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Nickel in F430

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Bioinorganic Chemistry

Part of the book series: Structure and Bonding ((STRUCTURE,volume 91))

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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  1. Chemistry Program, Roosevelt University, 430 South Michigan Avenue, 60605-1394, Chicago, IL, USA

    Joshua Telser

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Michael J. Clarke John B. Goodenough Christian K. Jørgensen David M. P. Mingos Graham A. Palmer Peter J. Sadler Raymond Weiss Robert J. P. Williams

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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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