Light-Controlled Chemical Reaction Pathways in Disulfide-Based Nonequilibrium Systems

Pathway selection in a complex chemical reaction network (CRN) enables organisms to adapt, evolve, and even learn in response to changing environments. Inspired by this, herein we report an artificial system, where light signal was used to manipulate the reaction pathways in a disulfide-based nonequilibrium CRN. By changing the photon energy and irradiation window, the anion or new radical -mediated pathways were selectively triggered, resulting in a user-defined evolution pathway. Additional photo dissipative cycles were achieved by UV (365 nm) irradiation, increasing the total number of reactions from 3 to 7. The emerging pathway selection of the CRN is accurately predictable and controllable even in complex organo-hydrogel materials. We demonstrate up to five-state autonomous sol-gel transitions and the formation of fuel-driven dissipative organo-hydrogel through both chemical and light input. This work represents a new approach to allowing CRNs to communicate with the environment that can be used in the development of materials with lifelike behaviors.