Precise synthesis of heterogeneous glycopolymers with well‐defined saccharide motifs in the side chain via post‐polymerization modification and recognition with lectin

Heterogeneous glycopolymers with different sugar units in the side chain have been receiving considerable attention due to their potential properties in enhancing molecular recognition abilities toward a specific receptor, yet there are limited synthetic approaches to introduce different sugar motifs into the glycopolymer backbone. Herein, a series of heterogeneous glycopolymers consisting of different sugar units in the side chains were synthesized by post‐polymerization modification of activated PFPA ester precursor polymers. The functionalized amines bearing two different sugar motifs have been synthesized by gradient CuAAC reaction, which could serve as a platform for achieving heterogeneous sugar units with functional control in concise steps. Isothermal titration calorimetry (ITC) measurements of the obtained glycopolymers with Concanavalin A indicated that the heterogeneous glycopolymers, poly(Man‐ β Glu‐OH) and poly(Man‐ β Ga‐OH) bearing α ‐ D ‐mannose and other non‐binding β‐ Glucose or β‐ Galatose units, show higher affinities toward Concanavalin A in comparison to monoglycopolymer poly(Man‐Alkyne‐OH) in which the non‐binding sugar motifs was substituted with non‐sugar unit due to synergistic effects of non‐binding sugar units. Moreover, this work allows for precise fabrication of a broad variety of glycopolymers in which it significantly broadens the library of accessible polymer structures, either homogeneous or heterogeneous glycopolymers.