Triblock copolymer-grafted restricted access materials with zwitterionic polymer outer layers for highly efficient extraction of fluoroquinolones and exclusion of proteins.

High-selectivity and high-exclusion restricted access materials (RAMs) benefit the analysis of biological samples. Herein, triblock copolymer-functionalized poly(4-vinylbenzyl chloride-co-divinylbenzene) (PVBC/DVB) microspheres were prepared via the sequential surface-initiated atom radical polymerization of hydrophobic styrene (St), ionic vinylimidazole (VIm), and zwitterionic sulfobetaine methacrylate (SBMA), affording RAMs with multiple interaction-adsorption sites and zwitterionic polymer exclusion sites on the internal and external surfaces of PVBC/DVB. The preferential extraction of fluoroquinolones (FQs) is realized based on the hydrophobic/π-π/ion exchange interactions due to the grafted poly-St-VIm, and the zwitterionic poly-SBMA block in the triblock copolymers can efficiently exclude various proteins. A sensitive detection method for FQs in chicken was established by solid phase extraction with RAMs as adsorbent combined with UPLC-MS/MS, achieving wide linearity (2.0-200.0 ng mL-1), low limit of detection (0.5 µg kg-1) and limit of quantification (1.5 µg kg-1), and good inter- and intraday precision with satisfactory recoveries (104.1%-117.7% and 115.3%-121.2% with RSDs < 12%).