Minimal catalytic dissipative assemblies <i>via</i> cooperation of an amino acid, a nucleobase precursor and a cofactor

Functions arising from cooperation between protobiopolymers have fueled the chemical emergence of living matter, which requires a continuous supply of energy to exist in a far-from-equilibrium state. Non-equilibrium conditions imparted by available energy sources have played critical roles in the appearance of complex co-assembled architectures, which exploit the properties of different classes of biopolymers. Such co-assemblies formed from mixtures of nitrogenous heterocycles as protonucleobases and peptide precursors might have acted as early versions of catalytic machinery, capable of sustaining chemical reaction networks. Herein, we show the generation of catalytic non-equilibrium networks from a mixture of a nitrogenous heterocycle, an amino acid and a cofactor driven by an aromatic substrate. The cooperation, a result of supramolecular interactions between different components, rendered the assemblies capable of activating the cofactor towards oxidative degradation of the substrate, which resulted in autonomous disassembly (negative feedback). Furthermore, utilising promiscuous hydrolytic capability, the transient co-assemblies could metabolise a precursor to generate additional amounts of the substrate, enhancing the lifetime (positive feedback) of the assemblies.