Wolfe cycle

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Wolfe cycle

The Wolfe Cycle is a methanogenic pathway used by archaea; the archaeon takes H2 and CO2 and cycles them through a various intermediates to create methane.[1] The Wolfe Cycle is modified in different orders and classes of archaea as per the resource availability and requirements for each species, but it retains the same basic pathway.[1] The pathway begins with the reducing carbon dioxide to formylmethanofuran.[1] The last step uses heterodisulfide reductase (Hdr) to reduce heterodisulfide into Coenzyme B and Coenzyme M using Fe4S4 clusters.[1][2] Evidence suggests this last step goes hand-in-hand with the first step, and feeds back into it, creating a cycle.[1] At various points in the Wolfe Cycle, intermediates that are formed are taken out of the cycle to be used in other metabolic processes.[1][3] Since intermediates are being taken out at various points in the cycle, there is also a replenishing (anaplerotic) reaction that feeds into the Wolfe cycle, this is to regenerate necessary intermediates for the cycle to continue.[1] Overall, including the replenishing reaction, the Wolfe Cycle has a total of nine steps.[1] While Obligate COA2 reducing methanogens perform additional steps to reduce CO2 to CHA3.

Discovery

In 1971, in a review published by Robert Stoner Wolfe, information regarding methanogenesis in M. bryantii was published. At the time, the only thing known about this process was that Coenzyme M was involved.[4] In addition, methanogenesis was thought to follow a linear pathway. It was not until 1986 that the reduction of COA2 to CHA4 was proposed to occur in a cycle when it was shown that Steps 8 and 1 are coupled.[4]

Steps

The Wolfe Cycle follows multiple pathways, depending on the microbe. Below are generalized steps in the Wolfe Cycle.

steps reactants Enzymes[4] Products used in cycle
1 COA2+MF+2HA+ Formyl-methanofuran dehydrogenase FormylMFR
2 NFormylMFR+HA4MPT Formyltransferase NFormylHA4MPT
3 FormylHA4MPT+HA+ methenyl-H4MPT cyclohydrolase methenylHA4MPT
4 MethenylHA4MPT+FA420HA2 methylene-H4MPT dehydrogenase methyleneHA4MPT
5 MethyleneHA4MPT+FA420HA2 methylene-H4MPT reductase methylHA4MPT
6 methylHA4MPT+HSCoM methyl-H4MPT/HSCoM methyl transferase CHA3SCoM
7 CHA3SCoM+HSCoB methyl-S-CoM reductase CoMSSCoB
8 CoMSSCoB+Fdx(ferredoxin) electron bifurcating hydrogenase-heterodisulfide reductase complex FdxA2+HSCoB+HSCoM
9 FA420+HA2+HCOA2H F420-reducing hydrogenase COA2+FA420H

References