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On the mechanism of methyl-coenzyme M reductase

机译:甲基辅酶M还原酶的作用机理

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摘要

Methyl-coenzyme M reductase (MCR) catalyzes the reaction of methyl-coenzyme M (CH_3-SCoM) and coenzyme B (HS-CoB) to methane and the corresponding heterodisulfide CoM-S-S-CoB.This unique reaction proceeds under strictly anaerobic conditions in the presence of coenzyme F_(430),a Ni-porphinoid.MCR is a large (alpha beta gamma)_2 heterohexameric protein complex containing two 50 e long active sites channels.Coenzyme F_(430) is embedded at the channel bottom and the substrates CH_3-SCoM and HS-CoB bind in front of F_(430) into a solvent free and hydrophobic channel segment.Two principally different catalytic mechanisms are currently discussed.Mechanism I is based on a nucleophilic attack of Ni(I) onto the methyl group of CH_3-SCoM yielding methyl-Ni(III) and mechanism II on an attack of Ni(I) onto the thioether sulfur of CH_3-SCoM generating a Ni(II)-SCoM intermediate.Both mechanisms are discussed in the light of a large number of data collected about MCR over the last twenty years.
机译:甲基辅酶M还原酶(MCR)催化甲基辅酶M(CH_3-SCoM)和辅酶B(HS-CoB)与甲烷和相应的杂二硫键CoM-SS-CoB的反应。这种独特的反应在严格的厌氧条件下进行镍酶-辅酶F_(430)的存在MCR是一种大型的(alpha beta gamma)_2异六聚体蛋白复合物,包含两个50个长的活性位点通道。辅酶F_(430)嵌入通道底部和底物CH_3-SCoM和HS-CoB在F_(430)的前面结合成无溶剂和疏水的通道段,目前讨论了两种主要不同的催化机理。机理I基于Ni(I)对甲基的亲核攻击CH_3-SCoM生成甲基-Ni(III)的机理和机理II对Ni(I)攻击CH_3-SCoM产生Ni(II)-SCoM中间体的硫醚硫的攻击。最近20年收集的有关MCR的数据数量。

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