Phenylboronic acid-functionalized magnetic metal-organic framework nanoparticles for magnetic solid phase extraction of five benzoylurea insecticides

Abstract

This research involves the construction of a phenylboronic acid-functionalized magnetic UiO-66 metal-organic framework (MOF) nanoparticle (CPBA@UiO-66@Fe₃O₄). Its design is primarily for the magnetic solid phase extraction (MSPE) of benzoylurea insecticides. An organic ligand, 2-amino terephthalic acid (2-ATPA), facilitated the introduction of amino groups while keeping the original crystal structure of UiO-66 intact. The constructed UiO-66 MOF showcases a porous structure and extensive surface area, thereby providing an optimal platform for further functionalization. The employment of 4-carboxylphenylboronic acid as a modifier notably amplified the extraction efficiency for benzoylureas. This improvement was due to the formation of B-N coordination and other secondary interactions. By integrating this with high-performance liquid chromatography (HPLC), we established a quantitative analytical method for benzoylurea insecticides. This method achieved a wide linear range (2.5–500 μg L⁻¹ or 5–500 μg L⁻¹), satisfactory recoveries (83.3–95.1%), and acceptable limits of detection (LODs: 0.3–1.0 μg L⁻¹). The developed method proved successful when applied to six tea infusion samples, representing China's six major tea categories. Semi-fermented and light-fermented tea samples demonstrated relatively higher spiking recoveries.