Pol Besenius

Printing of biologically functional constructs is significant for applications in tissue engineering and regenerative medicine. Designing bioinks remains remarkably challenging due to the multifaceted requirements in terms of the physical, chemical, and biochemical properties of the three‐dimensional matrix, such as cytocompatibility, printability, and shape fidelity. In order to promote matrix and materials stiffness, while not sacrificing stress relaxation mechanisms which support cell spreading, migration, and differentiation, this work reports an interpenetrating network (IPN) bioink design. The approach makes use of a chemically defined network, combining physical and chemical crosslinking units with a tunable composition and network density, as well as spatiotemporal control over post‐assembly material stiffening. To this end, star‐shaped poly(ethylene glycol)s functionalized with Phe‐Gly‐Gly tripeptide or photoactive stilbazolium are synthesized, and used to prepare three‐dimensional networks with cucurbit[8]uril (CB[8]) through supramolecular host–guest complexation. The hydrogel obtained shows fast relaxation and thus supports the proliferation and differentiation of cells. Upon irradiation, the mechanical properties of the hydrogel can be rapidly adapted via selective photochemical dimerization of stilbazolium within CB[8], leading to IPNs with increased form stability while retaining the dynamic nature of the hydrogels. This modular approach opens new design opportunities for extrudable and cell‐friendly dynamic biomaterials for applications in 3D‐bioprinting.