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Oxidative Addition of Singlet Oxygen to Model Building Blocks of the Aerucyclamide A Peptide: A First-Principles Approach.
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-01-09 , DOI: 10.1021/acs.jpca.9b10285 Tolga N V Karsili 1 , Barbara Marchetti 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-01-09 , DOI: 10.1021/acs.jpca.9b10285 Tolga N V Karsili 1 , Barbara Marchetti 1
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Singlet oxygen (1O2) is a significant source of biodamage in living organisms. 1O2 is a highly reactive excited electronic-state spin-configuration of molecular oxygen and is usually prepared via organic molecule sensitization. Despite the wealth of experimental studies on the 1O2-induced oxidation of several bio-organic molecules, the detailed mechanism of the oxidation process is largely unknown. Using high-level quantum chemical methods, we compute the potential energy profiles of the various electronic states associated with the [4 + 2]-cycloaddition reaction of O2 with a class of model peptide precursors that are based on derivatives of oxazole and thiazole. Experiments have shown that such oxazole/thiazole-based model peptides show a favorable reaction with 1O2. Upon increasing the molecular complexity, the bimolecular rate constant decreases and is attributed to the π-perturbing effects of the substituent of the oxazole/thiazole moiety. Our theoretical predictions are in excellent agreement with the experimental measurements and reveal a deep insight into the myriad electronic states that may hinder/promote the reaction of a given bio-organic molecule with 1O2.
中文翻译：
单线态氧到Aerucyclamide A肽的模型构建基的氧化加成：第一种原理方法。
单线态氧（1O2）是活生物体中生物破坏的重要来源。1O2是分子氧的高反应性激发电子态自旋构型，通常是通过有机分子敏化制备的。尽管有大量的实验研究了1O2诱导的几种生物有机分子的氧化，但氧化过程的详细机理尚不清楚。使用高级量子化学方法，我们计算与O2与基于恶唑和噻唑衍生物的一类模型肽前体的O2的[4 + 2]-环加成反应相关的各种电子态的势能图。实验表明，这种基于恶唑/噻唑的模型肽显示出与1O2的良好反应。随着分子复杂度的增加，双分子速率常数降低，并且归因于恶唑/噻唑部分的取代基的π-干扰作用。我们的理论预测与实验测量非常吻合，并揭示了对可能阻碍/促进特定生物有机分子与1O2反应的多种电子状态的深刻见解。
更新日期：2020-01-09
中文翻译：
单线态氧到Aerucyclamide A肽的模型构建基的氧化加成：第一种原理方法。
单线态氧（1O2）是活生物体中生物破坏的重要来源。1O2是分子氧的高反应性激发电子态自旋构型，通常是通过有机分子敏化制备的。尽管有大量的实验研究了1O2诱导的几种生物有机分子的氧化，但氧化过程的详细机理尚不清楚。使用高级量子化学方法，我们计算与O2与基于恶唑和噻唑衍生物的一类模型肽前体的O2的[4 + 2]-环加成反应相关的各种电子态的势能图。实验表明，这种基于恶唑/噻唑的模型肽显示出与1O2的良好反应。随着分子复杂度的增加，双分子速率常数降低，并且归因于恶唑/噻唑部分的取代基的π-干扰作用。我们的理论预测与实验测量非常吻合，并揭示了对可能阻碍/促进特定生物有机分子与1O2反应的多种电子状态的深刻见解。
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