Biocatalytic Feedback-Driven Temporal Programming of Self-Regulating Peptide Hydrogels.

Switchable self-assemblies respond to external stimuli with a transition between near-equilibrium states. Although being a key to present-day advanced materials, these systems respond rather passively, and do not display autonomous dynamics. For autonomous behavior, approaches must be found to orchestrate the time domain of self-assemblies, which would lead to new generations of dynamic and self-regulating materials. Herein, we demonstrate catalytic control of the time domain of pH-responsive peptide hydrogelators in a closed system. We program transient acidic pH states by combining a fast acidic activator with the slow, enzymatic, feedback-driven generation of a base (dormant deactivator). This transient state can be programmed over orders of magnitude in time. It is coupled to dipeptides to create autonomously self-regulating, dynamic gels with programmed lifetimes, which are used for fluidic guidance, burst release, and self-erasing rapid prototyping. [ABSTRACT FROM AUTHOR]