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.