Perovskite Nanosheet Hydrogels with Mechanochromic Structural Color.

Structural color colloidal sols of perovskite nanosheets were synthesized and were immobilized in a polymer hydrogel film by in situ photopolymerization, leading to a novel mechanochromic material. Visible absorption spectroscopy, polarized optical microscopy and small-angle X-ray scattering revealed that the nanosheets are aligned parallel to the film surface with the periodic distance of up to ca. 300 nm, giving the structural color tunable over full color range. The present structural color gel showed reversible mechanochromic response that detects weak stress of 1 kPa with the quick response time less than 1 ms as well as high mechanical toughness (compressive breaking stress of up to 3 MPa). These excellent properties are suitable for applications for mechano-sensors and displays.

High Virus Removal by Self-Organized Nanostructured 2D Liquid-Crystalline Smectic Membranes for Water Treatment.

To obtain high quality of drinking water free from biocontaminants is especially important issue. A new strategy employing smectic liquid-crystalline ionic membranes exhibiting 2D structures of layered nanochannels for water treatment is proposed for efficient virus removal and sufficient water flux. The smectic A (SmA) liquid-crystalline membranes obtained by in situ polymerization of an ionic mesogenic monomer are examined for removal of three distinct viruses with small size: Qß bacteriophage, MS2 bacteriophage, and Aichi virus. The semi-bilayer structure of the SmA significantly obstructs the virus penetration with an average log reduction value of 7.3 log10 or the equivalent of reducing 18 million viruses down to 1. Furthermore, the layered nanochannels of the SmA liquid crystal allow efficient water permeation compared to other types of liquid-crystalline membrane consisting of nanopores.

Mesoscopic Architectures Made of Electrically Charged Binary Colloidal Nanosheets in Aqueous System.

Inorganic layered materials can be converted to colloidal liquid crystals through exfoliation into inorganic nanosheets, and binary nanosheet colloids exhibit rich phase behavior characterized by multiphase coexistence. In particular, niobate-clay binary nanosheet colloids are characterized by phase separation at a mesoscopic (∼several tens of micrometers) scale whereas they are apparently homogeneous at a macroscopic scale. Although the mesoscopic structure of the niobate-clay binary colloid is advantageous to realize unusual photochemical functions, the structure itself has not been clearly demonstrated in real space. The present study investigated the structure of niobate-clay binary nanosheet colloids in detail. Four clay nanosheets (hectorite, saponite, fluorohectorite, and tetrasilisic mica) with different lateral sizes were compared. Small-angle X-ray scattering (SAXS) indicated lamellar ordering of niobate nanosheets in the binary colloid. The basal spacing of the lamellar phase was reduced by increasing the concentration of clay nanosheets, indicating the compression of the liquid crystalline niobate phase by the isotropic clay phase. Scattering and fluorescence microscope observations using confocal laser scanning microscopy (CLSM) demonstrated the phase separation of niobate and clay nanosheets in real space. Niobate nanosheets assembled into domains of several tens of micrometers whereas clay nanosheets were located in voids between the niobate domains. The results clearly confirmed the spatial separation of two nanosheets and the phase separation at a mesoscopic scale. Distribution of clay nanosheets is dependent on the employed clay nanosheets; the nanosheets with large lateral length are more localized or assembled. This is in harmony with larger basal spacings of niobate lamellar phase for large clay particles. Although three-dimensional compression of the niobate phase by the coexisting clay phase was observed at low clay concentrations, the basal spacing of niobate phase was almost constant irrespective of niobate concentrations at high clay concentrations, which was ascribed to competition of compression by clay phase and restoring of the niobate phase.

Preparation of Ultraviolet Curing Type Silicone Rubbers Containing Mesoporous Silica Fillers.

Here we have been focusing on mesoporous silica (MPS) as inorganic filler material to improve the mechanical strength of silicone rubbers. The MPS particles are more effective in reducing the coefficient of thermal expansion (CTE) and hardening silicone rubber composites when compared to commercially available nonporous silica particles. In this study, we utilize ultraviolet curing type silicone rubbers and prepare MPS composites according to a simple single-step method. From an industrial viewpoint, simplifying the fabrication processes is critical. The thermal stability and mechanical strength are examined in detail in order to showcase the effectiveness of MPS particles as filler materials.

Functional porous carbon-ZnO nanocomposites for high-performance biosensors and energy storage applications.

A one-pot synthesis method for the fabrication of biomass-derived activated carbon-zinc oxide (ZAC) nanocomposites using sugarcane bagasse as a carbon precursor and ZnCl2 as an activating agent is reported. For the first time, we used ZnCl2 as not only an activating agent and also for the synthesis of ZnO nanoparticles on the AC surface. ZAC materials with varying ZnO loading were prepared and characterized by a variety of analytical and spectroscopic techniques such as FE-SEM, FE-TEM, XRD, EA, XPS, and Raman spectroscopy. ZAC-modified glassy carbon electrodes (GCEs) were found to exhibit remarkable electrochemical properties for simultaneous detection of ascorbic acid (AA), dopamine (DA), and uric acid (UA) as well as hazardous pollutants such as hydrogen peroxide (H2O2) and hydrazine (N2H4) with desirable sensitivity, selectivity, and detection limits. Moreover, ZAC-modified stainless steel electrodes also showed superior performances for supercapacitor applications. The ZAC nanocomposites, which may be mass produced by the reported facile direct route from sugarcane bagasse, are not only eco-friendly but also cost-effective, and thus, are suitable as a practical platform for bio-sensing and energy storage applications.

Surfactant-Directed Synthesis of Mesoporous Pd Films with Perpendicular Mesochannels as Efficient Electrocatalysts.

Palladium (Pd) films with perpendicularly aligned mesochannels are expected to provide fascinating electrocatalytic properties due to their low diffusion resistance and the full utilization of their large surface area. There have been no studies on such mesoporous metal films, because of the difficulties in controlling both the vertical alignment of the molecular template and the crystal growth in the metallic pore walls. Here we report an effective approach for the synthesis of mesoporous Pd films with mesochannels perpendicularly aligned to the substrate by an elaborated electrochemical deposition. The films show a superior electrocatalytic activity by taking full advantage of the perpendicularly aligned mesochannels.

Polymeric micelle assembly with inorganic nanosheets for construction of mesoporous architectures with crystallized walls.

Here we propose a novel way to construct mesoporous architectures through evaporation-induced assembly of polymeric micelles with crystalline nanosheets. As a model study, we used niobate nanosheets exfoliated by the direct reaction of K4Nb6O17⋅3 H2O crystals with an aqueous solution of propylamine. The electrostatic interaction between negatively charged nanosheets and positively charged polymeric micelles enable us to form composite micelles with the nanosheets. Removal of the micelles by calcination results in robust mesoporous oxides with the original crystalline structure.

Gigantic swelling of inorganic layered materials: a bridge to molecularly thin two-dimensional nanosheets.

Platy microcrystals of a typical layered material, protonated titanate, have been shown to undergo an enormous degree of swelling in aqueous solutions of various amines, including tertiary amines, quaternary ammonium hydroxides, and primary amines. Introducing these solutions expanded the crystal gallery height by up to ~100-fold. Through systematic analysis, we determined that ammonium ion intercalation is predominantly affected by the acid-base equilibrium and that the degree of swelling or inflow of H2O is controlled by the osmotic pressure balance between the gallery and the solution environment, both of which are relatively independent of electrolyte identity but substantially dependent on molarity. In solutions of tertiary amines and quaternary ammonium hydroxides, the uptake of ammonium ions increases nearly linearly with increasing external concentration before reaching a saturation plateau, i.e., ~40% relative to the cation-exchange capacity of the crystals used. The only exception is tetrabutylammonium ions, which yield a lower saturation value, ~30%, owing to steric effects. The swelling behaviors in some primary amine solutions differ as a result of the effect of attractive forces between amine solute molecules on the solution osmotic pressure. Although the swelling is essentially colligative in nature, the stability of the resultant swollen structure is heavily dependent on the chemical nature of the guest ions. Intercalated ions of higher polarity and smaller size help stabilize the swollen structure, whereas ions of lower polarity and larger size lead readily to exfoliation. The insight gained from this study sheds new light on both the incorporation of guest molecules into a gallery of layered structures in general and the exfoliation of materials into elementary single-layer nanosheets.

Mesoporous silica particles as topologically crosslinking fillers for poly(N-isopropylacrylamide) hydrogels.

Here it is demonstrated that mesoporous silicas (MPSs) can be used as effective "topological crosslinkers" for poly(N-isopropylacrylamide) (PNIPA) hydrogels to improve the mechanical property. Three-dimensional bicontinuous mesporous silica is found to effectively reinforce the PNIPA hydrogels, as compared to nonporous silica and two-dimensional hexagonally ordered mesoporous silica.

Photo-Induced Anomalous Deformation of Poly(N-Isopropylacrylamide) Gel Hybridized with an Inorganic Nanosheet Liquid Crystal Aligned by Electric Field.

Poly-(N-isopropylacrylamide) (PNIPA) hydrogel films doped with uniaxially aligned liquid crystalline (LC) nanosheets adsorbed with a dye are synthesized and its anomalous photothermal deformation is demonstrated. The alignment of the nanosheet LC at the cm-scale is easily achieved by the application of an in-plane or out-of-plane AC electric field during photo-polymerization. A photoresponsive pattern is printable onto the gel with µm-scale resolution by adsorption of the dye through a pattern-holed silicone rubber. When the gel is irradiated with light, only the colored part is photothermally deformed. Interestingly, the photo-irradiated gel shows temporal expansion along one direction followed by anisotropic shrinkage, which is an anomalous behavior for a conventional PNIPA gel.

Monodisperse nanosheet mesophases.

Self-assemblies of anisotropic colloidal particles into colloidal liquid crystals and well-defined superlattices are of great interest for hierarchical nanofabrications that are applicable for various functional materials. Inorganic nanosheets obtained by exfoliation of layered crystals have been highlighted as the intriguing colloidal units; however, the size polydispersity of the nanosheets has been preventing precise design of the assembled structures and their functions. Here, we demonstrate that the anionic titanate nanosheets with monodisperse size reversibly form very unusual superstructured mesophases through finely tunable weak attractive interactions between the nanosheets. Transmission electron microscopy, polarizing optical microscopy, small-angle x-ray scattering, and confocal laser scanning microscopy clarified the reversible formation of the mesophases (columnar nanofibers, columnar nematic liquid crystals, and columnar nanofiber bundles) as controlled by counter cations, nanosheet concentration, solvent, and temperature.

Mesoporous metallic cells: design of uniformly sized hollow mesoporous Pt-Ru particles with tunable shell thicknesses.

A new class of hollow mesoporous Pt-Ru and Pt particles with uniform size, named 'mesoporous metallic cells', are synthesized through a dual-templating approach using colloidal silica particles and non-ionic surfactants. To realize the full potential of mesoporous metals as electrocatalysts, the shell thicknesses, compositions, and hollow cavity sizes are precisely controlled.

Nanostructure Control in Zinc Oxide Films and Microfibers through Bioinspired Synthesis of Liquid-Crystalline Zinc Hydroxide Carbonate; Formation of Free-Standing Materials in Centimeter-Level Lengths.

Free-standing zinc oxide in the forms of films and fibrous materials are expected to be used as functional devices such as piezoelectric devices and catalyst filters without being limited by the growth substrate. Herein, a synthetic morphology-control method for 2D and 1D free-standing ZnO materials with ordered and nanoporous structures by conversion of liquid-crystalline (LC) zinc hydroxide carbonate (ZHC) nanoplates is reported. As a new colloidal liquid crystal, the LC ZHC nanoplate precursors are obtained by a biomineralization-inspired method. The approach is to control the morphology and crystallographic orientation of ZHC crystals by using acidic macromolecules. Their nano-scale and oriented structures are examined. The LC oriented ZHC nanoplates have led to the synthesis of free-standing films and microfibers of ZHC in centimeter-level lengths, with the successful thermal conversion into free-standing films and microfibers of ZnO. The resultant ZnO films and ZnO microfibers have nanoporous structures and preferential crystallographic orientations that preserve the alignment of ZHC nanoplates before conversion.

Unusual reinforcement of silicone rubber compounds containing mesoporous silica particles as inorganic fillers.

We fabricate mesoporous silica/silicone composites in a simple way and systematically examine their thermal stability, swelling characteristic, mechanical strength, and transparency. Simple calculations show that more than 90 vol% of mesopores are filled with silicone rubbers. Compared to non-porous silica/silicone composites, mesoporous silica/silicone composites showed a lower coefficient of linear thermal expansion (CTE). In addition, dramatic improvements of the tensile strength and Young's modulus are obtained with mesoporous silica/silicone composites. Furthermore, mesoporous silica/silicone composites show higher transparency than non-porous silica/silicone composites.

Synthesis of mesoporous titania nanoparticles with anatase frameworks and investigation of their photocatalytic performance.

In this research paper, we synthesize various types of mesoporous titania nanoparticles (MTNs) with suitable surface area and pore size while creating anatase frameworks by applying hydrothermal treatment or calcination at different temperatures. Wide-angle XRD patterns and N2 adsorption-desorption isotherms reveal that the MTNs with crystallized anatase frameworks can be synthesized after an optimized hydrothermal treatment. In contrast, calcination of MTNs at high temperature caused the collapse of mesoporous structure, resulted in drastic reduction of the surface area of the MTNs. In addition, we investigate the photocatalytic activity of the prepared MTNs by measuring the degradation of methylene blue (MB). The results show that the reaction rates of the photocatalytic MB decomposition strongly depend on the degree of crystallinity in the MTNs frameworks and on the surface area of MTNs.

Angular-Independent Structural Colors of Clay Dispersions.

Clay mineral nanosheet colloids were found to show angular-independent structural colors after desalting. Naked-eye observation and UV-visible reflectance spectra showed that the color is tuned by varying the average nanosheet size and nanosheet concentration. The low angular-dependence of the structural color was also clarified by these observations, which is the first case for a nanosheet system. The present system is expected as an environmentally benign and low-cost structural color material for various applications.

Highly photoactive porous anatase films obtained by deformation of 3D mesostructures.

A transparent film of three-dimensional (3D) hexagonal (P6(3)/mmc) mesostructured titania was fabricated according to a modified procedure using triblock copolymer Pluronic P123. The precursor solution was diluted with ethanol and spin-coated to afford a transparent film with a thickness of less than 100 nm. The mesostructure was maintained (deteriorated) at 400 °C, converted to regularly arranged anatase nanopillars with sufficient porosity at 550 °C, and deformed at 700 °C to nanocrystals with intercrystalline mesospaces. The mesostructural variation was related to the degree of shrinkage of the film owing to condensation and crystallization of the titania frameworks. An anatase nanocrystal film having sufficient porosity and high crystallinity was most active in the photodegradation of methylene blue. Such intercrystalline mesospaces can be controlled by regular deformation of 3D mesostructures through anatase nanopillar structures. In addition to adequate crystallinity of the titania frameworks, smooth diffusion of target organic molecules and/or degraded organic compounds was important for effective photodegradation.

Aerosol-assisted synthesis of nanoporous silica/titania nanoparticles composites and investigation of their photocatalytic properties.

Nanoporous silica/titania nanoparticles composites with relatively large TiO2 content are successfully synthesized by aerosol-assisted co-assembly. By the hybridization of titania with nanoporous silica having high surface area, both the adsorption capability and the reaction rates for the photocatalytic decomposition of methylene blue (MB) are dramatically improved in comparison with unmodified titania nanoparticles without nanoporous silica. Through the quantitative evaluation of the amount of adsorbed and photo-decomposed organic molecule throughout the reaction process, the role of nanoporous silica layers on titania surface is clarified. Rational design of future hybrid photocatalyst with precisely controlled nanostructure will be possible by optimization of our synthetic procedure and careful study of the adsorption and photocatalytic properties.

Radial alignment of microtubules through tubulin polymerization in an evaporating droplet.

We report the formation of spherulites from droplets of highly concentrated tubulin solution via nucleation and subsequent polymerization to microtubules (MTs) under water evaporation by heating. Radial alignment of MTs in the spherulites was confirmed by the optical properties of the spherulites observed using polarized optical microscopy and fluorescence microscopy. Temperature and concentration of tubulins were found as important parameters to control the spherulite pattern formation of MTs where evaporation plays a significant role. The alignment of MTs was regulated reversibly by temperature induced polymerization and depolymerization of tubulins. The formation of the MTs patterns was also confirmed at the molecular level from the small angle X-ray measurements. This work provides a simple method for obtaining radially aligned arrays of MTs.

Photoinduced charge separation in a colloidal system of exfoliated layered semiconductor controlled by coexisting aluminosilicate clay.

We investigated photoinduced charge separation occurring in a multicomponent colloidal system composed of oxide nanosheets of photocatalytically active niobate and photochemically inert clay and electron accepting methylviologen dications (MV2+). The inorganic nanosheets were obtained by exfoliation of layered hexaniobate and hectorite clay. The niobate and clay nanosheets were spatially separated in the colloidally dispersed state, and the MV2+ molecules were selectively adsorbed on the clay platelets. UV irradiation of the colloids led to electron transfer from the niobate nanosheets to the MV2+ molecules adsorbed on clay. The photoinduced electron transfer produced methylviologen radical cations (MV*+), which was characterized by high yield and long lifetime. The yield and stability of the MV*+ species were found to depend strongly on the clay content of the colloid: from a few mol % to approximately 70 mol % of the yield and several tens of minutes to more than 40 h of the lifetime. The contents of the niobate nanosheets and MV2+ molecules and the aging of the colloid also affected the photoinduced charge separation. In the absence of MV2+ molecules in the colloid, UV irradiation induced electron accumulation in the niobate nanosheets. The stability of the electron-accumulated state also depended on the clay content. The variation in the photochemical behavior is discussed in relation to the viscosity of the colloid.