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

能够响应外部刺激的人工超分子系统的构建

• 批准号: 11450352
• 负责人: INOUYE Masahiko
• 金额: $ 9.02万
• 依托单位: TOYAMA MEDICAL AND PHARMACEUTICAL UNIVERSITY (2000-2001)Osaka Prefecture University (1999)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11450352/
• 关键词: Molecular Recognition; Artificial Receptors; Host Guest; Supramoleules; Nucleic Acid; DNA; Nucleotide; Sugar; 分子認識; ヌクレオチド; ホスト・ゲスト化学

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.

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。

项目成果

Takase, M. et al.: "Synthesis and Photochromic Properties of Ferrocene-Modified Bis(spirobenzopyran)s"Mol. Cryst. Liq. Cryst.. 344. 313-318 (2000)

Takase, M. 等人：“二茂铁改性双（螺苯并吡喃）的合成和光致变色特性”Mol。

Inouye, M.: "Synthetic Hydrogen-Bonding Receptors for Biologically Essential Monosaccharides"有機合成化学協会誌. 58. 1077-1083 (2000)

Inouye, M.：“生物必需单糖的合成氢键受体”有机合成化学学会杂志 58. 1077-1083 (2000)

Fujii, N. et al.: "Correlation Between the Loss of the chaperone-like Activity and the Oxidation, Isomerization・・・"Photochem. photobiol.. 74. 477-482 (2001)

Fujii, N. 等人：“类伴侣活性的丧失与氧化、异构化之间的相关性……” Photochem. 74. 477-482 (2001)

Inouye,M. et al.: "Synthesis and Photochromic Properties of Ferrocene-Modified Bis(spirobenzopyran)s"Mol.Cryst.Liq.Cryst.. 344. 313-318 (2000)

井上，M.

Inouye, M. et al.: "Glucopyranoside Recognition by Polypyridine-Macrocyclic Receptors Possessing a Wide Cavity with a Flexible Linkage"J. Org, Chem.. 64. 8170-8176 (1999)

Inouye, M. 等人：“具有柔性连接的宽腔的聚吡啶大环受体对吡喃葡萄糖苷的识别”J。