Polarity in Liquid Crystals Formed by Self-Assembled Umbrella-Shaped Subphthalocyanine Mesogens.

We investigated the properties of p-type semiconducting columnar phases in self-assembled umbrella-shaped mesogens that have subphthalocyanine cores and oligo-thienyl arms. These compounds have nonswitchable phases that exhibit remanent electric polarization and nonlinear optical activity. Additionally, these compounds can generate photocurrents in the visible spectral range due to their wide absorption band. The photocurrent can be significantly increased by doping materials with fullerene. The charge mobility shows an anomalous field dependence, which decreases with the temperature.

Fluid fibers in true 3D ferroelectric liquids.

We demonstrate an exceptional ability of a high-polarization 3D ferroelectric liquid to form freely suspended fluid fibers at room temperature. Unlike fluid threads in modulated smectics and columnar phases, where translational order is a prerequisite for forming liquid fibers, recently discovered ferroelectric nematic forms fibers with solely orientational molecular order. Additional stabilization mechanisms based on the polar nature of the mesophase are required for this. We propose a model for such a mechanism and show that these fibers demonstrate an exceptional nonlinear optical response and exhibit electric field-driven instabilities.

Holmium-Containing Metal-Organic Frameworks as Modifiers for PEBA-Based Membranes.

Recently, there has been an active search for new modifiers to create hybrid polymeric materials for various applications, in particular, membrane technology. One of the topical modifiers is metal-organic frameworks (MOFs), which can significantly alter the characteristics of obtained mixed matrix membranes (MMMs). In this work, new holmium-based MOFs (Ho-MOFs) were synthesized for polyether block amide (PEBA) modification to develop novel MMMs with improved properties. The study of Ho-MOFs, polymers and membranes was carried out by methods of X-ray phase analysis, scanning electron and atomic force microscopies, Fourier transform infrared spectroscopy, low-temperature nitrogen adsorption, dynamic and kinematic viscosity, static and dynamic light scattering, gel permeation chromatography, thermogravimetric analysis and contact angle measurements. Synthesized Ho-MOFs had different X-ray structures, particle forms and sizes depending on the ligand used. To study the effect of Ho-MOF modifier on membrane transport properties, PEBA/Ho-MOFs membrane retention capacity was evaluated in vacuum fourth-stage filtration for dye removal (Congo Red, Fuchsin, Glycine thymol blue, Methylene blue, Eriochrome Black T). Modified membranes demonstrated improved flux and rejection coefficients for dyes containing amino groups: Congo Red, Fuchsin (PEBA/Ho-1,3,5-H3btc membrane possessed optimal properties: 81% and 68% rejection coefficients for Congo Red and Fuchsin filtration, respectively, and 0.7 L/(m2s) flux).

Effects of cell excitation on photosynthetic electron flow and intercellular transport in Chara.

Impact of membrane excitability on fluidic transport of photometabolites and their cell-to-cell passage via plasmodesmata was examined by pulse-modulated chlorophyll (Chl) microfluorometry in Chara australis internodes exposed to dim background light. The cells were subjected to a series of local light (LL) pulses with a 3-min period and a 30-s pulse width, which induced Chl fluorescence transients propagating in the direction of cytoplasmic streaming along the photostimulated and the neighboring internodes. By comparing Chl fluorescence changes induced in the LL-irradiated and the adjoining internodes, the permeability of the nodal complex for the photometabolites was assessed in the resting state and after the action potential (AP) generation. The electrically induced AP had no influence on Chl fluorescence in noncalcified cell regions but disturbed temporarily the metabolite transport along the internode and caused a disproportionally strong inhibition of intercellular metabolite transmission. In chloroplasts located close to calcified zones, Chl fluorescence increased transiently after cell excitation, which indicated the deceleration of photosynthetic electron flow on the acceptor side of photosystem I. Functional distinctions of chloroplasts located in noncalcified and calcified cell areas were also manifested in different modes of LL-induced changes of Chl fluorescence, which were accompanied by dissimilar changes in efficiency of PSII-driven electron flow. We conclude that chloroplasts located near the encrusted areas and in the incrustation-free cell regions are functionally distinct even in the absence of large-scale variations of cell surface pH. The inhibition of transnodal transport after AP generation is probably due to Ca2+-regulated changes in plasmodesmal aperture.

Intercellular permeation and cyclosis-mediated transport of a fluorescent probe in Characeae.

Intercellular communication and transport is the essential prerequisite for the function of multicellular organisms. Simple diffusion as a transport mechanism is often inefficient in sustaining the effective exchange of metabolites, and other active transport mechanisms become involved. In this paper, we use the giant cells of characean algae as a model system to explore the role of advection and diffusion in intercellular transport. Using fluorescent dye as a tracer, we study the kinetics of the permeation of the fluorophore through the plasmodesmata complex in the node of tandem cells and its further distribution across the cell. To explore the role of cytoplasmic streaming and the nodal cell complex in the transport mechanism, we modulate the cytoplasmic streaming using action potential to separate the diffusive permeation from the advective contribution. The results imply that the plasmodesmal transport of fluorescent probe through the central and peripheral cells of the nodal complex is differentially regulated by a physiological signal, the action potential. The passage of the probe through the central cells of the nodal complex ceases transiently after elicitation of the action potential in the internodal cell, whereas the passage through the peripheral cells of the node was retained. A diffusion-advection model is developed to describe the transport kinetics and extract the permeability of the node-internode cell wall from experimental data.

Polarisation-driven magneto-optical and nonlinear-optical behaviour of a room-temperature ferroelectric nematic phase.

Nematics with a broken polar symmetry are one of the fascinating recent discoveries in the field of soft matter. High spontaneous polarisation and the fluidity of the ferroelectric nematic NF phase make such materials attractive for future applications and interesting for fundamental research. Here, we explore the polar and mechanical properties of a room-temperature ferroelectric nematic and its behaviour in a magnetic field. We show that NF is much less susceptible to the splay deformation than to the twist. The strong splay rigidity can be attributed to the electrostatic self-interaction of polarisation avoiding the polarisation splay.

Shear-induced birefringence in an optically isotropic cubic liquid crystalline phase.

We report an unusually strong flow-induced birefringence in an optically isotropic cubic phase occurring below the isotropic chiral conglomerate phase formed by a low-molecular-weight polycatenar mesogen. The transition into the birefringent state occurs thresholdless and the induced birefringence is comparable with that observed in polymeric systems. We suggest that the flow-induced deformation of the cubic structure is responsible for the strong rheo-optical response.

Superparamagnetic nanoparticles with LC polymer brush shell as efficient dopants for ferronematic phases.

Liquid crystal (LC) based magnetic materials consisting of LC hosts doped with functional magnetic nanoparticles enable optical switching of the mesogens at moderate magnetic field strengths and thereby open the pathway for the design of novel smart devices. A promising route for the fabrication of stable ferronematic phases is the attachment of a covalently bound LC polymer shell onto the surface of nanoparticles. With this approach, ferronematic phases based on magnetically blocked particles and the commercial LC 4-cyano-4'-pentylbiphenyl (5CB) liquid crystal were shown to have a sufficient magnetic sensitivity, but the mechanism of the magneto-nematic coupling is unidentified. To get deeper insight into the coupling modes present in these systems, we prepared ferronematic materials based on superparamagnetic particles, which respond to external fields with internal magnetic realignment instead of mechanical rotation. This aims at clarifying whether the hard coupling of the magnetization to the particle's orientation (magnetic blocking) is a necessary component of the magnetization-nematic director coupling mechanism. We herein report the fabrication of a ferronematic phase consisting of surface-functionalized superparamagnetic Fe3O4 particles and 5CB. We characterize the phase behavior and investigate the magneto-optical properties of the new ferronematic phase and compare it to the ferronematic system containing magnetically blocked CoFe2O4 particles to get information about the origin of the magneto-nematic coupling.

Solvent-dependent morphology and anisotropic microscopic dynamics of cellulose nanocrystals under electric fields.

Cellulose nanocrystals (CNCs) are interesting for the construction of biomaterials for energy delivery and packaging purposes. The corresponding processing of CNCs can be optimized through the variation of intercellulose interactions by employing different types of solvents, and thereby varying the degree of cellulose hydrogen bonding. The aim of this work is (i) to show how different types of solvents affect the self-assembled morphology of CNCs, (ii) to study the microscopic dynamics and averaged orientations on the CNCs in aqueous suspensions, including the effect of externally imposed electric fields, and (iii) to explore the nonlinear optical response of CNCs. The homogeneity of self-assembled chiral-nematic phase depends on both the polarity of the solvent and the CNC concentration. The variation of the chiral-nematic pitch length with concentration, as determined from real-space and Fourier images, is found to be strongly solvent dependent. The anisotropic microdynamics of CNCs suspension exhibits two modes, related to diffusion parallel and perpendicular to the (chiral-) nematic director. We have found also the coupling between translational and orientational motion, due to existing correlation length of twisted nematic elasticity. Preliminary second-harmonic generation experiments are performed, which reveal that relatively high field strengths are required to reorient chiral-nematic domains of CNCs.

On Droplet Coalescence in Quasi-Two-Dimensional Fluids.

Coalescence of droplets plays a crucial role in nature and modern technology. Various experimental and theoretical studies explored droplet dynamics in three-dimensional (3D) and on 2D solid or liquid substrates. In this paper, we demonstrate the complete coalescence of isotropic droplets in thin quasi-2D liquids-overheated smectic films. We observe the merging of micrometer-sized flat droplets using high-speed imaging and analyze the shape transformations of the droplets on the timescale of milliseconds. Our studies reveal the scaling laws of the coalescence time, which exhibits a different dependence on the droplet geometry from that in the case of droplets on a solid substrate. A theoretical model is proposed to explain the difference in behavior.

Femtosecond Laser-Based Integration of Nano-Membranes into Organ-on-a-Chip Systems.

Organ-on-a-chip devices are gaining popularity in medical research due to the possibility of performing extremely complex living-body-resembling research in vitro. For this reason, there is a substantial drive in developing technologies capable of producing such structures in a simple and, at the same time, flexible manner. One of the primary challenges in producing organ-on-chip devices from a manufacturing standpoint is the prevalence of layer-by-layer bonding techniques, which result in limitations relating to the applicable materials and geometries and limited repeatability. In this work, we present an improved approach, using three dimensional (3D) laser lithography for the direct integration of a functional part-the membrane-into a closed-channel system. We show that it allows the freely choice of the geometry of the membrane and its integration into a complete organ-on-a-chip system. Considerations relating to sample preparation, the writing process, and the final preparation for operation are given. Overall, we consider that the broader application of 3D laser lithography in organ-on-a-chip fabrication is the next logical step in this field's evolution.

Efficient ferronematic coupling with polymer-brush particles.

Switching of liquid crystal phases is of enormous technological importance and enables digital displays, thermometers and sensors. As an alternative to electric fields or temperature, magnetic fields are an interesting trigger, as they are on the one hand versatile to design, and on the other hand, they are compatible with a bouquet of applications. An interesting option to enable the magnetic switchability of nematic phases is by doping them with functional magnetic nanoparticles, but it remains a challenge to achieve well-compatibilized and stable ferronematic phases. Here, we report a new approach for the experimental realization of finely dispersed MNPs and nematic LC by creation of a surface-coupled mesogen-functionalized polymer brush, and the determination of their corresponding magneto-optical response. For this purpose, CoFe2O4 particles are equipped with a covalently attached polymeric shell carrying mesogenic groups and successfully dispersed in 4-pentyl-4'-cyanobiphenyl (5CB) to form a stable ferronematic phase at ambient concentration up to ∼1 vol%, as shown by DSC and Abbé refractometry. The magneto-optic response is detected in planar aligned LC cells. As compared to undoped 5CB, the hybrid system shows a significantly increased magnetic sensitivity, and the magneto-nematic surface anchoring is quantified by analysis of the magneto-nematic cross-correlation.

Frequency-dependent conversion of the torque of a rotating magnetic field on a ferrofluid confined in a spherical cavity.

The dynamics of magnetic nanoparticles in rotating magnetic fields is studied both experimentally and theoretically. The experimental investigation is focused on the conversion of the magnetic forces to a mechanical torque acting on a ferrofluid confined in a spherical cavity in a rotating magnetic field. Polydispersity usually present in diluted ferrofluids is shown to play a crucial role in the torque conversion. Important features observed experimentally are reproduced theoretically in studies on the dynamics of particles with uniaxial magnetic anisotropy in the presence of thermal noise. The phase lag between the rotating magnetic field and the induced rotating magnetization, as well as the corresponding torque which is transferred to the carrier fluid because of the mutual coupling between both, is analyzed as a function of the particle size. It is shown that for large particles the magnetic moment is locked to the anisotropy axis. On lowering the particle radius, Néel relaxation becomes increasingly important. Illustrative numerical calculations demonstrating this behavior are performed for magnetic parameters typical for iron oxide.

Structure and dynamics of a two-dimensional colloid of liquid droplets.

Droplet arrays in thin, freely suspended liquid-crystalline smectic A films can form two-dimensional (2D) colloids. The droplets interact repulsively, arranging locally in a more or less hexagonal arrangement with only short-range spatial and orientational correlations and local lattice cell parameters that depend on droplet size. In contrast to quasi-2D colloids described earlier, there is no 3D bulk liquid subphase that affects the hydrodynamics. Although the films are surrounded by air, the droplet dynamics are genuinely 2D, the mobility of each droplet in its six-neighbor cage being determined by the ratio of cage and droplet sizes, rather than by the droplet size as in quasi-2D colloids. These experimental observations are described well by Saffman's model of a diffusing particle in a finite 2D membrane. The experiments were performed in microgravity, on the International Space Station.

PH-dependent cell-cell interactions in the green alga Chara.

Characean internodal cells develop alternating patterns of acid and alkaline zones along their surface in order to facilitate uptake of carbon required for photosynthesis. In this study, we used a pH-indicating membrane dye, 4-heptadecylumbiliferone, to study the kinetics of alkaline band formation and decomposition. The differences in growth/decay kinetics suggested that growth occurred as an active, autocatalytic process, whereas decomposition was due to diffusion. We further investigated mutual interactions between internodal cells and found that their alignment parallel to each other induced matching of the pH banding patterns, which was mirrored by chloroplast activity. In non-aligned cells, the lowered photosynthetic activity was noted upon a rise of the external pH, suggesting that the matching of pH bands was due to a local elevation of membrane conductance by the high pH of the alkaline zones of neighboured cells. Finally, we show that the altered pH banding pattern caused the reorganization of the cortical cytoplasm. Complex plasma membrane elaborations (charasomes) were degraded via endocytosis, and mitochondria were moved away from the cortex when a previously acid region became alkaline and vice versa. Our data show that characean internodal cells react flexibly to environmental cues, including those originating from neighboured cells.

The role of structural anisotropy in the magnetooptical response of an organoferrogel with mobile magnetic nanoparticles.

We investigate the structure and the magnetooptical response of isotropic and anisotropic fibrillous organoferrogels with mobile magnetic nanoparticles (MNPs). We demonstrate that the presence of the gel network restricts the magnetooptical response of the ferrogel. Even though the ferrogel exhibits no magnetic hysteresis, an optical hysteresis has been found. This suggests that the magnetooptical response is primarily determined by the dynamics of self-assembly of the MNPs into shape-anisotropic agglomerates. Furthermore, we show that the optical anisotropy of the system can be fine-tuned by varying the concentration of the gelator and the MNPs, respectively. The optical response in structurally anisotropic gels becomes orientation-dependent, revealing an intricate interplay between the gel mesh and the MNPs.

Polar Order, Mirror Symmetry Breaking, and Photoswitching of Chirality and Polarity in Functional Bent-Core Mesogens.

In recent years, liquid crystals (LCs) responding to light or electrical fields have gained significant importance as multifunctional materials. Herein, two new series of photoswitchable bent-core liquid crystals (BCLCs) derived from 4-cyanoresorcinol as the central core connected to an azobenzene based wing and a phenyl benzoate wing are reported. The self-assembly of these molecules was characterized by differential scanning calorimetry (DSC), polarizing light microscopy (POM), electro-optical, dielectric, second harmonic generation (SHG) studies, and XRD. Depending on the direction of the COO group in the phenyl benzoate wing, core-fluorination, temperature, and the terminal alkyl chain length, cybotactic nematic and lamellar (smectic) LC phases were observed. The coherence length of the ferroelectric fluctuations increases continuously with decreasing temperature and adopts antipolar correlation upon the condensation into superparaelectric states of the paraelectric smectic phases. Finally, long-range polar order develops at distinct phase transitions; first leading to polarization modulated and then to nonmodulated antiferroelectric smectic phases. Conglomerates of chiral domains were observed in the high permittivity ranges of the synclinic tilted paraelectric smectic phases of these achiral molecules, indicating mirror symmetry breaking. Fine-tuning of the molecular structure leads to photoresponsive bent-core (BC)LCs exhibiting a fast and reversible photoinduced change of the mode of the switching between ferroelectric- and antiferroelectric-like as well as a light-induced switching between an achiral and a spontaneous mirror-symmetry-broken LC phase.

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.

Doping of nematic cyanobiphenyl liquid crystals with mesogen-hybridized magnetic nanoparticles.

Magnetic nanoparticles (MNPs) functionalized with (pro-)mesogenic ligands are implemented into a nematic liquid crystal (LC) and studied regarding both colloidal stability and magneto-optical behavior. In this study, the particle surface is specifically engineered to tune the MNP interactions with the LC host. For this purpose, four types of (pro-)mesogenic ligands (ML) are synthesized, which are composed of three structural parts, i.e., a rigid, LC motif (i.e., cyanobiphenyl) and a functional group for nanoparticle binding, both linked via a flexible spacer of different alkyl chain lengths. Electrostatically stabilized CoFe2O4 and γ-Fe2O3 nanoparticles with narrow size distribution and sizes below 3 nm are obtained via co-precipitation and subsequently functionalized to yield MNP@ML nanoparticles. Studies on the behaviour of the MNP@ML nanoparticles in the commercial LC host (i.e., 4-pentyl-4'-cyanobiphenyl (5CB)) in the bulk and in thin films in LC test cells, reveal the initial formation of some heterogeneities after transition from the isotropic to the nematic phase. Homogenous MNP@ML-5CB hybrids with long-term, colloidal stability, however, are obtained after magnetic separation of initially formed particle aggregates. In particular, MLs with carboxy groups and high structural flexibility (i.e., long linker lengths) are shown to be well suited to form stable MNP colloids, allowing for high MNP doping levels. As compared to undoped 5CB, the CoFe2O4@MLx-5CB hybrids show an increased sensitivity to the magnetic field, affecting the Fréedericksz transition. The strongest effect, however, is observed in magnetic and electric fields. The coupling of the ultrasmall, spherical MNPs with the LC director in the magnetic field suggests the formation of LC-induced, anisometric MNP clusters.

Photomanipulation of the anchoring strength using a spontaneously adsorbed layer of azo dendrimers.

We systematically studied the photoinduced anchoring transition in a nematic liquid crystal containing azo dendrimers. Because the azo dendrimers in the trans-isomer state were spontaneously adsorbed at substrate surfaces, which was confirmed by optical second-harmonic generation (SHG), a homeotropic orientation was established at the first stage. Ultraviolet (UV) light irradiation triggered a transition into a planar state which was accompanied by a suppression of the SH generation. The monotonic decrease of the effective scalar order parameter with increasing UV light intensity was determined by polarized attenuated total reflection infrared (ATR-IR) spectroscopy. The variation of anchoring strength and extrapolation length was evaluated by observing the Fréedericksz transition as a function of UV light intensity at a certain visible (VIS) light intensity. Such a photoinduced variation can be interpreted as a variation of the anchoring strength depending on the trans/cis ratio at the surfaces based on a modified Rapini-Papoular model. Thus, this system provides the opportunity for a controlled change in the anchoring strength.