大肠杆菌二氢叶酸还原酶催化的氢化物转移反应的动力学同位素效应的温度依赖性较小。
Small temperature dependence of the kinetic isotope effect for the hydride transfer reaction catalyzed by Escherichia coli dihydrofolate reductase.
作者信息
Pu Jingzhi, Ma Shuhua, Gao Jiali, Truhlar Donald G
机构信息
Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street S.E., Minneapolis, Minnesota 55455-0431, USA.
出版信息
J Phys Chem B. 2005 May 12;109(18):8551-6. doi: 10.1021/jp051184c.
Abstract
The H/D primary kinetic isotope effect (KIE) for the hydride transfer reaction catalyzed by Escherichia coli dihydrofolate reductase (ecDHFR) is calculated as a function of temperature employing ensemble-averaged variational transition-state theory with multidimensional tunneling. The calculated KIEs display only a small temperature dependence over the temperature range of 5 to 45 degrees C. We identify two key features that contribute to canceling most of the temperature dependence of the KIE that would be expected on the basis of simpler models. Related issues such as the isotope effects on Arrhenius preexponential factors, large differences between free energies of activation and Arrhenius activation energy, and fluctuations of effective barriers are also discussed.
摘要
利用多维隧穿的系综平均变分过渡态理论，计算了大肠杆菌二氢叶酸还原酶（ecDHFR）催化的氢化物转移反应的H/D初级动力学同位素效应（KIE）随温度的变化。计算得到的KIE在5至45摄氏度的温度范围内仅表现出很小的温度依赖性。我们确定了两个关键特征，它们有助于抵消基于更简单模型预期的KIE的大部分温度依赖性。还讨论了诸如同位素对阿仑尼乌斯指前因子的影响、活化自由能与阿仑尼乌斯活化能之间的巨大差异以及有效势垒的波动等相关问题。
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本文引用的文献
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J Chem Phys. 2004 Jun 22;120(24):11650-7. doi: 10.1063/1.1753262.
2
Hydrogen tunneling in quinoproteins.醌蛋白中的氢隧穿
Arch Biochem Biophys. 2004 Aug 1;428(1):41-51. doi: 10.1016/j.abb.2004.03.013.
3
Comparison of enzymatic and non-enzymatic nitroethane anion formation: thermodynamics and contribution of tunneling.酶促与非酶促硝基乙烷阴离子形成的比较：热力学与隧穿效应的贡献
J Am Chem Soc. 2004 May 26;126(20):6244-5. doi: 10.1021/ja0484606.
4
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J Am Chem Soc. 2004 May 12;126(18):5763-75. doi: 10.1021/ja039606o.
5
Tunneling and coupled motion in the Escherichia coli dihydrofolate reductase catalysis.大肠杆菌二氢叶酸还原酶催化过程中的隧道效应和耦合运动。
J Am Chem Soc. 2004 Apr 21;126(15):4778-9. doi: 10.1021/ja031683w.
6
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J Am Chem Soc. 2004 Mar 10;126(9):2820-8. doi: 10.1021/ja037233l.
7
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8
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9
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10
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