Graduate School of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, Nara 630-0036, Japan.
Chem Rec. 2009;9(5):271-98. doi: 10.1002/tcr.200900018.
From elemental particles to human beings, matter and living worlds in our universe are dissymmetric with respect to mirror symmetry. Since the early 19th century, the origin of biomolecular handedness has been puzzling scientists. Nature's elegant bottom-up preference, however, sheds light on new concepts of generating, amplifying, and switching artificial polymers, supramolecules, liquid crystals, and organic crystals that can exhibit ambidextrous circular dichroism in the UV/Visible region with efficiency in production under milder ambient conditions. In the 1920s, Kipping, who first synthesized polysilanes with phenyl groups, had much interest in the handedness of inorganic and organic substances from 1898 to 1909 in his early research life. Polysilanes--which are soluble Si-Si bonded chain-like near-UV chromophores that carry a rich variety of organic groups--may become a bridge between animate and inanimate polymer systems. The present account focuses on several mirror symmetry breaking phenomena exemplified in polysilanes carrying chiral and/or achiral side groups, which are in isotropic dilute solution, as polymer particles dispersed in solution, and in a double layer film immobilized at the solid surface, and subtle differences in the helix, by dictating ultimately ultraweak chiral forces at subatomic, atomic, and molecular levels.
从基本粒子到人类，我们宇宙中的物质和生命世界在镜像对称方面都是不对称的。自 19 世纪初以来，生物分子手性的起源一直令科学家感到困惑。然而，大自然优雅的自下而上的偏好为生成、放大和切换人工聚合物、超分子、液晶和有机晶体提供了新的概念，这些聚合物、超分子、液晶和有机晶体在温和的环境条件下可以表现出高效的、左右手性的圆二色性，在紫外线/可见光区域。20 世纪 20 年代，最早用苯基合成聚硅烷的基普森(Kipping)在 1898 年至 1909 年的早期研究生涯中对无机和有机物质的手性产生了浓厚的兴趣。聚硅烷是一种可溶性的 Si-Si 键合的近紫外发色团，带有丰富的有机基团，可能成为活物质和无生命聚合物系统之间的桥梁。本报告重点介绍了在携带手性和/或非手性侧基的聚硅烷中观察到的几种镜像对称破坏现象，这些聚硅烷在各向同性稀溶液中、作为分散在溶液中的聚合物颗粒、以及在双层膜中固定在固体表面上，通过在亚原子、原子和分子水平上最终决定超弱手性力，表现出螺旋细微的差异。
