Sol-gel-derived prussian blue-silicate amperometric glucose biosensor

A new type of inorganic biosensor is introduced. The sensor comprises glucose oxidase enzymes encapsulated in a sol-gel-derived Prussian blue-silicate hybrid network. Glucose is detected by the biocatalytic reduction of oxygen followed by catalytic reduction of hydrogen peroxide by the Prusian blue catalyst. The sol-gel silicate entails a rigid encapsulating matrix, the Prussian blue provides chemical catalysis and charge mediation from the reduction site to the supporting electrode, and the enzyme is responsible for the biocatalysis. The feasibility of a dual optical/electrochemical mode of analysis is also demonstrated.     

Preconcentration and Voltammetric Determination of the Antihypertensive Doxazosin on a C8 Modified Carbon Paste Electrode

 An electrochemical study of the doxazosin oxidative process at carbon paste electrodes using different voltammetric techniques has been carried out. The process is irreversible and controlled by adsorption, giving rise to an oxidation wave around 1.0 V in citric acid-citrate buffer (pH 3.0). A mechanism based on the oxidation of the amine group is postulated. Two methods based on adsorptive stripping (AdS) of doxazosin at the C₈-modified carbon paste electrode (C₈-MCPE), before its voltammetric determination, are studied, using differential pulse voltammetry (DPV) and square wave voltammetry (SWV) as redissolution techniques. By means of AdS-DPV and C₈-MCPE, doxazosin can be determined over the 1.0 × 10⁻⁹ to 3.0 × 10⁻⁸ mol L⁻¹ range with a variation coefficient of 2.2% (2.0 × 10⁻⁸ mol L⁻¹) and a limit of detection of 7.4 ×10⁻¹⁰ mol L⁻¹. If AdS-SWV is used, a linear range from 1.0 × 10⁻⁹ to 4.0 × 10⁻⁸ mol L⁻¹ is obtained, the variation coefficient being 2.8% (2.0 × 10⁻⁸ mol L⁻¹, and the limit of detection reached 7.7 × 10⁻¹⁰ mol L⁻¹. The AdS-DPV procedure was applied to the determination of doxazosin in urine and formulations. Received March 13, 1999. Revision December 23, 1999.     

A Comparison of Electron Transfer Kinetics of Three Common Carbon Electrode Surfaces in Acetonitrile and in Room Temperature Ionic Liquid 1‐Butyl‐3‐Methylimidiazonium Hexafluorophosphate: Correlation to Surface Structure and the Limit of the Diffusion Domain Approximation

We report the comparison of electron transfer kinetic parameters of the ferrocene redox couple in both acetonitrile and in room temperature ionic liquid (RTIL) 1‐butyl‐3‐methylimidiazonium hexafluorophosphate ([C₄mim] [PF₆]), using edge plane pyrolytic graphite (EPPG), basal plane pyrolytic graphite (BPPG) and glassy carbon (GC) electrodes. Each electrode surface was characterized using SEM and AFM and the surface morphology was analyzed in terms of surface heterogeneity including the distribution of edge plane defects. The experimental data were modeled using both one and two dimensional simulations to correlate the electron transfer parameters obtained with the different surface structure of each electrode. Furthermore, we show that the diffusion domain approximation (commonly used to accurately simulate electron transfer kinetics at graphitic surfaces) breaks down when a BPPG electrode is used in RTIL and demonstrate the near impossibility of assigning rate constant to the basal plane surface.     

Stability Improvement of Prussian Blue by a Protective Cellulose Acetate Membrane for Hydrogen Peroxide Sensing in Neutral Media

The cellulose acetate covered Prussian blue modified glassy carbon electrode (GCE/PB/CA) was fabricated as a novel hydrogen peroxide sensor. It was shown by scanning electron microscope (SEM) and atomic force microscope (AFM) that Prussian blue was covered and protected by cellulose acetate perfectly. The modified electrode showed a good electrocatalytic activity for H₂O₂ reduction in neutral aqueous solution. H₂O₂ was detected amperometrically in 0.05 mol/L phosphate buffer solutions (pH 7.0, containing 0.1 mol/L KCl as supporting electrolyte) at an applied potential of ?0.2 V (vs. SCE). The response current was proportional to the concentration of H₂O₂ in the range of 1.0×10^?5 mol/L to 2.5×10^?4 mol/L with the detection limit of 2.2×10^?6 mol/L at a signal to noise ratio 3.     

Voltammetry of Benzo[a]pyrene in Aqueous and Nonaqueous Media: Adsorptive Stripping Voltammetric Determination at Pencil Graphite Electrode

A detailed study of the electrochemical oxidation of Benzo[a]pyrene (BaP) at the glassy carbon and pencil graphite electrodes was carried out in aqueous and nonaqueous media. Using square‐wave stripping mode, the compound yielded a well‐defined voltammetric response at pencil graphite electrode in acetate buffer, pH 4.8 at +1.13 V (vs. Ag/AgCl) (a preconcentration step being carried out at a fixed potential of +0.70 V for 180 s). The process could be used to determine BaP concentrations in the range 0.25–1.25 μM, with a detection limit of 0.027 μM (6.82 μg L^?1). The applicability to assay of spiked human urine samples was also illustrated.     

Flow Injection Analysis of Aluminum Chlorohydrate in Antiperspirant Deodorants Using a Built‐in Three‐in‐one Screen‐Printed Silver Electrode

A screen‐printed silver strip with a built‐in three‐in‐one electrode (SPAgE) configuration of Ag‐working, Ag‐counter and Ag/Ag_xO (silver oxides) pseudoreference electrodes has been developed for sensitive and selective electrochemical flow injection analysis (FIA) of aluminum chlorohydrate (ACH) present in antiperspirants, through the free Cl^? ion liberated from ACH in aqueous medium, as a redox signal at Ag‐working electrode in pH 6 phosphate buffer solution (PBS). The solution phase and instrumental parameters were systematically optimized. The calibration graph was linear in the window 1–200 ppm concentration of ACH and the lowest detection limit (S/N=3) was 295 ppb with a slope of 0.0989 μA/ppm and regression coefficient of 0.998. Calculated relative standard deviation (RSD) values for the detection of 5 and 50 ppm ACH by this method are 2.21 % and 2.16 %, respectively. Four different antiperspirant deodorants real samples with and without ACH content were successfully analyzed and the detected values obtained were found to be in good agreement with the product labeled values.     

Elimination Voltammetry of Miniaturized Mercury Drop Electrodes

Elimination voltammetry with linear scan (EVLS) in connection with renewed mini‐ drop mercury electrodes provides valuable information about the character and kinetics of processes at electrode/electrolyte interfaces. Based on the experiment related to the hydrogen evolution, it is presented that the EVLS is more sensitive than other voltammetric methods. Using miniaturized mercury electrodes, the EVLS is capable of detecting the effect of spherical diffusion associated with both the scan rates and the size of an electrode drop.     

Synthesis and Characterization of Chromium Hexacyanoferrate/Multiwalled Carbon Nanotube Composite and Its Biosensing for L‐Cysteine

This work describes the electrochemical properties of glassy carbon electrodes (GCE) modified with chromium(III) hexacyanoferrate(II) (Crhf) nanoparticles attached multiwalled carbon nanotube (MWNTs). The morphological characterization of Crhf/MWNTs nanocomposites was examined by scanning electron microscopy (SEM), UV‐vis spectroscopy, and Fourier transform infrared spectrometry (FT‐IR). The electrocatalytic activity of these nanocomposites was investigated and showed a good electrocatalytic effect for oxidation of L ‐cysteine (L ‐Cys) in 0.1 M phosphate buffer solution (pH 3.0). Under optimum conditions linear calibration graphs were obtained over the L ‐Cys concentration range 5.0×10^?7 to 6.0×10^?5 M with a correlation coefficient of 0.9998 and a detection limit (signal‐to‐noise ratio was 3) of 1.0×10^?8 M. The proposed method is simple and it also showed excellent sensitivity and stability. The excellent electrocatalytic ability of the modified electrode towards L ‐Cys manifests that the Crhf/MWNTs can provide a new platform for biosensors and other biology.     

Cosmetic Electrochemistry II: Rapid and Facile Production of Metallic Electrocatalytic Ensembles

We demonstrate a facile methodology for the production of metallic electrocatalytic microdomain ensembles for a range of analytical sensing challenges. A commercially available off‐the‐shelf cosmetic product can change the voltammetric characteristics of a metallic macro‐electrode created electrolytically into that of a random ensemble of metallic microelectrode domains. Proof‐of‐concept is shown for three examples: a palladium ensemble for hydrazine sensing, a gold ensemble for arsenic(III) detection via anodic stripping voltammetry and platinum ensembles for the direct oxidation of arsenic(III). Last we demonstrate that the fabrication of metallic microdomains can be simplified by sputter coating screen printed electrochemical sensing platforms which are beneficially constructed using this cosmetic methodology. Given the facile fabrication and low cost of the underlying electrode substrate and the cosmetic modifier, the widespread implementation of this novel fabrication methodology is expected.