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Studies on the anti-aromaticity and molecular recognition properties of luminescent heterocyclic compounds related to bioluminescence

与生物发光相关的发光杂环化合物的反芳香性和分子识别特性研究

基本信息

批准号：
13640574
负责人：
TAKASHI Hirano
金额：
$ 2.24万
依托单位：
The University of Electro-Communications
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

项目摘要

3,7-Dihydroimidazo[1,2-a]pyrazin-3-one (imidazopyrazinone) ring system is an important heterocyclic structure for bioluminescent substrates isolated from marine luminescent organisms and has various useful characteristics, such as chemiluminescent, fluorescent, and solvatochromic properties. To make the bases of bioluminescence chemistry and biological imaging science of imidazopyrazinone derivatives, this research project aims to establish the fundamental physical properties of imidazopyrazinone derivatives. (1) At first, the fundamental physical properties of simple imidazopyrazinone derivatives were investigated by X-ray crystallography, UV/vis absorption spectroscopy, and MO calculations. The crystal structural analyses showed that the imidazopyrazinone π-system had a planar ring structure and characteristic bond length alternations, indicating that the π-system has a character of a zwitter-ionic resonance structure to increase aromaticity. The results of absorption spectral measurements clarified that the origin of solvatochromism was hydrogen-bonding interactions with hydrogen-bond donor solvent molecules. These observations were consistently evaluated by MO calculations. (2) Secondly, the phenyl-substituent effect on the physical property of imidazopyrazinone derivatives was investigated. The result indicated that an introduction of phenyl group at C8 caused an efficient change of the property of the imidazopyrazinone π-system, and it was succeeded in to expand the color range of the solvatochromism. (3) Finally, the ability of imidazopyrazinone derivatives to make a complex with a metal ion has been established. The spectroscopic character of an imidazopyrazinone derivative was varied by complex formation, and the tendency of the spectral change was dependent upon a Lewis acidity of a metal ion. Therefore, imidazopyrazinone derivatives are applicable as an indicator of a Lewis acidity of a metal ion.

3，7-二氢咪唑并[1，2-a]吡嗪-3-酮（咪唑并吡嗪酮）环体系是从海洋发光生物中分离的一种重要的生物发光底物杂环结构，具有发光、荧光和溶剂化变色等特性。本研究旨在建立咪唑并吡嗪酮类衍生物的基本物理性质，为咪唑并吡嗪酮类衍生物的生物发光化学和生物成像科学奠定基础。(1)首先，通过X射线晶体学、紫外/维斯吸收光谱和分子轨道计算研究了简单咪唑并吡嗪酮衍生物的基本物理性质。晶体结构分析表明，咪唑并吡嗪酮π-体系具有平面环状结构和特征性的键长交替，表明该π-体系具有两性离子共振结构的特征，从而增加了芳香性。吸收光谱的测量结果表明，溶剂化变色的起源是氢键供体溶剂分子之间的氢键相互作用。通过MO计算对这些观察结果进行了一致评价。(2)其次，研究了苯基取代基对咪唑并吡嗪酮衍生物物理性质的影响。结果表明，在C8位引入苯基后，有效地改变了咪唑并吡嗪酮π-体系的性质，并成功地扩大了溶剂化变色的显色范围。(3)最后，咪唑并吡嗪酮衍生物与金属离子形成络合物的能力已经确立。咪唑并吡嗪酮衍生物的光谱特征随络合物的形成而变化，并且光谱变化的趋势取决于金属离子的刘易斯酸性。因此，咪唑并吡嗪酮衍生物可用作金属离子的刘易斯酸度的指示剂。