Metal-independent decomposition of hydroperoxides by halogenated quinones: Detection and identification of a quinone ketoxy radical
文献类型：期刊论文
| 作者 | Zhu, Ben-Zhan; Shan, Guo-Qiang; Huang, Chun-Hua; Kalyanaraman, Balaraman; Mao, Li; Du, Yu-Guo |
| 刊名 | PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
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| 出版日期 | 2009-07-14 |
| 卷号 | 106期号:28页码:11466-11471 |
| 关键词 | ESR spin-trapping spin isomerization carbon-centered quinone ketoxy radical oxygen-centered quinone enoxy radical keto-enol tautomerization |
| 中文摘要 | We have shown recently that halogenated quinones could enhance the decomposition of hydroperoxides and formation of alkoxyl/hydroxyl radicals through a metal-independent mechanism. However, neither the proposed quinone enoxy radical intermediate, nor the major reaction products were unambiguously identified. In the present study, one of the major reaction products between 2,5-dichloro-1,4-benzoquinone (DCBQ) and t-butylhydroperoxide (t-BuOOH) was isolated and purified by semipreparative HPLC, and identified as 2-hydroxy-3-t-butoxy-5-chloro-1,4-benzoquinone [CBQ(OH)-O-t-Bu], which is the rearranged isomer of the postulated quinone-peroxide reaction intermediate. The formation of CBQ(OH)-O-t-Bu was found to be inhibited by the spin trapping agent 5,5-dimethyl-1-pyrroline N-oxide (DMPO), and concurrently, a new DMPO adduct with 1-chlorine isotope peak clusters at m/z 268 was observed. Further electron spin resonance (ESR) spin-trapping, (1)H-NMR and HPLC/Fourier transform ion cyclotron resonance (FTICR) mass spectrometric studies with oxygen-17-labeled and unlabeled hydrogen peroxide strongly suggest that the radical trapped by DMPO is a carbon-centered quinone ketoxy radical, which is the spin isomer of the proposed oxygen-centered quinone enoxy radical. Analogous results were observed when DCBQ was substituted by other halogenated quinones. This study represents the first detection and identification of an unusual carbon-centered quinone ketoxy radical, which provides direct experimental evidence to further support and expand our previously proposed mechanism for metal-independent decomposition of hydroperoxides by halogenated quinones. |
| WOS记录号 | WOS:000267972700009 |
| 源URL | [http://ir.rcees.ac.cn/handle/311016/21536]  |
| 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,Shan, Guo-Qiang,Huang, Chun-Hua,et al. Metal-independent decomposition of hydroperoxides by halogenated quinones: Detection and identification of a quinone ketoxy radical[J]. PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA,2009,106(28):11466-11471. |
| APA | Zhu, Ben-Zhan,Shan, Guo-Qiang,Huang, Chun-Hua,Kalyanaraman, Balaraman,Mao, Li,&Du, Yu-Guo.(2009).Metal-independent decomposition of hydroperoxides by halogenated quinones: Detection and identification of a quinone ketoxy radical.PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA,106(28),11466-11471. |
| MLA | Zhu, Ben-Zhan,et al."Metal-independent decomposition of hydroperoxides by halogenated quinones: Detection and identification of a quinone ketoxy radical".PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA 106.28(2009):11466-11471. |
入库方式： OAI收割
来源：生态环境研究中心
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