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...

Temperature and light tolerance of representative brown, green and red algae in tumble culture revealed by chlorophyll fluorescence measurements

Laminaria japonica, Undaria pinnatifida, Ulva lactuca, Grateloupia turuturu and Palmaria palmata are Suitable species that fit the requirements of a seaweed-animal integrated aquaculture system in terms of their viable biomass, rapid growth and promising nutrient uptake rates. fit this investigation, the responses of the optimal chlorophyll fluorescence yield of the five algal species in tumble Culture were assessed at a temperature range of 10 similar to 30 degrees C. The results revealed that Ulva lactuca was the most resistant species to high temperature, withstanding 30 degrees C for 4 h without apparent decline in the optimal chlorophyll fluorescence yield. While the arctic alga Palmaria palmata was the most vulnerable one, showing significant decline in the optimal chlorophyll fluorescence yield at 25 degrees C for 2 h. The cold-water species Laminaria japonica, however, demonstrated strong ability to cope with higher temperature (24 similar to 26 degrees C) for shorter time (within 24 h) without significant decline in the optimal chlorophyll fluorescence yield. Grateloupia turuturu showed a general decrease in the optimal chlorophyll fluorescence yield with the rising temperature from 23 to 30 degrees C, similar to the temperate kelp Undaria pinnatifida. Changes of chlorophyll fluorescence yields of these algae were characterized differently indicating the existence of species-unique strategy to cope with high light. Measurements of the optimal chlorophyll fluorescence yield after short exposure to direct solar irradiance revealed how long these exposures could be without significant photoinhibition or with promising recovery in photosynthetic activities. Seasonal pattern of alternation of algal species in tank culture in the Northern Hemisphere at the latitude of 36 degrees N was proposed according to these basic measurements.

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。

Experimental study on the impact of dinoflagellate Alexandrium species on populations of the rotifer Brachionus plicatilis

To investigate harmful effects of the dinoflagellate Alexandrium species on microzooplankton, the rotifer Brachionus plicatilis was chosen as an assay species, and tested with 10 strains of Alexandrium including one known non-PSP-producer (Alexandrium tamarense, AT-6). HPLC analysis confirmed the PSP-content of the various strains: Alexandrium lusitanicum, Alexandrium minutum and Alexandrium tamarense (ATHK, AT5-1, AT5-3, ATC102, ATC103) used in the experiment were PSP-producers. No PSP toxins were detected in the strains Alexandrium sp1, Alexandrium sp2. Exposing rotifer populations to the densities of 2000 cells ml(-1) of each of these 10 Alexandrium strains revealed that the (non-PSP) A. tarnarense (AT-6) and two other PSP-producing algae: A. lusitanicum, A. minutum, did not appear to adversely impact rotifer populations. Rotifers exposed to these three strains were able to maintain their population numbers, and in some cases, increase them. Although some increases in rotifer population growth following exposures to these three algal species were noted, the rate was less than for the non-exposed control rotifer groups. In contrast, the remaining seven algal strains (A. tamarense ATHK, AT5-1, AT5-3, ATC102, ATC103; also Alexandrium sp1 and Alexandrium sp2) all have adverse effects on the rotifers. Dosing rotifers with respective algal cell densities of 2000 cells ml-1 each, for Alexandrium spl, Alexandrium sp2, and A. tamarense strains ATHK and ATC103 showed mean lethal time (LT50) on rotifer populations of 21, 28, 29, and 36h, respectively. The remaining three species (A. tamarense strains AT5-1, AT5-3, ATC102) caused respective mean rotifer LT50S of 56, 56, and 71 h, compared to 160 h for the unexposed "starved control" rotifers. Experiments to determine ingestion rates for the rotifers, based on changes in their Chlorophyll a content, showed that the rotifers could feed on A. lusitanicum, A. minutum and A. tamarense strain AT-6, but could graze to little or no extent upon algal cells of the other seven strains. The effects on rotifers exposed to different cell densities, fractions, and growth phases of A. tamarense algal culture were respectively compared. It was found that only the whole algal cells had lethal effects, with strongest impact being shown by the early exponential growth phase of A. tamarense. The results indicate that some toxic mechanism(s), other than PSP and present in whole algal cells, might be responsible for the adverse effects on the exposed rotifers. (C) 2004 Elsevier B.V. All rights reserved.

Inhibition of egg hatching success and larvae survival of the scallop, Chlamys farreri, associated with exposure to cells and cell fragments of the dinoflagellate Alexandrium tamarense

We report an apparently novel toxic effect of the dinoflagellate Alexandrium tamarense, manifested by inhibition of the egg hatching success of the scallop, Chlamys farreri. The hatching rate of C. farreri approached only 30% of controls when its fertilised eggs were exposed for 36 h to A. tamarense cells or cellular fragments at a concentration of 100 cells/ml, and the hatching rate was just 5% after exposure to A. tamarense of 500 cells/ml. Similar exposures of the fertilised scallop eggs to two other algal species, the diatom Phaeodactylum tricornutum and the raphidophyte Heterosigma carterae, resulted in no such toxicity or inhibitory effects.. Likewise, exposure of eggs to standard STX toxin. as well as to A. tamarense cell contents (supernant of re-suspended algal cells following ultrasonication and centrifugation), did not elicit this inhibitory response. However, exposure of the scallop eggs to cell cultures, intact algal cells, or cell fragments of A. tamarense produced marked toxicity. The alga also influenced larvae at early D-shape stage of scallop. The survival rates began to decrease significantly after exposed for 6 days at concentration of 3000 cells/ml and above: no larvae could survive after 14-day exposure to A. tamarense at 10,000 cells/ml or 20-day at 5000 cells/ml. The results indicated the production of novel substances from A. tamarense which can cause adverse effects on egg hatching and survival of the scallop larvae, The experiment also found that the developmental stages before blastula was the developmental period most sensitive to the A. tamarense toxin(s) and the alga at early exponential stage had the strongest effect on egg hatching comparing with other growth phases. The adverse effect of A. tamarense on early development of scallops may cause decline of shellfish population and may have further impact on marine ecosystem. (C) 2001 Elsevier Science Ltd. All rights reserved.

Effects of acute temperature or salinity stress on the immune response in sea cucumber, Apostichopus japonicus

Invertebrates are increasingly raised in mariculture, where it is important to monitor immune function and to minimize stresses that could suppress immunity. The activities of phagocytosis, superoxide dismutase (SOD), catalase (CAT), myeloperoxiclase (MPO), and lysozyme (LSZ) were measured to evaluate the immune capacities of the sea cucumber, Apostichopus japonicus, to acute temperature changes (from 12 degrees C to 0 degrees C, 8 degrees C, 16 degrees C, 24 degrees C, and 32 degrees C for 72 h) and salinity changes (from 30 parts per thousand to 20 parts per thousand, 25 parts per thousand, and 35 parts per thousand for 72 h) in the laboratory. Phagocytosis was significantly affected by temperature increases in 3 h, and by salinity (25 parts per thousand and 35 parts per thousand) changes in 1 h. SOD activities decreased significantly in 0.5 h to 6 h samples at 24 degrees C. At 32 degrees C, SOD activities decreased significantly in 0.5 h and 1 h exposures, and obviously increased for 12 h exposure. CAT activities decreased significantly at 24 degrees C for 0.5 h exposure, and increased significantly at 32 degrees C in 3 h to 12 h exposures. Activities of MPO increased significantly at 0 degrees C in 0.5 h to 6 In exposures and at 8 degrees C for 1 h. By contrast, activities of MPO decreased significantly in 24 degrees C and 32 degrees C treatments. In elevated-temperature treatments, activities of LSZ increased significantly except at 32 degrees C for 6 h to 12 h exposures. SOD activity was significantly affected by salinity change. CAT activity decreased significantly after only 1 h exposure to salinity of 20 parts per thousand.. Activities of MPO and LSZ showed that A. japonicus tolerates limited salinity stress. High-temperature stress had a much greater effect on the immune capacities of A. japonicus than did low-temperature and salinity stresses. Crown Copyright (C) 2008 Published by Elsevier Inc. All rights reserved.

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.