Thoughtful design of a covalent organic framework with tailor-made polarity and pore size for the enrichment of bisphenols and their derivatives: Extraction performance, adsorption mechanism and toxicity evaluation

A stable, reusable and cost-effective covalent organic framework (COF) with medium polarity was successfully decorated on Fe3O4. The Fe3O4@COF contained tailor-made polarity and pore size that fitted well with bisphenols and their derivatives (BPs). When coupling magnetic solid-phase extraction (MSPE) with high-performance liquid chromatography (HPLC) detection, the Fe3O4@COF featured efficient recognition and enrichment for BPs due to π-π stacking, C–H⋯π interactions, pore-filling effect, dispersion force and hydrophobic interactions. Under optimized conditions, calibration plots exhibited good linearity (5–1000 ng mL−1), and limits of detection (LOD) ranged from 0.15 to 0.39 ng mL−1. The method was successfully employed in quantifying BPs in authentic lake and river water samples with satisfactory recoveries ranging from 81.4% to 120%. Molecular dynamics simulation revealed extraction mechanisms, and a microscopic behavior related to the clustering property of the emerging brominated compounds was first discovered. Ecotoxicological assessments of target pollutants were conducted from multiple aspects, highlighting the harmfulness of the chemicals and the significance of the analytical method. The proposed methodology offered sensitive detection and quantification, which was beneficial for the timely tracking of the concentration, transportation and distribution of BPs to better explore their environmental behavior and tackle contamination problems in complex environmental matrices. [Display omitted] •The designed COF, with lower cost, exhibits larger apertures than most COFs.•The clustering properties of bisphenol derivatives are first reported.•The pore size and polarity of the COF benefit the removal of clustered bisphenols.•The computer-aided design reduces trial and error in the application of extractants.•Toxicity studies highlight the harmfulness of emerging brominated chemicals.