4D Printing of shape-memory polymeric scaffolds for adaptive biomedical implantation.

4D printing has shown great potential in a variety of biomedical applications due to the adaptability and minimal invasiveness of fabricated devices. However, commonly employed shape memory polymers (SMPs) possess undesirable transition temperatures (Ttranss), leading to complications in implantation operations. Herein, we demonstrate 4D printing of a new SMP named poly(glycerol dodecanoate) acrylate (PGDA) with a Ttrans in a range of 20 °C - 37 °C making it appropriate for shape programming at room temperature and then shape deployment within the human body. In addition, the material possesses suitable rheological properties to allow for the fabrication of a variety of delicate 3D structures such as "triangular star", "six-petal flower", "honeycomb", "tube", tilted "truncated hollow cones", as well as overhanging "bridge", "cage", and "mesh". The printed 3D structures show shape memory properties including a large fixity ratio of 100% at 20 °C, a large recovery ratio of 98% at 37 °C, a stable cyclability of > 100 times, and a fast recovery speed of 0.4 s at 37 °C. Moreover, the Young's moduli of the printed structures can be decreased by 5 times due to the phase transition of PGDA, which is compatible with biological tissues. Finally, in vitro stenting and in vivo vascular grafting demonstrated the geometrical and mechanical adaptivity of the printed constructs for biomedical implantation. This newly developed PGDA SMP based 4D printing technology has the potential to pave a new route to the fabrication of shape memory scaffolds for personalized biomedical applications.