Analytical Application of Molecular Recognition by Photochemistry of Excited States

激发态光化学分子识别的分析应用

• 批准号: 16550064
• 负责人: NAKAMURA Hiroshi
• 金额: $ 2.3万
• 依托单位: HOKKAIDO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550064/
• 关键词: Anthracene; Naphthalene; TICT; Photo Dimerization; Fluorescence; Polyether; Alkaline Earth Metal Ion

New compounds which contain two anthracene units in the molecules combining with polyether were synthesized. These compounds will recognize molecules or ions at the excited state of the anthracene moieties.When these reagents are excited by UV light, the photo dimerization at anthracen rings occurred, and three regio-isomers formed. The ratio of the regio-isomers was changed by the addition of alkaline earth metal ions such as calcium ion. To elucidate this phenomenon, the complex formation constants for alkaline earth metal ions were evaluated. However, photometric method such as fluorescence or absorption spectrometry caused the photo dimerization. H-NMR titration method was adopted to evaluate the formation constants. From the result of formation constants, we found that calcium ion forms the most stable complex in alkaline earth metal ions. The chemical shift change at the complexation shows that the calcium complex takes the most suitable conformation for photo dimerization.A new compound which has two anthracene units linked to polyether via aromatic carboxamide moiety was synthesized. The compound with 2-anthracene analogue has large complexing ability with calcium ion, and shows large increase of fluorescence emission (40 fold) at the complexation.Tne new compounds which have naphthalene acetamide units was also synthesized. Although the methylene units was inserted between naphthalene and amide moietys, the excited state of naphthalene has been quenched and little emission was observed. This fact may be caused by combination of TICT mechanism and PET (photo induced electron transfer) mechanism. The conplexation of this compound with calcium ion induced an emission from naphthalene moiety, and this emission was caused from a decrease of TICT quenching efficiency by the complex formation.

合成了分子中含有两个蒽单元的新型化合物，与聚醚结合。这些化合物在蒽环的激发态下识别分子或离子，在紫外光激发下，蒽环发生光二聚反应，形成三种区域异构体。通过加入碱土金属离子如钙离子改变区域异构体的比例。为了阐明这一现象，碱土金属离子的络合物形成常数进行了评估。然而，光度法如荧光或吸收光谱法导致光二聚化。采用~ 1H-NMR滴定法测定了生成常数。由形成常数的结果可知，在碱土金属离子中，钙离子形成的络合物最稳定。络合过程中的化学位移变化表明，钙配合物具有最适合光二聚反应的构象。含2-蒽类似物的化合物与钙离子有很强的络合能力，络合时荧光发射有较大的增强（40倍），并合成了含萘乙酰胺单元的新化合物。虽然在萘和酰胺之间插入了亚甲基单元，但萘的激发态已被淬灭，几乎没有观察到发射。这一现象可能是由TICT机制和PET（光诱导电子转移）机制共同作用的结果。该化合物与钙离子的络合诱导了萘部分的发射，并且这种发射是由络合物形成导致的TICT猝灭效率降低引起的。

项目成果

Facile Formation of Water-Insoluble Cyclodextrin/Nafion Composite Films on Solid Surfaces

在固体表面上轻松形成水不溶性环糊精/Nafion 复合膜

• 发表时间: 2005
• 期刊: Journal of Colloid and Interface Science 288
• 作者: A.Ohashi;A.Tsuguchi;H.Imura;K.Ohashi;井村久則(分担執筆);井村久則(分担執筆);井村(分担執筆);Tatsuya Morozumi;T.MOROZUMI et al.;Tatsuya Morozumi;Kou Nakata
• 通讯作者: Kou Nakata

外部磁場による光誘起電子移動反応の制御

使用外部磁场控制光致电子转移反应

• 发表时间: 2004
• 期刊: オレオサイエンス 4(11)
• 作者: A.Ohashi;A.Tsuguchi;H.Imura;K.Ohashi;井村久則(分担執筆);井村久則(分担執筆);井村(分担執筆);Tatsuya Morozumi;T.MOROZUMI et al.;Tatsuya Morozumi;Kou Nakata;K.NAKATA et al.;Hisafumi Hiraga;中村 博
• 通讯作者: 中村 博

Control of Photo Induced Electron Transfer Reaction by External Magnetic Field

外磁场控制光致电子转移反应

• 发表时间: 2004
• 期刊: Oleoscience 4(11)
• 作者: A.Ohashi;A.Tsuguchi;H.Imura;K.Ohashi;井村久則(分担執筆);井村久則(分担執筆);井村(分担執筆);Tatsuya Morozumi;T.MOROZUMI et al.;Tatsuya Morozumi;Kou Nakata;K.NAKATA et al.;Hisafumi Hiraga;中村 博;Tatsuya Morozumi;H.HIRAGA et al.;H.NAKAMURA
• 通讯作者: H.NAKAMURA

Rotaxane Type Complexation Behavior of Cyclodextrins with a Series of Doner-Acceptor Covalently Linked Compounds

环糊精与一系列供体-受体共价连接化合物的轮烷型络合行为

• 发表时间: 2004
• 期刊: Journak of Inclusion Phenomena and Macrocyclic Chemistry 50
• 作者: A.Ohashi;A.Tsuguchi;H.Imura;K.Ohashi;井村久則(分担執筆);井村久則(分担執筆);井村(分担執筆);Tatsuya Morozumi;T.MOROZUMI et al.;Tatsuya Morozumi;Kou Nakata;K.NAKATA et al.;Hisafumi Hiraga;中村 博;Tatsuya Morozumi;H.HIRAGA et al.;H.NAKAMURA;T.MOROZUMI et al.
• 通讯作者: T.MOROZUMI et al.

Selective Psuedo-Rotaxane Complex Formation of Zinc(II)(t-butylatedtetraphenyl)porphyrin-Viologen Linked Compounds with tri-O-methyl-β-cyclodextrin

锌(II)(叔丁基化四苯基)卟啉-紫罗碱连接化合物与三-O-甲基-β-环糊精的选择性准轮烷络合物形成

• 发表时间: 2006
• 期刊: Journal of Inclusion Phenomena and Macrocyclic Chemistry (印刷中)
• 作者: A.Ohashi;A.Tsuguchi;H.Imura;K.Ohashi;井村久則(分担執筆);井村久則(分担執筆);井村(分担執筆);Tatsuya Morozumi
• 通讯作者: Tatsuya Morozumi