The kinetics of oligopeptides formation in the flow systems glycine–sodium trimetaphosphate–imidazole/N-methylimidazole at thermocyclic regime has been investigated by HPLC and ³¹P NMR methods in the ranges of temperature from 45 to 90 °C and pH from 8.5 to 11.5. Detailed reaction mechanisms have been proposed and justified by quantum chemical calculations using DFT method at the CAM-B3LYP/TZVP level with accounting solvent effect by the C-PCM model. A new imidazole catalysis mechanism by which imidazole reacts with cyclic N,O-phosphoryl glycine giving N-imidazolyl-O-glycyl phosphate as a key intermediate was proposed and validated. It is emphasized that while in the absence of imidazoles, prebiotic activation of amino acids occurs at the N-terminus, in the presence of imidazoles it shifts to the O-terminus. This means that in the peptide elongation N-imidazolyl-O-aminoacyl phosphates play in prebiotic systems the outstanding role similar to that of aminoacyl adenylates formed at the ATP and aminoacyl-tRNA synthetases presence in biosystems. The new crucial role of imidazoles in prebiotic evolution has been noticed. The systems used and modes of their conversion can be good models for prebiotic peptide syntheses in a flow thermocyclic regime.

中文翻译：

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流动系统甘氨酸-三偏磷酸钠-咪唑反应的动力学和机制：咪唑在益生元肽合成中的关键作用。

已通过 HPLC 和³¹ P NMR 方法在 45 至 90 °C 的温度和 8.5 至 11.5 的 pH 范围内研究了流动系统甘氨酸-三偏磷酸钠-咪唑/ N-甲基咪唑在热循环状态下形成寡肽的动力学。已经提出了详细的反应机理，并通过在 CAM-B3LYP/TZVP 水平上使用 DFT 方法进行量子化学计算并通过 C-PCM 模型计算溶剂效应来证明其合理性。咪唑与环状N , O-磷酰甘氨酸反应生成N-咪唑基-O的新咪唑催化机理提出并验证了作为关键中间体的-甘氨酰磷酸酯。需要强调的是，在没有咪唑的情况下，氨基酸的益生元活化发生在 N 端，而在咪唑的存在下，它转移到 O 端。这意味着在肽延伸过程中，N-咪唑基-O-氨酰基磷酸盐在益生元系统中发挥的突出作用类似于在生物系统中存在的 ATP 和氨酰基-tRNA 合成酶处形成的氨酰基腺苷酸。咪唑在益生元进化中的新关键作用已被注意到。所使用的系统及其转换模式可以成为流动热循环状态下益生元肽合成的良好模型。