Construction of Artificial Supraniolecular Systems Capable of being Responsive to External Stimuli

本研究计画旨在建构能对化学及物理等外界刺激产生反应的人工超分子系统。本项目取得的成果总结如下：1.人工糖受体的设计和合成。受体选择性地识别核糖，脱氧核糖和葡萄糖，分别，并采用基板诱导组织的构象（诱导适合机制）的识别策略。受体将天然的β-环糊精增溶到极性较小的溶剂中，如CHCl_3。目前正在利用受体选择性转化拟南芥。我们开发了一类新的水溶性环番，pyrenophanes，能够识别核碱基的疏水相互作用。的pyrenophanes只显示准分子发射，和发射淬灭后，识别的核碱基。我们正在研究蛋白核番与DNA的相互作用以及复合物的光化学性质.设计并合成了新型二茂铁修饰的人工核碱基受体。人工受体与二核苷酸强结合，其中受体的氢键基序以明确的方式与二核苷酸的两个核碱基残基相互作用。此外，人工受体将天然二核苷酸溶解到极性较低的溶剂中。由于二茂铁是一种氧化还原活性分子，具有电化学响应的新型人工受体的构建正在取得进展。

This research project is to construct artificial supramolecular systems capable of being responsive to external stimuli such as chemical and physical ones. Summary of the results obtained in this project is as follows:1. Artificial saccharide receptors were designed and synthesized. The receptors selectively recognized ribose, deoxyribose, and glucose, respectively, and employed the recognition strategy of substrate-induced organization of the conformation (induced-fit mechanism). The receptors solubilized the native saccharides into less-polar solvents such as CHCl_3. Selective transformation of saccharides by use of the receptors is now under way.2. We developed a new class of water-soluble cyclophanes, pyrenophanes, capable of recognizing nucleobases by hydrophobic interaction. The pyrenophanes showed only excimer-emission, and the emission was quenched upon recognition of nucleobases. We are now investigating the interactions between the pyrenophanes with DNA and the photochemical characteristics of the complexes.3. Novel ferrocene-modified artificial nucleobase receptors were designed and synthesized. The artificial receptors strongly bound to dinucleotides, in which the hydrogen-bonding motif of the receptors interacts with two nucleobase residues of the dinucleotides in a well-defined manner. Furthermore, the artificial receptors solubilized the native dinucleotides into less-polar solvents. As ferrocene is a redox-active molecule, the construction of a new type of artificial receptors possessing an electrochemical response is now progress.