Construction of Magnetic Covalent Organic Frameworks with Inherent Hydrophilicity for Efficiently Enriching Endogenous Glycopeptides in Human Saliva

In this work, a magnetic covalent organic framework (COF) with inherent hydrophilicity (denoted mCTpBD) was synthesized through interface deposition of a hydrophilic COF shell on amino group-functionalized magnetite particles via the reaction between a carboxyl group-containing monomer and benzidine. Thanks to the superior hydrophilicity, appropriate porous structure, and easy magnetic separation, the resulting mCTpBD exhibited excellent performance in conveniently enriching glycopeptides from standard samples with a high sensitivity of 0.5 fmol μL–1 and strong size-exclusion effect of up to 1:1000 (w/w). Furthermore, by using the mCTpBD adsorbent, endogenous glycopeptides in saliva of healthy people and patients with inflammatory bowel disease were successfully enriched and identified by the combined liquid chromatography–mass spectrometry/mass spectrometry technology, which indicates a promising prospective of core–shell magnetic composite microspheres with a hydrophilic COF shell in glycoproteomics research.