RESUMEN
We use optical and fluorescence microscopy, densitometry, cryo-transmission electron microscopy (cryo-TEM), spectroscopy, and synchrotron X-ray scattering to study the phase behavior of the reversible self-assembled chromonic aggregates of an anionic dye Sunset Yellow (SSY) in aqueous solutions crowded with an electrically neutral polymer polyethylene glycol (PEG) and doped with the salt NaCl. PEG causes the isotropic SSY solutions to condense into a liquid-crystalline region with a high concentration of SSY aggregates, coexisting with a PEG-rich isotropic (I) region. PEG added to the homogeneous nematic (N) phase causes separation into the coexisting N and I domains; the SSY concentration in the N domains is higher than the original concentration of PEG-free N phase. Finally, addition of PEG to the highly concentrated homogeneous N phase causes separation into the coexisting columnar hexagonal (C) phase and I phase. This behavior can be qualitatively explained by the depletion (excluded volume) effects that act at two different levels: at the level of aggregate assembly from monomers and short aggregates and at the level of interaggregate packing. We also show a strong effect of a monovalent salt NaCl on phase diagrams that is different for high and low concentrations of SSY. Upon the addition of salt, dilute I solutions of SSY show appearance of the condensed N domains, but the highly concentrated C phase transforms into a coexisting I and N domains. We suggest that the salt-induced screening of electric charges at the surface of chromonic aggregates leads to two different effects: (a) increase of the scission energy and the contour length of aggregates and (b) decrease of the persistence length of SSY aggregates.
RESUMEN
High-quality alignment control of liquid crystals (LCs) for ultrahigh-definition large-sized display is a challenging task. A conventional rubbing method has obvious limitations for fabricating large-sized displays with a small pixel size and an uneven inner surface. To comply with the current trend, we propose a simple and reliable polyimide-less in situ photoalignment. It was achieved using a visible-light-sensitive azo-dye and a mesogenic acrylate, both doped to host LCs. Without using a pretreated alignment layer, mono- and multidomain uniaxial alignments of LC molecules were induced by linearly polarized visible light (LPVL) and subsequently stabilized by unpolarized UV-light irradiation. The stepwise process was monitored by adopting a fluorescent indicator. By loading the mixture into a confined cell, azo-dyes were spontaneously adsorbed at inner surfaces of the cell, whereas reactive mesogens (RMs) were homogeneously dissolved in an LC host. The molecular orientational anisotropy of dyes at the surface, induced by LPVL, aligned the LC director perpendicular to the polarization direction. Upon the second step, UV-irradiation, the RMs in an LC host were photopolymerized into thin interfacial layers, stabilizing the aligned LC director. The overlaid cross-linked RM layers secured a thermal and a radiative stability of LC alignment. The RM layers completely screened the effect of azo-dyes, which can be easily randomized by heat and irradiation. The interfacial RM layer functioned as a permanently stable alignment layer. It provided sufficient azimuthal anchoring strength together with heat and light stabilities, which are essential for practical applications. Such sequential interfacial modifications through dual-wavelength processes can completely avoid interference between forming alignment and stabilization layers, inevitable if the same wavelength light is used. The proposed method provides a simple fabrication process and reliable alignment characteristics by employing effective in situ photoalignment and without using a traditional alignment layer. Therefore, it meets a current trend in the display market toward ultrahigh-resolution and large-area displays.
RESUMEN
Lyotropic chromonic liquid crystals (LCLCs) are formed by molecules with ionic groups at the periphery that associate into stacks through noncovalent self-assembly while in water. The very existence of the nematic (N) phase in the typical LCLC, the dye Sunset Yellow (SSY) is a puzzle, as the correlation length associated with the stacking, as measured in the X-ray experiments, is too short to explain the orientational order by the Onsager model. We propose that the aggregates can be more complex than simple rods and contain "stacking faults" such as junctions with a shift of neighboring molecules, 3-fold junctions, etc. We study how ionic additives, such as salts of different valency and pH-altering agents, alter the N phase of SSY purified by recrystallization. The additives induce two general trends: (a) stabilization of the N phase, caused by the mono and divalent salts (such as NaCl), and evidenced by the increase of the N-to-I transition temperature and the correlation length; (b) suppression of the N phase manifested in the decrease of the N-to-I transition temperature and in separation of the N phase into a more densely packed N phase or the columnar (C) phase, coexisting with a less condensed I phase. The scenario (b) can be triggered by simply increasing pH (adding NaOH). The effects produced by tetravalent spermine fall mostly into the category (b), but the detail depends on whether this additive is in its salt form or a free base form. The base form causes changes through changes in pH and possible excluded volume effects whereas the salt form might disrupt the structure of SSY aggregates.
RESUMEN
Liquid crystals are a class of industrially important materials whose optical properties make them useful particularly in display technology. Optical imaging of these materials provides information about their structure and physical properties. Coherent anti-Stokes Raman scattering (CARS) microscopy is used to provide three-dimensional chemical maps of liquid crystalline samples without the use of external labels. CARS is an optical imaging technique that derives contrast from Raman-active molecular vibrations in the sample. Compared to many other three-dimensional imaging techniques, CARS offers more rapid chemical characterization without the use of external dyes or contrast agents. The use of CARS to image chemical and orientational order in liquid crystals is demonstrated using several examples, and the limitations and benefits are discussed.
RESUMEN
The detailed structure of singularities of ordered field represents a fundamental problem in diverse areas of physics. At the defect cores, the deformations are so strong that the system explores states with symmetry different from that of an undistorted material. These regions are difficult to explore experimentally as their spatial extension is very small, a few molecular lengths in the condensed matter. Here we explore the cores of disclinations in the so-called chromonic nematics that extend over macroscopic length scales accessible for optical characterization. We demonstrate that the amplitude S and the phase (the director) of the order parameter vary along both the radial and azimuthal directions, in contrast to the classic models in which S varies only with the distance from the centre and depends only on the azimuthal coordinate. This unexpected core structure is explained by a strong coupling of the phase and amplitude of the order parameter in the free energy.
RESUMEN
Liquid crystals (LCs) represent a challenging group of materials for direct transmission electron microscopy (TEM) studies due to the complications in specimen preparation and the severe radiation damage. In this paper, we summarize a series of specimen preparation methods, including thin film and cryo-sectioning approaches, as a comprehensive toolset enabling high-resolution direct cryo-TEM observation of a broad range of LCs. We also present comparative analysis using cryo-TEM and replica freeze-fracture TEM on both thermotropic and lyotropic LCs. In addition to the revisits of previous practices, some new concepts are introduced, e.g., suspended thermotropic LC thin films, combined high-pressure freezing and cryo-sectioning of lyotropic LCs, and the complementary applications of direct TEM and indirect replica TEM techniques. The significance of subnanometer resolution cryo-TEM observation is demonstrated in a few important issues in LC studies, including providing direct evidences for the existence of nanoscale smectic domains in nematic bent-core thermotropic LCs, comprehensive understanding of the twist-bend nematic phase, and probing the packing of columnar aggregates in lyotropic chromonic LCs. Direct TEM observation opens ways to a variety of TEM techniques, suggesting that TEM (replica, cryo, and in situ techniques), in general, may be a promising part of the solution to the lack of effective structural probe at the molecular scale in LC studies.
RESUMEN
In modern transformation optics, one explores metamaterials with properties that vary from point to point in space and time, suitable for application in devices such as an "optical invisibility cloak" and an "optical black hole". We propose an approach to construct spatially varying and switchable metamaterials that are based on colloidal dispersions of metal nano-rods (NRs) in dielectric fluids, in which dielectrophoretic forces, originating in the electric field gradients, create spatially varying configurations of aligned NRs. The electric field controls orientation and concentration of NRs and thus modulates the optical properties of the medium. Using gold (Au) NRs dispersed in toluene, we demonstrate electrically induced change in refractive index on the order of 0.1.
RESUMEN
We present a simple and universal technique for assembling gold nanorods (NRs) using self-assembled stacks of lyotropic chromonic materials, without covalent bonding between NRs and the linking agent. The anisotropic electrostatic interaction between the chromonic stacks and NRs allows one to achieve either side-by-side or end-to-end assembly, depending on the surface charge of NRs. The assembled superstructures are stable within an extended temperature range; the degree of NR aggregation can be controlled by a number of factors influencing the self-assembly of chromonic materials, such as the concentration and pH of the solution.