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Medientyp:
E-Artikel
Titel:
A glycyl free radical as the precursor in the synthesis of carbon monoxide and cyanide by the [FeFe]‐hydrogenase maturase HydG
Beteiligte:
Nicolet, Yvain;
Martin, Lydie;
Tron, Cécile;
Fontecilla-Camps, Juan C.
Erschienen:
Wiley, 2010
Erschienen in:FEBS Letters
Sprache:
Englisch
DOI:
10.1016/j.febslet.2010.09.008
ISSN:
1873-3468;
0014-5793
Entstehung:
Anmerkungen:
Beschreibung:
<jats:p>HydG uses tyrosine to synthesize the CN<jats:sup>−</jats:sup>/CO ligands of [FeFe]‐hydrogenase active site. We have mutated two of the [4Fe–4S]‐cluster cysteine ligands of the HydG C‐terminal domain (CTD) to serine. The double mutant can still synthesize CN<jats:sup>−</jats:sup> but not CO. In a mutant lacking the CTD both CN<jats:sup>−</jats:sup> and CO synthesis are abolished. Like in ThiH, the initial steps of CN<jats:sup>−</jats:sup> synthesis are carried out in the TIM‐barrel domain of HydG but some component(s) of the CTD are later needed. The mutants indicate that CO synthesis is metal‐based and occurs in the CTD. We postulate that CN<jats:sup>−</jats:sup>/CO synthesis is initiated by H<jats:sub>2</jats:sub>N–CH–<jats:disp-formula><jats:graphic xmlns:xlink="http://www.w3.org/1999/xlink" position="anchor" xlink:href="graphic/feb2s0014579310007283-math-si1.gif"><jats:alt-text>urn:x-wiley:00145793:media:feb2s0014579310007283:feb2s0014579310007283-math-si1</jats:alt-text></jats:graphic></jats:disp-formula> Fragmentation of this radical into H<jats:sub>2</jats:sub>N–CH<jats:sub>2</jats:sub> and CO<jats:sub>2</jats:sub> or H<jats:sub>2</jats:sub>CNH and <jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/feb2s0014579310007283-math-si2.gif" xlink:title="urn:x-wiley:00145793:media:feb2s0014579310007283:feb2s0014579310007283-math-si2" /> provides plausible precursors for CN<jats:sup>−</jats:sup>/CO synthesis.</jats:p>