| Project/Area Number |
04640495
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | Ochanomizu University |
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Principal Investigator |
MAEDA Koko Ochanomizu University, Department of Chemistry, Professor, 理学部, 教授 (40017190)
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| Co-Investigator(Kenkyū-buntansha) |
MORI Yukie Ochanomizu University, Department of Chemistry, Research Associate, 理学部, 助手 (90239624)
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| Project Period (FY) |
1992 – 1993
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| Project Status |
Completed (Fiscal Year 1993)
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| Budget Amount *help |
¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1993: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1992: ¥900,000 (Direct Cost: ¥900,000)
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| Keywords | adsorption chemiluminescence / desorption chemiluminescence / biacridinylidene / superoxide / biisoquinolidene / surface of metal oxide / activated alumina / electron-transfer / ビアクリジリデン / 電子的酸化・還元 / 化学発光 / ラジカル機構 / 金属酸化物 / アルミナ表面 |
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| Research Abstract |
N,N-Disubstituted biacridinylidene (BA) has a novel chemiluminescence in an alumina slurry, yellowish green emission (adsorption chemiluminescence) and blue emission (desorption chemiluminescence). The luminescence has been investigated to reveal the reaction mechanisms. The results obtained are as a follows :
1)The emitter of the adsorption chemiluminescence was determined to be the excited singlet state of BA(BA^<**>)tenaciously adsorbed onto the alumina surface. When BA is adsorbed on the alumina surface in the nonpolar solvent slurry, electronic oxidation of BA by adsorbed molecular oxygen on the alumina surface resulted the formation of the cation radical BA^<+・> and superoxide O_2^<-・>. Following electron transfer from -O^- and/or -OH on alumina to BA^<+・> gave the excited state of BA^<**> adsorbed on the alumina surface.
2)The emitter of the desorption chemiluminescence was determined to be the excited singlet state of N-substituted acridone. On addition of a polar solvent into the slurry after the adsorption chemiluminescence ceased, the second blue emission appeared. Oxygenation of BA^<2+> by O_2*gave the excited state of acridone via dioxetane intermediate upon the desorption by the polar solvent.
3)Several kinds of metal oxides were also found to give adsorption chemiluminescence of BA.
4)As one of the other substrates, biisoquinolidene(BIQ), the benzolog of BA, was investigated. BIQ has much higher reactivity with molecular oxygen than BA even without metal oxide in nonpolar solvents and gives light emission. It is worthwhile to reveal the reaction mechanism.
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