Chain-Folding-Regulated Assembly of an Amphiphilic Glycopolymer with Outstanding Functional Group Display and Multivalent Interactions with Biological Targets

Abstract

This manuscript describes chain-folding-regulated hierarchical self-assembly of an amphiphilic polyurethane (P1), exhibiting superior surface functional group display and biological activity compared to an analogous amphiphilic block copolymer (P3) or a rigid polyurethane (P2) that is deprived of chain folding. In P1, intrachain hydrogen bonding directs the formation of a pleated structure that hierarchically assembles into hollow capsules. A glucose oxidase–peroxidase assay confirmed that this unique assembly of P1 allows displaying ∼50% glucose moieties on the outer surface, which significantly outperforms amphiphilic block copolymers. This renders outstanding multivalent binding with the lectin concanavalin A, as is evident by a very high association constant (∼105 M–1) and spontaneous glycocluster effect. In contrast, P2 or P3 fails to exhibit any notable glycocluster effect under identical conditions. Furthermore, P1, unlike P2 or P3, induced clustering of Staphylococcus aureus by targeting bacterial carbohydrate transporters, deactivated the bacteria, and prevented internalization into mammalian cells.