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Synthesizing oligomers from monomeric nucleotides in simulated hydrothermal environments.

Dimers and trimers of adenosine monophosphate (AMP) were synthesized from AMP in environments simulating hot vents on the sea floor of the primitive Earth. The simulated environments were made in the flow reactor, in which an aqueous solution of reactants was circulated from the hot to the cold region repeatedly. The oligomerization proceeded most significantly when the hot reaction solution at about 110 degrees C was abruptly ejected into the cold environment maintained at about 0 degree C.

Adenine Nucleotides↗

Hydrothermal circulation of seawater through hot vents and contribution of interface chemistry to prebiotic synthesis.

Synthesizing oligopeptides from glycine and alanine in a flow reactor, which stimulates constant hydrothermal circulation of seawater through hot vents on the primitive Earth, demonstrated that an exponential growth of the products is possible. The initial rapid growth of the product is a consequence of using the products formed in one cycle as the starting materials for the cycle of synthesis.

Alanine↗

Nonenzymatic template-directed condensation of short-chained oligouridylates on a poly(A) template.

An oligouridylate with chain-length of more than three was condensed on a polyadenylate [poly(A)] template with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDAC) in imidazole buffer. The condensation reaction proceeds via the phosphorimidazolide of the oligouridylate as an intermediate. Pentauridylate [(pU)5] was converted to decauridylate [(pU)10] in 10% yield at 0 degree C for 7 days in the presence of the poly(A) template, while no coupling product was obtained in the absence of the poly(A) template. The resulting linkage of the (pU)10 was mainly 2'-5' linkage.

Base Sequence↗

Abiotic synthesis of guanine with high-temperature plasma.

The origin of guanine has been unknown, though there are some reports concerning its abiotic synthesis. We show here that guanine, as well as uracil and cytosine, are synthesized from a 90%N2-10%CO-H2O gas mixture via a complex organic product produced with the high-temperature and rapid quenching technique. This result implies that a large amount of complex organic matter including precursors of bioorganic compounds might have been produced on the primitive earth after cometary impacts.

Carbon Monoxide↗

Formation of peptide bonds from metastable versus crystalline phase: implications for the origin of life.

Formation of peptide bonds was attempted by thermal activation of dry amino acids from aqueous solution that simulated prebiotic evaporative environments. The evaporation trend of amino acids solutions shows a bifurcation and can lead to either a crystalline phase (near equilibrium) or a metastable non-crystalline phase (far from equilibrium). Only amino acids in this metastable phase are able to form peptide bonds by thermal activation at temperatures that are generated by solar radiation today. We suggest that this metastable phase is the ideal initial material to trigger amino acid assemblage with protein-like structure because provide the driving force (supersaturation) for an intense interaction between monomers of different amino acids and allows activation of these monomers in plausible prebiotic conditions.

Amino Acids↗

Causation and the origin of life. Metabolism or replication first?

The conceptual gulf that separates the 'metabolism first' and 'replication first' mechanisms for the emergence of life continues to cloud the origin of life debate. In the present paper we analyze this aspect of the origin of life problem and offer arguments in favor of the 'replication first' school. Utilizing Wicken's two-tier approach to causation we argue that a causal connection between replication and metabolism can only be demonstrated if replication would have preceded metabolism. In conjunction with existing empirical evidence and theoretical reasoning, our analysis concludes that there is no substantive evidence for a 'metabolism first' mechanism for life's emergence, while a coherent case can be made for the 'replication first' group of mechanisms. The analysis reaffirms our conviction that life is an extreme expression of kinetic control, and that the emergence of metabolic pathways can be understood by considering life as a manifestation of 'replicative chemistry'.

Energy Metabolism↗

High-temperature life without photosynthesis as a model for Mars.

Discoveries in biology and developments in geochemistry over the past two decades have lead to a radical revision of concepts relating to the upper temperature at which life thrives, the genetic relationships among all life on Earth, links between organic and inorganic compounds in geologic processes, and the geochemical supply of metabolic energy. It is now apparent that given a source of geochemical energy, in the form of a mixture of compounds that is far from thermodynamic equilibrium, microorganisms can take advantage of the energy and thrive without the need for photosynthesis as a means of primary productivity. This means that life can exist in the subsurface of a planet such as Mars without necessarily exhibiting a surface expression. Theoretical calculations quantify the geochemically provided metabolic energy available to hyperthermophilic organisms in submarine hydrothermal systems on the Earth, and help to explain the enormous biological productivity of these systems. Efforts to place these models in the context of the early Earth reveal that substantial geochemical energy would have been available and that organic synthesis would have been thermodynamically favored as hydrothermal fluids mix with seawater.

Euryarchaeota↗

Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite.

The origin of the organic matter in carbonaceous meteorites remains controversial despite extensive study over the past 20 yr. Motivated by the expectation that the patterns of isotopic variation with molecular structure among the organic compounds would contain important clues to their origin, we have measured the carbon isotopic compositions for individual hydrocarbons and monocarboxylic acids from Murchison meteorite, a C2 carbonaceous chondrite which fell in Australia in 1969. With few exceptions, notably benzene, the volatile products are substantially isotopically heavier than their terrestrial counterparts, signifying their extraterrestrial origin. For both classes of compounds, the ratio of 13C to 12C decreases with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic ratio than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with the kinetically controlled synthesis of higher homologues from lower ones. The results suggest the possibility that the production mechanisms for hydrocarbons and carboxylic acids may be similar; they also impose constraints on the identity of the reactant species.

Carbon Dioxide↗

New estimates of asymmetric decomposition of racemic mixtures by natural beta-radiation sources.

The Vester-Ulbricht hypothesis suggests that the chirality of biological molecules originates from the beta-radiolysis of prebiotic racemic mixtures. Despite the inconclusiveness of past investigations, recent calculations have shown that beta particles, because of their helicity, radiolyse L- and D-enantiomers at slightly different rates, the asymmetry, AR, being predicted to be 10(-11) (new experimental tests, give /AR/ < 2 x 10(-9)). Before this, the size of the radiolysis-induced chiral polarization, eta R (eta triple bond (nL - nD)/(nL + nD) where nL and nD are the numbers of L and D molecules present), was estimated for different values of AR; according to Keszthelyi et al., if /AR/ approximately 10(-11), /eta R/ can never exceed the chiral polarization, /eta F/, produced by statistical fluctuations, thus invalidating the V-U hypothesis. Here we re-examine the major assumptions on which these calculations were based and find that several overly restrictive conditions were imposed, which, when relaxed, allow the condition /eta R/ > /eta F/, in accordance with the V-U hypothesis.

Amino Acids↗

The nature and origin of interstellar diamond.

Microscopic diamond was recently discovered in oxidized acid residues from several carbonaceous chondrite meteorites (for example, the C delta component of the Allende meteorite). Some of the reported properties of C delta seem in conflict with those expected of diamond. Here we present high spatial resolution analytical data which may help to explain such results. The C delta diamond is an extremely fine-grained (0.5-10 nm) single-phase material, but surface and interfacial carbon atoms, which may comprise as much as 25% of the total, impart an 'amorphous' character to some spectral data. These data support the proposed high-pressure conversion of amorphous carbon and graphite into diamonds due to grain-grain collisions in the interstellar medium although a low-pressure mechanism of formation cannot be ruled out.

Carbon↗

Submarine hot springs and the origin of life.

The discovery of hydrothermal vents at oceanic ridge crests and the appreciation of their importance in the element balance of the oceans is one of the main recent advances in marine geochemistry. It is likely that vents were present in the oceans of the primitive Earth because the process of hydrothermal circulation probably began early in the Earth's history. Here we examine the popular hypothesis that life arose in these vents. This proposal, however, is based on a number of misunderstandings concerning the organic chemistry involved. An example is the suggestion that organic compounds were destroyed on the surface of the early Earth by the impact of asteroids and comets, but at the same time assuming that organic syntheses can occur in hydrothermal vents. The high temperatures in the vents would not allow synthesis of organic compounds, but would decompose them, unless the exposure time at vent temperatures was short. Even if the essential organic molecules were available in the hot hydrothermal waters, the subsequent steps of polymerization and the conversion of these polymers into the first organisms would not occur as the vent waters were quenched to the colder temperatures of the primitive oceans.

Amino Acids↗

Carbon isotope composition of individual amino acids in the Murchison meteorite.

A significant portion of prebiotic organic matter on the early Earth may have been introduced by carbonaceous asteroids and comets. The distribution and stable-isotope composition of individual organic compounds in carbonaceous meteorites, which are thought to be derived from asteroidal parent bodies, may therefore provide important information concerning mechanistic pathways for prebiotic synthesis and the composition of organic matter on Earth before living systems developed. Previous studies have shown that meteorite amino acids are enriched in 13C relative to their terrestrial counterparts, but individual species were not distinguished. Here we report the 13C contents of individual amino acids in the Murchison meteorite. The amino acids are enriched in 13C, indicating an extraterrestrial origin. Alanine is not racemic, and the 13C enrichment of its D- and L-enantiomers implies that the excess of the L-enantiomer is indigenous rather than terrestrial contamination, suggesting that optically active materials were present in the early Solar System before life began.

Amino Acids↗