The formamide-based scenario of the origin of life through the eyes of a computational chemist
Dr. Judit E. Šponer, Academy of Sciences of the Czech Republic, Brno
The formamide-based synthesis of nucleic acid components offers a new alternative for the origin of informational polymers.1 This chemistry represents an elegant and continuous way from simple prebiotic precursors up to short catalytic oligonucleotides. Since this multistep synthesis proceeds in a very complex reaction mixture, it is very difficult to study its mechanism using purely experimental methods. Our presentation is aimed to illustrate that in such complicated cases computational chemistry might be instrumental to provide an atomic-level insight into the mechanistic details of the reactions. We show that the applicability of theoretical chemistry tools is not restricted to a simple verification of experimentally suggested reaction mechanisms, and, when properly done, computational methods can be used to propose mechanistic models on their own. This is especially important when experimental methods do not allow for obtaining accurate structural information on the reaction complexes under investigation.
In particular, we will address the thermal scenario elaborated by the Saladino and Di Mauro groups.1 We will examine the reaction pathways leading to the formation of nucleobases from formamide.1,2 We will analyze the steric and energetic conditions controlling the self-assembling and spontaneous polymerization of cyclic nucleotide precursors that could produce the first RNA oligomers.3 Further, we will scrutinize the simplest molecular architectures that could give rise to the catalytic activity of the most ancient RNA molecules.4
We will also consider a high-energy scenario for the origin of life from formamide. We will describe a chemistry that could contribute to the synthesis of nucelobases in a high-energy-density event, like a meteoritic impact, which is relevant to the Late Heavy Bombardment period of Earth’s history about 3.8 billion years ago.5,6
 R. Saladino, G. Botta, S. Pino, G. Costanzo, E. Di Mauro, Chem. Soc. Rev., 2012, 41, 5526.
 J. E. Šponer, A. Mládek, J. Šponer, M. Fuentes-Cabrera, J. Phys. Chem. A, 2012, 116, 720-726.
 J. E. Šponer, J. Šponer, A. Giorgi, E. Di Mauro, S. Pino, G. Costanzo, G. J. Phys. Chem. B 2015, 119, 2979-2989.
 P. Stadlbauer, J. Šponer, G. Costanzo, E. Di Mauro, S. Pino, J. E. Šponer, Chem. Eur. J. 2015, 21, 3596-3604.
 M. Ferus, S. Civiš, A. Mládek, J. Šponer, L. Juha, J. E. Šponer, J. Am. Chem. Soc., 2012, 134, 20788.
 M. Ferus, D. Nesvorný, J. Šponer, P. Kubelík, R. Michalčíková, V. Shestivská, J. E. Šponer, S. Civiš, Proc. Natl. Acad. Sci. U.S.A. 2015, 112, 657-662.