Preparation and characterization of ultrathin multilayer films based on polyoxometalate Mo8V2O28 center dot 7H(2)O

The ultrathin multilayer films of sphere-shaped polyoxomolybdate Mo8V2O28.7H(2)O (abbreviated to Mo8V2) and poly(allylamine hydrochloride) (DAH) have been prepared by the layer-by-layer (LbL) self-assembly method. The (Mo8V2/DAH)(m) multilayer films have been characterized by X-ray photoelectron spectra (XPS) and atomic force microscopy (AFM). The electrochemistry behavior of the film at room temperature was investigated.

Electropolymerization of azure B on a screen-printed carbon electrode and its application to the determination of NADH in a flow injection analysis system

The electrooxidation polymerization of azure B on screen-printed carbon electrodes in neutral phosphate buffer was studied. The poly(azure B) modified electrodes exhibited excellent electrocatalysis and stability for dihydronicotinamide adenine dinucleotide (NADH) oxidation in phosphate buffer (pH 6.9), with an overpotential of more than 400 mV lower than that at the bare electrodes. Different techniques, including cyclic voltammetry, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy have been employed to characterize the poly (azure B) film. Furthermore, the modified screen-printed carbon electrodes were found to be promising as an amperometric detector for the flow injection analysis (FIA) of NADH, typically with a dynamic range of 0.5 muM to 100 muM.

IrO2/SnO2 electrodes: prepared by sol-gel process and their electrocatalytic for pyrocatechol

IrO2/SnO2 (10%:90%, molar ratio) electrodes (ITEs) were prepared by the sol-gel method as an alternative to the electrode-position and thermal decomposition process. The electrodes were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), cyclic voltammetry (CV) and electrochemical impedance spectra (EIS). From the results of XRD, oxide films prepared at low temperature were in amorphous state, while hydrous IrO2 crystal and cassiterite phase SnO2 were formed at 300 degreesC or even to 500 degreesC. The highly porous structure was confirmed by AFM. The electrochemical experiments demonstrated that the sol-gel method made the ITEs having a fast electron transfer process with good stability and the optimal preparation temperature was 400 degreesC for the highest electroactivity. Furthermore, the electrocatalysis of pyrocatechol on the electrodes was investigated. A quasi-reversible process occurred and a linear range over three orders magnitude (1 x 10(-2) - 10 mM) was obtained by differential pulse voltammetry (DPV). Meanwhile the detection limit of pyrocatechol was 5 x 10(-3) mM. This study indicated that the sol-gel method was an appropriate route to prepare the IrO2/SnO2 electrodes for the electrocatalytic of pyrocatechol.

Facile preparation of amperometric laccase biosensor with multifunction based on the matrix of carbon nanotubes-chitosan composite

The carbon nanotubes-chitosan (CNTs-CS) composite provides a suitable biosensing matrix due to its good conductivity, high stability, and good biocompatibility. Enzymes can be firmly incorporated into the matrix without the aid of other cross-linking reagents. The composite is easy to form insoluble film in solution above pH 6.3. Based on this, a facilely fabricated amperometric biosensor by entrapping laccase into the CNTs-CS composite film has been developed. At pH 6.0, the fungi laccase incorporated into the composite film remains better catalytic activity than that dissolved in solution. The system is in favor of the accessibility of substrate to the active site of laccase, thus the affinity to substrates is improved greatly, such as 2,2'-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid) diammonium salt (ABTS), catechol, and 0, with K. values of 19.86 mu M, 9.43 mu M, and 3.22 mM, respectively. The major advantages of the as-prepared biosensor are: detecting different substrates (ABTS, catechol, and 02), possessing high affinity and sensitivity, durable long-term stability, and facile preparation procedure. On the other hand, the system can be applied in fabrication of biofuel cells as the cathodic catalysts based on its good electrocatalysis for oxygen reduction.

Selective penetration of liquid-phase organic probe molecules into SAM of 2-mercapto-3-n-octylthiophene

An inherently disorganized self-assembled monolayer (SAM) of 2-mercapto-3-n-octylthiophene (MOT) has been formed on a gold bead electrode from its dilute ethanolic solution. The disorganization of the monolayer is attributed to the loose packing of the aliphatic chains of the MOT adsorbates, which results from a large difference in dimension/or cross-sectional area between the head (thiophene thiolate) and the tail (alkane chain) groups. Electrochemical measurements including ac impedance spectroscopy and metal underpotential deposition have shown that the monolayer is almost pinhole free. However, the MOT SAM can be penetrated by an organic probe molecule with affinity for the alkane chain part of the monolayer. Some typical probe molecules with different size and hydrophilicity have been employed to assess the permselectivity of the monolayer. Measurement results demonstrate that the ability of the employed probe molecules to penetrate into the monoalyer is mainly dominated by their hydrophilicity/or hydrophobicity. The results presented here suggest the potential application of MOT monoalyer to effectively modify the electrode surface for several research areas such as electrochemical sensors, electrocatalysis, electroanalysis, and supported hybrid bilayer membranes.

Studies of perchlorate triggered ion-gate behavior of sBLM by electrochemiluminescence and its application to a sensor for perchlorate

Ru(bpy)(3)(2+) electrochemiluminescence (ECL) method and electrocatalysis method were first used to study the ion-gate behavior of supported lipid bilayer membrane (sBLM). We found that sBLM, made of dimethyldioctadecylammonium bromide (a kind of synthetic lipid), showed ion-gate behavior for the permeation of Ru(bpy)(3)(2+) in the presence of perchlorate anion. There existed a threshold concentration (0.1 muM) of perchlorate anion for ion-gate opening. Below the threshold the ion-gate was closed. Above the threshold, the number of opened ion-gate sites increased with the increase of perchlorate anion concentration and leveled off at concentrations higher than 1200 muM. Based on it, a new sensor for perchlorate was developed. Furthermore, the opening and closing of the ion-gate behavior was reversible, which means the sensor can repeatedly be used.

Sol-gel derived carbon ceramic electrode containing methylene blue-intercalted alpha-zirconium phosphate micro particles

Methylene blue-intercalated a-zirconium phosphate (MBZrP) micro particles in deionized water were deposited onto the surface of graphite powder to prepare graphite powder-supported MBZrP, which was subsequently dispersed into methyltrimethoxysilane-derived gels to yield a conductive composite. The composite was used as electrode material to fabricate a surface-renewable, rigid, leak-free carbon ceramic composite electrode, bulk-modified with methylene blue (MB). In the configuration, alpha-zirconium phosphate was employed as a solid host for MB, which acted as a catalyst. Graphite powder ensured conductivity by percolation, the silicate provided a rigid porous backbone and the methyl groups endowed hydrophobicity and thus limited the wetting section of the modified electrode. Peak currents of the MBZrP-modified electrode were surface-confined at low scan rates but diffusion-controlled at high scan rates. Square-wave voltammetric study revealed that MBZrP immobilized in carbon ceramic matrix presented a two-electron, three-proton redox process in acidic aqueous solution with pH ranged from 0.44 to 2.94. In addition, the chemically modified electrode showed an electrocatalytic activity toward nitrite reduction at +0.15 V (vs. Ag/AgCl) in acidic aqueous solution (pH=0.44). The linear range and detection limit are 1 x 10(-6)-4 x 10(-3) mol L-1 and 1.5 x 10(-7) mol L-1, respectively.

Fabrication and electrochemical behavior of a sol-gel-derived carbon ceramic composite electrode entrapping 2 : 18-molybdodiphosphate

A new type of inorganic-organic hybrid material incorporating carbon powder and alpha -type 2:18-molybdodiphosphate (P2Mo18) in a methyltrimethoxysilane (MTMOS) based gel has been produced by a sol-gel process and used to fabricate a chemically modified electrode. The P2Mo18-doped carbon ceramic composite electrode was characterized using SEM and cyclic voltammetry. Square-wave voltammetry with an excellent sensitivity was exploited to conveniently investigate the dependence of current and half-wave potential (E-1/2) on pH. The chemically modified electrode has some advantages over the modified film electrodes constructed by the conventional methods, such as long-term stability, reproducibility, and especially repeatability of surface-renewal by simple polishing in the event of surface fouling or dopant leaching. In addition, the modified electrode shows a good catalytic activity for the electrochemical reduction of bromate in an acidic aqueous solution. (C) 2000 Elsevier Science B.V. All rights reserved.

Sol-gel-derived carbon ceramic composite electrodes bulk-modified with 1 : 12-silicomolybdic acid

1:12-Silicomolybdic acid (SiMo12) doped carbon ceramic composite electrodes were fabricated by incorporating SiMo12 and graphite powder in a methyltrimethoxysilane-based gel and characterized by cyclic and square-wave voltammetry, It was demonstrated that the chemically modified electrodes were suitable for electrocatalytic reduction of bromate, The electrodes had the remarkable advantage of surface renewal owing to bulk modification, as web as simple preparation, good mechanical and chemical stability and reproducibility.

Preparation, structures, and electrochemistry of a new polyoxometalate-based organic/inorganic film on carbon surfaces

The preparation, structure, and electrochemical and electrocatalytical properties of a new polyoxometalate-based organic/inorganic film, composed of cetyl pyridinum 11-molybdovanadoarsenate (CPMVA) molecules, have been studied. Cyclic potential scanning in acetone solution led to a stable CPMVA film formed on a highly oriented pyrolytic graphite (HOPG) surface. X-ray photoelectron spectroscopy, scanning tunneling microscopy, and cyclic voltammetry were used for characterizing the structure and properties of the CPMVA film. These studies indicated that self-aggregated clusters were formed on a freshly cleaved HOPG surface, while a self-organized monolayer was formed on the precathodized HOPG electrode. The CPMVA film exhibited reversible redox kinetics both in acidic aqueous and in acetone solution, which showed that it could be used as a catalyst even in organic phase. The CPMVA film remained stable even at pH > 7.0, and the pH dependence of the film was much smaller than that of its inorganic film (H4AsMo11VO40) in aqueous solution. The CPMVA film showed strong electrocatalysis on the reduction of bromate, and the catalytic currents were proportional to the square of the concentration of bromate. The new kind of polyoxometalate with good stability may have extensive promise in catalysis.

Electrochemical behavior of redox species at carbon fibre microdisk array electrode modified with mixed-valent molybdenum(VI, V) oxide

In this study, electrode responses to a large number of electroactive species with different standard potentials at the molybdenum oxide-modified carbon fibre microdisk array (CFMA) electrode were investigated. The results demonstrated that the electrochemical behavior for those redox species with formal potentials more positive than similar to 0.0 V at the molybdenum oxide-modified CFMA electrode were affected by the range and direction of the potential scan, which were different from that at a bare CFMA electrode. If the lower limit of the potential scan was more positive than the reduction potential of the molybdenum oxide film, neither the oxidation nor the reduction peaks of the redox species tested could be observed. This indicates that electron transfer between the molybdenum oxide film on the electrode and the electroactive species in solution is blocked due to the existence of a high resistance between the film and electrolyte in these potential ranges. If the lower limit of the potential scan was more negative than the reduction potential of the molybdenum oxide film (similar to - 0.6 V), the oxidation peaks of these species occurred at the potentials near their formal potentials. In addition, the electrochemical behavior of these redox species at the molybdenum oxide-modified CFMA electrode showed a diffusionless electron transfer process. On the other hand, the redox species with formal potentials more negative than similar to - 0.2 V showed similar reversible voltammetric behaviors at both the molybdenum oxide-modified CFMA electrode and the bare electrode. This can be explained by the structure changes of the film before and after reduction of the film. In addition we also observed that the peak currents of some redox species at the modified electrode were much larger than those at a bare electrode under the same conditions, which has been explained by the interaction between these redox species and the reduction state of the molybdenum oxide film. (C) 2000 Elsevier Science Ltd. All rights reserved.

Influence of a kind of polyanion to hybrid bilayer membranes

Hybrid bilayer membrane consisting of self-assembled alkanethiol and lipid monolayer on gold electrode was fabricated by the paint - freeze method. The interaction of a kind of polyanion, K7Fe3+P2W17O62H2 with such bilayer membrane was investigated by cyclic voltammetry and ac impedance. The hybrid bilayer membrane on the gold electrode showed remarkable insulating property, however, the property was lessened to some extent after interaction with the polyanion. It was found the process was in-eversible. It is presumed that the interaction between the polyanion and lipid is an interaction of K7Fe3+P2W17O62H2 with the polar head group of PC, which lessens the interaction among PC polar head groups. The resulting molecular arrangement becomes looser, even some pores are produced.

Oxidation of NADH by dopamine incorporated in lipid film cast onto a glassy carbon electrode

Stable lipid film was made by casting lipid in chloroform onto a glassy carbon electrode. This model of a biological membrane was used to investigate the oxidation of dihydronicotinamide adenine dinucleotide (NADH) by dopamine. After this electrode had been immersed in dopamine solution for 10 h, it was found that some dopamine had been incorporated in the film. The cyclic voltammogram was obtained for the oxidation of 2.0 X 10(-3) mol 1(-1) NADH with dopamine incorporated in the films. All electrochemical experiments were performed in 0.005 mol 1(-1) phosphate buffer (pH 7.0) containing 0.1 mol 1(-1) NaCl without oxygen. The oxidation current increased gradually with successive sweeps and reached steady state. It was a different phenomenon from previous results. The anodic overpotential was reduced by about 130 mV compared with that obtained at a bare glassy carbon electrode. The diffusion coefficient for 2.0 X 10(-3) mol 1(-1) NADH was 6.7 X 10(-6) cm(2) s(-1). (C) 1999 Elsevier Science S.A. All rights reserved.

Acetylcholinesterase amperometric detection system based on a cobalt(II) tetraphenylporphyrin-modified electrode

An acetylcholinesterase (AChE) activity detection system was fabricated based on the electrocatalysis of cobalt(II) tetraphenylporphyrin of the electrooxidation of thiocholine chloride, which is the product of the hydrolysis of acetylthiocholine chloride by AChE. A simple modified method was used to form the base electrode. AChE was cross-linked on the base electrode by glutaraldehyde. The optimum working conditions are discussed and the characteristics of the detection system are evaluated.

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.