Biomimetic 4D‐Printed Breathing Hydrogel Actuators by Nanothylakoid and Thermoresponsive Polymer Networks

Abstract Shape‐morphing actuators, which can breathe with the accompany of morphology changes to mimic botanical events, are challenging to fabricate with soft hydrogel materials. Herein, 4D printed‐smart hydrogel actuators are reported that can not only dynamically deform but also generate oxygen (O 2 ) upon external stimulations. The printed breathing actuators featured with spinach leaf‐derived thylakoid membrane (nanothylakoid) for photothermal conversion and catalytical O 2 evolution, a poly( N ‐isopropylacrylamide) (PNIPA) thermoresponsive polymer network for generating deformation forces by swelling/shrinkage (rehydration/dehydration), and an asymmetric bilayer poly( N ‐isopropylacrylamide)/polyacrylamide (PNIPA/PAA) structure to amplify the mechanical motions. Upon thermal stimulation or laser irradiation, the actuator can reversibly bend/unbend because of the photothermal conversion of nanothylakoid and the printed thermoresponsive asymmetric bilayer structure. Additionally, the catalase‐like property of nanothylakoid imparts the actuator with O 2 evolution capability to breathe for further mimicking botanical systems. Notably, 4D printing can greatly facilitate and simplify the actuator fabrication process, including adjusting the size and layer compositions. This artificial breathing actuator with photothermal and catalytical properties provides a strategy in designing intelligent hydrogel systems and proves to be a highly promising material candidates in the fields of 3D/4D printing, automated robotics, and smart biomedical devices.