Spontaneous formation of autocatalytic sets with self-replicating inorganic metal oxide clusters.

ABSTRACT: Here we show how a simple inorganic salt can spontaneously form autocatalytic sets of replicating inorganic molecules that work via molecular recognition based on the {PMo12} ? [PMo12O40]3- Keggin ion, and {Mo36} ? [H3Mo57M6(NO)6O183(H2O)18]22- cluster. These small clusters are able to catalyze their own formation via an autocatalytic network, which subsequently template the assembly of gigantic molybdenum-blue wheel {Mo154} ? [Mo154O462H14(H2O)70]14-, {Mo132} ? [MoVI 72MoV 60O372(CH3COO)30(H2O)72]42- ball-shaped species containing 154 and 132 molybdenum atoms, and a {PMo12}?{Mo124Ce4} ? [H16MoVI 100MoV 24Ce4O376(H2O)56 (PMoVI 10MoV 2O40)(C6H12N2O4S2)4]5- nanostructure. Kinetic investigations revealed key traits of autocatalytic systems including molecular recognition and kinetic saturation. A stochastic model confirms the presence of an autocatalytic network involving molecular recognition and assembly processes, where the larger clusters are the only products stabilized by the cycle, isolated due to a critical transition in the network.

SUBMITTER: Miras HN 

PROVIDER: S-EPMC7245103 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature