Prebiotic Origin of Pre-RNA Building Blocks in a Urea "Warm Little Pond" Scenario.

Urea appears to be a key intermediate of important prebiotic synthetic pathways. Concentrated pools of urea likely existed on the surface of the early Earth, as urea is synthesized in significant quantities from hydrogen cyanide or cyanamide (widely accepted prebiotic molecules), it has extremely high water solubility, and it can concentrate to form eutectics from aqueous solutions. We propose a model for the origin of a variety of canonical and non-canonical nucleobases, including some known to form supramolecular assemblies that contain Watson-Crick-like base pairs.The dual nucleophilic-electrophilic character of urea makes it an ideal precursor for the formation of nitrogenous heterocycles. We propose a model for the origin of a variety of canonical and noncanonical nucleobases, including some known to form supramolecular assemblies that contain Watson-Crick-like base pairs. These reactions involve urea condensation with other prebiotic molecules (e. g., malonic acid) that could be driven by environmental cycles (e. g., freezing/thawing, drying/wetting). The resulting heterocycle assemblies are compatible with the formation of nucleosides and, possibly, the chemical evolution of molecular precursors to RNA. We show that urea eutectics at moderate temperature represent a robust prebiotic source of nitrogenous heterocycles. The simplicity of these pathways, and their independence from specific or rare geological events, support the idea of urea being of fundamental importance to the prebiotic chemistry that gave rise to life on Earth.

Asymmetric chiral growth of micron-size NaClO3 crystals in water aerosols.

We describe an aerosol-liquid cycle that launches the autocatalytic amplification of any initial imbalance of the order of 10(-7)% (1 ppb) up to total chiral purity in a single step process. Crystal nucleation of NaClO3 is initiated at the aerosol air-water interface where, due to the accumulation of ambient chiral impurities or added hydrophobic chiral aminoacids in tiny concentrations (ppb), the initial levorotatory (l) and dextrorotatory (d) excess will not be produced with equal probability. The enantiomeric yield is then enhanced up to homochirality by recycling the crystallites through a liquid phase. In the absence of added catalysts this process leads to preferential (d) homochiral crystallizations in a ratio of 4:1 which is due to ambient contamination. By adding only 2 ppb of (L) or (D) Phe, we induce a final preferential homochiral crystallization of (d) or (l) handedness, respectively, in a ratio of 2:1.

The effects of ferrous and other ions on the abiotic formation of biomolecules using aqueous aerosols and spark discharges.

It has been postulated that the oceans on early Earth had a salinity of 1.5 to 2 times the modern value and a pH between 4 and 10. Moreover, the presence of the banded iron formations shows that Fe(+2) was present in significant concentrations in the primitive oceans. Assuming the hypotheses above, in this work we explore the effects of Fe(+2) and other ions in the generation of biomolecules in prebiotic simulation experiments using spark discharges and aqueous aerosols. These aerosols have been prepared using different sources of Fe(+2), such as FeS, FeCl(2) and FeCO(3), and other salts (alkaline and alkaline earth chlorides and sodium bicarbonate at pH = 5.8). In all these experiments, we observed the formation of some amino acids, carboxylic acids and heterocycles, involved in biological processes. An interesting consequence of the presence of soluble Fe(+2) was the formation of Prussian Blue, Fe(4)[Fe(CN)(6)](3), which has been suggested as a possible reservoir of HCN in the initial prebiotic conditions on the Earth.

Prebiotic microreactors: a synthesis of purines and dihydroxy compounds in aqueous aerosol.

We report the synthesis of purine bases and other heterocycles and the formation of amino acids, hydroxy acids and dihydroxy compounds by the spark activation of an atmosphere of methane, nitrogen and hydrogen, in the presence of an aqueous aerosol. With the aid of the interface air-water, the organic material obtained shows greater amounts and diversity of molecules with biological interest than the products obtained in the absence of an aerosol. Our results support the suggestion that aerosols may have played a significant role in the prebiotic origin of molecular diversity and evolution.