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Methyl Coenzyme M Reductase

  • Chapter
Biochemistry of Nickel

Part of the book series: Biochemistry of the Elements ((BOTE,volume 12))

Abstract

The biogenesis of methane is carried out by a group of strictly anaerobic archaea (formerly termed archaebacteria), referred to as methanogens, that obtain energy from one-or two-carbon substrates according to the following reactions [reviewed by Daniels et al. (1984), Ferry (1992), Jones et al. (1987), and Thauer (1990)]:

EquationSource% MathType!MTEF!2!1!+- % feaagCart1ev2aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaGinaiaadI % eacqGHRaWkcaWGdbGaam4tamaaBaaaleaacaaIYaaabeaakiabgkzi % UkaadoeacaWGibWaaSbaaSqaaiaaisdaaeqaaOGaey4kaSIaaGOmai % aadIeadaWgaaWcbaGaaGOmaaqabaGccaWGpbaaaa!4396!]]</EquationSource><EquationSource Format="TEX"><![CDATA[$$4H + C{O_2} \to C{H_4} + 2{H_2}O$$
(6-1)
EquationSource% MathType!MTEF!2!1!+- % feaagCart1ev2aqatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaGinaiaadI % eacaWGdbGaam4taiaad+eacaWGibGaeyOKH4Qaam4qaiaadIeadaWg % aaWcbaGaaGinaaqabaGccqGHRaWkcaaIZaGaam4qaiaad+eadaWgaa % WcbaGaaGOmaaqabaGccqGHRaWkcaaIYaGaamisamaaBaaaleaacaaI % Yaaabeaakiaad+eaaaa!4791!]]</EquationSource><EquationSource Format="TEX"><![CDATA[$$4HCOOH \to C{H_4} + 3C{O_2} + 2{H_2}O$$
(6-2)
EquationSource% MathType!MTEF!2!1!+- % feaagCart1ev2aqatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaGinaiaado % eacaWGibWaaSbaaSqaaiaaiodaaeqaaOGaam4taiaadIeacqGHsgIR % caaIZaGaam4qaiaadIeadaWgaaWcbaGaaGinaaqabaGccqGHRaWkca % WGdbGaam4tamaaBaaaleaacaaIYaaabeaakiabgUcaRiaaikdacaWG % ibWaaSbaaSqaaiaaikdaaeqaaOGaam4taaaa!47B0!]]</EquationSource><EquationSource Format="TEX"><![CDATA[$$4C{H_3}OH \to 3C{H_4} + C{O_2} + 2{H_2}O$$
(6-3)
EquationSource% MathType!MTEF!2!1!+- % feaagCart1ev2aqatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaGinaiaado % eacaWGibWaaSbaaSqaaiaaiodaaeqaaOGaamOtaiaadIeadaqhaaWc % baGaaG4maaqaaiabgUcaRaaakiabgUcaRiaadIeadaWgaaWcbaGaaG % OmaaqabaGccaWGpbGaeyOKH4QaaG4maiaadoeacaWGibWaaSbaaSqa % aiaaisdaaeqaaOGaey4kaSIaam4qaiaad+eadaWgaaWcbaGaaGOmaa % qabaGccqGHRaWkcaaI0aGaamOtaiaadIeadaqhaaWcbaGaaGinaaqa % aiabgUcaRaaaaaa!4DD6!]]</EquationSource><EquationSource Format="TEX"><![CDATA[$$4C{H_3}NH_3^ + + {H_2}O \to 3C{H_4} + C{O_2} + 4NH_4^ + $$
(6-4)
EquationSource% MathType!MTEF!2!1!+- % feaagCart1ev2aqatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaGinaiaado % eacaWGpbGaey4kaSIaaGOmaiaadIeadaWgaaWcbaGaaGOmaaqabaGc % caWGpbGaeyOKH4Qaam4qaiaadIeadaWgaaWcbaGaaGinaaqabaGccq % GHRaWkcaaIZaGaam4qaiaad+eadaWgaaWcbaGaaGOmaaqabaaaaa!4519!]]</EquationSource><EquationSource Format="TEX"><![CDATA[$$4CO + 2{H_2}O \to C{H_4} + 3C{O_2}$$
(6-5)
EquationSource% MathType!MTEF!2!1!+- % feaagCart1ev2aqatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaam4qaiaadI % eadaWgaaWcbaGaaG4maaqabaGccaWGdbGaam4taiaad+eacaWGibGa % eyOKH4Qaam4qaiaadIeadaWgaaWcbaGaaGinaaqabaGccqGHRaWkca % WGdbGaam4tamaaBaaaleaacaaIYaaabeaaaaa!4396!]]</EquationSource><EquationSource Format="TEX"><![CDATA[$$C{H_3}COOH \to C{H_4} + C{O_2}$$
(6-6)

Using distinct pathways, these substrates and other substrates are all converted to a common methylated intermediate that is subsequently converted to methane. Each pathway involves a series of novel coenzymes. The structures and functions of these singular compounds have been reviewed (DiMarco et al.,1990; Rouvière and Wolfe, 1988), and only an overview is presented here. Carbon dioxide is reduced to the formyl level with the participation of a furan-containing compound, termed methanofuran. The formyl group is transferred to a special pterin, named tetrahydromethanopterin, where it is converted to the methenyl derivative and sequentially reduced to the meth­ylene and methyl levels. Reduction of the methenyltetrahydromethanopterin requires an unusual 5-deazaflavin, denoted coenzyme F420 as the electron donor. The methyl group is subsequently transferred to 2-mercaptoethanesulfonate (coenzyme M, HS-CoM) to form 2-(methylthio)ethanesulfonate (methyl coenzyme M, methyl-S-CoM), which is the direct precursor of methane. The ultimate source of electrons in each of these reactions is hydrogen, requiring the participation of nickel-containing hydrogenases (discussed in Chapter 4). Formate metabolism requires the action of formate dehydrogenase (containing an atypical molybdopterin cofactor) and a nickel-containing hydrogenase; the combined action of these enzymes results in the release of carbon dioxide and hydrogen gas.

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    Robert P. Hausinger

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Hausinger, R.P. (1993). Methyl Coenzyme M Reductase. In: Biochemistry of Nickel. Biochemistry of the Elements, vol 12. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-9435-9_6

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