Self-Healing Hydrogel Scaffolds through PET-RAFT Polymerization in Cellular Environment

[Image: see text] Photo electron/energy transfer-reversible addition–fragmentation chain transfer (PET-RAFT) has emerged as a powerful reversible-deactivation radical polymerization technique, enabling oxygen-tolerant polymerizations with exquisite spatiotemporal control through irradiation with visible light. In contrast to traditional free radical photo-polymerization, which often requires the use of DNA-damaging UV irradiation, PET-RAFT offers a more cytocompatible alternative for the preparation of polymeric materials in cell culture environments. Herein, we report the use of PET-RAFT for the fabrication of self-healing hydrogels using commercially available monomers, reaching high monomer conversions and cell encapsulation efficiencies. Our hydrogels showed the expected rheological and mechanical properties for the systems considered, together with excellent cytocompatibility and spatiotemporal control over the polymerization process. Moreover, hydrogels prepared through this method could be cut and healed again by simply adding further monomer and irradiating the system with visible light, even in the presence of mammalian cells. This study demonstrates for the first time the potential of PET-RAFT polymerization as a viable methodology for the synthesis of self-healing hydrogel scaffolds for cell encapsulation.