title: 1,2-Dithiolane-Derived Dynamic, Covalent Materials: Cooperative Self-Assembly and Reversible Cross-Linking.
abstract: The use of dithiolane-containing polymers to construct responsive and dynamic networks is an attractive strategy in material design. Here, we provide a detailed mechanistic study on the self-assembly and gelation behavior of a class of ABA triblock copolymers containing a central poly(ethylene oxide) block and terminal polycarbonate blocks with pendant 1,2-dithiolane functionalities. In aqueous solution, these amphiphilic block copolymers self-assemble into bridged flower micelles at high concentrations. The addition of a thiol initiates the reversible ring-opening polymerizations of dithiolanes in the micellar cores to induce the cross-linking and gelation of the micellar network. The properties of the resulting hydrogels depend sensitively on the structures of 1,2-dithiolanes. While the methyl asparagusic acid-derived hydrogels are highly dynamic, adaptable, and self-healing, those derived from lipoic acid are rigid, resilient, and brittle. The thermodynamics and kinetics of ring-opening polymerization of the two dithiolanes were investigated to provide important insights on the dramatically different properties of the hydrogels derived from the two different dithiolanes. The incorporation of both dithiolane monomers into the block copolymers provides a facile way to tailor the properties of these hydrogels.
authors.affiliation: Department of Chemistry, Stanford University , Stanford, California 94305, United States.
authors.forename: Xiangyi
authors.identifier: 0000-0003-4290-1600
authors.initials: X
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Stanford University , Stanford, California 94305, United States.
authors.forename: Robert M
authors.identifier: 0000-0001-9862-9509
authors.initials: RM
authors.lastname: Waymouth