Liquid Crystalline Phase Research Articles

Liquid-liquid crystalline phase separation of spider silk proteins.

Liquid-liquid phase separation (LLPS) of proteins can be considered an intermediate solubility regime between disperse solutions and solid fibers. While LLPS has been described for several pathogenic amyloids, recent evidence suggests that it is similarly relevant for functional amyloids. Here, we review the evidence that links spider silk proteins (spidroins) and LLPS and its role in the spinning process. Major ampullate spidroins undergo LLPS mediated by stickers and spacers in their repeat regions. During spinning, the spidroins droplets shift from liquid to crystalline states. Shear force, altered ion composition, and pH changes cause micelle-like spidroin assemblies to form an increasingly ordered liquid-crystalline phase. Interactions between polyalanine regions in the repeat regions ultimately yield the characteristic β-crystalline structure of mature dragline silk fibers. Based on these findings, we hypothesize that liquid-liquid crystalline phase separation (LLCPS) can describe the molecular and macroscopic features of the phase transitions of major ampullate spidroins during spinning and speculate whether other silk types may use a similar mechanism to convert from liquid dope to solid fiber.

Programmable orientation of blue phase soft photonic crystal

Understanding the structure formation and its underlying physical mechanism is a fundamental topic in condensed matter systems, with both academic and practical implications. Soft matter is playing a remarkable role in current era of information explosion, demonstrating enormous potential in integrated functional photonics. As unique soft photonic crystals with cubic symmetries, not only liquid crystalline blue phases (BPs) have circularly polarized selective reflection and ultra-fast electro-optical response, but also their three-dimensional photonic structures increase degrees-of-freedom for multiplexed optical modulation. In the thriving field of soft-matter-based photonics, precise and programmable engineering of BP crystal orientation is of vital importance for planar optical elements, which remains a challenging task due to the complexity of the nucleation process as well as the interaction between the BP building blocks and the boundary conditions. Aiming to gain a comprehensive understanding of how to tailor the orientation of BP crystals for the photonic applications of next generation, here we discuss the solutions for uniformity improvement and orientation control of BP crystals, about which a few of examples in combination with the underlying mechanisms are explained. In addition, the remaining challenges and the efforts that are expected are also reviewed. We expect this work provides a deeper understanding of phase transitions and resulting structures in soft crystals, which may open encouraging perspectives for their applications in photonics, biosensing, interfacial, and chemical engineering.

Liquid crystal and emulsifying properties of carboxymethyl glucoside as water-soluble surfactant

ABSTRACT Three derivatives of glucosides derived from n-dodecyl alcohol in a highly pure β-anomer were synthesised with the aim to yield the liquid crystalline phase at ambient temperature with improved water solubility. Effect of variation in headgroup polarity on thermal properties, liquid crystalline phases, and structures of these derivatives of n-dodecyl β-D-glucoside (β-GlcC12) has been examined through differential scanning calorimetry, optical polarising microscopy, and small- and wide-angle X-ray scattering, respectively. Derivative bearing two carboxymethyl and two hydroxyl groups at the sugar ring i.e. n-dodecyl 2,3-bis-O-[carboxymethyl]-β-D-glucopyranoside (2,3-diCOOH-β-GlcC12) exhibited lamellar phase at the room temperature in anhydrous condition by significantly reduced the melting and clearing temperatures compared to parent compound β-GlcC12. Under excess water condition, 2,3-diCOOH-β-GlcC12 was completely soluble to form a normal micellar solution. We further investigated its foaming performance and emulsifying ability in n-octane, n-dodecane, and n-hexadecane as the oil phase. Both aqueous solution of 2,3-diCOOH-β-GlcC12 emulsified with n-dodecane and n-hexadecane formed oil-in-water emulsion layer of more than 95% of the total system volume with n-dodecane/water system consistently maintains smaller particle sizes and a narrower polydispersity index. This supports the stronger emulsifying ability and better colloidal stability of the 2,3-diCOOH-β-GlcC12 in the n-dodecane/water system than in the n-hexadecane/water system.

Limitation and Potential of Lignin-Assisted Stabilisation of Oriented Liquid Crystalline Cellulosic Mesophase

This study aimed at progressing in the fundamental understanding of the lignin-assisted microstructural stabilisation observed in solution-processed materials based on the polymer blend of hydroxypropyl cellulose and hardwood organosolv lignin. Mechanical analysis, polarised infrared spectroscopy and wide-angle X-ray scattering of shear cast blend films revealed that the effect of lignin on the flow-oriented cellulosic mesophase is also valid for blends composed of ethyl cellulose as liquid crystalline matrix polymer and lignin derived oligomers from base-catalysed depolymerisation as dispersed “microstructural cementing agent”. The results underline the significant role of the solvent diffusion between the continuous cellulosic and the dispersed lignin phase, which is ascribed to polymer-/oligomer-solvent interactions. An abundance of the solvent within the lignin phase caused the disruption of the microstructural stabilisation effect. The concept of a balanced proton-donor activity was introduced linking the solvent diffusion with the lyotropic liquid crystalline phase formation, the macro- and microstructural blend morphology and aspects regarding the solution processing.

13C NMR studies and orientational order of rod-like mesogens with strongly polar terminal cyano group

ABSTRACT 13C NMR studies of two rod-like mesogens with core units consisting of two and three phenyl rings with strongly polar terminal cyano groups are reported. The two-ring mesogen displayed an enantiotropic smectic A (SmA) mesophase while for the three-ring mesogen, enantiotropic nematic and SmA mesophases were observed. The solution 13C NMR studies of both the mesogens are carried out besides static 13C NMR measurements in the liquid crystalline phase. For the two-ring mesogen, the chemical shift anisotropy (CSA) tensors of the core unit are determined by the 2D-separation of undistorted powder patterns by effortless recoupling (SUPER) experiment. Furthermore, 2D-separated local field (SLF) measurements are realised for both the mesogens in the liquid crystalline phase to determine the 13C-1H dipolar couplings to find the orientational order parameters of the phenyl rings. The main order parameter (Szz) of the two-ring mesogen varies from 0.63 to 0.53 across the SmA phase and for the three-ring mesogen, the Szz values are found to be ~0.73 in the SmA phase and ~0.69 in the nematic phase. The CSA values determined from the SUPER experiment are expected to be a significant utility for molecules with polar terminal nitro/cyano groups as ferroelectric nematic phases are realised in them.

Microemulsion Templating Synthesis of Hierarchical Porous Ag‐Doped SiO2‐TiO2 Composites for Efficient Degradation of Noxious Methylene Blue Dye: Effect of Calcination Environment

AbstractWe report herein a dual function mesoporous structure of titanium oxide based porous carbon with large surface‐to‐volume ratios for efficient degradation of noxious methylene blue dye (MB) from an aqueous environment. The mesoporous photocatalysts is fabricated via direct template synthesis of highly ordered silica‐titania monolith doped with Ag0/Ag2O starting from a quaternary microemulsion liquid crystalline phase. The produced monoliths are subjected in‐situ to doping by growing silver, in the cubic cavities, and on the silica/titania structure's domain. This study investigated the efficiency of novel composite materials, consisting of silver‐doped silica‐titania (SiO2/TiO2), which is synthesized using the microemulsion templating approach. The photocatalytic performance of the synthesized composite in the photodegradation of MB has been studied. The procedure of photodegradation was employed to achieve decolorization of the cationic MB dye using visible light. The catalyst effectively achieved the decolorization of the dyed solution through the processes of adsorption and photodegradation. The composite consisting of SiO2, TiO2, and Ag2O at a ratio of 1 : 1:0.5, which underwent calcination in an air environment (AgOST), exhibited a removal efficiency of 99 % compared to its calcined state under argon (AgSTC).

Structural investigation of the liquid crystalline phases of three homologues from the nOS5 series (n = 9, 10, 11) by X-ray diffraction

ABSTRACT Polarizing optical microscopy and differential scanning calorimetry are used to determine the phase sequence of three liquid crystalline 4-pentylphenyl-4’-n-alkyloxythiobenzoates with n = 9, 10, 11. The X-ray diffraction method is applied for structural characterisation of the liquid crystalline phases. The smectic layer spacing, tilt angle, average distance between the long axes of molecules and correlation length of the short-range order are determined as a function of temperature. For the crystal-like smectic phases with the hexagonal or herring-bone packing, the unit cell parameters are obtained. The presence of the tilted hexagonal phase for n = 10, 11 and tilted herring-bone phase for n = 9, 10 is indicated, although the direction of the tilt cannot be determined.

Ferroelectric Smectic C Liquid Crystal Phase with Spontaneous Polarization in the Direction of the Director.

In the previous study, the existence of an unidentified ferroelectric smectic phase is demonstrated in the low-temperature region of the ferroelectric smectic A phase, where the layer spacing decreases with decreasing temperature. In the present study, the phase is identified by taking 2D X-ray diffraction images of a magnetically oriented sample while allowing it to rotate and constructed a 3D reciprocal space with the sample rotation angle as the third axis for the whole picture of the reciprocal lattice vectors originating from the smectic structure. Consequently, circular diffraction images are obtained when the reciprocal lattice vectors are evenly distributed on the conical surface at a certain inclination angle in the reciprocal space. This result provides clear evidence that the phase in question is smectic C. The polarization properties also showed that the observed smectic C phase has spontaneous polarization in the direction parallel to the director and is identified as ferroelectric smectic C. These results provide a new type of classification for liquid crystalline phases that has been established over many years and is a significant contribution to the basic science of soft matter research.

Manipulation of Supramolecular Chirality in Bicontinuous Networks of Bent-Shaped Polycatenar Dimers.

Bicontinuous cubic liquid crystalline (LC) phases are of particular interest due their possible applications in electronic devices and special supramolecular chirality. Herein, we report the design and synthesis of first examples of achiral bent-shaped polycatenar dimers, capable of displaying mirror symmetry breaking in their cubic and isotropic liquid phases. The molecules have a taper-shaped 3,4,5-trialkoxybenzoate segment connected to rod-like building unit terminated with one terminal flexible chain. The two segments were connected using an aliphatic spacer with seven methylene units to induce bending of the whole structure. Investigated by the small-angle X-ray scattering (SAXS), a double network achiral cubic phase Cub/Ia3 d, which is a meso-structure, and a chiral triple network cubic phase Cub/I23[*] are formed. The molecules self-assemble into molecular helices and progress along the networks. Interestingly, different linking groups such as ester or azo linkages and core fluorination lead to distinct local helicity, resulting in an alkyl chain volume dependent phase transition sequence Ia3d(L)-I23*-Ia3d(S). The re-entry of Iad phase and loss of supramolecular chirality is attributed to the delicate influence of steric effect at the mono-substitute end and interhelix interaction. Besides, aromatic core fluorination was proved to be a successful tool stabilizing the cubic phases in these dimers.

On the Use of Reflection Polarized Optical Microscopy for Rapid Comparison of Crystallinity and Phase Segregation of P3HT:PCBM Thin Films.

Rapid, nondestructive characterization techniques for evaluating the degree of crystallinity and phase segregation of organic semiconductor blend thin films are highly desired for in-line, automated optoelectronic device fabrication facilities. Here, it is demonstrated that reflection polarized optical microscopy (POM), a simple technique capable of imaging local anisotropy of materials, is capable of determining the relative degree of crystallinity and phase segregationof thin films of polymer:fullerene blends. While previous works on POM of organic semiconductors have largely employed the transmission geometry, it is demonstrated that reflection POM provides 3× greater contrast. The optimal configuration is described to maximize contrast from POM images of polymer:fullerene films, which requires Köhler illumination and slightly uncrossed polarizers, with an uncrossing angle of ±3°. It is quantitatively demonstrated that contrast in POM images directly correlates with 1) the degree of polymer crystallinity and 2) the degree of phase segregation between polymer and fullerene domains. The origin of the bright and dark domains in POM is identified as arising from symmetry-broken liquid crystalline phases (i.e., dark conglomerates), and it is proven that they have no correlation with surface topography. The use of reflection POM as a rapid diagnostic tool for automated device fabrication facilities is discussed.

Electro-Optic Kerr Response in Optically Isotropic Liquid Crystal Phases

The results of an experimental investigation of the temperature and wavelength dependence of the Kerr constant (K) of mixtures with an increasing amount of chiral dopant in an isotropic liquid crystal phase are reported. The material was composed of a nematic liquid crystal (5CB) and a chiral dopant (CE2), which formed non-polymer-stabilized liquid crystalline blue phases with an exceptionally large value of K∼2 × 10−9 mV−2. The measurements were performed on liquid and blue phases at several concentrations covering a range of temperatures and using three wavelengths: 532 nm, 589 nm and 633 nm. The work focused on changes caused by concentration and their impact on the increase in the value of K, and it was found that in the case of the 5CB/CE2 mixture these changes were significant and quite systematic with temperature and wavelength. It is shown that the dispersion relation based on the single-band birefringence model described K well in isotropic liquid crystal phases at all of the measured concentrations. In an isotropic fluid, both temperature-dependent parameters in the dispersion relation had a simple linear form and, therefore, the K-surface could be described by only four constants. In the blue phase, the expression reproducing the temperature variation of K depended on concentration, which could vary from being almost linear to quasi-linear and could be represented well by an inverse exponential analytic expression.

Two-stage assembly of patchy ellipses: From bent-core particles to liquid crystal analogs.

We investigate the two-dimensional behavior of colloidal patchy ellipsoids specifically designed to follow a two-step assembly process from the monomer state to mesoscopic liquid-crystal phases via the formation of the so-called bent-core units at the intermediate stage. Our model comprises a binary mixture of ellipses interacting via the Gay-Berne potential and decorated by surface patches, with the binary components being mirror-image variants of each other-referred to as left-handed and right-handed ellipses according to the position of their patches. The surface patches are designed so as in the first stage of the assembly the monomers form bent-cores units, i.e., V-shaped dimers with a specific bent angle. The Gay-Berne interactions, which act between the ellipses, drive the dimers to subsequently form the characteristic phase observed in bent-core liquid crystals. We numerically investigate-by means of both Molecular Dynamics and Monte Carlo simulations-the described two-step process: we first optimize a target bent-core unit and then fully characterize its state diagram in temperature and density, defining the regions where the different liquid crystalline phases dominate.

Nanoscale View of Alignment and Domain Growth in a Hexagonal Columnar Liquid Crystal.

Highly ordered liquid crystalline (LC) phases have important potential for organic electronics. We studied the molecular alignment and domain structure in a columnar LC thin film with nanometer resolution during in situ heating using four-dimensional scanning transmission electron microscopy (4D STEM). The initial disordered vapor-deposited LC glass thin film rapidly ordered at its glass transition temperature into a hexagonal columnar phase with small (<10 nm), well-aligned, planar domains (columns oriented parallel to the surface). Upon further heating, the domains coarsen via bulk diffusion, then the film crystallizes, then finally transforms back to an LC phase at an even higher temperature. The LC phase at high temperature shows straight columns of molecules, which we attribute to structure inherited from the intermediate crystalline phase. Nanoscale 4D STEM offers direct insight into the mechanisms of domain reorganization, and intermediate crystallization is a potential approach to manipulate orientational order and texture at the nano- to mesoscale in LC thin films.

In silico study of DNA mononucleotide self-assembly.

Recent experiments have demonstrated the self-assembly and long-range ordering of concentrated aqueous solutions of DNA and RNA mononucleotides. These are found to form Watson-Crick pairs that stack into columns that become spatially organized into a columnar liquid-crystalline phase. In this work, we numerically investigate this phase behavior by adopting an extremely coarse-grained model in which nucleotides are represented as semi-disk-like polyhedra decorated with attractive (patchy) sites that mimic the stacking and pairing interactions. We carry out Monte Carlo simulations of these patchy polyhedra by adapting algorithms borrowed from computer graphics. This model reproduces the features of the experimental phase behavior, which essentially depends on the combination of pairing and stacking interactions.

Multiphoton‐And SHG‐Active Pyrimidine‐Based Liquid Crystalline Thin Films Toward 3D Optical Data Storage

AbstractAn original asymmetric achiral pyrimidine core molecule, with long carbon chains on one side and a coumarin fragment on the other, is designed. This advanced molecular structure enabled the spontaneous emergence of crystalline and liquid crystalline thin films with strong 2nd harmonic generation (SHG) without any corona polishing process or tedious deposition techniques. Moreover, pin‐pointed multiphoton absorption in the liquid crystalline phase effectively switches off the SHG signal locally and permanently, underlining its interest in 3D data storage. This prototypical material, which can be fully addressed by NLO processes, multiphoton writing, and SHG reading, paves the way for the development of efficient flexible materials for 3D optical data storage.

Supramolecular Arrangement and Conformational and Dynamic Properties of Chiral Smectic Liquid Crystals Obtained through Nuclear Magnetic Resonance: A Brief Review

Ferroelectric and antiferroelectric smectic liquid crystalline (LC) phases are still at the center of investigations and interests for both their fundamental properties and variety of technological applications. This review aims to report the main contributions based on different nuclear magnetic resonance (NMR) techniques to the study of chiral liquid crystalline calamitic mesogens forming smectic phases, such as the SmA, the SmC* (ferroelectric), and the SmC*A (antiferroelectric) phases. 2H NMR and 13C NMR techniques and their combination were of help in clarifying the local orientational properties (i.e., the molecular and fragments’ main orientational order parameters) at the transition between the SmA and the SmC* phases, and in the particular case of de Vries liquid crystals, NMR studies gave important clues regarding the actual models describing the molecular arrangement in these two phases formed by de Vries LCs. Moreover, this review describes how the combination of 2H NMR relaxation times’ analysis, 1H NMR relaxometry, and 1H NMR diffusometry was successfully applied to the study of chiral smectogens forming the SmC* and SmC*A phases, with the determination of relevant parameters describing both rotational molecular and internal motions, collective dynamics, and translational self-diffusion motions. Several cases will be reported concerning NMR investigations of chiral ferroelectric and antiferroelectric phases, underlining the great potential of combined NMR approaches to the study of supramolecular, conformational, and dynamic properties of liquid crystals.

Synthesis of new liquid crystal Schiff's bases bearing ester moiety, DFT calculation and mesomorphic studies

A new homologues series of liquid crystalline material (E)-4-(((3,4-dimethylphenyl) imino) methyl) phenyl4-n-alkoxybenzoate (SBn) synthesized. SBn compounds was subjected to analysis using infrared spectroscopy, proton magnetic resonance, 13C NMR, UV- visible and mass spectroscopy for characterization. The investigation of liquid crystalline phases and their transition enthalpies was carried out using a polarized optical microscope and differential scanning calorimetry, respectively. All compounds within the homologous series display mesogenic properties. The SB1 -SB7 homologues exhibit an enantiotropic nematic mesophase within the temperature range of 180–106 °C, while the SB14 -SB18 homologues show a smectic A mesophase at temperatures between 78 and 75 °C. Additionally, the SB8 -SB10 homologues exhibit a monotropic smectic A mesophase at 61–59 °C. The phase transitions observed in series SBn are compared with those of structurally related compounds to assess the influence of central linkage and lateral tail `substitution on their mesophase behavior. With the help of DFT; EHOMO and ELUMO energy gap were computed to be negative for all derivative molecules, indicating their stability and in the following order: SB4 > SB6 > SB8 > SB12. Dielectric through determined values of complex permittivity of the synthesised liquid crystal over a broad frequency range are reported. Determined static permittivity value of liquid crystal is 2.25, at room temperature. The compound SBn exhibited a relaxation peak in the dielectric loss spectra in the microwave frequency range, which may be assigned to the rotation of the end polar group of the molecule.

Specialized Listeria monocytogenes produce tailocins to provide a population-level competitive growth advantage.

Tailocins are phage tail-like bacteriocins produced by various bacterial species to kill kin competitors. Given that tailocin release is dependent upon cell lysis, regulation of tailocin production at the single-cell and population level remains unclear. Here we used flow cytometry, competition assays and structural characterization of tailocin production in a human bacterial pathogen, Listeria monocytogenes. We revealed that a specialized subpopulation, constituting less than 1% of the total bacterial population, differentiates to produce, assemble and store thousands of tailocin particles. Tailocins are packed in a highly ordered manner, clustered in a liquid crystalline phase that occupies a substantial volume of the cell. Tailocin production confers a competitive growth advantage for the rest of the population. This study provides molecular insights into tailocin production as a form of altruism, showing how cell specialization within bacterial populations can confer competitive advantages at the population level.

Correlation between preparation techniques and frictional properties of cellulose nanocrystals as additives in water-based lubricants

To explore the tribological characteristics of cellulose nanocrystals derived through various preparation techniques when utilized as additives in water-based lubricants, two types of cellulose nanocrystals (S-CNC and C-CNC) were chosen. These were produced via sulfuric acid hydrolysis and oxidation methods. The morphology and structural features were assessed through techniques such as Fourier-transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), laser confocal Raman spectroscopy, elemental analysis, scanning electron microscopy (SEM), and laser particle size analysis. According to thermogravimetric analysis (TGA), the thermal stability of S-CNC is slightly superior to that of C-CNC. S-CNC exhibits liquid crystallinity when the concentration exceeds 0.5 %, whereas C-CNC does not display liquid crystallinity at any concentration tested. Further investigation was conducted on the frictional properties of the two types of CNCs using a UMT reciprocating friction tester. The results indicate that both types of CNC exhibit significant friction reduction properties at various additive concentrations, provided the addition does not exceed w=1 %. When below their respective liquid crystalline phase concentrations, the friction reduction performance of S-CNC is slightly inferior to that of C-CNC; however, when above the liquid crystalline phase concentration, the friction reduction performance of S-CNC surpasses that of C-CNC. The addition of w=0.5 % S-CNC leads to a relative reduction of 63.4 % in the friction coefficient compared to the base system. Analysis of the steel plate surface contact angle and post-wear surface suggests that the lubrication mechanism of CNC involves the adsorption of polar functional groups such as hydroxyl or carboxyl groups from the CNC structure onto the friction pair surface, forming a lubricating protective film to varying degrees. Additionally, the liquid crystalline structure of S-CNC facilitates the formation of an ordered lubricating film, further enhancing the frictional properties. These findings provide valuable insights into the application of nanocellulose crystals as lubricant additives.

SURFACE ACTIVITY AND PHASE BEHAVIOUR OF POTASSIUM HEPTYLENE DECYL SUCCINATE / WATER BINARY SYSTEM

The surface activity of potassium heptylene decyl succinate (PHDS) at water-air interface was studied. The obtained results showed a very good correlation between the surface activity of PHDS and concentration of surfactant solutions and temperature of the system. The phase behaviour and structure of aggregates in PHDS)/water binary system were investigated. The phase diagram of the PHDS/water binary system was obtained depending on the concentration of components and temperature of the system. It was established that due to the double hydrocarbon chain of the PHDS molecule, the lamellar liquid crystalline phase exists across a wide range of the phase diagram. It was shown that upon the addition of water, the cross-sectional area of the PHDS molecules in lamellar liquid crystals is changed insignificantly. This result was associated with the invariability of the distance of the lipophilic layers of formed lamellar liquid crystals by PHDS molecules. On the basis of video-enhanced microscopic studies, it was established that in two-phase region of the phase diagram, lamellar liquid crystals coexist with water in the form of vesicles.