米非司酮的吸附伏安特性

在ＰＨ７．０Ｂｒｉｔｔｏｎ－Ｒｏｂｉｎｓｏｎ缓冲溶液中，米非司酮（Ｍｉｆｅｐｒｉｓｔｏｎｅ，ＲＵ４８６）在汞电极上有２个不可逆的线性扫描还原峰，峰电位分别为－１．２３Ｖ和－１．６８Ｖ。本文探讨了第一峰的电化学行为。     

血红素LB膜的电化学行为

采用循环伏安法研究了血红素与脑磷脂混合Y型LB（Langmuir-Blodgett）膜在玻碳电极上的电化学行为，结果表明血红素LB膜有良好的电化学活性，在0．1mol/L KCl溶液中有一对氧化还原峰（－0．42V／－0．30V）；将血红素LB膜转移到玻碳电极表面得到的血红素LB膜修饰电极（heme LB-GC）对溶液中溶解氧的电化学还原有良好的催化作用，其催化还原过程具有不可逆电荷传递特性。     

Mercury-free sono-electroanalytical detection of lead in human blood by use of bismuth-film-modified boron-doped diamond electrodes

We report the electroanalytical determination of lead by anodic stripping voltammetry at in-situ-formed, bismuth-film-modified, boron-doped diamond electrodes. Detection limits in 0.1 mol L^–1 nitric acid solution of 9.6x10^–8 mol L^–1 (0.2 ppb) and 1.1x10^–8 mol L^–1 (2.3 ppb) were obtained after 60 and 300 s deposition times, respectively. An acoustically assisted deposition procedure was also investigated and found to result in improved limits of detection of 2.6×10^–8 mol L^–1 (5.4 ppb) and 8.5×10^–10 mol L^–1 (0.18 ppb) for 60 and 300 s accumulation times, respectively. Furthermore, the sensitivity obtained under quiescent and insonated conditions increased from 5.5 (quiescent) to 76.7 A mol^–1 L (insonated) for 60 s accumulation and from 25.8 (quiescent) to 317.6 A mol^–1 L (insonated) for 300 s accumulation. Investigation of the use of ultrasound with diluted blood revealed detection limits of the order of 10^–8 mol L^–1 were achievable with excellent inter- and intra-reproducibility and sensitivity of 411.9 A mol^–1 L . For the first time, electroanalytical detection of lead in diluted blood is shown to be possible by use of insonated in-situ-formed bismuth-film-modified boron-doped diamond electrodes. This method is a rapid, sensitive, and non-toxic means of clinical sensing of lead in whole human blood.     

Simultaneous determination of trace uranium(VI) and zinc(II) by adsorptive cathodic stripping voltammetry with aluminon ligand

Uranium(VI) complexed with aluminon (3-[bis(3-carboxy-4-hydroxy-phenyl)methylene]-6-oxo-1,4-cyclohexadiene-1-carboxylic acid triammonium salt) was determined by adsorptive cathodic stripping voltammetry (ACSV) using a hanging mercury drop electrode. Trace uranium(VI) and zinc(II) can be simultaneously determined in a single scan in the presence of aluminon and urea. Optimal conditions were found to be: accumulation time; 180–200 s, accumulation potential; 50 mV versus Ag/AgCl, scan rate; 40 mV s⁻¹, supporting electrolyte; 0.1 M sodium acetate buffer at pH 6.5–7.0, and concentration of aluminon; 1×10⁻⁶ M. The linear range of uranium(VI) and zinc(II) were observed over the concentration range 2–33 and 30–120 ng ml⁻¹, respectively. The detection limit (S/N=3) are 0.2 ng ml⁻¹ (uranium) and 30 ng ml⁻¹ (zinc). A good reproducibility shows RSDs of 2.5–4.0% (n=10). The procedure offers high selectivity, with the presence of urea masking some metal ions.     

Thin‐Layer Cyclic Voltammetric and Scanning Electrochemical Microscopic Study of Antioxidant Activity of Ascorbic Acid at Liquid/Liquid Interface

An electron transfer reaction between ascorbic acid (H₂A) in an aqueous solution and oxidizing agent in an organic solution immiscible with water has been studied by thin‐layer cyclic voltammetry (TLCV) for charge transfer at the interface between two immiscible electrolyte solutions (ITIES). As an antioxidant, H₂A provide electrons through the aqueous/organic interface to reduce Fc⁺ and the procedure has been proved to be a one electron process again. In this work, the first combination of TLCV and scanning electrochemical microscopy (SECM) was achieved and showed a reasonable agreement between the results from the two different approaches. Otherwise, lower concentration ratios Kr of aqueous to organic reactants was adopted, which is given as evidence to the proposed procedure of Barker.     

The synthesis and characterisation of 1′-ethynyl-2,5-dimethylazaferrocene and derivatives

The synthesis of 1′-ethynyl-2,5-dimethylazaferrocene is reported along with its cyclic voltammetry measurements and the X-ray structure determination of its W(CO)₅-complex. Basic coordination and organic chemistry of 1′-ethynyl-2,5-dimethylazaferrocene is also presented via derivatives incorporating cis-Pt(dppe) and Si(Et)₃ units.     

Sulfide ion electrooxidation catalysed by cobalt phthalocyanine microcrystals

Electrooxidation of sulfide ion catalysed by microcrystals of cobalt phthalocyanine was investigated by cyclic voltammetry in 0.5M KNO₃ at pH 9.22. Traces of catalyst were immobilized at the surface of a paraffin-impregnated graphite electrode by the mechanical transfer of its powder. The electro-oxidation of HS^– proceeds in two irreversible steps, with the first peak between 0 V and –0.12 V and the second at 0.17 V. The first step is second order in HS^– and its product is the adsorbed disulfide, which may further dissociate to give adsorbed sulfur atoms. The reduction of sulfur occurs at –0.1 V.     

Catalytic Adsorptive Stripping Voltammetry of Germanium(IV) in the Presence of Gallic Acid and Vanadium(IV)‐EDTA

A highly sensitive and selective catalytic adsorptive cathodic striping procedure for the determination of trace germanium is presented. The method is based on adsorptive accumulation of the Ge(IV)‐gallic acid (GA) complex onto a hanging mercury drop electrode, followed by reduction of the adsorbed species. The reduction current is enhanced catalytically by addition of vanadium(IV)‐EDTA. The optimal experimental conditions include the use of 0.03 mol/L HClO₄ (pH1.6), 6.0×10^?3 mol/L GA, 3.0×10^?3 mol/L V(IV), 4.0×10^?3 mol/L EDTA, an accumulation potential of ?0.10 V(vs. Ag/AgCl), an accumulation time of 120 s and a differential pulse potential scan mode. The peak current is proportional to the concentration of Ge(IV) over the range of 3.0×10^?11 to 1.0×10^?8 mol/L and the detection limit is 2×10^?11 mol/L for a 120 s adsorption time. The relative standard deviation at 5.0×10^?10 mol/L level is 3.1%. No serious interferences were found. The method was applied to the determination of germanium in ore, mineral water and vegetable samples with satisfactory results.     

碳纤维微电极恒电位活化及测定金属离子的研究

碳纤维微电极已被广泛应用于电化学研究和分析测定,该电极尺寸极小,在分析性能上与常规电极有显著不同,在不镀汞的情况下,用碳纤维电极直接测定金属离子几乎没有明显的伏安响应,本文提出用+2.5 V恒电位预先活化碳纤维电极,使测定灵敏度大为提高,在双电极体系和静止溶液中,采用溶出伏安法可测定10~(-9)级金属离子,以同样的方法清洗电极,测定结果重现性良好,由于分析过程中不使用汞,该电极的测定范围大大增加,特别是用于氧化还原电位较正的金属离子测试,根据循环伏安法、扫描电镜和电子能谱的研究,发现碳纤维表面状况在处理前后有很大变化,并与测定灵敏度密切相关。     

Differential pulse voltammetric determination of P(V) following adsorptive accumulation of alpha-[PMo(12)O(40)](3-) on a polypyrrole-modified glassy carbon electrode

On the basis of the formation and pre-concentration of an α-Keggin-type [PMo₁₂O₄₀]³⁻ complex, a novel voltammetric method was developed for the determination of trace levels of P(V). The α-[PMo₁₂O₄₀]³⁻ complex was formed by heating a 5×10⁻⁴ M Mo(VI)-0.2 M HCl-40% (v/v) CH₃CN system containing a trace amount of P(V) at 70 °C for 30 min. During the electrochemical polymerization of pyrrole in the α-[PMo₁₂O₄₀]³⁻ solution, the α-[PMo₁₂O₄₀]³⁻ complex was accumulated into the polypyrrole film on a glassy carbon electrode. The differential pulse voltammetric peak current due to the α-[PMo₁₂O₄₀]³⁻ complex incorporated in the polypyrrole film was linearly dependent on the P(V) concentration in the range of 5×10⁻⁹-5×10⁻⁷ M; a detection limit of 2×10⁻⁹ M was achieved.