title: Controlled thermoresponsive hydrogels by stereocomplexed PLA-PEG-PLA prepared via hybrid micelles of pre-mixed copolymers with different PEG lengths.
abstract: The stereocomplexed hydrogels derived from the micelle mixture of two enantiomeric triblock copolymers, PLLA-PEG-PLLA and PDLA-PEG-PDLA, reported in 2001 exhibited sol-to-gel transition at approximately body temperature upon heating. However, the showed poor storage modulus (ca. 1000 Pa) determined their insufficiency as injectable implant biomaterials for many applications. In this study, the mechanical property of these hydrogels was significantly improved by the modifications of molecular weights and micelle structure. Co-micelles composed of block copolymers with two sizes of PEG block length were shown to possess unique and dissimilar properties from the micelles composed of single-sized block copolymers. The stereomixture of PLA-PEG-PLA comicelles showed a controllable sol-to-gel transition at a wide temperature range of 4 and 80 °C. The sol-gel phase diagram displays a linear relationship of temperature versus copolymer composition; hence, a transition at body temperature can be readily achieved by adjusting the mixed copolymer ratio. The resulting thermoresponsive hydrogels exhibit a storage modulus notably higher (ca. 6000 Pa) than that of previously reported hydrogels. As a physical network solely governed by self-reorganization of micelles, followed by stereocomplexation, this unique system offers practical, safe, and simple implantable biomaterials.
authors.affiliation: Department of Chemistry, The University of Memphis, Memphis, Tennessee 38152, United States.
authors.forename: Daniel G
authors.initials: DG
authors.lastname: Abebe
authors.forename: Tomoko
authors.initials: T
authors.lastname: Fujiwara
mesh_terms: D057446:Hydrodynamics; D020100:Hydrogels / Q000138:chemical synthesis / Q000737:chemistry*; D008823:Micelles; D008970:Molecular Weight; D010316:Particle Size; D011091:Polyesters / Q000138:chemical synthesis* / Q000737:chemistry; D011092:Polyethylene Glycols / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013499:Surface Properties; D013696:Temperature
chemical_list: D020100:Hydrogels; D008823:Micelles; D011091:Polyesters; C507889:polylactide-polyethylene glycol-polylactide; D011092:Polyethylene Glycols