Protecting Group-Free Synthesis of Glycopolymer-Type Amphiphilic Macromonomers and Their Use for the Preparation of Carbohydrate-Decorated Polymer Particles.

Jin Motoyanagi,Minh Nguyen,Masahiko Minoda,Tomonari Tanaka

doi:10.3390/biom9020072

Abstract

Polymer particles modified with carbohydrates on their surfaces are of significant interest, because their specific recognition abilities to biomolecules are valuable for developing promising materials in biomedical fields. Carbohydrate-decorated core-shell polymer particles are expected to be efficiently prepared by dispersion polymerization using a glycopolymer-based amphiphilic macromonomer as both a polymeric steric stabilizer and a monomer. To create glycopolymer-type macromonomers, we propose a new strategy combining living cationic polymerization of an alkynyl-functionalized vinyl ether (VE), and the click reaction for the preparation of glycopolymers having a polymerizable terminal group, and investigate their dispersion copolymerization with styrene for generating carbohydrate-decorated polymer particles. This study deals with (i) the synthesis of block copolymer-type amphiphilic macromonomers bearing a methacryloyl group at the α-terminus, and pendant alkynyl groups by living cationic polymerization of alkynyl-substituted VE (VEEP), (ii) the derivatization of maltose-carrying macromonomers by click chemistry of the pendant alkynyl groups of the precursor macromonomers with maltosyl azide without any protecting/deprotecting processes, and (iii) the preparation of maltose-decorated (Mal-decorated) polymer particles through the dispersion copolymerization of glycopolymer-type macromonomers with styrene in polar media. Moreover, this study concerns the specific interactions of the resultant polymer particles with the lectin concanavalin A (Con A).

Highlights

Surface-functionalized polymer particles have attracted increased attention because of their scientific and technical importance [1,2,3] as versatile materials with extremely large specific surface areas
We have already reported that poly(vinyl ether)-based hydrophilic macromonomers bearing functional side chains can produce monodispersed polymer particles, where the surfaces of the polymer particles can be modified with a variety of functions originating from the pendant functions of the macromonomers employed [11,12]
The product was purified by preparative size exclusion chromatography (SEC) to remove the unreacted isobutyl vinyl ether (IBVE) and VEEP

Summary

Introduction

Surface-functionalized polymer particles have attracted increased attention because of their scientific and technical importance [1,2,3] as versatile materials with extremely large specific surface areas. Polymer particles decorated with carbohydrates on their surfaces have been of great interest in the biomedical field, because they have the potential ability for providing useful materials for diagnosis based on their specific interactions with biomolecules, such as proteins and viruses, etc. The synthesis of well-defined glycopolymers have been achieved by the controlled polymerization of carbohydrate-containing monomers, or the post-functionalization of the precursor reactive polymers using carbohydrate-based agents as exemplified in copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) [15,16]. An alternative approach to the synthesis of well-defined glycopolymers is a CuAAC-based procedure, in which alkyne-carrying precursor polymers are precisely synthesized and decorated with azide-functionalized carbohydrates by click reaction

Methods

Results

Conclusion