A pH-sensitive polymer based on the poly(styrene-alt-maleic anhydride) co-polymer serves as basis to develop a microextraction method (pH-HGME) in direct combination with high-performance liquid chromatography (HPLC) and fluorescence detection (FD) for the determination of seven organic compounds, including three polycyclic aromatic hydrocarbons (PAHs), three monohydroxylated PAHs and one alkylphenol, in urine. The method bases on the structural modification of the pH-sensitive polymer in the aqueous sample at a high pH value, followed by the formation and insolubilization of a hydrogel containing the preconcentrated analytes by decreasing the pH, and the direct injection of the hydrogel-rich phase in the HPLC-FD system. The optimization of the main variables permitted the selection of low amounts of aqueous sample (10 mL), which was mixed with 10 mg of co-polymer also present in a low volume (150 µL) of concentrated NaOH. The method further requires the addition of 200 µL of concentrated HCl, 3 min of stirring, and 15 min of centrifugation. This pH-HGME-HPLC-FD method presented low limits of detection, ranging from 0.001 µg L-1 to 0.09 µg L-1 in ultrapure water, average relative recoveries of 96.9% for the concentration level of 0.60 µg L-1, and enrichment factors between 1.50 and 17.7. The proposed method also exhibited high precision, with intermediate relative standard deviations lower than 16% for a concentration level of 0.60 µg L-1. The developed pH-HGME-HPLC-FD method performed adequately when analyzing two human urine samples provided by a non-smoker male and a smoker female, respectively. One of the target analytes (2-hydroxynaphthalene) was quantified in both samples using the standard addition method, with a predicted concentration of 7.3 ± 0.4 µg L-1 in the non-smoker male urine and 19.3 ± 0.6 µg L-1 in the smoker female urine.
Keywords: Hydrogel; Liquid chromatography; Microextraction; Polycyclic aromatic hydrocarbons; Urine; pH-sensitive polymer.
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