title: Positioning colloids at the surfaces of cholesteric liquid crystal droplets.
abstract: 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 kBT 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 kBT 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.
authors.affiliation: Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA. nlabbott@wisc.edu.
authors.forename: Emre
authors.initials: E
authors.lastname: Bukusoglu
authors.affiliation: Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA. nlabbott@wisc.edu.
authors.forename: Xiaoguang
authors.initials: X
authors.lastname: Wang
authors.affiliation: Institute for Molecular Engineering, The University of Chicago, Chicago, IL 60637, USA.
authors.forename: Ye
authors.identifier: http://orcid.org/0000-0002-4618-9318
authors.initials: Y
authors.lastname: Zhou
authors.affiliation: Institute for Molecular Engineering, The University of Chicago, Chicago, IL 60637, USA.
authors.forename: José A
authors.identifier: http://orcid.org/0000-0001-7257-8889
authors.initials: JA
authors.lastname: Martínez-González
authors.affiliation: Institute for Molecular Engineering, The University of Chicago, Chicago, IL 60637, USA.
authors.forename: Mohammad
authors.initials: M
authors.lastname: Rahimi
authors.affiliation: Department of Chemical Engineering, Tsinghua University, Beijing 100084, China.
authors.forename: Qi
authors.initials: Q
authors.lastname: Wang
authors.affiliation: Institute for Molecular Engineering, The University of Chicago, Chicago, IL 60637, USA.
authors.forename: Juan J
authors.initials: JJ
authors.lastname: de Pablo
authors.affiliation: Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA. nlabbott@wisc.edu.
authors.forename: Nicholas L
authors.initials: NL
authors.lastname: Abbott