Perfluoroalkyl-functionalized hyper-crosslinked polymers for efficient solid-phase microextraction of fluorinated...

Fluorinated liquid crystal monomers (FLCMs) have been identified as emerging organic pollutants because of their persistence, bioaccumulation potential, and toxicity. They have been observed in various environmental matrices and have attracted significant public concern. However, research on the development of functional materials and reliable methods for the highly efficient extraction and sensitive determination of FLCMs for assessing the risk levels in soil remains limited. Herein, two types of pentadecafluorooctanoyl (PF)-functionalized hyper-crosslinked polymers (HCPs), namely HCP_PF-TPB and HCP_PF-TPC, were synthesized by a facile and cost-effective Friedel-Crafts reaction. HCP_PF-TPB demonstrated superior extraction performance and was selected to prepare fiber coating for the efficient solid-phase microextraction (SPME) of FLCMs. In addition, the underlying adsorption mechanism was systematically revealed through experiments and density functional theory (DFT) calculations. Under optimal SPME conditions, HCP_PF-TPB coated SPME fiber combined with gas chromatography-mass spectrometry (GC-MS) method was proposed for sensitive detection of nine FLCMs in soil, affording high enrichment factors (1091-1760), wide linear range (0.05-100 μg kg^-1), and low detection limits (0.010-0.028 μg kg^-1). This work provides a simple strategy for the synthesis of perfluoroalkyl-functionalized HCPs and offers a reliable method for the efficient extraction and sensitive quantification of FLCMs in complex environmental matrices, thus promoting the resolution of FLCMs critical problems in the environment.