Mandle Richard J
Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK.
Chemistry. 2017 Jul 3;23(37):8771-8779. doi: 10.1002/chem.201701167. Epub 2017 Jun 5.
The twist-bend nematic (N ) phase is a recently discovered liquid-crystalline phase that exhibits macroscopic chirality even when formed from achiral materials, and as such presents a unique testbed for studies concerning the spontaneous breaking of mirror symmetry in soft matter. It is primarily exhibited by materials for which the molecular structure is composed of two rigid aromatic units (such as biphenyl connected by a flexible spacer). The local structure of the N phase is nematic-like-with molecules having an average orientational order but no positional order-with a nanoscale helix in which the pitch (i.e., the repeat distance of the helix) is of the order of several nanometres. A helix is chiral, and so the bulk N phase-in the absence of a biasing chiral environment-spontaneously separates into macroscopic domains of opposite handedness. After discussing the structure of this mesophase and its elucidation, this concept article presents the molecular factors that determine its incidence. The apparent dependency primarily on molecular shape and bend angle rather than particular functional group combinations manifests in this mesophase being exhibited on length scales far beyond those of simple liquid-crystalline dimers, not only in oligomers and polymers, but also in aqueous suspensions of micron sized helical particles.
扭曲弯曲向列相(N相)是最近发现的一种液晶相,即使由非手性材料形成,也表现出宏观手性,因此为研究软物质中镜像对称性的自发破缺提供了一个独特的试验平台。它主要由分子结构由两个刚性芳香单元(如通过柔性间隔基连接的联苯)组成的材料表现出来。N相的局部结构类似向列相——分子具有平均取向序但无位置序——具有纳米级螺旋结构,其螺距(即螺旋的重复距离)约为几纳米。螺旋是手性的,因此在没有偏向手性环境的情况下,块状N相自发地分离成具有相反手性的宏观畴。在讨论了这种中间相的结构及其阐明之后,这篇概念文章介绍了决定其出现的分子因素。这种明显主要依赖于分子形状和弯曲角度而非特定官能团组合的情况,在这种中间相不仅在低聚物和聚合物中,而且在微米级螺旋颗粒的水悬浮液中,在远超过简单液晶二聚体的长度尺度上表现出来。