Synthesis, supramolecular assembly, and hydrogelation of poly(amino ester) ABA triblock copolymers
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Abstract
Poly(amino esters) derived from N-acylated-1,4-oxazepan-7-ones (OxPs) emerge as promising candidates in the development of new and degradable amphiphiles for hydrogel preparation and delivery formulations. Here, the synthesis of amphiphilic triblock copolymers by ring-opening copolymerization of OxP monomers with various pendant chains is reported. Copolymerization using organocatalysts and a bifunctional initiator afforded neutral P(OxPMe)-b-P(OxPBn)-b-P(OxPMe) and cationic P(OxPNH2+)-b-P(OxPBn)-b-P(OxPNH2+) amphiphilic triblock copolymers with controlled molar masses ranging from 4,600 to 8,500 g/mol and narrow dispersities (Đ ≤ 1.21). A panel of polymers with various block lengths and compositions was synthesized. Their self-assembly in water revealed the formation of nanostructures, including worm-like or spherical morphologies. Modulation of the copolymer composition and concentration enables control over hydrogelation and its macroscopic properties. Finally, we investigated the formulation of a hydrophobic fungicide and its inhibitory effect on spore proliferation, which shows great promise as dispensable and biodegradable hydrogel formulation for agrochemical applications.
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Biomacromolecules, 27, 1, ACS Publ., Columbus, Ohio, 2025, https://doi.org/10.1021/acs.biomac.5c01828