用于研究分支酸向预苯酸反应的近攻击构象方法。
The near attack conformation approach to the study of the chorismate to prephenate reaction.
作者信息
Hur Sun, Bruice Thomas C
机构信息
Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA 93106, USA.
出版信息
Proc Natl Acad Sci U S A. 2003 Oct 14;100(21):12015-20. doi: 10.1073/pnas.1534873100. Epub 2003 Oct 1.
Abstract
Standard free energies (DeltaGN degree) 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 DeltaGN degrees and the experimentally determined activation energies (DeltaG++) are linearly related with the slope of approximately equal to 1. 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.
摘要
针对分支酸向预苯酸的克莱森重排反应，在六种不同环境中计算了形成近攻击构象体（即那些能够直接转化为过渡态的基态构象体）的标准自由能（ΔG°N）：水、来自枯草芽孢杆菌和大肠杆菌的野生型酶、它们的Arg90Cit和Glu52Ala突变体以及1F7催化抗体。计算得到的ΔG°N值与实验测定的活化能（ΔG++）呈线性关系，斜率约等于1。这表明分支酸→预苯酸反应的相对速率主要取决于基态近攻击构象体形成的效率。
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2
Contributions of conformational compression and preferential transition state stabilization to the rate enhancement by chorismate mutase.分支酸变位酶通过构象压缩和优先稳定过渡态对速率增强的贡献。
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Investigation of solvent effects for the Claisen rearrangement of chorismate to prephenate: mechanistic interpretation via near attack conformations.对分支酸重排为预苯酸的克莱森重排反应的溶剂效应研究：通过近攻构象进行机理阐释
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