Electrochemical Study of the Self-exchange between Viologen-thiol Self assembled Monolayers and Alkanethiol Gold Electrodes

The preparation and cyclic voltammetric behaviors of self assembled monolayers (SAMs) containing electroactive viologen group have been investigated. Treatment of this viologen SAM with solutions of alkanethiols remits in replacing the electroactive third, shifting negatively its formal potentials and decreasing its heterogeneous elixtron transfer constants along with the immersion time. The aim of the work is to understand the exchange regularity of the mixed SANK on gold electrode surface.

Investigation on the Voltammetric Behaviors in Planar Bilayer Lipid Membranes

In the TCNQ-modified BLM, the voltammetric response is different due to the different methods used to prepare the membrane forming solution. The direct and indirect dissolved methods result in irreversible and reversible responses respectively. These results can be explained by the different styles of the orientation of TCNQ in the membrane. The reversible response is controlled by the diffusion of electroactive species in the interior of the membrane. When MB is used to modify the BLM, very complex voltammograms are obtained. The intersection of the voltammetric curves can be regarded to be owing to the appearance of new phase in the membrane caused by MB. But it disappears at lower scan rate. Peak current increases with decreasing scan rate. This indicates that the resistance of the membrane at lower scan rate is lower than that at higher scan rate. Asymmetric curve of MB incorporated BLM is ascribed to the different rates of redox reaction at the two membrane/solution interfaces.

Self-assembled monolayers of thiols on gold electrodes for bioelectrochemistry and biosensors

Monolayers of biological compounds including redox proteins and enzymes, and phospholipids have been immobilized on a gold electrode surface through self-assembling. These proteins and enzymes, such as cytochrome c, cytochrome c oxidase and horseradish peroxidase (HRP), immobilized covalently to the self-assembled monolayers (SAMs) of 3-mercaptopropionic acid on a gold electrode, communicate directly electrons with the electrode surface without mediators and keep their physiological activities. The electron transfer of HRP with the gold electrode can also be mediated by the alkanethiol SAMs with electroactive group viologens on the gold electrode surface. All these direct electrochemistries of proteins and enzymes might offer an opportunity to build a third generation of biosensors without mediators for analytes, such as H2O2, glucose and cholesterol. Monensin and valinomycin have been incorporated into the bilayers on the gold electrode consisting of the SAMs of alkanethiol and a lipid monolayer, which have high selectivity for monovalent ions, and the resulting Na+ or K+ sensor has a wide linear range and high stability. These self-assembly systems provide a good mimetic model for studying the physiological function of a membrane and its associated enzyme. (C) 1997 Elsevier Science S.A.

Electrochemical study of the interfacial characteristics of redox-active viologen thiol self-assembled monolayers

The electrochemical behavior of the electroactive self-assembled monolayers (SAMs) of thiol-functionalized viologen, CH3(CH2)(9)V2+(CH2)(8)SH, where V2+ is a viologen group, on the gold electrodes is examined by cyclic voltammetry and electrochemical a.c. impedance. A monolayer of viologen is immobilized on the gold electrode surface via the Au-S bond and the normal potentials corresponding to the two successive one-electron transfer processes of the viologen active centers are -310 mV and -652 mV (vs. Ag/AgCl) in 0.1 mol l(-1) phosphate buffer solution (pH 6.96) respectively. These results suggest that the viologen SAMs are stable and well-behaved monolayers. The experimental impedance data corresponding to different forms of viologen group have been fitted to equivalent electrical circuits, and the surface capacitances and resistances have been given. The heterogenous electron transfer rates of the first and the second redox processes are 7.57 s(-1) and 1.49 s(-1) respectively through a.c. impedance.

Study on ferrocene derivatives diffusion dynamics in polymer electrolyte by solid-state voltammetry

The diffusion rates of seven ferrocene derivatives have been estimated in polyelectrolyte PEG . LiClO4 by using non-steady-state chronoamperometry. The D-app of ferrocene derivatives increases with temperature, and the dependency of D-app on temperature obeys the Arrhenius equation. The D-app of ferrocene derivatives decreases with increasing size of electroactive species. The Delta D-app values of D-T>Tm and D-T T-m in the polyelectrolyte. On the other hand, the diffusion behaviour of ferrocene derivatives is qualitatively analyzed by using cyclic voltammetry. Copyright (C) 1996 Elsevier Science Ltd

Ac voltammetric and square wave voltammetric study of the self-assembled monolayers of thiol-functionalized viologen derivative

Electroactive self-assembled monolayers (SAMs) containing viologen group are formed through the adsorption of thiol-functionalized viologen compound CH3(CH2)(9)V2+(CH2)(8)SH, where V2+ is N,N'-dialkylbipyridinium (i.e. a viologen group), onto gold electrodes from methanol/water solution and its electrochemical behavior is investigated ty Ac voltammetry and square wave voltammetry, which have the high sensitivity against background charging. The viologen SAM formed is a sub-monolayer and the normal potentials corresponding to the two successive one-electron transfer processes of the active centers (viologen) are -360 mV and -750 mV (vs. Ag/AgCl) in 0.1 mol/L phosphate buffer solutions (pH 6.96) respectively, and the standard electron transfer rate constant is 9.0 s(-1). The electrochemical behavior of this SAM in various solutions has been preliminarily discussed.

AMPEROMETRIC BIOSENSORS BASED ON THE IMMOBILIZATION OF OXIDASES IN A PRUSSIAN BLUE FILM BY ELECTROCHEMICAL CODEPOSITION

Prussian blue has been formed by cyclic voltammetry onto the basal pyrolytic graphite surface to prepare a chemically modified electrode which provides excellent electrocatalysis for both oxidation and reduction of hydrogen peroxide. It is found for the first time that glucose oxidase or D-amino oxidase can be incorporated into a Prussian blue film during its electrochemical growth process. Two amperometric biosensors were fabricated by electrochemical codeposition, and the resulting sensors were protected by coverage with a thin film of Nafion. The influence of various experimental conditions was examined for optimum analytical performance. The glucose sensor responds rapidly to substrates with a detection limit of 2 x 10(-6) M and a linear concentration range of 0.01-3 mM. There was no interference from 2 mM ascorbic acid or uric acid. Another (D-amino acid) sensor gave a detection limit of 3 x 10(-5) M D-alanine, injected with a linear concentration range of 7.0 x 10(-5)-1.4 x 10(-2) M. Glucose and D-amino acid sensors remain relatively stable for 20 and 15 days, respectively. There is no obvious interference from anion electroactive species due to a low operating potential and excellent permselectivity of Nafion.

VOLTAMMETRY OF CYTOCHROME-C ENTRAPPED IN HYDROGEL MEMBRANE ON GRAPHITE ELECTRODE

The voltammetric behavior of cytochrome c entrapped in hydrogel membranes at paraffin wax-impregnated spectroscopic graphite electrodes (WISGE) was studied in this paper. A pair of well-defined peaks appeared at +70 mV (vs. Ag/AgCl). Beside these two peaks, another pair of peaks emerged at around +225 mV. Further investigations suggested that at least three states of cytochrome c existed in the membranes due to the special structure of the hydrogel. The native conformation of cytochrome c molecules was stabilized by the hydrophilic environment that was formed by the hydroxyl structure of the membranes and facilitated the cytochrome c electron transfer reaction at +70 mV. The molecules directly adsorbed on the surface of the graphite electrode were responsible for the redox peaks at around +225 mV. Whether the adsorption peaks were detectable or not was related to the thickness of membranes and the pre-retaining time before the formation of membranes.

INFLUENCE ON THE THIN-LAYER SPECTROELECTROCHEMISTRY - DIFFUSION WITHIN A THIN-LAYER CELL

The potential step and cyclic voltammetric experiments in the thin layer cell were studied by the digital simulation method in this work. A relationship between the time needed for exhaustive electrolysis of the electroactive species and the thickness of the thin layer cell was obtained. On the basis of this formula, the lower time limit for a kinetic plot of the following chemical reaction can be estimated. For the cyclic voltammetry, a semiempirical formula was derived for the peak-peak potential difference (Delta Ep) in terms of the sweep rate (v), thickness of the cell (d), diffusion coefficient (D) and electron transfer number (n) 59 - n Delta Ep/n Delta Ep = 0.328(RT D/nF vd(2))(1.20).

LIQUID-CHROMATOGRAPHY AMPEROMETRIC DETECTION OF CATECHOL, RESORCINOL, AND HYDROQUINONE WITH A COPPER-BASED CHEMICALLY MODIFIED ELECTRODE

A copper-based chemically modified electrode (CME) has been constructed and characterized for flow-through amperometric detection of catechol, resorcinol, and hydroquinone. Novel potential dependence of the detector response was first obtained for these analytes at the Cu CME, where negative peaks together with positive ones were observed in one definite chromatogram using amperometric detection. Its advantages in chromatographic applications were demonstrated. From these observations it is proposed that the detector response was governed by formation of copper complexes with the solutes. A dynamic linear range over two orders of magnitude was obtained, when operating the detector at +0.10 V vs. SCE, from which ng detection limits were achieved.

AN EXPERIMENTAL-STUDY ON MEMBRANE DISTILLATION CRYSTALLIZATION FOR TREATING WASTE-WATER IN TAURINE PRODUCTION

The solution of non-volatile solutes can be concentrated to saturation by membrane distillation. If the solute is easy to crystalize, the membrane distillation-crystallization phenomenon will appear during the membrane distillation of saturated solutions. It is possible that crystalline products are separated from concentrated solutions by a membrane process. In this work the PVDF capillary membrane, which was improved on hydrophobicity by using LiCl instead of a water-soluble polymer as an additive, has been used for treating the waste water of taurine. The crystalline product has been obtained from the waste water by the membrane distillation-crystallization technique. The results have shown good prospects for a membrane distillation application for treatment of industrial waste water.

LIQUID-CHROMATOGRAPHY AMPEROMETRIC DETECTION OF CARBOXYLIC-ACIDS AND PHENOLIC-ACIDS WITH A COPPER-BASED CHEMICALLY-MODIFIED ELECTRODE

A copper-based chemically-modified electrode has been constructed and characterized by various experimental parameters in flow-through amperometric detection of carboxylic acids and phenolic acids. Novel hydrodynamic voltamperograms were first obtained in flow-through amperometric detection with the Cu-based CME and subsequently negative and positive peaks were observed in a single chromatogram. This unique and flexible potential dependence could be of great benefit in chromatographic speciation and quantification. These observations suggest that the detector response was governed by the complexation reaction of copper ions with the solutes.

ELECTROCATALYSIS OF POLYPYRROLE-METHYLENE BLUE FILM MODIFIED ELECTRODE FOR DIRECT REDOX REACTION OF CYTOCHROME-C

The electron transfer process of hemeproteins on the electrode surface is considered a promising subject in the area of bioelectrochemistry. Electrochemists believe that electron transfer between electroactive proteins and electrode surface might be expected to simulate the electron transfer between proteins. This research provides information about the electron transfer mechanism in biological system. Cytochrome c is a typical electron transferring protein,

THIN-LAYER ELECTROCHEMICAL DETECTOR COATED WITH NAFION FILM

Electrochemical detection of the flow system has attracted considerable interest in recent years due to its high sensitivity and selectivity towards electroactive compounds. However, the improvement of sensitivity and selectivity is still a desire for practical application. In this note, a thin-layer electrochemical detector of the

海洋生物膜的电活性及其在微生物燃料电池中的应用基础研究

海洋电活性微生物（又称电活性生物膜，electroactive biofilms, EABs）是自然界存在的一类功能性微生物，能够将代谢有机物产生的电子直接或间接传递给电极，人们对其在环境中的广泛性及其在生物防腐、生物能源和生物修复中的应用正在开展广泛的研究。 本论文着眼于海洋天然生物膜的电活性，从微生物腐蚀和微生物燃料电池的角度，考察研究了海洋天然生物膜对316L SS腐蚀行为的影响，发现海洋天然生物膜能抑制316L SS腐蚀，系统研究了海洋生物膜与石墨等电极的电子传递过程，提出了电活性生物膜（EABs）与电极间的电子传递机制，并初步研究了海洋电活性生物膜在微生物燃料电池(MFCs)中的应用。 对附着天然海洋生物膜的316L SS研究发现，生物膜使316L SS电位正移了500mV （vs. Ag/AgCl）。316L SS表面附着海洋生物膜后，其孔蚀电位由原来的50mV增加到540mV，孔蚀敏感性降低；同时，海洋生物膜的附着导致316L SS的阻抗增加，由此，我们明确提出海洋生物膜能够抑制316L SS腐蚀的发生。进一步研究了生物膜抑制腐蚀发生的可能机理。循环伏安实验表明，海洋生物膜与不锈钢电极之间存在电子传递过程。扫描电镜（SEM）及能谱（EDS）分析发现有钙盐的沉积生成。通过以上结果我们提出了生物膜对腐蚀的抑制机制假设，即在电极与电活性海洋生物膜间发生了电子传递，海洋生物膜能够将电子传递给不锈钢，316L SS作为电子接受体受到保护。 为进一步研究天然海洋生物膜的这种电活性，我们选择不会发生腐蚀的惰性电极材料石墨，玻碳，碳纸电极验证生物膜的电活性。 首次考察了天然海洋生物膜对石墨电极和玻碳电极的开路电位变化的影响，结果显示随电极在天然海水中浸泡时间，石墨电极正移50mV vs. Ag/AgCl，玻碳电极正移了300 mV （vs. Ag/AgCl）。与316L SS相似，三种电极的变正趋势相同，都经历了三个阶段，即初始缓慢变正期，随后的指数变正期和以后的稳定期，此与生物膜在固体表面形成的趋势相似。伏安曲线及阻抗实验结果表明，在石墨，玻碳和碳纸电极材料表面附着海洋生物膜后，电流密度增加，电荷转移电阻减小，说明生物膜与电极间存在电子传递，并能加速电子传递过程，不同材料表面生物膜的电活性能力由大到小为石墨＞316L SS＞碳纸＞玻碳。 进一步研究了海洋沉积物-海水生物膜微生物燃料电池，初步建立了相应的电极材料和微生物燃料电池结构。我们选择石墨阳极和石墨阴极或316L SS阴极组装海泥沉积物(阳极区)和海水（阴极区）MFC，316L SS代替石墨做阴极最大输出电量达9mW.m-2，约为后者的2倍。两种MFC输出电流和功率密度随时间的延长而增加的趋势相同，都可以分为三个阶段，即初期的缓慢增加阶段，中期的指数增长阶段，后期的平台稳定期阶段。这也与生物膜在固体表面形成的趋势相似。此研究也说明优化316L SS表面性质筛选活性海洋生物膜用于MFC有其潜在的应用价值。