Design and construction of a hydrophilic coating on macroporous adsorbent resins for enrichment of glycopeptides

Although macroporous adsorbent resins (MARs) have been commercialized and widely applied in industrial and life fields, it is still of necessity to develop simple approaches to functionalize MARs. One of the most widely used methods to realize excellent fouling resistance performance is surface modification of hydrophilic polymers on substrates to fabricate an anti-biofouling coating. Herein, three kinds of hydrophilic poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) MAR were designed and facilely prepared by coating a layer of porous organic polymers (POPs) via either an epoxy–amine ring-opening polymerization or amine–aldehyde condensation reaction using isophthalaldehyde (IPA), 1,4,7,10-tetraazacyclododecane (cyclen), melamine and 1,3,5-triglycidyl isocyanurate (TGIC) as precursors. By taking advantage of their merits, such as large surface area, excellent hydrophilicity and unbiased affinity toward all types of glycopeptide, three functionalized hydrophilic MARs were successfully applied to capture glycopeptides from complex samples as hydrophilic interaction liquid chromatography (HILIC) sorbents. A total of 694 N-glycopeptides and 372 N-glycosylation sites were identified from 2 μL of human serum digest with poly(TC)@MAR, which were not only more than those of poly(MT)@MAR (286 N-glycosylation sites and 547 N-glycopeptides) and poly(IM)@MAR (669 N-glycopeptides and 355 N-glycosylation sites), but also more than those of other reported HILIC materials. This work provided a new and simple way to synthesize enrichment materials for liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) analysis of glycoproteomes.