Orientational Order Parameter Research Articles

Different Mechanisms of Translational Symmetry Breaking in Liquid-Crystal Coil–Rod–Coil Triblock Copolymers

A molecular-statistical theory of coil-rod–coil triblock copolymers with orientationally ordered rod-like fragments has been developed using the density functional approach. An explicit expression for the free energy has been obtained in terms of the direct correlation functions of the reference disordered phase, the Flory–Huggins parameter and the potential of anisotropic interaction between rigid rods. The theory has been used to derive several phase diagrams and to calculate numerically orientational and translational order parameter profiles for different polymer architecture as a function of the Flory–Huggins parameter, which specifies the short-range repulsion and as functions of temperature. In triblock copolymers, the nematic–lamellar transition is accompanied by the translational symmetry breaking, which can be caused by two different microscopic mechanisms. The first mechanism resembles a low dimensional crystallization and is typical for conventional smectic liquid crystals. The second mechanism is related to the repulsion between rod and coil segments and is typical for block copolymers. Both mechanisms are analyzed in detail as well as the effects of temperature, coil fraction and the triblock asymmetry on the transition into the lamellar phase.

Derivation of coarse-grained force fields for buckling-induced topological defects of liquid crystals.

Microscopic details of buckling-induced topological defects are required for molecular design of smectic liquid crystals to control buckling instability of the layers. In this study, we present a multiobjective optimization method to derive the coarse-grained (CG) force fields with sufficiently precise buckling characteristics including the molecular details for molecular dynamics (MD) simulations. We perform CGMD simulations of buckling deformation at sample points in the CG force field parameter space, from which the response surfaces of objective functions such as the scalar orientational order parameters, critical angles of layer collapse, and radial distribution functions are estimated. Since not all objective functions can be optimized simultaneously, we use a genetic algorithm to calculate the Pareto set of optimal solutions. We select the models with different molecular head-tail symmetries to study buckling deformation. The extracted CG model successfully reproduces the buckling deformation in terms of the collapse of smectic layers through the generation of dislocations with dipole disclinations. We also find that the molecular symmetry is a dominant factor to control the class of the buckling-induced dislocations.

All-atom molecular dynamics simulation of acrylamide-based triblock copolymers with thermal responsive end blocks in a mixed salt solution containing divalent cations

In this work, a new smart copolymer based on polyacrylamide with the triblock classification was presented in order to propose an efficient associating polymeric material to create a physical network structure in saline water. To tune the desired copolymer, the effect of amide's type and hydrophobic pendant moieties of the potentially thermoresponsive end blocks on the physicochemical characteristics of the intermediate water-soluble block was studied in a solution containing Ca2+, Mg2+ and Cl− via atomistic simulations. The investigation of ions' mechanism of action on the water's perturbations via the calculation of water's orientational order parameter demonstrated that the divalent ions, as strong chaotropic agents, changed the water's tetrahedrality. Moreover, the coordination complexes created by the divalent ions as the coordination center and the negatively charged elements of the blocks' amides as the complexing agents intensified this issue in the block-water interface via increasing the interfacial concentration of the cations. This phenomenon has affected the blocks' hydrophilicity and hydration levels, capturing and ordering of water by changing the water's interfacial tetrahedral H-bond network structure. These behavioral variations in the solution led to changes in the dimensional, conformational, dynamic and interactional characteristics of the copolymers' blocks.

Micro-alloying effects of Co on structural and dynamic properties of CeAlCu glass-forming melts by ab initio molecular dynamics simulations

The structural and dynamic properties of Ce70-xAl10Cu20Cox (x = 0, 0.5, 1, 2 and 5) glass-forming melts were investigated by ab initio molecular dynamics simulations. We found that Al or Cu atoms were dispersed homogeneously with minor Co addition. The bond orientational order parameter W^6 of Al decreased with Co addition, which agreed well with the experimental result. The short-range order was regulated with minor Co addition, which benefited the glass-forming ability. Strong hybridizations between Co 3d and Al 3p and Co 3d and Ce 5d were observed. The hybridizations are the physical origin of the bond-shortening effects and they contribute to the special atomic packing. We investigated the dynamic properties of the melts and found that the self-diffusion coefficient of Cu reached a minimum in the Ce69Al10Cu20Co1 melt. The investigation of Ce70-xAl10Cu20Cox glass-forming melts provide an improved understanding of the micro-alloying effects of Co at the atomic scale.

Deep Blue Fluorescent Material with an Extremely High Ratio of Horizontal Orientation to Enhance Light Outcoupling Efficiency (44%) and External Quantum Efficiency in Doped and Non-Doped Organic Light-Emitting Diodes

A novel bis-4Ph-substituted 9,10-dipehnylanthracene deep blue [1931 CIE (0.15, 0.08)] fluorescent compound, AnB4Ph, has been synthesized and characterized for organic light-emitting diode (OLED) applications. Our experimental study of AnB4Ph excludes the possibility of triplet-triplet annihilation, hybridized local and charge transfer, or thermally activated delayed fluorescent characteristics of the material. Since the solid-state photoluminescence quantum yield of AnB4Ph was determined to be 48%, assuming a 100% for the charge recombination efficiency, the light outcoupling efficiency (ηout) of an AnB4Ph non-doped OLED achieving an external quantum efficiency (EQE) of 5.3% is at least 44%, which is more than twofold higher than 20% for conventional OLEDs. Both grazing incidence wide-angle X-ray scattering (GIWAXS) and angle-dependent photoluminescence (ADPL) measurements reveal AnB4Ph having a high value of order parameter (SGIWAXS) of 0.61 for a ππ stacking along the normal direction and an orientation order parameter (SADPL) for a horizontal emitting dipole moment of -0.50 or Θ (horizontal-dipole ratios) of 100%, respectively. Otherwise, a refractive index (n) measurement provides a n = 1.80 for AnB4Ph thin films. Based on ηout = 1.2 × n-2, the calculated ηout is 37%, which is also in accordance with the results of GIWAXS and ADPL. We have also fabricated the classical fluorescent DPAVBi-doped AnB4Ph OLEDs, which display a true blue [1931 CIE (0.15 and 0.16)] electroluminescence with a high efficiency (EQE = 6.9%), surpassing the conventional ∼5% EQE. Based on an ηout of 42% for DPAVBi-doped AnB4Ph OLEDs, our studies suggest that the extremely horizontally aligned AnB4Ph host material exerts the same horizontal alignment on the DPAVBi dopant molecules.

Orientation order parameters and effective conductivity of a 2-D solid with partially disordered array of circular inhomogeneities

The paper focuses on the quantitative characterization of the microstructure of a two-dimensional heterogeneous solid with circular inhomogeneities that may vary from perfectly periodic arrangement to completely random one. This characterization is linked to the calculation of the effective conductivity of the material. The partially disordered system of disks is generated in the framework of the representative unit cell model using Metropolis algorithm. The orientation order metrics are taken as the structural parameters providing a quantitative measure of disorder, and their variation caused by the gradual disordering of the periodic system is assessed. The effective conductivity of the heterogeneous solid with partially disordered microstructure is evaluated by the multipole expansion method. It is shown that effective conductivity cannot be fully characterized by only one orientation order metric, and the required additional ones are identified.

Thermodynamics and self-organization of strongly coupled Coulomb clusters: An experimental study

In this experimental work, the thermodynamics and self-organization of classical two-dimensional Coulomb clusters are studied as a function of the cluster size. The experiments are carried out in a DC glow discharge argon plasma in the dusty plasma experimental device for clusters with different number of particles. Hexagonal symmetry around each individual particle is quantified using the local orientational order parameter (|ψ6|) for all the configurations. The screened Coulomb coupling parameter, which plays a key role in determining the thermodynamic nature of a Coulomb cluster, is estimated using Langevin dynamics and found to be sensitive to the number of particles present in the cluster. In addition, the process of self-organization and the dynamics of individual particles of the cluster as it changes from a metastable state to the ground state are examined through the estimation of dynamic entropy. Our findings suggest an intimate link between the configurational ordering and the thermodynamics of a strongly coupled Coulomb cluster system—an insight that might be of practical value in analyzing and controlling the microdynamics of a wider class of finite systems.

Molecular architecture dependence of mesogen rotation during uniaxial elongation of liquid crystal elastomers

Macroscopic deformation of liquid crystal elastomers (LCEs) has been assumed to result from the coupling dynamics of the elastic polymer network and liquid-crystalline mesogenic units. However, the microscopic dynamics of LCE molecules are extremely difficult to directly observe from experiments. In this work, in silico experiments of uniaxial elongation of LCEs were performed by molecular dynamics simulations. The molecular systems of main- and side-chain-type LCEs were constructed using coarse-graining techniques. The stress–strain curves as the response to an external force were obtained, and the orientational order parameter of the mesogens along the elongation axis was observed as evidence of symmetry breaking. For the main-chain LCEs, soft elasticity was clearly observed regardless of the details of the molecular architecture. A plateau region of the stress–strain curves appeared, corresponding to drastic symmetry breaking of the orientational order. In contrast, for the side-chain LCEs, the presence/absence of soft elasticity was highly dependent on the details of the molecular architecture. In some cases, rotation of the mesogens was inhibited by a local steric constraint by the main chain and crosslinked particles, which prevented the onset of soft elasticity.

Quantum-dots-dispersed bent-core nematic liquid crystal and cybotactic clusters: Experimental and theoretical insights.

We study a quantum-dots (QDs) dispersed bent-core nematic liquid crystalline system in planar geometry and present experimental measurements of the birefringence (Δn), order parameter (S), dielectric dispersion, absorption spectra, and optical textures with attention to variations with temperature. A bent-core liquid crystal (LC) 14-2M-CH_{3} is used as the host material and CdSe/ZnS core-shell type QDs are used as the dopant. The nematic (N) phase of the pristine (undoped) LC 14-2M-CH_{3} contains cybotactic clusters, which are retained by its QDs incorporated LC nanocomposite. Our experimental findings support: (i) reduced orientational order parameter of the QDs dispersed LC system compared to its pristine counterpart at fixed temperatures, (ii) reduced cybotactic cluster sizes due to the incorporation of QDs, and (iii) increased activation energies related to reduced cluster sizes. We complement the experiments with a novel Landau-de Gennes-type free energy for a doped bent-core LC system that qualitatively captures the doping-induced reduced order parameter and its dependence on the properties of the QDs and its variation with temperature.

Electrical stimulation of neonatal rat cardiomyocytes using conductive polydopamine-reduced graphene oxide-hybrid hydrogels for constructing cardiac microtissues

The development of diversified biomaterials in tissue engineering has been promoted by growing research into carbon-based nanomaterials. Usually, ideal scaffold materials should possess properties similar to the extracellular matrix of natural myocardial tissue. In this study, dopamine-reduced graphene oxide (GO), was prepared and doped into gelatin methacrylate (GelMA) hydrogels, resulting in novel conductive and mechanical properties for controlling cell growth. Cardiomyocytes (CMs) cultured on PDA-rGO-incorporated hydrogels (GelMA-PDA-rGO) had greater cytocompatibility than those cultured on GelMA hydrogels, as evidenced by higher cell survival rates and up-regulation of cardiac-relevant proteins. Finally, electrical stimulation was applied to facilitate the maturation of CMs which was seeded on different hydrogels. The findings revealed that electrical stimulation of conductive hybrid hydrogel scaffolds improved the orientational order parameter of sarcomeres (OOP). In addition, propagation of intercellular pacing signals, which improves the expression of gap junction proteins was noticed, likewise calcium handling capacity was present in conductive hybrid hydrogels compared to those in pure GelMA group. This study has shown that the combination of GelMA-PDA-rGO based conductive hydrogels and electrical stimulation possessed synergistic effects for engineering a more functional and mature myocardium layer as well as further application in drug screening and disease modeling in vitro.

Structure of cholinium glycinate biocompatible ionic liquid at graphite electrode interface.

We use constant potential molecular dynamics simulations to investigate the interfacial structure of the cholinium glycinate biocompatible ionic liquid (bio-IL) sandwiched between graphite electrodes with varying potential differences. Through number density profiles, we observe that the cation and anion densities oscillate up to ∼1.5 nm from the nearest electrode. The range of these oscillations does not change significantly with increasing electrode potential. However, the amplitudes of the cation (anion) density oscillations show a notable increase with increasing potential at the negative (positive) electrode. At higher potential differences, the bulkier N(CH3)3CH2 group of cholinium cations ([Ch]+) overcomes the steric barrier and comes closer to the negative electrode as compared to oxygen atom (O[Ch]+ ). We observe an increase in the interaction between O[Ch]+ and the positive electrode with a decrease in the distance between them on increasing the potential difference. We also observe hydrogen bonding between the hydroxyl group of [Ch]+ cations and oxygens of glycinate anions through the simulated tangential radial distribution function. Orientational order parameter analysis shows that the cation (anion) prefers to align parallel to the negative (positive) electrode at higher applied potential differences. Charge density profiles show a positive charge density peak near the positive electrode at all the potential differences because of the presence of partially positive charged hydrogen atoms of cations and anions. The differential capacitance (Cd) of the bio-IL shows two constant regimes, one for each electrode. The magnitude of these Cd values clearly suggests potential application of such bio-ILs as promising battery electrolytes.

Molecular-statistical theory of elasticity in nematic liquid crystals composed of polar and nonpolar molecules.

A molecular-statistical theory of the orientational elasticity of nematic liquid crystals has been developed employing the orientational deformation tensor which describes the rotation of the director. An explicit expression for the general elasticity tensor of the nematic phase has been obtained and the Frank elastic constants are expressed in terms of the three independent parameters of this tensor. Explicit expressions for the Frank elastic constants have been derived in the molecular field approximation in terms of the orientational order parameters and the corresponding coefficients of expansion of the intermolecular potential in spherical invariants. Frank elastic constants have been calculated numerically for nematic liquid crystals composed of both polar and nonpolar molecules together with the orientational order parameters using the classical Gay-Berne model interaction potential and the two of its popular modifications. The polarity of the uniaxial molecular shape has been directly introduced into the model potential by modifying the distance of closest approach. The elastic constants are presented as functions of temperature for different values of the molecular elongation, the anisotropy of the potential well and the molecular shape polarity. It has been shown that the elastic constants are much more sensitive to the details of the intermolecular interaction potential in comparison with the orientational order parameters. In particular, a relatively weak polarity of the molecular shape may result in an unusual decrease of the splay constant K_{11} which may vanish at some temperature leading to the instability of the homogeneous nematic phase. This may represent a mechanism of the formation of the splay-bend phase.

Inference of molecular orientation/ordering change nearby topological defects by the neural network function from the microscopic color information

Topological defects in liquid crystals (LCs) dominate molecular alignment/motion in many cases. Here, the neural network (NN) function has been introduced to predict the LC orientation condition (orientation angle and order parameter) at local positions around topological defects from the phase/polarization microscopic color images. The NN function was trained in advance by using the color information of an LC in a planar alignment cell for different orientation angles and temperatures. The photo-induced changes of LC molecules around topological defects observed by the time-resolved measurement was converted into the image sequences of the orientation angle and the order parameter change. We found that each pair of brushes with different colors around topological defects showed different orientation angle and ordering changes. The photo-induced change was triggered by the photoisomerization reaction of molecules, and one pair of brushes increased in its order parameter just after light irradiation, causing gradual rotation in the brush. The molecules in the other pair of brushes were disordered and rotated by the effect of the initially affected region. This combination approach of the time-resolved phase/polarization microscopy and the NN function can provide detailed information on the molecular alignment dynamics around the topological defects.

Ion conformation and orientational order in a dicationic ionic liquid crystal studied by solid-state nuclear magnetic resonance spectroscopy

Ionic liquids crystals belong to a special class of ionic liquids that exhibit thermotropic liquid-crystalline behavior. Recently, dicationic ionic liquid crystals have been reported with a cation containing two single-charged ions covalently linked by a spacer. In ionic liquid crystals, electrostatic and hydrogen bonding interactions in ionic sublayer and van der Waals interaction in hydrophobic domains are the main forces contributing to the mesophase stabilization and determining the molecular orientational order and conformation. How these properties in dicationic materials are compared to those in conventional monocationic analogs? We address this question using a combination of advanced NMR methods and DFT analysis. Dicationic salt 3,3′-(1,6-hexanediyl)bis(1-dodecylimidazolium)dibromide was studied. Local bond order parameters of flexible alkyl side chains, linker chain, and alignment of rigid polar groups were analyzed. The dynamic spacer effectively “decouples” the motion of two ionic moieties. Hence, local order and alignment in dicationic mesophase were similar to those in analogous single-chain monocationic salts. Bond order parameters in the side chains in the dicationic smectic phase were found consistently lower compared to double-chain monocationic analogs, suggesting decreasing contribution of van der Waals forces. Overall dication reorientation in the smectic phase was characterized by low values of orientational order parameter S. With increased interaction energy in the polar domain the layered structure is stabilized despite less ordered dications. The results emphasized the trends in the orientational order in ionic liquid crystals and contributed to a better understanding of interparticle interactions driving smectic assembly in this and analogous ionic mesogens.

Analysis of spatial orientation distribution of highly oriented polyimide film using micro ATR-FTIR spectroscopic imaging method

Molecular orientation of aromatic polyimides (PIs) and their precursor of poly(amic ester)s (PAE) in the biaxially oriented films were analyzed by polarized microscopic attenuated-total-reflection Fourier-transform infrared absorption spectroscopy (micro pATR-FTIR) imaging. The films were prepared by shearing a lyotropic liquid crystal (LC) solution of the PAE on a glass substrate and subsequent drying under a N2 flow, and the long axis of polymer chains were distributed around the shear direction. In the film, streak-shaped defects were observed along the shear direction with optical microscopy. Such structural heterogeneities on the micrometer (μm) scale are expected to be visualized in spatial distribution map of molecular orientation order acquired with micro pATR-FTIR imaging. In this study, uniaxial orientation order parameter, S, and a mean square cosine value, ⟨cos2ψ⟩, were used to quantify the degree of orientation of the PI main chain and that of aromatic imide plane, respectively. It was revealed that the films are apparently homogeneous in the spatial distribution map of the S, while the films exhibited obvious heterogeneity in that of ⟨cos2ψ⟩, in which “face-on” and “edge-on” orientation domains coexist. The results indicate that orientation direction of the rigid PI chains is fixed in the averaged orientation direction of the oriented PAE matrix during thermal imidization, while the aromatic imide ring can be rotated around the main chain. Furthermore, cracks in the PI film were successfully visualized by ATR-FTIR imaging, and the orientation distribution inside the cracks was investigated. Through this structural study, we validated the quantitative capability of the micro pATR-FTIR imaging method thorough the analyses of highly oriented PI films and demonstrated its ability to investigate μm-scale heterogeneity on the basis of molecular orientation analyses.

Effect of Molecular Weight on Electro – Optic Switching Times of Liquid Crystal Polymer Doped with Ceo2 Nanoparticles

Nonlinearity liquid crystal cell which doped with Ferroelectric nanoparticles characters studied in this paper according to their eclectic absorption. Polysiloxin series with side chain liquid polymers used with side chain polymers and molecular weight ran This study consternate on polymers electro. optic characteristic with various molecular weights by using the mesogenic units and a stable polysiloxane. Suspension sensitivity or Electro-visual response to the mark of the used electric field, a real character to electric liquid crystals. The addition of CeO2, nanoparticles to polymer rise dielectric anisotropy and minimize response times. It observed that the voltages raised with molecular weight rising, and when intensity value rise, we gain voltage operating. Spectrometer used infrared measurements to locate the orientational order parameters, for liquid crystals with a side series. The orientational order parameters rely on temperature with various molecular weights and the threshold voltage.

Rheology and structure of suspensions of spherocylinders via Brownian dynamics simulations

Brownian dynamics simulations were employed to investigate the rheological properties and structure of suspensions of rigid spherocylinders, as a model for rodlike colloids. The spherocylinders interacted only through a soft repulsive force that mimicked a hard spherocylinder interaction. The translational and rotational diffusivities of hard spherocylinder suspensions were reproduced. Liquid crystalline phases, including isotropic, nematic, and smectic and solid phases were identified using orientational and hexatic order parameters and pair distribution functions. Typical flow curves observed experimentally for rodlike colloidal suspensions were reproduced in the simulations, with two shear thinning regions that bracketed a viscosity plateau at intermediate Péclet numbers. The transient rheology and structure of suspensions that were nematic at rest exhibited a variety of behaviors that depended on the Péclet number and concentration. Systemwide domains that aligned in and kayaked about the vorticity direction, domains that rotated coherently locally, and layered domains were observed. Oscillations in the order parameter, viscosity, and the first and second normal stress differences were associated with changes in the structure.

Quantitative Analysis of Actin Cytoskeleton's Morphological Changes during EMT in Lung Cancer and Pre-Cancer Cell Lines

Lung cancer, a highly metastatic disease, is the world's leading cause of cancer death. Epithelial to mesenchymal Transition (EMT), a key element of the metastatic process in lung cancer, is accompanied by corresponding changes in cellular mechanical properties, principally resulting from actin stress fiber formation. The details of the micro and macro rearrangement processes involved in this cytoskeletal reorganization is not yet fully understood. Using standard transfection/ staining and imaging protocols, we identified a novel cellular phenotype during the EMT process. This interim phenotype was characterized by a disoriented (nest-like) stress fiber arrangement in contrast to the highly aligned (semi-parallel) cytoskeleton in the final mesenchymal cell. The formation of this nest-like pattern was consistent amongst different EMT induction techniques and concentrations. Drug treatment assays suggested that inhibition of the PI3K-Akt signaling pathway prevents the formation of the final semi-parallel phenotype from the nest-like phenotype. To quantify the actin cytoskeleton remodeling, we utilized computational extraction of actin stress fibers from wide-field and confocal microscopic images. We developed a computational tool that extracts the actin stress fibers as straight lines, quantified through their locations, lengths and relative orientations. This tool further statistically processes the orientation information to generate the Orientational Order Parameter (OOP), which serves as a figure of merit to classify cells into nest-like cytoskeletal phenotype and the semi-parallel cytoskeletal phenotype. This figure of merit could possibly be utilized for other cytoskeletal remodeling processes such as fibrosis, apoptosis, cell division and migration.

Mesoscale modelling of droplets' self-assembly in microfluidic channels.

A recently proposed mesoscale approach for the simulation of multicomponent flows with near-contact interactions is employed to investigate the early stage formation and clustering statistics of soft flowing crystals in microfluidic channels. Specifically, we first demonstrate the ability of the aforementioned mesoscale model to accurately reproduce main mechanisms leading to the formation of two basic droplet patterns (triangular and hexagonal), in close agreement with experimental evidence. Next, we quantitatively evaluate the device-scale clustering efficiency of the crystal formation process by introducing a new orientational order parameter, based on the Delaunay triangulation and Voronoi diagrams analysis of the droplet patterns. The mesoscale computational approach employed in this work proves to be an efficient tool to shed new light on the complex dynamics of dense emulsions, from short-scale thin-film hydrodynamics, all the way up to global structure formation and statistics of the resulting droplets ensembles.

General liquid-crystal theory for anisotropically shaped molecules: Symmetry, orientational order parameters, and system free energy.

A general theory of liquid crystals is presented, starting from the group-theory symmetry analysis of the constituting molecules. A particular attention is paid to the type of elastic free-energies and their relationships with the molecular symmetries. The orientational order-parameter tensors are identified for each molecular symmetry, in a consideration of consistently keeping the leading, characteristic elastic free energies in a model. The order parameters are expressed in terms of symmetric traceless tensors, some of high orders, for all major molecular symmetries, including seven groups of axial symmetries and seven groups of polyhedral symmetries. For spatially inhomogeneous liquid crystals, the couplings of these tensors in the elastic energies are derived by expanding the interaction energies between these molecules. The aim is to provide a general view of the molecular symmetries of individual molecules, orientational order parameters characterizing the orientational distribution functions, and the elastic free energies, all under one single group-theory approach.