DETERMINATION OF CYSTEINE AND REDUCED GLUTATHIONE IN HUMAN PLASMA BY LIQUID-CHROMATOGRAPHY WITH PULSED AMPEROMETRIC ELECTROCHEMICAL DETECTION USING A PLATINUM-PARTICLES MODIFIED GLASSY-CARBON ELECTRODE

An assay procedure utilizing pulsed amperometric detection at a platinum-particles modified electrode has been developed for the determination of cysteine and glutathione in blood samples following preliminary separation by reversed-phase liquid chromatography. A chemically modified electrode (CME) constructed by unique electroreduction from a platinum-salt solution to produce dispersed Pt particles on a glassy carbon surface was demonstrated to catalyze the electo-oxidation of sulfhydryl-containing compounds: DL-cysteine (CYS), reduced glutathione (GSH). When used as the sensing electrode in flow-system pulsed-amperometric detection (PAD), electrode fouling could be avoided using a waveform in which the cathodic reactivation process occurred at a potential of - 1.0 V vs. Ag/AgCl to achieve a cathodic desorption of atomic sulfur. A superior detection limit for these free thiols was obtained at a Pt particle-based GC electrode compared with other methods; this novel dispersed Pt particles CME exhibited high electrocatalytic stability and activity when it was employed as an electrochemical detector in FIA and HPLC for the determination of those organo-sulfur compounds.

KINETIC-STUDY OF ELECTROCATALYTIC REDUCTION OF HYDROGEN-PEROXIDE AT IRON(III) PORPHYRIN MODIFIED GLASSY-CARBON ELECTRODE IN ALKALINE-MEDIUM USING THE ROTATION-SCAN METHOD

Reduction of hydrogen peroxide at a glassy carbon (GC) electrode modified with sigma-bonded pyrrole iron(III) octaethylporphyrin complex, (OEP)Fe(Pyr), was studied by cyclic voltammetry and a rotating disk electrode. In 0.1N NaOH solution, it is shown that such an (OEP)Fe(Pyr)/GC electrode has a significant catalytic activity towards hydrogen peroxide reduction (E(D) = -0.80 V, k = 0.066 cm s(-1)); however, the electrode stability is low. The deactivation is observed when the reaction charge (Q) is passing through the (OEP)Fe(Pyr)/GC disk electrode. A linear rotation scan method is applied to study the kinetic process by determining the disk electrochemical response (i(D)) to rotation rate (omega) at a definite disk potential (E(D)). Considering that the number of adsorbed electroreduced catalyst molecules (Red) varies according to the disk potential, a factor theta(= Gamma(Red)/(Gamma(Red) + Gamma(Ox))) is introduced to describe the electrode surface area fraction for electroreduced species. The obtained Koutecky-Levich equation is applicable whatever the potential is.

ELECTROCHEMICAL STUDY OF PYRAZOLONE DERIVATIVES AT THE LIQUID/LIQUID INTERFACE

Pyrazolone derivatives, such as antipyrine, aminopyrine, and 4-aminoantipyrine, can transfer across the water/nitrobenzene interface to produce a pair of well-defined symmetric, reversible anodic-cathodic peaks by cyclic voltammetri. The transfer mechanis

PREPARATION OF PERIODATOCUPRATE(III) AND TELLURATOCUPRATE(III) BY ELECTROCHEMICAL AND OZONE OXIDATION

In the cyclic voltammograms of complexes with periodate and tellurate, the anodic and cathodic peaks were observed evidently for Cu(III)/Cu(II) couples in caustic potash aqueous solutions. Copper(III) complexes were obtained by utilizing ozone as oxidant

ELECTROCHEMICAL MECHANISM FOR FULLERENE FORMATION IN PLASMA ARCS

During the synthesis of fullerenes by dc plasma arcs, it has been found that the anodic graphite rod consistently burns up, while the cathodic graphite rod grows slag at its end. Further investigations revealed that the anodic and cathodic graphite rods p

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.

SENSITIVE AMPEROMETRIC DETECTION OF GLUCOSE BY REVERSED PHASE LIQUID-CHROMATOGRAPHY AT A PRUSSIAN BLUE CHEMICALLY MODIFIED ELECTRODE OF NOVEL CONSTRUCTION

A new liquid chromatography electrochemical (LCEC) scheme for glucose sensing has been developed on the basis of a Prussian Blue chemically modified electrode (CME) of novel construction and characterized in terms of various experimental parameters by the flow injection analysis (FIA) technique. Unique hydrodynamic voltammograms were obtained for the first time at the CME in the flow-through amperometric detection of glucose, and subsequently both anodic and cathodic peaks could be expected on monitoring the operating potential in the modest positive or negative region. The unique pH dependence on the CME response towards glucose makes it perfectly compatible with conventional reversed phase liquid chromatography systems. On the basis of these features, practical application in glucose LCEC detection has been effectively performed; a linear response range over three orders of magnitude and a detection limit of subpicomole level were readily obtained. The capability of the established LCEC mode in the direct sensing of urinary glucose has been demonstrated.

AMPEROMETRIC DETECTION OF CATECHOLAMINES WITH LIQUID-CHROMATOGRAPHY AT A NOVELLY CONSTRUCTED PRUSSIAN BLUE CHEMICALLY MODIFIED ELECTRODE

A novel Prussian blue chemically modified electrode (CME) was constructed and characterized for liquid chromatography electrochemical detection (LCEC) of catecholamines. Both anodic and cathodic peaks could be obtained by monitoring at constant applied potential at anodic and slightly cathodic potential ranges (0.3-0.7 and -0.2-0.1 V vs. SCE), respectively. When arranged in a series configuration, using the modified electrodes as generating and collecting detectors, extremely high effective collection efficiencies of 0.91 (for norepinephrine) and 0.58 (for dihydroxyphenylacetic acid) were achieved in dual-electrode LCEC for catecholamines; and a linear response range over 3 orders of magnitude and a detection limit of 10 pg were obtained with a downstream CME as the indicating detector.

CYCLIC VOLTAMMETRIC AND SPECTROELECTROCHEMICAL STUDIES OF COPPER IN ALKALINE-SOLUTION

The behaviour of the electroplated copper film electrode on tin oxide/glass or glassy carbon surface was studied in potassium hydroxide medium by cyclic voltammetry and in situ transmission spectroelectrochemistry. The results indicate that the electroplated copper film electrode is similar to a copper electrode and cyclic voltammetry with this electrode affords more resolution. The anodic peaks were found to correspond successively to the adsorption of oxygen, the formation of a surface layer of Cu2O, the formation of a surface layer of Cu(OH)2 or CuO and formation of a thick multilayer film of CuO. This is the first time it has been proposed that a surface layer of Cu(OH)2 or CuO is formed from the oxidation of the surface layer of Cu2O. Similarly, a clear interpretation is presented that the cathodic peaks correspond successively to the reduction of CuO to Cu2O, the reductions of Cu2O to Cu and the soluble Cu(II) species to Cu. On the other hand, a shoulder peak related to the chemical transformation of Cu(OH)2 to CuO was first observed.

AMPEROMETRIC DETECTION AT A CARBON-FIBER ARRAY RING GLASSY-CARBON DISK ELECTRODE IN A WALL-JET CELL

A wall-jet cell incorporating a carbon fibre array ring/glassy-carbon disk electrode has been constructed, and characterized by the cyclic voltammetry and flow-injection techniques. The ring (composed of several microdisks) and glassy-carbon disk electrode, can be used separately for different purposes, e.g., detection in solution without a supporting electrolyte, collection/shielding detection with dual-electrode and voltammetric/amperometric detection with series dual-electrode. The electrode shows better collection and shielding effects than usual ring-disk electrode in quiescent solution and the series dual-electrode in a thin-layer flow-through cell. The detection limit at the ring electrode is comparable with that at a conventional-size electrode, and has been used in the mobile phase without a supporting electrolyte, proving to be a promising detector for normal-phase liquid chromatography.

铜管不锈钢管腐蚀性能及铁牺牲阳极保护研究

铜管一直是电厂凝汽器的主要应用管材，但由于其抗冲刷和抵御污染物腐蚀的能力差，特别不耐氨蚀，美国和欧洲大量使用不锈钢管替代铜管作为冷凝管，然而不锈钢管在我国的运用仅处于初步阶段。 常使用锌、铝阳极对铜管进行牺牲阳极保护，然而存在着电位差过大、阳极溶解过快的问题。铁基牺牲阳极与铜电位差适当、来源广泛、价格便宜，在一些工程上有所应用，但是目前针对铁基牺牲阳极的理论研究报道很少。 本文选用紫铜管、304不锈钢管作为实验用管材，首先运用实验室全浸实验、极化曲线和电化学阻抗研究了二者在海水和淡水中的腐蚀性能以及CO2、溶解氧对其腐蚀的影响。结果表明：CO2会加速二者的腐蚀，溶解氧却对它们的腐蚀影响不同，促进铜管的腐蚀却抑制不锈钢管的腐蚀；随浸泡时间的延长，紫铜管由于表面产物膜的生成耐蚀性提高，304不锈钢管的耐蚀性却降低；淡水中，304不锈钢管和紫铜管都具有很好的耐蚀性能。随后，运用失重法和极化曲线对比研究了紫铜管、304不锈钢管的氨蚀性能，运用SEM分析和电化学阻抗研究了紫铜在不同浓度氨溶液中的腐蚀机理。发现，304不锈钢管的耐氨蚀能力远远好于铜管；溶解氧是影响氨蚀的关键因素，其对二者氨蚀的影响也不同；紫铜管在低氨浓度和高氨浓度溶液中腐蚀机理和产物不同，低氨浓度时形成保护性的产物膜（CuO 和Cu(OH)2），高氨浓度时由活化溶解控制，生成可溶的[Cu (NH3)4]2+。 选用工业纯铁、35钢为牺牲阳极材料。恒电流实验结果表明它们具有良好的牺牲阳极性能；通过极化曲线和自腐蚀电位测试分析，认为将二者用于铜管牺牲阳极保护是可行的；实验室阴极保护效果测试表明，工业纯铁和35钢对紫铜管具有良好的保护效果，保护度达90%以上。

海水和海泥中阴极保护系统的边界元计算

随着人们对能源需求的不断增加，深海海洋油气开发已引起了人们越来越大的兴趣，随之而来的是对海洋构筑物的设计和防护提出了更高的要求。由于在传统的阴极保护工程设计中，大多采用实际测量或经验估计的方法来掌握电位分布规律，很难真实的反映构筑物的实际状态，为了确保安全，往往采用较大的安全系数，不但会造成金属材料的浪费，而且还会在构筑物的局部造成保护不足或过保护。 本文研究了边界元方法（BEM）利用数值仿真技术对阴极保护状态下的海洋构筑物的保护状态进行模拟，从而获得阴极保护状态下的金属材料的电位分布。采用常数单元对于二维问题进行了研究，推导出了边界积分方程的离散化形式，并结合阴极保护环境下的阳极和阴极的极化曲线作为边界条件，建立了线性方程组。采用Newton-Raphson 迭代法和分段拟线性化的方法对边界条件做了线性化处理，应用FORTRAN语言开发出阴极保护的边界元仿真求解程序CPBEM，并利用该程序选择合适的算例进行了验证，结果表明该程序是有效和可行的。 通过管线钢在不同温度海泥埋片的腐蚀失重实验，证明了如果有充足的氧的供给的情况下，温度每增加10oC，腐蚀速度便增加一倍。阴极保护系统数值仿真的精确度最主要的影响因素就是阴极和阳极的极化曲线。而金属材料的极化曲线往往受到多种环境因素的影响，本文系统的讨论了在海泥介质中两种管线钢的腐蚀行为，对管线钢极化行为产生影响的各种环境因素，以及这些因素与金属的腐蚀速度之间的关系。首次将灰关联分析的手段运用到海泥介质的腐蚀，研究了环境因素对于ERW，SML两种管线钢在海泥中的腐蚀速率的影响。

Fabrication of Bismuth/Multi-walled Carbon Nanotube Composite Modified Glassy Carbon Electrode for Determination of Cobalt

A bismuth/multi-walled carbon nanotube (Bi/MWNT) composite modified electrode for determination of cobalt by differential pulse adsorptive cathodic stripping voltammetry is described. The electrode is fabricated by potentiostatic pre-plating bismuth film on an MWNT modified glassy carbon (GC) electrode. The Bi/MWNT composite modified electrode exhibits enhanced sensitivity for cobalt detection as compared with the bare GC, MWNT modified and bismuth film electrodes. Numerous key experimental parameters have been examined for optimum analytical performance of the proposed electrode. With an adsorptive accumulation of the Co(II)-dimethylglyoxime complex at -0.8 V for 200 s, the reduction peak current is proportional to the concentration of cobalt in the range of 4.0x10(-11)-1.0x10(-7) mol/L with a lower detection limit of 8.1x10(-11) mol/L. The proposed method has been applied Successfully to cobalt determination in seawater and lake water samples.

Adsorption and Corrosion Inhibition Behavior of Mild Steel by One Derivative of Benzoic-Triazole in Acidic Solution

A newly synthesized benzoic-triazole derivative 3,5-dimethylbenzoic acid [1,2,4]triazol-l-ylmethyl ester (DBT) was investigated as a corrosion inhibitor of mild steel in 1 M HCl solution using weight loss measurements, potentiodynamic polarization, SEM, and EIS methods. The results revealed that DBT was an excellent inhibitor, and the inhibition efficiencies obtained from weight loss and electrochemical experiments were in good agreement. Using the potentiodynamic polarization technique, the inhibitor was proved to have a mixed-type character for mild steel by suppressing both anodic and cathodic reactions on the metal surface. The number of water molecules (X) replaced by a molecule of organic adsorbate was determined from the Flory-Huggins, Dhar-Flory-Huggins, and Bockris-Swinkels substitutional adsorption isotherms applied to the data obtained from the gravimetric experiments performed on a mild steel specimen in 1 M HCl solution at 298 K.

Investigation on the corrosion inhibitive effect of 2H-pyrazole-triazole derivatives in acidic solution

Four research methods, such as weight loss test, electrochemical techniques, adsorption isotherm, and quantum chemical calculation, were employed in this paper to study the inhibition efficiency (IE) and inhibition mechanism of three 2H-pyrazole-triazole derivatives, BHOT, FHOT, and CHOT in 1 M HCl solution for mild steel. Using the electrochemical technique, three inhibitors were proved to show a mixed-type character for mild steel by suppressing both anodic and cathodic reactions on the steel surface. The adsorption models of three compounds were established at different temperatures according to their adsorption isotherms. The results of the quantum chemical calculation method indicated that the adsorption sites of 2H-pyrazole-triazole derivatives were strongly centralized on benzene ring, triazole ring, or other substituents. All the results showed that the three derivatives were excellent inhibitors in I M HCl solution for mild steel.