Spontaneous symmetry breaking in polar fluids.

Spontaneous symmetry breaking and emergent polar order are each of fundamental importance to a range of scientific disciplines, as well as generating rich phase behaviour in liquid crystals (LCs). Here, we show the union of these phenomena to lead to two previously undiscovered polar liquid states of matter. Both phases have a lamellar structure with an inherent polar ordering of their constituent molecules. The first of these phases is characterised by polar order and a local tilted structure; the tilt direction processes about a helix orthogonal to the layer normal, the period of which is such that we observe selective reflection of light. The second new phase type is anti-ferroelectric, with the constituent molecules aligning orthogonally to the layer normal. This has led us to term the phases the Sm C P H and SmAAF phases, respectively. Further to this, we obtain room temperature ferroelectric nematic (NF) and Sm C P H phases via binary mixture formulation of the novel materials described here with a standard NF compound (DIO), with the resultant materials having melting points (and/or glass transitions) which are significantly below ambient temperature. The new soft matter phase types discovered herein can be considered as electrical analogues of topological structures of magnetic spins in hard matter.

Toward Monodomain Nematic Liquid Crystal Elastomers of Arbitrary Thickness through PET-RAFT Polymerization.

Liquid crystal elastomers (LCEs) are polymeric materials that are proposed for a range of applications. However, to reach their full potential, it is desirable to have as much flexibility as possible in terms of the sample dimensions, while maintaining well-defined alignment. In this work, photoinduced electron/energy transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization is applied to the synthesis of LCEs for the first time. An initial LCE layer (∼100 µm thickness) is partially cured before a second layer of the precursor mixture is added. The curing reaction is then resumed and is observed by FTIR to complete within 15 min of irradiation, yielding samples of increased thickness. Monodomain samples that exhibit an auxetic response and are of thickness 250-300 µm are consistently achieved. All samples are characterized thermally, mechanically, and in terms of their order parameters. The LCEs have physical properties comparable to those of analogous LCEs produced via free-radical polymerization.

Controlling the Optical Properties of Transparent Auxetic Liquid Crystal Elastomers.

Determining the tunability of the optical coefficients, order parameter, and transition temperatures in optically transparent auxetic liquid crystal elastomers (LCEs) is vital for applications, including impact-resistant glass laminates. Here, we report measurements of the refractive indices, order parameters, and transition temperatures in a family of acrylate-based LCEs in which the mesogenic content varies from ∼50 to ∼85%. Modifications in the precursor mixture allow the order parameter, ⟨P2⟩, of the LCE to be adjusted from 0.46 to 0.73. The extraordinary refractive index changes most significantly with composition, from ∼1.66 to ∼1.69, in moving from a low to high mesogenic content. We demonstrate that all LCE refractive indices decrease with increasing temperature, with temperature coefficients of ∼10-4 K-1, comparable to optical plastics. In these LCEs, the average refractive index and the refractive index anisotropy are tunable via both chemical composition and order parameter control; we report design rules for both.

A wireless fluorescent flexible force sensor based on aggregation-induced emission doped liquid crystal elastomers.

Flexible strain sensors have drawn a lot of interest in various applications including human mobility tracking, rehabilitation/personalized health monitoring, and human-machine interaction, but suffer from interference of electromagnetic (EM). To overcome the EM interference, flexible force sensors without sensitive electronic elements have been developed, with drawbacks of bulky modules that hinders their applications in remote measurement with power-free environment. Therefore, it is highly desirable to fabricate a compact wireless flexible force sensor but it is still a challenge. Here, we demonstrate a fluorescent flexible force sensor based on aggregation-induced emission (AIE) doped liquid crystal elastomer (LCE) experimentally. The proposed force sensor film can be used to measure force through the variation of fluorescent intensity induced by the extension or contraction of LCE film, which leads to reduce or increase of the aggregation degree of AIE molecules within. This compact wireless force sensor features lightweight, low-cost, high flexibility, passivity and anti-EM interference, which also enables the naked eye observation. The proposed sensor provides inspiration and a platform for a new concept of non-contact detection, showing application potential in human-friendly interactive electronics and remote-control integration platform.

Room-temperature ferroelectric nematic liquid crystal showing a large and diverging density.

The ferroelectric nematic phase (NF) is a recently discovered phase of matter in which the orientational order of the conventional nematic liquid crystal state is augmented with polar order. Atomistic simulations suggest that the polar NF phase would be denser than conventional nematics owing to contributions from polar order. Using an oscillating U-tube densitometer, we obtain detailed temperature-dependent density values for a selection of conventional liquid crystals with excellent agreement with earlier reports. Having demonstrated the validity of our method, we then record density as a function of temperature for M5, a novel room-temperature ferroelectric nematic material. We present the first experimental density data for a NF material as well as density data for a nematic that has not previously been reported. We find that the room-temperature NF material shows a large (>1.3 g cm-3) density at all temperatures studied, notably including phases without polar order. An increase in density at phase transitions is observed. The magnitude of the increase for the intermediate-to-ferroelectric nematic (NX-NF) transition is an order of magnitude smaller than the isotropic-nematic (I-N) transition. We then probe potential consequences that may result from an elevated density through measurement of the refractive indices (no and ne). The navg of M5 is compared with 5CB and polar smectic liquid crystals. We observe how the highly polar nature of the system counteracts the effects of an increase in density. With knowledge of experimental density, we are able to derive an approximation that yields the polar order parameter, 〈P1〉, from polarisation measurements. Present results may be typical of ferroelectric nematic materials, potentially guiding material development, and is especially relevant for informing ongoing studies into this emerging class of materials.

Ultra-stable liquid crystal droplets coated by sustainable plant-based materials for optical sensing of chemical and biological analytes.

Herein, we demonstrate for the first time the synthesis of ultra-stable, spherical, nematic liquid crystal (LC) droplets of narrow size polydispersity coated by sustainable, biodegradable, plant-based materials that trigger a typical bipolar-to-radial configurational transition in dynamic response to chemical and biological analytes. Specifically, a highly soluble polymer, potato protein (PoP) and a physically-crosslinked potato protein microgel (PoPM) of ∼100 nm in diameter, prepared from the PoP, a byproduct of the starch industry, were compared for their ability to coat LC droplets. Although both PoP and PoPM were capable of reducing the interfacial tension between water and n-tetradecane <30 mN m-1, PoPM-coated LC droplets showed better stability than the PoP-coated droplets via a Pickering-like mechanism. Strikingly, the Pickering LC droplets outperformed PoP-stabilized droplets in terms of dynamic response with 5× lower detection limit to model chemical analytes (sodium dodecyl sulphate, SDS) due to the difference in SDS-binding features between the protein and the microgel. To eliminate the effect of size polydispersity on the response, monodisperse Pickering LC droplets of diameter ∼16 µm were additionally obtained using microfluidics, which mirrored the response to chemical as well as biological analytes, i.e., primary bile acid, an important biomarker of liver diseases. We demonstrate that these eco-friendly microgels used for creating monodisperse, ultra-stable, LC complex colloids are powerful templates for fabricating next generation, sustainable optical sensors for early diagnosis in clinical settings and other sensing applications.

The risk matrix: Drug-related deaths in prisons in England and Wales, 2015-2020.

This article explores the factors contributing to drug-related deaths in English and Welsh prisons between 2015 and 2020. Based on content analysis of all Prison and Probation Ombudsman 'other non-natural' fatal incident investigation reports, descriptive statistics were generated. Qualitative analysis explored the circumstances surrounding deaths and key risk factors. Most deaths were of men, whose mean age was 39 years. Drug toxicity was the main factor in causing death, exacerbated by underlying physical health conditions and risk-taking behaviours. A variety of substances were involved. New psychoactive substances became more important over time. A high proportion had recorded histories of substance use and mental illness. During this period, the prison system was under considerable stress creating dangerous environments for drug-related harm. This study highlights the process of complex interaction between substances used, individual characteristics, situational features and the wider environment in explaining drug-related deaths in prisons. Implications for policy and practice are discussed.

Light-Driven Dynamic Hierarchical Architecture of Three-Dimensional Self-Assembled Cholesteric Liquid Crystal Droplets.

Cholesteric liquid crystals have attracted much attention in biosensors, in communication systems, security identification, hierarchical materials assembly, and microlasers, due to their complex and interesting structures accompanied by particular optical properties making them low-cost, label-free and sensitive. However, the reports of CLC droplets with stable topological configurations are still very limited, which hinders the fast development and broad application of CLC droplet-based devices. In this paper, we manifest light-driven changes in the topological configuration of cholesteric liquid crystals droplets, examined experimentally. Photoresponsive azo-LC doped CLC droplets were manipulated by irradiation by UV light to form novel topological configurations with stable 3D structures. The phenomenon behind the configuration changes is the light-induced cholesteric-isotropic phase transition that takes place in liquid crystals. Several topological configurations of CLC droplets have been demonstrated such as closed-ring structures with cone-shaped centers and concentric elliptical centers, and open-ring structures formed under unidirectional illumination of UV light. Structures with parallel CLC pitch lines at the center and with a central point singularity are also formed under multidirectional illumination. The competition of the elastic energy and surface energy of the CLC droplets results in the formation of the new topological configurations. All proposed configurations are stable and controllable by light, which enable CLC droplets with novel topological structures with new characteristics and provide a lot of potential applications in biosensors and microlasers.

Talking really does matter: Lay perspectives from older people on talking about suicide in later life.

Background: The cumulative body of research on suicidality in later life describes its unique and complex features in older people when compared with that in other population groups. Yet significant gaps exist in how research informs the further development of suitable interventions. The perspectives of older people are also limited in research findings. Aims: Therefore, this exploratory study aimed to (1) identify potential barriers and enablers in discussing suicidal thoughts and their expression in later life from the perspectives of lay older people and (2) explore where opportunities might occur in approach, place, relationships, and language with older people to discuss suicidal thoughts and their expression. Method: We conducted in-depth qualitative individual interviews with 15 people aged 70-89 years. This method helped explore older peoples' own lay perspectives on suicidal thoughts in later life and how these are expressed, and their understanding of where and how people might seek support. Results: A total of three themes were generated from the dataset: (1) intergenerational and socio-cultural differences in suicide expression, (2) the normalization of suicidal thoughts in later life, and (3) the importance and difficulties of everyday discussion and opportunities to express suicidal thoughts. Conclusion: Suicidal thoughts and their expression appear commonly and are normalized in later life yet remain taboo and hidden. The participants revealed how such thoughts and behaviors are typically expressed through colloquial or "off-hand" remarks and comments and the importance of authentic listening. The findings highlight the importance of more informal discussions around these topics and how care professionals, practitioners, and providers might frame opportunities for dialogue with people who may want to access support. Further engagement with community-informed participatory research methods in which older people provide their own perspectives and experiences is important in addressing these gaps. There is a need for co-designing in developing screening, assessment, and signposting outside of clinical settings that can be used in everyday caring relationships with people in later life.

A mathematical model for the auxetic response of liquid crystal elastomers.

We develop a mathematical model that builds on the surprising nonlinear mechanical response observed in recent experiments on nematic liquid crystal elastomers. Namely, under uniaxial tensile loads, the material, rather than thinning in the perpendicular directions, becomes thicker in one direction for a sufficiently large strain, while its volume remains unchanged. Motivated by this unusual large-strain auxetic behaviour, we model the material using an Ogden-type strain-energy function and calibrate its parameters to available datasets. We show that Ogden strain-energy functions are particularly suitable for modelling nematic elastomers because of their mathematical simplicity and their clear formulation in terms of the principal stretches, which have a direct kinematic interpretation. This article is part of the theme issue 'The Ogden model of rubber mechanics: Fifty years of impact on nonlinear elasticity'.

Chiral nematic liquid crystal droplets as a basis for sensor systems.

For a series of phospholipid coated calamitic nematic liquid crystal droplets (5CB, 6CB, 7CB, E7 and MLC7023) of diameter ∼18 µm, the addition of chiral dopant leaves the sign of surface anchoring unchanged. Herein we report that for these chiral nematic droplets an analyte induced transition from a Frank-Pryce structure (with planar anchoring) to a nested-cup structure (with perpendicular anchoring) is accompanied by changes in the intensity of reflected light. We propose this system as both a general scheme for understanding director fields in chiral nematic liquid crystal droplets with perpendicular anchoring and as an ideal candidate to be utilised as the basis for developing cheap, single use LC-based sensor devices.

Exploring gendered differences among polish migrants in the UK in problematic drinking and pathways into and through alcohol treatment.

Few studies have focused on the gendered differences amongst Polish migrants in their use of alcohol or access to treatment services. This study explored the divergent pathways through alcohol use, misuse and treatment access in a group of Polish migrants in London. Using an intersectionality framework we examine the ways that social attitudes toward gender in both communities and access to services related to migrant status and class are experienced. With a view to informing treatment services we discuss how a better understanding of these pathways, and the factors likely to influence them, can be used to address challenges experienced by Polish migrant women with problematic alcohol use.

Assessing suicide ideation among older adults: a systematic review of screening and measurement tools.

OBJECTIVES: Rates of suicide in older adults may be higher than reported due to poor understandings of presentation of suicide ideation in this group. The objectives of this paper were to (i) review current measurement tools designed for older adults to detect suicide ideation and (ii) assess their psychometric properties. DESIGN: We used a systematic review approach to identify measurement tools developed specifically for older adults without cognitive decline or impairment. RESULTS: Ten articles that reported on a total of seven different measurement tools were identified. These included tools that focused on resiliency to suicide and those that measured risk of suicide behavior. There was wide variation across the articles: some were adaptations of existing scales to suit older populations, others were developed by authors; they varied in length from four to 69 items; a range of settings was used, and there was a mix of self-report and clinician-administered measures. Most displayed good psychometric properties, with both approaches showing similar quality. Limitations in terms of samples, settings, and measurement design are discussed. CONCLUSION: The case for specific measures for older adults is clear from this review. There appear to be unique factors that should be considered in understanding suicide ideation and behavior among older adults that may not be directly assessed in non-specific measurements. However, there is a need to expand the diversity of individuals included in measurement development to ensure they are appropriate across gender, culture and minority status, and for the views of professionals to be considered.

Direct Observation of Biaxial Nematic Order in Auxetic Liquid Crystal Elastomers.

Auxetic materials exhibit a negative Poisson's ratio, i.e., they become thicker rather than thinner in at least one dimension when strained. Recently, a nematic liquid crystal elastomer (LCE) was shown to be the first synthetic auxetic material at a molecular level. Understanding the mechanism of the auxetic response in LCEs is clearly important, and it has been suggested through detailed Raman scattering studies that it is related to the reduction of uniaxial order and emergence of biaxial order on strain. In this paper, we demonstrate direct observation of the biaxial order in an auxetic LCE under strain. We fabricated ~100 µm thick LCE strips with complementary geometries, exhibiting either planar or homeotropic alignment, in which the auxetic response is seen in the thickness or width of the sample, respectively. Polarized Raman scattering measurements on the planar sample show directly the reduction in the uniaxial order parameters on strain and suggest the emergence of biaxial order to mediate the auxetic response in the sample thickness. The homeotropic sample is studied via conoscopy, allowing direct observation of both the auxetic response in the width of the sample and increasing biaxiality in the LCE as it is strained. We verified that the mechanism of the auxetic response in auxetic LCEs is due to the emergence of the biaxial order and conclude such materials can be added to the small number of biaxial nematic systems that have been observed. Importantly, we also show that the mechanical Frèedericksz transition seen in some LCEs is consistent with a strain-induced transition from an optically positive to an optically negative biaxial system under strain, rather than a director rotation in a uniaxial system.

Influence of Liquid Crystallinity and Mechanical Deformation on the Molecular Relaxations of an Auxetic Liquid Crystal Elastomer.

Liquid Crystal Elastomers (LCEs) combine the anisotropic ordering of liquid crystals with the elastic properties of elastomers, providing unique physical properties, such as stimuli responsiveness and a recently discovered molecular auxetic response. Here, we determine how the molecular relaxation dynamics in an acrylate LCE are affected by its phase using broadband dielectric relaxation spectroscopy, calorimetry and rheology. Our LCE is an excellent model system since it exhibits a molecular auxetic response in its nematic state, and chemically identical nematic or isotropic samples can be prepared by cross-linking. We find that the glass transition temperatures (Tg) and dynamic fragilities are similar in both phases, and the T-dependence of the α relaxation shows a crossover at the same T* for both phases. However, for T>T*, the behavior becomes Arrhenius for the nematic LCE, but only more Arrhenius-like for the isotropic sample. We provide evidence that the latter behavior is related to the existence of pre-transitional nematic fluctuations in the isotropic LCE, which are locked in by polymerization. The role of applied strain on the relaxation dynamics and mechanical response of the LCE is investigated; this is particularly important since the molecular auxetic response is linked to a mechanical Fréedericksz transition that is not fully understood. We demonstrate that the complex Young's modulus and the α relaxation time remain relatively unchanged for small deformations, whereas for strains for which the auxetic response is achieved, significant increases are observed. We suggest that the observed molecular auxetic response is coupled to the strain-induced out-of-plane rotation of the mesogen units, in turn driven by the increasing constraints on polymer configurations, as reflected in increasing elastic moduli and α relaxation times; this is consistent with our recent results showing that the auxetic response coincides with the emergence of biaxial order.

A Fluorescence Sensor for Pb2+ Detection Based on Liquid Crystals and Aggregation-Induced Emission Luminogens.

Heavy metals, such as lead ions, are regarded as the main environmental contaminants and have a negative impact on human bodies, making detection technologies of lead ions critical. However, most existing detection methods suffer from time consumption, complicated sample pretreatment, and expensive equipment, which hinder their broad use in real-time detection. Herein, we show a new fluorescence sensor for detecting lead ions derived from liquid crystals doped with an aggregation-induced emission luminogen. The mechanism is based on the variation of fluorescence intensity caused by the disturbance of an ordered liquid crystal configuration in the presence of Pb2+, induced by DNAzyme and its catalytic cleavage. The proposed fluorescence sensor exhibits a low detection limit of 0.65 nM, which is 2 orders of magnitude lower than that previously reported in an optical sensor based on liquid crystals. The detection range of the Pb2+ fluorescence sensor is broad, from 20 nM to 100 µM, and it also selects lead ions from numerous metal ions exactly, resulting in a highly sensitive, highly selective, simple, and low-cost detection strategy of Pb2+ with potential applications in chemical and biological fields. This approach to designing a liquid crystal fluorescence sensor offers an inspiring stage for detecting biomacromolecules or other heavy metal ions by varying decorated molecules.

Liquid Crystal Elastomers for Biological Applications.

The term liquid crystal elastomer (LCE) describes a class of materials that combine the elastic entropy behaviour associated with conventional elastomers with the stimuli responsive properties of anisotropic liquid crystals. LCEs consequently exhibit attributes of both elastomers and liquid crystals, but additionally have unique properties not found in either. Recent developments in LCE synthesis, as well as the understanding of the behaviour of liquid crystal elastomers-namely their mechanical, optical and responsive properties-is of significant relevance to biology and biomedicine. LCEs are abundant in nature, highlighting the potential use of LCEs in biomimetics. Their exceptional tensile properties and biocompatibility have led to research exploring their applications in artificial tissue, biological sensors and cell scaffolds by exploiting their actuation and shock absorption properties. There has also been significant recent interest in using LCEs as a model for morphogenesis. This review provides an overview of some aspects of LCEs which are of relevance in different branches of biology and biomedicine, as well as discussing how recent LCE advances could impact future applications.

Production of giant unilamellar vesicles and encapsulation of lyotropic nematic liquid crystals.

We describe a modified microfluidic method for making Giant Unilamellar Vesicles (GUVs) via water/octanol-lipid/water double emulsion droplets. At a high enough lipid concentration we show that the de-wetting of the octanol from these droplets occurs spontaneously (off-chip) without the need to use shear to aid the de-wetting process. The resultant mixture of octanol droplets and GUVs can be separated by making use of the buoyancy of the octanol. A simpler microfluidic device and pump system can be employed and, because of the higher flow-rates and much higher rate of formation of the double emulsion droplets (∼1500 s-1 compared to up to ∼75 s-1), it is easier to make larger numbers of GUVs and larger volumes of solution. Because of the potential for using GUVs that incorporate lyotropic nematic liquid crystals in biosensors we have used this method to make GUVs that incorporate the nematic phases of sunset yellow and disodium chromoglycate. However, the phase behaviour of these lyotropic liquid crystals is quite sensitive to concentration and we found that there is an unexpected spread in the concentration of the contents of the GUVs obtained.

Protein Microgel-Stabilized Pickering Liquid Crystal Emulsions Undergo Analyte-Triggered Configurational Transition.

Herein, we report a novel approach that involves Pickering stabilization of micometer-sized liquid crystal (LC) droplets with biocompatible soft materials such as a whey protein microgel (WPM) to facilitate the analysis of analyte-induced configurational transition of the LC droplets. The WPM particles were able to irreversibly adsorb at the LC-water interface, and the resulting WPM-stabilized LC droplets possessed a remarkable stability against coalescence over time. Although the LC droplets were successfully protected by a continuous network of the WPM layer, the LC-water interface was still accessible for small molecules such as sodium dodecyl sulfate (SDS) that could diffuse through the meshes of the adsorbed WPM network or through the interfacial pores and induce an LC response. This approach was exploited to investigate the dynamic range of the WPM-stabilized LC droplet response to SDS. Nevertheless, the presence of the unadsorbed WPM in the aqueous medium reduced the access of SDS molecules to the LC droplets, thus suppressing the configuration transition. An improved LC response to SDS with a lower detection limit was achieved after washing off the unadsorbed WPM. Interestingly, the LC exhibited a detection limit as low as ∼0.85 mM for SDS within the initial WPM concentration ranging from 0.005 to 0.1 wt %. Furthermore, we demonstrate that the dose-response behavior was strongly influenced by the number of droplets exposed to the aqueous analytes and the type of surfactants such as anionic SDS, cationic dodecyltrimethylammonium bromide (DTAB), and nonionic tetra(ethylene glycol)monododecyl ether (C12E4). Thus, our results address key issues associated with the quantification of aqueous analytes and provide a promising colloidal platform toward the development of new classes of biocompatible LC droplet-based optical sensors.

Control of Director Fields in Phospholipid-Coated Liquid Crystal Droplets.

In liquid crystal (LC) droplets, small changes in surface anchoring energy can produce large changes in the director field which result in readily detectable optical effects. This makes them attractive for use as biosensors. Coating LC droplets with a phospholipid monolayer provides a bridge between the hydrophobic world of LCs and the water-based world of biology and makes it possible to incorporate naturally occurring biosensor systems. However, phospholipids promote strong perpendicular (homeotropic) anchoring that can inhibit switching of the director field. We show that the tendency for phospholipid layers to promote perpendicular anchoring can be suppressed by using synthetic phospholipids in which the acyl chains are terminated with bulky tert-butyl or ferrocenyl groups; the larger these end-group(s), the less likely the system is to be perpendicular/radial. Additionally, the droplet director field is found to be dependent on the nature of the LC, particularly its intrinsic surface properties, but not (apparently) on the sign of the dielectric anisotropy, the proximity to the melting/isotropic phase transition, the surface tension (in air), or the values of the Frank elastic constants.