Light-Active, Reversibly Shape-Shifting Block Copolymer Particles Using Photo-switchable Au Nanoparticle Surfactants
Seung Ho Kwon, Meng Xu, Jinwoo Kim, Eun Ji Kim, Young Jun Lee, Se Gyu Jang, Hongseok Yun, Bumjoon J. Kim
Abstract
Dynamic particles with switchable shapes in response to light have attracted great interest to develop programmable smart materials with superior spatial and temporal resolution. Herein, a facile strategy for light-responsive, shape-changing block copolymer (BCP) particles is developed. Key to this strategy is the design of azobenzene-grafted Au nanoparticles (Au@Azo NPs) as photoswitchable surfactants through photoisomerization of Azo ligands. Under visible light, onion-like polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) BCP particles with PS outer layer form due to the nonpolar nature of trans-Azo ligands, whereas the isomerization to polar cis-Azo surfactants with UV irradiation transforms these spheres into ellipsoids with both PS and P2VP exposed on their surfaces. This light-driven shape change is robust and reversible over multiple irradiation cycles. The reversible shape evolution between spherical and ellipsoidal BCP particles induced by photoactive Au@Azo NP surfactants is elucidated using a cryogenic electron microscope. Furthermore, light-dependent fluorescence and shape of the BCP particles are successfully demonstrated, enabling the visualization of particle shape into an optical signal.