Determination of fenthion and fenthion-sulfoxide, in olive oil and in river water, by square-wave adsorptive-stripping voltammetry.

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil. Due to the fact that fenthion does not give any electrochemical signal at mercury electrode, the method has been based on a previous oxidation of fenthion to its metabolite, fenthion-sulfoxide, by using KMnO(4). The metabolite gives rise to a peak due to an adsorptive-reductive process at -0.786 V. Fenthion is isolated from olive oil by carrying out a solid-liquid extraction procedure using silica cartridge, followed by a liquid-liquid partitioning with acetonitrile. The detection limit in olive oil is 78.8 ng g(-1) and recoveries for four levels of fortification are ranged from 85% to 109%. On the other hand, it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide, in river water. Pesticides are isolated from water by carrying out a liquid-liquid partitioning with trichloromethane. The detection limits are 0.41 ng g(-1) and 0.44 ng g(-1), for fenthion and fenthion-sulfoxide, respectively. Recoveries for three levels of fortification are ranged from 96% to 103% for fenthion and 94% to 104% for fenthion-sulfoxide.

Square wave adsorptive stripping voltametric determination of the mixture of nalidixic acid and its main metabolite (7-hydroxymethylnalidixic acid) by multivariate methods and artificial neural network.

Nalidixic acid (NA) and its main metabolite, 7-hydroximethylnalidixic acid (OHNA), are quinolones antibacterial used as agents used for the treatment of urinary tract infection. For both compounds an adsorption process on a hanging mercury electrode (HMDE). On this basis, a square wave adsorptive stripping voltammetry (SWadSV) method has been developed for the individual and simultaneous determination of NA and OHNA. The variables that affect to accumulation process, such as concentration of perchloric acid, accumulation potential and accumulation time have been optimised by using an experimental design (concretely a Box-Behnken design with three levels) together with the response surface methodology (RSM). Calibration curves were linear in the range (0-1.38)x10(-7)molL(-1) for NA and (0-3.23)x10(-8)molL(-1) for OHNA, in the optimized conditions, with detection limits of 9.48x10(-9)molL(-1) and 8.06x10(-10)molL(-1) for NA and OHNA, respectively. The method was applied to urine samples containing only one of the analytes with satisfactory recoveries. As the voltammetric signals of these compounds show a high overlapping, different chemometric methods, such as classical least squares (CLS), partial least squares (PLS), principal component regression (PCR) and artificial neural network (ANN) have been used for the resolution of the mixture. The analysis of these compounds in urine samples were carried out using the different chemometric tools and the best recoveries were obtained by using ANN. No pre-treatment of the sample was necessary.

Comparison of different fluorimetric signals for the simultaneous multivariate determination of tocopherols in vegetable oils.

This paper deals with the simultaneous determination of the quaternary mixture of tocopherols (alpha-, beta-, gamma-, and delta-T) performed using fluorimetric techniques and partial least squares (PLS-1) multivariate analysis. In this study, PLS-1 was applied to matrices made up of fluorescence excitation and emission spectra (EEM) and with fluorescence excitation, emission, and synchronous spectra (EESM) of tocopherols dissolved in hexane: diethyl ether (70:30 v/v). A calibration set of 55 samples based in a central composite plus a full factorial plus a fractionated factorial design was constructed. When synthetic samples were analyzed, recoveries around 100% were obtained and detection limits were calculated using EEM and EESM. For the analysis of the oils, the samples, diluted in hexane, were cleaned in silica cartridges and tocopherols were eluted with hexane: diethyl ether (90:10 v/v). The developed method was applied to different edible oils. The results are satisfactory for alpha-, beta-, and gamma-, but they are worse for delta-T.

Determination of sulphamethoxazole by photochemically induced fluorescence in drugs and milk.

A new first-derivative photochemically induced fluorescence (D-PF) method is proposed for the determination of sulphamethoxazole (SMXZ) in milk. A 50:50 (v/v) methanol: water medium, UV irradiation time of 2 min, and pH 5.70 were fixed. Standard addition method was used with the derivative spectra of the increase spectra as analytical signal. For determination in drugs, direct increase of fluorescence signal measure is used. In both cases the method is suitable for SMXZ concentrations comprised between 0.5 and 2.5 ppm.