Thermotropic Liquid Crystal Phases Research Articles

Discotic liquid crystals 45 years later. Dendronized discs and crowns increase liquid crystal complexity to columnar from spheres, cubic Frank-Kasper, liquid quasicrystals and memory-effect induced columnar-bundles

In 1977 Chandrasekhar laboratory reported the first examples of a new class of thermotropic liquid crystals self-organized from planar disc-like molecules substituted with alkyl groups. X-ray analysis demonstrated that these disc-like molecules stack on top of each other at irregular spacing in columns located in the paraffin melt of their alkyl groups. These supramolecular columns self-organize in a hexagonal array defined as the new thermotropic discotic or columnar hexagonal liquid crystal phase. This new thermotropic liquid crystal phase has translational periodicity in two dimensions and liquid-like disorder in the third one, along the column axis. In 2002 Bushby and Lozman dedicated a brief review article to the 25 anniversary of discotic liquid crystals. This review also included a brief discussion of supramolecular discs and columns self-organized from self-assembling dendrons and dendrimers. The current publication is not another review but a brief perspective on new liquid crystal phases self-organized from dendronized rigid planar and conformationally flexible discs as well as from crown-like molecules. Crown-like molecules are the most stable conformation of a transient unstable disc. All dendronized disc-like and crown molecules adopt a crown conformation that self-assemble helical columns and spherical helices. A large diversity of new liquid crystalline phases self-organize from these helical columns and spherical helices. They include helical columnar hexagonal phases from crowns and from supramolecular spheres, Frank-Kasper A15 (known as cubic phase of space group Pm3¯n), σ phase (also known as tetragonal of space group P42/mnm), 12-fold quasi liquid crystals (QLC) and supramolecular orientational memory (SOM) derived complex bundles of supramolecular columnar hexagonal arrays that are not yet completely elucidated. The impact of Chandrasekhar on the discovery of self-assembling dendrons and dendrimers via his biaxial nematic liquid crystal concept will also be discussed. This perspective is dedicated to the 45 anniversary of the discovery of discotic liquid crystals and to the memory of Professor Sivaramakrishna Chandrasekhar, a modest, respectful and great scientist.

Slave-master mechanism of thermotropic liquid crystal phase transitional behavior

We introduce the slave-master mechanism in the phase behavior of two-component systems where both components could exhibit some kind of (quasi) long-range order. The key feature of the mechanism is that one component strongly influences the other while the reverse influence is negligible. To illustrate the effect, we consider systems where each isolated component exhibits an order-disorder phase transition on varying a control parameter (e.g., temperature) to which we refer as the generalized temperature. We present a minimal model that shows robust slave-master behavior. As exemplary systems, we present thermotropic liquid crystals (LCs) exhibiting nematic and smectic A phase order, focusing on the interaction strength between orientational and translational order. Mixtures of nematic LC molecules and anisotropic nanoparticles are also presented. We show that qualitatively different behaviors could emerge via the specific nature of the inter-component interaction. Mastering this mechanism could lead to various applications based on phase tunable properties.

Unmasking the structure of a chiral cubic thermotropic liquid crystal phase by a combination of soft and tender resonant X-ray scattering.

A resonant X-ray scattering response for two structural models of a chiral cubic phase with a giant unit cell, one composed of a continuous grid and micelles and the other with three continuous grids, is studied theoretically and compared to experimental measurements. For both structural models resonant enhancement of all the symmetry-allowed diffraction peaks is predicted, as well as the existance of several symmetry forbidden peaks (pure resonant peaks). Experimental measurements were performed at the carbon and sulphur absorption edge. Only one pure resonant peak was observed, which is predicted by both models. Two low-angle symmetry allowed peaks, not observed in non-resonant scattering, were resonantly enhanced and their intensity angular dependence can distinguish between the two structural models.

Formation of spiral microstructures during crystallization of 4,4‘-azoxyanisole from a benzene solution

A phenomenon of formation of multiple “coffee rings” consisting of microcrystals in the 4,4‘-azoxyanisole - benzene system was experimentally and theoretically investigated. It is shown that by changing of the geometry of a drop, for example, by placing a metal ball in its center it is possible to fundamentally change the geometry of the “coffee ring”. Assumptions were made about the physical nature of the effect of the formation of a “coffee ring” of a spiral shape. The proposed geometric model of this phenomenon reflects well the physical processes occurring during spiral crystallization, and the model is in good agreement with the experimental data obtained by gravimetry. New approaches to the formation of microstructures of functional materials with a thermotropic liquid crystal phase on a glass substrate can be used to create devices for nano – and microelectronics and optical technology.

Straight-chain alkanediol derivatives leading to glassy cholesteric liquid crystals with visible reflection

ABSTRACT Straight-chain alkanediols such as ethylene glycol are commonly found in our daily life as they are used to produce cosmetics, antifreezes, polyesters and polyurethanes. In this article, we report on the promising potential use of straight-chain alkanediols for rewritable full-colour imaging applications by the preparation of glassy cholesteric liquid crystals (G-CLCs). A series of straight-chain alkanediol derivatives possessing two cholesteryl groups through carbonate ester linkages (Cn-DiCh) showed thermotropic cholesteric liquid crystal phase with visible reflection. The thermally induced shifting ranges of reflection peaks were dependent on the central carbon chain length (n) of Cn-DiCh. Although the pristine Cn-DiCh showed narrow wavelength ranges of the reflection peaks by changing the temperature, we successfully prepared a mixture of two different kinds of Cn-DiCh at their equivalent weight ratio, which exhibited the reflection peak shift throughout a wide visible-wavelength range between 400 nm and 850 nm. Moreover, the binary mixtures of Cn-DiCh were rapidly cooled from the CLC temperatures to 0°C, whereupon the reflection colours could be preserved even at room temperature over 2 months. Such rapid cooling treatment enabled the straightforward preparation of solid-state G-CLCs with visible reflection characteristics, thereby leading to the applications of rewritable full-colour imaging media.

Side Chain Effect of Hydroxypropyl Cellulose Derivatives on Reflection Properties.

Some cellulose derivatives are known to exhibit thermotropic and lyotropic cholesteric liquid crystal (CLC) phases with a visible reflection feature by changing the side chains and mixing with specific solvents, respectively. Although many studies have been reported so far, most of the derivatives have the side chains of linear alkyl groups, but not the bulky phenyl groups. In this report, we synthesized a series of hydroxypropyl cellulose (HPC) derivatives that possessed both linear propionyl esters and bulky (trifluoromethyl)phenyl carbamates in the side chains. The reflection peaks of HPC derivatives shifted to longer wavelengths upon heating due to an increase in the CLC helical pitch. Such thermally induced shifting behavior of the reflection peak was crucially dependent on not only the propionyl esterification degree, but also the substituents in the side chains of HPC derivatives. When the side chains of HPC were chemically modified with both propionyl esters and bulky substituents such as 3,5-bis(trifluoromethyl)phenyl carbamates, the reflection peaks emerged at longer wavelengths at the same temperature. This probably happened because of the steric hindrance of bulky side chains, as supported by the empirical molecular modeling calculation. Although the occupied volumes of (trifluoromethyl)phenyl groups were independent of the CLC phase temperature with visible Bragg reflection, the substituent position, i.e., substituent orientation of trifluoromethyl groups affected the CLC phase temperature. Moreover, we found that the hydrogen bonds between carbamate moieties in the HPC side chains play an important role in the thermally induced shift of reflection peaks.

Morphological, Liquid Crystal and Optical Band Energy Properties of Polyphosphates

New metallic liquid crystalline polyphosphates showed thermotropic nematic liquid crystal phases (2.13–2.24 eV). The surface morphology of polyphosphates was examined by the scanning electron microscope and showed rough surface and micro pore structure which an indication of the presence of several crystalline domains.

Nanoscratching technique for highly oriented liquid crystal materials

A simple, fast, and cost-effective technique to obtain highly oriented thermotropic and lyotropic liquid crystal (LC) phases using a simple nanoscratching method is presented. Highly aligned linear nanogrooves are fabricated by scratching substrates such as normal, indium tin oxide (ITO), curved glasses, and ITO-coated polyethylene terephthalate (PET) film using diamond lapping films. To demonstrate the feasibility of the platform, typical thermotropic and lyotropic LC materials in the nematic phase are used to demonstrate the well-aligned domains along with the resulting scratched nanogrooves. The polarised optical microscopy (POM) images show excellent dark and bright states depending on the sample rotation, proving that the LC molecules are well aligned. The electro-optical performance of the twisted nematic (TN) mode LC display fabricated using the nanogrooves is also measured and indicates reliable results compared with that of the conventional device. Indeed, scratch-induced nanogrooves are well generated on the curved substrate and ITO-coated PET film to show versatility of our technique. Our platform can suggest a new nanofabrication way to make various electro-optical devices as well as other patterning applications.

Effect of an n-Alkoxy-2,4-hexadiene Polymerizable Tail System on the Mesogenic Properties and Cross-Linking of Mono-Imidazolium-Based Ionic Liquid Crystal Monomers.

We demonstrate that an ether-based n-alkoxy-2,4-hexadiene polymerizable tail system is an effective and modular alternative to traditional ester-based polymerizable tail groups (i.e., acrylate, methacrylate, sorbate) and alkyl-1,3-diene tails for the design of radically polymerized ionic liquid crystal (ILC) monomers. Several series of nonsymmetric 1-vinylimidazolium-bromide-based ILC monomers containing these different polymerizable tail systems were synthesized and compared for their ability to form thermotropic liquid crystal (TLC) phases and to be photo-cross-linked with TLC phase retention. The n-alkoxy-2,4-hexadiene tail system was found to be more favorable/conducive to TLC phase formation than acrylate, methacrylate, and sorbate tails. It was more similar to the alkyl-1,3-diene tail system in terms of its more favorable effect on TLC behavior; however, it is more modular/easier to synthesize, more resistant to thermal Diels-Alder side reaction, and more isomerically pure, making it better for ILC monomer design. Also, the n-alkoxy-2,4-hexadiene tail system was found to be very amenable to radical photo-cross-linking with TLC phase retention. To demonstrate this feature, an example cross-linkable ILC monomer with this tail system was synthesized and polymerized in the smectic A TLC phase, and the monomer and polymerized material were characterized for their ionic conductivity behavior.

Thermotropic liquid crystals from biomacromolecules

Complexation of biomacromolecules (e.g., nucleic acids, proteins, or viruses) with surfactants containing flexible alkyl tails, followed by dehydration, is shown to be a simple generic method for the production of thermotropic liquid crystals. The anhydrous smectic phases that result exhibit biomacromolecular sublayers intercalated between aliphatic hydrocarbon sublayers at or near room temperature. Both this and low transition temperatures to other phases enable the study and application of thermotropic liquid crystal phase behavior without thermal degradation of the biomolecular components.

Phase sensitive molecular dynamics of self-assembly glycolipid thin films: A dielectric spectroscopy investigation

Glycolipid, found commonly in membranes, is also a liquid crystal material which can self-assemble without the presence of a solvent. Here, the dielectric and conductivity properties of three synthetic glycolipid thin films in different thermotropic liquid crystal phases were investigated over a frequency and temperature range of (10(-2)-10(6) Hz) and (303-463 K), respectively. The observed relaxation processes distinguish between the different phases (smectic A, columnar/hexagonal, and bicontinuous cubic Q) and the glycolipid molecular structures. Large dielectric responses were observed in the columnar and bicontinuous cubic phases of the longer branched alkyl chain glycolipids. Glycolipids with the shortest branched alkyl chain experience the most restricted self-assembly dynamic process over the broad temperature range studied compared to the longer ones. A high frequency dielectric absorption (Process I) was observed in all samples. This is related to the dynamics of the hydrogen bond network from the sugar group. An additional low-frequency mechanism (Process II) with a large dielectric strength was observed due to the internal dynamics of the self-assembly organization. Phase sensitive domain heterogeneity in the bicontinuous cubic phase was related to the diffusion of charge carriers. The microscopic features of charge hopping were modelled using the random walk scheme, and two charge carrier hopping lengths were estimated for two glycolipid systems. For Process I, the hopping length is comparable to the hydrogen bond and is related to the dynamics of the hydrogen bond network. Additionally, that for Process II is comparable to the bilayer spacing, hence confirming that this low-frequency mechanism is associated with the internal dynamics within the phase.

Dynamic Switching of the Circularly Polarized Luminescence of Disubstituted Polyacetylene by Selective Transmission through a Thermotropic Chiral Nematic Liquid Crystal

AbstractThe circularly polarized luminescence (CPL) of chiral disubstituted liquid‐crystalline polyacetylene (di‐LCPA) can be dynamically switched and amplified from left‐ to right‐handed CPL and vice versa through the selective transmission of CPL across a thermotropic chiral nematic liquid crystal (N*‐LC) phase. By combining a chiral di‐LCPA CPL‐emitting film with an N*‐LC cell and tuning the selective reflection band of the N*‐LC phase to coincide with the CPL emission band, a CPL‐switchable cell was constructed. The phase change induced by the thermotropic N*‐LC cell by varying the temperature leads to a change in the selective transmission of CPL, which enables the dynamic switching and amplification of CPL. It is anticipated that CPL‐switchable devices might find applications in switchable low‐threshold lasers and optical memory devices.

Dynamic switching of the circularly polarized luminescence of disubstituted polyacetylene by selective transmission through a thermotropic chiral nematic liquid crystal.

The circularly polarized luminescence (CPL) of chiral disubstituted liquid-crystalline polyacetylene (di-LCPA) can be dynamically switched and amplified from left- to right-handed CPL and vice versa through the selective transmission of CPL across a thermotropic chiral nematic liquid crystal (N*-LC) phase. By combining a chiral di-LCPA CPL-emitting film with an N*-LC cell and tuning the selective reflection band of the N*-LC phase to coincide with the CPL emission band, a CPL-switchable cell was constructed. The phase change induced by the thermotropic N*-LC cell by varying the temperature leads to a change in the selective transmission of CPL, which enables the dynamic switching and amplification of CPL. It is anticipated that CPL-switchable devices might find applications in switchable low-threshold lasers and optical memory devices.

Novel steric stabilizers for lyotropic liquid crystalline nanoparticles: PEGylated-phytanyl copolymers.

Lyotropic liquid crystalline nanostructured particles (e.g., cubosomes and hexosomes) are being investigated as delivery systems for therapeutics in biomedical and pharmaceutical applications. Long term stability of these particulate dispersions is generally provided by steric stabilizers, typically commercially available amphiphilic copolymers such as Pluronic F127. Few examples exist of tailored molecular materials designed for lyotropic liquid crystalline nanostructured particle stabilization. A library of PEGylated-phytanyl copolymers (PEG-PHYT) with varying PEG molecular weights (200-14K Da) was synthesized to assess their performance as steric stabilizers for cubosomes and to establish structure-property relationships. The PEGylated-lipid copolymers were first found to self-assemble in excess water in the absence of cubosomes and also displayed thermotropic liquid crystal phase behavior under cross-polarized light microscopy. An accelerated stability assay was used to assess the performance of the copolymers, compared to Pluronic F127, for stabilizing phytantriol-based cubosomes. Several of the PEGylated-lipid copolymers showed steric stabilizer effectiveness comparable to Pluronic F127. Using synchrotron small-angle X-ray scattering and cryo-transmission electron microscopy, the copolymers were shown to retain the native internal lyotropic liquid crystalline structure, double diamond cubic phase (Q2(D)), of phytantriol dispersions; an important attribute for controlling downstream performance.

Liquid Crystal Based Optical Sensor for Imaging Trypsin Activity at Interfaces Between Aqueous Phases and Thermotropic Liquid Crystals

In this study, we developed a liquid crystal (LC)-based optical sensor for monitoring enzymatic activity through orientational changes in liquid crystals (LCs) coupled to the properties of a poly--lysine (PLL)-based polymeric membrane. We prepared a PLL-based polymeric membrane at the planar interface between the thermotropic liquid crystal and aqueous phases. The PLL-based polymeric membrane was obtained by contacting the PLL solution with water immiscible LCs, 4-cyano-4'-pentyl-biphenyl (5CB) doped with adipoyl chloride. We then investigated the membrane properties by examining the permeability of the membrane to phospholipids, 1,2-didodecanoyl-rac-glycero-3-phosphocholine (DLPC). The permeability of the membrane to transport phospholipids was monitored through the orientational transition of 5CB in contact with the dispersions of DLPC. Since trypsin can enzymatically catalyze the hydrolysis of PLL, we incubated an aqueous trypsin solution with the membrane for 2 h at room temperature to cause an increase in the permeability of the polymeric membrane to DLPC. As a result, a bright to dark optical shift of LCs was observed, which implied that an enzymatic reaction between trypsin and PLL-based membrane occurred. Two control experiments using chymotrypsin and bovine serum albumin (BSA) revealed no sign of improved permeability based on the orientational transition of LCs.

Strong thermal optical nonlinearity caused by CdSe nanoparticles synthesised in smectic ionic liquid crystal

Spectral and nonlinear optical properties of cadmium octanoate composites containing CdSe nanoparticles (NPs) have been studied by using optical absorption spectroscopy and laser scanning technique (Z-scan). CdSe NPs are chemically synthesised in thermotropic ionic liquid crystal (ILC) phase of cadmium octanoate which is used as nanoreactor. Anisotropic glassy nanocomposites are obtained by the rapid cooling of the ILC phase of nanocomposites to room temperature. The sizes of the CdSe NPs are determined from the absorption spectra. The thermo-optical nonlinearity of the new nanocomposites is characterised by extremely large value of the nonlinear refractive index, n2, under relatively low-powered CW laser irradiation. This nonlinearity is caused by (1) the efficient light-induced heating due to the CdSe NPs strong exciton absorption, and (2) consequent thermal dissipation, which in turn, produces the photoelastic tensions in the glassy smectic matrix.

Alkyl-bis(imidazolium) salts: a new amphiphile platform that forms thermotropic and non-aqueous lyotropic bicontinuous cubic phases

New ionic amphiphiles with a hexyl-bridged bis(imidazolium) headgroup; Br(-), BF4(-), or Tf2N(-) anions; and a long n-alkyl tail can form thermotropic bicontinuous cubic liquid crystal phases in neat form and/or lyotropic bicontinuous cubic phases with several non-aqueous solvents or water.

Photoresponsive Poly(S-(o-nitrobenzyl)-l-cysteine)-b-PEO from a l-Cysteine N-Carboxyanhydride Monomer: Synthesis, Self-Assembly, and Phototriggered Drug Release

A photoresponsive S-(o-nitrobenzyl)-l-cysteine N-carboxyanhydride (NBC-NCA) monomer was for the first time designed, and the related poly(S-(o-nitrobenzyl)-l-cysteine)-b-poly(ethylene glycol) (PNBC-b-PEO) block copolymers were synthesized from the ring-opening polymerization (ROP) of NBC-NCA in DMF solution at 25 °C. Their molecular structures, physical properties, photoresponsive self-assembly, and drug release of PNBC-b-PEO were thoroughly investigated. The β-sheet conformational PNBC block within copolymers presented a thermotropic liquid crystal phase behavior, and the crystallinity of PEO block was progressively suppressed over the PNBC composition. The characteristic absorption peaks of these copolymers at about 310 and 350 nm increased over UV irradiation time and then leveled off, indicating that the o-nitrobenzyl groups were gradually photocleaved from copolymers until the completion of photocleavage. The PNBC-b-PEO copolymers self-assembled into spherical nanoparticles in aqueous solution, presenting a photoresponsive self-assembly behavior, together with a size reduction of nanoparticles after irradiation. The anticancer drug doxorubicin can be released in a controlled manner by changing the light irradiation time, which was induced by gradually photocleaving the PNBC core of nanoparticles. This work provides a facile strategy not only for the synthesis of photoresponsive polypeptide-based block copolymers but also for the fabrication of photoresponsive nanomedicine potential for anticancer therapy.

Synthesis, conformation transition, liquid crystal phase, and self‐assembled morphology of thermosensitive homopolypeptide

AbstractThermosensitive diethylene glycol‐derived poly(L‐glutamate) homopolypeptides (i.e., poly‐L‐EG2‐Glu) with different molecular weights (MW) (Mn,GPC = 5380–32520) were synthesized via the ring‐opening polymerization (ROP) of EG2‐L‐glutamate N‐carboxyanhydride (EG2‐Glu‐NCA) in N,N‐dimethylformamide solution at 50 °C. Their molecular structure, conformation transition, liquid crystal (LC) phase behavior, lower critical solution temperature (LCST) transition, and morphology evolution were thoroughly characterized by means of FTIR, 1H NMR, gel permeation chromatography, differential scanning calorimetry, wide angle X‐ray diffraction, polarized optical microscope, transmission electron microscope, and dynamic light scattering. In solid state, the homopolypeptide poly‐L‐EG2‐Glu presented a conformation transition from α‐helix to β‐sheet with increasing their MW at room temperature, while it mainly assumed an α‐helix of 80–86% in aqueous solution. Poly‐L‐EG2‐Glu showed a thermotropic LC phase with a transition temperature of about 100 °C in solid state, while it gave a reversible LCST transition of 34–36 °C in aqueous solution. The amphiphilic homopolypeptide poly‐L‐EG2‐Glu self‐assembled into nanostructures in aqueous solution, and their critical aggregation concentrations decreased with increasing MW. Interestingly, their morphology changed from spherical micelles to worm‐like micelles, then to fiber micelles with increasing MW. This work provides a simple method for the generation of different nanostructures from a thermosensitive biodegradable homopolypeptide. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Synthesis and Characterization of Self-Assembled Liquid Crystals: p-Alkoxybenzoic Acids

Thermotropic liquid crystal phases are ordered fluids found, for some molecules, at intermediate temperatures between the crystal and liquid states. Although technologically important, these materials typically receive little attention in the undergraduate curriculum. Here, we describe a laboratory activity for introductory organic chemistry students on the synthesis and characterization of the p-alkoxybenzoic acids. These compounds, through the formation of carboxylic acid dimers, exhibit liquid crystal phases common in rod-like (calamitic) molecules. The students are assigned different alkoxy chain lengths and synthesize the compounds through microwave-assisted nucleophilic substitution. Characterization of the phase behavior is then carried out by standard melting point techniques, differential scanning calorimetry, or polarized optical microscopy. The results for the class are pooled to allow the students to consider structure–property effects for the series. This activity allows students to explore s...