化学
一氧化氮介导的自由基聚合
非对映体
位阻效应
部分
反应性(心理学)
电子顺磁共振
电子效应
立体化学
自由基引发剂
组合化学
光化学
有机化学
核磁共振
自由基聚合
聚合
病理
物理
医学
替代医学
聚合物
作者
Risa Azuma,Toshihide Yamasaki,Miho C. Emoto,Hideo Sato‐Akaba,Kohei Sano,Masayuki Munekane,Hirotada Fujii,Takahiro Mukai
标识
DOI:10.1016/j.freeradbiomed.2022.11.033
摘要
2,2,6,6-Tetramethylpiperidin-N-oxyl (TEMPO)-type nitroxides are susceptible to bioreduction, leading to a loss of radical properties. Although it has been reported that the steric and electronic environments around the N-O moiety of nitroxides affect the reduction, how the relative configuration of nitroxide derivatives alters it is unclear. In this study, we investigated the effect of diastereomers on the radical properties of C2- and C4-disubstituted TEMPO-type nitroxides. We succeeded in isolating the diastereomers of the studied nitroxides for the first time. In addition, we compared the reactivities of nitroxide derivatives with different substituents at the C2 and C4 positions toward ascorbate reduction. We found that the bulky substituents at both C2 and C4 and the electronic effect of C4 affected the reduction of the isomers. C2- and C4-disubstituted nitroxides were administered to mice for electron spin resonance imaging to assess bioreduction in the brain. Similar to the reactivity to reduction in vitro, a difference in the bioreduction of diastereomers was observed in brain tissues. Our research strongly indicates that bioreduction can be controlled by changing the relative configuration, which can be used in the design of nitroxide derivatives for biological applications.
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