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Prebiotic Photoredox Synthesis from Carbon Dioxide and Sulfite

Liu, Ziwei and Wu, Long-Fei and Kufner, Corinna L. and Sasselov, Dimitar D. and Fischer, Woodward W. and Sutherland, John D. (2021) Prebiotic Photoredox Synthesis from Carbon Dioxide and Sulfite. . (Unpublished)

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Carbon dioxide (CO₂) is the major carbonaceous component of many planetary atmospheres including the Earth throughout its history, and prebiological chemistry that reduces this C1 feedstock to organics has accordingly been sought. Carbon fixation chemistry utilizing hydrogen as stoichiometric reductant tends to require high pressures and temperatures, and yields of products of potential use to nascent biology are low¹. Here we demonstrate efficient ultraviolet (UV) photoredox chemistry between CO₂ and sulfite (SO₃²⁻) that generates organics and sulfate (SO₄²⁻). The chemistry is initiated by electron photodetachment from SO₃²⁻giving sulfite radicals and hydrated electrons, which reduce CO₂ to its radical anion. By subjecting individual products and putative intermediates to the reaction conditions and analyzing the resultant mixtures, a network of ensuing reactions that can rationalize the products was revealed. In this way it was further discovered that citrate, malate, succinate, and tartrate can be generated by irradiation of glycolate in the presence of SO₃²⁻. 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 early Earth as well as on the surfaces of many rocky planets. The environmental availability of the carboxylate products on Earth could have driven the development of central carbon metabolism before the advent of biological CO₂ fixation.

Item Type:Report or Paper (Discussion Paper)
Related URLs:
URLURL TypeDescription Paper
Liu, Ziwei0000-0002-1812-2538
Kufner, Corinna L.0000-0001-7254-0581
Sasselov, Dimitar D.0000-0001-7014-1771
Fischer, Woodward W.0000-0002-8836-3054
Sutherland, John D.0000-0001-7099-4731
Additional Information:The content is available under CC BY NC ND 4.0 License. Feb 03, 2021. The authors thank 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. and 290360 to D.D.S.). C.L.K. and D.D.S. thank Wolfgang Zinth, Pablo Dominguez, Daniel Yahalomi, Gabriella Lozano for helpful discussions and experimental assistance, and acknowledge the Harvard Origins of Life Initiative. Author 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., W.W.F. evaluated the geochemical relevance of the chemistry. All authors co-wrote the manuscript. No conflict of interest.
Funding AgencyGrant Number
Medical Research Council (UK)MC_UP_A024_1009
Simons Foundation290362
Simons Foundation290360
Subject Keywords:carbon dioxide (CO₂); Photoreduction; Radical chemistry; Prebiotic Chemistry; Green Chemistry
Record Number:CaltechAUTHORS:20210716-205235654
Persistent URL:
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109884
Deposited By: Tony Diaz
Deposited On:16 Jul 2021 21:51
Last Modified:16 Jul 2021 21:51

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