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A validation of the developed new orientation method of solid samples as suspension in nematic liquid crystal (NLC), applied in linear-dichroic infrared (IR-LD) spectroscopy has been carried out using a model system DL-isoleucine (DL-isoleu). Accuracy, precision and the influence of the liquid crystal medium on peak positions and integral absorbances of guest molecules have been presented. Optimization of experimental conditions has been performed as well. An experimental design for quantitative evaluation of the impact of four input factors: the number of scans, the rubbing-out of KBr-pellets, the amount of studied compounds included in the liquid crystal medium and the ratios of Lorentzian to Gaussian peak functions in the curve fitting procedure on the spectroscopic signal at five different frequencies, indicating important specifities of the system has been studied.

Most paints contain pigments that absorb light and fade over time. A robust alternative can be found in nature, where structural coloration arises from the interference of light with submicron features. Plant‐derived, cellulose nanocrystals (CNCs) mimic these features by self‐assembling into a cholesteric liquid crystal that exhibits structural coloration when dried. While much research has been done on CNCs in aqueous solutions, less is known about transferring CNCs to apolar solvents that are widely employed in paints. This study uses a common surfactant in agricultural and industrial products to suspend CNCs in toluene . Surprisingly, a stable liquid crystal phase is formed within hours, even with concentrations of up to 50 wt%. Evaporating the apolar CNC suspensions results in photonic films with peak wavelengths ranging from 660 to 920 nm. The resulting flexible films have variable mechanical properties with surfactant content, allowing for an optical response with applied force. The films also act as humidity sensors, with increasing relative humidity swelling the films, yielding a redshift in the reflected wavelength. With the addition of a single surfactant, CNCs can be made compatible with existing production methods of industrial coatings, while improving the strength and responsiveness of structurally colored films to external stimuli.

Azo-Schiff bases contain an azo photochrome showing isomerization accompanying with color change, and an imine moiety (which can contribute to the metal complexation capability). The syntheses of these molecules will be described, and their dyes applications will be discussed, such as for fuel cells, as photometric or colorimetric sensors. In addition, liquid crystals and their antibacterial efficiencies will also be discussed.

Abstract The smart emulsification and demulsification system with the light response is a useful tool in various industries, including green chemistry, catalytic reaction, pharmaceuticals, and environmental remediation. Herein, an ionic liquid crystal compound with a light triggered switch based on the azobenzene group [(4‐{3‐methyl‐1‐[3‐(8‐octyloxyoctyl)oxy‐4‐oxobutanoyl]imidazo‐lium‐1‐yl}octyl)oxy] ‐N‐(4‐methylphenyl)benzene‐1,2‐diazene bromide (MOIAzo), was designed and synthesized, which could cause reversible transition between emulsification and demulsification through the light trigger. The ionic liquid has an efficient photoinduced liquefaction process, which dramatically lowers the melting point of ionic liquids from 79 to 9.2 oC. This significantly broadens the liquid state temperature of the ionic liquid crystal. The ionic liquid crystal MOIAzo exhibits both photoinduced and thermally induced nematic liquid crystal properties. The smart emulsion system was effectively employed in an eco‐friendly water‐saving dyeing process of cationic dyes for cationic dyeable polyester (CDP) fabrics, which used only half the amount of water compared with the conventional water bath dyeing method. After dyeing, the oil and water phases can be efficiently separated through the light irradiation, and the oil phase can be reused for the subsequent dyeing process. This novel smart emulsion dyeing method greatly reduces the water consumption and wastewater discharge. MOIAzo as a light‐triggered ionic liquid molecule opens up new dimensions in green chemistry.

Three homologous series of 3‑hydroxy-4-(((-4-benzoxazol-2-yl)phenyl)imino)methyl)phenyl-4-alkoxybenzoate (with ester linkage) and 5-(alkoxy)-2-(((4-(5-benzoxazol-2-yl)phenyl)imino)methylphenol (without ester linkage) Schiff based derivatives, bearing different substituents at 5 position i.e., 5-methylbenzoxazole, benzoxazole and 5-chlorobenzoxazole units at the end of the molecule and their Copper complexes were synthesised. The molecular structure of all the compounds were elucidated by different spectroscopic techniques such as FT-IR, 1H & 13C NMR and mass spectrometry together with elemental analysis. Their phase transition behaviour was investigated by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction. The structure-property relationships, compounds bearing a variety of polar substituents and changing the spacer from ester linked to without ester-linked has been studied. Substituents with stronger electron-withdrawing properties gave a wider mesomorphic temperature domain, in the order Cl > CH3 >H.

BackgroundLiquid crystal (LC) mesophases have an orientational and positional order that can be found in both synthetic and biological materials. These orders are maintained until some parameter, mainly the temperature or concentration, is changed, inducing a phase transition. Among these transitions, a special sequence of mesophases has been observed, in which priority is given to the direct smectic liquid crystal transition. The description of these transitions is carried out using the Landau–de Gennes (LdG) model, which correlates the free energy of the system with the orientational and positional order.MethodologyThis work explored the direct isotropic-to-smectic A transition studying the free energy landscape constructed with the LdG model and its relation to three curve families: (I) level-set curves, steepest descent, and critical points; (II) lines of curvature (LOC) and geodesics, which are directly connected to the principal curvatures; and (III) the Casorati curvature and shape coefficient that describe the local surface geometries resemblance (sphere, cylinder, and saddle).ResultsThe experimental data on 12-cyanobiphenyl were used to study the three curve families. The presence of unstable nematic and metastable plastic crystal information was found to add information to the already developed smectic A phase diagram. The lines of curvature and geodesics were calculated and laid out on the energy landscape, which highlighted the energetic pathways connecting critical points. The Casorati curvature and shape coefficient were computed, and in addition to the previous family, they framed a geometric region that describes the phase transition zone.Conclusion and significanceA direct link between the energy landscape’s topological geometry, phase transitions, and relevant critical points was established. The shape coefficient delineates a stability zone in which the phase transition develops. The methodology significantly reduces the impact of unknown parametric data. Symmetry breaking with two order parameters (OPs) may lead to novel phase transformation kinetics and droplets with partially ordered surface structures.

We selected and summarized the most important aspects of liquid crystal alignment. Alignment by the surface profile and flat surface alignment are discussed as the main factors leading to the high-quality orientation of liquid crystals. The advanced level of understanding and formulation allows linking the alignment layer properties to the molecular structure of the alignment material. The paper reviews and combines the latest knowledge about liquid crystal alignment, dwells upon the relationship between the polar and azimuthal anchoring energy, explains the major particularities regarding anchoring measurements in the case of birefringent alignment materials with truly high azimuthal anchoring energy, and observes the current trends of water-friendly alignment materials and their application in geometrical phase device fabrication.

The construction of a λ-shaped three side substituted alkoxy based molecular system (E1-E8) with azo-ester group was carried out and studied for liquid crystalline applications. The mesogenic behaviour and thermal stability of synthesized derivatives were checked and analyzed by POM, DSC and TGA analysis. These azo-ester based compounds show smectic C and nematic type mesomorphic properties. The observed texture patterns of the synthesized compounds are fan, broken fan, schlieren and threaded types. All derivatives shows broad temperature range of mesophase and further stabilized upto the room temperature. The structure-property relationship has been further studied to understand the effect of variable side-chain on liquid crystalline properties.

Enantioseparation of nineteen liquid crystalline racemic mixtures obtained based on (R,S)-2-octanol was studied in reversed-phase mode on an amylose tris(3-chloro-5-methylphenylcarbamate) (ReproSil Chiral-MIG) and a cellulose tris(3,5-dichlorophenylcarbamate) (ReproSil Chiral-MIC). These polysaccharide-based chiral stationary phase (CSP) columns for High-Performance Liquid Chromatography (HPLC) were highly effective in recognizing isomers of minor structural differences. The mobile phase (MP), which consists of acetonitrile (ACN)/water (H2O) at different volume ratios, was used. The mobile phases were pumped at a flow rate of 0.3, 0.5, or 1 mL·min−1 with a column temperature of 25 °C, using a UV detector at 254 nm. The order of the elution was also determined. The chromatographic parameters, such as resolution (Rs), selectivity (α), and the number of theoretical plates, i.e., column efficiency (N), were determined. The polysaccharide-based CSP columns have unique advantages in separation technology, and this study has shown the potential usefulness of the CSP columns in separating liquid crystalline racemic mixtures belonging to the same homologous series.

Sacran is a supergiant cyanobacterial polysaccharide that forms mesogenic supercoil rods that exhibit liquid crystalline (LC) gels at deficient concentrations of around 0.5 wt%, and has several bioactive stimuli-responsive functions. Here, we attempted to form oriented microfibers of sacran by electrospinning, following structural analyses of the sacran rods. A heterogeneous acid-hydrolysis method using a protonated cation-exchange resin was adopted to examine the short-time exposition of concentrated acid to sacran rods. From the supernatant, the oligomeric fraction that was soluble in water and methanol was isolated. The oligomeric fraction had a main sugar ratio of α-Glc:β-Glc:α-Xyl:β-Xyl:α-Rha of 2:5:1.5:1.5:4 (Glc:Xyl:Rha = 7 (=4 + 3):3:4), and it was speculated that the sacran structure includes rhamnoglucan and xyloglucan (4:3), which are generally rigid enough to exhibit LC. To make oriented microfibers of LC sacran, solubility testing was performed on sacran to find good new solvents of polyhydroxy alcohols such as ethylene glycol, 1,2-propanediol, and glycerol. The oriented film was prepared from a sacran aqueous solution where calcium compound particles deposited on the film are different from polyhydroxy alcohol solutions. Although sacran could not form microfibers by itself, polymer composite microfibers of sacran with poly(vinyl alcohol) were prepared by electrospinning. Cross-polarizing microscopy revealed the molecular orientation of the microfibers.

The report presents static, low-frequency, and dynamic dielectric properties in the isotropic liquid, nematic, and solid phases of MBBA and related nanocolloids with paraelectric BaTiO3 nanoparticles (spherical, d = 50 nm). MBBA (4-methoxybenzylidene-4′–butylaniline) is a liquid crystalline compound with a permanent dipole moment transverse to the long molecular axis. The distortions-sensitive analysis of the dielectric constant revealed its hidden pretransitional anomaly, strongly influenced by the addition of nanoparticles. The evolution of the dielectric constant in the nematic phase shows the split into two regions, with the crossover coinciding with the standard melting temperature. The ‘universal’ exponential-type behavior of the low-frequency contribution to the real part of the dielectric permittivity is found. The critical-like pretransitional behavior in the solid phase is also evidenced. This is explained by linking the Lipovsky model to the Mossotti catastrophe concept under quasi-negative pressure conditions. The explicit preference for the ‘critical-like’ evolution of the apparent activation enthalpy is worth stressing for dynamics. Finally, the long-range, ‘critical-like’ behavior of the dissipation factor (D = tgδ), covering the isotropic liquid and nematic phases, is shown.

Bent-core liquid crystals, a class of mesogenic compounds with non-linear molecular structures, are well known for their unconventional mesophases, characterized by complex molecular (and supramolecular) ordering and often featuring biaxial and polar properties. In the nematic phase, their unique behavior is manifested in the formation of nano-sized biaxial clusters of layered molecules (cybotactic groups). While this prompted their consideration in the quest for nematic biaxiality, experimental evidence indicates that the cybotactic order is only short-ranged and that the nematic phase is macroscopically uniaxial. By combining atomic force microscopy, neutron reflectivity and wide-angle grazing-incidence X-ray scattering, here, we demonstrate that multilayer films of a bent-core nematic, deposited on silicon by a combined Langmuir–Blodgett and Langmuir–Schaefer approach, exhibit macroscopic in-plane ordering, with the long molecular axis tilted with respect to the sample surface and the short molecular axis (i.e., the apex bisector) aligned along the film compression direction. We thus propose the use of Langmuir films as an effective way to study and control the complex anchoring properties of bent-core liquid crystals.

Abstract Blue phases (BPs), a unique manifestation of chirality in the liquid crystalline state, have gained considerable attention due to the unusual combination of properties such as sub-millisecond response times to electrical fields and Bragg reflection of circularly polarised light. Initially they were regarded as promising materials for the development of the next-level display technologies. However, in recent years, they have gained increasing attention as responsive photonic materials with sensing or optoelectronics properties (photonic mirrors and filters). A major limitation so far has been their narrow temperature range in which they usually exist. The aim of the present review is to summarise the recent efforts made to stabilise BPs by employing specific non-covalent bonds and the principles of supramolecular chemistry. 1 Introduction 2 Stabilisation of Blue Phases by Supramolecular Methods 2.1 Doping Approach 2.2 Design Approach 3 Conclusions and Outlook

Induction of the orthogonal smectic A phase occurs in mixtures of nematic compounds with positive and negative dielectric anisotropy. The aim of this work is to determine influence of a molecular structure of compounds on the induction strength of this phase. Cyclohexyl tolanes with the terminal group ‒OCF3, differing with a lateral substitution of a rigid core with fluorine atoms, were mixed with tolanes with two fluorine atoms in a lateral position and different lengths of a terminal alkoxy chain. Based on phase diagrams, obtained with the use of a polarising optical microscope, the influence of a structure of both types of compounds on the induction of the SmA phase is presented. Both, an increase in a number of fluorine atoms in a rigid core and a decrease in an alkoxy chain length cause a decrease in the strength of the SmA phase induction in the investigated systems.Keywords: chemistry, liquid crystals, smectic A phase induction, miscibility studies

A study on 5CB liquid crystal composites with SiO2 nanoparticles and an additional commixture with Fe3O4 nanoparticles using light transmission and SAW measurements is presented. The prepared liquid crystal composites exhibited an interesting memory effect characterized by the hysteresis of both light transmission and SAW attenuation responses investigated in the nematic phase. While in the case of SiO2 nanoparticles as dopants, the liquid crystal composite showed an improvement in the memory effect, the addition of Fe3O4 magnetic nanoparticles resulted in the memory effect decreasing. Additional studies showed a significant shift in both the threshold voltage and nematic–isotropic transition temperature. Measurements in the magnetic field confirmed the increasing memory effect according to that of pure 5CB. The properties of these composites could lead to a potential application for the fabrication of memory devices suitable for information storage.

We explore the influence of functionalized core–shell CdSe/ZnS quantum dots on the properties of the host liquid crystal compound 4-cyano-4′-octylbiphenyl (8CB) through electrooptical measurements. Two different diameters of quantum dots are used to investigate the size effects. We assess both the dispersion quality of the nanoparticles within the mixtures and the phase stability of the resulting anisotropic soft nanocomposites using polarizing optical microscopy. The temperature-mass fraction phase diagrams of the nanocomposites reveal deviations from the linear behavior in the phase stability lines. We measure the birefringence, the threshold voltage of the Fréedericksz transition, and the electrooptic switching times of the nanocomposite systems in planar cell geometry as functions of temperature, mass fraction, and diameter of the quantum dots. Beyond a critical mass fraction of the dopant nanoparticles, the nematic order is strongly reduced. Furthermore, we investigate the impact of the nanoparticle size and mass fraction on the viscoelastic coefficient. The anchoring energy at the interfaces of the liquid crystal with the cell and the quantum dots is estimated.

Thermotropic mesogens typically exist as liquid crystals (LCs) in a narrow region of high temperatures, making lowering their melting point with the temperature expansion of the mesophase state an urgent task. Para-substituted benzoic acids can form LCs through noncovalent dimerization into homodimers via hydrogen bonds, whose strength and, consequently, the temperature region of the mesophase state can be potentially altered by creating asymmetric heterodimers from different acids. This work investigates equimolar blends of p-n-alkylbenzoic (kBA, where k is the number of carbon atoms in the alkyl radical) and p-n-alkyloxybenzoic (kOBA) acids by calorimetry and viscometry to establish their phase transitions and regions of mesophase existence. Non-symmetric dimerization of acids leads to the extension of the nematic state region towards low temperatures and the appearance of new monotropic and enantiotropic phase transitions in several cases. Moreover, the crystal–nematic and nematic–isotropic phase changes have a two-step character for some acid blends, suggesting the formation of symmetric and asymmetric associates from heterodimers. The mixing of 6BA and 8OBA most strongly extends the region of the nematic state towards low temperatures (from 95–114 °C and 108–147 °C for initial homodimers, respectively, to 57–133 °C for the resulting heterodimer), whereas the combination of 4OBA and 5OBA gives the most extended high-temperature nematic phase (up to 156 °C) and that of 6BA and 9OBA (or 12OBA) provides the existence of a smectic phase at the lowest temperatures (down to 51 °C).

The design and development of new luminescent metallogels formed by cyclometalated palladium(II) complexes in protic solvents were investigated by a combination of differential scanning calorimetry (DSC), polarized optical microscopy (POM), and rheology. Cyclometalated palladium(II) complexes based on imine ligand and ancillary benzoylthiourea (BTU) ligand showed red emission in solid and gel states. The formation of a lyotropic liquid crystal phase was observed for the complex bearing shorter alkyl groups on the BTU ligand. This complex also behaved as a thermotropic liquid crystal that displays a monotropic smectic A phase (SmA). Dynamic rheology measurements (frequency sweep in the 5–90 °C range) of the 1-decanol solution of palladium(II) complexes highlighted their supramolecular self-association ability to generate 3D networks and form gels as a final result.

An important approach to molecular diagnostics is integrating organized substances that provide complex molecular level responses to introduced chemical and biological agents with conditions that optimize and distinguish such responses. In this respect, liquid crystal dispersions are attractive components of molecular diagnostic tools. This paper analyzes a colloid system, containing a nematic liquid crystal as a dispersed phase, and aqueous surfactant and polymer solutions as the continuous phases. We applied a microfluidic approach for tuning orientation of liquid crystal molecules in picoliter droplets immobilized on microchannel walls. Introduction of surfactant to the aqueous phase was found to proportionally increase the order parameter of liquid crystal molecules in microdroplets. Infusion of polymer solutions into surfactant-mediated microfluidic liquid crystal dispersions increased the order parameter at much lower surfactant concentrations, while further infusion of surfactant solutions randomized the orientation of liquid crystal molecules. These effects were correlated with the adsorption of surfactant molecules on surfaces of microdroplets, stabilizing the effect of a polymer matrix on bound surfactant ions and the formation of insoluble polymer–colloid aggregates, respectively. The revealed molecular behavior of liquid crystal dispersions may contribute to optimized synthesis of responsive liquid crystal dispersions for in-flow molecular diagnostics of polymers and colloids, and the development of functional laboratory-on-chip prototypes.

Electrical properties of molecular liquid crystals doped with nanomaterials have been extensively studied over the past two decades. In general, nanoparticles in liquid crystals can play a dual role acting as either ion capturing agents or ion generating objects. An interplay between ions and nanomaterials in liquid crystals can result in a great variety of nontrivial ionic effects. This perspective discusses the Langmuir adsorption model applied to describe ionic phenomena in molecular liquid crystals doped with nanoparticles. The applicability and limitations of this model are emphasized. Within a range of its applicability, the Langmuir adsorption model can be used to obtain a wealth of information about nanoparticle-induced ionic effects in molecular liquid crystals. In addition, this model also offers important improvements to standard experimental procedures for evaluation of electrical properties of advanced liquid crystal materials.

Abstract The development and applications of materials with efficient circularly polarized luminescence (CPL) have become an interdisciplinary frontier research topic. We summarize herein the recent advance in the development and applications of CPL‐active aggregates based on metal‐ligand coordination materials (termed as “coordination aggregates”). The materials surveyed are classified as aggregates of small‐molecular metal complexes, which include monocomponent assemblies of Pt(II) complexes and other complexes and binary aggregates of metal complexes, and CPL‐active metal‐ligand coordination helicates, polymers, and frameworks. The efforts in improving the dissymmetry luminescence factors and quantum yields of these materials and the use of the aggregation strategy in enhancing the performance of isolated molecules are discussed. The recent applications of chiral metal complexes in circularly polarized organic light‐emitting diodes (OLEDs) based on solution‐ or evaporation‐processed procedures are surveyed. In addition, the uses of lanthanide complexes in CPL‐contrast imaging and as CPL probes are highlighted. The common discussion on the mechanism of aggregation‐enhanced CPLs and a perspective on future works of CPL‐active coordination aggregates are finally given.

The comprehension of form generally assumes a euclidean three-dimensional perspective. I argue here that non-euclidean geometry has much to offer in understand­ing structures of atomic crystals, molecular liquid crystals and related mesoporous inorganic materials and biominerals.

Chromonic liquid crystals have recently received a lot of attention due to their spontaneous self-assembly in supramolecular columnar structures that, depending on their concentration in water, align to form a nematic liquid crystalline phase. The chirality may be induced in chromonics by adding chiral moieties to the nematic phase or enhanced by confining them in curved geometrical constraints. This review summarizes the recent research developments on chiral chromonic liquid crystals confined in spherical geometry, relating the results to what was observed for thermotropic liquid crystals in the same conditions. The review focuses on the studies carried out on commercially available nematic chromonics, investigating the effects on their topologies in different anchoring conditions and different chiral dopants and suggesting an application in the sensor field.

Objectives. Our aim was to study the dielectric properties of the 4-n-pentyloxybenzoic acid– N-(4-n-butyloxybenzylidene)-4’-methylaniline system and reveal how different concentrations of N-(4-n-butyloxybenzylidene)-4’-methylaniline additives affect the dielectric properties of 4-n-pentyloxybenzoic acid.Methods. System properties were investigated using polarization thermomicroscopy and dielcometry.Results. We found that dielectric anisotropy changes its sign from positive to negative at the transition temperature of the high-temperature nematic subphase to the low-temperature one. The anisotropy of the dielectric constant of N-4-n-butoxybenzylidene-4’-methylaniline has a positive value and increases as to the system approaches the crystalline phase. The crystal structure of the 4-n-pentyloxybenzoic acid contains dimers formed by two independent molecules due to a pair of hydrogen bonds. The crystal structure of N-(4-n-butoxybenzylidene)-4’-methylaniline contains associates formed by orientational interactions of two independent molecules. 4-n-Pentyloxybenzoic acid dimers (270 nm) and associates of N-4-n-butoxybenzylidene-4’- methylaniline (250 nm) proved to have approximately the identical length. Considering the close length values of the structural units of both compounds and the dielectric anisotropy sign, we assume that the N-4-n-butoxybenzylidene-4’-methylaniline associates are incorporated into the supramolecular structure of the 4-n-pentyloxybenzoic acid. The specific electrical conductivity of the compounds under study lies between 10−7 and 10−12 S∙cm−1. The relationship between the specific electrical conductivity anisotropy and the system composition in the nematic phase at the identical reduced temperature, obtained between 100 and 1000 Hz is symbatic. However, the electrical conductivity anisotropy values of the system obtained at 1000 Hz are lower compared to those obtained at 100 Hz. At N-(4-n-butoxybenzylidene)-4’-methylaniline concentrations between 30 and 60 mol %, the electrical conductivity anisotropy values are higher than those of the individual component.Conclusions. A change in the sign of the dielectric constant anisotropy of the 4-n-pentyloxybenzoic acid during nematic subphase transitions was established. We showed that the system has the highest dielectric constant anisotropy value when components have an equal number of moles. Highest electrical conductivity anisotropy values are observed when the concentration of the N-4-n-butoxybenzylidene-4᾽-methylaniline system lies between 30 and 60 mol %.

The photonic liquid crystalline (LC) dispersion of graphene oxide (GO) is prepared using centrifugation-induced size-fractionization. Under gravity, a series of successive centrifugations enable large GO sheets to sediment and fractionize into a narrowed size distribution. The resulting large GO sheets display large-area monodomain structures with uniform orientation, forming a photonic LC phase. The single lyotropic LC phase forms at the concentration > 0.34 wt% and structural coloring occurs at the concentration > 0.59 wt%. The structural color with different wavelength is tuned with various concentrations (0.59–0.92 wt%). GO membranes are supported on porous poly(ether sulphone) membranes from photonic LC dispersions by a vacuum-spin method. The photonic GO membrane demonstrates dramatic enhancement of water permeance (169.3 Lm−2 hr−1 bar−1), which is 12 times faster than the control GO membrane (13.2 Lm−2 hr−1 bar−1). The ion rejection of the photonic GO membrane (45–60%) is also significantly improved, as compared to the control GO membrane (30–48%). Organic dye rejection testing shows that the photonic GO membrane remains as high molecular rejection (> 90%) as the control GO membrane. This work may provide a new way to fabricate ordered GO membranes for fast nanofiltration.

The synthesis and thermotropic behaviour of some di-alkyloxy-phenyl-1,2,4-triazolium trifluoromethane-sulfonate salts bearing a seven-carbon atom perfluoroalkyl chain on the cation is herein described. The fluorinated salts presenting a 1,2,4-triazole as a core and differing in the length of two alkyloxy chains on the phenyl ring demonstrated a typical liquid crystalline behaviour. The mesomorphic properties of this set of salts were studied by differential scanning calorimetry and polarized optical microscopy. The thermotropic properties are discussed on the grounds of the tuneable structures of the salts. The results showed the existence of a monotropic, columnar, liquid crystalline phase for the salts tested. An increase in the temperature mesophase range and the presence of two enantiotropic mesophases for the sixteen-atom alkyloxy chain salt can be observed by increasing the length of the alkyloxy chain on the phenyl ring.

The transition from the isotropic (I) liquid to the nematic-type (N) uniaxial phase appearing as the consequence of the elongated geometry of elements seems to be a universal phenomenon for many types of suspensions, from solid nano-rods to biological particles based colloids. Rod-like thermotropic nematogenic liquid crystalline (LC) compounds and their mixtures with a molecular solvent (Sol) can be a significant reference for this category, enabling insights into universal features. The report presents studies in 4′-methoxybenzylidene-4-n-butylaniline (MBBA) and isooctane (Sol) mixtures, for which the monotectic-type phase diagram was found. There are two biphasic regions (i) for the low (TP1, isotropic liquid-nematic coexistence), and (ii) high (TP2, liquid-liquid coexistence) concentrations of isooctane. For both domains, biphasic coexistence curves’ have been discussed and parameterized. For TP2 it is related to the order parameter and diameter tests. Notable is the anomalous mean-field type behavior near the critical consolute temperature. Regarding the isotropic liquid phase, critical opalescence has been detected above both biphasic regions. For TP2 it starts ca. 20 K above the critical consolute temperature. The nature of pretransitional fluctuations in the isotropic liquid phase was tested via nonlinear dielectric effect (NDE) measurements. It is classic (mean-field) above TP1 and non-classic above the TP2 domain. The long-standing problem regarding the non-critical background effect was solved to reach this result.

Abstract Two series of N-methyliminodiacetic acid (MIDA) boronates were prepared and their mesomorphic properties were investigated. MIDA-substituted benzoic acid esters were synthesized via the Mitsunobu reaction. The second series of MIDA benzyl ether derivatives was prepared via Williamson etherification and subsequent borylation. Both series exhibit smectic A (SmA) phases. In the case of MIDA boronate esters, a substitution with perfluorinated side chains led to increased transition temperatures and broadening of the SmA phases. The phase geometries of the mesophases were determined by X-ray diffraction. Quantum-chemical calculations provided further insight into the packing model.

Abstract Within the past two decades, chromophores, which show aggregation‐induced emission (AIE), have gained considerable attention with respect to the development of luminescent liquid crystals. In contrast to common luminogens, AIE emitters do not suffer from aggregation‐caused quenching of the emission in the solid state. In this review, we summarize the recent development in the field of AIE‐active liquid crystals and show first model devices, which already prove the application potential of these materials. Currently, three different approaches are followed, to get access to luminescent liquid crystals––namely the synthetic approach yielding luminescent mesogens, the doping approach, and the supramolecular approach, which will be described and discussed in detail in this review.

Colloidal structures are crucial components in biological systems and provide a vivid and seemingly infinite source of inspiration for the design of functional bio-inspired materials. They form multi-dimensional confinements and shape living matter, and transport and protect bioactive molecules in harsh biological environments such as the stomach. Recently, colloidal nanostructures based on natural antimicrobial peptides have emerged as promising alternatives to conventional antibiotics. This contribution summarizes the recent progress in the understanding and design of these bio-inspired antimicrobial nanomaterials, and discusses their advances in the form of dispersions and as surface coatings. Their potential for applications in future food and healthcare materials is also highlighted. Further, it discusses challenges in the characterization of structure and dynamics in these materials.

This study examines the effects of substituents and hydrogen bonding, orientations of imine linkage on the behavior of benzylidene aniline compounds as liquid crystals (LC). Compounds 4-carboxy benzylidene-4-X-aniline (X = H, F, Cl, Br, CH3, OCH3) 1a–6a were synthesized by the reaction of aniline and its substituted derivatives with 4-formylbenzoic acid. Compounds 4-X-benzylidene-4-carboxy aniline (X = H, F, Cl, Br, CH3, OCH3) 1b–6b were synthesized by the reaction of benzaldehyde and its substituted derivatives with 4-aminobenzoic acid using absolute ethanol as the solvent. Synthesized compounds were characterized by FT IR and 1H NMR spectroscopy, liquid crystal properties were investigated using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM) techniques. Based on the mesomorphic properties, it was proven that the compounds 2b–4b are dimorphic exhibiting a smectic and nematic phase, compounds 5b, 6b are monomorphic exhibiting a nematic phase, while compounds 1a–6a and 1b have not shown any mesophase. For compounds 1a–6a hydrogen bonding and reversing imine linkage (in comparison with compounds 1b–6b) caused the absence of their mesomorphic properties.

Objective. The work’s objective is to develop methods for the thermodynamic modeling of systems of liquid crystal - organic solvent.Methods. Four binary systems of nematic 4-pentyloxybenzoic acid (5OBA) with n-alkanes (hexadecane, octadecane, icosane, and docosane) were investigated via thermal analysis methods (differential thermal analysis, polarization microscopy, visual polythermal analysis, and the polytherm solubility method). The accuracy in determining phase transitions temperatures is within 0.3 K. To describe the phase equilibria, models based on the Hildebrand and Hansen solubility parameters were used. Hansen solubility parameters were estimated using the Stefanis scheme. Hildebrand solubility parameters, molar volumes, and vaporization enthalpies were calculated using a group contribution scheme.Results. Phase equilibria in the systems of 5OBA with n-alkanes were studied. Four T-x diagrams were obtained by thermal analysis methods, coordinates of invariant points (eutectics and metatectics) were determined in the systems. A linear dependence of the metatectic coordinate (х1 is a fraction of 5OBA, mol. %) on the number of C atoms in the alkane (N) was established: x1 = -0.3131 x N + 85.467. Solubility polytherms of 5OBA with solvents of different polarity were obtained: n-alkanes (hexane, octane), cyclohexane, aromatic compounds (benzene, toluene, and o-xylene), chlorobenzene, ethyl acetate, acetone, 1,4-dioxane, alcohols (propan-2-ol, propan-1-ol, butan-1-ol), and acetonitrile. The dependence of 5OBA’s solubility on the difference in the solubility parameters of the components and the distance Ra was established.Conclusions. The model for regular solutions based on solubility parameters allows us to calculate the solubility polytherms of mesogens and to select solvents for the purification of mesogens by the mass crystallization method. The best solubility of 4-pentyloxybenzoic acid at 298 K appears in chlorobenzene.

The tunable properties of nematic liquid crystals (NLC) are here exploited in a peculiar leaky waveguide with artificial magnetic conductors as the lateral walls, a bottom metal ground plane, and a homogenized metasurface on top to obtain dynamic beamsteering at a fixed terahertz frequency. The waveguide consists of an NLC cell sandwiched between two dielectric layers. The proposed antenna system works on its transverse-magnetic leaky mode and is capable of radiating a beam that scans either by frequency or by changing the bias voltage applied across the NLC cell. The design parameters are optimized through a rigorous modal analysis of the structure, and the radiation performance is validated through full-wave simulations. The results are promising for the realization of next-generation tunable terahertz leaky-wave antennas.

This paper comments on a recent article "Revolutionary poetry and liquid crystal chemistry: Herman Gorter, Ada Prins and the interface between literature and science" by Hub Zwart (Foundations of Chemistry, published online: 10 July 2020), in which the author explores the influence of the liquid crystal research of Ada Prins on the epic poem Pan written by her long-time lover Herman Gorter. The present paper reviews the basic science of liquid crystals and explains the connections between the work of Prins and its influence on the poem. Other examples of the use of "liquid crystal" as a literary device are identified from renaissance poetry, and the uses of the metaphor in these poems are analysed from a scientific perspective. From these examples it is suggested that creative concepts from poetry may contain elements of substance that appear in hitherto unrecognised scientific realities. [ABSTRACT FROM AUTHOR]

Boron-containing organic compounds are well accepted as a class of compounds having excellent photophysical properties. In addition to the unique photophysical properties, the ease of synthesis and structural robustness make tetracoordinate boron complexes ideal for a variety of applications. While significant light has been thrown on their luminescence properties, there is no collective attention to their supramolecular chemistry. In this mini review, we discuss the progress made in the supramolecular chemistry of these compounds which includes their utility as building blocks for liquid crystalline materials and gels largely driven by various non-covalent interactions like H-bonding, CH-π interactions, BF-π interactions and Van der Waals forces. The organoboron compounds presented here are prepared from easy-to-synthesize chelating units such as imines, diiminates, ketoiminates and diketonates. Moreover, the presence of heteroatoms such as nitrogen, oxygen and sulfur, and the presence of aromatic rings facilitate non-covalent interactions which not only favor their formation but also helps to stabilize the self-assembled structures.

Surface protein gp-120 of HIV-1 virus plays an important role in the infection of HIV-1, but detection of gp-120 during the early stage of infection is very difficult. Herein, we report a binding bioassay based on an RNA aptamer B40t77, which binds specifically to gp-120. The bioassay is built upon a hydrophobic glass slide with surface immobilized gp-120. When the glass surface is incubated in a solution containing B40t77, the aptamer is able to bind to gp-120 specifically and remove it from the surface after a short incubation time of 30 min. The result of the binding event can be amplified by using liquid crystal (LC) into optical signals in the final step. By using this bioassay, we are able to detect as low as 1 μg/ml of gp-120 with high specificity within 30 min. No response is obtained when gp-120 is replaced by other protein such as bovine serum albumin (BSA). This is the first qualitative bioassay which provides a simple way for the detection of gp-120 with the naked eye. The assay is robust, low-cost and does not require additional labeling. Thus, the bioassay is potentially useful for the early detection of HIV-1 in resources-limited regions.

In this study, the amphiphilic salt lithium trifluoromethanesulfonylimide octadecane (C18LiTFSI) was used as a basis to investigate the effects of anion density and cation coordination sites within blended electrolytes with strong ionic aggregation. C18LiTFSI was previously reported as a single-component, ion-condensed electrolyte with a wide layered liquid crystalline phase regime. Three additive molecules with varyingly sized polar sulfonyl groups attached to an octodecane-tail were synthesized and mixed with C18LiTFSI. The thermal properties, morphology, and ionic conductivity of the blended electrolytes were characterized. It was found that the blended electrolytes exhibited layered liquid crystalline morphology over a narrower temperature range than the pure salt, and the ionic conductivity of the blended liquid crystalline electrolytes were generally lower than that of the pure salt. Surprising, the additives were found to have the greatest effect on the bulk ionic conductivity of the semicrystalline phase of the electrolytes. Addition of minor fractions of methylsulfonyloctadecane to C18LiTFSI resulted in increases in conductivity of over two orders of magnitude at room temperature, while addition of ethylsulfonyloctadecane or isopropylsulfonyloctadecane with the larger head group resulted in decreased ionic conductivity over the entire composition space and temperature range investigated.

A new family of liquid π-donors, lipophilic dihydrophenazine (DHP) derivatives, show remarkably high π-electron-donor property which exhibit supramolecular alternating copolymerization with 7,7,8,8-tetracyanoquinodimethane (TCNQ), giving ionic charge-transfer (ICT) complexes. The ICT complexes form distinct columnar liquid crystalline (LC) mesophases with well-defined alternating molecular alignment as demonstrated by UV-Vis-NIR spectra, IR spectra, and X-ray diffraction (XRD) patterns. These liquid crystalline ICT complexes display unique phase transitions in response to mechanical stress: the columnar ICT phase is converted to macroscopically oriented smectic-like mesophases upon applying shear force. Although there exist reports on the formation of ICT in the crystalline state, this study provides the first rational identification of ICT mesophases based on the spectroscopic and structural data. The liquid crystalline ICT phases are generated by strong electronic interactions between the liquid π-donors and solid acceptors. It clearly shows the significance of simultaneous fulfillment of strong π-donating ability and ordered self-assembly of the stable ICT pairs. The flexible, stimuli-responsive structural transformation of the ICT complexes offer a new perspective for designing processable CT systems with controlled hierarchical self-assembly and electronic structures.

Rapidly expanding and new applications of liquid crystal materials cover a wide range of technology products. A very incomplete list includes conventional and miniature high-resolution displays, AR/VR glasses, smart windows, dynamic lenses, tunable filters and retarders, electrically controlled sensors, reconfigurable antennas for wireless and space communications, and many other commercially available devices. The aforementioned devices are enabled by the collective reorientation of thermotropic molecular liquid crystals under the action of applied electric fields. The reorientation effects in liquid crystals can be altered by ionic contaminants typically present in mesogenic materials in small quantities. Therefore, information about ions in liquid crystals is very important because it allows for a proper selection of liquid crystal materials and uncompromised performance of liquid crystal devices. This information can be obtained by performing electrical measurements of liquid crystal materials. Measurements of basic electrical parameters (DC conductivity, charge mobility, and ion density) are carried out using sandwich-like liquid crystal cells of finite thickness. Once a cell is filled with liquid crystal materials, interactions between ions and the cell substrates will result in the time dependence of the ion density and DC electrical conductivity until a steady state is reached. In this paper, we show how complementary information about ionic processes in liquid crystal cells can be obtained by analyzing their transient and steady-state electrical properties.

Hydrogels, an advanced interactive system, is finding use as wound dressings, however, they exhibit restricted mechanical properties, macroscopic nature, and may not manage high exudate wounds or incorporate lipophilic actives. In this study, we developed a self-gelling solid lipid nanoparticle (SLNs) dressing to incorporate simvastatin (SIM), a lipophilic, potential wound-healing agent, clinically limited due to poor solubility (0.03 mg/mL) and absorption. The study explores unconventional and novel application of SIM. The idea was to incorporate a significant amount of SIM in a soluble form and release it slowly over a prolonged time. Further, a suitable polymeric surfactant was selected that assigned a self-gelling property to SLNs (SLN-hydrogel) so as to be used as a novel wound dressing. SLNs assign porosity, elasticity, and occlusivity to the dressing to keep the wound area moist. It will also provide better tolerance and sensory properties to the hydrogel. SIM loaded SLN-hydrogel was prepared employing an industry amenable high-pressure homogenization technique. The unique hydrogel dressing was characterized for particle size, zeta potential, Fourier transform infra-red spectroscopy, powder X-ray diffraction, differential scanning calorimetry, rheology, and texture. Significant loading of SIM (10% w/w) was achieved in spherical nanoparticule hydrogel (0.3 nm (nanoparticles) to 2 µm (gelled-matrix)) that exhibited good spreadability and mechanical properties and slow release up to 72 h. SLN-hydrogel was safe as per the organization for economic co-operation and development (OECD-404) guidelines, with no signs of irritation. Complete healing of excision wound observed in rats within 11 days was 10 times better than marketed povidone-iodine product. The presented work is novel both in terms of classifying a per se SLN-hydrogel and employing SIM. Further, it was established to be a safe, effective, and industry amenable invention.

The efficiency of photomobile polymers (PMP) in the conversion of light into mechanical work plays a fundamental role in achieving cutting-edge innovation in the development of novel applications ranging from energy harvesting to sensor approaches. Because of their photochromic properties, azobenzene monomers have been shown to be an efficient material for the preparation of PMPs with appropriate photoresponsivity. Upon integration of the azobenzene molecules as moieties into a polymer, they act as an engine, allowing fast movements of up to 50 Hz. In this work we show a promising approach for integrating ZnO nanoparticles into a liquid crystalline polymer network. The addition of such nanoparticles allows the trapping of incoming light, which acts as diffusive points in the polymer matrix. We characterized the achieved nanocomposite material in terms of thermomechanical and optical properties and finally demonstrated that the doped PMP was better performing that the undoped PMP film.

The synthesis and characterization of a new class of 1,2,4-oxadiazolylpyridinium as a cationic scaffold for fluorinated ionic liquid crystals is herein described. A series of 12 fluorinated heterocyclic salts based on a 1,2,4-oxadiazole moiety, connected through its C(5) or C(3) to an N-alkylpyridinium unit and a perfluoroheptyl chain, differing in the length of the alkyl chain and counterions, has been synthesized. As counterions iodide, bromide and bis(trifluoromethane)sulfonimide have been considered. The synthesis, structure, and liquid crystalline properties of these compounds are discussed on the basis of the tuned structural variables. The thermotropic properties of this series of salts have been investigated by differential scanning calorimetry and polarized optical microscopy. The results showed the existence of an enantiotropic mesomorphic smectic liquid crystalline phase for six bis(trifluoromethane)sulfonimide salts.

Recent advances in experimental studies of nanoparticle-driven stabilization of chiral liquid-crystalline phases are highlighted. The stabilization is achieved via the nanoparticles’ assembly in the defect lattices of the soft liquid-crystalline hosts. This is of significant importance for understanding the interactions of nanoparticles with topological defects and for envisioned technological applications. We demonstrate that blue phases are stabilized and twist-grain boundary phases are induced by dispersing surface-functionalized CdSSe quantum dots, spherical Au nanoparticles, as well as MoS2 nanoplatelets and reduced-graphene oxide nanosheets in chiral liquid crystals. Phase diagrams are shown based on calorimetric and optical measurements. Our findings related to the role of the nanoparticle core composition, size, shape, and surface coating on the stabilization effect are presented, followed by an overview of and comparison with other related studies in the literature. Moreover, the key points of the underlying mechanisms are summarized and prospects in the field are briefly discussed.

The operability of liquid crystal displays is strongly impacted by the orientation aspects of nematics, which in turn are affected by the alignment layer surface features. In this work, two polyimide (PI) structures are obtained based on a cycloaliphatic dianhydride and aromatic or aliphatic diamines with distinct flexibility. The attained PI films have high transmittance (T) for visible radiations, i.e., at 550 nm T > 80%. Here, a novel strategy for creating surface anisotropy in the samples that combines rubbing with a cloth and stretching via pressing is reported. Birefringence and atomic force microscopy (AFM) scans reveal that the generated orientation of the chains is affected by the chemical structure of the polymer and order of the steps involved in the surface treatment. Molecular modeling computations and wettability tests show that the PI structure and produced surface topography are competitive factors, which are impacting the intensity of the interactions with the nematic liquid crystals. The achieved results are of great relevance for designing of reliable display devices with improved uniform orientation of liquid crystals.

The effect of the liquid crystalline host on structural changes in magnetosomes based on ferronematics is studied using the surface acoustic wave (SAW) technique supported by some capacitance and light transmission measurements. The measurement of the attenuation response of SAW propagating along the interface between LC and the piezoelectric substrate is used to study processes of structural changes under magnetic field. The magnetosome nanoparticles of the same volume concentration were added to three different nematic LCs, 5CB, 6CB, and E7. Unlike to undoped LCs, the different responses of SAW attenuation under the influence of magnetic and electric fields in LCs doped with magnetosomes were observed due to characteristic structural changes. The decrease of the threshold field for doped LCs as compared with pure LCs and slight effects on structural changes were registered. The threshold magnetic fields of LCs and composites were determined from capacitance measurements, and the slight shift to lower values was registered for doped LCs. The shift of nematic-isotropic transition was registered from dependencies of SAW attenuation on temperature. The acoustic anisotropy measurement approved the previous supposition about the role of bulk viscosity in used SAW measurements. In addition, capacitance and light transmition investigations supported SAW results and pointed out conclusions about their magnetic field behavior. Obtained results are discussed and confronted with previous ones and coincide well with those observed using acoustic, optical, or dielectric techniques.

A simple, rapid, and sensitive analytical procedure has been developed and validated for the in vitro measurement of curcumin in samples from mucosae retention studies. Curcumin was analyzed by HPLC using a C18 column with UV detection at 425 nm. The mobile phase was acetonitrile and water (50:50 v/v) acidified with 2% acetic acid at a flow rate of 1.2 mL min−1. The curve range was linear for the receptor solution concentration range 0.5–75 μg mL−1. The specificity showed no interference with the biological matrix and excipients of the acceptor media. Intra and inter-day accuracy, and precision values were lower than 5% and were not statically different (P

Liquid crystals are interesting linear and nonlinear optical materials used to make a wide variety of devices beyond flat panel displays. Liquid crystalline materials can be used either as core or as cladding of switchable/reconfigurable waveguides with either an electrical or an optical control or both. In this paper, materials and main device structures of liquid crystals confined in different waveguide geometries are presented using different substrate materials, such as silicon, soda lime or borosilicate glass and polydimethylsiloxane. Modelling of the behaviour of liquid crystal nanometric molecular reorientation and related refractive index distribution under both low-frequency electric and intense optical fields is reported considering optical anisotropy of liquid crystals. A few examples of integrated optic devices based on waveguides using liquid crystalline materials as core for optical switching and filtering are reviewed. Reported results indicate that low-power control signals represent a significant feature of photonic devices based on light propagation in liquid crystals, with performance, which are competitive with analogous integrated optic devices based on other materials for optical communications and optical sensing systems.

We experimentally demonstrate that the plasmonic heat delivered by a single layer of homogeneously distributed gold nanoparticles (AuNPs), immobilized on a glass substrate, can be optically tuned by taking advantage of the properties of an organic layer based on azobenzene and nematic liquid crystal (NLC) molecules. The effect, which exploits the dependence of the NLC refractive index value on the molecular director orientation, is realized using the polarization-dependent, light-induced molecular reorientation of a thin film of photo-aligning material that the NLC is in contact with. The reversibility of the optically induced molecular director reorientation of the NLC enables an active modulation of the plasmonic photo-induced heat.

A novel finite-difference time-domain formulation for the modeling of general anisotropic dispersive media is introduced in this work. The method accounts for fully anisotropic electric or magnetic materials with all elements of the permittivity and permeability tensors being non-zero. In addition, each element shows an arbitrary frequency dispersion described by the complex-conjugate pole–residue pairs model. The efficiency of the technique is demonstrated in benchmark numerical examples involving electromagnetic wave propagation through magnetized plasma, nematic liquid crystals and ferrites.