Highly efficient nanocomposites based on molecularly imprinted magnetic covalent organic frameworks for selective...

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 (Q_e) 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.