In situ UV-vis and CD thin-layer spectroelectrochemistry study of the electrochemical behavior of L-noradrenaline in alkaline solution

Electrochemical redox behavior of noradrenaline in alkaline solution on a glassy carbon electrode has been investigated by in situ UV-vis and CD spectroelectrochemistry by using a long optical path thin-layer cell. The experimental data were processed by using a double logarithmic method of analysis together with nonlinear regression which confirmed that the first step in both the oxidation of noradrenaline and reduction of noradrenochrome is a two-electron irreversible process governed by an EE mechanism. The kinetic parameters of the electrode reactions, i.e., charge transfer coefficient and the number of electrons transferred, alpha(1)n(1) = 0.11 and alpha(2)n(2) = 0.23, formal potentials modified with kinetics, E-1(0') = 0.65 (+/- 0.01) V and E-2(0') = 0.72V and standard rate cnstants, k(1)(0) = 7.0(+/-0.5)x10(-5) cm s(-1), for the first and second steps in the oxidation process of noradrenaline, and similarly, alpha(1)n(1) = 0.33, alpha(2)n(2) = 0.58, E-1(0') = 0.37(+/-0.01) V, E-0' = -0.25 (+/-0.01) V and k(1)(0) approximate to k(2)(0) = 1.06 (+/-0.05)x10(-4) cm s(-1) for the first and second steps in the reduction process of noradrenochrome were also determined.

Orientation and electrocatalysis of riboflavin adsorbed on carbon substrate surfaces

Based on scanning tunnelling microscopy and electrochemical measurements, orientation and electrocatalytic function of riboflavin adsorbed on carbon substrates have been described for the first time. Scanning tunnelling micrographs show clearly that tip induction may result in an orientation change of the adsorbed riboflavin molecule on highly oriented pyrolytic graphite from the initially vertical orientation to the stable flat form. The adsorbed riboflavin as an effective mediator can accelerate the reduction of dioxygen which accepts two electrons from the reduced riboflavin to generate hydrogen peroxide. The rate constants of the electrocatalytic reaction in various pH solutions were determined using a rotating disc electrode modified with riboflavin. The pH effect and possible catalytic mechanism are discussed in detail.

Effect of structures of modifiers on electrochemistry of di-mu-oxo dimanganese 2,2'-bipyridine complex

The gold electrodes modified with 2-picolinic acid , nicotinic acid, iso-nicotinic or thiophene were prepared using membrane transfer method, The electrochemistry of di-mu-oxodimanganese 2,2'-bipyridine complex was studied in the acetic acid buffer solution at different modified gold electrodes, It was found that the modifiers which can promote the electrochemical reaction of the complex should be of at least two functional groups, One group can be bound to the electrode surface and the other can form electron transfer pathway between the modifier and the complex through sal; bridge or hydrogen bond, In addition, the mechanism of the electrochemical reaction was discussed.

REEVALUATION OF 2,2-BIPYRIDINE AND PYRAZINE AS PROMOTERS FOR DIRECT ELECTRON-TRANSFER BETWEEN CYTOCHROME-C AND METAL-ELECTRODES

Results from previous electrochemical studies have indicated that 2,2'-bipyridine and pyrazine do not function as promoters for heterogeneous electron transfer between cytochrome c and metal electrodes. Their lack of activity was attributed to the improper positioning of the two functional groups in 2,2'-bipyridine and the inefficient length of pyrazine. In the present study it was determined that both 2,2'-bipyridine and pyrazine act as promoters when self-absorbed over a sufficiently long dipping time or at roughened electrodes. The promoter characteristics of these two molecules were studied and compared with those of 4,4'-bipyridine. The difference in their promoter behavior appears to result primarily from their different strengths of adsorption and not because electrodes modified with 2,2'-bipyridine or pyrazine are unsuitable for accelerating direct electron transfer reactions in cytochrome c. These results have implications regarding the mechanism(s) of promoter effects in electrochemical reactions of cytochrome c.

污水生化处理过程仿真及在A~2/O工艺改进中的应用

基于国际水协会IWA发布的国际评价基准Benchmark,建立了与污水处理厂实际特性相近的标准仿真平台。对污水处理传统A2/O工艺做了合理改进,在不影响出水水质的情况下,取消内回流。应用该平台分别对晴天、雨天与暴雨三种天气的工艺过程模拟,验证了工艺改进的合理性。仿真结果表明,与传统A2/O工艺相比,出水指标差别不大,但污泥泵能耗降低约50%。

Preparation of titania-based catalysts for formaldehyde photocatalytic oxidation from TiCl4 by the sol-gel method

Titania sols were prepared by acid hydrolysis of a TiCl4 precursor instead of titanium alkoxides. The effect of acid concentration on the particle size and stability of sol was investigated. Stable titania sols with mean particle size of 14 nm could be obtained when the H+/Ti molar ratio was 0.5. The titania sols were modified with Pt, SiO2, ZrO2, WO3 and MoO3 to prepare a series of modified catalysts, which were used for the photocatalytic oxidation of formaldehyde at 37 degreesC. They showed different photocatalytic activities due to the influence of the additives. Comparing with pure TiO2, the addition of silica or zirconia increased the photocatalytic activity, while the addition of Pt and MoO3 decreased the activity, and the addition Of WO3 had little effect on the activity. It is of great significance that the conversion of formaldehyde was increased up to 94% over the SiO2-TiO2 catalyst. The increased activity was partly due to higher surface area and porosity or smaller crystallite size. A comparison of our catalyst compositions with the literature in this field suggested that the difference in activity due to the addition of a second metal oxide maybe caused by the surface chemistry of the catalysts, particularly the acidity. (C) 2001 Elsevier Science B.V. All rights reserved.

Ion-conducting polymers based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CPs) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo(oxyethylene) side chains of the type -O(CH2CH2O)(n)CH3 were synthesized and characterized, and complexed with lithium salts to form amorphous polymer electrolytes. Maximum conductivity close to 1.38 x 10(-4) S/cm was achieved at room temperature and at a [Li]/[EO] ratio (EO = ethylene oxide) of about 0.066. The temperature dependence of ionic conductivity suggested that the ion transport was controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moved to a higher salt concentration as the temperature increased, indicating that a larger number of charge carriers can be transferred through polymer chains, of which free volume is increased at higher temperature. IR results indicated that the ester in CPs might decompose at 140 degrees C and reproduce the maleic anhydride ring.

Study on the modified electrode of conducting polymers .3. Electron spin resonance characteristic of polypyrrole film electrode doped with heteropolyanions

The ESR of PPy films doped with Co (W2O7)(6)(10-) and CuW12O406- ions were reported and discussed. Results show that heteropolyanions not only play the role of neutralizing electricity in the PPy film, but also interact with the PPy molecular chain to form some adducts. The adducts affect the electronic structure of the PPy film and are unstable at more positive or more negative potentials. Dysonian ESR lineshape was recorded for the dry PPy film with CuW12O406- for the first time.

The investigation of exfoliation process of organic modified montmorillonite in thermoplastic polyurethane with different molecular weights

Cloisite 30B (30B) was melt-mixed with two kinds of thermoplastic polyurethane (TPU) with different molecular weights to discern the roles of molecular diffusion and shear in the exfoliation process. The higher level of exfoliation was achieved in TPU matrix with higher molecular weight due to the appropriate viscosity. In order to have an insight into the mechanism of exfoliation, the degree of dispersion and exfoliation of 30B was characterized by wide angle X-ray diffraction and transmission electron microscopy. The layers of 30B were exfoliated via a slippage process, which was also observed in polyamide 12 nanocomposites recently.

Synthesis, characterization and ionic conductivity of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Three comb polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 were synthesized and characterized, and the ionic conductivity of CP/salt complexes is reported. The conductivity of these complexes was about 10(-5)-10(-6) S cm(-1) at room temperature. The conductivity, which displayed non-Arrhenius behaviour, was analysed using the Vogel-Tammann-Fulcher equation. The conductivity maxima appear at lower salt concentration, when CP has longer side chains. Infrared (i.r.) was used to study the cation-polymer interaction. I.r. results also indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring. (C) 1997 Elsevier Science Ltd.

Ionic conductivity of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with lithium salts to form amorphous polymer electrolytes. CP/salt complexes showed conductivity up to 10(-5)Scm(-1) at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

Synthesis and ionic conductivity studies of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type-O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with LiNO3 to form an amorphous polymer electrolyte. CP/salt complexes showed conductivity up to 10(-5) S/cm at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results also indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

PENDANT FUNCTIONAL-GROUP COPOLYETHER SULFONES .1. SYNTHESIS AND CHARACTERIZATION OF NEW COPOLYETHER SULFONES WITH PENDANT ALDEHYDE GROUPS MODIFIED INTO PHENOLIC AZOMETHINE GROUPS

New functional copolyether sulfones with pendant aldehyde groups were synthesized by the classical polycondensation reaction between 4,4' -dichlorodiphenyl sulfone (I) and various bisphenols such as 5,5'-methylene bis-salicylaldehyde (II-2), 2,2-bis( 4-hydroxyphenyl)propane (III), and 2,6-bis(4-hydroxybenzylidene)cyclohexanone (IV). Condensation reaction with 4-aminophenol led to pendant phenolic azomethine groups containing copolyether sulfones. The structures of the resulting polymers were confirmed by IR, H-1-NMR spectra, and elemental analyses. The polymers were characterized by reduced viscosity, solubility, thermal stability, DSC, and x-ray diffraction measurements.

MECHANISM OF RADIATION CROSS-LINKING OF POLYMERS AND ITS RELATIONSHIP WITH STRUCTURAL MULTIPLICITY

In an attempt to explore the effect of structural multiplicity of polymers on the mechanism of radiation crosslinking, the adaptability of the Charlesby-Pinner's equation and its various modified versions are examined. It is recognized that both chemical and morphological multiplicity of polymer structure results in the multiplicity of crosslinking mechanism, and that any single equation can only be applicable to a certain step of the whole radiation process.

A New Modified Expanding Cavity Model for Characterizing the Spherical Indentation Behaviour of Bulk Metallic Glass with Pile-up

Spherical nanoindentation tests were performed on Zr41.2Ti13.8Cu12.5Ni10Be22.5 bulk metallic glass and pile-ups were observed around the indenter. A new modified expanding cavity model was developed to characterize the indentation deformation behavior of strain-hardening and pressure-dependent materials. By using this model, the representative stress-strain response of this bulk metallic glass to hardness and indentation in the elastic-plastic regime were obtained taking into consideration the effect of pile-up.