Introduction of functional groups to reactive ABA block-copolymers composed of poly(2-methacryloyloxyethyl phosphorylcholine) and poly(glycidyl methacrylate) for spontaneous hydrogel formation. (11th August 2017)

• Record Type: Journal Article
• Authors: Chantasirichot, Surasak; Inoue, Yuuki; Ishihara, Kazuhiko
• Is Part Of: Polymer. Volume 123(2017)
• Page Start: 100
• Page End: 106
• Publication Date: 2017-08-11
• Subjects: Hydrogel formation -- Phospholipid polymer -- ARGET-ATRP; Polymers -- Periodicals; Polymerization -- Periodicals; Polymères -- Périodiques; Polymérisation -- Périodiques; 547.7
• DOI: 10.1016/j.polymer.2017.07.010
• Languages: English
• ISSNs: 0032-3861

Abstract

Abstract: ABA block-type copolymers with poly(2-methacryloyloxyethyl phosphorylcholine(MPC)) as the middle B segment and poly(glycidyl methacrylate(GMA)) as the A segments (PM b G) were synthesized by an activator regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP). The PM b Gs were reactive copolymers, as the epoxide group available in the poly(GMA) segment could be chemically modified by nucleophilic addition reactions, which allowed the functionalization of PM b G with a wide range of functional groups for various purposes. The PM b Gs had narrow molecular weight distributions with predetermined chain lengths, while the length of the middle poly(MPC) segment could be designed and synthesized with a fixed degree of polymerization of both poly(GMA) segments in a single polymer chain. The functionalization of PM b Gs by 3-aminophenylboronic acid allowed the preparation of a phenylboronic acid moiety connecting ABA block-type copolymers (PM b Bs). The PM b Gs were also reacted with diethanolamine (DEA) to introduce hydroxyl groups. The DEA-functionalized copolymers (PM b Ds) could interact with PM b Bs in aqueous media, forming hydrogels spontaneously. As the reactive groups were separated by the poly(MPC) segment, the network structure depended on the polymerization degree of the poly(MPC) segment. The diffusivity of various proteins in the PM b B/PM b D hydrogels depended on the molecular weight of these proteins and was regulated by adjusting the chain length of poly(MPC) between cross-linking positions of the hydrogel network, that is, the polymerization degree of the poly(MPC) segment. Graphical abstract: Highlights: Well-defined block-type reactive phospholipid polymers were synthesized. Functional groups were introduced in the terminal segments to form network structure. The properties of hydrogels depended on the segment length of phospholipid polymer.