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醛氧化酶氧化亚胺离子过程中的初级氘同位素效应

Primary deuterium isotope effect in the oxidation of an iminium ion by aldehyde oxidase.

作者信息

Ruenitz P C, Thomas H G

出版信息

Arch Biochem Biophys. 1985 May 15;239(1):270-2. doi: 10.1016/0003-9861(85)90835-5.

DOI:10.1016/0003-9861(85)90835-5
PMID:4004259
Abstract

Studies of the rates of aldehyde oxidase-mediated oxidation of iminium ion (I) and its specifically labeled counterpart containing deuterium at the methine and methylene carbons of its seven-membered ring (I-d3), are reported. In separate incubations, the isotope effect (kH/kD) on Vmax was 3.3 and that on Km was 1.5. Co-incubation of equimolar amounts of I and I-d3 with aldehyde oxidase resulted in an isotope effect of 2.2 on product ratio. These results support hydrogen transfer from the methine carbon of the seven-membered ring to the molybdenum center of the enzyme as the rate-determining step in the conversion of I to its lactam metabolite (II).

摘要

报道了对亚胺离子(I)及其在七元环的次甲基和亚甲基碳上含有氘的特异性标记类似物(I-d3)的醛氧化酶介导氧化速率的研究。在单独孵育时,对Vmax的同位素效应(kH/kD)为3.3,对Km的同位素效应为1.5。等摩尔量的I和I-d3与醛氧化酶共同孵育,对产物比例的同位素效应为2.2。这些结果支持了从七元环的次甲基碳向酶的钼中心的氢转移是I转化为其内酰胺代谢物(II)的速率决定步骤。

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