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

对于界面上的分子识别，合成了氢键受体，并对它们的功能进行了评估，重点关注了生命系统中的识别功能。通过共振二次谐波(RSH)光谱、时间分辨全内反射荧光光谱(TIRF)、电化学扫描隧道显微镜(STM)、QCM、动态界面张力仪和液滴极谱分析了分子在界面上的反应和吸附行为。作为电子受体的荧光团和作为电子供体的离子受体通过聚亚甲基链连接。在这些系统中，激发的芘和离子受体之间分子内激基复合体的形成是由离子络合控制的，导致光谱反应允许分析…更有用的比率测量，即激基复合体排放物与单体排放物的比率，可以用来抵消环境影响。在芘/硫脲体系中，硫脲基团作为阴离子结合部位，阴离子结合增强的激基络合物发射的最大值被泡沫化为明显的阴离子依赖性。这种依赖性是利用激基复合体发射进行离子传感的另一个优点。在以氨基苯并-15-冠-5为阳离子结合中心的芘/酰胺-苯并-15-冠-5体系中，随着溶剂极性的增加，激基络合物发射的荧光峰值红移，表明发射的电荷转移性质。碱金属离子的加入降低了发光带的强度。在液-液界面上的分子识别方面，用电解液上升电极极谱研究了氢键受体与阴离子的络合反应，首次观察到了促进阴离子跨界面转移的现象。研究发现，无论硫酸盐的亲水性如何，它都具有显著的促进性。如上所述，我们开发了几种离子载体，并检测了它们的功能。一些离子载体可以通过液液界面上的氢键有效识别阴离子。较少

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