Liquid Crystal Institute, Kent State University, Kent, OH 44242, USA.
Proc Natl Acad Sci U S A. 2011 Mar 29;108(13):5163-8. doi: 10.1073/pnas.1100087108. Epub 2011 Mar 14.
In many colloidal systems, an orientationally ordered nematic (N) phase emerges from the isotropic (I) melt in the form of spindle-like birefringent tactoids. In cases studied so far, the tactoids always reveal a mirror-symmetric nonchiral structure, sometimes even when the building units are chiral. We report on chiral symmetry breaking in the nematic tactoids formed in molecularly nonchiral polymer-crowded aqueous solutions of low-molecular weight disodium cromoglycate. The parity is broken by twisted packing of self-assembled molecular aggregates within the tactoids as manifested by the observed optical activity. Fluorescent confocal microscopy reveals that the chiral N tactoids are located at the boundaries of cells. We explain the chirality induction as a replacement of energetically costly splay packing of the aggregates within the curved bipolar tactoidal shape with twisted packing. The effect represents a simple pathway of macroscopic chirality induction in an organic system with no molecular chirality, as the only requirements are orientational order and curved shape of confinement.
在许多胶体系统中,各向同性(I)熔体以纺锤状双折射向列型(N)相的形式出现。到目前为止,在已研究的情况下,向列型微纤总是呈现出镜像对称的非手性结构,即使构建单元是手性的也是如此。我们报告了在低分子量顺式二钠色甘酸钠的分子非手性聚合物拥挤的水溶液中形成的向列型微纤中手性对称性的破坏。手性对称性的破坏是通过微纤内自组装分子聚集体的扭曲堆积来体现的,如观察到的旋光性所示。荧光共焦显微镜显示,手性 N 型微纤位于细胞边界处。我们将手性诱导解释为用扭曲堆积代替聚集体在弯曲双极微纤形状内的能量成本高的倾斜堆积。该效应代表了在没有分子手性的有机体系中宏观手性诱导的简单途径,因为唯一的要求是取向有序和约束的弯曲形状。