The effect of heme environment on the hydrogen abstraction reaction of camphor in P450cam catalysis:: A QM/MM study
The effect of heme environment on the hydrogen abstraction reaction of camphor in P450cam catalysis:: A QM/MM study
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DOI：
10.1021/ja058196w
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发表时间：
2006-03-29
影响因子：
15
通讯作者：
Thiel, W
中科院分区：
文献类型：
--
作者：
Altun, A;Guallar, V;Thiel, W
已发表的QM/MM研究（Schöneboom，J.C.;科恩，S.;林，H.; Shaik，S.; Thiel，W.J. Am. Chem. Soc.2004，126，4017; Guallar，V.;弗里斯纳河A.J. Am. Chem.Soc.2004，126，8501）对P450中樟脑的H-提取的研究已在很大程度上得到解决。位于化合物I的氧代原子附近的结晶水分子903充当H-提取的催化剂，使势垒降低约4kcal/mol。自旋密度在A-丙酸侧链的血红素可以发生在不完全屏蔽的情况下，但计算的障碍没有重大影响。
The discrepancies between the published QM/MM studies (Schöneboom, J. C.; Cohen, S.; Lin, H.; Shaik, S.; Thiel, W.J. Am.Chem. Soc.2004,126, 4017; Guallar, V.; Friesner, R. A.J. Am. Chem.Soc.2004,126, 8501) on H-abstraction of camphor in P450camhave largely been resolved. The crystallographic water molecule 903 situated near the oxo atom of Compound I acts as a catalyst for H-abstraction, lowering the barrier by about 4 kcal/mol. Spin density at the A-propionate side chain of heme can occur in the case of incomplete screening but has no major effect on the computed barrier.