Electrochemical behavior of the molybdotungstate heteropoly complex with neodymium, K10H3[Nd(SiMo7W4O39)(2)]center dot xH(2)O in aqueous solution

The electrochemical behavior of the title compound (denoted Nd(SiMo7W4)(2)(13-)) in aqueous solution has been studied using cyclic voltammetry, sampled d.c. voltammetry, differential pulse voltammetry and bulk electrolysis with coulometry, The stable pH range of Nd(SiMo7W4)(2)(13-) is determined with UV-visible spectra. In the potential range between 0.70 and -0.45 V vs. SCE, the anion in pH 3.8 aqueous solution undergoes one-, one-, two- and two-electron steps of four redox processes attributed to electron addition and removal from the molybdate-oxo framework. The adsorption of the anion on the dropping mercury electrode and a self-inhibition influence of the adsorbed anions on the redox process of those anions dissolved in solution are found. The unusual dependence of the formal potentials on pH is explained with the competition of the protonation and ion-pair formation due to the high negative charge of Nd(SiMo7W4)(2)(13-) and its reduced forms. The electrocatalytic effects of the anion on the bromate are investigated.

DIRECT ELECTROCHEMICAL REACTIONS OF CYTOCHROME-C AT IODIDE-MODIFIED ELECTRODES

Quasi-reversible and direct electron transfer was observed between an iodide-modified Au electrode and cytochrome c, as well as between cytochrome c in an iodide-containing solution and a bare Au electrode. The results suggest that an electrostatic intera

THE APPLICATION OF ULTRAMICROELECTRODE IN HOMOGENEOUS CATALYTIC REACTION .5. ELECTROCHEMICAL-BEHAVIOR OF MACRO-MICRO-MACRO TRIPLE AND MICRO-MICRO TWIN ELECTRODES AND THE QUASI-FIRST-ORDER HOMOGENEOUS CATALYTIC REACTION (EC') AT GENERATION/COLLECTION ELECT

A new type of macro-micro-macro triple electrode has been fabricated, the steady-state currents of solution redox species have been observed at an ultramicroband electrode by linear potential scan voltammetry, and generation/collection experiments have al

ELECTROCHEMICAL CATALYSIS AT AN ULTRAMICROELECTRODE MODIFIED WITH REDOX SPECIES

General equations of the electrocatalytic reaction at an ultramicroelectrode modified with redox species have been described according to the Andrieux Saveant model. The electrocatalytic kinetic process has been discussed for the whole set of cases, ie (R), (R + S), (SR) (SR + E), (E), (R + E), (ER), (S), (ER + S) and (S + E) limiting situations. The effect of gamma on the catalytic steady state current shows that the higher the value of gamma, the lower the catalytic current. The kinetic process shifts rapidly from R to E with increasing values of gamma. It is favorable for catalysis only when gamma is very low. Therefore, the redox species modified ultramicroelectrode with thin film is utilized for electrocatalysis, and the larger the radius of ultramicroelectrode, the higher the catalytic efficiency.

APPLICATION OF ULTRAMICROELECTRODES IN STUDIES OF HOMOGENEOUS CATALYTIC REACTIONS .2. A THEORY OF QUASI-1ST AND 2ND-ORDER HOMOGENEOUS CATALYTIC REACTIONS

The analytical expressions of quasi-first and second order homogeneous catalytic reactions with different diffusion coefficients at ultramicrodisk electrodes under steady state conditions are obtained by using the reaction layer concept. The method of treatment is simple and its physical meaning is clear. The relationship between the diffusion layer, reaction layer, the electrode dimension and the kinetic rate constant at an ultramicroelectrode is discussed and the factor effect on the reaction order is described. The order of a catalytic reaction at an ultramicroelectrode under steady state conditions is related not only to C(Z)*/C(O)* but also to the kinetic rate constant and the dimension of the ultramicroelectrode; thus the order of reaction can be controlled by the dimension of the ultramicroelectrode. The steady state voltammetry of the ultramicroelectrode is one of the most simple methods available to study the kinetics of fast catalytic reactions.

ELECTROCATALYSIS AT A MICRODISK ELECTRODE MODIFIED WITH A REDOX SPECIES

The current equation of the electrocatalytic reaction at a microdisk electrode modified with redox species has been described and verified experimentally. There exists a linear relationship between plateau limiting current and the radius of the microdisk electrode for a catalytic process. The influence of the dimensions of the microdisk electrode on catalytic efficiency is discussed. The polyvinylferrocene (PVFc)-modified microdisk electrode prepared by the coating method was taken as a typical example, on which the electrocatalytic oxidation of ascorbic acid could be studied. The catalytic reaction rate constants were determined as an average value of 1.5 X 10(-7) cm3/mol s by this method, and are consistent with those obtained at a conventional electrode.

ELECTRODEPOSITION OF POLYCRYSTALLINE CD-RICH HG1-XCDXTE AND PHOTOELECTRO-CHEMICAL BEHAVIOR OF HG0.09CD0.91TE THIN-FILM

Electrodeposition process of polycrystalline Cd-rich Hg_(1-z)Cd_xTe (x>0.5) in acidic bath of CdSO_4+HTeO_2~+HgCl_2 was investigated. The simultaneous electrodeposition technique of three kinds of ions at the same potential has been achieved. The XRD, SEM and EDAX analysis of the thin film electrodeposited on titanium substrate showed a typical cubic zinc blende polycrystalline structure and homogeneous dispersion. The photoelectrochemical behavior of (1-x)=0.09 polycrystalline thin film in a polysulfide re...

Identification and molecular analysis of a stress-inducible Hsp70 from Sciaenops ocellatus

Hsp70 proteins are a family of molecular chaperones that are involved in many aspects of protein homeostasis. In this study, an Hsp70 homologue (SoHsp70) was identified from red drum Sciaenops ocellatus and analyzed at molecular level. The open reading frame of SoHsp70 is 1920 bp and intronless, with a 5'-untranslated region (UTR) of 399 bp and a 3'-UTR of 241 bp. The deduced amino acid sequence of SoHsp70 shares 84-92% overall identities with the Hsp70s of a number of fish species. In silico analysis identified in SoHsp70 three conserved Hsp70 domains involved in nucleotide and substrate binding. The coding sequence of SoHsp70 was subcloned into Escherichia coli, from which recombinant SoHsp70 was purified and, upon ATPase assay, found to exhibit apparent ATPase activity. Expressional analysis showed that constitutive expression of SoHsp70 was detectable in heart, liver, spleen, kidney, brain, blood, and gill. Experimental challenges with poly(I:C) and bacterial pathogens of Gram-positive and Gram-negative nature induced SoHsp70 expression in kidney to different levels. Stress-responsive analysis of SoHsp70 expression in primary cultures of red drum hepatocytes showed that acute heat shock treatment elicited a rapid induction of SoHsp70 expression which appeared after 10 min and 30 min of treatment. Exposure of hepatocytes separately to iron, copper, mercury, and hydrogen peroxide significantly unregulated SoHsp70 expression in time-dependent manners. Vaccination of red drum with a Streptococcus iniae bacterin was also found to induce SoHsp70 expression. Furthermore, recombinant SoHsp70 enhanced the immunoprotective effect of a subunit vaccine. Taken together, these results suggest that SoHsp70 is a stress-inducible protein that is likely to play a role in immunity and in coping with environmental and biological stresses. (C) 2010 Elsevier Ltd. All rights reserved.

Distribution and their pollution assessment of heavy metals in the sediments of the Yalu River Estuary and its adjacent coastal waters

The present paper deals with the distribution patterns of heavy metals and the associated influencing factors in the Yalu River Estuary and its adjacent coastal waters. Based upon the analysis of the surficial and core sediments measurements, the pollution of heavy metal and potential ecological risk were evaluated. The burial flux and contents of heavy metals (except for copper) have been continuously increasing since the 1920s. Therefore, the gross potential ecological risk for the sediments was high or very high, and the study area was endangered by heavy metals contamination. Heavy metals originated mainly from upstream pollutant input, correlation analysis showed that chromium, nickel, zinc, cadmium, lead, arsenic, and mercury in the sediments of the middle and west channels as well as the sea area of the western Yalu River Estuary concentrations were most probably derived from similar sources. In contrast, the metal of copper most probably originated from sources different from the other metals. Preliminary studies indicate that copper contamination was most likely the result of emission from mining activities situated at the upstream of the river. The contents of heavy metals in the sediments of estuarine turbidity maximum zone of Yalu River were larger than those of any other areas in the middle channel. With large portion of fine sediments, weaker hydrodynamics, and richer sources of heavy metals, the sediments of the west channel, were even more enriched with heavy metals than those of the middle channel.

四角蛤蜊Mactra veneriformis对镉和汞污染胁迫的生理响应

本论文基于对我国沿海重金属污染加剧以及滩涂贝类资源衰退现象的关注，围绕典型滩涂贝类四角蛤蜊生物化学、细胞生物学和免疫学特征开展研究，调查了渤海湾天津近岸海域四角蛤蜊体内重金属含量和分布规律，以及四角蛤蜊对沉积物重金属的富集能力。室内模拟研究了四角蛤蜊对重金属镉和汞的富集能力及同化机制（assimilation mechanism）差异性，四角蛤蜊各组织对镉和汞的解毒机理和负载能力，以及重金属胁迫对四角蛤蜊血细胞结构和功能的损伤效应。研究结果可望为探讨四角蛤蜊受重金属胁迫细胞水平上的响应机制，揭示重金属污染和贝类资源衰退的关系，建立快速可靠的重金属污染生物标志物指标体系，开展生态健康评估和生境修复等提供科学依据。主要研究结果如下： 1．查明了渤海湾天津近岸四角蛤蜊体内和表层沉积物中Cd、Pb、Cu、Zn、Mn、Cr和Ni七种重金属的含量和周年时空分布特征；表层沉积物中Cd具有较强的污染程度和潜在生态风险，四角蛤蜊对重金属元素Cd和Pb具有较高的富集能力，对环境重金属污染具有很好的指示作用。 2．查明了Cd对四角蛤蜊在24h，48h和96h的半致死浓度（LC50）分别为15.96mg/L、5.15mg/L和2.38mg/L，汞的24h，48h和96h LC50分别为3.71mg/L，0.61mg/L和0.21mg/L。镉和汞对四角蛤蜊的安全质量浓度分别为0.0238mg/L和0.0021mg/L。 3．四角蛤蜊软体部对Cd和Hg的富集能力有显著差异。暴露过程中，四角蛤蜊软体部Cd和Hg的增加量分别为0.12-7.7µg/g和0.002-0.024µg/g，富集率分别为0.3-6.2%和0.11-0.68%，吸收率常数分别为0.07-1.10和0.001-0.005。 4．四角蛤蜊受Cd和Hg胁迫后，外套膜、鳃和肝胰腺的金属硫蛋白（MT）含量均在暴露浓度和胁迫时间上都有极显著变化。组织内MT含量的大小关系为：肝胰腺＞鳃＞外套膜。肝胰腺可以作为双壳贝类MT重金属污染指示研究的目标组织。四角蛤蜊对Cd和Hg不同的解毒机制，导致组织中MT的表达含量和Cd胁迫显著相关，而与Hg胁迫无显著相关性。 5．四角蛤蜊肝胰腺和鳃中抗氧化系统酶、脂质过氧化产物、酸性磷酸酶（ACP）和碱性磷酸酶（ALP）在不同Cd胁迫浓度和暴露时间下有显著差异。与对照组相比，超氧化物歧化酶（SOD）、过氧化氢酶（CAT）、谷胱甘肽过氧化物酶（GPx）的活力和丙二醛（MDA）含量均随着暴露时间的增加而增加，达到一个峰值，然后减低。而ACP和ALP活力则表现出先被抑制，然后升高的变化趋势。肝胰腺中CAT和GPx活力高于鳃，鳃中SOD和MDA含量高于肝胰腺，这种差异与两种组织不同的解毒机理有关。 6．重金属胁迫能够造成四角蛤蜊血细胞超微结构的损伤、溶酶体膜稳定性改变、微核和总畸形核生成，各种损伤均表现出明显的浓度依赖效应。2μg/L Hg暴露14天后，血细胞溶酶体膜中性红保持时间（NRR）、微核生成率（MN）和总畸形核生成率（TNA）与对照组相比没有显著差异。相同暴露时间下，25 μg/L Hg处理组血细胞NRR值低于25 μg/L Cd处理组，而MN和TNA值则相反，说明Hg胁迫对四角蛤蜊血细胞溶酶体膜具有较强的损伤作用。研究发现，NRR、MN和TNA三种指标对于衡量重金属污染对四角蛤蜊血细胞的毒性效应有很好的协同检测作用，可望作为有效的生物标志物在环境监测技术中得以应用。

Synthesis and evaluation of a thiourea-modified chitosan derivative applied for adsorption of Hg(II) from synthetic wastewater

In this work, a thiourea-modified chitosan derivative (TMCD) was synthesized through two steps, O-carboxymethylated first and then modified by a polymeric Schiff's base of thiourea/glutaraldehyde. The adsorption behavior of mercury (II) ions onto TMCD was investigated through batch method. The maximum adsorption capacity for Hg(II) was found to be 6.29 mmol/g at pH 5.0 and both kinetic and thermodynamic parameters of the adsorption process were obtained. The results indicated that adsorption process was spontaneous exothermic reaction and kinetically followed pseudo-second-order model. The adsorption experiments also demonstrated TMCD had high adsorption selectivity towards Hg(II) ions when coexisted with Cu(II), Zn(II), Cd(II) and Ca(II) in solution and it could be easily regenerated and efficiently reused. (C) 2010 Elsevier B.V. All rights reserved.

Selective and specific detection of sulfate-reducing bacteria using potentiometric stripping analysis

A fast, sensitive and reliable potentiometric stripping analysis (PSA) is described for the selective detection of the marine pathogenic sulfate-reducing bacterium (SRB). Desulforibrio caledoiensis. The chemical and electrochemical parameters that exert influence on the deposition and stripping of lead ion, such as deposition potential, deposition time and pH value were carefully studied. The concentration of SRB was determined in acetate buffer solution (pH 5.2) under the optimized condition (deposition potential of -1.3 V. deposition time of 250 s, ionic strength of 0.2 mol L-1 and oxidant mercury (II) concentration of 40 mg L-1). A linear relationship between the stripping response and the logarithm of the bacterial concentration was observed in the range of 2.3 x 10 to 2.3 x 10(7) cfu mL(-1). In addition, the potentiometric stripping technique gave a distinct response to the SRB, but had no obvious response to Escherichia coli. The measurement system has a potential for further applications and provides a facile and sample method for detection of pathogenic bacteria. (C) 2010 Elsevier B.V. All rights reserved.

三塘湖盆地牛圈湖区储层特征研究—以齐古组、头屯河组为例

In view of few researches into pore textures and anisotropy characteristics of Qiguzu-toutunhezu reservoir in Niuquanhu block in Santanghu Basin, in order to enhance the hydrocarbon recovery of the region of interest and improve the reservoir development effect, with the employment of the experiments like cast thin slice, scanning electron microscope, conventional high pressure mercury penetration, constant speed mercury penetration and nuclear magnetic resonance, the thesis makes a thorough research into pore texture characteristics and anisotropy characteristics of the sandstone reservoir. The research shows that the microscopic pore textures are complicated, the anisotropy is high and waterflood development water/oil displacement efficiency is low, which are mainly caused by the high microscopic anisotropy of the reservoir. Specially, the research shows that Qiguzu-toutunhezu reservoir belongs to braided delta front intrafacies, the intergranular pore is the main type of pores, which take up 65.50 percent of total pores, intergranular dissolved pores, feldspar dissolved pores and lithic dissolved pores are on the second place, and there are few carbonate dissolved pores. The reservoir belongs to mesopore-fine throat and mesopore-medium throat. The pore distribution of the sandstone reservoir is comparatively centralized. The reservoir inhomogeneity is mainly caused by the throat inhomogeneity. Diagenesis mainly includes compaction, cementation, metasomatism and dissolution. Compared with compaction， cementation exerts more direct impact on the decline of the porosity of the sandstone reservoir ( pore loss factor is 63.75 percent in the cementing process). Based on the classification of diagenetic stages, the reservoir diagenesis is on the stage of the late period of early diagenetic stage to early period of late diagenetic stage. The study area of the small sandstone reservoir layer of the anisotropy of the relatively strong; plane, the anisotropy of the relatively weak. microscopic anisotropy of its relatively strong.

鄂尔多斯盆地志丹地区延长组储层综合评价

Sedimentary provenance direction，sedimentary facies，reservoir geological characteristic，pore structure； physical property characteristic，reservoir classification and evaluation ，forthermore，favorable area area are forecasted of Yanchang formation in ZhiDan region， by mainly study on the data of field section observation ，core observation, well logging explaination and routine microscope slice identification，scanning Electron Microscope and reservoir analysis of lithology and physical property , Under the guidance of such advanced theories and methods as sedimentology，reservoir sedimentology，lithological oil pool and so on，in the thesis. The following fruits are mainly achieved in this paper： Yanchang formation stratum is divided and correlated in this entire region， and the characteristic of oil layer unit is detailed discussed , respectively. According to main marker bed and supplementary ones.and research result shows that the source of provenance direction during Yanchang Formation mianly is north-east. Delta and lake are mainly developed in study area ，sub-facies and micro-facies are divided，distribution of sedimentary micro-facies in plane and palaeogeographic evolution are described，and gentle slope type- shallow water delta depositional model is established. Fine-grain arkose sandstone is the main reservoir，and which have experienced such different degree diagenesis as compaction, cementation, replacement and dissolution, and in which compaction and cementation are mainly factors to reduce sandstone physical property and dissolution effectively improved physical property during burial diagenesis procedure. All reservoirs of Yanchang Formation have entered A period of late diagenetic stage according to scheme of diagenesis period division . Intergranular porosity，dissolution porosity，fissure porosity are main pore types. And porosity structure are analyse by mercury penetration capillary pressure parameter，fine-shortness type and fine- length throat type are mainly developed. as a whole，the reservoir， with the characteristic of porosity and permeability altering apparently，strong inhomogeneity ， is a medium- porosity and medium permeability one. In plane，higher- porosity and higher-permeability are corresponded well with distributary channel area， physical property and inhomogeneity are affected by both deposition and diagenesis，and distributary channel and underwater distributary channel are favorable facies . According to such characteristic as lithology，physical property，pore structure ，diagenesis and sandstone distribution, the sandy reservoir can be classified 4 types, and the main sandy in every oil layer unit are evaluated according to the standard. The analysis result of petroleum concentration rule shows that Yanchang Formation are with not only favourable oil source rock，reservoir，covering combination ，but also good entrapment condition in study area. Lithology and structure-lithology oil pool are mainly developed ，based on condition of favorable reservoir developments，accounting for deliverability and sandstone superface elevation，zone of profitabilitis are forecasted.