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Prebiotic photoredox synthesis from carbon dioxide and sulfite

Nature Chemistry volume 13, pages 1126–1132 (2021)Cite this article

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Abstract

Carbon dioxide (CO2) is the major carbonaceous component of many planetary atmospheres, which includes the Earth throughout its history. Carbon fixation chemistry—which reduces CO2 to organics, utilizing hydrogen as the stoichiometric reductant—usually requires high pressures and temperatures, and the yields of products of potential use to nascent biology are low. Here we demonstrate an efficient ultraviolet photoredox chemistry between CO2 and sulfite that generates organics and sulfate. The chemistry is initiated by electron photodetachment from sulfite to give sulfite radicals and hydrated electrons, which reduce CO2 to its radical anion. A network of reactions that generates citrate, malate, succinate and tartrate by irradiation of glycolate in the presence of sulfite was also revealed. The simplicity of this carboxysulfitic chemistry and the widespread occurrence and abundance of its feedstocks suggest that it could have readily taken place on the surfaces of rocky planets. The availability of the carboxylate products on early Earth could have driven the development of central carbon metabolism before the advent of biological CO2 fixation.

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Fig. 1: Carboxysulfitic photoredox reaction network starting from bicarbonate (HCO3–) 1.
Fig. 2: Carboxysulfitic photoredox reaction network starting from glycolate 5.
Fig. 3: Connections between environmental chemistry and the development of metabolism.

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All data generated or analysed during this study are included in the manuscript and the Supplementary Information.

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Acknowledgements

We thank the J.D.S., D.D.S. and W.W.F. group members for helpful discussions. This research was supported by the Medical Research Council (MC_UP_A024_1009 to J.D.S.), the Simons Foundation (290362 to J.D.S., 290360 to D.D.S. and 554187 to W.W.F.). C.L.K. and D.D.S. thank W. Zinth, P. Dominguez, D. Yahalomi and G. Lozano for helpful discussions and experimental assistance, and acknowledge the Harvard Origins of Life Initiative.

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Authors and Affiliations

  1. MRC Laboratory of Molecular Biology, Cambridge Biomedical Campus, Cambridge, UK

    Ziwei Liu, Long-Fei Wu & John D. Sutherland

  2. Harvard-Smithsonian Center for Astrophysics, Massachusetts, MA, USA

    Corinna L. Kufner & Dimitar D. Sasselov

  3. Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA

    Woodward W. Fischer

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  1. Ziwei Liu
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Contributions

Z.L. discovered this carboxysulfitic chemistry and explored its scope under the supervision of J.D.S. and with the assistance of L.-F.W., C.L.K. performed the pump–probe experiments under the supervision of D.D.S. and W.W.F. evaluated the geochemical relevance of the chemistry. All the authors co-wrote the manuscript.

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Correspondence to John D. Sutherland.

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Extended data

Extended Data Fig. 1

Product concentrations and percentage yields after UV irradiation of solutions of NaHCO3 and Na2SO3.

Extended Data Fig. 2

Product concentrations and percentage yields after irradiation of individual bicarbonate reduction products (50 mM) and Na2SO3 (100 mM).

Supplementary information

Supplementary Information

Supplementary Figs. 1–32 and Tables 1–3.

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Liu, Z., Wu, LF., Kufner, C.L. et al. Prebiotic photoredox synthesis from carbon dioxide and sulfite. Nat. Chem. 13, 1126–1132 (2021). https://doi.org/10.1038/s41557-021-00789-w

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