Eletroanálise de derivados acetaldeído com hidrazina e determinação em amostras de álcool combustível por voltametria de onda quadrada

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

Eletroanálise de corantes alimentícios: determinação de índigo carmim e tartrazina

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

Determinação de zinco em álcool combustível opr voltametria de redissolução anódica

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

Análise voltamétrica do corante têxtil do tipo antraquinona empregando eletrodos de carbono impresso

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

Eletrodo modificado com filme de poli aminoácido para determinação de hidrazina em água de caldeira

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

Adsorptive potentiometric stripping analysis of nucleic acids at mercury electrodes

The application of adsorptive stripping potentiometry to the reductive detection of nucleic acids at mercury electrodes is reported. Compared to analogous voltammetric stripping modes, constant current potentiometric stripping analysis (PSA) effectively addresses the hydrogen discharge background problem, and hence greatly improves the characteristics of the superimposed cytosine/adenine (CA) reduction peak. Compared to earlier schemes for trace measurements of nucleic acids at mercury or carbon electrodes that rely on anodic signals arising from the guanine residue, convenient quantitation can now be carried out in connection with the cytosine and adenine residues. Variables influencing the adsorptive PSA response are explored and optimized. With five minute accumulation, the detection limits for tRNA, ssDNA and dsDNA are 30 mu g l(-1), 60 mu g l(-1) and 2 mg l(-1), respectively. Such different values reflect the strong dependence of the PSA CA signal upon the nucleic-acid structure. This allows the quantitation of ssDNA or tRNA in the presence of dsDNA, and offers new possibilities for electrochemical studies of DNA structure and interactions.

Determination of brilliant blue FCF in the presence and absence of erythrosine and quinoline yellow food colours by cathodic stripping voltammetry

A study of the voltammetric behaviour of the food colours brilliant blue FCF (C.I. 42090), erythrosine (C. I. 45430) and quinolin e yellow (C. I. 47005) in the pH range 2-10 have been carried out by cathodic stripping voltammetry. At pH 4.5 (acetate buffer) with an accumulation potential of 0 V and accumulation time of 30 s, the voltammograms presented well-defined reduction peaks at potential - 0.76 V for brilliant blue FCF, - 0.85 V for quinoline yellow and - 0.54 V for erythrosine. Linear calibration graphs were obtained from 8 to 80 mug l(-1) brilliant blue, from 4 to 43 mug l(-1) quinoline yellow and from 10 to 70 mug l(-1) erythrosine. The method has been successfully applied to identify and quantify binary mixtures of these dyes and applied for determining brilliant blue FCF in commercial food products.

Simultaneous determination of zinc, copper, lead, and cadmium in fuel ethanol by anodic stripping voltammetry using a glassy carbon-mercury-film electrode

A new, versatile, and simple method for quantitative analysis of zinc, copper, lead, and cadmium in fuel ethanol by anodic stripping voltammetry is described. These metals can be quantified by direct dissolution of fuel ethanol in water and subsequent voltammetric measurement after the accumulation step. A maximum limit of 20% (v/v) ethanol in water solution was obtained for voltammetric measurements without loss of sensitivity for metal species. Chemical and operational optimum conditions were analyzed in this study; the values obtained were pH 2.9, a 4.7-mum thickness mercury film, a 1,000-rpm rotation frequency of the working electrode, and a 600-s pre-concentration time. Voltammetric measurements were obtained using linear scan (LSV), differential pulse (DPV), and square wave (SWV) modes and detection limits were in the range 10(-9)-10(-8) mol L-1 for these metal species. The proposed method was compared with a traditional analytical technique, flame atomic absorption spectrometry (FAAS), for quantification of these metal species in commercial fuel ethanol samples.

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 ErCi mechanism. The electron number (le) 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 mug 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 mug 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. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Simultaneous determination of quinoline and pyridine compounds in gasoline and diesel by differential pulse voltammetry

The presence of trace basic organonitrogen compounds such as quinoline and pyridine in derivative petroleum fuels plays an important role in maintaining the engines of vehicles. However, these substances can contaminate the environment and so must be controlled because most of them are potentially carcinogenic and mutagenic. For these reasons, a reliable and sensitive method was developed for the determination of basic nitrogen compounds in fuel samples such as gasoline and diesel. This method utilizes preconcentration on an ion-exchange resin (Amberlyte IR - 120 H) followed by differential pulse voltammetry (DPV) on a glassy carbon electrode. The electrochemical behavior of quinoline and pyridine as 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) 0.1 mol L-1) for quinoline (-1.95 V) and pyridine (-2.52 V) vs. Ag vertical bar AgCl vertical bar KClsat reference electrode. The proposed DPV method displayed a good linear response from 0.10 to 300 mg L-1 and a limit of detection (LOD) of 5.05 and 0.25 mu g L-1 for quinoline and pyridine, respectively. Using the method of standard additions, the simultaneous determination of quinoline and pyridine in gasoline samples yielded 25.0 +/- 0.3 and 33.0 +/- 0.7 mg L-1 and in diesel samples yielded 80.3 +/- 0.2 and 131 +/- 0.4 mg L-1, respectively. Spike recoveries were 94.4 +/- 0.3% and 10 +/- 0.5% for quinoline and pyridine, respectively, in the fuel determinations. This proposed method was also compared with UV-vis spectrophotometric measurements. Results obtained for the two methods agreed well based on F and t student's tests.

Preconcentration of rutin at a poly glutamic acid modified electrode and its determination by square wave voltammetry

The voltammetric determination of rutin in 0.04 mol l(-1) B-R buffer (pH 4.0) by square wave voltammograms (+0.41 V vs. Ag/AgCl(sat.)) at a poly glutamic acid modified glassy carbon electrode was found to be several orders of magnitude lower than that on a bare glassy carbon electrode. Rutin can be preconcentrated on the films of poly glutamic acid and presented linear relationship from concentration of 7 x 10(-7) to 1 x 10(-5) mol l(-1) in 0.04 mol l(-1) B-R buffer pH 4.0. The method was successfully applied to the determination of rutin in pharmaceutical formulation without any pretreatment.

Dissociation and electrooxidation of primaquine diphosphate as an approach to the study of anti-chagas prodrugs mechanism of action

This paper describes the voltammetric behavior of primaquine as a previous support to the further understanding of the delivery and action mechanisms of its respective synthesized prodrugs. There are few papers describing the drug behavior and most of the time no correlation between oxidation process and pH is done. Our results showed that primaquine oxidation is a one-step reaction involving two electrons with the charge transfer process being strongly pH-dependent in acid medium and pH-independent in a weak basic medium, with the neutral form being easily oxidized.This leads to the conclusion that quinoline nitrogen ring neutralization is a determinant step to the formation of the oxidized primaquine form. The existence of a relationship between the primaquine dissociation equilibrium and its electrooxidation process is shown.This work points the importance of voltammetric methodology as a tool for further studies on quantitative relationship studies between chemical structure and biological activity (QSAR) for electroactive drugs. (C) 2000 Elsevier B.V. S.A. All rights reserved.

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) 0.1 mol L-1) for indole (-2.27 V) and carbazole (-2.67 V) versus Ag vertical bar AgCl vertical bar KClsat reference electrode. The proposed DPV method showed a good linear response range from 0.10 to 300 mg L-1 and a limit of detection (L.O.D) of 7.48 and 2.66 mu g L-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 +/- 0.9 mg L-1 and in spiked diesel samples were 9.29 +/- 1 and 142 +/- 1 mg L-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. (C) 2007 Elsevier B.V. All rights reserved.

Application of a glassy carbon electrode modified with poly(glutamic acid) in caffeic acid determination

Glassy carbon electrodes were coated with films of poly( glutamic acid) ( PG), and the modified electrode proved to be very effective in the oxidation of caffeic acid. The performance of the film was also tested with ascorbic acid, coumaric acid, ferulic acid, sinapic acid and chlorogenic acid. At pH 5.6, all the hydroxycinnamic acids yield a higher peak current intensity when oxidized after incorporation in the PG-modified electrode, and only the oxidation of ascorbic acid exhibits overpotential reduction. At pH 3.5 only caffeic and chlorogenic acid are incorporated in the modified electrode and exhibit a well-defined oxidation wave at +0.51 V and +0.48 V, which is the base for their determination. Linear calibration graphs were obtained from 9 x 10(-6) mol L-1 to 4 x 10(-5) mol L-1 caffeic acid by linear voltammetric scan and from 4 x 10(-6) mol L-1 to 3 x 10(-5) mol L-1 by square wave voltammetric scan. The method was successfully applied to the determination of caffeic acid in red wine samples without interference from other hydroxycinnamic acids or ascorbic acid.

Determination of iodide and idoxuridine at a glutaraldehyde-cross-linked poly-L-lysine modified glassy carbon electrode

The detection limit (about 0.017 mu g mL(-1)) for voltammetric determination of iodide (peak at +0.87 V vs. Ag/AgCl at pH 2) at a glutaraldehyde-cross-linked poly-L-lysine modified glassy carbon electrode involving oxidation to iodine was found to be several orders of magnitude lower than that for the voltammetric determination on a bare glassy carbon electrode. This method was applied successfully to the determination of iodide in two medicinal formulations. Idoxuridine was determined indirectly at the same electrode by accumulating it first at -0.8 V vs. Ag/AgCl. At this potential the C-I bond in the adsorbed idoxuridine is reduced giving iodide, which is then determined at the modified electrode. The method was successfully applied to the determination of idoxuridine in a urine sample.