Multivariate surface self-assembly strategy to fabricate ionic covalent organic framework surface grafting monolithic sorbent for enrichment of aristolochic acids prior to high performance liquid chromatography analysis

Herein, an ionic covalent organic framework (iCOF) surface grafting monolithic sorbent was prepared by the multivariate surface self-assembly strategy for in-tube solid-phase microextraction (SPME) of trace aristolochic acids (AAs) in serum, traditional Chinese medicines (TCMs) and Chinese patent drug. Via adjusting the proportion of ionic COF building block during the self-assembly, the density of quaternary ammonium ions in the iCOF was modulated for the enhanced adsorption of AAs. The successful preparation of iCOF surface grafting monolithic sorbent was confirmed by different means. A multiple mode mechanism involving π-π stacking, hydrophobic, electrostatic and hydrogen-bonding interactions was primarily attributed to the adsorption. Several in-tube SPME operating conditions, such as the dosage of ionic COF building block, ACN percentage and TFA percentage in the sampling solution, ACN percentage and TFA percentage in eluent and the collection time span, were optimized to develop the online in-tube SPME-HPLC method for analysis of AAs. Under the optimized conditions, a good linearity was obtained in the concentration range of 2 - 1000 ng/mL for target AAs in serum samples, the limits of detection (LODs) were less than 10 ng/mL, while the recoveries ranged from 90.3% to 98.7% with RSDs (n=5) below 7.9%. This study developed a feasible approach to iCOF functionalized monolithic sorbent for SPME and further exhibited the vast potential for the application of COF based monolithic sorbent in sample preparation.