Pyrophosphate formation from phospho(enol)pyruvate adsorbed onto precipitated orthophosphate: A model for prebiotic catalysis of transphosphorylations

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It has been postulated that adsorption and surface catalysis, as well as repeated drying and wetting cycles, were essential in the synthesis, interconversion and co-evolution of phosphorylated molecules, including ‘energy-rich’ compounds. We have investigated the formation of pyrophosphate from phospho(enol)pyruvate and orthophosphate. The reaction occurred within hours at 37°C, required the adsorption of phospho(enol)pyruvate onto sedimented phosphate, exhibited Michaelian-like behavior and showed positive cooperativity with respect to divalent cation concentration. Thus in ‘mild’, near-equilibrium conditions, the de-solvated surfaces of phosphate crystals can catalyze the formation of pyrophosphate with a kinetic behavior similar to that found in contemporary enzymes. The experimental system we describe may represent a model for the prebiotic catalysis of transphosphorylations.