The liquid crystalline state of matter arises from orientation-dependent, non-covalent interaction between molecules within condensed phases. Because the balance of intermolecular forces that underlies formation of liquid crystals is delicate, this state of matter can, in general, be easily perturbed by external stimuli (such as an electric field in a display). In this review, we present an overview of recent efforts that have focused on exploiting the responsiveness of liquid crystals as the basis of chemical and biological sensors. In this application of liquid crystals, the challenge is to design liquid crystalline systems that undergo changes in organization when perturbed by targeted chemical and biological species of interest. The approaches described below revolve around the design of interfaces that selectively bind targeted species, thus leading to surface-driven changes in the organization of the liquid crystals. Because liquid crystals possess anisotropic optical and dielectric properties, a range of different methods can be used to read out the changes in organization of liquid crystals that are caused by targeted chemical and biological species. This review focuses on principles for liquid crystal-based sensors that provide an optical output.

This Instructional Review describes methods and underlying principles that can be used to characterize both the orientations assumed spontaneously by liquid crystals (LCs) at interfaces and the strength with which the LCs are held in those orientations (so-called anchoring energies). The application of these methods to several different classes of LC interfaces is described, including solid and aqueous interfaces as well as planar and non-planar interfaces (such as those that define a LC-in-water emulsion droplet). These methods, which enable fundamental studies of the ordering of LCs at polymeric, chemically-functionalized and biomolecular interfaces, are described in this article at a level that can be easily understood by a non-expert reader such as an undergraduate or graduate student. We focus on optical methods because they are based on instrumentation that is found widely in research and teaching laboratories.

We report orientational anchoring transitions at aqueous interfaces of a water-immiscible, thermotropic liquid crystal (LC; nematic phase of 4′-pentyl-4-cyanobiphenyl) that are induced by changes in pH of the aqueous solution and the addition of simple electrolytes (NaCl) to the aqueous phase. Whereas measurements of the zeta potential on the aqueous side of the interface of LC-in-water emulsions prepared with 5CB confirm pH-dependent formation of an electrical double layer extending into the aqueous phase, quantification of the orientational ordering of the LC leads to the proposition that an electrical double layer is also formed on the LC-side of the interface with an internal electric field that drives the LC anchoring transition. Further support for this conclusion is obtained from measurements of the dependence of LC ordering on pH and ionic strength, as well as a simple model based on the Poisson-Boltzmann equation from which we calculate the contribution of an electrical double layer to the orientational anchoring energy of the LC. Overall, the results presented herein provide new fundamental insights into ionic phenomena at LC-aqueous interfaces, and expand the range of solutes known to cause orientational anchoring transitions at LC-aqueous interfaces beyond previously examined amphiphilic adsorbates.

Micrometer-scale droplets of thermotropic liquid crystals (LCs) suspended in aqueous media can act as exquisitely sensitive reporters of environmental analytes. [1][2][3][4][5][6][7][8] Aqueous emulsions of the nematic LC 4-cyano-4'-pentylbiphenyl (5CB), for example, can quantify exposure to bacterial endotoxin (a key component of the outer membranes of Gram-negative bacteria and a major cause of disease and contamination) at pg mL À1 concentrations. [4] The interaction of amphiphilic species with LC droplets promotes changes in orientational order that can be detected as changes in optical appearance [2,8] that reflect both the concentration and structure of the analyte. [2,4] The speed and sensitivity with which these changes occur, combined with the ease with which they can be detected using optical methods (e.g., polarized light microscopy), provide new principles for the design of dispersed, droplet-based sensors that can report on the presence of chemical and biological agents in aqueous solutions. [1][2][3][4][5][6][7][8] Here, we report the design of droplet-based LC sensors that can be immobilized directly on the surfaces of cells. We demonstrate that cells decorated with encapsulated LC droplets can report-in real-time and at the level of single droplets and individual cells-on the presence of toxic agents in surrounding media. This approach provides principles for the design of droplet-based LC sensors and methods for the local (mm scale) detection of agents in cellular environments in ways that are difficult to achieve in situ using free-floating LC droplets or other analytical methods. Our approach is based on the confinement of small droplets of nematic LC within covalently crosslinked, cell-adhesive polymer microcapsules.Our design incorporates several features important for the manipulation and immobilization of LC droplets in cellular environments: 1) encapsulation of LCs in polymeric microcapsules provides means to control LC droplet size, 2) sequestration of LC in a protective membrane prevents LC droplets from coalescing or wetting other surfaces (e.g., culture dishes) and can insulate cells from direct contact with the LC, 3) polymer capsules can be decorated with functionality that can interact with cell membranes to anchor droplets in specific locations, and 4) the use of capsules with semipermeable walls can protect the LC from contact with macromolecular components of culture media, while allowing smaller analytes to pass through unhindered. The work reported here demonstrates proof of concept and underscores the utility of these design features in the context of cell-based sensing using several different well-defined model systems.We selected the thermotropic LC known as E7 (Figure 1 A) here because it exhibits a nematic/isotropic transition temperature (ca. 60 8C) well above that used for mammalian Figure 1. A) Structures of E7 and HTAB. B, C) Schematic showing a SiO 2 particle coated with PEI/PVDMA multilayers (B) and reaction of azlactones to yield amine-functionalized coatings (C). E...

We report that specific anions (of sodium salts) added to aqueous phases at molar concentrations can trigger rapid, orientational ordering transitions in water-immiscible, thermotropic liquid crystals (LCs; e.g., nematic phase of 4′-pentyl-4-cyanobiphenyl, 5CB) contacting the aqueous phases. Anions classified as chaotropic, specifically iodide, perchlorate and thiocyanate, cause 5CB to undergo continuous, concentration-dependent transitions from planar to homeotropic (perpendicular) orientations at LC-aqueous interfaces within 20 s of addition of the anions. In contrast, anions classified as relatively more kosmotropic in nature (fluoride, sulfate, phosphate, acetate, chloride, nitrate, bromide, and chlorate) do not perturb the LC orientation from that observed without added salts (i.e., planar orientation). Surface pressure-area isotherms of Langmuir films of 5CB supported on aqueous salt solutions reveal ion-specific effects ranking in a manner similar to the LC ordering transitions. Specifically, chaotropic salts stabilized monolayers of 5CB to higher surface pressures and areal densities (12.6 mN/m at 27 Å2/molec. for NaClO4) and thus smaller molecular tilt angles (30° from the surface normal for NaClO4) than kosmotropic salts (5.0 mN/m at 38 Å2/molec. with a corresponding tilt angle of 53° for NaCl). These results and others reported herein suggest that anion-specific interactions with 5CB monolayers lead to bulk LC ordering transitions. Support for the proposition that these ion-specific interactions involve the nitrile group was obtained by using a second LC with nitrile groups (E7; ion-specific effects similar to 5CB were observed) and a third LC with fluorine-substituted aromatic groups (TL205; weak dipole and no ion-specific effects were measured). Finally, we also establish that anion-induced orientational transitions in micrometer-thick LC films involve a change in the easy axis of the LC. Overall, these results provide new insights into ionic phenomena occurring at LC-aqueous interfaces, and reveal that the long-range ordering of LC oils can amplify ion-specific interactions at these interfaces into macroscopic ordering transitions.

We report a study of the wetting and ordering of thermotropic liquid crystal (LC) droplets that are trapped (or “caged”) within micrometer-sized cationic polymeric microcapsules dispersed in aqueous solutions of surfactants. When they were initially dispersed in water, we observed caged, nearly spherical droplets of E7, a nematic LC mixture, to occupy ∼40% of the interior volume of the polymeric capsules [diameter of 6.7 ± 0.3 μm, formed via covalent layer-by-layer assembly of branched polyethylenimine and poly(2-vinyl-4,4-dimethylazlactone)] and to contact the interior surface of the capsule wall at an angle of ∼157 ± 11°. The internal ordering of LC within the droplets corresponded to the so-called bipolar configuration (distorted by contact with the capsule walls). While the effects of dodecyltrimethylammonium bromide (DTAB) and sodium dodecyl sulfate (SDS) on the internal ordering of “free” LC droplets are similar, we observed the two surfactants to trigger strikingly different wetting and configurational transitions when LC droplets were caged within polymeric capsules. Specifically, upon addition of SDS to the aqueous phase, we observed the contact angles (θ) of caged LC on the interior surface of the capsule to decrease, resulting in a progression of complex droplet shapes, including lenses (θ ≈ 130 ± 10°), hemispheres (θ ≈ 89 ± 5°), and concave hemispheres (θ < 85°). The wetting transitions induced by SDS also resulted in changes in the internal ordering of the LC to yield states topologically equivalent to axial and radial configurations. Although topologically equivalent to free droplets, the contributions that surface anchoring, LC elasticity, and topological defects make to the free energy of caged LC droplets differ from those of free droplets. Overall, these results and others reported herein lead us to conclude that caged LC droplets offer a platform for new designs of LC-droplet-based responsive soft matter that cannot be realized in dispersions of free droplets.

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