Organocatalytic Control over a Fuel‐Driven Transient‐Esterification Network

Signal transduction in living systems is the conversion of information into a chemical change, and is the principal process by which cells communicate. In nature, these functions are encoded in non‐equilibrium (bio)chemical reaction networks (CRNs) controlled by enzymes. However, man‐made catalytically controlled networks are rare. We incorporated catalysis into an artificial fuel‐driven out‐of‐equilibrium CRN, where the forward (ester formation) and backward (ester hydrolysis) reactions are controlled by varying the ratio of two organocatalysts: pyridine and imidazole. This catalytic regulation enables full control over ester yield and lifetime. This fuel‐driven strategy was expanded to a responsive polymer system, where transient polymer conformation and aggregation are controlled through fuel and catalyst levels. Altogether, we show that organocatalysis can be used to control a man‐made fuel‐driven system and induce a change in a macromolecular superstructure, as in natural non‐equilibrium systems.