Teamed boronate affinity-functionalized branched polyethyleneimine-modified magnetic nanoparticles for the selective capture of ginsenosides from rat plasma

Abstract Boronate-functionalized materials have been widely used for the selective separation and enrichment of glycoproteins and glycans. However, emerging boronic acid materials either use expensive boronic acid compounds containing electron-withdrawing groups combined with a graft structure or explore only simple methods for the synthesis of boronic acid structures with improved electron-withdrawing groups. In this study, polyethyleneimine (PEI)-assisted teamed boronate affinity (TBA)-functionalized magnetic nanoparticles (MNPs) (Fe3O4@PEI@TBA NPs) were designed to specifically capture trace ginsenosides from rat plasma under neutral conditions without requiring protein precipitation. The synergistic effect of the Fe3O4@PEI@TBA NPs exhibited higher affinity for ginsenosides (45.64 mg g−1) based on PEI dendrimer-assisted multivalent binding, the low pKa value of TBA and specific recognition sites. Additionally, the captured ginsenosides were quickly detected and characterized using ultra-high-performance liquid chromatography coupled with high-resolution mass spectrometry (UHPLC-MS) and an enriched in-house library. Compared to the 37 compounds identified using the methanol method, 63 ginsenoside prototypes and metabolites were successfully detected and identified in rat plasma by applying this novel integrated strategy. The strategy exhibited selectivity and identified more types and quantities of ginsenosides. Our study provided in-depth insight into the synergistic development of specific functional materials in combination with advanced analytical platforms for the selective capture and characterization of trace glycoconjugate families in analytical, engineering and biomedical fields under neutral conditions.