Prebiotic metabolism: Production by mineral photoelectrochemistry of α-ketocarboxylic acids in the reductive tricarboxylic acid cycle

A reductive tricarboxylic acid (rTCA) cycle could have fixed carbon dioxide as biochemically useful energy-storage molecules on early Earth. Nonenzymatic chemical pathways for some steps of the rTCA cycle, however, such as the production of the α-ketocarboxylic acids pyruvate and α- ketoglutarate, remain a challenging problem for the viability of the proposed prebiotic cycle. As a class of compounds, α-ketocarboxylic acids have high free energies of formation that disfavor their production. We report herein the production of pyruvate from lactate and of α-ketoglutarate from pyruvate in the millimolar concentration range as promoted by ZnS mineral photoelectrochemistry. Pyruvate is produced from the photooxidation of lactate with 70% yield and a quantum efficiency of 0.009 at 15°C across the wavelength range of 200-400nm. The produced pyruvate undergoes photoreductive back reaction to lactate at a 30% yield and with a quantum efficiency of 0.0024. Pyruvate alternatively continues in photooxidative forward reaction to α-ketoglutarate with a 50% yield and a quantum efficiency of 0.0036. The remaining 20% of the carbon follows side reactions that produce isocitrate, glutarate, and succinate. Small amounts of acetate are also produced. The results of this study suggest that α-ketocarboxylic acids produced by mineral photoelectrochemistry could have participated in a viable enzyme-free cycle for carbon fixation in an environment where light, sulfide minerals, carbon dioxide, and other organic compounds interacted on prebiotic Earth. Key Words: Origin of life-Prebiotic chemistry-Photoelectrochemistry-Zinc sulfide-Reductive tricarboxylic acid cycle-Pyruvate-Lactate-α- Ketoglutarate-Photooxidation-Photoreduction.