Self‐Regulating Colloidal Co‐Assemblies That Accelerate Their Own Destruction via Chemo‐Structural Feedback

Biological self‐assemblies self‐ and cross‐regulate each other via chemical reaction networks (CRNs) and feedback. Although artificial transient self‐assemblies have been realized via activation/deactivation CRNs, the transient structures themselves do mostly not engage in the CRN. We introduce a rational design approach for chemo‐structural feedback, and present a transient colloidal co‐assembly system, where the formed co‐assemblies accelerate their destruction autonomously. We achieve this by immobilizing enzymes of a deactivating acid‐producing enzymatic cascade on pH‐switchable microgels that can form co‐assemblies at high pH. Since the enzyme partners are immobilized on individual microgels, the co‐assembled state brings them close enough for enhanced acid generation. The amplified deactivator production (acid) leads to an almost two‐fold reduction in the lifetime of the transiently formed pH‐state. Our study thus introduces versatile mechanisms for chemo‐structural feedback.