Liquid-Crystalline Dynamic Networks Doped with Gold Nanorods Showing Enhanced Photocontrol of Actuation.

A near-infrared-light (NIR)- and UV-light-responsive polymer nanocomposite is synthesized by doping polymer-grafted gold nanorods into azobenzene liquid-crystalline dynamic networks (AuNR-ALCNs). The effects of the two different photoresponsive mechanisms, i.e., the photochemical reaction of azobenzene and the photothermal effect from the surface plasmon resonance of the AuNRs, are investigated by monitoring both the NIR- and UV-light-induced contraction forces of the oriented AuNR-ALCNs. By taking advantage of the material's easy processability, bilayer-structured actuators can be fabricated to display photocontrollable bending/unbending directions, as well as localized actuations through programmed alignment of azobenzene mesogens in selected regions. Versatile and complex motions enabled by the enhanced photocontrol of actuation are demonstrated, including plastic "athletes" that can execute light-controlled push-ups or sit-ups, and a light-driven caterpillar-inspired walker that can crawl forward on a ratcheted substrate at a speed of about 13 mm min-1 . Moreover, the photomechanical effects arising from the two types of light-triggered molecular motion, i.e., the trans-cis photoisomerization and a liquid-crystalline-isotropic phase transition of the azobenzene mesogens, are added up to design a polymer "crane" that is capable of performing light-controlled, robot-like, concerted macroscopic motions including grasping, lifting up, lowering down, and releasing an object.