Menaquinone biosynthesis: formation of aminofutalosine requires a unique radical SAM enzyme.

Menaquinone biosynthesis: formation of aminofutalosine requires a unique radical SAM enzyme.
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DOI:
10.1021/ja408594p
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发表时间:
2013-10-16
影响因子:
15
通讯作者:
Begley TP
Begley TP
中科院分区:
化学1区
文献类型:
--
作者:
Mahanta N;Fedoseyenko D;Dairi T;Begley TP

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Menaquinone(MK,维生素 K2)是一种脂溶性分子,参与细菌电子传递链。在哺乳动物细胞中,MK 作为一种必需维生素,可激活参与血液凝固和骨代谢的各种蛋白质。最近,在天蓝色链霉菌 A3(2) 中发现了该辅因子生物合成的新途径,其中分支酸在 MqnA 和一种未鉴定的酶的催化反应中转化为氨基呋他洛辛。在这里,我们重建了氨基呋他洛辛的生物合成,并证明缺失的酶(氨基呋他洛辛合酶,MqnE)是一种自由基SAM酶,它催化腺苷自由基加成到3-[(1-羧乙烯基)氧基]-苯甲酸的双键上。这是自由基 SAM 超家族中的一种新反应类型。
Menaquinone (MK, vitamin K2) is a lipid soluble molecule that participates in the bacterial electron transport chain. In mammalian cells, MK functions as an essential vitamin for the activation of various proteins involved in blood clotting and bone metabolism. Recently, a new pathway for the biosynthesis of this cofactor was discovered in Streptomyces coelicolor A3(2) in which chorismate is converted to aminofutalosine in a reaction catalyzed by MqnA and an unidentified enzyme. Here, we reconstitute the biosynthesis of aminofutalosine and demonstrate that the missing enzyme (aminofutalosine synthase, MqnE) is a radical SAM enzyme that catalyzes the addition of the adenosyl radical to the double bond of 3-[(1-carboxyvinyl) oxy]-benzoic acid. This is a new reaction type in the radical SAM superfamily.
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