Chirality, photochemistry and the detection of amino acids in interstellar ice analogues and comets

At some stage in the origin of life, an informational polymer must have arisen by purely chemical means. According to one version of the 'RNA world' hypothesis this polymer was RNA, but attempts to provide experimental support for this have failed. In particular, although there has been some success demonstrating that 'activated' ribonucleotides can polymerize to form RNA, it is far from obvious how such ribonucleotides could have formed from their constituent parts (ribose and nucleobases). Ribose is difficult to form selectively, and the addition of nucleobases to ribose is inefficient in the case of purines and does not occur at all in the case of the canonical pyrimidines. Here we show that activated pyrimidine ribonucleotides can be formed in a short sequence that bypasses free ribose and the nucleobases, and instead proceeds through arabinose amino-oxazoline and anhydronucleoside intermediates. The starting materials for the synthesis-cyanamide, cyanoacetylene, glycolaldehyde, glyceraldehyde and inorganic phosphate-are plausible prebiotic feedstock molecules, and the conditions of the synthesis are consistent with potential early-Earth geochemical models. Although inorganic phosphate is only incorporated into the nucleotides at a late stage of the sequence, its presence from the start is essential as it controls three reactions in the earlier stages by acting as a general acid/base catalyst, a nucleophilic catalyst, a pH buffer and a chemical buffer. For prebiotic reaction sequences, our results highlight the importance of working with mixed chemical systems in which reactants for a particular reaction step can also control other steps.

Sources of organic molecules on the early Earth divide into three categories: delivery by extraterrestrial objects; organic synthesis driven by impact shocks; and organic synthesis by other energy sources (such as ultraviolet light or electrical discharges). Estimates of these sources for plausible end-member oxidation states of the early terrestrial atmosphere suggest that the heavy bombardment before 3.5 Gyr ago either produced or delivered quantities of organics comparable to those produced by other energy sources. Which sources of prebiotic organics were quantitatively dominant depends strongly on the composition of the early terrestrial atmosphere. In the event of an early strongly reducing atmosphere, production by atmospheric shocks seems to have dominated that due to electrical discharges. Organic synthesis by ultraviolet light may, in turn, have dominated shock production, but only if a long-wavelength absorber such as H2S were supplied to the atmosphere at a rate sufficient for synthesis to have been limited by ultraviolet flux, rather than by reactant abundance. In the apparently more likely case of an early terrestrial atmosphere of intermediate oxidation state, atmospheric shocks were probably of little importance for direct organic production. For [H2]/[CO2] ratios of approximately 0.1, net organic production was some three orders of magnitude lower than for reducing atmospheres, with delivery of intact exogenous organics in interplanetary dust particles (IDPs) and ultraviolet production being the most important sources. At still lower [H2]/[CO2] ratios, IDPs may have been the dominant source of prebiotic organics on the early Earth. Endogenous, exogenous and impact-shock sources of organics could each have made a significant contribution to the origins of life.