Supramolecular Solvent-Based Vortex-Assisted Hollow Fibre Liquid-Phase Microextraction Technique Combined With High Performance Liquid Chromatography for the Determination of Estrogens in Milk Samples

Abstract

A fast, simple, environmental friendly and strong sample clean-up ability method for the determination of three estrogens (17β-estradiol (17β-E2), estrone (E1), and diethylstilbestrol (DES)) in milk samples has been developed by using supramolecular solvent-based vortex-assisted hollow fibre liquid-phase microextraction (SS-VA-HF-LPME) and high performance liquid chromatography. Method is based on estrogens was extracted from aqueous samples into a supramolecular solvent which were made up of n-octanol and ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM] BF4) impregnated in the wall pores and also filled inside the porous polypropylene hollow fiber membrane followed by vortex-mixing. The supramolecular solvent has better compatibility with the polarity of target analytes and the driving forces for the extraction include hydrogen bonding, hydrophobic and π-cation interactions between the analytes and the vesicular aggregates, thereby leading to high recoveries. Vortex can provide mild and effective mixing of sample solution and increase the contact between analytes and boundary layers of the hollow fibre. Therefore the mass transfer rate was enhanced. The parameters that affect the recoveries were studied and optimized. HF of 4 cm length was used and the pH 4.0 was employed. The percentages of n-octanol and [BMIM]BF4 were 10% and 3%, respectively. The extraction equilibrium time was 4 min. The method provided good linearity (andgt;0.998), repeatability (RSD% = 1.24–4.36), low detection limit (0.10–0.22 ng mL−1), and high enrichment factor (330).