Cross-Linked Cellulose Nanocrystal Membranes with Cholesteric Assembly.

Forming membranes by tangential flow deposition of cellulose nanocrystal (CNC) suspensions is an attractive new approach to bottom-up membrane fabrication, providing control of separation performance using shear rate and ionic strength. Previously, the stabilization of these membranes was achieved by irreversibly coagulating the deposited layer upon the permeation of a high-ionic-strength salt solution. Here, we demonstrate for the first time the chemical cross-linking of carboxyl-containing TEMPO-oxidized CNCs by Ag(I)-catalyzed oxidative decarboxylation and the stabilization of CNC membranes using this post-treatment. Cross-linking of TEMPO-CNCs was first demonstrated in suspension via turbidity, dynamic light scattering, and storage (G') and loss (G″) moduli measurements. Membranes were formed by filtering a 0.15 wt % TEMPO-CNC suspension onto a porous support, followed by permeation of the cross-linking solution containing AgNO3 and KPS through the deposited layer. Rejection for Blue Dextran with a 5 kDa molecular weight was 95.3 ± 1.9%, 90.6 ± 3.7%, and 95.9 ± 1.0% for membranes made from suspensions of TEMPO-CNC, desulfated TEMPO-CNC. and TEMPO-CNC with 100 mM NaCl, respectively. Suspensions with added NaCl led to membranes with improved stability and cholesteric self-assembly in the membrane layer. Membranes subjected to cross-linking post-treatment remained intact upon drying, while those stabilized physically using 200 mM AlCl3 solution were cracked, demonstrating the advantage of the cross-linking approach for scale-up, which requires drying of the membranes for module preparation and storage.

Optically responsive dry cholesteric liquid crystal marbles.

Dry liquid crystal marbles are structures that consist of cholesteric liquid crystal (CLC) droplets prepared by the mixture of chiral-doped thermotropic LCs encapsulated by cellulose nanocrystals (CNCs) that have been dried under ambient conditions. The characterizations revealed that CLC droplets were successfully encapsulated by self-standing CNC shells and responsive to the external gaseous stimulus. The dry LC marbles offer several advantages over previously reported LC-based gas sensors, such as fast response against minor external stimuli, and ease of handling, which make them particularly attractive for practical applications in sensing. We demonstrate the use of these marbles for detecting toluene vapor, a common industrial solvent and pollutant, which we also use to understand the response characteristics. The dry CLC marbles exhibit a significant response to toluene vapor with a detection limit below 500 ppm, attributed to the change of pitch size of the helical structure of CLC droplets induced by the toluene vapor. The CNC-capsulated CLC droplets were stable in emulsion for up to two weeks, and their dried form exhibited a sensitive response upon toluene exposure. The real-time experiments revealed that the LC marbles can be used multiple times without a significant loss of sensitivity, where 90 % of the maximum response was observed at 13.3 ± 4.7 s. These dry LC marbles can also be utilized in other areas, including drug delivery, optical devices, and biosensors.

Nanoparticle-Assisted Liquid Crystal Droplet Sensors Enable Analysis of Low-Concentration Species in Aqueous Medium.

We introduce nanoparticle-assisted liquid crystal (LC) droplet-based sensors that allow determination of low-level concentrations of aqueous soluble species. The silica nanoparticles functionalized with mixed monolayers composed of two distinct groups, hydrophobic alkane tail- and charged group-terminated silanes, facilitated ternary physical interactions between the model analytes (methylene blue (MB) or methyl orange (MO)) and the nematic mesogens 5CB (4-cyano-4'-pentylbiphenyl), and the interfacial species of the nanoparticle. The response of the LC droplets was measured upon nanoparticle adsorption as a function of analyte concentration, which was characterized by the optical determination of the configuration distributions of the LC droplets. We highlight the importance of the charging and the composition of the nanoparticle interfaces for analytical purposes that allow accurate determination of the concentration of the analytes on the order of 0.01 ppb. Such a low concentration corresponds to a low interfacial coverage of nanoparticles, indicating the promisingly high sensitivity of the sensor platform to target analytes. Distinct from the past examples of the LC-based sensors, the nanoparticle-assisted LC sensors allow detection of the species that do not directly cause an ordering transition at the LC-water interfaces, which allow a broader range of analytical targets. The sensor platform that we report herein can be easily tunable for a range of target molecules and will find use in the determination of a wide range of micropollutants in aqueous environments.

Understanding directed assembly of concentrated nanoparticles at energetically heterogeneous interfaces of cholesteric liquid crystal droplets.

Colloidal self-assembly has gained significant interest in scientific and technological advances. We investigated the self-assembly of the colloids at fluidic interfaces that mediate elastic interactions. Whereas past studies have reported the assembly of micrometer- or molecular-sized species at aqueous interfaces of liquid crystals (LCs), herein we study the assembly of intermediate-sized nanoparticles. Specifically, surface-modified silica nanoparticles (50 to 500 nm) were adsorbed at the liquid crystal-water interfaces and their positioning was investigated using electron microscopy after polymerization. The study revealed that the electric double layer forces and the elastic forces caused by LC strain are dominant in the assembly of nanoparticles and their contributions can be tuned to direct the self-assembly guided by the sub-interface symmetry of confined cholesteric LCs. At high ionic strengths, we observed a strong localization of nanoparticles at the defects, whereas intermediate strengths resulted in their partial enrichment into cholesteric fingerprint patterns with an interaction energy of ≈3 kBT. This result is comparable with the calculations based on the strength of the binary interactions of the nanoparticles. The findings also support the role of ion partitioning at the LC-aqueous interfaces on the formation of the assemblies. The results can be utilized for applications in sensors, microelectronics, and photonics.

Controlled release of microcargo from water-in-liquid crystal emulsions via interfacial shear induced by synthetic microstirrers.

Past studies demonstrated that the microcargo carrying aqueous droplets trapped in LCs through elastic stresses can be triggered to release by applying shear to LC-bulk interfaces. Herein, we report our investigations on the release mechanisms of such microcargo entrapped in aqueous droplets of W-in-LC emulsions via interfacial shear caused by the synthetic micro-stirrer microparticle assemblies of iron oxide particles rotated with a magnetic field. We show that a three fold control over the release rate of the tracer molecules is possible that have initial release rates of 14.3 ± 2.5 µg cm-2 h-1, 26.5 ± 3.4 µg cm-2 h-1, and 46.9 ± 4.6 µg cm-2 h-1 when the rotation of magnetic flux was 250, 500 and 1000 rpm, respectively. We measure the release rates to reduce to 5.4 ± 1.2 µg cm-2 h-1, 6.3 ± 0.7 µg cm-2 h-1, and 20.0 ± 3.2 µg cm-2 h-1 after 60 min of shearing at 250, 500 and 1000 rpm, respectively. We present evidence for the release mechanism resulting in such temporal release profiles that correlate with the magnitude of the shear applied to the interface, interfacial coverage of the microstirrers, and the creaming effect of the aqueous droplets doped with tracers. We also report that the influence of the interfacial density of the microparticles that showed an intermediate areal density is required to achieve a maximized release rate. Additionally, we found evidence of the influence of the droplet charge that critically determines the release. This study highlights the importance of the colloidal and interfacial phenomena in the release profiles of the dispersed droplets present in a LC medium.

Liquid crystal microcapillary-based sensors for affordable analytical applications.

Stimuli-responsive properties of liquid crystals (LCs), when combined with their optical properties, offer sensitive and rapid sensing applications. Here, we propose and demonstrate a microcapillary-based method to be applied for the online detection of amphiphilic species, which can be further used for tracking biological and chemical species in aqueous media. Specifically, we used compartments (300-1400 µm) of nematic 4-cyano-4'-pentylbiphenyl (5CB) that were positioned into cylindrical glass microcapillaries that promote homeotropic anchoring. The flat surfaces of the cylindrical LC compartments were in contact with an aqueous media. We characterized the equilibrium and nonequilibrium response of LCs upon a change in their anchoring at the aqueous interfaces. Upon anchoring transition, we observed the formation of a positively charged defect at the proximity of the interface that moved to the center of the LC compartment and reached equilibrium, a four-petal configuration. This transition was observed to take an average of 41 ± 19 min., which we related to the motion of the defect due to the imbalance of the elastic forces. During the transition, we observed metastable states which could be removed via thermal treatment. We showed the capillary sensors to be useful considering their ease of additional quantification. We also show that the sensors are reversible that facilitate temporal and cumulative quantification. The findings reported in this study can further be used to develop sensors for specific purposes that require continuous tracking of the chemical and biological species that is critical for the health and safety of the individuals and society.

Nanoparticle adsorption induced configurations of nematic liquid crystal droplets.

Nematic liquid crystal (LC) droplets have been widely used for the detection of molecular species. We investigate the response of micrometer sized nematic LC droplets against the adsorption of nanoparticles from aqueous media. We synthesized âˆ¼ 100 nm-in-diameter silica nanoparticles and modified their surfaces to mediate either planar or homeotropic LC anchoring and a pH-dependent charge. We show surface functionality- and concentration-dependent configurations of the droplets consistent with the change in the surface anchoring and the formation of local heterogeneities upon adsorption of the nanoparticles to LC-aqueous interfaces. The adsorption of nanoparticles modified with dimethyloctadecyl [3-(trimethoxysilyl) propyl] ammonium chloride (DMOAP, homeotropic) exhibit a transition from bipolar to radial, whereas the adsorption of -COOH-terminated counterparts (planar) did not cause a configuration transition. By manipulating the electrostatic interactions, we controlled the adsorption of the nanoparticles to the LC-aqueous interfaces, providing access to the physicochemical properties of the nanoparticles. We demonstrate a temporal change in the droplet configurations caused by the adsorption of the nanoparticles functionalized with -COOH/DMOAP mixed monolayers. These results provide a basis for studies in applications for the detection of nano-sized species, for sensing applications that combine nanoparticles with LCs, and for the synthesis of anisotropic composite particles with complex structures.

Controlling Ultrafiltration Membrane Rejection via Shear-Aligned Deposition of Cellulose Nanocrystals from Aqueous Suspensions.

Cellulose nanocrystals (CNCs) of 180 nm length and 8 nm diameter were deposited on porous supports by tangential flow filtration followed by salt permeation to form ultrafiltration membranes. At a high enough shear rate on the support surface, CNCs aligned in the direction of flow, showing a nematic order. The shear rates for transition to the nematic phase determined from rheology analysis, polarized optical microscopy, and membrane performance were consistent with one another, at ca. 10 s-1. Permeating an AlCl3 solution through the shear-aligned CNC deposit stabilized the CNC layer by screening repulsive electrostatic interactions, and the stable CNC layer was obtained. On changing the surface shear rate from 10 to 50 s-1, the order parameter of CNCs increased from 0.17 to 0.7 and the rejection for Blue Dextran (5 kDa) increased from 80.4 to 92.7% and that for ß-lactoglobulin (18 kDa) increased from 89.6 to 95.4%. Hence, a simple and scalable method for controlling rejection properties of ultrafiltration membranes is developed, which uses aqueous CNC suspensions to form the selective layer.

Chameleon skin-inspired polymeric particles for the detection of toluene vapor.

Inspired by the structural coloring in nature, especially the crystalline ordering and responsive characteristics of those found in chameleon skins, artificial photonic materials for sensor applications were fabricated. Cholesteric liquid crystals (CLCs) were employed in the templated synthesis of polymeric particles with periodic structures that allow visible light to undergo Bragg reflection and their response was tested against volatile organic compounds (VOCs). We demonstrate that the particles were responsive against toluene with detection limits on the order of 100 ppm. Such sensitivity was shown to be achieved due to the critical steps followed during the CLC-templated synthesis of particles that resulted in the storage of elastic energy in the anisotropic glassy polymer network. In addition, the design of particle-assisted sensor chips that allow easy integration into wearable optical devices for reliable, continuous and online tracking of VOC concentrations is presented. These results proved that sensors developed from the CLC-templated particles can be used multiple times without a significant loss of sensitivity and offered rapid, sensitive and battery-free detection.

Prolate and oblate chiral liquid crystal spheroids.

Liquid crystals are known to exhibit intriguing textures and color patterns, with applications in display and optical technologies. This work focuses on chiral materials and examines the palette of morphologies that arises when microdroplets are deformed into nonspherical shapes in a controllable manner. Specifically, geometrical confinement and mechanical strain are used to manipulate orientational order, phase transitions, and topological defects that arise in chiral liquid crystal droplets. Inspired by processes encountered in nature, where insects and animals often rely on strain and temperature to alter the optical appearance of dispersed liquid crystalline elements, chiral droplets are dispersed in polymer films and deformation induced by uniaxial or biaxial stretching. Our measurements are interpreted by resorting to simulations of the corresponding systems, thereby providing an in-depth understanding of the morphologies that arise in these materials. The reported structures and assemblies offer potential for applications in smart coatings, smart fabrics, and wearable sensors.

Strain-enhanced sensitivity of polymeric sensors templated from cholesteric liquid crystals.

Detection of volatile organic compounds (VOCs) is an important issue due to their harmful impact on human health. In this study, we aimed at enhancing the sensitivity of the anisotropic polymeric films templated from cholesteric liquid crystals (CLCs) in the identification of VOCs at concentrations on the order of 100 ppm. To increase sensitivity, we introduced negative strain to the films in the direction parallel to the helical axis and evaluated its effect on the sensitivity. Specifically, we used LC mixtures of reactive [4-(3-acryloyoxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester (RM257)], nonreactive E7 mesogen and chiral dopant [4-((1-methylheptyloxycarbonyl)phenyl-4-hexyloxybenzoate) (S-811)] to synthesize CLC-templated polymeric films with programmed strain profiles using a curved wedge cell, and measured their response against a range of toluene vapor concentrations. Based on the obtained results, we demonstrated a relationship between the negative strain in the cholesteric pitch and the sensitivity of the sensor based on spacial responses evaluated from the change in coloring of the film. Our results showed that negative strain helps to increase the sensitivity of the sensors up to 15 times compared to their unstrained counterparts. Moreover, 90% of the equilibrium response is achieved in less than one minute of exposure which offers rapid diagnosis of VOCs. Our tests for the reversibility of the sensors showed that the CLC-templated polymeric films can be used multiple times without a significant loss of sensitivity.

Identification and sorting of particle chirality using liquid crystallinity.

Particles dispersed in liquid crystals (LCs) have been shown to assemble due to the elastic interactions arising from the molecular anisotropy. Studies have shown that the alignment of the particles within LCs were strongly dependent on the surface director of LCs on particles. Different from the past studies involving particles with degenerate planar anchoring of LCs, this study shows that the azimuthal surface director can be used to control and finely tune the positioning of the particles in LCs. Specifically, polymeric particles with two flat surfaces that mediate parallel or non-parallel (chiral) anchoring were synthesized and dispersed in nematic 5CB with spatial variations in the director profile. Besides demonstration of their positioning, it was observed that the particles with same chiral handedness with the LC twist were distributed within the LC film, whereas particles with opposite handedness were repelled from the LC medium due to the elastic energy contributions. In addition, a pronounced effect of the surface anchoring of the particles were present on their orientation during non-equilibrium events such as sedimentation. Overall, the studies presented here will find potential use in sensors, separations, optics or soft robotic applications that will take advantages of chirality or chiral interactions.

Design Parameters and Principles of Liquid-Crystal-Templated Synthesis of Polymeric Materials via Photolithography.

The design parameters and principles for the synthesis of polymeric microscopic objects using a method that combines photolithography and liquid crystal (LC) molecular templates have been demonstrated. Specifically, mixtures of a reactive mesogen (RM257) and nonreactive LC (E7) were polymerized using UV light and a photomask. We used photomasks with circular, triangular, rectangular, square, star-shaped, and heart-shaped features to provide initial shapes to the objects. Then, the unreacted parts were extracted and the polymeric objects were allowed to shrink anisotropically as defined by the ordering symmetry of the LC mixture. The initial configuration of the LC mixtures played a critical role in determining the final shapes of the polymeric objects formed after shrinking, which resulted in chiral twisting and bending, leading to more than 20 different shapes. We found that the pitch size of the bulk chiral twisted objects depends linearly on the angle of chiral twist of the LCs, whereas it was independent of their thickness and length ranging from 1.5 to 160 µm and 100 µm to 2.45 cm, respectively. The shapes of the polymeric objects synthesized from LC films with bent LC ordering, however, were critically dependent on the thickness of the objects due to the interplay between the elastic energy and surface anchoring of the LCs. The critical role of LC elasticity was observed for thicknesses below 20 µm, above which surface anchoring was dominant in determining the shapes. Overall, the proposed method was shown to provide a precise control over the three-dimensional architectures of the objects with size range that covers the micro and macro scales, which would find use in fields ranging from emulsion stabilization and catalysis to micromachines and artificial muscles.

Liquid Crystal Templates Combined with Photolithography Enable Synthesis of Chiral Twisted Polymeric Microparticles.

Liquid crystals (LC), when combined with photolithography, enable synthesis of microparticles with 2D and 3D shapes and internal complexities. Films of nematic LCs are prepared using mixtures of reactive (RM257) and non-reactive mesogens with controlled alignment of LCs at the confining surfaces, photo-polymerized the RM257 using a photomask, and then extracted the unreacted mesogens to yield the polymeric microparticles. The extraction results in a controlled anisotropic shrinkage amount dependent on the RM257 content and the direction dependent on LC alignment. Control over the aspect ratio, size, and thickness of the microparticles are obtained with a coefficient of variance less than 2%. In addition, non-parallel LC anchoring at the two surfaces results in a controllable right- or left-handed twisting of microparticles. These methods may find substantial use in applications including drug delivery, emulsions, separations, and sensors, besides their potential in revealing new fundamental concepts in self-assembly and colloidal interactions.

Liquid Crystal-Templated Synthesis of Mesoporous Membranes with Predetermined Pore Alignment.

We demonstrate that polymeric films templated from liquid crystals (LCs) provide basic design principles for the synthesis of mesoporous films with predetermined pore alignment. Specifically, we used LC mixtures of reactive [4-(3-acryloyoxypropyloxy) benzoic acid 2-methyl-1,4-phenylene ester (RM257)] and nonreactive [4-cyano-4'-pentylbiphenyl (5CB)] mesogens confined in film geometries. The LC alignment was maintained by functionalization of the surfaces contacting the films during polymerization. Through photopolymerization followed by extraction of the unreacted mesogens, films of area in the order of 10 cm2 were obtained. We found that, when restricted to an area either through a mechanical or a configurational constraint, open and accessible pores were incorporated into the films. The average direction of the pores could be determined by the LC director during polymerization, and the average diameter of the pores can be tuned in the range of 10-40 nm by varying the reactive monomer concentration. The polymeric films synthesized here can potentially be used for the ultrafiltration purposes. We demonstrated successful separations of proteins and nanoparticles from aqueous media using the polymeric films. The films exhibited 2 orders of magnitude higher flux when the pores were aligned parallel to the permeate direction compared to the perpendicular direction. Overall, the outcomes of this study provide basic tools for the synthesis of porous polymeric films with predetermined pore directions that can potentially be suitable for separations, drug delivery, catalysts, and so forth.

Self-reporting and self-regulating liquid crystals.

Liquid crystals (LCs) are anisotropic fluids that combine the long-range order of crystals with the mobility of liquids1,2. This combination of properties has been widely used to create reconfigurable materials that optically report information about their environment, such as changes in electric fields (smart-phone displays) 3 , temperature (thermometers) 4 or mechanical shear 5 , and the arrival of chemical and biological stimuli (sensors)6,7. An unmet need exists, however, for responsive materials that not only report their environment but also transform it through self-regulated chemical interactions. Here we show that a range of stimuli can trigger pulsatile (transient) or continuous release of microcargo (aqueous microdroplets or solid microparticles and their chemical contents) that is trapped initially within LCs. The resulting LC materials self-report and self-regulate their chemical response to targeted physical, chemical and biological events in ways that can be preprogrammed through an interplay of elastic, electrical double-layer, buoyant and shear forces in diverse geometries (such as wells, films and emulsion droplets). These LC materials can carry out complex functions that go beyond the capabilities of conventional materials used for controlled microcargo release, such as optically reporting a stimulus (for example, mechanical shear stresses generated by motile bacteria) and then responding in a self-regulated manner via a feedback loop (for example, to release the minimum amount of biocidal agent required to cause bacterial cell death).

Strain-induced alignment and phase behavior of blue phase liquid crystals confined to thin films.

We report on the influence of surface confinement on the phase behavior and strain-induced alignment of thin films of blue phase liquid crystals (BPs). Confining surfaces comprised of bare glass, dimethyloctadecyl [3-(trimethoxysilyl)propyl] ammonium chloride (DMOAP)-functionalized glass, or polyvinyl alcohol (PVA)-coated glass were used with or without mechanically rubbing to influence the azimuthal anchoring of the BPs. These experiments reveal that confinement can change the phase behavior of the BP films. For example, in experiments performed with rubbed-PVA surfaces, we measured the elastic strain of the BPs to change the isotropic-BPII phase boundary, suppressing formation of BPII for film thicknesses incommensurate with the BPII lattice. In addition, we observed strain-induced alignment of the BPs to exhibit a complex dependence on both the surface chemistry and azimuthal alignment of the BPs. For example, when using bare glass surfaces causing azimuthally degenerate and planar anchoring, BPI oriented with (110) planes of the unit cell parallel to the contacting surfaces for thicknesses below 3 µm but transitioned to an orientation with (200) planes aligned parallel to the contacting surfaces for thicknesses above 4 µm. In contrast, BPI aligned with (110) planes parallel to confining surfaces for all other thicknesses and surface treatments, including bare glass with uniform azimuthal alignment. Complementary simulations based on minimization of the total free energy (Landau-de Gennes formalism) confirmed a thickness-dependent reorientation due to strain of BPI unit cells within a window of surface anchoring energies and in the absence of uniform azimuthal alignment. In contrast to BPI, BPII did not exhibit thickness-dependent orientations but did exhibit orientations that were dependent on the surface chemistry, a result that was also captured in simulations by varying the anchoring energies. Overall, the results in this paper reveal that the orientations assumed by BPs in thin films reflect a complex interplay of surface interactions and elastic energies associated with strain of the BP lattice. The results also provide new principles and methods to control the structure and properties of BP thin films, which may find use in BP-templated material synthesis, and BP-based optical and electronic devices.

Active Janus Particles at Interfaces of Liquid Crystals.

We report an investigation of the active motion of silica-palladium Janus particles (JPs) adsorbed at interfaces formed between nematic liquid crystals (LCs) and aqueous phases containing hydrogen peroxide (H2O2). In comparison to isotropic oil-aqueous interfaces, we observe the elasticity and anisotropic viscosity of the nematic phase to change qualitatively the active motion of the JPs at the LC interfaces. Although contact line pinning on the surface of the JPs is observed to restrict out-of-plane rotational diffusion of the JPs at LC interfaces, orientational anchoring of nematic LCs on the silica (planar) and palladium (homeotropic) hemispheres biases JP in-plane orientations to generate active motion almost exclusively along the director of the LC at low concentrations of H2O2 (0.5 wt %). In contrast, displacements perpendicular to the director exhibit the characteristics of Brownian diffusion. At higher concentrations of H2O2 (1-3 wt %), we observe an increasing population of JPs propelled parallel and perpendicular to the LC director in a manner consistent with active motion. In addition, under these conditions, we also observe a subpopulation of JPs (approximately 10%) that exhibit active motion exclusively perpendicular to the LC director. These results are discussed in light of independent measurements of the distribution of azimuthal orientations of the JPs at the LC interfaces and calculations of the elastic energies that bias JP orientations. We also contrast our observations at LC interfaces to past studies of self-propulsion of particles within and at the interfaces of isotropic liquids.

Patterned surface anchoring of nematic droplets at miscible liquid-liquid interfaces.

We report on the internal configurations of droplets of nematic liquid crystals (LCs; 10-50 µm-in-diameter; comprised of 4-cyano-4'-pentylbiphenyl and 4-(3-acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester) sedimented from aqueous solutions of sodium dodecyl sulfate (SDS) onto interfaces formed with pure glycerol. We observed a family of internal LC droplet configurations and topological defects consistent with a remarkably abrupt transition from homeotropic (perpendicular) to tangential anchoring on the surface of the LC droplets in the interfacial environment. Calculations of the interdiffusion of water and glycerol at the aqueous-glycerol interface revealed the thickness of the diffuse interfacial region of the two miscible liquids to be small (0.2-0.5 µm) compared to the diameters of the LC droplets on the experimental time-scale (15-120 minutes), leading us to hypothesize that the patterned surface anchoring was induced by gradients in concentration of SDS and glycerol across the diameter of the LC droplets in the interfacial region. This hypothesis received additional support from experiments in which the time of sedimentation of the LC droplets onto the interface was systematically increased and the droplets were photo-polymerized to preserve their configurations: the configurations of the LC droplets were consistent with a time-dependent decrease in the fraction of the surface area of each droplet exhibiting homeotropic anchoring. Specifically, LC droplets with <10% surface area with tangential anchoring exhibited a bulk point defect within the LC droplet, whereas droplets with >10% surface area with tangential anchoring exhibited a boojum defect within the tangential region and a disclination loop separated the regions with tangential and homeotropic anchoring. The topological charge of these LC droplet configurations was found to be consistent with the geometrical theorems of Poincaré and Gauss and also well-described by computer simulations performed by minimization of a Landau-de Gennes free energy. Additional experimental observations (e.g., formation of "Janus-like" particles with one hemisphere exhibiting tangential anchoring and the other perpendicular anchoring) and simulations (e.g., a size-dependent set of LC droplet configurations with <10% surface area exhibiting tangential anchoring) support our general conclusion that placement of LC droplets into miscible liquid-liquid interfacial environments with compositional gradients can lead to a rich set of LC droplet configurations with symmetries and optical characteristics that are not encountered in LC droplet systems in homogeneous, bulk environments. Our results also reveal that translocation of LC droplets across liquid-liquid interfaces can define new transition pathways that connect distinct configurations of LC droplets.