Abstract
The terminal step in methane generation by several methanogenic organisms, of which the best studied is the archaeon Methanobacterium thermoautotrophicum, is catalyzed by the enzyme S-methyl coenzyme M reductase (methylreductase, EC 1.8.-.-). This enzyme contains a macrocyclic tetrapyrrole-derived cofactor, F430, at the active site coordinating Ni(II) in the resting state. A Ni(I) state (Ni1F430) has been proposed as the active form of the cofactor. Extensive mechanistic and spectroscopic studies have been performed on the holoenzyme, isolated cofactor, and various synthetic model compounds. These studies are summarized in the present review.
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Abbreviations
- δ-ALA:
-
5-aminolevulinic acid
- Br-HTP:
-
7-(bromoheptanonyl)-l-Threonine-O3-phosphate
- BrPrSO3 :
-
3-bromopropanesulfonic acid
- CV:
-
cyclic voltammetry
- DMF:
-
N,N-dimethylformamide
- EG:
-
ethylene glycol
- ENDOR:
-
electron nuclear double resonance
- EPR:
-
electron paramagnetic resonance
- ESEEM:
-
electron spin echo envelope modulation
- EXAFS:
-
extended X-ray absorption fine structure
- Fc:
-
ferrocene
- F420 :
-
deazaflavin cofactor (N-(-N-l-lactyl-g-l-glutamyl)-l-glutamic acid phosphodiester of 7,8-didemethyl-8-hydroxy-5-deazariboflavin 5′-phosphate)
- F430 :
-
nickel tetrapyrrole pentacarboxylic acid cofactor
- F430Me5 :
-
nickel tetrapyrrole pentamethyl ester cofactor
- 4,11-dieneN4 :
-
5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene
- HPLC:
-
high pressure liquid chromatography
- HS-CoM:
-
2-thioethanesulfonic acid
- HS-HTP:
-
7-(mercaptoheptanoyl)-l-threonine-O3-phosphate
- MCD:
-
magnetic circular dichroism
- MCR:
-
methyl-coenzyme M reductase
- methyl coenzyme M:
-
2-(methylthio) ethanesulfonic acid
- MFR:
-
methanofuran (4-[N-(4,5,7-tricarboxyheptanoyl-g-l-glutamyl-g-l-glutamyl-)-p-(β-aminoethyl)phenoxymethyl]-2-(aminomethyl)furan)
- MO:
-
molecular orbital
- MPT:
-
methanopterin (2-amino-4-hydroxy-7-methylpteridine), NHE, normal hydrogen electrode
- NMR:
-
nuclear magnetic resonance
- NOE:
-
nuclear Overhauser effect
- OEiBC:
-
octaethylisobacteriochlorin (tct-2,3,7,8-tetrahydro-2,3,7,8,12,13,17,18-octaethylporphyrin dianion)
- RNA:
-
ribonucleic acid
- RR:
-
resonance Raman effect spectroscopy
- SCE:
-
saturated calomel (Hg2Cl2) reference electrode
- TBAP:
-
tetra-n-butylammonium perchlorate
- TEAP:
-
tetraethylammonium perchlorate
- TBAT:
-
tetra-n-butylammonium tetrafluoroborate
- TFE:
-
2,2,2-trifluoroethanol
- THF:
-
tetrahydrofuran
- UV:
-
ultraviolet
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The x-ray crystal structure of MCR has just been determined at 1.45 » resolution by RK Thauer and co-workers (Ermler U, Grabarse W, Shima S, Goubeaud M, Thauer RK Science, submitted for publication). Among its many important results, this study shows that the Ni(II) ion of F430 is axially coordinated by the thiol group of CoM and by the side chain amide oxygen of Glnα147. The structural information also allowed proposals on MCR mechanism.
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Telser, J. (1998). Nickel in F430 . In: Clarke, M.J., et al. Bioinorganic Chemistry. Structure and Bonding, vol 91. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0103374
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DOI: https://doi.org/10.1007/BFb0103374
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