Organocatalytic control over a fuel‐driven transient esterification network

Signal transduction in living systems is the conversion of information into a chemical change and the principal process by which cells communicate. This process enables phenomena as time-keeping and signal amplification. In nature, these functions are encoded in non-equilibrium (bio)chemical reaction networks (CRNs) controlled by enzymes, as integral part of biocatalytic pathways. Yet, man-made catalytically controlled networks are rare. Here, we incorporate catalysis in an artificial fuel-driven out-of-equilibrium CRN, where the forward (ester formation) and backward reaction (ester hydrolysis) are controlled by varying the ratio of two organocatalysts: pyridine and imidazole. This catalytic regulation enables full control over ester yield and lifetime. The fuel-driven strategy is expanded to a responsive polymer system, where transient polymer conformation and aggregation are controlled through fuel and catalysts levels. Altogether, we show how organocatalysis is an important tool to control a man-made fuel-driven system and induce a change in a macromolecular superstructure, as ubiquitously found in natural non-equilibrium systems.