Abstract
One of the most challenging fundamental problems in establishing prebiotically plausible routes for phosphorylation reactions using phosphate is that they are thermodynamically unfavorable in aqueous conditions. Diamidophosphate (DAP), a potentially prebiotically relevant compound, was shown to phosphorylate nucleosides in aqueous medium, albeit at a very slow rate (days/weeks). Here, we demonstrate that performing these reactions within an aerosol environment, a suitable model for the early Earth ocean-air interface, yields higher reaction rates when compared to bulk solution, thus overcoming these rate limitations. As a proof-of-concept, we demonstrate the effective conversion (~6.5–10%) of uridine to uridine-2′,3′-cyclophosphate in less than 1 h. These results suggest that aerosol environments are a possible scenario in which prebiotic phosphorylation could have occurred despite unfavorable rates in bulk solution.
Highlights
Krishnamurthy and co-workers[10] demonstrated phosphorylation of various prebiological molecules using diamidophosphate (DAP) in aqueous conditions
We report here that aerosols do have a positive effect on the phosphorylation reaction rates and observed significant formation of 2′,3′-cUMP in the aerosol-mediated reactions
Uridine and DAP were combined in solutions adjusted to pH 5.5 using HCl, followed by 20 min atomization of these solutions to form the aerosol phase, where the particles were suspended in an enclosed Teflon chamber. 2′,3′-cUMP was formed within the aerosols that were collected on a Teflon filter, reconstituted with H2O, and analyzed using liquid chromatography mass spectrometry (LC-MS)
Summary
Krishnamurthy and co-workers[10] demonstrated phosphorylation of various prebiological molecules (nucleosides, amino acids, and lipid precursors) using diamidophosphate (DAP) in aqueous conditions. DAP has been previously employed as a prebiotic phosphorylation reagent[11,12,13], and it can be synthesized via corrosion of schreibersite with aqueous ammonia[14] or reacting prebiotically available trimetaphosphate[15] with ammonia[16,17] In this study they demonstrated effective, one-pot phosphorylation reactions in both bulk solutions, and so-called “paste” conditions where they added only ~20–30 μL of water. Zare and co-workers recently detected the formation of sugar-phosphate and uridine ribonucleoside in aqueous microdroplets using phosphoric acid[9] They used an electrospray ionization (ESI) source for form the droplets, and analyzed the products via mass spectrometry. We report here that aerosols do have a positive effect on the phosphorylation reaction rates and observed significant formation of 2′,3′-cUMP in the aerosol-mediated reactions
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