Wolfe cycle

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Wolfe cycle Wolfe1.jpg
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 reducing methanogens perform additional steps to reduce CO2 to .

Contents

Discovery

In 1971, in a review published by Ralph 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 to 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.

stepsreactantsEnzymes [4] Products used in cycle
1Formyl-methanofuran dehydrogenase
2Formyltransferase
3methenyl-H4MPT cyclohydrolase
4methylene-H4MPT dehydrogenase
5methylene-H4MPT reductase
6methyl-H4MPT/HSCoM methyl transferase
7methyl-S-CoM reductase
8electron bifurcating hydrogenase-heterodisulfide reductase complex
9F420-reducing hydrogenase

References

  1. 1 2 3 4 5 6 7 8 Thauer, Rudolf K. (2012-09-18). "The Wolfe cycle comes full circle". Proceedings of the National Academy of Sciences. 109 (38): 15084–15085. Bibcode:2012PNAS..10915084T. doi: 10.1073/pnas.1213193109 . ISSN   0027-8424. PMC   3458314 . PMID   22955879.
  2. Wu, Jue; Chen, Shi-Lu (2022-02-18). "Key Piece in the Wolfe Cycle of Methanogenesis: The S–S Bond Dissociation Conducted by Noncubane [Fe 4 S 4 ] Cluster-Dependent Heterodisulfide Reductase" . ACS Catalysis. 12 (4): 2606–2622. doi:10.1021/acscatal.1c06036. ISSN   2155-5435.
  3. Vo, Chi Hung; Goyal, Nishu; Karimi, Iftekhar A; Kraft, Markus (January 2020). "First Observation of an Acetate Switch in a Methanogenic Autotroph ( Methanococcus maripaludis S2)". Microbiology Insights. 13: 117863612094530. doi:10.1177/1178636120945300. ISSN   1178-6361. PMC   7416134 . PMID   32843840.
  4. 1 2 3 Balch, William E.; Ferry, James G. (2021-01-01), Poole, Robert K.; Kelly, David J. (eds.), "Chapter One - The Wolfe cycle of carbon dioxide reduction to methane revisited and the Ralph Stoner Wolfe legacy at 100 years" , Advances in Microbial Physiology, 79, Academic Press: 1–23, doi:10.1016/bs.ampbs.2021.07.003, PMID   34836609, S2CID   244550528 , retrieved 2023-11-27