Development of Molecular Recognition Sensing Systems Using Frmation of Intra- and Inter-moleulcar Excimer

为实现本课题的研究目标，我们进行了以下研究.我们已经制备了在伯羟基或仲羟基之一上带有1-芘丁酸（1-PBA）或1-芘羧酸（1-PA）部分的γ-环糊精（γ-CD）衍生物。在γ-CD衍生物中，在伯羟基侧被1-PBA取代的γ-CD能够形成稳定的缔合二聚体，已经可应用于新型传感系统，其中胆酸衍生物可以检测到μ M的数量级，因为它们显示出激基缔合物发射的极大降低和单体发射的增加。对客人的反应被发现影响theiize，形状和极性。我们制备了三个和四个区域异构体的β-和γ-CD衍生物，分别，具有两个萘部分，可以形成激基缔合物分子内，并揭示了相互之间的位置和它们的取向的CD腔内外。此外，我们还对该类化合物作为分子识别传感器进行了初步研究。分子内激基缔合物的形成受客体的加入的影响;某些CD衍生物的激基缔合物荧光增强，而在其他情况下，同一客体以不同的强度减弱激基缔合物荧光。这些结果表明，利用CD衍生物作为多传感元件的体系，可以实现对化合物的分级和精确检测.我们制备了含丹磺酰基和二茂铁基团的β-环糊精衍生物，分别作为荧光探针和二色性探针，并揭示了它们在分子识别传感体系中的应用。我们还发现偶氮苯修饰的γ-CD可以通过光化学顺反异构化作用改变其与客体的结合能力，从而起到光开关多响应分子识别传感器的作用。

We have carried out the following studies to attain our objects of the titled project.1. We have prepared gamma-cyclodextrin (gamma-CD) derivatives bearing a 1-pyrenebutyric acid (1-PBA) or a 1-pyrenecarboxylic acid (1-PA) moiety at one of primary or secondary hydroxyl groups. Among the gamma-CD derivatives gamma-CDs substituted with 1-PBA at primary hydroxyl side capable of forming a stable association dimer have been applicable to a novel sensing system with which cholic acid derivatives could be detected down to the order of muM, because they showed enormous decrease in excimer emission and increase in monomer emission. The responses for guests were found to be affected theiize, shape, and polarity.2. We have prepared three and four regioisomers of beta-and gamma-CD derivatives, respectivelty, possessing two naphthalene moieties which can form excimer intramolecularly, and revealed mutual location between the fluorophores and their orientations in and out of the CD cavity. In addition, we have carried out a basic investigation using the compounds as molecular recognizing sensors. The formation of the intramolecular excimers was affected by the addition of guest ; the excimer fluorescence of some of the CD derivatives was increased and, in others cases, the same guest weakened the excimer fluores cence with different intensities. These results suggest that fractional and simultanious detection for the compounds can be realized by using a system in which CD derivatives are involved as multipe sensor elements.3. We have prepared beta-CD derivatives bearing dansyl and ferrocene moiety acting as a flurorescence and a dichroic probes, respectively, and have revealed that they were applicable to molecular recognizing sensing sensing system. We have also found that azobenzene-modified gamma-CD whose guest binding ability can be changed by photochemical cis-trans isomerization acts as a photoswitchable muiti-response molecular recognizing sensor.