Supramolecular interactions between catalytic species allow rational control over reaction kinetics

The adaptivity of biological reaction networks largely arises through non-covalent regulation of catalysts' activity. Such type of catalyst control is still nascent in synthetic chemical networks and thereby hampers their ability to display life-like behavior. Here, we report a bio-inspired system in which non-covalent interactions between two complementary phase-transfer catalysts are used to regulate reaction kinetics. While one catalyst gives bimolecular kinetics, the second displays autoinductive feedback, resulting in sigmoidal kinetics. When both catalysts are combined, the interactions between them allow rational control over the shape of the kinetic curves. Computational models are used to gain insight into the structure, interplay, and activity of each catalytic species, and the scope of the system is examined by optimizing the linearity of the kinetic curves. Combined, our findings highlight the effectiveness of regulating reaction kinetics using non-covalent catalyst interactions, but also emphasize the risk for unforeseen catalytic contributions in complex systems and the necessity to combine detailed experiments with kinetic modelling. The non-covalent interactions between two phase-transfer catalysts allow tuning of reaction kinetics from bimolecular, to pseudo 0 th order, to sigmoidal. Kinetic models and DFT calculations are used to obtain detailed insight in the system.