Biomimetic phosphoryl transfer catalysed by iron(II)-mineral precipitates

Iron(II) minerals have been found to catalyse the formation of pyrophosphate from activated phosphate compounds and inorganic phosphate at near neutral pH in water. Iron(II) phosphate catalyses the formation of pyrophosphate, from either acetyl phosphate or phosphoenolpyruvate as the activated phosphoryl donor, in yields of up to 25% and 14% respectively. Under similar conditions, these minerals also retard the hydrolysis of pyrophosphate. The catalysis of pyrophosphate formation is tolerant of sulfide ions: pyrophosphate being produced from acetyl phosphate in 12% yield in the presence of equimolar amounts of sulfide. These reactions mimic the extant biosynthesis of ATP from acetyl phosphate or phosphoenolpyruvate; they counter the concern that hydrolysis of polyphosphates would out-compete their accumulation under prebiotic conditions; and hence suggest a possible prebiotic route to polyphosphates under conditions that may have occurred on the early earth.