Photo-Switchable Cross-Linking in Polymer Gels: Effects on Surface Creasing and Network Relaxation during Swelling

Abstract

Polymer gels with photo-responsive cross-links enable tunable mechanics and surface morphologies, making them promising for adaptive materials. While prior work on coumarin cross-linked gels has focused on photo-mediated events in dilute solution, their network-level mechanical responses remain unclear. Here, we design PEG hydrogels with both permanent covalent and dynamic coumarin cross-links, allowing in situ modulation of cross-linking under wavelength specific UV light. Real-time FTIR and dynamic mechanical analysis show that post-cure 365 nm irradiation drives rapid dimerization, increasing storage modulus by up to 69\%, whereas cleavage of coumarin cross-links via 254 nm post-cure irradiation has a more limited effect due to attenuation in bulk samples. Surface imaging reveals that dynamic cross-linking governs swelling-induced crease formation and evolution. Together, these results establish design principles for hydrogels with programmable mechanics and adaptive surface topographies, advancing application in smart coatings, actuators, and responsive biomaterials.