Fabrication of a core-shell porphyrin-based magnetic covalent organic framework for effective extraction of PCPs in a wide polarity range

A novel porphyrin-based magnetic covalent organic framework (PCOF) was first reported by using a facile synthetic procedure. The Fe₃O₄@NH₂@PCOF nanospheres were utilized to effectively extract personal care products in a wide polarity range (log K_ow values from 1.96 to 7.60). The successful magnetic solid-phase extraction (MSPE) of target analytes could be ascribed to the sufficient oxygen-, nitrogen- and phenyl-containing functional groups of the COF layer, which are demonstrated to be of good compatibility with pollutants exhibiting different polarities by using molecular dynamics simulations, independent gradient model analysis and various characterizations. The MSPE extraction efficiency was enhanced by optimizing key parameters. The findings indicated that the method had a wide linearity range (1-500 ng mL^-1 for parabens and UV filters) and low detection limits (0.4-0.9 ng mL^-1 for parabens and 0.2-0.6 ng mL^-1 for UV filters). The accuracy was reflected by recoveries ranging from 74% to 114%. Satisfactory intra- and inter-day precisions from 3.0% to 9.8% and 0.5%-9.1% were obtained. Overall, the proposed MSPE-HPLC method is accurate and reliable for identifying parabens as well as UV filters in wastewater and swimming pool water. The potential of the method for evaluating human exposure risk was unfolded.