Benchmark calculations of proton affinities and gas-phase basicities of molecules important in the study of biological phosphoryl transfer
Benchmark calculations of proton affinities and gas-phase basicities of molecules important in the study of biological phosphoryl transfer
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DOI：
10.1039/b504941e
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发表时间：
2005-01-01
影响因子：
3.3
通讯作者：
York, DM
中科院分区：
文献类型：
--
作者：
Range, K;Riccardi, D;York, DM
提出了与生物磷酰基转移反应最相关的分子的质子亲和力和气相碱度的基准计算，并与现有的实验结果进行了比较。 The accuracy of proton affinity and gas-phase basicity results obtained from several multi-level model chemistries (CBS-QB3, G3B3, and G3MP2B3) and density-functional quantum models (PBE0, B1B95, and B3LYP) are assessed and compared.根据这些数据，引入了一组经验键焓、熵和自由能校正，大大提高了方法的准确性和预测能力。这些修正适用于预测目前尚不存在实验数据的重要生物磷酸盐和正膦的质子亲和力和气相碱度值。与混合量子力学/分子力学模拟中常用的半经验量子模型的结果进行了比较。数据表明，为了获得溶液、酶和核酶中磷酰基转移反应的定量准确性，有必要设计改进的半经验量子模型，提高相对质子亲和力值的准确性。
Benchmark calculations of proton affinities and gas-phase basicities of molecules most relevant to biological phosphoryl transfer reactions are presented and compared with available experimental results. The accuracy of proton affinity and gas-phase basicity results obtained from several multi-level model chemistries (CBS-QB3, G3B3, and G3MP2B3) and density-functional quantum models (PBE0, B1B95, and B3LYP) are assessed and compared. From these data, a set of empirical bond enthalpy, entropy, and free energy corrections are introduced that considerably improve the accuracy and predictive capability of the methods. These corrections are applied to the prediction of proton affinity and gas-phase basicity values of important biological phosphates and phosphoranes for which experimental data does not currently exist. Comparison is made with results from semiempirical quantum models that are commonly employed in hybrid quantum mechanical/molecular mechanical simulations. Data suggest that the design of improved semiempirical quantum models with increased accuracy for relative proton affinity values is necessary to obtain quantitative accuracy for phosphoryl transfer reactions in solution, enzymes, and ribozymes.