POLYANILINE-DISPERSED MERCURY-ELECTRODE FOR THE DETECTION OF MONOCHLORAMINE AND DICHLORAMINE

A novel type of electrochemical detector based on a polyaniline-dispersed mercury-coated glassy carbon chemically modified electrode was investigated for the detection of monochloramine and dichloramine. A polyaniline dispersed-mercury modified electrode, which was prepared by coating polyaniline on a thin mercury film electrode using fast-sweep voltammetry, was developed. The selectivity could be altered using various counter ions incorporated into the polymer. The results indicated that the use of a conducting polymer-based electrochemical sensor for the selective determination of chloramine is a feasible approach.

THE PREPARATION OF ELECTRODES MODIFIED WITH ISOPOLYMOLYBDIC ACID PLUS POLYANILINE FILM AND ITS CATALYTIC EFFECTS ON CHLORATE IONS

Electrodes modified with isopolymolybdic acid+polyaniline film, which exhibit high stability and activity in aqueous acidic solution, have been prepared successfully using two methods: one-step synthesis by electrochemical polymerization at a constant applied potential of +0.80 V/SCE or by cycling the potential at 100 mV/s between -0.12 and +0.85 V in 0.5 M H2SO4 containing 5.0x10(-2) M aniline and 5.0x10(-3) M H4Mo8O26, or two-step synthesis by doping the polyaniline film electrode with isopoly acid (IPA) under a cycling potential between -0.20 and +0.40 V in 0.5 M H2SO4 containing the H4Mo8O26 dopant. The thickness of the film and the amount of dopant in the polyaniline film can be controlled by experimental parameters such as the charge, time and the ratio of aniline to IPA in the solution. The experimental results show that electrodes modified with isopolymolybdic acid+polyaniline film using both methods have a strong catalytic effect on the reduction of chlorate anions. Comparison of the two methods of modification shows that the catalytic effect at the modified electrode prepared by the two-step method is greater than that at the electrode prepared by the one-step method.

FLOW-INJECTION ANALYSIS OF GLUCOSE AT AN AMPEROMETRIC GLUCOSE SENSOR-BASED ON ELECTROCHEMICAL CODEPOSITION OF PALLADIUM AND GLUCOSE-OXIDASE ON A GLASSY-CARBON ELECTRODE

A glassy carbon electrode (GCE) modified with palladium provides excellent electrocatalytic oxidation of hydrogen peroxide. When the electrolyte contains palladium chloride and glucose oxidase, the GCE can be modified by electrochemical codeposition at a given potential. The resulting modified surface was coated with a thin film of Nation to form a glucose sensor. Such a glucose sensor was successfully used in the flow-injection analysis of glucose with high stability and anti-poisoning ability. It gave a detection limit of 1 X 10(-7) M injected glucose, with a linear concentration range of 0.001-8 mM. There is no obvious interference from substances such as ascorbate and saccharides.

CHRONOAMPEROMETRIC STUDIES ON MIGRATION AND DIFFUSION OF COUNTERION IN POLY(3-METHYLTHIOPHENE)

Small amplitude potential step experiments were carried out to study the counterion transfer process in oxidized poly(3-methylthiophene) (PMT) film. The results demonstrate that anion transfer process in PMT film is migration rather than diffusion. A porous metal electrode model-single hole model, which takes into account both the ionic resistance of the film and the uncompensated solution resistance, was found suitable to describe the potential step experiments. According to this model, the ionic resistivity of oxidized PMT film was calculated to be 5.0 x 10(4) OMEGA.cm, and, in turn, the diffusion coefficent of ClO4- ion in PMT film 3.7 x 10(-9) cm2/s.

TENSILE PROPERTIES OF BLENDS OF POLY(ETHER SULFONE) WITH A POLY(ETHER IMIDE)

Blends of poly(ether sulphone) (PES) with a poly(ether imide) (PEI) in various proportions were prepared by the coprecipitation method. Mechanical properties and morphology of the blends were studied using tensile tests and scanning electron microscopy (SEM). The tensile moduli exhibit positive deviations from simple additivity. Marked positive deviations were also observed for ultimate strength. These results suggest that the PEI/PES blends are mechanically compatible. SEM study revealed that the blends are not homogeneous and the polymers are immiscible on the segmental level. However, the dispersions of the blends are rather fine. The interfaces between the two phases are excellently bonded; PEI and PES appear to interact well.

ELECTRODEPOSITION OF PLATINUM PARTICLES ON GLASSY-CARBON MODIFIED WITH COBALT PORPHYRIN AND NAFION FILM AND THEIR ELECTROCATALYTIC REDUCTION OF DIOXYGEN

In this paper, five types of chemically modified electrode (CMEs) prepared with the deposition of platinum particles on various surfaces of glassy carbon (GC) modified with cobalt porphyrin and Nafion(R) solution are characterized using the electron scanning microscope (SEM). Their activities in the four-electron reduction of dioxygen to water on the basis of their electrochemical data from cyclic voltammetric and rotating ring-disk electrode (RRDE) experiments are examined and compared. Platinum particles dispersed on the GC surface adsorbed with the cobalt porphyrin exhibit the highest activity for the electrocatalytic reduction of dioxygen. However it is interesting that the cobalt ion is lost from the center of the porphyrin ring during the preparation of the cobalt porphyrin + Nafion mixture solution, while the porphyrin ring still remains in the Nafion film, as shown by EDX analysis. The incorporation of the porphyrin may change the structure of the Nafion film into a looser form, since the platinum particles dispersed in the film are more readily exposed, resulting in more favourable mass transfer and higher activity for the electrocatalytic reduction of dioxygen.

ADVANCED ELECTROANALYTICAL CHEMISTRY IN CHINA .1. GENERAL ASPECT AND SOME METHODOLOGIES

The Research on Electroanalytical chemistry in China started mainly from the beginning of new China in 1949. It has already good basis and development nowadays. A review with references to the end of seventies has been published in "Reviews in Analytical Chemistry" 1) and in a book titled "Fifty years of Chinese Chemistry" edited by the Chinese Chemical Society in 1985 2). Since then more than thousand papers have been published, and it is impossible and also not necessary to describe all of them. This review only deals with the main progress of electroanalytical chemistry in China in recent years. Some new developed methodologies will be reviewed by S. Dong in the next article.

AN ELECTROCHEMICAL MICROSENSOR FOR CHLORIDE

The potential-response of a microdisk electrode made with a chloride-doped polypyrrole (PPY) film on a carbon fibre (CF) has been examined. The effect of the polymerization conditions on the response characteristics is discussed. The optimum conditions for preparing the electrode are: cycling potential from +0.8 to +1.0 V in 0.1-0.2M pyrrole (Py) containing 0.1M LiCl, electropolymerization time 15-20 min. The electrode gives a Nernstian response of 56-58 mV/pCl and a detection limit of 3.6 x 10(-5)M chloride. It has the advantages of low resistance, short conditioning time and fast response. It has been used satisfactorily for detection of chloride in serum.

A NEW KIND OF ION-SELECTIVE ELECTRODE BASED ON CONDUCTING POLYMER FILM

Organic conducting polymers have attracted much interest in material science. This letter reports potentiometric response behavior of polypyrrole (PPy)polymer film electrodes prepared by electrochemical polymerization, and a new kind of ion selective

Effective thermal conductivity of graded nonlinear composites with heat contact resistance

The perturbation expansion method is used to find the effective thermal conductivity of graded nonlinear composites having thermal contact resistance on the inclusion surface. As an example, we have studied the graded composites with cylindrical inclusions immersed in a homogeneous matrix. The thermal conductivity of the cylindrical inclusion is assumed to have a power-law profile of the radial distance r measured from its origin. For weakly nonlinear constitutive relations between the heat flow density q and the temperature field T, namely, q = -mu del T - chi vertical bar del T vertical bar(2) del T, in both the inclusion and the matrix regions, we have derived the temperature distributions using the perturbation expansion method. A nonlinear effective medium approximation of graded composites is proposed to estimate the effective linear and nonlinear thermal conductivities. by considering the temperature singularity on the inclusion surface due to the heat contact resistance. (c) 2006 Elsevier B.V. All rights reserved.

青藏高原及邻区面波频散反演--岩石圈-软流层体系结构研究

The Qinghai-Tibet Plateau lies in the place of the continent-continent collision between Indian and Eurasian plates. Because of their interaction the shallow and deep structures are very complicated. The force system forming the tectonic patterns and driving tectonic movements is effected together by the deep part of the lithosphere and the asthenosphere. It is important to study the 3-D velocity structures, the spheres and layers structures, material properties and states of the lithosphere and the asthenosphere for getting knowledge of their formation and evolution, dynamic process, layers coupling and exchange of material and energy. Based on the Rayleigh wave dispersion theory, we study the 3-D velocity structures, the depths of interfaces and thicknesses of different layers, including the crust, the lithosphere and the asthenosphere, the lithosphere-asthenosphere system in the Qinghai-Tibet Plateau and its adjacent areas. The following tasks include: (1)The digital seismic records of 221 seismic events have been collected, whose magnitudes are larger than 5.0 over the Qinghai-Tibet Plateau and its adjacent areas. These records come from 31 digital seismic stations of GSN , CDSN、NCDSN and part of Indian stations. After making instrument response calibration and filtering, group velocities of fundamental mode of Rayleigh waves are measured using the frequency-time analysis (FTAN) to get the observed dispersions. Furthermore, we strike cluster average for those similar ray paths. Finally, 819 dispersion curves (8-150s) are ready for dispersion inversion. (2)From these dispersion curves, pure dispersion data in 2°×2° cells of the areas (18°N-42°N, 70°E-106°E) are calculated by using function expansion method, proposed by Yanovskaya. The average initial model has been constructed by taking account of global AK135 model along with geodetic, geological, geophysical, receiving function and wide-angle reflection data. Then, initial S-wave velocity structures of the crust and upper mantle in the research areas have been obtained by using linear inversion (SVD) method. (3)Taking the results of the linear inversion as the initial model, we simultaneously invert the S wave velocities and thicknesses by using non-linear inversion (improved Simulated Annealing algorithm). Moreover, during the temperature dropping the variable-scale models are used. Comparing with the linear results, the spheres and layers by the non-linear inversion can be recognized better from the velocity value and offset. (4)The Moho discontinuity and top interface of the asthenosphere are recognized from the velocity value and offset of the layers. The thicknesses of the crust, lithosphere and asthenosphere are gained. These thicknesses are helpful to studying the structural differentia between the Qinghai-Tibet Plateau and its adjacent areas and among geologic units of the plateau. The results of the inversion will provide deep geophysical evidences for studying deep dynamical mechanism and exploring metal mineral resource and oil and gas resources. The following conclusions are reached by the distributions of the S wave velocities and thicknesses of the crust, lithosphere and asthenosphere, combining with previous researches. (1)The crust is very thick in the Qinghai-Tibet Plateau, varying from 60 km to 80 km. The lithospheric thickness in the Qinghai-Tibet Plateau is thinner (130-160 km) than its adjacent areas. Its asthenosphere is relatively thicker, varies from 150 km to 230 km, and the thickest area lies in the western Qiangtang. India located in south of Main Boundary thrust has a thinner crust (32-38 km), a thicker lithosphere of about 190 km and a rather thin asthenosphere of only 60 km. Sichuan and Tarim basins have the crust thickness less than 50km. Their lithospheres are thicker than the Qinghai-Tibet Plateau, and their asthenospheres are thinner. (2)The S-wave velocity variation pattern in the lithosphere-asthenosphere system has band-belted distribution along east-westward. These variations correlate with geology structures sketched by sutures and major faults. These sutures include Main Boundary thrust (MBT), Yarlung-Zangbo River suture (YZS), Bangong Lake-Nujiang suture (BNS), Jinshajiang suture (JSJS), Kunlun edge suture (KL). In the velocity maps of the upper and middle crust, these sutures can be sketched. In velocity maps of 250-300 km depth, MBT, BNS and JSJS can be sketched. In maps of the crustal thickness, the lithospheric thickness and the asthenospheric thickness, these sutures can be still sketched. In particular, MBT can be obviously resolved in these velocity maps and thickness maps. (3)Since the collision between India and Eurasian plate, the “loss” of surface material arising from crustal shortening is caused not only by crustal thickening but also by lateral extrusion material. The source of lateral extrusion lies in the Qiangtang block. These materials extrude along the JSJS and BNS with both rotation and dispersion in Daguaiwan. Finally, it extends toward southeast direction. (4)There is the crust-mantle transition zone of no distinct velocity jump in the lithosphere beneath the Qiangtang Terrane. It has thinner lithosphere and developed thicker asthenosphere. It implies that the crust-mantle transition zone of partial melting is connected with the developed asthenosphere. The underplating of asthenosphere may thin the lithosphere. This buoyancy might be the main mechanism and deep dynamics of the uplift of the Qinghai-Tibet hinterland. At the same time, the transport of hot material with low velocity intrudes into the upper mantle and the lower crust along cracks and faults forming the crust-mantle transition zone.

青藏高原横波速度与各向异性结构及其壳幔形变印迹

As the most spectacular and youngest case of continental collision on the Earth, to investigate the crust and mantle of Tibetan plateau, and then to reveal its characters of structure and deformation, are most important to understand its deformation mechanism and deep process. A great number of surface wave data were initially collected from events occurred between 1980 and 2002, which were recorded by 13 broadband digital stations in Eurasia and India. Up to 1,525 source-station Rayleigh waveforms and 1,464 Love wave trains were analysed to obtain group velocity dispersions, accompanying with the detail and quantitative assessment of the fitness of the classic Ray Theory, errors from focal and measurements. Assuming the model region covered by a mesh of 2ox2o-sized grid-cells, we have used the damped least-squares approach and the SVD to carry out tomographic inversion, SV- and SH-wave velocity images of the crust and upper mantle beneath the Tibetan Plateau and surroundings are obtained, and then the radial anisotropy is computed from the Love-Rayleigh discrepancy. The main results demonstrate that follows, a) The Moho beneath the Tibetan Plateau presents an undulating shape that lies between 65 and 74 km, and a clear correlation between the elevations of the plateau and the Moho topography suggests that at least a great part of the highly raised plateau is isostatically compensated. b) The lithospheric root presents a depth that can be substantiated at ~140 km (Qiangtang Block) and exceptionally at ~180 km (Lhasa Block), and exhibits laterally varying fast velocity between 4.6 and 4.7 km/s, even ~4.8 km/s under northern Lhasa Block and Qiangtang Block, which may be correlated with the presence of a shield-like upper mantle beneath the Tibetan Plateau and therefore looked as one of the geophysical tests confirming the underthrusting of India, whose leading edge might have exceeded the Bangong-Nujiang Suture, even the Jinsha Suture. c) The asthenosphere is depicted by a low velocity channel at depths between 140 and 220 km with negative velocity gradient and velocities as low as 4.2 km/s; d) Areas in which transverse radial anisotropy is in excess of ~4% and 6% on the average anisotropy are found in the crust and upper mantle underlying most of the Plateau, and up to 8% in some places. The strength, spatial configuration and sign of radial anisotropy seem to indicate the existence of a regime of horizontal compressive forces in the frame of the convergent orogen at the same time that laterally varying lithospheric rheology and a differential movement as regards the compressive driving forces. e) Slow-velocity anomalies of 12% or more in southern Tibet and the eastern edge of the Plateau support the idea of a mechanically weak middle-to-lower crust and the existence of crustal flow in Tibet.