The high-energy 3',5' phosphodiester linkages conserved in 3',5' cyclic GMPs offer a genuine solution for monomer activation required by the transphosphorylation reactions that could lead to the emergence of the first simple oligonucleotide sequences on the early Earth. In this work we provide an in-depth characterization of the effect of the reaction conditions on the yield of the polymerization reaction of 3',5' cyclic GMPs both in aqueous environment as well as under dehydrating conditions. We show that the threshold temperature of the polymerization is about 30 °C lower under dehydrating conditions than in solution. In addition, we present a plausible exergonic reaction pathway for the polymerization reaction, which involves transient formation of anionic centers at the O3' positions of the participating riboses. We suggest that excess Na(+) cations inhibit the polymerization reaction because they block the anionic mechanism via neutralizing the negatively charged O3'. Our experimental findings are compatible with a prebiotic scenario, where gradual desiccation of the environment could induce polymerization of 3',5' cyclic GMPs synthesized in liquid.

Institute of Biophysics Academy of Sciences of the Czech Republic Královopolská 135 CZ 61265 Brno Czech Republic

References provided by Crossref.org

Crystallization as a selection force at the polymerization of nucleotides in a prebiotic context

Acid-Catalyzed RNA-Oligomerization from 3',5'-cGMP

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Rewarming the Primordial Soup: Revisitations and Rediscoveries in Prebiotic Chemistry

Non-Enzymatic Oligomerization of 3', 5' Cyclic AMP

Four Ways to Oligonucleotides Without Phosphoimidazolides