The evolution of life from the prebiotic environment required a gradual process of chemical evolution towards greater molecular complexity. Elaborate prebiotically relevant synthetic routes to the building blocks of life have been established. However, it is still unclear how functional chemical systems evolved with direction using only the interaction between inherent molecular chemical reactivity and the abiotic environment. Here we demonstrate how complex systems of chemical reactions exhibit well-defined self-organization in response to varying environmental conditions. This self-organization allows the compositional complexity of the reaction products to be controlled as a function of factors such as feedstock and catalyst availability. We observe how Breslow’s cycle contributes to the reaction composition by feeding C2 building blocks into the network, alongside reaction pathways dominated by formaldehyde-driven chain growth. The emergence of organized systems of chemical reactions in response to changes in the environment offers a potential mechanism for a chemical evolution process that bridges the gap between prebiotic chemical building blocks and the origin of life.
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All data supporting the findings of this study are available within the paper and Supplementary Data and Supplementary Information. Source data are provided with this paper.
All programs used to analyse and plot the data are available on GitHub (https://github.com/huckgroup/formose-2021.git).
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This work was supported by funding from the Simons Collaboration on the Origins of Life (SCOL; award 477123, W.T.S.H., W.E.R.) and the Dutch Ministry of Education, Culture and Science (Functional Molecular Systems Gravity programme 024.001.035, W.T.S.H., W.E.R., E.D., P.D.). The funders had no role in study design, data collection and analysis, decision to publish or preparation of the manuscript. We thank P van Galen, R de Graaf and J del Pozo Mellado for support with GC–MS analysis.
The authors declare no competing interests.
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Detailed reaction types which describe the transformations shown in Fig. 1a (main text).
a Side schematic of the reactor depicting how inputs and the outlet were connected to the reactor and how the temperature was controlled. b Bottom view of the reactor showing the geometry of the inlet holes into the reactor.
The structures of compounds assigned in this work and their corresponding numbering scheme.
Extended Data Fig. 4 Mappings of key conditionals variations across data sets to the leaves of the dendrogram.
a Formaldehyde, b dihydroxyacetone, c CaCl2, d NaOH, e the ratio of CaCl2:NaOH, f The location of glycolaldehyde (2), erythrulose (9) and ribose (19) initiated reactions. The colour bars below each dendrogram indicate mapping of the colour to the value of each condition.
Conditions: formaldehyde (200 mM), dihydroxyacetone (25 mM amplitude, 50 mM offset, period 6 min.), CaCl2 (15 mM), NaOH (30 mM).
The data were determined from flow reactions at 21 °C, with inputs of dihydroxyacetone (25 mM amplitude, 50 mM offset, period three times the residence time), formaldehyde (200 mM), CaCl2 (15 mM), and NaOH (30 mM). Input concentrations are quoted as the initial concentration of compounds upon entering the continuous stirred-tank reactor.
a The C2-C3 reaction to create 14 via a six-membered ring transition state in which α-hydroxymethyl groups adopt lower energy equatorial positions. b A similar reaction and transition state as show in panel a from which compound 20 is formed. Dashed bonds indicate those formed and broken over the course of the reaction.
a The open-chain structure of 12. b The open-chain structure of 13. The likely conformation of the six-membered ring formed via coordination of Ca2+ to 12 (c) and 13 (d). Charges (Ca2+, O–) are omitted for clarity.
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Robinson, W.E., Daines, E., van Duppen, P. et al. Environmental conditions drive self-organization of reaction pathways in a prebiotic reaction network. Nat. Chem. 14, 623–631 (2022). https://doi.org/10.1038/s41557-022-00956-7
Nature Chemistry (2022)