POSS as a versatile platform for developing multifunctional water-soluble photoinitiators.

Conventional photoinitiators act only as non-structural initiating species and do not regulate network topology after radical generation. In this work, a strategy for actively modulating hydrogel crosslinking behavior through photoinitiator design is presented. Polyhedral oligomeric silsesquioxane-based nanophotoinitiators (POSS-PIs) were synthesized by functionalizing POSS with polyethylene glycol (PEG) chains of varying lengths and coupling them with I2959. Unlike conventional initiators, POSS-PIs function as multifunctional junctions that participate in network formation. This dual functionality significantly enhances photopolymerization efficiency, crosslinking density, and mechanical performance. Hydrogels incorporating POSS-PIs exhibited 8.30-fold increase in toughness while maintaining high stretchability and controlled swelling. Furthermore, 3D-printed GelMA/HEMA-POSS scaffolds demonstrated excellent biocompatibility, supporting WS1 cell adhesion, proliferation, and network formation over 10 days. These findings establish POSS-PIs as multifunctional photoinitiators capable of precisely tailoring hydrogel properties, expanding their potential applications in 3D bioprinting and biomedical engineering.