Nematic Structure Research Articles

The Nematic Chiral Liquid Crystal Structure of the Cardiac Myoarchitecture: Disclinations and Topological Singularities.

This is our second article devoted to the cardiac myoarchitecture considered as a nematic chiral liquid crystal (NCLC). While the first article focused on the myoarchitecture of the left ventricle (LV), this new article extends to the whole ventricular mass and introduces the concept of disclinations and topological singularities, which characterize the differences and relationships between the left and right ventricles (RV). At the level of the ventricular apices, we constantly observed a vortex shape at the LV apex, corresponding, in the terminology of liquid crystals, to a "+1 disclination"; we never observed this at the RV apex. At the level of the interventricular septum (IVS), we identified "-1/2 disclinations" at the anterior and posterior parts. During the perinatal period, there was a significant difference in their distribution, with more "-1/2 disclinations" in the posterior part of the IVS. After birth, concomitant to major physiological changes, the number of "-1/2 disclinations" significantly decreased, both in the anterior and posterior parts of the IVS. Finally, the description of the disclinations must be considered in any attempt to segment the whole ventricular mass, in biomechanical studies, and, more generally, for the characterization of myocardial remodeling.

Anti-counterfeiting Behaviour of Organic-Inorganic Hybrid Silica Film with a Chiral Smectic C Structure.

Artificial photonic materials based on chiral liquid-crystalline nanostructures have attracted increasing interests for their wide applications as sensors, anti-counterfeit measures, displays and colour filters. Although the structurally coloured films with chiral nematic structures or blue phases have been prepared, the ones fabricated by fixing chiral smectic C (SmC*) phases have been rarely reported. In this work, organic-inorganic hybrid silica (OIHS) films with a SmC* structure were reported for the first time. An organosilane (CSC) with an enantiotropic SmC* phase was synthesized. The OIHS films with a SmC* structure were fabricated by the polycondensation of CSC under an acidic condition. The colour patterns can be observed in the oblique view, but not be observed in the vertical view, which is mainly due to the light scattering of the nanoparticles on film surface and the selective Bragg reflection of film inside. Therefore, such properties make the OIHS films promising candidates for anti-counterfeiting applications.

Structural Color Controllable Humidity Response Chiral Nematic Cellulose Nanocrystalline Film.

Through self-assembly, environmentally friendly cellulose nanocrystals (CNCs) can form films with a photonic crystal structure whose pitch size can be adjusted in a variety of ways at the fabrication stage. Moreover, the films exhibit response performance to multiple stimuli, which offers extensive applications. Poly(ethylene glycol) (PEG) and CNCs combine to form a smaller chiral nematic domain that develops a solid film with a uniform spiral structure when slowly dried. By changing the composition of CNCs and PEG, flexible and flat photonic composite films with uniform structural colors from blue to red are prepared. Benefiting from the change in pitch size by insertion and detachment of water molecules into the chiral nematic structure, CNCs films and CNC-PEG composite films exhibit a reversible structural color change in response to different humidity. In addition, the chiral nematic films formed by the combination of glycerol and CNCs have a reversible stimulation response to hydrochloric acid gas. Similarly, adjusting the ratio of glycerol can control the pitch size of the films and, thus, the reflective color. In summary, the pitch size of the photonic crystal structure of the films can be precisely tuned by regulating the additive ratio, and the two prepared films have reversible responses to humidity and hydrochloric acid gas, respectively. The CNC-based films show promise in the application of colorimetric biosensors.

Chiral Liquid Crystalline Properties of Cellulose Nanocrystals: Fundamentals and Applications.

By using an independent self-assembly process that is occasionally controlled by evaporation, cellulose nanocrystals (CNCs) may create films (pure or in conjunction with other materials) that have iridescent structural colors. The self-forming chiral nematic structures and environmental safety of a new class of photonic liquid crystals (LCs), referred to as CNCs and CNC-embedded materials, make them simple to make and treat. The structure of the matrix interacts with light to give structural coloring, as opposed to other dye pigments, which interact with light by adsorption and reflection. Understanding how CNC self-assembly constructs structures is vital in several fields, including physics, science, and engineering. To constructure this review, the colloidal characteristics of CNC particles and their behavior during the formation of liquid crystals and gelling were studied. Then, some of the recognized applications for these naturally occurring nanoparticles were summarized. Different factors were considered, including the CNC aspect ratio, surface chemistry, concentration, the amount of time needed to produce an anisotropic phase, and the addition of additional substances to the suspension medium. The effects of alignment and the drying process conditions on structural changes are also covered. The focus of this study however is on the optical properties of the films as well as the impact of the aforementioned factors on the final transparency, iridescent colors, and versus the overall response of these bioinspired photonic materials. Control of the examined factors was found to be necessary to produce reliable materials for optoelectronics, intelligent inks and papers, transparent flexible support for electronics, and decorative coatings and films.

Flexible and Transferable Silver Nanowire Liquid Crystal Polymer Film Obtained via Photo‐Alignment Programming (Advanced Optical Materials 16/2022)

A non-contact photo-alignment technology was proposed to align silver nanowires (AgNWs) in a liquid crystal polymer (LCP) film with high order parameter. They are controlled to have planar alignment and twisted nematic structures in micro-multi-domains. The aligned AgNWs can be used to improve the mechanical properties of LCP films. The AgNW/LCP film can be programmed by micro-multi-domain photo-alignment for use in flexible and wearable devices. For further details see article number 2200950 by Jiatong Sun and co-workers.

Impact of random-field-type disorder on nematic liquid crystalline structures.

We study bicomponent systems where one component represents a liquid crystalline (LC) phase, and the other component randomly perturbs the LC order. Such systems can serve as a testbed to systematically analyse the impact of qualitatively different types of random-type sources of perturbation on the orientational and/or translational order. This mini-review presents typical representatives of such systems, where orientational and translational order is probed in nematic and smectic A LCs, respectively. As a source of perturbation, we consider either different porous matrices (control-pore glass, aerogels) or aerosil nanoparticles, which can form in LCs' different fractal-like network organizations. In such complex systems, LC ordering fingerprints the interplay among LC elastic forces, interfacial forces, and randomness. The resulting LC behaviour could be characterised by either long-range, quasi long-range, or short-range order. We demonstrate under which conditions random-field-like phenomena or interfacial effects dominate. However, these effects are relatively strongly entangled in most experimental systems, andindividual impacts cannot be precisely identified.

Flexible and Transferable Silver Nanowire Liquid Crystal Polymer Film Obtained via Photo‐Alignment Programming

AbstractThe self‐assembly of silver nanowires (AgNWs) with a high aspect ratio is highly desirable for practical applications; however, several challenges still exist. Herein, a non‐contact, simple, large‐scale, micro‐domain photo‐alignment technology is proposed to align AgNWs in a liquid crystal polymer (LCP) film, resulting in a high order parameter (above 0.9). The AgNWs are precisely controlled to have planar alignment and twisted nematic structures in micro‐multi‐domains. The AgNW/LCP precursor is frozen to shape the film via ultraviolet crosslinking, allowing it to be easily peeled off and transferred to various flexible and other functional substrates. The aligned AgNWs can be used to improve the mechanical properties of LCP films, as they exhibit high elongation‐at‐break and high strength‐at‐break. The AgNW/LCP film can also be further programmed by micro‐multi‐domain photo‐alignment for use in flexible and wearable devices.

Multimodal, Convertible, and Chiral Optical Films for Anti‐Counterfeiting Labels

AbstractDesigning a sustainable security model that carries multilevel information with numerous optical states will significantly enhance anti‐counterfeiting abilities to deter counterfeits, ranging from artworks, currencies, and foods to medicines, but is enormously challenging. Herein, ambient‐friendly, large‐area, quadruple‐level, and chiral luminescent materials are prepared by incorporating lanthanide complexes wrapped in poly(ethylene glycol) matrix into chiral nematic cellulose nanocrystal (CNC) films through a co‐assembly strategy. Due to the regulation of the chiral nematic structures, the composite films enable full‐color structural colors and tunable fluorescence. Notably, the brightest fluorescent film radiates right‐handed circularly polarized luminescence with an asymmetric factor over −0.36, a lifetime up to 510 µs, and an absolute quantum yield up to 66.7%. More interestingly, a fascinating chiro‐optical behavior ranging from azure to khaki can be controlled by a polarizing filter at given 0° and 90° rotation angles. This anti‐counterfeiting system showcases the comprehensive properties of bright and responsive photoluminescence, quadruple and convertible color, and flexible and solvent‐resistant abilities. This CNC‐derived photonic material can act as the multimodal security label on a model banknote, which greatly facilitates its development for practical applications.

The preparation of cellulose nanocrystal/1,3‐butylene glycol composite structural color films and humidity‐responsive

AbstractCellulose nanocrystals (CNCs) can self‐assemble in an aqueous solution to form a chiral nematic liquid crystal structure, which is maintained in the subsequent solid iridescent film and presents a unique structural color. In this study, in order to explore the effect of ultrasound on the optical properties of CNC, CNC films with a chiral nematic helix structure and different structural colors were prepared by ultrasonic‐assisted dispersion and natural static evaporation. Results showed that prolonging the ultrasonic duration significantly increased layer pitches and red‐shifted the color of CNC films, likely due to increased steric hindrance and a larger electric double layer. On this basis, CNC/1,3‐butylene glycol (BG) composite films were prepared with uniform and structural color. Results showed that BG was incorporated into CNCs most likely through hydrogen bonds. Moreover, the presence of BG increased the layer pitches and red‐shifted the structural color of CNC/BG composite films, which indicates that structural color of the film has a good stability response to humidity. On the whole, our work provides a new point of view in understanding the role of ultrasound and small‐molecule additives in the preparation of CNC‐based films.

Phase behavior of a lattice-gas model for biaxial nematics

We employ a lattice-gas extension of the Maier-Saupe model with discrete orientation states to study the phase behavior of a statistical model for biaxial nematogenic units in mean-field theory. The phase behavior of the system is investigated in terms of the strength of isotropic interaction between anisotropic objects, as well as the degree of biaxiality and the concentration of those units. We obtain phase diagrams with isotropic phases and stable biaxial and uniaxial nematic structures, various phase coexistences, many types of critical and multicritical behaviors, such as ordinary vapor-liquid critical points, critical end points, and tricritical points, and distinct Landau-like multicritical points. Our results widen the possibilities of relating the phenomenological coefficients of the Landau-de Gennes expansion to microscopic parameters, allowing an improved interpretation of theoretical fittings to experimental data.

Cellulose liquid crystal templated TiO2 chiral nematic foams

Aerogels with chiral nematic structure are promising candidates for structural coatings and optical devices. Cellulose nanocrystals (CNCs) are excellent photonic building blocks for the fabrication of chiral nematic aerogels. Conventional bottom-up fabrication process usually is complicated, energy and time consumption. Herein, a simple method for fabricating CNCs and polyethylene glycol (PEG) based foams with chiral nematic structure was proposed. After CNCs-PEG based solid films were swollen with N-methylmorpholine N-oxide (NMMO) aqueous solutions, the obtained hydrogels were freeze-dried, resulting in chiral nematic foams. During the process, both macropores and mesopores were created with chiral nematic phase retained inside foam walls. Owning numerous macropores and chiral nematic walls of varying axial directions, the chiral nematic foams exhibited a broad-band reflection phenomenon. Moreover, the representative Titanium diisopropoxide(bis-2,4-pentanedionate) was permeated into foam walls, and transformed into chiral nematic TiO2 foams after annealing. We envisage that the chiral nematic foams may have a promising application in the fields of chiral separation or chiral catalysis.

Biaxial planar nematic layered structures of highly confined prolate hard ellipsoids

This study investigated the nematic phase structures of hard uniaxial ellipsoidal rods having a short axis of 2b, a long axis of 2a, and the elongations k=2a2b=3 and 5 in strongly confined pores via the density functional theory with Zwanzig and hyper-netted-chain approximations. By increasing the density, the number of planar nematic layers gradually rise without any phase transition. These layering phenomena occurred between two biaxial structures with different numbers of planar layers in which the layers’ spacing was approximately 2b.

Sensitive chemoselectivity of cellulose nanocrystal films

Cellulose nanocrystals (CNCs), self-assembled into a chiral nematic structure film, create an advanced platform for the fabrication of remarkable sensing, photonic and chiral nematic materials. Despite extensive progress in the knowledge of functions of CNCs, their chemoselectivity has rarely been reported. Here, we report a brand-new perspective of CNCs in chemoselectivity, which shows sensitive selectivity even between isomers of monosaccharides and disaccharides by generating discernible crystal patterns. This sensitive selectivity of glucose homologs is attributed to the selective carbohydrate–carbohydrate interactions (CCIs) through generating hydrogen bonds between CNC units and the glucose homologs, endowing a remarkable color variation of the CNC films. Moreover, the CCIs are distinct for different immersion times and concentrations of glucose homologs, verified through Fourier Transform Infrared Spectroscopy (FTIR) spectra. Based on the sensitive CCIs, pristine CNC films are then used as templates to generate chiral mesoporous carbon films with tunable specific surface areas by assembly of CNC suspensions and the glucose homologs. We envision that the sensitive chemoselectivity of CNC films as well as precise structure modulation could provide insights into the recognition of carbohydrates and the preparation of mesoporous carbon in numerous practical applications. A pristine chiral nematic cellulose nanocrystal film with sensitive chemoselectivity to glucose homologues and even isomers of monosaccharides and disaccharide are prepared through self-assembly. For different kinds of glucose homologs, distinct crystal morphologies are formed due to the selective carbohydrate–carbohydrate interactions. Besides, the highly ordered left-helical layered structure of pristine cellulose nanocrystal film could be used as templates for the precise construction of delicate nanostructures.

An infinite set of integral formulae for polar, nematic, and higher order structures at the interface of motility-induced phase separation

Motility-induced phase separation (MIPS) is a purely non-equilibrium phenomenon in which self-propelled particles phase separate without any attractive interactions. One surprising feature of MIPS is the emergence of polar, nematic, and higher order structures at the interfacial region, whose underlying physics remains poorly understood. Starting with a model of MIPS in which all many-body interactions are captured by an effective speed function and an effective pressure function that depend solely on the local particle density, I derive analytically an infinite set of integral formulae for the ordering structures at the interface. I then demonstrate that half of these IF are in fact exact for generic active Brownian particle systems. Finally, I test these integral formulae by applying them to numerical data from direct particle dynamics simulation and find that they remain valid to a great extent.

Photonic Cellulose Films with Vivid Structural Colors: Fabrication and Selectively Chemical Response

Recent advances in structural-color cellulose nanocrystal (CNC) materials have been made toward chemical sensing applications; however, such materials lack sufficient color chroma for naked-eye observation, and their selective recognition to given chemicals as well as the corresponding mechanism has rarely been reported. Here, a dopamine-infiltration and post-polymerization approach is proposed to construct vivid structural-color composite films. The chiral nematic structure of CNC enables the structural coloration, while the strong light absorption of the polymeric co-phase, polydopamine (PDA) enhances the color chroma and visibility. By controlling the PDA amount, the composite films can detect organic solvents quantitatively and selectively via visible color changes. From the viewpoint of the compatibility and similitude principle, notably, a critical solubility parameter distance (R0) between PDA and "active" solvents is defined with a three-dimensional Hansen solubility sphere; this well constructs a rule for the sensing selectivity of the chemochromic composite films. The findings pave the foundation for the design of colorimetric sensors with specifically testing objects.

Circularly Polarized Luminescent Chiral Photonic Films Based on the Coassembly of Cellulose Nanocrystals and Gold Nanoclusters.

In this work, we studied the formation and properties of composite films coassembled by cellulose nanocrystals (CNCs) and bovine serum albumin-stabilized gold nanoclusters (BSA-AuNCs). The influences of the BSA-AuNC concentration on the structure and optical properties of CNC-based composite films were further studied. It was found that the composite film retained the chiral nematic structure and optical activity. The self-assembled CNC and BSA-AuNC helical superstructures can produce strong, left-handed, circularly polarized luminescence with dissymmetry factors up to 0.287. Meanwhile, the third component, polyethylene glycol, was introduced without affecting the structural color and fluorescence characteristics of the composite film to enhance the flexibility of the film. The simplicity of the film preparation, the abundance of CNCs, and the flexibility and stability of the composite films pave the way for the production of functional materials with integrated functions.

Tomographic measurement of dielectric tensors at optical frequency.

The dielectric tensor is a physical descriptor of fundamental light-matter interactions, characterizing anisotropic materials with principal refractive indices and optic axes. Despite its importance in scientific and industrial applications ranging from material science to soft matter physics, the direct measurement of the three-dimensional dielectric tensor has been limited by the vectorial and inhomogeneous nature of light scattering from anisotropic materials. Here, we present a dielectric tensor tomographic approach to directly measure dielectric tensors of anisotropic structures including the spatial variations of principal refractive indices and directors. The anisotropic structure is illuminated with a polarized plane wave with various angles and polarization states. Then, the scattered fields are holographically measured and converted into vectorial diffracted field components. Finally, by inversely solving a vectorial wave equation, the three-dimensional dielectric tensor is reconstructed. Using this approach, we demonstrate quantitative tomographic measurements of various nematic liquid-crystal structures and their fast three-dimensional non-equilibrium dynamics.

Capillary Flow Characterizations of Chiral Nematic Cellulose Nanocrystal Suspensions.

Studying the flow-induced alignment of anisotropic liquid crystalline materials is of major importance in the 3D printing of advanced architectures. However, in situ characterization and quantitative measurements of local orientations during the 3D printing process are challenging. Here, we report a microfluidic strategy integrated with polarized optical microscopy (POM) to perform the in situ characterization of the alignment of cellulose nanocrystals (CNCs) under the shear-flow condition of the 3D printer's nozzle in the direct ink writing process. To quantify the alignment, we exploited birefringence measurements under white and monochromatic light. We show that the flow-induced birefringence patterns are significantly influenced by the initial structure of the aqueous CNC suspensions. Depending on the CNC concentration and sonication treatment, various structures can form in the CNC suspensions, such as isotropic, chiral nematic (cholesteric), and nematic (gel-like) structures. In the chiral nematic phase, in particular, the shear flow in the microfluidic capillary has a distinct effect on the alignment of the CNC particles. Our experimental results, complemented by hydrodynamic simulations, reveal that at high flow rates (Er ≈ 1000), individual CNC particles align with the flow exhibiting a weak chiral structure. In contrast, at lower flow rates (Er ≈ 241), they display the double-twisted cylinder structure. Understanding the flow effect on the alignment of the chiral liquid crystal can pave the way to designing 3D printed architectures with internal chirality for advanced mechanical and smart photonic applications.

Facile adjustment on cellulose nanocrystals composite films with glycerol and benzyl acrylate copolymer for enhanced UV shielding property

In the present work, cellulose nanocrystals (CNCs) composite films with suitable applicable capabilities were prepared by facilely incorporating glycerol (Gly) and poly(benzyl acrylate) (PBA). Chemical and morphological variations during the fabrication of the films were systematically characterized. The properties of modified CNCs composite films including UV blocking ability, mechanical strength and thermal properties were characterized to assess their applicable potentials. As a result, the composite films have good UV shielding property in UVC (220–280 nm) region and UVB (280–320 nm) region. The shielding performance of the modified film in the ultraviolet absorption region reached 92.77% to 95.49% respectively, without damaging the original chiral nematic structure of the films. Along with the modification, BACNC film improved the mechanical properties, presenting the tensile strength 16 times higher compared to pure CNCs film. The nanocomposite films proposed in this work showed promising potentials in broad fields, such as food preservation, medical protection, and surface coating applications.

Highly Tough, Stretchable, and Solvent-Resistant Cellulose Nanocrystal Photonic Films for Mechanochromism and Actuator Properties.

Cellulose nanocrystals (CNCs)-derived photonic materials have confirmed great potential in producing renewable optical and engineering areas. However, it remains challenging to simultaneously possess toughness, strength, and multiple responses for developing high-performance sensors, intelligent coatings, flexible textiles, and multifunctional devices. Herein, the authors report a facile and robust strategy that poly(ethylene glycol) dimethacrylate (PEGDMA) can be converged into the chiral nematic structure of CNCs by ultraviolet-triggered free radical polymerization in an N,N-dimethylformamide solvent system. The resulting CNC-poly(PEGDMA) composite exhibits impressive strength (42MPa), stretchability (104%), toughness (31MJm-3 ), and solvent resistance. Notably, it preserves vivid optical iridescence, displaying stretchable variation from red, yellow, to green responding to the applied mechanical stimuli. More interestingly, upon exposure to spraying moisture, it executes sensitive actuation (4.6°s-1 ) and multiple complex 3D deformation behaviors, accompanied by synergistic iridescent appearances. Due to its structural anisotropy of CNC with typical left-handedness, the actuation shows the capability to generate a high probability (63%) of right-handed helical shapes, mimicking a coiled tendril. The authors envision that this versatile system with sustainability, robustness, mechanochromism, and specific actuating ability will open a sustainable avenue in mechanical sensors, stretchable optics, intelligent actuators, and soft robots.