Photo-responsive hydrogels based on a ruthenium complex: synthesis and degradation

Abstract

We report the synthesis of a photo responsive metallo-hydrogel based on a ruthenium(II) complex as a functional cross-linker. This metal complex contains reactive 4AAMP (= 4-(acrylamidomethyl)pyridine) ligands, which can be cleaved by light-induced ligand substitution. Ru[(bpy)₂(4AAMP)₂] cross-links 4-arm-PEG-SH macromonomers by thia-Michael-addition to the photocleavable 4AAMP ligand for the preparation of the hydrogel. Irradiation with green light at 529 nm leads to photodegradation of the metallo-hydrogel due to the ligand dissociation, which can be adjusted by adjusting the Ru[(bpy)₂(4AAMP)₂] concentration. The ligand substitution forming [Ru(bpy)₂(L)₂]²⁺ (L = H₂O and CH₃CN) can be monitored by ¹H NMR spectroscopy and UV-visible absorption. The control of degradation by light irradiation plays a significant role in modulating the elasticity and stiffness of the light sensitive metallo-hydrogel network. The photo-responsive hydrogel is a viable substrate for cell cultures.