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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Activities of α-COOH vs γ-COOH in N-Phosphoryl Amino Acids: A Theoretical Study
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Activities of α-COOH vs γ-COOH in N-Phosphoryl Amino Acids: A Theoretical Study

机译：N-磷酸氨基酸中α-COOH与γ-COOH的活性：理论研究

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摘要

The biomimic reactions of N-phosphoryl amino acids are very important in the study of many biochemical processes, such as origin of proteins and phosphorylation of amino acid residues in the proteins. the differences in reactivities between α-COOH and γ-COOH in phosphoryl amino acids were studied by ab initio and density functional methods. The pentacoordinate phosphoric intermediates 2 containing five-membered rings were predicted to be more stable than 3 with seven-membered rings. For intermediates 3, the isomers with apical-equatorial ring spanning arrangement were predicted to be more stable than those with diequatorial ring spanning arrangement. At the B3LYP/6-31G~(**) level, intermediates 2 were 66.56 kJ/mol lower in energy than 3. It was shown that the transition states 4 and 5 involving an α-COOH or γ-COOH group had energy barriers of ΔE = 57.59 kJ mol~(-1) and 120.93 kJ mol~(-1), respectively. The theoretical calculations suggested that the α-COOH group could be differentiated from the γ-COOH intramolecularly in amino acids by N-phosphorylation. These might be helpful to understand why only α-COOH, not γ-COOH, was involved in the biomimic reactions.
机译：N-磷酰基氨基酸的仿生反应在许多生化过程的研究中非常重要，例如蛋白质的起源和蛋白质中氨基酸残基的磷酸化。通过从头算和密度泛函方法研究了α-COOH和γ-COOH在磷酸氨基酸中的反应性差异。预测含有五元环的五配位磷酸中间体2比具有七元环的五中间体更稳定。对于中间体3，预计具有顶-赤道环跨度排列的异构体比具有赤道环跨度排列的异构体更稳定。在B3LYP / 6-31G〜（**）水平下，中间体2的能量比3降低66.56 kJ / mol。结果表明，涉及α-COOH或γ-COOH基团的过渡态4和5具有能垒。 ΔE分别为57.59 kJ mol〜（-1）和120.93 kJ mol〜（-1）。理论计算表明，通过N-磷酸化可以在氨基酸中将α-COOH基团与γ-COOH分子内区分开。这些可能有助于理解为什么只有α-COOH而不是γ-COOH参与了仿生反应。

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