Synthesis of Well‐Defined Side‐Chain Amino Acid‐Based Glycopolymers via Postpolymerization Modification: The Synergistic Effect of Amino Acids on Con A Recognition

ABSTRACT Incorporating amino acid motifs into the side chains of synthetic polymers provides vastly different properties and functionalities owing to their wide availability and biocompatibility. However, there are limited synthetic approaches to integrate amino acids with glycopolymers to date. Herein, we present an effective strategy for synthesizing well‐defined side‐chain amino acid‐based mannose‐glycopolymers via postpolymerization modification (PPM) of preinstalled side‐chain PFPA ester polymers with functional amines. The corresponding functional amines possessing an α ‐D‐mannose motif and amino acids in the side chain were prepared through sequential Steglich esterification and CuAAC reaction, which provided a straightforward method for the preparation of amino acid‐based sugar synthetic blocks with good function control. ITC measurements of side‐chain amino acid‐based glycopolymers with the model receptor, Concanavalin A (Con A), indicated that side‐chain amino acid‐based glycopolymers P(Lys‐ α ‐Man) and P(Cys‐ α ‐Man) show higher affinities to Con A in contrast to the control glycopolymer P( α ‐Man‐OH) without the side‐chain amino acid. We hypothesize that side‐chain amino acids offer a synergistic effect as nonbinding units for the binding of α ‐mannose units to Con A.