Interactions between proteins and cellulose in a liquid crystalline media: Design of a droplet based experimental platform.

Model systems are needed to provide controlled environment for the understanding of complex phenomena. Interaction between polysaccharides and proteins in dense medium are involved in numerous complex systems such as biomass conversion or plant use for food processing or biobased materials. In this work, cellulose nanocrystals (CNCs) were used to study proteins in a dense and organized cellulosic environment. This environment was designed within microdroplets using a microfluidic setup, and applied to two proteins, bovine serum albumin (BSA) and a GH7 endoglucanase, relevant to food and plant science, respectively. The CNC at 56.5 g/L organized in liquid crystalline structure and the distribution of the proteins was probed using synchrotron deep-UV radiation. The proteins were homogeneously distributed throughout the volume, but BSA significantly disturbed the droplet global organization, preferring partition in hydrophilic external micelles. In contrast, GH7 partitioned with the CNCs showing stronger non-polar interaction but without disruption of the system organization. Such results pave the road for the development of more complex polysaccharides - proteins in-vitro models.

Active boundary layers in confined active nematics.

The role of boundary layers in conventional liquid crystals is commonly related to the mesogen anchoring on confining walls. In the classical view, anchoring enslaves the orientational field of the passive material under equilibrium conditions. In this work, we show that an active nematic can develop active boundary layers that topologically polarize the confining walls. We find that negatively-charged defects accumulate in the boundary layer, regardless of the wall curvature, and they influence the overall dynamics of the system to the point of fully controlling the behavior of the active nematic in situations of strong confinement. Further, we show that wall defects exhibit behaviors that are essentially different from those of their bulk counterparts, such as high motility or the ability to recombine with another defect of like-sign topological charge. These exotic behaviors result from a change of symmetry induced by the wall in the director field around the defect. Finally, we suggest that the collective dynamics of wall defects might be described in terms of a model equation for one-dimensional spatio-temporal chaos.

Frustrated 'run and tumble' of swimming Escherichia coli bacteria in nematic liquid crystals.

In many situations, bacteria move in complex environments, as soils, oceans or the human gut-track, where carrier fluids show complex structures associated with non-Newtonian rheology. Many fundamental questions concerning the ability to navigate in such environments remain unsolved. Recently, it has been shown that the kinetics of bacterial motion in structured fluids as liquid crystals (LCs) is constrained by the orientational molecular order (or director field) and that novel spatio-temporal patterns arise. A question unaddressed so far is how bacteria change swimming direction in such an environment. In this work, we study the swimming mechanism of a single bacterium, Esherichia coli, constrained to move along the director field of a lyotropic chromonic liquid crystal confined to a planar cell. Here, the spontaneous 'run and tumble' motion of the bacterium gets frustrated: the elasticity of the LC prevents flagella from unbundling. Interestingly, to change direction, bacteria execute a reversal motion along the director field, driven by the relocation of a single flagellum, a 'frustrated tumble'. We characterize this phenomenon in detail experimentally, exploiting exceptional spatial and temporal resolution of bacterial and flagellar dynamics, using a two colour Lagrangian tracking technique. We suggest a possible mechanism accounting for these observations.

Elastic Instability of Cubic Blue Phase Nano Crystals in Curved Shells.

Many crystallization processes, including biomineralization and ice-freezing, occur in small and curved volumes, where surface curvature can strain the crystal, leading to unusual configurations and defect formation. The role of curvature on crystallization, however, remains poorly understood. Here, we study the crystallization of blue phase (BP) liquid crystals under curved confinement, which provides insights into the mechanism by which BPs reconfigure their three-dimensional lattice structure to adapt to curvature. BPs are a three-dimensional assembly of high-chirality liquid crystal molecules arranged into body-centered (BPI) or simple cubic (BPII) symmetries. BPs with submicrometer cubic-crystalline lattices exhibit tunable Bragg reflection and submillisecond response time to external stimuli such as an electric field, making them attractive for advanced photonic materials. In this work, we have systematically studied BPs confined in spherical shells with well-defined curvature and boundary conditions. The optical behavior of shells has also been examined at room temperature, where the cholesteric structure forms. In the cholesteric phase, perpendicular anchoring generates focal conic domains on the shell's surface, which transition into stripe patterns as the degree of curvature increases. Our results demonstrate that both higher degrees of curvature and strong spatial confinement destabilize BPI and reconfigure that phase to adopt the structure and optical features of BPII. We also show that the coupling of curvature and confinement nucleates skyrmions at greater thicknesses than those observed for a flat geometry. These findings are particularly important for integrating BPs into miniaturized and curved/flexible devices, including flexible displays, wearable sensors, and smart fabrics.

From nematic shells to nematic droplets: energetics and defect transitions.

In this work, we investigate the possibility of inducing valence transitions, i.e. transitions between different defect configurations, by transforming a nematic shell into a nematic droplet. Our shells are liquid crystal droplets containing a smaller aqueous droplet inside, which are suspended in an aqueous phase. When osmotically de-swelling the inner droplet, the shell progressively increases its thickness until it eventually becomes a single droplet. During the process, the shell energy landscape evolves, triggering a response in the system. We observe two different scenarios. Either the inner droplet progressively shrinks and disappears, inducing a defect reorganization, or it is expelled from the shell at a critical radius of the inner droplet, abruptly changing the geometry of the system. We use numerical simulations and modeling to investigate the origin of these behaviors. We find that the selected route depends on the defect structure and the energetics of the system as it evolves. The critical inner radius and time for expulsion depend on the osmotic pressure of the outer phase, suggesting that the flow through the shell plays a role in the process.

Active microfluidic transport in two-dimensional handlebodies.

Unlike traditional nematic liquid crystals, which adopt ordered equilibrium configurations compatible with the topological constraints imposed by the boundaries, active nematics are intrinsically disordered because of their self-sustained internal flows. Controlling the flow patterns of active nematics remains a limiting step towards their use as functional materials. Here we show that confining a tubulin-kinesin active nematic to a network of connected annular microfluidic channels enables controlled directional flows and autonomous transport. In single annular channels, for narrow widths, the typically chaotic streams transform into well-defined circulating flows, whose direction or handedness can be controlled by introducing asymmetric corrugations on the channel walls. The dynamics is altered when two or three annular channels are interconnected. These more complex topologies lead to scenarios of synchronization, anti-correlation, and frustration of the active flows, and to the stabilisation of high topological singularities in both the flow field and the orientational field of the material. Controlling textures and flows in these microfluidic platforms opens unexplored perspectives towards their application in biotechnology and materials science.

Temperature-Driven Anchoring Transitions at Liquid Crystal/Water Interfaces.

Controlling the anchoring of liquid crystal molecules at an interface with a water solution influences the entire organization of the underlying liquid crystal phase, which is crucial for many applications. The simplest way to stabilize such interfaces is by fabricating liquid crystal droplets in water; however, a greater sensitivity to interfacial effects can be achieved using liquid crystal shells, that is, spherical films of liquid crystal suspended in water. Anchoring transitions on those systems are traditionally triggered by the adsorption of surfactant molecules onto the interface, which is neither an instantaneous nor a reversible process. In this study, we report the ability to change the anchoring of 4-cyano-4'-pentylbiphenyl (5CB), one of the most widely used liquid crystals, at the interface with dilute water solutions of polyvinyl alcohol (PVA), a polymer commonly used for stabilizing liquid crystal shells, simply by controlling the temperature in the close vicinity of the liquid crystal clearing point. A quasi-static increase in temperature triggers an instantaneous reorientation of the molecules from parallel to perpendicular to the interfaces, owing to the local disordering effect of PVA on 5CB, prior to the phase transition of the bulk 5CB. We study this anchoring transition on both flat suspended films and spherical shells of liquid crystals. Switching anchoring entails a series of structural transformations involving the formation of transient structures in which topological defects are stabilized. The type of defect structure depends on the topology of the film. This method has the ability to influence both interfaces of the film nearly at the same time and can be applied to transform an initially polydisperse group of nematic shells into a monodisperse population of bivalent shells.

Structural transformations in tetravalent nematic shells induced by a magnetic field.

The role of applied fields on the structure of liquid crystals confined to shell geometries has been studied in past theoretical work, providing strategies to produce liquid crystal shells with controlled defect structure or valence. However, the predictions of such studies have not been experimentally explored yet. In this work, we study the structural transformations undergone by tetravalent nematic liquid crystal shells under a strong uniform magnetic field, using both experiments and simulations. We consider two different cases in terms of shell geometry and initial defect symmetry: (i) homogeneous shells with four s = +1/2 defects in a tetrahedral arrangement, and (ii) inhomogeneous shells with four s = +1/2 defects localized in their thinner parts. Consistently with previous theoretical results, we observe that the initial defect structure evolves into a bipolar one, in a process where the defects migrate towards the poles. Interestingly, we find that the defect trajectories and dynamics are controlled by curvature walls that connect the defects by pairs. Based on the angle between Bs, the local projection of the magnetic field on the shell surface, and n+½, a vector describing the defect orientations, we are able to predict the nature and shape of those inversion walls, and therefore, the trajectory and dynamics of the defects. This rule, based on symmetry arguments, is consistent with both experiments and simulations and applies for shells that are either homogeneous or inhomogeneous in thickness. By modifying the angle between Bs and n+½, we are able to induce, in controlled way, complex routes towards the final bipolar state. In the case of inhomogeneous shells, the specific symmetry of the shell allowed us to observe a hybrid splay-bend Helfrich wall for the first time.

Topological solitons, cholesteric fingers and singular defect lines in Janus liquid crystal shells.

Topological solitons are non-singular but topologically nontrivial structures in fields, which have fundamental significance across various areas of physics, similar to singular defects. Production and observation of singular and solitonic topological structures remain a complex undertaking in most branches of science - but in soft matter physics, they can be realized within the director field of a liquid crystal. Additionally, it has been shown that confining liquid crystals to spherical shells using microfluidics resulted in a versatile experimental platform for the dynamical study of topological transformations between director configurations. In this work, we demonstrate the triggered formation of topological solitons, cholesteric fingers, singular defect lines and related structures in liquid crystal shells. We show that to accommodate these objects, shells must possess a Janus nature, featuring both twisted and untwisted domains. We report the formation of linear and axisymmetric objects, which we identify as cholesteric fingers and skyrmions or elementary torons, respectively. We then take advantage of the sensitivity of shells to numerous external stimuli to induce dynamical transitions between various types of structures, allowing for a richer phenomenology than traditional liquid crystal cells with solid flat walls. Using gradually more refined experimental techniques, we induce the targeted transformation of cholesteric twist walls and fingers into skyrmions and elementary torons. We capture the different stages of these director transformations using numerical simulations. Finally, we uncover an experimental mechanism to nucleate arrays of axisymmetric structures on shells, thereby creating a system of potential interest for tackling crystallography studies on curved spaces.

Threading the Spindle: A Geometric Study of Chiral Liquid Crystal Polymer Microparticles.

Polymeric particles are strong candidates for designing artificial materials capable of emulating the complex twisting-based functionality observed in biological systems. In this Letter, we provide the first detailed investigation of the swelling behavior of bipolar polymer liquid crystalline microparticles. Deswelling from the spherical bipolar configuration causes the microparticles to contract anisotropically and twist in the process, resulting in a twisted spindle-shaped structure. We propose a model to describe the observed spiral patterns and twisting behavior.

Self-Regulated Smectic Emulsion with Switchable Lasing Application.

A structurally reversible smectic liquid crystal (LC) emulsion made of semifluorinated rod-type molecules in silicon oil, which is controlled by simple heating and cooling, is presented. Without adding any kind of additives, such as surfactants, polymers or emulsifiers, and without using any special tools, such as microfluidics or gas bubbling, the LC molecules spontaneously form monodisperse spherical and myelin-like structures upon cooling from the isotropic temperature. The LC emulsion can easily trap guest materials, providing a platform for repeatable and reliable switchable emulsification. For example, this interesting system enables the realization of an on-off lasing system by confining fluorescent dyes in the LC droplets.

Topological defects in cholesteric liquid crystal shells.

We investigate experimentally and numerically the defect configurations emerging when a cholesteric liquid crystal is confined to a spherical shell. We uncover a rich scenario of defect configurations, some of them non-existent in nematic shells, where new types of defects are stabilized by the helical ordering of the liquid crystal. In contrast to nematic shells, here defects are not simple singular points or lines, but have a large structured core. Specifically, we observe five different types of cholesteric shells. We study the statistical distribution of the different types of shells as a function of the two relevant geometrical dimensionless parameters of the system. By playing with these parameters, we are able to induce transitions between different types of shells. These transitions involve interesting topological transformations in which the defects recombine to form new structures. Surprisingly, the defects do not approach each other by taking the shorter distance route (geodesic), but by following intricate paths.

Waltzing route toward double-helix formation in cholesteric shells.

Liquid crystals, when confined to a spherical shell, offer fascinating possibilities for producing artificial mesoscopic atoms, which could then self-assemble into materials structured at a nanoscale, such as photonic crystals or metamaterials. The spherical curvature of the shell imposes topological constraints in the molecular ordering of the liquid crystal, resulting in the formation of defects. Controlling the number of defects, that is, the shell valency, and their positions, is a key success factor for the realization of those materials. Liquid crystals with helical cholesteric order offer a promising, yet unexplored way of controlling the shell defect configuration. In this paper, we study cholesteric shells with monovalent and bivalent defect configurations. By bringing together experiments and numerical simulations, we show that the defects appearing in these two configurations have a complex inner structure, as recently reported for simulated droplets. Bivalent shells possess two highly structured defects, which are composed of a number of smaller defect rings that pile up through the shell. Monovalent shells have a single radial defect, which is composed of two nonsingular defect lines that wind around each other in a double-helix structure. The stability of the bivalent configuration against the monovalent one is controlled by c = h/p, where h is the shell thickness and p the cholesteric helical pitch. By playing with the shell geometry, we can trigger the transition between the two configurations. This transition involves a fascinating waltz dynamics, where the two defects come closer while turning around each other.

Spherical nematic shells with a threefold valence.

We present a theoretical study of the energetics of thin nematic shells with two charge-one-half defects and one charge-one defect. We determine the optimal arrangement: the defects are located on a great circle at the vertices of an isosceles triangle with angles of 66^{∘} at the charge-one-half defects and a distinct angle of 48^{∘}, consistent with experimental findings. We also analyze thermal fluctuations around this ground state and estimate the energy as a function of thickness. We find that the energy of the three-defect shell is close to the energy of other known configurations having two charge-one and four charge-one-half defects. This finding, together with the large energy barriers separating one configuration from the others, explains their observation in experiments as well as their long-time stability.

Elastic interactions between topological defects in chiral nematic shells.

We present a self-consistent and robust theoretical model to investigate elastic interactions between topological defects in liquid crystal shells. Accounting for the nonconcentric nature of the shell in a simple manner, we are able to successfully and accurately explain and predict the positions of the defects, most relevant in the context of colloidal self-assembly. We calibrate and test our model on existing experimental data and extend it to all observed defects configurations in chiral nematic shells. We perform experiments to check further and confirm the validity of the present model. Moreover, we are able to obtain quantitative estimates of the energies of +1 or +3/2 disclination lines in cholesterics, whose intricate nature was only reported recently [A. Darmon, et al. Proc. Natl. Acad. Sci. USA 113, 9469 (2016)10.1073/pnas.1525059113].

Thermally sensitive reversible microgels formed by poly(N-Isopropylacrylamide) charged chains: a Hofmeister effect study.

In this study, we present a new method to obtain anionic and cationic stable colloidal nanogels from PNIPAM charged chains. The stability of the particles formed by inter-chain aggregation stems from the charged chemical groups attached at the sides of PNIPAM polymer chains. The particle formation is fully reversible-that is, it is possible to change from stable polymer solutions to stable colloidal dispersions and vice versa simply by varying temperature. In addition, we also demonstrate that the polymer LCST (lower critical solution temperature), the final particle size and the electrokinetic behavior of the particles formed are highly dependent on the electrolyte nature and salt concentration. These latter results are related to Hofmeister effects. The analysis of these results provides more insights about the origin of this ionic specificity, confirming that the interaction of ions with interfaces is dominated by the chaotropic/kosmotropic character of the ions and the hydrophobic/hydrophilic character of the surface in solution.

Defect coalescence in spherical nematic shells.

We study coalescence of topological defects in nematic liquid crystals confined to spherical shells using both experiments and computer simulations. We observe that the four s=+1/2 defects that are present due to topological constraints imposed by the spherical geometry coalesce by pairs after changing the molecular orientation at the outer surface from tangential to perpendicular; the result is the formation of two single s=+1 defects. It is noteworthy that the speed of the coalescence process is peaked when the defects are at opposite points on the equator of the shell; this maximum results from the thickness inhomogeneity of the shells.

Defect trajectories in nematic shells: role of elastic anisotropy and thickness heterogeneity.

We introduce the idea of transformation trajectories to describe the evolution of nematic shells in terms of defect locations and director field when the elastic anisotropy and the shell thickness heterogeneity vary. Experiments are compared to numerical results to clarify the exact role played by these two parameters. We demonstrate that heterogeneity in thickness is a result of a symmetry breaking initiated by buoyancy and enhanced by liquid crystal elasticity, and is irrespective of the elastic anisotropy. In contrast, elastic anisotropy--in particular, disfavored bend distortion--drives an asymmetric defect reorganization. These shell states can be both stable or metastable.

Smectic shells.

Confining a smectic liquid crystal between two spherical surfaces results in the formation of a complex defect structure characterized by a set of curvature walls that divide the sphere into crescent domains, causing the undulation of the smectic layers. In this paper, we examine in detail these smectic textures and discuss the various possible origins of the observed patterns.

Ion-specific aggregation of hydrophobic particles.

This work shows that colloidal stability and aggregation kinetics of hydrophobic polystyrene (PS) nanospheres are extremely sensitive to the nature of the salt used to coagulate them. Three PS latices and four aggregating electrolytes, which all share the same cation (Na(+)) but have various anions located at different positions in the classical Hofmeister series depending on their kosmotropic or chaotropic character, are used. The present study focuses on analyzing different aggregating parameters, such as critical coagulation concentrations (CCC), cluster size distributions (CSD), initial kinetic constants K(11), and fractal dimensions of the aggregates d(f). While aggregation induced by SO(4)(2-) and Cl(-) behaved according to the predictions of the classical Derjaguin-Landau-Verwey-Overbeek theory, important discrepancies are found with NO(3)(-), which become dramatic when using SCN(-). These discrepancies among the anions were far more significant when they acted as counterions rather than as co-ions. While SO(4)(2-) and Cl(-) trigger fast diffusion-limited aggregation, SCN(-) gives rise to a stationary cluster size distribution in a few aggregation times when working with cationic PS particles. Clear differences are found among all analyzed parameters (CCC, CSD, K(11), and d(f)), and the experimental findings show that particles aggregate in potential wells whose depth is controlled by the chaotropic character of the anion. This paper presents new experimental evidence that may help to understand the microscopic origin of Hofmeister effects, as the observations are consistent with appealing theoretical models developed in the last few years.