Pseudoeutectic of Isodimorphism to Design a Random Copolyester Enabling Body Temperature-Induced Shape Stretchability and Programmed Deformations

The combined biodegradable and stimulus-responsive elastomers are an emerging class of smart materials used for biomedical devices by virtue of their tunable deformable stability and biological mimetic functions. However, the inherent high-triggering temperature and nonprogrammed deformation behavior reduce their advantages. The biodegradable copolyester-based elastomer with one-step stretchable and programmable shape morphing enables the design of functional biomedical devices that would otherwise be impossible to realize with conventional manufacturing techniques. Shown here is that a dynamic random copolyester elastomer with comparable crystallinity and the combined body temperature responsiveness displays excellent shape stretchability, as well as strain-induced crystallization for shape maintaining. We demonstrate that the poly[(ε-caprolactone)-ran-(δ-valerolactone)] precursors via one-pot melt-induced transesterification exhibited tunable thermal characteristics with the lowest melting point of 29.3 °C. Upon further secondary photoinitiated thiol–ene click of acrylate-terminated precursors in the pseudoeutectic point and dynamic transesterification, the resulting architecture affords the elastomer with shape reconfiguration and responsiveness for programmable shape transformations on demand. Further results on in vitro cytocompatibility demonstrate that the elastomer could be employed as an important biomedical vascular stent, offering insights into the design of smart biomedical devices.