Electrochemistry of Microperoxidase-11 (MP-11) on Glassy Carbon Electrode Modified with Chitosan

In this paper, microperoxidase-11 (MP-11) was immobilized on glassy carbon electrode surface modified with chitosan by physical adsorption. The direct electrochemistry and the electrocatalytic behaviours to O-2 and the H2O2 of MP-11 on glassy carbon electrode modified with chitosan were characterized by cyclic voltammetry. The results indicate that MP-11 on modified electrode displays a quasi-reversible electrochemical process coupled with proton transfer in the phosphate buffer solutions(pH = 7.12). Direct electrochemical reaction of MP-11 on modified electrode has been realized. MP-11 on modified electrode can catalyze reduction for O-2 and H2O2. Both of the catalytic reductions are surface-controlled electrochemical process.

Fabrication and electrochemical behaviors of multilayers composed of heteropholyanions and poly(diallyldimethylammonium chloride) on 4-aminothiophenol modified gold electrodes

Multilayer films composed of heteropolyanions (HPAS, SiMo11 VO405-) and cationic polymer poly(diallyldimethylammonium chloride) on 4-aminothiophenol self-assembled-monolayer were fabricated by electrochemical growth. Growth processes of the composite films were characterized by cyclic voltammetry. The results prove the third redox peak of Mo increases more rapidly, otherwise the other Mo redox peaks increase very slowly when the number of layers of heteropolyanions is greater. The peak potentials of composite films shift linearly to negative position with higher pH, which implies that protons are involved in the redox processes of HPA. The investigation of electrocatalytic behaviors of composite films shows a good catalytic activity for the reductions of HNO2 and BrO3-. Catalytic currents increase with increasing number of layers of heteropolyanions, moreover, the catalytic currents have a good linear relationship with the concentrations of BrO3-.

ELECTROCHEMICAL STUDY OF ISOPOLY AND HETEROPOLY OXOMETALLATE FILM MODIFIED MICROELECTRODES .5. PREPARATION AND ELECTROCHEMICAL-BEHAVIOR OF A 2/18-MOLYBDODIPHOSPHATE ANION MONOLAYER MODIFIED ELECTRODE

In this paper a carbon fibre (CF) microelectrode modified with the 2:18-molybdodiphosphate anion by simple adsorption is described and its electrochemical behaviour is reported. The 2:18-molybdodiphosphate anion (alpha-P2Mo18O626-), which is a Dawson structure, undergoes five successive multielectron reductions in acidic solution. The first three redox waves correspond to the two-electron process, and the last two waves are four-electron and six-electron processes respectively. On the basis of the experimental results it is shown that the electrode process of alpha-P2Mo18O626- on the CF electrode in acidic solution is simultaneously controlled by the diffusion and adsorption of alpha-P2Mo18O626- anions. When the concentration of the alpha-P2Mo18O626- in the solution is reduced, the electrode process mainly exhibits non-diffusion-controlled behaviour, and the diffusion-limited process takes over as the concentration of alpha-P2Mo18O626- becomes higher. The CF electrode modified with a thin film of alpha-P2Mo18O626- exhibits very good stability and redox behaviour in aqueous acidic solution. The alpha-P2Mo18O626- is reduced to heteropoly blue, with an accompanying protonation process. The addition of more than six electrons to the alpha-P2Mo18O626- anion in an aqueous solution does not result in its decomposition. The result obtained is not the same as that reported previously.

CYCLIC VOLTAMMETRIC AND SPECTROELECTROCHEMICAL STUDIES OF COPPER IN ALKALINE-SOLUTION

The behaviour of the electroplated copper film electrode on tin oxide/glass or glassy carbon surface was studied in potassium hydroxide medium by cyclic voltammetry and in situ transmission spectroelectrochemistry. The results indicate that the electroplated copper film electrode is similar to a copper electrode and cyclic voltammetry with this electrode affords more resolution. The anodic peaks were found to correspond successively to the adsorption of oxygen, the formation of a surface layer of Cu2O, the formation of a surface layer of Cu(OH)2 or CuO and formation of a thick multilayer film of CuO. This is the first time it has been proposed that a surface layer of Cu(OH)2 or CuO is formed from the oxidation of the surface layer of Cu2O. Similarly, a clear interpretation is presented that the cathodic peaks correspond successively to the reduction of CuO to Cu2O, the reductions of Cu2O to Cu and the soluble Cu(II) species to Cu. On the other hand, a shoulder peak related to the chemical transformation of Cu(OH)2 to CuO was first observed.

Paleoenvironment evolution of the East Philippine Sea recorded in the new-type ferromanganese crust since the terminal Late Miocene

From systemic research of microstructure, geochemistry, uranium-series and Be-10 isotope dating on a new-type deepwater ferromanganese crust from the East Philippine Sea, the paleoenvironment evolution of the target area since the terminal Late Miocene was recovered. The vertical section changes of microstructure and chemical composition are consistent in the studied crust, which indicate three major accretion periods and corresponding paleoenvironment evolution of the crust. The bottom crust zone was formed in the terminal Late Miocene (5.6 Ma) with loose microstructure, high detritus content and high growth rate. Reductions of mineral element content, accretion rate and positive Ce-anomaly degree at 4.6 Ma indicate temporal warming, which went against the crust accretion and finally formed an accretion gap in the terminal Middle Pliocene (2.8-2.7 Ma). The more active Antarctic bottom seawaters in the Late Pliocene (2.7 Ma) facilitated the fast transfer to the top pure crust zone. Hereafter, with the further apart of volcanic source and the keeping increase of eolian material (1.0 Ma), although surrounding conditions were still favorable, mineral element content still shows an obvious reducing trend. It thereby offers new carrier and data for the unclear paleoceanographic research of the target area since the terminal Late Miocene.

Inhibition of bromophenols against PTP1B and anti-hyperglycemic effect of Rhodomela confervoides extract in diabetic rats

Protein tyrosine phosphatase 1B (PTP1B) plays an important role as a negative regulator in insulin signaling pathways. PTP1B is an effective target for the treatment of type 2 diabetes mellitus. Four bromophenol derivatives from red algae Rhodomela confervoides, 2,2',3,3'-tetrabromo-4,4',5,5'-tetra-hydroxydiphenyl methane (1), 3-bormo-4,5-bis(2,3-dibromo-4,5-dihydroxybenzyl) pyrocatechol (2), bis(2,3-dibromo-4,5-dihydroxybenzyl) ether (3) and 2,2',3-tribromo-3',4,4',5-tetrahydroxy-6'-ethyloxy-methyldiphenylmethane (4) showed significant inhibitory activity against PTP1B (IC50 were 2.4, 1.7, 1.5 and 0.84 mu mol/L, respectively) as potential therapeutical agents for the treatment of type 2 diabetes mellitus. The anti-hyperglycemic effects of the ethanol extracts from R. confervoides on streptozotocin-induced diabetes (STZ-diabetes) in male Wistar rats fed with high fat diet were investigated. The STZ-diabetic rats treated with medium-dose and high-dose alga extracts showed remarkable reductions in fasting blood glucose (FBG) as compared with the STZ-diabetic control. The results indicate that the in vivo anti-hyperglycemic activity of the R. confervoides extracts can be partially attributed to the inhibitory actions against PTP1B of the bromophenol derivatives and that may be of clinical importance in improving the management of type 2 diabetes mellitus.

Population dynamics and responses to management of plateau pikas Ochotona curzoniae

1. Plateau pikas Ochotona curzoniae are considered a pest species on the Tibetan Plateau because they compete with livestock for forage and their burrowing could contribute to soil erosion. The effectiveness of pest control programmes in Tibet has not been measured, and it is not known whether changes in livestock management have exacerbated problems with plateau pikas or compromised their control. This study measured the impact of control programmes and livestock management for forage conservation on populations of plateau pikas in alpine meadow in Naqu District, central Tibet, during 2004 and 2005.2. Current techniques for controlling plateau pikas in spring cause large reductions in abundance, but high density-dependent rates of increase result in no differences between treated and untreated populations by the following autumn. Rates of increase from spring to autumn are not influenced by standing plant biomass or concurrent grazing by yaks Bos grunniens and Tibetan sheep Ovis aries.3. In autumn there was significantly lower biomass outside fenced areas with year-round livestock grazing compared with inside fenced areas with equivalent or higher numbers of plateau pikas but predominantly winter grazing by livestock. Inside fenced areas, control of plateau pikas in spring produced no detectable effect on standing plant biomass at the end of the following summer compared with uncontrolled populations of plateau pikas.4. Regardless of their initial density, populations of plateau pikas declined rapidly over winter outside fenced areas where there was very low standing plant biomass in autumn. However, inside fenced areas with higher plant biomass in autumn, low-density populations of plateau pikas declined more slowly than high-density populations.5. Synthesis and applications. Current control programmes have limited effect because populations of plateau pikas can recover in one breeding season. There was no apparent increase in forage production in areas where plateau pikas were controlled. However, plateau pikas appear to benefit from changes in grazing management, with low-density populations declining less over winter inside fenced areas than elsewhere. It was not evident that control programmes are warranted or that they will improve the livelihoods of Tibetan herders.

On the correlation between microstructural changes of Ag-H-ZSM-5 catalysts and their catalytic performances in the selective catalytic reduction of NOx by methane

The silver catalyzed, selective catalytic reduction (SCR) of nitrogen oxides (NOx) by CH4, is shown to be a structure-sensitive reaction. Pretreatment has a great affect on the catalytic performances. Upon thermal treatment in inert gas stream, thermal induced changes in silver morphology lead to the formation of reduced silver species of clusters and particles. Catalysis over this catalyst indicates an initially higher activity but lower selectivity for the CH4-SCR of NOx Reaction induced restructuring of silver results in the formation of ill-defined silver oxides. This, in turn, impacts the adsorption properties and diffusivity of oxygen over silver catalyst, results in the decrease in activity but increase in selectivity of Ag-H-ZSM-5 catalyst for the CH4-SCR of NO.. (c) 2004 Elsevier B.V. All rights reserved.