Molecular Autocatalysis through Interfacial Recruitment of Catalytic Functional Groups

This is the authors' abstract. We don't add key points for this paper.

Autocatalysis enables nonlinear reactivity, self-amplification, and emergent chemical behavior. At the soft interfaces of emulsions and vesicles, autocatalysis has been linked to dynamic behavior such as growth, propagation, and oscillations. Most reported interfacial autocatalytic systems rely on assembly-driven physical effects such as reactant colocalization rather than well-defined catalytic interactions. Whether catalytic function can be molecularly encoded within assemblies, independent of assembly formation itself, remains unresolved. Here we demonstrate molecular autocatalysis through interfacial recruitment of catalytic functional groups. As product accumulates, catalytic groups are concentrated at the interface, creating a positive feedback loop that accelerates further synthesis. The molecular identity of the product, rather than assembly formation, controls autocatalytic behavior. We further show the generality of this mechanism across two distinct reaction classes, oxime condensation and thiol-Michael addition. Autocatalytic lipids self-assemble into growing vesicles, coupling molecular feedback to compartment propagation and establishing a general chemical strategy for self-amplifying soft matter systems.