4D Printing of Robust Hydrogels Consisted of Agarose Nanofibers and Polyacrylamide

Hydrogels combined with complex 3D shapes and robust mechanical properties are extremely desired soft platforms in the fields of biomaterials, recently, 4D printing has been developed to be further shaped to form required patterns. On the basis of the excellent thixotropy of Laponite and the thermal-reversible sol-gel transition of agarose and easy formation of nanofibers below 35 °C, a 4D printing hydrogel (4D Gel) was fabricated by in situ polymerizing acrylamide in the agarose matrix containing Laponite. The experimental results demonstrated that Laponite played an important role in the improvement of 4D printing, such as endowing the ink with shear-thinning behavior to extrude easily and excellent shape stability after printing. The mechanical properties of 4D Gel were unexpectedly higher than those of both agarose and polyacrylamide hydrogels. The 4D Gel showed the ability to further transform its shapes, and was used successfully to construct a whalelike hydrogel, which opened mouth and cocked tail by treating with an external force and then cooling, as well as the octopus like hydrogel with waved tentacles to seem to "come alive". This work opened a new avenue for creating more complex architectures than 3D with excellent properties, which is important in the macromolecule fields for the wide applications.