Design and Function of Molecular Complex Sensors Based on Supramolecular Structure

基于超分子结构的分子复合传感器的设计与功能

• 批准号: 12440208
• 负责人: HAYASHITA Takashi
• 金额: $ 9.41万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12440208/
• 关键词: Supramolecular chemistry; Molecular complex; Sensor; Cyclodextrin; Crown ether probe; Boronic acid probe; Alkali metal ion recognition; Sugar rcognition; ボロン酸プローブ

This study reports the supramolecular function of fluorescent probe/cyclodextrin (CyD) complexes for ion and molecule recognition in water. Benzo-15-crown-5 fluoroionophores, Cn-15C5 (n=1,3,5), with different alkyl spacer lengths were first examined to develop supramolecular Cn-15C5/γ-CyD complex sensors for alkali metal-ion recognition in water. In organic solutions, C3-15C5 shows moderate Na^+ selectivity based on 1:1 complex formation. However, the C3-15C5/γ-CyD complex is found to selectively respond to K^+ ion in water and to exhibit pyrene dimer emission. An equilibrium analysis of the γ-CyD inclusion complexes in water reveals that the major component for the dimer emission is a 2:1:1 complex of C3-15C5 with K^+ and γ-CyD. Although the K^+ sensitivity of the C5-15C5/γ-CyD complex is comparable to that of the C3-15C5/γ-CyD complex, it also responds to Na^+. The fluoroionophore C1-15C5, which has the shortest methylene spacer, exhibits no response to alkali metal cations in the presence of γ-CyD. Thus, the response function is strongly affected by the alkyl spacer length of Cn-15C5, and the highest K^+ selectivity in water is obtained for the C3-15C5/γ-CyD complex. The boronic acid fluoroionophore C4-PB/β-CyD complex binds sugars and produces increased fluorescence emission in water. A pH-fluorescence profile for the C4-PB/β-CyD complex reveals that the fluorescence intensity increases upon the formation of the boronate conjugate base. Upon the addition of fructose, the apparent pK_a decreases to a lower pH, resulting in increased fluorescence at neutral pH. The fluorescence emission response of the C4-PB/β-CyD complex upon sugar binding appears to be due to suppression of the photoinduced electron transfer (PET) from the pyrene donor to the trigonal arylboronic acid acceptor.

本研究报告了荧光探针/环糊精 (CyD) 复合物在水中识别离子和分子的超分子功能。首先研究了具有不同烷基间隔基长度的 Benzo-15-crown-5 氟离子载体 Cn-15C5 (n=1,3,5)，以开发用于识别水中碱金属离子的超分子 Cn-15C5/γ-CyD 复合物传感器。在有机溶液中，C3-15C5 基于 1:1 络合物形成而显示出中等的 Na^+ 选择性。然而，C3-15C5/γ-CyD 复合物被发现选择性地响应水中的 K^+ 离子并表现出芘二聚体发射。对水中 γ-CyD 包合物的平衡分析表明，二聚体发射的主要成分是 C3-15C5 与 K^+ 和 γ-CyD 的 2:1:1 络合物。尽管 C5-15C5/γ-CyD 复合物的 K^+ 敏感性与 C3-15C5/γ-CyD 复合物相当，但它也对 Na^+ 有响应。氟离子载体 C1-15C5 具有最短的亚甲基间隔基，在 γ-CyD 存在下对碱金属阳离子没有反应。因此，响应函数受到Cn-15C5的烷基间隔基长度的强烈影响，并且C3-15C5/γ-CyD复合物在水中获得了最高的K^+选择性。硼酸氟离子载体 C4-PB/β-CyD 复合物与糖结合并在水中产生增强的荧光发射。 C4-PB/β-CyD 复合物的 pH 荧光曲线表明，荧光强度随着硼酸盐共轭碱的形成而增加。添加果糖后，表观 pK_a 降低至较低 pH，导致中性 pH 下荧光增强。 C4-PB/β-CyD 复合物在糖结合时的荧光发射响应似乎是由于抑制了从芘供体到三方芳基硼酸受体的光诱导电子转移 (PET)。

项目成果

早下隆士, 山内晶世, 童 愛軍, 寺前紀夫 ほか: "水中における蛍光プローブ/シクロデキストリン複合体センサーの超分子機能"Bunseki kagaku. 50(6). 355-368 (2001)

Takashi Hayashita、Akiyo Yamauchi、Aigun Do、Norio Teramae 等：“荧光探针/环糊精复合物传感器在水中的超分子功能”Bunseki kagaku 50(6) (2001)。

T. Hayashita, A. Yamauchi, A. Kato, A.-J. Tong, B. D. Smith, N. Teramae: ""Supramolecular Function of Fluorescent Probe/Cyclodextrin Complex Sensors in Water""Bunseki Kagaku. 50(6). 355-368 (2001)

T. Hayashita、A. Yamauchi、A. Kato、A.-J。

A.Yamauchi,T.Hayashita,A.Kato,N.Teramae, et al.: "Selective Potassium Ion Recognition by Benzo-15-crown-5 Fluoroionophore/γ-Cyclodextrin Complex Sensors in Water"Analytical Chemistry. 72. 5841-5846 (2000)

A. Yamauchi、T. Hayashita、A. Kato、N. Teramae 等人：“水中 Benzo-15-crown-5 氟离子载体/γ-环糊精复合传感器的选择性钾离子识别”分析化学 72。5841- 5846 (2000)

A.Yamauchi, T.Hayashita, A.Kato, N.Teramae: "Supramolecular Crown Ether Probe/ γ-Cyclodextrin Complex Sensors for Alkali Metal Ion Recognition in Water"Bull.Chem.Soc.Jpn.. (in press).

A.Yamauchi、T.Hayashita、A.Kato、N.Teramae：“用于水中碱金属离子识别的超分子冠醚探针/γ-环糊精复合传感器”Bull.Chem.Soc.Jpn..（印刷中）。

T. Hayashita, S. Taniguchi, Y. Tanamura, T. Uchida, S. Nishizawa, N. Teramae, Y. S. Jin, J. C. Lee, R. A. Bartsch: ""A bibenzo-16-crown-5 Fluoroionophore for Selective Emission Ratio Sensing of Na^+ in Aqueous Dioxane Solution""J. Chem. Soc. Perkin Trans

T. Hayashita、S. Taniguchi、Y. Tanamura、T. Uchida、S. Nishizawa、N. Teramae、Y. S. Jin、J. C. Lee、R. A. Bartsch：“”一种用于选择性发射比传感的双苯并-16-冠-5 氟离子载体