Liquid Crystalline Droplets Research Articles

Systematic study of chromonic liquid crystal-based complex emulsions and their application in the preparation of silica nanomaterials

Multiple triphasic emulsions constitute versatile templates for the preparation of complex particles and capsules. In these emulsions the volume fractions and interfacial tensions between the phases dictate the droplet morphology, enabling various morphologies such as Janus, core-shell and snowman droplets. In this article, we describe the preparation of all-aqueous water-in-water (W/W) emulsions composed by a perylene-based chromonic liquid crystal and a hydrophilic polymer. This combination yields emulsions with liquid crystalline droplets exhibiting diverse configurations of the director, including the formation of twisted structures, from achiral mesogens. Three-phase multiple emulsions with various morphologies were obtained by the emulsification of W/W emulsions in either another aqueous phase or in hexadecane. The resulting droplet morphologies depended on the composition of the system. Furthermore, hollow silica particles with a chromonic-templated microporous structure were prepared via a sol−gel reaction within the liquid crystalline phase of water-in-water-in-oil emulsions. These findings show how the unique templating properties of chromonic liquid crystals can be applied to all-aqueous emulsions for the synthesis of complex silica particles, with a controlled structure both at the micro- and nanoscale.

Single-Step Control of Liquid-Liquid Crystalline Phase Separation by Depletion Gradients.

Fine-tuning nucleation and growth of colloidal liquid crystalline (LC) droplets, also known as tactoids, is highly desirable in both fundamental science and technological applications. However, the tactoid structure results from the trade-off between thermodynamics and nonequilibrium kinetics effects, and controlling liquid-liquid crystalline phase separation (LLCPS) in these systems is still a work in progress. Here, a single-step strategy is introduced to obtain a rich palette of morphologies for tactoids formed via nucleation and growth within an initially isotropic phase exposed to a gradient of depletants. The simultaneous appearance is shown of rich LC structures along the depleting potential gradient, where the position of each LC structure is correlated with the magnitude of the depleting potential. Changing the size (nanoparticles) or the nature (polymers) of the depleting agent provides additional, precise control over the resulting LC structures through a size-selective mechanism, where the depletant may be found both within and outside the LC droplets. The use of depletion gradients from depletants of varying sizes and nature offers a powerful toolbox for manipulation, templating, imaging, and understanding heterogeneous colloidal LC structures.

Morphogenesis of a chiral liquid crystalline droplet with topological reconnection and Lehmann rotation

Morphogenesis is a hierarchical phenomenon that produces various macroscopic structures in living organisms, with high reproducibility. This study demonstrates that such structural formation can also be observed in a chiral liquid crystalline droplet under a temperature gradient. Through specific control of the temperature change process, we were able to switch the final structure obtained as a result of the formation via the appearance and reconnection of loop defects in the transient state during structure formation. Simultaneously, the existence of the gradient resulted in a characteristic rotational phenomenon called Lehmann rotation, which was prominently induced in the transient state. By demonstrating three-dimensional measurements of the flow field, we revealed the existence of Marangoni convection in the state. Consequently, it is indicated that the convection results in high-speed Lehmann rotation and large structural deformation with topological changes, thereby playing a significant role in the structure formation.

Non-enzymatic oligonucleotide ligation in coacervate protocells sustains compartment-content coupling

Modern cells are complex chemical compartments tightly regulated by an underlying DNA-encoded program. Achieving a form of coupling between molecular content, chemical reactions, and chassis in synthetic compartments represents a key step to the assembly of evolvable protocells but remains challenging. Here, we design coacervate droplets that promote non-enzymatic oligonucleotide polymerization and that restructure as a result of the reaction dynamics. More specifically, we rationally exploit complexation between end-reactive oligonucleotides able to stack into long physical polymers and a cationic azobenzene photoswitch to produce three different phases—soft solids, liquid crystalline or isotropic coacervates droplets—each of them having a different impact on the reaction efficiency. Dynamical modulation of coacervate assembly and dissolution via trans-cis azobenzene photo-isomerization is used to demonstrate cycles of light-actuated oligonucleotide ligation. Remarkably, changes in the population of polynucleotides during polymerization induce phase transitions due to length-based DNA self-sorting to produce multiphase coacervates. Overall, by combining a tight reaction-structure coupling and environmental responsiveness, our reactive coacervates provide a general route to the non-enzymatic synthesis of polynucleotides and pave the way to the emergence of a primitive compartment-content coupling in membrane-free protocells.

Evaporation-Driven Liquid–Liquid Crystalline Phase Separation in Droplets of Anisotropic Colloids

Drying a colloidal droplet involves complex physics that is often accompanied by evaporation-induced concentration gradients inside of the droplet, offering a platform for fundamental and technological opportunities, including self-assembly, thin film deposition, microfabrication, and DNA stretching. Here, we investigate the drying, liquid crystalline structures, and deposit patterns of colloidal liquid crystalline droplets undergoing liquid-liquid crystalline phase separation (LLCPS) during evaporation. We show that evaporation-induced progressive up-concentration inside the drying droplets makes it possible to cross, at different speeds, various thermodynamic stability states in solutions of amyloid fibril rigid filamentous colloids, thus allowing access to both metastable states, where phase separation occurs via nucleation and growth, as well as to unstable states, where phase separation occurs via the more elusive spinodal decomposition, leading to the formation of liquid crystalline microdroplets (or tactoids) of different shapes. We present the tactoids "phase diagram" as a function of the position within the droplet and elucidate their hydrodynamics. Furthermore, we demonstrate that the presence of the amyloid fibrils not only does not enhance the pinning behavior during droplet evaporation but also slightly suppresses it, thus minimizing the coffee-ring effect. We observed that microsize domains with cholesteric structure emerge in the drying droplet close to the droplet's initial edge, yet such domains are not connected to form a uniform cholesteric dried film. Finally, we demonstrate that a fully cholesteric dried layer can be generated from the drying droplets by regulating the kinetics of the evaporation process.

Pathway complexity in fibre assembly: from liquid crystals to hyper-helical gelmorphs.

Pathway complexity results in unique materials from the same components according to the assembly conditions. Here a chiral acyl-semicarbazide gelator forms three different gels of contrasting fibre morphology (termed 'gelmorphs') as well as lyotropic liquid crystalline droplets depending on the assembly pathway. The gels have morphologies that are either hyperhelical (HH-Gel), tape-fibre (TF-Gel) or thin fibril derived from the liquid crystalline phase (LC-Gels) and exhibit very different rheological properties. The gelator exists as three slowly interconverting conformers in solution. All three gels are comprised of an unsymmetrical, intramolecular hydrogen bonded conformer. The kinetics show that formation of the remarkable HH-Gel is cooperative and is postulated to involve association of the growing fibril with a non-gelling conformer. This single molecule dynamic conformational library shows how very different materials with different morphology and hence very contrasting materials properties can arise from pathway complexity as a result of emergent interactions during the assembly process.

Light-induced dynamics of liquid-crystalline droplets on the surface of iron-doped lithium niobate crystals

We investigated the effect of a photovoltaic field generated on the surface of iron-doped lithium niobate crystals on sessile droplets of a ferroelectric nematic liquid crystalline and a standard nematic liquid crystalline material present on this surface. When such an assembly is illuminated with a laser beam, a wide range of dynamic phenomena are initiated. Droplets located outside the laser spot are dragged in the direction of the illuminated area, while droplets located inside the illuminated region tend to bridge each other and rearrange into tendril-like structures. In the ferroelectric nematic phase (NF), these processes take place via the formation of conical spikes evolving into jet streams, similar to the behavior of droplets of conventional dielectric liquids exposed to overcritical electric fields. However, in contrast to traditional liquids, the jet streams of the NF phase exhibit profound branching. In the nematic phase (N) of both the ferroelectric nematic and the standard nematic material, dynamic processes occur via smooth-edged continuous features typical for conventional liquids subjected to under-critical fields. The difference in dynamic behavior is attributed to the large increase of dielectric permittivity in the ferroelectric nematic phase with respect to the dielectric permittivity of the nematic phase.

Confinement-Induced Fabrication of Liquid Crystalline Polymeric Fibers.

In aqueous media, liquid crystalline droplets typically form spherical shapes in order to minimize surface energy. Recently, non-spherical geometry has been reported using molecular self-assembly of surfactant-stabilized liquid crystalline oligomers, resulting in branched and randomly oriented filamentous networks. In this study, we report a polymerization of liquid crystalline polymeric fibers within a micro-mold. When liquid crystal oligomers are polymerized in freely suspended aqueous media, curvilinear and randomly networked filaments are obtained. When reactive liquid crystalline monomers are oligomerized in a micro-channel, however, highly aligned linear fibers are polymerized. Within a top-down microfabricated mold, a bottom-up molecular assembly was successfully achieved in a controlled manner by micro-confinement, suggesting a unique opportunity for the programming architecture of materials via a hybrid approach.

Modelling of filamentous phage-induced antibiotic tolerance of P. aeruginosa.

Filamentous molecules tend to spontaneously assemble into liquid crystalline droplets with a tactoid morphology in environments with high concentration on non-adsorbing molecules. Tactoids of filamentous Pf bacteriophage, such as those produced by Pseudomonas aeruginosa, have been linked to increased antibiotic tolerance. We modelled this system and show that tactoids composed of filamentous Pf virions can lead to antibiotic tolerance by acting as an adsorptive diffusion barrier. The continuum model, reminiscent of descriptions of reactive diffusion in porous media, has been solved numerically and good agreement was found with the analytical results, obtained using a homogenisation approach. We find that the formation of tactoids significantly increases antibiotic diffusion times which may lead to stronger antibiotic resistance.

Photocontrollable Crystallization at the Topological Defect of a Liquid Crystalline Droplet.

Photocontrollable crystallization at topological defects in a liquid crystal (LC) droplet was demonstrated. The molecules dissolved in a surfactant solution outside the LC droplet were moved into the droplet via light absorption. Nuclei emerged tens of seconds after light irradiation and moved toward the topological defect located at the droplet center, thus forming a branch-shaped crystal. This phenomenon was reproduced for multiple different molecules; photoinduced migration, nucleation, and crystal formation were discussed as a plausible mechanism.

Plasmonic Amyloid Tactoids (Adv. Mater. 51/2021)

Liquid-Crystalline Droplets In article number 2106155, Raffaele Mezzenga and co-workers demonstrate a schematic representation of amyloid fibrils confined within a liquid-crystalline droplet formed by liquid–liquid-crystalline phase separation, and organized in a chiral nematic conformation, capable of guiding the spatial and orientational distribution of functionalized gold nanorods added to the colloidal system.

Liquid-liquid crystalline phase separation in biological filamentous colloids: nucleation, growth and order-order transitions of cholesteric tactoids.

The process of liquid–liquid crystalline phase separation (LLCPS) in filamentous colloids is at the very core of multiple biological, physical and technological processes of broad significance. However, the complete theoretical understanding of the process is still missing. LLCPS involves the nucleation, growth and up-concentration of anisotropic droplets from a continuous isotropic phase, until a state of equilibrium is reached. Herein, by combining the thermodynamic extremum principle with the Onsager theory, we describe the nucleation and growth of liquid crystalline droplets, and the evolution of their size and concentration during phase separation, eventually leading to a multitude of order–order phase transitions. Furthermore, a decreasing pitch behaviour can be predicted using this combined theory during tactoid growth, already observed experimentally but not yet explained by present theories. The results of this study are compared with the experimental data of cholesteric pitch, observed in three different systems of biological chiral liquid crystals. These findings give an important framework for predicting the formation, growth and phase behaviour of biological filamentous colloids undergoing LLCPS, advancing our understanding of liquid–liquid phase separation and self-assembly mechanisms in biological systems, and provide a valuable rationale for developing nanomaterials and applications in nanotechnology.

Flow-induced order\u2013order transitions in amyloid fibril liquid crystalline tactoids

Liquid crystalline droplets, also known as tactoids, forming by nucleation and growth within the phase diagram region where isotropic and nematic phases coexist, challenge our understanding of liquid crystals under confinement due to anisotropic surface boundaries at vanishingly small interfacial tension, resulting in complex, non-spherical shapes. Little is known about their dynamical properties, since they are mostly studied under quiescent, quasi-equilibrium conditions. Here we show that different classes of amyloid based nematic and cholesteric tactoids undergo order–order transitions by flow-induced deformations of their shape. Tactoids align under extensional flow, undergoing extreme deformation into highly elongated prolate shapes, with the cholesteric pitch decreasing as an inverse power-law of the tactoids aspect ratio. Free energy functional theory and experimental measurements are combined to rationalize the critical elongation above which the director-field configuration of tactoids transforms from bipolar and uniaxial cholesteric to homogenous and to debate on the thermodynamic nature of these transitions.

Horizontal Transportation of a Maltese Cross Pattern in Nematic Liquid Crystalline Droplets under a Direct-Current Electric Field

The deformation of director field in a nematic liquid crystalline droplet under an electric field was analyzed. In the absence of the electric field, a Maltese cross pattern was observed at the cen...

Active forces shape the metaphase spindle through a mechanical instability

The metaphase spindle is a dynamic structure orchestrating chromosome segregation during cell division. Recently, soft matter approaches have shown that the spindle behaves as an active liquid crystal. Still, it remains unclear how active force generation contributes to its characteristic spindle-like shape. Here we combine theory and experiments to show that molecular motor-driven forces shape the structure through a barreling-type instability. We test our physical model by titrating dynein activity in Xenopus egg extract spindles and quantifying the shape and microtubule orientation. We conclude that spindles are shaped by the interplay between surface tension, nematic elasticity, and motor-driven active forces. Our study reveals how motor proteins can mold liquid crystalline droplets and has implications for the design of active soft materials.

Self-excited oscillation of the director field in cholesteric liquid crystalline droplets under a temperature gradient

In this study, we demonstrate a self-excited oscillation induced in cholesteric liquid crystalline droplets under a temperature gradient. At equilibrium, a winding Maltese cross pattern with a point defect was observed via polarised microscopy in the droplets dispersed in an isotropic solvent. When the temperature gradient was applied, the pattern was deformed owing to the Marangoni convection induced by the gradient. Here, when both the droplet size and temperature gradient were sufficiently large, the periodic movement of the defect together with the pattern deformation was observed, which demonstrated the self-excited oscillation of the director field. To describe this phenomenon, we theoretically analysed the flow and director fields by using Onsager’s variational principle. This principle enabled the simplified description of the phenomenon; consequently, the time evolution of the director field could be expressed by the phenomenological equations for the two parameters characterising the field. These equations represented the van der Pol equation, which well expressed the mechanism of the self-excited oscillation.

Phage liquid crystalline droplets form occlusive sheaths that encapsulate and protect infectious rod-shaped bacteria

The opportunistic pathogen Pseudomonas aeruginosa is a major cause of antibiotic-tolerant infections in humans. P. aeruginosa evades antibiotics in bacterial biofilms by up-regulating expression of a symbiotic filamentous inoviral prophage, Pf4. We investigated the mechanism of phage-mediated antibiotic tolerance using biochemical reconstitution combined with structural biology and high-resolution cellular imaging. We resolved electron cryomicroscopy atomic structures of Pf4 with and without its linear single-stranded DNA genome, and studied Pf4 assembly into liquid crystalline droplets using optical microscopy and electron cryotomography. By biochemically replicating conditions necessary for antibiotic protection, we found that phage liquid crystalline droplets form phase-separated occlusive compartments around rod-shaped bacteria leading to increased bacterial survival. Encapsulation by these compartments was observed even when inanimate colloidal rods were used to mimic rod-shaped bacteria, suggesting that shape and size complementarity profoundly influences the process. Filamentous inoviruses are pervasive across prokaryotes, and in particular, several Gram-negative bacterial pathogens including Neisseria meningitidis, Vibrio cholerae, and Salmonella enterica harbor these prophages. We propose that biophysical occlusion mediated by secreted filamentous molecules such as Pf4 may be a general strategy of bacterial survival in harsh environments.

Photo-controllable rotational motion of cholesteric liquid crystalline droplets in a dispersion system.

A photo-controllable rotational motion was demonstrated for an isolated cholesteric liquid crystalline droplet in a surfactant solution. The droplet showed unidirectional rigid-body rotation with UV light irradiation and the rotational rate could be controlled by the light intensity. Furthermore, the rotational direction could be controlled by the chirality of dopants. The motion was explained by the rotational torque induced by the photo-induced gradient of chemical concentrations and/or temperature inside the droplet from the theory of the Lehmann effect, and the possible mechanisms are discussed.

Optical motion control of liquid crystalline droplets by host-guest molecular interaction.

Photo-induced motion is demonstrated for a photo-responsive dye-doped liquid crystal (LC) droplet in a surfactant solution. The LC droplets started rolling on a substrate during UV irradiation and moved either toward or away from the UV light, depending on the functional groups of the guest dyes. The mechanism is explained by the Marangoni flow caused by the photo-isomerization-induced adsorption and desorption of the dye molecules to and from the LC/solution interfaces.

Light-Responsive Microstructures in Droplets of the Twist-Bend Nematic Phase.

We report on the structure and optical manipulation of the director configurations in emulsions of liquid-crystalline droplets of a compound exhibiting the nematic (N) and the twist-bend nematic (NTB) phases. We demonstrate a decrease in the ratio of the bent elastic constant K33 to the splay constant K11 by nearly 2 orders of magnitude with decreasing temperature in the N phase. The director structures in liquid-crystal droplets doped with a photoswitchable surfactant without and under ultraviolet (UV) light are discussed in light of the strong elastic anisotropy of the investigated compound. We also compare our findings with the results obtained in doped nematic droplets of a conventional 4-cyano-4'-pentylbiphenyl (5CB) liquid crystal. The dynamics of droplets in the NTB phase by UV light irradiation are also studied using polarizing and confocal microscopies.