Flower-like calix[6]arene-based covalent organic framework for membrane extraction of sulfonamides in animal-derived food through host-guest interaction prior to determination with ultra-high performance liquid chromatography-tandem mass spectrometry.

Supramolecular macrocycle-based covalent organic frameworks (COFs) are promising adsorbents for adsorption of hazards due to their host-guest recognition property. However, most supramolecular macrocycles are conformationally flexible, making them challenging to introduce into COFs. In this work, a calix[6]arene-based COF (CX6-BD COF) was fabricated with a unique flower-like morphology and high crystallinity. Especially, the cavity of CX6 exhibited host-guest inclusion interaction for sulfonamides (SAs), which was verified by quantum chemistry calculation. The integration of the porosity of COFs with the recognition cavity of CX6 made CX6-BD COF display excellent enrichment performance for SAs, with good enrichment factors (EFs) between 77 and 96. The material was employed as an adsorbent for COF membrane filter extraction, coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) to simultaneously enrich and determine seven SAs in animal-derived food. The analytical method showed a wide linear range (0.01-100 µg/L and 0.05-100 µg/L) and low detection limits (3-10 ng/L). The established method was successfully applied to sensitively determine SAs in chicken, pork and beef samples, which achieved satisfactory recoveries (73.8-113%). These results demonstrated CX6-BD COF has good application potential in determination of trace and ultra-trace SAs in complex food matrices as an adsorbent.