Herein, the synthesis, characterization, and application of a novel synthetic hydrogel based on the photoinitiated cross-linking of poly(vinylphosphonates) is presented. First, statistical copolymers with adjustable ratios of the monomers diallyl vinylphosphonate (DAlVP) and diethyl vinylphosphonate (DEVP), as well as different molecular weights, were obtained via rare earth metal-mediated group-transfer polymerization (REM-GTP) while maintaining narrow polydispersities. The copolymers were cross-linked by applying photoinitiated thiol-ene click chemistry (lambda = 365 nm). The network formation was monitored via oscillatory rheology coupled with UV-irradiation, revealing the high spatiotemporal control of the reaction. Moreover, the equilibrium storage moduli of poly(vinylphosphonate)-based hydrogels increased with a growing number of DAlVP units and upon application of a different cross-linker, which was additionally confirmed by nanoindentation experiments. In contrast, the water uptake of hydrogels decreased with higher DAlVP amounts in the corresponding hydrogels due to lower chain mobility and an overall increase in the hydrophobicity of the samples. Upon successful functionalization of P(DEVP-stat-DAlVP) copolymers with sodium 3-mercaptopropane-1-sulfonate, as indicated via H-1 DOSY NMR, the respective cross-linked materials displayed a remarkable increase in the water uptake; thus, presenting highly hydrophilic gels with an apparent interplay between water uptake, cross-linking density, and functionalization degree. Finally, the purified hydrogels showed cytocompatibility and enabled cell adhesion of human umbilical artery smooth muscle cells (HUASMCs) after direct seeding. The materials further allowed the adhesion and growth of an endothelial layer, triggered no pro-inflammatory response as evidenced by cytokine release of M0 macrophages, and exhibited antibacterial properties toward S. aureus and E. coli.
