Gated Photoreactivity of Pyrene Copolymers in Multiresponsive Cross-Linked starPEG-Hydrogels

The synthesis and manufacturing of multiresponsive polymer hydrogels using simple components is a notable challenge. Pyrene is an excimer-forming fluorophore mostly used as microenvironmental probe and for the localization of molecules in close proximity in artificial and biomaterials. Here we make use of the solvophobic preaggregation and photolysis properties of pyrene to construct multiresponsive hydrogels. We synthesize poly(ethylene glycol) (PEG) hydrogels from well-defined pyrene-substituted macro-cross-linkers and elucidate their intricate intra- and intermolecular excimer formation pathways. We find that controlling the water content of the hydrogels through the degree of swelling acts as a gating stimulus governing the photoinduced solvolysis of pyrenylmethyl esters from their poly(methacrylate) backbone. This allows the implementation of a simple transient photolithography process. We thus demonstrate that multiresponsive soft materials with complex optical and mechanical responses can be obtained with comparatively little synthetic effort.