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.
Highlights
Biological self-replication is driven by complex machinery requiring large amounts of sequence information too complex to have formed spontaneously [1,2,3,4]
We present an inorganic autocatalytic, based on molybdenum blue, that is formed spontaneously when a simple inorganic salt of sodium molybdate is reduced under acidic conditions
This study demonstrates how autocatalytic sets, based on simple inorganic salts, can lead to the spontaneous emergence of self-replicating systems and solves the mystery of how gigantic molecular nanostructures of molybdenum blue can form in the first place
Summary
Biological self-replication is driven by complex machinery requiring large amounts of sequence information too complex to have formed spontaneously [1,2,3,4]. As a result we hypothesized that the formation of such complex gigantic inorganic clusters was only possible due to the utilization of a number of common building blocks (“Mo1,” “Mo2,” and “Mo6”) able to form embedded autocatalytic sets (Fig. 1). This is because in general the formation mechanism of large clusters via the polymerization of molybdenum oxide cannot explain why only very specific products are formed since the utilized building-block library could in principle form thousands of structures of comparable stability via a combinatorial explosion process. This is interesting because the formation mechanism of the class of inorganic gigantic protein sized molecules known as molybdenum blues has been a mystery, since the statistical formation of a plethora of clusters should prevent the formation of “magic numbers” of well-defined nanomolecules [15]
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
