Stabilization of Prebiotic Vesicles by Peptides Depends on Sequence and Chirality: A Mechanism for Selection of Protocell-Associated Peptides.

Cells require oligonucleotides and polypeptides with specific, homochiral sequences to perform essential functions, but it is unclear how such oligomers were selected from random sequences at the origin of life. Cells were probably preceded by simple compartments such as fatty acid vesicles, and oligomers that increased the stability, growth, or division of vesicles could have thereby increased in frequency. We therefore tested whether prebiotic peptides alter the stability or growth of vesicles composed of a prebiotic fatty acid. We find that three of 15 dipeptides tested reduce salt-induced flocculation of vesicles. All three contain leucine, and increasing their length increases the efficacy. Also, leucine-leucine but not alanine-alanine increases the size of vesicles grown by multiple additions of micelles. In a molecular simulation, leucine-leucine docks to the membrane, with the side chains inserted into the hydrophobic core of the bilayer, while alanine-alanine fails to dock. Finally, the heterochiral forms of leucine-leucine, at a high concentration, rapidly shrink the vesicles and make them leakier and less stable to high pH than the homochiral forms do. Thus, prebiotic peptide-membrane interactions influence the flocculation, growth, size, leakiness, and pH stability of prebiotic vesicles, with differential effects due to sequence, length, and chirality. These differences could lead to a population of vesicles enriched for peptides with beneficial sequence and chirality, beginning selection for the functional oligomers that underpin life.

Three-stage formation of cap carbonates after Marinoan snowball glaciation consistent with depositional timescales and geochemistry.

At least two global "Snowball Earth" glaciations occurred during the Neoproterozoic Era (1000-538.8 million years ago). Post-glacial surface environments during this time are recorded in cap carbonates: layers of limestone or dolostone that directly overlie glacial deposits. Postulated environmental conditions that created the cap carbonates lack consensus largely because single hypotheses fail to explain the cap carbonates' global mass, depositional timescales, and geochemistry of parent waters. Here, we present a global geologic carbon cycle model before, during, and after the second glaciation (i.e. the Marinoan) that explains cap carbonate characteristics. We find a three-stage process for cap carbonate formation: (1) low-temperature seafloor weathering during glaciation generates deep-sea alkalinity; (2) vigorous post-glacial continental weathering supplies alkalinity to a carbonate-saturated freshwater layer, rapidly precipitating cap carbonates; (3) mixing of post-glacial meltwater with deep-sea alkalinity prolongs cap carbonate deposition. We suggest how future geochemical data and modeling refinements could further assess our hypothesis.

Favorable Environments for the Formation of Ferrocyanide, a Potentially Critical Reagent for Origins of Life.

Cyanide and its derivatives play important roles in prebiotic chemistry through a variety of possible mechanisms. In particular, cyanide has been shown to allow for the synthesis of ribonucleotides and amino acids. Although dissolved hydrogen cyanide can be lost as a gas or undergo hydrolysis reactions, cyanide can also potentially be stored and stockpiled as ferrocyanide (Fe(CN)6-4), which is more stable. Furthermore, ferrocyanide aids in some prebiotic synthetic reactions. Here, we investigate the formation rates and yields of ferrocyanide as a function of various environmental parameters, such as the pH, temperature, and concentration. We find that ferrocyanide formation rates and yields are optimal at slightly alkaline conditions (pH 8-9) and moderate temperatures (≈20-30 °C). Given the wide range of possible lake environments likely available on early Earth, our results help to constrain the environmental conditions that would favor cyanide- and ferrocyanide-based prebiotic chemistries. We construct lake box models and find that ferrocyanide may be able to form and reach significant concentrations for prebiotic chemistry on the time scale of years under favorable conditions.

UV Transmission in Prebiotic Environments on Early Earth.

Ultraviolet (UV) light is likely to have played important roles in surficial origins of life scenarios, potentially as a productive source of energy and molecular activation, as a selective means to remove unwanted side products, or as a destructive mechanism resulting in loss of molecules/biomolecules over time. The transmission of UV light through prebiotic waters depends upon the chemical constituents of such waters, but constraints on this transmission are limited. Here, we experimentally measure the molar decadic extinction coefficients for a number of small molecules used in various prebiotic synthetic schemes. We find that many small feedstock molecules absorb most at short (∼200 nm) wavelengths, with decreasing UV absorption at longer wavelengths. For comparison, we also measured the nucleobase adenine and found that adenine absorbs significantly more than the simpler molecules often invoked in prebiotic synthesis. Our results enable the calculation of UV photon penetration under varying chemical scenarios and allow further constraints on plausibility and self-consistency of such scenarios. While the precise path that prebiotic chemistry took remains elusive, improved understanding of the UV environment in prebiotically plausible waters can help constrain both the chemistry and the environmental conditions that may allow such chemistry to occur.

Natural soda lakes provide compatible conditions for RNA and membrane function that could have enabled the origin of life.

The origin of life likely occurred within environments that concentrated cellular precursors and enabled their co-assembly into cells. Soda lakes (those dominated by Na+ ions and carbonate species) can concentrate precursors of RNA and membranes, such as phosphate, cyanide, and fatty acids. Subsequent assembly of RNA and membranes into cells is a long-standing problem because RNA function requires divalent cations, e.g. Mg2+, but Mg2+ disrupts fatty acid membranes. The low solubility of Mg-containing carbonates limits soda lakes to moderate Mg2+ concentrations (∼1 mM), so we investigated whether both RNAs and membranes function within these lakes. We collected water from Last Chance Lake and Goodenough Lake in Canada. Because we sampled after seasonal evaporation, the lake water contained ∼1 M Na+ and ∼1 mM Mg2+ near pH 10. In the laboratory, nonenzymatic, RNA-templated polymerization of 2-aminoimidazole-activated ribonucleotides occurred at comparable rates in lake water and standard laboratory conditions (50 mM MgCl2, pH 8). Additionally, we found that a ligase ribozyme that uses oligonucleotide substrates activated with 2-aminoimidazole was active in lake water after adjusting pH from ∼10 to 9. We also observed that decanoic acid and decanol assembled into vesicles in a dilute solution that resembled lake water after seasonal rains, and that those vesicles retained encapsulated solutes despite salt-induced flocculation when the external solution was replaced with dry-season lake water. By identifying compatible conditions for nonenzymatic and ribozyme-catalyzed RNA assembly, and for encapsulation by membranes, our results suggest that soda lakes could have enabled cellular life to emerge on Earth, and perhaps elsewhere.