AMPEROMETRIC DETECTION OF AMINO-ACIDS IN A FLOW-INJECTION SYSTEM WITH A NICKEL(II)-MODIFIED ELECTRODE WITH AN EASTMAN-AQ POLYMER FILM

Amperometic flow measurements were made at +0.55 V (vs. Ag/AgCl) in 0.1 mol l-1 KOH electrolyte with an Ni(II) chemically modified electrode (CME) with an Eastman-AQ polymer film. The use and characteristics of a Ni(II)-containing crystalline and polymer-modified electrode obtained by a double coating step as a detector for amino acids in a flow-injection system using reversed-phase liquid chromatography are described. The detection of these analytes is based on the higher oxidation state of nickel (NiOOH) controlled by the applied potential. The electroanalytical parameters and the detection current for a series of amines and amino acids were investigated. The use of such a CME in the flow-injection technique was found to be suitable in a solution at low pH. The linear range for glycine is 5 X 10(-6)-0.1 mol 1-1 with a detection limit of 1.0 X 10(-6) mol l-1. A 1 X 10(-4) mol 1-1 mixture of serine and tyrosine was also detected after separation on an Nucleosil C18 column.

THE PREPARATION OF ELECTRODES MODIFIED WITH ISOPOLYMOLYBDIC ACID PLUS POLYANILINE FILM AND ITS CATALYTIC EFFECTS ON CHLORATE IONS

Electrodes modified with isopolymolybdic acid+polyaniline film, which exhibit high stability and activity in aqueous acidic solution, have been prepared successfully using two methods: one-step synthesis by electrochemical polymerization at a constant applied potential of +0.80 V/SCE or by cycling the potential at 100 mV/s between -0.12 and +0.85 V in 0.5 M H2SO4 containing 5.0x10(-2) M aniline and 5.0x10(-3) M H4Mo8O26, or two-step synthesis by doping the polyaniline film electrode with isopoly acid (IPA) under a cycling potential between -0.20 and +0.40 V in 0.5 M H2SO4 containing the H4Mo8O26 dopant. The thickness of the film and the amount of dopant in the polyaniline film can be controlled by experimental parameters such as the charge, time and the ratio of aniline to IPA in the solution. The experimental results show that electrodes modified with isopolymolybdic acid+polyaniline film using both methods have a strong catalytic effect on the reduction of chlorate anions. Comparison of the two methods of modification shows that the catalytic effect at the modified electrode prepared by the two-step method is greater than that at the electrode prepared by the one-step method.

IMPEDANCE STUDY OF THE INTERFACES BETWEEN LITHIUM, POLYANILINE, LITHIUM-DOPED MNO2 AND MODIFIED POLY(ETHYLENE OXIDE) ELECTROLYTE

Impedance study was carried out for the interfaces between lithium, polyaniline (PAn), lithium-doped MnO2 and modified poly(ethylene oxide) (PEO) electrolyte under various' conditions. The interfacial charge-transfer resistances R(ct) on PEO/PAn, R(ct) on PEO/LiMn2O4 increase with depth-of-discharge and decrease after the charge of the cell containing modified PEO as electrolyte. The charge-transfer resistance R(ct) on PEO/PAn is higher than R(ct) on PEO/LiMn2O4 under the same condition, since inserted species and mechanism are different for both cases. In the case of PAn, an additional charge-transfer resistance might be related to the electronic conductivity change in discharge/charge potential range, as it was evident from a voltammetry curve. With increasing cycle numbers, the charge-transfer resistance increases gradually. The impedance results also have shown that at low frequency the diffusion control is dominant in the process of the charge and discharge of Li/PEO/PAn or Li/PEO/LiMn2O4 cell. The diffusion coefficients have been calculated from impedance data.

CUPRIC HEXACYANOFERRATE COLLOID DOPED POLYPYRROLE FILM-MODIFIED ELECTRODE

Anionic colloid cupric hexacyanoferrate (CuHCF) was incorporated into polypyrrole (PPy) films in the course of electrochemical polymerization of pyrrole from aqueous solution containing pyrrole and CuHCF colloid. The films obtained were dark brown in color. Three redox peaks appeared in the cyclic voltammogram (CV). The peaks around 0.7 V (vs, SCE) showed cation-selective properties. X-ray photoelectron spectroscopic analysis and ultraviolet-visible (UV-vis) spectroscopic properties of the film were investigated.

INDIGO-CARMINE-MODIFIED POLYPYRROLE FILM ELECTRODE

Functionalized polypyrrole films were prepared electrochemically in the presence of indigo-carmine from aqueous solution. The film shows a couple of reversible redox peaks superimposed on a large background of polypyrrole. The redox reaction is pH dependent. The film has good stability in air and can be cycled between -0.1 and 0.4 V (Ag/AgCl) for several hours without any significant changes in the voltammograms. UV-visible spectra indicate the incorporation of indigo-carmine into the polymer matrix.

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.

GAS PERMEABILITIES OF POLY(TRIMETHYLSILYLPROPYNE) MEMBRANES SURFACE MODIFIED WITH CF4 PLASMA

Surface fluorination of poly (trimethylsilylpropyne) (PTMSP) membranes by CF4 plasma was studied. The surface fluorination of the membranes was carried out in an atmosphere of CF4 in a capacitively coupled discharge apparatus with external electrodes. Dramatic increase in selectivity (P(O2)/P(N2)) was observed. The effect of fluorination conditions such as duration of treatment and discharge power on the permeabilities of the membranes was studied. X-ray photoelectron spectrometric data of modified PTMSP membranes showed a drastic alternation in the surface layer. The P(O2) and P(O2)/P(N2) of the membranes were observed to be dependent on the F/C atomic ratio. At F/C > 1, the P(O2/P(N2) value of the membranes could be more than four.

ELECTROCHEMICAL CATALYSIS AT AN ULTRAMICROELECTRODE MODIFIED WITH REDOX SPECIES

General equations of the electrocatalytic reaction at an ultramicroelectrode modified with redox species have been described according to the Andrieux Saveant model. The electrocatalytic kinetic process has been discussed for the whole set of cases, ie (R), (R + S), (SR) (SR + E), (E), (R + E), (ER), (S), (ER + S) and (S + E) limiting situations. The effect of gamma on the catalytic steady state current shows that the higher the value of gamma, the lower the catalytic current. The kinetic process shifts rapidly from R to E with increasing values of gamma. It is favorable for catalysis only when gamma is very low. Therefore, the redox species modified ultramicroelectrode with thin film is utilized for electrocatalysis, and the larger the radius of ultramicroelectrode, the higher the catalytic efficiency.

EFFECT OF PH ON THE ELECTRON-TRANSFER OF CYTOCHROME-C ON A GOLD ELECTRODE MODIFIED WITH BIS(4-PYRIDYL)DISULPHIDE

The adsorption of bis(4-pyridyl)disulphide (PySSPy) and 4.4'-bipyridyl (PyPy) on a gold electrode was studied using cyclic voltammetry. The adsorption isotherms and equilibrium constants (1 X 10(6) mol-1 l for PyPy and 6 x 10(6) Mol-1 l for PySSPy) were determined. The effect of pH on the electrochemical behaviour of cytochrome c was studied on the PySSPy-modified gold electrode. The results show that cytochrome c can only transfer electrons on a deprotonated electrode surface. When the pH is decreased, the standard heterogeneous rate constant of cytochrome c on the modified gold electrode decreases and the electrochemical behaviour changes from a quasi-reversible to an irreversible process.

SURFACE-MODIFIED HYDROPHILIC MEMBRANES IN MEMBRANE DISTILLATION

The porosity and the hydrophobicity of membranes are two essential requirements for membrane distillation (MD) of aqueous solutions. So far, the hydrophobic porous membranes used in MD studies have been prepared from hydrophobic materials. In this work, hydrophilic cellulose acetate and cellulose nitrate membranes were modified into hydrophobic membranes by radiation grafting polymerization and plasma polymerization, and used in MD studies successfully. The results indicated that modified membranes with good performance in MD can be obtained if the modifying conditions are controlled appropriately. Especially plasma polymerization, in which many particular kinds of monomer could be polymerized onto the surface of porous materials, has become an efficient method to prepare hydrophobic porous membrane with high performance from hydrophilic membranes. It will stimulate the development and practical application of MD.

ELECTROCHEMICAL-BEHAVIOR OF HEXACYANOFERRATE(II) ON A GOLD ELECTRODE MODIFIED WITH BIS(4-PYRIDYL)DISULFIDE

The electrochemical behaviour of hexacyanoferrate(II) has been studied by using a bis(4-pyridyl)disulfide modified gold electrode. On the protonated electrode surface, hexacyanoferrate(II) can transfer an electron reversibly but no apparent adsorption was detected. On the deprotonated electrode surface, electron transfer by hexacyanoferrate(II) was more difficult. The electrochemical reversibility varied with the pH of the solution. Relationships between the currents or the standard heterogeneous rate constants and pH were derived.

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.

ELECTROCHEMICAL STUDY OF ISOPOLY AND HETEROPOLY OXOMETALLATE FILM MODIFIED MICROELECTRODES .5. PREPARATION AND ELECTROCHEMICAL-BEHAVIOR OF A 2/18-MOLYBDODIPHOSPHATE ANION MONOLAYER MODIFIED ELECTRODE

In this paper a carbon fibre (CF) microelectrode modified with the 2:18-molybdodiphosphate anion by simple adsorption is described and its electrochemical behaviour is reported. The 2:18-molybdodiphosphate anion (alpha-P2Mo18O626-), which is a Dawson structure, undergoes five successive multielectron reductions in acidic solution. The first three redox waves correspond to the two-electron process, and the last two waves are four-electron and six-electron processes respectively. On the basis of the experimental results it is shown that the electrode process of alpha-P2Mo18O626- on the CF electrode in acidic solution is simultaneously controlled by the diffusion and adsorption of alpha-P2Mo18O626- anions. When the concentration of the alpha-P2Mo18O626- in the solution is reduced, the electrode process mainly exhibits non-diffusion-controlled behaviour, and the diffusion-limited process takes over as the concentration of alpha-P2Mo18O626- becomes higher. The CF electrode modified with a thin film of alpha-P2Mo18O626- exhibits very good stability and redox behaviour in aqueous acidic solution. The alpha-P2Mo18O626- is reduced to heteropoly blue, with an accompanying protonation process. The addition of more than six electrons to the alpha-P2Mo18O626- anion in an aqueous solution does not result in its decomposition. The result obtained is not the same as that reported previously.

ELECTROCHEMICAL STUDY OF ISOPOLY-OXOMETALLATE AND HETEROPOLY-OXOMETALLATE FILM MODIFIED MICROELECTRODES .2. ELECTROCHEMICAL-BEHAVIOR OF ISOPOLYMOLYBDIC ACID MONOLAYER MODIFIED CARBON-FIBER MICROELECTRODES

In this paper the electrochemical properties of isopolymolybdic anion thin film modified carbon fibre (CF) microelectrode prepared by simple dip coating have been described. The modified electrode shows three couples of surface redox waves between + 0.70 and - 0.1 V vs. sce in 2 M H2SO4 solution with good stability and reversibility. The pH of solution has a marked effect on the electrochemical behaviour and stability of the film, the stronger the acidity of electrolyte solution is, the better the stability and reversibility of isopolymolybdic anion film CF microelectrode will be. The scanning potential range strongly influences on the electrochemical behaviour of the film. The isopolymolybdic anion film prepared by the dip coating resulting a monolayer with estimated surface concentration (F) 2.8 x 10(-11) mol cm-2. From the half-peak widths and peak areas of the surface redox waves of the film electrode, the first three surface waves are corresponding to two-electron processes. The electron energy spectra show the products by six electrons reduction are a mixture of Mo(VI) and Mo(V) species. The electrochemical reaction of the isopolymolybdic anion monolayer can be expressed as Mo8O264- + mH+ + 2ne half arrow right over half arrow left [HmMo8-2n(VI)Mo2n(V)O26](4,2n-m)-n = 1, 2, 3; m = 2, 5, 7.

ISOPOLYMOLYBDIC ACID-POLY(4-VINYL)PYRIDINE FILM MODIFIED ELECTRODE

Electrochemical polymerization of 4-vinylpyridine produced a uniform poly(4-vinyl)pyridine(PVP) film on the glassy carbon (GC) electrode surface. The isopolymolybdic acid-PVP film-modified electrode was prepared by soaking the PVP/GC electrode in the 0.05 M H2SO4 aqueous solution containing 0.005 M isopolymolybdic acid (H4Mo8O26). The latter (catalyst) is incorporated and held in the PVP film electrostatically. The electrochemical behavior and electrocatalytic properties of this H4Mo8O26-PVP/GC electrode was described. The results indicate that this modified electrode has good stability and electrocatalytic activity on the reduction of chlorate and bromate ions in aqueous solution. The catalytic process is regarded as an EC mechanism.