title: Reactivity landscape of pyruvate under simulated hydrothermal vent conditions.
abstract: Pyruvate is an important "hub" metabolite that is a precursor for amino acids, sugars, cofactors, and lipids in extant metabolic networks. Pyruvate has been produced under simulated hydrothermal vent conditions from alkyl thiols and carbon monoxide in the presence of transition metal sulfides at 250 °C [Cody GD et al. (2000) Science 289(5483):1337-1340], so it is plausible that pyruvate was formed in hydrothermal systems on the early earth. We report here that pyruvate reacts readily in the presence of transition metal sulfide minerals under simulated hydrothermal vent fluids at more moderate temperatures (25-110 °C) that are more conducive to survival of biogenic molecules. We found that pyruvate partitions among five reaction pathways at rates that depend upon the nature of the mineral present; the concentrations of H2S, H2, and NH4Cl; and the temperature. In most cases, high yields of one or two primary products are found due to preferential acceleration of certain pathways. Reactions observed include reduction of ketones to alcohols and aldol condensation, both reactions that are common in extant metabolic networks. We also observed reductive amination to form alanine and reduction to form propionic acid. Amino acids and fatty acids formed by analogous processes may have been important components of a protometabolic network that allowed the emergence of life.
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder, CO 80309, USA.
authors.forename: Yehor
authors.initials: Y
authors.lastname: Novikov
authors.forename: Shelley D
authors.initials: SD
authors.lastname: Copley
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D002384:Catalysis; D060086:Hydrothermal Vents / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry; D008670:Metals / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D010084:Oxidation-Reduction; D019289:Pyruvic Acid / Q000737:chemistry*; D013440:Sulfides / Q000737:chemistry; D013696:Temperature
chemical_list: D000447:Aldehydes; D007659:Ketones; D008670:Metals; D013440:Sulfides; D019289:Pyruvic Acid; C116609:3-hydroxybutanal
keywords: abiogenesis; catalysis; prebiotic chemistry