Spontaneous Formation of Autocatalytic Sets with Self-Replicating Inorganic Metal Oxide Clusters

Biological self-replication is driven by complex machinery requiring large amounts of sequence information too complex to have formed spontaneously. This presents a fundamental problem for understanding the origins self-replication and by extension, life. One route for the emergence of self-replicators is via autocatalytic sets, but experimentally these have been based on RNA and require sequence information. Showing an example outside of biology, would give insights into how the universal ‘life-like’ chemistry can be. Here we show how a simple inorganic salt can spontaneously form information-rich, autocatalytic sets of replicating inorganic molecules that work via molecular recognition based on the {PMo12} Keggin ion, and {Mo36} cluster. These small clusters are involved in an autocatalytic network, where the assembly of gigantic molybdenum blue wheel (Mo154-blue), {Mo132} ball containing 154 and 132 molybdenum atoms, and a new {PMo12}Ì{Mo124 Ce4} nanostructure are templated by the smaller clusters which are themselves able to catalyse their own formation. Kinetic investigations revealed key traits of autocatalytic systems including molecular recognition and kinetic saturation. A stochastic model confirms the presence of an autocatalytic network driven by molecular recognition, where the larger clusters are the only products stabilised by information contained in the cycle, isolated due to a critical transition in the network. This study demonstrates how information-rich autocatalytic sets, based on simple inorganic salts, can spontaneously emerge which are capable of collective self-reproduction outside of biology.