Self-assembled Liquid Crystals Research Articles

Optical vector field rotation and switching with near-unity transmission by fully developed chiral photonic crystals

State-of-the-art nanostructured chiral photonic crystals (CPCs), metamaterials, and metasurfaces have shown giant optical rotatory power but are generally passive and beset with large optical losses and with inadequate performance due to limited size/interaction length and narrow operation bandwidth. In this work, we demonstrate by detailed theoretical modeling and experiments that a fully developed CPC, one for which the number of unit cells N is high enough that it acquires the full potentials of an ideal (N → ∞) crystal, will overcome the aforementioned limitations, leading to a new generation of versatile high-performance polarization manipulation optics. Such high-N CPCs are realized by field-assisted self-assembly of cholesteric liquid crystals to unprecedented thicknesses not possible with any other means. Characterization studies show that high-N CPCs exhibit broad transmission maxima accompanied by giant rotatory power, thereby enabling large (>π) polarization rotation with near-unity transmission over a large operation bandwidth. Polarization rotation is demonstrated to be independent of input polarization orientation and applies equally well on continuous-wave or ultrafast (picosecond to femtosecond) pulsed lasers of simple or complex (radial, azimuthal) vector fields. Liquid crystal-based CPCs also allow very wide tuning of the operation spectral range and dynamic polarization switching and control possibilities by virtue of several stimuli-induced index or birefringence changing mechanisms.

Effects of Labile Mesogens on the Morphology of Liquid Crystalline Block Copolymers in Thin Films

The self-assembly of liquid crystals (LCs) in small volumes is mediated by the anchoring conditions of the constituent mesogens at the confining surfaces. In hierarchically ordered systems such as ...

Photo-tunable epsilon-near-zero behavior in a self-assembled liquid crystal - nanoparticle hybrid material.

Dynamic tuning of electromagnetic response is an important parameter to realize exotic applications of optical metamaterials. Self-assembly achieved via the incorporation of soft materials is an attractive approach to achieve tunable optical properties. Among the soft materials, liquid crystals are highly sought after due to the inherent soft-stimuli responsiveness. This article reports experimental evidence of tunable epsilon-near-zero (ENZ) behavior brought about by an optical field in a self-assembled liquid crystal – nanoparticle system. The material consists of Au nanoparticles capped with a photo-active chiral liquid crystal ligand. In the liquid crystalline state, the system self-assembles into a helical lamellar superstructure, confirmed by polarizing optical microscopy, HRTEM, XRD, and circular dichroism studies. Upon irradiation with UV light, the localized surface plasmon resonance peak of Au red-shifts by ∼10 nm and gets restored with white light illumination. The effective permittivity of the system obtained from ellipsometry indicates ENZ behavior in the visible spectrum with a bandwidth of ∼45 nm which gets enhanced by a factor of 1.6 on UV illumination. Theoretical calculations, carried out using the effective medium approach, support the experimental findings, making the system an efficient ENZ metamaterial in the optical regime.

Interrogating helical nanorod self-assembly with fractionated cellulose nanocrystal suspensions

The helical self-assembly of cholesteric liquid crystals is a powerful motif in nature, enabling exceptional performance in many biological composites. Attempts to mimic these remarkable materials by drying cholesteric colloidal nanorod suspensions often yield films with a non-uniform mosaic-like character, severely degrading optical and mechanical properties. Here we show—using the example of cellulose nanocrystals—that these problems are due to rod length dispersity: uncontrolled phase separation results from a divergence in viscosity for short rods, and variations in pitch can be traced back to a twisting power that scales with rod length. We present a generic, robust and scalable method for fractionating nanorod suspensions, allowing us to interrogate key aspects of cholesteric self-assembly that were previously hidden by colloid dispersity. By controlled drying of fractionated suspensions, we can obtain mosaic-free films that are uniform in colour. Our findings unify conflicting observations and open routes to biomimetic artificial materials with performance that can compete with that of nature’s originals.

Emerging nanoscience with discotic liquid crystals

Discotic liquid crystals (DLCs) are one-dimensional organic semiconducting materials and represent new low cost, rejuvenating materials in optoelectronics. The development of novel supramolecular materials based on liquid crystals (LCs) hybridized with various metallic, semiconducting, and carbon-based materials with optimized functionalities on the nanometer scale attracted much attention in liquid crystal nanoscience. The ability to combine supramolecular liquid crystalline chemistry with nanoscience is very attractive for several reasons. This review focuses on our recent advances in discotic liquid crystal nanoscience. Driven by the self-assembly of both liquid crystals and nanostructures, LC–nanomaterial nanocomposites (LC–NCs) are spontaneously formed through molecular self-organization at the nanometer scale. The careful design of different LC–NCs through enhanced LC properties opened a new era for organic electronics. A brief introduction to LCs is presented with emphasis on DLCs, which is followed by recent developments in the self-assembly of various nanostructures in discotics. We focus on how nanostructures can be self-assembled in such supramolecular materials so that self-organizing functional systems of discotics can be created with tuned physical properties, such as the thermal stability, optoelectronic and dielectric parameters, and response time, in LCs. We conclude this review by discussing the further development of nanoscience with LCs and applications in organic electronics. Our recent studies on how nanostructures can be self-assembled in discotic liquid crystals to create self-organizing functional systems of discotics with tuned physical properties are reviewed. In the first part of the article, charge carrier and semiconducting properties of discotic liquid crystals in the form of 1-D molecular wires are described. The second part of this report summarized our recent results on self-assembly of Ag, Au, Cu, and graphene nanoparticles, carbon dots, CdTe and CdSe quantum dots, gold nanorods, CdS nanoribbons, silver nanodisks, and graphene sheets in discotics.

Lyotropic Chromonic Liquid Crystals and Their Impurities Reveal the Importance of the Position of Functional Groups in Self-Assembly.

We study the effect of purification and impurities on the self-assembly and phase behavior of lyotropic chromonic liquid crystals (LCLCs). LCLC molecules in water stack to form aggregates; then, the elongated nanoaggregates align to make liquid crystalline phases. Utilizing multiple experimental techniques, we unveil impurities in commercial Sunset Yellow FCF (SSY), a representative LCLC, and how the precipitation-based purification promotes the formation of the aggregates and mesophase. We further explore the roles of intrinsic impurities, i.e., byproducts of the SSY synthesis, whose molecular structures are almost identical to that of SSY but differ only in the number and position of sulfonate groups. Combining quantum chemical calculations of molecular structures and experimental investigation of aggregate structures and phase behavior, we propose that the impurities of the planar shapes behave as planar SSY, i.e., participating in aggregate formation, whereas the nonplanar one disrupts the nematic phase. These results highlight the critical roles of the impurities and deepen our understanding of self-assembled aggregates and their aligned mesophases.

Influence of functional groups on the self-assembly of liquid crystals

Functional groups in the molecule play an important role in the molecular organization process. To reveal the influence of functional groups on the self-assembly at interface, herein, the self-assembly structures of three liquid crystal molecules, which only differ in the functional groups, are explicitly characterized by using scanning tunneling microscopy (STM). The high-resolution STM images demonstrate the difference between the supramolecular assembly structures of three liquid crystal molecules, which attribute to the hydrogen bonding interaction and π-π stacking interaction between different functional groups. The density functional theory (DFT) results also confirm the influence of these functional groups on the self-assemblies. The effort on the self-assembly of liquid crystal molecules at interface could enhance the understanding of the supramolecular assembly mechanism and benefit the further application of liquid crystals.

Water Treatment: High Virus Removal by Self‐Organized Nanostructured 2D Liquid‐Crystalline Smectic Membranes for Water Treatment (Small 23/2020)

In article number 2001721, Takeshi Sakamoto, Hiroyuki Katayama, Takashi Kato, and co-workers achieve high virus removal for liquid-crystalline water treatment membranes. The liquid crystal forms 2D lamellar nanochannels allowing superior virus removal while maintaining efficient water flux. The removal efficiency is 99.999994%. Self-assembly of smectic liquid crystals and subsequent photopolymerization leads to the formation of nanostructured 2D materials.

Quantum Chemical Investigations on C14C10-Branched-Chain Glucoside Isomers Towards Understanding Self-Assembly

Density Functional Theory (DFT) calculations have been carried out using a Polarizable Continuum Model (PCM) in an attempt to investigate the electro-molecular properties of branched-chain glucoside (C14C10-D-glucoside) isomers. The results showed that αconfiguration of pyranoside form is thermodynamically the most stable, while the solution should contain much more β than α, according to the calculated Boltzmann distribution. Additionally, C14C10-β-D-xylopyranoside is studied for comparison with its glucoside analog in order to investigate the electronic effect of the hydroxymethyl (−CH2-OH) group at position 5-C. The topological parameters of intramolecular X-H∙∙∙Y hydrogen bonds were analyzed and the nature of these interactions were considered using the Atoms in Molecules (AIM) approach. Moreover, natural bond orbital analysis (NBO) was performed to define bond orders, charge, and lone pair electrons on each atom and effective non-bonding interactions. HOMO/LUMO analysis allowed the description of investigated isomers and led to a further understanding of their behaviors. The computational results, especially intramolecular hydrogen bonding and molecular electronic potential analysis are directly relevant to liquid crystal self-assembly and membrane biophysics.

Liquid crystal ionic self-assembly and anion-selective photoluminescence in discotic azatriphenylenes

We report on the straightforward synthesis of a new series of ionic discotic liquid crystals based on positively charged azatriphenylene.

A self-assembled liquid crystal honeycomb of highly stretched (3-1-1)-hexagons.

A new liquid crystalline honeycomb phase is reported, containing highly stretched giant hexagonal cells with two opposing walls spanned by three consecutive end-to-end H-bonded rods, the (3-1-1) hexagons.

Elastic colloidal monopoles and reconfigurable self-assembly in liquid crystals.

Monopole-like electrostatic interactions are ubiquitous in biology1 and condensed matter2-4, but they are often screened by counter-ions and cannot be switched from attractive to repulsive. In colloidal science, where the main goal is to develop colloidal particles2,3 that mimic and exceed the diversity and length scales of atomic and molecular assembly, electrostatically charged particles cannot change the sign of their surface charge or transform from monopoles to higher-order multipoles4. In liquid-crystal colloids5-7, elastic interactions between particles arise to minimize the free energy associated with elastic distortions in the long-range alignment of rod-like molecules around the particles5. In dipolar6,8, quadrupolar8-12 and hexadecapolar13 nematic colloids, the symmetries of such elastic distortions mimic both electrostatic multipoles14 and the outermost occupied electron shells of atoms7,15,16. Electric and magnetic switching17,18, spontaneous transformations19 and optical control20 of elastic multipoles, as well as their interactions with topological defects and surface boundary conditions, have been demonstrated in such colloids21-23. However, it has long been understood5,24 that elastic monopoles should relax to uniform or higher-order multipole states because of the elastic torques that they induce5,7. Here we develop nematic colloids with strong elastic monopole moments and with elastic torques balanced by the optical torques induced by ambient light. We demonstrate the monopole-to-quadrupole reconfiguration of these colloidal particles by unstructured light, which resembles the driving of atoms between the ground state and various excited states. We show that the sign of the elastic monopoles can be switched, and that like-charged monopoles attract whereas oppositely charged ones repel, unlike in electrostatics14. We also demonstrate the out-of-equilibrium dynamic assembly of these colloidal particles. This diverse and surprising behaviour is explained using a model that considers the balance of the optical and elastic torques that are responsible for the excited-state elastic monopoles and may lead to light-powered active-matter systems and self-assembled nanomachines.

Pressure-Responsive Hierarchical Chiral Photonic Aerogels.

Pressure-responsive chiral photonic aerogels are fabricated by combining liquid crystal self-assembly and ice-templating processes. The aerogels have a hierarchical structure in which the primary 2D chiral nematic structured walls of cellulose nanocrystals form ribbons that support a secondary 3D cellular network. Owing to the flexibility of the aerogels in solvent, the 3D structure of the aerogel can easily be transformed to a 2D structure by pressure-induced rearrangement. The aerogels vary from white in color, which arises from light scattering, to a reflective photonic crystal displaying bright iridescent colors that depend on the immersed solvent. A solvent-sensitive ink that shows quick color response to different solvents is designed using the pressure-responsive photonic aerogel. This material demonstrates a new response mechanism for the design of smart and mechanoresponsive photonic materials.

Polymorphic transitions mediated by surfactants in liquid crystal nanodroplet

ABSTRACTRecently, 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 RND (amount of surfactant molecules). Furthermore, difference of the self-assembly structure also appeared inside the droplet depending on RND. 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.

Self-assembly of liquid crystals in nanoporous solids for adaptive photonic metamaterials.

Nanoporous media exhibit structures significantly smaller than the wavelengths of visible light and can thus act as photonic metamaterials. Their optical functionality is not determined by the properties of the base materials, but rather by tailored, multiscale structures, in terms of precise pore shape, geometry, and orientation. Embedding liquid crystals in pore space provides additional opportunities to control light-matter interactions at the single-pore, meta-atomic scale. Here, we present temperature-dependent 3D reciprocal space mapping using synchrotron-based X-ray diffraction in combination with high-resolution birefringence experiments on disk-like mesogens (HAT6) imbibed in self-ordered arrays of parallel cylindrical pores 17 to 160 nm across in monolithic anodic aluminium oxide (AAO). In agreement with Monte Carlo computer simulations we observe a remarkably rich self-assembly behaviour, unknown from the bulk state. It encompasses transitions between the isotropic liquid state and discotic stacking in linear columns as well as circular concentric ring formation perpendicular and parallel to the pore axis. These textural transitions underpin an optical birefringence functionality, tuneable in magnitude and in sign from positive to negative via pore size, pore surface-grafting and temperature. Our study demonstrates that the advent of large-scale, self-organised nanoporosity in monolithic solids along with confinement-controllable phase behaviour of liquid-crystalline matter at the single-pore scale provides a reliable and accessible tool to design materials with adjustable optical anisotropy, and thus offers versatile pathways to fine-tune polarisation-dependent light propagation speeds in materials. Such a tailorability is at the core of the emerging field of transformative optics, allowing, e.g., adjustable light absorbers and extremely thin metalenses.

Heliconical-layered nanocylinders (HLNCs) – hierarchical self-assembly in a unique B4 phase liquid crystal morphology

Hierarchical self-assembly in bent-core liquid crystals – the B4 phase with heliconical-layered nanocylinder morphology.

Strong CPL of achiral AIE-active dyes induced by supramolecular self-assembly in chiral nematic liquid crystals (AIE-N*-LCs).

Chiral binaphthyl enantiomers (Guest 1) were doped into commercial nematic liquid crystals (N-LCs, Host E7) to form chiral nematic liquid crystals (N*-LCs). The new ternary AIE-N*-LCs prepared by introducing four achiral AIE dyes (Guest 2) into N*-LCs can give rise to strong CPL responses with high luminescence dissymmetry factor (gem) values of up to1.42.

Supramolecular self-assembly and physical-gel formation in disc-like liquid crystals: a scalable predictive model for gelation and an application in photovoltaics.

The application of triphenylene-based discotic liquid crystal derivatives as physical gelators is investigated. In particular, we focus on 2,3,6,7,10,11-hexakis-pentyloxytriphenylene (HAT5) and the longer alkyl chain homologue (HAT6). The driving mechanisms behind and parameter space of non-covalent physical gel formation is studied. A Hansen solubility parameter (HSP) approach is used to predict physical gelation of these disc-like liquid crystalline molecules in a variety of common organic and inorganic solvents important to electrochemical devices. Our results show that HSP analysis is very useful for the prediction of gel formation. The results are transferrable and can form the basis for future investigations into liquid crystalline physical gels. Furthermore, we use acetonitrile as a solvent and apply the gels as electrolytes in dye sensitized solar cells. It is observed that using a binary mixture of gelators results in average photovoltaic power conversion efficiencies as high as 7.21%, compared to a 5.9% reference electrolyte. This is attributed to a reduction in electron recombination at the n-type interface and provides further insight about hybrid gelators. Coupled with an increase in device stability, the results are promising for gel-based dye sensitized solar cells as well as potentially other electrolytic devices such as batteries and supercapacitors.

Reducing Structural Defects and Oxygen-Containing Functional Groups in GO-Hybridized CNTs Aerogels: Simultaneously Improve the Electrical and Mechanical Properties To Enhance Pressure Sensitivity

Three-dimensional graphene oxide-carbon nanotube (GO-CNT, abbreviated as GCNT) aerogels can find wide applications in various fields. Especially, low-density GCNT aerogels featuring both high conductivity and superelasticity are essential requirements for the construction of highly sensitive pressure sensor. However, simultaneous improvement on the electrical and mechanical properties of low-density GCNT is still a great challenge owing to their disordered microstructure, severe structural defects and massive oxygen-containing functional groups. Here, a structurally ordered and less defective GCNT aerogel featuring both high conductivity and superelasticity has been fabricated through alkali induced self-assembly of GO liquid crystals (GO LCs) and CNTs. Our methodology relies on the double roles of KOH solution as dispersant for CNTs and an inducer for the self-assembly of GO LCs nanosheets. The less-defective CNTs acting as reinforcement material contributes to the robust structure networks, leading to the significantly improved conductivity (2.4 S m-1) and elasticity (14.3 kPa) of GCNT. Benefiting from these outstanding properties of GCNT aerogels, the assembled pressure sensor exhibits an ultrahigh sensitivity of 1.22 kPa-1, rapid response time of 28 ms and excellent cycling stability, which enables it as a high-performance sensing platform to monitor various human motions in real time.

Nonenzymatic Polymerization into Long Linear RNA Templated by Liquid Crystal Self-Assembly.

Self-synthesizing materials, in which supramolecular structuring enhances the formation of new molecules that participate to the process, represent an intriguing notion to account for the first appearance of biomolecules in an abiotic Earth. We present here a study of the abiotic formation of interchain phosphodiester bonds in solutions of short RNA oligomers in various states of supramolecular arrangement and their reaction kinetics. We found a spectrum of conditions in which RNA oligomers self-assemble and phase separate into highly concentrated ordered fluid liquid crystal (LC) microdomains. We show that such supramolecular state provides a template guiding their ligation into hundred-bases long chains. The quantitative analysis presented here demonstrates that nucleic acid LC boosts the rate of end-to-end ligation and suppresses the formation of the otherwise dominant cyclic oligomers. These results strengthen the concept of supramolecular ordering as an efficient pathway toward the emergence of the RNA World in the primordial Earth.