ABSTRACT
Chiral liquid crystals (CLCs) self-assemble into a helical structure and can efficiently reflect circularly polarized light with corresponding handedness. Utilizing a curved glass substrate and polymerization of photoaligned CLCs, the operation of focusing and diffraction of incident light can be performed efficiently by a single component. When focusing and diffraction in a planar CLC cell are combined between two glass plates, the imaging suffers from astigmatism in the resulting spectrum. In this work, we demonstrate the operation of a spectrometer with low astigmatism using a polymerized CLC layer on a curved substrate. Two samples are fabricated, and the resulting components are operating in the wavelength range of 500-650 nm. Numerical optical modeling is used to minimize transverse aberrations and obtain a highly linear mapping on a camera sensor. In this way, it is demonstrated that a single reflective thin-film optical CLC component with a thickness of only a few micrometers can be used to realize a compact and efficient spectrometer.
ABSTRACT
Gyroid, double diamond and the body-centred "Plumber's nightmare" are the three most common bicontinuous cubic phases in lyotropic liquid crystals and block copolymers. While the first two are also present in solvent-free thermotropics, the latter had never been found. Containing six-fold junctions, it was unlikely to form in the more common phases with rod-like cores normal to the network columns, where a maximum of four branches can join at a junction. The solution has therefore been sought in side-branched mesogens that lie in axial bundles joined at their ends by flexible "hinges". But for the tightly packed double framework, geometric models predicted that the side-chains should be very short. The true Plumber's nightmare reported here, using fluorescent dithienofluorenone rod-like mesogen, has been achieved with, indeed, no side chains at all, but with 6 flexible end-chains. Such molecules normally form columnar phases, but the key to converting a complex helical column-forming mesogen into a framework-forming one was the addition of just one methyl group to each pendant chain. A geometry-based explanation is given.
ABSTRACT
Tree bark has been proven as an effective passive air sampler, particularly where access to active sampling methods is limited. In this study, 60 target liquid crystal monomers (LCMs; comprising 10 cyanobiphenyl and analogs (CBAs), 13 biphenyl and analogs (BAs), and 37 fluorinated biphenyl and analogs (FBAs)) were analyzed in 34 tree barks collected from the vicinity of a liquid crystal display (LCD) manufacturer situated in the Pearl River Delta, South China. The concentrations of LCMs in tree barks ranged from 1400 to 16000 ng/g lipid weight, with an average of 5900 ng/g lipid weight. Generally, bark levels of BAs exponentially decreased within 5 km of the LCD manufacturer. The profiles of LCMs in tree barks are similar to previously reported patterns in gaseous phase, suggesting bark's efficacy as a sampler for gaseous LCMs. The inclusion of different congeners in existing studies on the environmental occurrence of LCMs has hindered the horizontal comparisons. Therefore, this study established a list of priority LCMs based on environmental monitoring data and the publicly accessible production data. This list comprised 146 LCMs, including 63 REACH registered LCMs that haven't been analyzed in any study and 56 belonging to 4 types of mainstream LCMs.
ABSTRACT
Liquid crystal elastomers (LCEs), consisting of polymer networks and liquid crystal mesogens, show a reversible phase change under thermal stimuli. However, the kinetic performance is limited by the inherently low thermal conductivity of the polymers. Transforming amorphous bulk into a fiber enhances thermal conductivity through the alignment of polymer chains. Challenges are present due to their rigid networks, while cross-links are crucial for deformation. Here, we employ hydrodynamic alignment to orient the LCE domains assisted by controlled in situ cross-linking and to remarkably reduce the diameter to submicrons. We report that the intrinsic thermal conductivity of LCE fibers at room temperature reaches 1.44 ± 0.32 W/m-K with the sub-100 nm diameter close to the upper limit determined in the quasi-1D regime. Combining the outstanding thermal conductivity and thin diameters, we anticipate these fibers to exhibit a rapid response and high force output in thermomechanical systems. The fabrication method is expected to apply to other cross-linked polymers.
ABSTRACT
Liquid crystal monomers (LCMs) are identified as emerging organic contaminations with largely unexplored health impacts. To elucidate their toxic mechanisms, support the establishment of environmental discharge and management standards, and promote effective LCMs control, this study constructs a database covering 20,545 potential targets of 1431 LCMs, highlighting 9 key toxic target proteins that disrupt the nervous system and metabolic functions. GO and KEGG pathway analysis suggests LCMs severely affect nervous system, linked to neurodegenerative diseases and mental health disorders, with toxicity variations driven by electronegativity and structural complexity of LCM terminal groups. To achieve tiered control of LCMs, construct toxicity risk control lists for 9 key toxic target proteins, suitable for the graded control of LCMs, management recommendations are provided based on toxicity levels. These lists were validated for reliability and offer reliable toxicity predictions for LCMs. SHAP analysis points to electronic properties, molecular shape, and structural characteristics of LCMs as primary health impact factors. As the first study integrating machine learning with computational toxicology to outline LCMs health impacts, it aims to enhance public understanding of LCM toxicity risks and support the development of environmental standards, effective management of LCM production and emissions, and reduction of public exposure risks.
ABSTRACT
BACKGROUND: Liquid crystal monomers (LCMs) have been classified as emerging organic pollutants. Efficient isolation and extraction is a critical step in the determination, and then knowing the occurrence and distribution of LCMs in environmental waters. However, the reported sample preparation techniques still suffer some dilemmas such as using large amount of organic solvent, low extraction capacity, tedious operation procedure and employment of expensive extraction column. To circumvent the disadvantages, new extraction format and adsorbent with quickness, less consumption of organic solvent, superior extraction performance and low cost should be developed for the analysis of LCMs. RESULTS: Using 1H,1H,2H,2H-heptadecafluorodecyl acrylate and 9-vinylanthracene as mixed functional monomers, a task specific magnetic adsorbent (TSMA) was prepared by one-pot hydrothermal technique for the highly efficient capture of LCMs under magnetic solid phase extraction (MSPE) format. Due to the abundant functional groups, the developed TSMA/MSPE presented satisfactory capture performance towards LCMs. Satisfactory enrichment factors (132-212) and high adsorption capacity (18 mg/g) were obtained. Additionally, the relevant adsorption mechanism was studied by the combination of density functional theory calculation and experiments about adsorption kinetics and adsorption isotherm. Under the beneficial conditions, a sensitive and reliable method for the monitoring of studied LCMs in environmental waters was established by the combination of TSMA/MSPE with HPLC equipped with diode array detector (DAD). The achieved limits of detection and spiked recoveries were 0.0025-0.0061 µg/L and 81.0-112 %, respectively. Finally, the developed method was employed to monitor LCMs levels in the North Creek watershed of Jiulong River. SIGNIFICANCE AND NOVELTY: The current study provided a new adsorbent for quick and efficient capture of LCMs at trace levels. In addition, a sensitive, reliable and anti-intereference method for the monitoring of trace LCMs in actual waters was established. Moreover, for the first, the contents, occurrence and distribution of LCMs in North Creek watershed was investigated based on the developed method.
ABSTRACT
A novel room-temperature liquid crystal of tetraphenylethylene derivative (TPE-DHAB) was synthesized using an ionic self-assembly strategy. The TPE-DHAB complex exhibits typical aggregation-induced emission properties and a unique helical supramolecular structure. Moreover, the generation and handedness inversion of circularly polarized luminescence (CPL) can be achieved through further chiral solvation, providing a facile approach to fabricate room-temperature liquid crystalline materials with controllable supramolecular structures and tunable CPL properties through a synergistic strategy of ionic self-assembly and chiral solvation process.
ABSTRACT
Dynamic covalent bonds endow liquid crystal elastomers (LCEs) with network rearrangeability, facilitating the fixation of mesogen alignment induced by external forces and enabling reversible actuation. In comparison, the bond exchange of supramolecular interactions is typically too significant to stably maintain the programmed alignment, particularly under intensified external stimuli. Nevertheless, the remaking and recycling of supramolecular interaction-based polymer networks are more accessible than those based on dynamic covalent bonds, as the latter are difficult to completely dissociate. Thus, preparing an LCE that possesses both supramolecular-like exchangeability and covalent bond-level stability remains a significant challenge. In this work, we addressed this issue by employing metal-ligand bonds as the crosslinking points of LCE networks. As such, mesogen alignment can be repeatedly encoded through metal-ligand bond exchange and stably maintained after programming, since the bond exchange rate is sufficiently slow when the programming and actuation temperatures are below the bond dissociation temperature. More importantly, the metal-ligand bonds can be completely dissociated at high temperatures, allowing the LCE network to be dissolved in a solvent and reshaped into desired geometries via solution casting. Building on these properties, our LCEs can be fabricated into versatile actuators, such as reversible folding origami, artificial muscles, and soft robotics.
ABSTRACT
The rapid and accurate identification of live pathogens with high proliferative ability is in great demand to mitigate foodborne infection outbreaks. Herein, we have developed an ultrasensitive image-based aptasensing array to directly detect live Salmonella typhimurium (S.T) cells. This method relies on the long-range orientation of surfactant-decorated liquid crystals (LCs) and the superiority of aptamers (aptST). The self-assembling of hydrophobic surfactant tails leads to a perpendicular/vertical ordered film at the aqueous/LC interface and signal-off response. The addition of aptST perturbed LCs' ordering into a planar/tilted state at the aqueous phase due to electrostatic interactions between the surfactant with the aptST, and a signal-on response. Following the conformational switch of aptST in the presence of live S. typhimurium, a relative reversing signal-off response was observed upon the target concentration. This aptasensor could promptly confirm the presence of S. typhimurium without intricate DNA-extraction or pre-enrichment stats over a linear range of 1-1.1 × 106 CFU/mL and a detection limit of 1.2 CFU/mL within â¼30 min. These results were successfully validated using molecular and culture-based methods in spiked-milk samples, with a 92.61-104.61 % recovery value. Meanwhile, the flexibility of this portable sensing platform allows for its development and adoption for the precise detection of various pathogens in food and the environment.
ABSTRACT
Osteoid plays a crucial role in directing cell behavior and osteogenesis through its unique characteristics, including viscoelasticity and liquid crystal (LC) state. Thus, integrating osteoid-like features into 3D printing scaffolds proves to be a promising approach for personalized bone repair. Despite extensive research on viscoelasticity, the role of LC state in bone repair has been largely overlooked due to the scarcity of suitable LC materials. Moreover, the intricate interplay between LC state and viscoelasticity in osteogenesis remains poorly understood. Here, we developed innovative hydrogel scaffolds with osteoid-like LC state and viscoelasticity using digital light processing with a custom LC ink. By utilizing these LC scaffolds as 3D research models, we discovered that LC state mediates high protein clustering to expose accessible RGD motifs to trigger cell-protein interactions and osteogenic differentiation, while viscoelasticity operates via mechanotransduction pathways. Additionally, our investigation revealed a synergistic effect between LC state and viscoelasticity, amplifying cell-protein interactions and osteogenic mechanotransduction processes. Furthermore, the interesting mechanochromic response observed in the LC hydrogel scaffolds suggests their potential application in mechanosensing. Our findings shed light on the mechanisms and synergistic effects of LC state and viscoelasticity in osteoid on osteogenesis, offering valuable insights for the biomimetic design of bone repair scaffolds.
ABSTRACT
Conventional light diffusers have periodic surface profiles, periodic refractive index distributions, or light scattering layers containing colloids. In all such structures the optical directivity of the light diffuser is cannot typically be controlled. Here we propose an electrically tunable light diffuser based on the application of ultrasound to a nematic liquid crystal (LC) material. The ultrasonic LC diffuser consists of an LC layer sandwiched by two glass discs and an ultrasonic transducer. The electrodes of the transducer are divided in a circumferential direction so that a resonant non-coaxial flexural vibration mode can be generated on the diffuser by controlling the electrical input signals. A continuous reversed-phase sinusoidal electric signal to the transducer generates the non-coaxial resonant flexural vibration mode on the glass disc, inducing an acoustic radiation force acting on the boundary between the LC layer and glass discs. This effect changes the molecular orientation of the LC and the transmitted light distribution. The diffusion angle of the transmitted light depends on the input voltage amplitude, and the diffusion angle was maximized at 16.0 V. The vibrational distribution and the diffusion directivity could be rotated by adjusting the input voltages to different electrodes, meaning that an ultrasonic LC diffuser with a thin structure and no moving mechanical parts provided a tunable light-diffusing functionality with rotatable directivity.
ABSTRACT
This proposed design presents a novel bandpass filter employing a Marchand balun to attain ultra-wideband (UWB) performance extending from 3.1 to 10.7 GHz with 6.8 GHz central frequency and 110% FBW. The UWB bandpass filter's fractional bandwidth can be tailored owing to the diverse input/output impedances of the planar Marchand balun. This adaptability is accomplished by connecting two planar Marchand baluns consecutively, leveraging the concepts of transversal filter ideas and multilayer LCP technology resulting in 0.3 dB and 12 dB insertion and return losses respectively. In-depth guidelines for the formulation and synthesis of the UWB bandpass filter are incorporated.
ABSTRACT
Photoisomerizable molecules in liquid crystals (LCs) allow for photoinduced phase transitions, facilitating applications in a wide variety of photoresponsive materials. In contrast to the widely investigated azobenzene structure, research on the photoinduced phase-transition behavior of imine-based LCs is considerably limited. We herein report the thermal and photoinduced phase-transition behaviors of photoisomerizable imine-based LC dimers with twist-bend nematic (NTB) phases. We synthesize two homologous series of ester- and thioether-linked N-(4-cyanobenzylidene)aniline-based bent-shaped LC dimers with an even number of carbon atoms (n = 2, 4, 6, 8, and 10) in the central alkylene spacers, namely, CBCOOnSBA(CN) and CBOCOnSBA(CN), possessing oppositely directed ester linkages, C=OO and OC=O, respectively. Their thermal phase-transition behavior is examined using polarizing optical microscopy and differential scanning calorimetry. All dimers form a monotropic NTB phase below the temperature of the conventional nematic (N) phase upon cooling. Remarkably, the NTB phases of CBCOOnSBA(CN) (n = 2, 4, 6, and 8) and CBOCOnSBA(CN) (n = 6 and 8) supercool to room temperature and vitrify without crystallization. In addition, the phase-transition temperatures and entropy changes of CBCOOnSBA(CN) are lower than those of CBOCOnSBA(CN) at the same n. Under UV light irradiation, the NTB and N phases transition to the N and isotropic phases, respectively, and reversibly return to their initial LC phases when the UV light is turned off.
ABSTRACT
Here we present the cascade converter (CC), which provides real-time imaging of ionizing radiation (IoR) distribution. It was designed and manufactured with the simplest architecture, utilizing liquid crystal display (LCD) technology. Based on two merged substrates with transparent electrodes, armed with functional layers, with the cell filled with nematic liquid crystal, a display-like, IoR-stimulated CC was achieved. The CC comprises low-absorbing polymer substrates (made of polyethylene terephthalate-PET) armed with a transparent ITO electrode covered with a thin semipermeable membrane of polymer (biphenylperfluorocyclobutyl: BP-PFCB) doped with functional nanoparticles (NPs) of Lu2O3:Eu. This stack was covered with a photoconductive layer of α-Se and finally with a thin polyimide (PI) layer for liquid crystal alignment. The opposite substrate was made of LCD-type glass with ITO and polyimide aligning layers. Both substrates form a cell with a twisted structure of nematic liquid crystal (TN) driven with an effective electric field Eeff. An effective electric field driving TN structure is generated with a sum of (1) a bias voltage VBIAS applied to ITO transparent electrodes and (2) the photogenerated additional voltage VXray induced between ITO and α-Se layers with a NPs-doped BP-PFCB polymer layer in-between. The IoR (here, X-ray) conversion into real imaging of the IoR distribution was achieved in the following stages: (1) conversion of IoR distribution into non-ionizing red light emitted with functional NPs, (2) transformation of red light into an electric charge distributed in a layer of the photoconductive α-Se, which is what results in the generation of distributed voltage VXray, and (3) a voltage-mediated, distributed switching of the TN structure observed with the naked eye. The presented imaging device is characterized by a simple structure and a simple manufacturing process, with the potential for use as a portable element of IoR detection and as a dosimeter.
ABSTRACT
The dielectric properties of synclinic (ferroelectric SmC*) and anticlinic (antiferroelectric SmCA*) smectic liquid crystals composed of molecules of one chiral version (S) are presented and compared with properties of racemic mixture (R, S), showing SmC and SmCA phases. The racemic mixture completely loses its ferroelectric and antiferroelectric properties. Surprisingly, only one dielectric mode observed in the antiferroelectric SmCA* phase disappeared in the dielectric response of the racemic SmCA phase. Additionally, we observed that in the SmC phase, seen in the racemic mixture, the weak dielectric mode (named the X mode) is detected, which seems to be the continuation of the PL mode existing in the racemic SmCA. Moreover, this mode in the racemic SmC has nothing to do with the Goldstone mode, typical for the SmC* phase. This paper describes in detail the real and imaginary parts of dielectric permittivity in smectic phases for the enantiomer and racemate with and without a DC field, compares the properties of the X and PL modes, and discusses the full scheme of dielectric modes in enantiomer and racemate.
ABSTRACT
Cholesteric liquid crystal microcapsules (CLCMs) are used to improve the stability of liquid crystals while ensuring their stimulus response performance and versatility, with representative applications such as sensing, anticounterfeiting, and smart fabrics. However, the reflectivity and angular anisotropy decrease because of the anchoring effect of the polymer shell matrix, and the influence of particle size on this has not been thoroughly studied. In this study, the effect of synthesis technology on microcapsule particle size was investigated using a complex coalescence method, and the effect of particle size on the reflectivity and angular anisotropy of CLCMs was investigated in detail. A particle size of approximately 66 µm with polyvinyl alcohol (PVA, 1:1) exhibited a relative reflectivity of 16.6% and a bandwidth of 20 nm, as well as a narrow particle size distribution of 22 µm. The thermosetting of microcapsules coated with PVA was adjusted and systematically investigated by controlling the mass ratio. The optimized mass ratio of microcapsules (66 µm) to PVA was 2:1, increasing the relative reflectivity from 16.6% (1:1) to 32.0% (2:1) because of both the higher CLCM content and the matching between the birefringence of the gelatin-arabic shell system and PVA. Furthermore, color based on Bragg reflections was observed in the CLCM-coated ortho-axis and blue-shifted off-axis, and this change was correlated with the CLCM particle size. Such materials are promising for anticounterfeiting and color-based applications with bright colors and angular anisotropy in reflection.
ABSTRACT
Aggregation-induced emitters or AIEgens are generally signified by their stronger photoluminescence in aggregation than in the solution state. Due to high emission efficiency in aggregate and solid states and good processability, organic AIEgens drew attention to the development of advanced luminescent materials. However, as mesogenic materials self-assemble to a different molecular arrangement in different phases, achieving liquid crystallinity and AIE properties in the same molecule would provide a valuable tool to develop solvent-independent AIEgenic materials. With this goal, the present work reports the synthesis of new organic thermotropic liquid crystalline compounds exhibiting aggregation-induced emission (AIE). The synthesized compounds exhibit strong green luminescence in a solid state which sharply quenches upon entering smectic mesophase by heating. This is in addition to the exhibition of dispersion medium (solvent)-dependent emission, thus providing a dual mode of AIE. The mesogenic property of the synthesized compounds was studied by XRD, POM, and DSC. The AIE was studied by fluorescence spectroscopy and variable temperature fluorescence microscopy. A DFT study was carried out to gain an insight into the AIEgenic behavior of the material.
ABSTRACT
Liquid crystals with high dielectric anisotropy, low operational thresholds, and significant birefringence (Δn) represent a key focus in soft matter research. This work introduces a novel series of hydrogen-bonded liquid crystals (HBLCs) derived from 4-n-alkoxybenzoic, 4-alkoxy-3-fluorobenzoic derivatives (nOBAF), 4-alkoxy-2,3-fluorobenzoic derivatives (nOBAFF), and 2-fluoro-4-nitrobenzoic acid. The HBLCs were characterized using Fourier transform infrared spectroscopy, and their thermal behavior was evaluated via differential scanning calorimetry. Optical observations were conducted using polarized optical microscopy. The results indicate that mixtures containing benzoic acid with a bilateral fluorine substituent exhibit both SmA and SmC phases, while those with a unilateral fluorine substituent exhibit nematic and SmA phases. Moreover, an increase in the length of the alkoxy chain results in an expanded mesophase temperature range. This study demonstrates that the presence of a fluorine substituent and the incorporation of an NO2 group in the molecular structure result in an increase in dielectric permittivity, DC conductivity, dielectric anisotropy, and birefringence.
ABSTRACT
Auxetics are materials displaying a negative Poisson's ratio, i.e., getting thicker in one or both transverse axes when subject to strain. In 2018, liquid crystal elastomers (LCEs) displaying auxetic behaviour, achieved via a biaxial reorientation, were first reported. Studies have since focused on determining the physics underpinning the auxetic response, with investigations into structure-property relationships within these systems so far overlooked. Herein, we report the first structure-property relationships in auxetic LCEs, examining the effect of changes to the length of the spacer chain. We demonstrate that for LCEs with between six and four carbons in the spacer, an auxetic response is observed, with the threshold strain required to achieve this response varying from 56% (six carbon spacers) to 81% (four carbon spacers). We also demonstrate that Poisson's ratios as low as -1.3 can be achieved. Further, we report that the LCEs display smectic phases with spacers of seven or more carbons; the resulting internal constraints cause low strains at failure, preventing an auxetic response. We also investigate the dependence of the auxetic threshold on the dynamics of the samples, finding that when accounting for the glass transition temperature of the LCEs, the auxetic thresholds converge around 56%, regardless of spacer length.
ABSTRACT
Fluorinated liquid-crystal monomers (FLCMs), a new class of potential persistent, bioaccumulative and toxic (PBT) emerging pollutants, are extensively utilized in the display panel of various electronic devices. These compounds have been found in various environmental matrixes and dietary. Our previous studies have documented their ubiquitous occurrence in high fat foodstuffs. Infants, a vulnerable group, are more susceptible to the impacts of these pollutants compared to adults. Herein, we provided an assessment of the health risks posed by FLCMs to infants, focusing on their exposure through infant formula. The presence of FLCMs was detected in all infant formulas, with median concentration of 16.5 ng/g dry weight (dw) and the 95th percentile concentration of 65.7 ng/g dw. The most prevalent pollutant in these formulas was 2-fluoro-4-[4'-propyl-1,1'-bi(cyclohexyl)-4-yl] phenyl trifluoromethyl ether (FPrBP), with median and a 95th percentile concentration of 12.2 ng/g dw and 23.8 ng/g dw, accounting for 55.2% to the total FLCMs. Infants aged 0-6 months had the highest estimated daily intakes (EDIs) of FLCMs, with the EDImedian of 267 ng/kg bw/day. FPrBP and 4-[trans-4-(trans-4-Propylcyclohexyl) cyclohexyl]-1-trifluoromethoxybenzene (PCTB) together made up 83.3% of the total EDIs in median exposure scenario of 0-6 months infant. The highest EDI value was 1.30 × 103 ng/kg bw/day, 77.1% of which was attributed to a combination of FPrBP, 4â³-ethyl-2'-fluoro-4-propyl-1,1':4',1â³-terphenyl (EFPT), 2-[4'-[difluoro(3,4,5-trifluoro-2-methyl-phenoxy)methyl]-3',5'-difluoro-[1,1'-biphenyl]-4-yl]-5-ethyl-tetrahydro-pyran (DTMPMDP), 4-[Difluoro-(3,4,5-trifluoro-2-methyl-phenoxy)-methyl]-3,5-difluoro-4'-propyl-1,1-biphenyl (DTMPMDB), 2,3-difluoro-1-methyl-4-[(trans, trans)-4'-pentyl[1,1'-bicyclohexyl]-4-yl]benzene (DMPBB) and PCTB. It's worth noting that FLCMs have higher exposure risk. Based on the threshold of toxicological concern (TTC) method, the EDImedian of FPrBP (183 ng/kg bw/day) and FPCB (3.27 ng/kg bw/day) were beyond their TTC values (2.5 ng/kg bw/day) in 0-6 months infant, implying their prospective health risk.