Development of Molecular Recognition Reaction at the Interface and Analysis of Recognition Functions by Laser Spectroscopy

界面分子识别反应的进展及激光光谱识别功能分析

基本信息

批准号：
09440249
负责人：
TERAMAE Norio
金额：
$ 7.81万
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：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09440249/
关键词：
Molecular Recognition Hydrogen Bonding Thiourea Reactions at the Interface Laser Spectroscopy Second Harmonic Generation Ion Transfer at the Interface 界面張力

项目摘要

As to molecular recognitions at the interface, hydrogen bonding receptors were synthesized and their functions were evaluated, paying attentions to recognition functions used in living systems. Reactivities and adsorption behaviors of molecules at the interface were analyzed by resonant second harmonic(RSH) spectroscopy, time resolved total internal reflection fluorescence spectroscopy(TIRF), electrochemical STM, QCM, dynamic interfacial tensiometry, and liquid droplet polarographic measurements.As a new generation of fluoroionophores based on the photoinduced electron transfer process, novel pyrene-based receptors which are donor-spacer-acceptor systems were developed. A fluorophore as an electron acceptor, pyrene, was linked to an ion receptor as an electron donor by a polymethylene chain. In these systems, a formation of an intramolecular exciplex between the excited pyrene and the ion receptor is controlled by ion complexation, resulting in the spectral responses to allow analytica … More lly useful ratiometric measurements, that is, a ratio of the exciplex emissin to the monomer emission can be used to cancel out the environmental effect. In a pyrene/thiourea system, where the thiourea group functions as an anion binding site, the maxima of the exciplex emission enhanced by anion binding were foamed to be clearly anion dependent. This dependency is another advantage of the exploitation of the exciplex emission for ion sensing. In a pyrene/amidobenzo-15-crown-5 system, where the amidobenzo-15-crown-5 group functions as an cation binding site, the fluorescence maximum of the exciplex emission was red-shifted with increasing solvent polarity, indicating the charge-transfer nature of the emission. The intensity of the emission band decreased by adding alkali metal ions. This decrease reflects the stabilities of the 1 : 1 complex.As for molecular recognitions at liquid-Liquid interfaces, complexation reactions of hydrogen-bonding reveptors with anions were examined by electrolyte ascending electrode polarography, and the facilitated aniontransfer across the interface was observed for the first time. It was found that sulfate was remarkably facilitated regardless its hydrophilic nature.As mentioned above, several ionophores were developed and examined their functions. Some of the ionophores were demonstrated to recognize anions effectively through hydrogen-bond at liwuid-liquid interfaces. Less

至于界面处的分子识别，合成了氢键受体并评估了其功能，请注意生活系统中使用的识别功能。通过谐振第二谐波（RSH）光谱法分析分子在界面处的反应活力和吸附行为开发了基于pyrene的新型受体，即供体间隔者系统。荧光团作为电子受体pyrene，通过聚甲基链将离子受体作为电子供体链接。在这些系统中，激发吡啶和离子受体之间的分子内赋形剂的形成受离子络合的控制，从而产生了光谱响应以允许分析性的响应……更有用的比率测量值，即，将象度发射与单元发射的比率可以用于消除环境效应。在tiourea组充当阴离子结合位点的pyrene/thiourea系统中，通过阴离子结合增强的赋形剂发射的最大值被起泡以显然是阴离子依赖性的。离子灵敏度。在Pyrene/Amidobenzo-15-Crown-5系统中，其中Amidobenzo-15-Crown-5组充当阳离子结合位点，赋形剂发射的最大荧光随溶剂的极性增加了红变红色，表明发射的电荷转移性质。发射带的强度通过添加碱金属离子降低。这种降低反映了1：1复合物的稳定性。是在液态液界面上分子识别的稳定性，通过电解质上升的电极图检查了氢键键合的氢键反应与阴离子的络合反应，并且首次观察到跨界面的支持的阴离子转移。人们发现，无论其亲水性质如何，硫酸盐都是明显准备的。如上所述，开发了几个离子载体并检查了其功能。某些离子载体被证明可以通过液体液体界面的氢键有效地识别阴离子。较少的