Unidirectional current flow of reversible redox couples on a MoO3 film-modified microelectrode

In this paper, we have investigated the reactivity of the molybdenum oxide film toward some standard redox systems (e.g., ferrocene (Fc) and its derivatives) and observed a few interesting phenomena. The results demonstrate that the electrochemical behaviour of Fc and its derivatives at the oxide-modified carbon fiber (CF) microelectrode differs from that at a bare CF microelectrode, The conductivity of the molybdenum oxide film is seriously affected by the range and the direction of the potential scan, which influences the electrochemical behaviour of these redox systems at the film electrode. If the cycling potential is more positive than the reduction potential of the molybdenum oxide film, the reduction and oxidation peak currents of Fc and its derivatives could not be observed. The result indicates that the molybdenum oxide film on a microelectrode surface cannot transfer electrons between the surface of the electrode and Fc or its derivatives due to the existence of a high resistance between the interface in these potential ranges. On the other hand, if the lower limit of the scan potential was extended to a potential more negative than the reduction peak potential of the film, the oxidation peak of Fc or its derivatives appeared at about the potential relative to E-0 of Fc or its derivatives on the bare electrode, and the peak current is proportional to the concentration of these couples in the electrolyte. To our surprise, the peak height on the modified electrode is much larger than that on the bare CF microelectrode under the same conditions in the range of low concentration of these couples, and the oxidation peak potential of these couples is more negative than that on the bare CF microelectrode. On the basis of the experimental observation, we propose that these redox couples may undergo an interaction with the reduction state of the molybdenum oxide film. The new phenomena that we observed have been explained by using this interaction. (C) 1997 Elsevier Science S.A.

Rapid automated in-situ monitoring of total dissolved iron and total dissolved manganese in underground water by reverse-flow injection with chemiluminescence detection during the process of water treatment

Measurement of iron and manganese is very important in evaluating the quality of natural waters. We have constructed an automated Fe(II), total dissolved iron(TDI), Mn(II), and total dissolved manganese(TDM) analysis system for the quality control of underground drinking water by reverse flow injection analysis and chemiluminescence detection(rFIA-CL), The method is based on the measurement of the metal-catalyzed light emission from luminol oxidation by potassium periodate. The typical signal is a narrow peak, in which the height is proportional to light emitted and hence to the concentration of metal ions. The detection limits were 3 x 10(-6) mu g ml(-1) for Fe(II) and the linear range extents up to 1.0 x 10(-4) and 5 x 10(-6) mu g ml(-1) for Mn(II) cover a linear range to 1.0 x 10(-4) mu g ml(-1). This method was used for automated in-situ monitoring of total dissolved iron and total dissolved in underground water during water treatment. (C) 1997 Elsevier Science B.V.

GAS-PHASE ION-MOLECULE REACTIONS OF BUCKMINSTERFULLERENE C-60 WITH SOME SMALL ORGANIC-COMPOUNDS IN MASS-SPECTROMETER

In chemical ionization mass spectrometry (CIMS) gas phase C-60(+) or C-60 can react with fragment ions from three chloromethane and four multichloroethane molecular ions via ion-molecule reactions. A dozen of gas-phase adduct ions of C-60 are observed, and most of them contain chlorine atoms. The results of the comparison and analysis show that the relative intensities of adductions are not directly proportional to the corresponding fragment ions in the MS of reagents,which implies that some fragment ions containing radicals are more reactive with C-60(+) or C-60. This indicates that the alkene-like C-60(+) or C-60 can act as a radical sponge in addition reactions.

SURFACE FRACTALS IN BLOCK-COPOLYMERS

A surface fractal model was presented to describe the interface in block copolymers. It gives a simple power-law relationship between the scattering intensity I(q) and the wave vector q in a relatively wide range as qxi >> 1, I(q) is-proportional-to q(D-6

A STUDY OF CATALYTIC PROPERTIES OF PEROVSKITE-TYPE OXIDES LAMNYCO1-YO3 .1. THE RELATIONSHIP BETWEEN THE TYPE OF OXYGEN SPECIES AND THE CATALYTIC PROPERTY IN AMMONIA OXIDATION

The type of oxygen species in perovskite-type oxides LaMnyCo1-yO3 (y = 0.0, 0.1, 0.3, 0.5, 0.7, 0.9, 1.0) has been studied by means of XRD, XPS and TPD. The catalytic activity in ammonia oxidation was also investigated. It was found that there were three desorption peaks in TPD curve corresponding to three types of oxygen species (alpha, beta, beta'). The desorption temperatures were 293 K less-than-or-equal-to T(alpha) less-than-or-equal-to 773 K, 773 K less-than-or-equal-to T(beta) less-than-or-equal-to K and T(beta') greater-than-or-equal-to 1073 K respectively. The relationship among the composition, structure and the catalytic property of.the catalyst was correlated and could be explainned with a model based on solid defect reaction and the interaction between Co and Mn ions. The adsorption strength and quantity of a oxygen are proportional to the catalytic activity. The, result indicates that the synergetic effect between B-site ions seems to the benefit of the ammonis oxidation reaction.

STUDIES ON RADIATION-INDUCED LOSS OF WEIGHT OF A COPOLYMER OF TETRAFLUOROETHYLENE AND HEXAFLUOROPROPYLENE

The radiation-induced loss of weight of F-46 was found to be proportional to irradiation dose and affected markedly by irradiation temperature.

ELECTROCATALYTIC OXIDATION OF ASCORBIC ACID AT POLYANILINE FILM MODIFIED GLASSY CARBON ELECTRODES

A conducting polyaniline (PAn) film modified glassy carbon (GC) electrode was prepared by electrochemical polymerization. The electrochemical behavior of ascorbic acid (AH(2)) in aqueous solution at this PAn modified electrode was studied in detail. The experimental results show that PAn film modified electrode has good electrocatalytic activity on the oxidation of ascorbic acid in aqueous solution over a wide range of pH value, among which pH 4 is the optimum condition. The oxidation process of ascorbic acid at PAn film electrode can be regarded as an EC catalytic mechanism. The kinetic process of the catalytic reaction was investigated by rotating disk electrode (RDE) coated with PAn films. The rate constant of the catalytic reaction was evaluated. The catalytic peak currents are proportional to the concentrations tions of ascorbic acid in the range of 5 x 10(-2)-1 x 10(-6) mol . L-1. The PAn film elec trodes give very stable responce for the oxidation of ascorbic acid. The present investigation shows the posibility of using PAn film modified electrode for the determination of ascorbic acid.

EVALUATION OF THE EFFECT OF WAVELENGTH POSITIONING ERRORS ON KALMAN FILTERING RESULTS IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

This work evaluates the effect of wavelength positioning errors in spectral scans on analytical results when the Kalman filtering technique is used for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). The results show that a positioning accuracy of 0.1 pm is required in order to obtain accurate and precise estimates for analyte concentrations. The positioning error in sample scans is more crucial than that in model scans. The relative bias in measured analyte concentration originating from a positioning error in a sample scan increases linearly with an increase in the magnitude of the error and the peak distance of the overlapping lines, but is inversely proportional to the signal-to-background ratio. By the use of an optimization procedure for the positions of scans with the innovations number as the criterion, the wavelength positioning error can be reduced and, correspondingly, the accuracy and precision of analytical results improved.

Statistical distribution of wave-surface elevation for second-order random directional ocean waves in finite water depth

Based on the second-order random wave solutions of water wave equations in finite water depth, a statistical distribution of the wave-surface elevation is derived by using the characteristic function expansion method. It is found that the distribution, after normalization of the wave-surface elevation, depends only on two parameters. One parameter describes the small mean bias of the surface produced by the second-order wave-wave interactions. Another one is approximately proportional to the skewness of the distribution. Both of these two parameters can be determined by the water depth and the wave-number spectrum of ocean waves. As an illustrative example, we consider a fully developed wind-generated sea and the parameters are calculated for various wind speeds and water depths by using Donelan and Pierson spectrum. It is also found that, for deep water, the dimensionless distribution reduces to the third-order Gram-Charlier series obtained by Longuet-Higgins [J. Fluid Mech. 17 (1963) 459]. The newly proposed distribution is compared with the data of Bitner [Appl. Ocean Res. 2 (1980) 63], Gaussian distribution and the fourth-order Gram-Charlier series, and found our distribution gives a more reasonable fit to the data. (C) 2002 Elsevier Science B.V. All rights reserved.

Fabrication of Bismuth/Multi-walled Carbon Nanotube Composite Modified Glassy Carbon Electrode for Determination of Cobalt

A bismuth/multi-walled carbon nanotube (Bi/MWNT) composite modified electrode for determination of cobalt by differential pulse adsorptive cathodic stripping voltammetry is described. The electrode is fabricated by potentiostatic pre-plating bismuth film on an MWNT modified glassy carbon (GC) electrode. The Bi/MWNT composite modified electrode exhibits enhanced sensitivity for cobalt detection as compared with the bare GC, MWNT modified and bismuth film electrodes. Numerous key experimental parameters have been examined for optimum analytical performance of the proposed electrode. With an adsorptive accumulation of the Co(II)-dimethylglyoxime complex at -0.8 V for 200 s, the reduction peak current is proportional to the concentration of cobalt in the range of 4.0x10(-11)-1.0x10(-7) mol/L with a lower detection limit of 8.1x10(-11) mol/L. The proposed method has been applied Successfully to cobalt determination in seawater and lake water samples.

PCBs and its coupling with eco-environments in Southern Yellow Sea surface sediments

In this paper, the spatial distribution and source of the PCBs in surface sediments of the Southern Yellow Sea (SYS) and influencing factors, such as the sediment characteristics (components, relative proportions and total organic carbon contents), and hydrodynamic conditions were analyzed. PCB concentrations in the surface sediments ranged from 518-5848 pg/g, with average values of 1715 pg/g decreasing sharply compared to last year. In the study area, the PCB pollution level in the middle area was the highest, followed by that of the east coast and the west coast, respectively. Although the PCB level in the coastal areas was lower than that in the middle areas, it was proven in our study that the Yellow Sea obtained PCBs by virtue of river inputs. There was a positive and pertinent correlation between the clay proportion and PCB concentrations, and the increase of the PCB concentrations was directly proportional to the increase of TOC contents, with r = 0.61, but it was contrary to the sediment grain size. Consequently, the factors controlling PCB distribution had direct or indirect relationships with sediment grain size; moreover, the hydrodynamic conditions determined the sediment components and grain size. In conclusion, hydrodynamic conditions of the Yellow Sea were the most important influencing factors effecting the distribution of PCBs in the surface sediments of the SYS. (C) 2007 Elsevier Ltd. All rights reserved.

Strain H-2-419-4 of Haematococcus pluvialis induced by ethyl methanesulphonate and ultraviolet radiation

Two strains H-2-410 and H-2-419 were obtained from the chemically mutated survivors of wild Haematococcus pluvialis 2 by using ethyl methanesulphonate (EMS). Strains H2-410 and H2-419 showed a fast cell growth with 13% and 20% increase in biomass compared to wild type, respectively. Then H-2-419-4, a fast cell growth and high astaxanthin accumulation strain, was obtained by exposing the strain H2-419 to ultraviolet radiation (UV) further. The total biomass, the astaxanthin content per cell, astaxanthin production of H-2-4194 showed 68%, 28%, and 120% increase compared to wild H. pluvialis 2, respectively. HPLC (High Performance Liquid Chromatography) data showed also an obvious proportional variation of different carotenoid compositions in the extracts of H2-4194 and the wild type, although no peak of carotenoids appeared or disappeared. Therefore, the main compositions in strain H-2-419-4, like its wild one, were free of astaxanthin, monoester, and diester of astaxanthin. The asexual reproduction in survivors after exposed to UV was not synchronous, and different from the normal synchronous asexual reproduction as the mother cells were motile instead of non-motile. Interestingly, some survivors from UV irradiation produced many mini-spores (or gamete?), the spores moved away from the mother cell gradually 4 or 5 days later. This is quite similar to sexual reproduction described by Elliot in 1934. However, whether this was sexual reproduction remains questionable, as no mating process has been observed.

Study on steel corrosion in different seabed sediments

A series of simulation experiments on carbon steel (A(3) steel) and low alloy steel (16 Mn steel) in marine atmosphere (MA), seawater (SW) and seabed sediment (SBS) including rough sea sand, fine sea sand and seabed mud were carried out indoors for a year or so by means of individually hanging plates (IHP) and electrically connected hanging plates (ECHP). The corrosion of steels in SBS was mainly due to the macrogalvanic cell effect. The steel plates at the bottom of SBS, as the anode of a macrogalvanic cell, showed the heaviest corrosion with a corrosion rate of up to 0.12 mm/a, approximately equal to that of steel plates in marine atmosphere. The test results showed that the corrosion rates of A(3) and 16 Mn steel in marine environment were in the order: MA > SW > SBS by the IHP method; and MA > SBS > SW by the ECHP method. The corrosion rates of steels in the water/sediment interface were directly proportional to the grain size of the SBS by the ECHP method, but those of steels in the water/sediment interface did not vary with the grain size of SBS by the IHP method. The corrosion rate of low-alloy steel was a little higher than that of carbon steel. The results of this study have important applications for design of offshore steel structures such as oil platform, pier, and port.

Infrared heater arrays for warming ecosystem field plots

There is a need for methodology to warm open-field plots in order to study the likely effects of global warming on ecosystems in the future. Herein, we describe the development of arrays of more powerful and efficient infrared heaters with ceramic heating elements. By tilting the heaters at 45 degrees from horizontal and combining six of them in a hexagonal array, good uniformity of warming was achieved across 3-m-diameter plots. Moreover, there do not appear to be obstacles (other than financial) to scaling to larger plots. The efficiency [eta(h) (%); thermal radiation out per electrical energy in] of these heaters was higher than that of the heaters used in most previous infrared heater experiments and can be described by: eta(h) = 10 + 25exp(-0.17 u), where u is wind speed at 2 m height (m s(-1)). Graphs are presented to estimate operating costs from degrees of warming, two types of plant canopy, and site windiness. Four such arrays were deployed over plots of grass at Haibei, Qinghai, China and another at Cheyenne, Wyoming, USA, along with corresponding reference plots with dummy heaters. Proportional integral derivative systems with infrared thermometers to sense canopy temperatures of the heated and reference plots were used to control the heater outputs. Over month-long periods at both sites, about 75% of canopy temperature observations were within 0.5 degrees C of the set-point temperature differences between heated and reference plots. Electrical power consumption per 3-m-diameter plot averaged 58 and 80 kW h day(-1) for Haibei and Cheyenne, respectively. However, the desired temperature differences were set lower at Haibei (1.2 degrees C daytime, 1.7 degrees C night) than Cheyenne (1.5 degrees C daytime, 3.0 degrees C night), and Cheyenne is a windier site. Thus, we conclude that these hexagonal arrays of ceramic infrared heaters can be a successful temperature free-air-controlled enhancement (T-FACE) system for warming ecosystem field plots.

机器人标定技术研究

机器人标定是离线编程技术实用化的关键技术之一 ,测量手段是制约其发展的一个重要因素 .本文提出了一种简单实用的测量方法 .同时建立了具有完备性、比例性、连续性的 RH6 - A型机器人的真实运动学模型 .并根据测量结果 ,成功地辨识出了机器人的几何结构参数 ,提高了机器人的绝对精度 .