Many soft-matter and biophysical systems are composed of monomers which reversibly assemble into rod-like aggregates. The aggregates can then order into liquid-crystal phases if the density is high enough, and liquid-crystal ordering promotes increased growth of aggregates. Systems that display coupled aggregation and liquid-crystal ordering include wormlike micelles, chromonic liquid crystals, DNA and RNA, and protein polymers and fibrils. Coarse-grained molecular models that capture key features of coupled aggregation and liquid-crystal ordering common to many different systems are lacking; in particular, the role of monomer aspect ratio and aggregate flexibility in controlling the phase behavior are not well understood. Here we study a minimal system of sticky cylinders using Monte Carlo simulations and analytic theory. Cylindrical monomers interact primarily by hard-core interactions but can stack and bind end to end. We present results for several different cylinder aspect ratios and a range of end-to-end binding energies. The phase diagrams are qualitatively similar to those of chromonic liquid crystals, with an isotropic-nematic-columnar triple point. The location of the triple point is sensitive to the monomer aspect ratio.We find that the aggregate persistence length varies with temperature in a way that is controlled by the interaction potential; this suggests that the form of the interaction potential affects the phase behavior of the system. Our analytic theory shows improvement compared to previous theory in quantitatively predicting the I-N transition for relatively stiff aggregates, but requires a better treatment of aggregate flexibility.
Understanding and controlling the director field configuration, shape, and orientation in nematic and cholesteric liquid crystals is of fundamental importance in several branches of science. Liquid crystalline droplets, also known as tactoids, which spontaneously form by nucleation and growth within the biphasic region of the phase diagram where isotropic and nematic phases coexist, challenge our current understanding of liquid crystals under confinement, due to the influence of anisotropic surface boundaries at vanishingly small interfacial tension and are mostly studied under quiescent, quas…
We propose a geometrical characterization of amorphous liquid structures that suppress crystallization by competing locally with crystalline order. We introduce for this purpose the crystal affinity of a liquid, a simple measure of its propensity to accumulate local crystalline structures on cooling. This quantity is explicitly related to the high temperature structural covariance between local fluctuations in crystal order and that of competing liquid structures: favouring a structure that, due to poor overlap properties, anticorrelates with crystalline order reduces the affinity of the liqui…
Synthetic Laponite-clay particles with platelet-like shape display strong aging when dispersed in aqueous solutions, preventing latter from reaching their natural liquid-crystalline equilibrium state. Here we introduce a facile method that successfully prevents this aging behaviour and enables accessing the systems' liquid-crystal and crystalline phases. We graft the comb-like polymer, poly(L-lysine)-g-poly(ethylene glycol) (PLL-PEG), onto the clay surfaces from solution, thereby screening the negative surface charges and thus ensuring steric stabilisation. We show zeta-sizer and rheology meas…
We propose a survey of those oxadiazole compounds, which are mesogenic. We will see that they can have bend-shaped molecules, a biaxial nematic phase, or other interesting peculiarities in the nematic and smectic phase. With large electric dipoles and luminescent properties, these materials are also very appealing for technological applications.
Lattice Boltzmann simulations have become a method of choice to solve the hydrodynamic equations of motion of a number of complex fluids. Here we review some recent applications of lattice Boltzmann to study the hydrodynamics of liquid crystalline materials. In particular, we focus on the study of (a) the exotic blue phases of cholesteric liquid crystals, and (b) active gels - a model system for actin plus myosin solutions or bacterial suspensions. In both cases lattice Boltzmann studies have proved useful to provide new insights into these complex materials.
This paper reviews the research work on the liquid crystalline (LC) polymer vesicles (polymersomes), where the thermotropic nematic and smectic phases are displayed in the lyotropic bilayer polymer membrane. LC polymersomes possess the properties of both liquid crystals and polymers, the two essential soft matters. LC polymersomes offer, on the one hand, novel examples of the interplay between orientational order and the curved geometry of a two dimensional membrane. Spherical, ellipsoidal and tetrahedral vesicles are discussed. On the other hand, LC polymersomes enable novel design of stimuli…
We investigate the self-organization of a binary mixture of similar sized rods and dipolar soft spheres by means of Monte-Carlo simulations. We model the interparticle interactions by employing anisotropic Gay-Berne, dipolar and soft-sphere interactions. In the limit of vanishing magnetic moments we obtain a variety of fully miscible liquid crystalline phases including nematic, smectic and lamellar phases. For the magnetic mixture, we find that the liquid crystalline matrix supports the formation of orientationally ordered ferromagnetic chains. Depending on the relative size of the species the…
We consider patchy gold nanoparticles decorated by liquid crystalline ligands. The cases of two, three, four and six symmetrically arranged patches of ligands are discussed, as well as the cases of their equatorial and uniform arrangement. A solution of decorated nanoparticles is considered within a flat pore with the solid walls and the interior filled by a polar solvent. The ligands form physical crosslinks between the nanoparticles due to strong liquid crystalline interaction, turning the solution into a gel-like structure. Gelation is done repeatedly starting each time from freshly equilib…
The influence of the molecular structure of the nematic liquid crystal (NLC) on the photoalignment process at the NLC -- polymer interface has been investigated experimentally. NLCs having exclusively phenyl-, or cyclohexane rings in the rigid core, as well as NLCs containing both phenyl and cyclohexane groups have been considered. Substantial differences have been found in the photoalignment process depending on the molecular structure of the NLC, supporting the assumption that the polymer -- NLC interface should be regarded as a coupled system, where the two components mutually influence eac…
The report presents pressure-related broadband dielectric spectroscopy (BDS) studies in liquid crystalline octyloxycyanbiphenyl and its nanocolloid with BaTiO3 nanoparticles, focused on the low-frequency ionic domain and the impact of pretransitional fluctuations. Hence basic exogenic (pressure) and endogenic (nanoparticles) impacts on dielectric properties are addressed. The innovative derivative-based analysis revealed functional 'critical-like' descriptions of ionic contributions to dielectric permittivity and electric conductivity. The supplementary dielectric constant scan, yielding insig…
The swimming of cells, far from any boundary, can arise in the absence of long-range liquid-crystalline order within the cytoplasm, but simple models of this effect are lacking. Here we present a two-dimensional model of droplet self-propulsion involving two scalar fields, representing the cytoplasm and a contractile cortex. An active stress results from coupling between these fields; self-propulsion results when rotational symmetry is spontaneously broken. The swimming speed is predicted, and shown numerically, to vary linearly with the activity parameter and with the droplet area fraction. T…
We study electrostatic interaction between molecules of the DNA in which a number of phosphate groups of the sugar-phosphate backbone are exchanged for the pyrophosphate ones. We employ a model in which the DNA is considered as a one-dimensional lattice of dipoles and charges corresponding to base pairs and (pyro)phosphate groups, respectively. The interaction between molecules of the DNA is described by a pair potential $U$ of electrostatic forces between the two sets of dipoles and charges belonging to respective lattices describing the molecules. Minima of potential $U$ indicate orientation…
The origin and structure of self assembled chiral liquid crystalline Blue Phase III (BPIII) have remained an enigma despite efforts spreading over decades. We report here an off-lattice NVT molecular dynamics simulation study of a system of polar chiral ellipsoidal molecules, which spontaneously exhibits BPIII , considering coarse-grained attractive-repulsive pair interaction appropriate for anisotropic liquid crystal mesogens. We have observed that suitable selection of chiral and dipolar strengths not only gives rise to thermodynamically stable BPIII but novel Smectic and Bilayered BPIII as …
Modeling and simulation studies using a high-order Landau-de Gennes type model for the direct isotropic/smectic-A liquid crystal transition are presented showing the existence of meta-stable nematic pre-ordering under certain conditions, in agreement with experimental observations (Tokita, M. et al. Macromolecules 2006, 39, 2021-2023)
Recent experimental realization of ferroelectric nematic liquid crystalline phases stimulated material development and numerous experimental studies of these new phases, guided by their fundamental and applicative interest. In this Perspective, we give an overview of this emerging field by linking history and theoretical predictions to a general outlook of the development and properties of the materials exhibiting ferroelectric nematic phases. We will highlight the most relevant observations up-to-date, e.g., giant dielectric permittivity values, polarization values an order of magnitude large…
Materials exhibiting a large caloric effect could lead to the development of new generation of heat-management technologies that will have better energy efficiency and be potentially more environmentally friendly. The focus of caloric materials investigations has shifted recently from solid-state materials toward soft materials, such as liquid crystals and liquid crystalline elastomers. It has been shown recently that a large electrocaloric effect exceeding 7 K can be observed in smectic liquid crystals. Here, we report on a significant elastocaloric response observed by direct elastocaloric m…
We investigated the effect of a photovoltaic field generated on the surface of iron-doped lithium niobate crystals on droplets of a ferroelectric nematic liquid crystalline and a standard nematic liquid crystalline material deposited on this surface. When such 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 p…
We investigate nonlinear rheology of dilute liquid crystalline polymer solutions under time dependent two-directional shear flow. We analyze the Smoluchowski equation, which describes the dynamics of the orientation of a liquid crystalline polymer, by employing technique of the full counting statistics. In the adiabatic limit, we derive the expression for time integrated currents generated by a Berry-like curvature. Using this expression, it is shown that the expectation values of the time-integrated angular velocity of a liquid crystalline polymer and the time-integrated stress tensor are gen…
Surface interactions can cause freely suspended thin liquid crystalline films to form phases different from the bulk material, but it is not known what happens at the surface of thick films. Edge dislocations can be used as a marker for the boundary between the bulk center and the reconstructed surface. We use noncontact mode atomic force microscopy to determine the depth of edge dislocations below the surface of freely suspended thick films of 4-n-heptyloxybenzylidene-4-n-heptylaniline (7O.7) in the crystalline B phase. 3.0 +/- 0.1 nm high steps are found with a width that varies with tempera…
We derive a Föppl-von Kármán-type constitutive model for solid liquid crystalline plates where the nematic director may or may not rotate freely relative to the elastic network. To obtain the reduced two-dimensional model, we rely on the deformation decomposition of a nematic solid into an elastic deformation and a natural shape change. The full solution to the resulting equilibrium equations consists of both the deformation displacement and stress fields. The model equations are applicable to a wide range of thin nematic bodies subject to optothermal stimuli and mechanical loads. For illustra…
A swollen phase observed between the liquid-crystalline phase and the interdigitated phase induced by pressure and/or adding ethanol in DPPC aqueous solution
Dispersions of rodlike colloidal particles exhibit a plethora of liquid crystalline states, including nematic, smectic A, smectic B, and columnar phases. This phase behavior can be explained by presuming the predominance of hard-core volume exclusion between the particles. We show here how the self-organization of rodlike colloids can be controlled by introducing a weak and highly localized directional attractive interaction between one of the ends of the particles. This has been performed by functionalizing the tips of filamentous viruses by means of regioselectively grafting fluorescent dyes…
Liquid cellular compartments spatially segregate from the cytoplasm and can regulate aberrant protein aggregation, a process linked to several medical conditions, including Alzheimer's and Parkinson's diseases. Yet the mechanisms by which these droplet-like compartments affect protein aggregation remain unknown. Here, we combine kinetic theory of protein aggregation and liquid-liquid phase separation to study the spatial control of irreversible protein aggregation in the presence of liquid compartments. We find that, even for weak interactions between the compartment constituents and the aggre…
We consider a confined sheared active polar liquid crystal with a uniform orientation and study the effect of variations in the magnitude of polarization. Restricting our analysis to one-dimensional geometries, we demonstrate that with asymmetric boundary conditions, this system is characterized, macroscopically, by a linear shear stress vs. shear strain relationship that does not pass through the origin: At a zero strain rate, the fluid sustains a non-zero stress. Analytic solutions for the polarization, density, and velocity fields are derived for asymptotically large or small systems and ar…
Swimming-limited aggregation of bacteria in liquid crystals
Laboratoire de Physique et Mécanique des Milieux Hétérogènes (PMMH), ESPCI Paris, PSL University, CNRS, Sorbonne University, and Paris Cité University（异质介质物理与力学实验室，巴黎高等物理化工学院，PSL大学，法国国家科学研究中心，索邦大学，巴黎西岱大学）；Laboratoire Gulliver, ESPCI Paris, PSL University, CNRS（高卢实验室，巴黎高等物理化工学院，PSL大学，法国国家科学研究中心）；Institut Universitaire de France (IUF)（法国高等研究院）；Institute of Physics, University of Amsterdam（阿姆斯特丹大学物理研究所）
An extension to a high-order model for the direct isotropic/smectic-A liquid crystalline phase transition was derived to take into account thermal effects including anisotropic thermal diffusion and latent heat of phase-ordering. Multi-scale multi-transport simulations of the non-isothermal model were compared to isothermal simulation, showing that the presented model extension corrects the standard Landau-de Gennes prediction from constant growth to diffusion-limited growth, under shallow quench/undercooling conditions. Non-isothermal simulations, where meta-stable nematic pre-ordering preced…
We present a dielectric study on the dynamics of supercooled glycerol during crystallization. We explore the transformation into a solid phase in real time by monitoring the temporal evolution of the amplitude of the dielectric signal. Neither the initial nucleation or the crystal growth influence the liquid dynamics visibly. For one of the samples studied, a tiny fraction of glycerol remained in the disordered state after the end of the transition. We examined the nature of the alpha relaxation in this frustrated crystal and find that it is virtually identical to the bulk dynamics. In additio…
We have numerically studied a liquid composed of achiral, bent-shaped molecules built of tangent spheres. The system is known to spontaneously break mirror symmetry, as it forms a macroscopically chiral, twist-bend nematic phase [Phys. Rev. Lett. 115, 147801 (2015)]. Here, we have examined the full phase diagram of such liquid and observed several phases characterized by orientational and/or translational ordering of molecules. Apart from conventional nematic, smectic A, and the above-mentioned twist-bend nematic phase, we have identified antiferroelectric smectic A phase. For large densities …
We consider the mesoscopic model for the liquid crystalline brush that might serve as a photoswitchable aligning surface for preorientation of low molecular weight liquid crystals in a bulk. The brush is built by grafting the polymer chains of a side-chain molecular architecture, with the side chains terminated by a chromophore unit mimicking the azobenzene unit, to a substrate. When irradiated with ultraviolet light, the chromophores photoisomerize into a non-mesogenic cis state and the whole system turns into an ordinary polymer brush with no orientational order and two states: the collapsed…
The phase-field-crystal model is used to access the structure and thermodynamics of interfaces between two coexisting liquid crystalline phases in two spatial dimensions. Depending on the model parameters there is a variety of possible coexistences between two liquid crystalline phases including a plastic triangular crystal (PTC). Here, we calculate numerically the profiles for the mean density and the nematic order tensor across the interface for isotropic-PTC and columnar-PTC respectively smectic A-PTC coexistence. As a general finding, the width of the interface with respect to the nematic …
The blue phases are observed in highly chiral liquid crystalline compositions that nascently organize into a three-dimensional, crystalline nanostructure. The periodicity of the unit cell lattice parameters is on the order of the wavelength of visible light and accordingly, the blue phases exhibit a selective reflection as a photonic crystal. Here, we detail the synthesis of liquid crystalline elastomers (LCEs) that retain blue phase I, blue phase II, and blue phase III. The mechanical properties and deformation of LCEs retaining the blue phases are contrasted to the cholesteric phase in fully…
A theoretical model of shape-anisometric particles embedded in a cubic lattice is formulated for binary mixtures combining rod-like, plate-like and spherical particles. The model aims at providing a tool for the prediction and interpretation of complex phase behavior in a variety of liquid crystalline colloids, biological and macromolecular systems. Introducing just repulsive interactions among the particles, a rich variety of phase structures and multiphasic equilibria is obtained, including isotropic, nematic, lamellar and columnar phases, demixing into phases of the same or different symmet…
Using x-ray photon correlation spectroscopy, we studied the dynamics in the nematic phase of a nanorodsuspension. The collective diffusion coefficient in the plane perpendicular to the director varies sharply with the wave vector. Combining the structure factor and the diffusion coefficient, we find that the hydrodynamic function of the phase decreases by more than a factor of 10 when going from length scales comparable to the interparticle distance toward larger values. Thus, the collective dynamics of the nematic phase experiences strong and scale-dependent slowing down, in contrast with iso…
We present results from Monte Carlo simulations of liquid crystalline dendrimers (LCDrs) adsorbed on flat, impenetrable substrates. A tractable coarse grained force field for the inter-dendritic and the dendrimer-substrate interactions is introduced. We investigate the conformational and ordering properties of single, end-functionalized LCDrs under homeotropic, random (or degenerate) planar and unidirectional planar aligning substrates. Depending on the anchoring conditions of the mesogenic units of the LCDr and on temperature a variety of stable LCDr states, differing in their topology, are o…
Physical properties of composite materials can be pre-engineered by controlling their structure and composition at the mesoscale. Yet, approaches for achieving this are limited and rarely scalable. We introduce a new breed of self-assembled nematogels formed by an orientationally ordered network of thin cellulose nanofibers infiltrated with a thermotropic nematic fluid. The interplay of orientational ordering within the nematic network and that of the small-molecule liquid crystal around it yields a composite with highly tunable optical properties. By means of combining experimental characteri…
The electro-optic Kerr effect in cholesteric blue phase liquid crystals is known to occur on sub-millisecond time scales, which is much faster than director reorientation in nematic liquid crystals. Using two-beam interference microscopy, we report the presence of a very slow response in the Kerr effect, with a characteristic time of several seconds or more. Using a simplified model for the reorientation dynamics, we attribute the slow response to the coupling between the local director reorientation and field-induced deformation of the lattice. We provide evidence for our argument by showing …
We study the aggregation phenomenon in lyotropic chromonic liquid crystals as the molecular concentration changes and condensing agents are added into the system. Using properties of the critical points of the Oseen-Frank energy of a nematic liquid crystal, combined with the geometric constraints of the hexagonal columnar chromonic phases, we show that the minimizers of the total energy are topologically equivalent to tori, in agreement with available experimental evidence on chromonic liquid crystals and DNA condensates, in viral capsids as well as in free solution. We model the system as bi-…
