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Introduction to Enzyme and Coenzyme Chemistry - E-Library Home

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250 Chapter 11<br />

O<br />

HN<br />

NH<br />

+<br />

H 3 N<br />

H 3 C<br />

+<br />

S<br />

CO 2<br />

−<br />

HO<br />

O<br />

OH<br />

Ad<br />

S-adenosyl Met<br />

9<br />

6<br />

H C<br />

H 2<br />

[4Fe4S] red [4Fe4S] ox<br />

H 2 C Ad<br />

O<br />

L-Met<br />

HO<br />

OH<br />

O<br />

CO 2 H<br />

H 3 C<br />

O<br />

Ad<br />

HN<br />

NH<br />

O<br />

O<br />

9<br />

HO OH H 2 C<br />

O<br />

AdoMet HN<br />

AdoMet H 2 C<br />

CH 3<br />

S<br />

NH<br />

6<br />

[4Fe4S]<br />

CO 2 H<br />

CO 2 H<br />

HN<br />

H<br />

S<br />

NH<br />

H<br />

H<br />

CO 2 H<br />

HN<br />

H 2 C<br />

S<br />

NH<br />

6<br />

CO 2 H<br />

[FeS]<br />

[FeS]<br />

Figure 11.15 Mechanism for biotin synthase.<br />

that the enzyme eVectively self-destructs in order <strong>to</strong> complete one catalytic<br />

cycle, which is one of several remarkable features of this enzyme.<br />

Sulphur insertion reactions have also appeared in the biosynthesis of coenzymes<br />

thiamine <strong>and</strong> molybdopterin, <strong>and</strong> in the modiWed RNA base thio-uridine.<br />

This area of enzymology is therefore exp<strong>and</strong>ing rapidly at present, <strong>and</strong> the<br />

emergence of X-ray crystal structures of these enzymes is eagerly awaited.<br />

11.6 Oxidised amino acid cofac<strong>to</strong>rs <strong>and</strong> quinoproteins<br />

At the same time that protein radicals were being discovered in enzyme active<br />

sites, several unusual amino acid cofac<strong>to</strong>rs were being studied. In the active site<br />

of galac<strong>to</strong>se oxidase from Fusarium spp., a copper metallo-enzyme, a modiWed

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