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.