The near attack conformation approach to the study of the chorismate to prephenate reaction
The near attack conformation approach to the study of the chorismate to prephenate reaction
复制标题
DOI：
10.1073/pnas.1534873100
复制
发表时间：
2003-10-14
影响因子：
11.1
通讯作者：
Bruice, TC
中科院分区：
文献类型：
--
作者：
Hur, S;Bruice, TC
标准自由能（DeltaG（N）度）形成近攻击构象，这些基态构象，可以直接转换为过渡态，计算克莱森重排的分支酸预苯酸盐在六种不同的环境：水，野生型酶从枯草芽孢杆菌和大肠杆菌，其Arg 90 Cit和Glu 52 Ala突变体，和1F 7催化抗体。计算得到的Δ G（N）值和实验测定的活化能（Δ G（双匕首））与斜率近似为1成线性关系。这表明分支酸酯-预苯酸酯反应的相对速率压倒性地取决于基态中近攻击构象的形成效率。
Standard free energies (DeltaG(N)degrees) for formation of near attack conformers, those ground state conformers that can convert directly to the transition state, were calculated for the Claisen rearrangement of chorismate to prephenate in six different environments: water, wild-type enzymes from Bacillus subtilis and Escherichia coli, their Arg90Cit and Glu52Ala mutants, and the 1F7 catalytic antibody. Values of the calculated DeltaG(N)degreess and the experimentally determined activation energies (DeltaG(double dagger)) are linearly related with the slope of approximate to1. This demonstrates that the relative rate of the chorismate --> prephenate reaction is overwhelmingly dependent on the efficiency of formation of near attack conformers in the ground state.