Selective Detection of Dopamine and Its Metabolite,DOPAC, in the Presence of Ascorbic Acid Using Diamond Electrode Modified by the Polymer Film

The surface of boron‐doped diamond (BDD) electrode is modified by the polymer film for the first time. The cationic polymer film of N,N‐dimethylaniline (DMA) is electrochemically deposited on BDD electrode surface. This polymer (PDMA) film‐coated BDD electrode is used as a sensor which selectively detect dopamine (DA) in the presence of ascorbic acid (AA). This electrode also can detect both DA and its metabolite, 3,4‐dihydroxy phenyl acetic acid (DOPAC) in the presence of AA in the range of the physiological concentrations of these species. Favorable ionic interaction (i.e., electrostatic attraction) between the PDMA film and AA or DOPAC lowers their oxidation potentials and enhances the current response for AA and DOPAC compared to that at the bare electrode. The PDMA film also shows a hydrophobic interaction with DA and DOPAC. In cyclic voltammetric measurements, the PDMA film‐coated electrode can successfully separate the oxidation potentials for AA and DA coexisting in the same solution and the separation is about 200 mV. AA oxidizes at more negative potential than DA. In square‐wave voltammetry, the sensitivity of the PDMA film‐coated BDD electrode for DA in the presence of higher concentration of AA is higher than that of the PDMA film‐coated glassy carbon electrode. The hydrodynamic amperometric experiments confirm that the oxidation of AA is not affected by the oxidized product of DA and vice versa. So, unlike the bare electrode the catalytic oxidation of AA by the oxidized DA is eliminated at the PDMA film‐coated BDD electrode. The sensitivities of the modified electrode for AA, DA and DOPAC, which are present in the same solution with their physiological concentration ratios, are calculated to be 0.070, 0.363 and 0.084 μA μM^?1, respectively. The modified electrode exhibits a stable and sensitive response to DA.     

纳米级TiO2粉体的制备研究——Ⅱ.絮凝剂及其浓度的影响

采用溶胶-凝胶-超临界流体干燥(SCFD)法制备纳米级TiO₂超细粉，详细考察了不同絮凝剂及其浓度对TiO₂织构和结构性质的影响。结果表明，利用强碱溶液作为絮凝剂，浓度为5 mol·L^-1是制备大孔高比表面TiO₂超细粉较为适宜的条件。     

单分散二氧化钛超微粒子的制备

以四丁氧基钛为原料，采用溶胶－凝胶法制备了超微二氧化钛粉末．改变热处理气氛、升温速率、水与四丁氧基钛的摩尔比以及溶剂，分别得到７ｎｍ球形单相锐钛矿以及四方形（４０ｎｍ×１０ｎｍ）、球形（４４ｎｍ）的主相金红石超微粒子．     

A novel zirconocene/ultradispersed diamond black powder supported catalytic system for ethylene polymerization

A novel carrier of ultradispersed diamond black powder (UDDBP) was used to support metallocene catalyst. Al₂O₃ was also used as carrier in order to compare with UDDBP. Supported catalysts for ethylene polymerization were synthesized by two different reaction methods. One way was direct immobilization of the metallocene on the support, the other was adsorption of MAO onto the support followed by addition of the metallocene. Four supported catalysts Cp₂ZrCl₂/UDDBP, Cp₂ZrCl₂/Al₂O₃, Cp₂ZrCl₂/MAO/UDDBP and Cp₂ZrCl₂/Al₂O₃/MAO were obtained. The content of the zirconium in the supported catalyst was determined by UV spectroscopy. The activity of the ethylene polymerization catalyzed by supported catalyst was investigated. The influence of Al/Zr molar ratio and polymerization temperature on the activity was discussed. The polymerization rate was also observed.     

CuO超细粉体的形貌与红外特性研究

CuO作为一种多功能精细无机材料，在印染、陶瓷、玻璃及医药等领域的应用已有数十年的历史，作为催化剂的主要活性成分，近年来在氧化、加氢、C１化学合成、NOx还原、CO及碳氢化合物燃烧、精细化工等多种催化反应中也得到了广泛的应用。可以推测，当CuO材料的粒度达到纳米级时，将使它的功能更加独特，应用更为广泛。因此CuO纳米材料的制备方法、聚集状态、与其他组分或载体的作用状况及催化活性等成为当前功能材料发展的研究热点之一犤１～８犦。我们在前文中报道了直接热解Cu２（OH）２CO３所得CuO粒径小、分布均匀、比表面积大，…     

O／W微乳液中聚吡咯超微粒子的制备

选择合适的ＳＤＢＳ／吡咯／Ｈ２Ｏ三组分Ｏ／Ｗ微乳液与吡咯单体共存的两相体系，以单体相为单体源，在Ｏ／Ｗ三组分微乳液中进行了吡咯聚合，所得聚吡咯粒子大小仅为２～３ｎｍ，分布较均匀，且具有较好的导电性能．     

不同干燥过程对超细TiO2粉体性质的影响

考察了采用不同干燥工艺制备的TiO2粉体在粒子形貌、颗粒大小与分布、晶相组成以及比表面积和孔结构等织构和结构性质方面的差异。结果表明，利用常规的干燥方法，由水凝胶脱水所得的颗粒，颗粒间严重团聚，颗粒粒径大且分布不均匀，比表面积和孔体积最小；由醇凝胶直接脱水，则可以显著提高粉体的织构性能．而采用超临界流体干燥法则可以进一步提高粉体的性能，比表面积由水凝胶的4．88m2·g－1增大到113．8m2·g－1，提高了近30倍；孔体积由0．027cm3·g－1增大到0．41cm3·g-1．大约提高了15倍；而且其能够有效地防止粒子间的团聚，较好地保持了湿凝胶的网络结构，使颗粒尺寸降低且分布均匀，可重复性好．     

Manganese detection in marine sediments: anodic vs. cathodic stripping voltammetry

Three different electroanalytical techniques for the detection of manganese in marine sediments are evaluated. The anodic stripping voltammetry of manganese at an in situ bismuth-film-modified boron-doped diamond electrode and cathodic stripping voltammetry at a carbon paste electrode are shown to lack the required sensitivity and reproducibility whereas cathodic stripping voltammetry at a bare boron-doped diamond electrode is shown to be reliable and selective with a limit of detection, from applying a 60 s accumulation period of 7.4 × 10⁻⁷ M and a sensitivity of 0.24 A M⁻¹. The method was used to evaluate the manganese content of marine sediments taken from Šibenik, Croatia.     

Electroanalytical Determination of Carbaryl in Natural Waters on Boron Doped Diamond Electrode

The anodic voltammetric behavior of carbaryl on a boron‐doped diamond electrode in aqueous solution is reported. The results, obtained by square‐wave voltammetry at 0.1 mol L^?1 Na₂SO₄ and pH 6.0, allow the development of a method to determine carbaryl, without any previous step of extraction, clean‐up, preconcentration or derivatization, in the range 2.5–30.0×10^?6 mol L^?1, with a detection limit of 8.2±0.2 μg L^?1 in pure water. The analytical sensitivity of this electrochemical method diminished slightly, from 3.07 mA mmol^?1 L to 2.90 mA mmol^?1L, when the electrolyte was prepared with water samples collected from two polluted points in an urban creek. In these conditions, the recovery efficiencies obtained were around 104%. The effect of other pesticides (fenthion and 4‐nitrophenol) was evaluated and found to exert a negligible influence on carbaryl determination. The square‐wave voltammetric data obtained for carbaryl were typical of an irreversible electrode process with mass transport control. The combination of square‐wave voltammetry and diamond electrodes is an interesting and desirable alternative for analytical determinations.     

Electrocatalytic Reduction of Chromium(VI) by Thionin: Electrochemical Properties and Mechanistic Study

The electrochemical properties of aqueous thionin (an electroactive water soluble dye) of pH 1–12 were investigated by cyclic voltammetry at a boron doped diamond(BDD) electrode. A well defined reversible redox couple was observed in acidic, neutral and alkaline solutions. The standard potential and kinetic parameters for thionin were obtained by fitting experimental cyclic voltammograms to those generated by the DigiSim program. The electrogenerated reduced form of thionin has been used as an efficient organic catalyst for the reduction of Cr(VI) at a BDD electrode immersed in aqueous media. The cyclic voltammetry measurements indicate that an electrocatalytic process occurs, where electrochemically generated thionin reduced species (Leucothionin) is oxidized by Cr(VI) back to the parent thionin species via a EC' reaction mechanism. The determination of catalytic rate constant (K_cat) was accomplished again by fitting experimental cyclic voltammograms with simulated ones.