RESUMO
In this paper, an alternative voltammetric method for the determination of elemental sulphur in cosmetic products is presented. It is based on the decrease of triphenylphosphine oxidation current in the presence of elemental sulphur by using a glassy carbon electrode. A solution of 2% (m/v) acetic acid and 0.6 mol L-1 sodium acetate in methanol was used as a supporting electrolyte. The experimental conditions for indirect determination of elemental sulphur were established. Using square-wave voltammetry, the analytical curve was linear in the elemental sulphur concentration range of 9.94-271 µmol L-1, with a detection limit of 2.59 µmol L-1. The method was successfully applied to determine elemental sulphur in soap bars and anti-acne cream, without any preliminary sample treatment, therefore, it is shortened and simplified. The results obtained with the indirect voltammetric method were not statistically different in comparison with a titrimetric one, at a 95% confidence level. Additionally, excellent recovery percentages were obtained, proving no matrix interferences.
RESUMO
The present paper describes the synthesis of molecularly imprinted polymer - poly(methacrylic acid)/silica and reports its performance feasibility with desired adsorption capacity and selectivity for cholesterol extraction. Two imprinted hybrid materials were synthesized at different methacrylic acid (MAA)/tetraethoxysilane (TEOS) molar ratios (6:1 and 1:5) and characterized by FT-IR, TGA, SEM and textural data. Cholesterol adsorption on hybrid materials took place preferably in apolar solvent medium, especially in chloroform. From the kinetic data, the equilibrium time was reached quickly, being 12 and 20 min for the polymers synthesized at MAA/TEOS molar ratio of 6:1 and 1:5, respectively. The pseudo-second-order model provided the best fit for cholesterol adsorption on polymers, confirming the chemical nature of the adsorption process, while the dual-site Langmuir-Freundlich equation presented the best fit to the experimental data, suggesting the existence of two kinds of adsorption sites on both polymers. The maximum adsorption capacities obtained for the polymers synthesized at MAA/TEOS molar ratios of 6:1 and 1:5 were found to be 214.8 and 166.4 mg g(-1), respectively. The results from isotherm data also indicated higher adsorption capacity for both imprinted polymers regarding to corresponding non-imprinted polymers. Nevertheless, taking into account the retention parameters and selectivity of cholesterol in the presence of structurally analogue compounds (5-α-cholestane and 7-dehydrocholesterol), it was observed that the polymer synthesized at the MAA/TEOS molar ratio of 6:1 was much more selective for cholesterol than the one prepared at the ratio of 1:5, thus suggesting that selective binding sites ascribed to the carboxyl group from MAA play a central role in the imprinting effect created on MIP.