José Luis Hidalgo-Hidalgo de Cisneros

Electrochemical Study of 4-Nitrophenol at a Modified Carbon Paste Electrode

Abstract A zeolite-modified carbon paste electrode (CPE) has been used for the determination of 4-nitrophenol by differential pulse voltammetry (DPV). The electrochemical reduction of 4-nitrophenol at −1.0 V is carried out in a Britton-Robinson medium at pH 3.5. The cyclic voltammetric (CV) behaviour has been investigated to study the nature of the process. Studies on the effect of pH were carried out over the pH range 2–9 with the Britton-Robinson buffer solution, and the influence of pH on peak height and peak potential was analyzed. A linear relationship between peak intensity and concentration is obtained in the range 0.2–10 mg L−1, with a detection limit of 0.04 mg L−1; a relative standard deviation of 1.5% for a 5 mg L−1 4-nitrophenol concentration and a relative error of 2.6% were also obtained (n=11).

Alumina sol-gel/sonogel-carbon electrode based on acetylcholinesterase for detection of organophosphorus pesticides.

Two new amperometric biosensors based on immobilization of acetylcholinesterase on a sonogel-carbon electrode for detection of organophosphorous compounds are proposed. The electrodes were prepared applying high-energy ultrasounds directly to the precursors. The first biosensor was obtained by simple entrapping acetylcholinesterase in Al(2)O(3) sol-gel matrix on the sonogel-carbon. The second biosensor was produced in a sandwich configuration. Its preparation involved adsorption of the enzyme and modification via a polymeric membrane such as polyethylene glycol and the ion-exchanger Nafion. The optimal enzyme loading was found to be 0.7 mIU. Both biosensors showed optimal activity in 0.2 M phosphate buffer, pH 7.0, at an operating potential of 210 mV. The detection limit achieved for chlorpyriphos-ethyl-oxon was 2.5x10(-10)M at a 10-min incubation time.

Determination of wear metals in marine lubricating oils by microwave digestion and atomic absorption spectrometry

Abstract The difficulties associated with the development of a microwave-assisted acid digestion of lubricating oils in determination of wear metals are presented. The interest of this sample treatment lies in its basis for determining the total metal contents with enough sensitivity by flame atomic absorption spectrometry (FAAS). It allows earlier diagnosis of the engine state than is obtained by the widely applied simple dilution procedure. Another advantage is the avoidance of contamination and loss of the metals to be determined. The procedure employs nitric acid and hydrogen peroxide in a four-stage programme. Fe, Cu, Cr and Pb are determined by FAAS as representative of engine wear. The limits of detection are 0.1 μg/g for Fe and Cr and 0.05 μg/g for Cu and Pb. A comparison with other procedures is presented for spiked samples. Different types of used lubricating oils supplied by an oil company were analysed to prove the suitability of the procedure proposed.

Use of a bentonite-modified carbon paste electrode for the determination of some phenols in a flow system by differential-pulse voltammetry

The electrochemical behaviour of some phenols (methyl-, chloro- and nitrophenols) included in the US Environmental Protection Agency List of Priority Pollutants at a bentonite-modified carbon paste electrode in a flow system was studied. A fixed proportion of artificial sea-water was used in the sample solution so that the applicability of the methodology to marine environments could be tested. Amounts of bentonite from 5 to 10% were used. For methyl- and nitrophenols, a good stability of the electrode surface activity was observed after a series of repeated injections, with relative standard deviations between 0.40 and 2.98% (n = 16). Recovery studies were carried out on real sea-water samples spiked with 0.5 or 2.5 mg l - 1 of the pollutants; recoveries from 95.4 to 101.1% were obtained.

Use of a Sonogel-Carbon electrode modified with bentonite for the determination of diazepam and chlordiazepoxide hydrochloride in tablets and their metabolite oxazepam in urine

Sonogel-Carbon electrode (SngCE) modified with bentonite (BENT) shows an interesting alternative electrode to be used in the determination of 1,4-benzodiazepines by square wave adsorptive cathodic stripping voltammetry (SWAdCSV). Diazepam (DZ) and chlordiazepoxide hydrochloride (CPZ), were determined using SngCE modified by 5% BENT. An electrochemical study of different parameters (such as pH, buffer type, ionic strength, accumulation potential, scan rate, and accumulation time) which affect the determination of DZ and CPZ is reported. Linear concentration ranges of 0.028-0.256 μg mL(-1) DZ (r=0.9997) and 0.034-0.302 μg mL(-1) CPZ (r=0.9997) are successfully obtained after an accumulation time of 60s. The quantification and detection limits were calculated to be 14.0 and 4.0 ng mL(-1) for DZ, and 16.0 and 5.0 ng mL(-1) for CPZ, respectively. The surface of the proposed electrode was characterized by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX). The developed method was applied to the analysis of commercially available tablets and human urine real samples. Analysis was performed with better precision, very low detection limits, and faster than previously reported voltammetric techniques.

Amperometric inhibition biosensors based on horseradish peroxidase and gold sononanoparticles immobilized onto different electrodes for cyanide measurements.

New biosensors based on inhibition for the detection of cyanide and the comparison of the analytical performances of nine enzyme biosensor designs by using three different electrodes: Sonogel-Carbon, glassy carbon and gold electrodes were discussed. Three different horseradish peroxidase immobilization procedures with and without gold sononanoparticles were studied. The amperometric measurements were performed at an applied potential of -0.15V vs. Ag/AgCl in 50mM sodium acetate buffer solution pH=5.0. The apparent kinetic parameters (Kmapp, Vmaxapp) of immobilized HRP were calculated in the absence of inhibitor (cyanide) by using caffeic acid, hydroquinone, and catechol as substrates. The presence of gold sononanoparticles enhanced the electron transfer reaction and improved the analytical performance of the biosensors. The HRP kinetic interactions reveal non-competitive binding of cyanide with an apparent inhibition constant (Ki) of 2.7μM and I50 of 1.3μM. The determination of cyanide can be achieved in a dynamic range of 0.1-58.6μM with a detection limit of 0.03μM which is lower than those reported by previous studies. Hence this biosensing methodology can be used as a new promising approach for detecting cyanide.

Investigation of biosensor signal bioamplification: comparison of direct electrochemistry phenomena of individual Laccase, and dual Laccase-Tyrosinase copper enzymes, at a Sonogel-Carbon electrode.

Direct electrochemistry of Trametes versicolor Laccase (LAC) was found at a Sonogel-Carbon electrode. The bioamplification, performed by dual immobilization of this enzyme and Mushroom Tyrosinase (TYR), of the bio-electrocatalytic reduction of O(2) was investigated. The calculated alpha transfer coefficients were 0.64 and 0.67, and the heterogeneous electron-transfer rate constants were 6.19 and 8.52 s(-1), respectively, for the individual LAC and dual LAC-TYR-based Nafion/Sonogel-Carbon bio-electrodes. The responses of the dual enzymes electrode to polyphenols were stronger than those of the individual LAC or TYR biosensors. Hypotheses are offered about the mechanism of bioamplification. The surfaces of the biosensors were also characterized by AFM.

Voltammetric determination of 2-nitrophenol at a bentonite-modified carbon paste electrode

A bentonite-modified carbon paste electrode has been applied to the determination of 2-nitrophenol by differential pulse voltammmetry. The electrochemical reduction of 2-nitrophenol at −0.8 V is carried out in an artificial sea water-formic acid/sodium formate medium at pH 4. The peak height was found to be dependent on the pH over the range 2–11; the presence of a secondary process was observed in the pH range 8–11. The peak potential showed a dependence on pH, with two linear regions with different slopes. A linear relationship between peak intensity and concentration was obtained in the range 0.07–10 mgl−1, with a detection limit of 0.03 mg 1−1 and a coefficient of variation of 1.3% at 5 mg 1−1. The effects of organic and inorganic species on the 2-nitrophenol determination were studied with a view to testing the resolution of the voltammetric technique. The proposed method has been applied to sea water samples with good results.

Graphite grains studded with silver nanoparticles: description and application in promoting direct biocatalysis between heme protein and the resulting carbon paste electrode.

The impregnation of graphite grains with silver nanoparticles (AgNPs) is proposed for making a novel carbon paste electrode (CPE). The resulting material promotes direct electron transfer and direct biocatalysis of embedded heme protein. It is demonstrated that the impregnation of graphite grains with AgNPs of 16-25 nm, incorporated in a CPE, can promote measurable bio-electrochemical phenomena involving hemoglobin and myoglobin. Unlike other biosensors prepared with simple carbon, those based on carbon grains studded with AgNPs show well-defined and quasi-reversible voltammetric peak with heterogeneous electron transfer rate k(s) of approximately 0.037±0.007 and 0.013±0.005s(-1) for hemoglobin and myoglobin, respectively. The embedded proteins also retain their bio-catalytical activity for hydrogen peroxide and nitrite reduction with linear ranges of 0.5-3000 μM and 30-150 μM, sensitivities of 73.6±0.6nA μM(-1) and 5.72±0.11 nA μM(-1), and detection limits close to 0.08 μM and 5.80 μM, for these two analytes respectively. These results support the viability of this preliminary approach for the development of advanced third-generation biosensors.

β-Sonogel-Carbon electrodes: A new alternative for the electrochemical determination of catecholamines

In this work, a new alternative for the electrochemical determination of catecholamines based on beta-cyclodextrin-Sonogel-Carbon electrodes is reported. The incorporation of beta-CD and graphite in the preparation of the Sonogel-Carbon material leads to a modification of the electrode surface properties which causes a significant increase in the oxidation peak current of biomolecules such as dopamine, L-epinephrine, D,L-norepinephrine and catechol. This phenomenon might be attributed to the formation of an inclusion complex between beta-CD and the catecholamines. The amount of beta-CD necessary to form the Sonogel electrode was studied and optimization of electrochemical parameters, perm selectivity and mechanical stability of the sensor are discussed. Scanning electron microscopy and electrochemical impedance spectroscopy measurements were employed to characterize the electrical parameters and the structural properties of the new electrode surface, respectively. Cyclic voltammetry (CV) and Adsorptive differential pulse voltammetry (AdDPV) measurements were also used to explore the electrochemical behaviour of the electrode versus the quoted catecholamines. The beta-CD-Sonogel-Carbon electrode offers fast and linear responses towards dopamine, norepinephrine, epinephrine and catechol, with good and low detection limits: 0.164, 0.294, 0.699 and 0.059 micromol L(-1), respectively.