the CHOP therapy.

  17. Electrochemical determination of thioredoxin redox states

    Czech Academy of Sciences Publication Activity Database

    Dorčák, Vlastimil; Paleček, Emil

    2009-01-01

    Roč. 81, č. 4 (2009), s. 1543-1548 ISSN 0003-2700 R&D Projects: GA AV ČR(CZ) KAN400310651; GA ČR(CZ) GA301/07/0490; GA MŠk(CZ) LC06035 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : thioredoxin redox states * constant current chronopotentiometric stripping * carbon and mercury electrodes Subject RIV: BO - Biophysics Impact factor: 5.214, year: 2009

  18. Cerium; crystal structure and position in the periodic table.

    Science.gov (United States)

    Johansson, Börje; Luo, Wei; Li, Sa; Ahuja, Rajeev

    2014-09-17

    The properties of the cerium metal have intrigued physicists and chemists for many decades. In particular a lot of attention has been directed towards its high pressure behavior, where an isostructural volume collapse (γ phase → α phase) has been observed. Two main models of the electronic aspect of this transformation have been proposed; one where the 4f electron undergoes a change from being localized into an itinerant metallic state, and one where the focus is on the interaction between the 4f electron and the conduction electrons, often referred to as the Kondo volume collapse model. However, over the years it has been repeatedly questioned whether the cerium collapse really is isostructural. Most recently, detailed experiments have been able to remove this worrisome uncertainty. Therefore the isostructural aspect of the α-γ transition has now to be seriously addressed in the theoretical modeling, something which has been very much neglected. A study of this fundamental characteristic of the cerium volume collapse is made in present paper and we show that the localized [rlhar2 ] delocalized 4f electron picture provides an adequate description of this unique behavior. This agreement makes it possible to suggest that an appropriate crossroad position for cerium in The Periodic Table.

  19. Enhancing the Electronic Conductivity of Vanadium-tellurite Glasses by Tuning the Redox State

    DEFF Research Database (Denmark)

    Kjeldsen, Jonas; Yue, Yuanzheng

    Transition metal oxides are used in a variety of electronic purposes, e.g., vanadium tellurite as cathode material in high-power demanding batteries. By tuning the redox state of vanadium, it is possible to achieve a lower internal resistance within the entire battery unit, thus a higher capacity....... In this work we vary the redox state of a given vanadium tellurite system by performing post heat-treatment in controlled atmosphere. This process is in theory not limited only to varying electronic conductivity, but also varying the glass structure, and hence, changing properties of the glasses, e.g, thermal...... and mechanical properties. Finally we give insight into the relation between the redox state and electronic conductivity....

  20. Some Environmentally Relevant Reactions of Cerium Oxide

    Directory of Open Access Journals (Sweden)

    Janoš Pavel

    2014-12-01

    Full Text Available Reactive forms of cerium oxide were prepared by a thermal decomposition of various precursors, namely carbonates, oxalates and citrates, commercially available nanocrystalline cerium oxide (nanoceria was involved in the study for comparison. Scanning electron microscopy (SEM and x-ray diffraction analysis (XRD were used to examine the morphology and crystallinity of the samples, respectively, whereas the Brunauer-Emmett-Teller (BET method of nitrogen adsorption was used to determine surface areas. Interactions of cerium oxide with some phosphorus-containing compounds were investigated. Some of the examined samples, especially those prepared by annealing from carbonate precursors, exhibited an outstanding ability to destroy highly toxic organophosphates, such as pesticides (parathion methyl, or nerve agents (soman, VX. There were identified some relations between the degradation efficiency of cerium oxides and their crystallinity. It was also shown that cerium oxide is able to destroy one of widely used flame retardants - triphenyl phosphate. A phosphatase-mimetic activity of various cerium oxides was examined with the aid of a standardized phosphatase test.

  1. Regulatory redox state in tree seeds

    Directory of Open Access Journals (Sweden)

    Ewelina Ratajczak

    2017-12-01

    Full Text Available Peroxiredoxins (Prx are important regulators of the redox status of tree seeds during maturation and long-term storage. Thioredoxins (Trx are redox transmitters and thereby regulate Prx activity. Current research is focused on the association of Trx with Prx in tree seeds differing in the tolerance to desiccation. The results will allow for better understanding the regulation of the redox status in orthodox, recalcitrant, and intermediate seeds. The findings will also elucidate the role of the redox status during the loss of viability of sensitive seeds during drying and long-term storage.

  2. Local Structure of Cerium in Aluminophosphate and Silicophosphate Glasses

    International Nuclear Information System (INIS)

    Rygel, Jennifer L.; Chen, Yongsheng; Pantano, Carlo G.; Shibata, Tomohiro; Du, Jincheng; Kokou, Leopold; Woodman, Robert; Belcher, James

    2011-01-01

    The local structure of cerium in two systematic compositional series of glasses, nominally CeP 3 O 9 -AlP 3 O 9 and CeP 3 O 9 -SiP 2 O 7 , was interrogated using X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy. XPS revealed that, for glasses melted in air, ≥95% of cerium ions are Ce 3+ . This was independently confirmed using X-ray absorption near edge spectroscopy (XANES). Ce K-edge extended X-ray absorption fine structure (EXAFS) has been used to determine the local structure of Ce 3+ . Near the metaphosphate composition, cerium was found to have an average cerium coordination number of ∼7.0 and an average cerium-oxygen bond length of 2.41 (angstrom). The average cerium coordination number and average cerium-oxygen bond distance were found to increase with decreasing cerium concentration in both compositional series. Rare-earth clustering is suggested based on numerical calculations for glasses containing ≥14 and ≥15 mol% Ce 2 O 3 for the aluminophosphate and silicophosphate series, respectively.

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

    Science.gov (United States)

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

    2015-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Laura Nocito

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

  5. Computational assignment of redox states to Coulomb blockade diamonds.

    Science.gov (United States)

    Olsen, Stine T; Arcisauskaite, Vaida; Hansen, Thorsten; Kongsted, Jacob; Mikkelsen, Kurt V

    2014-09-07

    With the advent of molecular transistors, electrochemistry can now be studied at the single-molecule level. Experimentally, the redox chemistry of the molecule manifests itself as features in the observed Coulomb blockade diamonds. We present a simple theoretical method for explicit construction of the Coulomb blockade diamonds of a molecule. A combined quantum mechanical/molecular mechanical method is invoked to calculate redox energies and polarizabilities of the molecules, including the screening effect of the metal leads. This direct approach circumvents the need for explicit modelling of the gate electrode. From the calculated parameters the Coulomb blockade diamonds are constructed using simple theory. We offer a theoretical tool for assignment of Coulomb blockade diamonds to specific redox states in particular, and a study of chemical details in the diamonds in general. With the ongoing experimental developments in molecular transistor experiments, our tool could find use in molecular electronics, electrochemistry, and electrocatalysis.

  6. Measurement of Redox Potential in Nanoecotoxicological Investigations

    Directory of Open Access Journals (Sweden)

    Ratna Tantra

    2012-01-01

    Full Text Available Redox potential has been identified by the Organisation for Economic Co-operation and Development (OECD as one of the parameters that should be investigated for the testing of manufactured nanomaterials. There is still some ambiguity concerning this parameter, i.e., as to what and how to measure, particularly when in a nanoecotoxicological context. In this study the redox potentials of six nanomaterials (either zinc oxide (ZnO or cerium oxide (CeO2 dispersions were measured using an oxidation-reduction potential (ORP electrode probe. The particles under testing differed in terms of their particle size and dispersion stability in deionised water and in various ecotox media. The ORP values of the various dispersions and how they fluctuate relative to each other are discussed. Results show that the ORP values are mainly governed by the type of liquid media employed, with little contributions from the nanoparticles. Seawater was shown to have reduced the ORP value, which was attributed to an increase in the concentration of reducing agents such as sulphites or the reduction of dissolved oxygen concentration. The lack of redox potential value contribution from the particles themselves is thought to be due to insufficient interaction of the particles at the Pt electrode of the ORP probe.

  7. Measurement of redox potential in nanoecotoxicological investigations.

    Science.gov (United States)

    Tantra, Ratna; Cackett, Alex; Peck, Roger; Gohil, Dipak; Snowden, Jacqueline

    2012-01-01

    Redox potential has been identified by the Organisation for Economic Co-operation and Development (OECD) as one of the parameters that should be investigated for the testing of manufactured nanomaterials. There is still some ambiguity concerning this parameter, i.e., as to what and how to measure, particularly when in a nanoecotoxicological context. In this study the redox potentials of six nanomaterials (either zinc oxide (ZnO) or cerium oxide (CeO(2))) dispersions were measured using an oxidation-reduction potential (ORP) electrode probe. The particles under testing differed in terms of their particle size and dispersion stability in deionised water and in various ecotox media. The ORP values of the various dispersions and how they fluctuate relative to each other are discussed. Results show that the ORP values are mainly governed by the type of liquid media employed, with little contributions from the nanoparticles. Seawater was shown to have reduced the ORP value, which was attributed to an increase in the concentration of reducing agents such as sulphites or the reduction of dissolved oxygen concentration. The lack of redox potential value contribution from the particles themselves is thought to be due to insufficient interaction of the particles at the Pt electrode of the ORP probe.

  8. Study on the uranium-cerium extraction and his application to the treatment of irradiated uranium

    International Nuclear Information System (INIS)

    Lobao, Afonso dos Santos Tome

    1979-01-01

    It was made a study on the behavior of uranium and cerium(IV) extraction, using the latter element as a plutonium simulator in a flowsheet of the treatment of irradiated uranium. Cerium(IV) was used under the same conditions as a plutonium in the Purex process because the admitted similar properties. An experimental work was initiated to determine the equilibrium curves of uranium, under the following conditions: concentration of 1 to 20 g U/1 and acidity varying from 1 to 5M in HNO 3 . Other parameters studied were the volumetric ratio of the phases and the influence of the concentration of TBP (tri-n-butyl phosphate). To guarantee the cerium(IV) extraction, the diluent (varsol) was previously treated with 10% potassium dichromate in perchloric acid, potassium permanganate in 1M sulphuric acid and concentrated sulphuric acid at 70 deg to eliminate reducing compounds. The results obtained for cerium extraction, allowed a better understanding of its behavior in solution. The results permitted to conclude that the decontamination for cerium are very high in the first Purex extraction cycle. The easy as cerium(IV) is reduced to the trivalent state contributes a great deal to its decontamination. (author)

  9. Metabolism of cerium 144 in rat. Distribution - elimination - dosimetry; Metabolisme du cerium 144 chez le rat. Distribution - elimination - dosimetrie

    Energy Technology Data Exchange (ETDEWEB)

    Remy, Jacques

    1959-07-01

    This academic report concerns a study during which cerium 144 has been intravenously injected to three-month old rats under the form of cerium chloride in aqueous solution with pH of 9,5. Rats have then been sacrificed at different times after the injection, and organ or tissue samplings have been performed to study the isotope distribution in their bodies. This allowed the calculation of internal irradiation doses locally received by the animal, and also to identify critical organs with respect to cerium 144. Thus, until the twentieth day after injection, liver is the critical organ. After, it is the skeleton, for the rest of the animal's life. The bone internal irradiation is the highest danger for an internal cerium 144 contamination, due to threats on body hematopoietic functions [French] Le Cerium 144 est injecte a des rats de trois mois par voie intraveineuse, sous forme de chlorure en solution aqueuse a pH = 9,5. Une telle solution est colloidale. Les rats sont sacrifies par groupe de 5 a des temps differents apres l'injection et des prelevements d'organes ou de tissus sont effectues qui permettent d'etudier la distribution de l'isotope dans l'organisme. Cette etude de la distribution du Cerium 144 dans l'organiqme du rat a permis egalement le calcul des doses d'irradiation interne recues localement par l'animal. Ces donnees permettent de definir les organes critiques de l'organisme pour le Cerium 144: Jusqu'au 20eme jour l'organe critique est le foie. Ce sera ensuite le squelette, et ce, pendant toute la vie de l'animal. L'irradiation interne de l'os constitue, en raison des menaces qu'elle comporte pour les fonctions hematopoietiques de l'organisme, le plus grand danger d'une contamination interne par le Cerium 144.

  10. Effect of correlation on the band structure of α-cerium

    International Nuclear Information System (INIS)

    Rao, R.S.; Singh, R.P.

    1975-01-01

    The electronic band structure of f.c.c. phase of the rare earth metal cerium (α-cerium) has been calculated using a formulation of the crystal potential where correlation also has been included in addition to exchange. The Green's function method of Korringa-Kohn and Rostoker has been used due to obvious advantages in calculation. The calculations indicate that the s-d bands are hybridized with the f-levels but the f-bands are fairly narrow and lie slightly above the Fermi level. The structure of the bands is qualitatively similar to those of calculations by others except for a general shift of the entire set of bands by about 0.1 Ryd. Thd density of states has also been calculated from the bands obtained. The spin susceptibility of α-cerium has also been calculated using the Kohn-Sham method. However, the calculated additional contributions to the band structure values cannot still explain the large experimental values reported in the literature. (author)

  11. Solid-soluted content of cerium in solid solution of sphene

    International Nuclear Information System (INIS)

    Zhao Wei; Teng Yuancheng; Li Yuxiang; Ren Xuetan; Huang Junjun

    2010-01-01

    The sphene solid solution was synthesized by solid-state method,with calcium carbonate, silica, titanium dioxide, cerium oxalate and alumina as raw materials. The solid-soluted content of cerium in sphene was researched by means of X-ray diffraction (XRD), backscattering scanning electron microscopy (BSE), energy dispersive spectroscopy (EDS) and so on. The influence of A l3+ ion introduction to sphene on the solid-soluted content of cerium in sphene solid solution was studied. The results indicate that when introducing Al 3+ to sphene as electrovalence compensation, Ce 4+ could be well solidified to Ca 1-x Ce x Ti 1-2x A l2x SiO 5 , and the solid-soluted content is approximately 12.61%. With no electrovalence compensation, Ce 4+ could be solidified to Ca 1-2x Ce x TiSiO 5 , and the solid-soluted content is approximately 10.98%. The appropriate synthesis temperature of sphene solid solution is 1 260 degree C.(authors)

  12. Structural, optical, morphological and dielectric properties of cerium oxide nanoparticles

    International Nuclear Information System (INIS)

    Prabaharan, Devadoss Mangalam Durai Manoharadoss; Sadaiyandi, Karuppasamy; Mahendran, Manickam; Sagadevan, Suresh

    2016-01-01

    Cerium oxide (CeO 2 ) nanoparticles were prepared by the precipitation method. The average crystallite size of cerium oxide nanoparticles was calculated from the X-ray diffraction (XRD) pattern and found to be 11 nm. The FT-IR spectrum clearly indicated the strong presence of cerium oxide nanoparticles. Raman spectrum confirmed the cubic nature of the cerium oxide nanoparticles. The Scanning Electron Microscopy (SEM) analysis showed that the nanoparticles agglomerated forming spherical-shaped particles. The Transmission Electron Microscopic (TEM) analysis confirmed the prepared cerium oxide nanoparticles with the particle size being found to be 16 nm. The optical absorption spectrum showed a blue shift by the cerium oxide nanoparticles due to the quantum confinement effect. The dielectric properties of cerium oxide nanoparticles were studied for different frequencies at different temperatures. The dielectric constant and the dielectric loss of the cerium oxide nanoparticles decreased with increase in frequency. The AC electrical conductivity study revealed that the conduction depended on both the frequency and the temperature. (author)

  13. Structural, optical, morphological and dielectric properties of cerium oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Prabaharan, Devadoss Mangalam Durai Manoharadoss [Department of Physics, NPR College of Engineering and Technology, Natham, Dindigul, Tamil Nadu (India); Sadaiyandi, Karuppasamy [Department of Physics, Alagappa Government Arts College, Karaikudi, Sivaganga, Tamil Nadu (India); Mahendran, Manickam [Department of Physics, Thiagarajar College of Engineering, Madurai, Tamil Nadu (India); Sagadevan, Suresh, E-mail: duraiphysics2011@gmail.com [Department of Physics, AMET University (India)

    2016-03-15

    Cerium oxide (CeO{sub 2}) nanoparticles were prepared by the precipitation method. The average crystallite size of cerium oxide nanoparticles was calculated from the X-ray diffraction (XRD) pattern and found to be 11 nm. The FT-IR spectrum clearly indicated the strong presence of cerium oxide nanoparticles. Raman spectrum confirmed the cubic nature of the cerium oxide nanoparticles. The Scanning Electron Microscopy (SEM) analysis showed that the nanoparticles agglomerated forming spherical-shaped particles. The Transmission Electron Microscopic (TEM) analysis confirmed the prepared cerium oxide nanoparticles with the particle size being found to be 16 nm. The optical absorption spectrum showed a blue shift by the cerium oxide nanoparticles due to the quantum confinement effect. The dielectric properties of cerium oxide nanoparticles were studied for different frequencies at different temperatures. The dielectric constant and the dielectric loss of the cerium oxide nanoparticles decreased with increase in frequency. The AC electrical conductivity study revealed that the conduction depended on both the frequency and the temperature. (author)

  14. Jet formation in cerium metal to examine material strength

    Energy Technology Data Exchange (ETDEWEB)

    Jensen, B. J., E-mail: bjjensen@lanl.gov; Cherne, F. J.; Prime, M. B.; Yeager, J. D.; Ramos, K. J.; Hooks, D. E.; Cooley, J. C.; Dimonte, G. [Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States); Fezzaa, K. [Argonne National Laboratory, Argonne, Illinois 60439 (United States); Iverson, A. J.; Carlson, C. A. [National Security Technologies LLC, Los Alamos, New Mexico 87544 (United States)

    2015-11-21

    Examining the evolution of material properties at extreme conditions advances our understanding of numerous high-pressure phenomena from natural events like meteorite impacts to general solid mechanics and fluid flow behavior. Recent advances in synchrotron diagnostics coupled with dynamic compression platforms have introduced new possibilities for examining in-situ, spatially resolved material response with nanosecond time resolution. In this work, we examined jet formation from a Richtmyer-Meshkov instability in cerium initially shocked into a transient, high-pressure phase, and then released to a low-pressure, higher-temperature state. Cerium's rich phase diagram allows us to study the yield stress following a shock induced solid-solid phase transition. X-ray imaging was used to obtain images of jet formation and evolution with 2–3 μm spatial resolution. From these images, an analytic method was used to estimate the post-shock yield stress, and these results were compared to continuum calculations that incorporated an experimentally validated equation-of-state (EOS) for cerium coupled with a deviatoric strength model. Reasonable agreement was observed between the calculations and the data illustrating the sensitivity of jet formation on the yield stress values. The data and analysis shown here provide insight into material strength during dynamic loading which is expected to aid in the development of strength aware multi-phase EOS required to predict the response of matter at extreme conditions.

  15. Electrochemical reduction of cerium oxides in molten salts

    International Nuclear Information System (INIS)

    Claux, B.; Serp, J.; Fouletier, J.

    2011-01-01

    This brief article describes a pyrochemical process that is used by CEA to turn actinide oxides into metal actinides. This process is applied to Cerium oxides (CeO 2 ) that simulate actinide oxides well chemically as cerium belongs to the lanthanide family. The process is in fact an electrolysis of cerium oxide in a bath of molten calcium chloride salt whose temperature is between 800 and 900 Celsius degrees. At those temperatures calcium chloride becomes a ionic liquid (Ca 2+ and Cl - ) that is a good electrical conductor and is particularly well-adapted as solvent to an electrolytic process. The electrolysis current allows the transformation of solvent Ca 2+ ions into metal calcium which, in turn, can reduce cerium oxide into metal cerium through chromatically. Experimental data shows the reduction of up to 90% of 10 g samples of CeO 2 in a 6 hour long electrolysis while the best reduction rate ever known was 80% so far. This result is all the more promising that cerium oxides are more difficult to reduce than actinide oxides from the thermodynamical perspective

  16. Contribution to research on the metabolism of fission product. Studies on the physico-chemical state and the metabolic fate of radio-cerium solution; Contribution a l'etude du metabolisme des produits de fission. Recherches sur l'etat physico-chimique et le devenir metabolique des solutions de radiocerium

    Energy Technology Data Exchange (ETDEWEB)

    Aeberhardt, A [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    This paper describes a study of the physico-chemical state of radio-cerium in dilute solutions on the tracer scale, as a function of the pH of the solution. The way in which this radioelement is transported in the blood is studied in vitro and in vivo, with reference to the ionic or colloidal state of the radio-cerium used. The distribution of cerium amongst the various components of the blood is studied by a new method of blood fractionation and by paper electrophoresis. Evidence of a cerium globulin connection is shown in the case of ionic cerium. A study of the initial distribution of radio-cerium in rats, after intravenous administration of ionic or colloidal solutions, shows considerable differences according to the physico-chemical state of the cerium injected. (author) [French] Ce travail presente une etude de l'etat physico-chimique du radiocerium en solutions diluees a l'echelle des indicateurs, en fonction du pH de la solution. En fonction de l'etat ionique ou colloidal du radiocerium utilise, le mode de transport de ce radioelement dans le sang est etudie in vitro et in vivo. La distribution du cerium entre les differents constituants du sang est etudiee par une methode nouvelle de fractionnement du sang et par electrophorese sur papier. L'existence d'une liaison cerium-globuline est mise en evidence dans le cas du cerium ionique. L'etude de la distribution initiale du radiocerium, chez le rat apres administration par voie veineuse de solutions ionique ou colloidale, montre des differences importantes en fonction de l'etat physico-chimique du cerium injecte. (auteur)

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

    Science.gov (United States)

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

    2009-01-01

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

  18. Valence instabilities in cerium intermetallics

    International Nuclear Information System (INIS)

    Dijkman, W.H.

    1982-01-01

    The primary purpose of this investigation was to study the magnetic behaviour of cerium in intermetallic compounds, that show an IV behaviour, e.g. CeSn 3 . In the progress of the investigations, it became of interest to study the effect of changes in the lattice of the IV compound by substituting La or Y for Ce, thus constituting the Cesub(1-x)Lasub(x)Sn 3 and Cesub(1-x)Ysub(x)Sn 3 quasibinary systems. A second purpose was to examine the possibility of introducing instabilities in the valency of a trivalent intermetallic cerium compound: CeIn 3 , also by La and Y-substitutions in the lattice. Measurements on the resulting Cesub(1-x)Lasub(x)In 3 and Cesub(1-x)Ysub(x)In 3 quasibinaries are described. A third purpose was to study the (gradual) transition from a trivalent cerium compound into an IV cerium compound. This was done by examining the magnetic properties of the CeInsub(x)Snsub(3-x) and CePbsub(x)Snsub(3-x) systems. Finally a new possibility was investigated: that of the occurrence of IV behaviour in CeSi 2 , CeSi, and in CeGa 2 . (Auth.)

  19. Chronopotentiometric determination of redox states of peptides

    Czech Academy of Sciences Publication Activity Database

    Dorčák, Vlastimil; Paleček, Emil

    2007-01-01

    Roč. 19, č. 23 (2007), s. 2405-2412 ISSN 1040-0397 R&D Projects: GA AV ČR(CZ) IAA500040513; GA ČR(CZ) GA301/07/0490; GA MŠk(CZ) LC06035 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : peptide redox states * constant current chronopotentiometry * catalytic hydrogen evolution Subject RIV: BO - Biophysics Impact factor: 2.949, year: 2007

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

    Science.gov (United States)

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

    2015-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Bruno Chausse

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

  2. Determination of silver and cerium in the liver and the kidney from a severely burned infant treated with silver sulfadiazine and cerium nitrate

    International Nuclear Information System (INIS)

    Hirakawa, Keiko

    1983-01-01

    Silver and cerium in the liver and the kidney from severely burned infant were analyzed by neutron activation method. The patient was treated topically with cerium nitrate/silver sulfadiazine cream and cerium nitrate solution for 3 months. Then, the treatment with these drugs was stopped because o f abdominal distention. The patient died 1 month after the cessation of the treatment with these drugs. The tissue specimens, blank liver sample and reference standards were irradiated with TRIGA MARK II Reactor of Rikkyo University. About 1 month after the irradiation, the activities were measured with a Ge(Li) detector coupled to a 4096 channel pulse height analyzer. A large amount of silver was detected both in the liver and in the kidney and a trace of cerium only in the liver. A considerable amount of silver was detected in the liver and its quantity was about 1600 times more than that of normal livers reported by Hamilton, Minski and Cleary (1972 -- 73). Neither silver nor cerium were detected in the blank liver. These results suggest that prolonged topical chemotherapy of cerium nitrate/silver sulfadiazine cream and cerium nitrate solution for the extensive burn injuries causes considerable absorption of silver and cerium into the liver and the kidney. (author)

  3. Membrane assisted liquid-liquid extraction of cerium

    International Nuclear Information System (INIS)

    Soldenhoff, K.M.

    2000-02-01

    Membrane assisted liquid-liquid extraction of cerium was investigated, with emphasis placed on the study of the reaction chemistry and the kinetics of non-dispersive solvent extraction and stripping with microporous membranes. A bulk liquid membrane process was developed for the purification of cerium(IV) from sulfate solutions containing other rare earth elements. The cerium process was studied in both a flat sheet contained liquid membrane configuration and with hollow fibre contactors. Di-2-ethylhexyl phosphoric acid (DEHPA) was identified as a suitable extractant for cerium(IV) from sulfuric acid solution, with due consideration of factors such as extraction ability, resistance to degradation, solvent selectivity and potential for sulfate transfer into a strip solution. A detailed study of the extraction of cerium(IV) with DEHPA defined the extraction reaction chemistry. The Ce/DEHPA/sulfate system was also investigated with a flat sheet bulk liquid membrane configuration, using both sulfuric and hydrochloric acid as receiver solutions. These tests identified that hydrophobic membranes provide better mass transfer for extraction and hydrophilic membranes are better for stripping. The presence of an impurity, mono 2-ethylhexyl phosphoric acid (MEHPA), was found to have a dramatic accelerating effect on the rate of the chemical extraction reaction. This was attributed to its higher interfacial activity and population compared to DEHPA, and the fact that MEHPA was also found to be an active carrier for cerium(IV). The mass transfer rate of membrane assisted extraction and stripping of cerium, using hydrophobic and hydrophilic microporous membranes, respectively, was investigated using a modified Lewis-type cell. It was quantitatively demonstrated that the extraction process was mainly controlled by membrane diffusion and the stripping process was controlled by the chemical reaction rate, with membrane diffusion becoming important at low distribution coefficients

  4. Obtainment of cerium dioxide for use as spectrochemical standard

    International Nuclear Information System (INIS)

    Silva Queiroz, C.A. da; Hespanhol, E.C.B.; Abrao, A.

    1992-01-01

    This paper describes a simple method for cerium separation and purification. Cerium is previously precipitated with N H 3 /air/H 2 O 2 system in a mixed chlorides solution obtained from Brazilian monazite treatment. The cerium fraction as cerium chloride is run down throughout a strong cationic resin bed and then the rare earth impurities separation is done by elution of the resin with separation ammonium salt of EDTA. None retainer ion is used in the purification technique by ion exchange. (author)

  5. Selected cerium phase diagrams

    International Nuclear Information System (INIS)

    Gschneidner, K.A. Jr.; Verkade, M.E.

    1974-09-01

    A compilation of cerium alloy phase equilibria data based on the most reliable information available is presented. The binary systems selected are those of cerium with each of the following twenty nine elements which might be commonly found in steels: Al, Sb, As, Bi, Ca, C, Cr, Co, Nb, Cu, Fe, Pb, Mg, Mn, Mo, Ni, N, O, P, Se, Si, Ag, S, Te, Sn, Ti, W, and Zn. A brief discussion, a summary of crystal lattice parameters where applicable, and a list of references is included for each element surveyed. (U.S.)

  6. Novel in situ coordinated cerium salt/acrylonitrile-butadiene rubber composite

    International Nuclear Information System (INIS)

    Han, Jianjun; Lu, Haifeng; Zhang, Jie; Feng, Shengyu

    2012-01-01

    A novel rubber composite of acrylonitrile-butadiene rubber (NBR) filled with cerium salt particles was vulcanized via in situ coordination for the first time. The resulting materials exhibit good mechanical properties. Curing characteristics analysis, differential scanning calorimetry, X-ray photoelectron spectroscopy, tensile testing, and an equilibrium swelling method were used for the characterization of the composite. The results in this paper indicate that the composite is a kind of elastomer based on the in situ coordination crosslinking interactions between the nitrile groups (–CN) of NBR and cerium ions. The mechanical properties of vulcanized cerium salt/ NBR rubber are altered when changing the sorts of cerium salt. Moreover, these materials show good irradiation resistance because of the introduction of the cerium salt. -- Highlights: ► Cerium salts were firstly used to vulcanize the acrylonitrile-butadiene rubber. ► Cerium salts act as not only crosslink agents but also reinforcing fillers in the matrix. ► These materials show good irradiation resistance and mechanical properties at same time.

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

    Science.gov (United States)

    Blackstone, N W

    2001-06-01

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

  8. LUMINESCENT PROPERTIES OF SILICATE GLASSES WITH CERIUM IONS AND ANTIMONY

    Directory of Open Access Journals (Sweden)

    A. M. Klykova

    2014-05-01

    Full Text Available The paper deals with the results of an experimental study of luminescence excitation spectra and luminescence of silicate glasses containing cerium ions and antimony. The aim of this work was to study the features of the luminescence and the effect of UV irradiation and heat treatment on luminescence and the state of cerium ions and antimony in glass. We investigated glass system Na2O-ZnO-Al2O3-SiO2-NaF-NaBr with additives CeO2 and Sb2O3. Synthesis was carried out in platinum crucibles in the air at 14500C. The samples were polished glass plates with a thickness of 0.5-1 mm. UV irradiation was carried out with a mercury lamp having a wide range of radiation in the spectral range 240-390 nm. It was conducted in a Nabertherm muffle furnaces. Luminescence spectra and excitation spectra were measured using a spectrofluorimeter MPF-44A (PerkinElmer at the room temperature. Measured luminescence spectra were corrected in view of the spectral sensitivity of the photodetector for spectrofluorimeter. Adjustment of the excitation spectra for the spectral dependence of the intensity of the excitation source was not carried out. During the experiments it was found that in silicate glasses Sb3+ ions can exist in two energy states, which corresponds to a different environment with oxygen ions. Heat treatment of these glasses in an oxidizing atmosphere leads to an increase in ion concentration of Sb3+ ions with a greater amount of oxygen in the environment. In glasses containing antimony and cerium ions, ultraviolet irradiation causes a change in the valence of cerium ions and antimony, which is accompanied by luminescence quenching. Subsequent heat treatment of glass leads to the inverse processes and restore luminescence excitation spectra. The study of fluorescent properties of silicate glasses with cerium and antimony ions led to the conclusion of the practical significance of this work. Promising multifunctional materials can be created on the basis of

  9. Two-phase titration of cerium(3) by permanganate

    International Nuclear Information System (INIS)

    Lazarev, A.I.; Lazareva, V.I.; Gerko, V.V.

    1986-01-01

    Reaction of cerium (3) and permanganate was investigated at a room temperature depending on PH, concentrations of pyrophosphate, cerium (3), tetraphenylphosphonium and foreign compounds. Selective method of two-phase titration determination of cerium (3) by permanganate without using silver compounds, preliminary separation of chlorides, nitrates, was developed. The method was tested using alloys based on iron, nickel, REE, copper, cobalt (S r ≤0.008). Correctness is proved with method of standard additives

  10. Novel in situ coordinated cerium salt/acrylonitrile-butadiene rubber composite

    Energy Technology Data Exchange (ETDEWEB)

    Han, Jianjun [Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China); Lu, Haifeng, E-mail: lhf@sdu.edu.cn [Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China); Zhang, Jie [Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China); Feng, Shengyu, E-mail: fsy@sdu.edu.cn [Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China)

    2012-09-14

    A novel rubber composite of acrylonitrile-butadiene rubber (NBR) filled with cerium salt particles was vulcanized via in situ coordination for the first time. The resulting materials exhibit good mechanical properties. Curing characteristics analysis, differential scanning calorimetry, X-ray photoelectron spectroscopy, tensile testing, and an equilibrium swelling method were used for the characterization of the composite. The results in this paper indicate that the composite is a kind of elastomer based on the in situ coordination crosslinking interactions between the nitrile groups (-CN) of NBR and cerium ions. The mechanical properties of vulcanized cerium salt/ NBR rubber are altered when changing the sorts of cerium salt. Moreover, these materials show good irradiation resistance because of the introduction of the cerium salt. -- Highlights: Black-Right-Pointing-Pointer Cerium salts were firstly used to vulcanize the acrylonitrile-butadiene rubber. Black-Right-Pointing-Pointer Cerium salts act as not only crosslink agents but also reinforcing fillers in the matrix. Black-Right-Pointing-Pointer These materials show good irradiation resistance and mechanical properties at same time.

  11. Biredox ionic liquids with solid-like redox density in the liquid state for high-energy supercapacitors.

    Science.gov (United States)

    Mourad, Eléonore; Coustan, Laura; Lannelongue, Pierre; Zigah, Dodzi; Mehdi, Ahmad; Vioux, André; Freunberger, Stefan A; Favier, Frédéric; Fontaine, Olivier

    2017-04-01

    Kinetics of electrochemical reactions are several orders of magnitude slower in solids than in liquids as a result of the much lower ion diffusivity. Yet, the solid state maximizes the density of redox species, which is at least two orders of magnitude lower in liquids because of solubility limitations. With regard to electrochemical energy storage devices, this leads to high-energy batteries with limited power and high-power supercapacitors with a well-known energy deficiency. For such devices the ideal system should endow the liquid state with a density of redox species close to the solid state. Here we report an approach based on biredox ionic liquids to achieve bulk-like redox density at liquid-like fast kinetics. The cation and anion of these biredox ionic liquids bear moieties that undergo very fast reversible redox reactions. As a first demonstration of their potential for high-capacity/high-rate charge storage, we used them in redox supercapacitors. These ionic liquids are able to decouple charge storage from an ion-accessible electrode surface, by storing significant charge in the pores of the electrodes, to minimize self-discharge and leakage current as a result of retaining the redox species in the pores, and to raise working voltage due to their wide electrochemical window.

  12. Colloidal stabilization of cerium-gadolinium oxide (CGO) suspensions via rheology

    DEFF Research Database (Denmark)

    Marani, Debora; Sudireddy, Bhaskar Reddy; Bentzen, Janet Jonna

    2015-01-01

    colloidally stable state. The method was applied to explore the ability of four commercial dispersants (acidic affine, neutral, basic affine, and polyvinylpyrrolidone (PVP)) to disperse cerium-gadolinium oxide (CGO) in ethanol. Only the acidic affine and the PVP dispersants were found to efficiently disperse...

  13. Preparation of cerium oxide for lens polishing powder

    International Nuclear Information System (INIS)

    Injarean, Uthaiwan; Rodthongkom, Chouvana; Pichestapong, Pipat; Changkrurng, Kalaya

    2003-10-01

    Cerium is an element of rare earth group which is called lanthanide series. It is found in the ores like monazite and xenotime which are the tailings of tin mines in the south of Thailand. Cerium is used mostly as lens polishing powder besides the applications in other industries. In this study, cerium extracted from monazite ore breakdown by alkaline process was used for the preparation of lens polishing powder. Cerium hydroxide cake from the process was dissolved by hydrochloric acid and precipitated with oxalic acid. The oxalate precipitate then was calcined to oxide powder and its particle size was measured. Precipitation conditions being studied are concentration of feed cerium chloride solution, concentration of oxalic acid used for the precipitation, concentration of sulfuric acid used as precipitation control reagent and the precipitation temperature. It was found that the appropriate precipitation conditions yielded the fine oxide powder with particle size about 12μm. The oxide powder can be ground to the size of 1-3 μm which is suitable for making lens polishing powder

  14. Enhanced energy density of carbon-based supercapacitors using Cerium (III) sulphate as inorganic redox electrolyte

    International Nuclear Information System (INIS)

    Díaz, Patricia; González, Zoraida; Santamaría, Ricardo; Granda, Marcos; Menéndez, Rosa; Blanco, Clara

    2015-01-01

    Highlights: •Ce 2 (SO 4 ) 3 /H 2 SO 4 redox electrolyte as a new route to increase the energy density of SCs. •Increased operating cell voltage with no electrolyte decomposition. •Redox reactions on the battery-type electrode. •The negative electrode retains its capacitor behaviour. •Outstanding energy density values compared to those measured in H 2 SO 4 . -- ABSTRACT: The energy density of carbon based supercapacitors (CBSCs) was significantly increased by the addition of an inorganic redox species [Ce 2 (SO 4 ) 3 ] to an aqueous electrolyte (H 2 SO 4 ). The development of the faradaic processes on the positive electrode not only significantly increased the capacitance but also the operational cell voltage of these devices (up to 1.5 V) due to the high redox potentials at which the Ce 3+ /Ce 4+ reactions occur. Therefore, in asymmetric CBSCs assembled using an activated carbon as negative electrode and MWCNTs as the positive one, the addition of Ce 2 (SO 4 ) 3 moderately increases the energy density of the device (from 1.24 W h kg −1 to 5.08 W h kg −1 ). When a modified graphite felt is used as positive electrode the energy density of the cell reaches values as high as 13.84 W h kg −1 . The resultant systems become asymmetric hybrid devices where energy is stored due to the electrical double layer formation in the negative electrode and the development of the faradaic process in the positive electrode, which acts as a battery-type electrode

  15. Dissolution properties of cerium dibutylphosphate corrosion inhibitors

    NARCIS (Netherlands)

    Soestbergen, van M.; Erich, S.J.F.; Huinink, H.P.; Adan, O.C.G.

    2013-01-01

    The corrosion inhibitor cerium dibutylphosphate, Ce(dbp)3, prevents corrosion by cerium and dbp deposition at the alkaline cathode and acidic anode respectively. The pH dependent Ce(dbp)3 solubility seems to play an essential role in the inhibition degree. We found that Ce(dbp)3 scarcely dissolves

  16. Air, aqueous and thermal stabilities of Ce3+ ions in cerium oxide nanoparticle layers with substrates

    KAUST Repository

    Naganuma, Tamaki

    2014-01-01

    Abundant oxygen vacancies coexisting with Ce3+ ions in fluorite cerium oxide nanoparticles (CNPs) have the potential to enhance catalytic ability, but the ratio of unstable Ce3+ ions in CNPs is typically low. Our recent work, however, demonstrated that the abundant Ce3+ ions created in cerium oxide nanoparticle layers (CNPLs) by Ar ion irradiation were stable in air at room temperature. Ce valence states in CNPs correlate with the catalytic ability that involves redox reactions between Ce3+ and Ce4+ ions in given application environments (e.g. high temperature in carbon monoxide gas conversion and immersion conditions in biomedical applications). To better understand the mechanism by which Ce3+ ions achieve stability in CNPLs, we examined (i) extra-long air-stability, (ii) thermal stability up to 500 °C, and (iii) aqueous stability of Ce 3+ ions in water, buffer solution and cell culture medium. It is noteworthy that air-stability of Ce3+ ions in CNPLs persisted for more than 1 year. Thermal stability results showed that oxidation of Ce 3+ to Ce4+ occurred at 350 °C in air. Highly concentrated Ce3+ ions in ultra-thin CNPLs slowly oxidized in water within 1 day, but stability was improved in the cell culture medium. Ce 3+ stability of CNPLs immersed in the medium was associated with phosphorus adsorption on the Ce3+ sites. This study also illuminates the potential interaction mechanisms of stable Ce3+ ions in CNPLs. These findings could be utilized to understand catalytic mechanisms of CNPs with abundant oxygen vacancies in their application environments. © The Royal Society of Chemistry 2014.

  17. Gas sensing behaviour of cerium oxide and magnesium aluminate

    Indian Academy of Sciences (India)

    Gas sensing behaviour of cerium oxide and magnesium aluminate composites ... A lone pairof the electron state was identified from the electro paramagnetic ... carbon monoxide (CO) (at 0.5, 1.0 and 1.5 bar) and ethanol (at 50 and 100 ppm) was ... The magnitude of the temperature varied linearly regardless of the gas ...

  18. Co/Zr substitution in a cerium-zirconium oxide by catalytic steam reforming of bio-ethanol

    International Nuclear Information System (INIS)

    Vargas, J.C.; Thomas, S.; Roger, A.C.; Kiennemann, A.; Vargas, J.C.

    2006-01-01

    This work deals with the production of hydrogen by bio-ethanol catalytic steam reforming. The aim is to develop a catalyst active in ethanol conversion, selective in hydrogen and resistant to deactivation, particularly those induced by the formation of carbon deposition. The metal-support interaction being one of the keys of this challenge, catalysts in which a transition metal is inserted into an oxide by a liquid synthesis method (by the precursor method) have been developed. The initial insertion of cobalt into a cerium oxide-zirconia structure presents the advantages to increase the redox properties of the host oxide and to allow a stable reduction of a cobalt part while favoring the metal-support interaction. (O.M.)

  19. Click-PEGylation - A mobility shift approach to assess the redox state of cysteines in candidate proteins.

    Science.gov (United States)

    van Leeuwen, Lucie A G; Hinchy, Elizabeth C; Murphy, Michael P; Robb, Ellen L; Cochemé, Helena M

    2017-07-01

    The redox state of cysteine thiols is critical for protein function. Whereas cysteines play an important role in the maintenance of protein structure through the formation of internal disulfides, their nucleophilic thiol groups can become oxidatively modified in response to diverse redox challenges and thereby function in signalling and antioxidant defences. These oxidative modifications occur in response to a range of agents and stimuli, and can lead to the existence of multiple redox states for a given protein. To assess the role(s) of a protein in redox signalling and antioxidant defence, it is thus vital to be able to assess which of the multiple thiol redox states are present and to investigate how these alter under different conditions. While this can be done by a range of mass spectrometric-based methods, these are time-consuming, costly, and best suited to study abundant proteins or to perform an unbiased proteomic screen. One approach that can facilitate a targeted assessment of candidate proteins, as well as proteins that are low in abundance or proteomically challenging, is by electrophoretic mobility shift assays. Redox-modified cysteine residues are selectively tagged with a large group, such as a polyethylene glycol (PEG) polymer, and then the proteins are separated by electrophoresis followed by immunoblotting, which allows the inference of redox changes based on band shifts. However, the applicability of this method has been impaired by the difficulty of cleanly modifying protein thiols by large PEG reagents. To establish a more robust method for redox-selective PEGylation, we have utilised a Click chemistry approach, where free thiol groups are first labelled with a reagent modified to contain an alkyne moiety, which is subsequently Click-reacted with a PEG molecule containing a complementary azide function. This strategy can be adapted to study reversibly reduced or oxidised cysteines. Separation of the thiol labelling step from the PEG

  20. Cerium-modified Aurivillius-type sodium lanthanum bismuth titanate with enhanced piezoactivities

    International Nuclear Information System (INIS)

    Wang Chunming; Zhao Liang; Wang Jinfeng; Zheng Limei; Du Juan; Zhao Minglei; Wang Chunlei

    2009-01-01

    The electrical, piezoelectric and dielectric properties of cerium-modified Aurivillius-type sodium lanthanum bismuth titanate (Na 0.5 La 0.5 Bi 4 Ti 4 O 15 , NLBT) ceramics were investigated. It was found the piezoelectric activities of NLBT ceramics were significantly improved by cerium modification. The piezoelectric coefficient d 33 and Curie temperature T c for the 0.50 wt.% cerium-modified NLBT were found to be 29 pC/N and 573 deg. C, respectively. The reasons for piezoelectric activities improvement by cerium modification were given. A small dielectric abnormity was observed in NLBT ceramics, which can be suppressed by cerium modification.

  1. Specific Features of the Response of Cerium to Pulsed Actions

    Science.gov (United States)

    Atroshenko, S. A.; Zubareva, A. N.; Morozov, V. A.; Savenkov, G. G.; Utkin, A. V.

    2018-02-01

    Experimental studies of cerium at high rates and nanosecond durations of action have been performed. The isomorphic phase transition was studied upon shock compression. The spall strength of cerium has been determined. Cerium demonstrates anomalous compressibility upon dynamic loading. Stress waves dampen under action of a high-current electron beam due to the energy dissipation during fragmentation and twinning.

  2. A contribution to the radiologic findings in cerium pneumoconiosis

    International Nuclear Information System (INIS)

    Hecht, F.M.; Wesch, H.; Deutsches Krebsforschungszentrum, Heidelberg

    1980-01-01

    Report on a 69 year old man, who had been employed as photographer in the printing industry and who had been exposed to Cerium for 40 years. The chest X-ray which was performed 9 years after the end of the exposure displayes striate densities of the lungs, which must be considered as a late stage of Cerium-pneumoconiosis. The changes which were found fulfill the code 't 1/0 RO, RM, RU, LO, LM, LU, p 0/1 RO, RM, LO, LM, em, tbu' according to the 'ILO U/C 1971 classification of pneumoconiosis'. The diagnosis could be substantiated by measureing Cerium in the lung parenchyma qualitatively and quantitatively using neutrone activating analysis. The radiolgic findings of the Cerium pneumoconiosis are discussed. (orig.) [de

  3. Plant redox proteomics

    DEFF Research Database (Denmark)

    Navrot, Nicolas; Finnie, Christine; Svensson, Birte

    2011-01-01

    PTMs in regulating enzymatic activities and controlling biological processes in plants. Notably, proteins controlling the cellular redox state, e.g. thioredoxin and glutaredoxin, appear to play dual roles to maintain oxidative stress resistance and regulate signal transduction pathways via redox PTMs......In common with other aerobic organisms, plants are exposed to reactive oxygen species resulting in formation of post-translational modifications related to protein oxidoreduction (redox PTMs) that may inflict oxidative protein damage. Accumulating evidence also underscores the importance of redox....... To get a comprehensive overview of these types of redox-regulated pathways there is therefore an emerging interest to monitor changes in redox PTMs on a proteome scale. Compared to some other PTMs, e.g. protein phosphorylation, redox PTMs have received less attention in plant proteome analysis, possibly...

  4. An alternative preparation method for ion exchanged catalysts: Solid state redox reaction

    DEFF Research Database (Denmark)

    Schneider, E.; Hagen, A.; Grunwaldt, J.-D.

    2004-01-01

    A new method for modifying zeolites with zinc is proposed. The solid state redox reaction between metallic zinc and ZSM-5 zeolites with different Si/Al ratios was investigated by temperature programmed hydrogen evolution (TPHE), X-ray absorption near edge structure (XANES) and diffuse reflectance...... infrared Fourier transform spectroscopy (DRIFTS). The evolution of hydrogen was detected at temperatures above 620 K. The source of hydrogen was the solid state redox reaction of the metal with protons of the support. The samples exhibit catalytic activity in ethane aromatization indicating that zinc...... should be located at the same sites as in catalysts prepared by conventional methods. Combination of XANES and catalytic activity point to zinc being mainly present in tetrahedral geometry under reaction conditions....

  5. Adsorption of Some Hazardous Radionuclides on Cerium(IV) Antimonate

    International Nuclear Information System (INIS)

    Aly, H.F.; Zakaria, E.S.; Shady, S.A.; El-Naggar, I.M.

    1999-01-01

    Cerium(IV) antimonate had been prepared by the dropwise addition of 0.6 M antimony pentachloride and 0.6 M cerium ammonium nitrate solutions by a molar radio of Ce/Sb 0.75. Exchange isotherms for H +/ Co 2+ , H +/ Cs +, H +/ Zn 2+ , H +/ Sr 2+ and H +/ Eu 3+ have been determined at 25, 40 and 60 degree. Besides it was proved that europium is physically adsorbed while zinc, strontium, cobalt and cesium are chemically adsorbed. Moreover, the heat of adsorption of zinc, strontium, cobalt and cesium on cerium(IV) antimonate had been calculated and indicated that cerium(IV) antimonate is of endothermic behaviour towards these ions. Also the distribution coefficients of these ions were determined and it was found that the selectivity in the order: Eu 3+ >Sr 2+ > Cs +> Na +

  6. Metabolism of cerium 144 in rat. Distribution - elimination - dosimetry

    International Nuclear Information System (INIS)

    Remy, Jacques

    1959-01-01

    This academic report concerns a study during which cerium 144 has been intravenously injected to three-month old rats under the form of cerium chloride in aqueous solution with pH of 9,5. Rats have then been sacrificed at different times after the injection, and organ or tissue samplings have been performed to study the isotope distribution in their bodies. This allowed the calculation of internal irradiation doses locally received by the animal, and also to identify critical organs with respect to cerium 144. Thus, until the twentieth day after injection, liver is the critical organ. After, it is the skeleton, for the rest of the animal's life. The bone internal irradiation is the highest danger for an internal cerium 144 contamination, due to threats on body hematopoietic functions [fr

  7. Optical imaging of mitochondrial redox state in rodent model of retinitis pigmentosa

    Science.gov (United States)

    Maleki, Sepideh; Gopalakrishnan, Sandeep; Ghanian, Zahra; Sepehr, Reyhaneh; Schmitt, Heather; Eells, Janis; Ranji, Mahsa

    2013-01-01

    Oxidative stress (OS) and mitochondrial dysfunction contribute to photoreceptor cell loss in retinal degenerative disorders. The metabolic state of the retina in a rodent model of retinitis pigmentosa (RP) was investigated using a cryo-fluorescence imaging technique. The mitochondrial metabolic coenzymes nicotinamide adenine dinucleotide (NADH) and flavin adenine dinucleotide (FAD) are autofluorescent and can be monitored without exogenous labels using optical techniques. The cryo-fluorescence redox imaging technique provides a quantitative assessment of the metabolism. More specifically, the ratio of the fluorescence intensity of these fluorophores (NADH/FAD), the NADH redox ratio (RR), is a marker of the metabolic state of the tissue. The NADH RR and retinal function were examined in an established rodent model of RP, the P23H rat compared to that of nondystrophic Sprague-Dawley (SD) rats. The NADH RR mean values were 1.11±0.03 in the SD normal and 0.841±0.01 in the P23H retina, indicating increased OS in the P23H retina. Electroretinographic data revealed a significant reduction in photoreceptor function in P23H animals compared to SD nozrmal rats. Thus, cryo-fluorescence redox imaging was used as a quantitative marker of OS in eyes from transgenic rats and demonstrated that alterations in the oxidative state of eyes occur during the early stages of RP.

  8. Investigation of AA2024-T3 surfaces modified by cerium compounds: A localized approach

    International Nuclear Information System (INIS)

    Paussa, L.; Andreatta, F.; De Felicis, D.; Bemporad, E.; Fedrizzi, L.

    2014-01-01

    Highlights: •The precipitation of cerium compounds occurs on the entire AA2024-T3 surface. •The matrix is less involved in the cerium precipitation. •Cerium intensely precipitates on Mg-rich IM particles. •The electrochemical behavior of Mg-rich IM particles influences the mechanism of cerium precipitation. -- Abstract: The precipitation of cerium compounds on polished AA2024-T3 surfaces was investigated following an electrochemical and microstructural localized approach. It was found that cerium precipitation occurs on the entire surface covering intermetallic particles and the matrix as well. The matrix is the region where the precipitation of cerium is less favoured. The highest amount of cerium was observed on magnesium-rich intermetallic particles. The localized analyses suggest that precipitation of cerium on magnesium-rich intermetallic particles could happen following two mechanisms: the former based on a potential reversal of the intermetallic particles and the latter due to a partial magnesium dissolution

  9. The influence of operational parameters on the performance of an undivided zinc–cerium flow battery

    International Nuclear Information System (INIS)

    Leung, P.K.; Ponce de Leon, C.; Walsh, F.C.

    2012-01-01

    Highlights: ► The performance of an undivided zinc–cerium flow battery under different conditions of temperature, concentration and electrolyte flow rate, was evaluated. ► Mixed electrolytes were considered; methanesulfonate and sulfate anions were tested. ► In a 30 min charge/discharge at 20 mA cm −2 , charge and energy efficiencies were 82% and 72%, respectively. ► After 4 h charge, the conversion of Ce(III) to Ce(IV) became less efficient with the oxygen evolution reaction becoming more favored. ► After a larger number of cycles the carbon felt electrode was electro- and chemically-oxidized by Ce(IV) leading to degradation of the positive electrode. - Abstract: An undivided zinc–cerium redox flow battery was studied under a wide range of operational conditions, including: (i) electrolyte composition; the concentrations of ([Zn 2+ ], [Ce 3+ ] and [H + ]), (ii) current density (0–80 mA cm −2 ), (iii) electrolyte flow linear velocity (0.64–7.0 cm s −1 ) and (iv) temperature (20–60 °C). The charge efficiency increased at higher current densities and at higher electrolyte flow velocities. Unlike the divided zinc–cerium system, the charge–discharge performance decreased at higher temperature, since oxygen evolution became increasingly favored at the positive electrode. The use of a low acid concentration led to a poor conversion of Ce(III) to Ce(IV) ions during the discharge cycle. Mixed electrolytes containing methanesulfonate and sulfate anions have been evaluated at a high Ce(III) ion concentration, e.g. 0.4 mol dm −3 . After charging the battery for 4 h, the conversion of Ce(III) to Ce(IV) ions became less efficient over time due to a greater fraction of the current being used in oxygen evolution. Critical aspects for improvements in the battery performance are considered.

  10. Lattice dynamics of α-cerium

    International Nuclear Information System (INIS)

    Smith, G.S.

    1985-01-01

    The lattice dynamics of the fcc α-phase of cerium metal was investigated using inelastic neutron scattering techniques. This phase of cerium is an example of a mixed-valent system. Various physical properties of α-Ce suggest that there may be coupling between the phonons and the f d transitions associated with the mixed valence phenomenon. These measurements of the dispersion curves provide important information about the electron-phonon interaction in this phase of cerium. These studies were not performed in the past because single crystals of α-Ce were not available. We were able to prepare a single α-Ce crystal using a high temperature, high pressure technique. The sample was of sufficient size for inelastic neutron scattering experiments, but the measurements were complicated because of the large mosaic spread (approx.7.0 0 ) of the crystal. It was possible, however, to obtain a set of dispersion curves along the [00zeta], [zeta,zeta,0], and [zeta,zeta,zeta] symmetry directions. Comparison of the dispersion curves with those of fcc γ-Ce indicate that the branches exhibit anomalous features that may be related to the mixed-valence effects

  11. Systems of cerium(3) nitrate-dimethyl amine nitrate-water and cerium(3) nitrate-dimethyl amine nitrate-water

    International Nuclear Information System (INIS)

    Mininkov, N.E.; Zhuravlev, E.F.

    1976-01-01

    Solubility of solid phases in the systems cerium(3)nitrate-water-dimethyl amine nitrate and cerium(3)nitrate-water-dimethyl amine nitrate has been st ed by the method of isothermal sections at 25 and 50 deo. C. It has been shown that one anhydrous compound is formed in each system with a ratio of cerium(3) nitrate to amine nitrate 1:5. The compounds formed in the systems have been separated from the corresponding solutions and studied by microcrystalloscopic, X-ray phase, thermal and infrared spectroscopic methods. On the basis of spectroscopic studies the following formula has been assigned to the compound: [(CH 3 ) 2 NH 2 + ] 5 x[Ce(NO 3 ) 8 ]. The thermal analysis of the compound has shown that its melting point is 106 deg C. The solubility isotherms in the system Ce(NO 3 ) 3 -H 2 O-(C 2 H 5 ) 2 NHxHNO 3 consist of three branches which intersect in two eutonic points

  12. Method of cerium separation from other lanthanides and yttrium

    International Nuclear Information System (INIS)

    Tran, Duc Hiep; Mostecky, J.

    1988-01-01

    Cerium is separated from a suspension produced during the aerial oxidation process. The suspension is subject to a cyclic process of two-stage fractional dissolution. Following the first dissolution, almost all cerium remains undissolved while 95% of the other lanthanides pass into the solution. The filtrate of the second stage of dissolution containing about 5% of ceriumm is returned for oxidation with the next batch of hydroxide mixed concentrate. Following oxidation, the two-stage fractional dissolution is repeated. This cycling provides quantitative cerium separation from other rare earth elements. (E.S.)

  13. Characterization of platinized and unplatinized cerium dioxide and other cerium containing catalyst supports

    International Nuclear Information System (INIS)

    Daniel, D.W.

    1984-01-01

    The adsorption of CO on platinized cerium dioxide has been investigated by FTIR (Fourier Transform Infrared Spectroscopy). Four active surface sites and two adsorption geometries were found for the oxidized catalyst. Although the metallic sites and both geometries, linear and bridged, were retained upon reduction the two cationic sites were not. During stepwise desorption, CO dissociates leaving behind adsorbed carbon inhibiting readsorption. At elevated temperatures CeO 2 oxidizes Pt. The large decrease in CO adsorption resulting from high temperature reduction was reversed by reoxidation. XPS (X-ray Photoelectron Spectroscopy) data provided no evidence of encapsulation and XRD (X-ray Diffraction) showed the retention of a constant particle size. The results were interpreted as electronic metal-support interaction. The addition of H 2 or D 2 to adsorbed CO at 25 0 C caused spillover of the CO onto the support and a decrease in CO band frequency. When O 2 was added to preadsorbed CO a new band associated with oxygen and CO coadsorbed on a single Pt atom appeared. Carbon dioxide dissociation at room temperature is proposed to occur via a Langmuir-Hinshelwood mechanism. CO adsorption on platinized titania, silica, ceria/titania, ceria/silica, and cerium titanate has also been studied by the same techniques. The adsorption/desorption behavior of the cerium/titania and the single oxide systems paralleled that of Pt/CeO 2

  14. Stepwise hydrochloric acid extraction of monazite hydroxides for the recovery of cerium lean rare earths, cerium, uranium and thorium

    International Nuclear Information System (INIS)

    Swaminathan, T.V.; Nair, V.R.; John, C.V.

    1988-01-01

    Monazite sand is normally processed by the caustic soda route to produce mixed rare earth chloride, thorium hydroxide and trisodium phosphate. Bulk of the mixed rare earth chloride is used for the preparation of FC catalysts. Recently some of the catalyst producers have shown preference to cerium depleted (lanthanum enriched) rare earth chloride rather than the natural rare earth chloride obtained from monazite. Therefore, a process for producing cerium depleted rare earth chloride, cerium, thorium and uranium from rare earth + thorium hydroxide obtained by treating monazite, based on stepwise hydrochloric acid extraction, was developed in the authors laboratory. The process involves drying of the mixed rare earth-thorium hydroxide cake obtained by monazite-caustic soda process followed by stepwise extraction of the dried cake with hydrochloric acid under specified conditions

  15. Studies on the promotion of nickel—alumina coprecipitated catalysts: III. Cerium oxide

    NARCIS (Netherlands)

    Lansink Rotgerink, H.G.J.; Slaa, J.C.; van Ommen, J.G.; Ross, J.R.H.

    1988-01-01

    Three series of cerium-promoted nickel—alumina catalysts with different nickel-to-aluminium ratios each containing different amounts of cerium have been prepared and characterized. The calcination and reduction behaviour were found not to be altered by the presence of cerium. Part of the promoter

  16. Cerium-doped scintillating fused-silica fibers

    Science.gov (United States)

    Akchurin, N.; Cowden, C.; Damgov, J.; Dragoiu, C.; Dudero, P.; Faulkner, J.; Kunori, S.

    2018-04-01

    We report on a set of measurements made on (scintillating) cerium-doped fused-silica fibers using high-energy particle beams. These fibers were uniformly embedded in a copper absorber in order to utilize electromagnetic showers as a source of charged particles for generating signals. This new type of cerium-doped fiber potentially offers myriad new applications in calorimeters in high-energy physics, tracking systems, and beam monitoring detectors for future applications. The light yield, pulse shape, attenuation length, and light propagation speeds are given and discussed. Possible future applications are also explored.

  17. Engineering redox balance through cofactor systems.

    Science.gov (United States)

    Chen, Xiulai; Li, Shubo; Liu, Liming

    2014-06-01

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

  18. Cerium, uranium, and plutonium behavior in glass-bonded sodalite, a ceramic nuclear waste form

    International Nuclear Information System (INIS)

    Lewis, M. A.; Lexa, D.; Morss, L. R.; Richmann, M. K.

    1999-01-01

    Glass-bonded sodalite is being developed as a ceramic waste form (CWF) to immobilize radioactive fission products, actinides, and salt residues from electrometallurgical treatment of spent nuclear reactor fuel. The CWF consists of about 75 mass % sodalite, 25 mass % glass, and small amounts of other phases. This paper presents some results and interpretation of physical measurements to characterize the CWF structure, and dissolution tests to measure the release of matrix components and radionuclides from the waste form. Tests have been carried out with specimens of the CWF that contain rare earths at concentrations similar to those expected in the waste form. Parallel tests have been carried out on specimens that have uranium or plutonium as well as the rare earths at concentrations similar to those expected in the waste forms; in these specimens UCl 3 forms UO 2 and PuCl 3 forms PuO 2 . The normalized releases of rare earths in dissolution tests were found to be much lower than those of matrix elements (B, Si, Al, Na). When there is no uranium in the CWF, the release of cerium is two to ten times lower than the release of the other rare earths. The low release of cerium may be due to its tetravalent state in uranium-free CWF. However, when there is uranium in the CWF, the release of cerium is similar to that of the other rare earths. This trivalent behavior of cerium is attributed to charge transfer or covalent interactions among cerium, uranium, and oxygen in (U,Ce)O 2

  19. In vivo NAD assay reveals the intracellular NAD contents and redox state in healthy human brain and their age dependences

    Science.gov (United States)

    Zhu, Xiao-Hong; Lu, Ming; Lee, Byeong-Yeul; Ugurbil, Kamil; Chen, Wei

    2015-01-01

    NAD is an essential metabolite that exists in NAD+ or NADH form in all living cells. Despite its critical roles in regulating mitochondrial energy production through the NAD+/NADH redox state and modulating cellular signaling processes through the activity of the NAD+-dependent enzymes, the method for quantifying intracellular NAD contents and redox state is limited to a few in vitro or ex vivo assays, which are not suitable for studying a living brain or organ. Here, we present a magnetic resonance (MR) -based in vivo NAD assay that uses the high-field MR scanner and is capable of noninvasively assessing NAD+ and NADH contents and the NAD+/NADH redox state in intact human brain. The results of this study provide the first insight, to our knowledge, into the cellular NAD concentrations and redox state in the brains of healthy volunteers. Furthermore, an age-dependent increase of intracellular NADH and age-dependent reductions in NAD+, total NAD contents, and NAD+/NADH redox potential of the healthy human brain were revealed in this study. The overall findings not only provide direct evidence of declined mitochondrial functions and altered NAD homeostasis that accompany the normal aging process but also, elucidate the merits and potentials of this new NAD assay for noninvasively studying the intracellular NAD metabolism and redox state in normal and diseased human brain or other organs in situ. PMID:25730862

  20. Preparation of high-purity cerium nitrate; Preparacao de nitrato de cerio de alta pureza

    Energy Technology Data Exchange (ETDEWEB)

    Avila, Daniela Moraes; Silva Queiroz, Carlos Alberto da; Santos Mucillo, Eliana Navarro dos [Instituto de Pesquisas Energeticas e Nucleares (IPEN), Sao Paulo, SP (Brazil)

    1995-12-31

    The preparation of high-purity cerium nitrate has been carried out Cerium oxide has been prepared by fractioned precipitation and ionic exchange techniques, using a concentrate with approximately 85% of cerium oxide from NUCLEMON as raw material. Five sequential ion-exchange columns with a retention capacity of 170 g each have been used. The ethylenediamine-tetraacetic acid (EDTA) was used as eluent. The cerium content has been determined by gravimetry and iodometry techniques. The resulting cerium oxide has a purity > 99%. This material was transformed in cerium nitrate to be used as precursor for the preparation of Zirconia-ceria ceramics by the coprecipitation technique. (author) 2 tabs.

  1. Synthesis and crystal kinetics of cerium oxide nanocrystallites prepared by co-precipitation process

    International Nuclear Information System (INIS)

    Shih, C.J.; Chen, Y.J.; Hon, M.H.

    2010-01-01

    Cerium oxide nanocrystallites were synthesized at a relatively low temperature using cerium nitrate as starting materials in a water solution by a co-precipitation process. Effect of calcination temperature on the crystallite growth of cerium oxide nano-powders was investigated by X-ray diffraction, transmission electron microscopy and electron diffraction. The crystallization temperature of the cerium oxide powders was estimated to be about 273 K by XRD analysis. When calcined from 473 to 1273 K, the crystallization of the face-centered cubic phase was observed by XRD. The crystallite size of the cerium oxide increased from 10.0 to 43.8 nm with calcining temperature increasing from 673 to 1273 K. The activation energy for growth of cerium oxide nanoparticles was found to be 16.0 kJ mol -1 .

  2. Synthesis and crystal kinetics of cerium oxide nanocrystallites prepared by co-precipitation process

    Energy Technology Data Exchange (ETDEWEB)

    Shih, C.J., E-mail: cjshih@kmu.edu.tw [Department of Fragrance and Cosmetics Science, Kaohsiung Medical University, 100 Shi-Chuan 1st Road, Kaohsiung 807, Taiwan (China); Chen, Y.J. [Institute of Biomedical Sciences, National Sun Yat-Sen University, Kaohsiung 804, Taiwan (China); Hon, M.H. [Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan (China)

    2010-05-15

    Cerium oxide nanocrystallites were synthesized at a relatively low temperature using cerium nitrate as starting materials in a water solution by a co-precipitation process. Effect of calcination temperature on the crystallite growth of cerium oxide nano-powders was investigated by X-ray diffraction, transmission electron microscopy and electron diffraction. The crystallization temperature of the cerium oxide powders was estimated to be about 273 K by XRD analysis. When calcined from 473 to 1273 K, the crystallization of the face-centered cubic phase was observed by XRD. The crystallite size of the cerium oxide increased from 10.0 to 43.8 nm with calcining temperature increasing from 673 to 1273 K. The activation energy for growth of cerium oxide nanoparticles was found to be 16.0 kJ mol{sup -1}.

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

    Science.gov (United States)

    Cardaci, Simone; Ciriolo, Maria Rosa

    2012-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Simone Cardaci

    2012-01-01

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

  5. Ce(III)/Ce(IV) in methanesulfonic acid as the positive half cell of a redox flow battery

    International Nuclear Information System (INIS)

    Leung, P.K.; Ponce de Leon, C.; Low, C.T.J.; Walsh, F.C.

    2011-01-01

    The characteristics of the Ce(III)/Ce(IV) redox couple in methanesulfonic acid were studied at a platinum disk electrode (0.125 cm 2 ) over a wide range of electrolyte compositions and temperatures: cerium (III) methanesulfonate (0.1-1.2 mol dm -3 ), methanesulfonic acid (0.1-5.0 mol dm -3 ) and electrolyte temperatures (295-333 K). The cyclic voltammetry experiments indicated that the diffusion coefficient of Ce(III) ions was 0.5 x 10 -6 cm 2 s -1 and that the electrochemical kinetics for the oxidation of Ce(III) and the reduction of Ce(IV) was slow. The reversibility of the redox reaction depended on the electrolyte composition and improved at higher electrolyte temperatures. At higher methanesulfonic acid concentrations, the degree of oxygen evolution decreased by up to 50% when the acid concentration increased from 2 to 5 mol dm -3 . The oxidation of Ce(III) and reduction of Ce(IV) were also investigated during a constant current batch electrolysis in a parallel plate zinc-cerium flow cell with a 3-dimensional platinised titanium mesh electrode. The current efficiencies over 4.5 h of the process Ce(III) to Ce(IV) and 3.3 h electrolysis of the reverse reaction Ce(IV) to Ce(III) were 94.0 and 97.6%, respectively. With a 2-dimensional, planar platinised titanium electrode (9 cm 2 area), the redox reaction of the Ce(III)/Ce(IV) system was under mass-transport control, while the reaction on the 3-dimensional mesh electrode was initially under charge-transfer control but became mass-transport controlled after 2.5-3 h of electrolysis. The effect of the side reactions (hydrogen and oxygen evolution) on the current efficiencies and the conversion of Ce(III) and Ce(IV) are discussed.

  6. Assessing Covalency in Cerium and Uranium Hexachlorides: A Correlated Wavefunction and Density Functional Theory Study

    Directory of Open Access Journals (Sweden)

    Reece Beekmeyer

    2015-11-01

    Full Text Available The electronic structure of a series of uranium and cerium hexachlorides in a variety of oxidation states was evaluated at both the correlated wavefunction and density functional (DFT levels of theory. Following recent experimental observations of covalency in tetravalent cerium hexachlorides, bonding character was studied using topological and integrated analysis based on the quantum theory of atoms in molecules (QTAIM. This analysis revealed that M–Cl covalency was strongly dependent on oxidation state, with greater covalency found in higher oxidation state complexes. Comparison of M–Cl delocalisation indices revealed a discrepancy between correlated wavefunction and DFT-derived values. Decomposition of these delocalisation indices demonstrated that the origin of this discrepancy lay in ungerade contributions associated with the f-manifold which we suggest is due to self-interaction error inherent to DFT-based methods. By all measures used in this study, extremely similar levels of covalency between complexes of U and Ce in the same oxidation state was found.

  7. Effect of cerium oxide addition on electrical properties of ZnO

    Energy Technology Data Exchange (ETDEWEB)

    Ibrahim, D.M. [National Research Center, Dokki, Giza (Egypt). Dept. of Ceramics; Mounir, M. [Dept. of Physics, Cairo Univ., Giza (Egypt); Mahgoub, A.S. [Cairo Univ., Giza (Egypt). Dept. of Chemistry; Turky, G. [Dept. of Physics, National Research Center, Dokki, Giza (Egypt); El-Desouky, O.A. [Cer. Cleopatra Co., Ramadan City (Egypt)

    2002-07-01

    Mixtures of ZnO and Ce{sub 6} O{sub 11} as additive were prepared by solid state reaction from the calcined oxides with the following proportions: 0.03, 0.08, 0.1, 0.2 and 0.4 mole. Disc specimens 1.2 cm 5 cm in diameter and 0.3 cm thickness were processed under a force of 70 kN and fired at 1150 C/ 30 minutes. XRD revealed the presence of limited solid solution of cerium in ZnO, as evident from the shift in the peaks [0.03-0.04 A ] up to 0.1 mole addition and remains constant. SEM revealed the presence of inter-granular phase. EDAX showed it to be a mixture of ZnO and Ce{sub 6}O{sub 11}. Also cerium was detected in the ZnO grains confirming the XRD results. RCL circuit was used to measure the capacitance and resistance at different frequencies at room temperature. The dielectric constant and conductivity were calculated. The change in resistivity with temperature was followed up to 523 K. The change in dielectric strength with temperature at spot frequency of 10 kHz is demonstrated. The electrical conductivity was found to increase with the proportion of cerium oxide up to 0.2 mole then decreased. (orig.)

  8. Synthesis and characterization of magnesium doped cerium oxide for the fuel cell application

    International Nuclear Information System (INIS)

    Kumar, Amit; Kumari, Monika; Kumar, Mintu; Kumar, Sacheen; Kumar, Dinesh

    2016-01-01

    Cerium oxide has attained much attentions in global nanotechnology market due to valuable application for catalytic, fuel additive, and widely as electrolyte in solid oxide fuel cell. Doped cerium oxide has large oxygen vacancies that allow for greater reactivity and faster ion transport. These properties make cerium oxide suitable material for SOFCs application. Cerium oxide electrolyte requires lower operation temperature which shows improvement in processing and the fabrication technique. In our work, we synthesized magnesium doped cerium oxide by the co-precipitation method. With the magnesium doping catalytic reactivity of CeO_2 was increased. Synthesized nanoparticle were characterized by the XRD and UV absorption techniques.

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

    Science.gov (United States)

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

    2013-12-01

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

  10. Chloroplast Redox Poise

    DEFF Research Database (Denmark)

    Steccanella, Verdiana

    the redox status of the plastoquinone pool and chlorophyll biosynthesis. Furthermore, in the plant cell, the equilibrium between redox reactions and ROS signals is also maintained by various balancing mechanisms among which the thioredoxin reductase-thioredoxin system (TR-Trx) stands out as a mediator......The redox state of the chloroplast is maintained by a delicate balance between energy production and consumption and is affected by the need to avoid increased production of reactive oxygen species (ROS). Redox power and ROS generated in the chloroplast are essential for maintaining physiological...... metabolic pathways and for optimizing chloroplast functions. The redox poise of photosynthetic electron transport components like plastoquinone is crucial to initiate signaling cascades and might also be involved in key biosynthetic pathways such as chlorophyll biosynthesis. We, therefore, explored...

  11. Defect states and room temperature ferromagnetism in cerium oxide nanopowders prepared by decomposition of Ce-propionate

    DEFF Research Database (Denmark)

    Mihalache, V.; Grivel, J. C.; Secu, M.

    2018-01-01

    . An improvement of ferromagnetism and intensity of defect-related PL emission was observed when annealing the products in which nanocrystalline cerium oxide coexists with Ce - oxicarbonate traces, Ce2O2CO3. The experimental results were explained based on the following considerations: room temperature......Four batches of cerium oxide powders (with nanocrystallite size of 6.9 nm–572 nm) were prepared from four precursor nanopowders by thermal decomposition of Ce-propionate and annealing in air between 250 °C–1200 °C for 10 min–240 min. Ceria formation reactions, structure, vibrational, luminescence...... and magnetic properties were investigated by differential scanning calorimetry, x-ray diffraction, electron microscopy, infrared spectroscopy, photoluminescence and SQUID. All the samples exhibit room temperature ferromagnetism, RTFM, (with coercivity, Hc, of 8 Oe - 121 Oe and saturation magnetization, Ms...

  12. Thin film ionic conductors based on cerium oxide

    International Nuclear Information System (INIS)

    Haridoss, P.; Hellstrom, E.; Garzon, F.H.; Brown, D.R.; Hawley, M.

    1994-01-01

    Fluorite and perovskite structure cerium oxide based ceramics are a class of materials that may exhibit good oxygen ion and/or protonic conductivity. The authors have successfully deposited thin films of these materials on a variety of substrates. Interesting orientation relationships were noticed between cerium oxide films and strontium titanate bi-crystal substrates. Near lattice site coincidence theory has been used to study these relationships

  13. Redox-Based Regulation of Bacterial Development and Behavior.

    Science.gov (United States)

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

    2017-06-20

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

  14. Antimicrobial cerium ion-chitosan crosslinked alginate biopolymer films: A novel and potential wound dressing.

    Science.gov (United States)

    Kaygusuz, Hakan; Torlak, Emrah; Akın-Evingür, Gülşen; Özen, İlhan; von Klitzing, Regine; Erim, F Bedia

    2017-12-01

    Wound dressings require good antiseptic properties, mechanical strength and, more trustably, natural material ingredients. Antimicrobial properties of cerium ions and chitosan are known and alginate based wound dressings are commercially available. In this study, the advantages of these materials were combined and alginate films were crosslinked with cerium(III) solution and chitosan added cerium(III) solution. Films were characterized by Fourier transform infrared spectroscopy (FTIR), light transmittance, scanning electron microscopy (SEM), swelling experiments, water vapor transmittance tests, and mechanical stretching tests. The antibacterial and physical properties of the films were compared with those of conventional calcium alginate films. Both cerium ion crosslinked and cerium ion-chitosan crosslinked alginate films gained antibacterial activity against Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria. Cerium alginate-chitosan films showed high resistance to being deformed elastically. Results show that cerium alginate-chitosan films can be flexible, ultraviolet-protecting, and antibacterial wound dressings. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Effects of iron concentration and redox states on failure of boron-free ...

    Indian Academy of Sciences (India)

    Effects of iron concentration and redox states on failure of boron-free E-glass fibres under applied stress in different conditions ... Materials, Donghua University, Shanghai 201620, China; Material Research Center, Missouri University of Science and Technology, Rolla 65409, USA; Fiber Glass Science and Technology, ...

  16. Casting Characteristics of High Cerium Content Aluminum Alloys

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, D; Rios, O R; Sims, Z C; McCall, S K; Ott, R T

    2017-09-05

    This paper compares the castability of the near eutectic aluminum-cerium alloy system to the aluminum-silicon and aluminum-copper systems. The alloys are compared based on die filling capability, feeding characteristics and tendency to hot tear in both sand cast and permanent mold applications. The castability ranking of the binary Al–Ce systems is as good as the aluminum-silicon system with some deterioration as additional alloying elements are added. In alloy systems that use cerium in combination with common aluminum alloying elements such as silicon, magnesium and/or copper, the casting characteristics are generally better than the aluminum-copper system. In general, production systems for melting, de-gassing and other processing of aluminum-silicon or aluminum-copper alloys can be used without modification for conventional casting of aluminum-cerium alloys.

  17. Comparison of Titration ICP and XRF Spectrometry Methods in Determination of Cerium in Lens Polishing Powder

    International Nuclear Information System (INIS)

    Ninlaphruk, Sumalee; Pichestapong, Pipat; Mungpayabal, Harinate; Jiyavaranant, Thitima; Srisukho, Supapan; Chaisai, Prapassurn

    2004-10-01

    Three analytical methods in determination of cerium in cerium oxide separated from monazite ore for producing lens polishing powder were compared. These methods are titration ICP and XRF spectrometry techniques. The cerium oxide sample with estimated 45% cerium content needed to be digested and converted into solution before the analysis. The analytical results shown significantly no difference between each method. However, the titration method was found to be more convenient and suitable for quality control in the production of cerium oxide as it does not require standard cerium and the complicated analytical instruments

  18. Direct growth of cerium oxide nanorods on diverse substrates for superhydrophobicity and corrosion resistance

    International Nuclear Information System (INIS)

    Cho, Young Jun; Jang, Hanmin; Lee, Kwan-Soo; Kim, Dong Rip

    2015-01-01

    Graphical abstract: - Highlights: • Cerium oxide nanorods were uniformly grown on diverse substrates. • Changes in growth conditions led to morphology evolution of cerium oxide nanostructures. • The grown cerium oxide nanostructures were single or poly crystalline. • Direct growth of cerium oxide nanorods made the diverse substrates superhydrophobic and anti-corrosive without any surface modifiers. - Abstract: Superhydrophobic surfaces with anti-corrosion properties have attracted great interest in many industrial fields, particularly to enhance the thermal performance of offshore applications such as heat exchangers, pipelines, power plants, and platform structures. Nanostructures with hydrophobic materials have been widely utilized to realize superhydrophobicity of surfaces, and cerium oxide has been highlighted due to its good corrosion resistive and intrinsically hydrophobic properties. However, few studies of direct growth of cerium oxide nanostructures on diverse substrates have been reported. Herein we report a facile hydrothermal method to directly grow cerium oxide nanorods on diverse substrates, such as aluminum alloy, stainless steel, titanium, and silicon. Diverse substrates with cerium oxide nanorods exhibited superhydrophobicity with no hydrophobic modifiers on their surfaces, and showed good corrosion resistive properties in corrosive medium. We believe our method could pave the way for realization of scalable and sustainable corrosion resistive superhydrophobic surfaces in many industrial fields

  19. Direct growth of cerium oxide nanorods on diverse substrates for superhydrophobicity and corrosion resistance

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Young Jun; Jang, Hanmin; Lee, Kwan-Soo [School of Mechanical Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Kim, Dong Rip, E-mail: dongrip@hanyang.ac.kr [School of Mechanical Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Institute of Nano Science and Technology, Hanyang University, Seoul 133-791 (Korea, Republic of)

    2015-06-15

    Graphical abstract: - Highlights: • Cerium oxide nanorods were uniformly grown on diverse substrates. • Changes in growth conditions led to morphology evolution of cerium oxide nanostructures. • The grown cerium oxide nanostructures were single or poly crystalline. • Direct growth of cerium oxide nanorods made the diverse substrates superhydrophobic and anti-corrosive without any surface modifiers. - Abstract: Superhydrophobic surfaces with anti-corrosion properties have attracted great interest in many industrial fields, particularly to enhance the thermal performance of offshore applications such as heat exchangers, pipelines, power plants, and platform structures. Nanostructures with hydrophobic materials have been widely utilized to realize superhydrophobicity of surfaces, and cerium oxide has been highlighted due to its good corrosion resistive and intrinsically hydrophobic properties. However, few studies of direct growth of cerium oxide nanostructures on diverse substrates have been reported. Herein we report a facile hydrothermal method to directly grow cerium oxide nanorods on diverse substrates, such as aluminum alloy, stainless steel, titanium, and silicon. Diverse substrates with cerium oxide nanorods exhibited superhydrophobicity with no hydrophobic modifiers on their surfaces, and showed good corrosion resistive properties in corrosive medium. We believe our method could pave the way for realization of scalable and sustainable corrosion resistive superhydrophobic surfaces in many industrial fields.

  20. Dielectric parameters of blood plasma of rats treated with cerium-144 and external irradiation

    International Nuclear Information System (INIS)

    Hadzhidekova, E.; Kiradzhiev, G.; Paskalev, Z.; Miloslavov, V.

    1988-01-01

    Investigation was carried out of the dielectric parameters of blood plasma of male Wistar rats treated with cerium 144 in doses of 370 kBq/animal and external gamma irradiation in doses of 200 cGy and 400 cGy. The radioactive cerium was introduced intraperitoneally 1 h after the external irradiation with dose rate of 1,6 cGy/sec. The permittivity ε, the time of relaxation τ and the coefficient of Debaye κ of plasma protein molecules were determined at the 1st, 3rd, 10th, 15th, and 30th days after treatement for frequence ranges of 1,4, 2,2, 3,6 and 6 MHz. At the same terms the content of cerium 144 was measured in the organs of predilectional accumulation of cerium. It was established that the treatment only with cerium lead to most essential changes of dielectric parameters at frequence of 3,6 MHz. The external irradiation didn't influence essentially the kinetics of absorbed cerium. In combination of both radiation factors the action of cerium was predominant

  1. Critical indices for reversible gamma-alpha phase transformation in metallic cerium

    Science.gov (United States)

    Soldatova, E. D.; Tkachenko, T. B.

    1980-08-01

    Critical indices for cerium have been determined within the framework of the pseudobinary solution theory along the phase equilibrium curve, the critical isotherm, and the critical isobar. The results obtained verify the validity of relationships proposed by Rushbrook (1963), Griffiths (1965), and Coopersmith (1968). It is concluded that reversible gamma-alpha transformation in metallic cerium is a critical-type transformation, and cerium has a critical point on the phase diagram similar to the critical point of the liquid-vapor system.

  2. Characterization of microstructure and catalytic of cerium oxide obtained by colloidal solution

    International Nuclear Information System (INIS)

    Senisse, C.A.L.; Bergmann, C.P.; Alves, A.K.

    2012-01-01

    This study investigated to obtain particles of cerium oxide, for use as catalysts for the combustion of methane using the technique of through polymeric colloidal solution. Obtaining the colloidal system is based on hydrolysis of salts such as cerium acetylacetonate, cerium nitrate in the presence of additives such as polyvinylbutyral (PVB), polyvinylpyrrolidone (PVP) and polyvinyl acetate (PVA), at concentrations of 5, 10 and 15% in aqueous or alcoholic medium. These solutions containing ions of interest were subjected to a heat treatment at 650° C for 30 minutes, with heating rate of 2 ° C/ min. After heat treatment, the fibers were characterized according to their morphology, surface area, crystallinity, weight loss and catalytic activity. Samples obtained from cerium acetylacetonate were more reactive than the cerium nitrate to the combustion of methane, as showed greater conversions and higher temperatures reached during the process, which is of utmost importance since the combustion catalytic methane is used for generating thermal energy. After the reaction with methane, the samples underwent significant change in surface area, probably due to the intensity of combustion reactions of the nitrate and the generation of heat involved in this reaction, which gave rise to coarse particles. During the combustion process using the obtained from particles of cerium acetylacetonate, there was the release of large quantities of nitrogen compared to the results of assays with the particles obtained with cerium nitrate. (author)

  3. a redox state-controlled toxicity of cerium oxide nanoparticles

    Indian Academy of Sciences (India)

    2017-09-22

    Sep 22, 2017 ... neutralized by the altered surface chemistry of CeNPs with high (Ce (+3)/Ce (+4)) ratio. On the contrary ... microbial cell wall is permeable to ions only and not to ..... depicted by its very low solubility constant in water. In addi-.

  4. Redox Regulation of Mitochondrial Function

    Science.gov (United States)

    Handy, Diane E.

    2012-01-01

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

  5. EXAFS and XANES analysis of plutonium and cerium edges from titanate ceramics for fissile materials disposal

    International Nuclear Information System (INIS)

    Fortner, J. A.; Kropf, A. J.; Bakel, A. J.; Hash, M. C.; Aase, S. B.; Buck, E. C.; Chamerlain, D. B.

    1999-01-01

    We report x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) spectra from the plutonium L III edge and XANES from the cerium L II edge in prototype titanate ceramic hosts. The titanate ceramics studied are based upon the hafnium-pyrochlore and zirconolite mineral structures and will serve as an immobilization host for surplus fissile materials, containing as much as 10 weight % fissile plutonium and 20 weight % (natural or depleted) uranium. Three ceramic formulations were studied: one employed cerium as a ''surrogate'' element, replacing both plutonium and uranium in the ceramic matrix, another formulation contained plutonium in a ''baseline'' ceramic formulation, and a third contained plutonium in a formulation representing a high-impurity plutonium stream. The cerium XANES from the surrogate ceramic clearly indicates a mixed III-IV oxidation state for the cerium. In contrast, XANES analysis of the two plutonium-bearing ceramics shows that the plutonium is present almost entirely as Pu(IV) and occupies the calcium site in the zirconolite and pyrochlore phases. The plutonium EXAFS real-space structure shows a strong second-shell peak, clearly distinct from that of PuO 2 , with remarkably little difference in the plutonium crystal chemistry indicated between the baseline and high-impurity formulations

  6. Nanoparticulate cerium dioxide and cerium dioxide-titanium dioxide composite thin films on glass by aerosol assisted chemical vapour deposition

    International Nuclear Information System (INIS)

    Qureshi, Uzma; Dunnill, Charles W.; Parkin, Ivan P.

    2009-01-01

    Two series of composite thin films were deposited on glass by aerosol assisted chemical vapour deposition (AACVD)-nanoparticulate cerium dioxide and nanoparticulate cerium dioxide embedded in a titanium dioxide matrix. The films were analysed by a range of techniques including UV-visible absorption spectroscopy, X-ray diffraction, scanning electron microscopy and energy dispersive analysis by X-rays. The AACVD prepared films showed the functional properties of photocatalysis and super-hydrophilicity. The CeO 2 nanoparticle thin films displaying photocatalysis and photo-induced hydrophilicity almost comparable to that of anatase titania.

  7. Separation of cerium and fractionation of rare earths from mixed chlorides

    International Nuclear Information System (INIS)

    Silva Queiroz, C.A. da; Sood, S.P.; Abrao, A.

    1982-01-01

    The separation of cerium from rare earths chlorides solutions by precipitation with hydrogen peroxide/air/dil. ammonium hydroxide; purification of cerium; fractionation by ion exchange and analytical control of the process are presented. (A.R.H.) [pt

  8. Solid-state electroanalytical characterization of the nonaqueous proton-conducting redox gel containing polyoxometallates

    International Nuclear Information System (INIS)

    Lewera, Adam; Zukowska, Grazyna; Miecznikowski, Krzysztof; Chojak, Malgorzata; Wieczorek, Wladyslaw; Kulesza, Pawel J.

    2005-01-01

    A novel polymetacrylate-based redox-conducting polymeric gel, into which Keggin-type polyoxometallate, phosphododecatungstic acid (H 3 PW 12 O 40 ), had been incorporated, was electrochemically characterized in the absence of external liquid supporting electrolyte using an ultramicrodisk-working electrode. The phosphotungstate component (15 wt.% of the gel block) was entrapped as the polar organic solvent solution within pores of the polymer matrix. H 3 PW 12 O 40 plays bifunctional role: it provides well-behaved redox centers and serves as strong acid (source of mobile protons). The solid-state voltammetric properties of the system are defined by the reversible one-electron transfers between phosphotungstate redox centers. The following parameters have been determined from the combination of potential step experiments performed in two limiting (radial and linear) diffusional regimes: the concentration of heteropolytungstate redox centers, 6 x 10 -2 mol dm -3 , and the apparent diffusion coefficient, 5 x 10 -7 cm 2 s -1 . The room temperature ionic (protonic) conductivity of the bulk gel was equal to 1.6 x 10 -3 S cm -1 . The charge propagation mechanism was found to be primarily controlled by physical diffusion of heteropolytungstate units within the gel pores rather than by electron hopping (self-exchange) between mixed-valence sites

  9. Unacylated ghrelin does not alter mitochondrial function, redox state and triglyceride content in rat liver in vivo

    Directory of Open Access Journals (Sweden)

    Gianluca Gortan Cappellari

    2015-12-01

    Full Text Available Changes in liver mitochondrial function with more oxidized redox state and enhanced inflammation may contribute to the onset of obesity- and insulin resistance-associated hepatic complications, including non-alcoholic fatty liver disease and steato-hepatitis. Unacylated ghrelin (UnAG is a gastric hormone reported to be associated with lower oxidative stress in different cell types, but its potential effects on liver mitochondrial function, redox state and inflammation in vivo remains undetermined. We investigated the impact of chronic UnAG overexpression (Tg Myh6/Ghrl leading to systemic upregulation of circulating hormone on mitochondrial ATP production, redox state (oxidized-to-total glutathione and inflammation markers in lean mice. Compared to wild-type animals (wt, Tg Myh6/Ghrl had superimposable liver weight, triglyceride content and plasma lipid profile. Liver mitochondrial enzyme activities and ATP production as well as oxidized-to-total glutathione were also similar in the two groups. In addition, no differences were observed in tissue inflammation marker TNF-alpha between wild-type and Tg Myh6/Ghrl animals. Thus, chronic systemic UnAG upregulation does not alter liver triglyceride content, mitochondrial function, redox state and inflammation markers in lean mice. These findings do not support a major role of UnAG as a physiological modulator of in vivo liver oxidative-lipid metabolism and inflammation.

  10. Two-phase titration of cerium(III) by permanganate

    International Nuclear Information System (INIS)

    Lazarev, A.I.; Lazareva, V.I.; Gerko, V.V.

    1987-01-01

    This paper presents a method for the two-phase titrimetric determination of cerium(III) with permanganate which does not require an expenditure of sugar and preliminary removal of chlorides and nitrates. The interaction of cerium(III) with permanganate at room temperature was studied as a function of the pH, the concentration of pyrophosphate, tetraphenylphosphonium (TPP), permanganate, and extraneous compounds, the rate of titration, and the time of stay of the solution in air before titration. The investigations were conducted according to the following methodology: water, solution of cerium(III) pyrophosphate, and TPP were introduced into an Erlenmeyer flask with a side branch near the bottom for clearer observation of the color of the chloroform phase. The authors established the given pH value, poured the water into a volume of 50 ml, and added chloroform. The result was titrated with permanganate solutions of various concentrations until a violet color appeared in the chloroform phase

  11. Mapping of redox state of mitochondrial cytochromes in live cardiomyocytes using Raman microspectroscopy

    DEFF Research Database (Denmark)

    Brazhe, Nadezda A; Treiman, Marek; Brazhe, Alexey R

    2012-01-01

    This paper presents a nonivasive approach to study redox state of reduced cytochromes [Formula: see text], [Formula: see text] and [Formula: see text] of complexes II and III in mitochondria of live cardiomyocytes by means of Raman microspectroscopy. For the first time with the proposed approach ...

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

    Science.gov (United States)

    Li, Lin Z.

    2012-01-01

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

  13. Ground-state thermodynamics of bistable redox-active donor-acceptor mechanically interlocked molecules.

    Science.gov (United States)

    Fahrenbach, Albert C; Bruns, Carson J; Cao, Dennis; Stoddart, J Fraser

    2012-09-18

    Fashioned through billions of years of evolution, biological molecular machines, such as ATP synthase, myosin, and kinesin, use the intricate relative motions of their components to drive some of life's most essential processes. Having control over the motions in molecules is imperative for life to function, and many chemists have designed, synthesized, and investigated artificial molecular systems that also express controllable motions within molecules. Using bistable mechanically interlocked molecules (MIMs), based on donor-acceptor recognition motifs, we have sought to imitate the sophisticated nanoscale machines present in living systems. In this Account, we analyze the thermodynamic characteristics of a series of redox-switchable [2]rotaxanes and [2]catenanes. Control and understanding of the relative intramolecular movements of components in MIMs have been vital in the development of a variety of applications of these compounds ranging from molecular electronic devices to drug delivery systems. These bistable donor-acceptor MIMs undergo redox-activated switching between two isomeric states. Under ambient conditions, the dominant translational isomer, the ground-state coconformation (GSCC), is in equilibrium with the less favored translational isomer, the metastable-state coconformation (MSCC). By manipulating the redox state of the recognition site associated with the GSCC, we can stimulate the relative movements of the components in these bistable MIMs. The thermodynamic parameters of model host-guest complexes provide a good starting point to rationalize the ratio of GSCC to MSCC at equilibrium. The bistable [2]rotaxanes show a strong correlation between the relative free energies of model complexes and the ground-state distribution constants (K(GS)). This relationship does not always hold for bistable [2]catenanes, most likely because of the additional steric and electronic constraints present when the two rings are mechanically interlocked with each other

  14. Magnetic and Mössbauer Study of Cerium-Based Reactive Sorbent

    Czech Academy of Sciences Publication Activity Database

    Jirásková, Yvonna; Buršík, Jiří; Životský, O.; Luňáček, J.; Janos, P.

    2017-01-01

    Roč. 131, č. 4 (2017), s. 1096-1098 ISSN 0587-4246. [CSMAG 2016 - Czech and Slovak Conference on Magnetism /16./. Košice, 13.06.2016-17.06.2016] R&D Projects: GA MŠk(CZ) LQ1601 Institutional support: RVO:68081723 Keywords : Cerium-based sorbent * magnetic properties * phase composition * composite Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 0.469, year: 2016

  15. Processing and Characterization of Sol-Gel Cerium Oxide Microspheres

    Energy Technology Data Exchange (ETDEWEB)

    McClure, Zachary D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Padilla Cintron, Cristina [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2016-09-27

    Of interest to space exploration and power generation, Radioisotope Thermoelectric Generators (RTGs) can provide long-term power to remote electronic systems without the need for refueling or replacement. Plutonium-238 (Pu-238) remains one of the more promising materials for thermoelectric power generation due to its high power density, long half-life, and low gamma emissions. Traditional methods for processing Pu-238 include ball milling irregular precipitated powders before pressing and sintering into a dense pellet. The resulting submicron particulates of Pu-238 quickly accumulate and contaminate glove boxes. An alternative and dust-free method for Pu-238 processing is internal gelation via sol-gel techniques. Sol-gel methodology creates monodisperse and uniform microspheres that can be packed and pressed into a pellet. For this study cerium oxide microspheres were produced as a surrogate to Pu-238. The similar electronic orbitals between cerium and plutonium make cerium an ideal choice for non-radioactive work. Before the microspheres can be sintered and pressed they must be washed to remove the processing oil and any unreacted substituents. An investigation was performed on the washing step to find an appropriate wash solution that reduced waste and flammable risk. Cerium oxide microspheres were processed, washed, and characterized to determine the effectiveness of the new wash solution.

  16. Investigation of multi-state charge-storage properties of redox-active organic molecules in silicon-molecular hybrid devices for DRAM and Flash applications

    Science.gov (United States)

    Gowda, Srivardhan Shivappa

    Molecular electronics has recently spawned a considerable amount of interest with several molecules possessing charge-conduction and charge-storage properties proposed for use in electronic devices. Hybrid silicon-molecular technology has the promise of augmenting the current silicon technology and provide for a transitional path to future molecule-only technology. The focus of this dissertation work has been on developing a class of hybrid silicon-molecular electronic devices for DRAM and Flash memory applications utilizing redox-active molecules. This work exploits the ability of molecules to store charges with single-electron precision at room temperature. The hybrid devices are fabricated by forming self-assembled monolayers of redox-active molecules on Si and oxide (SiO2 and HfO2) surfaces via formation of covalent linkages. The molecules possess discrete quantum states from which electrons can tunnel to the Si substrate at discrete applied voltages (oxidation process, cell write), leaving behind a positively charged layer of molecules. The reduction (erase) process, which is the process of electrons tunneling back from Si to the molecules, neutralizes the positively charged molecular monolayer. Hybrid silicon-molecular capacitor test structures were electrically characterized with an electrolyte gate using cyclic voltammetry (CyV) and impedance spectroscopy (CV) techniques. The redox voltages, kinetics (write/erase speeds) and charge-retention characteristics were found to be strongly dependent on the Si doping type and densities, and ambient light. It was also determined that the redox energy states in the molecules communicate with the valence band of the Si substrate. This allows tuning of write and read states by modulating minority carriers in n- and p-Si substrates. Ultra-thin dielectric tunnel barriers (SiO2, HfO2) were placed between the molecules and the Si substrate to augment charge-retention for Flash memory applications. The redox response was

  17. Cerium oxide and platinum nanoparticles protect cells from oxidant-mediated apoptosis

    International Nuclear Information System (INIS)

    Clark, Andrea; Zhu Aiping; Sun Kai; Petty, Howard R.

    2011-01-01

    Catalytic nanoparticles represent a potential clinical approach to replace or correct aberrant enzymatic activities in patients. Several diseases, including many blinding eye diseases, are promoted by excessive oxidant stress due to reactive oxygen species (ROS). Cerium oxide and platinum nanoparticles represent two potentially therapeutic nanoparticles that de-toxify ROS. In the present study, we directly compare these two classes of catalytic nanoparticles. Cerium oxide and platinum nanoparticles were found to be 16 ± 2.4 and 1.9 ± 0.2 nm in diameter, respectively. Using surface plasmon-enhanced microscopy, we find that these nanoparticles associate with cells. Furthermore, cerium oxide and platinum nanoparticles demonstrated superoxide dismutase catalytic activity, but did not promote hemolytic or cytolytic pathways in living cells. Importantly, both cerium oxide and platinum nanoparticles reduce oxidant-mediated apoptosis in target cells as judged by the activation of caspase 3. The ability to diminish apoptosis may contribute to maintaining healthy tissues.

  18. How the redox state of tobacco 'Bel-W3' is modified in response to ozone and other environmental factors in a sub-tropical area?

    International Nuclear Information System (INIS)

    Dias, Ana P.L.; Dafre, Marcelle; Rinaldi, Mirian C.S.; Domingos, Marisa

    2011-01-01

    This study intended to determine whether the redox state in plants of Nicotiana tabacum 'Bel-W3' fluctuates in response to the environmental factors in a sub-tropical area contaminated by ozone (Sao Paulo, SE - Brazil) and which environmental factors are related to this fluctuation, discussing their biomonitoring efficiency. We comparatively evaluated the indicators of redox state (ascorbic acid, glutathione, superoxide dismutase, ascorbate peroxidase, and glutathione reductase) and leaf injury in 17 field experiments performed in 2008. The redox state was explained by the combined effects of chronic levels of O 3 and meteorological variables 4-6 days prior to the plant sampling. Moderate leaf injury was observed in most cases. The redox state of tobacco decreases few days after their placement in the sub-tropical environment, causing them to become susceptible to oxidative stress imposed by chronic doses of O 3 . Its bioindicator efficiency would not be diminished in such levels of atmospheric contamination. - Research highlights: → Nicotiana tabacum 'Bel-W3' is potentially a bioindicator of O 3 in the sub-tropics. → However, it is unknown if its redox state would affect its bioindicator performance under sub-tropical environmental conditions. → This study revealed that the redox state of tobacco decreases few days after their placement in the sub-tropical environment, causing them to become susceptible to oxidative stress imposed by chronic doses of O 3 . → Therefore, its bioindicator efficiency would not be diminished in such levels of atmospheric contamination. → However, the bioindicator efficiency N. tabacum 'Bel-W3' for biomonitoring O 3 should be regionally modeled in the sub-tropics, based on both its redox state and on the flux of O 3 through stomata, in response to the varying micro-meteorological conditions that govern both physiological processes. - The bioindicator efficiency of tobacco plants is not restrained under chronic doses of O 3 in

  19. Structure and Electronic Properties of Cerium Orthophosphate: Theory and Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Adelstein, Nicole; Mun, B. Simon; Ray, Hannah; Ross Jr, Phillip; Neaton, Jeffrey; De Jonghe, Lutgard

    2010-07-27

    Structural and electronic properties of cerium orthophosphate (CePO{sub 4}) are calculated using density functional theory (DFT) with the local spin-density approximation (LSDA+U), with and without gradient corrections (GGA-(PBE)+U), and compared to X-ray diffraction and photoemission spectroscopy measurements. The density of states is found to change significantly as the Hubbard parameter U, which is applied to the Ce 4f states, is varied from 0 to 5 eV. The calculated structural properties are in good agreement with experiment and do not change significantly with U. Choosing U = 3 eV for LDSA provides the best agreement between the calculated density of states and the experimental photoemission spectra.

  20. Solid-state electroanalytical characterization of the nonaqueous proton-conducting redox gel containing polyoxometallates

    Energy Technology Data Exchange (ETDEWEB)

    Lewera, Adam [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Zukowska, Grazyna [Department of Chemistry, Warsaw University of Technology, Noakowskiego 3, PL-00-664 Warsaw (Poland); Miecznikowski, Krzysztof [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Chojak, Malgorzata [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Wieczorek, Wladyslaw [Department of Chemistry, Warsaw University of Technology, Noakowskiego 3, PL-00-664 Warsaw (Poland); Kulesza, Pawel J. [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland)]. E-mail: pkulesza@chem.uw.edu.pl

    2005-04-22

    A novel polymetacrylate-based redox-conducting polymeric gel, into which Keggin-type polyoxometallate, phosphododecatungstic acid (H{sub 3}PW{sub 12}O{sub 40}), had been incorporated, was electrochemically characterized in the absence of external liquid supporting electrolyte using an ultramicrodisk-working electrode. The phosphotungstate component (15 wt.% of the gel block) was entrapped as the polar organic solvent solution within pores of the polymer matrix. H{sub 3}PW{sub 12}O{sub 40} plays bifunctional role: it provides well-behaved redox centers and serves as strong acid (source of mobile protons). The solid-state voltammetric properties of the system are defined by the reversible one-electron transfers between phosphotungstate redox centers. The following parameters have been determined from the combination of potential step experiments performed in two limiting (radial and linear) diffusional regimes: the concentration of heteropolytungstate redox centers, 6 x 10{sup -2} mol dm{sup -3}, and the apparent diffusion coefficient, 5 x 10{sup -7} cm{sup 2} s{sup -1}. The room temperature ionic (protonic) conductivity of the bulk gel was equal to 1.6 x 10{sup -3} S cm{sup -1}. The charge propagation mechanism was found to be primarily controlled by physical diffusion of heteropolytungstate units within the gel pores rather than by electron hopping (self-exchange) between mixed-valence sites.

  1. Thermal Treatment of Cerium Oxide and Its Properties: Adsorption Ability versus Degradation Efficiency

    Directory of Open Access Journals (Sweden)

    Pavel Janoš

    2014-01-01

    Full Text Available Cerium oxide belongs to the most important heterogeneous catalysts, but its applicability as so-called reactive sorbent for the degradation of toxic chemicals was only recently discovered. For these purposes, cerium oxide is prepared by precipitation of insoluble cerium salts (carbonates with a subsequent thermal decomposition. Properties of cerium oxide prepared from the carbonate precursor are strongly affected by the temperature during the calcination. Main physicochemical properties of cerium oxide (specific surface area, crystallinity, and surface chemistry were examined in dependence on the calcination temperature. As the adsorptive properties of CeO2 are undoubtedly of great importance in the abovementioned applications, the adsorption ability was studied using an azo dye Acid Orange 7 (AO7 as a model compound. The highest sorption efficiency towards AO7 exhibited sorbents prepared at temperatures below 700°C, which was attributed mainly to the presence of hydroxyl groups on the oxide surface. A strong correlation was found between an adsorption efficiency of cerium oxides and their degradation efficiency for organophosphate pesticide parathion methyl. The >Ce–OH groups on the sorbent surface are responsible for the dye binding by the surface-complexation mechanism, and probably also for the nucleophilic cleavage of the P–O–aryl bond in the pesticide molecule.

  2. Label-free electrochemical immunosensor based on cerium oxide nanowires for Vibrio cholerae O1 detection

    International Nuclear Information System (INIS)

    Tam, Phuong Dinh; Thang, Cao Xuan

    2016-01-01

    This paper developed a label-free immunosensor based on cerium oxide nanowire for Vibrio cholerae O1 detection application. The CeO 2 nanowires were synthesized by hydrothermal reaction. The immobilization of Anti-V. cholerae O1 onto CeO 2 nanowire-deposited sensor was performed via an amino ester, which was created by using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide, and sulfo-N-hydroxysuccinimide. The electrochemical responses of the immunosensor were studied by electrochemical impedance spectroscopy with [Fe (CN) 6 ] 3−/4− as redox probe. A linear response in electron transfer resistance for cell of V. cholerae O1 concentration was found in the range of 1.0 × 10 2 CFU/mL to 1.0 × 10 4 CFU/mL. The detection limit of the immunosensor was 1.0 × 10 2 CFU/mL. The immunosensor sensitivity was 56.82 Ω/CFU·mL −1 . Furthermore, the parameters affecting immunosensor response were also investigated, as follows: pH value, immunoreaction time, incubation temperature, and anti-V. cholerae O1 concentration. - Highlights: • A label-free immunosensor based on cerium oxide nanowire for Vibrio cholerae O1 detection application was developed. • A linear response was found in the range of 1.0 × 10 2 CFU/mL to 1.0 × 10 4 CFU/mL. • The detection limit of the immunosensor was 1.0 × 10 2 CFU/mL. • The immunosensor sensitivity was 56.82 Ω/CFU.mL −1 .

  3. Bulletin of Materials Science | News

    Indian Academy of Sciences (India)

    Synthesis, characterization and electrochemical performance of Li 2 Ni x Fe 1 ..... Two-dimensional cadmium selenide electronic and optical properties: first ...... Fabrication of low specific resistance ceramic carbon composites by colloidal processing .... strategy: a redox state-controlled toxicity of cerium oxide nanoparticles.

  4. An Economic Model and Experiments to Understand Aluminum-Cerium Alloy Recycling

    Science.gov (United States)

    Iyer, Ananth V.; Lim, Heejong; Rios, Orlando; Sims, Zachary; Weiss, David

    2018-04-01

    We provide an economic model to understand the impact of adoption, sorting and pricing of scrap on the recycling of a new aluminum-cerium (AlCe) alloy for use in engine blocks in the automobile industry. The goal of the laboratory portion of this study is to investigate possible effects of cerium contamination on well-established aluminum recycling streams. Our methodology includes three components: (1) focused data gathering from industry supply chain participants, (2) experimental data through laboratory experiments to understand the impact of cerium on existing alloys and (3) an economic model to understand pricing incentives on a recycler's separation of AlCe engine blocks.

  5. Extraction-differential-photometric method to determine rare earths of cerium subgroup

    International Nuclear Information System (INIS)

    Askerov, D.N.; Gusejnov, I.K.; Melikov, A.A.

    1985-01-01

    The extraction - photometric method to determine great quantities of rare earths of the cerium subgroup as a complex with antipyrine A and diphenylguanidine is developed. Isobutyl and n-butyl alcohols are used as extractants. It is established that proportional dependence between relative optical density and concentration of rare earths of the cerium subgroup in the solution takes place in the concentration interval of 10.3-14.7 μg of rare earths in 1 ml of the solution. Determination error is+-1.12%. The technique is used to determine rare earths of the cerium subgroup in rare earth oxides of a mixed composition, as well as in monozite and loparite

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

    Science.gov (United States)

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

    2017-09-01

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

  7. Inhibition of pH fronts in corrosion cells due to the formation of cerium hydroxide

    NARCIS (Netherlands)

    Soestbergen, M. van; Erich, S.J.F.; Huinink, H.P.; Adan, O.C.G.

    2013-01-01

    The effect of cerium-based corrosion inhibitors on the pH front between the alkaline cathode and acidic anode in corrosion cells has been studied. The cerium component of these inhibitors can affect the pH front since it precipitates in an alkaline environment as cerium hydroxide, which is important

  8. Cerium phosphate nanotubes: synthesis, characterization and biosensing

    Science.gov (United States)

    Meng, Ling; Yang, Lige; Zhou, Bo; Cai, Chenxin

    2009-01-01

    Cerium phosphate (CeP) nanotubes have been synthesized and confirmed by x-ray diffraction (XRD) and transmission electron microscopy (TEM). The 1D nanomaterial has a monoclinic crystal structure with a mean width of 15-20 nm and a length up to several micrometers. The nanotubes have been employed as electrode substrates for immobilization and direct electrochemistry of heme proteins/enzymes with myoglobin (Mb) as a model. The electrochemical characteristics of the Mb-CeP/GC electrode were studied by voltammetry. After being immobilized on the nanotubes, Mb can keep its natural structure and undergo effective direct electron transfer reaction with a pair of well-defined redox peaks at -(367 ± 3) mV (pH 7.5). The apparent electron transfer rate constant is (9.1 ± 1.4) s-1. The electrode displays good features in the electrocatalytic reduction of H2O2, and thus can be used as a biosensor for detecting the substrate with a low detection limit (0.5 ± 0.05 µM), a wide linear range (0.01-2 mM), high sensitivity (14.4 ± 1.2 µA mM-1), as well as good stability and reproducibility. CeP nanotubes can become a simple and effective biosensing platform for the integration of heme proteins/enzymes and electrodes, which can provide analytical access to a large group of enzymes for a wide range of bioelectrochemical applications.

  9. Cerium phosphate nanotubes: synthesis, characterization and biosensing

    International Nuclear Information System (INIS)

    Meng Ling; Yang Lige; Zhou Bo; Cai Chenxin

    2009-01-01

    Cerium phosphate (CeP) nanotubes have been synthesized and confirmed by x-ray diffraction (XRD) and transmission electron microscopy (TEM). The 1D nanomaterial has a monoclinic crystal structure with a mean width of 15-20 nm and a length up to several micrometers. The nanotubes have been employed as electrode substrates for immobilization and direct electrochemistry of heme proteins/enzymes with myoglobin (Mb) as a model. The electrochemical characteristics of the Mb-CeP/GC electrode were studied by voltammetry. After being immobilized on the nanotubes, Mb can keep its natural structure and undergo effective direct electron transfer reaction with a pair of well-defined redox peaks at -(367 ± 3) mV (pH 7.5). The apparent electron transfer rate constant is (9.1 ± 1.4) s -1 . The electrode displays good features in the electrocatalytic reduction of H 2 O 2 , and thus can be used as a biosensor for detecting the substrate with a low detection limit (0.5 ± 0.05 μM), a wide linear range (0.01-2 mM), high sensitivity (14.4 ± 1.2 μA mM -1 ), as well as good stability and reproducibility. CeP nanotubes can become a simple and effective biosensing platform for the integration of heme proteins/enzymes and electrodes, which can provide analytical access to a large group of enzymes for a wide range of bioelectrochemical applications.

  10. Solvent extraction of cerium (III) with high molecular weight amines

    International Nuclear Information System (INIS)

    Chatterjee, A.; Basu, S.

    1992-01-01

    The use of high molecular weight amines in the extraction of cerium (III) as EDTA complex from neutral aqueous medium is reported. The extraction condition was optimised from the study of effects of several variables like concentration of amine and EDTA pH nature of diluents etc. The method has been applied for the determination of cerium in few mineral samples. (author). 7 refs., 5 tabs

  11. Study of cerium diffusion in undoped lithium-6 enriched glass with Rutherford backscattering spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xiaodong, E-mail: xzhang39@utk.edu [Department of Nuclear Engineering, University of Tennessee, TN 37996 (United States); Moore, Michael E.; Lee, Kyung-Min; Lukosi, Eric D. [Department of Nuclear Engineering, University of Tennessee, TN 37996 (United States); Hayward, Jason P. [Department of Nuclear Engineering, University of Tennessee, TN 37996 (United States); Oak Ridge National Lab, Oak Ridge, TN 37831 (United States)

    2016-07-01

    Undoped lithium-6 enriched glasses coated with pure cerium (99.9%) with a gold protection layer on top were heated at three different temperatures (500, 550, and 600 °C) for varied durations (1, 2, and 4 h). Diffusion profiles of cerium in such glasses were obtained with the conventional Rutherford backscattering technique. Through fitting the diffusion profiles with the thin-film solution of Fick’s second law, diffusion coefficients of cerium with different annealing temperatures and durations were solved. Then, the activation energy of cerium for the diffusion process in the studied glasses was found to be 114 kJ/mol with the Arrhenius equation.

  12. Optical properties of cerium oxide (CeO2) nanoparticles synthesized by hydroxide mediated method

    Science.gov (United States)

    Ali, Mawlood Maajal; Mahdi, Hadeel Salih; Parveen, Azra; Azam, Ameer

    2018-05-01

    The nanoparticles of cerium oxide have been successfully synthesized by hydroxide mediated method, using cerium nitrate and sodium hydroxide as precursors. The microstructural properties were analyzed by X-ray diffraction technique (XRD). The X-ray diffraction results show that the cerium oxide nanoparticles were in cubic structure. The optical absorption spectra of cerium oxide were recorded by UV-VIS spectrophotometer in the range of 320 to 600 nm and photoluminescence spectra in the range of 400-540 nm and have been presented. The energy band gap was determined by Tauc relationship. The crystallite size was determined from Debye-Scherer equation and came out to be 6.4 nm.

  13. Study of cerium diffusion in undoped lithium-6 enriched glass with Rutherford backscattering spectrometry

    Science.gov (United States)

    Zhang, Xiaodong; Moore, Michael E.; Lee, Kyung-Min; Lukosi, Eric D.; Hayward, Jason P.

    2016-07-01

    Undoped lithium-6 enriched glasses coated with pure cerium (99.9%) with a gold protection layer on top were heated at three different temperatures (500, 550, and 600 °C) for varied durations (1, 2, and 4 h). Diffusion profiles of cerium in such glasses were obtained with the conventional Rutherford backscattering technique. Through fitting the diffusion profiles with the thin-film solution of Fick's second law, diffusion coefficients of cerium with different annealing temperatures and durations were solved. Then, the activation energy of cerium for the diffusion process in the studied glasses was found to be 114 kJ/mol with the Arrhenius equation.

  14. Hydrogen production of Enterobacter aerogenes altered by extracellular and intracellular redox states

    Energy Technology Data Exchange (ETDEWEB)

    Nakashimada, Y.; Rachman, M.A.; Kakizono, T.; Nishio, N. [Hiroshima University, Higashi-Hiroshima (Japan). Graduate School of Advanced Sciences of Matter, Department of Molecular Biotechnology

    2002-12-01

    Enterobacter aerogenes HU-101, tested for its hydrogen production in batch cultures on various substrates, produced the highest amount of hydrogen when the substrate was glycerol. The yield of hydrogen is a function of the degree to which the substrates are reduced. To examine the effect of intracellular redox state on hydrogen yield, glucose-limiting chemostat cultures were carried out at various pH using strain HU-101 and its mutant AY-2. For both strains, the molar yield and the production rate of hydrogen and the hydrogenase activity in the cell-free extract were optimal at the culture pH of 6.3. The highest NADH/NAD ratio in both strains was also observed at pH 6.3, at which the ratio in AY-2 was more than two-fold that of HU-101. Furthermore, NAD(P)H-dependent hydrogen formation was observed in the cell-free extract of AY-2, and hydrogenase activity was found not in the cytoplasmic but in the cell membrane fraction, suggesting that a high intracellular redox state, that is a high NADH/NAD ratio, would accelerate hydrogen production by driving membrane-bound NAD(P)H-dependent hydrogenase. (author)

  15. 3D imaging of the mitochondrial redox state of rat hearts under normal and fasting conditions

    Directory of Open Access Journals (Sweden)

    He N. Xu

    2014-03-01

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

  16. 3D IMAGING OF THE MITOCHONDRIAL REDOX STATE OF RAT HEARTS UNDER NORMAL AND FASTING CONDITIONS.

    Science.gov (United States)

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

    2014-03-01

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

  17. Study of phase transitions in cerium in shock-wave experiments

    Directory of Open Access Journals (Sweden)

    Zhernokletov M.V.

    2015-01-01

    Full Text Available Cerium has a complex phase diagram that is explained by the presence of structure phase transitions. Planar gauges were used in various combinations in experiments for determination of sound velocity dependence on pressure in cerium by the technique of PVDF gauge. The data of time dependence on pressure profiles with use of x(t diagrams and the D(u relation for cerium allowed the definition of the Lagrangian velocity of the unloading wave CLagr and the Eulerian velocity CEul by taking into account the compression σ. These results accords with data obtained by using the technique of VISAR and a manganin-based gauge, and calculated pressure dependence of isentropic sound velocity according to the VNIITF EOS. Metallography analysis of post-experimental samples did not find any changes in a phase composition.

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

    Science.gov (United States)

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

    2014-01-01

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

  19. The solvent extraction of cerium from sulphate solution - mini plant trials

    International Nuclear Information System (INIS)

    Soldenhoff, K.; Wilkins, D.; Ring, R.

    1998-01-01

    Full text: The Mt. Weld deposit in Western Australia has a complex rare earth mineralisation. The rare earth phosphate minerals, which include monazite, are amenable to conventional caustic cracking followed by hydrochloric acid dissolution of the trivalent rare earths. The presence of the mineral cerianite in the ore, which is unaffected by the alkali attack, results in rejection of a considerable proportion of the cerium to the acid leach residue. The recovery of cerium from a sulphate solution, resulting from the processing of such a residue, is the subject of the current paper. The liquor treated by solvent extraction contained 63 g L -1 rare earths and the cerium to total rare earth ratio was 75%. Other impurities, including Fe and Th, totalled 2000 ppm. A solvent mixture of commercially available extractants in a low aromatic content diluent was used to extract Ce 4+ selectively over the trivalent rare earths. Partial co-extraction of Fe and Th occurred but it was found that these elements were not easily stripped and therefore selective back extraction of cerium was possible. The cerium was stripped from the organic phase by hydrochloric acid and hydrogen peroxide. In continuous counter-current trials two extraction stages and three strip stages were used. In order to produce two grades of strip liquor, stripping was divided into two circuits. The first strip circuit consisting of a single stage, contained proportionally more of the trivalent rare earths. The second strip circuit, consisting of two stages, removed the remaining cerium with proportionally less of the rare earths. A bleed solvent stream was treated for removal of impurities to prevent build-up in the solvent. In the continuous counter current trials, 95% Ce 4+ extraction was achieved and the Ce to total rare earth ratio was upgraded to > 99%

  20. Influence of agglomeration of cerium oxide nanoparticles and speciation of cerium(III) on short term effects to the green algae Chlamydomonas reinhardtii

    Energy Technology Data Exchange (ETDEWEB)

    Röhder, Lena A. [Eawag, Swiss Federal Institute of Aquatic Science and Technology, Department of Environmental Toxicology, Dübendorf 8600 (Switzerland); ETH-Zurich, Institute of Biogeochemistry and Pollutant Dynamics, Zürich 8092 (Switzerland); Brandt, Tanja [Eawag, Swiss Federal Institute of Aquatic Science and Technology, Department of Environmental Toxicology, Dübendorf 8600 (Switzerland); Sigg, Laura [Eawag, Swiss Federal Institute of Aquatic Science and Technology, Department of Environmental Toxicology, Dübendorf 8600 (Switzerland); ETH-Zurich, Institute of Biogeochemistry and Pollutant Dynamics, Zürich 8092 (Switzerland); Behra, Renata, E-mail: Renata.behra@eawag.ch [Eawag, Swiss Federal Institute of Aquatic Science and Technology, Department of Environmental Toxicology, Dübendorf 8600 (Switzerland)

    2014-07-01

    Highlights: • Phosphate-dispersed CeO₂ NP did not affect photosynthetic yield in C. reinhardtii. • Agglomerated CeO₂ NP slightly decreased photosynthetic yield. • Cerium(III) was shown to affect photosynthetic yield and intracellular ROS level. • Slight effects of CeO₂ NP were caused by dissolved Ce³⁺ ions present in suspensions. • Wild type and cell wall free mutant of C. reinhardtii showed the same sensitivity. - Abstract: Cerium oxide nanoparticles (CeO₂ NP) are increasingly used in industrial applications and may be released to the aquatic environment. The fate of CeO₂ NP and effects on algae are largely unknown. In this study, the short term effects of CeO₂ NP in two different agglomeration states on the green algae Chlamydomonas reinhardtii were examined. The role of dissolved cerium(III) on toxicity, its speciation and the dissolution of CeO₂ NP were considered. The role of cell wall of C. reinhardtii as a barrier and its influence on the sensitivity to CeO₂ NP and cerium(III) was evaluated by testing both, the wild type and the cell wall free mutant of C. reinhardtii. Characterization showed that CeO₂ NP had a surface charge of ~0 mV at physiological pH and agglomerated in exposure media. Phosphate stabilized CeO₂ NP at pH 7.5 over 24 h. This effect was exploited to test CeO₂ NP dispersed in phosphate with a mean size of 140 nm and agglomerated in absence of phosphate with a mean size of 2000 nm. The level of dissolved cerium(III) in CeO₂ NP suspensions was very low and between 0.1 and 27 nM in all tested media. Exposure of C. reinhardtii to Ce(NO₃)₃ decreased the photosynthetic yield in a concentration dependent manner with EC₅₀ of 7.5 ± 0.84 μM for wild type and EC₅₀ of 6.3 ± 0.53 μM for the cell wall free mutant. The intracellular level of reactive oxygen species (ROS) increased upon exposure to Ce(NO₃)₃ with effective concentrations similar to those inhibiting photosynthesis. The agglomerated Ce

  1. Endoplasmic reticulum redox state is not perturbed by pharmacological or pathological endoplasmic reticulum stress in live pancreatic β-cells.

    Directory of Open Access Journals (Sweden)

    Irmgard Schuiki

    Full Text Available Accumulation of unfolded, misfolded and aggregated proteins in the endoplasmic reticulum (ER causes ER stress. ER stress can result from physiological situations such as acute increases in secretory protein biosynthesis or pathological conditions that perturb ER homeostasis such as alterations in the ER redox state. Here we monitored ER redox together with transcriptional output of the Unfolded Protein Response (UPR in INS-1 insulinoma cells stably expressing eroGFP (ER-redox-sensor and mCherry protein driven by a GRP78 promoter (UPR-sensor. Live cell imaging, flow cytometry and biochemical characterization were used to examine these parameters in response to various conditions known to induce ER stress. As expected, treatment of the cells with the reducing agent dithiothreitol caused a decrease in the oxidation state of the ER accompanied by an increase in XBP-1 splicing. Unexpectedly however, other treatments including tunicamycin, thapsigargin, DL-homocysteine, elevated free fatty acids or high glucose had essentially no influence on the ER redox state, despite inducing ER stress. Comparable results were obtained with dispersed rat islet cells expressing eroGFP. Thus, unlike in yeast cells, ER stress in pancreatic β-cells is not associated with a more reducing ER environment.

  2. Redox homeostasis: The Golden Mean of healthy living

    Directory of Open Access Journals (Sweden)

    Fulvio Ursini

    2016-08-01

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

  3. The different aspects of magnetism in cerium compounds

    International Nuclear Information System (INIS)

    Sereni, J. G.

    1999-01-01

    Different factors related to the formation of the Cerium magnetic ground state are analyzed from its electronic structure, following a decreasing scale of energy. The studied behaviours include from nonmagnetic states, like those with valence instability, to different magnetic phase diagrams. The competition between the Kondo effect, which screens the magnetic moments and the magnetic interactions, that tends to order them is also described. In the ordered phase boundary the phenomena related to the incipient magnetisms are analyzed and related to deviations from the Fermi liquid behaviour and divergences of the thermodynamic parameters when the temperature tend to zero. Some experimental techniques are described and the difference between thermodynamical and control parameters analyzed. Particular attention is paid to the effect of pressure and ligand substitution. (Author) 22 refs

  4. Spectrofluorimetric determination of cerium by flow injection analysis

    International Nuclear Information System (INIS)

    Liu Shaorong; Meng Jian; Liu Wenhua

    1990-01-01

    A spectrofluorimetric method for the determination of cerium (λ ex/em:251/365 nm) in hydrochloric acid solution by flow injection analysis is presented. It has well developed the normal spectrofluorimetric method for determination of cerium and has made: 1, the determination procedure shortened; 2, the determination speed increased to about 180 samples per hour; 3, the determination range widened to 0.05-100.0 ppm CeO 2 , abouot two times as wide as the normal spectrofluorimetric method; and 4, the relative standard deviation lessened (about 0.47% for 0.1 ppm CeO 2 , n = 13)

  5. Comparison of glassy slag waste forms produced in laboratory crucibles and in a bench-scale plasma furnace

    International Nuclear Information System (INIS)

    Feng, X.; Wronkiewicz, D.J.; Brown, N.R.; Gong, M.; Whitworth, C.; Filius, K.; Battleson, D.

    1994-01-01

    Vitrification is currently the best demonstrated available technology for the disposal of high-level radioactive wastes. An innovative vitrification approach known as minimum additive waste stabilization (MAWS) is being developed. Both homogeneous glass and glassy slags have been used in implementing MAWS. Glassy slags (vitro-ceramics) are glass-crystal composites, and they are composed of various metal oxide crystalline phases embedded in an aluminosilicate glass matrix. Glassy slags with compositions developed in crucible melts at Argonne National Laboratory (ANL) were successfully produced in a bench-scale Retech plasma centrifugal furnace (PCF) by MSE, Inc. Detailed examinations of these materials showed that the crucible melts and the PCF produced similar glass and crystalline phases. The two sets of glassy slags exhibited similar chemical durability in terms of normalized releases of their major components. The slags produced in the PCF furnace using metals were usually less oxidized, although this had no effect on the corrosion behavior of the major components of the slags. However, the normalized release rate of cerium was initially lower for the PCF slags. This difference diminished with time as the redox sates of the metal oxides in slags began to be controlled by exposure to air in the tests. Thus, the deference in cerium release due to the differences in slag redox state may be transitory. The cerium solubility is a complex function of redox state and solution pH and Eh

  6. Baseline and post-stress seasonal changes in immunocompetence and redox state maintenance in the fishing bat Myotis vivesi

    Science.gov (United States)

    Ibáñez-Contreras, Alejandra; Miranda-Labra, Roxana U.; Flores-Martínez, José Juan

    2018-01-01

    Little is known of how the stress response varies when animals confront seasonal life-history processes. Antioxidant defenses and damage caused by oxidative stress and their link with immunocompetence are powerful biomarkers to assess animal´s physiological stress response. The aim of this study was A) to determine redox state and variation in basal (pre-acute stress) immune function during summer, autumn and winter (spring was not assessed due to restrictions in collecting permit) in the fish-eating Myotis (Myotis vivesi; Chiroptera), and B) to determine the effect of acute stress on immunocompetence and redox state during each season. Acute stress was stimulated by restricting animal movement for 6 and 12 h. The magnitude of the cellular immune response was higher during winter whilst that of the humoral response was at its highest during summer. Humoral response increased after 6 h of movement restriction stress and returned to baseline levels after 12 h. Basal redox state was maintained throughout the year, with no significant changes in protein damage, and antioxidant activity was modulated mainly in relation to variation to environment cues, increasing during high temperatures and decreasing during windy nights. Antioxidant activity increased after the 6 h of stressful stimuli especially during summer and autumn, and to a lesser extent in early winter, but redox state did not vary. However, protein damage increased after 12 h of stress during summer. Prolonged stress when the bat is engaged in activities of high energy demand overcame its capacity to maintain homeostasis resulting in oxidative damage. PMID:29293551

  7. Effect of additions of cerium, lanthanum, and zirconium on the state of plantinum and the activity of aluminoplatinum catalysts for the complete oxidation of hydrocarbons

    International Nuclear Information System (INIS)

    Drozdov, V.A.; Davydov, A.A.; Popovskii, V.V.; Tsyrul'nikov, P.G.

    1986-01-01

    It is shown from an analysis of the diffuse reflectance spectra that additions of cerium, lanthanum or zirconium to aluminoplatinum catalyst stabilize the platinum in an oxidized state. This leads to a change in the specific catalytic activity (SCA) towards the total oxidation of methane and butane. The SCA of modified, reduced samples is greater than the SCA of samples that were calcined in air. This is because of the greater activity of metallic platinum compared to the ionic form

  8. Environmental Geochemistry of Cerium: Applications and Toxicology of Cerium Oxide Nanoparticles

    Directory of Open Access Journals (Sweden)

    Jessica T. Dahle

    2015-01-01

    Full Text Available Cerium is the most abundant of rare-earth metals found in the Earth’s crust. Several Ce-carbonate, -phosphate, -silicate, and -(hydroxide minerals have been historically mined and processed for pharmaceutical uses and industrial applications. Of all Ce minerals, cerium dioxide has received much attention in the global nanotechnology market due to their useful applications for catalysts, fuel cells, and fuel additives. A recent mass flow modeling study predicted that a major source of CeO2 nanoparticles from industrial processing plants (e.g., electronics and optics manufactures is likely to reach the terrestrial environment such as landfills and soils. The environmental fate of CeO2 nanoparticles is highly dependent on its physcochemical properties in low temperature geochemical environment. Though there are needs in improving the analytical method in detecting/quantifying CeO2 nanoparticles in different environmental media, it is clear that aquatic and terrestrial organisms have been exposed to CeO2 NPs, potentially yielding in negative impact on human and ecosystem health. Interestingly, there has been contradicting reports about the toxicological effects of CeO2 nanoparticles, acting as either an antioxidant or reactive oxygen species production-inducing agent. This poses a challenge in future regulations for the CeO2 nanoparticle application and the risk assessment in the environment.

  9. Electrorefining of Cerium in LiCl-KCl Molten Salts

    International Nuclear Information System (INIS)

    Campbell-Kelly, R.P.; Paget, T.J.

    2010-01-01

    Electrorefining of cerium from cerium-gallium alloys has been demonstrated in lithium chloride-potassium chloride salts at temperatures below 500 deg. C, with excellent current efficiencies and high product yields. These experiments are being carried out as non-active trials for a process for the purification of impure actinide metals. The results reported show anodic current efficiencies consistently close to 100%, and in several experiments complete oxidation of the cerium in the feed occurred. The cathodic product is hard and metallic, and incorporates a significant amount of salt into its structure. The product can be consolidated into a dense, pure metal by melting under calcium chloride at 850 deg. C. The yield of this consolidation step varies between 16 and 75%, seeming to depend on the total mass of metal being consolidated and the quality of inert atmosphere. A small-scale electrochemical cell has been demonstrated which will be used in initial active experiments. (authors)

  10. A Protocol for Electrochemical Evaluations and State of Charge Diagnostics of a Symmetric Organic Redox Flow Battery

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Wentao; Vemuri, Rama S.; Hu, Dehong; Yang, Zheng; Wei, Xiaoliang

    2017-01-01

    Redox flow batteries have been considered as one of the most promising stationary energy storage solutions for improving the reliability of the power grid and deployment of renewable energy technologies. Among the many flow battery chemistries, nonaqueous flow batteries have the potential to achieve high energy density because of the broad voltage windows of nonaqueous electrolytes. However, significant technical hurdles exist currently limiting nonaqueous flow batteries to demonstrate their full potential, such as low redox concentrations, low operating currents, under-explored battery status monitoring, etc. In an attempt to address these limitations, we report a nonaqueous flow battery based on a highly soluble, redox-active organic nitronyl nitroxide radical compound, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO). This redox materials exhibits an ambipolar electrochemical property with two reversible redox pairs that are moderately separated by a voltage gap of ~1.7 V. Therefore, PTIO can serve as both anolyte and catholyte redox materials to form a symmetric flow battery chemistry, which affords the advantages such as high effective redox concentrations and low irreversible redox material crossover. The PTIO flow battery shows decent electrochemical cyclability under cyclic voltammetry and flow cell conditions; an improved redox concentration of 0.5 M PTIO and operational current density of 20 mA cm-2 were achieved in flow cell tests. Moreover, we show that Fourier transform infrared (FTIR) spectroscopy could measure the PTIO concentrations during the PTIO flow battery cycling and offer reasonably accurate detection of the battery state of charge (SOC) as cross-validated by electron spin resonance measurements. This study suggests FTIR can be used as a reliable online SOC sensor to monitor flow battery status and ensure battery operations stringently in a safe SOC range.

  11. Corrosion resistance of flaky aluminum pigment coated with cerium oxides/hydroxides in chloride and acidic electrolytes

    International Nuclear Information System (INIS)

    Niroumandrad, S.; Rostami, M.; Ramezanzadeh, B.

    2015-01-01

    Graphical abstract: - Highlights: • Flaky aluminum pigments were modified with cerium nitrate salt. • pH value of 3.0 was chosen as the optimized pH for the cerium solution. • Corrosion resistance of the pigment significantly increased after modification. • Alkaline pre-treatment prior to modification affected the cerium layer performance. - Abstract: The objective of this study was to enhance the corrosion resistance of lamellar aluminum pigment through surface treatment by cerium oxides/hydroxides. The surface composition of the pigments was studied by energy-dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The corrosion resistance of the pigment was evaluated by conventional hydrogen evolution measurements in acidic solution and electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution. Results showed that the Ce-rich coating composed of Ce 2 O 3 and CeO 2 was precipitated on the pigment surface after immersion in the cerium solution. The corrosion resistance of pigment was significantly enhanced after modification with cerium layer.

  12. Corrosion resistance of flaky aluminum pigment coated with cerium oxides/hydroxides in chloride and acidic electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Niroumandrad, S. [Institute for Color Science and Technology (ICST), PO 16765-654, Tehran (Iran, Islamic Republic of); Rostami, M. [Department of Nanomaterials and Nanocoatings, Institute for Color Science and Technology (ICST), PO 16765-654, Tehran (Iran, Islamic Republic of); Ramezanzadeh, B., E-mail: ramezanzadeh-bh@icrc.ac.ir [Department of Surface Coatings and Corrosion, Institute for Color Science and Technology (ICST), PO 16765-654, Tehran (Iran, Islamic Republic of)

    2015-12-01

    Graphical abstract: - Highlights: • Flaky aluminum pigments were modified with cerium nitrate salt. • pH value of 3.0 was chosen as the optimized pH for the cerium solution. • Corrosion resistance of the pigment significantly increased after modification. • Alkaline pre-treatment prior to modification affected the cerium layer performance. - Abstract: The objective of this study was to enhance the corrosion resistance of lamellar aluminum pigment through surface treatment by cerium oxides/hydroxides. The surface composition of the pigments was studied by energy-dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The corrosion resistance of the pigment was evaluated by conventional hydrogen evolution measurements in acidic solution and electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution. Results showed that the Ce-rich coating composed of Ce{sub 2}O{sub 3} and CeO{sub 2} was precipitated on the pigment surface after immersion in the cerium solution. The corrosion resistance of pigment was significantly enhanced after modification with cerium layer.

  13. Cerium oxide nanozyme modulate the ‘exercise’ redox biology of skeletal muscle

    Science.gov (United States)

    Arya, Aditya; Sethy, Niroj Kumar; Gangwar, Anamika; Bhargava, Neelima; Dubey, Amarish; Roy, Manas; Srivastava, Gaurav; Singh, Sushil Kumar; Das, Mainak; Bhargava, Kalpana

    2017-05-01

    ‘Exercise’ is a double-edged sword for the skeletal muscle. Small amount of ROS generated during mild exercise, is essential for normal force generation; whereas large quantity of ROS generated during intense exercise, may cause contractile dysfunction, resulting in muscle weakness and fatigue. One of the key question in skeletal muscle physiology is ‘could antioxidant therapy improve the skeletal muscle endurance? A question, which has resulted in contradictory experimental findings till this date. This work has addressed this ‘very question’ using a synthetic, inorganic, antioxidant nano-material viz., ‘cerium oxide nanozyme’ (CON). It has been introduced in the rat by intramuscular injection, and the skeletal muscle endurance has been evaluated. Intramuscular injections of CON, concurrent with exercise, enhanced muscle mass, glycogen and ATP content, type I fiber ratio, thus resulting in significantly higher muscle endurance. Electron microscope studies confirmed the presence of CON in the vicinity of muscle mitochondria. There was an increase in the number and size of the muscle mitochondria in the CON treated muscle, following exercise, as compared to the untreated group with only exercised muscle. Quantitative proteomics data and subsequent biological network analysis studies, identified higher levels of oxidative phosphorylation, TCA cycle output and glycolysis in CON supplemented exercised muscle over only exercised muscle. This was further associated with significant increase in the mitochondrial respiratory capacity and muscle contraction, primarily due to higher levels of electron transport chain proteins like NDUFA9, SDHA, ATP5B and ATP5D, which were validated by real-time PCR and western blotting. Along with this, persistence of CON in muscle was evaluated with ICP-MS analysis, which revealed clearance of the particles after 90 d, without exhibiting any inflammation or adverse affects on the health of the experimental animals. Thus a

  14. Molecular and physiological responses to titanium dioxide and cerium oxide nanoparticles in Arabidopsis

    Science.gov (United States)

    - Changes in tissue transcriptomes and productivity of Arabidopsis thaliana were investigated during exposure of plants to two widely-used engineered metal oxide nanoparticles, titanium dioxide (nano-titanium) and cerium dioxide (nano-cerium). Microarray analyses confirmed that e...

  15. Polymerization of acrylamide initiated with Ce(IV- and KMnO4–mercaptosuccinic acid redox systems in acid-aqueous medium

    Directory of Open Access Journals (Sweden)

    2007-03-01

    Full Text Available By using mercaptosuccinic acid-cerium(IV sulfate and mercaptosuccinic acid-KMnO4 redox systems in acid aqueous medium, the polymerization of acrylamide monomer was performed at room temperatures. Water soluble acrylamide polymers which contain mercaptosuccinic acid end-groups were synthesized. The dependence of polymerization yield and the molecular weight of polymer on the initiator concentration(nMSA=nCe(IV at different acid concentrations, polymerization time, temperature, and concentration of sulfuric acid was investigated. The decrease in the initiator concentration resulted in an increase in the molecular weights but a decrease in the yield. The increase of reaction temperature from 20 to 60°C resulted in an increase in the molecular weights and slight decrease of the yield of polymer. Cerium and manganese ions are reduced to Ce(III and Mn(II ions respectively in polymerization reaction. The existence of Ce(III ion bound to polymer was investigated by UV-visible spectrometry and fluorescence measurements. The amount of Mn(II which is incorporated to the polymer was determined.

  16. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries.

    Science.gov (United States)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-12-23

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn 4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g -1 based on solid-state redox reaction of oxide ions.

  17. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

    Science.gov (United States)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-01-01

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions. PMID:28008955

  18. Electrochemical reduction of cerium oxide into metal

    Energy Technology Data Exchange (ETDEWEB)

    Claux, Benoit [CEA, Valduc, F-21120 Is-sur-Tille (France); Universite de Grenoble, LEPMI-ENSEEG, 1130 rue de la Piscine, BP75, F-38402 St Martin d' Heres Cedex (France); Serp, Jerome, E-mail: jerome.serp@cea.f [CEA, Valduc, F-21120 Is-sur-Tille (France); Fouletier, Jacques [Universite de Grenoble, LEPMI-ENSEEG, 1130 rue de la Piscine, BP75, F-38402 St Martin d' Heres Cedex (France)

    2011-02-28

    The Fray Farthing and Chen (FFC) and Ono and Suzuki (OS) processes were developed for the reduction of titanium oxide to titanium metal by electrolysis in high temperature molten alkali chloride salts. The possible transposition to CeO{sub 2} reduction is considered in this study. Present work clarifies, by electro-analytical techniques, the reduction pathway leading to the metal. The reduction of CeO{sub 2} into metal was feasible via an indirect mechanism. Electrolyses on 10 g of CeO{sub 2} were carried out to evaluate the electrochemical process efficiency. Ca metal is electrodeposited at the cathode from CaCl{sub 2}-KCl solvent and reacts chemically with ceria to form not only metallic cerium, but also cerium oxychloride.

  19. Energy-dispersive X-ray fluorescence analysis of cerium in ferrosilicon

    International Nuclear Information System (INIS)

    Marbec, E.R.

    1987-01-01

    The cerium was determined in ferrosilicon samples by energy-dispersive X-ray fluorescence techniques (XRF) techniques, with a secondary target of gadolinium. The methods employed were: comparison and linear regression with reference materials with cerium concentration between 0.4 and 1.0%. The samples were prepared in the form of pellets and the analytical results are reported as an average of five determinations with a confidence limits at 95% probability. (Author) [es

  20. Analysis of the effects of cerium on calcium ion in the protoplasts of ...

    African Journals Online (AJOL)

    Administrator

    2011-09-12

    Sep 12, 2011 ... African Journal of Biotechnology Vol. 10(52), pp. ... Paper. Analysis of the effects of cerium on calcium ion in the .... plasma membrane (Zeng et al., 2003). Recently .... cerium on vegetable growth of wheat (Triticum aestivum L.).

  1. How the redox state of tobacco 'Bel-W3' is modified in response to ozone and other environmental factors in a sub-tropical area?

    Energy Technology Data Exchange (ETDEWEB)

    Dias, Ana P.L.; Dafre, Marcelle; Rinaldi, Mirian C.S. [Instituto de Botanica, Caixa Postal 3005, 01061-970 Sao Paulo, SP (Brazil); Domingos, Marisa, E-mail: mmingos@superig.com.b [Instituto de Botanica, Caixa Postal 3005, 01061-970 Sao Paulo, SP (Brazil)

    2011-02-15

    This study intended to determine whether the redox state in plants of Nicotiana tabacum 'Bel-W3' fluctuates in response to the environmental factors in a sub-tropical area contaminated by ozone (Sao Paulo, SE - Brazil) and which environmental factors are related to this fluctuation, discussing their biomonitoring efficiency. We comparatively evaluated the indicators of redox state (ascorbic acid, glutathione, superoxide dismutase, ascorbate peroxidase, and glutathione reductase) and leaf injury in 17 field experiments performed in 2008. The redox state was explained by the combined effects of chronic levels of O{sub 3} and meteorological variables 4-6 days prior to the plant sampling. Moderate leaf injury was observed in most cases. The redox state of tobacco decreases few days after their placement in the sub-tropical environment, causing them to become susceptible to oxidative stress imposed by chronic doses of O{sub 3}. Its bioindicator efficiency would not be diminished in such levels of atmospheric contamination. - Research highlights: Nicotiana tabacum 'Bel-W3' is potentially a bioindicator of O{sub 3} in the sub-tropics. However, it is unknown if its redox state would affect its bioindicator performance under sub-tropical environmental conditions. This study revealed that the redox state of tobacco decreases few days after their placement in the sub-tropical environment, causing them to become susceptible to oxidative stress imposed by chronic doses of O{sub 3}. Therefore, its bioindicator efficiency would not be diminished in such levels of atmospheric contamination. However, the bioindicator efficiency N. tabacum 'Bel-W3' for biomonitoring O{sub 3} should be regionally modeled in the sub-tropics, based on both its redox state and on the flux of O{sub 3} through stomata, in response to the varying micro-meteorological conditions that govern both physiological processes. - The bioindicator efficiency of tobacco plants is not

  2. Label-free electrochemical immunosensor based on cerium oxide nanowires for Vibrio cholerae O1 detection

    Energy Technology Data Exchange (ETDEWEB)

    Tam, Phuong Dinh, E-mail: phuongdinhtam@gmail.com; Thang, Cao Xuan, E-mail: thang.caoxuan@hust.edu.vn

    2016-01-01

    This paper developed a label-free immunosensor based on cerium oxide nanowire for Vibrio cholerae O1 detection application. The CeO{sub 2} nanowires were synthesized by hydrothermal reaction. The immobilization of Anti-V. cholerae O1 onto CeO{sub 2} nanowire-deposited sensor was performed via an amino ester, which was created by using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide, and sulfo-N-hydroxysuccinimide. The electrochemical responses of the immunosensor were studied by electrochemical impedance spectroscopy with [Fe (CN) {sub 6}] {sup 3−/4−} as redox probe. A linear response in electron transfer resistance for cell of V. cholerae O1 concentration was found in the range of 1.0 × 10{sup 2} CFU/mL to 1.0 × 10{sup 4} CFU/mL. The detection limit of the immunosensor was 1.0 × 10{sup 2} CFU/mL. The immunosensor sensitivity was 56.82 Ω/CFU·mL{sup −1}. Furthermore, the parameters affecting immunosensor response were also investigated, as follows: pH value, immunoreaction time, incubation temperature, and anti-V. cholerae O1 concentration. - Highlights: • A label-free immunosensor based on cerium oxide nanowire for Vibrio cholerae O1 detection application was developed. • A linear response was found in the range of 1.0 × 10{sup 2} CFU/mL to 1.0 × 10{sup 4} CFU/mL. • The detection limit of the immunosensor was 1.0 × 10{sup 2} CFU/mL. • The immunosensor sensitivity was 56.82 Ω/CFU.mL{sup −1}.

  3. Influences of the main anodic electroplating parameters on cerium oxide films

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yang; Yang, Yumeng; Du, Xiaoqing; Chen, Yu [Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang (China); Zhang, Zhao, E-mail: eaglezzy@zjuem.zju.edu.cn [Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang (China); Zhang, Jianqing [Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang (China); State Key Laboratory for Corrosion and Protection of Metals, Shenyang 110016 (China)

    2014-06-01

    Cerium oxide thin films were fabricated onto 316 L stainless steel via a potentiostatically anodic electrodeposition approach in the solutions containing cerium(III) nitrate (0.05 M), ammonia acetate (0.1 M) and ethanol (10% V/V). The electrochemical behaviors and deposition parameters (applied potential, bath temperature, dissolving O{sub 2} and bath pH) have been investigated. Results show that, the electrochemical oxidation of Ce{sup 3+} goes through one electrochemical step, which is under charge transfer control. The optimum applied potential for film deposition is 0.8 V. Bath temperature plays a significant effect on the deposition rate, composition (different colors of the film) and surface morphology of the deposits. Due to the hydrolysis of Ce{sup 3+}, cerous hydroxide is facility to form when the bath temperature is higher than 60 °C. The electroplating bath pH is another key role for the anodic deposition of cerium oxide thin films, and the best bath pH is around 6.20. N{sub 2} or O{sub 2} purged into the bath will result in film porosities and O{sub 2} favors cerium oxide particles and film generation.

  4. Growth and characterization of Sm3+ doped cerium oxalate single crystals

    Directory of Open Access Journals (Sweden)

    Minu Mary C

    2016-07-01

    Full Text Available Single crystals of Sm3+ doped cerium oxalate decahydrate were synthesized using single diffusion gel technique and the conditions influencing the size, morphology, nucleation density and quality of the crystals were optimized. Highly transparent single crystals of average size 3 mm × 2 mm × 1 mm with well-defined hexagonal morphology were grown during a time period of two weeks. X-ray powder diffraction analysis revealed that the grown crystals crystallize in the monoclinic system with space group P21/c as identical with the pure cerium oxalate. The various functional groups of the oxalate ligand and the water of crystallization were identified by Fourier transform infrared spectroscopy. The photoluminescence spectrum of the Sm3+ doped cerium oxalate indicated that the Sm3+ ions are optically active in the cerium oxalate matrix. The crystal has a strong and efficient orange red emission with a wavelength peak at 595 nm and hence can be effectively used for optical amplification. Microhardness measurements of the crystal revealed that they belong to the soft material category.

  5. Intracellular antioxidants dissolve man-made antioxidant nanoparticles: using redox vulnerability of nanoceria to develop a responsive drug delivery system.

    Science.gov (United States)

    Muhammad, Faheem; Wang, Aifei; Qi, Wenxiu; Zhang, Shixing; Zhu, Guangshan

    2014-01-01

    Regeneratable antioxidant property of nanoceria has widely been explored to minimize the deleterious influences of reactive oxygen species. Limited information is, however, available regarding the biological interactions and subsequent fate of nanoceria in body fluids. This study demonstrates a surprising dissolution of stable and ultrasmall (4 nm) cerium oxide nanoparticles (CeO2 NPs) in response to biologically prevalent antioxidant molecules (glutathione, vitamin C). Such a redox sensitive behavior of CeO2 NPs is subsequently exploited to design a redox responsive drug delivery system for transporting anticancer drug (camptothecin). Upon exposing the CeO2 capped and drug loaded nanoconstruct to vitamin c or glutathione, dissolution-accompanied aggregation of CeO2 nanolids unleashes the drug molecules from porous silica to achieve a significant anticancer activity. Besides stimuli responsive drug delivery, immobilization of nanoceria onto the surface of mesoporous silica also facilitates us to gain a basic insight into the biotransformation of CeO2 in physiological mediums.

  6. Redox homeostasis: The Golden Mean of healthy living.

    Science.gov (United States)

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

    2016-08-01

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

  7. Synthesis, characterization and antibacterial activity of hybrid chitosan-cerium oxide nanoparticles: As a bionanomaterials.

    Science.gov (United States)

    Senthilkumar, R P; Bhuvaneshwari, V; Ranjithkumar, R; Sathiyavimal, S; Malayaman, V; Chandarshekar, B

    2017-11-01

    The hybrid chitosan cerium oxide nanoparticles were prepared for the first time by green chemistry approach using plant leaf extract. The intense peak observed around 292nm in the UV-vis spectrum indicate the formation of cerium oxide nanoparticles. The XRD pattern revealed that the hybrid chitosan-cerium oxide nanoparticles have a polycrystalline structure with cubic fluorite phase. The FTIR spectrum of prepared samples showed the formation of Ce-O bonds and chitosan main chains COC and CO. The FESEM image of hybrid chitosan cerium oxide nanoparticles revealed that the particles are spherical in shape with grains size varying from 23.12nm to 89.91nm. EDAX analysis confirmed the presence of Ce, O, C and N elements in the prepared sample. TEM images showed that the prepared hybrid chitosan-cerium oxide nanoparticles are predominantly uniform in size and most of the particles are spherical in shape with less agglomeration and the particles size varies from 3.61nm to 24.40nm. The prepared chitosan cerium oxide nanoparticles of 50μL concentration showed good antibacterial properties against test pathogens, which was confirmed by the FESEM analysis. The prepared small particle size facilitate that these hybrid ChiCO 2 NPs could effectively be used in biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. The quasi-steady state of all-vanadium redox flow batteries: A scale analysis

    International Nuclear Information System (INIS)

    Sharma, A.K.; Vynnycky, M.; Ling, C.Y.; Birgersson, E.; Han, M.

    2014-01-01

    Highlights: • We present a transient 2D model for a VRFB (conservation of species and charge); • Carry out scale analysis of the species conservation equation; • Derive the condition characterizing the quasi-steadiness of VRFB operation; • Verify it by comparing charge-discharge curve with transient simulations. - Abstract: In general, mathematical models for all-vanadium redox flow batteries (VRFB) that seek to capture the transport phenomena are transient in nature. In this paper, we carry out scale analysis of VRFB operation and derive the conditions when it can be assumed to be quasi-steady state in nature, i.e., time-dependence only through a boundary condition. We find that it is true for typical tank volume and flow rate employed for VRFBs. The proposed analysis is generic and can also be employed for other types of redox flow batteries

  9. Post-GOE redox insights from Mo isotopes, Ce anomalies, and Mn from the 2.24 Ga Kazput Formation

    Science.gov (United States)

    Thoby, M.; Konhauser, K.; Philippot, P.; Killingsworth, B.; Warchola, T.; Lalonde, S.

    2017-12-01

    Following the Great Oxidation event (GOE) defined from 2.45 to 2.2 Ga, an event marking the first appearance of widespread atmospheric oxygen, a combination of decreased Mn(II) supply from land and increased Mn(IV)-precipitation in the oceans should have resulted in lower concentrations of Mn in seawater. Nevertheless, it appears that some early Proterozoic marine sediments record high seawater Mn concentrations hundreds of millions of years after the GOE. Here we investigate a Mn excursion associated with marine carbonates and shales of the 2.31 Ga Kazput Formation. Samples were recovered from drill core collected during the Turee Creek Drilling Project (TCDP). Using molybdenum (Mo) isotope data coupled with cerium (Ce) anomalies, we define the redox condition of the Kazput depositional environment. Initial results show no Mo fractionation and few cerium anomalies in carbonates, pointing to an anoxic basin without Mn oxide precipitates. Additionally, XRF data on the shales indicates an association of Mn with calcium (Ca) suggesting an anoxic environment at the time of their deposition. Our results provide new insights into the nature and environment of the Turee Creek basin and the extent of oxygenation of surface waters after the GOE.

  10. Oxochloroalkoxide of the Cerium (IV and Titanium (IV as oxides precursor

    Directory of Open Access Journals (Sweden)

    Machado Luiz Carlos

    2002-01-01

    Full Text Available The Cerium (IV and Titanium (IV oxides mixture (CeO2-3TiO2 was prepared by thermal treatment of the oxochloroisopropoxide of Cerium (IV and Titanium (IV. The chemical route utilizing the Cerium (III chloride alcoholic complex and Titanium (IV isopropoxide is presented. The compound Ce5Ti15Cl16O30 (iOPr4(OH-Et15 was characterized by elemental analysis, FTIR and TG/DTG. The X-ray diffraction patterns of the oxides resulting from the thermal decomposition of the precursor at 1000 degreesC for 36 h indicated the formation of cubic cerianite (a = 5.417Å and tetragonal rutile (a = 4.592Å and (c = 2.962 Å, with apparent crystallite sizes around 38 and 55nm, respectively.

  11. Procedure for the separation of cerium from crude phosphates and rare earth concentrates

    International Nuclear Information System (INIS)

    Richter, H.; Koenig, O.; Schmitt, A.; Grauss, H.; Freitag, S.

    1986-01-01

    The invention has to do with a procedure for the separation of cerium from crude phosphates and rare earth phosphate concentrates originating from the partial neutralization of nitric crude phosphate decomposition solutions. It is aimed at the cerium separation from the raw material at an early stage of reprocessing without preceding elimination of other components and impurities. The rare earth phosphate concentrates or crude phosphates are dissolved in nitric acid, the Ce 3+ is oxidized with potassium permanganate or magnanese(IV) hydroxide, and cerium(IV) phosphate is precipitated as pure substance by decreasing the acidity of the solution

  12. Corrosion of Zn5Al and Zn55Al alloys with cerium, praseodymium and neodymium

    International Nuclear Information System (INIS)

    Alikhanova, S.D.

    2017-01-01

    The present work is devoted to corrosion of Zn5Al and Zn55Al alloys with cerium, praseodymium and neodymium. The purpose of present work is elaboration of optimal composition of zinc-aluminium alloys Zn5Al and Zn55Al alloyed by rare-earth metals of cerium subgroup which are used as anode covers for protection of steel from corrosion. Therefore, the regularities of change of corrosion-electrochemical properties in various corrosive mediums have been determined; processes mechanisms of high temperature oxidation of alloys in solid state have been studied; in the products of alloys oxidation their phase components have been defined and their role in the corrosion process have been revealed; the optimal compositions of zinc-aluminium alloys alloyed by rare earth metals, which are protected by two patents of the Republic of Tajikistan have been elaborated.

  13. Oxidative stress induced by cerium oxide nanoparticles in cultured BEAS-2B cells

    International Nuclear Information System (INIS)

    Park, Eun-Jung; Choi, Jinhee; Park, Young-Kwon; Park, Kwangsik

    2008-01-01

    Cerium oxide nanoparticles of different sizes (15, 25, 30, 45 nm) were prepared by the supercritical synthesis method, and cytotoxicity was evaluated using cultured human lung epithelial cells (BEAS-2B). Exposure of the cultured cells to nanoparticles (5, 10, 20, 40 μg/ml) led to cell death, ROS increase, GSH decrease, and the inductions of oxidative stress-related genes such as heme oxygenase-1, catalase, glutathione S-transferase, and thioredoxin reductase. The increased ROS by cerium oxide nanoparticles triggered the activation of cytosolic caspase-3 and chromatin condensation, which means that cerium oxide nanoparticles exert cytotoxicity by an apoptotic process. Uptake of the nanoparticles to the cultured cells was also tested. It was observed that cerium oxide nanoparticles penetrated into the cytoplasm and located in the peri-region of the nucleus as aggregated particles, which may induce the direct interaction between nanoparticles and cellular molecules to cause adverse cellular responses

  14. State of charge monitoring of vanadium redox flow batteries using half cell potentials and electrolyte density

    Science.gov (United States)

    Ressel, Simon; Bill, Florian; Holtz, Lucas; Janshen, Niklas; Chica, Antonio; Flower, Thomas; Weidlich, Claudia; Struckmann, Thorsten

    2018-02-01

    The operation of vanadium redox flow batteries requires reliable in situ state of charge (SOC) monitoring. In this study, two SOC estimation approaches for the negative half cell are investigated. First, in situ open circuit potential measurements are combined with Coulomb counting in a one-step calibration of SOC and Nernst potential which doesn't need additional reference SOCs. In-sample and out-of-sample SOCs are estimated and analyzed, estimation errors ≤ 0.04 are obtained. In the second approach, temperature corrected in situ electrolyte density measurements are used for the first time in vanadium redox flow batteries for SOC estimation. In-sample and out-of-sample SOC estimation errors ≤ 0.04 demonstrate the feasibility of this approach. Both methods allow recalibration during battery operation. The actual capacity obtained from SOC calibration can be used in a state of health model.

  15. Production of cerium dioxide microspheres by an internal gelation sol–gel method

    Energy Technology Data Exchange (ETDEWEB)

    Katalenich, Jeffrey A.

    2017-03-27

    An internal gelation sol-gel technique was used to prepare cerium dioxide microspheres with uniform diameters near 100 µm. In this process, chilled aqueous solutions containing cerium, hexamethylenetetramine (HMTA), and urea are transformed into a solid gel by heat addition and are subsequently washed, dried, and sintered to produce pure cerium dioxide. Cerous nitrate and ceric ammonium nitrate solutions were compared for their usefulness in microsphere production. Gelation experiments were performed with both cerous nitrate and ceric ammonium nitrate to determine desirable concentrations of cerium, HMTA, and urea in feed solutions as well as the necessary quantity of ammonium hydroxide added to cerium solutions. Analysis of the pH before and after sample gelation was found to provide a quantitative metric for optimal parameter selection along with subjective evaluations of gel qualities. The time necessary for chilled solutions to gel upon inserting into a hot water bath was determined for samples with a variety of parameters and also used to determine desirable formulations for microsphere production. A technique for choosing the optimal mixture of ceric ammonium nitrate, HMTA, and urea was determined using gelation experiments and used to produce microspheres by dispersion of the feed solution into heated silicone oil. Gelled spheres were washed to remove excess reactants and reaction products before being dried and sintered. X-ray diffraction of air-dried microspheres, sintered microspheres, and commercial CeO2 powders indicated that air-dried and sintered spheres were pure CeO2.

  16. Effects of PEG4000 template on sol-gel synthesis of porous cerium titanate photocatalyst

    Science.gov (United States)

    Zhang, Wenjie; Tao, Yingjie; Li, Chuanguo

    2018-04-01

    Porous cerium titanate was synthesized by sol-gel method, using polyethylene glycol (PEG4000) as template agent. Brannerite structured CeTi2O6 in monoclinic system is the major substance formed in the materials. Formation of CeO2 and rutile TiO2 depends on the amount of PEG4000. The addition of PEG4000 leads to production of fine particles in the samples, but it does not apparently affect the band gap energy. Pore volume of the cerium titanate sample continuously increases with rising PEG4000 amount. The sample obtained using 3.5 g PEG4000 has BET surface area of 16.2 m2/g and pore volume of 0.0232 cm3/g. The addition of PEG4000 can obviously promote photocatalytic activity of cerium titanate, which can be proven by both enhanced production of hydroxyl radical and ofloxacin degradation efficiency. As much as 95.2% of the initial ofloxacin molecules are removed from the solution after 50 min of photocatalytic degradation on the cerium titanate obtained using 3.5 g PEG4000, while only 48.4% ofloxacin is removed on cerium titanate obtained without PEG4000.

  17. Analysis of cerium-composite polymer-electrolyte membranes during and after accelerated oxidative-stability test

    Science.gov (United States)

    Shin, Dongwon; Han, Myungseong; Shul, Yong-Gun; Lee, Hyejin; Bae, Byungchan

    2018-02-01

    The oxidative stability of membranes constructed from a composite of pristine sulfonated poly(arylene ether sulfone) and cerium was investigated by conducting an accelerated oxidative-stability test at the open-circuit voltage (OCV). The membranes were analyzed in situ through OCV and impedance measurements, cyclic voltammetry, and linear-sweep voltammetry to monitor the electrochemical properties during the stability test. Although the high-frequency resistance of a composite membrane was slightly higher than that of a pristine membrane because of the exchange of protons from the sulfonic acid with cerium ions, the composite membrane maintained its potential for much longer than the pristine membrane. The effect of the cerium ions as radical scavengers was confirmed by analyzing the drain water and chemical structure after operation. These post-operation analyses confirmed that cerium ions improved the oxidative stability of the hydrocarbon-based polymer during fuel-cell operation. It is clear that the cerium-based radical scavengers prevented chemical degradation of the polymer membrane as well as the electrode in terms of hydrogen cross-over, polymer-chain scission, and the electrochemical surface area, while they rarely diffused outward from the membrane.

  18. Electronically Induced Redox Barriers for Treatment of Groundwater

    National Research Council Canada - National Science Library

    Sale, Tom; Gilbert, David

    2006-01-01

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

  19. Immobilization of simulated radioactive soil waste containing cerium by self-propagating high-temperature synthesis

    International Nuclear Information System (INIS)

    Mao, Xianhe; Qin, Zhigui; Yuan, Xiaoning; Wang, Chunming; Cai, Xinan; Zhao, Weixia; Zhao, Kang; Yang, Ping; Fan, Xiaoling

    2013-01-01

    A simulated radioactive soil waste containing cerium as an imitator element has been immobilized by a thermite self-propagating high-temperature synthesis (SHS) process. The compositions, structures, and element leaching rates of products with different cerium contents have been characterized. To investigate the influence of iron on the chemical stability of the immobilized products, leaching tests of samples with different iron contents with different leaching solutions were carried out. The results showed that the imitator element cerium mainly forms the crystalline phases CeAl 11 O 18 and Ce 2 SiO 5 . The leaching rate of cerium over a period of 28 days was 10 −5 –10 −6 g/(m 2 day). Iron in the reactants, the reaction products, and the environment has no significant effect on the chemical stability of the immobilized SHS products

  20. Immobilization of simulated radioactive soil waste containing cerium by self-propagating high-temperature synthesis

    Science.gov (United States)

    Mao, Xianhe; Qin, Zhigui; Yuan, Xiaoning; Wang, Chunming; Cai, Xinan; Zhao, Weixia; Zhao, Kang; Yang, Ping; Fan, Xiaoling

    2013-11-01

    A simulated radioactive soil waste containing cerium as an imitator element has been immobilized by a thermite self-propagating high-temperature synthesis (SHS) process. The compositions, structures, and element leaching rates of products with different cerium contents have been characterized. To investigate the influence of iron on the chemical stability of the immobilized products, leaching tests of samples with different iron contents with different leaching solutions were carried out. The results showed that the imitator element cerium mainly forms the crystalline phases CeAl11O18 and Ce2SiO5. The leaching rate of cerium over a period of 28 days was 10-5-10-6 g/(m2 day). Iron in the reactants, the reaction products, and the environment has no significant effect on the chemical stability of the immobilized SHS products.

  1. Synthesis of cerium oxide catalysts supported on MCM-41 molecular sieve

    International Nuclear Information System (INIS)

    Souza, E.L.S.; Barros, T.R.B.; Sousa, B.V. de

    2016-01-01

    Porous materials have been widely studied as catalysts and catalyst support. The MCM-41 structure is the one that has been most studied because of its application possibilities in chemical processes. This work aimed to obtain and characterize cerium oxide catalysts supported on MCM-41 molecular sieve. The molecular sieve was synthesized by the conventional method with the following molar composition: 1 SiO2: 0.30 CTABr: NH3 11: 144 H2O. Then, 25% w/w cerium was incorporated into the MCM-41 using the wet impregnation process and the material obtained was activated by calcination. From the XRD patterns was confirmed the structure of the molecular sieve, and were identified the cerium oxide phases in its structure. The textural catalysts characteristics were investigated by isotherms of N2 adsorption/desorption (BET method). (author)

  2. Imidazolium ionic liquids as solvents for cerium(IV)-mediated oxidation reactions

    OpenAIRE

    Mehdi, Hasan; Bodor, Andrea; Lantos, Diana; Horváth, István T; De Vos, Dirk; Binnemans, Koen

    2007-01-01

    Use of imidazolium ionic liquids as solvents for organic transformations with tetravalent cerium salts as oxidizing agents was evaluated. Good solubility was found for ammonium hexanitratocerate(IV) (ceric ammonium nitrate, CAN) and cerium(IV) triflate in 1-alkyl-3-methylimidazolium triflate ionic liquids. Oxidation of benzyl alcohol to benzaldehyde in 1-ethyl-3-methylimidazolium triflate was studied by in-situ FTIR spectroscopy and 13C NMR spectroscopy on carbon-13-labeled benzyl alcohol. Ca...

  3. Procedure for the separation of cerium from rare earth phosphate mixtures

    International Nuclear Information System (INIS)

    Richter, H.; Grauss, H.; Schmitt, A.; Schade, H.; Lindeholz, M.; Lorenz, E.; Weickart, J.

    1986-01-01

    The invention is concerned with a procedure for the separation of cerium from rare earth concentrates originating from the partial neutralization of nitric crude phosphate decomposition solutions without preceding elimination of impurities from the raw material. The rare earth phosphates are treated with an excess of concentrated nitric acid through which the Ce 3+ , contained in the solution, is oxidized to Ce 4+ and precipitated as cerium(IV) phosphate by neutralization with alkalis

  4. Synthesis and structure of cerium nitrosocarbonylcyanmethanid complex

    International Nuclear Information System (INIS)

    Gerasimenko, H.; Scopenko, V.V.; Kapshuk, A.A.

    1998-01-01

    Full text: The complex compound [CeL 4 Dy 2 ]Na*2Ac (where L- nitrosocarbonylcyanmethanid, Dy -- dipyridile, Ac - acetone) were synthesised by interaction of cerium chloride and sodium nitrosocarbonylcyanmethanid from acetone solution. After two hours of mixing the dipyridil solution in acetone was added for complex stabilization. After filtration solution was put to desiccator for crystallisation. The complex was studied using IR- and UV-spectroscopy. The structure of the complex was determined using X-ray structure analysis. It was found that the structure of the complex belongs to orthorhombic Pna2(1) syngony with the unit cell parameters 17.010, 16.280 and 16.340Angstroms, respectively. It was found that cerium in the compound was eight co-ordinated. Four nitroso ligands were co-ordinated by bidentate bridge method and two dipyridiles by bidentate-cycle method

  5. Fixation of radioactive cerium-144 on white blood cells. Possibilities for use in physiopathology; Fixation du cerium radioactif ({sup 144}Ce) sur les globules blancs. Possibilites d'emploi en physiopathologie

    Energy Technology Data Exchange (ETDEWEB)

    Aeberhardt, A [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1958-07-01

    From the study of the means of transport of cerium in the blood of various laboratory animals, after intra-venous injection of {sup 144}Ce-{sup 144}Pr without carrier, we have been able to show up the part played by the white cells in the transport of this fission product during its passage in the blood. This observation has led to the study, in vitro, of the methods of cerium fixation on the white cells, with a view to determining the possibilities of using this property for white cell labelling, the methods used up to the present not being entirely satisfactory. Using the method for the separation of the known constituents of the blood proposed by us in 1956, we have studied the cerium fixation under various conditions: - on suspensions of white cells from the rabbit, - on a suspension of human white cells, - on the white cells in whole from the rabbit. (author) [French] L'etude du mode de transport du cerium dans le sang chez differents animaux de laboratoire, apres injection intra-veineuse de {sup 144}Ce-{sup 144}Pr sans entraineur, nous a permis de mettre en evidence le rale des globules blancs dans le transport de ce produit de fission au cours de son passage dans le sang. Cette constatation nous a conduit a etudier, in vitro, les modalites de la fixation du cerium sur les globules blancs afin de preciser les possibilites d'utilisation de cette propriete pour le marquage des globules blancs, les methodes employees jusqu'ici ne donnant pas entiere satisfaction. Disposant de la methode de separation des elements figures du sang que nous avons proposee en 1956, nous avons etudie la fixation du cerium, dans diverses conditions: - sur des suspensions de globules blancs de lapin, - sur une suspension de globules blancs humains, - sur les globules blancs dans le sang total de lapin. (auteur)

  6. Destruction of commercial pesticides by cerium redox couple mediated electrochemical oxidation process in continuous feed mode

    International Nuclear Information System (INIS)

    Balaji, Subramanian; Chung, Sang Joon; Ryu, Jae-Yong; Moon, Il Shik

    2009-01-01

    Mediated electrochemical oxidation was carried out for the destruction of commercial pesticide formulations using cerium(IV) in nitric acid as the mediator electrolyte solution in a bench scale set up. The mediator oxidant was regenerated in situ using an electrochemical cell. The real application of this sustainable process for toxic organic pollutant destruction lies in its ability for long term continuous operation with continuous organic feeding and oxidant regeneration with feed water removal. In this report we present the results of fully integrated MEO system. The task of operating the continuous feed MEO system for a long time was made possible by continuously removing the feed water using an evaporator set up. The rate of Ce(IV) regeneration in the electrochemical cell and the consumption for the pesticide destruction was matched based on carbon content of the pesticides. It was found that under the optimized experimental conditions for Ce(III) oxidation, organic addition and water removal destruction efficiency of ca. 99% was obtained for all pesticides studied. It was observed that the Ce(IV) concentration was maintained nearly the same throughout the experiment. The stable operation for 6 h proved that the process can be used for real applications and for possible scale up for the destruction of larger volumes of toxic organic wastes.

  7. Purification of cerium, neodymium and gadolinium for low background experiments

    Directory of Open Access Journals (Sweden)

    Boiko R.S.

    2014-01-01

    Full Text Available Cerium, neodymium and gadolinium contain double beta active isotopes. The most interesting are 150Nd and 160Gd (promising for 0ν2β search, 136Ce (2β+ candidate with one of the highest Q2β. The main problem of compounds containing lanthanide elements is their high radioactive contamination by uranium, radium, actinium and thorium. The new generation 2β experiments require development of methods for a deep purification of lanthanides from the radioactive elements. A combination of physical and chemical methods was applied to purify cerium, neodymium and gadolinium. Liquid-liquid extraction technique was used to remove traces of Th and U from neodymium, gadolinium and for purification of cerium from Th, U, Ra and K. Co-precipitation and recrystallization methods were utilized for further reduction of the impurities. The radioactive contamination of the samples before and after the purification was tested by using ultra-low-background HPGe gamma spectrometry. As a result of the purification procedure the radioactive contamination of gadolinium oxide (a similar purification efficiency was reached also with cerium and neodymium oxides was decreased from 0.12 Bq/kg to 0.007 Bq/kg in 228Th, from 0.04 Bq/kg to <0.006 Bq/kg in 226Ra, and from 0.9 Bq/kg to 0.04 Bq/kg in 40K. The purification methods are much less efficient for chemically very similar radioactive elements like actinium, lanthanum and lutetium.

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

    Science.gov (United States)

    Pan, Feng; Wang, Qing

    2015-11-18

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

  9. Redox Species of Redox Flow Batteries: A Review

    Directory of Open Access Journals (Sweden)

    Feng Pan

    2015-11-01

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

  10. Investigating the Influence of the Cerium loading in prepared Y zeolite from Iraqi kaolin on its Catalytic Performance

    Directory of Open Access Journals (Sweden)

    Karim Khalifa Esgair

    2018-01-01

    Full Text Available In this study, the effects of different loading doses of cerium in the prepared NaY zeolite from Iraqi kaolin were investigated. Al-Duara refinery atmospheric residue fluid catalytic cracking was selected as palpation reaction for testing the catalytic activity of cerium loading NaY zeolite. The insertion of cerium in NaY zeolites has been synthesized by simple ion exchange methods. Three samples of modified zeolite Y have been obtained by replacing the sodium ions in the original sample with cerium and the weight percent added are 0.35, 0.64, and 1.06 respectively. The effects of cerium loading to zeolite Y in different weight percent on the cracking catalysts were studied by employing a laboratory fluidized bed reactor. The experiments have been performed with weight hourly space velocity (WHSV range from 6 to 24 h-1, and the temperature range from 450 to 510 oC. The activity of the catalyst with 1.06 wt% cerium has been shown to be much greater than that of the sample parent NaY. Also it was observed that the addition of the cerium causes an increase in the thermal stability of the zeolite.

  11. Redox State of the Neoarchean Earth Environment

    Science.gov (United States)

    Zerkle, Aubrey L.; Claire, Mark W.; Domagal-Goldman, Shawn; Farquhar, James; Poulton, Simon W.

    2011-01-01

    A Titan-like organic haze has been hypothesized for Earth's atmosphere prior to widespread surface oxygenation approx.2.45 billion years ago (Ga). We present a high-resolution record of quadruple sulfur isotopes, carbon isotopes, and Fe speciation from the approx.2.65-2.5 Ga Ghaap Group, South Africa, which suggest a linkage between organic haze and the biogeochemical cycling of carbon, sulfur, oxygen, and iron on the Archean Earth. These sediments provide evidence for oxygen production in microbial mats and localized oxygenation of surface waters. However, this oxygen production occurred under a reduced atmosphere which existed in multiple distinct redox states that correlate to changes in carbon and sulfur isotopes. The data are corroborated by photochemical model results that suggest bi-stable transitions between organic haze and haze-free atmospheric conditions in the Archean. These geochemical correlations also extend to other datasets, indicating that variations in the character of anomalous sulfur fractionation could provide insight into the role of carbon-bearing species in the reducing Archean atmosphere.

  12. Synthesis of cerium oxide (CeO{sub 2}) nanoparticles using simple CO-precipitation method

    Energy Technology Data Exchange (ETDEWEB)

    Farahmandjou, M.; Zarinkamar, M.; Firoozabadi, T. P., E-mail: farahamndjou@iauvaramin.ac.ir [Islamis Azad University, Varamin-Phisva Branch, Department of Physics, Varamin (Iran, Islamic Republic of)

    2016-11-01

    Synthesis of cerium oxide (CeO{sub 2}) nanoparticles was studied by new and simple co-precipitation method. The cerium oxide nanoparticles were synthesized using cerium nitrate and potassium carbonate precursors. Their physicochemical properties were characterized by high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (Sem), X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (Ftir) and UV-Vis spectrophotometer. XRD pattern showed the cubic structure of the cerium oxide nanoparticles. The average particle size of CeO{sub 2} was around 20 nm as estimated by XRD technique and direct HRTEM observations. The surface morphological studies from Sem and Tem depicted spherical particles with formation of clusters. The sharp peaks in Ftir spectrum determined the existence of CeO{sub 2} stretching mode and the absorbance peak of UV-Vis spectrum showed the bandgap energy of 3.26 eV. (Author)

  13. Direct growth of cerium oxide nanorods on diverse substrates for superhydrophobicity and corrosion resistance

    Science.gov (United States)

    Cho, Young Jun; Jang, Hanmin; Lee, Kwan-Soo; Kim, Dong Rip

    2015-06-01

    Superhydrophobic surfaces with anti-corrosion properties have attracted great interest in many industrial fields, particularly to enhance the thermal performance of offshore applications such as heat exchangers, pipelines, power plants, and platform structures. Nanostructures with hydrophobic materials have been widely utilized to realize superhydrophobicity of surfaces, and cerium oxide has been highlighted due to its good corrosion resistive and intrinsically hydrophobic properties. However, few studies of direct growth of cerium oxide nanostructures on diverse substrates have been reported. Herein we report a facile hydrothermal method to directly grow cerium oxide nanorods on diverse substrates, such as aluminum alloy, stainless steel, titanium, and silicon. Diverse substrates with cerium oxide nanorods exhibited superhydrophobicity with no hydrophobic modifiers on their surfaces, and showed good corrosion resistive properties in corrosive medium. We believe our method could pave the way for realization of scalable and sustainable corrosion resistive superhydrophobic surfaces in many industrial fields.

  14. A Protocol for Electrochemical Evaluations and State of Charge Diagnostics of a Symmetric Organic Redox Flow Battery.

    Science.gov (United States)

    Duan, Wentao; Vemuri, Rama S; Hu, Dehong; Yang, Zheng; Wei, Xiaoliang

    2017-02-13

    Redox flow batteries have been considered as one of the most promising stationary energy storage solutions for improving the reliability of the power grid and deployment of renewable energy technologies. Among the many flow battery chemistries, non-aqueous flow batteries have the potential to achieve high energy density because of the broad voltage windows of non-aqueous electrolytes. However, significant technical hurdles exist currently limiting non-aqueous flow batteries to demonstrate their full potential, such as low redox concentrations, low operating currents, under-explored battery status monitoring, etc. In an attempt to address these limitations, we recently reported a non-aqueous flow battery based on a highly soluble, redox-active organic nitronyl nitroxide radical compound, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO). This redox material exhibits an ambipolar electrochemical property, and therefore can serve as both anolyte and catholyte redox materials to form a symmetric flow battery chemistry. Moreover, we demonstrated that Fourier transform infrared (FTIR) spectroscopy could measure the PTIO concentrations during the PTIO flow battery cycling and offer reasonably accurate detection of the battery state of charge (SOC), as cross-validated by electron spin resonance (ESR) measurements. Herein we present a video protocol for the electrochemical evaluation and SOC diagnosis of the PTIO symmetric flow battery. With a detailed description, we experimentally demonstrated the route to achieve such purposes. This protocol aims to spark more interests and insights on the safety and reliability in the field of non-aqueous redox flow batteries.

  15. Study of the effect of cerium nitrate on AA2024-T3 by means of electrochemical micro-cell technique

    International Nuclear Information System (INIS)

    Paussa, L.; Andreatta, F.; Rosero Navarro, N.C.; Durán, A.; Fedrizzi, L.

    2012-01-01

    Highlights: ► We evaluate the cerium nitrate effect on the electrochemical behavior of AA2024-T3. ► We examine how AA2024-T3 microstructure affects cerium precipitation mechanism. ► The entire AA2024-T3 surface is involved in cerium precipitation. ► Anodic and cathodic inhibitions are both provided by cerium precipitation. ► Mg-rich intermetallics are preferential sites for cerium precipitation. - Abstract: This work evaluates the effect of cerium nitrate as corrosion inhibitor for AA2024-T3 in the view of its introduction in sol–gel coatings able to provide self-healing ability. Since it is well established that deposition of Ce species is activated by the local pH increase, the objective of this paper is to investigate the behavior of AA2024-T3 (open circuit potential and polarization curves) in the presence of Ce species in aggressive solutions by means of a local technique, the electrochemical micro-cell. This technique enables the investigation of small areas with resolution in the micrometer range by the use of glass capillaries to define the working electrode area. The micro-cell results clearly displayed that the entire AA2024-T3 area exposed to the cerium-containing electrolyte was involved in the cerium precipitation mechanism. The heterogeneous electrochemical behavior of the microstructure is minimized by the formation of a cerium-containing layer able to protect the metal substrate.

  16. Continuous Flow-Resonance Raman Spectroscopy of an Intermediate Redox State of Cytochrome-C

    DEFF Research Database (Denmark)

    Forster, M.; Hester, R. E.; Cartling, B.

    1982-01-01

    An intermediate redox state of cytochrome c at alkaline pH, generated upon rapid reduction by sodium dithionite, has been observed by resonance Raman (RR) spectroscopy in combination with the continuous flow technique. The RR spectrum of the intermediate state is reported for excitation both...... in the (alpha, beta) and the Soret optical absorption band. The spectra of the intermediate state are more like those of the stable reduced form than those of the stable oxidized form. For excitation of 514.5 nm, the most prominent indication of an intermediate state is the wave-number shift of one RR band from...... 1,562 cm-1 in the stable oxidized state through 1,535 cm-1 in the intermediate state to 1,544 cm-1 in the stable reduced state. For excitation at 413.1 nm, a band, present at 1,542 cm-1 in the stable reduced state but not present in the stable oxidized state, is absent in the intermediate state. We...

  17. Determination of trace amounts of cerium in silicate rocks based on its candoluminescence in a calcium oxide based matrix

    International Nuclear Information System (INIS)

    Belcher, R.; Nasser, T.A.K.; Polo-Diez, L.; Townshend, A.

    1977-01-01

    A very sensitive method for the determination of cerium (above 10 ng ml -1 ) has been developed (Belcher et al., Analyst;100:415(1975)), based on the measurement of the green candoluminescence produced by cerium in a calcium oxide-calcium sulphate matrix, with sulphuric acid as a coactivator, when the matrix is inserted into a hydrogen-nitrogen-air flame. This paper describes the application of this method to the determination of trace amounts of cerium in rocks. It involves the fusion of the sample with lithium metaborate, and does not require the isolation of cerium from other components of the rock, before measuring the candoluminescence intensity of the cerium. (author)

  18. Development of electrolytic process in molten salt media for light rare-earth metals production. The metallic cerium electrodeposition

    International Nuclear Information System (INIS)

    Restivo, T.A.G.

    1994-01-01

    The development of molten salt process and the respective equipment aiming rare-earth metals recovery was described. In the present case, the liquid cerium metal electrodeposition in a molten electrolytes of cerium chloride and an equimolar mixture of sodium and potassium chlorides in temperatures near 800 C was studied. Due the high chemical reactivity of the rare-earth metals in the liquid state and their molten halides, an electrolytic cell was constructed with controlled atmosphere, graphite crucibles and anodes and a tungsten cathode. The electrolytic process variables and characteristics were evaluated upon the current efficiency and metallic product purity. Based on this evaluations, were suggested some alterations on the electrolytic reactor design and upon the process parameters. (author). 90 refs, 37 figs, 20 tabs

  19. Ultrastructural Analysis of Human Breast Cancer Cells during Their Overtime Interaction with Cerium Oxide Nanoparticles

    KAUST Repository

    AlAbbadi, Shatha H.

    2016-12-01

    Cerium oxide nanoparticles have been proposed as an anticancer agent, thanks to their ability of tuning the redox activity in accordance to different conditions, which lead to selective roles on healthy and cancer cells. Recent evidence suggested the ability of these nanoparticles to be toxic against cancer cells, while confer protection from oxidative stress, toward healthy cells. The main focus of this study was to determine the ultrastructural effects of cerium oxide nanoparticles over multiple incubation time of 1, 3, and 7 days on breast healthy and cancer cells. Cellular characterizations were carried out using electron microscopes, both transmission and scanning electron microscopes, while the viability assessments were performed by propidium iodide and trypan blue viability assays. The obtained results of the viability assays and electron microscopy suggested higher toxic effects on the cancer cell line viability by using a nanoceria dose of 300 μg/mL after 1 day of treatment. Such effects were shown to be preserved at 3 days, and in a longer time point of 7 days. On the contrary, the healthy cells underwent less effects on their viability at time point of 1 and 7 days. The 3 days treatment demonstrated a reduction on the number of cells that did not correlate with an increase of the dead cells, which suggested a possible initial decrease of the cell growth rate, which could be due to the high intracellular loading of nanoparticles. To conclude, the overall result of this experiment suggested that 300 μg/mL of CeO2 nanoparticles is the most suitable dose, within the range and the time point tested, which induces long-lasting cytotoxic effects in breast cancer cells, without harming the normal cells, as highlighted by the viability assays and ultrastructural characterization of electron microscopy analysis.

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

    Science.gov (United States)

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

    2017-07-26

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

  1. Methods study of homogeneity and stability test from cerium oxide CRM candidate

    International Nuclear Information System (INIS)

    Samin; Susanna TS

    2016-01-01

    The methods study of homogeneity and stability test from cerium oxide CRM candidate has been studied based on ISO 13258 and KAN DP. 01. 34. The purpose of this study was to select the test method homogeneity and stability tough on making CRM cerium oxide. Prepared 10 sub samples of cerium oxide randomly selected types of analytes which represent two compounds, namely CeO_2 and La_2O_3. At 10 sub sample is analyzed CeO_2 and La_2O_3 contents in duplicate with the same analytical methods, by the same analyst, and in the same laboratory. Data analysis results calculated statistically based on ISO 13528 and KAN DP.01.34. According to ISO 13528 Cerium Oxide samples said to be homogeneous if Ss ≤ 0.3 σ and is stable if | Xr – Yr | ≤ 0.3 σ. In this study, the data of homogeneity test obtained CeO_2 is Ss = 2.073 x 10-4 smaller than 0.3 σ (0.5476) and the stability test obtained | Xr - Yr | = 0.225 and the price is < 0.3 σ. Whereas for La_2O_3, the price for homogeneity test obtained Ss = 1.649 x 10-4 smaller than 0.3 σ (0.4865) and test the stability of the price obtained | Xr - Yr | = 0.2185 where the price is < 0.3 σ. Compared with the method from KAN, a sample of cerium oxide has also been homogenized for Fcalc < Ftable and stable, because | Xi - Xhm | < 0.3 x n IQR. Provided that the results of the evaluation homogeneity and stability test from CeO_2 CRM candidate test data were processed using statistical methods ISO 13528 is not significantly different with statistical methods from KAN DP.01.34, which together meet the requirements of a homogeneous and stable. So the test method homogeneity and stability test based on ISO 13528 can be used to make CRM cerium oxide. (author)

  2. In situ57Fe Moessbauer Investigation of Solid-State Redox Reactions of Lithium Insertion Electrodes for Advanced Batteries

    International Nuclear Information System (INIS)

    Sakai, Yoichi; Ariyoshi, Kingo; Ohzuku, Tsutomu

    2002-01-01

    A novel in situ electrochemical cell for 57 Fe Moessbauer measurements was developed in order to clarify the mechanisms of solid-state redox reactions in lithium insertion materials containing iron. Our in situ Moessbauer technique was successfully applied to the determination as to which transition metal ion was a redox center in the insertion electrodes, such as LiFe 0.5 Mn 1.5 O 4 , LiFeTiO 4 , or LiFe 0.25 Ni 0.75 O 2 , for the lithium-ion batteries.

  3. Cerium anomaly across the mid-Tournaisian carbon isotope excursion (TICE)

    Science.gov (United States)

    Jiang, G.; Morales, D. C.; Maharjan, D. K.

    2015-12-01

    The Early Mississippian (ca. 359-345 Ma) represents one of the most important greenhouse-icehouse climate transitions in Earth history. Closely associated with this critical transition is a prominent positive carbon isotope excursion (δ13C ≥ +5‰) that has been documented from numerous stratigraphic successions across the globe. This δ13C excursion, informally referred to as the TICE (mid-Tournaisian carbon isotope excursion) event, has been interpreted as resulting from enhanced organic carbon burial, with anticipated outcomes including the lowering of atmospheric CO2 and global cooling, the growth of continental ice sheets and sea-level fall, and the increase of ocean oxygenation and ocean redox changes. The casual relationship between these events has been addressed from various perspectives but not yet clearly demonstrated. To document the potential redox change associated with the perturbation of the carbon cycle, we have analyzed rare earth elements (REE) and trace elements across the TICE in two sections across a shallow-to-deep water transect in the southern Great Basin (Utah and Nevada), USA. In both sections, the REE data show a significant positive cerium (Ce) anomaly (Ce/Ce* = Ce/(0.5La+0.5Pr)). Prior to the positive δ13C shift, most Ce/Ce* values are around 0.3 (between 0.2 and 0.4). Across the δ13C peak, Ce/Ce* values increase up to 0.87, followed by a decrease back to 0.2~0.3 after the δ13C excursion (Figure 1). The positive Ce anomaly is best interpreted as recording expansion of oxygen minimum zone and anoxia resulted from increased primary production. This is consistent with a significant increase of nitrogen isotopes (δ15N) across the δ13C peak. Integration of the carbon, nitrogen, and REE data demonstrates a responsive earth systems change linked to the perturbation of the Early Mississippian carbon cycle.

  4. Redox-capacitor to connect electrochemistry to redox-biology.

    Science.gov (United States)

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

    2014-01-07

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

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

    Science.gov (United States)

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

    2016-04-01

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

  6. Phase segregation in cerium-lanthanum solid solutions

    NARCIS (Netherlands)

    Belliere, V.; Joorst, G; Stephan, O; de Groot, FMF; Weckhuysen, BM

    2006-01-01

    Electron energy-loss spectroscopy (EELS) in combination with scanning transmission electron microscopy ( STEM) reveals that the La enrichment at the surface of cerium-lanthanum solid solutions is an averaged effect and that segregation occurs in a mixed oxide phase. This separation occurs within a

  7. Effect of cerium on structure modifications of a hybrid sol–gel coating, its mechanical properties and anti-corrosion behavior

    International Nuclear Information System (INIS)

    Cambon, Jean-Baptiste; Esteban, Julien; Ansart, Florence; Bonino, Jean-Pierre; Turq, Viviane; Santagneli, S.H.; Santilli, C.V.; Pulcinelli, S.H.

    2012-01-01

    Highlights: ► New sol–gel routes to replace chromates for corrosion protection of aluminum. ► Effect of cerium concentration on the microstructure of xerogel. ► Electrochemical and mechanical performances of hybrid coating with different cerium contents. ► Good correlation between the different results with an optimal cerium content of 0.01 M. -- Abstract: An organic–inorganic hybrid coating was developed to improve the corrosion resistance of the aluminum alloy AA 2024-T3. Organic and inorganic coatings derived from glycidoxypropyl-trimethoxysilane (GPTMS) and aluminum tri-sec-butoxide Al(O s Bu) 3 , with different cerium contents, were deposited onto aluminum by dip-coating process. Corrosion resistance and mechanical properties were investigated by electrochemical impedance measurements and nano-indentation respectively. An optimal cerium concentration of 0.01 M was evidenced. To correlate and explain the hybrid coating performances in relation to the cerium content, NMR experiments were performed. It has been shown that when the cerium concentration in the hybrid is higher than 0.01 M there are important modifications in the hybrid structure that account for the mechanical properties and anti-corrosion behavior of the sol–gel coating.

  8. 234U/230Th ratio as an indicator of redox state, and U, Th and Ra behavior in briney aquifers

    International Nuclear Information System (INIS)

    Laul, J.C.; Smith, M.R.; Hubbard, N.

    1985-06-01

    The 234 U/ 230 Th ratio serves as an in-situ indicator of the redox state in groundwater aquifers. The higher this ratio, the more U there is in the +6 state and thus a lesser reducing environment. Radium is retarded in the shallow aquifer and its sorption is dependent on the CaSO 4 content and redox state. Relative to Ra, U and Th are highly sorbed. The total retardation factor for Th is approx.1400 and mean sorption time for 228 Th is approx.10 days in the shallow zone. The desorption rate of Ra is significantly slower in the shallow than in the deep aquifer. There is no effect of colloids in brines. 6 refs., 5 figs., 2 tabs

  9. Dry sliding wear behaviour of Al-12Si-4Mg alloy with cerium addition

    International Nuclear Information System (INIS)

    Anasyida, A.S.; Daud, A.R.; Ghazali, M.J.

    2010-01-01

    The purpose of this work is to understand the effect of cerium addition on wear resistance behaviour of as-cast alloys. Al-12Si-4 Mg alloys with 1-5 wt% cerium addition were prepared using the casting technique. A sliding wear test was carried out under applied loads of 10 N, 30 N and 50 N at a fixed sliding speed of 1 m/s using a pin-on-disc configuration. The wear test was conducted in dry conditions at room temperature of ∼25 o C. Detailed analysis of the microstructure, worn surface, collected debris and microhardness was undertaken in order to investigate the differences between the as-cast alloys with different levels of cerium addition. The addition of 1-5 wt% cerium was found to lead to the precipitation of intermetallic phases (Al-Ce), resulting a needle-like structures. Increasing cerium content up to 2 wt% improved both wear resistance and microhardness of as-cast alloys. Addition of more than 2 wt% cerium, however, led to a decrease in microhardness, resulting in lower wear resistance of the alloys. Moderate wear was observed at all loads, with specific wear rates (K') ranging from 6.82 x 10 -5 with 2 wt% Ce at applied load of 50 N to 21.48 x 10 -5 mm 3 /N m without added Ce at an applied load of 10 N. Based on K' ranges, the as-cast alloys exhibited moderate wear regimes, and the mechanism of wear is a combination of abrasion and adhesion. Alloy containing 2 wt% Ce, with the highest hardness and lowest K' value, showed the greatest wear resistance.

  10. The development of a method for the simultaneous measurement of cerium (IV) and chromium (VI) species in nitric acid media - 16124

    International Nuclear Information System (INIS)

    Nickson, Ian D.; Boxall, Colin; Jackson, Angela; Whillock, Guy O.H.

    2009-01-01

    The corrosion of stainless steel in nitric acid media is a major concern for the nuclear industry. Several reprocessing schemes such as PUREX (Plutonium Uranium Reduction Extraction) and UREX (Uranium Reduction Extraction) utilise nitric acid media, and an understanding of the behaviour of key chemical species in these process streams is vital if their effect on associated corrosion reactions and their rates is to be accurately assessed and quantified. This will allow for more accurate prediction of the working lifetime of any stainless steel surface in contact with the process stream in question. Two such key species that are found in nuclear process streams are cerium as Ce (IV) and chromium as Cr(VI), both of which may act as corrosion accelerants. The redox chemistry of cerium and chromium in highly active liquor (HAL) will depend on nitrous acid concentration, temperature, acidity, total nitrate and possibly the influence of other dissolved species and hence an analytical technique for the on-line measurement of these quantities would be useful for lifetime prediction and corrosion prevention. As a result of this, a strategy for the simultaneous measurement of both Ce(IV) and Cr(VI) species in the presence of other ions typically found in process streams (such as Iron, Magnesium Neodymium and Aluminium) has been developed. The work presented will discuss the design and implementation of the electrochemical techniques that we have used in the development of this strategy and in the measurement of the species in question. (authors)

  11. Corrosion electrochemical behaviors of silane coating coated magnesium alloy in NaCl solution containing cerium nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Luo, F.; Li, Q.; Zhong, X.K.; Gao, H.; Dai, Y.; Chen, F.N. [School of Chemistry and Chemical Engineering, Southwest University Chongqing (China)

    2012-02-15

    Sol-gel coatings cannot provide adequate corrosion protection for metal/alloys in the corrosive environments due to their high crack-forming potential. This paper demonstrates the possibility to employ cerium nitrate as inhibitor to decrease the corrosion development of sol-gel-based silane coating on the magnesium alloy in NaCl solution. Cerium nitrate was added into the NaCl solution where the silane coating coated magnesium alloy was immersed. Scanning electron microscopy (SEM) was used to examine surface morphology of the silane coating coated magnesium alloy immersed in NaCl solutions doped and undoped with cerium nitrate. The corrosion electrochemical behaviors were investigated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) tests. The results showed that the introduction of cerium nitrate into NaCl solution could effectively inhibit the corrosion of the silane coating coated magnesium alloy. Moreover, the influence of concentration of cerium nitrate on the corrosion inhibition and the possible inhibiting mechanism were also discussed in detail. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Effect of cerium substitution on structural and magnetic properties of magnetite nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Padalia, Diwakar, E-mail: Padalia.diwakar@gmail.com [Department of Physics, G.B.Pant University of Agriculture & Technology, Pantnagar, Uttrakhand (India); Johri, U.C. [Department of Physics, G.B.Pant University of Agriculture & Technology, Pantnagar, Uttrakhand (India); Zaidi, M.G.H. [Supercritical Fluid Processing Laboratory, Department of Chemistry, G.B.Pant University of Agriculture & Technology, Pantnagar, Uttrakhand (India)

    2016-02-01

    The current work presents the synthesis and properties of cerium doped magnetite (Fe{sub 3}O{sub 4}) nanoparticles synthesized by standard chemical co-precipitation method using NH{sub 4}OH as co-precipitating agent. The effects of cerium ion substitution on structural and magnetic properties of magnetite (Fe{sub 3}O{sub 4}) nanoparticles were reported. These materials were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometer (VSM). The cerium content has a significant influence on structural and magnetic properties. The X-ray diffraction study confirmed the formation of single-phase magnetite with space group Fd3m and crystallite size ranging from 39 to 58 nm. The addition of cerium resulted in a reduction of crystallite size and an increase of cell parameters. FTIR measurements confirmed the formation of different samples and suggested that the reduction of Fe{sup +3} to Fe{sup +2} preferred on a site adjacent to Ce{sup +4}. Magnetic measurements revealed that the saturation magnetization (Ms) and remanence (M{sub r}) decreased while the coercivity (H{sub C}) and squareness (M{sub r}/M{sub S}) increased with increasing cerium content. - Highlights: • There is an increase in cell parameters and strain with Ce-content. • Samples show the presence of secondary phase after 1.0% doping level. • Ce-ions prefer octahedral sites and charge neutrality is accompanied by Fe{sup +3} → Fe{sup +2}. • Magnetization decreases due to weakening of the super exchange interactions. • Squareness and coercivity start to increase with Ce content.

  13. Effect of calcination temperature on the crystallite growth of cerium oxide nano-powders prepared by the co-precipitation process

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jian-Chih [Department of Orthopaedics, Kaohsiung Medical University Hospital, Kaohsiung 807, Taiwan (China); Chen, Wen-Cheng [School of Dentistry, College of Dental Medicine, Kaohsiung Medical University, Kaohsiung 807, Taiwan (China); Tien, Yin-Chun [Department of Orthopaedics, Kaohsiung Medical University Hospital, Kaohsiung 807, Taiwan (China); Shih, Chi-Jen, E-mail: cjshih@kmu.edu.t [Department of Fragrance and Cosmetics Science, Kaohsiung Medical University, 100 Shi-Chuan1st Road, Kaohsiung 80708, Taiwan (China)

    2010-04-30

    Cerium oxide nanocrystallites were synthesized by a co-precipitation process at a relatively low temperature, using cerium (III) nitrate as the starting material in a water solution with pH in the range of 8-9. The effect of calcination temperature on the crystallite growth of cerium oxide nano-powders was investigated by X-ray diffraction, transmission electron microscopy and electron diffraction. The crystallization temperature of the cerium oxide powders was estimated to be about 273 K, by XRD analysis. When calcined at temperatures from 473 to 1273 K, face-centered cubic phase crystallization was observed by XRD. The crystallite size of the cerium oxide increased from 12.0 to 48 nm as the calcining temperature increased from 473 to 1273 K, in the pH range 8-9. The activation energy for the growth of cerium oxide nanoparticles was found to have very low values of 17.5 kJ/mol for pH = 8 and 16.0 kJ/mol for pH = 9.

  14. Ab initio MCHF structural calculations of Mg-like cerium

    Science.gov (United States)

    Wajid, Abdul; Jabeen, S.; Husain, Abid

    2018-05-01

    Energy levels and emission line wavelengths of high-Z materials are useful for impurity diagnostics in the next generation fusion devices. For this here we have calculated E1, M2 transitions, oscillator strengths, and transition probabilities for transitions among the terms belonging to the 2p63s2, 2p63s3p, 2p63p2 and 2p63s3d for the Magnesium like cerium (Ce XLVII) using the GRASP2K package based on the fully relativistic multi-configuration Dirac-Fock method. The electron correlation effects, Breit interaction and quantum electrodynamics effects to the atomic state wave functions and the corresponding energies have been taken into account.

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

    Directory of Open Access Journals (Sweden)

    Hossain eSazzad

    2016-05-01

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

  16. Mesoporous cerium oxide nanospheres for the visible-light driven photocatalytic degradation of dyes

    Directory of Open Access Journals (Sweden)

    Subas K. Muduli

    2014-04-01

    Full Text Available A facile, solvothermal synthesis of mesoporous cerium oxide nanospheres is reported for the purpose of the photocatalytic degradation of organic dyes and future applications in sustainable energy research. The earth-abundant, relatively affordable, mixed valence cerium oxide sample, which consists of predominantly Ce7O12, has been characterized by powder X-ray diffraction, X-ray photoelectron and UV–vis spectroscopy, and transmission electron microscopy. Together with N2 sorption experiments, the data confirms that the new cerium oxide material is mesoporous and absorbs visible light. The photocatalytic degradation of rhodamin B is investigated with a series of radical scavengers, suggesting that the mechanism of photocatalytic activity under visible-light irradiation involves predominantly hydroxyl radicals as the active species.

  17. Assessement of the effect of Pyrimetin in combined injury with external irradiation and oral cerium-144 incorporation

    International Nuclear Information System (INIS)

    Kiradzhiev, G.; Khadzhidekova, E.

    1985-01-01

    The effect of the preparation Pyrimetin on rats, subjected to external irradiation combined with oral cerium 144 incorporation was studied. LD 50/30 of cerium-144 was used as biological criterion. It was shown that by this criterion Pyrimetin essentially abolished the potentiated by external radiation effect of cerium. Probably, the preparation leads to normalization of the gastro-intestinal motor function and the dose loading of the colon

  18. Altering properties of cerium oxide thin films by Rh doping

    International Nuclear Information System (INIS)

    Ševčíková, Klára; Nehasil, Václav; Vorokhta, Mykhailo; Haviar, Stanislav; Matolín, Vladimír

    2015-01-01

    Highlights: • Thin films of ceria doped by rhodium deposited by RF magnetron sputtering. • Concentration of rhodium has great impact on properties of Rh–CeO x thin films. • Intensive oxygen migration in films with low concentration of rhodium. • Oxygen migration suppressed in films with high amount of Rh dopants. - Abstract: Ceria containing highly dispersed ions of rhodium is a promising material for catalytic applications. The Rh–CeO x thin films with different concentrations of rhodium were deposited by RF magnetron sputtering and were studied by soft and hard X-ray photoelectron spectroscopies, Temperature programmed reaction and X-ray powder diffraction techniques. The sputtered films consist of rhodium–cerium mixed oxide where cerium exhibits a mixed valency of Ce 4+ and Ce 3+ and rhodium occurs in two oxidation states, Rh 3+ and Rh n+ . We show that the concentration of rhodium has a great influence on the chemical composition, structure and reducibility of the Rh–CeO x thin films. The films with low concentrations of rhodium are polycrystalline, while the films with higher amount of Rh dopants are amorphous. The morphology of the films strongly influences the mobility of oxygen in the material. Therefore, varying the concentration of rhodium in Rh–CeO x thin films leads to preparing materials with different properties

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

    Science.gov (United States)

    Macalady, Donald L.; Walton-Day, Katherine

    2011-01-01

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

  20. Obtainment of cerium dioxide for use as spectrochemical standard. Obtencao de dioxido de cerio para uso como padrao espectroquimico

    Energy Technology Data Exchange (ETDEWEB)

    Silva Queiroz, C.A. da; Hespanhol, E C.B.; Abrao, A [Instituto de Pesquisas Energeticas e Nucleares (IPEN), Sao Paulo, SP (Brazil)

    1992-01-01

    This paper describes a simple method for cerium separation and purification. Cerium is previously precipitated with N H{sub 3}/air/H{sub 2} O{sub 2} system in a mixed chlorides solution obtained from Brazilian monazite treatment. The cerium fraction as cerium chloride is run down throughout a strong cationic resin bed and then the rare earth impurities separation is done by elution of the resin with separation ammonium salt of EDTA. None retainer ion is used in the purification technique by ion exchange. (author).

  1. First heats of cerium solution in liquid aluminium, gallium, indium, tin, lead and bismuth

    International Nuclear Information System (INIS)

    Yamshchikov, L.F.; Lebedev, V.A.; Nichkov, I.F.; Raspopin, S.P.; Shein, V.G.

    1983-01-01

    Cerium solution heats in liquid alluminium, gallium, indium, tin, lead and bismuth are determined in high temperature mixing calorimeter with an isothermal shell. The statistical analysis carried out proves that values of cerium solution heat in fusible metals obtained by the methods of electric motive forces and calorimety give a satisfactory agreement

  2. Redox Conditions in Selected Principal Aquifers of the United States

    Science.gov (United States)

    McMahon, P.B.; Cowdery, T.K.; Chapelle, F.H.; Jurgens, B.C.

    2009-01-01

    Reduction/oxidation (redox) processes affect the quality of groundwater in all aquifer systems. Redox processes can alternately mobilize or immobilize potentially toxic metals associated with naturally occurring aquifer materials, contribute to the degradation or preservation of anthropogenic contami-nants, and generate undesirable byproducts, such as dissolved manganese (Mn2+), ferrous iron (Fe2+), hydrogen sulfide (H2S), and methane (CH4). Determining the kinds of redox processes that occur in an aquifer system, documenting their spatial distribution, and understanding how they affect concentrations of natural or anthropogenic contaminants are central to assessing and predicting the chemical quality of groundwater. This Fact Sheet extends the analysis of U.S. Geological Survey authors to additional principal aquifer systems by applying a framework developed by the USGS to a larger set of water-quality data from the USGS national water databases. For a detailed explanation, see the 'Introduction' in the Fact Sheet.

  3. Redox characteristics of the eukaryotic cytosol

    DEFF Research Database (Denmark)

    López-Mirabal, H Reynaldo; Winther, Jakob R

    2007-01-01

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

  4. The Magnetic Response of Europium Implanted in Cerium and in Platinum as Investigated by the PAC-Method

    International Nuclear Information System (INIS)

    Zeitz, W.-D.; Unterricker, S.; Schneider, F.; Samokhvalov, V.; Potzger, K.; Weber, A.; Dietrich, M.

    2004-01-01

    The magnetic response of europium in γ-cerium and in platinum was studied by applying the perturbed angular correlation spectroscopy. The probe nuclei were 147 Eu(11/2 - ) and 149 Eu(11/2 - ). The response in γ-Ce was determined by the electronic S = J = 7/2 ground state of divalent Eu. In Pt, on the other hand, Eu is trivalent (J = 0 ground state). Here the magnetic contributions originate from Van Vleck terms of the whole multiplet system.

  5. Enhanced hot ductility of a Cr–Mo low alloy steel by rare earth cerium

    International Nuclear Information System (INIS)

    Jiang, X.; Song, S.-H.

    2014-01-01

    The hot ductility of a 1Cr–0.5Mo low alloy steel is investigated over a temperature range of 700–1050 °C using a Gleeble thermomechanical simulator in conjunction with various characterization techniques. The steel samples undoped and doped with cerium are heated at 1300 °C for 3 min and then cooled with a rate of 5 K s −1 down to different test temperatures, followed by tensile deformation until fracture. The results show that the hot ductility of the steel, evaluated by the reduction in area, can be substantially enhanced by a minor addition of cerium, especially in the range 800–1000 °C. In the austenite–ferrite dual-phase region, cerium may delay the formation of proeutectoid ferrite layers along austenite grain boundaries, thereby increasing the hot ductility of the steel. In the single austenite region, grain boundary segregation of cerium may increase the grain boundary cohesion, toughening the steel and thus raising the resistance to grain boundary sliding as well as promoting dynamic recrystallization. Consequently, the hot ductility of the steel is enhanced

  6. Direct determination of the redox status of cysteine residues in proteins in vivo

    Energy Technology Data Exchange (ETDEWEB)

    Hara, Satoshi [Chemical Resources Laboratory, Tokyo Institute of Technology, Nagatsuta 4259-R1-8, Midori-ku, Yokohama 226-8503 (Japan); Tatenaka, Yuki; Ohuchi, Yuya [Dojindo Laboratories, 2025-5 Tabaru, Mashiki-machi, Kumamoto 861-2202 (Japan); Hisabori, Toru, E-mail: thisabor@res.titech.ac.jp [Chemical Resources Laboratory, Tokyo Institute of Technology, Nagatsuta 4259-R1-8, Midori-ku, Yokohama 226-8503 (Japan); Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), Tokyo 102-0075 (Japan)

    2015-01-02

    Highlights: • A new DNA-maleimide which is cleaved by UV irradiation, DNA-PCMal, was developed. • DNA-PCMal can be used like DNA-Mal to analyze the redox state of cysteine residues. • It is useful for detecting the thiol redox status of a protein in vivo by Western blotting method. • Thus, DNA-PCMal can be a powerful tool for redox proteomics analysis. - Abstract: The redox states of proteins in cells are key factors in many cellular processes. To determine the redox status of cysteinyl thiol groups in proteins in vivo, we developed a new maleimide reagent, a photocleavable maleimide-conjugated single stranded DNA (DNA-PCMal). The DNA moiety of DNA-PCMal is easily removed by UV-irradiation, allowing DNA-PCMal to be used in Western blotting applications. Thereby the state of thiol groups in intracellular proteins can be directly evaluated. This new maleimide compound can provide information concerning redox proteins in vivo, which is important for our understanding of redox networks in the cell.

  7. The effects of cerium doping on the size, morphology, and optical properties of α-hematite nanoparticles for ultraviolet filtration

    Energy Technology Data Exchange (ETDEWEB)

    Cardillo, Dean [Institute for Superconducting and Electronic Materials, AIIM Facility, University of Wollongong Innovation Campus, Squires Way, North Wollongong, NSW 2500 (Australia); Konstantinov, Konstantin, E-mail: konstan@uow.edu.au [Institute for Superconducting and Electronic Materials, AIIM Facility, University of Wollongong Innovation Campus, Squires Way, North Wollongong, NSW 2500 (Australia); Devers, Thierry [Centre de Recherche sur la Matière Divisée, Institut de Physique, site de Chartres, Université d’Orléans (France)

    2013-11-15

    Highlights: • Possible application of cerium-doped α-hematite as ultraviolet filter. • Nanoparticles obtained through co-precipitation technique using various cerium doping levels followed by annealing. • Comprehensive materials characterisation utilizing XRD, DSC/TGA, STEM, UV–vis spectroscopy. • Increasing cerium content reduces particle sizing and alters morphology. • Solubility of cerium in hematite seen between 5 and 10% doping, 10% cerium doping greatly enhances attenuation in ultraviolet region and increases optical bandgap. - Abstract: Metal oxide nanoparticles have potential use in energy storage, electrode materials, as catalysts and in the emerging field of nanomedicine. Being able to accurately tailor the desirable properties of these nanoceramic materials, such as particle size, morphology and optical bandgap (E{sub g}) is integral in the feasibility of their use. In this study we investigate the altering of both the structure and physical properties through the doping of hematite (α-Fe{sub 2}O{sub 3}) nanocrystals with cerium at a range of concentrations, synthesised using a one-pot co-precipitation method. This extremely simple synthesis followed by thermal treatment results in stable Fe{sub 2−x}Ce{sub x}O{sub y} nanoceramics resulting from the burning of any unreacted precursors and transformation of goethite-cerium doped nanoparticle intermediate. The inclusion of Ce into the crystal lattice of these α-Fe{sub 2}O{sub 3} nanoparticles causes a significantly large reduction in mean crystalline size and alteration in particle morphology with increasing cerium content. Finally we report an increase optical semiconductor bandgap, along with a substantial increase in the ultraviolet attenuation found for a 10% Ce-doping concentration which shows the potential application of cerium-doped hematite nanocrystals to be used as a pigmented ultraviolet filter for cosmetic products.

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

    Science.gov (United States)

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

    2009-01-01

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

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

    Science.gov (United States)

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

    2017-05-10

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

  10. Ceria nanoparticles vis-à-vis cerium nitrate as corrosion inhibitors for silica-alumina hybrid sol-gel coating

    Energy Technology Data Exchange (ETDEWEB)

    Lakshmi, R.V. [Surface Engineering Division, Council of Scientific and Industrial Research – National Aerospace Laboratories, HAL Airport Road, Kodihalli, Bengaluru 560017 (India); Aruna, S.T., E-mail: staruna194@gmail.com [Surface Engineering Division, Council of Scientific and Industrial Research – National Aerospace Laboratories, HAL Airport Road, Kodihalli, Bengaluru 560017 (India); Sampath, S. [Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bengaluru 560012 (India)

    2017-01-30

    Highlights: • Corrosion protection efficiency comparison of ceria nanoparticles and cerium nitrate. • Silica-alumina hybrid coating exhibited good barrier protection. • Detailed XPS study confirm the hybrid structure and presence of Ce species in coating. • Loss of cerium ions not prevalent in ceria doped coating unlike that of cerium nitrate. • Ceria increased the coating integrity, corrosion inhibition and barrier protection. - Abstract: The present work provides a comparative study on the corrosion protection efficiency of defect free sol-gel hybrid coating containing ceria nanoparticles and cerium nitrate ions as corrosion inhibitors. Less explored organically modified alumina-silica hybrid sol-gel coatings are synthesized from 3-glycidoxypropyltrimethoxysilane and aluminium-tri-sec-butoxide. The microemulsion derived nanoparticles and the hybrid coatings are characterized and compared with coatings containing cerium nitrate. Corrosion inhibiting capability is assessed using electrochemical impedance spectroscopy. Scanning Kelvin probe measurements are also conducted on the coatings for identifying the apparent corrosion prone regions. Detailed X-ray photoelectron spectroscopy (XPS) analysis is carried out to comprehend the bonding and corrosion protection rendered by the hybrid coatings.

  11. Effects of uncoated and citric acid coated cerium oxide nanoparticles, bulk cerium oxide, cerium acetate, and citric acid on tomato plants

    International Nuclear Information System (INIS)

    Barrios, Ana Cecilia; Rico, Cyren M.; Trujillo-Reyes, Jesica; Medina-Velo, Illya A.; Peralta-Videa, Jose R.; Gardea-Torresdey, Jorge L.

    2016-01-01

    Little is known about the physiological and biochemical responses of plants exposed to surface modified nanomaterials. In this study, tomato (Solanum lycopersicum L.) plants were cultivated for 210 days in potting soil amended with uncoated and citric acid coated cerium oxide nanoparticles (nCeO_2, CA + nCeO_2) bulk cerium oxide (bCeO_2), and cerium acetate (CeAc). Millipore water (MPW), and citric acid (CA) were used as controls. Physiological and biochemical parameters were measured. At 500 mg/kg, both the uncoated and CA + nCeO_2 increased shoot length by ~ 9 and ~ 13%, respectively, while bCeO_2 and CeAc decreased shoot length by ~ 48 and ~ 26%, respectively, compared with MPW (p ≤ 0.05). Total chlorophyll, chlo-a, and chlo-b were significantly increased by CA + nCeO_2 at 250 mg/kg, but reduced by bCeO_2 at 62.5 mg/kg, compared with MPW. At 250 and 500 mg/kg, nCeO_2 increased Ce in roots by 10 and 7 times, compared to CA + nCeO_2, but none of the treatments affected the Ce concentration in above ground tissues. Neither nCeO_2 nor CA + nCeO_2 affected the homeostasis of nutrient elements in roots, stems, and leaves or catalase and ascorbate peroxidase in leaves. CeAc at 62.5 and 125 mg/kg increased B (81%) and Fe (174%) in roots, while at 250 and 500 mg/kg, increased Ca in stems (84% and 86%, respectively). On the other hand, bCeO_2 at 62.5 increased Zn (152%) but reduced P (80%) in stems. Only nCeO_2 at 62.5 mg/kg produced higher total number of tomatoes, compared with control and the rest of the treatments. The surface coating reduced Ce uptake by roots but did not affect its translocation to the aboveground organs. In addition, there was no clear effect of surface coating on fruit production. To our knowledge, this is the first study comparing the effects of coated and uncoated nCeO_2 on tomato plants. - Highlights: • At 500 mg/kg, coated and bare NPs increased stem length by 13 and 9%, respectively. • Coated NPs at 500 mg/kg increased CAT activity in

  12. Effects of uncoated and citric acid coated cerium oxide nanoparticles, bulk cerium oxide, cerium acetate, and citric acid on tomato plants

    Energy Technology Data Exchange (ETDEWEB)

    Barrios, Ana Cecilia [Department of Chemistry, The University of Texas at El Paso, 500 W. University Avenue, El Paso, TX 79968 (United States); Rico, Cyren M. [Department of Chemistry, The University of Texas at El Paso, 500 W. University Avenue, El Paso, TX 79968 (United States); University of California Center for Environmental Implications of Nanotechnology (UC CEIN), The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); Trujillo-Reyes, Jesica [Department of Chemistry, The University of Texas at El Paso, 500 W. University Avenue, El Paso, TX 79968 (United States); Medina-Velo, Illya A. [Department of Chemistry, The University of Texas at El Paso, 500 W. University Avenue, El Paso, TX 79968 (United States); University of California Center for Environmental Implications of Nanotechnology (UC CEIN), The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); Peralta-Videa, Jose R. [Department of Chemistry, The University of Texas at El Paso, 500 W. University Avenue, El Paso, TX 79968 (United States); Environmental Science and Engineering Ph.D. Program, The University of Texas at El Paso, 500 W. University Avenue, El Paso, TX 79968 (United States); University of California Center for Environmental Implications of Nanotechnology (UC CEIN), The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); Gardea-Torresdey, Jorge L., E-mail: jgardea@utep.edu [Department of Chemistry, The University of Texas at El Paso, 500 W. University Avenue, El Paso, TX 79968 (United States); Environmental Science and Engineering Ph.D. Program, The University of Texas at El Paso, 500 W. University Avenue, El Paso, TX 79968 (United States); University of California Center for Environmental Implications of Nanotechnology (UC CEIN), The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States)

    2016-09-01

    Little is known about the physiological and biochemical responses of plants exposed to surface modified nanomaterials. In this study, tomato (Solanum lycopersicum L.) plants were cultivated for 210 days in potting soil amended with uncoated and citric acid coated cerium oxide nanoparticles (nCeO{sub 2}, CA + nCeO{sub 2}) bulk cerium oxide (bCeO{sub 2}), and cerium acetate (CeAc). Millipore water (MPW), and citric acid (CA) were used as controls. Physiological and biochemical parameters were measured. At 500 mg/kg, both the uncoated and CA + nCeO{sub 2} increased shoot length by ~ 9 and ~ 13%, respectively, while bCeO{sub 2} and CeAc decreased shoot length by ~ 48 and ~ 26%, respectively, compared with MPW (p ≤ 0.05). Total chlorophyll, chlo-a, and chlo-b were significantly increased by CA + nCeO{sub 2} at 250 mg/kg, but reduced by bCeO{sub 2} at 62.5 mg/kg, compared with MPW. At 250 and 500 mg/kg, nCeO{sub 2} increased Ce in roots by 10 and 7 times, compared to CA + nCeO{sub 2}, but none of the treatments affected the Ce concentration in above ground tissues. Neither nCeO{sub 2} nor CA + nCeO{sub 2} affected the homeostasis of nutrient elements in roots, stems, and leaves or catalase and ascorbate peroxidase in leaves. CeAc at 62.5 and 125 mg/kg increased B (81%) and Fe (174%) in roots, while at 250 and 500 mg/kg, increased Ca in stems (84% and 86%, respectively). On the other hand, bCeO{sub 2} at 62.5 increased Zn (152%) but reduced P (80%) in stems. Only nCeO{sub 2} at 62.5 mg/kg produced higher total number of tomatoes, compared with control and the rest of the treatments. The surface coating reduced Ce uptake by roots but did not affect its translocation to the aboveground organs. In addition, there was no clear effect of surface coating on fruit production. To our knowledge, this is the first study comparing the effects of coated and uncoated nCeO{sub 2} on tomato plants. - Highlights: • At 500 mg/kg, coated and bare NPs increased stem length by 13 and 9

  13. Opinion: the red-light response of stomatal movement is sensed by the redox state of the photosynthetic electron transport chain.

    Science.gov (United States)

    Busch, Florian A

    2014-02-01

    Guard cells regulate CO2 uptake and water loss of a leaf by controlling stomatal movement in response to environmental factors such as CO2, humidity, and light. The mechanisms by which stomata respond to red light are actively debated in the literature, and even after decades of research it is still controversial whether stomatal movement is related to photosynthesis or not. This review summarizes the current knowledge of the red-light response of stomata. A comparison of published evidence suggests that stomatal movement is controlled by the redox state of photosynthetic electron transport chain components, in particular the redox state of plastoquinone. Potential consequences for the modeling of stomatal conductance are discussed.

  14. Elevated oxidative stress monitored via the albumin-thiol redox state is correlated with matrix metalloproteinase-3 elevation in patients with rheumatoid arthritis.

    Science.gov (United States)

    Kizaki, Kazuha; Yoshizumi, Yusuke; Takahashi, Teppei; Era, Seiichi

    2015-01-01

    In rheumatoid arthritis (RA), matrix metalloproteinase-3 (MMP-3) and oxidative stress contribute to joint destruction. However, little is known about the relationship between MMP-3 and oxidative stress in RA. We measured the albumin-thiol redox state as a marker of oxidative stress, MMP-3, and the DAS-28 score calculated using CRP values among forty-seven patients (9 males and 38 females) with RA. According to the serum MMP-3 levels, they were divided into two groups (group A: within normal ranges of 36.9-121.0 ng/mL for men and 17.3-59.7 ng/mL for women; group B: above normal ranges). The albumin-thiol redox state in group B was significantly oxidized compared with that in group A (p < 0.01). The percentage of oxidized albumin-thiol showed a positive correlation with serum MMP-3 (r = 0.52). DAS-28 and CRP were also correlated with the percentage of oxidized albumin-thiol (r = 0.46, r = 0.44). The albumin-thiol redox state was significantly oxidized in correlation with serum MMP-3 elevation in RA.

  15. Organ specific mapping of in vivo redox state in control and cigarette smoke-exposed mice using EPR/NMR co-imaging

    Science.gov (United States)

    Caia, George L.; Efimova, Olga V.; Velayutham, Murugesan; El-Mahdy, Mohamed A.; Abdelghany, Tamer M.; Kesselring, Eric; Petryakov, Sergey; Sun, Ziqi; Samouilov, Alexandre; Zweier, Jay L.

    2014-01-01

    In vivo mapping of alterations in redox status is important for understanding organ specific pathology and disease. While electron paramagnetic resonance imaging (EPRI) enables spatial mapping of free radicals, it does not provide anatomic visualization of the body. Proton MRI is well suited to provide anatomical visualization. We applied EPR/NMR co-imaging instrumentation to map and monitor the redox state of living mice under normal or oxidative stress conditions induced by secondhand cigarette smoke (SHS) exposure. A hybrid co-imaging instrument, EPRI (1.2 GHz) / proton MRI (16.18 MHz), suitable for whole-body co-imaging of mice was utilized with common magnet and gradients along with dual EPR/NMR resonators that enable co-imaging without sample movement. The metabolism of the nitroxide probe, 3–carbamoyl–proxyl (3-CP), was used to map the redox state of control and SHS-exposed mice. Co-imaging allowed precise 3D mapping of radical distribution and reduction in major organs such as the heart, lungs, liver, bladder and kidneys. Reductive metabolism was markedly decreased in SHS-exposed mice and EPR/NMR co-imaging allowed quantitative assessment of this throughout the body. Thus, in vivo EPR/NMR co-imaging enables in vivo organ specific mapping of free radical metabolism and redox stress and the alterations that occur in the pathogenesis of disease. PMID:22296801

  16. In vivo (31) P MRS assessment of intracellular NAD metabolites and NAD(+) /NADH redox state in human brain at 4 T.

    Science.gov (United States)

    Lu, Ming; Zhu, Xiao-Hong; Chen, Wei

    2016-07-01

    NAD(+) and NADH play key roles in cellular respiration. Intracellular redox state defined by the NAD(+) /NADH ratio (RX) reflects the cellular metabolic and physiopathological status. By taking advantage of high/ultrahigh magnetic field strengths, we have recently established a novel in vivo (31) P MRS-based NAD assay for noninvasive and quantitative measurements of intracellular NAD concentrations and redox state in animal and human brains at 16.4 T, 9.4 T and 7 T. To explore its potential for clinical application, in this study we investigated the feasibility of assessing the NAD metabolism and redox state in human brain at a lower field of 4 T by incorporating the (1) H-decoupling technique with the in vivo (31) P NAD assay. The use of (1) H decoupling significantly narrowed the linewidths of NAD and α-ATP resonances, resulting in higher sensitivity and better spectral resolution as compared with the (1) H-coupled (31) P spectrum. These improvements made it possible to reliably quantify cerebral NAD concentrations and RX, consistent with previously reported results obtained from similar age human subjects at 7 T. In summary, this work demonstrates the capability and utility of the (1) H-decoupled (31) P MRS-based NAD assay at lower field strength; thus, it opens new opportunities for studying intracellular NAD metabolism and redox state in human brain at clinical settings. This conclusion is supported by the simulation results, indicating that similar performance and reliability as observed at 4T can be achieved at 3 T with the same signal-to-noise ratio. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  17. Investigation of cerium salt/sulfuric acid anodizing technology for 1420 aluminum alloy

    Energy Technology Data Exchange (ETDEWEB)

    Di Li; Yue Peng Deng; Bao Lan Guo; Guo Qiang Li [Beijing Univ. of Aeronautics and Astronautics (China). Dept. of Mater. Sci. and Eng.

    2000-07-01

    In this paper, the effect of cerium addition agent on the property of anodized coating of 1420 Al alloy has been studied by corrosion experiment (immersion test and neutral salt spray test), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and measurement of polarization curves. The result show that only pitting could be observed in all corrosion tests while intergranular corrosion and exfoliation corrosion did not appear on 1420 Al-Li alloys. When organic carboxylic acid S or the cerium (IV) salt was added into sulfuric acid anodizing electrolyte separately, there was no significant improvement in corrosion resistance of anodized film. However, in the case of adding them into sulfuric acid anodizing electrolyte together, the corrosion resistance of anodized film increased greatly owing to synergistic effect. The synergistic effect may relate to the formation of cerium-organic carboxylic acid S complex compound and its effects on film growth and film structure. (orig.)

  18. Charge transfer cross sections for dysprosium and cerium

    Energy Technology Data Exchange (ETDEWEB)

    Adachi, Hajime; Tamura, Koji; Okazaki, Tetsuji; Shibata, Takemasa [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1998-06-01

    Symmetric resonant charge transfer cross sections between singly ionized ions and the parent atoms were measured for dysprosium and cerium in the impact energy of 200-2000eV. The cross sections were determined from the ratio between the number of ions produced by charge transfer and those in primary ion beam. The primary ion beam was produced by a laser ion source in which their atoms were ionized by laser resonant photo-ionization. The slow ions produced by charge transfer and fast primary ions were detected with Faraday cups. The obtained cross sections were (1.82{+-}0.14) x 10{sup -14} cm{sup 2} for dysprosium and (0.88{+-}0.12) x 10{sup -14} cm{sup 2} for cerium in the above energy range. The difference of these values can mostly be explained by considering the electron configurations of these atoms and ions. (author)

  19. Charge transfer cross sections for dysprosium and cerium

    International Nuclear Information System (INIS)

    Adachi, Hajime; Tamura, Koji; Okazaki, Tetsuji; Shibata, Takemasa

    1998-06-01

    Symmetric resonant charge transfer cross sections between singly ionized ions and the parent atoms were measured for dysprosium and cerium in the impact energy of 200-2000eV. The cross sections were determined from the ratio between the number of ions produced by charge transfer and those in primary ion beam. The primary ion beam was produced by a laser ion source in which their atoms were ionized by laser resonant photo-ionization. The slow ions produced by charge transfer and fast primary ions were detected with Faraday cups. The obtained cross sections were (1.82±0.14) x 10 -14 cm 2 for dysprosium and (0.88±0.12) x 10 -14 cm 2 for cerium in the above energy range. The difference of these values can mostly be explained by considering the electron configurations of these atoms and ions. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-09-24

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

  1. Redox Impact on Starch Biosynthetic Enzymes in Arabidopsis thaliana

    DEFF Research Database (Denmark)

    Skryhan, Katsiaryna

    Summary The thesis provides new insight into the influence of the plant cell redox state on the transient starch metabolism in Arabidopsis thaliana with a focus on starch biosynthetic enzymes. Two main hypotheses forms the basis of this thesis: 1) photosynthesis and starch metabolism are coordina......Summary The thesis provides new insight into the influence of the plant cell redox state on the transient starch metabolism in Arabidopsis thaliana with a focus on starch biosynthetic enzymes. Two main hypotheses forms the basis of this thesis: 1) photosynthesis and starch metabolism...... are coordinated by the redox state of the cell via post-translational modification of the starch metabolic enzymes containing redox active cysteine residues and these cysteine residues became cross-linked upon oxidation providing a conformational change leading to activity loss; 2) cysteine residues...... of chloroplast enzymes can play a role not only in enzyme activity and redox sensitivity but also in protein folding and stability upon oxidation. Several redox sensitive enzymes identified in this study can serve as potential targets to control the carbon flux to and from starch during the day and night...

  2. Redox-flow battery of actinide complexes

    International Nuclear Information System (INIS)

    Yamamura, Tomoo; Shiokawa, Yoshinobu

    2006-01-01

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

  3. Exposure, Health and Ecological Effects Review of Engineered Nanoscale Cerium and Cerium Oxide Associated with its Use as a Fuel Additive

    Science.gov (United States)

    Advances of nanoscale science have produced nanomaterials with unique physical and chemical properties at commercial levels which are now incorporated into over 1000 products. Nanoscale cerium (di) oxide (CeO(2)) has recently gained a wide range of applications which includes coa...

  4. Thermometric titrimetry Studies of the cerium(IV) oxidation of alpha-mercaptocarboxylic acids.

    Science.gov (United States)

    Alexander, W A; Mash, C J; McAuley, A

    1969-04-01

    The cerium(IV) oxidation of thioglycollic, thiolactic and thiomalic acids has been examined by thermometric titration. The titration curves indicate stoichiometries of more than 1 mole of cerium(IV) per mole of alpha-thiol, suggesting possible side-reactions. In the presence of methyl acrylate, however, the expected ratio is observed. The overall heat of each reaction has been derived. Only with a titration method of this kind where allowance can be made for side-reactions can the heats of reaction for these systems be measured.

  5. Highly Stable Anion Exchange Membranes for High-Voltage Redox-Flow Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Yushan [Univ. of Delaware, Newark, DE (United States)

    2018-02-26

    membrane in the sulfuric acid system was also achieved due to the high acid doping ability of the polymer structure. The cationic 9MeOTTP+-F6PBI PTFE reinforced membrane shows a cerium (IV) permeability that is 27-fold lower than that of Nafion 212. Excellent voltage and energy efficiencies with a 9MeOTTP+-F6PBI PTFE reinforced membrane were demonstrated in an all-vanadium redox flow battery (VRFB).

  6. Fabrication of mesoporous cerium dioxide films by cathodic electrodeposition.

    Science.gov (United States)

    Kim, Young-Soo; Lee, Jin-Kyu; Ahn, Jae-Hoon; Park, Eun-Kyung; Kim, Gil-Pyo; Baeck, Sung-Hyeon

    2007-11-01

    Mesoporous cerium dioxide (Ceria, CeO2) thin films have been successfully electrodeposited onto ITO-coated glass substrates from an aqueous solution of cerium nitrate using CTAB (Cetyltrimethylammonium Bromide) as a templating agent. The synthesized films underwent detailed characterizations. The crystallinity of synthesized CeO2 film was confirmed by XRD analysis and HR-TEM analysis, and surface morphology was investigated by SEM analysis. The presence of mesoporosity in fabricated films was confirmed by TEM and small angle X-ray analysis. As-synthesized film was observed from XRD analysis and HR-TEM image to have well-crystallized structure of cubic phase CeO2. Transmission electron microscopy and small angle X-ray analysis revealed the presence of uniform mesoporosity with a well-ordered lamellar phase in the CeO2 films electrodeposited with CTAB templating.

  7. Catalysts with Cerium in a Membrane Reactor for the Removal of Formaldehyde Pollutant from Water Effluents

    Directory of Open Access Journals (Sweden)

    Mirella Gutiérrez-Arzaluz

    2016-05-01

    Full Text Available We report the synthesis of cerium oxide, cobalt oxide, mixed cerium, and cobalt oxides and a Ce–Co/Al2O3 membrane, which are employed as catalysts for the catalytic wet oxidation (CWO reaction process and the removal of formaldehyde from industrial effluents. Formaldehyde is present in numerous waste streams from the chemical industry in a concentration low enough to make its recovery not economically justified but high enough to create an environmental hazard. Common biological degradation methods do not work for formaldehyde, a highly toxic but refractory, low biodegradability substance. The CWO reaction is a recent, promising alternative that also permits much lower temperature and pressure conditions than other oxidation processes, resulting in economic benefits. The CWO reaction employing Ce- and Co-containing catalysts was carried out inside a slurry batch reactor and a membrane reactor. Experimental results are reported. Next, a mixed Ce–Co oxide film was supported on an γ-alumina membrane used in a catalytic membrane reactor to compare formaldehyde removal between both types of systems. Catalytic materials with cerium and with a relatively large amount of cerium favored the transformation of formaldehyde. Cerium was present as cerianite in the catalytic materials, as indicated by X-ray diffraction patterns.

  8. The Redox Code.

    Science.gov (United States)

    Jones, Dean P; Sies, Helmut

    2015-09-20

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

  9. Exposure of cerium oxide nanoparticles to kidney bean shows disturbance in the plant defense mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Majumdar, Sanghamitra [Department of Chemistry, The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); University of California Center for Environmental Implications of Nanotechnology (UC CEIN) (United States); Peralta-Videa, Jose R. [Department of Chemistry, The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); Environmental Science and Engineering PhD Program, The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); University of California Center for Environmental Implications of Nanotechnology (UC CEIN) (United States); Bandyopadhyay, Susmita [Environmental Science and Engineering PhD Program, The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); University of California Center for Environmental Implications of Nanotechnology (UC CEIN) (United States); Castillo-Michel, Hiram [European Synchrotron Radiation Facility, B.P. 220-38043 Grenoble, Cedex (France); Hernandez-Viezcas, Jose-Angel [Department of Chemistry, The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); University of California Center for Environmental Implications of Nanotechnology (UC CEIN) (United States); Sahi, Shivendra [Department of Biology, Western Kentucky University, Bowling Green, KY 42101 (United States); Gardea-Torresdey, Jorge L., E-mail: jgardea@utep.edu [Department of Chemistry, The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); Environmental Science and Engineering PhD Program, The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); University of California Center for Environmental Implications of Nanotechnology (UC CEIN) (United States)

    2014-08-15

    Graphical abstract: - Highlights: • Kidney bean roots uptake nCeO{sub 2} primarily without biotransformation. • Cerium reached the root vascular tissues through gaps in the Casparian strip. • On longer exposure to high concentration, roots demonstrate stress response. • In leaves, guaiacol peroxidase plays a major role in ROS scavenging. - Abstract: Overwhelming use of engineered nanoparticles demands rapid assessment of their environmental impacts. The transport of cerium oxide nanoparticles (nCeO{sub 2}) in plants and their impact on cellular homeostasis as a function of exposure duration is not well understood. In this study, kidney bean plants were exposed to suspensions of ∼8 ± 1 nm nCeO{sub 2} (62.5 to 500 mg/L) for 15 days in hydroponic conditions. Plant parts were analyzed for cerium accumulation after one, seven, and 15 days of nCeO{sub 2} exposure. The primary indicators of stress like lipid peroxidation, antioxidant enzyme activities, total soluble protein and chlorophyll contents were studied. Cerium in tissues was localized using scanning electron microscopy and synchrotron μ-XRF mapping, and the chemical forms were identified using μ-XANES. In the root epidermis, cerium was primarily shown to exist as nCeO{sub 2}, although a small fraction (12%) was biotransformed to Ce(III) compound. Cerium was found to reach the root vascular tissues and translocate to aerial parts with time. Upon prolonged exposure to 500 mg nCeO{sub 2}/L, the root antioxidant enzyme activities were significantly reduced, simultaneously increasing the root soluble protein by 204%. In addition, leaf's guaiacol peroxidase activity was enhanced with nCeO{sub 2} exposure in order to maintain cellular homeostasis.

  10. Determination of extinction coefficients of human hemoglobin in various redox states.

    Science.gov (United States)

    Meng, Fantao; Alayash, Abdu I

    2017-03-15

    The role of hemoglobin (Hb) redox forms in tissue and organ toxicities remain ambiguous despite the well-documented contribution of Hb redox reactivity to cellular and subcellular oxidative changes. Moreover, several recent studies, in which Hb toxicity were investigated, have shown conflicting outcomes. Uncertainties over the potential role of these species may in part be due to the protein preparation method of choice, the use of published extinction coefficients and the lack of suitable controls for Hb oxidation and heme loss. Highly purified and well characterized redox forms of human Hb were used in this study and the extinction coefficients of each Hb species (ferrous/oxy, ferric/met and ferryl) were determined. A new set of equations were established to improve accuracy in determining the transient ferryl Hb species. Additionally, heme concentrations in solutions and in human plasma were determined using a novel reversed phase HPLC method in conjugation with our photometric measurements. The use of more accurate redox-specific extinction coefficients and method calculations will be an invaluable tool for both in vitro and in vivo experiments aimed at determining the role of Hb-mediated vascular pathology in hemolytic anemias and when Hb is used as oxygen therapeutics. Published by Elsevier Inc.

  11. Cyclic electron flow is redox-controlled but independent of state transition.

    Science.gov (United States)

    Takahashi, Hiroko; Clowez, Sophie; Wollman, Francis-André; Vallon, Olivier; Rappaport, Fabrice

    2013-01-01

    Photosynthesis is the biological process that feeds the biosphere with reduced carbon. The assimilation of CO2 requires the fine tuning of two co-existing functional modes: linear electron flow, which provides NADPH and ATP, and cyclic electron flow, which only sustains ATP synthesis. Although the importance of this fine tuning is appreciated, its mechanism remains equivocal. Here we show that cyclic electron flow as well as formation of supercomplexes, thought to contribute to the enhancement of cyclic electron flow, are promoted in reducing conditions with no correlation with the reorganization of the thylakoid membranes associated with the migration of antenna proteins towards Photosystems I or II, a process known as state transition. We show that cyclic electron flow is tuned by the redox power and this provides a mechanistic model applying to the entire green lineage including the vast majority of the cases in which state transition only involves a moderate fraction of the antenna.

  12. Synthesis and characterization of platinum supported on alumina doped with cerium catalyst

    International Nuclear Information System (INIS)

    Yusof Abdullah; Abd Fatah Awang Mat; Mohd Ali Sufi; Sarimah Mahat; Razali Kassim; Nurhaslinda Abdullah.

    1996-03-01

    The synthesis and characterization of gamma-alumina doped with cerium as platinum support for the automobile exhaust catalyst are described. Platinum/alumina/ceria catalyst were prepared by impregnation of hexachloroplatinic acid and sintered at 500 degree Celsius to obtain metal dispersions of 1.0 wt%. Catalyst distribution inside the powder and the effects of the addition of cerium to alumina were analyzed by the scanning electron microscopy (SEM) and x-ray fluorescence spectroscopy (XRF). The results showed that the alumina - supported catalysts contained well dispersion of the noble metal

  13. Redox fronts

    International Nuclear Information System (INIS)

    Chapman, N.; McKinley, I.; Shea, M.; Smellie, J.

    1993-01-01

    This article describes the investigations of redox fronts performed at the Osamu Utsumi mine. Results obtained by modelling groups on the rate of movement of the redox fronts and on the chemical reactions involved are discussed. Some of the most important rockwater interactions which occur at redox fronts can be modelled reasonably well but the complex redox chemistry of elements like sulphur is poorly simulated. The observed enrichment of many trace elements close to the redox fronts could be of significance for high-level waste repositories, but cannot be quantified by existing models. (author) 6 figs., 1 tab

  14. The impact of aging, hearing loss, and body weight on mouse hippocampal redox state, measured in brain slices using fluorescence imaging.

    Science.gov (United States)

    Stebbings, Kevin A; Choi, Hyun W; Ravindra, Aditya; Llano, Daniel Adolfo

    2016-06-01

    The relationships between oxidative stress in the hippocampus and other aging-related changes such as hearing loss, cortical thinning, or changes in body weight are not yet known. We measured the redox ratio in a number of neural structures in brain slices taken from young and aged mice. Hearing thresholds, body weight, and cortical thickness were also measured. We found striking aging-related increases in the redox ratio that were isolated to the stratum pyramidale, while such changes were not observed in thalamus or cortex. These changes were driven primarily by changes in flavin adenine dinucleotide, not nicotinamide adenine dinucleotide hydride. Multiple regression analysis suggested that neither hearing threshold nor cortical thickness independently contributed to this change in hippocampal redox ratio. However, body weight did independently contribute to predicted changes in hippocampal redox ratio. These data suggest that aging-related changes in hippocampal redox ratio are not a general reflection of overall brain oxidative state but are highly localized, while still being related to at least one marker of late aging, weight loss at the end of life. Copyright © 2016 Elsevier Inc. All rights reserved.

  15. Cerium fluoride nanoparticles protect cells against oxidative stress

    International Nuclear Information System (INIS)

    Shcherbakov, Alexander B.; Zholobak, Nadezhda M.; Baranchikov, Alexander E.; Ryabova, Anastasia V.; Ivanov, Vladimir K.

    2015-01-01

    A novel facile method of non-doped and fluorescent terbium-doped cerium fluoride stable aqueous sols synthesis is proposed. Intense green luminescence of CeF 3 :Tb nanoparticles can be used to visualize these nanoparticles' accumulation in cells using confocal laser scanning microscopy. Cerium fluoride nanoparticles are shown for the first time to protect both organic molecules and living cells from the oxidative action of hydrogen peroxide. Both non-doped and terbium-doped CeF 3 nanoparticles are shown to provide noteworthy protection to cells against the vesicular stomatitis virus. - Highlights: • Facile method of CeF 3 and CeF 3 :Tb stable aqueous sols synthesis is proposed. • Naked CeF 3 nanoparticles are shown to be non-toxic and to protect cells from the action of H 2 O 2 . • CeF 3 and CeF 3 :Tb nanoparticles are shown to protect living cells against the vesicular stomatitis virus

  16. Cerium fluoride nanoparticles protect cells against oxidative stress

    Energy Technology Data Exchange (ETDEWEB)

    Shcherbakov, Alexander B.; Zholobak, Nadezhda M. [Zabolotny Institute of Microbiology and Virology, National Academy of Sciences of Ukraine, Kyiv D0368 (Ukraine); Baranchikov, Alexander E. [Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Moscow 119991 (Russian Federation); Ryabova, Anastasia V. [Prokhorov General Physics Institute of the Russian Academy of Sciences, Moscow 119991 (Russian Federation); National Research Nuclear University MEPhI (Moscow Engineering Physics Institute), Moscow 115409 (Russian Federation); Ivanov, Vladimir K., E-mail: van@igic.ras.ru [Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Moscow 119991 (Russian Federation); National Research Tomsk State University, Tomsk 634050 (Russian Federation)

    2015-05-01

    A novel facile method of non-doped and fluorescent terbium-doped cerium fluoride stable aqueous sols synthesis is proposed. Intense green luminescence of CeF{sub 3}:Tb nanoparticles can be used to visualize these nanoparticles' accumulation in cells using confocal laser scanning microscopy. Cerium fluoride nanoparticles are shown for the first time to protect both organic molecules and living cells from the oxidative action of hydrogen peroxide. Both non-doped and terbium-doped CeF{sub 3} nanoparticles are shown to provide noteworthy protection to cells against the vesicular stomatitis virus. - Highlights: • Facile method of CeF{sub 3} and CeF{sub 3}:Tb stable aqueous sols synthesis is proposed. • Naked CeF{sub 3} nanoparticles are shown to be non-toxic and to protect cells from the action of H{sub 2}O{sub 2}. • CeF{sub 3} and CeF{sub 3}:Tb nanoparticles are shown to protect living cells against the vesicular stomatitis virus.

  17. Ground-state kinetics of bistable redox-active donor-acceptor mechanically interlocked molecules.

    Science.gov (United States)

    Fahrenbach, Albert C; Bruns, Carson J; Li, Hao; Trabolsi, Ali; Coskun, Ali; Stoddart, J Fraser

    2014-02-18

    The ability to design and confer control over the kinetics of theprocesses involved in the mechanisms of artificial molecular machines is at the heart of the challenge to create ones that can carry out useful work on their environment, just as Nature is wont to do. As one of the more promising forerunners of prototypical artificial molecular machines, chemists have developed bistable redox-active donor-acceptor mechanically interlocked molecules (MIMs) over the past couple of decades. These bistable MIMs generally come in the form of [2]rotaxanes, molecular compounds that constitute a ring mechanically interlocked around a dumbbell-shaped component, or [2]catenanes, which are composed of two mechanically interlocked rings. As a result of their interlocked nature, bistable MIMs possess the inherent propensity to express controllable intramolecular, large-amplitude, and reversible motions in response to redox stimuli. In this Account, we rationalize the kinetic behavior in the ground state for a large assortment of these types of bistable MIMs, including both rotaxanes and catenanes. These structures have proven useful in a variety of applications ranging from drug delivery to molecular electronic devices. These bistable donor-acceptor MIMs can switch between two different isomeric states. The favored isomer, known as the ground-state co-conformation (GSCC) is in equilibrium with the less favored metastable state co-conformation (MSCC). The forward (kf) and backward (kb) rate constants associated with this ground-state equilibrium are intimately connected to each other through the ground-state distribution constant, KGS. Knowing the rate constants that govern the kinetics and bring about the equilibration between the MSCC and GSCC, allows researchers to understand the operation of these bistable MIMs in a device setting and apply them toward the construction of artificial molecular machines. The three biggest influences on the ground-state rate constants arise from

  18. Differentiating cancerous from normal breast tissue by redox imaging

    Science.gov (United States)

    Xu, He N.; Tchou, Julia; Feng, Min; Zhao, Huaqing; Li, Lin Z.

    2015-02-01

    Abnormal metabolism can be a hallmark of cancer occurring early before detectable histological changes and may serve as an early detection biomarker. The current gold standard to establish breast cancer (BC) diagnosis is histological examination of biopsy. Previously we have found that pre-cancer and cancer tissues in animal models displayed abnormal mitochondrial redox state. Our technique of quantitatively measuring the mitochondrial redox state has the potential to be implemented as an early detection tool for cancer and may provide prognostic value. We therefore in this present study, investigated the feasibility of quantifying the redox state of tumor samples from 16 BC patients. Tumor tissue aliquots were collected from both normal and cancerous tissue from the affected cancer-bearing breasts of 16 female patients (5 TNBC, 9 ER+, 2 ER+/Her2+) shortly after surgical resection. All specimens were snap-frozen with liquid nitrogen on site and scanned later with the Chance redox scanner, i.e., the 3D cryogenic NADH/oxidized flavoprotein (Fp) fluorescence imager. Our preliminary results showed that both NADH and Fp (including FAD, i.e., flavin adenine dinucleotide) signals in the cancerous tissues roughly tripled to quadrupled those in the normal tissues (pcancerous tissues than in the normal ones (pcancer and non-cancer breast tissues in human patients and this novel redox scanning procedure may assist in tissue diagnosis in freshly procured biopsy samples prior to tissue fixation. We are in the process of evaluating the prognostic value of the redox imaging indices for BC.

  19. Reactive removal of 2-chloroethyl ethyl sulfide vapors under visible light irradiation by cerium oxide modified highly porous zirconium (hydr) oxide

    Energy Technology Data Exchange (ETDEWEB)

    Mitchell, Joshua K.; Arcibar-Orozco, Javier A.; Bandosz, Teresa J., E-mail: tbandosz@ccny.cuny.edu

    2016-12-30

    Highlights: • Microporous zirconium-cerium (hydr) oxides were synthetized. • Ce presence narrowed the band gap of the materials. • The samples showed a high efficiency for removal of CEES vapors. • 1,2-Bis (ethyl thio) ethane and ethyl vinyl sulfide were the main reaction products. • 5% (Ce/Zr mol) addition of cerium oxide results in the best performing material. - Abstract: Highly porous cerium oxide modified Zr(OH){sub 4} samples were synthesized using a simple one stage urea precipitation method. The amorphicity level of zirconium hydroxide did not change upon addition of cerium oxide particles. A unique aspect of the cerium oxide-modified materials is the presence of both the oxide (CeO{sub 2}) and hydroxide (Zr(OH){sub 4}) phases resulting in a unique microporous structure of the final material. Extensive characterization using various chemical and physical methods revealed significant differences in the surface features. All synthesized materials were microporous and small additions of cerium oxide affected the surface chemistry. These samples were found as effective catalysts for a decontamination of mustard gas surrogate, 2-chloroethyl ethyl sulfide (CEES). Cerium oxide addition significantly decreased the band gap of zirconium hydroxide. Ethyl vinyl sulfide and 1,2-bis (Ethyl thio) ethane were identified as surface reaction products.

  20. The study on preparation of high dispersion and pure cerium dioxide for producing automotive exhaust catalysts

    International Nuclear Information System (INIS)

    Le Minh Tuan; Nguyen Trong Hung; Nguyen Thanh Chung

    2003-01-01

    The multi-stage counter-current solvent extraction process using TBP as the solvent has been carried out for purifying cerium and the ammonium carbonate precipitation method has been used to produce the cerium oxide of high dispersion and pure. The flow sheet of extraction system includes 3 extraction stages with O/A = 0.7,2 stripping stages and 4 scrubbing stages with O/A = 5. The condition for ammonium carbonate precipitation, drying and calcination have been investigated and a procedure that seem to be practically suitable to prepare cerium dioxide powder with great specific surface area for producing automotive exhaust catalyst has been proposed. (LMT)

  1. Corrosion resistance of flaky aluminum pigment coated with cerium oxides/hydroxides in chloride and acidic electrolytes

    Science.gov (United States)

    Niroumandrad, S.; Rostami, M.; Ramezanzadeh, B.

    2015-12-01

    The objective of this study was to enhance the corrosion resistance of lamellar aluminum pigment through surface treatment by cerium oxides/hydroxides. The surface composition of the pigments was studied by energy-dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The corrosion resistance of the pigment was evaluated by conventional hydrogen evolution measurements in acidic solution and electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution. Results showed that the Ce-rich coating composed of Ce2O3 and CeO2 was precipitated on the pigment surface after immersion in the cerium solution. The corrosion resistance of pigment was significantly enhanced after modification with cerium layer.

  2. Complex formation of transferrin with tetravalent plutonium and cerium

    International Nuclear Information System (INIS)

    Subramanian, M.S.; Oomen, I.K.

    1981-01-01

    Gel filtration experiments with 239 Pu labelled In Vitro bovine serum showed that the metal ion is bound to the transferrin of the serum proteins as in the case of iron labelled serum. This was confirmed by polyacrylamide gel electrophoresis. The ovotransferrin prepared from chicken egg white which was devoid of hemopexin contaminant was found to complex both tetravalent plutonium and cerium giving visible absorption peak at 365 and 435 nm respectively. The binding capacity of ovotransferrin with tetravalent plutonium and cerium, determined by spectrophotometric titration indicates that two metal ions are bound to each protein molecule as in the case of iron. The average molecular weight computed from this binding capacity measurements was found to be 71,000-75,000. The number of protons liberated for each metal ion bound was found to be three as in the case of iron. (author)

  3. Synthesis and ion-exchange properties of cerium(IV) molybdate

    Energy Technology Data Exchange (ETDEWEB)

    Srivastava, S K; Singh, Raj Pal; Agrawal, Sushma; Kumar, Satish [Roorkee Univ. (India). Dept. of Chemistry

    1977-01-01

    The synthesis, ion exchange properties, and the separation of a number of cation pairs on the columns of cerium (IV) molybdate is discussed. In order to obtain the product in gel form showing a high exchange capacity and suitable for column operation, preliminary experiments were performed to determine the optimum conditions of precipitation, i.e., the concentration of ceric and molybdate solutions, mixing ratio, pH of precipitation and the order of mixing. Cerium (IV) molybdate, prepared under the optimum conditions of concentration, acidity etc., shows exchange capacity of 0.96 meg per g of exchanger. The sorption of a large number of metal ions has been investigated and the compound shows promising behaviour as cation exchanger. Numerous separations of analytical and radiochemical interest have been performed on the column of this exchanger with great efficiency.

  4. Synthesis and ion-exchange properties of cerium(IV) molybdate

    International Nuclear Information System (INIS)

    Srivastava, S.K.; Raj Pal Singh; Sushma Agrawal; Satish Kumar

    1977-01-01

    The synthesis, ion exchange properties, and the separation of a number of cation pairs on the columns of cerium (IV) molybdate is discussed. In order to obtain the product in gel form showing a high exchange capacity and suitable for column operation, preliminary experiments were performed to determine the optimum conditions of precipitation, i.e., the concentration of ceric and molybdate solutions, mixing ratio, pH of precipitation and the order of mixing. Cerium (IV) molybdate, prepared under the optimum conditions of concentration, acidity etc., shows exchange capacity of 0.96 meg per g of exchanger. The sorption of a large number of metal ions has been investigated and the compound shows promising behaviour as cation exchanger. Numerous separations of analytical and radiochemical interest have been performed on the column of this exchanger with great efficiency. (T.G.)

  5. Crystalline cerium(IV) phosphates

    International Nuclear Information System (INIS)

    Herman, R.G.; Clearfield, A.

    1976-01-01

    The ion exchange behaviour of seven crystalline cerium(IV) phosphates towards some of the alkali metal cations is described. Only two of the compounds (A and C) possess ion exchange properties in acidic solutions. Four others show some ion exchange characteristics in basic media with some of the alkali cations. Compound G does not behave as an ion exchanger in solutions of pH + , but show very little Na + uptake. Compound E undergoes ion exchange with Na + and Cs + , but not with Li+. Both Li + and Na + are sorbed by compounds A and C. The results are indicative of structures which show steric exclusion phenomena. (author)

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

    DEFF Research Database (Denmark)

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

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

  7. Appearance of minimum on the curve of cerium melting

    International Nuclear Information System (INIS)

    Boguslavskij, Yu.Ya.; Grigor'ev, S.B.

    1986-01-01

    It is shown by means of simple and obvious thermodynamical considerations that the reduced stability line continues up to the solid phase boundary. The existence of this line causes the appearance of minimum on the fcc cerium melting curve

  8. Study of cerium doped magnetite (Fe 3O 4:Ce)/PMMA nanocomposites

    Science.gov (United States)

    Padalia, Diwakar; Johri, U. C.; Zaidi, M. G. H.

    2012-03-01

    The paper presents the synthesis and properties of polymer nanocomposite material based on cerium doped magnetite (Fe 3O 4) as filler material and poly methyl methacrylate (PMMA) as host matrix. The magnetite (Fe 3O 4) particles were synthesized by co-precipitation route using stable ferrous and ferric salts with ammonium hydroxide as precipitating agent. Further, they doped by cerium oxide (CeO 2) non-stoichiometrically. The composite material was fabricated by solvent evaporation method. Here 2.4 GHz microwaves were used to study the effect of microwaves heating on polymerization. The phase and crystal structure is determined by X-ray diffraction (XRD). The average crystallite size of the composites varies from 28 to 35 nm. The chemical structure is confirmed by Fourier transform infrared (FTIR) spectroscopy. The magnetic and thermal properties are investigated by vibrating sample magnetometer (VSM) and differential scanning calorimetry (DSC). The thermal study shows that the microwave heated samples possess higher glass transition temperature ( Tg). The magnetic results suggest that coercivity ( HC) and squareness ( Mr/ Ms) of the loop increases with increasing doping percent of cerium.

  9. Cascade redox flow battery systems

    Science.gov (United States)

    Horne, Craig R.; Kinoshita, Kim; Hickey, Darren B.; Sha, Jay E.; Bose, Deepak

    2014-07-22

    A reduction/oxidation ("redox") flow battery system includes a series of electrochemical cells arranged in a cascade, whereby liquid electrolyte reacts in a first electrochemical cell (or group of cells) before being directed into a second cell (or group of cells) where it reacts before being directed to subsequent cells. The cascade includes 2 to n stages, each stage having one or more electrochemical cells. During a charge reaction, electrolyte entering a first stage will have a lower state-of-charge than electrolyte entering the nth stage. In some embodiments, cell components and/or characteristics may be configured based on a state-of-charge of electrolytes expected at each cascade stage. Such engineered cascades provide redox flow battery systems with higher energy efficiency over a broader range of current density than prior art arrangements.

  10. REDOX state analysis of platinoid elements in simulated high-level radioactive waste glass by synchrotron radiation based EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Okamoto, Yoshihiro, E-mail: okamoto.yoshihiro@jaea.go.jp [Condensed Matter Chemistry Group, Quantum Beam Science Center, Japan Atomic Energy Agency, Shirakata 2-4, Tokai-mura, Ibaraki 319-1195 (Japan); Shiwaku, Hideaki [Quantum Beam Science Center, Japan Atomic Energy Agency, Kouto 1-1-1, Sayo-cho, Hyogo 679-5143 (Japan); Nakada, Masami [Nuclear Engineering Science Center, Japan Atomic Energy Agency, Shirakata 2-4, Tokai-mura, Ibaraki 319-1195 (Japan); Komamine, Satoshi; Ochi, Eiji [Japan Nuclear Fuel Limited, 4-108 Aza Okitsuke, Oaza Obuchi, Rokkasho-mura, Aomori 030-3212 (Japan); Akabori, Mitsuo [Nuclear Engineering Science Center, Japan Atomic Energy Agency, Shirakata 2-4, Tokai-mura, Ibaraki 319-1195 (Japan)

    2016-04-01

    Extended X-ray Absorption Fine Structure (EXAFS) analyses were performed to evaluate REDOX (REDuction and OXidation) state of platinoid elements in simulated high-level nuclear waste glass samples prepared under different conditions of temperature and atmosphere. At first, EXAFS functions were compared with those of standard materials such as RuO{sub 2}. Then structural parameters were obtained from a curve fitting analysis. In addition, a fitting analysis used a linear combination of the two standard EXAFS functions of a given elements metal and oxide was applied to determine ratio of metal/oxide in the simulated glass. The redox state of Ru was successfully evaluated from the linear combination fitting results of EXAFS functions. The ratio of metal increased at more reducing atmosphere and at higher temperatures. Chemical form of rhodium oxide in the simulated glass samples was RhO{sub 2} unlike expected Rh{sub 2}O{sub 3}. It can be estimated rhodium behaves according with ruthenium when the chemical form is oxide.

  11. Steric and electronic effects of 1,3-disubstituted cyclopentadienyl ligands on metallocene derivatives of Cerium, Titanium, Manganese, and Iron

    Energy Technology Data Exchange (ETDEWEB)

    Sofield, Chadwick Dean [Univ. of California, Berkeley, CA (United States)

    2000-05-01

    Sterically demanding 1,3-disubstituted cyclopentadienyl ligands were used to modify the physical properties of the corresponding metallocenes. Sterically demanding ligands provided kinetic stabilization for trivalent cerium compounds. Tris(di-t-butylcyclopentadienyl)cerium was prepared and anion competition between halides and cyclopentadienyl groups which had complicated synthesis of the tris(cyclopentadienyl)compound was qualitatively examined. Bis(di-t-butylcyclopentadienyl)cerium methyl was prepared and its rate of decomposition, by ligand redistribution, to tris(di-t-butylcyclopentadienyl)cerium was shown to be slower than the corresponding rate for less sterically demanding ligands. Asymmetrically substituted ligands provided a symmetry label for examination of chemical exchange processes. Tris[trimethylsilyl(t-butyl)cyclopentadienyl]cerium was prepared and the rate of interconversion between the C1 and C3 isomers was examined. The enthalpy difference between the two distereomers is 7.0 kJ/mol. The sterically demanding cyclopentadienyl ligands ansa-di-t-butylcyclopentadiene (Me2Si[(Me3C)2C5H3]2), ansa-bis(trimethylsilyl)cyclopentadiene (Me2Si[(Me3Si)2C5H3]2) and tetra-t-butylfulvalene and metallocene derivatives of the ligands were prepared and their structures were examined by single crystal X-ray crystallography. The effect that substituents on the cyclopentadienyl ring have on the pi-electron system of the ligand was examined through interaction between ligand and metal orbitals. A series of 1,3-disubstituted manganocenes was prepared and their electronic states were determined by solid-state magnetic susceptibility, electron paramagnetic resonance, X-ray crystallography, and variable temperature UV-vis spectroscopy. Spin-equilibria in [(Me3C)2C5H3]2Mn and [(Me3

  12. Redox chemistry of americium in nitric acid media

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-07-01

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

  13. Redox chemistry of americium in nitric acid media

    International Nuclear Information System (INIS)

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

    2004-01-01

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

  14. Fabrication of Cerium Oxide and Uranium Oxide Microspheres for Space Nuclear Power Applications

    Energy Technology Data Exchange (ETDEWEB)

    Jeffrey A. Katalenich; Michael R. Hartman; Robert C. O' Brien

    2013-02-01

    Cerium oxide and uranium oxide microspheres are being produced via an internal gelation sol-gel method to investigate alternative fabrication routes for space nuclear fuels. Depleted uranium and non-radioactive cerium are being utilized as surrogates for plutonium-238 (Pu-238) used in radioisotope thermoelectric generators and for enriched uranium required by nuclear thermal rockets. While current methods used to produce Pu-238 fuels at Los Alamos National Laboratory (LANL) involve the generation of fine powders that pose a respiratory hazard and have a propensity to contaminate glove boxes, the sol-gel route allows for the generation of oxide microsphere fuels through an aqueous route. The sol-gel method does not generate fine powders and may require fewer processing steps than the LANL method with less operator handling. High-quality cerium dioxide microspheres have been fabricated in the desired size range and equipment is being prepared to establish a uranium dioxide microsphere production capability.

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

    Science.gov (United States)

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

    2014-08-01

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

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

    Science.gov (United States)

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

    2009-01-01

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

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

    Science.gov (United States)

    Yamamoto, So; Uno, Shigeyasu

    2018-02-28

    This paper describes a paper-based biochemical sensor that realizes redox cycling with close interelectrode distance. Two electrodes, the generator and collector electrodes, can detect steady-state oxidation and reduction currents when suitable potential is held at each electrode. The sensor has two gold plates on both sides of a piece of chromatography paper and defines the interelectrode distance by the thickness of the paper (180 μm) without any micro-fabrication processes. Our proposed sensor geometry has successfully exhibited signatures of redox cycling. As a result, the concentration of ferrocyanide as reversible redox molecules was successfully quantified under the interference by ascorbic acid as a strong irreversible reducing agent. This was possible because the ascorbic acids are completely consumed by the irreversible reaction, while maintaining redox cycling of reversible ferrocyanide. This suggests that a sensor based on the redox cycling method will be suitable for detecting target molecules at low concentration.

  18. Redox behaviors of iron by absorption spectroscopy and redox potential measurement

    International Nuclear Information System (INIS)

    Oh, Jae Yong

    2010-02-01

    This work is performed to study the redox (reduction/oxidation) behaviors of iron in aqueous system by a combination of absorption spectroscopy and redox potential measurements. There are many doubts on redox potential measurements generally showing low accuracies and high uncertainties. In the present study, redox potentials are measured by utilizing various redox electrodes such as Pt, Au, Ag, and glassy carbon (GC) electrodes. Measured redox potentials are compared with calculated redox potentials based on the chemical oxidation speciation of iron and thermodynamic data by absorption spectroscopy, which provides one of the sensitive and selective spectroscopic methods for the chemical speciation of Fe(II/III). From the comparison analyses, redox potential values measured by the Ag redox electrode are fairly consistent with those calculated by the chemical aqueous speciation of iron in the whole system. In summary, the uncertainties of measured redox potentials are closely related with the total Fe concentration and affected by the formation of mixed potentials due to Fe(III) precipitates in the pH range of 6 ∼ 9 beyond the solubility of Fe(III), whilst being independent of the initially prepared concentration ratios between Fe(II) and Fe(III)

  19. Cerium concentrate and mixed rare earth chloride by the oxidative decomposition of bastnaesite in molten sodium hydroxide

    International Nuclear Information System (INIS)

    Iijima, Toshio; Kato, Kazuhiro; Kuno, Toyohiko; Okuwaki, Akitsugu; Umetsu, Yoshiaki; Okabe, Taijiro

    1993-01-01

    Bastnaesite was treated in molten NaOH at 623-777 K for 10-60 min under atmosphere. Cerium-(III) in the ore was easily oxidized 95% or more within 30 min to give an oxidation product composed of solid solutions of CeO 2 -rich and CeO 2 -lean phases and Ce-free rare earth oxide phase. Simultaneously fluoride ion was removed 97% or more. Cerium concentrate was prepared from the oxidation product by leaching with 0.1-3 M HCl solution. The yield of cerium concentrate and the CeO 2 content reached 55-57% and 70-72%, respectively. Mixed rare earth chloride is composed of about 90% rare earth chloride and 10% alkaline earth chloride, and the contents of CeCl 3 , LaCl 3 , NdCl 3 , and PrCl 3 are 11.5, 58.5, 14.4, and 5.4%, respectively. The particle size of resulting cerium concentrate was fairly uniform and about 0.1 μm

  20. Redox control of electric melters with complex feed compositions. Part I: analytical methods and models

    International Nuclear Information System (INIS)

    Bickford, D.F.; Diemer, R.B. Jr.

    1985-01-01

    The redox state of glass from electric melters with complex feed compositions is determined by balance between gases above the melt, and transition metals and organic compounds in the feed. Part I discusses experimental and computational methods of relating flowrates and other melter operating conditions to the redox state of glass, and composition of the melter offgas. Computerized thermodynamic computational methods are useful in predicting the sequence and products of redox reactions and in assessing individual process variations. Melter redox state can be predicted by combining monitoring of melter operating conditions, redox measurement of fused melter feed samples, and periodic redox measurement of product. Mossbauer spectroscopy, and other methods which measure Fe(II)/Fe(III) in glass, can be used to measure melter redox state. Part II develops preliminary operating limits for the vitrification of High-Level Radioactive Waste. Limits on reducing potential to preclude the accumulation of combustible gases, accumulation of sulfides and selenides, and degradation of melter components are the most critical. Problems associated with excessively oxidizing conditions, such as glass foaming and potential ruthenium volatility, are controlled when sufficient formic acid is added to adjust melter feed rheology

  1. Mechanochemical synthesis and spark plasma sintering of the cerium silicides

    Energy Technology Data Exchange (ETDEWEB)

    Alanko, Gordon A.; Jaques, Brian; Bateman, Allyssa [Department of Materials Science and Engineering, College of Engineering, Boise State University, 1910 University Drive, Boise, ID 83725 (United States); Butt, Darryl P., E-mail: darrylbutt@boisestate.edu [Department of Materials Science and Engineering, College of Engineering, Boise State University, 1910 University Drive, Boise, ID 83725 (United States); Center for Advanced Energy Studies, 995 University Boulevard, Idaho Falls, ID 83401 (United States)

    2014-12-15

    Highlights: • Ce{sub 5}Si{sub 3}, Ce{sub 3}Si{sub 2}, CeSi, CeSi{sub 2−x} and CeSi{sub 2} were mechanochemically synthesized. • Temperature and pressure were monitored to investigate reaction progress. • All syntheses proceeded through a MSR event followed by rapid solid-state diffusion. • Milling time before MSR correlates well with effective heat of formation. • Some synthesized material was densified by spark plasma sintering. - Abstract: The cerium silicides, Ce{sub 5}Si{sub 3}, Ce{sub 3}Si{sub 2}, CeSi, CeSi{sub 2−y}, and CeSi{sub 2−x}, have been prepared from the elements by mechanochemical processing in a planetary ball mill. Preparation of the cerium silicide Ce{sub 5}Si{sub 4} was unsuccessfully attempted and potential reasons for this are discussed. Temperature and pressure of the milling vial were monitored in situ to gain insight into the mechanochemical reaction kinetics, which include a mechanically-induced self-propagating reaction (MSR). Some prepared powders were consolidated by spark plasma sintering to high density. Starting materials, as-milled powders, and consolidated samples were characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy. The results obtained help elucidate key questions in mechanochemical processing of intermetallics, showing first phase formation similar to thin films, MSR ignition times that are composition- and milling speed-dependent, and sensitivity of stable compound formation on the impact pressure. The results demonstrate mechanochemical synthesis as a viable technique for rare earth silicides.

  2. Synthesis of mesoporous cerium-zirconium mixed oxides by hydrothermal templating method

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Mesoporous cerium-zirconium mixed oxides were prepared by hydrothermal method using cetyl trimethyl ammonium bromide (CTAB) as template.The effects of amount of template,pH value of solution and hydrothermal temperature on mesostructure of samples were systematically investigated.The final products were characterized by XRD,TEM,FT-IR,and BET.The results indicate that all the cerium-zirconium mixed oxides present a meso-structure.At molar ratio of n(CTAB)/n((Ce)+(Zr))=0.15,pH value of 9,and hydrothermal temperature of 120 ℃,the samples obtained possess a specific surface area of 207.9 m2/g with pore diameter of 3.70 nm and pore volume of 0.19 cm3/g.

  3. Changes in Athlete’s Redox State Induced by Habitual and Unaccustomed Exercise

    Directory of Open Access Journals (Sweden)

    Dusica Z. Djordjevic

    2012-01-01

    Full Text Available The purpose of this study was to assess the influence of sport-specific and nonspecific bouts of exercise on athletes’ redox state. Blood samples were collected from 14 handball players immediately before and after graded exercise test on the cycle ergometer and handball training. Levels of superoxide anion radical (O2-, hydrogen peroxide (H2O2, nitrites (NO2- as markers of nitric oxide, index of lipid peroxidation (TBARs, glutathione (GSH, superoxide dismutase (SOD, and catalase (CAT activity were determined. Exercise intensity was assessed by a system for heart rate (HR monitoring. Average athletes’ HR was not significantly different between protocols, but protocols differed in total time and time and percentage of time that athletes spent in every HR zone. The laboratory exercise test induced a significant increase of H2O2 and TBARs as well as the decrease of the SOD and CAT activity, while after specific handball training, levels of NO2- were increased and SOD activity decreased. It seems that unaccustomed short intensive physical activity may induce oxidative stress in trained athletes, while sport-specific activity of longer duration and proper warm-up period may not. Further research should show whether the change of protocol testing and the implementation of various supplementations and manual methods can affect the redox equilibrium.

  4. Synergism between cerium nitrate and sodium dodecylbenzenesulfonate on corrosion of AA5052 aluminium alloy in 3 wt.% NaCl solution

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jie; Wang, Dapeng; Gao, Lixin; Zhang, Daquan, E-mail: zhdq@sh163.net

    2016-12-15

    Highlights: • Effectively prevent corrosion of AA5052 alloy by using the mixture of cerium nitrate and sodium dodecylbenzenesulfonate. • Synergistic mechanism of the combination of cerium nitrate and sodium dodecylbenzenesulfonate. • Structure of the complex formed between cerium ions and dodecylbenzenesulfonate. • The optimal adsorption model of dodecylbenzenesulfonate on the Al{sub 2}O{sub 3} and CeO{sub 2} surface. - Abstract: The synergistic inhibition effect of rare earth cerium nitrate and sodium dodecylbenzenesulfonate (DBS) on corrosion of AA5052 aluminium alloy in 3 wt.% NaCl solution was investigated by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curve, scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FT-IR). The results show that the single cerium nitrate or DBS has a limited inhibition effect against corrosion of AA5052 alloy. The combination cerium ions with DBS produced strong synergistic effect on corrosion inhibition for AA5052 alloy and rendered a negaitve shift of the corrosion potential. The formation of the complex of Al(DBS){sub 3} and Ce(DBS){sub 3} stabilized the passive film of Al{sub 2}O{sub 3} and CeO{sub 2}, retarding both the cathodic and anodic processes of AA5052 alloy corrosion reaction significantly.

  5. Nanostructured sol-gel coatings doped with cerium nitrate as pre-treatments for AA2024-T3

    International Nuclear Information System (INIS)

    Zheludkevich, M.L.; Serra, R.; Montemor, M.F.; Yasakau, K.A.; Salvado, I.M. Miranda; Ferreira, M.G.S.

    2005-01-01

    Nanostructured hybrid sol-gel coatings doped with cerium ions were investigated in the present work as pre-treatments for the AA2024-T3 alloy. The sol-gel films have been synthesized from tetraethylorthosilicate (TEOS) and 3-glycidoxypropyltrimethoxysilane (GPTMS) precursors. Additionally the hybrid sol was doped with zirconia nanoparticles prepared from hydrolyzed tetra-n-propoxyzirconium (TPOZ). Cerium nitrate, as corrosion inhibitor, was added into the hybrid matrix or into the oxide nanoparticles. The chemical composition and the structure of the hybrid sol-gel films were studied by XPS (X-ray photoelectron spectroscopy) and AFM (atomic force microscopy), respectively. The evolution of the corrosion protection properties of the sol-gel films was studied by EIS (electrochemical impedance spectroscopy), which can provide quantitative information on the role of the different pre-treatments. Different equivalent circuits, for different stages of the corrosion processes, were used in order to model the coating degradation. The models were supported by SEM (scanning electron microscopy) measurements. The results show that the sol-gel films containing zirconia nanoparticles present improved barrier properties. Doping the hybrid nanostructured sol-gel coatings with cerium nitrate leads to additional improvement of the corrosion protection. The zirconia particles present in the sol-gel matrix seem to act as nanoreservoirs providing a prolonged release of cerium ions. The nanostructured sol-gel films doped with cerium nitrate can be proposed as a potential candidate for substitution of the chromate pre-treatments for AA2024-T3

  6. Cerium Modified Pillared Montmorillonite Supported Cobalt Catalysts for Fischer Tropsch Synthesis

    International Nuclear Information System (INIS)

    Ahmad, N.; Ali, Z.; Abbas, S. M.; Hussain, F.

    2015-01-01

    Fischer-Tropsch (FT) synthesis was accomplished over Al-pillared Montmorillonite supported 20 wt% Co modified with different weight% of cerium catalysts. These catalysts were prepared by impregnation method while structural characterizations of the prepared samples were performed by XRD, TPR, NH/sub 3/TPD, TGA, BET, XRF and SEM techniques. The Fischer Tropsch reaction was studied in fixed bed micro catalytic reactor at temperature range of 220, 260 and 275 degree C and at different pressure (1, 5 and 10 bars). From the activity results, it was found that by pillaring NaMMT with Al higher catalytic activity and lower methane selectivity of NaMMT was achieved. Furthermore, the results of FT synthesis reaction revealed that cerium incorporation increased the dispersion of Co/sub 3/O/sub 4/ on the surface and consequently resulted in enhanced catalytic activity. Additionally, the C/sub 5/-C/sub 12/ hydrocarbons and methane selectivity increased while C/sub 22+/ hydrocarbons selectivity was decreased over cerium modified catalysts. Higher reaction temperature (>220 degree C) resulted in significant enhancement in CO conversion and methane selectivity. Though, increase in pressure from 1 to 10 bars eventually resulted in increase in C/sub 5+/ hydrocarbons and decrease in methane and C/sub 2/-C/sub 5/ hydrocarbons selectivity. (author)

  7. Extraction of Cerium (IV) Using Di–n-butylsulfoxide in Chloroform ...

    African Journals Online (AJOL)

    NICO

    2015-01-12

    Jan 12, 2015 ... Cerium is the most abundant among rare earth metals and is extracted from monazite, allanite and ... Variamine blue, 2,4, dihydroxy benzophenoe benzoic hydrazone, ... thoroughly for colour development. The reagent blank ...

  8. Thermodynamic Studies of the Phase Relationships of Nonstoichiometric Cerium Oxides at Higher Temperatures

    DEFF Research Database (Denmark)

    Sørensen, Ole Toft

    1976-01-01

    Partial molar thermodynamic quantities for oxygen in nonstoichiometric cerium oxides were determined by thermogravimetric analysis in CO/CO2 mixtures in the temperature range 900–1400°C. Under these conditions compositions within the range 2.00 greater-or-equal, slanted O/M greater-or-equal, slan......Partial molar thermodynamic quantities for oxygen in nonstoichiometric cerium oxides were determined by thermogravimetric analysis in CO/CO2 mixtures in the temperature range 900–1400°C. Under these conditions compositions within the range 2.00 greater-or-equal, slanted O/M greater...

  9. New tools for redox biology: From imaging to manipulation.

    Science.gov (United States)

    Bilan, Dmitry S; Belousov, Vsevolod V

    2017-08-01

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

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  11. Determination of Ideal Broth Formulations Needed to Prepare Hydrous Cerium Oxide Microspheres via the Internal Gelation Process

    Energy Technology Data Exchange (ETDEWEB)

    Collins, Jack Lee [ORNL; Chi, Anthony [ORNL

    2009-02-01

    A simple test tube methodology was used to determine optimum process parameters for preparing hydrous cerium oxide microspheres via the internal gelation process.1 Broth formulations of cerium ammonium nitrate [(NH4)2Ce(NO3)6], hexamethylenetetramine, and urea were found that can be used to prepare hydrous cerium oxide gel spheres in the temperature range of 60 to 90 C. A few gel-forming runs were made in which microspheres were prepared with some of these formulations to be able to equate the test-tube gelation times to actual gelation times. These preparations confirmed that the test-tube methodology is reliable for determining the ideal broth formulations.

  12. Effect of cerium and thermomechanical processing on microstructure

    Indian Academy of Sciences (India)

    The effect of cerium content and thermomechanical processing on structure and properties of Fe–10.5 wt.%Al–0.8 wt%C alloy has been investigated. Alloys were prepared by a combination of air induction melting with flux cover (AIMFC) and electroslag remelting (ESR). The ESR ingots were hot-forged and hotrolled at ...

  13. Polyarene mediators for mediated redox flow battery

    Science.gov (United States)

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

    2018-01-02

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-09-07

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

  15. Study of cerium doped magnetite (Fe3O4:Ce)/PMMA nanocomposites

    International Nuclear Information System (INIS)

    Padalia, Diwakar; Johri, U.C.; Zaidi, M.G.H.

    2012-01-01

    The paper presents the synthesis and properties of polymer nanocomposite material based on cerium doped magnetite (Fe 3 O 4 ) as filler material and poly methyl methacrylate (PMMA) as host matrix. The magnetite (Fe 3 O 4 ) particles were synthesized by co-precipitation route using stable ferrous and ferric salts with ammonium hydroxide as precipitating agent. Further, they doped by cerium oxide (CeO 2 ) non-stoichiometrically. The composite material was fabricated by solvent evaporation method. Here 2.4 GHz microwaves were used to study the effect of microwaves heating on polymerization. The phase and crystal structure is determined by X-ray diffraction (XRD). The average crystallite size of the composites varies from 28 to 35 nm. The chemical structure is confirmed by Fourier transform infrared (FTIR) spectroscopy. The magnetic and thermal properties are investigated by vibrating sample magnetometer (VSM) and differential scanning calorimetry (DSC). The thermal study shows that the microwave heated samples possess higher glass transition temperature (T g ). The magnetic results suggest that coercivity (H C ) and squareness (M r /M s ) of the loop increases with increasing doping percent of cerium.

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

    Directory of Open Access Journals (Sweden)

    Sara Franceschelli

    2016-09-01

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

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

    Science.gov (United States)

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

    2013-01-01

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

  18. Development of redox stable, multifunctional substrates for anode supported SOFCS

    DEFF Research Database (Denmark)

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

    2017-01-01

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

  19. Thermal decomposition study of uranyl nitrate and cerium hydroxide in a spray dryer

    International Nuclear Information System (INIS)

    Silva Wildhagen, G.R. da.

    1993-05-01

    A study, in a spray dryer system based on drying and thermal decomposition of uranyl nitrate solutions aiming the production of uranium trioxide adequate for the use in posterior steps of reduction and hydro fluorination in nuclear fuel cycle; and cerium hydroxide suspensions for the production of cerium oxide with high surface area is presented. Thus, the project and construction of a countercurrent spray dryer was elaborated for capacity of 10 Kg U O 3 /h and 3,5 k Ce O 2 /h. The methodology used in these experiments consisted in the analysis of several parameters (concentration and flow rate of the feed, atomization pressure and inlet temperature of the dryer) over the physical and chemical properties of the products. Using the obtained results, with the help of a mathematical model, it was developed the project of a continuous pilot unity for the production of uranium trioxide or cerium oxide, with capacity of 20 Kg U O 3 /h or 10 Kg Ce O 2 /h, respectively. (author)

  20. Cerium valence change in the solid solutions Ce(Rh1-xRux)Sn

    International Nuclear Information System (INIS)

    Niehaus, Oliver; Riecken, Jan F.; Winter, Florian; Poettgen, Rainer; Muenster Univ.; Abdala, Paula M.; Chevalier, Bernard

    2013-01-01

    The solid solutions Ce(Rh 1-x Ru x )Sn were investigated by means of susceptibility measurements, specific heat, electrical resistivity, X-ray absorption spectroscopy (XAS), and 119 Sn Moessbauer spectroscopy. Magnetic measurements as well as XAS data show a cerium valence change in dependence on the ruthenium content. Higher ruthenium content causes an increase from 3.22 to 3.45 at 300 K. Furthermore χ and χ -1 data indicate valence fluctuation for cerium as a function of temperature. For example, Ce(Rh 0.8 Ru 0.2 )Sn exhibits valence fluctuations between 3.42 and 3.32 in the temperature range of 10 to 300 K. This could be proven by using the interconfiguration fluctuation (ICF) model introduced by Sales and Wohlleben. Cerium valence change does not influence the tin atoms as proven by 119 Sn Moessbauer spectroscopy, but it influences the electrical properties. Ce(Rh 0.9 Ru 0.1 )Sn behaves like a typical valence fluctuating compound, and higher ruthenium content causes an increase of the metallic behavior. (orig.)

  1. Redox kinetics and mechanism in silicate melts

    International Nuclear Information System (INIS)

    Cochain, B.

    2009-12-01

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

  2. Fixation of radioactive cerium-144 on white blood cells. Possibilities for use in physiopathology

    International Nuclear Information System (INIS)

    Aeberhardt, A.

    1958-01-01

    From the study of the means of transport of cerium in the blood of various laboratory animals, after intra-venous injection of 144 Ce- 144 Pr without carrier, we have been able to show up the part played by the white cells in the transport of this fission product during its passage in the blood. This observation has led to the study, in vitro, of the methods of cerium fixation on the white cells, with a view to determining the possibilities of using this property for white cell labelling, the methods used up to the present not being entirely satisfactory. Using the method for the separation of the known constituents of the blood proposed by us in 1956, we have studied the cerium fixation under various conditions: - on suspensions of white cells from the rabbit, - on a suspension of human white cells, - on the white cells in whole from the rabbit. (author) [fr

  3. Indirect flow injection determination of N-acetyl-L-cysteine using cerium(IV) and ferroin

    International Nuclear Information System (INIS)

    Vieira, Heberth Juliano; Fatibello-Filho, Orlando

    2005-01-01

    An indirect flow injection spectrophotometric procedure is proposed for the determination of N-acetyl-L-cysteine in pharmaceutical formulations. In this system, ferroin ([Fe(II)-(fen) 2 ] 2+ ) in excess, with a strong absorption at 500 nm, is oxidized by cerium(IV) yielding cerium(III) and [Fe(III)-(fen) 2 ] 3+ (colorless), thus producing a baseline. When N-acetyl-L-cysteine solution is introduced into the flow injection system, it reacts with cerium(IV) increasing the analytical signal in proportion to the drug concentration. Under optimal experimental conditions, the linearity of the analytical curve for N-acetyl-L-cysteine ranged from 6.5x10 -6 to 1.3x10 -4 mol L -1 . The detection limit was 5.0x10 -6 mol L -1 and recoveries between 98.0 and 106% were obtained. The sampling frequency was 60 determinations per hour and the RSD was smaller than 1.4% for 2.2x10 -5 mol L -1 N-acetyl-L-cysteine. (author)

  4. Corrosion behaviors in physiological solution of cerium conversion coatings on AZ31 magnesium alloy

    International Nuclear Information System (INIS)

    Cui Xiufang; Yang Yuyun; Liu Erbao; Jin Guo; Zhong Jinggao; Li Qingfen

    2011-01-01

    In this paper, a non-toxic Ce-based conversion coating was obtained on the surface of bio-medical AZ31 magnesium alloys. The micro-morphology of the coating prepared with optimal technical parameters and immersed in physiological solution (Hank's solution) in different time was observed by scanning electron microscopy (SEM), composition of the cerium conversion coating and corrosion products in Hank's solution were characterized by X-ray photoelectron spectroscopy (XPS) and energy dispersive spectroscopy (EDS), respectively. In addition, the corrosion property in Hank's solution was studied by electrochemical experiment and immersion test. The results show that the dense Ce-based conversion coating is obtained on the surface of AZ31 magnesium alloys in optimal technical parameters and the conversion coating consists of a mass of trivalent and tetravalent cerium oxides. The cerium conversion coating can provide obvious protection of magnesium alloys and can effectively reduce the degradation speed in Hank's solution. Also the degradation products have little influence on human body.

  5. Cerium-loaded algae exoskeletons for active corrosion protection of coated AA2024-T3

    International Nuclear Information System (INIS)

    Denissen, Paul J.; Garcia, Santiago J.

    2017-01-01

    Highlights: •Nanoporous diatom algae exoskeletons allow for local inhibitor loading. •Cerium loaded exoskeletons show diffusion controlled release from coatings. •In-situ opto-electrochemical analysis allows for accurate corrosion evaluation. •Raman spectroscopy allows for precise identification of Ce at IMs in a scribe. •High levels of protection were obtained with the Ce-diatom coatings. -- Abstract: The use of micron sized nanoporous diatom algae exoskeletons for inhibitor storage and sustained corrosion protection of coated aluminium structures upon damage is presented. In this concept the algae exoskeleton allows local inhibitor loading, limits the interaction between the cerium and the epoxy/amine coating and allows for diffusion-controlled release of the inhibitor when needed. The inhibitor release and corrosion protection by loaded exoskeletons was evaluated by UV/Vis spectrometry, a home-built optical-electrochemical setup, and Raman spectroscopy. Although this concept has been proven for a cerium-epoxy-aluminium alloy system the main underlying principle can be extrapolated to other inhibitor-coating-metal systems.

  6. Eucalyptus tolerance mechanisms to lanthanum and cerium: subcellular distribution, antioxidant system and thiol pools.

    Science.gov (United States)

    Shen, Yichang; Zhang, Shirong; Li, Sen; Xu, Xiaoxun; Jia, Yongxia; Gong, Guoshu

    2014-12-01

    Guanglin 9 (Eucalyptus grandis × Eucalyptus urophlla) and Eucalyptus grandis 5 are two eucalyptus species which have been found to grow normally in soils contaminated with lanthanum and cerium, but the tolerance mechanisms are not clear yet. In this study, a pot experiment was conducted to investigate the tolerance mechanisms of the eucalyptus to lanthanum and cerium. Cell walls stored 45.40-63.44% of the metals under lanthanum or cerium stress. Peroxidase and catalase activities enhanced with increasing soil La or Ce concentrations up to 200 mg kg(-1), while there were no obvious changes in glutathione and ascorbate concentrations. Non-protein thiols concentrations increased with increasing treatment levels up to 200 mg kg(-1), and then decreased. Phytochelatins concentrations continued to increase under La or Ce stress. Therefore, the two eucalyptus species are La and Ce tolerant plants, and the tolerance mechanisms include cell wall deposition, antioxidant system response, and thiol compound synthesis. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Effect of ultrasound on the structural and textural properties of copper-impregnated cerium-modified zirconium-pillared bentonite

    International Nuclear Information System (INIS)

    Tomul, Fatma

    2011-01-01

    In this study, the synthesis of zirconium-pillared bentonite modified with cerium was performed via two different methods by the application of conventional and ultrasonic treatments during the intercalation stage. To synthesise copper-impregnated pillared clays by wet impregnation, cerium-modified zirconium-pillared clays were used as supportive materials after being calcined at 300 °C. Ultrasonic treatment significantly decreased the required processing time compared with the conventional treatment of the synthesised pillared bentonites. Chemical analysis confirmed the incorporation of Zr 4+ , Ce 4+ and Cu 2+ species into the pillared bentonites. X-ray diffraction (XRD) patterns of zirconium- and cerium/zirconium-pillared bentonites prepared by conventional treatment show that one large d-spacing above 3.5 nm corresponds to the mesoporous delaminated part, and another small d-spacing above 1.7 nm is indicative of the microporous pillared part. Zirconium- and cerium/zirconium-pillared bentonites prepared via ultrasonic treatment exhibited similar results, with the same high d-spacing but with a second low-intensity d-spacing above 1.9 nm. The delaminated structures of the pillared bentonites synthesised by both methods were conserved after copper impregnation. Nitrogen-adsorption isotherm analysis showed that the textural characteristics of products synthesised by ultrasonic treatment were comparable to those of products synthesised by conventional treatment. Fourier-transform infrared spectroscopy (FTIR) analyses showed the presence of Brønsted- and Lewis-acid sites, and zirconium-pillared clays synthesised by conventional treatment exhibited increased numbers of Brønsted- and Lewis-acid sites after cerium addition and copper impregnation. However, the products synthesised by ultrasonic treatment exhibited an increased number of Brønsted- and Lewis-acid sites after cerium addition, but a decreased number of acid sites after copper impregnation.

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

    DEFF Research Database (Denmark)

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

    2012-01-01

    Reversible switching of conductance using redox triggered switching of a polymer-modified electrode is demonstrated. A bifunctional monomer comprising a central electroswitchable core and two bithiophene units enables formation of a film through anodic electropolymerization. The conductivity...... of the polymer can be switched electrochemically in a reversible manner by redox triggered opening and closing of the diarylethene unit. In the closed state, the conductivity of the modified electrode is higher than in the open state....

  9. Effect of HCl pre-treatment on corrosion resistance of cerium-based conversion coatings on magnesium and magnesium alloys

    International Nuclear Information System (INIS)

    Brunelli, Katya; Dabala, Manuele; Calliari, Irene; Magrini, Maurizio

    2005-01-01

    The corrosion protection afforded by a cerium conversion coating, formed by immersion in a solution containing rare earth salt and hydrogen peroxide, on pure magnesium and two magnesium alloys, AZ91 and AM50, has been studied. The effect of HCl pre-treatments on the morphology and on the corrosion resistance of the cerium conversion layer was investigated. A thicker and more homogeneous distribution of the conversion coating was obtained when the sample surface was pre-treated with acid. Higher amounts of cerium on the surface of the pre-treated samples were detected. The cerium conversion coating increased the corrosion resistance of the alloys because it ennobled the corrosion potential and decreased both the anodic and cathodic current. The acid pre-treatment further increased the corrosion resistance of the coated alloys. After five days of immersion in chloride environment the untreated samples showed localized corrosion while the chemical conversion coated samples appeared unaffected

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

    Science.gov (United States)

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

    2008-01-30

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

  11. Zirconia dispersion as a toughening agent in alumina - Influence of the cerium oxide

    International Nuclear Information System (INIS)

    Gritti, Olivier

    1987-01-01

    The improvement of mechanical properties of alumina can be obtained by fine dispersion of zirconia particles. The addition of cerium oxide as a stabilizer of the tetragonal phase has been examined. Different powder preparations, based on impregnation of the alumina powder by zirconium and cerium precursor salts, have been studied. Parameters, such as properties of alumina powder and cerium oxide content, for the production of reactive powders have been determined by two laboratory processes. The sintering of these powders in air at 1600 deg. C has resulted in dense materials with homogeneous microstructure. The mechanical properties, in particular the biaxial flexure strength and the toughness, have been determined in the temperature range 20 deg. C-900 deg. C. A reinforcement of about 80 pc in comparison with alumina is achieved. The optimal composition is (Al 2 O 3 ) 0.8 (ZrO 2 ) 0.18 (CeO 2 ) 0.02 . In the other hand, powder preparation by spray drying has been chosen for an approach to a larger scale process. The sintered ceramics made with these powders present a double microstructure which does not affect the mechanical properties. The presence of cerium oxide produces the following improvements: - increased mobility of the intergranular zirconia inclusions which results in a faster densification; - stabilization of a tetragonal phase without prohibiting the stress induced transformation; - increase of the critical sizes of the tetragonal → monoclinic transformation; - a large decrease in the transformation kinetic in water at 300 deg. C in comparison with that observed for alumina-zirconia doped with yttrium oxide. (author) [fr

  12. Binding of histone H1 to DNA is differentially modulated by redox state of HMGB1.

    Directory of Open Access Journals (Sweden)

    Eva Polanská

    Full Text Available HMGB1 is an architectural protein in chromatin, acting also as a signaling molecule outside the cell. Recent reports from several laboratories provided evidence that a number of both the intracellular and extracellular functions of HMGB1 may depend on redox-sensitive cysteine residues of the protein. In this study we demonstrate that redox state of HMGB1 can significantly modulate the ability of the protein to bind and bend DNA, as well as to promote DNA end-joining. We also report a high affinity binding of histone H1 to hemicatenated DNA loops and DNA minicircles. Finally, we show that reduced HMGB1 can readily displace histone H1 from DNA, while oxidized HMGB1 has limited capacity for H1 displacement. Our results suggested a novel mechanism for the HMGB1-mediated modulation of histone H1 binding to DNA. Possible biological consequences of linker histones H1 replacement by HMGB1 for the functioning of chromatin are discussed.

  13. Ediacaran Redox Fluctuations

    Science.gov (United States)

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

    2013-12-01

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

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

    Science.gov (United States)

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

    2016-01-01

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

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

    Science.gov (United States)

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

    2016-12-01

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

  16. Soil organic matter influences cerium translocation and physiological processes in kidney bean plants exposed to cerium oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Majumdar, Sanghamitra [Department of Chemistry, The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); University of California Center for Environmental Implications of Nanotechnology (UC CEIN), El Paso, TX (United States); Peralta-Videa, Jose R. [Department of Chemistry, The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); Environmental Science and Engineering PhD Program, The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); University of California Center for Environmental Implications of Nanotechnology (UC CEIN), El Paso, TX (United States); Trujillo-Reyes, Jesica [Department of Chemistry, The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); Sun, Youping [Texas AgriLife Research Center at El Paso, Texas A& M University System, 1380 A & M Circle, El Paso, TX 79927 (United States); Barrios, Ana C. [Department of Chemistry, The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); Niu, Genhua [Texas AgriLife Research Center at El Paso, Texas A& M University System, 1380 A & M Circle, El Paso, TX 79927 (United States); Margez, Juan P. Flores- [Autonomous University of Ciudad Juarez, Departamento de Química y Biología, Instituto de Ciencias Biomédicas, Anillo envolvente PRONAF y Estocolmo, Ciudad Juarez, Chihuahua 32310, México (Mexico); Gardea-Torresdey, Jorge L., E-mail: jgardea@utep.edu [Department of Chemistry, The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); Environmental Science and Engineering PhD Program, The University of Texas at El Paso, 500 West University Ave., El Paso, TX 79968 (United States); University of California Center for Environmental Implications of Nanotechnology (UC CEIN), El Paso, TX (United States)

    2016-11-01

    Soil organic matter plays a major role in determining the fate of the engineered nanomaterials (ENMs) in the soil matrix and effects on the residing plants. In this study, kidney bean plants were grown in soils varying in organic matter content and amended with 0–500 mg/kg cerium oxide nanoparticles (nano-CeO{sub 2}) under greenhouse condition. After 52 days of exposure, cerium accumulation in tissues, plant growth and physiological parameters including photosynthetic pigments (chlorophylls and carotenoids), net photosynthesis rate, transpiration rate, and stomatal conductance were recorded. Additionally, catalase and ascorbate peroxidase activities were measured to evaluate oxidative stress in the tissues. The translocation factor of cerium in the nano-CeO{sub 2} exposed plants grown in organic matter enriched soil (OMES) was twice as the plants grown in low organic matter soil (LOMS). Although the leaf cover area increased by 65–111% with increasing nano-CeO{sub 2} concentration in LOMS, the effect on the physiological processes were inconsequential. In OMES leaves, exposure to 62.5–250 mg/kg nano-CeO{sub 2} led to an enhancement in the transpiration rate and stomatal conductance, but to a simultaneous decrease in carotenoid contents by 25–28%. Chlorophyll a in the OMES leaves also decreased by 27 and 18% on exposure to 125 and 250 mg/kg nano-CeO{sub 2}. In addition, catalase activity increased in LOMS stems, and ascorbate peroxidase increased in OMES leaves of nano-CeO{sub 2} exposed plants, with respect to control. Thus, this study provides clear evidence that the properties of the complex soil matrix play decisive roles in determining the fate, bioavailability, and biological transport of ENMs in the environment. - Highlights: • Ce translocation to leaves was facilitated by higher organic matter (OM) in soil. • Lower soil OM increased leaf cover area in nano-CeO{sub 2} exposed plants. • Nano-CeO{sub 2} effects on metabolic processes were more

  17. Obesity-Associated Oxidative Stress: Strategies Finalized to Improve Redox State

    Directory of Open Access Journals (Sweden)

    Valeria Gasperi

    2013-05-01

    Full Text Available Obesity represents a major risk factor for a plethora of severe diseases, including diabetes, cardiovascular disease, non-alcoholic fatty liver disease, and cancer. It is often accompanied by an increased risk of mortality and, in the case of non-fatal health problems, the quality of life is impaired because of associated conditions, including sleep apnea, respiratory problems, osteoarthritis, and infertility. Recent evidence suggests that oxidative stress may be the mechanistic link between obesity and related complications. In obese patients, antioxidant defenses are lower than normal weight counterparts and their levels inversely correlate with central adiposity; obesity is also characterized by enhanced levels of reactive oxygen or nitrogen species. Inadequacy of antioxidant defenses probably relies on different factors: obese individuals may have a lower intake of antioxidant- and phytochemical-rich foods, such as fruits, vegetables, and legumes; otherwise, consumption of antioxidant nutrients is normal, but obese individuals may have an increased utilization of these molecules, likewise to that reported in diabetic patients and smokers. Also inadequate physical activity may account for a decreased antioxidant state. In this review, we describe current concepts in the meaning of obesity as a state of chronic oxidative stress and the potential interventions to improve redox balance.

  18. Obesity-Associated Oxidative Stress: Strategies Finalized to Improve Redox State

    Science.gov (United States)

    Savini, Isabella; Catani, Maria Valeria; Evangelista, Daniela; Gasperi, Valeria; Avigliano, Luciana

    2013-01-01

    Obesity represents a major risk factor for a plethora of severe diseases, including diabetes, cardiovascular disease, non-alcoholic fatty liver disease, and cancer. It is often accompanied by an increased risk of mortality and, in the case of non-fatal health problems, the quality of life is impaired because of associated conditions, including sleep apnea, respiratory problems, osteoarthritis, and infertility. Recent evidence suggests that oxidative stress may be the mechanistic link between obesity and related complications. In obese patients, antioxidant defenses are lower than normal weight counterparts and their levels inversely correlate with central adiposity; obesity is also characterized by enhanced levels of reactive oxygen or nitrogen species. Inadequacy of antioxidant defenses probably relies on different factors: obese individuals may have a lower intake of antioxidant- and phytochemical-rich foods, such as fruits, vegetables, and legumes; otherwise, consumption of antioxidant nutrients is normal, but obese individuals may have an increased utilization of these molecules, likewise to that reported in diabetic patients and smokers. Also inadequate physical activity may account for a decreased antioxidant state. In this review, we describe current concepts in the meaning of obesity as a state of chronic oxidative stress and the potential interventions to improve redox balance. PMID:23698776

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

    Science.gov (United States)

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

    1991-01-01

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

  20. Structure, dielectric and electrical properties of cerium doped barium zirconium titanate ceramics

    International Nuclear Information System (INIS)

    Feng Hongjun; Hou Jungang; Qu Yuanfang; Shan Dan; Yao Guohua

    2012-01-01

    Highlights: ► Rare-earth doped barium zirconate titanate (BZT) ceramics, Ba(Zr 0.25 Ti 0.75 )O 3 + xCeO 2 , (x = 0–1.5 at%) were obtained by a solid state reaction route. ► Morphological analysis on sintered samples by scanning electron microscopy shows that the addition of rare-earth ions affects the growth of the grain and remarkably changes the grain morphology. ► The effect of rare-earth addition to BZT on dielectric and electrical properties is analyzed, demonstrating that the samples with x = 0.4 and x = 0.6 could be semiconducting in air atmosphere. - Abstract: Rare-earth doped barium zirconium titanate (BZT) ceramics, Ba(Zr 0.25 Ti 0.75 )O 3 + xCeO 2 , (x = 0–1.5 at%) were obtained by a solid state reaction route. Perovskite-like single-phase compounds were confirmed from X-ray diffraction data and the lattice parameters were refined by the Rietveld method. It is found that, integrating with the lattice parameters and the distortion of crystal lattice, there is an alternation of substitution preference of cerium ions for the host cations in perovskite lattice. Morphological analysis on sintered samples by scanning electron microscopy shows that the addition of rare-earth ions affects the growth of the grain and remarkably changes the grain morphology. The effect of rare-earth addition to BZT on dielectric and electrical properties is analyzed. High values of dielectric tunability are obtained for cerium doped BZT. Especially, the experimental results on the effect of the contents of rare-earth addition on the resistivity of BZT ceramics were investigated, demonstrating that the samples with x = 0.4 and x = 0.6 could be semiconducting in air atmosphere.

  1. Corrosion inhibition of 7000 series aluminium alloys with cerium diphenyl phosphate

    Energy Technology Data Exchange (ETDEWEB)

    Hill, Julie-Anne [Department of Materials Engineering and Australian Centre of Excellence for Electromaterials Science, Wellington Rd, Monash University, Clayton, Victoria (Australia); Markley, Tracey [Department of Materials Engineering and Australian Centre of Excellence for Electromaterials Science, Wellington Rd, Monash University, Clayton, Victoria (Australia); CSIRO, Division of Materials Science and Technology, Clayton, Victoria (Australia); Forsyth, Maria, E-mail: maria.forsyth@deakin.edu.au [Department of Materials Engineering and Australian Centre of Excellence for Electromaterials Science, Wellington Rd, Monash University, Clayton, Victoria (Australia); Howlett, Patrick C. [Department of Materials Engineering and Australian Centre of Excellence for Electromaterials Science, Wellington Rd, Monash University, Clayton, Victoria (Australia); Hinton, Bruce R.W. [Department of Materials Engineering and Australian Centre of Excellence for Electromaterials Science, Wellington Rd, Monash University, Clayton, Victoria (Australia); Defence Science and Technology Organisation, Melbourne, Victoria (Australia)

    2011-02-03

    Graphical abstract: Scanning electron micrographs of microtomed surface shows pristine surface free of corrosion related 'mud cracking' inset for an inhibited AA7050 specimen when only 150 ppm Ce(dpp)3 is present in 0.1 M NaCl solution. Display Omitted Research highlights: > The thin film of hydrolysis products of Ce(dpp)3 and aluminium oxide is proposed to cause the inhibition. > The film consists of discrete Ce rich particles and a thin film over the matrix of Ce, P and Al oxides. > Discrete deposition of Ce is specifically influenced by Cu rich intermetallics. - Abstract: Cerium diphenyl phosphate (Ce(dpp){sub 3}) has previously been shown to be a strong corrosion inhibitor for aluminium-copper magnesium alloy AA2024-T3 and AA7075 in chloride solutions. Surface characterisation including SEM and ToF-SIMS coupled with electrochemical impedance spectroscopy (EIS) measurements are used to propose a mechanism of corrosion inhibition which appears to involve the formation of a complex oxide film of aluminium and cerium also incorporating the organophosphate component. The formation of a thin complex film consisting of hydrolysis products of the Ce(dpp){sub 3} compound and aluminium oxide is proposed to lead to the observed inhibition. SEM analysis shows that some intermetallics favour the creation of thicker deposits predominantly containing cerium oxide compounds.

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

    OpenAIRE

    Kristina Wedege; Emil Dražević; Denes Konya; Anders Bentien

    2016-01-01

    Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined ...

  3. Redox-controlled memristive switching in the junctions employing Ti reactive electrodes

    Directory of Open Access Journals (Sweden)

    Haitao Li

    2011-09-01

    Full Text Available We have proposed a kind of memristive device based on the junctions employing Ti as the reactive electrodes. The role of electrically-derived redox of Ti in such memristive switching is shown. The structural and chemical evidence of the electrically-derived oxidation is presented by TEM and XPS experiment, respectively. Due to the redox of the top electrode Ti and the consequent drift of oxygen vacancies, the device shows two distinct resistance states under a sweeping voltage loading. ON state is controlled by tunneling process, while OFF state is controlled by Schottky emission conductive mechanism. The failure behaviors of such memristive junctions are also discussed. In the light of the redox principle, we demonstrate that the devices could be recovered by loading a long electrical reduction treatment.

  4. Bioavailability of cerium oxide nanoparticles to Raphanus sativus L. in two soils.

    Science.gov (United States)

    Zhang, Weilan; Musante, Craig; White, Jason C; Schwab, Paul; Wang, Qiang; Ebbs, Stephen D; Ma, Xingmao

    2017-01-01

    Cerium oxide nanoparticles (CeO 2 NP) are a common component of many commercial products. Due to the general concerns over the potential toxicity of engineered nanoparticles (ENPs), the phytotoxicity and in planta accumulation of CeO 2 NPs have been broadly investigated. However, most previous studies were conducted in hydroponic systems and with grain crops. For a few studies performed with soil grown plants, the impact of soil properties on the fate and transport of CeO 2 NPs was generally ignored even though numerous previous studies indicate that soil properties play a critical role in the fate and transport of environmental pollutants. The objectives of this study were to evaluate the soil fractionation and bioavailability of CeO 2 NPs to Raphanus sativus L (radish) in two soil types. Our results showed that the silty loam contained slightly higher exchangeable fraction (F1) of cerium element than did loamy sand soil, but significantly lower reducible (F2) and oxidizable (F3) fractions as CeO 2 NPs concentration increased. CeO 2 NPs associated with silicate minerals or the residue fraction (F4) dominated in both soils. The cerium concentration in radish storage root showed linear correlation with the sum of the first three fractions (r 2  = 0.98 and 0.78 for loamy sand and silty loam respectively). However, the cerium content in radish shoots only exhibited strong correlations with F1 (r 2  = 0.97 and 0.89 for loamy sand and silty loam respectively). Overall, the results demonstrated that soil properties are important factors governing the distribution of CeO 2 NPs in soil and subsequent bioavailability to plants. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  5. Synthesis of cerium and nickel doped titanium nanofibers for hydrolysis of sodium borohydride.

    Science.gov (United States)

    Tamboli, Ashif H; Gosavi, S W; Terashima, Chiaki; Fujishima, Akira; Pawar, Atul A; Kim, Hern

    2018-07-01

    A recyclable titanium nanofibers, doped with cerium and nickel doped was successfully synthesized by using sol-gel and electrospinning method for hydrogen generation from alkali free hydrolysis of NaBH 4 . The resultant nanocomposite was characterized to find out the structural and physical-chemical properties by a series of analytical techniques such as FT-IR (Fourier transform infrared spectroscopy), XRD (X-ray diffraction), SEM (scanning electron microscope), EDX (energy-dispersive X-ray spectroscopy),N 2 adsorption-desorption and BET (Brunauer-Emmett-Teller), etc. The results revealed that cerium and nickel nanoparticles were homogeneously distributed on the surface of the TiO 2 nanofibers due to having similar oxidation state and atomic radium of TiO 2 nanofibers with CeO 2 and NiO for the effective immobilization of metal ions. The NiO doped catalyst showed superior catalytic performance towards the hydrolysis reaction of NaBH 4 at room temperature. These catalysts have ability to produce 305 mL of H 2 within the time of 160 min at room temperature. Additionally, reusability test revealed that the catalyst is active even after five runs of hydrolytic reaction, implying the as-prepared NiO doped TiO 2 nanofibers could be considered as a potential candidate catalyst for portable hydrogen fuel system such as PEMFC (proton exchange membrane fuel cells). Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Coulometric microdetermination of organic compounds with manganese(III) and cerium(IV)

    International Nuclear Information System (INIS)

    Chateau-Gosselin, M.; Patriarche, G.J.

    1977-01-01

    The oxidation of compounds such as hydroquinon, p-aminophenol, paracetamol and phenacetin was performed using cerium(IV) and manganese(III) coulometrically electrogenerated. Quantitative results obtained are excellent even at the microscale level. (author)

  7. Metabolic Control of Redox and Redox Control of Metabolism in Plants

    Science.gov (United States)

    Fernie, Alisdair R.

    2014-01-01

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

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

    Science.gov (United States)

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

    2017-11-02

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

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

    Directory of Open Access Journals (Sweden)

    Masood Ahmad Rizvi

    2015-03-01

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

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

    Science.gov (United States)

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

    2015-08-01

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

  11. Effect of coating parameters on the microstructure of cerium oxide conversion coatings

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Benedict Y.; Edington, Joe; O' Keefe, Matthew J

    2003-11-25

    The microstructure and morphology of cerium oxide conversion coatings prepared under different deposition conditions were characterized by transmission electron microscopy (TEM). The coatings were formed by a spontaneous reaction between a water-based solution containing CeCl{sub 3} and aluminum alloy 7075-T6 substrates. Microstructural characterization was performed to determine the crystallinity of the coatings and to obtain a better understanding of the deposition parameters on coating microstructure. The results of TEM imaging and electron diffraction analysis indicated that the as-deposited coating was composed of nanocrystalline particles of a previously unreported cerium compound. The particles of the coatings produced using glycerol as an additive were found to be much finer than those of the coatings prepared in the absence of glycerol. This indicates that glycerol may act as a grain refiner and/or growth inhibitor during coating deposition. After deposition, the coated panels were treated for 5 min in a phosphate sealing solution. The sealing treatment converted the as-deposited coating into hydrated cerium phosphate. Panels coated from solutions containing no glycerol followed by phosphate sealing performed poorly in salt fog tests. With glycerol addition, the corrosion resistance of the coatings that were phosphate sealed improved considerably, achieving an average passing rate of 85%.

  12. Ultrathin, epitaxial cerium dioxide on silicon

    Energy Technology Data Exchange (ETDEWEB)

    Flege, Jan Ingo, E-mail: flege@ifp.uni-bremen.de; Kaemena, Björn; Höcker, Jan; Schmidt, Thomas; Falta, Jens [Institute of Solid State Physics, University of Bremen, Otto-Hahn-Allee 1, 28359 Bremen (Germany); Bertram, Florian [Photon Science, Deutsches Elektronensynchrotron (DESY), Notkestraße 85, 22607 Hamburg (Germany); Wollschläger, Joachim [Department of Physics, University of Osnabrück, Barbarastraße 7, 49069 Osnabrück (Germany)

    2014-03-31

    It is shown that ultrathin, highly ordered, continuous films of cerium dioxide may be prepared on silicon following substrate prepassivation using an atomic layer of chlorine. The as-deposited, few-nanometer-thin Ce{sub 2}O{sub 3} film may very effectively be converted at room temperature to almost fully oxidized CeO{sub 2} by simple exposure to air, as demonstrated by hard X-ray photoemission spectroscopy and X-ray diffraction. This post-oxidation process essentially results in a negligible loss in film crystallinity and interface abruptness.

  13. Amplified and in situ detection of redox-active metabolite using a biobased redox capacitor.

    Science.gov (United States)

    Kim, Eunkyoung; Gordonov, Tanya; Bentley, William E; Payne, Gregory F

    2013-02-19

    Redox cycling provides a mechanism to amplify electrochemical signals for analyte detection. Previous studies have shown that diverse mediators/shuttles can engage in redox-cycling reactions with a biobased redox capacitor that is fabricated by grafting redox-active catechols onto a chitosan film. Here, we report that redox cycling with this catechol-chitosan redox capacitor can amplify electrochemical signals for detecting a redox-active bacterial metabolite. Specifically, we studied the redox-active bacterial metabolite pyocyanin that is reported to be a virulence factor and signaling molecule for the opportunistic pathogen P. aeruginosa. We demonstrate that redox cycling can amplify outputs from various electrochemical methods (cyclic voltammetry, chronocoulometry, and differential pulse voltammetry) and can lower the detection limit of pyocyanin to 50 nM. Further, the compatibility of this biobased redox capacitor allows the in situ monitoring of the production of redox-active metabolites (e.g., pyocyanin) during the course of P. aeruginosa cultivation. We anticipate that the amplified output of redox-active virulence factors should permit an earlier detection of life-threatening infections by the opportunistic pathogen P. aeruginosa while the "bio-compatibility" of this measurement approach should facilitate in situ study of the spatiotemporal dynamics of bacterial redox signaling.

  14. Evaluation of mechanically treated cerium (IV) oxides as corrosion inhibitors for galvanized steel

    Energy Technology Data Exchange (ETDEWEB)

    Deflorian, F., E-mail: flavio.deflorian@ing.unitn.it [Department of Materials Engineering and Industrial Technology, University of Trento, Via Mesiano 77, 38123 Trento (Italy); Fedel, M.; Rossi, S. [Department of Materials Engineering and Industrial Technology, University of Trento, Via Mesiano 77, 38123 Trento (Italy); Kamarchik, P. [PPG Industries, Coatings Innovation Center, 4325 Rosanna Drive, Allison Park, PA 15101 (United States)

    2011-09-30

    The use of cerium salts as corrosion inhibitors for hot dip galvanized steel has been object of a numerous studies in the last few years. The role of cerium ions as corrosion inhibitors was proved: cerium is able to block the cathodic sites of the metal, forming insoluble hydroxides and oxides on the zinc surface. This fact leads to a dramatic decrease of the cathodic current densities and, therefore, to a reduction the overall corrosion processes. On the other hand, the potential of cerium oxides as corrosion inhibitors was also proposed. However, the real effectiveness of this kind of anticorrosive pigments has not been clarified yet. In this work cerium (IV) oxides are considered as corrosion inhibitors for galvanized steel. The corrosion inhibition mechanism of mechanically treated (milled) CeO{sub 2} alone and in combination with milled SiO{sub 2} nanoparticles was investigated. For this purpose milled CeO{sub 2}, CeO{sub 2} and SiO{sub 2} milled together and milled SiO{sub 2} particles were studied as corrosion inhibitors in water solution. Therefore, the different mechanically treated particles were dispersed in 0.1 M NaCl solution to test their effectiveness as corrosion inhibitors for galvanized steel. The galvanized steel was immersed in the different solutions and the corrosion inhibition efficiency of the different particles was measured by means of electrochemical techniques. For this purpose, electrochemical impedance spectroscopy (EIS) measurements were carried out, monitoring the evolution of the corrosion processes occurring at the metal surface with the immersion time in the solution. The effect of the different pigments was also investigated by carrying out anodic and cathodic polarization measurements. The polarization curves were acquired under conditions of varied pH. The experimental measurements suggest that the mechanical treatment performed on the SiO{sub 2} and CeO{sub 2} particles promote the formation of an effective corrosion pigment

  15. In vivo assessment of intracellular redox state in rat liver using hyperpolarized [1-13 C]Alanine.

    Science.gov (United States)

    Park, Jae Mo; Khemtong, Chalermchai; Liu, Shie-Chau; Hurd, Ralph E; Spielman, Daniel M

    2017-05-01

    The intracellular lactate to pyruvate concentration ratio is a commonly used tissue assay biomarker of redox, being proportional to free cytosolic [NADH]/[NAD + ]. In this study, we assessed the use of hyperpolarized [1- 13 C]alanine and the subsequent detection of the intracellular products of [1- 13 C]pyruvate and [1- 13 C]lactate as a useful substrate for assessing redox levels in the liver in vivo. Animal experiments were conducted to measure in vivo metabolism at baseline and after ethanol infusion. A solution of 80-mM hyperpolarized [1- 13 C]alanine was injected intravenously at baseline (n = 8) and 45 min after ethanol infusion (n = 4), immediately followed by the dynamic acquisition of 13 C MRS spectra. In vivo rat liver spectra showed peaks from [1- 13 C] alanine and the products of [1- 13 C]lactate, [1- 13 C]pyruvate, and 13 C-bicarbonate. A significantly increased 13 C-lactate/ 13 C-pyruvate ratio was observed after ethanol infusion (8.46 ± 0.58 at baseline versus 13.58 ± 0.69 after ethanol infusion; P alanine is presented, with the validity of the proposed 13 C-pyruvate/ 13 C-lactate metric tested using an ethanol challenge to alter liver redox state. Magn Reson Med 77:1741-1748, 2017. © 2017 International Society for Magnetic Resonance in Medicine. © 2017 International Society for Magnetic Resonance in Medicine.

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

    OpenAIRE

    Rizvi, Masood Ahmad; Teshima, Norio; Maqsood, Syed Raashid; Akhoon, Showket Ahmad; Peerzada, Ghulam Mustafa

    2015-01-01

    Transition metal ions in their free state bring unwanted biological oxidations generating oxidative stress. The ligand modulated redox potential can be indispensable in prevention of such oxidative stress by blocking the redundant bio-redox reactions. In this study we investigated the comparative ligand effect on the thermo-kinetic aspects of biologically important cysteine iron (III) redox reaction using spectrophotometric and potentiometric methods. The results were corroborated...

  17. Dynamics of α-Hb chain binding to its chaperone AHSP depends on heme coordination and redox state.

    Science.gov (United States)

    Kiger, Laurent; Vasseur, Corinne; Domingues-Hamdi, Elisa; Truan, Gilles; Marden, Michael C; Baudin-Creuza, Véronique

    2014-01-01

    AHSP is an erythroid molecular chaperone of the α-hemoglobin chains (α-Hb). Upon AHSP binding, native ferric α-Hb undergoes an unprecedented structural rearrangement at the heme site giving rise to a 6th coordination bond with His(E7). Recombinant AHSP, WT α-Hb:AHSP and α-Hb(HE7Q):AHSP complexes were expressed in Escherichia coli. Thermal denaturation curves were measured by circular dichroism for the isolated α-Hb and bound to AHSP. Kinetics of ligand binding and redox reactions of α-Hb bound to AHSP as well as α-Hb release from the α-Hb:AHSP complex were measured by time-resolved absorption spectroscopy. AHSP binding to α-Hb is kinetically controlled to prevail over direct binding with β-chains and is also thermodynamically controlled by the α-Hb redox state and not the liganded state of the ferrous α-Hb. The dramatic instability of isolated ferric α-Hb is greatly decreased upon AHSP binding. Removing the bis-histidyl hexacoordination in α-HbH58(E7)Q:AHSP complex reduces the stabilizing effect of AHSP binding. Once the ferric α-Hb is bound to AHSP, the globin can be more easily reduced by several chemical and enzymatic systems compared to α-Hb within the Hb-tetramer. α-Hb reduction could trigger its release from AHSP toward its final Hb β-chain partner producing functional ferrous Hb-tetramers. This work indicates a preferred kinetic pathway for Hb-synthesis. The cellular redox balance in Hb-synthesis should be considered as important as the relative proportional synthesis of both Hb-subunits and their heme cofactor. The in vivo role of AHSP is discussed in the context of the molecular disorders observed in thalassemia. © 2013 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    Baier, Margarete; Dietz, Karl-Josef

    2005-06-01

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

  19. Factors affecting the performance of the Zn-Ce redox flow battery

    International Nuclear Information System (INIS)

    Nikiforidis, Georgios; Cartwright, Rory; Hodgson, David; Hall, David; Berlouis, Leonard

    2014-01-01

    The Hull Cell was used to investigate the impact of current density j on the morphology and uniformity of zinc electrodeposited from a 2.5 mol dm −3 Zn 2+ solution in 1.5 mol dm −3 methanesulfonic acid at 40 °C onto carbon-composite surfaces. The range of the applied deposition current density used was between 1 mA cm −2 and 100 mA cm −2 . Good, robust deposits were obtained when j ≥ 10 mA cm 2 whereas at j's lower than this, patchy films formed due to the competing hydrogen evolution reaction (HER) on the bare carbon-composite surface. An understanding of these effects and its application in the redox flow battery enabled both the coulombic and cell potential efficiencies to be maintained at relatively high values, 90% and 69% respectively, indicating a successful inhibition of the HER on the fully formed Zn layer. Flow velocity at the low Reynolds number in the cell (Re <200) had little impact on the electrochemical cell performance. Depletion of the cerium species became an issue for long charge times

  20. Exposure and Health Effects Review of Engineered Nanoscale Cerium and Cerium Dioxide Associated with its Use as a Fuel Additive - NOW IN PRINT IN THE JOURNAL

    Science.gov (United States)

    Advances of nanoscale science have produced nanomaterials with unique physical and chemical properties at commercial levels that are now incorporated into over 1000 products. Nanoscale cerium (di) oxide (Ce02) has recently gained a wide range of applications which includes coatin...

  1. Optical redox imaging indices discriminate human breast cancer from normal tissues

    Science.gov (United States)

    Xu, He N.; Tchou, Julia; Feng, Min; Zhao, Huaqing; Li, Lin Z.

    2016-01-01

    Abstract. Our long-term goal was to investigate the potential of incorporating redox imaging technique as a breast cancer (BC) diagnosis component to increase the positive predictive value of suspicious imaging finding and to reduce unnecessary biopsies and overdiagnosis. We previously found that precancer and cancer tissues in animal models displayed abnormal mitochondrial redox state. We also revealed abnormal mitochondrial redox state in cancerous specimens from three BC patients. Here, we extend our study to include biopsies of 16 patients. Tissue aliquots were collected from both apparently normal and cancerous tissues from the affected cancer-bearing breasts shortly after surgical resection. All specimens were snap-frozen and scanned with the Chance redox scanner, i.e., the three-dimensional cryogenic NADH/Fp (reduced nicotinamide adenine dinucleotide/oxidized flavoproteins) fluorescence imager. We found both Fp and NADH in the cancerous tissues roughly tripled that in the normal tissues (predox ratio Fp/(NADH + Fp) was ∼27% higher in the cancerous tissues (predox ratio alone could predict cancer with reasonable sensitivity and specificity. Our findings suggest that the optical redox imaging technique can provide parameters independent of clinical factors for discriminating cancer from noncancer breast tissues in human patients. PMID:27896360

  2. Magnetic susceptibility of Variscan granite-types of the Spanish Central System and the redox state of magma

    Energy Technology Data Exchange (ETDEWEB)

    Villaseca, C.; Ruiz-Martínez, V.C.; Pérez-Soba, C.

    2017-07-01

    Magnetic susceptibility (MS) has been measured in Variscan granites from central Spain. They yield values in the order of 15 to 180μSI units for S- and I-type granites, indicating that both types belong to the ilmenite series. Only samples from magnetite-bearing leucogranites from the I-type La Pedriza massif show high MS values, in the order of 500-1400μSI, reflecting the presence of this ferromagnetic mineral. Mineral chemistry of magmatic Fe-rich minerals (mainly biotite) suggests similar oxidation values for both granite types. MS values change in highly fractionated granites accordingly either with the presence of rare new Fe-oxide phases (some I-type leucogranites) or with the marked modal amount decrease of Fe-rich minerals (I- and S-type leucogranites). The redox state in highly fractionated granite melts is mostly controlled by magmatic processes that modify redox conditions inherited from the source region. Thus, the occurrence of magnetite or ilmenite in granites is primarily controlled by the oxidation state of the source material but also by the differentiation degree of the granite melt. The presence of magnetite in some Variscan I-type leucogranites might be a consequence of crystal fractionation processes in a more limited mafic mineral assemblage than in S-type granite melts.

  3. Study of cyclic oxidation for stainless steels AISI 309 T 253 M A, with low additions of cerium

    International Nuclear Information System (INIS)

    Velazquez F, G.L.; Martinez, M.; Ruiz, A.

    1998-01-01

    It has been detected that the addition of small amounts (<1%) of the so called 'reactive elements' such as Cerium to Fe-Cr alloys that was utilized in oxidating environment at high temperatures improving its resistance to oxidation under isothermal and cyclic conditions. In this work, it was evaluated the behavior under cyclic oxidation conditions for an austenitic stainless steel at chromium-nickel (253MA) with cerium addition, and comparing it with the AISI 310S austenitic stainless steel. The cyclic oxidation essays consist of five cycles by 24 hours each one, following of a cooling in air until ambient temperature from the temperatures of 850, 900 and 950 Centigrade, registering the gain mass of the specimen at end of each cycle. In order to this were prepared samples with dimensions of 20 mm. x 10 mm. x 1 mm. Later to the oxidation essays was evaluated the morphology of the corrosion products layer by scanning electron microscopy. The present phases were identified by X-ray diffraction and by chemical microanalysis by Dispersive energy (EDAX). The results obtained show that the steel with cerium addition, presents a higher adherence and resistance to the spalling noting that the cerium promotes the casting anchor of the oxides layer to matrix and by reducing the grain size of the layer improving its plasticity. Additionally the cerium promotes the preferential oxidation of the forming elements of protective layers like the chromium. (Author)

  4. The Comparison of One-Session Intensive Aerobic Exercise Effects on Glutathione Redox State of Red Blood Cells in Professional, Recreational Athletes and Nonathletes

    Directory of Open Access Journals (Sweden)

    Farnaz Seifi-Skishahr

    2015-04-01

    Full Text Available Background & objectives: The “redox” state represents the oxidation/reduction potential within the cell in a way that more “redox” is the marker of health, while the more oxidized reflects predisposition to diseases. Different types of exercise training may change the thiol/disulfide ratio of redox couples such as glutathione and represent a shift in redox balance. This study was assessed the influence of high-intensity aerobic exercise on glutathione redox state in red blood cells in professional, recreational athletes and nonathletes.   Methods: Ten voluntary well trained (WT, moderately trained (MT and untrained men subjectswere randomly selected for this semi-experimental study (mean ages of 21.10±1.72 21.70±1.88 and 20.10±1.44, respectively. Blood samples were collected before, immediately, 10 min and 30 min after acute aerobic exercise with 75%VO2max. The levels of reduced glutathione (GSH, oxidized glutathione (GSSG and (GSH/GSSG in red blood cells (RBCs as well as serum levels of cortisol and creatine kinase (CK were measured.   Results: The results showed reduction, elevation and no changes in RBCs GSH/GSSG ratio in UT, MT and WT groups, respectively. The lowest levels of GSH/GSSG ratio in RBCs and the highest one were detected in the WT and MT groups, respectively. The serum levels of cortisol and creatine kinase were increased following the exercise in three groups.   Conclusion: It is concluded that acute aerobic exercise with high intensity does not change redox balance in well trained subjects, however it is capable to shift redox balance towards more reducing environment in moderately trained subjects and also to more oxidizing one in untrained subjects.

  5. Influence of preliminary deformation and phase strengthening on γ reversible α transformation kinetics in cerium under pressure

    International Nuclear Information System (INIS)

    Larionov, L.V.; Livshits, L.D.; Peresada, G.I.; AN SSSR, Moscow. Inst. Fiziki Zemli)

    1985-01-01

    Using the methods of piezo- and resistometry the influence of preliminary plastic deformation, phase transformation induced strengthening and heat treatment on kinetics of γ reversible α transformation in cerium is studied. It is shown, that the used methods of preliminary treatment of sample material do not change pressure value of γ → α and α →γ transformation initiation and do not affect hysteresis value, but affect considerably its kinetics. Preliminary plastic deformation and structural strengthening increase the average formation rate of a new phase. According to the data of tensile tests, structural strengthening, apprearing as a result of one cycle of γ → α → γ transformation, increases cerium strength characteristics 6y 30-50% with simultaneous decrease in plasticity. Metallographic studies confirm martensitic character of γ → α → γ transformations in cerium

  6. Spectrophotometric study of the complexes of cerium and uranides with diethylenetetraaminepentaacetic acid (DTPA); Contribution a l'etude de la complexation du cerium et des uranides par l'acide diethylenetetraminepentaacetique (DTPA)

    Energy Technology Data Exchange (ETDEWEB)

    Hafez, M B [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1968-03-01

    A spectrophotometric determination was made of the complexes of cerium and uranides in their different degrees of oxidation with diethylenetriaminepentaacetic acid (DTPA). Two physico-chemical states, the ionic and hydrolysis ones, were considered. In the former case, we studied the influence of the pH on the formation of the complex, and whenever the complexes were stable, we determined the molecular ratio and calculated their stability constants. In the latter case, we studied the conditions of solubilization of the precipitate by formation of complexes soluble in water as a function of pH, age of the precipitate and time of precipitate-chelate contact. (authors) [French] Etude spectrophotometrique de la complexation du cerium et des uranides (uranium, neptunium, plutonium et americium) dans leurs differents etats d'oxydation par l'acide diethylenetriaminepentaacetique (DTPA). Deux etats physicochimiques ont retenu notre attention, l'etat ionique et l'etat precipite d'hydrolyse. Dans le premier cas, nous avons etudie l'influence du pH sur la formation du complexe, et dans tous les cas ou le complexe est stable, nous avons determine le rapport moleculaire (5) [element]/[chelatant] du complexe forme et nous avons calcule leurs constantes de stabilite. Dans le deuxieme cas, l'etat de precipite d'hydrolyse, nous avons etudie les conditions de solubilisation du precipite, par formation du complexe, en fonction du pH, de l'age du precipite et du temps de contact precipite - chelatant. (auteurs)

  7. Photocatalytic action of cerium molybdate and iron-titanium oxide hollow nanospheres on Escherichia coli

    Energy Technology Data Exchange (ETDEWEB)

    Kartsonakis, I. A., E-mail: ikartsonakis@ims.demokritos.gr; Kontogiani, P.; Pappas, G. S.; Kordas, G. [NCSR ' DEMOKRITOS' , Sol-Gel Laboratory, Institute of Advanced Materials, Physicochemical Processes, Nanotechnology and Microsystems (Greece)

    2013-06-15

    This study is focused on the production of hollow nanospheres that reveal antibacterial action. Cerium molybdate and iron-titanium oxide hollow nanospheres with a diameter of 175 {+-} 15 and 221 {+-} 10 nm, respectively, were synthesized using emulsion polymerization and the sol-gel process. Their morphology characterization was accomplished using scanning electron microscopy. Their antibacterial action was examined on pure culture of Escherichia coli considering the loss of their viability. Both hollow nanospheres presented photocatalytic action after illumination with blue-black light, but those of cerium molybdate also demonstrated photocatalytic action in the dark. Therefore, the produced nanospheres can be used for antibacterial applications.

  8. The Redox Proteome*

    Science.gov (United States)

    Go, Young-Mi; Jones, Dean P.

    2013-01-01

    The redox proteome consists of reversible and irreversible covalent modifications that link redox metabolism to biologic structure and function. These modifications, especially of Cys, function at the molecular level in protein folding and maturation, catalytic activity, signaling, and macromolecular interactions and at the macroscopic level in control of secretion and cell shape. Interaction of the redox proteome with redox-active chemicals is central to macromolecular structure, regulation, and signaling during the life cycle and has a central role in the tolerance and adaptability to diet and environmental challenges. PMID:23861437

  9. Redox activity distinguishes solid-state electron transport from solution-based electron transfer in a natural and artificial protein: cytochrome C and hemin-doped human serum albumin.

    Science.gov (United States)

    Amdursky, Nadav; Ferber, Doron; Pecht, Israel; Sheves, Mordechai; Cahen, David

    2013-10-28

    Integrating proteins in molecular electronic devices requires control over their solid-state electronic transport behavior. Unlike "traditional" electron transfer (ET) measurements of proteins that involve liquid environments and a redox cycle, no redox cofactor is needed for solid-state electron transport (ETp) across the protein. Here we show the fundamental difference between these two approaches by macroscopic area measurements, which allow measuring ETp temperature dependence down to cryogenic temperatures, via cytochrome C (Cyt C), an ET protein with a heme (Fe-porphyrin) prosthetic group as a redox centre. We compare the ETp to electrochemical ET measurements, and do so also for the protein without the Fe (with metal-free porphyrin) and without porphyrin. As removing the porphyrin irreversibly alters the protein's conformation, we repeat these measurements with human serum albumin (HSA), 'doped' (by non-covalent binding) with a single hemin equivalent, i.e., these natural and artificial proteins share a common prosthetic group. ETp via Cyt C and HSA-hemin are very similar in terms of current magnitude and temperature dependence, which suggests similar ETp mechanisms via these two systems, thermally activated hopping (with ~0.1 eV activation energy) >190 K and tunneling by superexchange Fe(3+) + e(-)), measured by electrochemistry of HSA-hemin are only 4 times lower than those for Cyt C. However, while removing the Fe redox centre from the porphyrin ring markedly affects the ET rate, it hardly changes the ETp currents through these proteins, while removing the macrocycle (from HSA, which retains its conformation) significantly reduces ETp efficiency. These results show that solid-state ETp across proteins does not require the presence of a redox cofactor, and that while for ET the Fe ion is the main electron mediator, for ETp the porphyrin ring has this function.

  10. Evaluation of Antiproliferative Potential of Cerium Oxide Nanoparticles on HeLa Human Cervical Tumor Cell

    Directory of Open Access Journals (Sweden)

    Zoriţa Diaconeasa

    2015-05-01

    Full Text Available Cerium oxide nanoparticles (CeO2 nanoparticles as nanomaterials have promising biomedical applications. In this paper, the cytotoxicity induced by CONPs human cervical tumor cells was investigated. Cerium oxide nanoparticles were synthesized using the precipitation method. The nanoparticles were found to inhibit the proliferation of HeLa human cervical tumor cells in a dose dependent manner but did not showed to be cytotoxic as analyzed by MTT assay. The administrated treatment decreased the HeLa cell viability cells from 100% to 65% at the dose of 100 μg/mL.

  11. The kinetics of the cerium(IV)-uranium(IV) reaction at low sulfate concentrations

    International Nuclear Information System (INIS)

    Michaille, P.; Kikindai, T.

    1977-01-01

    The rate of oxidation of uranium(IV) by cerium(IV) was measured with a stopped-flow spectrophotometer at sulfuric acid concentrations of 2 x 10 -6 to 0.5 M. At a constant hydrogen ion concentration of 0.5 M, the maximum rate constant was observed for 2 x 10 -3 M sulfuric acid; at that concentration, two sulfate ions were involved in the activated complex. The dependence of the rate constant on the hydrogen ion concentration showed that the reaction paths involving one or two sulfate ions also involved one hydroxyl ion, whereas one hydrogen ion was involved in the five sulfate dependent path. Spectrophotometric measurements supported the existence of a hydrolyzed monosulfatocomplex of cerium(IV). (author)

  12. Thermal expansion and transformation behavior of cerium and plutonium alloys: an application of the Aptekar-Ponyatovsky regular solution model.

    Science.gov (United States)

    Lawson, A C; Lashley, J C

    2011-09-14

    In this paper we apply the Aptekar-Ponyatovsky (AP) regular solution thermodynamic model to the analysis of experimental data for the coefficient of thermal expansion (CTE) and determine the AP model parameters for unalloyed cerium metal, Ce-Th-La alloys, and Pu-Ga alloys. We find that the high temperature CTE of cerium metal follows the predictions of the AP model based on low temperature, high pressure data. For Ce-Th-La alloys we use the AP parameters to track the suppression of the first-order γ-α cerium transition. We show the AP model accounts for the negative CTE observed for Pu-Ga alloys and is equivalent to an earlier invar model. Finally, we apply the AP parameters obtained for Pu-Ga alloys to rationalize the observed δ-α transformation pressures of these alloys. We show that the anomalous values of the Grüneisen and Grüneisen-Anderson parameters are important features of the thermal properties of plutonium. A strong analogy between the properties of plutonium and cerium is confirmed.

  13. Electrochemical separation of cerium and yttrium in molten chlorides on liquid-metallic electrodes

    International Nuclear Information System (INIS)

    Yamshchikov, L.F.; Lebedev, V.A.; Nichkov, I.F.

    1978-01-01

    An estimating calculation of the coefficients of separation of cerium and yttrium in the process of electrolysis in molten salts on liquid electrodes of aluminium, gallium, indium, lead, tin, antimonium and zinc is carried out. The calculation of the separation coefficients was carried out according to the known values of activation coefficients of cerium and yttrium in fusible metals. The electrolysis was carried out at 973 K in the argon air in the cell with an eutectic mixture of NaCl and KCl as an elactrolyte. It is shown that the salten phase is concentrated by yttrium, and the melallic one- by cerium on all the electrodes. The value of the separation coefficient of Ce and Y is considerably high and continuously increases on the fusible metals in the Zn, In, Ga, Al, Pb, Sn, Sb series. The experimental values of the separation coefficients practically coincide with the theoretically calculated ones, testifying to the possibility of the effective separation of elements even in a single-staged possibility of the effective separation of elements even in a single-staged process. An electrolysis of molten salts is not inferior in its selectivity to the universally recognized methods of the fine purification of substances permitting to separate Ce and Y with the Ksub(sep) approximately equal to 10

  14. Redox Behavior of Fe2+/Fe3+ Redox Couple by Absorption Spectroscopy and Measurement

    International Nuclear Information System (INIS)

    Oh, J. Y.; Park, S.; Yun, J. I.

    2010-01-01

    Redox behavior has influences on speciation and other geochemical reactions of radionuclides such as sorption, solubility, and colloid formation, etc. It is one of the factors for evaluation of long-term safety assessment under high-level radioactive waste (HLW) disposal conditions. Accordingly, redox potential (Eh) measurement in aquatic system is important to investigate the redox conditions. Eh is usually measured with redox active electrodes (Pt, Au, glassy carbon, etc.). Nevertheless, Eh measurements by general methods using electrodes provide low accuracy and high uncertainty problem. Therefore, Eh calculated from the concentration of redox active elements with a proper complexing reagent by using UV-Vis absorption spectroscopy is progressed. Iron exists mostly as spent nuclear waste container material and in hydro-geologic minerals. In this system, iron controls the redox condition in near-field area and influences chemical behavior and speciation of radionuclides including redox sensitive actinides such as U, Np, and Pu. In the present work, we present the investigation on redox phenomena of iron in aquatic system by a combination of absorption spectroscopy and redox potential measurements

  15. Study of cerium doped magnetite (Fe{sub 3}O{sub 4}:Ce)/PMMA nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Padalia, Diwakar, E-mail: Padalia.diwakar@gmail.com [Department of Physics, G.B. Pant University of Agriculture and Technology, Pantnagar, Uttrakhand (India); Johri, U.C. [Department of Physics, G.B. Pant University of Agriculture and Technology, Pantnagar, Uttrakhand (India); Zaidi, M.G.H. [Supercritical Fluid Processing Laboratory, Department of Chemistry, G.B. Pant University of Agriculture and Technology, Pantnagar, Uttrakhand (India)

    2012-03-01

    The paper presents the synthesis and properties of polymer nanocomposite material based on cerium doped magnetite (Fe{sub 3}O{sub 4}) as filler material and poly methyl methacrylate (PMMA) as host matrix. The magnetite (Fe{sub 3}O{sub 4}) particles were synthesized by co-precipitation route using stable ferrous and ferric salts with ammonium hydroxide as precipitating agent. Further, they doped by cerium oxide (CeO{sub 2}) non-stoichiometrically. The composite material was fabricated by solvent evaporation method. Here 2.4 GHz microwaves were used to study the effect of microwaves heating on polymerization. The phase and crystal structure is determined by X-ray diffraction (XRD). The average crystallite size of the composites varies from 28 to 35 nm. The chemical structure is confirmed by Fourier transform infrared (FTIR) spectroscopy. The magnetic and thermal properties are investigated by vibrating sample magnetometer (VSM) and differential scanning calorimetry (DSC). The thermal study shows that the microwave heated samples possess higher glass transition temperature (T{sub g}). The magnetic results suggest that coercivity (H{sub C}) and squareness (M{sub r}/M{sub s}) of the loop increases with increasing doping percent of cerium.

  16. Characterization of composite metal-ceramic of nickel-oxide cerium doped gadolinium

    International Nuclear Information System (INIS)

    Silva, M.L.A. da; Varela, M.C.R.S.

    2016-01-01

    Composite nickel doped cerium oxide are used in SOFC anode materials. In this study we evaluated the effect of the presence of gadolinium on the properties of composite nickel and ceria and. The supports were synthesized by sol-gel method. The impregnation with nickel nitrate was taken sequentially, followed by calcination. The materials were characterized by X-ray diffraction, measurement of specific surface area, temperature programmed reduction, Raman spectroscopy. The presence of gadolinium retained the fluorite structure of ceria by forming a solid solution, also not influencing significantly on the specific surface area of the support. On the other hand, there was a decrease in the area catalysts, which can be attributed to sintering of nickel. Furthermore, addition of gadolinium favored the formation of intrinsic and extrinsic vacancies in cerium oxide, which leads to an increase in the ionic conductivity of the solid, desirable property for an SOFC anode catalyst. (author)

  17. Growth of monodisperse nanocrystals of cerium oxide during synthesis and annealing

    International Nuclear Information System (INIS)

    Ghosh, Swapankumar; Divya, Damodaran; Remani, Kottayilpadi C.; Sreeremya, Thadathil S.

    2010-01-01

    Monodisperse cerium oxide nanocrystals have been successfully synthesised using simple ammonia precipitation technique from cerium(III) nitrate solution at different temperatures in the range 35-80 o C. The activation energy for growth of CeO 2 nanocrystals during the precipitation is calculated as 11.54 kJ/mol using Arrhenius plot. Average crystal diameter was obtained from XRD analysis, HR-TEM and light scattering (PCS). The analysis of size data from HR-TEM images and PCS clearly indicated the formation of highly crystalline CeO 2 particles in narrow size range. CeO 2 nanocrystals precipitated at 35 o C were further annealed at temperatures in the range 300-700 o C. The activation energy for crystal growth during annealing is also calculated and is close to the reported values. An effort is made to predict the mechanism of crystal growth during the precipitation and annealing.

  18. Molecular absorption spectra of beryllium, cerium, lanthanum, iron, and platinum salts

    International Nuclear Information System (INIS)

    Daidoji, Hidehiro

    1980-01-01

    The absorption spectra of some salts of beryllium, cerium, lanthanum, iron and platinum in air-acetylene flame were measured in the wavelength range from 200 to 400 nm. A Hitachi 207 type atomic absorption spectrophotometer was used. A deuterium lamp, a home-made continuous radiation lamp and some hollow cathode lamps were used as light sources. The new molecular absorption spectra of cerium, lanthanum and platinum and the absorption spectra due to Be(OH) 2 , LaO, PtH, FeO and FeCl in 200-400 nm region were obtained. Emission spectra of CeO, LaO and FeOH were also obtained. These molecular absorption bands were estimated as absorption errors of maximum 15 times to the sensitivity of each elements in atomic absorption spectrometry. In addition, spectral line interferences of iron were observed in atomic absorption spectrometry of Zn, Cd, Ni, Cu and Cr. (author)

  19. Preparation and characterization of gelatin/cerium(Ⅲ) film

    Institute of Scientific and Technical Information of China (English)

    黄崇军; 黄雅钦; 田娜; 童元建; 殷瑞贤

    2010-01-01

    A novel gelatin film with antibacterial activity was prepared by electrostatic crosslinking using cerium (Ⅲ) nitrate hexahydrate as the crosslinking agent. The structure and properties of the films were investigated by Fourier transform infrared spectra, tensile tests, thermogravimetric analysis, static drop contact angle and disc diffusion method. The results showed that cross-linking could not only improve the thermal and mechanical properties and lower the hydrophilic property of the films, but also make...

  20. Photocatalytic action of cerium molybdate and iron-titanium oxide hollow nanospheres on Escherichia coli

    International Nuclear Information System (INIS)

    Kartsonakis, I. A.; Kontogiani, P.; Pappas, G. S.; Kordas, G.

    2013-01-01

    This study is focused on the production of hollow nanospheres that reveal antibacterial action. Cerium molybdate and iron-titanium oxide hollow nanospheres with a diameter of 175 ± 15 and 221 ± 10 nm, respectively, were synthesized using emulsion polymerization and the sol–gel process. Their morphology characterization was accomplished using scanning electron microscopy. Their antibacterial action was examined on pure culture of Escherichia coli considering the loss of their viability. Both hollow nanospheres presented photocatalytic action after illumination with blue–black light, but those of cerium molybdate also demonstrated photocatalytic action in the dark. Therefore, the produced nanospheres can be used for antibacterial applications.

  1. Preparation of Carbon-Platinum-Ceria and Carbon-Platinum-Cerium catalysts and its application in Polymer Electrolyte Fuel Cell: Hydrogen, Methanol, and Ethanol

    Science.gov (United States)

    Guzman Blas, Rolando Pedro

    This thesis is focused on fuel cells using hydrogen, methanol and ethanol as fuel. Also, in the method of preparation of catalytic material for the anode: Supercritical Fluid Deposition (SFD) and impregnation method using ethylenediaminetetraacetic acid (EDTA) as a chelating agent. The first part of the thesis describes the general knowledge about Hydrogen Polymer Exchange Membrane Fuel Cell (HPEMFC),Direct Methanol Fuel Cell (DMFC) and Direct Ethanol Fuel Cell (DEFC), as well as the properties of Cerium and CeO2 (Ceria). The second part of the thesis describes the preparation of catalytic material by Supercritical Fluid Deposition (SFD). SFD was utilized to deposit Pt and ceria simultaneously onto gas diffusion layers. The Pt-ceria catalyst deposited by SFD exhibited higher methanol oxidation activity compared to the platinum catalyst alone. The linear sweep traces of the cathode made for the methanol cross over study indicate that Pt-Ceria/C as the anode catalyst, due to its better activity for methanol, improves the fuel utilization, minimizing the methanol permeation from anode to cathode compartment. The third and fourth parts of the thesis describe the preparation of material catalytic material Carbon-Platinum-Cerium by a simple and cheap impregnation method using EDTA as a chelating agent to form a complex with cerium (III). This preparation method allows the mass production of the material catalysts without additional significant cost. Fuel cell polarization and power curves experiments showed that the Carbon-Platinum-Cerium anode materials exhibited better catalytic activity than the only Vulcan-Pt catalysts for DMFC, DEFC and HPEMFC. In the case of Vulcan-20%Pt-5%w Cerium, this material exhibits better catalytic activity than the Vulcan-20%Pt in DMFC. In the case of Vulcan-40% Pt-doped Cerium, this material exhibits better catalytic activity than the Vulcan-40% Pt in DMFC, DEFC and HPEMFC. Finally, I propose a theory that explains the reason why the

  2. Redox regulation of cell proliferation: Bioinformatics and redox proteomics approaches to identify redox-sensitive cell cycle regulators.

    Science.gov (United States)

    Foyer, Christine H; Wilson, Michael H; Wright, Megan H

    2018-03-29

    Plant stem cells are the foundation of plant growth and development. The balance of quiescence and division is highly regulated, while ensuring that proliferating cells are protected from the adverse effects of environment fluctuations that may damage the genome. Redox regulation is important in both the activation of proliferation and arrest of the cell cycle upon perception of environmental stress. Within this context, reactive oxygen species serve as 'pro-life' signals with positive roles in the regulation of the cell cycle and survival. However, very little is known about the metabolic mechanisms and redox-sensitive proteins that influence cell cycle progression. We have identified cysteine residues on known cell cycle regulators in Arabidopsis that are potentially accessible, and could play a role in redox regulation, based on secondary structure and solvent accessibility likelihoods for each protein. We propose that redox regulation may function alongside other known posttranslational modifications to control the functions of core cell cycle regulators such as the retinoblastoma protein. Since our current understanding of how redox regulation is involved in cell cycle control is hindered by a lack of knowledge regarding both which residues are important and how modification of those residues alters protein function, we discuss how critical redox modifications can be mapped at the molecular level. Crown Copyright © 2018. Published by Elsevier Inc. All rights reserved.

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  4. A density functional theory study on the active center of Fe-only hydrogenase: characterization and electronic structure of the redox states.

    Science.gov (United States)

    Liu, Zhi-Pan; Hu, P

    2002-05-08

    We have carried out extensive density functional theory (DFT) calculations for possible redox states of the active center in Fe-only hydrogenases. The active center is modeled by [(H(CH(3))S)(CO)(CN(-))Fe(p)(mu-DTN)(mu-CO)Fe(d)(CO)(CN(-))(L)](z)() (z is the net charge in the complex; Fe(p)= the proximal Fe, Fe(d) = the distal Fe, DTN = (-SCH(2)NHCH(2)S-), L is the ligand that bonds with the Fe(d) at the trans position to the bridging CO). Structures of possible redox states are optimized, and CO stretching frequencies are calculated. By a detailed comparison of all the calculated structures and the vibrational frequencies with the available experimental data, we find that (i) the fully oxidized, inactive state is an Fe(II)-Fe(II) state with a hydroxyl (OH(-)) group bonded at the Fe(d), (ii) the oxidized, active state is an Fe(II)-Fe(I) complex which is consistent with the assignment of Cao and Hall (J. Am. Chem. Soc. 2001, 123, 3734), and (iii) the fully reduced state is a mixture with the major component being a protonated Fe(I)-Fe(I) complex and the other component being its self-arranged form, Fe(II)-Fe(II) hydride. Our calculations also show that the exogenous CO can strongly bond with the Fe(II)-Fe(I) species, but cannot bond with the Fe(I)-Fe(I) complex. This result is consistent with experiments that CO tends to inhibit the oxidized, active state, but not the fully reduced state. The electronic structures of all the redox states have been analyzed. It is found that a frontier orbital which is a mixing state between the e(g) of Fe and the 2 pi of the bridging CO plays a key role concerning the reactivity of Fe-only hydrogenases: (i) it is unoccupied in the fully oxidized, inactive state, half-occupied in the oxidized, active state, and fully occupied in the fully reduced state; (ii) the e(g)-2 pi orbital is a bonding state, and this is the key reason for stability of the low oxidation states, such as Fe(I)-Fe(I) complexes; and (iii) in the e(g)-2 pi orbital

  5. Ab initio molecular dynamics study of the properties of cerium in liquid sodium at 1000 K temperature

    Energy Technology Data Exchange (ETDEWEB)

    Samin, Adib; Li, Xiang; Zhang, Jinsuo [Nuclear Engineering Program, Department of Mechanical and Aerospace Engineering, The Ohio State University, 201 W 19th Avenue, Columbus, Ohio 43210 (United States); Mariani, R. D. [Idaho National Laboratory, Materials and Fuels Complex, Idaho Falls, Idaho 83415 (United States); Unal, Cetin [Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, New Mexico 87545 (United States)

    2015-12-21

    For liquid-sodium-cooled fast nuclear reactor systems, it is crucial to understand the behavior of lanthanides and other potential fission products in liquid sodium or other liquid metal solutions such as liquid cesium-sodium. In this study, we focus on lanthanide behavior in liquid sodium. Using ab initio molecular dynamics, we found that the solubility of cerium in liquid sodium at 1000 K was less than 0.78 at. %, and the diffusion coefficient of cerium in liquid sodium was calculated to be 5.57 × 10{sup −9} m{sup 2}/s. Furthermore, it was found that cerium in small amounts may significantly alter the heat capacity of the liquid sodium system. Our results are consistent with the experimental results for similar materials under similar conditions.

  6. Visualization of Nicotine Adenine Dinucleotide Redox Homeostasis with Genetically Encoded Fluorescent Sensors.

    Science.gov (United States)

    Zhao, Yuzheng; Zhang, Zhuo; Zou, Yejun; Yang, Yi

    2018-01-20

    Beyond their roles as redox currency in living organisms, pyridine dinucleotides (NAD + /NADH and NADP + /NADPH) are also precursors or cosubstrates of great significance in various physiologic and pathologic processes. Recent Advances: For many years, it was challenging to develop methodologies for monitoring pyridine dinucleotides in situ or in vivo. Recent advances in fluorescent protein-based sensors provide a rapid, sensitive, specific, and real-time readout of pyridine dinucleotide dynamics in single cells or in vivo, thereby opening a new era of pyridine dinucleotide bioimaging. In this article, we summarize the developments in genetically encoded fluorescent sensors for NAD + /NADH and NADP + /NADPH redox states, as well as their applications in life sciences and drug discovery. The strengths and weaknesses of individual sensors are also discussed. These sensors have the advantages of being specific and organelle targetable, enabling real-time monitoring and subcellular-level quantification of targeted molecules in living cells and in vivo. NAD + /NADH and NADP + /NADPH have distinct functions in metabolic and redox regulation, and thus, a comprehensive evaluation of metabolic and redox states must be multiplexed with a combination of various metabolite sensors in a single cell. Antioxid. Redox Signal. 28, 213-229.

  7. Potential redox behaviour on industrial wastes treatment; Evolucion del potencial redox en tratamiento y depuracion industrial de aguas

    Energy Technology Data Exchange (ETDEWEB)

    Marin Galvin, R.; rodriguez Mellado, J. M.; Ruiz Montoya, M.; Jimenez Gamero, C. [Departamento Quimica Fisica y Termodinamica aplicada, Facultad de ciencias, Universidad de Cordoba (Spain)

    1995-12-31

    A study over the behaviour of redox potential in waters and wastewaters under industrial treatment processes has been carried out. In both cases, the potential-time curves obtained were in a logarithmical shape being more strongly distorted when the waters contained more dissolved and suspended compounds. Oxygen fundamentally leads the redox state in wastewaters, although ozone and chlorine almost oxygen lead the redox potential in raw waters intended to drinking water production. In this way, by increasing 210 m V the E{sub H} value of water or maintaining the rH>21.8 it can be industrially sterilized the drinking water. On the other hand, increases of 350 mV in the EH values from wastewaters influent to plant to the treated waters, allowed discarding 450 mg/l of DQO and 9 mg/l of NH{sub 3} from the former. Finally, the exploitation of the Wastewaters Treatment Plant by regulation of the E{sub H} values can suppose a good practice. (Author) 14 refs.

  8. Molecular Orbital Principles of Oxygen-Redox Battery Electrodes.

    Science.gov (United States)

    Okubo, Masashi; Yamada, Atsuo

    2017-10-25

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

  9. Performance characteristics of silver cerium vanadate batteries

    OpenAIRE

    Arof , Abdul; Kamaluddin , Burhanuddin; Radhakrishna , S.

    1993-01-01

    Stoichiometric ratios of AR grade AgI, Ag2O, V2O5 and CeO2 were melted in a furnace and the melt was rapidly quenched to liquid nitrogen temperature to form a glass. The glassy nature of the sample has been confirmed by powder X-ray diffraction technique. The microstructure and microanalysis studies of the silver cerium vanadate (SCV) have been carried out by scanning electron microscopy (SEM) and energy dispersive analysis of X-rays (EDAX). The SEM micrograph of the as-quenched melt showed c...

  10. Redox reactions with empirical potentials: Atomistic battery discharge simulations

    OpenAIRE

    Dapp, Wolf B.; Müser, Martin H.

    2013-01-01

    Batteries are pivotal components in overcoming some of today's greatest technological challenges. Yet to date there is no self-consistent atomistic description of a complete battery. We take first steps toward modeling of a battery as a whole microscopically. Our focus lies on phenomena occurring at the electrode-electrolyte interface which are not easily studied with other methods. We use the redox split-charge equilibration (redoxSQE) method that assigns a discrete ionization state to each ...

  11. Growth of monodisperse nanocrystals of cerium oxide during synthesis and annealing

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Swapankumar, E-mail: swapankumar.ghosh2@mail.dcu.ie; Divya, Damodaran [National Institute for Interdisciplinary Science and Technology (NIIST), Council of Scientific and Industrial Research (CSIR) (India); Remani, Kottayilpadi C. [Sree Neelakanda Government Sanskrit College, Department of Chemistry (India); Sreeremya, Thadathil S. [National Institute for Interdisciplinary Science and Technology (NIIST), Council of Scientific and Industrial Research (CSIR) (India)

    2010-06-15

    Monodisperse cerium oxide nanocrystals have been successfully synthesised using simple ammonia precipitation technique from cerium(III) nitrate solution at different temperatures in the range 35-80 {sup o}C. The activation energy for growth of CeO{sub 2} nanocrystals during the precipitation is calculated as 11.54 kJ/mol using Arrhenius plot. Average crystal diameter was obtained from XRD analysis, HR-TEM and light scattering (PCS). The analysis of size data from HR-TEM images and PCS clearly indicated the formation of highly crystalline CeO{sub 2} particles in narrow size range. CeO{sub 2} nanocrystals precipitated at 35 {sup o}C were further annealed at temperatures in the range 300-700 {sup o}C. The activation energy for crystal growth during annealing is also calculated and is close to the reported values. An effort is made to predict the mechanism of crystal growth during the precipitation and annealing.

  12. Redox active molecules cytochrome c and vitamin C enhance heme-enzyme peroxidations by serving as non-specific agents for redox relay

    International Nuclear Information System (INIS)

    Gade, Sudeep Kumar; Bhattacharya, Subarna; Manoj, Kelath Murali

    2012-01-01

    Highlights: ► At low concentrations, cytochrome c/vitamin C do not catalyze peroxidations. ► But low levels of cytochrome c/vitamin C enhance diverse heme peroxidase activities. ► Enhancement positively correlates to the concentration of peroxide in reaction. ► Reducible additives serve as non-specific agents for redox relay in the system. ► Insight into electron transfer processes in routine and oxidative-stress states. -- Abstract: We report that incorporation of very low concentrations of redox protein cytochrome c and redox active small molecule vitamin C impacted the outcome of one-electron oxidations mediated by structurally distinct plant/fungal heme peroxidases. Evidence suggests that cytochrome c and vitamin C function as a redox relay for diffusible reduced oxygen species in the reaction system, without invoking specific or affinity-based molecular interactions for electron transfers. The findings provide novel perspectives to understanding – (1) the promiscuous role of cytochrome b 5 in the metabolism mediated by liver microsomal xenobiotic metabolizing systems and (2) the roles of antioxidant molecules in affording relief from oxidative stress.

  13. Geochemistry of Natural Redox Fronts

    International Nuclear Information System (INIS)

    Hofmann, B.A.

    1999-05-01

    Redox fronts are important geochemical boundaries which need to be considered in safety assessment of deep repositories for radioactive waste. In most cases, selected host-rock formations will be reducing due to the presence of ferrous minerals, sulphides, etc. During construction and operation of the repository, air will be introduced into the formation. After repository closure, oxidising conditions may persist locally until all oxygen is consumed. In the case of high-level waste, radiolysis of water may provide an additional source of oxidants. Oxidising conditions within a repository are thus possible and potentially have a strong influence on the mobility of many elements. The rate of movement of redox fronts, the boundary between oxidising and reducing environments, and their influence on migrating radionuclides are thus important factors influencing repository performance. The present report is a review of elemental behaviour at natural redox fronts, based on published information and work of the author. Redox fronts are geochemically and geometrically variable manifestations of a global interface between generally oxidising geochemical milieux in contact with the atmosphere and generally reducing milieux in contact with rocks containing ferrous iron, sulphide and/or organic carbon. A classification of redox fronts based on a subdivision into continental near-surface, marine near-surface, and deep environments is proposed. The global redox interface is often located close to the surface of rocks and sediments and, sometimes, within bodies of water. Temperature conditions are close to ambient. A deeper penetration of the global redox front to depths of several kilometres is found in basins containing oxidised sediments (red beds) and in some hydrothermal circulation systems. Temperatures at such deep redox fronts may reach 200 o C. Both near-surface and deep redox fronts are sites of formation of economic deposits of redox-sensitive elements, particularly of

  14. Optical imaging the redox status change during cell apoptosis

    Science.gov (United States)

    Su, Ting; Zhang, Zhihong; Lin, Juqiang; Luo, Qingming

    2007-02-01

    Many cellular events involve the alteration in redox equilibrium, globally or locally. In many cases, excessive reactive oxygen species (ROS) production is the underlying cause. Several green fluoresecence protein based indicators are constructed to measure redox status in cells, e.g, rxYFP and roGFPs, which allow real time detection. reduction and oxidization-sensitive GFP (RoGFPs) are more useful due to ratiometric variation by excitation, making the measurement more accurate. Utilizing one of those roGFPs called roGFP1, we establish a mitochondrial redox state probing platform in HeLa cells with laser scan confocal microscopy (LSCM) as detection system. Control experiments confirmed that our platform could produce stable ratiometric values, which made the data more accurately reflect the real environmental changes of redox status that roGFP1 probed. Using exogenous H IIO II and DTT, we evaluated the reactivity and reversibility of roGFP1. The minimal hydrogen peroxide concentration that roGFP1 could show detectable ratiometric changes in our system was about 200μM. Preliminarily applying our platform to exploring the redox status during apoptosis, we observed an increase in ratiometric, suggesting an excessive ROS production.

  15. Redox signaling in plants.

    Science.gov (United States)

    Foyer, Christine H; Noctor, Graham

    2013-06-01

    Our aim is to deliver an authoritative and challenging perspective of current concepts in plant redox signaling, focusing particularly on the complex interface between the redox and hormone-signaling pathways that allow precise control of plant growth and defense in response to metabolic triggers and environmental constraints and cues. Plants produce significant amounts of singlet oxygen and other reactive oxygen species (ROS) as a result of photosynthetic electron transport and metabolism. Such pathways contribute to the compartment-specific redox-regulated signaling systems in plant cells that convey information to the nucleus to regulate gene expression. Like the chloroplasts and mitochondria, the apoplast-cell wall compartment makes a significant contribution to the redox signaling network, but unlike these organelles, the apoplast has a low antioxidant-buffering capacity. The respective roles of ROS, low-molecular antioxidants, redox-active proteins, and antioxidant enzymes are considered in relation to the functions of plant hormones such as salicylic acid, jasmonic acid, and auxin, in the composite control of plant growth and defense. Regulation of redox gradients between key compartments in plant cells such as those across the plasma membrane facilitates flexible and multiple faceted opportunities for redox signaling that spans the intracellular and extracellular environments. In conclusion, plants are recognized as masters of the art of redox regulation that use oxidants and antioxidants as flexible integrators of signals from metabolism and the environment.

  16. An Auger and XPS survey of cerium active corrosion protection for AA2024-T3 aluminum alloy

    Energy Technology Data Exchange (ETDEWEB)

    Uhart, A. [IPREM-ECP-UMR CNRS 5254, Université de Pau et des Pays de l' Adour, Technopole Hélioparc, 2 Avenue Président Pierre Angot, 64053 Pau Cedex 09 (France); Ledeuil, J.B. [IPREM-ECP-UMR CNRS 5254, Université de Pau et des Pays de l' Adour, Technopole Hélioparc, 2 Avenue Président Pierre Angot, 64053 Pau Cedex 09 (France); Université de Toulouse, UPS-INP-CNRS, Institut Carnot CIRIMAT, 118 Route de Narbonne, 31062 Toulouse Cedex 09 (France); Gonbeau, D. [IPREM-ECP-UMR CNRS 5254, Université de Pau et des Pays de l' Adour, Technopole Hélioparc, 2 Avenue Président Pierre Angot, 64053 Pau Cedex 09 (France); Dupin, J.C., E-mail: dupin@univ-pau.fr [IPREM-ECP-UMR CNRS 5254, Université de Pau et des Pays de l' Adour, Technopole Hélioparc, 2 Avenue Président Pierre Angot, 64053 Pau Cedex 09 (France); Bonino, J.P.; Ansart, F. [Université de Toulouse, UPS-INP-CNRS, Institut Carnot CIRIMAT, 118 Route de Narbonne, 31062 Toulouse Cedex 09 (France); Esteban, J. [Messier-Bugatti-Dowty, Etablissement de Molsheim, 3, rue Antoine de St Exupéry, 67129 Molsheim (France)

    2016-12-30

    Graphical abstract: Coupled SAM/SEM survey of cerium inhibitor migration towards corrosion pits in a conversion coating over AA2024-T3 substrate. - Highlights: • XPS evidenced the proximity of the inhibitor with the surface AA2024 alloy. • Cerium conversion coatings with [Ce] = 0.1 M offer the best corrosion resistance. • SAM shown the migration of Ce + III entities towards the corrosion pits or crevices. • High resolution analyses (Auger) connecting the nano-scale order with the chemical distribution.

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

    Science.gov (United States)

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

    2018-01-20

    The nicotinamide adenine dinucleotide (NAD + )/reduced NAD + (NADH) and NADP + /reduced NADP + (NADPH) redox couples are essential for maintaining cellular redox homeostasis and for modulating numerous biological events, including cellular metabolism. Deficiency or imbalance of these two redox couples has been associated with many pathological disorders. Recent Advances: Newly identified biosynthetic enzymes and newly developed genetically encoded biosensors enable us to understand better how cells maintain compartmentalized NAD(H) and NADP(H) pools. The concept of redox stress (oxidative and reductive stress) reflected by changes in NAD(H)/NADP(H) has increasingly gained attention. The emerging roles of NAD + -consuming proteins in regulating cellular redox and metabolic homeostasis are active research topics. The biosynthesis and distribution of cellular NAD(H) and NADP(H) are highly compartmentalized. It is critical to understand how cells maintain the steady levels of these redox couple pools to ensure their normal functions and simultaneously avoid inducing redox stress. In addition, it is essential to understand how NAD(H)- and NADP(H)-utilizing enzymes interact with other signaling pathways, such as those regulated by hypoxia-inducible factor, to maintain cellular redox homeostasis and energy metabolism. Additional studies are needed to investigate the inter-relationships among compartmentalized NAD(H)/NADP(H) pools and how these two dinucleotide redox couples collaboratively regulate cellular redox states and cellular metabolism under normal and pathological conditions. Furthermore, recent studies suggest the utility of using pharmacological interventions or nutrient-based bioactive NAD + precursors as therapeutic interventions for metabolic diseases. Thus, a better understanding of the cellular functions of NAD(H) and NADP(H) may facilitate efforts to address a host of pathological disorders effectively. Antioxid. Redox Signal. 28, 251-272.

  18. Molecular imaging of in vivo redox dynamics using magnetic resonance system

    International Nuclear Information System (INIS)

    Utsumi, Hideo; Yasukawa, Keiji

    2008-01-01

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

  19. Cerium chloride stimulated controlled conversion of B-to-Z DNA in self-assembled nanostructures

    International Nuclear Information System (INIS)

    Bhanjadeo, Madhabi M.; Nayak, Ashok K.; Subudhi, Umakanta

    2017-01-01

    DNA adopts different conformation not only because of novel base pairs but also while interacting with inorganic or organic compounds. Self-assembled branched DNA (bDNA) structures or DNA origami that change conformation in response to environmental cues hold great promises in sensing and actuation at the nanoscale. Recently, the B-Z transition in DNA is being explored to design various nanomechanical devices. In this communication we have demonstrated that Cerium chloride binds to the phosphate backbone of self-assembled bDNA structure and induce B-to-Z transition at physiological concentration. The mechanism of controlled conversion from right-handed to left-handed has been assayed by various dye binding studies using CD and fluorescence spectroscopy. Three different bDNA structures have been identified to display B-Z transition. This approach provides a rapid and reversible means to change bDNA conformation, which can be used for dynamic and progressive control at the nanoscale. - Highlights: • Cerium-induced B-to-Z DNA transition in self-assembled nanostructures. • Lower melting temperature of Z-DNA than B-DNA confirmed by CD spectroscopy. • Binding mechanism of cerium chloride is explained using fluorescence spectroscopy. • Right-handed to left-handed DNA conformation is also noticed in modified bDNA structure.

  20. Assessment of the abatement of acelsulfame K using cerium doped ZnO as photocatalyst

    International Nuclear Information System (INIS)

    Calza, P.; Gionco, C.; Giletta, M.; Kalaboka, M.; Sakkas, V.A.; Albanis, T.; Paganini, M.C.

    2017-01-01

    Highlights: • Hydrothermal synthesis and characterization of Ce doped ZnO. • The abatement of ACE K is assessed in ultrapure water and in river water matrix. • Demonstrated higher degradation activity than P25 under visible light. • The degradation activity is less affected in river water than for P25. - Abstract: In the present study, we investigated the possibility to abate Acesulfame K, a persistent emerging contaminant, in aqueous media using zinc oxide based materials. For this purpose, bare and Ce-doped zinc oxide was prepared via an easy and cheap hydrothermal process using different cerium salts as precursors. Their photocatalytic performance was evaluated in different media, namely ultrapure and river water under both UV–vis and visible light. Commercial TiO_2 P25 was also employed and used as a reference photocatalyst for comparison purposes. The obtained results pointed out that cerium doped zinc oxide composites exhibit higher performance than TiO_2 P25, especially under visible light and in the presence of organic matter, when the activity of the latter is greatly depressed. In particular, ZnO doped with cerium (1%) was the most effective material, and could be a promising alternative to TiO_2 P25, especially in the treatment of natural waters.

  1. Effect of nano-sized cerium-zirconium oxide solid solution on far-infrared emission properties of tourmaline powders

    Science.gov (United States)

    Guo, Bin; Yang, Liqing; Hu, Weijie; Li, Wenlong; Wang, Haojing

    2015-10-01

    Far-infrared functional nanocomposites were prepared by the co-precipitation method using natural tourmaline (XY3Z6Si6O18(BO3)3V3W, where X is Na+, Ca2+, K+, or vacancy; Y is Mg2+, Fe2+, Mn2+, Al3+, Fe3+, Mn3+, Cr3+, Li+, or Ti4+; Z is Al3+, Mg2+, Cr3+, or V3+; V is O2-, OH-; and W is O2-, OH-, or F-) powders, ammonium cerium(IV) nitrate and zirconium(IV) nitrate pentahydrate as raw materials. The reference sample, tourmaline modified with ammonium cerium(IV) nitrate alone was also prepared by a similar precipitation route. The results of Fourier transform infrared spectroscopy show that tourmaline modified with Ce and Zr has a better far-infrared emission property than tourmaline modified with Ce alone. Through characterization by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), the mechanism for oxygen evolution during the heat process in the two composite materials was systematically studied. The XPS spectra show that Fe3+ ratio inside tourmaline modified with Ce alone can be raised by doping Zr. Moreover, it is showed that there is a higher Ce3+ ratio inside the tourmaline modified with Ce and Zr than tourmaline modified with Ce alone. In addition, XRD results indicate the formation of CeO2 and Ce1-xZrxO2 crystallites during the heat treatment and further TEM observations show they exist as nanoparticles on the surface of tourmaline powders. Based on these results, we attribute the improved far-infrared emission properties of Ce-Zr doped tourmaline to the enhanced unit cell shrinkage of the tourmaline arisen from much more oxidation of Fe2+ to Fe3+ inside the tourmaline caused by the change in the catalyst redox properties of CeO2 brought about by doping with Zr4+. In all samples, tourmaline modified with 7.14 wt.% Ce and 1.86 wt.% Zr calcined at 800∘C for 5 h has the best far-infrared emission property with the maximum emissivity value of 98%.

  2. Microstructure and electrochemical behavior of cerium conversion coating modified with silane agent on magnesium substrates

    Science.gov (United States)

    Lei, Li; Shi, Jing; Wang, Xin; Liu, Dan; Xu, Haigang

    2016-07-01

    The cerium conversion coating with and without different concentrations of silane agent bis-(γ-triethoxysilylpropyl)-tetrasulfide (BTESPT) modification is obtained on magnesium alloys. Detailed properties of the coatings and the role of BTESPT as an additive are studied and followed with careful discussion. The coating morphology, wettability, chemical composition and corrosion resistance are characterized by scanning electronic microscope (SEM), water contact-angle, X-ray photoelectron spectroscopy (XPS), potentiodynamic measurements and electrochemical impedance spectroscopy (EIS). The electrochemical behavior of the coatings is investigated using EIS. The results indicate that the coating morphology and composition can be controlled by changing silane concentration. The combination of cerium ions and silane molecules could promote the formation of more homogenous and higher hydrophobic coating. The coating turns to be more compact and the adhesive strength between the coating and the magnesium substrate are strongly improved with the formation of Sisbnd Osbnd Si and Sisbnd Osbnd M chemical bonds. The optimum corrosion resistance of the coating in the corrosive media is obtained by 25 ml L-1 BTESPT modification. This whole study implies that the cerium conversion coating modified with certain silane agent deserves cautiousness before its application for corrosion resistance.

  3. Preparation and Characterization of Cerium (III Doped Captopril Nanoparticles and Study of their Photoluminescence Properties

    Directory of Open Access Journals (Sweden)

    Ghamami Shahriar

    2016-01-01

    Full Text Available In this research Ce3+ doped Captopril nanoparticles (Ce3+ doped CAP-NP were prepared by a cold welding process and have been studied. Captopril may be applied in the treatment of hypertension and some types of congestive heart failure and for preventing kidney failure due to high blood pressure and diabetes. CAP-NP was synthesized by a cold welding process. The cerium nitrate was added at a ratio of 10% and the optical properties have been studied by photoluminescence (PL. The synthesized compounds were characterized by Fourier transform infrared spectroscopy. The size of CAP-NP was calculated by X-ray diffraction (XRD. The size of CAP-NP was in the range of 50 nm. Morphology of surface of synthesized nanoparticles was studied by scanning electron microscopy (SEM. Finally the luminescence properties of undoped and doped CAP-NP were compared. PL spectra from undoped CAP-NP show a strong pack in the range of 546 nm after doped cerium ion into the captopril appeared two bands at 680 and 357 nm, which is ascribed to the well-known 5d–4f emission band of the cerium.

  4. Redox calcination study of Synroc D powder containing simulated SRL waste

    International Nuclear Information System (INIS)

    Chen, C.

    1982-01-01

    According to Ringwood [A.E. Ringwood, W. Sinclair, and G.M. McLaughlin, Nuclear Waste Immobilization, Lawrence Livermore Laboratory, Livermore, Rept. UCRL-15147 (1979)], the iron oxidation state is important in controlling, the spinel mineralogy and composition if the amount of titania (TiO 2 ) consumed in spinel formation is to be minimized in favor of the formation of the Synroc phases, zirconolite, perovskite, and nepheline. In our redox calcination studies we observed that the iron oxidation state of FeO/Fe 2 O 3 can be controlled by the redoxcalcining atmosphere. In a CO atmosphere, the oxidation state was reduced to less than 7 wt % Fe 2 O 3 . With appropriate CO 2 /CO gas mixtures the resultant iron oxidation states were in the range of 45 to 59 wt % Fe 2 O 3 . Direct rotary redox calcination of spray dried powder at 600 0 C, without prior air calcination, showed increased redox efficiency when compared to powder that had been previously air calcined at 650 0 C. We believe this is caused by a reduction in particle size. Rotary calcination at 800 0 C in argon has no measurable reduction affect on the iron oxidation state of Synroc D powder

  5. Review on anionic redox for high-capacity lithium- and sodium-ion batteries

    International Nuclear Information System (INIS)

    Zhao, Chenglong; Lu, Yaxiang; Hu, Yong-Sheng; Chen, Liquan; Wang, Qidi; Li, Baohua

    2017-01-01

    Rechargeable batteries, especially lithium-ion batteries, are now widely used as power sources for portable electronics and electric vehicles, but material innovations are still needed to satisfy the increasing demand for larger energy density. Recently, lithium- and sodium-rich electrode materials, including the A 2 MO 3 -family layered compounds (A  =  Li, Na; M  =  Mn 4+ , Ru 4+ , etc), have been extensively studied as potential high-capacity electrode materials for a cumulative cationic and anionic redox activity. Negatively charged oxide ions can potentially donate electrons to compensate for the absence of oxidable transition metals as a redox center to further increase the reversible capacity. Understanding and controlling the state-of-the-art anionic redox processes is pivotal for the design of advanced energy materials, highlighted in rechargeable batteries. Hence, experimental and theoretical approaches have been developed to consecutively study the diverting processes, states, and structures involved. In this review, we attempt to present a literature overview and provide insight into the reaction mechanism with respect to the anionic redox processes, proposing some opinions as target oriented. It is hoped that, through this discussion, the search for anionic redox electrode materials with high-capacity rechargeable batteries can be advanced, and practical applications realized as soon as possible. (topical review)

  6. Electron donating and acid-base properties of cerium oxide and its mixed oxides with alumina

    International Nuclear Information System (INIS)

    Sugunan, S.; Jalaja, J.M.

    1994-01-01

    The electron donating properties of cerium oxide activated at 300, 500 and 800 degC and of its mixed oxides with alumina were examined based on the adsorption of electron acceptors exhibiting different electron affinities. The surface acidity/basicity of the oxides was determined by titrimetry; the H 0,max values are given. The limit of electron transfer from the oxide surface lies within the region of 1.77 and 2.40 eV in terms of the electron affinity of the electron acceptor. Cerium oxide promotes the electron donor nature of alumina while leaving the limit of electron transfer unchanged. 2 tabs., 4 figs., 13 refs

  7. High-resolution imaging of redox signaling in live cells through an oxidation-sensitive yellow fluorescent protein

    DEFF Research Database (Denmark)

    Maulucci, Giuseppe; Labate, Valentina; Mele, Marina

    2008-01-01

    We present the application of a redox-sensitive mutant of the yellow fluorescent protein (rxYFP) to image, with elevated sensitivity and high temporal and spatial resolution, oxidative responses of eukaryotic cells to pathophysiological stimuli. The method presented, based on the ratiometric...... quantitation of the distribution of fluorescence by confocal microscopy, allows us to draw real-time "redox maps" of adherent cells and to score subtle changes in the intracellular redox state, such as those induced by overexpression of redox-active proteins. This strategy for in vivo imaging of redox...

  8. Real-time quantification of subcellular H2O2 and glutathione redox potential in living cardiovascular tissues.

    Science.gov (United States)

    Panieri, Emiliano; Millia, Carlo; Santoro, Massimo M

    2017-08-01

    Detecting and measuring the dynamic redox events that occur in vivo is a prerequisite for understanding the impact of oxidants and redox events in normal and pathological conditions. These aspects are particularly relevant in cardiovascular tissues wherein alterations of the redox balance are associated with stroke, aging, and pharmacological intervention. An ambiguous aspect of redox biology is how redox events occur in subcellular organelles including mitochondria, and nuclei. Genetically-encoded Rogfp2 fluorescent probes have become powerful tools for real-time detection of redox events. These probes detect hydrogen peroxide (H 2 O 2 ) levels and glutathione redox potential (E GSH ), both with high spatiotemporal resolution. By generating novel transgenic (Tg) zebrafish lines that express compartment-specific Rogfp2-Orp1 and Grx1-Rogfp2 sensors we analyzed cytosolic, mitochondrial, and the nuclear redox state of endothelial cells and cardiomyocytes of living zebrafish embryos. We provide evidence for the usefulness of these Tg lines for pharmacological compounds screening by addressing the blocking of pentose phosphate pathways (PPP) and glutathione synthesis, thus altering subcellular redox state in vivo. Rogfp2-based transgenic zebrafish lines represent valuable tools to characterize the impact of redox changes in living tissues and offer new opportunities for studying metabolic driven antioxidant response in biomedical research. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. The Intra- or Extracellular Redox State Was Not Affected by a High vs. Low Glycemic Response Diet in Mice

    Science.gov (United States)

    Kleckner, Amber S.; Wong, Siu; Corkey, Barbara E.

    2015-01-01

    A low glycemic response (LGR) vs. high glycemic response (HGR) diet helps curtail the development of obesity and diabetes, though the mechanisms are unknown. We hypothesized that consumption of a HGR vs. a LGR diet would lead to a more oxidized circulating redox state and predicted that a HGR diet would increase fat accumulation, reduce insulin sensitivity, and impair metabolic acclimation to a high fat diet in a mouse model. Hence, male C57BL/6 mice consumed a HGR or LGR diet for 16 weeks and a subset of the mice subsequently consumed a high fat diet for 4 weeks. We found that body mass increased at a faster rate for those consuming the HGR diet. Percent body fat was greater and percent lean mass was lesser in the HGR group starting at 12 weeks. However, the groups did not differ in terms of glucose tolerance at week 14 and metabolic parameters (respiratory exchange ratio, heat production, activity) at weeks 4 or 15. Moreover, mice on either diet did not show differences in metabolic acclimation to the high fat leg of the study. At the termination of the study, the groups did not differ in terms of redox pairs (lactate/pyruvate and β-hydroxybutyrate/acetoacetate) or thioredoxin reductase activity in blood. Also, total and oxidized glutathione levels and lipid peroxidation were similar in blood and liver. Correlations between baseline measures, longitudinal parameters, environmental conditions, and terminal metrics revealed that individual mice have innate propensities to metabolic regulation that may be difficult to perturb with diet alone; for example, starting mass correlated negatively with energy expenditure 4 weeks into the study and total hepatic glutathione at the end of the study. In conclusion, these data suggest that the mechanism by which HGR carbohydrates contributes to obesity is not via prolonged oxidation of the circulating redox state. PMID:26030878

  10. The Intra- or Extracellular Redox State Was Not Affected by a High vs. Low Glycemic Response Diet in Mice.

    Directory of Open Access Journals (Sweden)

    Amber S Kleckner

    Full Text Available A low glycemic response (LGR vs. high glycemic response (HGR diet helps curtail the development of obesity and diabetes, though the mechanisms are unknown. We hypothesized that consumption of a HGR vs. a LGR diet would lead to a more oxidized circulating redox state and predicted that a HGR diet would increase fat accumulation, reduce insulin sensitivity, and impair metabolic acclimation to a high fat diet in a mouse model. Hence, male C57BL/6 mice consumed a HGR or LGR diet for 16 weeks and a subset of the mice subsequently consumed a high fat diet for 4 weeks. We found that body mass increased at a faster rate for those consuming the HGR diet. Percent body fat was greater and percent lean mass was lesser in the HGR group starting at 12 weeks. However, the groups did not differ in terms of glucose tolerance at week 14 and metabolic parameters (respiratory exchange ratio, heat production, activity at weeks 4 or 15. Moreover, mice on either diet did not show differences in metabolic acclimation to the high fat leg of the study. At the termination of the study, the groups did not differ in terms of redox pairs (lactate/pyruvate and β-hydroxybutyrate/acetoacetate or thioredoxin reductase activity in blood. Also, total and oxidized glutathione levels and lipid peroxidation were similar in blood and liver. Correlations between baseline measures, longitudinal parameters, environmental conditions, and terminal metrics revealed that individual mice have innate propensities to metabolic regulation that may be difficult to perturb with diet alone; for example, starting mass correlated negatively with energy expenditure 4 weeks into the study and total hepatic glutathione at the end of the study. In conclusion, these data suggest that the mechanism by which HGR carbohydrates contributes to obesity is not via prolonged oxidation of the circulating redox state.

  11. Nutritional quality assessment of tomato fruits after exposure to uncoated and citric acid coated cerium oxide nanoparticles, bulk cerium oxide, cerium acetate and citric acid.

    Science.gov (United States)

    Barrios, Ana Cecilia; Medina-Velo, Illya A; Zuverza-Mena, Nubia; Dominguez, Osvaldo E; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

    2017-01-01

    Little is known about the effects of surface modification on the interaction of nanoparticles (NPs) with plants. Tomato (Solanum lycopersicum L.) plants were cultivated in potting soil amended with bare and citric acid coated nanoceria (nCeO 2, nCeO 2 +CA), cerium acetate (CeAc), bulk cerium oxide (bCeO 2 ) and citric acid (CA) at 0-500 mg kg -1 . Fruits were collected year-round until the harvesting time (210 days). Results showed that nCeO 2 +CA at 62.5, 250 and 500 mg kg -1 reduced dry weight by 54, 57, and 64% and total sugar by 84, 78, and 81%. At 62.5, 125, and 500 mg kg -1 nCeO 2 +CA decreased reducing sugar by 63, 75, and 52%, respectively and at 125 mg kg -1 reduced starch by 78%, compared to control. The bCeO 2 at 250 and 500 mg kg -1 , increased reducing sugar by 67 and 58%. In addition, when compared to controls, nCeO 2 at 500 mg kg -1 reduced B (28%), Fe (78%), Mn (33%), and Ca (59%). At 125 mg kg -1 decreased Al by 24%; while nCeO 2 +CA at 125 and 500 mg kg -1 increased B by 33%. On the other hand, bCeO 2 at 62.5 mg kg -1 increased Ca (267%), but at 250 mg kg -1 reduced Cu (52%), Mn (33%), and Mg (58%). Fruit macromolecules were mainly affected by nCeO 2 +CA, while nutritional elements by nCeO 2 ; however, all Ce treatments altered, in some way, the nutritional quality of tomato fruit. To our knowledge, this is the first study comparing effects of uncoated and coated nanoceria on tomato fruit quality. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  12. Fasting, but Not Aging, Dramatically Alters the Redox Status of Cysteine Residues on Proteins in Drosophila melanogaster

    Directory of Open Access Journals (Sweden)

    Katja E. Menger

    2015-06-01

    Full Text Available Altering the redox state of cysteine residues on protein surfaces is an important response to environmental challenges. Although aging and fasting alter many redox processes, the role of cysteine residues is uncertain. To address this, we used a redox proteomic technique, oxidative isotope-coded affinity tags (OxICAT, to assess cysteine-residue redox changes in Drosophila melanogaster during aging and fasting. This approach enabled us to simultaneously identify and quantify the redox state of several hundred cysteine residues in vivo. Cysteine residues within young flies had a bimodal distribution with peaks at ∼10% and ∼85% reversibly oxidized. Surprisingly, these cysteine residues did not become more oxidized with age. In contrast, 24 hr of fasting dramatically oxidized cysteine residues that were reduced under fed conditions while also reducing cysteine residues that were initially oxidized. We conclude that fasting, but not aging, dramatically alters cysteine-residue redox status in D. melanogaster.

  13. Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

    Science.gov (United States)

    Bamberger, C.E.

    A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

  14. The redox state of the apoplast influences the acclimation of photosynthesis and leaf metabolism to changing irradiance.

    Science.gov (United States)

    Karpinska, Barbara; Zhang, Kaiming; Rasool, Brwa; Pastok, Daria; Morris, Jenny; Verrall, Susan R; Hedley, Pete E; Hancock, Robert D; Foyer, Christine H

    2018-05-01

    The redox state of the apoplast is largely determined by ascorbate oxidase (AO) activity. The influence of AO activity on leaf acclimation to changing irradiance was explored in wild-type (WT) and transgenic tobacco (Nicotiana tobaccum) lines containing either high [pumpkin AO (PAO)] or low [tobacco AO (TAO)] AO activity at low [low light (LL); 250 μmol m -2  s -1 ] and high [high light (HL); 1600 μmol m -2  s -1 ] irradiance and following the transition from HL to LL. AO activities changed over the photoperiod, particularly in the PAO plants. AO activity had little effect on leaf ascorbate, which was significantly higher under HL than under LL. Apoplastic ascorbate/dehydroascorbate (DHA) ratios and threonate levels were modified by AO activity. Despite decreased levels of transcripts encoding ascorbate synthesis enzymes, leaf ascorbate increased over the first photoperiod following the transition from HL to LL, to much higher levels than LL-grown plants. Photosynthesis rates were significantly higher in the TAO leaves than in WT or PAO plants grown under HL but not under LL. Sub-sets of amino acids and fatty acids were lower in TAO and WT leaves than in the PAO plants under HL, and following the transition to LL. Light acclimation processes are therefore influenced by the apoplastic as well as chloroplastic redox state. © 2017 John Wiley & Sons Ltd.

  15. Cerium compounds in the fashion of the light actinides

    International Nuclear Information System (INIS)

    Koelling, D.D.

    1984-01-01

    Researchers familiar with the light actinides easily recognize in cerium compounds a microcosm of the rich variety of properties seen in the light actinides. The parallelism seen between comparable cerium and actinide compounds strongly suggests that the same physical models are applicable. The most significant is the relative size of the f-orbital. Localization is generally tighter in Ce compounds than uranium compounds, making Ce roughly analogous to Np through Am. A way to see the actinide parallelism is to compare Hill plots. Compounds in the different regions of the plots (representing different physics) are isostructural compounds with the same companion (B) elements. The most common materials exhibiting a direct f-f interaction are the cubic Laves compounds. Accordingly, we have determined the band structures of CeRu 2 , CeRh 2 , CeIr 2 , CeOs 2 , and CeNi 2 . Compounds illustrative of the interaction of f-orbitals with ligand orbitals are the Cu 3 Au structured materials. Materials calculated in this class are CeRh 3 , CePd 3 , and CeSn 3 - the materials of much interest as mixed valent. Although the focus is on the Ce compounds, calculations performed on uranium isomorphs are used to highlight the interesting physics

  16. Redox Proteomics and Platelet Activation: Understanding the Redox Proteome to Improve Platelet Quality for Transfusion

    Science.gov (United States)

    Sonego, Giona; Abonnenc, Mélanie; Tissot, Jean-Daniel; Prudent, Michel; Lion, Niels

    2017-01-01

    Blood banks use pathogen inactivation (PI) technologies to increase the safety of platelet concentrates (PCs). The characteristics of PI-treated PCs slightly differ from those of untreated PCs, but the underlying reasons are not well understood. One possible cause is the generation of oxidative stress during the PI process. This is of great interest since reactive oxygen species (ROS) act as second messengers in platelet functions. Furthermore, there are links between protein oxidation and phosphorylation, another mechanism that is critical for cell regulation. Current research efforts focus on understanding the underlying mechanisms and identifying new target proteins. Proteomics technologies represent powerful tools for investigating signaling pathways involving ROS and post-translational modifications such as phosphorylation, while quantitative techniques enable the comparison of the platelet resting state versus the stimulated state. In particular, redox cysteine is a key player in platelet activation upon stimulation by different agonists. This review highlights the experiments that have provided insights into the roles of ROS in platelet function and the implications for platelet transfusion, and potentially in diseases such as inflammation and platelet hyperactivity. The review also describes the implication of redox mechanism in platelet storage considerations. PMID:28208668

  17. Intracellular Redox State Revealed by In Vivo 31P MRS Measurement of NAD+ and NADH Contents in Brains

    Science.gov (United States)

    Lu, Ming; Zhu, Xiao-Hong; Zhang, Yi; Chen, Wei

    2015-01-01

    Purpose Nicotinamide adenine dinucleotide (NAD), in oxidized (NAD+) or reduced (NADH) form, plays key roles in cellular metabolism. Intracellular NAD+/NADH ratio represents the cellular redox state; however, it is difficult to measure in vivo. We report here a novel in vivo 31P MRS method for noninvasive measurement of intracellular NAD concentrations and NAD+/NADH ratio in the brain. Methods It uses a theoretical model to describe the NAD spectral patterns at a given field for quantification. Standard NAD solutions and independent cat brain measurements at 9.4 T and 16.4 T were used to evaluate this method. We also measured T1 values of brain NAD. Results Model simulation and studies of solutions and brains indicate that the proposed method can quantify submillimolar NAD concentrations with reasonable accuracy if adequate 31P MRS signal-to-noise ratio and linewidth were obtained. The NAD concentrations and NAD+/NADH ratio of cat brains measured at 16.4 T and 9.4 T were consistent despite the significantly different T1 values and NAD spectra patterns at two fields. Conclusion This newly established 31P MRS method makes it possible for the first time to noninvasively study the intracellular redox state and its roles in brain functions and diseases, and it can potentially be applied to other organs. PMID:23843330

  18. Particle size effect of redox reactions for Co species supported on silica

    International Nuclear Information System (INIS)

    Chotiwan, Siwaruk; Tomiga, Hiroki; Katagiri, Masaki; Yamamoto, Yusaku; Yamashita, Shohei; Katayama, Misaki; Inada, Yasuhiro

    2016-01-01

    Conversions of chemical states during redox reactions of two silica-supported Co catalysts, which were prepared by the impregnation method, were evaluated by using an in situ XAFS technique. The addition of citric acid into the precursor solution led to the formation on silica of more homogeneous and smaller Co particles, with an average diameter of 4 nm. The supported Co 3 O 4 species were reduced to metallic Co via the divalent CoO species during a temperature-programmed reduction process. The reduced Co species were quantitatively oxidized with a temperature-programmed oxidation process. The higher observed reduction temperature of the smaller CoO particles and the lower observed oxidation temperature of the smaller metallic Co particles were induced by the higher dispersion of the Co oxide species, which apparently led to a stronger interaction with supporting silica. The redox temperature between CoO and Co 3 O 4 was found to be independent of the particle size. - Graphical abstract: Chemical state conversions of SiO 2 -supported Co species and the particle size effect have been analyzed by means of in situ XAFS technique. The small CoO particles have endurance against the reduction and exist in a wide temperature range. Display Omitted - Highlights: • The conversions of the chemical state of supported Co species during redox reaction are evaluated. • In operando XAFS technique were applied to measure redox properties of small Co particles. • A small particle size affects to the redox temperatures of cobalt catalysts.

  19. Expression, purification, crystallization and X-ray crystallographic studies of different redox states of the active site of thioredoxin 1 from the whiteleg shrimp Litopenaeus vannamei

    International Nuclear Information System (INIS)

    Campos-Acevedo, Adam A.; Garcia-Orozco, Karina D.; Sotelo-Mundo, Rogerio R.; Rudiño-Piñera, Enrique

    2013-01-01

    Analysis of the different redox states of the catalytic cysteines in four crystallographic structures of thioredoxin 1 from the Pacific whiteleg shrimp L. vannamei highlights their reactivity and corroborates the existence of a structural dimer mediated by an interface of 12 residues which includes a disulfide bridge between the Cys73 residues of each monomer. Thioredoxin (Trx) is a 12 kDa cellular redox protein that belongs to a family of small redox proteins which undergo reversible oxidation to produce a cystine disulfide bond through the transfer of reducing equivalents from the catalytic site cysteine residues (Cys32 and Cys35) to a disulfide substrate. In this study, crystals of thioredoxin 1 from the Pacific whiteleg shrimp Litopenaeus vannamei (LvTrx) were successfully obtained. One data set was collected from each of four crystals at 100 K and the three-dimensional structures of the catalytic cysteines in different redox states were determined: reduced and oxidized forms at 2.00 Å resolution using data collected at a synchrotron-radiation source and two partially reduced structures at 1.54 and 1.88 Å resolution using data collected using an in-house source. All of the crystals belonged to space group P3 2 12, with unit-cell parameters a = 57.5 (4), b = 57.5 (4), c = 118.1 (8) Å. The asymmetric unit contains two subunits of LvTrx, with a Matthews coefficient (V M ) of 2.31 Å 3 Da −1 and a solvent content of 46%. Initial phases were determined by molecular replacement using the crystallographic model of Trx from Drosophila melanogaster as a template. In the present work, LvTrx was overexpressed in Escherichia coli, purified and crystallized. Structural analysis of the different redox states at the Trx active site highlights its reactivity and corroborates the existence of a dimer in the crystal. In the crystallographic structures the dimer is stabilized by several interactions, including a disulfide bridge between Cys73 of each LvTrx monomer, a

  20. Synthesis, spectral characterization and redox properties of iron (II ...

    Indian Academy of Sciences (India)

    Unknown

    Arylazoheterocycles and their chemistry of transition and non-transition metals have been explored for more than two decades.1 Owing to their pH-response, photoactivity, light electron communication, stabilization of low valent metal oxidation state, exhibition of serial redox states of complexes, isolation of anion radicals, ...

  1. Characterization of plasma thiol redox potential in a common marmoset model of aging

    Directory of Open Access Journals (Sweden)

    James R. Roede

    2013-01-01

    Full Text Available Due to its short lifespan, ease of use and age-related pathologies that mirror those observed in humans, the common marmoset (Callithrix jacchus is poised to become a standard nonhuman primate model of aging. Blood and extracellular fluid possess two major thiol-dependent redox nodes involving cysteine (Cys, cystine (CySS, glutathione (GSH and glutathione disulfide (GSSG. Alteration in these plasma redox nodes significantly affects cellular physiology, and oxidation of the plasma Cys/CySS redox potential (EhCySS is associated with aging and disease risk in humans. The purpose of this study was to determine age-related changes in plasma redox metabolites and corresponding redox potentials (Eh to further validate the marmoset as a nonhuman primate model of aging. We measured plasma thiol redox states in marmosets and used existing human data with multivariate adaptive regression splines (MARS to model the relationships between age and redox metabolites. A classification accuracy of 70.2% and an AUC of 0.703 were achieved using the MARS model built from the marmoset redox data to classify the human samples as young or old. These results show that common marmosets provide a useful model for thiol redox biology of aging.

  2. Simple preparation of fluorescent composite films based on cerium and europium doped LaF3 nanoparticles

    Science.gov (United States)

    Secco, Henrique de L.; Ferreira, Fabio F.; Péres, Laura O.

    2018-03-01

    The combination of materials to form hybrids with unique properties, different from those of the isolated components, is a strategy used to prepare functional materials with improved properties aiming to allow their application in specific fields. The doping of lanthanum fluoride with other rare earth elements is used to obtain luminescent particles, which may be useful to the manufacturing of electronic devices' displays and biological markers, for instance. The application of the powder of nanoparticles has limitations in some fields; to overcome this, the powder may be incorporated in a suitable polymeric matrix. In this work, lanthanum fluoride nanoparticles, undoped and doped with cerium and europium, were synthesized through the co-precipitation method in aqueous solution. Aiming the formation of solid state films, composites of nanoparticles in an elastomeric matrix, the nitrile rubber (NBR), were prepared. The flexibility and the transparency of the matrix in the regions of interest are advantages for the application of the luminescent composites. The composites were applied as films using the casting and the spin coating techniques and luminescent materials were obtained in the samples doped with europium and cerium. Scanning electron microscopy images showed an adequate dispersion of the particles in the matrix in both film formation techniques. Aggregates of the particles were detected in the samples which may affect the uniformity of the emission of the composites.

  3. Redox reactions with empirical potentials: atomistic battery discharge simulations.

    Science.gov (United States)

    Dapp, Wolf B; Müser, Martin H

    2013-08-14

    Batteries are pivotal components in overcoming some of today's greatest technological challenges. Yet to date there is no self-consistent atomistic description of a complete battery. We take first steps toward modeling of a battery as a whole microscopically. Our focus lies on phenomena occurring at the electrode-electrolyte interface which are not easily studied with other methods. We use the redox split-charge equilibration (redoxSQE) method that assigns a discrete ionization state to each atom. Along with exchanging partial charges across bonds, atoms can swap integer charges. With redoxSQE we study the discharge behavior of a nano-battery, and demonstrate that this reproduces the generic properties of a macroscopic battery qualitatively. Examples are the dependence of the battery's capacity on temperature and discharge rate, as well as performance degradation upon recharge.

  4. Far infrared properties of PbTe doped with cerium

    International Nuclear Information System (INIS)

    Nikolic, P.M.; Koenig, W.; Vujatovic, S.S.; Blagojevic, V.; Lukovic, D.; Savic, S.; Radulovic, K.; Urosevic, D.; Nikolic, M.V.

    2007-01-01

    Single crystal samples of lead telluride doped with cerium were made using the Bridgman method. Far infrared reflectivity spectra in the temperature range from 10 to 300 K are presented. The experimental data were numerically analyzed using a fitting procedure based on the plasmon-phonon interaction model and optical parameters were determined. Two additional local modes were observed at about 138 and 337 cm -1 . The origin of these local vibrational impurity modes was discussed

  5. Experimental and theoretical study of bound and quasibound states of Ce{sup -}

    Energy Technology Data Exchange (ETDEWEB)

    Walter, C. W.; Gibson, N. D.; Li, Y.-G.; Matyas, D. J.; Alton, R. M.; Lou, S. E.; Field, R. L. III; Hanstorp, D.; Pan, Lin; Beck, Donald R. [Department of Physics and Astronomy, Denison University, Granville, Ohio 43023 (United States); Department of Physics, University of Gothenburg, SE-412 96 Gothenburg (Sweden); Department of Physics, Michigan Technological University, Houghton, Michigan 49931 (United States)

    2011-09-15

    The negative ion of cerium is investigated experimentally with tunable infrared laser photodetachment spectroscopy and theoretically with relativistic configuration interaction in the continuum formalism. The relative cross section for neutral atom production is measured with a crossed ion-beam-laser-beam apparatus over the photon energy range of 0.54-0.75 eV. A rich resonance spectrum is revealed near the threshold with, at least, 12 peaks observed due to transitions from bound states of Ce{sup -} to either bound or quasibound excited states of the negative ion. Theoretical calculations of the photodetachment cross sections enable identification of the transitions responsible for the measured peaks. Two of the peaks are due to electric dipole-allowed bound-bound transitions in Ce{sup -}, making cerium only the second atomic negative ion that has been demonstrated to support multiple bound states of opposite parity. In addition, combining the experimental data with the theoretical analysis determines the electron affinity of cerium to be 0.628(10) eV and the fine structure splitting of the ground state of Ce{sup -} ({sup 4} H{sub 7/2}-{sup 4} H{sub 9/2}) to be 0.097 75(4) eV.

  6. Properties of a epoxy-based powder coating containing modified montmorillonite with cerium

    International Nuclear Information System (INIS)

    Beux, A.R.D.; Piazza, D.; Zattera, A.J.; Ferreira, C.A.; Scienza, L.C.

    2014-01-01

    Organic coatings are widely used to prevent corrosion in metal structures. The incorporation of nanofiller the polymer matrix in order to obtain polymer nanocomposites has been arousing scientific and technological interest, because it provides significant improvements when incorporated into pure polymeric materials or conventional composites. In the present study were been developed epoxy-based powder coating with addition of different concentrations (2, 4 and 8% (w / w)) of the montmorillonite type Cloisite® 15A modified with cerium in the melt state on a double-screw extruder co-rotating. The coatings were characterized by average particle size, time (gel time) gel, X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). Coatings with intercalated structure was observed in the XRD analysis and confirmed by SEM to the observe an increase in the concentration of tactoids an increased filler content. (author)

  7. Redox active molecules cytochrome c and vitamin C enhance heme-enzyme peroxidations by serving as non-specific agents for redox relay

    Energy Technology Data Exchange (ETDEWEB)

    Gade, Sudeep Kumar; Bhattacharya, Subarna [Heme and Flavo Proteins Laboratory, 204, Center for Biomedical Research, VIT University, Vellore, Tamil Nadu 632014 (India); Manoj, Kelath Murali, E-mail: satyamjayatu@yahoo.com [Heme and Flavo Proteins Laboratory, 204, Center for Biomedical Research, VIT University, Vellore, Tamil Nadu 632014 (India)

    2012-03-09

    Highlights: Black-Right-Pointing-Pointer At low concentrations, cytochrome c/vitamin C do not catalyze peroxidations. Black-Right-Pointing-Pointer But low levels of cytochrome c/vitamin C enhance diverse heme peroxidase activities. Black-Right-Pointing-Pointer Enhancement positively correlates to the concentration of peroxide in reaction. Black-Right-Pointing-Pointer Reducible additives serve as non-specific agents for redox relay in the system. Black-Right-Pointing-Pointer Insight into electron transfer processes in routine and oxidative-stress states. -- Abstract: We report that incorporation of very low concentrations of redox protein cytochrome c and redox active small molecule vitamin C impacted the outcome of one-electron oxidations mediated by structurally distinct plant/fungal heme peroxidases. Evidence suggests that cytochrome c and vitamin C function as a redox relay for diffusible reduced oxygen species in the reaction system, without invoking specific or affinity-based molecular interactions for electron transfers. The findings provide novel perspectives to understanding - (1) the promiscuous role of cytochrome b{sub 5} in the metabolism mediated by liver microsomal xenobiotic metabolizing systems and (2) the roles of antioxidant molecules in affording relief from oxidative stress.

  8. Selective anodic dissolution of cerium from aluminium alloys under potentiostatic conditions

    International Nuclear Information System (INIS)

    Gol'dshtejn, S.L.; Raspopin, S.P.; Seleznev, V.D.; Tunin, A.V.; Fedorov, V.A.

    1975-01-01

    A study was made of selective anodic dissolution of aluminum alloys containing cerium in concentrations from 0.5 to 10% by mass. The electropurification was carried out with the aid of a potentiostatic setup at 700 deg C in atmosphere of purified argon. Liquid aluminum served as the cathode, with chlorine half-cell as reference electrode and the melt of equimolar KCl-NaCl mixture as the electrolyte. The ''current-time'' plots are presented for selective ionization of cerium from aluminum alloys at preset potential values on the installation. For PHIsub(preset)=-2.04 v the current of potentiostatic electrolysis fades out to that of the supporting electrolyte, and the process itself proceeds at a rate that provides maximal extraction of cerium from the alloy (csub9finite)approximately equal to 0.002% by mass) at minimal ionization of the metalsolvent (Δ Msub(Al)approximately equal to 0.2). Alloys containing not less then 1% by mass of Ce exhibit a characteristic abrupt change of the attenuation coefficient apparently owing to nonlinear dependence of unbalance (ΔE) of signals at the input of the potentiostat. The ''ΔE-c'' function for Al alloy containing 0.5% by mass of Ce can be approximated by linear function. In this case the current of potentiostatic electrolysis approaches the value of the limiting diffusion current. To obtain the relationship between the magnitude of the limiting current of Ce ionization and the initial composition of the dissolving alloy, measurements were made under potentiodynamic conditions at a scanning rate of approximately equal to 500 mv/min. The results indicate that isub(intermediate) is directly proportional to csub(initial). It was shown that under the conditions employed, practically complete (csub(finite)<=0.004% by mass) extraction of the electronegative component is possible without noticeable ionization of the metal-solvent

  9. Influence of annealing on texture properties of cerium oxide thin films

    International Nuclear Information System (INIS)

    Arunkumar, P.; Suresh Babu, K.; Ramaseshan, R.; Dash, S.

    2013-01-01

    Future power demand needs an energy source with higher efficiency, better power density, clean energy and fuel flexibility. Solid oxide fuel cell (SOFC) is one of the potential sources for future needs. Though the polymer and direct methanol based electrolyte are much suitable, for versatile applications (portable devices) they are having major challenges such as design, platinum based catalyst, lower power density and fuel flexibility (free from hydrocarbons). However, in SOFC the high operating temperature is the only major issue. Operating temperature of SOFC could be reduced by proper selection of electrolyte material which should have minimum ionic conductivity of 0.1 Scm -1 at reduced activation energy. This can be achieved by thin film based doped cerium oxide electrolyte for SOFC, leads to Intermediate Temperature Solid Oxide Fuel Cell (ITSOFC). In the present work, we focus on the synthesis of cerium oxide and 20 mol % samarium doped cerium oxide (SDC) nanoparticles by co-precipitation method and to synthesis thin films of the same. Pellets of those powders were heat treated at different temperatures and used as targets for e-beam evaporation to fabricate thin film based electrolyte. Stoichiometry of both powders and thin films were confirmed by XRF and EPMA. GIXRD profiles of ceria and SDC thin films are shown below and a preferred orientation effect is observed in SDC films. In SDC films the X-ray peaks have a shift towards lower angles, due to the difference in ionic radii of Ce 4+ and Sm 3+ . The band gap of CeO 2 (2.88 eV) from optical absorption technique indicates the presence of Ce 3+ with Ce 4+ , indirectly shows the concentration of oxygen vacancies which is required for the thin film electrolyte

  10. Energy transfer and thermal studies of Pr 3+ doped cerium oxalate ...

    Indian Academy of Sciences (India)

    The analysis of energy level diagrams of cerium and praseodymium ions indicates that the energy gap between the sensitizer and the activator ions varies in a small range suggesting a possible energy transfer from the Ce3+ to Pr3+. The emission and absorption spectra of these crystals were recorded. The overlapping of ...

  11. Effect of long-term fertilization on humic redox mediators in multiple microbial redox reactions.

    Science.gov (United States)

    Guo, Peng; Zhang, Chunfang; Wang, Yi; Yu, Xinwei; Zhang, Zhichao; Zhang, Dongdong

    2018-03-01

    This study investigated the effects of different long-term fertilizations on humic substances (HSs), humic acids (HAs) and humins, functioning as redox mediators for various microbial redox biotransformations, including 2,2',4,4',5,5'- hexachlorobiphenyl (PCB 153 ) dechlorination, dissimilatory iron reduction, and nitrate reduction, and their electron-mediating natures. The redox activity of HSs for various microbial redox metabolisms was substantially enhanced by long-term application of organic fertilizer (pig manure). As a redox mediator, only humin extracted from soils with organic fertilizer amendment (OF-HM) maintained microbial PCB 153 dechlorination activity (1.03 μM PCB 153 removal), and corresponding HA (OF-HA) most effectively enhanced iron reduction and nitrate reduction by Shewanella putrefaciens. Electrochemical analysis confirmed the enhancement of their electron transfer capacity and redox properties. Fourier transform infrared analysis showed that C=C and C=O bonds, and carboxylic or phenolic groups in HSs might be the redox functional groups affected by fertilization. This research enhances our understanding of the influence of anthropogenic fertility on the biogeochemical cycling of elements and in situ remediation ability in agroecosystems through microorganisms' metabolisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Influence of processing conditions on the glass-crystal transition into borosilicate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Deschanels, X.; Cachia, J.N.; Lopez, C.; Peuget, S. [CEA Marcoule, BP 17171, 30207 Bagnols sur Ceze (France)

    2008-07-01

    The precipitation of a crystalline phase in glass is observed when one element exceeds its loading limit (i.e.: solubility limit). In this work we have studied the solubility of different actinides and surrogates (lanthanides and hafnium) in borosilicate glass used for the immobilization of the high-level nuclear waste (HLW glasses). The results obtained show an increase of the solubility limits of these elements with the processing temperature and the redox potential of the melt. The elements at the oxidation state (III) exhibit a higher solubility than the element at oxidation state (IV). In this framework, cerium is an interesting element because its oxidation state tunes from (IV) to (III) as a function of the processing conditions. It is shown that the solubility of cerium can be multiplied by a factor of 20 at 1100 C. degrees. In order to have a better understanding of the mechanisms that underline the evolution of the solubility, XAFS and NMR investigation has been undertaken. Trivalent elements present the characteristics of network-modified cations while tetravalent elements look like network-former cations.

  13. Redox rhythm reinforces the circadian clock to gate immune response.

    Science.gov (United States)

    Zhou, Mian; Wang, Wei; Karapetyan, Sargis; Mwimba, Musoki; Marqués, Jorge; Buchler, Nicolas E; Dong, Xinnian

    2015-07-23

    Recent studies have shown that in addition to the transcriptional circadian clock, many organisms, including Arabidopsis, have a circadian redox rhythm driven by the organism's metabolic activities. It has been hypothesized that the redox rhythm is linked to the circadian clock, but the mechanism and the biological significance of this link have only begun to be investigated. Here we report that the master immune regulator NPR1 (non-expressor of pathogenesis-related gene 1) of Arabidopsis is a sensor of the plant's redox state and regulates transcription of core circadian clock genes even in the absence of pathogen challenge. Surprisingly, acute perturbation in the redox status triggered by the immune signal salicylic acid does not compromise the circadian clock but rather leads to its reinforcement. Mathematical modelling and subsequent experiments show that NPR1 reinforces the circadian clock without changing the period by regulating both the morning and the evening clock genes. This balanced network architecture helps plants gate their immune responses towards the morning and minimize costs on growth at night. Our study demonstrates how a sensitive redox rhythm interacts with a robust circadian clock to ensure proper responsiveness to environmental stimuli without compromising fitness of the organism.

  14. Nanoceria and bulk cerium oxide effects on the germination of asplenium adiantum-nigrum spores

    Directory of Open Access Journals (Sweden)

    Aranzazu Gomez-Garay

    2016-12-01

    Full Text Available Aim of study: The effect of cerium oxide engineered nanoparticles on the spore germination of the fern. Asplenium adiantum-nigrum. Area of study: France, Britanny Region, Finistére Department, Plougonvelin, in rocks near the sea. Material and methods: Asplenium spores were cultured in vitro on agar medium with Nano-CeO2 (less than 25 nm particle size and bulk-CeO2. The addition of each nano- and bulk particles ranged from 0 to 3000 mg L-1. Observations on rhizoidal and prothallial cells during first stages of gametophyte development were made. The No-Observed-Adverse-Effect concentration (NOAEC and Lowest-Observed-Adverse-Effect-Concentration (LOEC values for spore germination rate data were analyzed.  Main results: Germination was speeded up by 100 to 2000 mg L-1 nanoceria, while bulk cerium oxide had the same effect for 500 to 200 mg L-1 concentrations. Present results showed cellular damage in the protonema while rhizoid cells seemed not to be affected, as growth and membrane integrity remained. Research highlights: Both nanosized and bulk cerium oxide are toxic for the fern Asplenium adiantum-nigrum, although diverse toxicity patterns were shown for both materials. Diverse toxic effects have been observed: chloroplast membrane damage and lysis, cell wall and membrane disruption which leads to cell lysis; and alterations in morphology and development. Keywords: Nanoparticles; rhizoid; prothallus; chloroplast; fern.

  15. Nanoceria and bulk cerium oxide effects on the germination of asplenium adiantum-nigrum spores

    Energy Technology Data Exchange (ETDEWEB)

    Gomez-Garay, A.; Pintos, B.; Manzanera, J.A.; Prada, C.; Martin, L.; Gabriel y Galan, J.M.

    2016-07-01

    Aim of the study: The effect of cerium oxide engineered nanoparticles on the spore germination of the fern. Asplenium adiantum-nigrum. Area of study: France, Britanny Region, Finistére Department, Plougonvelin, in rocks near the sea. Material and methods: Asplenium spores were cultured in vitro on agar medium with Nano-CeO2 (less than 25 nm particle size) and bulk-CeO2. The addition of each nano- and bulk particles ranged from 0 to 3000 mg L-1. Observations on rhizoidal and prothallial cells during first stages of gametophyte development were made. The No-Observed-Adverse-Effect concentration (NOAEC) and Lowest-Observed-Adverse-Effect-Concentration (LOEC) values for spore germination rate data were analyzed. Main results: Germination was speeded up by 100 to 2000 mg L-1 nanoceria, while bulk cerium oxide had the same effect for 500 to 200 mg L-1 concentrations. Present results showed cellular damage in the protonema while rhizoid cells seemed not to be affected, as growth and membrane integrity remained. Research highlights: Both nanosized and bulk cerium oxide are toxic for the fern Asplenium adiantum-nigrum, although diverse toxicity patterns were shown for both materials. Diverse toxic effects have been observed: chloroplast membrane damage and lysis, cell wall and membrane disruption which leads to cell lysis; and alterations in morphology and development. (Author)

  16. Characterisation of the Redox Sensitive NMDA Receptor

    KAUST Repository

    Alzahrani, Ohood

    2016-05-01

    Glucose entry into the brain and its subsequent metabolism to L-lactate, regulated by astrocytes, plays a major role in synaptic plasticity and memory formation. A recent study has shown that L-lactate produced by the brain upon stimulation of glycolysis, and glycogen-derived L-lactate from astrocytes and its transport into neurons, is crucial for memory formation. A recent study revealed the molecular mechanisms that underlie the role of L-lactate in neuronal plasticity and long-term memory formation. L-lactate was shown to induce a cascade of molecular events via modulation of redox-sensitive N-Methyl-D-aspartate (NMDA) receptor activity that was mimicked by nicotinamide adenine dinucleotide hydride (NADH) co-enzyme. This indicated that changes in cellular redox state, following L-lactate transport inside the cells and its subsequent metabolism, production of NADH, and favouring a reduced state are the key effects of L-lactate. Therefore, we are investigating the role of L-lactate in modulating NMDA receptor function via redox modulatory sites. Accordingly, crucial redox-sensitive cysteine residues, Cys320 and Cys87, of the NR2A NMDA receptor subunit are mutated using site-directed mutation, transfected, and expressed in HEK293 cells. This cellular system will then be used to characterise and monitor its activity upon Llactate stimulation, compared to the wild type. This will be achieved by calcium imaging, using fluorescent microscopy. Our data shows that L-lactate potentiated NMDA receptor activity and increased intracellular calcium influx in NR1/NR2A wild type compared to the control condition (WT NR1/NR2A perfused with (1μM) glutamate and (1μM) glycine agonist only), showing faster response initiation and slower decay rate of the calcium signal to the baseline. Additionally, stimulating with L-lactate associated with greater numbers of cells having high fluorescent intensity (peak amplitude) compared to the control. Furthermore, L-lactate rescued the

  17. Density-functional theory for f-electron systems. The α-γ phase transition in cerium

    International Nuclear Information System (INIS)

    Casadei, Marco

    2013-01-01

    Rare earths are technologically important and scientifically highly interesting elements. The description of the volume collapse exhibited by some rare earth metals poses a great challenge to density-functional theory (DFT) since local/semi-local functionals (LDA/GGA) only partially capture the associated phase transitions. In this work this problem is approached by treating all electrons at the same quantum mechanical level, using both hybrid functionals (e.g. PBE0 and HSE06) and exact-exchange plus correlation in the random-phase approximation (EX+cRPA). The performance of recently developed beyond RPA schemes is also assessed. The isostructural α-γ phase transition in cerium is the most studied. The exact exchange contribution in PBE0 and HSE06 is crucial to produce two distinct solutions that can be associated with the α and γ phases. The two solutions emerge in bulk as well as in cluster calculations. Most notable is their presence in the cerium dimer. However, quantitative agreement with the extrapolated phase diagram requires EX+cRPA. So far the EX+cRPA correction can only be applied to cerium clusters and not to the bulk. A cluster of 19 atoms cut from the fcc crystal structure (the same that characterizes the α and γ phases) was therefore determined as representative. (EX+cRPA) rate at PBE0 for Ce 19 provides good agreement with the extrapolated transition pressure to zero temperature. We predict that a pressure induced phase transition should exist at or close to zero. A finite temperature phase diagram can be drawn in reasonable agreement with experiment by adding entropic effects. The cerium neighbors are also studied: lanthanum, which has no f electrons, praseodymium, with three f electrons and a volume collapse, and neodymium, with four f electrons and no volume collapse. Multiple solutions are also present for these f electron elements, confirming the importance of exact-exchange for f electron systems.

  18. Cerium sorption in grounds modified by anti-deflation treatment

    International Nuclear Information System (INIS)

    Firsova, L.P.; Bogatyrev, I.O.

    2001-01-01

    Influence of soils and grounds treatment by anti-deflation compositions on the size of the soil particles was studied. Under static conditions sorption of 144 Ce by turf-podsolic soils prior to an after their modification by the anti-deflation reagents, i.e. bitumens and insoluble in water polyelectrolytic complexes, was considered. Degrees of 144 Ce sorption in the soil-solution systems, depending on solutions pH, presence of alkali metal carbonates and cerium concentration, were determined [ru

  19. Far infrared properties of PbTe doped with cerium

    Energy Technology Data Exchange (ETDEWEB)

    Nikolic, P.M. [Institute of Technical Sciences SASA, Knez Mihailova 35/IV, 11000 Belgrade (Serbia)]. E-mail: nikolic@sanu.ac.yu; Koenig, W. [Max Planck Institut fuer Festkoerperforschung, Heisenbergstrasse 1, 7000 Stuttgart 80 (Germany); Vujatovic, S.S. [Institute of Technical Sciences SASA, Knez Mihailova 35/IV, 11000 Belgrade (Serbia); Blagojevic, V. [Faculty of Electronic Engineering, University of Belgrade, Bulevar Kralja Aleksandra 73, 11000 Belgrade (Serbia); Lukovic, D. [Institute of Technical Sciences SASA, Knez Mihailova 35/IV, 11000 Belgrade (Serbia); Savic, S. [Institute of Technical Sciences SASA, Knez Mihailova 35/IV, 11000 Belgrade (Serbia); Radulovic, K. [Institute of Technical Sciences SASA, Knez Mihailova 35/IV, 11000 Belgrade (Serbia); Urosevic, D. [Mathematical Institute SASA, Knez Mihailova 35/I, 11000 Belgrade (Serbia); Nikolic, M.V. [Center for Multidisciplinary Studies of the University of Belgrade, Kneza Viseslava 1, Belgrade (Serbia)

    2007-05-16

    Single crystal samples of lead telluride doped with cerium were made using the Bridgman method. Far infrared reflectivity spectra in the temperature range from 10 to 300 K are presented. The experimental data were numerically analyzed using a fitting procedure based on the plasmon-phonon interaction model and optical parameters were determined. Two additional local modes were observed at about 138 and 337 cm{sup -1}. The origin of these local vibrational impurity modes was discussed.

  20. Redox Pioneer: Professor Vadim N. Gladyshev.

    Science.gov (United States)

    Hatfield, Dolph L

    2016-07-01

    Professor Vadim N. Gladyshev is recognized here as a Redox Pioneer, because he has published an article on antioxidant/redox biology that has been cited more than 1000 times and 29 articles that have been cited more than 100 times. Gladyshev is world renowned for his characterization of the human selenoproteome encoded by 25 genes, identification of the majority of known selenoprotein genes in the three domains of life, and discoveries related to thiol oxidoreductases and mechanisms of redox control. Gladyshev's first faculty position was in the Department of Biochemistry, the University of Nebraska. There, he was a Charles Bessey Professor and Director of the Redox Biology Center. He then moved to the Department of Medicine at Brigham and Women's Hospital, Harvard Medical School, where he is Professor of Medicine and Director of the Center for Redox Medicine. His discoveries in redox biology relate to selenoenzymes, such as methionine sulfoxide reductases and thioredoxin reductases, and various thiol oxidoreductases. He is responsible for the genome-wide identification of catalytic redox-active cysteines and for advancing our understanding of the general use of cysteines by proteins. In addition, Gladyshev has characterized hydrogen peroxide metabolism and signaling and regulation of protein function by methionine-R-sulfoxidation. He has also made important contributions in the areas of aging and lifespan control and pioneered applications of comparative genomics in redox biology, selenium biology, and aging. Gladyshev's discoveries have had a profound impact on redox biology and the role of redox control in health and disease. He is a true Redox Pioneer. Antioxid. Redox Signal. 25, 1-9.

  1. Real-time monitoring of capacity loss for vanadium redox flow battery

    Science.gov (United States)

    Wei, Zhongbao; Bhattarai, Arjun; Zou, Changfu; Meng, Shujuan; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

    2018-06-01

    The long-term operation of the vanadium redox flow battery is accompanied by ion diffusion across the separator and side reactions, which can lead to electrolyte imbalance and capacity loss. The accurate online monitoring of capacity loss is therefore valuable for the reliable and efficient operation of vanadium redox flow battery system. In this paper, a model-based online monitoring method is proposed to detect capacity loss in the vanadium redox flow battery in real time. A first-order equivalent circuit model is built to capture the dynamics of the vanadium redox flow battery. The model parameters are online identified from the onboard measureable signals with the recursive least squares, in seeking to keep a high modeling accuracy and robustness under a wide range of working scenarios. Based on the online adapted model, an observer is designed with the extended Kalman Filter to keep tracking both the capacity and state of charge of the battery in real time. Experiments are conducted on a lab-scale battery system. Results suggest that the online adapted model is able to simulate the battery behavior with high accuracy. The capacity loss as well as the state of charge can be estimated accurately in a real-time manner.

  2. Cerium oxide nanoparticles stimulate proliferation of primary mouse embryonic fibroblasts in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Popov, Anton L., E-mail: antonpopovleonid@gmail.com [Institute of Theoretical and Experimental Biophysics, Russian Academy of Sciences, Pushchino, Moscow region (Russian Federation); Popova, Nelly R. [Institute of Theoretical and Experimental Biophysics, Russian Academy of Sciences, Pushchino, Moscow region (Russian Federation); Selezneva, Irina I. [Institute of Theoretical and Experimental Biophysics, Russian Academy of Sciences, Pushchino, Moscow region (Russian Federation); Pushchino State Institute of Natural sciences, Pushchino, Moscow region (Russian Federation); Akkizov, Azamat Y. [Kabardino-Balkarian State University, Nalchik (Russian Federation); Ivanov, Vladimir K. [Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow (Russian Federation); National Research Tomsk State University, Tomsk (Russian Federation)

    2016-11-01

    The increasing application of cell therapy technologies in the treatment of various diseases requires the development of new effective methods for culturing primary cells. The major limitation for the efficient use of autologous cell material is the low rate of cell proliferation. Successful cell therapy requires sufficient amounts of cell material over a short period of time with the preservation of their differentiation and proliferative potential. In this regard, the development of novel, highly efficient stimulators of proliferative activity in stem cells is a truly urgent task. In this paper we have demonstrated that citrate-stabilized cerium oxide nanoparticles (nanoceria) enhance the proliferative activity of primary mouse embryonic fibroblasts in vitro. Cerium oxide nanoparticles stimulate cell proliferation in a wide range of concentrations (10{sup −3} M–10{sup −9} M) through reduction of intracellular levels of reactive oxygen species (ROS) during the lag phase of cell growth and by modulating the expression level of the major antioxidant enzymes. We found the optimal concentration of nanoceria, which provides the greatest acceleration of cell proliferation in vitro, while maintaining the levels of intracellular ROS and mRNA of antioxidant enzymes in the physiological range. Our results confirm that nanocrystalline ceria can be considered as a basis for effective and inexpensive supplements in cell culturing. - Highlights: • Citrate-stabilized cerium oxide nanoparticles are shown to stimulate proliferation of primary embryonic cells in vitro. • Some of mechanisms involved in stimulating of the proliferation by CeO{sub 2} have been uncovered. • The most effective (optimal) concentration of CeO{sub 2} nanoparticles for stimulation of proliferation was determined.

  3. Mycobacterium tuberculosis has diminished capacity to counteract redox stress induced by elevated levels of endogenous superoxide.

    Science.gov (United States)

    Tyagi, Priyanka; Dharmaraja, Allimuthu T; Bhaskar, Ashima; Chakrapani, Harinath; Singh, Amit

    2015-07-01

    Mycobacterium tuberculosis (Mtb) has evolved protective and detoxification mechanisms to maintain cytoplasmic redox balance in response to exogenous oxidative stress encountered inside host phagocytes. In contrast, little is known about the dynamic response of this pathogen to endogenous oxidative stress generated within Mtb. Using a noninvasive and specific biosensor of cytoplasmic redox state of Mtb, we for first time discovered a surprisingly high sensitivity of this pathogen to perturbation in redox homeostasis induced by elevated endogenous reactive oxygen species (ROS). We synthesized a series of hydroquinone-based small molecule ROS generators and found that ATD-3169 permeated mycobacteria to reliably enhance endogenous ROS including superoxide radicals. When Mtb strains including multidrug-resistant (MDR) and extensively drug-resistant (XDR) patient isolates were exposed to this compound, a dose-dependent, long-lasting, and irreversible oxidative shift in intramycobacterial redox potential was detected. Dynamic redox potential measurements revealed that Mtb had diminished capacity to restore cytoplasmic redox balance in comparison with Mycobacterium smegmatis (Msm), a fast growing nonpathogenic mycobacterial species. Accordingly, Mtb strains were extremely susceptible to inhibition by ATD-3169 but not Msm, suggesting a functional linkage between dynamic redox changes and survival. Microarray analysis showed major realignment of pathways involved in redox homeostasis, central metabolism, DNA repair, and cell wall lipid biosynthesis in response to ATD-3169, all consistent with enhanced endogenous ROS contributing to lethality induced by this compound. This work provides empirical evidence that the cytoplasmic redox poise of Mtb is uniquely sensitive to manipulation in steady-state endogenous ROS levels, thus revealing the importance of targeting intramycobacterial redox metabolism for controlling TB infection. Copyright © 2015 The Authors. Published by

  4. Further results on cerium fluoride crystals

    International Nuclear Information System (INIS)

    Anderson, S.; Auffray, E.; Aziz, T.; Baccaro, S.; Banerjee, S.; Bareyre, P.; Barone, L.E.; Borgia, B.; Boutet, D.; Burq, J.P.; Chemarin, M.; Chipaux, R.; Dafinei, I.; D'Atanasio, P.; De Notaristefani, F.; Dezillie, B.; Dujardin, C.; Dutta, S.; Faure, J.L.; Fay, J.; Ferrere, D.; Francescangeli, O.; Fuchs, B.A.; Ganguli, S.N.; Gillespie, G.; Goyot, M.; Gupta, S.K.; Gurtu, A.; Heck, J.; Herve, A.; Hillemanns, H.; Holdener, F.; Ille, B.; Joensson, L.; Kierstead, J.; Krenz, W.; Kway, W.; Le Goff, J.M.; Lebeau, M.; Lebrun, P.; Lecoq, P.; Lemoigne, Y.; Loomis, G.; Lubelsmeyer, K.; Madjar, N.; Majni, G.; El Mamouni, H.; Mangla, S.; Mares, J.A.; Martin, J.P.; Mattioli, M.; Mauger, G.J.; Mazumdar, K.; Mengucci, P.; Merlo, J.P.; Moine, B.; Nikl, N.; Pansart, J.P.; Pedrini, C.; Poinsignon, J.; Polak, K.; Raghavan, R.; Rebourgeard, P.; Rinaldi, D.; Rosa, J.; Rosowsky, A.; Sahuc, P.; Samsonov, V.; Sarkar, S.; Schegelski, V.; Schmitz, D.; Schneegans, M.; Seliverstov, D.; Stoll, S.; Sudhakar, K.; Svensson, A.; Tonwar, S.C.; Topa, V.; Vialle, J.P.; Vivargent, M.; Wallraff, W.; Weber, M.J.; Winter, N.; Woody, C.; Wuest, C.R.; Yanovski, V.

    1993-01-01

    A systematic investigation of the properties of cerium fluoride monocrystals has been performed by the 'Crystal Clear' collaboration in view of a possible use of such crystals for the construction of high precision electromagnetic calorimeters for the future generation of high luminosity accelerators. A large sample of different crystals grown by several producers has been studied. The spectroscopic characteristics, the transmission, luminescence and excitation spectra and the decay time curves are analysed. The light yield of the different crystals is measured with photomultipliers and Si photodiodes and compared to reference standards like BGO and NaI(Tl). The radiation damage behaviour is then presented for γ and neutron irradiations, at different doses and dose rates, including thermal and optical bleaching. (orig.)

  5. Brain oxidative metabolism of the newborn dog: correlation between 31P NMR spectroscopy and pyridine nucleotide redox state.

    Science.gov (United States)

    Mayevsky, A; Nioka, S; Subramanian, V H; Chance, B

    1988-04-01

    The effects of both anoxia and short- and long-term hypoxia on brain oxidative metabolism were studied in newborn dogs. Oxidative metabolism was evaluated by two independent measures: in vivo continuous monitoring of mitochondrial NADH redox state and energy stores as calculated from the phosphocreatine (PCr)/Pi levels measured by 31P nuclear magnetic resonance (NMR) spectroscopy. The hemodynamic response to low oxygen supply was further evaluated by measuring the changes in the reflected light intensity at 366 nm (the excitation wavelength for NADH). The animal underwent surgery and was prepared for monitoring of the two signals (NADH and PCr/Pi). It was then placed inside a Phosphoenergetics 260-80 NMR spectrometer magnet with a 31-cm bore. Each animal (1-21 days old) was exposed to short-term anoxia or hypoxia as well as to long-term hypoxia (1-2 h). The results can be summarized as follow: (a) In the normoxic brain, the ratio between PCr and Pi was greater than 1 (1.2-1.4), while under hypoxia or asphyxia a significant decrease that was correlated to the FiO2 levels was recorded. (b) A clear correlation was found between the decrease in PCr/Pi values and the increased NADH redox state developed under decreased O2 supply to the brain. (c) Exposing the animal to moderately long-term hypoxia led to a stabilized low-energy state of the brain with a good recovery after rebreathing normal air. (d) Under long-term and severe hypoxia, the microcirculatory autoregulatory mechanism was damaged and massive vasoconstriction was optically recorded simultaneously with a significant decrease in PCr/Pi values.(ABSTRACT TRUNCATED AT 250 WORDS)

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

    Science.gov (United States)

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

    2014-03-26

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

  7. Cerium and yttrium oxide nanoparticles are neuroprotective

    International Nuclear Information System (INIS)

    Schubert, David; Dargusch, Richard; Raitano, Joan; Chan, S.-W.

    2006-01-01

    The responses of cells exposed to nanoparticles have been studied with regard to toxicity, but very little attention has been paid to the possibility that some types of particles can protect cells from various forms of lethal stress. It is shown here that nanoparticles composed of cerium oxide or yttrium oxide protect nerve cells from oxidative stress and that the neuroprotection is independent of particle size. The ceria and yttria nanoparticles act as direct antioxidants to limit the amount of reactive oxygen species required to kill the cells. It follows that this group of nanoparticles could be used to modulate oxidative stress in biological systems

  8. Cerium oxide for the destruction of chemical warfare agents: A comparison of synthetic routes

    Czech Academy of Sciences Publication Activity Database

    Janos, P.; Henych, Jiří; Pelant, O.; Pilařová, V.; Vrtoch, L.; Kormunda, M.; Mazanec, K.; Štengl, Václav

    2016-01-01

    Roč. 304, MAR (2016), s. 259-268 ISSN 0304-3894 Institutional support: RVO:61388980 Keywords : Cerium oxide * Chemical warfare agents * Organophosphate compounds * Decontamination Subject RIV: CA - Inorganic Chemistry Impact factor: 6.065, year: 2016

  9. Effect of Thickness on the Morphology and Corrosion Behavior of Cerium-Based Conversion Coatings on AZ31B Magnesium Alloy

    Science.gov (United States)

    Castano, Carlos E.; Maddela, Surender; O'Keefe, Matthew J.; Wang, Yar-Ming

    Cerium-based conversion coatings (CeCCs) were deposited onto AZ31B magnesium alloy substrates using a spontaneous reaction of CeCl3, H2O2 and gelatin in a water-based solution. The coating thickness was adjusted by controlling the immersion time in the deposition solution. Prior to deposition, the AZ31B substrates were treated using an acid pickling in nitric acid and then an alkaline cleaning in sodium metasilicate pentahydrate. After deposition, the coated samples were immersed in a phosphate bath that converted cerium oxide/hydroxide into cerium phosphate. Electrochemical impedance spectroscopy, potentiodynamic polarization and neutral salt spray testing studies indicated that 100 nm thick CeCC had better corrosion performance than 400 nm coatings. Characterization of the CeCCs by transmission electron microscopy (TEM) revealed a three layer structure with different compositions.

  10. Interactions between sub-10-nm iron and cerium oxide nanoparticles and 3T3 fibroblasts: the role of the coating and aggregation state

    International Nuclear Information System (INIS)

    Safi, M; Sarrouj, H; Berret, J-F; Sandre, O; Mignet, N

    2010-01-01

    Recent nanotoxicity studies revealed that the physico-chemical characteristics of engineered nanomaterials play an important role in the interactions with living cells. Here, we report on the toxicity and uptake of cerium and iron oxide sub-10-nm nanoparticles by NIH/3T3 mouse fibroblasts. Coating strategies include low-molecular weight ligands (citric acid) and polymers (poly(acrylic acid), M W = 2000 g mol -1 ). Electrostatically adsorbed on the surfaces, the organic moieties provide a negatively charged coating in physiological conditions. We find that most particles were biocompatible, as exposed cells remained 100% viable relative to controls. Only the bare and the citrate-coated nanoceria exhibit a slight decrease in mitochondrial activity at very high cerium concentrations (>1 g l -1 ). We also observe that the citrate-coated particles are internalized/adsorbed by the cells in large amounts, typically 250 pg/cell after 24 h incubation for iron oxide. In contrast, the polymer-coated particles are taken up at much lower rates (<30 pg/cell). The strong uptake shown by the citrated particles is related to the destabilization of the dispersions in the cell culture medium and their sedimentation down to the cell membranes. In conclusion, we show that the uptake of nanomaterials by living cells depends on the coating of the particles and on its ability to preserve the colloidal nature of the dispersions.

  11. Interactions between sub-10-nm iron and cerium oxide nanoparticles and 3T3 fibroblasts: the role of the coating and aggregation state

    Science.gov (United States)

    Safi, M.; Sarrouj, H.; Sandre, O.; Mignet, N.; Berret, J.-F.

    2010-04-01

    Recent nanotoxicity studies revealed that the physico-chemical characteristics of engineered nanomaterials play an important role in the interactions with living cells. Here, we report on the toxicity and uptake of cerium and iron oxide sub-10-nm nanoparticles by NIH/3T3 mouse fibroblasts. Coating strategies include low-molecular weight ligands (citric acid) and polymers (poly(acrylic acid), MW = 2000 g mol - 1). Electrostatically adsorbed on the surfaces, the organic moieties provide a negatively charged coating in physiological conditions. We find that most particles were biocompatible, as exposed cells remained 100% viable relative to controls. Only the bare and the citrate-coated nanoceria exhibit a slight decrease in mitochondrial activity at very high cerium concentrations (>1 g l - 1). We also observe that the citrate-coated particles are internalized/adsorbed by the cells in large amounts, typically 250 pg/cell after 24 h incubation for iron oxide. In contrast, the polymer-coated particles are taken up at much lower rates (<30 pg/cell). The strong uptake shown by the citrated particles is related to the destabilization of the dispersions in the cell culture medium and their sedimentation down to the cell membranes. In conclusion, we show that the uptake of nanomaterials by living cells depends on the coating of the particles and on its ability to preserve the colloidal nature of the dispersions.

  12. Interactions between sub-10-nm iron and cerium oxide nanoparticles and 3T3 fibroblasts: the role of the coating and aggregation state

    Energy Technology Data Exchange (ETDEWEB)

    Safi, M; Sarrouj, H; Berret, J-F [Matiere et Systemes Complexes, UMR 7057 CNRS, Universite Denis Diderot Paris VII, Batiment Condorcet, 10 rue Alice Domon et Leonie Duquet, F-75205 Paris (France); Sandre, O [UPMC Universite Paris VI-Laboratoire de Physico-chimie des Electrolytes, Colloides et Sciences Analytiques, UMR 7195 UPMC Universite Paris 6/CNRS/ESPCI Paristech, 4 place Jussieu, F-75252 Paris Cedex 05 (France); Mignet, N, E-mail: jean-francois.berret@univ-paris-diderot.fr [CNRS UMR 8151, Faculte de Pharmacie, 4 avenue de l' Observatoire, F-75270 Paris (France)

    2010-04-09

    Recent nanotoxicity studies revealed that the physico-chemical characteristics of engineered nanomaterials play an important role in the interactions with living cells. Here, we report on the toxicity and uptake of cerium and iron oxide sub-10-nm nanoparticles by NIH/3T3 mouse fibroblasts. Coating strategies include low-molecular weight ligands (citric acid) and polymers (poly(acrylic acid), M{sub W} = 2000 g mol{sup -1}). Electrostatically adsorbed on the surfaces, the organic moieties provide a negatively charged coating in physiological conditions. We find that most particles were biocompatible, as exposed cells remained 100% viable relative to controls. Only the bare and the citrate-coated nanoceria exhibit a slight decrease in mitochondrial activity at very high cerium concentrations (>1 g l{sup -1}). We also observe that the citrate-coated particles are internalized/adsorbed by the cells in large amounts, typically 250 pg/cell after 24 h incubation for iron oxide. In contrast, the polymer-coated particles are taken up at much lower rates (<30 pg/cell). The strong uptake shown by the citrated particles is related to the destabilization of the dispersions in the cell culture medium and their sedimentation down to the cell membranes. In conclusion, we show that the uptake of nanomaterials by living cells depends on the coating of the particles and on its ability to preserve the colloidal nature of the dispersions.

  13. Cerium compounds in the fashion of the light actinides

    International Nuclear Information System (INIS)

    Koelling, D.D.

    1985-01-01

    Researchers familiar with the light actinides easily recognize in cerium compounds a microcosm of the rich variety of properties seen in the light actinides. The parallelism seen between comparable cerium and actinide compounds strongly suggests that the same physical models are applicable. The most significant is the relative size of the f-orbital. Localization is generally tighter in Ce compounds than uranium compounds, making Ce roughly analogous to Np through Am. A way to see the actinide parallelism is to compare Hill plots. Compounds in the different regions of the plots (representing different physics) are isostructural compounds with the same companion (B) elements. The most common materials expected to exhibit direct f-f interaction are the cubic Laves compounds. Accordingly, we have determined the band structures of CeRu 2 , CeRh 2 , CeIr 2 , and CeNi 2 . Surprisingly, it was found that an f-d interaction overshadows any direct f-f interaction in these systems. Compounds illustrative of the interaction of f-orbitals with ''ligand'' orbitals are the Cu 3 Au structured materials. Materials calculated in this class are CeRh 3 , CePd 3 , and CeSn 3 - the materials of much interest as ''mixed valent''. Although the focus is on the Ce compounds, calculations performed on uranium isomorphs are used to highlight the interesting physics. (orig.)

  14. Conductivity in redox modified conducting polymers. In-situ conductivity of poly(cyclopentadithiophenes) bearing p-nitrophenyl and 4-N-methylpyridinium groups

    Energy Technology Data Exchange (ETDEWEB)

    Zotti, G. [Consiglio Nazionale delle Ricerche, (Italy). Istituto di Polarografia ed Elettrochimica Preparativa; Berlin, A. [Milan Univ. (Italy). Dipartimento di Chimica Organica e Industriale; Pagani, G. [Milan Univ. (Italy). Dipartimento di Chimica Organica e Industriale; Schiavon, G. [Consiglio Nazionale delle Ricerche, (Italy). Istituto di Polarografia ed Elettrochimica Preparativa; Zecchin, S. [Consiglio Nazionale delle Ricerche, (Italy). Istituto di Polarografia ed Elettrochimica Preparativa

    1995-01-01

    Redox-modified polythiophenes exhibiting the highest mixed-valence conductivities of any polymer containing a pendant redox group are reported. The ordering of the polymer, in which the backbone has been oxidized to a bipolaron conducting state and the redox sites have been reduced to a mixed-valence conducting state, encourages inter-site hopping and results in the high conductivities. Electron interactions are shown not have an influence on the conduction. (orig.)

  15. Content of redox-active compounds (ie, antioxidants) in foods consumed in the United States.

    Science.gov (United States)

    Halvorsen, Bente L; Carlsen, Monica H; Phillips, Katherine M; Bøhn, Siv K; Holte, Kari; Jacobs, David R; Blomhoff, Rune

    2006-07-01

    Supplements containing ascorbic acid, alpha-tocopherol, or beta-carotene do not protect against oxidative stress-related diseases in most randomized intervention trials. We suggest that other redox-active phytochemicals may be more effective and that a combination of different redox-active compounds (ie, antioxidants or reductants) may be needed for proper protection against oxidative damage. We aimed to generate a ranked food table with values for total content of redox-active compounds to test this alternative antioxidant hypothesis. An assay that measures the total concentration of redox-active compounds above a certain cutoff reduction potential was used to analyze 1113 food samples obtained from the US Department of Agriculture National Food and Nutrient Analysis Program. Large variations in the content of antioxidants were observed in different foods and food categories. The food groups spices and herbs, nuts and seeds, berries, and fruit and vegetables all contained foods with very high antioxidant contents. Most food categories also contained products almost devoid of antioxidants. Of the 50 food products highest in antioxidant concentrations, 13 were spices, 8 were in the fruit and vegetables category, 5 were berries, 5 were chocolate-based, 5 were breakfast cereals, and 4 were nuts or seeds. On the basis of typical serving sizes, blackberries, walnuts, strawberries, artichokes, cranberries, brewed coffee, raspberries, pecans, blueberries, ground cloves, grape juice, and unsweetened baking chocolate were at the top of the ranked list. This ranked antioxidant food table provides a useful tool for investigations into the possible health benefit of dietary antioxidants.

  16. Effect of cerium additive and secondary phase analysis on Ag0.5Bi0 ...

    Indian Academy of Sciences (India)

    Technical University of Madrid (UPM), Madrid 28012, Spain. MS received 27 ... XRD analysis showed the presence of pyrochlore structure and secondary phase when more .... The present work reports the effect of incorporation of cerium in ...

  17. Separation of uranium(V I) from binary solution mixtures with thorium(IV), zirconium(IV) and cerium(III) by foaming

    International Nuclear Information System (INIS)

    Shakir, K.; Aziz, M.; Benyamin, K.

    1992-01-01

    Foam separation has been investigated for the removal of uranium(V I), thorium(IV), zirconium(IV) and cerium(III) from dilute aqueous solutions at pH values ranging from about I to about II. Sodium laurel sulphate (Na L S) and acetyl trimethyl ammonium bromide (CTAB), being a strong anionic and a strong cationic surfactants, were used as collectors. The results indicate that Na L S can efficiently remove thorium(IV), zirconium(IV) and cerium(III) but not uranium(V I). CTAB, on the other hand, can successfully float only uranium(V I) and zirconium(IV). These differences in flotation properties of the different cations could be used to establish methods for the separation of uranium(V I) from binary mixtures with thorium(IV), zirconium(IV) or cerium(III). The results are discussed in terms of the hydrolytic behaviour of the tested cations and properties of used collectors.2 fig., 1 tab

  18. Reactivity in the removal of SO{sub 2} and NO{sub x} on Co/Mg/Al mixed oxides derived from hydrotalcites

    Energy Technology Data Exchange (ETDEWEB)

    Palomares, A.E. [Department of Chemical and Nuclear Engineering, Universidad Politecnica Valencia, Avda. de los Naranjos s/n, 46022 Valencia (Spain); Lopez-Nieto, J.M.; Corma, A. [Instituto de Tecnologia Quimica, UPV-CSIC, Universidad Politecnica de Valencia, Avenida de los Naranjos s/n., 46022 Valencia (Spain); Lazaro, F.J.; Lopez, A. [Instituto Ciencia de Materiales de Aragon (CSIC- Universidad de Zaragoza), 50015 Zaragoza (Spain)

    1999-04-05

    Metal containing hydrotalcites, where metal oxides present redox properties and hydrotalcite shows a basic character, appear to be new important environmental catalysts for the removal of SO{sub x} and NO{sub x}. Redox and basic properties of a mixed Co/Mg/Al oxide derived from hydrotalcites are tuned in order to achieve the optimal catalytic behavior required. This sample has been characterized showing that cobalt is present in two forms, as isolated and well dispersed paramagnetic ions, and as very small Co-containing particles (in the nanometric range), with an internal antiferromagnetic ordering at low temperature. The redox properties of cobalt allow the reduction of NO with propane at high temperatures and in presence of oxygen. The reduced cobalt species are proposed as the active sites. Nevertheless, for the removal of SO{sub 2} and contrary to the case of Cu/Mg/Al samples, the addition of an oxidant as cerium oxide on Co/Mg/Al is necessary in order to oxidize SO{sub 2} to SO{sub 3}. In this case, similar results than those obtained with previously reported catalyst, i.e. cerium or copper-cerium hydrotalcite, are obtained. These results indicate that this catalyst could be an adequate material for the simultaneous removal of SO{sub 2} and NO{sub x} in a FCC unit

  19. Sodium nitrate-cerium nitrate-water ternary system at 25 deg C

    International Nuclear Information System (INIS)

    Fedorenko, T.P.; Onishchenko, M.K.

    1978-01-01

    Solubility isotherm of sodium nitrate-cerium nitrate-water system at 25 deg C consists of three crystallization branches of initial salts and double compound of the composition 2NaNO 3 xCe(NO 3 ) 3 x2H 2 O. Sodium nitrate introduced in the solution strengthens complexing. Physico-chemical characteristics are in a good agreement with solubility curve

  20. Alteration of the redox state with reactive oxygen species for 5-fluorouracil-induced oral mucositis in hamsters.

    Directory of Open Access Journals (Sweden)

    Fumihiko Yoshino

    Full Text Available Oral mucositis is often induced in patients receiving cancer chemotherapy treatment. It has been reported that oral mucositis can reduce quality of life, as well as increasing the incidence of mortality. The participation of reactive oxygen species (ROS in the pathogenesis of oral mucositis is well known, but no report has actually demonstrated the presence of ROS. Thus, the purpose of this study was thus to demonstrate the involvement of ROS and the alteration of the redox state in oral mucositis using an in vivo L-band electron spin resonance (ESR technique. An oral mucositis animal model induced by treatment of 5-fluorouracil with 10% acetic acid in hamster cheek pouch was used. Lipid peroxidation was measured as the level of malondialdehyde determined by the thiobarbituric acid reaction. The rate constants of the signal decay of nitroxyl compounds using in vivo L-band ESR were calculated from the signal decay curves. Firstly, we established the oral mucositis animal model induced by treatment of 5-fluorouracil with acetic acid in hamster cheek pouch. An increased level of lipid peroxidation in oral mucositis was found by measuring malondialdehyde using isolated hamster cheek pouch ulcer. In addition, as a result of in vivo L-band ESR measurements using our model animals, the decay rate constants of carbamoyl-PROXYL, which is a reagent for detecting the redox balance in tissue, were decreased. These results suggest that a redox imbalance might occur by excessive generation of ROS at an early stage of oral mucositis and the consumption of large quantities of antioxidants including glutathione in the locality of oral mucositis. These findings support the presence of ROS involved in the pathogenesis of oral mucositis with anti-cancer therapy, and is useful for the development of novel therapies drugs for oral mucositis.

  1. Effects of ethylenediaminetetraacetic acid (EDTA)and diethylenetriaminepentaacetic acid (DTPA) derivatives on penetration of ytterbium-169 and cerium-144 into the rat offspring

    Energy Technology Data Exchange (ETDEWEB)

    Baltrukiewicz, Z; Burakowski, T; Derecki, J [Wojskowy Inst. Higieny i Epidemiologii, Warsaw (Poland)

    1976-01-01

    Penetration of radioactive ytterbum-169 and cerium-144 into fetuses was determined at the end of pregnancy and penetration into the organism of suckling rats was studied during feeding with the milk of exposed mothers when EDTA or DTPA derivatives were being administered. Injection of ytterbum-169 as a complex with EDTA or DTPA or injection of Na/sub 2/Ca EDTA or Na/sub 3/Ca DTPA 1h after administration of cerium-144 to mothers reduced penetration of both radionuclides into offsprings in relation to the animals receiving no complex compounds. It was observed that the action of DTPA was stronger than that of EDTA. Passage of ytterbium with milk and across the placenta was greater than the passage of cerium.

  2. Redox regulation in photosynthetic organisms: signaling, acclimation, and practical implications.

    Science.gov (United States)

    Foyer, Christine H; Noctor, Graham

    2009-04-01

    Reactive oxygen species (ROS) have multifaceted roles in the orchestration of plant gene expression and gene-product regulation. Cellular redox homeostasis is considered to be an "integrator" of information from metabolism and the environment controlling plant growth and acclimation responses, as well as cell suicide events. The different ROS forms influence gene expression in specific and sometimes antagonistic ways. Low molecular antioxidants (e.g., ascorbate, glutathione) serve not only to limit the lifetime of the ROS signals but also to participate in an extensive range of other redox signaling and regulatory functions. In contrast to the low molecular weight antioxidants, the "redox" states of components involved in photosynthesis such as plastoquinone show rapid and often transient shifts in response to changes in light and other environmental signals. Whereas both types of "redox regulation" are intimately linked through the thioredoxin, peroxiredoxin, and pyridine nucleotide pools, they also act independently of each other to achieve overall energy balance between energy-producing and energy-utilizing pathways. This review focuses on current knowledge of the pathways of redox regulation, with discussion of the somewhat juxtaposed hypotheses of "oxidative damage" versus "oxidative signaling," within the wider context of physiological function, from plant cell biology to potential applications.

  3. The fairytale of the GSSG/GSH redox potential.

    Science.gov (United States)

    Flohé, Leopold

    2013-05-01

    The term GSSG/GSH redox potential is frequently used to explain redox regulation and other biological processes. The relevance of the GSSG/GSH redox potential as driving force of biological processes is critically discussed. It is recalled that the concentration ratio of GSSG and GSH reflects little else than a steady state, which overwhelmingly results from fast enzymatic processes utilizing, degrading or regenerating GSH. A biological GSSG/GSH redox potential, as calculated by the Nernst equation, is a deduced electrochemical parameter based on direct measurements of GSH and GSSG that are often complicated by poorly substantiated assumptions. It is considered irrelevant to the steering of any biological process. GSH-utilizing enzymes depend on the concentration of GSH, not on [GSH](2), as is predicted by the Nernst equation, and are typically not affected by GSSG. Regulatory processes involving oxidants and GSH are considered to make use of mechanistic principles known for thiol peroxidases which catalyze the oxidation of hydroperoxides by GSH by means of an enzyme substitution mechanism involving only bimolecular reaction steps. The negligibly small rate constants of related spontaneous reactions as compared with enzyme-catalyzed ones underscore the superiority of kinetic parameters over electrochemical or thermodynamic ones for an in-depth understanding of GSH-dependent biological phenomena. At best, the GSSG/GSH potential might be useful as an analytical tool to disclose disturbances in redox metabolism. This article is part of a Special Issue entitled Cellular Functions of Glutathione. Copyright © 2012 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2015-11-11

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

  5. Electrical switching and memory phenomena observed in redox-gradient dendrimer sandwich devices

    OpenAIRE

    Li, JianChang; Blackstock, Silas C.; Szulczewski, Greg J.

    2005-01-01

    We report on the fabrication of dendrimer sandwich devices with electrical switching and memory properties. The storage media is consisted of a redox-gradient dendrimer layer sandwiched in organic barrier thin films. The dendrimer layer acts as potential well where redox-state changes and consequent electrical transitions of the embedded dendrimer molecules are expected to be effectively triggered and retained, respectively. Experimental results indicated that electrical switching could be re...

  6. Cerium(III-Selective Membrane Electrode Based on Dibenzo-24-crown-8 as a Neutral Carrier

    Directory of Open Access Journals (Sweden)

    Susheel K. Mittal

    2010-01-01

    Full Text Available Cerium(III-selective membrane electrodes have been prepared using dibenzo-24-crown-8 (DB24C8 as an electroactive material. A membrane having a composition: DB24C8 (4.5%, plasticizer (NPOE, 62.5% and PVC (33% gives the best performance. It works well over a wide Ce(III ion-concentration range of 1x10-5 M to 1x10-1 M with a Nernstian slope of 19.0 mV/decade and a detection limit of 3x10-5 M. It has a fast response time of 20 seconds and has an average lifetime of four months. The internal solution concentration does not have a significant effect on the response of the electrode except for a change in intercept of the calibration curves. The working pH range for Ce(III solutions (1x10-2 M and 1x10-3 M is 3.5-8.0. The proposed sensor shows a good selectivity for cerium(III with respect to alkali, alkaline earth, some transition and rare earth metal ions that are normally present along with cerium in its ores. The proposed sensor was investigated in partially non-aqueous media using acetone, methanol and DMSO mixtures with water. The electrode was further used as an indicator electrode for the potentiometric titration of Ce(III solution against oxalic acid solution.

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

    International Nuclear Information System (INIS)

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

    2010-01-01

    from oxidation using transportation under liquid N 2 from drilling site to laboratory glove-box. The m rel parameters for clay minerals in this sample were measured by combining acid digestion method and Moessbauer spectrometry. Sodium concentration (∼0.06 mol/L) and pH (∼7.2) of the solution contacting the clay are known from thermodynamic modelling and direct measurement in instrumented boreholes on site. As a consequence, application of Equation 1 should lead to a correct estimate of the redox potential in the clay rock. Calculated E clay is equal to + 0.32 V. This value is clearly not realistic. Expected value is in the range [- 0.2 V; - 0.16 V] according to the presence of sulphate and pyrite in the system. This disagreement points out (i) either an absence of true equilibrium between the redox state as probed by the Fe(III)/Fe(II) couple in the clay structure and the redox state of solution species or (ii) the non-applicability of Equation 1 for very reduced clay with low iron content. Additional O 2 kinetics experiments and use of the empirical relationship relating O 2 consumption kinetics to the redox potential of Fe(III)/Fe(II) redox couple defined by Wehrli (1990) seems to support the second hypothesis together with preliminary cyclic voltammetric measurements on our clay modified electrodes

  8. Dissecting Redox Biology Using Fluorescent Protein Sensors.

    Science.gov (United States)

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

    2016-05-01

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

  9. Redox Buffer Strength

    Science.gov (United States)

    de Levie, Robert

    1999-04-01

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

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

    Science.gov (United States)

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

    2010-09-15

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

  11. Iterative absolute electroanalytical approach to characterization of bulk redox conducting systems.

    Science.gov (United States)

    Lewera, Adam; Miecznikowski, Krzysztof; Chojak, Malgorzata; Makowski, Oktawian; Golimowski, Jerzy; Kulesza, Pawel J

    2004-05-15

    A novel electroanalytical approach is proposed here, and it is demonstrated with the direct and simultaneous determination of two unknowns: the concentration of redox sites and the apparent diffusion coefficient for charge propagation in a single crystal of dodecatungstophosphoric acid. This Keggin-type polyoxometalate serves as a model bulk redox conducting inorganic material for solid-state voltammetry. The system has been investigated using an ultramicrodisk working electrode in the absence of external liquid supporting electrolyte. The analytical method requires numerical solution of the combination of two equations in which the first one describes current (or charge) in a well-defined (either spherical or linear) diffusional regime and the second general equation describes chronoamperometric (or normal pulse voltammetric current) under mixed (linear-spherical) conditions. The iterative approach is based on successive approximations through calculation and minimizing the least-squares error function. The method is fairly universal, and in principle, it can be extended to the investigation of other bulk systems including sol-gel processed materials, redox melts, and solutions on condition that they are electroactive and well behaved, they contain redox centers at sufficiently high level, and a number of electrons for the redox reaction considered is known.

  12. A novel strategy for global analysis of the dynamic thiol redox proteome.

    Science.gov (United States)

    Martínez-Acedo, Pablo; Núñez, Estefanía; Gómez, Francisco J Sánchez; Moreno, Margoth; Ramos, Elena; Izquierdo-Álvarez, Alicia; Miró-Casas, Elisabet; Mesa, Raquel; Rodriguez, Patricia; Martínez-Ruiz, Antonio; Dorado, David Garcia; Lamas, Santiago; Vázquez, Jesús

    2012-09-01

    Nitroxidative stress in cells occurs mainly through the action of reactive nitrogen and oxygen species (RNOS) on protein thiol groups. Reactive nitrogen and oxygen species-mediated protein modifications are associated with pathophysiological states, but can also convey physiological signals. Identification of Cys residues that are modified by oxidative stimuli still poses technical challenges and these changes have never been statistically analyzed from a proteome-wide perspective. Here we show that GELSILOX, a method that combines a robust proteomics protocol with a new computational approach that analyzes variance at the peptide level, allows a simultaneous analysis of dynamic alterations in the redox state of Cys sites and of protein abundance. GELSILOX permits the characterization of the major endothelial redox targets of hydrogen peroxide in endothelial cells and reveals that hypoxia induces a significant increase in the status of oxidized thiols. GELSILOX also detected thiols that are redox-modified by ischemia-reperfusion in heart mitochondria and demonstrated that these alterations are abolished in ischemia-preconditioned animals.

  13. Adaptive changes in renal mitochondrial redox status in diabetic nephropathy

    Energy Technology Data Exchange (ETDEWEB)

    Putt, David A.; Zhong, Qing; Lash, Lawrence H., E-mail: l.h.lash@wayne.edu

    2012-01-15

    Nephropathy is a serious and common complication of diabetes. In the streptozotocin (STZ)-treated rat model of diabetes, nephropathy does not typically develop until 30 to 45 days post-injection, although hyperglycemia occurs within 24 h. We tested the hypothesis that chronic hyperglycemia results in a modest degree of oxidative stress that is accompanied by compensatory changes in certain antioxidants and mitochondrial redox status. We propose that as kidneys progress to a state of diabetic nephropathy, further adaptations occur in mitochondrial redox status. Basic parameters of renal function in vivo and several parameters of mitochondrial function and glutathione (GSH) and redox status in isolated renal cortical mitochondria from STZ-treated and age-matched control rats were examined at 30 days and 90 days post-injection. While there was no effect of diabetes on blood urea nitrogen, measurement of other, more sensitive parameters, such as urinary albumin and protein, and histopathology showed significant and progressive worsening in diabetic rats. Thus, renal function is compromised even prior to the onset of frank nephropathy. Changes in mitochondrial respiration and enzyme activities indicated existence of a hypermetabolic state. Higher mitochondrial GSH content and rates of GSH transport into mitochondria in kidneys from diabetic rats were only partially due to changes in expression of mitochondrial GSH carriers and were mostly due to higher substrate supply. Although there are few clear indicators of oxidative stress, there are several redox changes that occur early and change further as nephropathy progresses, highlighting the complexity of the disease. Highlights: ►Adaptive changes in renal mitochondrial and redox status in diabetic rats. ►Modest renal dysfunction even prior to onset of nephropathy. ►Elevated concentrations of mitochondrial GSH in diabetic kidneys. ►Change in GSH due partly to increased protein expression of transporter.

  14. Adaptive changes in renal mitochondrial redox status in diabetic nephropathy

    International Nuclear Information System (INIS)

    Putt, David A.; Zhong, Qing; Lash, Lawrence H.

    2012-01-01

    Nephropathy is a serious and common complication of diabetes. In the streptozotocin (STZ)-treated rat model of diabetes, nephropathy does not typically develop until 30 to 45 days post-injection, although hyperglycemia occurs within 24 h. We tested the hypothesis that chronic hyperglycemia results in a modest degree of oxidative stress that is accompanied by compensatory changes in certain antioxidants and mitochondrial redox status. We propose that as kidneys progress to a state of diabetic nephropathy, further adaptations occur in mitochondrial redox status. Basic parameters of renal function in vivo and several parameters of mitochondrial function and glutathione (GSH) and redox status in isolated renal cortical mitochondria from STZ-treated and age-matched control rats were examined at 30 days and 90 days post-injection. While there was no effect of diabetes on blood urea nitrogen, measurement of other, more sensitive parameters, such as urinary albumin and protein, and histopathology showed significant and progressive worsening in diabetic rats. Thus, renal function is compromised even prior to the onset of frank nephropathy. Changes in mitochondrial respiration and enzyme activities indicated existence of a hypermetabolic state. Higher mitochondrial GSH content and rates of GSH transport into mitochondria in kidneys from diabetic rats were only partially due to changes in expression of mitochondrial GSH carriers and were mostly due to higher substrate supply. Although there are few clear indicators of oxidative stress, there are several redox changes that occur early and change further as nephropathy progresses, highlighting the complexity of the disease. Highlights: ►Adaptive changes in renal mitochondrial and redox status in diabetic rats. ►Modest renal dysfunction even prior to onset of nephropathy. ►Elevated concentrations of mitochondrial GSH in diabetic kidneys. ►Change in GSH due partly to increased protein expression of transporter.

  15. Cerium intermetallics CeTX. Review III

    Energy Technology Data Exchange (ETDEWEB)

    Poettgen, Rainer; Janka, Oliver [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Chevalier, Bernard [Bordeaux Univ., Pessac (France). Inst. de Chimie de la Matiere Condensee de Bordeaux

    2016-05-01

    The structure-property relationships of CeTX intermetallics with structures other than the ZrNiAl and TiNiSi type are systematically reviewed. These CeTX phases form with electron-poor and electron-rich transition metals (T) and X = Mg, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, and Bi. The review focusses on the crystal chemistry, the chemical bonding peculiarities, and the magnetic and transport properties. Furthermore {sup 119}Sn Moessbauer spectroscopic data, high-pressure studies, hydrogenation reactions and the formation of solid solutions are reviewed. This paper is the third of a series of four reviews on equiatomic intermetallic cerium compound [Part I: R. Poettgen, B. Chevalier, Z. Naturforsch. 2015, 70b, 289; Part II: R. Poettgen, B. Chevalier, Z. Naturforsch. 2015, 70b, 695].

  16. Investigation of the redox-dependent modulation of structure and dynamics in human cytochrome c

    Energy Technology Data Exchange (ETDEWEB)

    Imai, Mizue [Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810 (Japan); Saio, Tomohide [Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810 (Japan); Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810 (Japan); Kumeta, Hiroyuki [Faculty of Advanced Life Science, Hokkaido University, Sapporo 001-0021 (Japan); Uchida, Takeshi [Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810 (Japan); Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810 (Japan); Inagaki, Fuyuhiko [Faculty of Advanced Life Science, Hokkaido University, Sapporo 001-0021 (Japan); Ishimori, Koichiro, E-mail: koichiro@sci.hokudai.ac.jp [Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810 (Japan); Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810 (Japan)

    2016-01-22

    Redox-dependent changes in the structure and dynamics of human cytochrome c (Cyt c) were investigated by solution NMR. We found significant structural changes in several regions, including residues 23–28 (loop 3), which were further corroborated by chemical shift differences between the reduced and oxidized states of Cyt c. These differences are essential for discriminating redox states in Cyt c by cytochrome c oxidase (CcO) during electron transfer reactions. Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion experiments identified that the region around His33 undergoes conformational exchanges on the μs-ms timescale, indicating significant redox-dependent structural changes. Because His33 is not part of the interaction site for CcO, our data suggest that the dynamic properties of the region, which is far from the interaction site for CcO, contribute to conformational changes during electron transfer to CcO. - Highlights: • Solution structure and dynamics analysis for human Cyt c by NMR. • Structural changes responsible for the discrimination of the redox state in Cyt c. • Conformational exchange in the region outside of the interaction site for CcO. • Less flexibility and rigid structure of the interaction site on Cyt c for CcO.

  17. Mixed mode and sequential oscillations in the cerium-bromate-4-aminophenol photoreaction

    Energy Technology Data Exchange (ETDEWEB)

    Bell, Jeffrey G.; Wang Jichang [Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario N9B 3P4 (Canada)

    2013-09-15

    Cerium was introduced to the bromate-aminophenol photochemical oscillator to implement coupled autocatalytic feedbacks. Mixed mode and sequential oscillations emerged in the studied system, making it one of the few chemical oscillators known to support consecutive bifurcations in a batch system. The complex reaction behavior showed a strong dependence on the intensity of illumination supplied to the system. Removal of illumination during an oscillatory window affected both the frequency and amplitude of the oscillation but did not fully extinguish them, indicating that the cerium-bromate-4-aminophenol oscillator was photosensitive rather than photo-controlled. A moderate light intensity allowed for a slow evolution of the system, which proved to be critical for the emergence of transient complex oscillations. Variation of individual reaction parameters was carried out, which indicated that the development of complex oscillations occur in a narrow region and a phase diagram in the 4-aminophenol and sulfuric acid plane demonstrated this. Simulations provide strong support that transient complex oscillations observed experimentally arise from the coupling of two autocatalytic cycles.

  18. Microstructure and electrochemical behavior of cerium conversion coating modified with silane agent on magnesium substrates

    Energy Technology Data Exchange (ETDEWEB)

    Lei, Li; Shi, Jing, E-mail: shijing@ouc.edu.cn; Wang, Xin, E-mail: wangxin.hd@163.com; Liu, Dan; Xu, Haigang

    2016-07-15

    Graphical abstract: The unmodified coating shows averaged static water contact angles of a little more than 50º, which is clearly hydrophilic for water solutions. With the silane concentration increases, the water contact angles show an increase tendency. Especially, when the silane addition is increased to 25 ml L-1, the coating surface presents a hydrophobic feature, with static water contact angle of more than 110º. - Highlights: • BTESPT modification can effectively improve the uniformity, hydrophobic performance, chemical stability and corrosion inhibition capability of traditional cerium conversion coating. • Si-O-Si linkage builds a robust structure to increase of the coating density. Si−O−Mg bonds strengthen the adhesion between the coating/substrate. • The system modified with 25 ml L{sup −1} BTESPT displays the optimum corrosion protection performance. - Abstract: The cerium conversion coating with and without different concentrations of silane agent bis-(γ-triethoxysilylpropyl)-tetrasulfide (BTESPT) modification is obtained on magnesium alloys. Detailed properties of the coatings and the role of BTESPT as an additive are studied and followed with careful discussion. The coating morphology, wettability, chemical composition and corrosion resistance are characterized by scanning electronic microscope (SEM), water contact-angle, X-ray photoelectron spectroscopy (XPS), potentiodynamic measurements and electrochemical impedance spectroscopy (EIS). The electrochemical behavior of the coatings is investigated using EIS. The results indicate that the coating morphology and composition can be controlled by changing silane concentration. The combination of cerium ions and silane molecules could promote the formation of more homogenous and higher hydrophobic coating. The coating turns to be more compact and the adhesive strength between the coating and the magnesium substrate are strongly improved with the formation of Si−O−Si and Si

  19. Microstructure and electrochemical behavior of cerium conversion coating modified with silane agent on magnesium substrates

    International Nuclear Information System (INIS)

    Lei, Li; Shi, Jing; Wang, Xin; Liu, Dan; Xu, Haigang

    2016-01-01

    Graphical abstract: The unmodified coating shows averaged static water contact angles of a little more than 50º, which is clearly hydrophilic for water solutions. With the silane concentration increases, the water contact angles show an increase tendency. Especially, when the silane addition is increased to 25 ml L-1, the coating surface presents a hydrophobic feature, with static water contact angle of more than 110º. - Highlights: • BTESPT modification can effectively improve the uniformity, hydrophobic performance, chemical stability and corrosion inhibition capability of traditional cerium conversion coating. • Si-O-Si linkage builds a robust structure to increase of the coating density. Si−O−Mg bonds strengthen the adhesion between the coating/substrate. • The system modified with 25 ml L"−"1 BTESPT displays the optimum corrosion protection performance. - Abstract: The cerium conversion coating with and without different concentrations of silane agent bis-(γ-triethoxysilylpropyl)-tetrasulfide (BTESPT) modification is obtained on magnesium alloys. Detailed properties of the coatings and the role of BTESPT as an additive are studied and followed with careful discussion. The coating morphology, wettability, chemical composition and corrosion resistance are characterized by scanning electronic microscope (SEM), water contact-angle, X-ray photoelectron spectroscopy (XPS), potentiodynamic measurements and electrochemical impedance spectroscopy (EIS). The electrochemical behavior of the coatings is investigated using EIS. The results indicate that the coating morphology and composition can be controlled by changing silane concentration. The combination of cerium ions and silane molecules could promote the formation of more homogenous and higher hydrophobic coating. The coating turns to be more compact and the adhesive strength between the coating and the magnesium substrate are strongly improved with the formation of Si−O−Si and Si−O−M chemical

  20. Characterization of uranium redox state in organic-rich Eocene sediments.

    Science.gov (United States)

    Cumberland, Susan A; Etschmann, Barbara; Brugger, Joël; Douglas, Grant; Evans, Katy; Fisher, Louise; Kappen, Peter; Moreau, John W

    2018-03-01

    The presence of organic matter (OM) has a profound impact on uranium (U) redox cycling, either limiting or promoting the mobility of U via binding, reduction, or complexation. To understand the interactions between OM and U, we characterised U oxidation state and speciation in nine OM-rich sediment cores (18 samples), plus a lignite sample from the Mulga Rock polymetallic deposit in Western Australia. Uranium was unevenly dispersed within the analysed samples with 84% of the total U occurring in samples containing >21 wt % OM. Analyses of U speciation, including x-ray absorption spectroscopy and bicarbonate extractions, revealed that U existed predominately (∼71%) as U(VI), despite the low pH (4.5) and nominally reducing conditions within the sediments. Furthermore, low extractability by water, but high extractability by a bi-carbonate solution, indicated a strong association of U with particulate OM. The unexpectedly high proportion of U(VI) relative to U(IV) within the OM-rich sediments implies that OM itself does not readily reduce U, and the reduction of U is not a requirement for immobilizing uranium in OM-rich deposits. The fact that OM can play a significant role in limiting the mobility and reduction of U(VI) in sediments is important for both U-mining and remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.