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

doi:10.7517/j.issn.1674-0475.1999.02.111

Abstract

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

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.

References

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

[1]	CHANG Shunzhou, XIANG Kaiqiang, MING Wei, ZHANG Zhizhong, TIAN Baozhu, ZHANG Jinlong. Synthesis and Properties of a pH Fluorescent Probe Based on PET Mechanism [J]. Imaging Science and Photochemistry, 2018, 36(5): 425-433.
[2]	CAO Hongyu, SHI Fei, TANG Qian, WANG Lihao, ZHENG Xuefang. Effect and Mechanism of Photo-induced Hemoglobin Kinetics Reaction with Free Cysteine [J]. Imaging Science and Photochemistry, 2018, 36(2): 149-160.
[3]	WU Shikang. The Electron-transfer and Energy-transfer between Surface Plasmon and Semiconductor in Photo-catalysts [J]. Imaging Science and Photochemistry, 2018, 36(1): 1-13.
[4]	WANG Zhijia, CHEN Kepeng, LIU Ya, ZHAO Jianzhang, ZAFAR Mahmood, JI Wei, HAN Keli. Controlling and Application of the Triplet Excited State of Organic Chromphores [J]. Imaging Science and Photochemistry, 2017, 35(3): 211-232.
[5]	YANG Ke, ZHANG Yan, XU Jianhua. The Application of Electron Transfer Photo-oxidation Reaction in Organic Synthesis [J]. Imaging Science and Photochemistry, 2014, 32(5): 433-446.
[6]	JIANG Xiao-ming, YU Xiao-cui, ZHAO Sui, AN Jing-yi. The Effect of the Interfering Groups on the Aggregation Behavior of Sodium Alkylbenzenesulfonate by Steady-State Fluorescence and ESR [J]. Imaging Science and Photochemistry, 2011, 29(5): 383-388.
[7]	LI Yi, ZHANG Xiao-hui, ZENG Yi, CHEN Jin-ping, LI Ying-ying. Photoinduced Electron/Energy Transfer within Light-Harvesting Dendrimers [J]. Imaging Science and Photochemistry, 2011, 29(4): 246-269.
[8]	WANG Zhong-li, GAO Yun-yan, OU Zhi-ze, GUO Chuang-long, LI Hai-xia, JIN He-lin. Synthesis of Isoalloxazine Modified C₆₀-polypropylene Acid and Its Interaction with DNA [J]. Imaging Science and Photochemistry, 2011, 29(3): 181-193.
[9]	LI Xu-bing, WANG Xiao-jun, WANG Ge-xia, XING Ling-bao, ZHANG Li-ping, TONG Zhen-he, WU Li-zhu. Photoinduced Electron Transfer in Self-assembly CBPQT and N-P₄-N [J]. Imaging Science and Photochemistry, 2010, 28(4): 241-246.
[10]	TAN Guang-hui, WEI Shu-quan, ZHAO Jun-ming, ZHANG Peng, WANG Bing-nan, ZHENG Peng, LIU Yan, JIN Ying-xue. Synthesis of Ketonpiprazine from N-phthalimido Dipeptides by Photoinduced Single Electron Transfer [J]. Imaging Science and Photochemistry, 2010, 28(2): 131-136.
[11]	WU Shi-kang, WANG Peng-fei. Some Problems on the Organic Semi-conductor Hetero-junction [J]. Imaging Science and Photochemistry, 2010, 28(2): 147-158.
[12]	JIN Mi-mi, OU Zhi-ze, GAO Yun-yan, HAO Ping, YIN Wei-feng, LIU Li-hua. Spectroscopic Study on the Interaction of Metal Complexes of Hypocrellin A with Human Serum Albumin [J]. Imaging Science and Photochemistry, 2010, 28(1): 1-9.
[13]	JU Wei, LI Jin-pei. Probing the Development Process of AgBr in AAO Template [J]. Imaging Science and Photochemistry, 2008, 26(6): 452-459.
[14]	YANG Shao-peng, LI Chun-lei, FAN Shan-shan, LI Xiao-wei, FU Guang-sheng. Ultrafast Kinetics Characteristics of Fluorescence in Anionic-Cationic Cyanine Dyes [J]. Imaging Science and Photochemistry, 2007, 25(5): 364-373.
[15]	HUANG Xin, LI Zhong-yu, BIN Yue-jing, HUANG Lei, ZHANG Fu-shi. Study on Synthesis and Spectral Properties of Phthalocyanine Conjugating Luminols [J]. Imaging Science and Photochemistry, 2007, 25(3): 209-213.