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.

Anisotropic Self-Oscillating Reaction in Liquid Crystalline Nanosheet Hydrogels.

Anisotropic chemical wave propagation of self-oscillating Belousov-Zhabotinsky (BZ) reaction was demonstrated in the poly( N-isopropylacrylamide) gel films embedded with macroscopically aligned liquid crystalline inorganic nanosheets. Although the average propagation rate of chemical wave v̅ was 3.56 mm min-1 in the gels without nanosheets, the propagation was retarded in the gels with 1 wt % of nanosheets: [Formula: see text] = 1.89 mm min-1 and [Formula: see text] = 1.33 mm min-1 along the direction parallel and perpendicular to the nanosheet planes, respectively. Thus, the wave propagation is anisotropic with the anisotropy ratio [Formula: see text] = 1.42 in these gels and the periodic patterns formed by the BZ reaction were concentric ellipses, different from circles seen in isotropic gels. Furthermore, the propagation rate and degree of anisotropy were controllable by nanosheet concentration. These phenomena can be explained that the diffusion of molecules inside the gel is effectively hindered along the direction perpendicular to the nanosheet planes due to the very large aspect ratio of the aligned nanosheets. The present systems will be applicable for anisotropic self-oscillating soft actuators with one-dimensional motions as well as for ideal model system of BZ reactions.

In situ observation of the evaporation-induced self-assembling process of PS-b-PEO diblock copolymers for the fabrication of titania films by confocal laser scanning microscopy.

The drying process of clear precursor solutions for fabricating highly porous titania films was observed by CLSM. Further, we succeeded in detecting the formation of micelles in the precursor solution containing high-molecular-weight PS-b-PEO diblock copolymers at the initial stage of the drying process as the direct evidence that this synthesis consisted of the EISA process.

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.

Liquid crystalline inorganic nanosheets for facile synthesis of polymer hydrogels with anisotropies in structure, optical property, swelling/deswelling, and ion transport/fixation.

Macroscopically anisotropic hydrogels were synthesized by hybridization of poly(N-isopropylacrylamide) with liquid crystalline inorganic nanosheets; their anisotropies in the structure and properties are demonstrated.