An automated solid-phase microextraction method based on magnetic molecularly imprinted polymer as fiber coating for detection of trace estrogens in milk powder

A new automated solid-phase micro extraction (SPME) sampling method was developed for quantitative enrichment of estrogens (ES) from milk powder, using magnetic molecularly imprinted polymer (MMIP) as fiber coating. The method (MMIP-SPME) was built with several electromagnetic stainless steel fibers, placed in parallel for simultaneously extraction. The MMIP was synthesized using core-shell Fe3O4@SiO2 nanoparticles (NPs) as magnetic support. Estradiol (E2) was employed as the template molecule, acrylamide (AA) as functional monomer, and ethylene glycol dimethacrylate (EGDMA) as cross-linker. MMIP can be easily absorbed or desorbed from fibers when the current is turned on or off, creating magnetism. Compared to traditional MIP-SPME, the prepared procedure of MMIP-SPME is time-saving and organic solvent-free. The proposed device significantly improved the efficiency of separation and enrichment of estrogens from complex matrices thereby and facilitating the pretreatment steps by electromagnetically controlled extraction fibers to achieve full automation. Several experimental parameters were studied, including extraction and desorption kinetics, solution pH, desorption solution, ratio, and shuttle rate. The newly developed MMIP-SPME showed good sensitivity and high binding capacity, fast adsorption kinetics and desorption kinetics for estrone (E1), estradiol (E2), estriol (E3) and diethylstilbestrol (DES) under optimized conditions. The detection limits for the four estrogens were 1.5-5.5 ng g−1 with excellent reproducibility (RSD values less than 7.1%) when milk powder samples spiked with analytes at 20, 100 and 250 ng g−1 were studied.