Fluorine-Functionalized Covalent-Organic-Framework-Coated Stir Bar for the Extraction of Benzoylurea Insecticides in Pear Juice and Beverage Followed by High-Performance Liquid Chromatography–Ultraviolet Detection

A fluorinated covalent organic framework (COF), named F-COF, was fabricated via simple room-temperature synthesis. With the characteristics of rich fluorine atoms, hydrophobicity, and large conjugated structure, F-COF was evaluated for the extraction of five benzoylurea insecticides (BUs) containing fluorine atoms, benzene ring, and urea bridge. Specifically, F-COF-coated stir bars were prepared by physical adhesion and exhibited higher extraction recovery (73–93 versus 40–85%) toward BUs than commercial stir bars in a shorter extraction time (50 min versus 24 h). The adsorption behavior of BUs on F-COF was explored, and it was assumed that the halogen bond (O–F), hydrophobic interaction, electrostatic interaction, and π–π stacking contributed to the adsorption. On the basis of it, a method combining stir bar sorptive extraction with liquid chromatography–ultraviolet detector was developed for trace analysis of five BUs. Under the optimal conditions, the limits of detection for BUs were found to be 0.301–0.672 μg/L, with the linear range of 1.0/2.0–500 μg/L and relative standard deviations of <8.0% (c = 5 μg/L and n = 7). The accuracy of the proposed method was validated by the recovery test, and the recoveries of target BUs in spiked pear juice and pear beverage were 82.0–113 and 84.0–112%, respectively.