Liquid Crystalline Solutions Research Articles

Preparation and chiroptical properties of cellulose chlorophenylcarbamate–silica hybrids having a chiral nematic mesomorphic structure

An attempt was made to fabricate optically functional cellulosic–silica hybrid materials wherein a helically ordered mesomorphic structure of the cellulosic component was fixed. Cellulose 3-chlorophenylcarbamate (3Cl-CPC) and cellulose 4-chlorophenylcarbamate (4Cl-CPC) were synthesized by carbanilating reaction of cellulose with 3-chlorophenyl or 4-chlorophenyl isocyanate in a homogeneous solution system. The hydrophobic cellulose derivatives were examined for the solubility and liquid crystallinity in various solvents containing alkoxysilane as a main component. Concentrated (∼40 wt%) solutions of 3Cl-CPC in 3-aminopropyltrimethoxysilane (APTMS) and those of 4Cl-CPC in a mixed solvent of tetramethoxysilane (TMOS)/N,N-dimethylformamide (DMF)/dichloroacetic acid (DCA) formed a chiral nematic mesophase to impart vivid reflection colors. These liquid crystalline solutions were subjected to a sol–gel conversion process of the respective alkoxysilane components in moist air. In the process for the 4Cl-CPC lyotropic system, we utilized a "surface-coating solvent" consisting of TMOS/phenyltrimethoxysilane/DCA to facilitate the sol–gel reaction of TMOS and also to preserve the reflective coloration. Thereby a left-handed chiral nematic hybrid series of 4Cl-CPC–silica was successfully obtained as a monolithic glassy bulk showing iridescent colors. The 3Cl-CPC/APTMS lyotropics were readily converted into a colored solid form without any coating solution, resulting in production of a right-handed chiral nematic series of 3Cl-CPC–silica. Besides investigating the chiroptical characteristics of the liquid crystalline solutions and hybrids, we preliminarily tried separating a racemic compound into two enantiomers by open column chromatography using the cellulosic–silica hybrids as a filler material of the column.

A Photoaddressable Liquid Crystalline Phase Transition in Graphene Oxide Nanocomposites

AbstractThe multifunctionality of graphene has the potential to unlock important developments in nanocomposite science. However, the manipulation of graphene without interfering with its unique properties and while controlling its spatial organization remains challenging. Here, the formation of a photoaddressable liquid crystalline (LC) solution through the stabilization of graphene oxide (GO) with photocleavable brushes is described. The LC behavior leads to the thermodynamic entrapment of GO into low aspect ratio domains that fail to display the properties typically predicted for graphene nanocomposites. The morphology and structural and electronic performance of these nanocomposites are regenerated through the brush cleavage, which controls the phase transition of the LC phase. These results show that kinetic control of graphene assembly can be an attractive tool toward the dynamic regulation of processable sol states and structured percolated networks for rational composite manufacturing.

Lyotropic 'hairy' TiO2 nanorods.

We report the synthesis of the first stable, solution-processable and photocrosslinkable hybrid organic/inorganic titanium dioxide nanorods as ‘hairy rods’ coated with phosphonate ligands with photoreactive coumarin groups located in a terminal position. The relationships between the chemical structure of the diethyl-ω-[(7-oxycoumaryl)-n-alkyl]phosphonate ligands on the ligand exchange rate (LER) and the solubility of the resultant ligand-stabilized titanium dioxide nanorods in organic solvents are elucidated. These TiO2 nanorods, with an organic ligand coating, are short enough (aspect ratio = 5–8) to be dissolved in chlorobenzene at high concentrations, but long enough to form lyotropic nematic liquid crystals. These colloidal solutions are used to deposit a thin, uniform layer of hybrid organic/inorganic TiO2 nanorods with their long axes in the plane of a flat, smooth substrate through a self-organization process. Standard photolithographic patterning creates an insoluble dielectric layer of the desired thickness, smoothness and uniformity and with a dielectric constant of sufficient magnitude, k = 8, suitable for the fabrication of multilayer, plastic electronic devices using solution-based fabrication techniques, such as ink-jet printing, used in roll-to-roll manufacturing.

Micelle-Mediated Self-Assembly of Microfibers Bridging Millimeter-Scale Gap To Form Three-Dimensional-Ordered Polysaccharide Membranes.

Micelle-mediated three-dimensional-ordered polysaccharide membranes are constructed by introducing cationic/anionic surfactant into a liquid crystalline polysaccharide solution. Upon drying mixtures of the polysaccharide solution with the surfactant such as cetyltrimethylammonium bromide or sodium dodecyl sulfate (SDS), the polymeric microfibers deposit as a nucleus to form a membrane, bridging millimeter-scale gap with high probability. In particular, in a solution with SDS micellar structures, the microscale fibers with diameter ∼1 μm disassemble into nanoscale fibers with diameter ∼50 nm. This transformation allows the polymeric network to become finer in nanoscale, and the vertical membrane is formed much more easily than that from a pure polysaccharide solution. Furthermore, it is clarified that the vertical membrane has been successfully formed with three-dimensionally ordered microstructures with a linearly oriented and layered structure. This method will shed light on the preparation of hybrid materials with biocompatibility and responsivity to stimuli such as magnetics, electrics, and optics via hybridization with nanomaterials dispersed by surfactants.

(Invited) Morphological Diversity and Space-Recognition of Polysaccharide Microfibers on Evaporative Interface

The geometric structures of soft materials can be controlled on the macro-scale by using interfacial or mechanical instability, e.g.fingering patterns of viscous liquids and buckling patterns of gels during swelling/deswelling. These patterns can be used as smart materials for capturing/releasing and mass-transportation applications. Here we introduce the emergence of uniaxially oriented membranes by drying an aqueous liquid-crystalline solution, composed of megamolecular supra-polysaccharides, sacran, in a limited space. In addition, by controlling the geometry of the evaporation front, multiple nuclei emerge that grow into vertical membraneswith uniaxial orientation. Notably, the membrane, composed of microfiber, is rationally formed along the dynamic three-phase contact line. As a result of the self-organization, the membrane macroscopically partitions the three-dimensional cuboid cell. We envision that such uniaxially oriented membranes, obtained through partitioning phenomena, can be used as soft biomaterials, like anisotropic dialysis membranes with directional controllability in the medical and pharmaceutical field.

Liquid fibres and their networks from cellulose-based liquid crystalline solutions

ABSTRACTThe production of fibres and films with enhanced mechanical properties, from liquid crystalline cellulose-based systems, has always been a challenge. Previous works indicate that the use of spinning and electrospinning allows the fabrication of non-woven membranes with optical and mechanical characteristics distinct from casting films. The subsequent interactions of the micro/nanofibres inside membranes can modify their topology and geometry so they are found crucial for tuning the membranes’ properties. In this work, we deal with the evolution of networks made of highly stretched liquid filaments. Three main mechanisms were identified: the thinning of filaments feeding growing nodes, breaking of the thinner filaments before the thicker ones and the zipping of pairs of filaments crossing at small angles.

Unidirectionally-oriented Membrane Formation of Supra-polysaccharides Sacran and Application to Drug Delivery System

The geometric structures of soft materials can be controlled on the macro-scale using interfacial or mechanical instability, e.g., fingering patterns of viscous liquid and buckling patterns of gels during swelling/deswelling. These patterns can be used as smart materials for capturing/releasing and mass-transportation applications. Here we introduce the emergence of a uniaxially oriented membrane by drying an aqueous liquid-crystalline solution, composed of megamolecular supra-polysaccharides "sacran", from a limited space. By controlling the geometries of the evaporation front, multiple nuclei emerge that grow into upright membranes with uniaxial orientation. Notably, the uniaxially orientated membrane composed of rod-like microdomains is rationally formed along the dynamic three-phase contact line. Besides, the membrane macroscopically partitions the three-dimensional cuboid cell for evaporating the aqueous solution. We envision that such a uniaxially oriented membrane can be used as soft biomaterials such as dialysis membranes with directional controllability in medical and pharmaceutical fields.

Swimming in an anisotropic fluid: How speed depends on alignment angle

Swimming microorganisms commonly encounter anisotropic environments, such as a biofilm or a liquid-crystalline solution. A simple theory for a Taylor sheet in a nematic liquid crystal is used to calculate how the swimming speed depends on the angle between the swimmer and the nematic director and also on the torque that tends to align the swimmer with the director.

Formation of Polysaccharide Membranes by Splitting of Evaporative Air–LC Interface

AbstractSelf‐assembly methods for colloidal crystals are widely developed by using the evaporative interface and capillary forces. Recently, a distinct phenomenon is discovered of macrospace partitioning by a polysaccharide membrane formed in a limited space by drying its aqueous liquid crystalline solution. Differing from typical fingering patterns, here, the viscous solution is in a nonequilibrium process between the polymer deposition and hydration during drying. By drying in limited space with a narrow gap, the nonequilibrium state causes accumulation of small depositions at several specific points and the deposited polymer bridging the substrates. Here, the split meniscus should make the area of the evaporative interface larger. To describe the correlation between the interfacial curve and the partitioning, the geometric effects of the evaporation front are discussed experimentally and numerically. By controlling the evaporation front three dimensionally, the necessary conditions for the vertical membrane formation are verified multilaterally. In future, this approach will help deposition control of not only the polysaccharides but also other biopolymers exhibiting microrod assembly.

Tough and Porous Hydrogels Prepared by Simple Lyophilization of LC Gels.

Porous hydrogels possessing mechanical toughness were prepared from sacran, a supergiant liquid crystalline (LC) polysaccharide produced from Aphanothece sacrum. First, layered hydrogels were prepared by thermal cross-linking of film cast over a sacran LC solution. Then, anisotropic pores were constructed using a freeze-drying technique on the water-swollen layered hydrogels. Scanning electron microscopic observation revealed that pores were observable only on the side faces of sponge materials parallel to the layered structure but never on the top or bottom faces. The pore size, porosity, and swelling behavior were controlled by the thermal-cross-linking temperature. To clarify the freezing effect, a freeze–thawing method was used for comparison. The freeze–thawed hydrogels also formed layers but no pores. The mechanical properties and network structures of hydrogels were also studied, clarifying that porous hydrogels, even those with a high quantity of pores, were tough owing to the pores orienting along the layer direction like tunnels.

Morphological and Rheological Characterization of Chitosan Liquid-Crystalline Solutions and Gels

Morphological and Rheological Characterization of Chitosan Liquid-Crystalline Solutions and Gels

Emergence of polysaccharide membrane walls through macro-space partitioning via interfacial instability

Living organisms in drying environments build anisotropic structures and exhibit directionality through self-organization of biopolymers. However, the process of macro-scale assembly is still unknown. Here, we introduce a dissipative structure through a non-equilibrium process between hydration and deposition in the drying of a polysaccharide liquid crystalline solution. By controlling the geometries of the evaporation front in a limited space, multiple nuclei emerge to grow vertical membrane walls with macroscopic orientation. Notably, the membranes are formed through rational orientation of rod-like microassemblies along the dynamic three-phase contact line. Additionally, in the non-equilibrium state, a dissipative structure is ultimately immobilized as a macroscopically partitioned space by multiple vertical membranes. We foresee that such oriented membranes will be applicable to soft biomaterials with direction controllability, and the macroscopic space partitionings will aid in the understanding of the space recognition ability of natural products under drying environments.

Methods for the Self-integration of Megamolecular Biopolymers on the Drying Air-LC Interface.

Living organisms that use water are always prone to drying in the environment. Their activities are driven by biopolymer-based micro- and macro-structures, as seen in the cases of moving water in vascular bundles and moisturizing water in skin layers. In this study, we developed a method for assessing the effect of aqueous liquid crystalline (LC) solutions composed of biopolymers on drying. As LC biopolymers have megamolecular weight, we chose to study polysaccharides, cytoskeletal proteins, and DNA. The observation of biopolymer solutions during drying under polarized light reveals milliscale self-integration starting from the unstable air-LC interface. The dynamics of the aqueous LC biopolymer solutions can be monitored by evaporating water from a one-side-open cell. By analyzing the images taken using cross-polarized light, it is possible to recognize the spatio-temporal changes in the orientational order parameter. This method can be useful for the characterization of not only artificial materials in various fields, but also natural living tissues. We believe that it will provide an evaluation method for soft materials in the biomedical and environmental fields.

Drying-Induced Self-Similar Assembly of Megamolecular Polysaccharides through Nano and Submicron Layering.

We propose a self-similar assembly to generate planar orientation of megamolecular polysaccharides on the nanometer scale and submicron scale. Evaporating the aqueous liquid crystalline (LC) solution on a planar air-LC interface induces polymer layering by self-assembly and rational action of macroscopic capillary forces between the layers. To clarify the mechanisms of nanometer- and submicron-scale layering, the polymer films are investigated by electron microscopy.

Milliscale Self-Integration of Megamolecule Biopolymers on a Drying Gas-Aqueous Liquid Crystalline Interface.

A drying environment is always a proposition faced by dynamic living organisms using water, which are driven by biopolymer-based micro- and macrostructures. Here, we introduce a drying process for aqueous liquid crystalline (LC) solutions composed of biopolymer with extremely high molecular weight components such as polysaccharides, cytoskeletal proteins, and DNA. On controlling the mobility of the LC microdomain, the solutions showed milliscale self-integration starting from the unstable gas-LC interface during drying. In particular, we first identified giant rod-like microdomains (∼1 μm diameter and more than 20 μm length) of the mega-molecular polysaccharide, sacran, which is remarkably larger than other polysaccharides. These microdomains led to the formation of a single milliscale macrodomain on the interface. In addition, the dried polymer films on a solid substrate also revealed that such integration depends on the size of the microdomain. We envision that this simple drying method will be useful not only for understanding the biopolymer hierarchization at the macroscale level but also for preparation of surfaces with direction controllability, as seen in living organisms, for use in various fields such as diffusion, mechanics, and photonics.

Monodomain hydrogels prepared by shear-induced orientation and subsequent gelation

Shear-induced orientation of liquid crystalline hydroxypropylcellulose solution with reactants is frozen by subsequent polymerization and gelation process, resulting in monodomain hydrogel with anisotropic optical, swelling, and mechanical properties.

Chiral Nematic Structure of Cellulose Nanocrystal Suspensions and Films; Polarized Light and Atomic Force Microscopy.

Cellulosic liquid crystalline solutions and suspensions form chiral nematic phases that show a rich variety of optical textures in the liquid crystalline state. These ordered structures may be preserved in solid films prepared by evaporation of solvent or suspending medium. Film formation from aqueous suspensions of cellulose nanocrystals (CNC) was investigated by polarized light microscopy, optical profilometry and atomic force microscopy (AFM). An attempt is made to interpret qualitatively the observed textures in terms of the orientation of the cellulose nanocrystals in the suspensions and films, and the changes in orientation caused by the evaporative process. Mass transfer within the evaporating droplet resulted in the formation of raised rings whose magnitude depended on the degree of pinning of the receding contact line. AFM of dry films at short length scales showed a radial orientation of the CNC at the free surface of the film, along with a radial height variation with a period of approximately P/2, ascribed to the anisotropic shrinkage of the chiral nematic structure.

Side Chain Conformational Distributions of a Small Protein Derived from Model-Free Analysis of a Large Set of Residual Dipolar Couplings.

Accurate quantitative measurement of structural dispersion in proteins remains a prime challenge to both X-ray crystallography and NMR spectroscopy. Here we use a model-free approach based on measurement of many residual dipolar couplings (RDCs) in differentially orienting aqueous liquid crystalline solutions to obtain the side chain χ1 distribution sampled by each residue in solution. Applied to the small well-ordered model protein GB3, our approach reveals that the RDC data are compatible with a single narrow distribution of side chain χ1 angles for only about 40% of the residues. For more than half of the residues, populations greater than 10% for a second rotamer are observed, and four residues require sampling of three rotameric states to fit the RDC data. In virtually all cases, sampled χ1 values are found to center closely around ideal g–, g+ and t rotameric angles, even though no rotamer restraint is used when deriving the sampled angles. The root-mean-square difference between experimental 3JHαHβ couplings and those predicted by the Haasnoot-parametrized, motion-adjusted Karplus equation reduces from 2.05 to 0.75 Hz when using the new rotamer analysis instead of the 1.1-Å X-ray structure as input for the dihedral angles. A comparison between observed and predicted 3JHαHβ values suggests that the root-mean-square amplitude of χ1 angle fluctuations within a given rotamer well is ca. 20°. The quantitatively defined side chain rotamer equilibria obtained from our study set new benchmarks for evaluating improved molecular dynamics force fields, and also will enable further development of quantitative relations between side chain chemical shift and structure.

A cellulosic liquid crystal pool for cellulose nanocrystals: Structure and molecular dynamics at high shear rates

Cellulose and its derivatives, such as hydroxypropylcellulose (HPC) have been studied for a long time but they are still not well understood particularly in liquid crystalline solutions. These systems can be at the origin of networks with properties similar to liquid crystalline (LC) elastomers. The films produced from LC solutions can be manipulated by the action of moisture allowing for instance the development of a soft motor (Geng et al., 2013) driven by humidity. Cellulose nanocrystals (CNC), which combine cellulose properties with the specific characteristics of nanoscale materials, have been mainly studied for their potential as a reinforcing agent. Suspensions of CNC can also self-order originating a liquid–crystalline chiral nematic phases. Considering the liquid crystalline features that both LC-HPC and CNC can acquire, we prepared LC-HPC/CNC solutions with different CNC contents (1, 2 and 5wt.%). The effect of the CNC into the LC-HPC matrix was determined by coupling rheology and NMR spectroscopy – Rheo-NMR a technique tailored to analyse orientational order in sheared systems.

Structural Orientations of Cellulose Acetate Phthalate/Ethyl Cellulose Blends in Solution

Cellulose acetate phthalate/ethyl cellulose blends were investigated by means of attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), thermogravimetry/differential thermal analysis (TGA-DTGA), shear viscosity and oscillatory shear tests. The studies showed a higher thermal stability, induced by the occurrence of hydrogen bonding, more predominant in ethyl cellulose and blends with higher content of ethyl cellulose. The effect of solution concentrations in N,N-dimethylacetamide, blend compositions and shear rate on the rheological functions generated regions with properties typical for liquid crystalline solutions in the shear field. These studies are suggested to be useful in identification of liquid crystal properties, required in some electrotechnical applications.