Shape-Changing Bottlebrush Polymers

Bottlebrush polymers (BBPs), composed of relatively short polymeric side chains densely grafted on a polymer backbone, exhibit many unique characteristics and hold promise for a variety of applications. This Perspective focuses on environmentally induced shape-changing behavior of BBPs at interface and in solution, particularly worm/star-globule shape transitions. While BBPs with a single type of homopolymer or random copolymer side chains have been shown to undergo pronounced worm-to-globule shape changes in response to external stimuli, the collapsed brushes are unstable and prone to aggregation. By introducing a second, solvophilic polymer into the side chains, either as a distinct type of side chain or as the outer block of block copolymer side chains, the collapsed brushes not only are stabilized but also create unimolecular micellar nanostructures, which can be used for, e.g., encapsulation and delivery of substances. The current challenges in the design, synthesis, and characterization of stimuli-responsive shape-changing BBPs are discussed.