title: Thermally induced changes in amphiphilicity drive reversible restructuring of assemblies of ABC triblock copolymers with statistical polyether blocks.
abstract: ABC triblock copolymers in which a block with stimulus-dependent solvophilicity resides between solvophilic and solvophobic end blocks can undergo reversible transitions between different thermodynamically stable assemblies in the presence or absence of stimulus. As a new example of such a copolymer system, thermoresponsive poly(ethylene oxide)-b-poly(ethylene oxide-stat-butylene oxide)-b-poly(isoprene) (E-BE-I) triblock copolymers with narrow molecular weight distributions (M(w)/M(n): 1.05-1.18) were prepared by sequential living anionic and nitroxide-mediated radical polymerizations. The specific copolymers examined (9.0 ≤ M(n) ≤ 14.4 kg/mol, 14% ≤ wt % isoprene ≤35%) form near-spherical aggregates with narrow size distributions at 25 °C. The thermoresponsive behavior of these polymers was studied by applying cloud point, DLS, and TEM measurements to a representative polymer, E(2.3)BE(5.3)I(2.3). The transformation of polymer aggregates from spherical micelles to vesicles (polymersomes) at elevated temperatures was detected by DLS and TEM studies, both with and without cross-linking of polymer assemblies. The rate of transformation with E-BE-I systems is more rapid than that observed for poly(ethylene oxide)-b-poly(N-isopropylacrylamide)-b-poly(isoprene) assemblies, suggesting that interchain hydrogen bonding of responsive blocks after dehydration plays an important role in the kinetics of aggregate rearrangement.
authors.affiliation: Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, United States.
authors.forename: Yu
authors.initials: Y
authors.lastname: Cai
authors.forename: Katherine B
authors.initials: KB
authors.lastname: Aubrecht
authors.forename: Robert B
authors.initials: RB
authors.lastname: Grubbs
mesh_terms: D004987:Ethers / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D058105:Polymerization; D011108:Polymers / Q000737:chemistry*; D013696:Temperature; D014867:Water / Q000737:chemistry
chemical_list: D004987:Ethers; D011108:Polymers; D014867:Water