The active species of 'CO2' utilized by formylmethanofuran dehydrogenase from methanogenic Archaea

Formylmethanofuran dehydrogenase from methanogenic Archaea catalyzes the reversible conversion of CO2 and methanofuran to formylmethanofuran, which is an intermediate in methanogenesis from CO2, a biological process yielding approximately 0.3 billion tons of CH4 per year. With the enzyme from Methanosarcina barkeri, it is shown that CO2 rather than HCO3- is the active species of 'CO2' utilized by the dehydrogenase. Evidence is also presented that the enzyme catalyzes a methanofuran-dependent exchange between CO2 and the formyl group of formylmethanofuran. The results are consistent with N-carboxymethanofuran being an intermediate in CO2 reduction to formylmethanofuran.