Development of Versatile Metal-Organic Framework Functionalized Magnetic Graphene Core-Shell Biocomposite for Highly Specific Recognition of Glycopeptides

Protein N-glycosylation is a ubiquitous and important post-translational modification that has been involved in the development and progression of a series of human-related diseases. Until recently, the highly selective capturing of glycopeptides from complex biosamples was still significant and challenging work due to their changeable structures, ultralow abundance, and strong ion-suppressing effect. Here we first report the preparation and characterization of a novel, hydrophilic, porous biocomposite composed of magnetic graphene functionalized with metalorganic frameworks (MOFs) (MG@Zn-MOFs) able to recognize glycopeptides. Thanks to its strong magnetic responsiveness, large specific surface area, excellent biocompatibility, and unique size-exclusion effect, the MG@Zn-MOFs showed outstanding sensitivity and selectivity and good recyclability in glycopeptides analysis. More excitingly, in practical application, 517 N-glycopeptides within 151 unique glycoproteins were clearly identified from human serum (1 mu L) treated with the MG@Zn-MOFs, which is the best result among published reports so far. All the results demonstrate the promising commercialized usage of the biocomposite for the enrichment of glycopeptides in complex samples through a convenient and efficient process. Furthermore, it is anticipated that our strategy may offer promising guidance to develop new biocomposites functionalized with bio-MOFs for glycoproteomic applications.