Highly efficient nanocomposites based on molecularly imprinted magnetic covalent organic frameworks for selective extraction of bisphenol A from liquid matrices.

Highly efficient nanocomposites, hydrophobic molecularly imprinted magnetic covalent organic frameworks (MI-MCOF), have been farbricated by a facile Schiff-base reaction. The MI-MCOF was based on terephthalaldehyde (TPA) and 1,3,5-tris(4-aminophenyl) benzene (TAPB) as functional monomer and crosslinker, anhydrous acetic acid as catalyst, bisphenol AF as dummy template, and NiFe2O4 as magnetic core. This organic framework significantly reduced the time consumption of conventional imprinted polymerization and avoided the use of traditional initiator and cross-linking agents. The synthesized MI-MCOF exhibited superior magnetic responsivity and affinity, as well as high selectivity and kinetics for bisphenol A (BPA) in water and urine samples. The equilibrium adsorption capacity (Qe) of BPA on the MI-MCOF was 50.65 mg g-1, which was 3-7-fold higher than of its three structural analogues. The imprinting factor of BPA reached up to 3.17, and the selective coefficients of three analogues were all > 2.0, evidencing the excellent selectivity of fabricated nanocomposites to BPA. Based on the MI-MCOF nanocomposites, the magnetic solid-phase extraction (MSPE), combined with HPLC and fluorescence detection (HPLC-FLD), offered superior analytical performance: wide linear range of 0.1-100 μg L-1, high correlation coefficient of 0.9996, low limit of detection of 0.020 μg L-1, good recoveries of 83.5-110%, and relative standard deviations (RSDs) of 0.5-5.7% in environmental water, beverage, and human urine samples. Consequently, the MI-MCOF-MSPE/HPLC-FLD method provides a good prospect in selective extraction of BPA from complex matrices while replacing traditional magnetic separation and adsorption materials.