Lyotropic Liquid Crystal Phases Research Articles

Thermotropic “Plumber's Nightmare”—A Tight Liquid Organic Double Framework

AbstractGyroid, 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.

Thermotropic "Plumber's Nightmare"-A Tight Liquid Organic Double Framework.

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.

Dielectric anisotropy in self-assembling MXene-based lyotropic nematic compounds

The formation of a lyotropic liquid crystal phase at the level of MXene-based aqueous dispersions due to the self-assembling capacity of these two-dimensional (2D) materials has been previously successfully reported. However, the influence of electrical external factors has been less studied in spite of the fact that understanding the electrical behaviour of 2D-based liquid crystal compounds is vital for fostering the development of new innovative applications. Consequently, within this paper, we report an in-depth evaluation of the dielectric properties of liquid crystalline phases in Ti3C2 MXene aqueous dispersions. The dependence on the low voltage of planar ε⊥′ to homeotropic ε∥′ orientational transition is emphasized and discussed, while the influence of the electric field frequency at the level of dielectric anisotropy is assessed in respect to various concentrations of MXene flakes within the same 2D-based compounds. Nonetheless, dielectric spectroscopy highlights the biphasic nature (containing both nematic and isotropic phases) of the studied aqueous Ti3C2 MXene inks visible up to 20% MXene. Above this concentration, the existence of a pure nematic phase in the dispersion of highMXene concentration (>20 wt%) was detected based on the evaluation of dielectric permittivity against various voltage values.

Self-assembled lyotropic liquid crystals from natural surfactant: A study on their structural, rheological and antimicrobial behaviour

Soft self-assembled systems with smart functions have been explored over the past decades for diverse applications. However, the toxicity of synthetic surfactant based self-assembled systems and their stability always remain a point of concern. There is always a great quest to find an alternative to overcome such shortcomings of self-assembled systems. Hence, in this context, we made an effort to engineer self-assembled lyotropic liquid crystals (LLCs) using different concentrations of the medicinal plant Glycyrrhiza glabra L. in the nonaqueous polar media of glycerol, ethylene glycol and formamide. These nonaqueous solvents with considerable polarity, high cohesive energy, dipole moment and hydrogen bonding ability, not only offer the perfect environment for self-assembly, but also provide longtime stability. Nematic lyotropic ordering is obtained for studied systems at different concentrations of Glycyrrhiza glabra L./ nonaqueous solvents as confirmed via polarising optical microscopy (POM) and X-ray diffraction (XRD) analysis. Electrostatic and hydrogen bonding interactions among polar solvents and amphiphilic Glycyrrhiza glabra L. molecules could be responsible for nematic ordering. FTIR spectroscopy is employed to confirm the hydrogen bonding in LLCs. The prepared LLCs are studied through static, dynamic rheology under the shear range 1–100 s-1 to explore their fluidic behaviour and establish correlation with structural parameters. The studied LLC systems from three solvents exhibit non-Newtonian shear thinning behaviour at all concentrations. The dynamic rheology tests indicate the elastic behaviour of all LLC systems. LLCs derived from glycerol exhibit soft-solid gel-like behaviour, while weak gel-type behaviour is observed for ethylene glycol and formamide-based LLCs. Considering the medicinal value of prepared LLCs, their antibacterial activity has been checked against the gram-positive bacteria Bacillus subtilis. LLC phases show strong antibacterial activity, about 2–3 times better than that of the standard drug streptomycin used for this study.

On-Demand Crack Formation on DNA Film via Organic Solvent-Induced Dehydration.

Crack is found on the soil when severe drought comes, which inspires the idea to rationalize patterning applications using dried deoxyribonucleic acid (DNA) film. DNA is one of the massively produced biomaterials in nature, showing the lyotropic liquid crystal (LC) phase in highly concentrated conditions. DNA nanostructures in the hydrated condition can be orientation controlled, which can be extended to make dryinginduced cracks. The controlled crack generation in oriented DNA films by inducing mechanical fracture through organic solvent-induced dehydration (OSID) using tetrahydrofuran (THF) is explored. The corresponding simulations show a strong correlation between the long axis of DNA due to the shrinkage during the dehydration and in the direction of crack propagation. The cracks are controlled by simple brushing and a 3D printing method. This facile way of aligning cracks will be used in potential patterning applications.

Synergistic Effect and Phase Behavior of SCG-CAPB-H2O Ternary Compound System

The physical properties of sodium cocoyl glycinate (SCG) and the synergistic effects within the SCG/CAPB complex system were investigated using visible–ultraviolet spectrophotometry and a surface tension meter. Analysis of the synergistic parameters of the complex system revealed that the combination of SCG and cocamidopropyl betaine (CAPB) yielded superior results compared to the individual use of SCG. Building upon this, the ternary phase behavior of the SCG/CAPB/H2O system was further explored. Different lyotropic liquid crystal phases were identified using polarized optical microscopy (POM) and small-angle X-ray scattering (SAXS). Surfactant solutions with varying mass fractions exhibited diverse phase behaviors, including the micellar phase (L1), micelle–solid mixed phase (L1-S), hexagonal phase (H), and lamellar phase (Lα), with the insoluble solid phase predominating. The investigation of the ternary phase diagram of SCG/CAPB/H2O provided valuable guidance for detergent formulation screening, enriched the understanding of sodium cocoyl glycinate complex systems, and further promoted the utilization of amino acid-based surfactants in the field of personal care products.

Microviscosity-Assisted Disaggregation of a Model Ophthalmic Drug and FRET-Controlled Singlet Oxygen Generation in Lyotropic Liquid Crystals.

Different phases of lyotropic liquid crystals (LLCs), made up of mesogen-like sodium dodecyl sulfate (SDS), mainly bestow different bulk viscosities. Along with this, the role of microviscosities of the individual LLC phases is of immense interest because a minute change in it due to guest incorporation can cause significant alteration in their property as a potential energy transfer scaffold. Recently, LLCs have been identified as plausible drug delivery agents for ocular treatments. In this direction, the present work illustrates photophysical modulations of an important laser dye as well as an ophthalmic medicine, coumarin 6 (C6), inside different LLC phases in an aqueous medium. C6 molecules spontaneously accumulate in water, leading to aggregation-caused quenching (ACQ) of fluorescence. However, the different phases of the LLCs prepared from SDS and water helped in disintegrating the C6 colonies to various extents depending upon the microviscosity. The heterogeneity in the LLC phases, in turn, could modulate the Förster resonance energy transfer (FRET) between C6 and the LLC incorporated with N-doped carbon nanoparticles (N-CNPs). The N-CNPs act as potential photosensitizers and generate singlet oxygen (1O2), a reactive oxygen species (ROS), to different extents. Microviscosities of the prepared LLCs were calculated by using fluorescence correlation spectroscopy (FCS). The different phases of the LLCs, viz., lamellar and hexagonal, with different microviscosities controlled the extent of C6 disaggregation and hence the FRET and the ROS generation. The results are encouraging since ROS generation has a significant role in the vision mechanism and PDT-based applications. LLC-based drug administration with potential FRET to control ROS generation may become handy in ophthalmology. The LLC phases used in this experiment not only served the purpose of drug delivery but also the photophysical events therein are compatible with the ocular environment.

Phase Behavior and Rheological Properties of Size-Fractionated MXene (Ti3C2Tx) Dispersions.

Understanding the dispersion behavior of MXenes is interesting from a fundamental colloid science perspective and critical to enabling the fluid-phase manufacturing of MXene devices with controlled microstructures and properties. However, the polydispersity, irregular shape, and charged surfaces of MXenes result in a complex phase behavior that is difficult to predict through theoretical calculations. As two-dimensional (2D) nanomaterials, MXenes can form lyotropic liquid crystal phases, gels, and aggregates. This work aims to elucidate the effects of MXene (Ti3C2Tx) sheet size on their phase behavior and associated rheological properties. Aqueous dispersions of large sheets with an average lateral dimension of 3.0 μm, small sheets with an average lateral dimension of 0.3 μm, and a bimodal mixture of the two sizes were investigated by using cross-polarized optical microscopy and rheology. At low concentrations, the large MXene dispersions exhibited lyotropic liquid crystal behavior and extended aligned textures, but increasing concentration resulted in the formation of dense flocs. Dispersions of small sheets formed small birefringent domains with increasing concentration but lacked long-range ordering. A bimodal mixture of these sizes enabled the formation of liquid crystalline phases with extended aligned textures with less floc formation. These results provide insights into using polydispersity to tune dispersion microstructure and rheological properties that can be applied to designing dispersions for fluid-phase manufacturing methods, such as direct ink writing.

Lyotropic liquid crystal phases of monoolein in protic ionic liquids.

Monoolein-based liquid crystal phases are established media that are researched for various biological applications, including drug delivery. While water is the most common solvent for self-assembly, some ionic liquids (ILs) can support lipidic self-assembly. However, currently, there is limited knowledge of IL-lipid phase behavior in ILs. In this study, the lyotropic liquid crystal phase behavior of monoolein was investigated in six protic ILs known to support amphiphile self-assembly, namely ethylammonium nitrate, ethanolammonium nitrate, ethylammonium formate, ethanolammonium formate, ethylammonium acetate, and ethanolammonium acetate. These ILs were selected to identify specific ion effects on monoolein self-assembly, specifically increasing the alkyl chain length of the cation or anion, the presence of a hydroxyl group in the cation, and varying the anion. The lyotropic liquid crystal phases with 20-80 wt. % of monoolein were characterized over a temperature range from 25 to 65 °C using synchrotron small angle x-ray scattering and cross-polarized optical microscopy. These results were used to construct partial phase diagrams of monoolein in each of the six protic ILs, with inverse hexagonal, bicontinuous cubic, and lamellar phases observed. Protic ILs containing the ethylammonium cation led to monoolein forming lamellar and bicontinuous cubic phases, while those containing the ethanolammonium cation formed inverse hexagonal and bicontinuous cubic phases. Protic ILs containing formate and acetate anions favored bicontinuous cubic phases across a broader range of protic IL concentrations than those containing the nitrate anion.

Self-assembly of the imidazolium surfactant in aprotic ionic liquids. The anion effect of aprotic ionic liquids.

The structure of ionic liquids (ILs) has an influence on their physiochemical properties, determining their performance as self-assembly media. In this study, we focus on the anion effect of aprotic ionic liquids (AILs). The aggregation behaviours of the cationic surfactant 1-hexadecyl-3-methylimidazolium bromide (C16mimBr) have been investigated in the imidazolium AILs with the 1-ethyl-3-methyl imidazolium cation and different anions, including nitrate, ethylsulfate, bis(trifluoromethylsulfonyl) imide and tetrafluoroborate. Surface adsorption parameters of C16mimBr were determined using surface tension measurements, and the critical micellization concentration values in AILs vary for their different cohesive energy. The micellar and lamellar lyotropic liquid crystal phases emerge with the increase of C16mimBr concentrations. The structure and properties of aggregates were determined using small angle X-ray scattering, polarized optical microscopy, rheology and differential scanning calorimetry. The anion effects of AILs on the phase behaviours and structure and properties of aggregates were analysed and discussed. The lamellar lyotropic liquid crystals have shown good conductivity, as confirmed by electrochemical impedance spectroscopy characterization. Our results enhance the understanding of the structure effect of ILs as self-assembly media and contribute to the design of tailorable solvents.

Shear-induced flow and dynamics of the nematic phase of Sunset Yellow lyotropic chromonic liquid crystal

ABSTRACT Fundamental understanding of rheological properties of lyotropic chromonic liquid crystals is inadequate compared to their thermotropic counterparts in spite of the growing interest in these materials. Here, we investigate the rheological properties of a lyotropic chromonic nematic liquid crystal (LCLC), prepared by dissolving 32 wt% of Sunset Yellow (SSY) in water. The flow curves (stress-strain rate, σ − γ ˙ ) at different temperatures exhibit three flow regimes R1, R2 and R3, respectively. At room temperature, in R1 ( γ ˙ < γ ˙ cl ) and R3 ( γ ˙ > γ ˙ cu ) the sample exhibits Newtonian flow behaviour ( σ ∝ γ ˙ ), whereas, in R2 ( γ ˙ cl < γ ˙ < γ ˙ cu ), it shows a power-law dependence ( σ ∼ γ ˙ β ). With increasing shear rate the change of stress from R1 to R2 is continuous, whereas the change is discontinuous from R2 to R3. We observe stress fluctuations under steady shear in regime R2 similar to those reported in worm-like micellar systems and in thermotropic twist-bend nematic liquid crystals. The non-monotonic flow behaviour and the stress dynamics are corroborated using in situ rheo-microscopy.

Liquid Crystalline and Gel Properties of Luminescent Cyclometalated Palladium Complexes with Benzoylthiourea Ligands.

The design and development of new luminescent metallogels formed by cyclometalated palladium(II) complexes in protic solvents were investigated by a combination of differential scanning calorimetry (DSC), polarized optical microscopy (POM), and rheology. Cyclometalated palladium(II) complexes based on imine ligand and ancillary benzoylthiourea (BTU) ligand showed red emission in solid and gel states. The formation of a lyotropic liquid crystal phase was observed for the complex bearing shorter alkyl groups on the BTU ligand. This complex also behaved as a thermotropic liquid crystal that displays a monotropic smectic A phase (SmA). Dynamic rheology measurements (frequency sweep in the 5-90 °C range) of the 1-decanol solution of palladium(II) complexes highlighted their supramolecular self-association ability to generate 3D networks and form gels as a final result.

Liquid crystalline reduced graphene oxide composite fibers as artificial muscles

Soft materials are known for their compliance, adaptivity and dexterity. They have been well-pursued to create artificial muscles for robotic applications, however, at the cost of load bearing, bit rates and energy efficiency compared with their rigid body counterparts. Despite significant efforts to improve their performance, very few can match the biological muscles, achieving fast speed, high elasticity, and high power density simultaneously. Here, we self-assemble composite fibers by wet-spinning graphene oxide (GO) nanosheets in their lyotropic liquid crystal (LLC) phase mixed with conducting polymers and depleting agent, poly(ethylene glycol), followed by chemical reduction of GO. The resulting reduced GO (rGO) nanosheets are highly aligned and closely packed, which is essential to their high mechanical strength and toughness and actuation behaviors. The composite fiber exhibits fast (80 ms) and reversible bending via electrostatic repulsion between the rGO sheets. When the fibers are plied with nylon yarns, our actuators can achieve 75 J/kg work capacity and 924 W/kg power density without diminishing the bending strain and efficiency up to 10,000 cycles.

Uniaxial - biaxial lyotropic cholesteric phase transition of lyotropic liquid crystals

ABSTRACT A Landau model is proposed to describe the uniaxial – biaxial lyotropic cholesteric phase transition of lyotropic liquid crystals (LLC). The model free energy is based on a mixture of rod-shaped and disc-shaped micelles. The possibility of the existence of two biaxial lyotropic cholesteric phases and two uniaxial lyotropic cholesteric phases of LLC is discussed. The phase transitions between two biaxial lyotropic cholesteric phases and two uniaxial lyotropic cholesteric phases are explored. Qualitative comparisons between theoretical predictions and recent experimental results are discussed.

Automation of liquid crystal phase analysis for SAXS, including the rapid production of novel phase diagrams for SDS-water-PIL systems.

Lyotropic liquid crystal phases (LCPs) are widely studied for diverse applications, including protein crystallization and drug delivery. The structure and properties of LCPs vary widely depending on the composition, concentration, temperature, pH, and pressure. High-throughput structural characterization approaches, such as small-angle x-ray scattering (SAXS), are important to cover meaningfully large compositional spaces. However, high-throughput LCP phase analysis for SAXS data is currently lacking, particularly for patterns of multiphase mixtures. In this paper, we develop semi-automated software for high throughput LCP phase identification from SAXS data. We validate the accuracy and time-savings of this software on a total of 668 SAXS patterns for the LCPs of the amphiphile hexadecyltrimethylammonium bromide (CTAB) in 53 acidic or basic ionic liquid derived solvents, within a temperature range of 25-75 °C. The solvents were derived from stoichiometric ethylammonium nitrate (EAN) or ethanolammonium nitrate (EtAN) by adding water to vary the ionicity, and adding precursor ions of ethylamine, ethanolamine, and nitric acid to vary the pH. The thermal stability ranges and lattice parameters for CTAB-based LCPs obtained from the semi-automated analysis showed equivalent accuracy to manual analysis, the results of which were previously published. A time comparison of 40 CTAB systems demonstrated that the automated phase identification procedure was more than 20 times faster than manual analysis. Moreover, the high throughput identification procedure was also applied to 300 unpublished scattering patterns of sodium dodecyl-sulfate in the same EAN and EtAN based solvents in this study, to construct phase diagrams that exhibit phase transitions from micellar, to hexagonal, cubic, and lamellar LCPs. The accuracy and significantly low analysis time of the high throughput identification procedure validates a new, rapid, unrestricted analytical method for the determination of LCPs.

Phytantriol phase behaviour in choline chloride urea and water mixtures.

Deep eutectic solvents (DES) are tailorable non-aqueous solvents with promising properties for a range of applications, from industrial dissolution of plant products to biomedicine. They are mixtures of hydrogen bond donors and acceptors with low melting points that can be tailored to specific applications, and many support the self-assembly of amphiphilic molecules into lyotropic liquid crystal phases. Self-assembled lipid structures have potential for numerous applications, including drug delivery. These ordered structures can act as carriers, slow-release vehicles, or microreactors. Lipid self-assembly in non-aqueous solvents, such as deep eutectic solvents, is important for applications at extreme temperatures, or involving water-insoluble or water sensitive components. However, lipid self-assembly in these solvents remains largely unexplored. In this paper, we have examined the self-assembly of phytantriol, a non-ionic lipid, at 10 and 30 wt% in the deep eutectic solvent choline chloride:urea, with and without water. Self-assembly was assessed using small angle X-ray scattering and cross polarised optical microscopy at temperatures from 25-66 °C. We found that pure choline chloride:urea supports a Pn3m cubic phase similar to that formed in water. However, mixtures of the DES with water resulted in phytantriol forming an inverse hexagonal phase and influenced the phase transition temperatures. These results demonstrate that choline chloride:urea can support diverse phase behaviour, and also provides a mechanism for tailoring the phase for particular applications simply by controlling the amount of water in the solvent. In the future this could lead to methods of triggered release of drugs and biomolecules by the simple addition of water which could be critical for drug delivery applications.

Cross-linkable, phosphobetaine-based, zwitterionic amphiphiles that form lyotropic bicontinuous cubic phases.

The design, synthesis, and lyotropic liquid crystal phase behaviour of six cross-linkable, phosphobetaine-based, zwitterionic amphiphiles are described. Two form a QII phase with aq. NH4Cl solution, giving 3D-nanoporous membrane materials that can be used for water desalination and are not susceptible to ion exchange like traditional ionic analogues.

An NMR Study on Hydration and Molecular Interaction of Phytantriol-Based Liquid Crystals.

Phytantriol-based lyotropic liquid crystals (LLCs) have emerged as a new nanodrug delivery system. However, the understanding of phytantriol-based LLCs is lacking. In this study, we use NMR technology to characterize LLC formation over two months. Three samples in different phases were prepared with different hydration states. NMR data, including 1D-1H, 13C-{1H}, 2D-HSQC, HMBC, COSY, NOESY, etc., were collected. A comprehensive analysis of these NMR data was performed on the three phases of phytantriol-based LLCs. The following results were achieved from the study. First, the 1H and 13C-{1H} spectra of phytantriol were assigned. Second, the change of NMR spectra during the formation of the phases was observed, and the change of hydration was calculated for the time-dependent phase formation. Third, the correlation peaks of 2D-NOESY were used to describe the spatial relationship of lipids-water interaction and lipid-lipid interaction.

Aggregation behaviours of sulfobetaine zwitterionic surfactants in EAN

Ionic liquids have become one kind of the most promising solvents for self-assembly. The aggregation behaviours of various surfactants have been studied in numerous ionic liquids, especially the cationic and nonionic surfactants. In this work, we would explore the aggregation behaviours of sulfobetaine zwitterionic surfactants (SB3-n, n = 12, 14, 16) in the protic ionic liquid ethylammonium nitrate (EAN). The micellization behaviour was studied by surface tension measurement and the critical micellization concentrations are much larger than those in water. The micellar phase and hexagonal lyotropic liquid crystal phase are formed by SB3-12 and SB3-14 in EAN while an additional micellar cubic lyotropic liquid crystal phase is formed in the SB3-16/EAN system. The structure of aggregates was characterized by the small angle X-ray scattering while optical and viscoelastic properties by polarized optical microscopy and rheology. The alkyl chain length effect of SB3-n on aggregation behaviours was discussed and compared with those in the other surfactant/EAN systems. Our results would provide the thorough understanding on aggregation behaviours of sulfobetaine zwitterionic surfactants in EAN.

Light-Responsive Molecular Release from Cubosomes Using Swell-Squeeze Lattice Control.

Stimuli-responsive materials are crucial to advance controlled delivery systems for drugs and catalysts. Lyotropic liquid crystals (LLCs) have well-defined internal structures suitable to entrap small molecules and can be broken up into low-viscosity dispersions, aiding their application as delivery systems. In this work, we demonstrate the first example of light-responsive cubic LLC dispersions, or cubosomes, using photoswitchable amphiphiles to enable external control over the LLC structure and subsequent on-demand release of entrapped guest molecules. Azobenzene photosurfactants (AzoPS), containing a neutral tetraethylene glycol head group and azobenzene-alkyl tail, are combined (from 10-30 wt %) into monoolein-water systems to create LLC phases. Homogenization of the bulk LLC forms dispersions of particles, ∼200 nm in diameter with internal bicontinuous primitive cubic phases, as seen using small-angle X-ray scattering and cryo-transmission electron microscopy. Notably, increasing the AzoPS concentration leads to swelling of the cubic lattice, offering a method to tune the internal nanoscale structure. Upon UV irradiation, AzoPS within the cubosomes isomerizes within seconds, which in turn leads to squeezing of the cubic lattice and a decrease in the lattice parameter. This squeeze mechanism was successfully harnessed to enable phototriggerable release of trapped Nile Red guest molecules from the cubosome structure in minutes. The ability to control the internal structure of LLC dispersions using light, and the dramatic effect this has on the retention of entrapped molecules, suggests that these systems may have huge potential for the next-generation of nanodelivery.