Formamide reaction network in gas phase and solution via a unified theoretical approach: Toward a reconciliation of different prebiotic scenarios
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Significance: The qualitative and quantitative description of chemical reactions is a formidable problem. Determining pathways, energetics, and kinetics requires costly accurate quantum approaches. Typically, this amounts to a simplification of gas-phase reactions into elementary steps, which, in turn, are usually directly translated in solution. The topology-based method hereby presented allows instead an unbiased exploration of both gas-phase and aqueous-phase reactions. Its application to formamide, a centerpiece of prebiotic chemistry, unveils very different reaction networks between gas and solution regimes, indicating, in the liquid phase, new pathways, intermediates, and products. The new scheme allows us also to demonstrate the comparable relative stability of formamide, hydrogen cyanide, and formic acid, thus contributing insight to a heated current debate in the prebiotic chemistry community.
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Formamide and HCN are interconnected through a hydrolytic/dehydration process, which could have allowed alternating between both through a cycling physical process such as wetting-drying cycles.
“Their methods of synthesis, abundance in the universe and reactivities are actually similar, mostly because they are interconnected through a hydrolytic/dehydration process (see Scheme 6),86 which could have allowed alternating between both through some kind of cycling physical process (e.g., wetting-drying cycles as a consequences of geological events).”
From The protometabolic nature of prebiotic chemistry (2023) · cites this paper as [86]
Compared with HCN, formamide yields a wider variety of prebiotic biomolecules because the presence of oxygen allows an interplay of oxygenous and nitrogenous reactive species that is not possible in HCN oligomerization alone.
“In comparison to the chemistry of HCN, the reasons why formamide yields a wider variety of prebiotic biomolecules are diverse.84–89 The presence of oxygen in its structure allows an interplay of oxygenous and nitrogenous reactive species that is not possible in the HCN oligomerization alone.”
From The protometabolic nature of prebiotic chemistry (2023) · cites this paper as [86]
Cites
Saladino, R., Carota, E., Botta, G., Kapralov, M., Timoshenko, G. N., Rozanov, A. Y., Krasavin, E., & Di Mauro, E. (2015) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1422225112 · Cited by 200 · see citing works
Shock synthesis of amino acids from impacting cometary and icy planet surface analogues
Martins, Z., Price, M. C., Goldman, N., Sephton, M. A., & Burchell, M. J. (2013) · Nature Geoscience · doi:10.1038/ngeo1930 · Cited by 178 · see citing works
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The protometabolic nature of prebiotic chemistry
Nogal, N., Sanz-Sánchez, M., Vela-Gallego, S., Ruiz-Mirazo, K., & de la Escosura, A. (2023) · Chemical Society Reviews · doi:10.1039/d3cs00594a · Cited by 61 · see citing works
Estimating the Capacity for Production of Formamide by Radioactive Minerals on the Prebiotic Earth
Adam, Z. R., Hongo, Y., Cleaves, H. J., Yi, R., Fahrenbach, A. C., Yoda, I., & Aono, M. (2018) · Scientific Reports · doi:10.1038/s41598-017-18483-8 · Cited by 52 · see citing works
Bizzarri, B. M., Saladino, R., Delfino, I., García-Ruiz, J. M., & Di Mauro, E. (2021) · International Journal of Molecular Sciences · doi:10.3390/ijms22020917 · Cited by 33 · see citing works
- Authors
- Pietrucci, F., & Saitta, A. M.
- Affiliations
- Centre National de la Recherche Scientifique (FR)
- Corresponding author
- Pietrucci, Fabio
- Venue
- Proceedings of the National Academy of Sciences
- Publisher
- National Academy of Sciences
- Published
- 2015-11-23
- Volume
- 112
- Issue
- 49
- Pages
- 15030-15035
- ISSN
- 0027-8424 (ISSN-L)
- 1091-6490
- PMC
- PMC4679036
- OpenAlex
- W2254133415
- Cited by
- 144
- References
- 2
- Citations by year
- 2026: 8 · 2025: 9 · 2024: 12 · 2023: 13 · 2022: 13 · 2021: 21 · 2020: 19 · 2019: 18 · 2018: 13 · 2017: 7 · 2016: 11
- FWCI
- 5.88
- Type
- journal article
- Language
- en
- Open access
- bronze
- doi.org
- Locations
- Proceedings of the National Academy of Sciences (publishedVersion)
- Europe PMC (PubMed Central) (publishedVersion)
- PubMed Central (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Université Pierre et Marie Curie
- Grand Équipement National De Calcul Intensif
- Topics
- Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Advanced Physical and Chemical Molecular Interactions
- Physical Sciences › Chemistry › Organic Chemistry › Chemical Reaction Mechanisms
- Keywords
- formamide, prebiotic chemistry, reaction networks, hydrogen cyanide, reaction mechanism, solvent effects, gas-phase reactions, solution-phase reactions, metadynamics, collective variables, formic acid, ammonium formate, ab initio molecular dynamics
- MeSH terms
- Ammonia, Carbon Monoxide, Formamides, Formates, Solutions, Prebiotics
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