Mechanism of metal-independent decomposition of organic hydroperoxides and formation of alkoxyl radicals by halogenated quinones
文献类型：期刊论文
| 作者 | Zhu, Ben-Zhan ; Zhao, Hong-Tao ; Kalyanaraman, Balaraman ; Liu, Jun ; Shan, Guo-Qiang ; Du, Yu-Guo ; Frei, Balz |
| 刊名 | PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
 |
| 出版日期 | 2007-03-06 |
| 卷号 | 104期号:10页码:3698-3702 |
| 关键词 | electron spin resonance spin-trapping 2 2 reactive intermediate metal chelators 5-dichloro-1 5-dichlorosemiquinone anion radical 4-benzoquinone |
| 英文摘要 | The metal-independent decomposition of organic hydroperoxides and the formation of organic alkoxyl radicals in the absence or presence of halogenated quinones were studied with electron spin resonance (ESR) and the spin-trapping agent 5,5-dimethyl-1-pyrroline N-oxide (DMPO). We found that 2,5-dichloro-1,4-benzoquinone (DCBQ) markedly enhanced the decomposition of tert-butylhydroperoxide (t-BuOOH), leading to the formation of the DMPO adducts with t-butoxyl radicals (t-BuO center dot) and methyl radicals ((CH3)-C-center dot)The formation of DMPO/t-BuO center dot and DMPO/(CH3)-C-center dot was dose-dependent with respect to both DCBQ and t-BuOOH and was not affected by iron- or copper-specific metal chelators. Comparison of the data obtained with DCBQ and t-BuOOH with those obtained in a parallel study with ferrous iron and t-BuOOH strongly suggested that t-BuO center dot was produced by DCBQ and t-BuOOH through a metal-independent mechanism. Other halogenated quinones were also found to enhance the decomposition of t-BuOOH and other organic hydroperoxides such as cumene hydroperoxide, leading to the formation of the respective organic alkoxyl radicals in a metal-independent manner. Based on these data, we propose a mechanism for DCBQ-mediated t-BuOOH decomposition and formation of t-BuO center dot: a nucleophilic attack of t-BuOOH on DCBQ, forming a chloro-t-butylperoxyl-1,4-benzoquinone intermediate, which decomposes homolytically to produce t-BuO center dot. This represents a mechanism of organic alkoxyl radical formation not requiring the involvement of redox-active transition metal ions. |
| WOS记录号 | WOS:000244972400008 |
| 源URL | [http://ir.rcees.ac.cn/handle/311016/22475]  |
| 专题 | 生态环境研究中心_环境化学与生态毒理学国家重点实验室 |
| 推荐引用方式 GB/T 7714 | Zhu, Ben-Zhan,Zhao, Hong-Tao,Kalyanaraman, Balaraman,et al. Mechanism of metal-independent decomposition of organic hydroperoxides and formation of alkoxyl radicals by halogenated quinones[J]. PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA,2007,104(10):3698-3702. |
| APA | Zhu, Ben-Zhan.,Zhao, Hong-Tao.,Kalyanaraman, Balaraman.,Liu, Jun.,Shan, Guo-Qiang.,...&Frei, Balz.(2007).Mechanism of metal-independent decomposition of organic hydroperoxides and formation of alkoxyl radicals by halogenated quinones.PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA,104(10),3698-3702. |
| MLA | Zhu, Ben-Zhan,et al."Mechanism of metal-independent decomposition of organic hydroperoxides and formation of alkoxyl radicals by halogenated quinones".PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA 104.10(2007):3698-3702. |
入库方式： OAI收割
来源：生态环境研究中心
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