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Photonic metamaterials combined with liquid crystals (LCs) for tunability is a great niche for building miniature devices with high performance such as fast flat tunable lenses, tunable filters, and waveplates. Sub-wavelength or nano-grating surfaces are homogenized to uniaxial waveplates with negative birefringence of unique dispersion when the period is less than the wavelength by at least a few times. This uniaxial metasurface, combined with the LC layer, is shown to act as a tunable retardation achromatic waveplate with 8 μm thick LC layer operating over wide spectral and angular ranges, as compared to using two nematic liquid crystal (NLC) retarders of thicknesses on the order of 30–60 μm, when no metasurface is used. Hence the device becomes miniature and 50× faster due to the thinner liquid crystal layer. The silicon nano-grating of 351 nm pitch and 0.282 fill factor is designed and fabricated to operate in the short-wave infrared range (SWIR). Switching between three achromatic retardation levels: full-, half-, and quarter-waveplates is accomplished by changing the applied voltages on the NLC cell with a switching time of a few milliseconds. This device has applications in fast broadband shutters, low coherence phase shift interferometry, ellipso-polarimetry, dynamic control of light intensity, and smart windows.

Monoolein liquid crystals find use in foods and pharmaceuticals. Our hypotheses were: (a) liquid crystal symmetry dominates yielding and large deformation, and (b) strain rate frequency superposition (SRFS) may be used to determine mesophase long and short relaxation times.Liquid crystal microstructure and rheology were characterised as a function of temperature and composition. Their structure was assessed using small angle X-ray scattering (SAXS) and polarised light microscopy. Small and large deformation rheology was characterised using frequency and amplitude sweeps, large amplitude oscillatory shear tests, and SRFS.We have contributed to the structure-rheology relationship governing the properties of the lamellar, cubic, and hexagonal mesophases. Initially, we characterised a number of monoolein-water binary phase transitions, which showed similar behaviour with earlier efforts. Frequency sweeps revealed that the cubic phases had the highest elasticity followed by the lamellar and hexagonal phases. The stiffening and thickening ratios, extracted from the Lissajous-Bowditch plots, were used to quantify intra-cycle non-linearities. The cubic phases displayed abrupt yielding with more pronounced stiffening and thinning behaviour compared to the others. Each liquid crystal phase displayed unique rheological behaviour upon large deformation and, by linking rheology with SAXS and composition, we show that their symmetry defined their rheology.

Liquid crystals (LCs), discovered more than 130 years ago, are now emerging in the field of biomedicine. This article highlights the recent uses of lipid lyotropic LCs in therapeutics delivery, imaging, and tissue engineering and invites the scientific community to continue exploring the design of more complex LCs.

This review article comprises three contents: 1) a general introduction of liquid crystals (LCs) and their chronological developments until their current status, 2) the descriptions of the achievements of defect-free and optically high-quality LC displays (LCDs), and 3) the description of the new and alternative methods for improving existing LCD technologies in terms of high-speed response, viewing angles, and power consumption through nanoparticle doping and optical compensation on a laboratory level. When these technologies are successfully developed, they will be used in the industry, where the fabrication process will be performed in a large-clean room using automated robotics.

Cell-cell interaction dictates cell morphology and organization, which play a crucial role in the micro-architecture of tissues that guides their biological and mechanical functioning. Here, we investigate the effect of cell density on the responses of cells seeded on flat substrates using a novel statistical thermodynamics framework. The framework recognizes the existence of nonthermal fluctuations in cellular response and thereby naturally captures entropic interactions between cells in monolayers. In line with observations, the model predicts that cell area and elongation decrease with increasing cell seeding density-both are a direct outcome of the fluctuating nature of the cellular response that gives rise to enhanced cell-cell interactions with increasing cell crowding. The modeling framework also predicts the increase in cell alignment with increasing cell density: this cellular ordering is also due to enhanced entropic interactions and is akin to nematic ordering in liquid crystals. Our simulations provide physical insights that suggest that entropic cell-cell interactions play a crucial role in governing the responses of cell monolayers.

Stimuli-responsive materials are crucial to advance controlled delivery systems for drugs and catalysts. Lyotropic liquid crystals (LLCs) have well-defined internal structures suitable to entrap small molecules and can be broken up into low-viscosity dispersions, aiding their application as delivery systems. In this work, we demonstrate the first example of light-responsive cubic LLC dispersions, or cubosomes, using photoswitchable amphiphiles to enable external control over the LLC structure and subsequent on-demand release of entrapped guest molecules. Azobenzene photosurfactants (AzoPS), containing a neutral tetraethylene glycol head group and azobenzene-alkyl tail, are combined (from 10-30 wt %) into monoolein-water systems to create LLC phases. Homogenization of the bulk LLC forms dispersions of particles, ∼200 nm in diameter with internal bicontinuous primitive cubic phases, as seen using small-angle X-ray scattering and cryo-transmission electron microscopy. Notably, increasing the AzoPS concentration leads to swelling of the cubic lattice, offering a method to tune the internal nanoscale structure. Upon UV irradiation, AzoPS within the cubosomes isomerizes within seconds, which in turn leads to squeezing of the cubic lattice and a decrease in the lattice parameter. This squeeze mechanism was successfully harnessed to enable phototriggerable release of trapped Nile Red guest molecules from the cubosome structure in minutes. The ability to control the internal structure of LLC dispersions using light, and the dramatic effect this has on the retention of entrapped molecules, suggests that these systems may have huge potential for the next-generation of nanodelivery.

Three kinds of bent-shaped dimeric molecules are synthesized by fluorine substitution of C16 molecules, and influences of the substitution on the polar smectic phases are examined. The fluorine-substituted C16 molecules form the SmAP

ConspectusBottom-up materials design by the conceiving of new molecular building blocks is powerful and chemists are uniquely qualified to innovate. Liquid crystals (LCs) and related soft crystals, collectively called mesophases, naturally create materials with dynamic properties. The thermotropic LC state has a liquid-like intermolecular disorder, but the cooperative nature of these materials facilitates a long-range directional order (alignment) that couples strongly to applied electric/magnetic fields and interfaces. Thermotropic LCs are held together by mesogen cores, which are often unsaturated with anisotropic polarizability, and are appended with flexible (often

The synthesis of bent-shaped mesogens and mesogenic dimers has renewed the field of liquid crystals in many ways during the previous decades, for example, through the discovery of ‘exotic’ mesophases such as the twist-bend nematic phase and the biaxial SmA phase (SmAb). Recently, we reported on the observation of a SmAb with a bent- shaped dimer, and on its fast electro-optic effect that we interpreted as a biaxial Fréedericksz transition (BFrTr) of the secondary m-director under applied electric field (C. Meyer et al., Phys. Rev. X, 11, 031012 (2021)). In this study, we used dielectric and birefringence techniques to directly measure the splay, Km11, and bend, Km33, elastic constants that characterise the elastic distortion modes of the m-director. We observed that during the BFrTr, domains of opposite tilt appear and are often enclosed in elliptical defect loops, just like those observed during the usual Fréedericksz transition of common nematics, which allowed us to obtain the third (twist) elastic constant Km22, from the defect loop ellipticity. Although Km11 and Km33 are of the same order of magnitude as K11 and K33 in the nematic phase of bent-shaped dimers, Km22 is an order of magnitude smaller than Km11 and Km33 and also than K22 of 5CB. We argue that these features could be generic for the intercalated SmAb phase of bent-shaped dimers.

Liquid crystals (LCs), when supported on reactive surfaces, undergo changes in ordering that can propagate over distances of micrometers, thus providing a general and facile mechanism to amplify atomic-scale transformations on surfaces into the optical scale. While reactions on organic and metal substrates have been coupled to LC-ordering transitions, metal oxide substrates, which offer unique catalytic activities for reactions involving atmospherically important chemical species such as oxidized sulfur species, have not been explored. Here, we investigate this opportunity by designing LCs that contain 4'-cyanobiphenyl-4-carboxylic acid (CBCA) and respond to surface reactions triggered by parts-per-billion concentrations of SO

Biosensing using liquid crystals has a tremendous potential by coupling the high degree of sensitivity of their alignment to their surroundings with clear optical feedback. Many existing set-ups use birefringence of nematic liquid crystals, which severely limits straightforward and frugal implementation into a sensing platform due to the sophisticated optical set-ups required. In this work, we instead utilize chiral nematic liquid crystal microdroplets, which show strongly reflected structural color, as sensing platforms for surface active agents. We systematically quantify the optical response of closely related biological amphiphiles and find unique optical signatures for each species. We detect signatures across a wide range of concentrations (from micromolar to millimolar), with fast response times (from seconds to minutes). The striking optical response is a function of the adsorption of surfactants in a nonhomogeneous manner and the topology of the chiral nematic liquid crystal orientation at the interface requiring a scattering, multidomain structure. We show that the surface interactions, in particular, the surface packing density, to be a function of both headgroup and tail and thus unique to each surfactant species. We show lab-on-a-chip capability of our method by drying droplets in high-density two-dimensional arrays and simply hydrating the chip to detect dissolved analytes. Finally, we show proof-of-principle in vivo biosensing in the healthy as well as inflamed intestinal tracts of live zebrafish larvae, demonstrating CLC droplets show a clear optical response specifically when exposed to the gut environment rich in amphiphiles. Our unique approach shows clear potential in developing on-site detection platforms and detecting biological amphiphiles in living organisms.

Among the three basic states of matter (solid, liquid, and gas), the liquid state has always eluded general theoretical approaches for describing liquid energy and heat capacity. In this Viewpoint, we derive the phonon theory of liquids and biological fluids stemming from Frenkel's microscopic picture of the liquid state. Specifically, the theory predicts the existence of phonon gaps in vibrational spectra of liquids and a thermodynamic boundary in the supercritical state. Direct experimental evidence reaffirming these theoretical predictions was achieved through a combination of techniques using static compression X-ray diffraction and inelastic X-ray scattering on deeply supercritical argon in a diamond anvil cell. Furthermore, these findings inspired and then led to the discovery of phonon gaps in liquid crystals (mesogens), block copolymers, and biological membranes. Importantly, phonon gaps define viscoelastic crossovers in cellular membranes responsible for lipid self-diffusion, lateral molecular-level stress propagation, and passive transmembrane transport of small molecules and solutes. Finally, molecular interactions mediated by external stimuli result in synaptic activity controlling biological membranes' plasticity resulting in learning and memory. Therefore, we also discuss learning and memory effects─equally important for neuroscience as well as for the development of neuromorphic devices─facilitated in biological membranes by external stimuli.

Owing to the rapid and significant progress in advanced materials and life sciences, nanotechnology is increasingly gaining in popularity. Among numerous bio-mimicking carriers, inverse lyotropic liquid crystals are known for their unique properties. These carriers make accommodation of molecules with varied characteristics achievable due to their complicated topologies. Besides, versatile symmetries of inverse LCNPs (lyotropic crystalline nanoparticles) and their aggregating bulk phases allow them to be applied in a wide range of fields including drug delivery, food, cosmetics, material sciences etc. In this review, in-depth summary, discussion and outlook for inverse lyotropic liquid crystals are provided.

In NMR spectroscopy, residual dipolar couplings (RDCs) have emerged as one of the most exquisite probes of biological structure and dynamics. The measurement of RDCs relies on the partial alignment of the molecule of interest, for example by using a liquid crystal as a solvent. Here, we establish bacterial type 1 pili as an alternative liquid-crystalline alignment medium for the measurement of RDCs. To achieve alignment at pilus concentrations that allow for efficient NMR sample preparation, we elongated wild-type pili by recombinant overproduction of the main structural pilus subunit. Building on the extraordinary stability of type 1 pili against spontaneous dissociation and unfolding, we show that the medium is compatible with challenging experimental conditions such as high temperature, the presence of detergents, organic solvents or very acidic pH, setting it apart from most established alignment media. Using human ubiquitin, HIV-1 TAR RNA and camphor as spectroscopic probes, we demonstrate the applicability of the medium for the determination of RDCs of proteins, nucleic acids and small molecules. Our results show that type 1 pili represent a very useful alternative to existing alignment media and may readily assist the characterization of molecular structure and dynamics by NMR., Angewandte Chemie. International Edition, ISSN:1433-7851, ISSN:1521-3773, ISSN:0570-0833

We present in situ calorimetry, thermal conductivity, and thermal diffusivity measurements of materials using temperature-sensing optical wireless integrated circuits (OWiCs). These microscopic and untethered optical sensors eliminate input wires and reduce parasitic effects. Each OWiC has a mass of ∼100 ng, a 100-μm-scale footprint, and a thermal response time of microseconds. We demonstrate that they can measure the thermal properties of nearly any material, from aerogels to metals, on samples as small as 100 ng and over thermal diffusivities covering four orders of magnitude. They also function over a broad temperature range, and we present proof-of-concept measurements of the thermodynamic phase transitions in both liquid crystal 5CB and gadolinium.

Funding: Engineering and Physical Sciences Research Council - EP/P010482/1; Leverhulme Trust - RPG-2016-047; Royal Society - SRF\R1\201089; China Scholarship Council - 201603780001; Horizon 2020 Framework Programme - 838885; Fonds De La Recherche Scientifique - FNRS - 2.5020.11; Fonds De La Recherche Scientifique - FNRS - F.4534.21; Horizon 2020 Framework Programme - 101023743. The use of thermally activated delayed fluorescence (TADF) emitters and emitters that show preferential horizontal orientation of their transition dipole moment (TDM) are two emerging strategies to enhance the efficiency of OLEDs. We present the first example of a liquid crystalline multi-resonance TADF (MR-TADF) emitter, DiKTa-LC. The compound possesses a nematic liquid crystalline phase between 80 °C and 110 °C. Importantly, the TDM of the spin-coated film shows preferential horizontal orientation, with an anisotropy factor, a, of 0.28, which is preserved in doped poly(vinylcarbazole) films. Green-emitting (λEL = 492 nm) solution-processed OLEDs based on DiKTa-LC showed an EQEmax of 13.6%. We thus demonstrate for the first time how self-assembly of a liquid crystalline TADF emitter can lead to the so-far elusive control of the orientation of the transition dipole in solution-processed films, which will be of relevance for high-performance solution-processed OLEDs. Publisher PDF

Recent studies have suggested that liquid crystal monomers (LCMs) are emerging contaminants in the environment, and knowledge of this class of substances is very rare. Here, we reviewed existing LCM-related documents, i.e., publications and patents, and established a database involving 1173 LCMs. These 1173 LCMs were further calculated for their physicochemical properties, i.e., persistence (P), bioaccumulation (B), long-range transport potential (LRTP), and Arctic contamination and bioaccumulation potential (ACBAP). We found that 476 out of them were PB chemicals (99% of them were halogenated), and 320 of them could have ACBAP properties (67% of them were halogenated). This LCM database was further applied for suspect screening of LCMs in

The liquid crystal properties and viscoelasticity of the natural bone extracellular matrix (ECM) play a decisive role in guiding cell behavior, conducting cell signals, and regulating mineralization. Here, we develop a facile approach for preparing a novel polysaccharide hydrogel with liquid crystal properties and viscoelasticity similar to those of natural bone ECM. First, a series of chitin whisker/chitosan (CHW/CS) hydrogels were prepared by chemical cross-linking with genipin, in which CHW can self-assemble to form cholesteric liquid crystals under ultrasonic treatment and CS chains can enter into the gaps between the helical layers of the CHW cholesteric liquid crystal phase to endow morphological stability and good mechanical properties. Subsequently, the obtained chemically cross-linked liquid crystal hydrogels were immersed into the desired concentration of the NaCl solution to form physical cross-linking. Due to the Hofmeister effect, the as-prepared dual-cross-linked liquid crystal hydrogels showed an enhanced modulus, viscoelasticity similar to that of natural ECM with relatively fast stress relaxation behavior, and fold surface morphology. Compared to both CHW/CS hydrogels without liquid crystal properties and CHW/CS liquid crystal hydrogels without further physical cross-linking, the dual-cross-linked CHW/CS liquid crystal hydrogels are more favorable for the adhesion, proliferation, and osteogenic differentiation of bone marrow mesenchymal stem cells. This approach could inspire the design of hydrogels mimicking the liquid crystal properties and viscoelasticity of natural bone ECM for bone repair.

A supramolecular, lyotropic liquid crystalline alignment medium based on an azobenzene‐containing 1,3,5‐benzenetricarboxamide (BTA) building block is described and investigated. As we demonstrate, this water‐based system is suitable for the investigation of various water‐soluble analytes and allows for a scaling of alignment strength through variation of temperature. Additionally, alignment is shown to reversibly collapse above a certain temperature, yielding an isotropic solution. This collapse allows for isotropic reference measurements, which are typically needed in addition to those in an anisotropic environment, to be performed using the same sample just by varying the temperature. The medium described thus provides easy access to anisotropic NMR observables and simplifies structure elucidation techniques based thereon.

We demonstrate a facile method to fabricate a recyclable cell-alignment scaffold using nanogrooves based on sublimable liquid crystal (LC) material. Randomly and uniaxially arranged smectic LC structures are obtained, followed by sublimation and recondensation processes, which directly produce periodic nanogrooves with dimensions of a couple of hundreds of nanometers. After treatment with osmium tetroxide (OsO

Refereed/Peer-reviewed Chronic Pseudomonas aeruginosa wound infections are highly prevalent and often untreatable due to biofilm formation, resulting in high antimicrobial tolerance. Standard antibiotic therapy for P. aeruginosa infections involves tobramycin, yet it is highly ineffective as monotherapy as tobramycin cannot penetrate the biofilm to elicit its antimicrobial effect. Lipid liquid crystal nanoparticles (LCNPs) have previously been shown to increase the antimicrobial efficacy and penetration of tobramycin against P. aeruginosa biofilms in vitro and ex vivo. Here, for the first time, we have developed a chronic P. aeruginosa biofilm infection in full-thickness wounds in mice to examine the potential of LCNPs to improve the effect of tobramycin, preclinically. After three doses, administered once a day, tobramycin-LCNPs significantly reduced the P. aeruginosa bacterial load in murine wounds 1000-fold more than unformulated tobramycin, which in turn showed no significant difference to the saline control treatment. Consistent with the improved P. aeruginosa eradication, the tobramycin-LCNPs promoted wound healing. In comparison to previous in vitro and ex vivo data, we show a strong in vitro-in vivo correlation between P. aeruginosa biofilm infection models. The enhanced activity of tobramycin-LCNPs in vivo in the preclinical murine model demonstrates the strong potential of LCNPs as a next-generation formulation approach to improve the efficacy of tobramycin against P. aeruginosa biofilm wound infections.

To address the need for localized chemotherapy against unresectable solid tumors, an injectable in situ depot-forming lipidic lyotropic liquid crystal system (L3CS) is explored that can provide spatiotemporal control over drug delivery. Although liquid crystals have been studied extensively before but their application as an injectable intratumoral depot system for locoregional chemotherapy has not been explored yet. The developed L3CS in the present study is a low-viscosity injectable fluid having a lamellar phase, which transforms into a hexagonal mesophase depot system on subcutaneous or intratumoral injection. The transformed depot system can be preprogrammed to provide tailored drug release intratumorally, over a period of one week to one month. To establish the efficacy of the developed L3CS, doxorubicin is used as a model drug. The drug release mechanism is studied in detail both in vitro and in vivo, and the efficacy of the developed system is investigated in the murine 4T1 tumor model. The direct intratumoral injection of the L3CS provided localized delivery of doxorubicin inside the tumor and restricted its access within the tumor only for a sustained period of time. This led to an over 10-fold reduction in tumor burden, reduced cardiotoxicity, and a significant increase in the median survival rate, compared to the control group. The developed L3CS thus provides an efficient strategy for localized chemotherapy against unresectable solid tumors with a great degree of spatial and temporal control over drug delivery.

Liquid crystal monomers (LCMs) in liquid crystal displays (LCDs) may be released into the environment, especially in electronic waste (e-waste) recycling industrial parks with a high pollution risk. However, little has been known about the environmental release and human exposure to LCMs until now. Herein, a total of 45 LCMs were detected in LCDs of commonly used smartphones and computers by high-resolution mass spectrometry with suspect screening analysis. Fluorinated biphenyls and their analogs were the dominant LCMs. Based on available standards of the screening results and previous studies, 55 LCMs were quantified in samples from an e-waste recycling industrial park in Central China. The LCMs were frequently detected in outdoor dust (

Nematic liquid crystal (LC) droplets have been widely used for the detection of molecular species. We investigate the response of micrometer sized nematic LC droplets against the adsorption of nanoparticles from aqueous media. We synthesized ti 100 nm-in-diameter silica nanoparticles and modified their sur-faces to mediate either planar or homeotropic LC anchoring and a pH-dependent charge. We show sur -face functionality-and concentration-dependent configurations of the droplets consistent with the change in the surface anchoring and the formation of local heterogeneities upon adsorption of the nanoparticles to LC-aqueous interfaces. The adsorption of nanoparticles modified with dimethyloctadecyl [3-(trimethoxysilyl) propyl] ammonium chloride (DMOAP, homeotropic) exhibit a transition from bipolar to radial, whereas the adsorption of -COOH-terminated counterparts (planar) did not cause a configura-tion transition. By manipulating the electrostatic interactions, we controlled the adsorption of the nanoparticles to the LC-aqueous interfaces, providing access to the physicochemical properties of the nanoparticles. We demonstrate a temporal change in the droplet configurations caused by the adsorption of the nanoparticles functionalized with -COOH/DMOAP mixed monolayers. These results provide a basis for studies in applications for the detection of nano-sized species, for sensing applications that combine nanoparticles with LCs, and for the synthesis of anisotropic composite particles with complex structures. (c) 2021 Elsevier Inc. All rights reserved.

Introducing polymerizable monomers into a binary hexagonal lyotropic liquid crystalline (LLC) template is a straightforward way for retaining the nanostructure but will decrease attractive intra- and inter- aggregate interactions. It is therefore crucial to understand the interfacial interactions at nanoscale after introducing the monomers but prior to polymerization. Herein, active species, poly (ethylene glycol) diacrylate (PEGDA) and 2-hydroxyethyl methacrylate (HEMA), were introduced into hexagonal LLC of dodecyl trimethylammonium bromide and water to explore the structural variables, dimensional stability, and dynamic property. At a proper volume ratio of PEGDA/HEMA (1/4), the system presents excellent homogeneity with a higher dimensional stability and lower dynamic property from rheological assessments, thereby achieving robust, free-standing, and transparent membranes after photo-polymerization. The unique property of the system also lies in the much lower order–disorder transition temperature (45 °C) that facilitates the reorientation of mesochannels. They are in contrast inaccessible for the ternary system only with PEGDA, though the nanostructure for both systems could be retained. An insight into subtle variations in these parameters allows us to prepare a polymerizable template possessing higher dimensional stability and suitable flexibility via molecular design, thereby enabling simultaneous structural alignment and retention for the development of functional nanomaterials.

An untethered, soft robot using liquid crystal elastomer (LCE) actuators, onboard power, and wireless Bluetooth control was developed. LCE actuators were thermally triggered using Joule heating and demonstrated an ∼5 N force pull capacity per LCE. A20% repeatable strain was demonstrated over100 cycles with minimal loss of strain at high cycle numbers. The LCE actuators were horizontally oriented to maximize conversion of LCE contraction to overall robot movement. A battery and control board were integrated into the body of the robot, which allowed for Bluetooth control of the LCE on/off cycle. System level programming and design were implemented to offset the slow recovery associated with LCE actuators. The multiple LCE actuator legs were programmed to allow individual control of on/off cycles for each leg. LCE leg actuation was alternated between inner and outer legs to provide horizontal movement with minimized loss of motion during the LCE recovery cycle by actuating one set of legs during the recovery cycle of the other set for a maximum movement speed of 1.27 cm/min. Path control was also demonstrated by turning the robot by actuating two LCE legs on one side of the robot. The robot was able to pull up to 1400 g in ideal frictional conditions, allowing the possibility of payload transport, additional battery storage, or onboard sensors. Additional design considerations are discussed to further improve overall robot speed in the future by combining system and material level design considerations.

Liquid crystal elastomers (LCEs) play role in tissue engineering investigations, with the combination of orientational ordering generated by liquid crystal (LC) moieties and the elastic capabilities of polymers. Liquid crystal-based polymer materials require a thorough understanding of their features that set them apart from other smart materials for proper design and application. LCEs offer many advantages for their widespread use in the field of biomaterials, by virtue of their simplicity of processing, anisotropic behavior, and responding to numerous external stimuli. Especially, LCEs have widespread usage in bioengineering applications such as scaffolds due to their biocompatibility, viability, and proliferation properties of these materials. This study introduces a brief overview of the new areas of liquid crystal-based elastomer applications combining both biomaterials and engineering.

Oriented arrays of nanofibers are ubiquitous in nature and have been widely used in recreation of the biological functions such as bone and muscle tissue regenerations. However, it remains a challenge to produce nanofiber arrays with a complex organization by using current fabrication techniques such as electrospinning and extrusion. In this work, we propose a method to fabricate the complex organization of nanofiber structures templated by a spatially varying ordered liquid crystal host, which follows the pattern produced by a maskless projection display system. By programming the synchronization of the rotated polarizer and projected segments with different shapes, various configurations of nanofiber organization ranging from a single to two-dimensional lattice of arbitrary topological defects are created in a deterministic manner. The nanofiber arrays can effectively guide and promote neurite outgrowth. The application of nanofibers with arced profiles and topological defects on neural tissue organization is also demonstrated. This finding, combined with the versatility and programmability of nanofiber structures, suggests that they will help solve challenges in nerve repair, neural regeneration, and other related tissue engineering fields.

Liquid crystal elastomers (LCEs) with large deformation under external stimuli have attracted extensive attention in various applications such as soft robotics, 4D printing, and biomedical devices. However, it is still a great challenge to reduce the damage to collimation and enhance the mechanical and actuation properties of LCEs simultaneously. Here, we construct a new method of a double cross-linking network structure to improve the mechanical properties of LCEs. The ureidopyrimidinone (UPy) group with quadruple hydrogen bonds was used as the physical cross-linking unit, and pentaerythritol tetra(3-mercaptopropionate) was used as the chemical cross-link. The LCEs showed a strong mechanical tensile strength of 8.5 MPa and excellent thermally induced deformation (50%). In addition, the introduction of quadruple hydrogen bonds endows self-healing ability to extend the service life of LCEs. This provides a generic strategy for the fabrication of high-strength LCEs, inspiring the development of actuators and artificial muscles.

We report colloidally stable emulsions of thermotropic liquid crystals (LCs) that can detect the presence of amphiphilic analytes in aqueous environments. Our approach makes use of a Pickering stabilization strategy consisting of surfactant-nanoparticle complexes (SiO

Suspensions of microswimmers in liquid crystals demonstrate remarkably complex dynamics and serve as a model system for studying active nematics. So far, experimental realization of microswimmers suspended in liquid crystalline media has relied on biological microorganisms that impose strict limitations on the compatible media and makes it difficult to regulate activity. Here, we demonstrate that acoustically powered bubble microswimmers can efficiently self-propel in a lyotropic liquid crystal. The velocity of the swimmers is controlled by the amplitude of the acoustic field. Histograms of swimming directions with respect to the local nematic field reveal a bimodal distribution: the swimmers tend to either fully align with or swim perpendicular to the director field of the liquid crystal, occasionally switching between these two states. The bubble-induced streaming from a swimmer locally melts the liquid crystal and produces topological defects at the tail of the swimmer. We show that the defect proliferation rate increases with the angle between the swimmer's velocity and the local orientation of the director field.

Herein, a signal-on liquid crystal microarray (LCM) sensor is designed for the first time with a micro-spectral optical sensing signal. Depending on the change of the orientation of the LC molecules in the LCM films and the intensity of the spectral peaks of the PhCs, the signal-on LCM biosensor achieves the detection of AFB1 and the Partial Response Mechanism (PSM) of the LCM films is discovered.

As a toxic substance, ammonia can cause serious irritation to the human respiratory system and lungs. Although many detection techniques have been reported, most of them have drawbacks, such as expensive devices and complex and time-consuming fabrication processes. Thus, it is important to develop a simple method for ammonia detection. In this paper, we demonstrate a highly sensitive fluorescent sensor for ammonia detection based on aggregation-induced emission luminogen-doped liquid crystals without the use of polarizers. The homeotropic orientation of the liquid crystals on a modified substrate can be disturbed by ammonia, resulting in the fluorescence intensity change of an aggregation-induced emission luminogen. This aggregation-induced emission luminogen-doped liquid crystal-based fluorescent sensor for ammonia detection exhibited a low detection limit of 5.4 ppm, which is 3 times lower than previously reported liquid crystal-based optical sensors. The detection range is also broad from 0 ppm to 1600 ppm. Meanwhile, this sensor can be applied to detect aqueous ammonia with a low limit of detection of 1.8 ppm. The proposed fluorescent sensor for ammonia detection based on an aggregation-induced emission luminogen-doped liquid crystal is highly sensitive, highly selective, simple, and low cost with wide potential applications in chemical and biological fields. This strategy of designing a liquid crystal fluorescent sensor provides an inspiring stage for other toxic chemical substrates by changing specific decorated molecules.

Microlasers integrated with biological systems have received tremendous attention for their intense light intensity and narrow linewidth recently, serving as a powerful tool for studying complex dynamics and interactions in scattered biological micro-environments. However, manipulation of microlasers with controllable motions and versatile functions remains elusive. Herein, we introduce the concept of motor-like microlasers formed by magnetic-doped liquid crystal droplets, in which the direction and velocity could be controlled by altering internal magnetic nanoparticles or external magnetic fields. Both translational and rotatory motions of the lasing resonator could be continually changed in real-time. Lasing-encoded motors carrying different functions and lasing wavelengths were also achieved. Finally, we demonstrate the potential of motor-like microlasers by functioning as a localized stimulation emission light source to stimulate or illuminate living cells, providing a novel approach for switching on/off light emissions and subcellular imaging. Laser emitting micromotors offer a facile system for precise manipulation of microlasers in biological fluids, providing new insight into the development of programmable on-chip laser devices and laser-emitting intelligent systems. Agency for Science, Technology and Research (A*STAR) Published version We would like to thank the support from China Scholarship Council (Grant No. 202006250152). All the authors would like to acknowledge the support from A*STAR. This research is supported by A*STAR under its AME IRG Grant (Project No. A20E5c0085).

Pore-forming toxins (PFTs) produced by pathogenic bacteria serve as prominent virulence factors with potent cell-killing activity. Most of the β-barrel PFTs form transmembrane oligomeric pores in the membrane lipid bilayer in the presence of cholesterol. The pore-formation mechanisms of the PFTs highlight well-orchestrated regulated events in the membrane environment, which involve dramatic changes in the protein structure and organization. Also, concerted crosstalk between protein and membrane lipid components appears to play crucial roles in the process. Membrane-damaging lesions formed by the pore assembly of the PFTs would also be expected to impose drastic alterations in the membrane organization, details of which remain obscure in most of the cases. Prior reports have established that aqueous interfaces of liquid crystals (LCs) offer promise as responsive interfaces for biomolecular events (at physiologically relevant concentrations), which can be visualized as optical signals. Inspired by this, herein, we sought to understand the lipid membrane interactions of a β-barrel PFT

Absorption measurements allow the orientational order parameter of four dyes in the lyotropic chromonic liquid crystal di-sodium cromoglycate (DSCG) to be determined. The dye order parameters are small, except for dyes that intercalate between the DSCG molecules of the rod-like assemblies. The dye order parameters decrease with increasing temperature faster than the nematic order parameter of the DSCG assemblies. For intercalating dyes, the measured dye order parameter varies with the wavelength of the measurement because both intercalated and non-intercalated dye molecules contribute. On the contrary, measurements of the dye order parameter using fluorescence are sensitive only to intercalated dye molecules and produce values that reflect the order parameter of the DSCG assemblies. Therefore, the temperature and concentration dependence of the DSCG order parameter is also explored, since data of this kind on this often-studied system are lacking. Finally, the association constant of one of the intercalating dyes with the DSCG assemblies is determined, yielding a value considerably less than what is found for the same dye with DNA.

The authors report a self-oriented beacon liquid crystal (LC) biosensor for kanamycin (Kana) detection with gold nanoparticle (AuNPs) signal enhancement. In this study, an assay was proposed for Kana detection using the aptamer as a self-oriented beacon. Without an additional orientation agent, the Kana aptamer was used as a self-oriented beacon both as an orientation agent for the LCs and as a signal recognition probe for biological molecules. Gold nanoparticles are blended with desired concentrations of the target molecules, which can greatly improve the performance of the biosensor. In the presence of Kana, AuNPs-Kana-aptamer conjugates will form on the sensing interface of the biosensor, which can remarkably destroy the orientated arrangement of the LCs, resulting in changes in the corresponding polarized images of the LCs. The limit of Kana detection is as low as 0.1 pmol L

Self-assembly of rod-like molecules with sticky ends (blue) and lateral chains (red) depending on chain volume and strength of core-chain segregation, forms honeycombs with triangular (p6mm), rectangular (c2mm), and square (p4mm) cells.

A newly developed LC command system can be used as a secret pattern indicator. Encrypted military operation is deciphered by adjusting the polarizer configuration.

Funder: Chinese Scholarship Council : Cambridge Scholarship, Funder: Croucher Foundation : Cambridge International Scholarship, Hydroxypropyl cellulose (HPC) is a widely commercialized cellulose derivative. While it is typically used as a binder or stabilizer for foods and pharmaceuticals, it can also form a cholesteric liquid crystal in aqueous solution. Moreover, at high HPC concentrations this lyotropic and thermotropic mesophase is known to reflect structural color. However, it remains a challenge to retain this vibrant coloration into the solid state. Here, by combining the emulsification of a HPC mesophase with drying at elevated temperature, we produce solid microparticles that can reflect color across the visible spectrum, from blue to green and red. This method provides a facile and scalable pathway to fabricate structurally colored, edible pigments, which can displace existing synthetic additives used in a wide range of foods and cosmetics.

Advances of liquid crystalline and anisotropic materials chemistry in Belarus are discussed and considered using examples of synthetic approaches developed in recent decades. It was shown that anisotropic and liquid crystalline compounds can be obtained using targeted transformations of the corresponding 3,6-disubstituted cyclohex-2-enones, trans-2,5-disubstituted cyclohexanones, 5-substituted cyclohexane-1,3-diones, 3,5-disubstituted 2-isoxazolines, 1,2-disubstituted cyclopropanols and unsaturated epoxyketones.

POCI-01-0145-FEDER-007688 UIDB/50025/2020-2023 EUTOPIA CA17139 Cellulose-based thermotropic and lyotropic liquid crystals can be obtained from macromolecules or colloidal particles, such as cellulose nanocrystals. Thermotropic liquid crystals are produced by the effect of temperature, while lyotropic liquid crystals occur in solution for a given range of concentration, pressure, and temperature. Cellulose liquid crystals can form chiral nematic phases characterized by Bragg-type reflections of circularly polarized light. This characteristic is related to a helical structure formed by pseudo nematic layers twisted around an optical axis. The helical structure is characterized by the values of pitch and helicity. The later can be right- (R) or left- (L) handed. Cellulose liquid crystals are well described in literature. They are a source of materials for many applications, including the production of photonic chiral materials. Although many questions remain unanswered such as the origin of helicity of cellulosic chiral structures and those related to out-ofequilibrium systems. In this paper, we are focused at the out-of-equilibrium systems obtained from lyotropic cellulose-based liquid crystals. The development of colorful patterns involving the pitch variation in space and time of self-organized cellulose cholesteric structures is revised. publishersversion published

In contrast to conventional hard actuators, soft actuators offer many vivid advantages, such as improved flexibility, adaptability, and reconfigurability, which are intrinsic to living systems. These properties make them particularly promising for different applications, including soft electronics, surgery, drug delivery, artificial organs, or prosthesis. The additional degree of freedom for soft actuatoric devices can be provided through the use of intelligent materials, which are able to change their structure, macroscopic properties, and shape under the influence of external signals. The use of such intelligent materials allows a substantial reduction of a device's size, which enables a number of applications that cannot be realized by externally powered systems. This review aims to provide an overview of the properties of intelligent synthetic and living/natural materials used for the fabrication of soft robotic devices. We discuss basic physical/chemical properties of the main kinds of materials (elastomers, gels, shape memory polymers and gels, liquid crystalline elastomers, semicrystalline ferroelectric polymers, gels and hydrogels, other swelling polymers, materials with volume change during melting/crystallization, materials with tunable mechanical properties, and living and naturally derived materials), how they are related to actuation and soft robotic application, and effects of micro/macro structures on shape transformation, fabrication methods, and we highlight selected applications.

This work established a liquid crystal (LC) aptasensor for simple and rapid detection of ibuprofen, a typical pharmaceuticals and personal care products (PPCPs) pollutant. A negatively charged DNA aptamer specific for ibuprofen and a positively charged amphiphilic surfactant, hexadecyltrimethylammonium bromide (CTAB), were incubated with the sample and then directly added onto the LC interface. In the presence of ibuprofen, the specific binding of ibuprofen with the DNA aptamer will release CTAB, which then adsorbed at the LC-aqueous interface and induced the orientational change of LCs to homeotropic orientation with a dark optical signal output. While in the absence of ibuprofen, the DNA aptamer binds with CTAB through hydrophobic and electrostatic interactions, LCs remained in the planar orientation with a bright optical signal output. This LC aptasensor also has good specificity for ibuprofen and can even detect ibuprofen drug in tap water. Moreover, the response time of the LC aptasensor is fast in minutes. Additionally, this LC aptasensor benefits in monitoring the water quality and inspires the exploration of a general platform for PPCPs detection.

Smart soft materials are envisioned to be the building blocks of the next generation of advanced devices and digitally augmented technologies. In this context, liquid crystals (LCs) owing to their responsive and adaptive attributes could serve as promising smart soft materials. LCs played a critical role in revolutionizing the information display industry in the 20th century. However, in the turn of the 21st century, numerous beyond-display applications of LCs have been demonstrated, which elegantly exploit their controllable stimuli-responsive and adaptive characteristics. For these applications, new LC materials have been rationally designed and developed. In this Review, we present the recent developments in light driven chiral LCs, i.e., cholesteric and blue phases, LC based smart windows that control the entrance of heat and light from outdoor to the interior of buildings and built environments depending on the weather conditions, LC elastomers for bioinspired, biological, and actuator applications, LC based biosensors for detection of proteins, nucleic acids, and viruses, LC based porous membranes for the separation of ions, molecules, and microbes, living LCs, and LCs under macro- and nanoscopic confinement. The Review concludes with a summary and perspectives on the challenges and opportunities for LCs as smart soft materials. This Review is anticipated to stimulate eclectic ideas toward the implementation of the nature's delicate phase of matter in future generations of smart and augmented devices and beyond.

Responsive functional composite fibre mats that are mechanically stable and impervious to water exposure are produced by coaxial electrospinning of thermotropic liquid crystal (LC) core inside a water-based solution of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) forming the sheath. Because thermotropic LCs usually cannot be spun inside water-based solutions due to excessive interfacial tension (Formula presented.), a n enabling step is the addition of ethanol or dioxane to the LC as a co-solvent compatible with both core and sheath fluids. This reduces (Formula presented.) sufficiently that coaxial jet spinning is possible. After spinning, thermal cross-linking of the PVA+PAA sheath yields LC-functionalised fibres that can be manipulated by hand and remain intact even upon full immersion in water. The LC core retains its behaviour, nematics showing well-aligned birefringence and transitioning to isotropic upon heating above the clearing point, and cholesterics showing selective reflection which is even enhanced upon water immersion due to the removal of sheath scattering. Our results pave the way to producing LC-functionalised responsive fibre mats using durable polymer sheaths, thereby enabling numerous innovative applications in wearable technology, and they also open new opportunities to study LCs in confinement, without visible impact of the container walls.

Physical interfaces widely exist in nature and engineering. Although the formation of passive interfaces is well elucidated, the physical principles governing active interfaces remain largely unknown. Here, we combine simulation, theory, and cell-based experiment to investigate the evolution of an active–active interface. We adopt a biphasic framework of active nematic liquid crystals. We find that long-lived topological defects mechanically energized by activity display unanticipated dynamics nearby the interface, where defects perform “U-turns” to keep away from the interface, push the interface to develop local fingers, or penetrate the interface to enter the opposite phase, driving interfacial morphogenesis and cross-interface defect transport. We identify that the emergent interfacial morphodynamics stems from the instability of the interface and is further driven by the activity-dependent defect–interface interactions. Experiments of interacting multicellular monolayers with extensile and contractile differences in cell activity have confirmed our predictions. These findings reveal a crucial role of topological defects in active–active interfaces during, for example, boundary formation and tissue competition that underlie organogenesis and clinically relevant disorders.

Transport of ions through solid polymeric electrolytes (SPEs) involves a complicated interplay of ion solvation, ion-ion interactions, ion-polymer interactions, and free volume. Nonetheless, prevailing viewpoints on the subject promote a significantly simplified picture, likening ion transport in a polymer to that in an unstructured fluid at low solute concentrations. Although this idealized liquid transport model has been successful in guiding the design of homogeneous electrolytes, structured electrolytes provide a promising alternate route to achieve high ionic conductivity and selectivity. In this perspective, we begin by describing the physical origins of the idealized liquid transport mechanism and then proceed to examine known cases of decoupling between the matrix dynamics and ionic transport in SPEs. Specifically we discuss conditions for "decoupled" mobility that include a highly polar electrolyte environment, a percolated path of free volume elements (either through structured or unstructured channels), high ion concentrations, and labile ion-electrolyte interactions. Finally, we proceed to reflect on the potential of these mechanisms to promote multivalent ion conductivity and the need for research into the interfacial properties of solid polymer electrolytes as well as their performance at elevated potentials.

Formation of high viscous inverse lyotropic liquid crystalline phases in situ upon exposure of low viscous drug-loaded lipid preformulations to synovial fluid provides a promising approach for design of depot formulations for intra-articular drug delivery. Rational formulation design relies on a fundamental understanding of the synovial fluid-mediated dynamic structural transitions occurring at the administration site. At conditions mimicking the in vivo situation, we investigated in real-time such transitions at multiple positions by synchrotron small-angle X-ray scattering (SAXS) combined with an injection-cell. An injectable diclofenac-loaded quaternary preformulation consisting of 72/8/10/10% (w/w) glycerol monooleate/1,2-dioleoyl-glycero-3-phospho-rac-(1-glycerol)/ethanol/water was injected into hyaluronic acid solution or synovial fluid. A fast generation of a coherent drug depot of inverse bicontinuous Im3m and Pn3m cubic phases was observed. Through construction of 2D spatial maps from measurements performed 60 min after injection of the preformulation, it was possible to differentiate liquid crystalline rich- and excess hyaluronic acid solution- or synovial fluid-rich regimes. Synchrotron SAXS findings confirmed that the exposure of the preformulation to the media leads to alterations in structural features in position- and time-dependent manners. Effects of biologically relevant medium composition on the structural features, and implications for development of formulations with sustained drug release properties are highlighted.

Statement of problem Because few 3D-printing resins have been specifically developed for liquid crystal display (LCD) 3D printers, mono-LCD users may use digital light processing (DLP) 3D-printing resins. However, the suitability of these resins requires evaluation. Purpose The purpose of this in vitro study was to evaluate whether 3D-printing resins designed for DLP 3D printers can be used successfully in a mono-LCD 3D printer. Material and methods 3D printers based on photopolymerization and 3D-printing resin for interim restorations were used in this study. Enlighten AA temp and NextDent C&B MFH were printed from both the MiiCraft Ultra 125 and Phrozen Sonic printers, followed by postpolymerization by using the FormCure and PhrozenCure units for different times. The flexural strength and cytotoxicity of the specimens were evaluated. Results After postpolymerization treatment, the flexural strength of Enlighten AA temp and NextDent C&B MFH from both 3D printers was over the 50-MPa minimal requirement for the flexural strength of interim resins specified in the International Standards Organization (ISO) 10477 standard. With 15 minutes of FormCure and 1 minute of PhrozenCure postpolymerization, 4 material-printer combinations reached nearly 100% in cell viability. Conclusions Interim resins designed for DLP 3D printers can be successfully used in mono-LCD 3D printers if the printed specimens are postpolymerized in a more powerful postpolymerization unit or in a less powerful postpolymerization unit for a longer time.