Development of the Novel Chemiluminescence Systems Involved in the Interface of Liquid and Metal Oxide

液体与金属氧化物界面新型化学发光系统的开发

• 批准号: 04640495
• 负责人: MAEDA Koko
• 金额: $ 0.9万
• 依托单位: Ochanomizu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04640495/
• 关键词: 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

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.

n-取代的双骨丁基（BA）在氧化铝浆中具有新颖的化学发光和蓝色发射（脱义化学发光）。当Ba表面上的Texcccited Singlet satete（Ba^**>）。电子从氧化铝上的-o^ - 和/或-oH转移到Ba^<+・>给出了Ba^<**>氧化铝表面的激发状态。2）脱甲的发射极是确定的。引用的n-填充性尖龙的态状态。发现BAINOLIDENE（BIQ）的吸附化学发光为其他底物，即使没有金属氧化物在非极性溶剂中，BIQ与分子氧的反应性更高。反应机制。

项目成果

Y.Mori: "Structure of Diiodide Salts of N-Heteroaromatic Dications" Acta Cryst.Sect.C. 49. 1398-1401 (1993)

Y.Mori：“N-杂芳族双阳离子的二碘盐的结构”Acta Cryst.Sect.C。

Y.Mori,M.Sasaki,S.Yamada,K.Maeda: "Thermochromism of 5,10,15,20-tetraarylporphyrines at low temperature" Bull.Chem.Soc.Jpn.,. 65. 3358-3361 (1992)

Y.Mori，M.Sasaki，S.Yamada，K.Maeda：“5,10,15,20-四芳基卟啉在低温下的热致变色”Bull.Chem.Soc.Jpn.，。

J.Ohkanda,Y.Mori K.Maeda,E.Osawa: "Stractural aspects of the mechanical and thermal dissociation of the central bond in bis(triarylchromenyl)" J.Chem.Soc.,Perkin Trans.2,. 59-63 (1992)

J.Okanda，Y.Mori K.Maeda，E.Osawa：“双（三芳基色烯基）中心键的机械和热解离的结构方面”J.Chem.Soc.，Perkin Trans.2，。

Y.Mori: "Structures of 2,2'-Polymethylene-1,1'-biisoquinolinium Dibromides" Acta Cryst.C48. 894-897 (1992)

Y.Mori：“2,2-聚亚甲基-1,1-二异喹啉鎓二溴化物的结构”Acta Cryst.C48。

K.Maeda: Chemiluminescence Properties of Adsorbed Biacridylidenes. "Photochemistry on Solid Surface". Elsevier, 184-195 (1989)

K.Maeda：吸附的双吖啶基的化学发光特性。