Selective cationic covalent organic framework for high throughput rapid extraction of novel polyfluoroalkyl substances.

Novel per- and polyfluoroalkyl substances (PFASs) raise global concerns due to their toxic effects on environment and human health. However, researches on analytical methods of novel PFASs are lacking. Here, a kind of selective cationic covalent organic framework (iCOF) was designed and loaded on the surface of cotton as an adsorbent. Then, a simple solid-phase extraction (SPE) method based on the cotton@iCOF was developed for high throughput rapid extraction of six novel PFASs in water samples, coupled with ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) determination. Several important SPE parameters, such as the amount of iCOF, sample pH, desorption conditions and salinity were systematically investigated. Under optimal conditions, the limits of detection and quantification of this SPE-UHPLC-MS/MS method were as low as 0.08-2.14 ng/L and 0.28-7.15 ng/L, respectively. The recoveries were 77.9-117.6 % for the tap water and surface water, and F-53 B in surface water were detected. Notably, this SPE process was rapid (1 h for 500 mL water sample) compared with commercial SPE (normal 2-3 h), owing to little resistance of cotton@iCOF and omission of nitrogen blowing process, and high throughput with 12 samples concurrently extracted. Additionally, various characterization means and density functional theory (DFT) calculations showed that ion-exchange effect, hydrophobic interaction, hydrogen bonding and ordered channel structure synergistically contributed to the PFASs adsorption on cotton@iCOF. The cotton@iCOF-based SPE method with simplicity, rapidity, selectivity and efficiency provided new research ideas for the analysis and control of ionic emerging pollutants in water.