Experimental probing of dynamic self-organized columnar assemblies in colloidal liquid crystals.

Self-organized supramolecular assemblies are widespread in nature and technology in the form of liquid crystals, colloids, and gels. The reversible nature of non-covalent bonding leads to dynamic functions such as stimuli-responsive switching and self-healing, which are unachievable from an isolated molecule. However, multiple intermolecular interactions generate diverse conformational and configurational molecular motions over various time scales in their self-assembled states, and their specific dynamics remains unclear. In the present study, we have experimentally unveiled the static structures and dynamical behaviors in columnar colloidal liquid crystals by a coherent X-ray scattering technique using refined model samples. We have found that controlling the size distribution of the colloidal nanoplates dramatically changed their static and dynamic properties. Furthermore, the resulting dynamical behaviors obtained by X-ray photon correlation spectroscopy have been successfully decomposed into multiple distinct modes, allowing us to explore the dynamical origin in the colloidal liquid-crystalline state. The present approaches using a columnar liquid crystal may contribute to a better understanding of the dynamic nature of molecular assemblies and dense colloidal systems and bring valuable insights into rational design of functional properties of self-assembled materials such as stimuli-responsive liquid crystals, self-healing gels, and colloidal crystals. For these materials, the motion of constituent particles and molecules in the self-assembled state is a key factor for structural formation and dynamically responsive performance.

Reentrant 2D Nanostructured Liquid Crystals by Competition between Molecular Packing and Conformation: Potential Design for Multistep Switching of Ionic Conductivity.

The front cover artwork is provided by Takashi Kato at the University of Tokyo. The image shows three assembled structures of smectic liquid crystals that show reentrant behavior. Read the full text of the Research Article at 10.1002/cphc.202200927.

Reentrant 2D Nanostructured Liquid Crystals by Competition between Molecular Packing and Conformation: Potential Design for Multistep Switching of Ionic Conductivity.

Reentrant phenomena in soft matter and biosystems have attracted considerable attention because their properties are closely related to high functionality. Here, we report a combined experimental and computational study on the self-assembly and reentrant behavior of a single-component thermotropic smectic liquid crystal toward the realization of dynamically functional materials. We have designed and synthesized a mesogenic molecule consisting of an alicyclic trans,trans-bicyclohexyl mesogen and a polar cyclic carbonate group connected by a flexible tetra(oxyethylene) spacer. The molecule exhibits an unprecedented sequence of layered smectic phases, in the order: smectic A-smectic B-reentrant smectic A. Electron density profiles and large-scale molecular dynamics simulations indicate that competition between the stacking of bicyclohexyl mesogens and the conformational flexibility of tetra(oxyethylene) chains induces this unusual reentrant behavior. Ion-conductive reentrant liquid-crystalline materials have been developed, which undergo the multistep conductivity changes in response to temperature. The reentrant liquid crystals have potential as new mesogenic materials exhibiting switching functions.

Investigating the local structure of Ti based MXene materials by temperature dependent X-ray absorption spectroscopy.

The local structures of Ti based MXene-type electrode materials have been studied by Ti K-edge X-ray absorption fine structure measurements as a function of temperature to obtain direct information on the local bond lengths and their stiffness. In particular, the parent MAX phases Ti2AlC and Ti3AlC2 and their etched MXene systems are characterized and their properties compared. We find that selective etching has a substantial effect on the local structural properties of the Ti based MXene materials. It leads to an increase in the interatomic distances, i.e. a decrease in the covalency, and corresponding bond stiffness, that is a likely cause of higher achievable performances. The obtained results underline the importance of the local atomic correlations as limiting factors in the diffusion capacity of ion batteries.

Gemini Thermotropic Smectic Liquid Crystals for Two-Dimensional Nanostructured Water-Treatment Membranes.

We have developed a two-dimensional (2D) liquid-crystalline (LC) nanostructured water-treatment membrane showing high virus rejection ability (over 99.99997% for bacteriophage Qß) and improved water permeation. Polymerizable gemini amphiphiles have been designed and synthesized. They have H-shaped gemini-type structures of thermotropic smectic liquid crystals composed of cationic imidazolium moieties. One of the gemini amphiphiles shows a smectic A phase with an interdigitated bilayer structure. A cross-linked self-standing 2D nanostructured polymer film has been obtained by in situ photopolymerization of the gemini amphiphile in the smectic phase. The length of linkers in gemini amphiphiles affects the formation of LC phases. The 2D nanostructured membrane also showed selective salt rejection.

Shear-induced liquid-crystalline phase transition behaviour of colloidal solutions of hydroxyapatite nanorod composites.

Liquid-crystalline (LC) bio-inspired materials based on colloidal nanoparticles with anisotropic morphologies such as sheets, plates, rods and fibers were used as functional materials. They show stimuli-responsive behaviour under mechanical force and in electric and magnetic fields. Understanding the effects of external stimuli on the structures of anisotropic colloidal particles is important for the development of highly ordered structures. Recently, we have developed stimuli-responsive hydroxyapatite (HAP)-based colloidal LC nanorods that are environmentally-friendly functional materials. In the present study, the ordering behaviour of HAP nanorod dispersions, which show LC states, has been examined using in situ small-angle neutron scattering and rheological measurements (Rheo-SANS) under shearing force. The structural analyses and dynamic viscosity observations provided detailed information about the effects of shear force on the structural changes of HAP nanorods in D2O dispersion. The present Rheo-SANS measurements unraveled three kinds of main effects of the shear force: the enhancement of interactions between the HAP nanorods, the alignment of HAP nanorods to the shear flow direction, and the formation and disruption of HAP nanorod assemblies. Simultaneous analyses of dynamic viscosity and structural changes revealed that the HAP nanorod dispersions exhibited distinctive rheological properties accompanied by their ordered structural changes.

Nanostructured liquid-crystalline Li-ion conductors with high oxidation resistance: molecular design strategy towards safe and high-voltage-operation Li-ion batteries.

Nanostructured, uncharged liquid-crystalline (LC) electrolyte molecules having bicyclohexyl and cyclic carbonate moieties have been developed for application in Li-ion batteries as quasi-solid electrolytes, which suppress leakage and combustion. Towards the development of safe and high performance Li-ion batteries, we have designed Li-ion conductive LC materials with high oxidation resistance using density functional theory (DFT) calculation. The DFT calculation suggests that a mesogen with a bicyclohexyl moiety is suitable for the high-oxidation-resistance LC electrolytes compared to a mesogen containing phenylene moieties. A tri(oxyethylene) chain introduced between the cyclic carbonate and the bicyclohexyl moiety in the core part tunes the viscosity and the miscibility with Li salts. The designed Li-ion conductive LC molecules exhibit smectic LC phases over a wide temperature range, and they are miscible with added lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt up to 5 : 5 in molar ratio in their smectic phases. The resulting LC mixtures with LiTFSI show oxidation resistance above 4.0 V vs. Li/Li+ in cyclic voltammetry measurements. The enhanced oxidation resistance improves the performance of Li half-cells containing LC electrolytes.

Bioinspired selective synthesis of liquid-crystalline nanocomposites: formation of calcium carbonate-based composite nanodisks and nanorods.

Here we report new organic/inorganic hybrid colloidal liquid crystals that consist of colloidal calcium carbonate (CaCO3)/poly(acrylic acid) (PAA) hybrid nanodisks. We selectively synthesized anisotropic liquid-crystalline CaCO3-based nanodisk and nanorod composites in water/methanol mixtures, which formed discotic and calamitic nematic liquid crystals in their colloidal dispersions, respectively. The vaterite nanodisks and calcite nanorods were selectively synthesized in methanol-rich and water-rich solutions, respectively. The observation of these materials with transmission electron microscopy clarified the atomic-scale structures of these nanodisks and nanorods, revealing the self-organized CaCO3/PAA hybrid structures with the ability to form colloidal liquid crystals. The liquid crystals were prepared under mild and aqueous conditions by methods using acidic polymers inspired by the biomineralization process. The present approach provides new insights into the design of organic/inorganic hybrid colloidal liquid crystals and development of environmentally friendly functional hybrid materials.

Liquid-Crystalline Hydroxyapatite/Polymer Nanorod Hybrids: Potential Bioplatform for Photodynamic Therapy and Cellular Scaffolds.

Recently, we found that self-organization of hydroxyapatite (HAp) with poly(acrylic acid) (PAA) leads to the formation of liquid-crystalline (LC) nanorod hybrids that form aligned films and show stimuli-responsive properties. Here, we demonstrate that these biocompatible HAp/PAA hybrid nanorods represent a platform technology as drug nanocarriers for photodynamic cancer therapy and as bioscaffolds for the control of cellular alignment and growth. To use hybrid nanorods as a drug nanocarrier, we introduced methylene blue (MB), a typical photosensitizer for photodynamic therapy, into the PAA nanolayer covering the surface of the HAp nanocrystals through electrostatic interactions. The stable MB-loaded HAp/PAA hybrid nanorods efficiently produced singlet oxygen from MB upon light irradiation and showed remarkable photodynamic therapeutic effects in cancer cells. Moreover, taking advantage of the mechanically responsive LC alignment properties of the HAp/PAA hybrid nanorods, macroscopically oriented bioscaffolds were prepared through a spin-coating process. The cells cultured on the oriented scaffolds showed cellular alignment and elongation along the oriented direction of the hybrid nanorods. The HAp/PAA hybrid nanorods demonstrate potential in drug delivery and tissue engineering. These unique LC HAp/PAA hybrid nanorods have significant potential as a platform for the development of various types of biomaterial.

Negative dielectric constant of water confined in nanosheets.

Electric double-layer capacitors are efficient energy storage devices that have the potential to account for uneven power demand in sustainable energy systems. Earlier attempts to improve an unsatisfactory capacitance of electric double-layer capacitors have focused on meso- or nanostructuring to increase the accessible surface area and minimize the distance between the adsorbed ions and the electrode. However, the dielectric constant of the electrolyte solvent embedded between adsorbed ions and the electrode surface, which also governs the capacitance, has not been previously exploited to manipulate the capacitance. Here we show that the capacitance of electric double-layer capacitor electrodes can be enlarged when the water molecules are strongly confined into the two-dimensional slits of titanium carbide MXene nanosheets. Using electrochemical methods and theoretical modeling, we find that dipolar polarization of strongly confined water resonantly overscreens an external electric field and enhances capacitance with a characteristically negative dielectric constant of a water molecule.

Tuning the c-Axis Orientation of Calcium Phosphate Hybrid Thin Films Using Polymer Templates.

The orientation of the c-axis in octacalcium phosphate (OCP) nanocrystals that were incorporated into hybrid thin films was successfully tuned using poly(vinyl alcohol) (PVA) thin-film templates of varying thicknesses. This approach was inspired by biomineralization. Thicker PVA templates enhanced the c-axis orientation of the OCP crystals perpendicular to the substrate. Using this approach with a 900 nm thick PVA template, OCP/PVA hybrid thin films (1.8 µm thick) with a c-axis orientation perpendicular to the substrate were formed. Hydroxyapatite (HAP) hybrid thin films that also exhibited a perpendicular c-axis orientation were obtained through the topotactic transformation of the OCP/PVA hybrid thin films in aqueous solution. The thickness change of the polymer templates had a significant effect on the structure of the OCP nanocrystals in the hybrid thin films. The structural control of the OCP hybrid thin films that were formed through the biomineralization-inspired approach allowed the formation of HAP hybrid thin films with controlled structures.

MXene as a Charge Storage Host.

The development of efficient electrochemical energy storage (EES) devices is an important sustainability issue to realize green electrical grids. Charge storage mechanisms in present EES devices, such as ion (de)intercalation in lithium-ion batteries and electric double layer formation in capacitors, provide insufficient efficiency and performance for grid use. Intercalation pseudocapacitance (or redox capacitance) has emerged as an alternative chemistry for advanced EES devices. Intercalation pseudocapacitance occurs through bulk redox reactions with ultrafast ion diffusion. In particular, the metal carbide/nitride nanosheets termed MXene discovered in 2011 are a promising class of intercalation pseudocapacitor electrode materials because of their compositional versatility for materials exploration (e.g., Ti2CT x, Ti3C2T x, V2CT x, and Nb2CT x, where T is a surface termination group such as F, Cl, O, or OH), high electrical conductivity for high current charge, and a layered structure of stacked nanosheets for ultrafast ion intercalation. Various MXene electrodes have been reported to exhibit complementary battery performance, such as large specific capacity at high charge/discharge rates. However, general design strategies of MXenes for EES applications have not been established because of the limited understanding of the electrochemical mechanisms of MXenes. This Account describes current knowledge of the fundamental electrochemical properties of MXenes and attempts to clarify where intercalation capacitance ends and intercalation pseudocapacitance begins. MXene electrodes in aqueous electrolytes exhibit intercalation of hydrated cations. The hydrated cations form an electric double layer in the interlayer space to give a conventional capacitance within the narrow potential window of aqueous electrolytes. When nonaqueous electrolytes are used, although solvated cations are intercalated into the interlayer space during the initial stage of charging, the confined solvation shell should gradually collapse because of the large inner potential difference in the interlayer space. Upon further charging, desolvated ions solely intercalate, and the atomic orbitals of the desolvated cations overlap with the orbitals of MXene to form a donor band. The formation of the donor band induces the reduction of MXene, giving rise to an intercalation pseudocapacitance through charge transfer from the ions to MXene sheets. Differences in the electrochemical reaction mechanisms lead to variation of the electrochemical responses of MXenes (e.g., cyclic voltammetry curves, specific capacitance), highlighting the importance of establishing a comprehensive grasp of the electrochemical reactions of MXenes at an atomic level. Because of their better charge storage kinetics compared with those of typical materials used in present EES devices, aqueous/nonaqueous asymmetric capacitors using titanium carbide MXene electrodes are capable of efficient operation at high charge/discharge rates. Therefore, the further development of novel MXene electrodes for advanced EES applications is warranted.

Stimuli-responsive hydroxyapatite liquid crystal with macroscopically controllable ordering and magneto-optical functions.

Liquid crystals are mostly formed by self-assembly of organic molecules. In contrast, inorganic materials available as liquid crystals are limited. Here we report the development of liquid-crystalline (LC) hydroxyapatite (HAp), which is an environmentally friendly and biocompatible biomineral. Its alignment behavior, magneto-optical properties, and atomic-scale structures are described. We successfully induce LC properties into aqueous colloidal dispersions of rod-shaped HAp by controlling the morphology of the material using acidic macromolecules. These LC HAp nanorod materials are macroscopically oriented in response to external magnetic fields and mechanical forces. We achieve magnetic modulation of the optical transmission by dynamic control of the LC order. Atomic-scale observations using transmission electron microscopy show the self-organized inorganic/organic hybrid structures of mesogenic nanorods. HAp liquid crystals have potential as bio-friendly functional materials because of their facile preparation, the bio-friendliness of HAp, and the stimuli-responsive properties of these colloidal ordered fluids.

Noncovalent Approach to Liquid-Crystalline Ion Conductors: High-Rate Performances and Room-Temperature Operation for Li-Ion Batteries.

We report advanced liquid-crystalline (LC) electrolytes for use in lithium-ion batteries (LIBs). We evaluated the potential of LC electrolytes with a half cell composed of Li metal and LiFePO4 which is a conventional positive electrode for LIBs. Low-molecular-weight carbonates of ethylene carbonate or propylene carbonate were incorporated into the two-dimensional (2D) nanostructured electrolyte composed of mesogen-containing carbonate and lithium bis(trifluoromethylsulfonyl)imide. The incorporation of low-molecular-weight carbonates increased the ionic conductivity with maintaining 2D nanostructures in the LC state. High-power performances at relatively high current densities induced by higher ionic conductivities have been achieved by LC electrolytes with low-molecular-weight carbonates. Furthermore, room-temperature operation of LIBs using LC electrolytes is reported for the first time. In the research field of electrolytes for LIBs, we demonstrate the progress of a new category of LC electrolytes.

Bioinspired Environmentally Friendly Amorphous CaCO3-Based Transparent Composites Comprising Cellulose Nanofibers.

Amorphous calcium carbonate (ACC) stabilized by acidic macromolecules is a useful material for the development of environmentally friendly composites. In this study, we synthesized transparent and mechanically tough ACC-based composite materials by the incorporation of water-dispersible cellulose derivatives, namely, carboxymethyl cellulose (CMC) and surface-modified crystalline cellulose nanofibers (CNFs). A solution mixing method used in the present work proved to be a powerful and efficient method for the production of mechanically tough and environmentally friendly materials. Molecular-scale interactions between carboxyl groups and Ca2+ ions induce homogeneous dispersion of CNFs in the composites, and this gives composite films with high transparency and high mechanical properties. The composite films of CMC, CNFs, and ACC at the mixture ratios of 40, 40, and 20 wt %, showed high mechanical properties of 15.8 ± 0.93 GPa for the Young's modulus and 268 ± 20 MPa for the tensile strength. These designed materials that are based on ACC may open up new opportunities in many fields in applications that require the use of environmentally friendly, biodegradable, mechanically tough, and transparent composite materials.

Sodium-Ion Intercalation Mechanism in MXene Nanosheets.

MXene, a family of layered compounds consisting of nanosheets, is emerging as an electrode material for various electrochemical energy storage devices including supercapacitors, lithium-ion batteries, and sodium-ion batteries. However, the mechanism of its electrochemical reaction is not yet fully understood. Herein, using solid-state (23)Na magic angle spinning NMR and density functional theory calculation, we reveal that MXene Ti3C2Tx in a nonaqueous Na(+) electrolyte exhibits reversible Na(+) intercalation/deintercalation into the interlayer space. Detailed analyses demonstrate that Ti3C2Tx undergoes expansion of the interlayer distance during the first sodiation, whereby desolvated Na(+) is intercalated/deintercalated reversibly. The interlayer distance is maintained during the whole sodiation/desodiation process due to the pillaring effect of trapped Na(+) and the swelling effect of penetrated solvent molecules between the Ti3C2Tx sheets. Since Na(+) intercalation/deintercalation during the electrochemical reaction is not accompanied by any substantial structural change, Ti3C2Tx shows good capacity retention over 100 cycles as well as excellent rate capability.

Chitin: Formation of Helically Structured Chitin/CaCO3 Hybrids through an Approach Inspired by the Biomineralization Processes of Crustacean Cuticles (Small 38/2015).

Biomineral-inspired hybrids forming helically ordered structures are developed by T. Kato and co-workers on page 5127. These helical hybrids consist of liquid-crystalline chitin and CaCO3 . They resemble the structures of crustacean cuticles such as the exoskeleton of a lobster or crayfish. These hybrids are formed through CaCO3 crystallization on the liquidcrystalline chitin templates. Polymer-stabilized amorphous CaCO3 is incorporated into the liquid-crystalline chitin templates. This approach is useful for the development of new hierarchical hybrid materials from abundant natural resources.

Formation of Helically Structured Chitin/CaCO3 Hybrids through an Approach Inspired by the Biomineralization Processes of Crustacean Cuticles.

Chitin/CaCO3 hybrids with helical structures are formed through a biomineralization-inspired crystallization process under ambient conditions. Liquid-crystalline chitin whiskers are used as helically ordered templates. The liquid-crystalline structures are stabilized by acidic polymer networks which interact with the chitin templates. The crystallization of CaCO3 is conducted by soaking the templates in the colloidal suspension of amorphous CaCO3 (ACC) at room temperature. At the initial stage of crystallization, ACC particles are introduced inside the templates, and they crystallize to CaCO3 nanocrystals. The acidic polymer networks induce CaCO3 crystallization. The characterization of the resultant hybrids reveals that they possess helical order and homogeneous hybrid structures of chitin and CaCO3 , which resemble the structure and composition of the exoskeleton of crustaceans.

Pseudocapacitance of MXene nanosheets for high-power sodium-ion hybrid capacitors.

High-power Na-ion batteries have tremendous potential in various large-scale applications. However, conventional charge storage through ion intercalation or double-layer formation cannot satisfy the requirements of such applications owing to the slow kinetics of ion intercalation and the small capacitance of the double layer. The present work demonstrates that the pseudocapacitance of the nanosheet compound MXene Ti2C achieves a higher specific capacity relative to double-layer capacitor electrodes and a higher rate capability relative to ion intercalation electrodes. By utilizing the pseudocapacitance as a negative electrode, the prototype Na-ion full cell consisting of an alluaudite Na2Fe2(SO4)3 positive electrode and an MXene Ti2C negative electrode operates at a relatively high voltage of 2.4 V and delivers 90 and 40 mAh g(-1) at 1.0 and 5.0 A g(-1) (based on the weight of the negative electrode), respectively, which are not attainable by conventional electrochemical energy storage systems.

Liquid-crystalline calcium carbonate: biomimetic synthesis and alignment of nanorod calcite.

Liquid-crystalline CaCO3 has been prepared for the first time. The nanorods of CaCO3 calcite are obtained by bio-inspired crystallization through aqueous colloidal precursors of amorphous CaCO3 stabilized by poly(acrylic acid). The synthesized calcite nanocrystals have well-tuned morphologies that are preferable for formation of liquid-crystalline phases in concentrated aqueous colloidal solution. The one-dimensional alignment of calcite crystals is achieved by mechanical shearing of the aqueous colloidal solution showing liquid-crystalline phases. These CaCO3-based liquid crystals formed by a self-organization process in mild conditions may have great potential for use as environmentally friendly materials.