Detection of Several Carbohydrates Using Boron-doped Diamond Electrodes Modified with Nickel Hydroxide Nanoparticles.

In this work the electrooxidations of glucose, galactose, mannose, rhamnose, xylose and arabinose are studied at a nickel hydroxide nanoparticle modified boron-doped diamond electrode and compared to an unmodified electrode. These carbohydrates are very important in the second-generation ethanol production process. Nickel hydroxide modified boron-doped diamond was characterized by scanning electron microscopy and energy dispersive X-ray. Electrochemical impedance spectroscopy was employed to study the interface properties of surface-modified electrodes in the absence and presence of the carbohydrates. Limits of detection were 5.3 × 10(-5), 6.8 × 10(-5), 2.7 × 10(-4), 6.9 × 10(-5), 8.8 × 10(-5) and 2.6 × 10(-5) mol L(-1) for glucose, galactose, mannose, rhamnose, arabinose, xylose, respectively.

Electrooxidation and Determination of Dopamine Using a Nafion®-Cobalt Hexacyanoferrate Film Modified Electrode.

The electrocatalysis of dopamine has been studied using a cobalt hexacyanoferrate film (CoHCFe)-modified glassy carbon electrode. Using a rotating disk CoHCFe-modified electrode, the reaction rate constant for dopamine was found to be 3.5 × 105 cm³ mol-1 s-1 at a concentration of 5.0 × 10-5 mol L-1. When a Nafion® film is applied to the CoHCFe-modified electrode surface a high selectivity for the determination of dopamine over ascorbic acid was obtained. The analytical curve for dopamine presented linear dependence over the concentration range from 1.2 × 10-5 to 5.0 × 10-4 mol L-1 with a slope of 23.5 mA mol-1 L and a linear correlation coefficient of 0.999. The detection limit of this method was 8.9 × 10-6 mol L-1 and the relative standard deviation for five measurements of 2.5 × 10-4 mol L-1 dopamine was 0.58%.

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica for differential pulse adsorptive stripping analysis of nickel in ethanol fuel.

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica (SiAt-SPCPE) was applied to Ni(2+) determination in commercial ethanol fuel samples. The proposed method comprised four steps: (1) Ni(2+) preconcentration at open circuit potential directly in the ethanol fuel sample, (2) transference of the electrode to an electrochemical cell containing DMG, (3) differential pulse voltammogram registering and (4) surface regeneration by polishing the electrode. The proposed method combines the high Ni(2+) adsorption capacity presented by 2-aminothiazole organofunctionalized silica with the electrochemical properties of the Ni(DMG)(2) complex, whose electrochemical reduction provides the analytical signal. All experimental parameters involved in the proposed method were optimized. Using a preconcentration time of 20 min, it was obtained a linear range from 7.5 x 10(-9) to 1.0 x 10(-6) mol L(-1) with detection limit of 2.0 x 10(-9) mol L(-1). Recovery values between 96.5 and 102.4% were obtained for commercial samples spiked with 1.0 micromol L(-1) Ni(2+) and the developed electrode was totally stable in ethanolic solutions. The contents of Ni(2+) found in the commercial samples using the proposed method were compared to those obtained by graphite furnace atomic absorption spectroscopy by using the F- and t-test. Neither the F- nor t-values exceeded the critical values at 95% confidence level, confirming that there are not statistical differences between the results obtained by both methods. These results indicate that the developed electrode can be successfully employed to reliable Ni(2+) determination in commercial ethanol fuel samples without any sample pretreatment or dilution step.

Copper determination in ethanol fuel by differential pulse anodic stripping voltammetry at a solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica.

Solid paraffin-based carbon paste electrodes modified with 2-aminothiazole organofunctionalized silica have been applied to the anodic stripping determination of copper ions in ethanol fuel samples without any sample treatment. The proposed method comprised four steps: (1) copper ions preconcentration at open circuit potential directly in the ethanol fuel sample; (2) exchange of the solution and immediate cathodic reduction of the absorbate at controlled potential; (3) differential pulse anodic stripping voltammetry; (4) electrochemical surface regeneration by applying a positive potential in acid media. Factors affecting the preconcentration, reduction and stripping steps were investigated and the optimum conditions were employed to develop the analytical procedure. Using a preconcentration time of 20min and reduction time of 120s at -0.3V versus Ag/AgCl(sat) a linear range from 7.5x10(-8) to 2.5x10(-6)mol L(-1) with detection limit of 3.1x10(-8)mol L(-1) was obtained. Interference studies have shown a decrease in the interference effect according to the sequence: Ni>Zn>Cd>Pb>Fe. However, the interference effects of these ions have not forbidden the application of the proposed method. Recovery values between 98.8 and 102.3% were obtained for synthetic samples spiked with known amounts of Cu(2+) and interfering metallic ions. The developed electrode was successfully applied to the determination of Cu(2+) in commercial ethanol fuel samples. The results were compared to those obtained by flame atomic absorption spectroscopy by using the F-test and t-test. Neither F-value nor t-value have exceeded the critical values at 95% confidence level, confirming that there are no significant differences between the results obtained by both methods.

Simultaneous determination of neutral nitrogen compounds in gasoline and diesel by differential pulse voltammetry.

The presence of trace neutral organonitrogen compounds as carbazole and indole in derivative petroleum fuels plays an important role in the car's engine maintenance. In addition, these substances contribute to the environmental contamination and their control is necessary because most of them are potentially carcinogenic and mutagenic. For those reasons, a reliable and sensitive method was proposed for the determination of neutral nitrogen compounds in fuel samples, such as gasoline and diesel using preconcentration with modified silica gel (Merck 70-230 mesh ASTM) followed by differential pulse voltammetry (DPV) technique on a glassy carbon electrode. The electrochemical behavior of carbazole and indole studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF(4) 0.1molL(-1)) for indole (-2.27V) and carbazole (-2.67V) versus Ag|AgCl|KCl(sat) reference electrode. The proposed DPV method showed a good linear response range from 0.10 to 300mgL(-1) and a limit of detection (L.O.D) of 7.48 and 2.66mugL(-1) for indole and carbazole, respectively. The results showed that simultaneous determination of indole and carbazole presents in spiked gasoline samples were 15.8+/-0.3 and 64.6+/-0.9mgL(-1) and in spiked diesel samples were 9.29+/-1 and 142+/-1mgL(-1), respectively. The recovery was evaluated and the results shown the values of 88.9+/-0.4 and 90.2+/-0.8% for carbazole and indole in fuel determinations. The proposed method was also compared with UV-vis spectrophotometric measures and the results obtained for the two methods were in good agreement according to the F and t Student's tests.

Flow injection amperometric determination of procaine in pharmaceutical formulation using a screen-printed carbon electrode.

A rapid and simple method for procaine determination was developed by flow injection analysis (FIA) using a screen-printed carbon electrode (SPCE) as amperometric detector. The present method is based on the amine/hydroxylamine oxidation from procaine monitored at 0.80 V on SPCE in sodium acetate solution pH 6.0. Using the best experimental conditions assigned as: pH 6.0, flow rate of 3.8 mL min(-1), sample volume of 100 microL and analytical path of 30 cm it is possible to construct a linear calibration curve from 9.0x10(-6) to 1.0x10(-4) mol L(-1). The relative standard deviation for 5.0x10(-5) mol L(-1) procaine (15 repetitions using the same electrode) is 3.2% and detection limit calculated is 6.0x10(-6) mol L(-1). Recoveries obtained for procaine gave a mean values from 94.8 to 102.3% and an analytical frequency of 36 injections per hour was achieved. The method was successfully applied for the determination of procaine in pharmaceutical formulation without any pre-treatment, which are in good accordance with the declared values of manufacturer and an official method based on spectrophotometric analysis.

Study of electrochemical oxidation and determination of albendazole using a glassy carbon-rotating disk electrode.

In this work, electrochemical oxidation of albendazole (ABZ) was carried out using a glassy carbon-rotating disk electrode. Development of electroanalytical methodology for ABZ quantification in pharmaceutical formulations was also proposed by using linear sweep voltammetric technique. Electrochemical oxidation is observed for ABZ at E(1/2)=0.99 V vs. Ag/AgCl(sat), when an anodic wave is observed. Kinetic parameters obtained for ABZ oxidation exhibited a standard heterogeneous rate constant for the electrodic process equal to (1.51+/-0.07) x 10(-5) cm s(-1), with a alphan(a) value equal to 0.76. Limiting current dependence against ABZ concentration exhibited linearity on 5.0 x 10(-5) to 1.0 x 10(-2) mol l(-1) range, being obtained a detection limit of 2.4 x 10(-5) mol l(-1). Proposed methodology was applied to ABZ quantification in pharmaceutical formulations.

A disposable electrochemical sensor for the rapid determination of levodopa.

Levodopa (L-dopa), the biological precursor of catecholamines, is the most widely prescribed drug in the treatment of Parkinson's disease. The present work presents a proposal for the application of a gold screen-printed electrode an electrochemical sensor for monitoring L-dopa in stationary solution and a flow system. Using the electrooxidation of L-dopa at +0.63 V in acetate buffer pH 3.0 on a gold screen-printed electrode it is possible to obtain a linear calibration curve from 9.9 x 10(-5) to 1.2 x 10(-3) mol L(-1) and a detection limit of 6.8 x 10(-5) mol L(-1). Under amperometric conditions (E(app) = 0.8 V; flow rate = 14.1 mL min(-1); pH 3.0), an analytical calibration graph for l-dopa was obtained from 1.0 x 10(-6) mol L(-1) 6.6 x 10(-4) mol L(-1) with a detection limit of 9.9 x 10(-7) mol L(-1). The method was successfully applied to the determination of L-dopa in commercial dosage forms without any pre-treatment.

Determination of acetaldehyde in fuel ethanol by high-performance liquid chromatography with electrochemical detection.

The cyclic voltammetric behavior of acetaldehyde and the derivatized product with 2,4-dinitrophenylhydrazine (DNPHi) has been studied at a glassy carbon electrode. This study was used to optimize the best experimental conditions for its determination by high-performance liquid chromatographic (HPLC) separation coupled with electrochemical detection. The acetaldehyde-2,4-dinitrophenylhydrazone (ADNPH) was eluted and separated by a reversed-phase column, C18, under isocratic conditions with the mobile phase containing a binary mixture of methanol/LiCl(aq) at a concentration of 1.0 x 10(-3) M (80:20 v/v) and a flow rate of 1.0 mL min(-1). The optimum condition for the electrochemical detection of ADNPH was +1.0 V vs. Ag/AgCl as a reference electrode. The proposed method was simple, rapid (analysis time 7 min) and sensitive (detection limit 3.80 microg L(-1)) at a signal-to-noise ratio of 3:1. It was also highly selective and reproducible [standard deviation 8.2% +/- 0.36 (n = 5)]. The analytical curve of ADNPH was linear over the range of 3-300 mg L(-1) per injection (20 microL), and the analytical recovery was > 99%.

Electrochemical study of hydroxychloroquine and its determination in plaquenil by differential pulse voltammetry.

Hydroxychloroquine (HCQ) is a halogenated aminoquinoline that presents wide biological activity, often being used as an antimalarial drug. The electrochemical reduction of HCQ was investigated by cyclic voltammetry and chronoamperometry using glassy carbon electrodes. By cyclic voltammetry, in acid medium, only the cathodic peak was observed. The electrochemical behavior of this peak is dependent on pH and the electrodic process occurs through an E(r)C(i) mechanism. The electron number (1e) consumed in the reduction of HCQ was obtained by chronoamperometry. A method for the electrochemical determination of HCQ in pharmaceutical tablets was developed using differential pulse voltammetry. The detection limit reached was 11.2 microg ml(-1) of HCQ with a relative standard deviation of 0.46%. A spectrophotometric study of HCQ has been also carried out utilizing a band at 343 nm. The obtained detection limit and the relative standard deviation were 0.1 microg ml(-1) and 0.36%, respectively. The electrochemical methods are sufficiently accurate and precise to be applied for HCQ determination, in laboratorial routine, which can be used to determine the drug at low level.

Voltammetric characteristics of miconazole and its cathodic stripping voltammetric determination.

Miconazole is reduced at mercury electrode above pH 6 involving organometallic compound formation, responsible for an anomalous polarographic behavior. The electrodic process presents a large contribution of the adsorption effects. The drug can be determined by cathodic stripping voltammetry from 8.0 x 10(-8) to 1, 5 x 10(-6) molL-1 in Britton-Robinson buffer pH 8.0, when pre-accumulated for 30s at an accumulation potential of 0V. A relative standard deviation of 3.8% was obtained for ten measurements of 1.0 x 10(-7) molL-1 miconazole in B-R buffer pH 8.0 and a limit detection of 1, 7 x 10(-8) molL-1 was determined using 60s of deposition time and scan rate of 100 mVs-1. The proposed method is simple, precise and it was applied successfully for the determination of the miconazole in pure form and in commercial formulations, showing mean recoveries of 99.7-98.4%.

Voltammetric characteristics of miconazole and its cathodic stripping voltammetric determination

Miconazole is reduced at mercury electrode above pH 6 involving organometallic compound formation, responsible for an anomalous polarographic behavior. The electrodic process presents a large contribution of the adsorption effects. The drug can be determined by cathodic stripping voltammetry from 8.0 x 10-8 to 1, 5 x 10-6 molL-1 in Britton-Robinson buffer pH 8.0, when pre-accumulated for 30s at an accumulation potential of 0V. A relative standard deviation of 3.8 percent was obtained for ten measurements of 1.0 x 10-7 molL-1 miconazole in B-R buffer pH 8.0 and a limit detection of 1, 7 x 10-8 molL-1 was determined using 60s of deposition time and scan rate of 100 mVs-1. The proposed method is simple, precise and it was applied successfully for the determination of the miconazole in pure form and in commercial formulations, showing mean recoveries of 99.7-98.4 percent