Development of Sensitizers and Chemiluminescent Reagents intending to create new Super-function

开发敏化剂和化学发光试剂，旨在创造新的超功能

• 批准号: 15550037
• 负责人: KIMURA Masaru
• 金额: $ 2.05万
• 依托单位: OKAYAMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550037/
• 关键词: Functional Chemistry; Super Function; Chemiluminescence; Chemosensor; Bioluminescence; Lophine; Lophine peroxide; Imidazole; 光増感剤; ジアザペリレン; アゼピニウムカチオン; ルミノール; シアニン色素; 化学発光剤; 太陽電池; 増感剤; ルテノセン

We have explored function-accumulating system for generation of a new super-function. Recently many investigations on chemo-sensors as the super-function have employed chelation-enhanced fluorescence. However, metal ion-based functional chemi luminescent systems have not been reported for the lophines. We presented the first potential signaling system incorporating a chelating ability and CL property. We have prepared 4,5-diphenyl-2-(2-pyridyl)-imidazole and developed to 2-(2-hydroxyphenyl)-4,5-diphenylimidazole 1 bearing a chelating function. The CL efficiency of 1 was 0.28 times that of lophine peroxide on initiation with KOH/MeOH. When the trigger base was changed to TBAF/THF, the efficiency was 530-fold in dry DMF. Singlet oxygen was detected from the reaction of lophine hydroperoxides in the presence of a singlet oxygen detector. In order to examine the substituent effect on the formation of singlet oxygen, 2-(p-substituted phenyl) lophine peroxides were tested. An electron-attracting group contributed to the efficient formation of singlet oxygen, while an electron-donating group enhanced the chemiluminescence. As the second example, a 2,11-diaza[3,3]paracyclo(9,10)anthracenophane derivative possessing an ethylenediamine host function has been prepared.Further we reported a unique-unexpected rearrangement from [benzene anthracene]biplanemers to energy-stored compounds and a azepine chemistry as a side work.We have achieved outstanding research goals in their functional chemistry and photochemistry of biplanemers as shown above. We are very much grateful for the financial support from the KAKEN fund.

我们探索了一种新的超函数的生成函数累加系统。近年来，许多化学传感器的研究都采用了螯合增强荧光的方法。然而，基于金属离子的功能化化学发光体系还没有报道用于洛芬。我们提出了第一个潜在的信号系统，结合螯合能力和CL性能。我们合成了4，5-二苯基-2-（2-吡啶基）-咪唑，并发展成具有螯合功能的2-（2-羟基苯基）-4，5-二苯基咪唑1。在KOH/MeOH引发下，1的CL效率是过氧化洛芬的0.28倍。当触发碱改变为TBAF/THF时，在无水DMF中效率为530倍。在单线态氧检测器的存在下，从洛啡氢过氧化物的反应中检测单线态氧。为了研究取代基对单线态氧形成的影响，测试了2-（p-取代苯基）洛芬过氧化物。吸电子基团有助于单线态氧的有效形成，而供电子基团增强化学发光。作为第二个例子，我们合成了一个具有乙二胺主体功能的2，11-二氮杂[3，3]对（9，10）蒽并环衍生物，并报道了一个独特的从[苯蒽]双平面异构体到储能化合物的重排反应和氮杂卓化学，在双平面异构体的功能化学和光化学方面取得了突出的研究成果。我们非常感谢卡肯基金的资金支持。

项目成果

the First Synthesis of A Delocalized Azepinium Ion and Its Electrophilic Character;

离域氮杂鎓离子的首次合成及其亲电特性；

• 发表时间: 2004
• 期刊: J.Org.Chem. 69
• 作者: S.Satake;Y.Kubota;C.Cordonier;H.Okamoto;M.Kimura
• 通讯作者: M.Kimura

Development of Functional Imidazole Derivatives : A New Chemiluminescent Chemosensor

功能性咪唑衍生物的开发：一种新型化学发光化学传感器

• 发表时间: 2005
• 期刊: Bull.Chem.Soc.Jpn. 78
• 作者: MASARU KIMURA 他2名;MASARU KIMURA;MASAR KIMURA 他3名;MASARU KIMURA 他3名;MASARU KIMURA;MASARU KIMURA 他1名;M.TSUNENAGA;M.Kimura
• 通讯作者: M.Kimura

New trends in Structural Organic Chemistry

结构有机化学新趋势

• 发表时间: 2005
• 作者: MASARU KIMURA 他2名;MASARU KIMURA;MASAR KIMURA 他3名;MASARU KIMURA 他3名;MASARU KIMURA;MASARU KIMURA 他1名;M.TSUNENAGA;M.Kimura;Y.Kubota;H.Okamoto;C.E.J.Cordonier;K.Satake;H.Takemura
• 通讯作者: H.Takemura

Location effect of an OH group on the chemiluminescence efficiency of 4-hydroperoxy-2-(o-, m-, or p-hydroxyphenyl)-4,5-diphenyl-4H-isoimidazoles

• DOI: 10.1016/j.tetlet.2005.01.084
• 发表时间: 2005-03
• 期刊: Tetrahedron Letters
• 影响因子: 1.8
• 作者: Mitsuru Tsunenaga;H. Iga;M. Kimura

Electrophilic Behavior of the Delocalized Azepinium Ion : Friedel-Crafts Reactions with ・・・

离域氮杂鎓离子的亲电行为：与...的弗里德尔-克来福特反应

• 发表时间: 2005
• 期刊: Org.Lett. 7
• 作者: Hideki Okamoto;Mami Kohno;Kyosuke Satake;Masaru Kimura;M.Kimura;Y.Kubota
• 通讯作者: Y.Kubota