Driving parts of Krebs cycle in reverse through mineral photochemistry

Scenarios for driving the Krebs cycle in reverse in the absence of enzymatic networks have received much attention in the literature of prebiotic evolution because repeated cycling provides a core mechanism for the synthesis of useful biomolecules from carbon dioxide. Here, we show that three of the five reductive steps in the cycle can be driven photochemically at high yield by a ZnS colloid. The results show the conversion of oxaloacetate to malate, fumarate to succinate, and oxoglutarate to oxalosuccinate. The experimental conditions of circumneutral pH and 288 K, as well as the ZnS semiconductor photocatalyst particles (sphalerite), are believed to have been prevalent in the waters of early Earth. These findings therefore both establish and constrain the plausibility of the occurrence of heretofore difficult chemical conversions in prebiotic metabolic systems.