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Nat Chem. 2013 Jun;5(6):525-8. doi: 10.1038/nchem.1649. Epub 2013 May 19.

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

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School of Chemistry and Biochemistry, and NASA Astrobiology Institute Center for Ribosomal Origins and Evolution, Georgia Institute of Technology, Atlanta, Georgia 30332, USA.


Mg(2+) 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 Fe(2+). We hypothesize that Fe(2+) was an RNA cofactor when iron was abundant, and was substantially replaced by Mg(2+) 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 Mg(2+) and replacing it with Fe(2+), expands the catalytic repertoire of RNA. Fe(2+) 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.

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