Smectic Membranes Research Articles

Development of liquid-crystalline smectic nanoporous membranes for the removal of SARS-CoV-2 and waterborne viruses

Water-treatment membranes were prepared from smectic liquid-crystalline monomers. Tuning of their molecular-assembled structures enabled efficient removal of viruses including SARS-CoV-2.

Molecular Order Determines Gas Transport through Smectic Liquid Crystalline Polymer Membranes with Different Chemical Compositions

Amorphous polymers are often used for gas separation but have a trade-off between gas permeability and selectivity. Here, the effect of chemical composition and temperature on gas permeability and solubility in well-ordered LC polymer membranes is investigated. Membranes with various compositions of a monomethacrylate LC (M1) with a crown ether functionality to enhance CO2 solubility and a smectic diacrylate (M2) cross-linker were fabricated, while all having the same order (smectic C) and alignment (planar). Single gas sorption and permeation data show for the membranes with 30 wt % M1 a higher CO2 solubility coefficient compared to membranes without M1, which results in a higher CO2 permeability and selectivity. For membranes that contain more than 30 wt % M1 decreasing layer spacings lead to reduced gas solubilities that result in lower gas permeabilities without additional selectivity gain toward CO2. The effect of temperature is demonstrated by comparing single gas sorption and permeation data below and above the Tg of the membranes. The diffusion coefficient increases above the Tg of the membranes with increasing M1 content leading to higher CO2 permeabilities and selectivities. These results show that not only the chemical composition but also the layer spacing of the smectic structures determines the gas separation performance of smectic LC polymer membranes.

Tuning the Gas Separation Performances of Smectic Liquid Crystalline Polymer Membranes by Molecular Engineering.

The effect of layer spacing and halogenation on the gas separation performances of free-standing smectic LC polymer membranes is being investigated by molecular engineering. LC membranes with various layer spacings and halogenated LCs were fabricated while having a planar aligned smectic morphology. Single permeation and sorption data show a correlation between gas diffusion and layer spacing, which results in increasing gas permeabilities with increasing layer spacing while the ideal gas selectivity of He over CO2 or He over N2 decreases. The calculated diffusion coefficients show a 6-fold increase when going from membranes with a layer spacing of 31.9 Å to membranes with a layer spacing of 45.2 Å, demonstrating that the layer spacing in smectic LC membranes mainly affects the diffusion of gasses rather than their solubility. A comparison of gas sorption and permeation performances of smectic LC membranes with and without halogenated LCs shows only a limited effect of LC halogenation by a slight increase in both solubility and diffusion coefficients for the membranes with halogenated LCs, resulting in a slightly higher gas permeation and increased ideal gas selectivities towards CO2. These results show that layer spacing plays an important role in the gas separation performances of smectic LC polymer membranes.

Removal of viruses from their cocktail solution by liquid-crystalline water-treatment membranes

Liquid-crystalline (LC) water-treatment membranes obtained by in situ photopolymerization of ionic mesogenic monomers have been shown to efficiently remove viruses. In our previous works, bicontinuous cubic (Cubbi) and smectic (Sm) LC membranes prepared from ionic taper- and rod-shaped polymerizable mesogens, respectively, were used for this purpose. Here, we report the results of virus removal by columnar (Col) LC water-treatment membranes having ionic nanochannels obtained from ionic taper-shaped mesogens. These effects are compared with those obtained for Cubbi membranes. The effects of these Col and Cubbi LC ionic membranes on the removal of several viruses from their cocktail solution are also examined.

Colloidal membranes of chiral rod-like particles.

We study colloidal (or smectic) membranes composed of chiral rod-like particles through Monte Carlo simulations. These objects are formed due to the presence of Asakura-Oosawa spheres acting as depletants and creating an effective attraction between the rods. The membranes' shape and structure can be influenced by several parameters, e.g. the number of spheres and rods, their length and their interaction. In order to compare simulation results to an elastic theory, we follow two ansatzes, approximating the free elastic energy in different ways. Both of them lead to reasonable results and capture the behaviour of the colloidal membrane system. One approximation, however, is not suited for achiral rods, where twisting occurs due to surface energy rather than elastic energy. We extract the inverse cholesteric pitch and twist penetration depth for chiral rods with this approximation. The other one is used to introduce a complementary method to estimate elastic constants from the shape of colloidal membranes. Besides, we describe the transition from homogeneously twisted membranes to membranes composed of substructures that occur when the chiral interaction exceeds a length-dependent threshold. We believe that our detailed study and discussion of different aspects of this model system are valuable from a fundamental research viewpoint and suitable for material design suggestions.

Water Treatment: High Virus Removal by Self‐Organized Nanostructured 2D Liquid‐Crystalline Smectic Membranes for Water Treatment (Small 23/2020)

In article number 2001721, Takeshi Sakamoto, Hiroyuki Katayama, Takashi Kato, and co-workers achieve high virus removal for liquid-crystalline water treatment membranes. The liquid crystal forms 2D lamellar nanochannels allowing superior virus removal while maintaining efficient water flux. The removal efficiency is 99.999994%. Self-assembly of smectic liquid crystals and subsequent photopolymerization leads to the formation of nanostructured 2D materials.

High Virus Removal by Self‐Organized Nanostructured 2D Liquid‐Crystalline Smectic Membranes for Water Treatment

To obtain high quality of drinking water free from biocontaminants is especially important issue. A new strategy employing smectic liquid-crystalline ionic membranes exhibiting 2D structures of layered nanochannels for water treatment is proposed for efficient virus removal and sufficient water flux. The smectic A (SmA) liquid-crystalline membranes obtained by in situ polymerization of an ionic mesogenic monomer are examined for removal of three distinct viruses with small size: Qβ bacteriophage, MS2 bacteriophage, and Aichi virus. The semi-bilayer structure of the SmA significantly obstructs the virus penetration with an average log reduction value of 7.3 log10 or the equivalent of reducing 18 million viruses down to 1. Furthermore, the layered nanochannels of the SmA liquid crystal allow efficient water permeation compared to other types of liquid-crystalline membrane consisting of nanopores.

Elastic moduli of a smectic membrane: a rod-level scaling analysis

Chiral rodlike colloids exposed to strong depletion attraction may self-assemble into chiral membranes whose twisted director field differs from that of a 3D bulk chiral nematic. We formulate a simple microscopic variational theory to determine the elastic moduli of rods assembled into a bidimensional smectic membrane. The approach is based on a simple Onsager–Straley theory for a non-uniform director field that we apply to describe rod twist within the membrane. A microscopic approach enables a detailed estimate of the individual Frank elastic moduli (splay, twist and bend) as well as the twist penetration depth of the smectic membrane in relation to the rod density and shape. We find that the elastic moduli are distinctly different from those of a bulk nematic fluid, with the splay elasticity being much stronger and the curvature elasticity much weaker than for rods assembled in a three-dimensional nematic fluid. We argue that the use of the simplistic one-constant approximation in which all moduli are assumed to be of equal magnitude is not appropriate for modelling the structure-property relation of smectic membranes.

Structures in the meniscus of smectic membranes: the role of dislocations?

We report an experimental investigation of the structure of periodic patterns observed in the meniscus of free-standing smectic films. Combination of polarizing optical microscopy and phase shifting interferometry enabled us to obtain new information on the structure of the meniscus, and in particular, on the topography of the smectic-air interface. We investigate the profile of the undulations in the striped structure in the thin part of the meniscus, change of the stripe period with the meniscus thickness and subsequent transition into a two-dimensional structure. It is shown that the two-dimensional structure has an unusual complex profile of "egg-box" type. The striped texture occurs upon cooling from the nontilted smectic-A to the smectic-C* phase, whereas the two-dimensional pattern is present in both phases. We discuss the possible origin of the modulated structures, the role of the dislocations in the meniscus, the elasticity of smectic layers, and the mechanical stress induced by dislocations.

Hydrodynamic interactions in freely suspended liquid crystal films.

Hydrodynamic interactions play an important role in biological processes in cellular membranes, a large separation of length scales often allowing such membranes to be treated as continuous, two-dimensional (2D) fluids. We study experimentally and theoretically the hydrodynamic interaction of pairs of inclusions in two-dimensional, fluid smectic liquid crystal films suspended in air. Such smectic membranes are ideal systems for performing controlled experiments as they are mechanically stable, of highly uniform structure, and have well-defined, variable thickness, enabling experimental investigation of the crossover from 2D to 3D hydrodynamics. Our theoretical model generalizes the Levine-MacKintosh theory of point-force response functions and uses a boundary-element approach to calculate the mobility matrix for inclusions of finite extent. We describe in detail the theoretical and computational approach previously outlined in Z. Qi et al., Phys. Rev. Lett. 113, 128304 (2014)PRLTAO0031-900710.1103/PhysRevLett.113.128304 and extend the method to study the mutual mobilities of inclusions with asymmetric shapes. The model predicts well the observed mutual mobilities of pairs of circular inclusions in films and the self-mobility of a circular inclusion in the vicinity of a linear boundary.

Nanoparticle Aggregation and Fractal Growth in Fluid Smectic Membranes

We observe directly the diffusion and aggregation of buckyball clusters dispersed in thin, freely-suspended films of smectic liquid crystal using reflected light microscopy. The buckyballs at early times are barely resolvable, nanoscale clusters, which diffuse stochastically in the film. Clusters eventually coalesce to form micron-scale, fractal aggregates whose effective radius increases approximately linearly with time, so that after several days, millimeter-size fractals extend across the entire film. The measured fractal dimension of these final networks suggests that the aggregation of the buckyball clusters in the film is a diffusion-limited process.

Mutual diffusion of inclusions in freely suspended smectic liquid crystal films.

We study experimentally and theoretically the hydrodynamic interaction of pairs of circular inclusions in two-dimensional, fluid smectic membranes suspended in air. By analyzing their Brownian motion, we find that the radial mutual mobilities of identical inclusions are independent of their size but that the angular coupling becomes strongly size dependent when their radius exceeds a characteristic hydrodynamic length. These observations are described well for arbitrary inclusion separations by a model that generalizes the Levine-MacKintosh theory of point-force response functions and uses a boundary-element approach to calculate the mobility matrix for inclusions of finite extent.

Pore dynamics in lipid membranes

Transient circular pores can open in plasma membrane of cells due to mechanical stress, and failure to repair such pores lead to cell death. Similar pores in the form of defects also exist among smectic membranes, such as in myelin sheaths or mitochondrial membranes. The formation and growth of membrane defects are associated with diseases, for example multiple sclerosis. A deeper understanding of membrane pore dynamics can provide a more refined picture of membrane integrity-related disease development, and possibly also treatment options and strategies. Pore dynamics is also of great importance regarding healthcare applications such as drug delivery, gene or as recently been implied, cancer therapy. The dynamics of pores significantly differ in stacks which are confined in 2D compared to those in cells or vesicles. In this short review, we will summarize the dynamics of different types of pores that can be observed in biological membranes, which include circular transient, fusion and hemi-fusion pores. We will dedicate a section to floral and fractal pores which were discovered a few years ago and have highly peculiar characteristics. Finally, we will discuss the repair mechanisms of large area pores in conjunction with the current cell membrane repair hypotheses.

Measurement of the interface tension of smectic membranes in water

A simple method is proposed to measure the interfacial tension of a smectic liquid crystal (LC) in freely suspended film geometry in aqueous environment. The method is based upon the evaluation of the deformation of smectic bubbles by the buoyancy of a trapped air volume. The advantages over classical suspended smectic droplet experiments in water are the considerably shorter equilibration times, and most important, the much larger density differences between the fluids. The latter allow a much more accurate force determination. Bulk elastic force contributions can be practically neglected in the thin smectic films. Values for a smectic C mixture of two disubstituted phenylpyrimidines are reported.

Dynamics of freely floating smectic bubbles

We introduce smectic freely floating microbubbles and report their unusual dynamic properties. In equilibrium, they form minimal surfaces like soap films, but shape transformations of closed smectic membranes not in contact with menisci involve complex layer rearrangements. Very small distortions of the spherical equilibrium shape can relax by damped oscillations, driven by surface tension. Larger film area changes require the creation and motion of islands and layer dislocations. Then, film area changes are slow compared to natural oscillation frequencies. Quasi-stationary intermediate shapes evolve on the time scale of dislocation dynamics. These shape transformations are reminiscent of vesicles, in which the surface tension is effectively zero. We prepare smectic shells from collapsing catenoids and analyze their behavior with optical high-speed imaging.

Undulation Instabilities in the Meniscus of Smectic Membranes

Using optical microscopy, phase shifting interferometry, and atomic force microscopy, we characterize the undulated structures which appear in the meniscus of freestanding ferroelectric smectic-C* films. We demonstrate that these periodic structures correspond to undulations of the smectic-air interface. The resulting striped pattern disappears in the untilted smectic-A phase. The modulation amplitude and wavelength of the instability both depend on meniscus thickness. We study the temperature evolution and propose a model that qualitatively accounts for the observations.

Smectic membranes in aqueous environment

We present a study of thermotropic smectic liquid crystal films in aqueous environment. Macroscopic freely suspended films in water with a size up to 7.4 × 15 mm2 were prepared with the help of a surfactant, which ensures a strong homeotropic anchoring at liquid crystal/water interfaces. The films were studied by optical microscopy and ellipsometry. Attention was paid to the stability and the thinning transitions which occurred at temperatures above the bulk smectic- A -isotropic transition temperature. In addition, we investigated the formation and rupture kinetics of thin smectic membranes separating water droplets in microfluidic devices. Besides possible applications in discrete microfluidics, smectic films in aqueous environment may expand the general range of possible studies of freely suspended smectic films.

Anomalous elasticity in nematic and smectic elastomer tubule phases

We study anomalous elasticity in the tubule phases of nematic and smectic elastomer membranes, which are flat in one direction and crumpled in another. These phases share the same macroscopic symmetry properties including spontaneously broken in-plane isotropy and hence belong to the same universality class. Below an upper critical value D_{c}=3 of the membranes' intrinsic dimension D , thermal fluctuations renormalize the elasticity with respect to elastic displacements along the tubule axis so that elastic moduli for compression along the tubule axis and for bending the tubule axis become length-scale dependent. This anomalous elasticity belongs to the same universality class as that of d -dimensional conventional smectic liquid crystals with D taking on the role of d . For physical tubule phases, D=2 , this anomaly is of power-law type and thus might by easier to detect experimentally than the logarithmic anomaly in conventional smectics.

Different mechanisms of nucleation and self-organization of droplets in ferroelectric smectic membranes

New mechanisms of droplet nucleation and self-organization in ferroelectric membranes are described. The droplets may be accompanied by different number of topological defects (zero, one, two) whose location may be on the droplet boundary or in the membrane. Nucleation and self-organization of droplets with total topological charge S = 0 , S = + 1 and S = - 1 were investigated. We found that an S = - 1 topological defect may be the center of both droplet nucleation and chain formation. This mechanism of chaining drastically differs from the droplet self-organization described earlier which is realized by attraction of droplet-defect pairs. Our observations demonstrate new possibilities for manipulating the inclusions and their self-organization in smectic membranes.

Nucleation of lamellar domains from a sponge phase under shear flow: Shape selection of nuclei in a nonequilibrium steady state

It is a fundamental physical problem how a state is selected in a nonequilibrium steady state where the energy is continuously dissipated. This problem is common to phase transitions in liquids under shear flow and those in solids under deformation or electric current. In particular, soft matter often exhibits a strong nonlinear response to an external field, since its structural susceptibility to the external field is extremely large due to its softness and flexibility. Here we study the nucleation and growth process of the lamellar phase from the sponge phase under shear flow in a bilayer-forming surfactant system. We found an interesting shape selection of lamellar nuclei under shear flow between multilamellar vesicles (onions) and cylinders (leeks). These two types of behavior are separated sharply at a critical shear rate: a slight change of the shear rate is enough to switch one behavior to the other. We also found that, under a sufficiently strong shear flow, nucleated onions decrease their size with time, and eventually transform into leeks. This suggests that leeks may be the stable morphology under steady shear flow. However, the stability is limited only to the lamellar-sponge coexistence region. When a system enters into the lamellar phase region by further cooling, leeks lose their stability and break up into rather monodisperse onions, presumably via Rayleigh-like instability of a fluid tube. On the basis of these results, we draw a dynamic state diagram of smectic membrane organization under shear flow.