Nanoscale View of Alignment and Domain Growth in a Hexagonal Columnar Liquid Crystal.

Highly ordered liquid crystalline (LC) phases have important potential for organic electronics. We studied the molecular alignment and domain structure in a columnar LC thin film with nanometer resolution during in situ heating using four-dimensional scanning transmission electron microscopy (4D STEM). The initial disordered vapor-deposited LC glass thin film rapidly ordered at its glass transition temperature into a hexagonal columnar phase with small (<10 nm), well-aligned, planar domains (columns oriented parallel to the surface). Upon further heating, the domains coarsen via bulk diffusion, then the film crystallizes, then finally transforms back to an LC phase at an even higher temperature. The LC phase at high temperature shows straight columns of molecules, which we attribute to structure inherited from the intermediate crystalline phase. Nanoscale 4D STEM offers direct insight into the mechanisms of domain reorganization, and intermediate crystallization is a potential approach to manipulate orientational order and texture at the nano- to mesoscale in LC thin films.

Microgels sense wounds' temperature, pH and glucose.

Wound healing concerns almost all bed-side related diseases. With our increasing comprehension of healing nature, the physical and chemical natures behind the wound microenvironment have been decoupled. Wound care demands timely screening and prompt diagnosis of wound complications such as infection and inflammation. Biosensor by the way of exhaustive collection, delivery, and analysis of data, becomes indispensable to arrive at an ideal healing upshot and controlling complications by capturing in-situ wound status. Electrochemical based sensors carry some potential unstable performance subjected to the electrical circuitry and power access and contamination. The colorimetric sensors are free from those concerns. We report that microsensors designed from O/W/O of capillary fluids can continuously monitor wound temperature, pH and glucose concentration. We combined three different types of microgels to encapsulate liquid crystals of cholesterol, nontoxic fuel litmus and two glucose-sensitizing enzymes. A smartphone applet was then developed to convert wound healing images to RGB of digitalizing data. The microgel dressing effectively demonstrates the local temperature change, pH and glucose levels of the wound in high resolution where a microgel is a 'pixel'. They are highly responsive, reversible and accurate. Monitoring multiple physicochemical and physiological indicators provides tremendous potential with insight into healing processing.

Electro-Optic Response of Polymer-Stabilized Cholesteric Liquid Crystals with Different Polymer Concentrations.

Polymer-stabilized cholesteric liquid crystals (PSCLCs) have emerged as promising candidates for one-dimensional photonic lattices that enable precise tuning of the photonic band gap (PBG). This work systematically investigates the effect of polymer concentrations on the AC electric field-induced tuning of the PBG in PSCLCs, in so doing it explores a range of concentrations and provides new insights into how polymer concentration affects both the stabilization of cholesteric textures and the electro-optic response. We demonstrate that low polymer concentrations (≈3 wt. %) cause a blue shift in the short wavelength band edge, while high concentrations (≈10 wt. %) lead to a contraction and deterioration of the reflection band. Polarization optical microscopy was conducted to confirm the phase transition induced by the application of an electric field. The observations confirm that increased polymer concentration stabilizes the cholesteric texture. Particularly, the highly desired fingerprint texture was stabilized in a sample with 10 wt. % of the polymer, whereas it was unstable for lower polymer concentrations. Additionally, higher polymer concentrations also improved the dissymmetry factor and stability of the lasing emission, with the dissymmetry factor reaching the value of around 2 for samples with 10 wt. % of polymer additive. Our results provide valuable comprehension into the design of advanced PSCLC structures with tunable optical properties, enhancing device performance and paving the way for innovative photonic applications.

Miscibility Studies of Bismesogen CBnCB Forming Nematic Twist-Bend Phase with Cyanobiphenyls nCB.

This work aims to determine how the nematic twist-bend phase (NTB) of bismesogens containing two rigid parts of cyanobiphenyls connected with a linking chain containing n = 7, 9, and 11 methylene groups behaves in mixtures with structurally similar cyanobiphenyls nCB, n = 4-12, 14. The whole phase diagrams are presented for the CB7CB-nCB system. For the other systems, CB9CB-nCB and CB11CB-nCB, only curves corresponding to NTB-N phase transition are presented. Based on the temperature-concentration range of the existence of NTB phase, it was established that an increase in the alkyl chain length of CBnCB causes an increase in the stability of the NTB phase. But surprisingly, an increase in the alkyl chain length of nCB compounds does not change the slope of the NTB-N equilibrium line on phase diagrams. It is slightly bigger when the nCB compound has the same length of alkyl chain as the length of the linking group of a bismesogen. XRD studies were carried out for two mixtures.

Ion-Pairing Chromonic Liquid Crystals via Alternately Stacked Assembly of Amphiphilic Charged π-Electronic Systems.

In this study, a new assembly strategy for lyotropic chromonic liquid crystals (LCLCs) is proposed using iπ-iπ interactions, mainly comprising electrostatic and dispersion forces, between charged π-electronic systems to form stacking structures supported by the hydration of triethylene glycol (TEG) units.  Meso-TEG-aryl-substituted porphyrin AuIII complex, an amphiphilic π-electronic cation, showed diverse states and assembly modes in ion pairs depending on the coexisting counteranions.  The PCCp- ion pair formed a hexagonal columnar (Colh) LC phase based on a charge-by-charge assembly, suggesting the formation of an ordered arrangement of charged p-electronic systems through iπ-iπ interactions, with reduced interactions between the TEG chains.  Furthermore, in the presence of water, LCLC behaviors in the Colh and nematic columnar phases according to the amount of water were observed for the PCCp- ion pair via iπ-iπ interactions.  Magnetic-field-induced orientation of the charge-by-charge columnar structures upon dehydration was observed.  Furthermore, single-stranded charge-by-charge columnar structures, as components of the LCLCs, were observed using transmission electron microscopy (TEM).

A Multiresponsive Ferrocene-Based Chiral Overcrowded Alkene Twisting Liquid Crystals.

The reversible modulation of chirality has gained significant attention not only for fundamental stereochemical studies but also for numerous applications ranging from liquid crystals (LCs) to molecular motors and machines. This requires the construction of switchable molecules with (multiple) chiral elements in a highly enantioselective manner, which is often a significant synthetic challenge. Here, we show that the dimerization of an easily accessible enantiopure planar chiral ferrocene-indanone building block affords a multi-stimuli-responsive dimer (FcD) with pre-determined double bond geometry, helical chirality, and relative orientation of the two ferrocene motifs in high yield. This intrinsically planar chiral switch can not only undergo thermal or photochemical E/Z isomerization but can also be reversibly and quantitatively oxidized to both a monocationic and a dicationic state which is associated with significant changes in its (chir)optical properties. Specifically, FcD acts as a chiral dopant for cholesteric LCs with a helical twisting power (HTP) of 13 µm-1 which, upon oxidation, drops to near zero, resulting in an unprecedently large redox-tuning of the LC reflection color by up to 84 nm. Due to the straightforward stereoselective synthesis, FcD, and related chiral switches, are envisioned to be powerful building blocks for multi-stimuli-responsive molecular machines and in LC-based materials.

Ionic Liquid Crystals as Chromogenic Materials.

Ionic liquid crystals (ILCs), a class of soft matter materials whose properties can be tuned by the wise pairing of the cation and anion, have recently emerged as promising candidates for different applications, combining the characteristics of ionic liquids and liquid crystals. Among those potential uses, this review aims to cover chromogenic ILCs. In this context, examples of photo-, electro- and thermochromism based on ILCs are provided. Furthermore, thermotropic and lyotropic ionic liquid crystals are also summarised, including the most common chemical and phase structures, as well as the advantages of confining these materials. This manuscript also comprises the following main experimental techniques used to characterise ILCs: Differential Scanning Calorimetry (DSC), Polarised Optical Microscopy (POM) and X-Ray Powder Diffraction (XRD). Chromogenic ILCs can be interesting smart materials for energy and health purposes.

Topology-driven collective dynamics of nematic colloidal entanglement.

Entanglement in a soft condensed matter system is enabled in the form of entangled disclination lines by using colloidal particles in nematic liquid crystals. These topological excitations are manifested as colloidal entanglement at equilibrium. How to further utilize nonequilibrium disclination lines to manipulate colloidal entanglement remains a nontrivial and challenging task. In this work, we use experiments and simulations to demonstrate the reconfigurations of nematic colloidal entanglement in light-driven spatiotemporal evolutions of disclination lines. Colloidal entanglement can sense subtle changes in the topological structures of disclination lines and realize chirality conversion. This conversion is manifested as the "domino effect" of the collective rotation of colloids in the disclination lines. By programming the topological patterns and the geometry of the disclination lines, colloidal entanglement can be assembled and split. More remarkably, a double-helix entangled structure can be formed by controlling the changes in the morphology of the disclination lines. Thus, this work will provide opportunities to program colloidal composites for smart materials and micromachines.

Modulating the Conductivity of Light-Responsive Ionic Liquid Crystals.

In this work, we describe the phase behaviour and the dielectric and conductivity response of new light-responsive ionic liquid crystals, ILCs, which can be applied as controllable electrolytes. The materials include two different dicationic viologens, the asymmetric 6BP18 and the symmetric EV2ON(Tf)2, containing bistriflimide as the counterions, mixed with 5% and 50% molar, respectively, of one new photoresponsive mesogen called CNAzO14. These mixtures exhibit liquid crystal behaviour, light responsiveness through the E-Z photoisomerisation of the azobenzene groups in CNAzO14, and strong dielectric responses. The 5%-CNAzO14/Ev2ON(Tf)2 mixture displays direct current conductivities in the 10-7 S·cm-1 range, which can be increased by a two-fold factor upon the irradiation of UV light at 365 nm. Our findings set the grounds for designing new smart ionic soft materials with nanostructures that can be tuned and used for energy conversion and storage applications.

Comparative computational analysis of orthoconic antiferroelectric liquid crystals: DFT analysis.

CONTEXT: The study undertakes a comparative analysis of four distinct semi-fluorinated chiral Organic Active Ferroelectric Liquid Crystals (OAFLCs). The comparative analysis of the compounds is done by using various parameters, including thermodynamic, non-linear optical, electrical, atomic charge distribution, and atomic orientations. We use optimization algorithms to look at chemical reactivity, electrical properties, intermolecular interactions, and static hyperpolarizability. Sample 4 is the best choice for a wide range of display applications. This research contributes to understanding the nuanced properties of semi-fluorinated chiral OAFLCs and highlights Sample 4's potential for novel applications in display technology, owing to its superior stability and optimized properties. This study helps to enhance our understanding of the comparative analysis of semi-fluorinated chiral OAFLCs for potential advancements in display technologies by incorporating findings from key studies. METHOD: The simulations are performed using density functional theory (DFT) with the B3LYP functional for predicting molecular properties, and Vibrational Energy Distribution Analysis (VEDA) software is used to perform the vibrational analysis of the molecules.

Lyotropic liquid crystal emulsions of LAVR-289: Influence of internal mesophase structure on cytotoxicity and in-vitro antiviral activity.

Emerging and reemerging viruses pose significant public health threats, underscoring the urgent need for new antiviral drugs. Recently, a novel family of antiviral acyclic nucleoside phosphonates (ANP) composed of a 4-(2,4-diaminopyrimidin-6-yl)oxy-but-2-enyl phosphonic acid skeleton (O-DAPy nucleobase) has shown promise. Among these, LAVR-289 stands out for its potent inhibitory effects against various DNA viruses. Despite its efficacy, LAVR-289s poor water solubility hampers effective drug delivery. To address this, innovative delivery systems utilizing lipidic derivatives have been explored for various administration routes. Submicron lyotropic liquid crystals (LLCs) are particularly promising drug carriers for the encapsulation, protection, and delivery of lipophilic drugs like LAVR-289. This study focuses on developing submicron-sized lipid mesophase dispersions, including emulsified L2 phase, cubosomes, and hexosomes, by adjusting lipidic compounds such as Dimodan® U/J, Lecithins E80, and Miglyol® 812 N. These formulations aim to enhance the solubility and bioavailability of LAVR-289. In vitro evaluations demonstrated that LAVR-289-loaded LLCs at a concentration of 1 µM efficiently inhibited vaccinia virus in infected human cells, with no observed cytotoxicity. Notably, hexosomes exhibited the most favorable antiviral outcomes, suggesting that the internal mesophase structure plays a critical role in optimizing the therapeutic efficacy of this drug class.

The Casimir-like effect induced by active nematics.

We consider an active nematic phase and use hydrodynamical equations of it to model the activity as an internal field. The interaction of this field with the nematic director in a confined geometry is included in the Hamiltonian of the system. Based on this model Hamiltonian and the standard field theoretical approach, the Casimir-like force induced between the boundaries of such a confined film is discussed. The force depends on the geometrical shape and the dynamical character of the constituents of our active phase, as well as the anchoring conditions. For homeotropically aligned rod-like particles which in principle tend to align along a planar flow field, extensile activity enhances the attraction present in a thin nematic film. As the film thickness increases the force reduces. Beyond a critical thickness, a planar flow field instantaneous to a bend distortion sets in. Near but below the threshold of this activity-induced instability, the force crosses zero and repulsively diverges right at the critical threshold of this so-called flow instability. For contractile rods, in the same geometry as above, the structure is stable and the Casimir-like force diminishes by an exponential factor as a function of the film thickness. On the other side for a planar director alignment, rod-like contractile particles can induce opposite shear flows at the boundaries creating a splay distortion for the director between the plates. In this configuration, we obtain the same universal pretransitional behavior for the force as above. Vice versa, for extensile rod-like particles in this geometry, the director fluctuations become massive and the Casimir-like force diminishes again by an exponential factor as the film thickness increases. The effect of the active field on thermal fluctuations of the director and the fluctuation-induced Casimir force per area is derived through a "semi"-dynamical approach as well. However, the results of the calculation due to a mathematical sum over the fluctuating modes do not lead to an approved closed form.

Unveiling the structural influence of nematic mesogens on customizable temperature and spectral responses.

Rapid and accurate detection and visualization of temperature variations near the human body hold significant importance. This study presents thermochromic colloids capable of adjusting the detectable temperature range and reflection wavelength over a wide spectrum. The systematic investigation focuses on understanding the influence of the molecular structure of nematic mesogens on the morphological dynamics of cholesteric liquid crystal droplets and their associated thermochromic behaviors. A tunable colorimetric temperature range (i.e., from 10 to 40 °C) and high sensitivity (i.e., Δλ ΔT-1 > 100nm °C-1) are realized through precise modulation of the alkyl chain lengths in cyanobiphenyls molecules, combined with a cholesteryl oleyl carbonate as a chiral dopant. We demonstrate the efficiency of a binary mixture of different mesogens, enabling customized structural colors with desired temperature responses. Finally, inspired by the ability of the octopus to camouflage through the elongation or contraction of its pigment cells, thermochromic droplets are embedded within a polymer matrix, resulting in a portable skin patch that offers quick, reversible, and direct temperature visualization of the human body.

Fine-Tuning the Microstructure and Photophysical Characteristics of Fluorescent Conjugated Copolymers Using Photoalignment and Liquid-Crystal Ordering.

Replicating the microstructural basis and the near 100% excitation energy transfer efficiency in naturally occurring light-harvesting complexes (LHCs) remains challenging in synthetic energy-harvesting devices. Biological photosynthesis regulates active ensembles of light-absorbing and funneling chlorophylls in proteins in response to fluctuating sunlight. Here, use of long-range liquid crystal (LC) ordering to tailor chain orientation and packing structure in liquid crystalline conjugated polymer (LCCP) layers for bio-mimicry of certain structural basis and light-harvesting properties of LHCs is reported. It is found that long-range orientational ordering in an LC phase of poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT) copolymer stabilizes a small fraction of randomly-oriented F8BT nanocrystals dispersed in an amorphous matrix of F8BT chains, resembling a self-doped host-guest system whereby excitation energy funneling and photoluminescence quantum efficiencies are enhanced significantly by triggering 3D donor-to-acceptor Förster resonance energy transfer (FRET) and dominant intrachain emission in the nano-crystal acceptor. Further, photoalignment of nematic F8BT layers is combined with LC orientational ordering to fabricate large-area-extended monodomains exhibiting >60% crystallinity and ≈20 nm-long interchain packing order. Remarkably, these monodomains demonstrate strong linearly polarized emission, whilst also promoting a new band-edge absorption species and an extra emissive interchain excited state as compared to the non-aligned films.

13C CSA Tensors and Orientational Order of Model and Dimer Mesogens Comprising of Phenyl Benzoate.

A Model mesogen and its symmetrical Dimer made up of phenyl benzoate core unit are investigated by 13C NMR spectroscopy. The existence of layer order in smectic A and smectic C phases of Dimer mesogen is established by powder X-ray diffraction. The chemical shift anisotropy (CSA) tensors of Model mesogen are determined by 2D separation of undistorted powder patterns by effortless recoupling (SUPER) experiment and are utilized for calculating the order parameters employing the alignment-induced chemical shifts (AIS). Additionally, 2D separated local field (SLF) NMR is availed for extracting 13C-1H dipolar couplings for both mesogens and used for computing the order parameters. A good agreement in the order parameters calculated from 13C-1H dipolar couplings and AIS is observed. Accordingly, the main order parameter (Szz) for the phenyl rings of the Model mesogen is found to be in the range 0.54 - 0.82, and for the Dimer mesogen, the values span 0.64 - 0.82 across mesophases. Since the phenyl benzoate core unit is frequently employed structural moiety for constructing the main chain as well as side chain liquid crystalline polymers and liquid crystalline elastomers, the CSA tensors reported here will be of immense utility for the structural characterization of these materials.

An Up-to-Date Overview of Liquid Crystals and Liquid Crystal Polymers for Different Applications: A Review.

Liquid crystals have been extensively used in various applications, such as optoelectronic devices, biomedical applications, sensors and biosensors, and packaging, among others. Liquid crystal polymers are one type of liquid crystal material, combining their intrinsic properties with polymeric flexibility for advanced applications in displays and smart materials. For instance, liquid crystal polymers can serve as drug nanocarriers, forming cubic or hexagonal mesophases, which can be tailored for controlled drug release. Further applications of liquid crystals and liquid crystal polymers include the preparation of membranes for separation processes, such as wastewater treatment. Furthermore, these materials can be used as ion-conducting membranes for fuel cells or lithium batteries due to their broad types of mesophases. This review aims to provide an overall explanation and classification of liquid crystals and liquid crystal polymers. Furthermore, the great potential of these materials relies on their broad range of applications, which are determined by their unique properties. Moreover, this study provides the latest advances in liquid crystal polymer-based membranes and their applications, focusing especially on fuel cells. Moreover, future directions in the applications of various liquid crystals are highlighted.

Circularly Polarized Luminescence Chirality Inversion and Dual Anticounterfeiting Labels Based on Fluorescent Cholesteric Liquid Crystal Particles.

The development of materials with circularly polarized luminescence (CPL) properties is a promising but challenging frontier in advanced materials science. Modulating the chiral properties of chiral polymers has also been a focus of research. Studies have been conducted to control the ground-state chirality of chiral polymers by adjusting the concentration of the chiral dopant. However, the chirality inversion of CPL of fluorescent liquid crystal particles by chiral dopant concentration has not been reported. Here, we report the preparation of fluorescent cholesteric liquid crystal (FCLC) particles that display polarizable structural color and CPL, demonstrating how varying the chiral dopant amount can reverse the CPL direction, leading to systems where the rotation directions of polarizable structural color and CPL either align or differ. This study confirmed the critical role played by the formation of the twist grain boundary phase in inducing the inversion of the ground-state chirality of FCLC particles and, subsequently, triggering the inversion process of CPL chirality. Furthermore, it leverages chiral structural color and fluorescence of FCLC particles to develop a sophisticated dual verification system. This system, utilizing both circularly polarized light and fluorescence, offers enhanced anticounterfeiting protection for high-value items.

Are Critical Fluctuations Responsible for Glass Formation?

The dynamic heterogeneities occurring just before the transition to the glassy phase have been named as the cause of amorphization in supercooled systems. Numerous studies conducted so far have confirmed this hypothesis, and based on it, a widely accepted solution to the puzzle of glass transition has been developed. This report focuses on verifying the existence of a strong pretransitional anomaly near the glass transition Tg. For this purpose, supercooled liquid-crystalline systems with a strong rod-like structure were selected. Based on the obtained experimental data, we demonstrate in this article that the previously postulated dynamic heterogeneities exhibit a critical characteristic, meaning a strong pretransitional anomaly can be observed with the described critical exponent α=0.5. Due to this property, it can be concluded that these heterogeneities are critical fluctuations, and consequently, the transition to the glassy state can be described based on the theory of critical phenomena. To measure the pretransitional anomaly near Tg in supercooled liquid-crystalline systems, broadband dielectric spectroscopy (BDS) and nonlinear dielectric effect (NDE) methods were applied. The exponent α provides insight into the nature and intensity of critical fluctuations in the system. A value of α=0.5 suggests that the fluctuations become increasingly intense as the system approaches the critical point, contributing to the divergence in specific heat. Understanding the role of critical fluctuations in the glass transition is crucial for innovating and improving a wide range of materials for energy storage, materials design, biomedical applications, food preservation, and environmental sustainability. These advancements can lead to materials with superior properties, optimized manufacturing processes, and applications that meet the demands of modern technology and sustainability challenges.

Hydrodynamics of a disk in a thin film of weakly nematic fluid subject to linear friction.

To make progress towards the development of a theory on the motion of inclusions in thin structured films and membranes, we here consider as an initial step a circular disk in a two-dimensional, uniaxially anisotropic fluid layer. We assume overdamped dynamics, incompressibility of the fluid, and global alignment of the axis of anisotropy. Motion within this layer is affected by additional linear friction with the environment, for instance, a supporting substrate. We investigate the induced flows in the fluid when the disk is translated parallel or perpendicular to the direction of anisotropy. Moreover, expressions for corresponding mobilities and resistance coefficients of the disk are derived. Our results are obtained within the framework of a perturbative expansion in the parameters that quantify the anisotropy of the fluid. Good agreement is found for moderate anisotropy when compared to associated results from finite-element simulations. At pronounced anisotropy, the induced flow fields are still predicted qualitatively correctly by the perturbative theory, although quantitative deviations arise. We hope to stimulate with our investigations corresponding experimental analyses, for example, concerning fluid flows in anisotropic thin films on uniaxially rubbed supporting substrates.

Liquid crystals from curved colloidal rods: waves, twists and more.

The curvature of elongated microscopic building blocks plays a crucial role on their self-assembly into orientationally ordered phases. While rod-like molecules form a handful of liquid crystal (LC) phases, curved or banana-shaped molecules show more than fifty phases, with fascinating physical properties, such as chirality or polarity. Despite the fundamental and technological importance of these so-called 'banana-shaped liquid crystals', little is known about their microscopic details at the single-molecule level. Curved colloidal liquid crystals-liquid crystals formed by curved colloidal rods-are excellent model systems to optically resolve the structure and dynamics of curved building blocks within these condensed phases. Recent advances in the synthesis of curved rod-like particles have unlocked the potential for studying-at the single-particle level-the intimate relationship between shape and phase symmetry, and even confirmed the stability of elusive LC phases. Further developments in this nascent field promise exciting findings, such as the first observation of the colloidal twist-bend nematic phase or the fabrication of functional materials with curvature-dependent properties. In this Report on Progress, we will highlight recent advances in the synthesis and assembly of curved colloidal liquid crystals and discuss the upcoming challenges and opportunities of this field.