ELECTROCHEMICAL STUDY OF ISOPOLY-OXOMETALLATES AND HETEROPOLY-OXOMETALLATES FILM MODIFIED MICROELECTRODES .3. FURTHER STUDY OF ELECTRODE PROCESS OF ISOPOLYMOLYBDIC ANION DOPED IN POLYANILINE FILM

The isopolymolybdic anion-polyaniline film modified carbon fiber (CF) microelectrode with high stability and electroactivity in aqueous acid solution has been successfully prepared by cycling the potential between -0.15 V and +0.85 V vs. sce at 100 mV s-1 or applying constant potential (+0.85 V) for electropolymerization in a 0.5 M H2SO4 solution containing 5.0 x 10(-2) M aniline and 5.0 x 10(-3) M H4Mo8O26. The electrochemical behaviour of the isopolymolybdic anion entrapped in the polyaniline film is strongly influenced by the sweep-potential range besides the acidity of electrolyte solution. In some acidic electrolyte solution (eg 0.5 M H2SO4), the change of the sweep-potential range causes the structure alternation of the isopolymolybdic anion and resulting in a new electrode process. The cyclic voltammogram of Mo8O264- in 0.5 M H2SO4 solution exhibits three two-electron reversible waves between +0.70 and -0.20 V. However, when the potential sweeps to the lower-limit of -0.3 V, where the fourth four-electron cathodic wave appears, the redoxidation process of the reduction product of Mo8O264- becomes relatively complicated. The 10-electron reduction product seems to change into other isopolyanion (this unknown structure isopolyanions are simply called [Mo-O]), which can be reoxidized to Mo8O264- by five successive two-electron oxidation steps from -0.30 to +0.70 V. However, when the lower-limit of the cycling potential is maintained at -0.30 V and the upper-limit reduces to +0.40 V from +0.70 V, the [Mo-O] in the film exhibits four two-electron reversible waves. We have presented a novel explanation about its electrode reaction mechanism on the basis of our experimental results.

ELECTROCHEMICAL STUDY OF ISOPOLY AND HETEROPOLY OXOMETALLATE FILM MODIFIED MICROELECTRODES .5. PREPARATION AND ELECTROCHEMICAL-BEHAVIOR OF A 2/18-MOLYBDODIPHOSPHATE ANION MONOLAYER MODIFIED ELECTRODE

In this paper a carbon fibre (CF) microelectrode modified with the 2:18-molybdodiphosphate anion by simple adsorption is described and its electrochemical behaviour is reported. The 2:18-molybdodiphosphate anion (alpha-P2Mo18O626-), which is a Dawson structure, undergoes five successive multielectron reductions in acidic solution. The first three redox waves correspond to the two-electron process, and the last two waves are four-electron and six-electron processes respectively. On the basis of the experimental results it is shown that the electrode process of alpha-P2Mo18O626- on the CF electrode in acidic solution is simultaneously controlled by the diffusion and adsorption of alpha-P2Mo18O626- anions. When the concentration of the alpha-P2Mo18O626- in the solution is reduced, the electrode process mainly exhibits non-diffusion-controlled behaviour, and the diffusion-limited process takes over as the concentration of alpha-P2Mo18O626- becomes higher. The CF electrode modified with a thin film of alpha-P2Mo18O626- exhibits very good stability and redox behaviour in aqueous acidic solution. The alpha-P2Mo18O626- is reduced to heteropoly blue, with an accompanying protonation process. The addition of more than six electrons to the alpha-P2Mo18O626- anion in an aqueous solution does not result in its decomposition. The result obtained is not the same as that reported previously.

PHOTOELECTROCHEMISTRY OF ELECTRODEPOSITED POLYCRYSTALLINE CUINSE2 THIN-FILMS .1. ELECTRODEPOSITION OF CUINSE2 FILMS

Electrodeposition of CuInSe2 was investigated in acidic solutions containing Cu2+, In3+ and HSeO2+ ions. The electrodeposition condition was optimized with the aim of obtaining uniform thin films on titanium substrate. The mechanism of the electrodeposition process is discussed. Structure analysis of the deposited film shows a typical polycrystalline chalcopyrite structure, good crystallinity and homogeneous dispersion. The photoelectrochemical cells made of these kinds of deposited films in polysulfide redox solution give distinct photoresponse.

FLOW-INJECTION AMPEROMETRIC DETECTION OF HYDRAZINE BY ELECTROCATALYTIC OXIDATION AT A PRUSSIAN BLUE FILM-MODIFIED ELECTRODE

A Prussian Blue-modified glassy carbon electrode prepared by simple adsorption exhibited excellent electrocatalytic activity in the oxidation of hydrazine in acidic media. A film of the perfluorosulphonic acid polymer Nafion coated on top of the Prussian Blue-modified glassy carbon electrode can improve the mechanical stability of the Prussian Blue layer in the flow stream. Hydrazine was detected by flow-injection analysis at the modified electrode with high sensitivity. The limit of detection was 0.6 ng.

AMPEROMETRIC FLOW-INJECTION ANALYSIS OF HYDRAZINE BY ELECTROCATALYTIC OXIDATION AT COBALT TETRAPHENYLPORPHYRIN MODIFIED ELECTRODE WITH HEAT-TREATMENT

Chemically modified electrodes prepared by treating the cobalt tetraphenylporphyrin modified glassy-carbon electrode at 750-degrees (HCME) are shown to catalyze the electrooxidation of hydrazine. The oxidation occurred at +0.63 V vs. Ag/AgCl (saturated potassium chloride) in pH 2.5 media. The catalytic response is evaluated with respect to solution pH, potential scan-rate, concentration dependence and flow-rate. The catalytic stability of the HCME is compared with that of the cobalt tetraphenylporphyrin adsorbed glassy-carbon electrode. The stability of the HCME was excellent in acidic solution and even in solutions containing organic solvent (50% CH3OH). When used as the sensing electrode in amperometric detection in flow-injection analysis, the HCME permitted sensitive detection of hydrazine at 0.5 V. The limit of detection was 0.1 ng. The linear range was from 50 ng to 2.4-mu-g. The method is very sensitive and selective.

ELECTROCHEMICAL STUDY OF ISOPOLYOXOMETALLATES AND HETEROPOLYOXOMETALLATES FILM MODIFIED MICROELECTRODES .1. PRETREATMENT AND MODIFICATION OF THE MO80-26(4-) MODIFIED CARBON-FIBER MICROELECTRODE

In this paper the preparation of isopoly- and heteropolyoxometallates (IPA and HPA) thin film modified carbon fiber (CF) microelectrodes and the factor that influences the modification of IPA and HPA films are described. IPA and HPA film modified CF microelectrodes can all be prepared by cyclic potential scan and simple dip coating. The modified electrodes prepared are very stable and reversible in acidic solution with monolayer characteristics. The electrochemical pretreatment of CF microelectrodes plays an important role in the modification of IPA and HPA film. The absorption of IPA and HPA film on electrode surfaces has been discussed on the basis of surface conditions of the CF microelectrode and the structure of IPA and HPA.

LIQUID-CHROMATOGRAPHY WITH ELECTROCATALYTIC DETECTION OF CYSTEINE, N-ACETYLCYSTEINE AND GLUTATHIONE BY A PRUSSIAN BLUE FILM-MODIFIED ELECTRODE

Chemically modified electrodes prepared by adsorbing prussian blue on a glassy carbon electrode are shown to catalyse the electro-oxidation of cysteine, N-acetylcysteine and glutathione in acidic media. The catalytic response is evaluated with respect to the potential scan rate, the solution pH, the concentration dependence, and other variables. Covering the electrode with Nafion(R) film improved the stability and reproducibility in liquid chromatography with electrochemical detection to the extent that repetitive sample injections produced relative standard deviations of less than 5% over several hours of operation. The limit of detection was 4 pmol for cysteine, 33 pmol for glutathione and 61 pmol for N-acetylcysteine.

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...

INVESTIGATION OF ELECTROCHEMICAL-BEHAVIOR OF ARS ON GC ELECTRODE BY SPECTROELECTROCHEMISTRY WITH LOPTLC

The electrochemical behavior of Alizarin Red S(ARS) on GC electrode has been studied in acidic condition by spectroelectrochemistry with LOPTLC. It was found that there are three electrochemical reactions and followed by a chemical reaction of ARS in the potential range of 1.00——0.60V. The mechanism of electrode reactions has been studied and suggested based on the informations obtained from electrochemical and insitu spectroelectrochemical experiments.

Microprojectile bombardment of Laminaria japonica gametophytes and rapid propagation of transgenic lines within a bubble-column bioreactor

A human acidic fibroblast growth factor gene, hafgf, was successfully transferred into Laminaria japonica (kelp) gametophytes via microprojectile bombardment using the biolistic PDS-1000/He gene gun. Following phosphinothricin screening, PCR detection and Southern blot analysis, transgenic L. japonica gametophytes were cultivated in an illuminated bubble-column bioreactor to optimize growth conditions. A maximal final dry cell density of 1,695 mg l(-1) was obtained in a batch culture having an initial dry cell density of 129.75 mg l(-1). This was achieved using an aeration rate of 1.08 l air min(-1) l(-1) culture in a medium containing 1.5 mM inorganic nitrate and 0.15 mM phosphate. In addition, the relationship between different nitrogen sources and growth of transgenic gametophytes indicated that both urea and sodium nitrate were effective nitrogen sources for cell growth, while ammonium ions inhibited growth of these gametophytes.

A simple method for DNA extraction from sporophyte in the brown alga Laminaria japonica

A simple method was developed for extracting DNA from brown algae Laminaria japonica, which possess large amounts of acidic polysaccharides. Firstly, the sporophyte were washed by eliminating polysaccaride buffer to remove the polysaccharides and then ground in liquid nitrogen. Secondly, the powders were treated with lysing buffer. Thirdly, KAc was used to eliminate the remaining acidic polysaccharides. The extracted DNA was purified using a chloroform-isoamyl alcohol ( 24: 1 v/v), and precipitated in cold isopropanol. The yield was from 18.7 to 37.5 mu g g(-1) (wet weight) and the purity of total DNA was determined spectrophotometrically as the ratio of A(260)/A(280), which was about 1.7 - 1.9. The extracted DNA was of high quality and suitable for molecular analyses, such as PCR, restriction enzyme digestion. This method is a reproducible, simple, and rapid technique for routine DNA extraction from sporophyte in Laminaria japonica. Furthermore, the low cost of this method makes it attractive for large-scale studies.

Cloning and recombinant expression of a crustin-like gene from Chinese shrimp, Fenneropenaeus chinensis

Antimicrobial peptides or proteins (AMPs) are proved to be one of the most important humoral factors to resist pathogen infection. As an antimicrobial protein, crustin had been described in invertebrates as a component of the innate immune system. A crustin-like gene (CruFc) was cloned from haemocytes of Chinese shrimp Fenneropenaeus chinensis by 3' and 5'-RACE PCR. The full-length cDNA consists of 523 with 405 bp open reading frame encoding 134 amino acids and the deduced peptide contains a putative signal peptide of 17 amino acids. The sequence also contains a whey-acidic protein (WAP) domain at the C-terminal. Transcripts of CruFc were mainly detected in haemocytes and gill by RT-PCR analysis. In addition, another full-length cDNA named CshFc was also cloned from haemocytes of Chinese shrimp and its inferred amino acid sequence lacks the WAP-type 'four-disulfide core' domain. The fusion proteins containing CruFc and CshFc were, respectively, produced and the antimicrobial assays revealed that the recombinant CruFc could inhibit the growth of grain-positive bacteria in vitro but the recombinant CshFc could not inhibit at the same conditions. The difference of antimicrobial activity between recombinant CruFc and CshFc provides the evidence that the four-disulfide core domain of crustin may play an important role in its biological function. (c) 2006 Elsevier B.V. All rights reserved.

Origin of a native sulfur chimney in the Kueishantao hydrothermal field, offshore northeast Taiwan

Analyses of rare earth and trace element concentrations of native sulfur samples from the Kueishantao hydrothermal field were performed at the Seafloor Hydrothermal Activity Laboratory of the Key Laboratory of Marine Geology and Environment, Institute of Oceanology, Chinese Academy of Sciences. Using an Elan DRC II ICP-MS, and combining the sulfur isotopic compositions of native sulfur samples, we studied the sources and formation of a native sulfur chimney. The results show, when comparing them with native sulfur from crater lakes and other volcanic areas, that the native sulfur content of this chimney is very high (99.96%), the rare earth element (REE) and trace element constituents of the chimney are very low (Sigma REE < 21x10(-9)), and the chondrite-normalized REE patterns of the native sulfur samples are similar to those of the Kueishantao andesite, implying that the interaction of subseafloor fluid-andesite at the Kueishantao hydrothermal field was of short duration. The sulfur isotopic compositions of the native sulfur samples reveal that the sulfur of the chimney, from H2S and SO2, originated by magmatic degassing and that the REEs and trace elements are mostly from the Kueishantao andesite and partly from seawater. Combining these results with an analysis of the thermodynamics, it is clear that from the relatively low temperature (< 116 degrees C), the oxygenated and acidic environment is favorable for formation of this native sulfur chimney in the Kueishantao hydrothermal field.

Distribution and mobility of metals in agricultural soils near a copper smelter in South China

The distribution and mobility of heavy metals in the paddy soils surrounding a copper smelting plant in south China was investigated. We assessed the degree of metal contamination using an index of geoaccumulation. The metals were divided into two groups: (1) Cu, Zn, Pb and Cd, whose concentrations were heavily affected by anthropogenic inputs, and (2) Ni, Co and Cr, which were mainly of geochemical origin. Concentrations of Cu, Cd, Zn, and Pb in the polluted soils were higher than the Chinese soil quality criteria. The chemical partitioning patterns of Pb, Zn and Cu indicated that Pb was largely associated with the residual and NH2OH HCl extractable fractions. In contrast, Cd was predominantly associated with the MgCl2 extractable fraction. A large proportion of Cu was bound to the acidic H2O2 extractable fractions, while Zn was predominantly found in the residual phase. The fraction of mobile species, which potentially is the most harmful to the environment, was found to be elevated compared to unpolluted soils in which heavy metals are more strongly bound to the matrix. The mobility of the metals was studied by water extraction using a modification of Tessier's procedure, and the order of mobility was Zn > Cd > Cu > Ce > Pb.

Intracellular copper/zinc superoxide dismutase from bay scallop Argopecten irradians: Its gene structure, mRNA expression and recombinant protein

Superoxide dismutases are an ubiquitous family of enzymes that function to efficiently catalyze the dismutation of superoxide anions. Two unique and highly compartmentalized bay scallop Argopecten irradians superoxide dismutases: MnSOD and ecCuZnSOD, have been molecularly characterized in our previous study. To complete characterize the SOD family in A. irradians, a novel intracellular copper/zinc SOD from the A. irradians (Ai-icCuZnSOD) was obtained and characterized. The full-length cDNA of Ai-icCuZnSOD was 1047 bp with a 459 bp open reading frame encoding 152 amino acids. The genomic length of the Ai-icCuZnSOD gene was about 4279 bp containing 4 exons and 3 introns. The promoter region containing many putative transcription factor binding sites were analyzed. Furthermore, quantitative reverse transcriptase real-time PCR (qRT-PCR) analysis indicated that the highest expression of the Ai-icCuZnSOD was detected in gill and the expression profiles in hemocytes of bay scallops challenged with bacteria Vibrio anguillarum and lipopolysaccharide (LPS) were different. The result presented an increased expression after injection with LPS whereas no significant changes were observed after V. anguillarum injection. A fusion protein containing Ai-icCuZnSOD was produced in vitro. The rAi-icCuZnSOD is a stable enzyme, retaining more than 80% of its activity between 10 and 60 degrees C and keeping above 88% of its activity at pH values between 5.8 and 9. Ai-icCuZnSOD is more stable under alkaline than acidic conditions. Crown Copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.