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Study on function-programmed molecular systems based on shape control

基于形状控制的功能编程分子系统研究

基本信息

批准号：
16550119
负责人：
KUBO Yuji
金额：
$ 2.3万
依托单位：
Saitama University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

项目摘要

We summarized our research results on the title.1.Cooperative chirality induction using a bis(Zn(II)-prophyrin) with a large ring-size crown ether 1Our interest in developing novel molecular systems possessing "dynamic" functions coupled with chirality let us to synthesize a crown ether-bis(Zn(II)-porphyrin) conjugate with the large ring-based conformation flexibility. The achiral-to-chiral transformation upon complexation with chiral diamines is assisted by K^+ accommodated in the crown moiety. Further, the ionophoric property of crown ether enables us to read out the chirality of amino acids using circular dichroism (CD) spectra through liquid (1 in CH_2Cl_2) - (amino acids in 1N KOH aqueous solution) two-phase extraction. In this way, an intrigued synergistic effect of crown ether and porphyrins was observed on chirality induction.2.A self-organized chiral probe using 15-crown-5-derived metalloporphyrin 2Although 15-crown-5-derived Zn(II)-porphyrin 2a shows no CD spectra when adding … More a chiral diamine, the presence of K^+ in the solution allowed us to detect a significant CD spectra correlated with the chirality. The insight can be ascribed to a [K^+-chiral diamine - (2a)_2] complex formation. Similar phenomena were also observed for the case of Mg(II) porphyrin derivative 2b and chiral aminoalcohols.3.Self-organized molecular sensorsAlizarin-phenylboronic acid interactions have been used in a new design strategy for self-organized fluorescent sensors of metal ions and anions. First, Alizarin Red S (ARS), which binds effectively to phenylboronic acid (PBA) at neutral conditions in water, proved to be an excellent fluorescent indicator for the selective detections of metal ions ; the fluorescent ARS-PBA ensemble causes an efficient and selective quenching in the fluorescence by adding metal ions. It was also found that anion-induced phenylboronates can bind effectively to alizarin and greatly enhance the fluorescence in MeOH. The observation makes it possible to design new self-organized anion sensory systems. Less

1.双（Zn（II）-卟啉）配合物与大环冠醚的协同手性诱导1我们对开发具有“动态”功能和手性的新型分子体系的兴趣使我们合成了一种具有大环构象柔性的冠醚-双（Zn（II）-卟啉）配合物。与手性二胺络合后的非手性到手性转化由冠醚部分中的K^+辅助。此外，冠醚的离子化性质使我们能够通过液体（1在CH_2Cl_2中）-（氨基酸在1 N KOH水溶液中）两相萃取的圆二色性（CD）光谱读出氨基酸的手性。2.15-冠-5-衍生的金属卟啉2a的自组织手性探针的研究虽然15-冠-5-衍生的Zn（II）-卟啉2a在加入15-冠-5-衍生的金属卟啉2a时没有显示出CD光谱，但在加入15-冠-5-衍生的金属卟啉2a时，15-冠-5-衍生的Zn（II）-卟啉2a的CD光谱没有显示出CD光谱，而15-冠-5-衍生的Zn（II）-卟啉2a的CD光谱没有显示出CD光谱。 ...更多信息由于K^+是一种手性二胺，溶液中K^+的存在使我们能够检测到与手性相关的显著CD光谱。这一发现可归因于[K^+-手性二胺-（2a）_2]络合物的形成。对于镁（II）卟啉衍生物2b和手性氨基醇的情况也观察到类似的现象。3.自组织分子传感器茜素-苯基硼酸相互作用已用于金属离子和阴离子自组织荧光传感器的新设计策略中。首先，茜素红S（ARS），它有效地结合到苯基硼酸（PBA）在中性条件下，在水中，被证明是一个很好的荧光指示剂，用于选择性检测金属离子;荧光ARS-PBA系综引起一个有效的和选择性淬灭的荧光通过添加金属离子。在甲醇溶液中，阴离子诱导的苯基硼酸酯能有效地与茜素结合，并使茜素的荧光强度大大增强。这一发现为设计新的自组织负离子传感系统提供了可能。少