Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA.
Institute for Molecular Engineering, The University of Chicago, Chicago, IL 60637, USA.
Soft Matter. 2016 Oct 26;12(42):8781-8789. doi: 10.1039/c6sm01661h.
We report on the internal configurations of aqueous dispersions of droplets of cholesteric liquid crystals (LCs; 5-50 μm-in-diameter; comprised of 4-cyano-4'-pentylbiphenyl and 4-(1-methylheptyloxycarbonyl)phenyl-4-hexyloxybenzoate) and their influence on the positioning of surface-adsorbed colloids (0.2 or 1 μm-in-diameter polystyrene (PS)). When N = 2D/P was less than 4, where D is the droplet diameter and P is the cholesteric pitch, the droplets adopted a twisted bipolar structure (TBS) and colloids were observed to assume positions at either the poles or equator of the droplets. A statistical analysis of the distribution of locations of the colloids revealed a potential well of depth 2.7 kT near the equator, a conclusion that was supported by computer simulations performed via the minimization of the Landau-de Gennes free energy (well depth of 7 kT from simulation). In contrast, for N > 4, a majority of the droplets exhibited a radial spherical structure (RSS) characterized by a pair of closely spaced surface defects (angle of separation with respect to the center of the droplet θ < 5°) connected by a disclination winding to/from the droplet center, which led to the positioning of pairs of colloids with well-defined spacing at these surface defects. The separation of the pairs of surface-adsorbed colloids was colloid size-dependent, ranging from 1.11 ± 0.04 μm for 1 μm-in-diameter colloids to 1.7 ± 0.2 μm for 200 nm-in-diameter colloids. We also observed long-lived metastable configurations in which the two surface point defects were separated by much larger distances (corresponding to populations with angles of θ = 20 ± 10° and 85 ± 10° with respect to the center), and observed these pairs of defects to also position pairs of colloids. A third configuration, the diametrical spherical structure (DSS) was also observed. Consistent with the predictions of computer simulations, we found experimentally that the DSS is indeed composed of disconnected defect rings positioned along the diameter of the droplet. Overall, these results reveal that the rich palette of defects exhibited by confined cholesteric LC systems (equilibrium and metastable) provide the basis of a versatile class of templates that enable the surface positioning of colloids in ways that are not possible with achiral LC droplets.
我们报告了直径为 5-50μm 的胆甾相液晶液滴(由 4-氰基-4'-戊基联苯和 4-(1-甲基庚氧基羰基)苯基-4-己氧基苯甲酸酯组成)的水基分散体的内部结构及其对表面吸附胶体(直径为 0.2 或 1μm 的聚苯乙烯(PS))定位的影响。当 N=2D/P 小于 4 时,其中 D 是液滴直径,P 是胆甾相螺距,液滴采用扭曲双极结构(TBS),胶体观察到位于液滴的两极或赤道处。胶体位置分布的统计分析表明,在赤道附近存在一个深度为 2.7 kT 的势阱,这一结论得到了通过最小化朗道-德热内斯自由能进行计算机模拟的支持(模拟得到的势阱深度为 7 kT)。相比之下,对于 N>4,大多数液滴表现出具有一对紧密间隔的表面缺陷的径向球型结构(RSS)(相对于液滴中心的分离角θ<5°),由向/远离液滴中心的螺旋位错连接,这导致了具有明确定距的一对胶体在这些表面缺陷处的定位。吸附在表面的胶体对的分离与胶体尺寸有关,对于直径为 1μm 的胶体为 1.11±0.04μm,对于直径为 200nm 的胶体为 1.7±0.2μm。我们还观察到长寿命的亚稳构型,其中两个表面点缺陷之间的距离要大得多(对应于角度θ=20±10°和 85±10°的种群),并观察到这些缺陷对也定位胶体对。还观察到第三种结构,即直径球型结构(DSS)。与计算机模拟的预测一致,我们从实验中发现,DSS 实际上是由沿着液滴直径排列的不连续缺陷环组成的。总的来说,这些结果表明,受限胆甾相 LC 系统(平衡和亚稳)所表现出的丰富缺陷调色板为胶体的表面定位提供了一个多功能模板的基础,这种模板能够以手性 LC 液滴不可能的方式实现胶体的表面定位。