利用ESR技术研究α-蒎烯,β-蒎烯光敏氧化反应机理

doi:10.7517/j.issn.1674-0475.1999.02.111

影像科学与光化学 ›› 1999, Vol. 17 ›› Issue (2): 111-119.DOI: 10.7517/j.issn.1674-0475.1999.02.111

利用ESR技术研究α-蒎烯,β-蒎烯光敏氧化反应机理

魏彦虎, 陈景荣, 张宝文, 曹怡

中国科学院感光化学研究所, 北京100101

收稿日期:1998-06-12 修回日期:1998-09-09 出版日期:1999-05-20 发布日期:1999-05-20
通讯作者: 张宝文
基金资助:
国家自然科学基金资助项目(批准号:29733100,29572072)

STUDIES ON THE MECHANISM OF PHOTOSENSITIZED OXIDATION OF -PINENE,-PINENE BY MEANS OF ESR TECHNIQUE

WEI Yan-hu, CHEN Jing-rong, ZHANG Bao-wen, CAO Yi

Institute of Photographic Chemistry, The Chinese Academy of Sciences, Beijing 100101, P.R.China

Received:1998-06-12 Revised:1998-09-09 Online:1999-05-20 Published:1999-05-20

摘要/Abstract

摘要： 本文主要利用电子顺磁共振(ESR)自旋捕获技术研究9,10 二氰基蒽(DCA)敏化α-蒎烯(αP),β-蒎烯(βP)光氧化反应.提供了在乙腈中α-蒎烯和β-蒎烯的光氧化反应过程中存在超氧负离子基(O₂^-)和单重态氧(¹O₂)的直接证据;在四氯化碳溶剂中只捕获到¹O₂;在正己烷中没有捕获到O₂^-或¹O₂.ESR实验结果进一步证明在乙腈中光敏氧化反应的¹O₂可能来自O₂^-和反应底物α、β-蒎烯正离子自由基之间的电荷复合(CR).

关键词: 敏化光氧化, 电子转移, 自旋捕获, 电子顺磁共振

Abstract: In this work, the mechanism of sensitizedphotooxidations of pinene and pinene by 9,10dicyanoanthracene(DCA) were studied by means of electron spin resonance(ESR) spin trapping method, and 5,5dimethylpyrrolineNoxide(DMPO), 2,2,6,6tetramethylpiperidine(TMP) and tbutylNoxide (tBN) were respectively used as trapping media to trap O₂^- ,¹O₂ and carbon center radicals producted in reactions. In acetonitrile, the existence of O₂^-,¹O₂ and carboncenter radicals was directly confirmed in ESR experiments;¹O₂ was only detected in carbon tetrachloride solution; no ESR signals were detected in nhexane solution. The results of ESR experiments show that the sensitized photooxidations is competitive reactions among O2,¹O₂ and carboncenter radicals, and ¹O₂ comes from the charge recombination(CR) between O2 and or pinene cation radical in acetonitrile solution, and indicate that the photooxidation undergoes the mechanism of oxidation of ¹O₂ in carbon tetrachloride solution and ¹O₂ comes from different mechanism in acetonitrile and carbon tetrachloride, but no DCA sensitized oxidation occurs in nhexane solution.

Key words: sensitized photooxidation, electron transfer, spin trapping, electron spin resonance

魏彦虎, 陈景荣, 张宝文, 曹怡. 利用ESR技术研究α-蒎烯,β-蒎烯光敏氧化反应机理[J]. 影像科学与光化学, 1999, 17(2): 111-119.

WEI Yan-hu, CHEN Jing-rong, ZHANG Bao-wen, CAO Yi. STUDIES ON THE MECHANISM OF PHOTOSENSITIZED OXIDATION OF -PINENE,-PINENE BY MEANS OF ESR TECHNIQUE[J]. Imaging Science and Photochemistry, 1999, 17(2): 111-119.

参考文献

1 Schaap A P, et al. Mechanisms of photooxygenation 2.formation of 1,2-dioxetanes via 9,10-dicyanoanthranene-sensitized electron transfer processes. J.Am.Chem.Soc., 1980,102:389
2 Eriksen J, et al. Photosensitized oxygenation of alkenes and sulfides via a non-singlet-oxygen mechanism. J.Am.Chem.Soc.,1977, 99:6455
3 Araki Y, et al.Chemistry of singlet oxygen 47.9,10-dicyanoanthracene-sensitized photooxygenation of alkyl-substiteted olefins. J.Am.Chem.Soc.,1984,106:4570
4 a) Zhang B W, et al.Sensitized photooxidation of pinenes by dicyanoanthracene.Photochemistry and Photobiology,1984,40(5):581; b) Cao Y, Zhang B W, et al. Singlet oxygen reactions in cyanoaromatic sensitized photooxidations. J.Photochem.,1987,38:131
5 王海,徐广智,等. 苯甲醇在二氧化钛超微粒表面的光诱导电子转移和光反应过程研究.感光科学与光化学,1993,11(4):318 Wang H,Xu G Z, et al.Study of the photo-induced electron transfer and photoreaction process of benzyl alcohol on the surface of TiO₂ colloid.Photographic Science and Photochemistry,1993,11(4):318)
6 张建中,黄宁娜,等. 在血卟啉衍生物光敏体系中DMPO捕集自由基的ESR研究.化学学报,1986,44:627 Zhang J Z, Huang N N,et al. ESR studies of radical produced in the photosensitive systems of hematoprophyrin derivatives by spin trapping agent DMPO.Acta Chimica Sinica,1986,44:627
7 Vladimir C, et al. ESR Parameters of 5,5-dimethylpyrrolidine 1-oxide(DMPO)spin adducts in the photochemical decomposition of azo compounds.Magn.Reson.Chem.,1991,29(4):402
8 HU Y Zh, Jiang L J. Generation of semiquinone radical anion and reactive oxygen ( ¹O₂, and O₂^-) during the photosensitization of a water-soluble perylenequinone derivative. J.Photochemistry and Photobiology B:Biology,1996,33:51
9 张宝文,等. 四氯化碳中的9,10-二氰基蒽敏化光氧化反应.科学通报,1985,24:1879 Zhang B W, et al.Reaction of sensitized-photooxidation by 9,10-dicyanoanthracene in carbon tetrachloride.Kexue Tongbao,1985,24:1879

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利用ESR技术研究α-蒎烯,β-蒎烯光敏氧化反应机理

STUDIES ON THE MECHANISM OF PHOTOSENSITIZED OXIDATION OF -PINENE,-PINENE BY MEANS OF ESR TECHNIQUE

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