Structure鈭扲eactivity Relationship of Piperidine Nitroxide: Electrochemical, ESR and Computational Studies
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- 作者：Toshihide Yamasaki ; Fumiya Mito ; Yuko Ito ; Sokkar Pandian ; Yuichi Kinoshita ; Koji Nakano ; Ramachandran Murugesan ; Kiyoshi Sakai ; Hideo Utsumi ; Ken-ichi Yamada
- 刊名：Journal of Organic Chemistry
- 出版年：2011
- 出版时间：January 21, 2011
- 年：2011
- 卷：76
- 期：2
- 页码：435-440
- 全文大小：830K
- 年卷期：v.76,no.2(January 21, 2011)
- ISSN：1520-6904
文摘
We have synthesized several nitroxides with different substituents which vary the steric and electronic environment around the N鈭扥 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鈭抣owest unoccupied molecular orbital energy gap, but not with solvent accessible surface area of the N鈭扥 moiety, supporting the experimental results and suggesting that the electronic factors largely determine the radicals鈥?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.