Towards cell-adhesive, 4D printable PCL networks through dynamic covalent chemistry.

In recent years, the development of biodegradable, cell-adhesive polymeric implants and minimally invasive surgery has significantly advanced healthcare. These materials exhibit multifunctional properties like self-healing, shape-memory, and cell adhesion, which can be achieved through novel chemical approaches. Engineering of such materials and their scalability using a classical polymer network without complex chemical synthesis and modification has been a great challenge, which potentially can be resolved using biobased dynamic covalent chemistry (DCC). Here, we report a scalable, self-healable, biodegradable, and cell-adhesive poly(ε-caprolactone) (PCL)-based vitrimer scaffold, using imine exchange, free from the limitations of melting transitions and supramolecular interactions in 4D-printed PCL. PCL's typical hydrophobicity hinders cell adhesion; however, our design, based on photopolymerization of PCL-dimethacrylate and methacrylate-terminated vanillin-based imine, achieves a water contact angle of 64°. The polymer network, fabricated in varying proportions, exhibited a co-continuous phase morphology, achieving optimal shape fixity (91 ± 1.7%) and shape recovery (92.5 ± 0.1%) at physiological temperature (37 °C). Additionally, the scaffold promoted cell adhesion and proliferation and reduced oxidative stress at the defect site. This multifunctional material shows the potential of DCC-based research in developing smart biomedical devices with complex geometries, paving the way for novel applications in regenerative medicine and implant design.