Flow injection amperometric determination of persulfate in cosmetic products using a Prussian Blue film-modified electrode

A flow-injection system with a glassy carbon disk electrode modified with Prussian Blue film is proposed for the determination of persulfate in commercial samples of hair bleaching boosters by amperometry. The detection was obtained by chronoamperometric technique and the sample is injected into the electrochemical cell in a wall jet configuration. Potassium chloride at concentration of 0.1 mol L-1 acted as sample carrier at a flow rate of 4.0 mL min-1 and supporting-electrolyte. For 0.025 V (vs. Ag/AgCl) applied voltage, the proposed system handles ca. 160 samples per hour (1.0 10-4 - 1.0 10-3 mol L-1 of persulfate), consuming about 200 μL sample and 11 mg KCl per determination. Typical linear correlations between electrocatalytic current and persulfate concentration was ca. 0.9998. The detection limit is 9.0 10-5 mol L-1 and the calculated amperometric sensibility 3.6 103 μA L mol -1. Relative standard deviation (n =12) of a 1.0 10-4 mol L-1 sample is about 2.2%. The method was applied to persulfate determination in commercial hair-bleaching samples and results are in agreement with those obtained by titrimetry at 95% confidence level and good recoveries (95 - 112%) of spiked samples were found. © 2003 by MDPI.

Decolourization of anthraquinone reactive dye by electrochemical reduction on reticulated glassy carbon electrode

The electrochemistry reduction for the removal of Reactive Blue 4 (RB4) dye from aqueous solution using reticulated glassy carbon electrode is investigated. At pH < 8.0 the anthraquinone group of the RB4 dye are reduced in one cathodic step to hidroquinone after a reversible two-electron process involving a precedent two protons reaction. A stable semiquinone is detected by spectrophotometric technique. At pH > 8.0 the reduction process involves two reversible 2-electron steps, whose species are generated by a protonation equilibrium of anthraquinone group. The results shows that 60% of color removal was obtained after 3 hours of RB4 dye electrolysis at acidic and neutral conditions and only 37% at alkaline conditions. Simultaneously 64% of total organic carbon was removed after electrolysis at pH 2.0.

Voltammetric determination of dipyrone using a N,N′- ethylenebis(salicylideneaminato)oxovanadium(IV) modified carbon-paste electrode

The preparation and electrochemical characterization of a carbon paste electrode modified with N.N′-ethylenebis(salicylideneiminato) oxovanadium(IV) complex ([VO(Salen)]) as well as its behavior as electrocatalyst toward the oxidation of dipyrone were investigated. The electrochemical behavior of the modified electrode and the electrooxidation of dipyrone were explored using cyclic voltammetry. The voltammetric response of the modified electrode is based on two reactions. One electrochemical related to the oxidation of the metallic center of the [VO(Salen)] and the other involving the chemical redox process involving the oxidized form of the complex and the reduced form of dipyrone. The best voltammetric response was observed for a paste composition of 25% (m/m) [VO(Salen)], KCl solution pH from 5.5 to 8.0 as the electrolyte and potential scan rate of 10 mV s-1 in the presence of dipyrone. A linear voltammetric response for dipyrone was obtained in the concentration range from 9.9 × 106 to 2.8 × 10 -3 mol L-1, with a detection limit of 7.2 × 10 -6 mol L-1. Among of several compounds tested as potential interference, only ascorbic acid presented some interference. The proposed electrode is useful for the quality control and routine analysis of dipyrone in pharmaceutical formulations.

Screen-printed carbon electrode modified with poly-L-histidine applied to voltammetric determination of chromium (VI)

The present work reports the use of a screen-printed carbon electrode (SPCE) modified by poly-L-histidine film to determine chromium (VI). Stable films can be formed by direct addition of PH solution 1 % (w/v) on the electrode surface, followed by heating at 80°C during 5 min. Calibration curves can be constructed for Cr(VI) from 1.0 × 10-5 mol L-1 to 7.0 × 10-5 mol L-1 Cr (VI) in acetate buffer pH 4 using a preconcentration step of 60s at open circuit potential. A relative standard deviation of 3.2% was for five determination of 4.0 × 10 -5 mol L-1 Cr (VI). The method was successful applied to determination of Cr(VI) in wastewater samples from a leather dyeing industry. copyright The Electrochemical Society.

New methodology for pH measurements in fuel ethanol using glass electrode

Studies carried out with glass electrode in anhydrous ethanol and ethanol-water solutions for measuring pH values have shown that this parameter depends on the solution composition, the contact time with the solution, the utilized temperature, and the type of electrolyte used. It was also observed that the glass electrode behavior in an acid medium differs from an alkaline medium. These studies provided correction factors for pH values from 2 to 12, allowing the realization of proper measurements of the hydrogen ionic activity in the ethanol-water and anhydrous ethanol solutions. However, these correction factors could not be applied to the fuel ethanol. Alternatively, a new method was developed for the correction of the pH values, which can be applied in hydrous and anhydrous fuel ethanol samples. Copyright © 2011 by ASTM International.

Voltammetric determination of sulfite using graphite paste electrode modified with nanoparticles of copper pentacyanonitrosylferrate

Copper Pentacyanonitrosylferrate (NCuNP) nanoparticles were prepared in formamide solvent. The material was characterized by Infrared (FTIR), X-Ray Diffraction (XRD) and Ultraviolet-Visible (UV-Vis) Spectroscopy. The Cyclic Voltammogram (CV) the modified graphite paste electrode with NCuNP exhibits two redox couples with (Eθ,)1 = 0.29 and (E θ,)2 = 0.86 V attribute at Cu(I)/Cu (II) and Fe(II)(CN)5NO/Fe(III)(CN) 5NO processes, respectively (KCl = 1.0 mol L-1; v = 20 mV s-1). The redox couple with (Eθ,)2 presents an electrocatalytic response for sulfite. The modified graphite paste electrode gives a linear response of 7.0 × 10-4 to 3.0 × 10-2 mol L-1 (r = 0.998), for sulfite determination with Detection Limit (DL) of 1.76 × 10-3 mol L-1 and an amperometric sensitivity of 3.38 mA/mol L-1 and relative standard desviations ± 3% (n=3). ©The Electrochemical Society.

Electrochemical determination of antimalarial drug amodiaquine in maternal milk using a hemin-based electrode

Voltammetric analysis of amodiaquine using a hemin biosensor revealed a well-defined peak at 0.14 V (vs. Ag/AgCl), corresponding to the oxidation of amodiaquine at pH 7.0. The electrodic behavior indicated that the oxidation process was irreversible, and that it was controlled by diffusion. In addition to advantages such as high selectivity and sensitivity, the method developed could be used for the analysis of breast milk containing amodiaquine without any need for prior sample treatment, an important consideration in routine analysis laboratories. Measurements of the drug contained in breast milk were used to validate the technique. The detection limit for standard solutions was 3.30 mg L-1, and the quantification limit was 11.0 mg L-1. ©The Electrochemical Society.

Determination of Mg (II) in biodiesel by adsorptive stripping voltammetry at a mercury film electrode in the presence of sodium thiopentone

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

New label free CA125 detection based on gold nanostructured screen-printed electrode

This paper describes the optimisation and the analytical performances of a label-free impedimetric immunosensor for the detection of tumour marker CA125 based on gold nanoparticles modified screen-printed graphite electrode. Experimental conditions of each step for the developed immunosensor were studied and optimised. The immunosensor response varied linearly (r2 = 0.996) with antigen concentration between 0 and 100 U/mL. The estimated detection limit was 6.7 U/mL. The electrochemical immunosensor allowed unambiguous identification of CA125, while no significant non-specific signal was detected in the case of all negative controls. The analytical usefulness of the impedimetric immunosensor was finally demonstrated analysing serum samples. © 2012 Elsevier B.V. All rights reserved.

Voltammetric determination of ethyl acetate in ethanol fuel using a Fe 3+/Nafion®-coated glassy carbon electrode

A voltammetric method for the determination of ethyl acetate in ethanol fuel using a Fe3+/Nafion®-coated glassy carbon electrode (GCE) is proposed. The ethyl acetate present in the ethanol fuel was previously converted to acetohydroxamic acid via pretreatment with hydroxylamine chloride. The acetohydroxamic acid promptly reacted with the iron (III) present in the film, producing iron (III) acetohydroxamate, which presents a well-defined voltammetric peak current at -0.02 V. Optimization of the voltammetric parameters for the cyclic, linear sweep, square wave, and differential pulse modalities was carried out for this chemically-modified electrode. Square wave voltammetry afforded the best response for acetohydroxamic acid detection. The analytical curve for this species was linear from 9 to 100 μmol L 1 according to the following equation: ip (μA) = 0.27 + 2.55Cacetohydroxamic acid (μmol L 1), with linear correlation coefficient equal to 0.993. The technique presented limit of detection equal to 5.3 μmol L 1 and quantification limit of 17.6 μmol L 1. The proposed method was compared to the official method of ethyl acetate analysis (Gas Chromatography), and a satisfactory correlation was found between these techniques. © 2012 Elsevier Ltd. All rights reserved.

Electrochemical behavior and voltammetric determination of pyrazinamide using a poly-histidine modified electrode

Pyrazinamide (Pyrazinecarboxamide-PZA) is a drug that is used to treatment tuberculosis. In the present work, the voltammetric behavior of PZA was studied using a screen-printed modified electrode (SPCE). The modified electrode was constructed using poly-histidine films, and it showed an electrocatalytic effect, thus promoting a decrease in PZA reduction potential and improving the voltammetric response. Cyclic voltammetry and electrochemical impedance spectroscopy techniques have been employed in order to elucidate of the electrodic reaction. The results allowed the proposal that in the PZA reduction, a further chemical reaction occurs that corresponds to a second-order process which is subsequent to the electrode reaction. In addition, a sensitive voltammetric method was developed, and it was successfully applied for PZA determination in human urine samples. The best response was found using SPCE modified with poly-histidine prepared by histidine monomer electropolymerization (SPCE/EPH). The electroanalytical performance of the SPCE/EPH was investigated by linear sweep (LSV), differential pulse (DPV), and square wave voltammetry (SWV). A linear relationship between peak current and PZA concentrations was obtained from 9.0 × 10-7 to 1.0 × 10-4 mol L-1 by using DPV. The limit of detection at 5.7 × 10 -7 mol L-1 was estimated, and a relative standard deviation of the 5.0 × 10-6 mol L-1 of PZA of 10 measurement was 3.7%. © 2012 Elsevier B.V. All rights reserved.

Development of an electrochemical sensor based on nanostructured hausmannite-type manganese oxide for detection of sodium ions

The preparation and electrochemical characterization of hausmannite-type manganese oxide to use as a sensing material for sodium ion is described. This paper reports a new via synthetic to obtain of the hausmannite-type manganese oxide and its application in the construction of modified electrode as a voltammetric sensor. The electrochemical activity of hausmannite-type manganese oxide is controlled by intercalation/deintercalation of the sodium ions within the oxide lattice. The detection is based on the measurement of anodic current generated by oxidation of MnIII-MnIV at electrode surface. The best electrochemical response was obtained for a sensor composition of 20% (w/w) hausmannite oxide in the paste, a TRIS buffer solution of pH 6.0-7.0 and a scan rate of 50 mV s-1. A sensitive linear voltammetric response for sodium ions was obtained in the concentration range of 2.01 × 10 -5-2.09 × 10-4 mol L-1 with a slope of 355 μA L mmol-1 and a detection limit of 7.50 × 10 -6 mol L-1 using cyclic voltammetry. The use of hausmannite has significantly improved the selectivity of the sensor compared to the birnessite-type manganese oxide modified electrode. Under the working conditions, the proposed method was successfully applied to determination of sodium ions in urine samples. © 2013 Elsevier B.V.

Electrochemical behavior of ruthenium-hexacyanoferrate modified glassy carbon electrode and catalytic activity towards ethanol electrooxidation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Determination of Glycerol in Biodiesel Using a Nickel(II) Oxyhydroxide Chemically Modified Electrode by Cyclic Voltammetry

A glassy carbon electrode chemically modified with nickel oxyhydroxide from a nickel hexacyanoferrate (NiHCF) film was used to determine glycerol in biodiesel by cyclic voltammetry. The modified electrode exhibited a linear response to glycerol concentration in the range from 0.05 to 0.35mmol L-1, and a detection limit of 0.030mmol L-1. The glycerol concentration found in the biodiesel sample was 0.156mmol L-1. The method developed in this study showed a recovery of (100.3±5.0)%. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of Total Nitrosamines in Vegetables Cultivated Organic and Conventional Using Diamond Electrode

Vegetables were analyzed for total N-nitrosamines (NAs) and the influence of disinfection processes was assessed. Differences in NAs found in cabbage, spinach, and broccoli were determined by square wave voltammetry using a boron-doped diamond electrode. Analysis of samples showed that all samples contained detectable levels of NAs but the results indicated that organic contained less than conventionally grown products. The sum of the total NAs was higher in the cabbage samples, ranging between 2.8-3.1 ppb and lower in broccoli samples at 0.2-1.1 ppb. The method described is simple, rapid, selective, and sensitive. The results suggested that the disinfection process affects the level of NAs, in this manner affecting the level of human exposure to NAs. © 2012 Springer Science+Business Media New York.