Molecular Crystals and Liquid Crystals Reconï¬پgurable Colloidal Swarms in Nematic Liquid...
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Reconfigurable Swarms of Colloidal Particles Electrophoretically Driven in Nematic Liquid Crystals Sergi Hernàndez-Navarroac, Pietro Tiernobc, Jordi Ignés-Mullolac & Francesc Saguésac a Department of Physical Chemistry, Universitat de Barcelona, Barcelona, Catalonia, Spain b Department of Structure and Constituents of Matter, Universitat de Barcelona, Barcelona, Catalonia, Spain c Institute of Nanoscience and Nanotechnogy, Universitat de Barcelona, Catalonia, Spain Published online: 06 Jul 2015.
To cite this article: Sergi Hernàndez-Navarro, Pietro Tierno, Jordi Ignés-Mullol & Francesc Sagués (2015) Reconfigurable Swarms of Colloidal Particles Electrophoretically Driven in Nematic Liquid Crystals, Molecular Crystals and Liquid Crystals, 610:1, 163-172, DOI: 10.1080/15421406.2015.1025635
To link to this article: http://dx.doi.org/10.1080/15421406.2015.1025635
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Mol. Cryst. Liq. Cryst., Vol. 610: pp. 163–172, 2015 Copyright © Taylor & Francis Group, LLC ISSN: 1542-1406 print/1563-5287 online DOI: 10.1080/15421406.2015.1025635
Reconfigurable Swarms of Colloidal Particles Electrophoretically Driven in Nematic
SERGI HERNÀNDEZ-NAVARRO,1,3 PIETRO TIERNO,2,3
JORDI IGNÉS-MULLOL,1,3,∗ AND FRANCESC SAGUÉS1,3
1Department of Physical Chemistry, Universitat de Barcelona, Barcelona, Catalonia, Spain 2Department of Structure and Constituents of Matter, Universitat de Barcelona, Barcelona, Catalonia, Spain 3Institute of Nanoscience and Nanotechnogy, Universitat de Barcelona, Catalonia, Spain
We present experiments where anisometric colloidal microparticles dispersed in a ne- matic liquid crystal cell with homeotropic anchoring conditions are dynamically as- sembled by means of liquid-crystal-enabled electrophoresis (LCEEP) using an AC electric field perpendicular to the confining plates. A nematic host with negative dielec- tric anisotropy leads to a driving force parallel to the cell plates. We take advantage of the resulting gliding anchoring conditions and the degeneracy in the direction of particle motion to design reconfigurable trajectories using a photosensitive anchoring layer (azosilane self-assembled monolayer), as the particle trajectory follows the local director orientation.
Keywords electrophoresis; colloids; self-assembly; azobenzene; swarms
The assembly and transport of microscopic entities, such as particles, droplets, or mi- croorganisms, is a permanently motivating challenge in Soft Materials science. Colloid assembly can be tuned by controlling their size  and shape , their surface chemistry [3, 4], or by suspending the inclusions in a liquid crystal . Optical trapping techniques are often employed to achieve direct control over the placement of colloidal inclusions, and holographic tweezers allow to extend such control to a few hundreds of particles , although the technique is limited by the field of view of the optical system. Recently, new perspectives for the assembly and transport of colloids through the interplay of phoretic and osmotic mechanisms have been demonstrated [7, 8].
When electric fields are involved, Direct Current (DC) driving of colloids can lead to unwanted effects such as ion migration or electrolysis, which can be avoided by using
∗Address correspondence to Jordi Ignés-Mullol, Universitat de Barcelona, Marti i Franques 1 08028, Barcelona, Catalonia, Spain. E-mail: email@example.com
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164 S. Hernàndez-Navarro et al.
Alternating Current (AC) fields. For AC driving to be effective, the fore-aft symmetry of individual particles must be broken. This has been realized with metallo-dielectric Janus particles driven in aqueous media , where symmetry is broken by the particle inhomoge- neous surface. More recently, the use of a nematic liquid crystal (NLC) host has showed the capability to transport homogeneous solid [10–12] or liquid inclusions  along the local nematic director. In this Liquid Crystal Enabled Electrophoresis (LCEEP), symmetry is broken by the NLC director field around the inclusion, which must have a nonzero dipolar component in order for LCEEP propulsion to be effective. When a microscale inclusion is dispersed in a NLC, the distortion of the director field leads to the formation of de- fects around the particle, with a configuration that depends on the particle shape and on the anchoring conditions. For spherical particles, tangential boundary conditions result in the formation of two surface defects (boojums) leading to a quadrupolar symmetry of the director, while homeotropic boundary conditions lead either to an equatorial ring defect (quadrupolar symmetry) or to a single hyperbolic hedgehog point defect (dipolar symme- try) [5, 14, 15]. LCEEP has been demonstrated with spherical solid or liquid inclusions, and the required dipolar symmetry has been achieved by means of suitable particle surface functionalization. However, it may be challenging to prepare a sample with a large number of spherical inclusions featuring a single hedgehog point defect configuration.
In this work we use anisometric pear-shaped solid inclusions with tangential boundary conditions embedded in a NLC. Particle shape guarantees non-quadrupolar elastic distor- tions of the director field, thus enabling LCEEP propulsion when subjected to an external AC electric field. By employing photoelastic modulations of the NLC matrix we are able to separate particle driving and steering , demonstrating an unparalleled ability to control the assembly of arbitrarily large ensembles of inclusions, and to drive the formed clusters as swarms along reconfigurable paths.
Preparation of Photosensitive Glass-ITO Plates
NLC cells were prepared using 0.7 mm thick microscope slides of size 15×25 mm2, coated with a thin layer of indium-tin oxide (ITO) with a sheet resistance of 100 � per square (VisionTek Systems). Photosensitive glass-ITO plates were prepared as shown in Fig. 1. In a first step, clean and dry plates where coated with a self-assembled monolayer of (3-aminopropyl) triethoxysilane (APTES, Sigma-Aldrich) , and subsequently rinsed with toluene, methanol (99.9%, Scharlau) and ultrapure water. Plates were then stored in a desiccator for 2 h before further use. In a second step, an amide bond was formed between the amino terminal group of APTES and the custom-synthesized azobenzene 4-octyl-4′- (carboxy-3-propyloxy)azobenzene (8Az3COOH) . This bond formation was typically performed  in a dimethylformamide (DMF, peptide synthesis grade, Scharlau) medium using pyBOP (>97%, Fluka) as the coupling agent. APTES-functionalized plates were rinsed in DMF and submerged in a Petri dish with 5 ml of DMF to which 1 ml of DMF containing 0.6 mg of 8Az3COOH and 1 ml of DMF containing 1.0 mg of pyBOP were added. Additionally, 6 μL of N-ethyldiisopropylamine (>98%, Fluka) were added to obtain the nec