Electron transfer reactions in methanogens

Methanogenic bacteria comprise a specialized group of obligately anaerobic microorganisms able to reduce a limited number of substrates to CH₄. The intermediates involved in this reduction process remain bound to a series of typical C₁-carriers. Reducing equivalents are either obtained from the oxidation of H₂ or from oxidation of carbon substrates to CO₂. Electron transfer reactions thus constitute the very essence of the process of methanogenesis.

In recent years much progress has been made in the elucidation of the special metabolic pathways and the nature of the C₁-carriers involved in methanogenic bacteria. The energy generated at the oxidoreduction reactions, notably at the methylreductase step, is conserved by ATP synthesis. The energy is used for cell carbon synthesis and, in catalytic amounts, for the reductive activation of some methanogenic enzymes. Before the condensing reaction resulting in the formation of acetyl-CoA takes place, 2 C₁-units are reduced or oxidized depending on the substrate to a carbonyl and a -CH₃ group. Formation of the latter proceeds via the methanogenic route. Intermediary cell carbon synthesis starting from acetyl-CoA involves reductive carboxylations and oxidoreductions by the participation of the enzymes of the tricarboxylic acid cycle.