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

合成具有可控螺旋方向的螺旋聚合物已引起高分子化学的极大兴趣。在这项研究中，我们开发了一系列的螺旋聚合物，其螺旋度可以诱导后与小的手性分子络合。通过IR、UV和CD光谱研究了螺旋诱导和螺旋手性记忆的机理，发现聚（4-羧基苯基异腈）也可能具有类似但不寻常的螺旋手性记忆。在这种情况下，在聚合物上诱导的大分子螺旋度可以在没有任何非手性胺的情况下被“记忆”。大部分制备的聚（苯乙炔）是可溶于水，并表现出ICDS与游离氨基酸在水中通过静电相互作用。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。带有非手性寡聚甘氨酸残基的聚苯乙炔在水中可以与手性寡肽如丙氨酸三聚体通过氢键作用形成单手螺旋。另一种动态螺旋聚（苯乙炔）与庞大的冠醚作为侧链响应于一个非常小的对映异构体的氨基酸（小于0.005%的对映异构体过量的丙氨酸，例如）的不平衡，并表现出ICD具有很强的正非线性效应。光学活性的。通过<60>非手性富勒烯单体与光学活性苯乙炔的共聚反应，制备了C_ -螺旋聚苯乙炔，其中非手性C_-<60>侧基沿聚合物主链呈螺旋排列，并具有明显的螺旋沿着排列，从而在富勒烯发色团区域表现出ICD结构.上述这些方法可用于构建在单手螺旋阵列中具有所需侧基的新型螺旋聚合物。

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.