Systematic investigation of alkali metal ion transfer across the micro- and nano-water/1,2-dichloroethane interfaces facilitated by dibenzo-18-crown-6

Facilitated alkali metal ion (M+= Li+, Na+, K+, Rb+, and Cs+) transfers across the micro- and nano-water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nanopipets by dibenzo-18-crown-6 (DB18C6) have been investigated systematically using cyclic voltammetry. The theory developed by Matsuda et al. was applied to estimate the association constants of DB18C6 and M+ in the DCE phase based on the experimental voltammetric results. The kinetic measurements for alkali metal ion transfer across the W/DCE interface facilitated by DB18C6 were conducted using nanopipets or-submicropipets, and the standard rate constants (k(0)) were evaluated by analysis of the experimental voltammetric data. They increase in the following order: k(Cs+)(0) < k(Li+)(0) < k(Rb+)(0) < k(Na+)(0) < k(K+)(0), which is in accordance with their association constants except Cs+ and Li+.

Colloid chemical approach to nanoelectrode ensembles with highly controllable active area fraction

A novel "bottom-up" approach to highly controllable nanoelectrode ensembles (NEEs) has been developed using colloidal nanoparticle self-assembly techniques. Ibis solution-based strategy allows flexible control over nanoelectrode size, shape, and interspacing of the as-prepared NEEs. Atomic force microscopy (AFM) was proved to be a powerful tool to monitor the NEE topography, which yields parameters that can be used to calculate the fractional nanoelectrode area of the NEEs. AFM, ac impedance, and cyclic voltammetry studies demonstrate that most of nanoelectrodes on the NEEs (at least by 9-min self-assembly) are not diffusionally isolated under conventional ac frequency range and scan rates. As a result, the NEEs behave as "nanoelectrode-patch" assemblies. Besides, the as-prepared NEEs by different self-assembling times show an adjustable sensitivity to heterogeneous electron-transfer kinetics, which may be helpful to sensor applications. Like these NEEs constructed by other techniques, the present NEEs prepared by chemical self-assembly also exhibit the enhancement of electroanalytical detection limit consistent with NEE theory prediction.

Organic-phase enzyme electrode for phenolic determination based on a functionalized sol-gel composite

An amperometric biosensor for monitoring phenols in the organic phase was constructed by the silica sol-gel immobilization of tyrosinase on a glassy carbon electrode. The organic-inorganic hybrid materials with different sol-gel precursors and polymers were optimized, and the experimental conditions, such as the effect of the solvent, operational potential and enzyme loading were explored for the optimum analytical performance of the enzyme electrode. The biosensor can reach 95% of steady-state current in about 18 s, and the trend in the sensitivity of different phenols is as follows: catechol > phenol >p-cresol. In addition, the apparent Michaelis-Menten constants (K-m(app)) and the stability of the enzyme electrode were discussed. (C) 2000 Elsevier Science S.A. All rights reserved.

Amperometric quantification of polar organic solvents based on a tyrosinase biosensor

A novel amperometric biosensor for quantification of the electrochemically inert polar organic solvents based on tyrosinase electrode was preliminarily reported. The biosensor was fabricated by simply syringing an aqueous solution of tyrosinase/PVAVP (PVAVP: copolymer of poly(vinyl alcohol) grafting with 4-vinylpyridine) onto glassy carbon electrode surface followed by drying the modified electrode at +4 degrees C in a refrigerator. The current generated from electrochemical reduction of quinone is a probe signal. The biosensor can be used for quantification of polar organic solvents, and its mechanism was characterized with in situ steady-state amperometry-quartz crystal microbalance experiments. The detection limit, sensitivity, and dynamic range for certain organic solvents are dependent on the kind and concentration of the substrate probe and the hydrophobicity of the immobilization matrix. The response time for all the tested organic solvents is less than 2 min.

Sol-gel-derived amperometric biosensor for hydrogen peroxide based on methylene green incorporated in Nafion film

A hydrogen peroxide biosensor was fabricated by coating a sol-gel-peroxidase layer onto a Nafion-methylene green modified electrode. Immobilization of methylene green (MG) was attributed to the electrostatic force between MG(+) and the negatively charged sulfonic acid groups in Nafion polymer, whereas immobilization of horseradish peroxidase was attributed to the encapsulation function of the silica sol-gel network. Cyclic voltammetry and chronoamperometry were employed to demonstrate the feasibility of electron transfer between sol-gel-immobilized peroxidase and a glassy carbon electrode. Performance of the sensor was evaluated with respect to response time, sensitivity as well as operational stability. The enzyme electrode has a sensitivity of 13.5 mu A mM(-1) with a detection limit of 1.0 x 10(-7) M H2O2, and the sensor achieved 95% of the steady-state current within 20 s. (C) 2000 Elsevier Science B.V. All rights reserved.

Effect on the property of the photoinduced carrier transport of CdS as sensitizer for TiO2 nanoparticulate thin films

The TiO2 nanoparticle thin films have been sensitized in situ with CdS nanoparticles. The SPS measurement showed that large surface state density was present on the TiO2 nanoparticles and the surface state can be efficiently decreased by sensitization as well as selecting suitable heat treatment, Both the photocurrent response and the charge recombination kinetics in TiO2 thin films were strongly influenced by trapping/detrapping of surface states. The slow photocurrent response of TiO2 nanoparticulate thin films upon the illumination was attributed to the trap saturation effects, The semiconductor sensitization made the slow photoresponse disappeared and the steady-state photocurrent value increased drastically, which suggested that the sensitization of TiO2 thin films with CdS could get a better charge separation and provide a simple alternative to minimize the effect of surface state on the photocurrent response.

Voltammetric study of the sodium ion transfer across micro-water/1,2-dichloroethane interface facilitated by terminal-vinyl liquid crystal crown ether

Sodium ion transfer across micro-water/1,2-dichloroethane (DCE) interface facilitated by a novel ionophore, terminal-vinyl liquid crystal crown ether (LCCE) was studied by cyclic voltammetry. LCCEs have potential applications because of their physicochemical properties and the utilization of crown ethers as selective ionophoric units in other functionalized compounds are interesting. Host-guest-type behavior for such compounds in the liquid-crystalline state is studied. The experimental results suggest that the transfer of the sodium ion facilitated by LCCE was controlled by diffusion of LCCE from bulk solution of DCE to the interface. The diffusion coefficient of LCCE in DCE was calculated to be equal to (3.62 +/- 0.20) x 10(-6) cm(2)/s. Steady-state voltammograms are due to sodium ion transfer facilitated by the formation of 1: 1 metal (M)-LCCE complex at the interface and the mechanism tends to be transfer by interfacial complexation or dissociation (TIC or TID). The stability constant of the complex formed was determined to be log beta(o) = 5.5 in DCE phase. The influence of parameters such as concentration of sodium ion and concentration of LCCE on the sodium ion transfer was investigated.

Construction of a heteropolyanion-modified electrode by a two-step sol-gel method and its electro catalytic applications

The sol-gel technique was used here to construct heteropolyanion-containing modified electrodes. This involves two steps, i.e. the first forming a functionalized sol-gel thin film on the surface of the glassy carbon electrode and then immersing the electrode into a heteropolyanion solution to incorporate the heteropolyanion into the sol-gel film. Here a Dawson-type heteropolyanion, K6P2W18O62 (P2W18), was used as a representative to illuminate the behavior of the as-prepared composite film. The electrochemical performance of the P2W18-modified electrode was studied with respect to the pH effect and long-term stability. The modified electrode exhibited a high electrocatalytic response for the reduction of BrO3- and NO2-. Steady-state amperometry was applied to characterize the electrode as an amperometric sensor for the determination of NO2-. The sensor had a linear range from 0.02 to 34 mM and a detection limit of 5 x 10(-6) M. (C) 2001 Elsevier Science B.V. All rights reserved.

Fabrication of nanometer-sized electrodes and tips for scanning electrochemical microscopy

A novel method for fabrication of nanometer-sized electrodes and tips suitable for scanning electrochemical microscopy (SECM) is reported. A fine etched Pt wire is coated with polyimide, which was produced by polymerization on the Pt surface initiated by heat. This method can prepare electrodes with effective radii varying from a few to hundreds of nanometers. Scanning electron microscopy, cyclic voltammetry, and SECM were used to characterize these electrodes. Well-defined steady-state voltammograms could be obtained in aqueous or in 1,2-dichloroethane solutions. Ibis method produced the nanoelectrodes with exposed Pit on the apex, and they can also be employed as the nanotips for SECM investigations. Different sizes of Pt nanotips made by this method were employed to evaluate the kinetics of the redox reaction of Ru(NH3)6(3+) on the surface of a large Pt electrode by SECM, and the standard rate constant kappa (o) of this system was calculated from the best fit of the SECM approach curve. This result is similar to the values obtained by analysis of the obtained voltammetric data.

Photosensitization of TiO2 nanoparticulate thin film electrodes by CdS nanoparticles

Surface photovoltage spectra (SPS) measurements of TiO2 show that a large surface state density is present on the TiO2 nanoparticles and these surface states can be efficiently decreased by sensitization using US nanoparticles as well as by suitable heat treatment. The photoelectrochemical behavior of the bare TiO2 thin film indicates that the mechanism of photoelectron transport is controlled by the trapping/detrapping properties of surface states within the thin films, The slow photocurrent response upon the illumination can be explained by the trap saturation effect. For a TiO2 nanoparticulate thin film sensitized using US nanoparticles, the slow photocurrent response disappears and the steady-state photocurrent increases drastically, which suggests that photosensitization can decrease the effect of surface states on photocurrent response.

Amperometric biosensor for hydrogen peroxide based on sol-gel/hydrogel composite thin film

A reagentless amperometric hydrogen peroxide biosensor was developed. Horseradish peroxidase (HRP) was immobilized in a novel sol-gel organic-inorganic hybrid matrix that is composed of silica sol and a grafting copolymer of poly(vinyl alcohol) with 4-vinylpyridine (PVA-g-PVP). Tetrathiafulvalene (TTF) was employed as a mediator and could lower the operating potential to -50 mV (versus Ag/AgCl). The sensor achieved 95% of the steady-state current in 15 s. Linear calibration for hydrogen peroxide was up to 1.3 mM with the detection limit of 2.5 x 10(-7)M. The enzyme electrode retained about 94% of its initial activity after 30 days of storage in a dry state at 4 degreesC.

Excimer formation in uniaxially stretched polymer films

The steady-state fluorescence properties of naphthalene-labeled polymers dispersed in poly(methyl methacrylate) (PMMA) cast films were studied under tensile loadings at 80 degreesC. The labeled polymers were composed of methyl methacrylate (MMA) and 1-naphthylmethyl methacrylate (NMMA). Three of the copolymers were used in this work, and the contents of NMMA were 0.59 mol % (CP1), 22.0 mol % (CP2), and 56.7 mol % (CP3), respectively. The fluorescence spectra of the films containing CP1 and CP2were unchanged during elongation. For the film containing CP3, the excited monomer emission of naphthyl groups at around 337 nm decreased with increasing applied tensile strain. The strain enhanced the emission ascribed to the excimer of the naphthyl groups in the region of 390-420 nm. The ratio of fluorescence intensities at 400 nm and 337 mn, I-400/I-337, increased with the applied strain, which indicates that CP3 is a sensitive probe for detecting the structural changes of polymer matrices. The obtained results mean that the excimer-forming sites in the PMMA films during elongation depend both on the applied strain and the concentration of naphthyl groups in the dispersed polymer probes. (C) 2001 John Wiley & Sons, Inc.

Fabrication of agar-gel microelectrodes and their application in the study of ion transfer across the agar-water 1,2-dichloroethane interface

In this paper, we describe a simple procedure to make agar-gel microelectrodes by filling micropipettes. These microelectrodes were used to study K+ transfer across the agar-water \ 1,2-dichloroethane interface facilitated by dibenzo-18-crown-6 (DB18C6), and the transfer of tetraethylammonium (TEA(+)). The results observed were similar to those obtained at micro-liquid \ liquid interfaces. The effect of various amounts of agar in the aqueous phase was optimized and 3% agar was chosen based on the potential window and solidification time. The different shapes of micro-agar-gel electrodes were prepared in a similar way. The fabricated agar-gel microelectrodes obey the classical micro-disk steady-state current equation, which is different from the behavior of a normal micropipette filled with aqueous solution without silanization. (C) 2001 Elsevier Science B.V. All rights reserved.

Hydrogen peroxide biosensor based on sol-gel-derived glasses doped with Eastman AQ polymer

A hydrogen peroxide biosensor based on sol-gel-derived glasses doped with poly(ester sulfonic acid) Eastman AQ 55D was constructed. Thionine (TH), as a mediator, was incorporated in this matrix by electrostatic force between TH+ and the negatively charged sulfonic acid group in Eastman AQ polymer. Performance and characteristics of the sensor were evaluated with respect to response time, sensitivity and storage stability. The enzyme electrode has a sensitivity of 11.36 muA mM(-1) with a detection limit of 5.0 x 10(-7) M H2O2, and the sensor achieved 95% of the steady state current within 20 s. (C) 2001 Elsevier Science B.V. All rights reserved.

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.