Development of Molecular Memory System Using Hydrogen Bonding-Based Dynamic Controlled Recognition Process

利用基于氢键的动态控制识别过程开发分子记忆系统

基本信息

批准号：
13031039
负责人：
YASHIMA Eiji
金额：
$ 16.96万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

The synthesis of helical polymers with controlled helix-sense has aroused considerable interest in polymer chemistry. In this study, we developed a series of helical polymers whose helicity could be induced upon complexation with small chiral molecules. We also investigated the mechanism of the helicity induction and the memory of helical chirality by means of IR, UV, and CD spectroscopies.We found that a similar, but unusual memory of the helical chirality is also possible for poly (4-carboxyphenyl isocyanide). In this case, the macromolecular helicity induced on the polymer could be "memorized" without any achiral amines. Most of the poly(phenylacetylenes) prepared were soluble in water and exhibited ICDS with free amino acids through electrostatic interactions in water. Particularly, poly(phenylacetylene)s bearing the phosphonate residues were highly sensitive to the chirality of a variety of biomolecules including amino acids and peptides. A poly(phenylacetylene) bearing an achiral oligoglycine residue could form a one-handed helix with chiral oligopeptides such as an alanine trimer through hydrogen-bonding interaction in water. Another dynamic helical poly(phenlacetylene) with the bulky crown ether as the pendant responded to an extremely small enantiomeric imbalance in amino acids (less than 0.005% enantiomeric excess of alanine for example) and exhibits ICDs with a strong positive non-linear effect. An optically active. C_<60>-based helical poly(phenyl-acetylene) was also prepared by the copolymerization of an achiral fullerene monomer with an optically active phenylacetylene, where the achiral C_<60> pendants arrange in a helical array with a predominant screw-sense along the polymer backbone, thus exhibiting an ICD in the fullerene chromophore region. These methodologies described above are useful for constructing a novel helical polymer with the desired pendant in a one-handed helical array.

具有受控螺旋方向的螺旋聚合物的合成引起了人们对高分子化学的极大兴趣。在这项研究中，我们开发了一系列螺旋聚合物，其螺旋度可以在与小手性分子络合时诱导。我们还通过红外、紫外和圆二色光谱研究了螺旋性诱导和螺旋手性记忆的机制。我们发现聚(4-羧基苯基异氰化物)也可能有类似但不寻常的螺旋手性记忆。在这种情况下，聚合物上诱导的大分子螺旋性可以在没有任何非手性胺的情况下被“记忆”。制备的大多数聚苯乙炔可溶于水，并通过水中的静电相互作用与游离氨基酸表现出ICDS。特别是，带有膦酸酯残基的聚苯乙炔对包括氨基酸和肽在内的多种生物分子的手性高度敏感。带有非手性寡甘氨酸残基的聚苯乙炔可以通过水中的氢键相互作用与手性寡肽（例如丙氨酸三聚体）形成单手螺旋。另一种动态螺旋聚（苯乙炔），以庞大的冠醚作为侧链，对氨基酸中极小的对映体不平衡（例如丙氨酸对映体过量小于0.005%）做出反应，并表现出具有强正非线性效应的ICD。具有光学活性。基于C_<60>的螺旋聚(苯乙炔)也通过非手性富勒烯单体与光学活性苯乙炔的共聚来制备，其中非手性C_<60>侧链以螺旋阵列形式排列，并沿螺旋方向占主导地位。聚合物主链，从而在富勒烯发色团区域表现出 ICD。上述这些方法可用于构建一种新型螺旋聚合物，其具有单手螺旋阵列中所需的悬垂物。