Controlled Synthesis of Glycopolymer-type Macromonomers and their Use for the Preparation of Carbohydrate-Decorated Polymer Particles

• Material Type: 博士論文
• Title: Controlled Synthesis of Glycopolymer-type Macromonomers and their Use for the Preparation of Carbohydrate-Decorated Polymer Particles
• Author/Editor: NGUYEN MINH TAN
• Author Heading: NGUYEN MINH TAN
• Publication Date: 2019-03-25
• Publication Date (W3CDTF): 2019-03-25
• Alternative Title: グライコポリマーからなるマクロモノマーの精密合成と糖残基で表面修飾されたポリマー微粒子創製への展開
• Degree grantor/type: 京都工芸繊維大学
• Date Granted: 2019-03-25
• Dissertation Number: 甲第914号
• Degree Type: 博士(工学)
• Text Language Code: eng
• Subject Heading: Glycopolymer; Glycopolymer-Type Macromonomer; Carbohydrate-Decorated Polymer Particle; Dispersion Polymerization; Living Cationic Polymerization; RAFT Polymerization; Click Reaction; Poly(vinyl ether); Alkynyl-Group-Substituted Vinyl Ether
• Target Audience: 一般
• Note (General): type:Thesis; Macromonomers containing one or more polymerizable groups in the polymer chains have been recognized as useful building blocks of various polymer assembly architectures. Among them, the use of amphiphilic macromonomers for the dispersion or emulsion copolymerization with hydrophobic monomers in polar media can produce polymer particles of a wide range of sizes. The resultant polymer particles are categorized as hairy or core-shell particles and hence afford stable aqueous dispersions, where the dispersion stability is attributed to the steric stabilization attained by the hydrophilic polymer chains fixed on the particle surfaces. It is worth noting that the surface functionality of the particles can be widely designed by varying the structure of the macromonomers because the polymer chain moieties are covalently attached to the particle surfaces. In particular, polymer particles decorated with carbohydrates on their surfaces have been of great interest in the biomedical field, because they have potential ability for providing useful materials for diagnosis based on their specific interactions with biomolecules such as proteins and viruses etc. In order to produce carbohydrate-decorated polymer particles, the author designed novel amphiphilic glycopolymer-type macromonomers, which are synthesized by controlled polymerizations, thereby possess well-defined architecture consisting of pendant carbohydrate moieties and a terminal vinyl group. Moreover, chain lengths of the macromonomers and composition ratios of the block copolymer-type versions can be precisely controlled. This thesis deals with the following research topics: (i) The synthetic strategies for yielding various glycopolymer-type macromonomers were developed. Firstly, a combination of living cationic polymerization of alkyne-substituted vinyl ether (VEEP) and copper(I)-catalyzed azide alkyne cycloaddition (CuAAC) allowed the poly(vinyl ether) (polyVE)-based glycopolymer-type macromonomers, where the precursor macromonomer having pendant alkynes and a methacryloyl group at α-terminus was synthesized by living cationic polymerization of VEEP, followed by CuAAC click reaction with maltosyl azide. The resultant glycopolymer-type macromonomer possesses both pendant maltose residues and a terminal polymerizable group at α-end. (ii) The synthetic methodology in (i) was then applied for the synthesis of amphiphilic glycopolymer-type macromonomers composed of a hydrophobic poly(alkylVE) segment and a maltose-substituted hydrophilic polyVE segment. Through the dispersion copolymerization with styrene in polar media, this amphiphilic macromonomer afforded core-shell polymer particles decorated with maltose residues on their surfaces. (iii) An alternative approach for the synthesis of glycopolymer-type macromonomers was developed based on the living radical copolymerization by RAFT (reversible addition-fragmentation chain transfer) process of maltose-containing and other acrylamides and subsequent functional conversion of the terminal function. The precursor maltose-carrying polyacrylamide was successfully synthesized by RAFT copolymerization, and its terminal trithiocarbonate function was reduced and then subjected to thiol-ene reaction with a diacrylate compound to give the target macromonomer. The obtained macromonomer possess both pendant maltose residues and an acryloyl group at ω-end, and was found to be capable of forming maltose-decorated core-shell polymer particles by dispersion copolymerization with styrene in polar media. (iv) Lectin binding assay using concanavalin A (Con A) revealed that the prepared maltose-decorated polymer particles specifically interact with Con A.
• Format (IMT): application/pdf
• Source: fulltext; http://repository.lib.kit.ac.jp/repo/repository/10212/2524/D1-0914_h1.pdf; http://repository.lib.kit.ac.jp/repo/repository/10212/2524/D1-0914.pdf
• Access Restrictions: インターネット公開
• Data Provider (Database): 国立情報学研究所 : 学術機関リポジトリデータベース（IRDB）（機関リポジトリ）; https://irdb.nii.ac.jp
• Original Data Provider (Database): 京都工芸繊維大学 : ＫＩＴ学術成果コレクション