Double salts of ionic-liquid-based surfactants in microextraction: application of their mixed hemimicelles as novel sorbents in magnetic-assisted micro-dispersive solid-phase extraction for the determination of phenols.

Abstract

The use of mixed hemimicelles of ionic liquid (IL)-based surfactants in a magnetic-based micro-dispersive solid-phase extraction (m-μdSPE) approach is described. Not only is the symmetric monocationic IL-based surfactant 1,3-didodecylimidazolium bromide (C12C12Im-Br) studied for first time in m-μdSPE, but double-salt (DS) IL (DSIL)-based surfactants are also examined. Nine DSIL-based surfactants were formed by combination of C12C12Im-Br with other IL-based surfactants, including nonsymmetric monocationic and dicationic ILs combined at three different molar fractions. The analytical application was focused on the determination of a group of eight phenols, including bisphenolA, in water samples. The best results were obtained with the DSIL formed by C12C12Im-Br (molar fraction 0.5) and 1-hexadecyl-3-methylimidazolium bromide (C16MIm-Br), after proper optimization of the overall method in combination with high-performance liquid chromatography (HPLC) and diode-array detection (DAD). The optimum conditions for 100mL of water samples require a small amount (10mg) of Fe3O4 magnetic nanoparticles, a low content (5.0mg of C12C12Im-Br and 3.9mg of C16MIm-Br) of the selected DSIL, pH11, a sonication time of 2.5min, and an equilibration time of 5min with the aid of NdFeB magnets, followed by elution of phenols, evaporation, and reconstitution with 0.5mL of acetonitrile. The overall m-μdSPE-HPLC-DAD method is characterized for limits of detection down to 1.3μg · L(-1), intraday relative standard deviations lower than 13% (n = 3), and interday relative standard deviations lower than 17% (n = 9), with a spiking level of 15μg · L(-1); with enrichment factors between 15.7 and 141, and average relative recoveries of 99.9%.