Faculty of Molecular Chemistry and Engineering, Graduate School of Science and Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan.
Department of Biobased Materials Science, Graduate School of Science and Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan.
Biomolecules. 2019 Feb 19;9(2):72. doi: 10.3390/biom9020072.
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 -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).
多糖在其表面的聚合物颗粒具有重要的意义，因为它们对生物分子的特定识别能力对于开发生物医学领域有前途的材料是有价值的。通过使用基于糖聚合物的两亲性大分子单体作为聚合性空间稳定剂和单体的分散聚合，预计可以有效地制备多糖修饰的核壳聚合物颗粒。为了制备糖聚合物型大分子单体，我们提出了一种新的策略，即将炔基官能化的乙烯基醚（VE）的活性阳离子聚合与点击反应相结合，以制备具有可聚合端基的糖聚合物，并研究它们与苯乙烯的分散共聚，以生成多糖修饰的聚合物颗粒。本研究涉及：（i）通过炔基取代的 VE（VEEP）的活性阳离子聚合，在 -末端和支链炔基基团上接枝甲基丙烯酰基的嵌段共聚物型两亲性大分子单体的合成，（ii）通过前体大分子单体的支链炔基与麦芽寡糖叠氮化物的点击化学反应，无需任何保护/脱保护过程，对带有麦芽寡糖的大分子单体进行衍生化，以及（iii）通过在极性介质中用糖聚合物型大分子单体与苯乙烯进行分散共聚，制备麦芽糖修饰（Mal 修饰）的聚合物颗粒。此外，本研究还涉及到所得聚合物颗粒与凝集素伴刀豆球蛋白 A（Con A）的特异性相互作用。
