Development of Novel Photo-responsive Compounds with Multi Molecular Recognition Sites

本文研究了新型光响应型主体分子对碱金属和碱土金属阳离子的选择性识别。1)合成了两种侧臂两端都带有Py基团的双臂套索醚，并用荧光光谱研究了它们对碱金属和碱土金属阳离子的络合性能。金属离子络合时，随着单体释放量的增加，Py准分子的释放量减少。这一发现归因于冠环和两个侧臂之一的运动抑制改变了两个芘环的空间距离，基于与金属阳离子的络合，对碱土金属离子的选择性高度依赖于主体腔和客体大小的适合性。2)描述了新型的含芘环的单氮杂环型荧光指示剂，并描述了它们的荧光特性…考察了水中碱金属和碱土金属阳离子存在时的电化学性质。金属离子的检测是基于PET机理，通过主体化合物荧光强度的变化来实现的。在水溶液中，由于Ba2+与Ba2+的络合能力很弱，加入Ba2+后荧光很弱，但Triton X-100胶束的存在使荧光团对Ba2+的检测具有很高的灵敏度和选择性。此外，还利用了单氮杂环型荧光团与Ba^&lt；2+&gt；的络合行为作为一种新的芘功能化的探针用于CMC的测定。将PET法测定的cmc值与DPH、ANS、Py探针的常规荧光法测定的cmC值以及文献值进行比较，可以看出，该方法适用于各种非离子和阴离子表面活性剂的cmc测定，也适用于cmc极低的非离子表面活性剂的cmc测定，且优于其他任何一种荧光法。这一显著的成就可能是由于芘环的高灵敏度，探针在芘上的较高溶解度(由于存在加密官能团)，以及基于PET机制的荧光强度的急剧变化

This research deals with the selective discrimination of alkali metal and alkaline earth metal cations by novel photo-responsive host molecules. -The results obtained through this work are summarized as follows.1)Two types of double-armed lariat ethers with pyrene moieties at each end of two sidearms were synthesized and their complexation properties toward alkali metal and alkaline earth metal cations were examined by fluorescence spectroscopy. Pyrene excimer emission decreased accompanied by an increase in monomer emission upon metal ion complexation. This finding is ascribed to the change of the spatial distance of two pyrene rings by movement suppression of both the crown ring and one of the two sidearms based on complexation with the metal cation The selectivity for alkaline earth metal cations was highly dependent on the fitness of the host cavity and the guest size.2)Novel monoazacryptand-type fluorescent indicators with a pyrene ring were described and their fluorescent charact … More eristics in the presence of alkali metal and alkaline earth metal cations in waterwere examined. The detection of metal cations was performed by the change of the fluorescence intensity of host compounds based on PET mechanism. In aqueous solution, the fluorophore showed little fluorescence upon the addition of Ba^<2+> because of the very weak complexation ability with Ba^<2+>, but the coexistence of Triton X-100 micelles enabled the fluorophore to detect Ba^<2+> with very high sensitivity and selectivity. Moreover, the complexation behavior between the monoazacryptand-type fluorophore and Ba^<2+> was utilized as anew pyrene-functionalized probe for CMC determination. From a comparison of the CMC values obtained by the PET method versus the CMC values obtained by conventional fluorescent methods utilizing DPH, ANS and pyrene probes as well as the literature values, one can conclude that this PET method was useful for the CMC determination of various nonionic and anionic surfactants, and for the CMC determination of nonionic surfactants with arvery low CMC, and was more effective than any other fluorescent method. This notable achievement may be due to the high sensitivity of the pyrene ring, the higher solubility of the probe (due to the presence of the cryptand functionality) over pyrene, and a drastic change in the fluorescence intensity based on the PET mechanism Less