RNA with iron(II) as a cofactor catalyses electron transfer

Author:  ["Chiaolong Hsiao","I-Chun Chou","C. Denise Okafor","Jessica C. Bowman","Eric B. O'Neill","Shreyas S. Athavale","Anton S. Petrov","Nicholas V. Hud","Roger M. Wartell","Stephen C. Harvey","Loren Dean Williams"]

Publication:  Nature Chemistry

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Tags:     Chemistry

Abstract

Mg2+ is essential for RNA folding and catalysis. However, for the first 1.5 billion years of life on Earth RNA inhabited an anoxic Earth with abundant and benign Fe2+. We hypothesize that Fe2+ was an RNA cofactor when iron was abundant, and was substantially replaced by Mg2+ during a period known as the ‘great oxidation’, brought on by photosynthesis. Here, we demonstrate that reversing this putative metal substitution in an anoxic environment, by removing Mg2+ and replacing it with Fe2+, expands the catalytic repertoire of RNA. Fe2+ can confer on some RNAs a previously uncharacterized ability to catalyse single-electron transfer. We propose that RNA function, in analogy with protein function, can be understood fully only in the context of association with a range of possible metals. The catalysis of electron transfer, requisite for metabolic activity, may have been attenuated in RNA by photosynthesis and the rise of O2. Removing Mg2+ from RNA and replacing it with Fe2+ confers on some RNAs the ability to catalyse single-electron transfer. Here, it is hypothesized that Fe2+ was an RNA cofactor on the early Earth, when iron was benign and abundant, and was replaced by Mg2+ during a period known as the great oxidation, brought on by photosynthesis.

Cite this article

Hsiao, C., Chou, IC., Okafor, C. et al. RNA with iron(II) as a cofactor catalyses electron transfer. Nature Chem 5, 525–528 (2013). https://doi.org/10.1038/nchem.1649

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