Organometallic Complex Formed by an Unconventional Radical S-Adenosylmethionine Enzyme

被引：17

作者：

Dong, Min ^{[1
]}

Horitani, Masaki ^{[2
]}

Dzikovski, Boris ^{[1
]}

Pandelia, Maria-Eirini ^{[3
]}

Krebs, Carsten ^{[4
,5
]}

Freed, Jack H. ^{[1
]}

Hoffman, Brian M. ^{[2
]}

Lin, Hening ^{[1
,6
]}

机构：

[1] Cornell Univ, Dept Chem & Chem Biol, Ithaca, NY 14853 USA

[2] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA

[3] Brandeis Univ, Dept Biochem, Waltham, MA 02453 USA

[4] Penn State Univ, Dept Chem, University Pk, PA 16802 USA

[5] Penn State Univ, Dept Biochem & Mol Biol, University Pk, PA 16802 USA

[6] Cornell Univ, Howard Hughes Med Inst, Ithaca, NY 14853 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2016年 / 138卷 / 31期

关键词：

BIOSYNTHESIS; MECHANISM; INTERMEDIATE; INHIBITION; CATALYSIS;

D O I：

10.1021/jacs.6b04155

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Pyrococcus horikoshii Dph2 (PhDph2) is an unusual radical S-adenosylmethionine (SAM) enzyme involved in the first step of diphthamide biosynthesis. It catalyzes the reaction by cleaving SAM to generate a 3-amino-3-carboxypropyl (ACP) radical. To probe the reaction mechanism, we synthesized a SAM analogue (SAMcA), in which the ACP group of SAM is replaced with a 3-carboxyally1 group. SAMcA. is cleaved by PhDph2, yielding a paramagnetic (S = 1/2) species, which is assigned to a complex formed between the reaction product, alpha-sulfinyl-3-butenoic acid, and the [4Fe-4S] cluster. Electron nuclear double resonance (ENDOR) measurements with C-13 and H-2 isotopically labeled SAM(CA) support a sr-complex between the C=C double bond of asulfinyl-3-butenoic acid and the unique iron of the [4Fe-4S] cluster. This is the first example of a radical SAM-related [4Fe-4S](+) cluster forming an organometallic complex with an alkene, shedding additional light on the mechanism of PhDph2 and expanding our current notions for the reactivity of [4Fe-4S] clusters in radical SAM enzymes.

引用

页码：9755 / 9758

页数：4

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