Boric-Acid-Functionalized Covalent Organic Framework for Specific Enrichment and Direct Detection of cis-Diol-Containing Compounds by Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry.

Design and synthesis of a novel matrix that serves as highly selective adsorption material are significant for the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) analysis of small molecules in complicated biosamples. In this work, we presented a facile one-pot strategy for the synthesis of boric-acid-functionalized covalent organic frameworks (B-COFs) by using 2,4,6-trihydroxy-1,3,5-benzenetrialdehyde, benzidine, and 4-aminophenyl-boronic acid as ligands. Compared with bare COFs, the B-COFs have similar crystallinity, specific surface, and well-developed pore structure. The surface area and average pore size of B-COFs were 238.0 m/g and 1.2 nm, respectively. The resulting material was used as an adsorbent for selective enrichment of cis-diol-containing compounds based on an affinity reaction between phenylboronic acid and cis-diol. Using luteolin, riboflavin, and pyrocatechol as model analytes, the enrichment ability of B-COFs as a matrix was examined by MALDI-TOF MS assay, and its high selectivity against target analytes was obtained in the presence of 100 times more anti-nonspecific compounds than that even in the complicated biosample. The limits of detection for luteolin, riboflavin, and pyrocatechol were as low as fg/mL with B-COF enrichment. The B-COFs were further employed and validated for specific enrichment and direct detection of target analytes with complex samples such as human serum, milk, and Capsicum samples. Large surface area, numerous boric-acid active sites, and super stability make B-COFs with high enrichment capacity, high selectivity and sensitivity, satisfying reproducibility, and excellent applicability in MALDI-TOF MS assays.