权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

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.

具有可控螺旋感的螺旋聚合物的合成引起了聚合物化学领域的广泛关注。在这项研究中，我们开发了一系列的螺旋聚合物，这些聚合物可以通过与小手性分子络合而诱导螺旋度。利用红外光谱、紫外光谱和CD光谱研究了螺旋诱导和螺旋手性记忆的机理。我们发现聚（4-羧基苯基异氰酸酯）也有类似的，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可以在没有任何非手性胺的情况下被“记忆”。制备的聚苯基乙炔大部分可溶于水，并通过水中静电相互作用与游离氨基酸发生ICDS。特别是含有膦酸盐残基的聚苯乙炔对包括氨基酸和多肽在内的多种生物分子的手性非常敏感。含有非手性寡甘氨酸残基的聚苯乙炔在水中通过氢键相互作用可与手性寡肽如丙氨酸三聚体形成单手螺旋。另一种动态螺旋聚（苯乙炔），其庞大的冠醚作为垂坠对极小的氨基酸对映体不平衡（例如，丙氨酸对映体过量小于0.005%）做出反应，并表现出强烈的正非线性效应。具有光学活性。用非手性富勒烯单体与具有旋光性的苯乙炔共聚制备了C_<60>基的螺旋聚苯乙炔，其中非手性C_<60>链链沿聚合物主链呈螺旋状排列，从而在富勒烯发色团区表现出ICD。上述方法可用于构建具有单手螺旋阵列所需垂坠的新型螺旋聚合物。