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.

具有控制螺旋透光素的螺旋聚合物的合成引起了人们对聚合物化学的浓厚兴趣。在这项研究中，我们开发了一系列的螺旋聚合物，这些聚合物可以在与小手性分子络合后诱导其螺旋性。我们还通过IR，UV和CD光谱镜研究了螺旋感应的机理和螺旋手性的记忆。我们发现，对于聚（4-羧基苯基异氰化物），也可以使用类似但异常的螺旋手性记忆。在这种情况下，可以在没有任何刺激胺的情况下“记忆”在聚合物上诱导的大分子螺旋。制备的大多数聚（苯乙烯）都是在水中溶于水中的，并通过水中的静电相互作用表现出具有游离氨基酸的ICD。特别是，载磷酸残基的聚（苯乙烯）S对包括氨基酸和肽在内的多种生物分子的手性高度敏感。携带精神寡素残基的聚（苯乙烯）可以通过手性寡肽形成单手螺旋，例如通过水中的氢键相互作用，例如丙氨酸三聚体。另一个动态的螺旋聚（苯甲苯二甲苯），呈庞大的牙冠，因为吊坠对氨基酸的极小对映体不平衡做出了反应（例如，小于0.005％的对映体的丙氨酸过量），并表现出具有强阳性非线性效应的ICD。光学活动。 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.上面描述的这些方法可用于在单手螺旋阵列中构建具有所需吊坠的新型螺旋聚合物。