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厌氧细菌中不同寻常的脱水反应:将羰游基(自由基阴离子)视为酶促反应中的活性中间体。

Unusual dehydrations in anaerobic bacteria: considering ketyls (radical anions) as reactive intermediates in enzymatic reactions.

作者信息

Buckel W

机构信息

Laboratorium für Mikrobiologie, Philipps-Universität, Marburg, Germany.

出版信息

FEBS Lett. 1996 Jun 24;389(1):20-4. doi: 10.1016/0014-5793(96)00530-3.

DOI:10.1016/0014-5793(96)00530-3
PMID:8682197
Abstract

Dehydratases have been detected in anaerobic bacteria which use 2-, 4- or 5-hydroxyacyl-CoA as substrates and are involved in the removal of hydrogen atoms from the unactivated beta- or gamma-positions. In addition there are bacterial dehydratases acting on 1,2-diols which are substrates lacking any activating group. These enzymes contain either FAD, or flavins + iron-sulfur clusters or coenzyme B12. It has been proposed that the overall dehydrations are actually reductions followed by oxidations or vice versa mediated by these prosthetic groups. Whereas the gamma-hydrogen of 5-hydroxyvaleryl-CoA is activated by a transient two-election alpha, beta-oxidation, the other substrates are proposed to require either a transient one-electron reduction or an oxidation to a ketyl (radical anion).

摘要

已在厌氧细菌中检测到脱水酶,这些细菌利用2-、4-或5-羟基酰基辅酶A作为底物,并参与从未活化的β-或γ-位去除氢原子。此外,还有作用于1,2-二醇的细菌脱水酶,1,2-二醇是缺乏任何活化基团的底物。这些酶要么含有黄素腺嘌呤二核苷酸(FAD),要么含有黄素+铁硫簇,要么含有辅酶B12。有人提出,整体脱水实际上是由这些辅基介导的还原反应后再进行氧化反应,反之亦然。虽然5-羟基戊酰辅酶A的γ-氢通过瞬时双电子α,β-氧化被激活,但其他底物则被认为需要瞬时单电子还原或氧化成酮基(自由基阴离子)。

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