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 .
![{\displaystyle {\mathrm {CO} {\vphantom {A}}_{\smash[{t}]{2}}}}](https://wikimedia.org/api/rest_v1/media/math/render/svg/c3ed885c7553085f5d3a2bb0a63616656248699d)
![{\displaystyle {\mathrm {CH} {\vphantom {A}}_{\smash[{t}]{3}}}}](https://wikimedia.org/api/rest_v1/media/math/render/svg/6fa928948f17e9e2abce6a5d8c74311777d5e407)
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]
![{\displaystyle {\mathrm {CH} {\vphantom {A}}_{\smash[{t}]{4}}}}](https://wikimedia.org/api/rest_v1/media/math/render/svg/c8c15a92ab74116087e2eb09cb8c2db1f4e61356)
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 | Formyl-methanofuran dehydrogenase | ||
| 2 | Formyltransferase | ||
| 3 | methenyl-H4MPT cyclohydrolase | ||
| 4 | methylene-H4MPT dehydrogenase | ||
| 5 | methylene-H4MPT reductase | ||
| 6 | methyl-H4MPT/HSCoM methyl transferase | ||
| 7 | methyl-S-CoM reductase | ||
| 8 | electron bifurcating hydrogenase-heterodisulfide reductase complex | ||
| 9 | F420-reducing hydrogenase |
![{\displaystyle {\mathrm {CO} {\vphantom {A}}_{\smash[{t}]{2}}{}+{}\mathrm {MF} {}+{}2\,\mathrm {H} {\vphantom {A}}^{+}}}](https://wikimedia.org/api/rest_v1/media/math/render/svg/fff9763b23817659dcfb3523dd3e0e456647fbc2)
![{\displaystyle {\mathrm {N} {-}\mathrm {Formyl} {}-{}\mathrm {MFR} {}+{}\mathrm {H} {\vphantom {A}}_{\smash[{t}]{4}}\mathrm {MPT} }}](https://wikimedia.org/api/rest_v1/media/math/render/svg/e86d30f08fe6e6b4759b61e783441cb62724f428)
![{\displaystyle {\mathrm {N} {-}\mathrm {Formyl} {-}\mathrm {H} {\vphantom {A}}_{\smash[{t}]{4}}\mathrm {MPT} }}](https://wikimedia.org/api/rest_v1/media/math/render/svg/dc0083a17cceaa55d900a3a1c81e2b24e1a60e63)
![{\displaystyle {\mathrm {Formyl} {}-{}\mathrm {H} {\vphantom {A}}_{\smash[{t}]{4}}\mathrm {MPT} {}+{}\mathrm {H} {\vphantom {A}}^{+}}}](https://wikimedia.org/api/rest_v1/media/math/render/svg/ce86d58363f79c5f2e667016ace04987b305f4f1)
![{\displaystyle {\mathrm {methenyl} {-}\mathrm {H} {\vphantom {A}}_{\smash[{t}]{4}}\mathrm {MPT} }}](https://wikimedia.org/api/rest_v1/media/math/render/svg/38e8541d75dee9482f23a1cc8b9f928ed25f9522)
![{\displaystyle {\mathrm {Methenyl} {}-{}\mathrm {H} {\vphantom {A}}_{\smash[{t}]{4}}\mathrm {MPT} {}+{}\mathrm {F} {\vphantom {A}}_{\smash[{t}]{420}}\mathrm {H} {\vphantom {A}}_{\smash[{t}]{2}}}}](https://wikimedia.org/api/rest_v1/media/math/render/svg/e9d034d03c3cb75b941edc1d6fa818b66de62635)
![{\displaystyle {\mathrm {methylene} {-}\mathrm {H} {\vphantom {A}}_{\smash[{t}]{4}}\mathrm {MPT} }}](https://wikimedia.org/api/rest_v1/media/math/render/svg/12ff222e322436c2ab94c99855263c07faf36246)
![{\displaystyle {\mathrm {Methylene} {}-{}\mathrm {H} {\vphantom {A}}_{\smash[{t}]{4}}\mathrm {MPT} {}+{}\mathrm {F} {\vphantom {A}}_{\smash[{t}]{420}}\mathrm {H} {\vphantom {A}}_{\smash[{t}]{2}}}}](https://wikimedia.org/api/rest_v1/media/math/render/svg/1722568a2d6fe5e23f05413eddeef42d3eb8c0b2)
![{\displaystyle {\mathrm {methyl} {-}\mathrm {H} {\vphantom {A}}_{\smash[{t}]{4}}\mathrm {MPT} }}](https://wikimedia.org/api/rest_v1/media/math/render/svg/be788dffa1c6e7b87939e908ae8ad96b36eec79a)
![{\displaystyle {\mathrm {methyl} {-}\mathrm {H} {\vphantom {A}}_{\smash[{t}]{4}}\mathrm {MPT} {}+{}\mathrm {HS} {-}\mathrm {CoM} }}](https://wikimedia.org/api/rest_v1/media/math/render/svg/97929eec720d6f65a3f27d05261daf3b842bb83f)
![{\displaystyle {\mathrm {CH} {\vphantom {A}}_{\smash[{t}]{3}}{-}\mathrm {S} {-}\mathrm {CoM} }}](https://wikimedia.org/api/rest_v1/media/math/render/svg/d7dc7c3afec75c7ccd61a34ec975bc4b206817b1)
![{\displaystyle {\mathrm {CH} {\vphantom {A}}_{\smash[{t}]{3}}{-}\mathrm {S} {-}\mathrm {CoM} {}+{}\mathrm {HS} {-}\mathrm {CoB} }}](https://wikimedia.org/api/rest_v1/media/math/render/svg/48374a713f22e7559671a5d459cf6845dda6b11c)
![{\displaystyle {\mathrm {F} {\vphantom {A}}_{\smash[{t}]{420}}{}+{}\mathrm {H} {\vphantom {A}}_{\smash[{t}]{2}}{}+{}\mathrm {HCO} {\vphantom {A}}_{\smash[{t}]{2}}\mathrm {H} }}](https://wikimedia.org/api/rest_v1/media/math/render/svg/eff34790e462e3d6bd56837648b809f0117cceb1)
![{\displaystyle {\mathrm {CO} {\vphantom {A}}_{\smash[{t}]{2}}{}+{}\mathrm {F} {\vphantom {A}}_{\smash[{t}]{420}}\mathrm {H} }}](https://wikimedia.org/api/rest_v1/media/math/render/svg/226513ee81de23f1419982182a3400a78f95a880)
References
- ^ a b c d e f g h 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.
- ^ 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.
- ^ 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.
- ^ a b c 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
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