Structure-Reactivity Relationship of Piperidine Nitroxide : Electrochemical, ESR and Computational Studies
Structure-Reactivity Relationship of Piperidine Nitroxide : Electrochemical, ESR and Computational Studies
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哌啶氮氧化物的结构-反应性关系：电化学、ESR 和计算研究
DOI：
10.1021/jo101961m
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
et al
中科院分区：
文献类型：
--
作者：
Toshihide Yamasaki;et al
我们已经合成了几种具有不同取代基的氮氧自由基，这些取代基改变了N-O部分周围的空间和电子环境，并系统地研究了取代基对自由基稳定性的作用。我们的研究结果表明，抗坏血酸的反应性与衍生物的氧化还原电位相关。此外，从头计算也表明还原速率与计算的单占据分子轨道-最低未占据分子轨道能隙之间存在相关性，但与N-O部分的溶剂可及表面积无关，支持了实验结果，并表明电子因素在很大程度上决定了自由基的稳定性。因此，有可能进行虚拟筛选的氮氧自由基，以优化其稳定性，这可以帮助合理地设计新的氮氧自由基，为他们的潜在用途在体内。
We have synthesized several nitroxides with different substituents which vary the steric and electronic environment around the N−O moiety and have systematically investigated the role of substituents on the stability of the radicals. Our results demonstrated the reactivity toward ascorbate correlates with the redox potential of the derivatives. Furthermore, ab initio calculations also indicated a correlation between the reduction rate and the computed singly occupied molecular orbital−lowest unoccupied molecular orbital energy gap, but not with solvent accessible surface area of the N−O moiety, supporting the experimental results and suggesting that the electronic factors largely determine the radicals’ stability. Hence, it is possible to perform virtual screening of nitroxides to optimize their stability, which can help to rationally design novel nitroxides for their potential use in vivo.