Tunable Fluorine-Functionalized Scholl-Coupled Microporous Polymer for the Selective Adsorption and Ultrasensitive Analysis of Environmental Liquid-Crystal Monomers.

Abstract

Liquid-crystal monomers (LCMs), especially fluorinated biphenyls and analogues (FBAs), are identified to be an emerging generation of persistent organic pollutants. However, there is a dearth of information about their occurrence and distribution in environmental water and lacustrine soil samples. Herein, a series of fluorine-functionalized Scholl-coupled microporous polymers (FSMP-X, X = 1-3) were designed and synthesized for the highly efficient and selective enrichment of FABs. Their hydrophobicity, porosity, chemical stability, and adsorption performance (capacity, rate, and selectivity) were regulated preciously. The best-performing material (FSMP-2) was employed as the on-line fluorous solid-phase extraction (on-line FSPE) adsorbent owing to its high adsorption capacity (313.68 mg g-1), fast adsorption rate (1.05 g h-1), and specific selectivity for FBAs. Notably, an enrichment factor of up to 590.2 was obtained for FSMP-2, outperforming commercial C18 (12.6-fold). Also, the underlying adsorption mechanism was uncovered by density functional theory calculations and experiments. Based on this, a novel and automated on-line FSPE-high-performance liquid chromatography method was developed for ultrasensitive (detection limits: 0.0004-0.0150 ng mL-1) and low matrix effect (73.79-113.3%) determination of LCMs in lake water and lacustrine soils. This study offers new insight into the highly selective quantification of LCMs and the first evidence for their occurrence and distribution in these environmental samples.