A simple solvothermal process for fabrication of a metal-organic framework with an iron oxide enclosure for the determination of organophosphorus pesticides in biological samples.

An active magnetic metal-organic framework (MOF) hybrid material was prepared using a novel in situ solvothermal method in the presence of magnetite (Fe3O4) particles, that holds much promise for large-scale synthesis. MIL-101(Fe), an iron terephthalate with pore structure and high resistance to water and common solvents, was functionalized as a model with superparamagnetic qualities, using Fe3O4. The electrostatic interaction between Fe3O4 and metal ions was thereby used to chemically stabilize magnetic nanoparticles, and thus MOF crystals were uniformly enclosed by Fe3O4 to form a homogeneous magnetic product identified as a Fe3O4/MIL-101 composite. This hybrid material with magnetic susceptibility but with the lowest possible loading amount of Fe3O4 was examined, and its potential application for magnetic solid-phase extraction of six organophosphorus pesticides (OPPs) from human hair and urine samples, followed by gas chromatography analysis, was assessed. The main effect parameters including solution ionic strength, desorption solvent, extraction time and desorption time were investigated in sequence. Under optimized conditions, this method showed low detection limits (0.21-2.28 ng/mL), wide linearity, and good precision (1.8-8.7% for intra-day, 2.9-9.4% for inter-day). The matrix interference produced by hair or urine could be effectively eliminated using this method, and satisfactory recoveries of the spiked samples were 76.8-94.5% and 74.9-92.1%, respectively, indicating that the Fe3O4/MIL-101 sorbents are feasible for the analysis of trace analytes from biological samples.