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Picosecond-Millisecond Dynamics of Mlecular Recognition Processes

分子识别过程的皮秒-毫秒动力学

基本信息

批准号：
11440215
负责人：
KITAMURA Noboru
金额：
$ 8.13万
依托单位：
HOKKAIDO UNIVERSITY
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 2000
项目状态：
已结题

项目摘要

Several photochemical receptors were synthesized and their molecular or ion recognition processes were studied on the basis of steady-state and time-resolved spectroscopy.1). Ru (II) Complex Having Crown-Ether Moiety at 3, 3'-Positions of 2, 2'-Bipyridine (CE-bpy) : Ru (bpy)_2(CE-bpy) was synthesized for the first time. Upon addition of a sodium or pottasium ion, the emission spectrum of the complex varied considerably, while the absorption spectrum was almost insensitive to the ion. Emission titration by a sodium ion in acetinitrile demonstrated the association constant being 10^3 M^<-1>. Emission dynamics of the complex was also influened by the presence of the ion.2). Ru (II) Complex Having Calixarene Tetrasulfonate as Counter Cation (RuB-Calix) : Addition of calixarene tetrasulfonate into an aqueous solution of tris (, 2'-bipyridine) ruthenium (II) afforded pure RuB-Calix crystals. In solution. The emission intensity of the hybrid complex increased in the presence of a sodium, magn … More esium, or aluminum ion. In the absence of an ion, RuB and calixarene produced a hybrid complex and the excited state of RuB was quenched by the calixarene moiety. In the presence of an *n, counter cation exchange proceeds and, thus, the amount of free RuB increased. These processes were well explained by emission dynamic experiments.3). Photochemistry of Molecular Hinge : The "Molecular Hinge" first reported by Hamilton et al. was reinvestigated by absorption and fluorescence spectroscopy. Upon hudrogen bonding interaction between the molecular inge and butylthymine, both absorption and fluorescence spectra of the hinge changed dramatically. Fluorescence dynamic demonstrated static interaction between the host and guest.4). Spectroscopic Study on Hydrogen Bonding Interaction of Barbitul derivatives : Baribitul derivatives having an aromatic hydrocarbon moiety such as pyrene, anthracene, or N-ethylcarbazole were synthesized and their hydrogen bonding interaction with diaminopyridine were studied in acetonitrile and THF. Less

合成了几种光化学受体，并在稳态和时间分辨光谱的基础上研究了它们的分子或离子识别过程。首次合成了2，2 ′-联吡啶3，3 ′-位冠醚结构的Ru（II）配合物（CE-bpy）：Ru（bpy）_2（CE-bpy）。当加入钠或钾离子时，络合物的发射光谱变化很大，而吸收光谱对离子几乎不敏感。钠离子在乙腈中的发射滴定表明缔合常数为10^3 M^<-1>。配合物的发射动力学也受到离子存在的影响。具有杯芳烃四磺酸盐作为抗衡阳离子的Ru（II）络合物（RuB-Calix）：将杯芳烃四磺酸盐添加到三（1，2 '-联吡啶）钌（II）的水溶液中，得到纯RuB-Calix晶体。在溶液中。在钠、镁离子存在下，杂化复合物的发射强度增加， ...更多信息铯或铝离子。在没有离子存在下，RuB和杯芳烃产生杂化复合物，并且RuB的激发态被杯芳烃部分猝灭。在an *n的存在下，进行抗衡阳离子交换，因此，游离RuB的量增加。排放动力学实验很好地解释了这些过程。分子铰链的光化学：用吸收光谱和荧光光谱重新研究了由汉密尔顿等人首次报道的“分子铰链”。当丁基胸腺嘧啶与分子间发生氢键作用时，铰链的吸收光谱和荧光光谱都发生了显著的变化。荧光动力学表明主客体之间存在静态相互作用。巴比妥衍生物的氢键相互作用的光谱研究：合成了具有芳烃部分如芘、蒽或N-乙基咔唑的巴比妥衍生物，并在乙腈和THF中研究了它们与二氨基吡啶的氢键相互作用。少