Modeling Controlled Photodegradation in Optically Thick Hydrogels.

There is a growing interest in developing dynamically responsive hydrogels whose material properties are modulated by environmental cues, including with light. These photoresponsive hydrogels afford spatiotemporal control of material properties through an array of photoaddition and photodegradation reactions. For photoresponsive hydrogels to be utilized most effectively in a broad range of applications, the photoreaction behavior should be well understood, enabling the design of dynamic materials with uniform or anisostropic material properties. Here, a general statistical-kinetic model has been developed to describe controlled photodegradation in hydrogel polymer networks containing photolabile crosslinks. The heterogeneous reaction rates that necessarily accompany photochemical reactions were described by solving a system of partial differential equations that quantify the photoreaction kinetics in the material. The kinetics were coupled with statistical descriptions of network structure in chain polymerized hydrogels to model material property changes and mass loss that occur during the photodegradation process. Finally, the physical relevance of the model was demonstrated by comparing model predictions with experimental data of mass loss and material property changes in photodegradable, PEG-based hydrogels.