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Reduction Kinetics (reduction + kinetics)
Selected AbstractsProbing the access of protons to the K pathway in the Paracoccus denitrificans cytochrome c oxidaseFEBS JOURNAL, Issue 2 2005Oliver-M. In recent studies on heme-copper oxidases a particular glutamate residue in subunit II has been suggested to constitute the entry point of the so-called K pathway. In contrast, mutations of this residue (E78II) in the Paracoccus denitrificans cytochrome c oxidase do not affect its catalytic activity at all (E78IIQ) or reduce it to about 50% (E78IIA); in the latter case, the mutation causes no drastic decrease in heme a3 reduction kinetics under anaerobic conditions, when compared to typical K pathway mutants. Moreover, both mutant enzymes retain full proton-pumping competence. While oxidized-minus-reduced Fourier-transform infrared difference spectroscopy demonstrates that E78II is indeed addressed by the redox state of the enzyme, absence of variations in the spectral range characteristic for protonated aspartic and glutamic acids at ,,1760 to 1710 cm,1 excludes the protonation of E78II in the course of the redox reaction in the studied pH range, although shifts of vibrational modes at 1570 and 1400 cm,1 reflect the reorganization of its deprotonated side chain at pH values greater than 4.8. We therefore conclude that protons do not enter the K channel via E78II in the Paracoccus enzyme. [source] Evaluation of RuxWySez Catalyst as a Cathode Electrode in a Polymer Electrolyte Membrane Fuel CellFUEL CELLS, Issue 1 2010K. Suárez-Alcántara Abstract The oxygen reduction reaction (ORR) on RuxWySez is of great importance in the development of a novel cathode electrode in a polymer electrolyte membrane fuel cell (PEMFC) technology. The RuxWySez electrocatalyst was synthesised in an organic solvent for 3,h. The powder was characterised by transmission electron microscopy (TEM), and powder X-ray diffraction (XRD). The electrocatalyst consisted of agglomerates of nanometric size (,50,150,nm) particles. In the electrochemical studies, rotating disc electrode (RDE) and rotating ring-disc electrode (RRDE) techniques were used to determine the oxygen reduction kinetics in 0.5,M H2SO4. The kinetic studies include the determination of Tafel slope (112,mV,dec,1), exchange current density at 25,°C (1.48,×,10,4,mA,cm,2) and the apparent activation energy of the oxygen reaction (52.1,,,0.4,kJ,mol,1). Analysis of the data shows a multi-electron charge transfer process to water formation, with 2% H2O2 production. A single PEMFC with the RuxWySez cathode catalysts generated a power density of 180,mW,cm,2. Performance achieved with a loading of 1.4,mg,cm,2 of a 40,wt% RuxWySez and 60,wt% carbon Vulcan (i.e. 0.56,mg,cm,2 of pure RuxWySez). Single PEMFC working was obtained with hydrogen and oxygen at 80,°C with 30,psi. [source] Shape-Controlled Synthesis of Pd Nanocrystals in Aqueous SolutionsADVANCED FUNCTIONAL MATERIALS, Issue 2 2009Byungkwon Lim Abstract This article provides an overview of recent developments regarding synthesis of Pd nanocrystals with well-controlled shapes in aqueous solutions. In a solution-phase synthesis, the final shape taken by a nanocrystal is determined by the twin structures of seeds and the growth rates of different crystallographic facets. Here, the maneuvering of these factors in an aqueous system to achieve shape control for Pd nanocrystals is discussed. L -ascorbic acid, citric acid, and poly(vinyl pyrrolidone) are tested for manipulating the reduction kinetics, with citric acid and Br, ions used as capping agents to selectively promote the formation of {111} and {100} facets, respectively. The distribution of single-crystal versus multiple-twinned seeds can be further manipulated by employing or blocking oxidative etching. The shapes obtained for the Pd nanocrystals include truncated octahedron, icosahedron, octahedron, decahedron, hexagonal and triangular plates, rectangular bar, and cube. The ability to control the shape of Pd nanocrystals provides a great opportunity to systematically investigate their catalytic, electrical, and plasmonic properties. [source] Effects of Mixing Granular Iron with Sand on the Kinetics of Trichloroethylene ReductionGROUND WATER MONITORING & REMEDIATION, Issue 2 2009Erping Bi A substantial cost of granular iron permeable reactive barriers is that of the granular iron itself. Cutting the iron with sand can reduce costs, but several performance issues arise. In particular, reaction rates are expected to decline as the percentage of iron in the blend is diminished. This might occur simply as a function of iron content, or mass transfer effects may play a role in a much less predictable fashion. Column experiments were conducted to investigate the performance consequences of mixing Connelly granular iron with sand using the reduction kinetics of trichloroethylene (TCE) to quantify the changes. Five mixing ratios (i.e., 100%, 85%, 75%, 50%, and 25% of iron by weight) were studied. The experimental data showed that there is a noticeable decrease in the reaction rate when the content of sand is 25% by weight (iron mass to pore volume ratio, Fe/Vp = 3548 g/L) or greater. An analysis of the reaction kinetics, using the Langmuir-Hinshelwood rate equation, indicated that mass transfer became an apparent cause of rate loss when the iron content fell below 50% by weight (Fe/Vp = 2223 g/L). Paradoxically, there were tentative indications that TCE removal rates were higher in a 15% sand + 85% iron mixture (Fe/Vp = 4416 g/L) than they were in 100% iron (Fe/Vp = 4577 g/L). This subtle improvement in performance might be due to an increase of iron surface available for contact with TCE, due to grain packing in the sand-iron mixture. [source] Optical in-situ study of the oxidation and reduction kinetics of Yb-substituted YAG epitaxial filmsPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 1 2005N. V. Martynyuk Abstract The optical spectra of the Yb-substituted Yb3Al5O12 (YAG) epitaxial films and the Yb ions recharging kinetics have been investigated by means of in-situ optical spectroscopy in the temperature range between 900 and 1100 °C at oxidation and reduction condition. This work continues the studies of the spectral properties of Yb:YAG epitaxial films represented in [1] and optical in-situ study of the re-oxidation kinetics of Yb3Al5O12 (YbAG) crystal represented in [2] where the model of internal oxidation of ytterbium ions Yb2+ , Yb3+ in the bulk crystal was developed and proofed. The changes of the absorption spectra of Yb:YAG film during oxidation and reduction were attributed to the recharging process Yb3+ , Yb2+. It was found that the oxidation kinetics in epitaxial films do not agree to the model [2] and do not follow a parabolic rate law in contrary to bulk YbAG single crystal. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] DE-loop mutations affect ,2 microglobulin stability, oligomerization, and the low-pH unfolded formPROTEIN SCIENCE, Issue 7 2010Carlo Santambrogio Abstract ,2 microglobulin (,2m) is the light chain of class-I major histocompatibility complex (MHC-I). Its accumulation in the blood of patients affected by kidney failure leads to amyloid deposition around skeletal joints and bones, a severe condition known as Dialysis Related Amyloidosis (DRA). In an effort to dissect the structural determinants of ,2m aggregation, several ,2m mutants have been previously studied. Among these, three single-residue mutations in the loop connecting strands D and E (W60G, W60V, D59P) have been shown to affect ,2m amyloidogenic properties, and are here considered. To investigate the biochemical and biophysical properties of wild-type (w.t.) ,2m and the three mutants, we explored thermal unfolding by Trp fluorescence and circular dichroism (CD). The W60G mutant reveals a pronounced increase in conformational stability. Protein oligomerization and reduction kinetics were investigated by electrospray-ionization mass spectrometry (ESI-MS). All the mutations analyzed here reduce the protein propensity to form soluble oligomers, suggesting a role for the DE-loop in intermolecular interactions. A partially folded intermediate, which may be involved in protein aggregation induced by acids, accumulates for all the tested proteins at pH 2.5 under oxidizing conditions. Moreover, the kinetics of disulfide reduction reveals specific differences among the tested mutants. Thus, ,2m DE-loop mutations display long-range effects, affecting stability and structural properties of the native protein and its low-pH intermediate. The evidence presented here hints to a crucial role played by the DE-loop in determining the overall properties of native and partially folded ,2m. [source] Synthesis of Gold Microplates Using Bovine Serum Albumin as a Reductant and a StabilizerCHEMISTRY - AN ASIAN JOURNAL, Issue 1 2010Leslie Au Abstract Gold microplates were synthesized in aqueous solutions by reducing HAuCl4 with the hydroxyl groups in both serine and threonine of bovine serum albumin (BSA), which is a globular protein in its native state. In this article, we systematically investigated the effects of temperature, pH value, the concentration of BSA, and ionic species on the reduction kinetics and thus the size and morphology of the final product. The optimal experimental conditions for producing uniform Au microplates include the following: an elevated temperature in the range of 55,65,°C, an acidic solution with pH,3, and the presence of NaCl (0.14,M). We found that if any one of these parameters was deviated from the optimal condition, Au microplates would not be formed in high yields. We also found that the surfaces of the as-synthesized Au microplates were covered by a dense array of BSA bumps. [source] | ||||||||||