Prebiotic Phosphorylation of Uridine using Diamidophosphate in Aerosols

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.

A critical analysis of electrospray techniques for the determination of accelerated rates and mechanisms of chemical reactions in droplets

“…Accelerated reaction rates are also observed in millimetersized droplets levitated either acoustically 33 or by the Leidenfrost effect, 19,34,35 as well as for evaporating droplets deposited on a surface. 36 Reaction rate acceleration has also been reported in other less commonly used approaches, including atomized sub-micron droplets suspended in an environmental chamber, 37 guided collisions of electrodynamically levitated micron-sized charged droplets, 38 thin-lms, 36,39,40 desorption ESI (DESI) MS, 41 laser ablation ESI-MS, 42 paper spray MS, 11,43 droplet imbibition, 44 and micro-emulsions. 45 In this work, we focus on the growing body of literature using ESI/ESSI-MS to investigate reaction rates and mechanisms in nano-and micro-droplets.…”

“…Quantication of competing gas-phase reactions. Some of the less commonly used approaches (environmental chambers, 37 guided collisions of charged micro-droplets, 38 droplet micro-emulsions 45 ) possess some or all of the desirable requirements listed above. For this reason, they have the potential of contributing to the understanding of the acceleration of reaction rates in droplets and of the role of surface processes.…”

Diamidophosphate (DAP): A Plausible Prebiotic Phosphorylating Reagent with a Chem to BioChem Potential?

“…Castañeda et al [26] . investigated the effect of aerosol environment (to mimic the early Earth ocean‐air interface) on DAP‐mediated phosphorylation of uridine 20 and observed rapid phosphorylation of uridine within hours to form the corresponding 2′,3′‐cyclophosphate 21 (Scheme 3d).…”

Carbamoyl phosphate and its substitutes for the uracil synthesis in origins of life scenarios

“…Phosphoramidates + urea. Urea had been found unreactive when contacted with P3m, so we tested its reactivity with respect to a solution containing phosphoramidates, which are considered to be better phosphorylating agents 66 than trimetaphosphate. Urea (0.102 g, 1.7 mmol) was dissolved into 2.5 mL of the phosphoramidates solution (obtained by P3m ammonolysis, cf.…”