Dominant Factors Affecting Rheological Properties of Cellulose Derivatives Forming Thermotropic Cholesteric Liquid Crystals with Visible Reflection.

Hydroxypropyl cellulose (HPC) derivatives with alkanoyl side chains are known to form thermotropic cholesteric liquid crystals (CLCs) with visible reflection. Although the widely investigated CLCs are requisite for tedious syntheses of chiral and mesogenic compounds from precious petroleum resources, the HPC derivatives easily prepared from biomass resources would contribute to the realization of environment-friendly CLC devices. In this study, we report the linear rheological behavior of thermotropic CLCs of HPC derivatives possessing alkanoyl side chains of different lengths. In addition, the HPC derivatives have been synthesized by the complete esterification of hydroxy groups in HPC. The master curves of these HPC derivatives were almost identical at reference temperatures, with their light reflection at 405 nm. The relaxation peaks appeared at an angular frequency of ~102 rad/s, suggesting the motion of the CLC helical axis. Moreover, the dominant factors affecting the rheological properties of HPC derivatives were strongly dependent on the CLC helical structures. Further, this study provides one of the most promising fabrication strategies for the highly oriented CLC helix by shearing force, which is indispensable to the development of advanced photonic devices with eco-friendliness.

Cholesteric Liquid Crystals with Thermally Stable Reflection Color from Mixtures of Completely Etherified Ethyl Cellulose Derivative and Methacrylic Acid.

Cellulose derivatives have attracted attention as environmentally friendly materials that can exhibit a cholesteric liquid crystal (CLC) phase with visible light reflection. Previous reports have shown that the chemical structures and the degrees of substitution of cellulose derivatives have significant influence on their reflection properties. Although many studies have been reported on CLC using ethyl cellulose (EC) derivatives in which the hydroxy groups are esterified, there have been no studies on EC derivatives with etherified side chains. In this article, we optimized the Williamson ether synthesis to introduce pentyl ether groups in the EC side chain. The degree of substitution with pentyl ether group (DSPe), confirmed via 1H-NMR spectroscopic measurements, was controlled using the solvent and the base concentration in this synthesis. All the etherified EC derivatives were soluble in methacrylic acid (MAA), allowing for the preparation of lyotropic CLCs with visible reflection. Although the reflection peak of lyotropic CLCs generally varies with temperature, the reflection peak of lyotropic CLCs of completely etherified EC derivatives with MAA could almost be preserved in the temperature range from 30 to 110 °C even without the aid of any crosslinking. Such thermal stability of the reflection peak of CLCs may be greatly advantageous for fabricating new photonic devices with eco-friendliness.

Rheological Properties of Cholesteric Liquid Crystal with Visible Reflection from an Etherified Hydroxypropyl Cellulose Derivative.

Optical properties of hydroxypropyl cellulose (HPC) derivatives have been widely investigated for their ability to exhibit cholesteric liquid crystal (CLC) phase. However, there are only a limited number of studies on their rheological properties even though they are quite important for the applications of such HPC derivatives to the versatile CLC photonic devices. In this article, we report on the optical and rheological properties of an HPC derivative possessing pentyl ether groups in the side-chains. The etherified HPC derivative exhibited thermotropic CLC phase with light reflection in the temperature range between 25 °C and 120 °C. After the HPC derivative was heated once at isotropic phase, followed by being cooled to the CLC phase, the reflection peak could not be observed, even at the CLC phase. At this stage, the HPC derivative exhibited solid-like rheological responses compared to that of sheared at a constant shear rate of 1.0 s-1. Such differences in the optical and rheological properties of the HPC derivative can be ascribed to the difference in CLC orientation state. From the rheological results, the etherified HPC derivative showed liquid-like behavior rather than the esterified HPC derivatives. This evidence provides a promising clue for fabricating high-quality CLC devices by the facile CLC orientation.

Size-Controllable Synthesis of Monodisperse Magnetite Microparticles Leading to Magnetically Tunable Colloidal Crystals.

Colloidal crystals (CCs) are periodic arrays of monodisperse microparticles. Such CCs are very attractive as they can be potentially applicable as versatile photonic devices such as reflective displays, sensors, lasers, and so forth. In this article, we describe a promising methodology for synthesizing monodisperse magnetite microparticles whose diameters are controllable in the range of 100-200 nm only by adjusting the base concentration of the reaction solution. Moreover, monodisperse magnetite microparticles in aqueous suspensions spontaneously form the CC structures under an external magnetic field, leading to the appearance of Bragg reflection colors. The reflection peak can be blue-shifted from 730 nm to 570 nm by the increase in the external magnetic field from 28 mT to 220 mT. Moreover, the reflection properties of CCs in suspension depend on the microparticle concentration in suspension and the diameter of the magnetite microparticles. Both fine-control of microparticle diameter and investigation of magneto-optical properties of CCs would contribute to the technological developments in full-color reflective displays and sensors by utilizing these monodisperse magnetite microparticles.

Room-Temperature Cholesteric Liquid Crystals of Cellulose Derivatives with Visible Reflection.

Hydroxypropyl cellulose (HPC) derivatives with alkanoyl side chains have attracted attention as bio-based cholesteric liquid crystal (CLC) materials with reflection colors. By taking advantage of the ability to change the reflection color in response to external stimuli, the thermotropic CLCs can be applied to a wide variety of photonic devices for a sustainable society of future generations. However, the thermotropic CLCs of HPC derivatives substituted with only one kind of alkanoyl group are not suitable for such applications because they do not exhibit visible reflection at room temperature. In this report, we describe a promising strategy to control the reflection colors of HPC derivatives at room temperature by introducing two kinds of alkanoyl groups with different lengths into the side chains of HPCs, which also enables the fine control of temperature dependence on the reflection wavelength. By chemically optimizing the side chain, we successfully prepared room-temperature thermotropic CLCs of HPC derivatives with visible reflection. This report would contribute toward the development of versatile photonic applications by CLCs produced from biomass.

Colloidal Crystal Films with Narrow Reflection Bands by Hot-Pressing of Polymer-Grafted Silica Particles.

Previous reports have shown that colloidal crystal (CC) films with visible Bragg reflection characteristics can be fabricated by the surface modification of monodisperse silica particles (SiPs) with poly(methyl methacrylate) (PMMA) chains, followed by hot-pressing at 150 °C. However, the reflection bands of the CC films were very broad due to their relative disordering of SiPs. In this report, we attempted to fabricate the CC films using SiPs surface-modified with poly(n-octyl acrylate) (POA) chains by hot-pressing. When the cast films of POA-grafted SiPs were prepared by hot-pressing at 100 °C, the reflection bands were narrow rather than those of CC films of PMMA-grafted SiPs. This can be ascribed to easy disentanglement of POA chains during the hot-pressing process, thereby enabling the formation of well-ordered CC structures. Moreover, the reflection colors of CC films could be easily tuned by controlling the molecular weight of POA chains grafted on the SiP surface.

Colloidal Photonic Crystals of Reusable Hydrogel Microparticles for Sensor and Laser Applications.

Although a wide variety of techniques have been developed to date for the fabrication of high-quality colloidal photonic crystals (CPCs) using monodisperse silica and polystyrene microparticles, poly(N-isopropylacrylamide) (PNIPA) hydrogel microparticles have rarely been utilized for the preparation of active CPCs despite the intriguing feature of temperature-responsive volume changes. This report describes the promising potential abilities of PNIPA hydrogel microparticles for sensor and laser applications. Monodisperse PNIPA hydrogel microparticles were synthesized by emulsion polymerization, and the microparticle diameter was finely controlled by adjusting the surfactant concentration. Such hydrogel microparticles spontaneously formed uniform CPCs with visible Bragg reflection even in fluid suspensions. The addition of small amounts of ionic substances into the centrifuged and deionized CPC suspensions enabled the on-demand color switching between Bragg reflection and white turbidity with temperature, leading to temperature- and ion-sensing applications. Moreover, our expanding experiments successfully demonstrated the optically excited laser action with a single and narrow peak from CPC suspensions with light-emitting dyes by the photonic band gap effect. After the light-emitting dyes were simply removed from the CPC suspensions by centrifugation, the purified PNIPA hydrogel microparticles were permanently reusable as the CPC laser microcavities to generate the laser action at other wavelengths using different dyes. This study contributes the circular economy concept using reusable hydrogel microparticles for the realization of a sustainable society.