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Structure and Function of chiral Helical Foldamers Constructed by Three-Centered Hydrogen Bonding

三中心氢键构建的手性螺旋折叠体的结构与功能

基本信息

批准号：
18550117
负责人：
AKAZOME Motohiro
金额：
$ 2.61万
依托单位：
Chiba University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18550117/
关键词：
Peptide Chemistry Three-centered hydrogen bond Supramolecular Chemistry Foldamer

项目摘要

We have found the 2-aminophenoxyacetic acid oligomer constructs 2-fold helical structure by three-centered hydrogen-bond. When the N-terminus of the oligomer has a nitro group, their different chromophores complicate the UV and CD spectra of their oligomers. In this context, we transformed the nitro group of oligomers into the spectroscopically-resembling methoxyactamide moiety so as to easily characterize the folding structure by the UV and CD spectra. On the UV spectra in cyclohexane, the tetramer showed hypochromic effect caused by stacking of benzene rings. Here, we characterized the chiral helical structure as new functionalized foldmers. 1. Synthesis and characterization of foldamers having different side chains: As seen in leucine zipper protein, intermolecular interactions between isobutyl groups may form bundle of alpha-helix. The spectra of foldamer having isobutyl group are similar to that of methyl group. On their H-NMR spectra, up-field shift of two terminal methyl groups of isobutyl group was observed. Since no evidence to form bundle of helical structure was found, additional molecular interaction such as hydrophobic interactions will be required to form a bundle of foldamers. 2. In the above conjunction, we found that cyclic trimers of 3-aminophenoxyactic acids construct a bowl-shaped structure, which was not affected by solvents and their side chains.

我们发现2-氨基苯氧乙酸寡聚体通过三中心氢键形成2重螺旋结构。当低聚物的N-末端具有硝基时，它们的不同发色团使它们的低聚物的UV和CD光谱复杂化。在这种情况下，我们将硝基的低聚物转化成光谱上类似的甲氧基乙酰胺部分，以便容易地通过UV和CD光谱表征折叠结构。在环己烷中的紫外光谱中，四聚体表现出由苯环堆积引起的减色效应。在这里，我们的特点是手性螺旋结构作为新的功能化的折叠体。1.具有不同侧链的折叠体的合成和表征：如在亮氨酸拉链蛋白中所见，异丁基基团之间的分子间相互作用可形成α-螺旋束。具有异丁基的折叠体的光谱与具有甲基的折叠体的光谱相似。在它们的核磁共振氢谱上，观察到异丁基的两个末端甲基的高场位移。由于没有发现形成螺旋结构束的证据，因此需要额外的分子相互作用，例如疏水相互作用来形成折叠体束。2.在上述结合中，我们发现3-氨基苯氧基乙酸的环状三聚体构建了碗状结构，这不受溶剂和它们的侧链的影响。