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.

Amperometric enzyme electrode for the determination of hydrogen peroxide based on sol-gel/hydrogel composite film

A new type of organic-inorganic composite material was prepared by sol-gel method, and a peroxidase biosensor was fabricated by simply dropping sor-gel-peroxidase mixture onto glassy carbon electrode surface. The sol-gel composite film and enzyme membrane were characterized by Fourier-transform infrared (FT-IR) spectroscopy and EQCM, the electrochemical behavior of the biosensor was studied with potassium hexacyanoferrate(II) as a mediator, and the effects of pH and operating potential were explored for optimum analytical performance by using amperometric method. The response time of the biosensor was about 10 s; the linear range was up to 3.4 mM with a detection limit of 5 x 10(-7) M. The sensor also exhibited high sensitivity (15 mu A mM(-1)) and good long-term stability. In addition, the performance of the biosensor was investigated using flow injection analysis (FIA), and the determination of hydrogen peroxide in real samples was discussed. (C)2000 Elsevier Science B.V. All rights reserved.

Multilayer assembly of Mn-substituted Keggin-type [ZnW11O39Mn(H2O)](8-) on chemically modified glassy carbon electrode and its electrocatalytic properties

Through layer-by-layer assembly, undecatungstozincates monosubstituted by transition metals Mn, ZnW11 Mn (H2O) O-39(8-) was successfully immobilized on a glassy carbon electrode surface grafted covalently by 4-aminobenzoic acid. The electrochemical behavior of these polyoxometalates was investigated. Cyclic voltammetry proves the uniform growth of the film. They exhibit some special electrochemical properties in the films, different from those in homogeneous aqueous solution. The effect of pH on the redox behavior of ZnW11Mn(H2O)O-39(8-) in the film was discussed in detail. The multilayer film electrodes have an excellent electrocatalytic response to the reduction of H2O2 and BrO3-, and to the oxidation of ascorbic acid.

Electrocatalytic oxidation of ascorbic acid by ferrocene in lipid film cast on a glassy carbon electrode

A ferrocene-dimyristoyl phosphatidylcholine (DMPC) film electrode was prepared by casting the solution of ferrocene and DMPC in chloroform onto a glassy carbon electrode surface. Ferrocene retained in the biological membrane gave a couple of irreversible peaks of cyclic voltammogram. The electrode exhibited good electrocatalytic activity for the oxidation of ascorbic acid (H(2)A) in phosphate buffer (pH 6.64) with an anodic peak potential of +340 mV (vs. Ag/AgCl). The anodic current was directly proportional to the square root of the scan rate below 150 mV s(-1). The influence of the pH value was investigated and it was observed that pH 6.64 was the suitable value to the anodic peak potential and current. The thickness of the film and the interference of uric acid were also studied. The electrode can be used to determine H(2)A in the presence of equimolar uric acid. The catalytic peak current increased linearly with the concentration of H(2)A in the range of 1 X 10(-4)-5 X 10(-3) mol L-1.

Investigation of the model compounds at 4-aminobenzoic acid modified glassy carbon electrode by scanning electrochemical microscopy

In this paper, we studied the reactions of both potassium ferricyanide and hexaammineruthenium(III) chloride at a 4-aminobenzoic acid (4-ABA) modified glassy carbon electrode (GCE) by scanning electrochemical microscopy (SECM) in different pH solutions. The surface of the modified electrode has carboxyl groups, the dissociation of which are strongly dependent upon the solution pH values. The rate constant kb of the oxidation of ferrocyanide on the modified electrode can be obtained by fitting the experimental tip current-distance (I-T-d) curves with the theoretical values. The surface pK(a) of the 4-ABA modified GCE was estimated from the plot of standard rate constant k(o) versus the solution pH and is equal to 3.2, which is in good agreement with the reported result. The SECM approach curves for Ru(NH3)(6)(3+) both on the bare and the modified electrodes show similar diffusion control processes. These results can be explained by the electrostatic interactions between the modified electrode surface and the model compounds with different charges. (C) 2001 Elsevier Science BN. All rights reserved.

Electrochemical synthesis of Ag nanoparticles on functional carbon surfaces

In this paper, we present a new method of fabricating metal nanoparticles on carbon substrates through molecular design. Scanning tunneling microscopy measurements show that the electrochemically synthesized Ag nanoparticles are homogeneously dispersed on the modified highly oriented pyrolytic graphite (HOPG) surface with a narrow particle size distribution. Moreover, the size and number density of Ag nanoparticles on the grafted HOPG surface can be easily changed through control of the experimental conditions. (C) 2001 Elsevier Science B.V. All rights reserved.

Potential-induced transformation for surfactant aggregates on a metal surface

Surfactant adsorption on metal surfaces has been used to limit the activity of the electrode surface and to stabilize colloidal clusters and nanoparticles in solution, but the adsorption and relative potential-induced structure change of the surfactant were not known. Here, the adsorption of sodium dodecyl sulfate (SDS) on a Au(111) surface under potential control was investigated by in situ scanning tunneling microscopy (STM). The STM images showed that the morphology of SDS on Au(111) was changed from a hemi-cylindrical micellar monolayer to a compact and uniform bilayer through control of the potential. The transition between the hemimicellar monolayer and the compact bilayer is not reversed after a period of time. The model of potential-induced transformation for SDS aggregates on Au(111) was established. (C) 2001 Elsevier Science B.V. All rights reserved.

In-situ FTIR study on adsorption and oxidation of native and thermally denatured calf thymus DNA at glassy carbon electrodes

In-situ Fourier transform infra-red (FTIR) spectra of native and thermally denatured calf thymus DNA (CT DNA) adsorbed and/or oxidized at a glassy carbon (GC) electrode surface are reported. The adsorption of native DNA occurs throughout the potential range (-0.2 similar to 1.3 V) studied, and the adsorbing state of DNA at electrode surface is changed from through the C=O band of bases and pyrimidine rings to through the C=O of cytosine and imidazole rings while the potential shifts negatively from 1.3 V to -0.2 V. An in-situ FTIR spectrum of native CT DNA adsorbed at GC electrode surface is similar to that of the dissolved DNA, indicating that the structure of CT DNA is not distorted while it is adsorbed at the GC electrode surface. In the potential range of -0.2 similar to 1.30 V, the temperature-denatured CT DNA is adsorbed at the electrode surface first, then undergoes electrochemical oxidation reaction and following that, diffuses away from the electrode surface. (C) 2001 Elsevier Science B.V. All rights reserved.

Cobalt(II)hexacyanoferrate film modified glassy carbon electrode for construction of a glucose biosensor

An amperometric glucose biosensor was constructed based on a glassy carbon electrode modified with a Cobalt(II)hexacyanoferrate film which catalyzes electroreduction of hydrogen peroxide. Gelatin was used as immobilization matrix. Interference could be effectively eliminated by the combination of low detection potential with a Nafion coating. A low applied potential can avoid oxidation of interferences such as ascorbic acid, uric acid, p-acetyl-aminophenol, etc.. Nafion coating prevents interferences from access to the electrode surface by electrostatic repulsion. A wide linear range of detection was obtained. Analytical performance parameters are given and kinetic analysis discussed.

EQCM characterization of self-assembled kinetics of 4-pyridyl hydroquinone at Pt surface and its ion transfer in electrochemical redox

The adsorbed kinetics, proton transportation in electrochemical redox process of 4-pyridyl hydroquinone (4PHQ) self-assembled monolayer (SAM) modified Pt electrode were studied by electrochemical quartz crystal microbalance (EQCM) in situ. It proved that the electrode was modified by a monolayer and underwent a rapid electron transfer. It was a slow adsorbed kinetic process. The ion transfer in the electrochemical redox at the SAM-modified electrode surface mainly involved into the hydrate hydrogen ion.

Chemiluminescent determination of glucose with a modified carbon paste electrode

A flow injection analysis detection method for glucose is presented which is based on the oxidation of glucose by glucose oxidase followed by chemiluminescent detection of hydrogen peroxide. Both glucose oxidase and hematin, a chemiluminescent reaction catalyst, were bulk-immobilized conveniently by direct mixing with carbon paste, which allows renewal of the electrode surface by simply polishing or cutting to expose a new and fully active surface in the case of fouling. Luminol in reagent solution passed through the flow cell and reacted with hydrogen peroxide produced by the enzyme reactor in the presence of the catalyst to yield light. An applied potential of -0.4 V avoided the electrode fouling effectively. The log-log plot of the emitted light intensity vs glucose concentration was linear over the range of 1-100 mmol L-1 with a correlation coefficient of 0.992. Application of this method to other chemiluminescent and bioluminescent systems is suggested. (C) 1999 Academic Press.

Self-gelatinizable graft copolymer of poly(vinyl alcohol) with 4-vinylpyridine as an immobilization matrix for the construction of a tyrosinase-based amperometric biosensor

A tyrosinase-based amperometric biosensor using a self-gelatinizable graft copolymer of poly(vinyl alcohol) with 4-vinylpyridine (PVA-g-PVP) as an immobilization matrix was constructed. The 4-vinylpyridine component of PVA-g-PVP enhances the adherence to a glassy carbon electrode surface. The content of 4-vinylpyridine in this immobilization matrix plays a key role in retaining the activity of tyrosinase. A simple, milder method was adopted by simply syringing the copolymer-tyrosinase aqueous solution on to the electrode surface and allowing water to evaporate at 4 degrees C in a refrigerator. Several parameters, including copolymer composition; pH, applied potential and enzyme membrane composition, ware optimized. The enzyme membrane composition can be varied to obtain higher sensitivity or a wider linear detection range. The biosensor was used for the determination of phenol, p-cresol and catechol. The biosensor exhibited excellent reproducibility, stability and sensitive response and can be used in flow injection analysis. The biosensor showed an extended linear range in hydrophilic organic solvents and it can be used in monitoring organic reaction processes. The analytical performance demonstrated this immobilization matrix is suitable for the immobilization of tyrosinase.

Electrocatalytic oxidation and flow amperometric detection of hydrazine at an electropolymerized 4-vinylpyridine/palladium film electrode

A poly(4-vinyl)pyridine (PVP)/Pd film electrode was constructed for the electrocatalytic detection of hydrazine. The preparation of the PVP/GC electrode was performed by electropolymerization of the monomer 4-vinylpyridine onto the surface of a glassy carbon electrode. Subsequently, palladium is electrodeposited onto the polymer modified electrode surface. The ion-exchange function of PVP polymer is helpful to this process in view of the tetrachlorapalladate anion. Compared with the Pd/GC electrode, the modified electrode displays a better mechanical stability in a flowing stream. The PVP/Pd film electrode exhibits higher sensitivity when detecting hydrazine with a detection limit of 0.026 ng (S/N=3).

Interfacial characteristics of the self-assembly system of poly-L-lysine 3-mercaptopropionic acid gold electrode

The interfacial characteristics of poly-L-lysine (PL) attached on self-assembled monolayers (SAMs) of 3-mercaptopropionic acid (MPA) were studied by an electrochemical method. The results indicated that PL\MPA layer inhibited partly the diffusion process of redox species in solution, and the electrode surface behaved like a microelectrode array. Its permeation effect was also strongly affected by Mg2+. The more Mg2+ ions were added into the electrolyte solution, the greater the difficulty with which the electron transfer of potassium ferricyanide took place. The three different conformations of PL on the electrode surface had different influences on the electron transfer processes of ferricyanide. PL in random coil state hindered most strongly the electron transfer behavior of ferricyanide,while the alpha-helical PL had nearly no effect and the effect of the beta-sheet state PL was intermediate of these. (C) 1997 Elsevier Science S.A.

Scanning tunnelling microscopy observation of cytochrome-c denaturation induced by bromopyrogal red on highly oriented pyrolytic graphite

The denaturation of cytochrome-e (cyt-c) induced by bromopyrogal red (BPR) was studied by scanning tunnelling microscopy (STM) on the electrochemically pretreated highly oriented pyrolytic graphite (HOPG) surface. STM images reveal that denatured cyt-c molecules exist in variable states including aggregates, globular compact, partially unfolded and combined with BPR molecule. The apparently low image contrast of denatured cyt-c observed in this experiment comparing to that of native cyt-c molecules, and the relative low image contrast of the unfolded part comparing with the compact globular part, are ascribed to the unfavourable tunnelling paths for the conformational variations of denatured cyt-c molecules. (C) 1997 Elsevier Science B.V.