Polymorphic transitions mediated by surfactants in liquid crystal nanodroplet

Recently, various techniques have been developed using photonic crystals. Liquid crystals (LC) confined in a nanodroplet mimicked photonic crystals, such as those of opal. Therefore, investigating the phase behaviour of LC molecules in nanodroplets is very important in the next-generation optical field. In this study, the chemical interaction between surfactants and LCs in nanodroplets is reproduced using a dissipative particle dynamics method. We identify the phase behaviour of LCs and investigate how the chemical interaction affect on the orientation of LCs. In particular, by adding surfactant molecules, various morphological behaviours were observed in the LC nanodroplet. The phase transition temperature varied depending on R_ND (amount of surfactant molecules). Furthermore, difference of the self-assembly structure also appeared inside the droplet depending on R_ND. Our simulation offers a theoretical guide to control morphologies of self-assembled LCs inside a nanodroplet, a novel system that may find applications in nanofluidic devices or in photonic crystal technology.     

Orientation control over bent-core smectic liquid crystal phases

Bent-core smectic liquid crystal (LC) phases (B phases) have been widely studied since their unusual polar and chiral properties were discovered in the 1990s. Relatively few studies have examined the mechanisms by which the orientation of the B phase may be controlled to produce the type of macroscopic domain that is essential for organic semiconductor, optical device and patterning applications. This review is intended to cover recent progress towards controlling the B phases upon layering, including anisotropic treatment methods and topographical confinement methods. Finally, this review closes with a discussion of B smectic phases that have been fabricated for use in certain applications.     

Hydrophilic interaction chromatography

Separation of polar compounds on polar stationary phases with partly aqueous eluents is by no means a new separation mode in LC. The first HPLC applications were published more than 30 years ago, and were for a long time mostly confined to carbohydrate analysis. In the early 1990s new phases started to emerge, and the practice was given a name, hydrophilic interaction chromatography (HILIC). Although the use of this separation mode has been relatively limited, we have seen a sudden increase in popularity over the last few years, promoted by the need to analyze polar compounds in increasingly complex mixtures. Another reason for the increase in popularity is the widespread use of MS coupled to LC. The partly aqueous eluents high in ACN with a limited need of adding salt is almost ideal for ESI. The applications now encompass most categories of polar compounds, charged as well as uncharged, although HILIC is particularly well suited for solutes lacking charge where coulombic interactions cannot be used to mediate retention. The review attempts to summarize the ongoing discussion on the separation mechanism and gives an overview of the stationary phases used and the applications addressed with this separation mode in LC.     

New hydrogen-bonded comblike polyimides with mesogenic side chains for stable orientation and fast switching of liquid crystals

ABSTRACT

New supramolecular comblike polyimides with mesogenic side chains for stable homeotropic orientation and fast electro-optical switching of liquid crystals (LCs) have been prepared through selective intermolecular hydrogen bonding between 4-(4-heptylphenyl)benzoic acid (4HPB) and host polyimide. A low concentration of 4HPB as the mesogenic guest molecule was hydrogen-bonded to polyimide backbone leading to the self-assembled comblike polyimide with enhanced homeotropic orientation properties. The electro-optical characteristics of the LC device containing hydrogen-bonded comblike polyimide exhibited better performance than those of LC cell with conventional polyimide. Because the conventional covalent approach for preparation of polyimides requires considerable synthetic efforts to achieve new functionality in polyimide materials, the proposed noncovalent method is a simple one and highly cost effective. Our controlled methodology should find wide application for the fabrication of functional alignment materials requiring high orientation ability.     

Correlations between surface and bulk liquid crystal alignment observed with optical second-harmonic generation

Abstract

We report a direct experimental observation of surface-induced liquid crystal (LC) monolayer orientation and its relation to the LC bulk alignment. Using optical second-harmonic generation from these LC monolayers, adsorbed on rubbed polymer surfaces, we determined both the polar and azimuthal orientation of the LC molecules. A close correlation between the rubbing-induced azimuthal orientational distribution of the LC monolayers and the resulting LC bulk pretilt angle has been observed. A simple model based on epitaxial growth of the bulk LC on top of the first LC monolayer is proposed to explain this correlation.     

Alignment of liquid crystals using Langmuir‒Blodgett films of unsymmetrical bent-core liquid crystals

ABSTRACT

The properties of the thin films of liquid crystal (LC) molecules can be governed easily by external fields. The anisotropic structure of the LC molecules has a large impact on the electrical and optical properties of the film. The Langmuir monolayer (LM) of LC molecules at the air–water interface is known to exhibit a variety of surface phases which can be transferred onto a solid substrate using the Langmuir?Blodgett (LB) technique. Here, we have studied the LM and LB films of asymmetrically substituted bent-core LC molecules. The morphology of LB film of the molecules is found to be a controlling parameter for aligning bulk LC in the nematic phase. It was found that the LB films of the bent-core molecules possessing defects favour the planar orientation of nematic LC, whereas the LB films with fewer defects show homeotropic alignment. The defect in LB films may introduce splay or bend distortions in the nematic near the alignment layer which can govern the planar alignment of the bulk LC. The uniform layer of LB film facilitates the molecules of nematic to anchor vertically due to a strong van der Waals interaction between the aliphatic chains leading to a homeotropic alignment.     

Water‐soluble top coats for orientation control of liquid crystal‐containing block copolymer films

An easily removable, water‐soluble top coat of polyvinylpyrrolidone (PVP) is used to control the orientation of microdomains in a liquid crystalline block copolymer (LC BCP, poly(ethylene oxide)‐block‐poly(6‐(4‐methoxy‐azobenzene‐4′‐butyl) hexyl methacrylate)). The corresponding LC homopolymer is also investigated for comparison. Atomic force microscopy is used to determine the orientation of the cylindrical microdomains of the LC BCP. UV–vis spectroscopy and grazing incidence wide‐angle X‐ray scattering are used to determine the orientation of the LC mesogens in the LC homopolymer and the LC BCP films annealed both with and without a top coat. Once the LC BCP morphology is self‐assembled, the PVP top coat layer can be easily removed with water or alcohol. The facile removal of the top coat improves the processability of BCPs in technological applications, and enables direct investigation of the BCP morphology in scientific studies. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1569–1574     

Controlling domain orientation of liquid crystalline block copolymer in thin films through tuning mesogenic chemical structures

Controlling the macroscopic orientation of nanoscale periodic structures of amphiphilic liquid crystalline block copolymers (LC BCPs) is important to a variety of technical applications (e.g., lithium conducting polymer electrolytes). To study LC BCP domain orientation, a series of LC BCPs containing a poly(ethylene oxide) (PEO) block as a conventional hydrophilic coil block and LC blocks containing azobenzene mesogens is designed and synthesized. LC ordering in thin films of the BCP leads to the formation of highly ordered, microphase‐separated nanostructures, with hexagonally arranged PEO cylinders. Substitution on the tail of the azobenzene mesogen is shown to control the orientation of the PEO cylinders. When the substitution on the mesogenic tails is an alkyl chain, the PEO cylinders have a perpendicular orientation to the substrate surface, provided the thin film is above a critical thickness value. In contrast, when the substitution on the mesogenic tails has an ether group the PEO cylinders assemble parallel to the substrate surface regardless of the film thickness value. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 532–541     

Compositional Analysis of Epoxy Resin Formulations

Abstract

Liquid chromatographic (LC) methods are developed for the quality control of epoxy resin formulations. Primary components in two different commercial resin formulations are separated by LC and identified by Fourier transform infrared spectroscopy. Standard test methods for fingerprinting and specific component analysis are established. Examples are given of applications of the test methods to determine compositional variations in prepregs and to establish acceptance criteria for prepreg quality control.     

Recent Advances in HPLC Analysis of Analgesics

Abstract

Recent developments in HPLC analysis of analgesics have been rapid, paralleling the growth of chromatographic sciences as a whole. Although analgesics have been used for hundreds of years and chromatgraphic separations have been carried out on them for decades, liquid chromatographic analysis of analgesics has advanced most rapidly in the past 5–7 years . The present review will focus on applications of HPLC to the analysis of commercial analgesics in this time period with emphasis on novel developments and applications associated with the improved accuracy, sensitivity and specificity in herent in current LC systems.     

Inducing Planar Orientation in Side‐Chain Liquid‐Crystalline Polymer Systems via Interfacial Control

For efficient photoresponses of liquid‐crystal (LC) azobenzene (Az) polymer systems, planar LC orientation of the Az mesogenic group is required because the light irradiation process usually occurs with normal incidence to the film surface. However, LC molecules with a rodlike shape tend to orient perpendicularly to the film surface according to the excluded volume effect theory. This review introduces new approaches for inducing planar orientation in side‐chain LC Az polymer films via interface and surface molecular designs. The planar orientation offers efficient in‐plane photoalignment and photoswitching to hierarchical LC architectures from molecular LC mesogens and LC phases to mesoscopic microphase‐separated structures. These approaches are expected to provide new concepts and possibilities in new LC polymer devices.

     

Applications of Poly(Ethylene)Glycol (PEG) in Separation Science

The wide range of applications of poly(ethylene)glycol (PEG) in primarily chromatography and other closely related analytical methods has been reviewed. PEG has been used as mobile phase modifier in capillary electrophoresis (CE) as well as ion exchange, size exclusion, and hydrophobic interaction liquid chromatography (LC) methods. Generally in the presence of PEG, LC retention of macromolecules is altered and stability of their structure is maintained. PEG was effective in CE as a permanent coating for fused silica capillaries to shield free silanol groups that can cause protein adsorption to the wall resulting in band broadening and low recovery of the separated proteins. In gas chromatography, PEG-based stationary phases were applied for separation of polar analytes. PEG could also serve as an extraction medium in solid phase microextraction and aqueous two phase systems. Selected analytical applications, primarily LC and CE, involving PEG to facilitate the determination of either small molecules or macromolecules such as proteins in their native form are discussed and representative figures provided.

     

Dynamic self-assembly of nanoparticles using thermotropic liquid crystals

ABSTRACT

3D nanoparticle-based materials with reconfigurable structure have gained vast attention due to the unique possibility of tailoring nanoparticle-related quantum confinement effects. These properties make active nanoparticle assemblies promising candidates for future optoelectronic and metamaterial technologies; however, integration of these materials into real-world applications is still challenging. In this context, the use of stimuli responsive liquid-crystals (LCs) offers a fascinating and industrially feasible strategy for active directing of NPs. Here, we briefly review LCs/NPs hybrid systems in which dynamic behaviour is achieved by affecting either LC matrix or LC ligands. We also experimentally evaluate a complementary strategy based on directly affecting metallic core of LC-covered NPs in an Ostwald ripening process.     

Applications of liquid crystals in biosensing and organic light-emitting devices: future aspects

ABSTRACT

This article summarises recent advances made in our laboratory towards the development of new technological applications, such as biosensors and organic light-emitting diodes (OLEDs) based on liquid crystals (LCs) other than LC displays. The study of biomolecular interaction using LC material relies on the specific interaction between the LC and the biomolecule of interest at interfaces that permit the biomolecular events to be amplified into easily measured signals for various sensing applications. In the first part, we emphases recent studies in the design and modulation of LC-based interfaces based on robust colloidal LC gels for biological amplification, qualitative and quantitative understanding of important biomolecular interactions at LC–aqueous interfaces for diagnostic and laboratory applications and design of LC droplets that hold promise to act as a marker for cells and cell-based interactions. In the second part, we described design of organic materials for application in OLEDs on various discotic monomers, dimers and oligomers. These molecules have the ability to transport charges, holes and electrons. In addition, because of the high conductivity and π–π stacking, they are considered as the advanced materials for practical applications. The technological advances in our laboratory using discotic LCs will be briefly presented in this article.     

Peripheral chain length-dependent complex phase behaviour in C3-symmetric hexa-alkylated liquid crystals

We report the thermal and self-assembly properties of C₃-symmetric liquid crystalline (LC) molecules consisting of a conformationally tunable triazole-based mesogen and six-fold alkyl chains. Unlike the LC compound (1) based on non-crystallisable octyl chains, 2 and 3, which have crystallisable dodecyl and tetradecyl chains, respectively, exhibit a cold crystallisation which only takes place under slow heating conditions (2°C/min). In contrast with the vertically interdigitated lamellar crystalline phase of 1, a laterally interdigitated bilayered lamellar structure driven by the crystallisation of the dodecyl or tetradecyl chains is observed in the cold crystallisation temperature range. In addition to their crystalline morphology, 2 and 3 show LC morphological behaviour distinct from that of 1, 2 and 3 exhibit a hexagonal columnar LC phase consisting of T-shaped conformers rather than the lamellar LC phase of 1. The morphological transformation from the lamellar (1) to the columnar phase (2 and 3) can be rationalised by the alleviation of the conformational energy of the longer alkyl chains. Consequently, the simple variation of alkyl chain length in the C₃-symmetric LC system results in contrasting thermal and assembly properties in the crystalline and LC phases.     

Graphene and liquid crystal mediated interactions

ABSTRACT

The two-dimensional graphene-honeycomb structure can interact with the liquid crystal’s (LC) benzene rings through π–π electron stacking. This LC–graphene interaction gives rise to a number of interesting physical and optical phenomena in the LC. In this paper, we present a combination of a review and original research of the exploration of novel themes of LC ordering at the nanoscale graphene surface and its macroscopic effects on the LC’s nematic and smectic phases. We show that monolayer graphene films impose planar alignment on the LC, creating pseudo-nematic domains (PNDs) at the surface of graphene. In a graphene-nematic suspension, these PNDs enhance the orientational order parameter, exhibiting a giant enhancement in the dielectric anisotropy of the LC. These anisotropic domains interact with the external electric field, resulting in a non-zero dielectric anisotropy in the isotropic phase as well. We also show that graphene flakes in an LC reduce the free ion concentration in the nematic media by an ion-trapping process. The reduction of mobile ions in the LC is found to have subsequent impacts on the LC’s rotational viscosity, allowing the nematic director to respond quicker on switching the electric field on and off. In a ferroelectric LC (smectic-C* phase), suspended graphene flakes enhance the spontaneous polarisation by improving the tilted smectic-C* ordering resulting from the π–π electron stacking. This effect accelerates the ferroelectric-switching phenomenon. Graphene can possess strain chirality due to a soft shear mode. This surface chirality of graphene can be transmitted into LC molecules exhibiting two types of chiral signatures in the LCs: an electroclinic effect (a polar tilt of the LC director perpendicular to, and linear in, an applied electric field) in the smectic-A phase, and a macroscopic helical twist of the LC director in the nematic phase. Finally, we show that a graphene-based LC cell can be fabricated without using any aligning layers and ITO electrodes. Graphene itself can be used as the electrodes as well as the aligning layers, obtaining an electro-optic effect of the LC inside the cell.     

Flat optics with cholesteric and blue phase liquid crystals

ABSTRACT

The cholesteric (Ch) phase is an ancient liquid crystal (LC) phase, with its roots dating back to the days of Friedrich Reinitzer. It is most well known for its ability to selectively reflect circularly polarised light with the same rotation handedness as the helical structure, and have found applications in polarising and display devices. Most studies to date utilising the reflective properties of ChLCs, however, have treated ChLCs as simple dielectric mirrors in which light follows the law of reflection. We have recently shown that through controlling the phase of the Ch helix, it is possible to control the phase of reflected light. Because the phase can be controlled over 0–2π, the reflected wavefront from a planar device can be designed to possess non-specular properties, such as deflection and lensing. In this paper, we aim to provide a comprehensive understanding of the phenomenon by presenting theoretical and experimental results on the dependence of the reflected light phase on the helix phase, and the effect of chiral handedness on the phenomenon. Also, we show that wavefront manipulation based on the same concept can be achieved in Ch blue phases (BPs), which are chiral LCs with three-dimensional periodicity.     

Thin films of discotic liquid crystals and their applications

ABSTRACT

Discotic liquid crystals (DLCs) are considered as fascinating systems due to their unique property of self-assembly to yield different columnar structures. DLCs are organic semiconductors and create pathways for the development of numerous optical and electrical devices. The thin films of DLCs can be considered as low dimensional system which can exhibit remarkable optical and physical properties. In this article, we present a review on ultrathin films of some interesting DLC molecules at air–water and air–solid interfaces. The Langmuir monolayer and Langmuir–Blodgett films of DLC molecules are extensively studied. The ultrathin films of DLC molecules can yield highly anisotropic layer wherein the molecular orientation and aggregation can have large impact on the physicochemical properties of the film. Different surface phases with different molecular orientations as function of surface density and temperature can be obtained by forming the Langmuir monolayer of the DLC molecules at the air–water interface. The Langmuir monolayer in a particular phase can be deposited onto the active area of a device layer-by-layer by employing a highly controlled Langmuir–Blodgett technique. Here, we report some interesting results related on molecular orientation of the DLC molecules at different interfaces. Such aggregation of DLC molecules in ultrathin films may find applications in thin film-based electro-optical devices.     

Influence of meta-extended rigid-core,complementary hydrogen bonding and flexible chain on polymorphism in Schiff-base liquid crystals: (4)MeOBD(3)AmBA:nOBAs

ABSTRACT

Schiff-base complementary hydrogen-bonded liquid crystals (HBLC), viz., (4)_MeOBD(3)_AmBA:nOBAs with flexible chain length for n = 3,4,5,6,7,8,9,10,11 and 12 are reported. ¹H; ¹³C-NMR and Infra-Red spectroscopy used to confirm the formation of HBLCs. LC phases and transition temperatures (T_c) determined by polarised optical microscopy (POM) and differential scanning calorimetry (DSC). T_c and enthalpy (?H) determined by DSC also. Odd-Even effect observed at clearing and melting transitions. Influence of Schiff base and Oxygen as bridging atom promote smectic phase abundance. HBLCs exhibit tetra- or penta-phase variance. Maximum (penta) phase variance is exhibited by n = 8 and 12 with long flexible chain. Prevalent abundance of quasi-two-dimensional (2D) LC phases of SmF and SmI is observed. Nematic phase is quenched. Lower (n = 4) and intermediate (n = 6) members exhibited SmB_cryst phase. Predominant occurrence of enantiotropic LC phases is noticed. All members exhibited 3D tilted SmG phase. A-C transition exhibited by intermediate homologues (for n = 7, 8, 9 and 10) is found to be either second order or with very small enthalpy. Phase diagram reveals the abundance of multi-critical points with LC phasesinvolving exotic symmetries. Influence of meta-extended rigid core, complementary HB and flexibility is studied for the LC phase abundance with characteristic structural order. POM and DSC results are discussed in the wake of reports in other achiral calamitic LCs.     

Studies on the mesophase formation mechanism of polybenzoxazines: polymerisation induction

ABSTRACT

To study the mesophase formation mechanism of polybenzoxazine, a novel linear benzoxazine oligomer bearing cholesteryl side groups [poly(PC-AC)] was designed and synthesised through thermally activated ring-opening polymerisation of a monofunctional benzoxazine monomer (PC-AC). The PC-AC was obtained by Mannich condensation reaction using mesomorphic amine of cholesteryl 4-aminobenzoate, p-cresol and paraformaldehyde as starting materials. During the isothermal polymerisation of PC-AC monomer, the phase evolution from a crystal phase to an isotropic molten phase and then to a liquid crystal (LC) phase was observed. Since it is PC-AC oligomers that form the LC phase, ‘polymerisation-induced LC’ mechanism is put forward. We believe that the structure factors including the confined formation of intramolecular hydrogen bonding and the side chain position of mesogenic units also play an important role in the formation of the LC phase. Furthermore, poly(PC-AC) exhibits a smectic mesophase. This work provides new insight into the LC phase formation mechanism of polybenzoxazines. This is very helpful to guide the rational design and synthesis of polymers with high thermal conductivity and high-temperature resistance.