Miras, H. N. , Mathis, C., Xuan, W., Long, D. , Pow, R. and Cronin, L. (2020) Spontaneous formation of autocatalytic sets with self-replicating inorganic metal oxide clusters. Proceedings of the National Academy of Sciences of the United States of America, 117(20), pp. 10699-10705. (doi: 10.1073/pnas.1921536117) (PMID:32371490) (PMCID:PMC7245103)
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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} ≡ [MoVI72MoV60O372(CH3COO)30(H2O)72]42– ball-shaped species containing 154 and 132 molybdenum atoms, and a {PMo12}⊂{Mo124Ce4} ≡ [H16MoVI100MoV24Ce4O376(H2O)56 (PMoVI10MoV2O40)(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.
| Item Type: | Articles |
|---|---|
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Xuan, Mr Weimin and Pow, Robert and Mathis, Dr Cole and Moiras, Professor Haralampos and Long, Dr Deliang and Cronin, Professor Lee |
| Authors: | Miras, H. N., Mathis, C., Xuan, W., Long, D., Pow, R., and Cronin, L. |
| College/School: | College of Science and Engineering > School of Chemistry College of Science and Engineering > School of Engineering |
| Journal Name: | Proceedings of the National Academy of Sciences of the United States of America |
| Publisher: | National Academy of Sciences |
| ISSN: | 0027-8424 |
| ISSN (Online): | 1091-6490 |
| Published Online: | 05 May 2020 |
| Copyright Holders: | Copyright © 2020 The Authors |
| First Published: | First published in Proceedings of the National Academy of Sciences of the United States of America 117(20):10699-10705 |
| Publisher Policy: | Reproduced under a Creative Commons license |
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