論文

Oriented attachment of homogeneously shaped nanoblocks, such as nanocubes and nanorods, is attracting attention as a fundamental process of non-classical crystal growth to produce specific ordered architectures of functional materials. Although lateral alignments of horizontally oriented nanorod are commonly observed at the air-liquid and liquid-solid interfaces in dispersion systems, the accumulation of vertically oriented nanorods on a substrate has rarely been produced in a wide area over a millimeter-sized flat surface. Here, we achieved homogeneous stacking of vertical fluorapatite nanorods with a large aspect ratio (~6) in a toluene-hexane mixture system through a gradual decrease in the dispersibility. Micrometer-thick flat films in which the c direction of fluorapatite nanorods was arranged perpendicularly to the surface were deposited on a substrate with a diameter of over 20 mm. The wide-area accumulation of vertical nanorods occurs through the self-assembly of laterally arranged clusters of nanorods covered with a stabilizing agent and subsequent gentle sedimentation on the substrate surface. This journal is

Micrometre-thick calcareous shells consisting of c-axis-oriented calcite nanorods are produced on an organic sheet as foraminiferal tests and isopod cornea cuticles. Here, we produced mineral films similar to biogenic calcareous shells on a self-standing polymer sheet in a supersaturated solution system by multistep crystal growth with the adjustment of the concentration ratio of poly(acrylic acid) (PAA) as a soluble controlling agent. In the initial stage, selective high-density nucleation was achieved at a relatively low PAA to calcium ion ratio (R = 1.0-1.2) to form of a calcite seed layer on the surface of conventional polyvinyl alcohol. Calcite nanorods elongated in the c direction were then grown perpendicularly to the seed layer in the progressive stages at a relatively high PAA ratio (R = 1.5-2.0). The artificial mineral films consisting of c-axis-oriented nanorods are suggested to exhibit mechanical properties similar to those of biogenic calcareous shells.

Oxide ion-conducting porous films were produced on a substrate by evaporation-induced self-assembly of rare earth-doped CeO 2 (REDC) nanocubes 4-5 nm in size and subsequent mild calcination at 400 °C. Mesocrystalline structures comprising iso-oriented REDC nanocubes were formed by ordered assembly based on strict attachment of their {100} faces. Enhanced oxide-ion conductivities in a temperature range of 250-350 °C were observed on the mesocrystalline films consisting of Sm-doped CeO 2 (SDC) nanocubes. The specific electrical properties of the mesocrystalline films are ascribed to improved surface-ion conduction due to a large specific surface area and a high crystallographic connectivity of SDC nanocubes.

The nanometer-scale bending structure in the enamel-dentin interfacial region of bovine teeth was clarified using detailed electron micrographs. We found that enamel prisms of width 5-10 μm in the enamel are regarded as a bundle of nanometer-scale hydroxyapatite (HA) fibers of width 20-30 nm that are connected to the enamel-dentin interface. The radial arrangements of HA fibers elongated in the c-axis were formed on the dentin surface at the boundary. The orientation adjustment of the HA fibers was observed through stepwise bending with a gradual change of the c direction in the ordered parallel array of the enamel prisms. Our observation suggests that the crystallographic ordering in the enamel layer originates from the growth-induced orientation of HA crystals in the interfacial region.

The micrometric morphology of anhydrous β-guanine crystals is adequately designed by various organisms for their specific optical properties. We successfully controlled the morphology of an anhydrous β-guanine crystal through the transformation of an amorphous intermediate consisting of guanine sodium salt under aqueous conditions. Biomimetic platy and columnar guanine crystals were selectively produced from the amorphous intermediate by changing the crystallization conditions.

The essence of morphological design has been a fascinating scientific problem with regard to understanding biological mineralization. Particularly shaped amorphous silicas (plant opals) play an important role in the vital activity in rice plants. Although various organic matters are associated with silica accumulation, their detailed functions in the shape-controlled mineralization process have not been sufficiently clarified. In the present study, cellulose nanofibers (CNFs) were found to be essential as a scaffold for silica accumulation in rice husks and leaf blades. Prior to silicification, CNFs ~ 10 nm wide are sparsely stacked in a space between the epidermal cell wall and the cuticle layer. Silica nanoparticles 20–50 nm in diameter are then deposited in the framework of the CNFs. The shape-controlled plant opals are formed through the intrafibrillar mineralization of silica nanoparticles on the CNF scaffold.

Most biominerals are composed of mesocrystals, in which individual nanoparticle building units have a defined long-range order on the atomic scale in at least one direction. Although the crystal size and orientation of the mesostructures are spatially designed in biological architectures, it has been difficult to achieve adequate control of the crystal growth to produce modulated mesostructures in artificial aqueous systems. Here, we propose a simple physicochemical approach for the spatial design of nanostructures using an aqueous solution system. The ordered arrays of oriented fluorapatite (FA) rods similar to tooth enamel are produced on a polymer substrate in a supersaturated solution. We succeeded in reversible switching of the growth mode of FA between single-crystalline rods and mesocrystalline grains through the disturbance of the solution. The primary crystal size was tuned between micrometric rods ∼0.5 μm wide and >5 μm long and nanoscale grains ∼10 nm wide and 50 nm long without a drastic change in the c direction. Hierarchical architectures consisting of iso-oriented FA microrods and nanograins were constructed via temporal control of the crystal growth mode by switching a physicochemical parameter, such as the degree of supersaturation at the growth front.

Silica membranes having macrochannels with mesoporous walls were spontaneously fabricated using a self-organized process with rapid gelation of concentrated silicate and surfactant precursor solutions. The specific hierarchical porous framework consisting of straight macrochannels ca. 1 μm in diameter is similar to that of a biological silica frustule of diatoms. We applied the diatom-mimetic channeled mesoporous silica membranes to high-permeability-rate filtration and enhanced photocatalytic systems. The presence of macrochannels was found to improve the performance of the mesoporous silica membranes in filtration and as a photocatalyst carrier.

A 3-dimensional polypyrrole-palladium nanocomposite material was prepared by transferring a sponge structure of a sea urchin spine via chemical oxidative polymerization. The nanocomposite material was successfully coated with nickel, maintaining the 3-dimensional sponge structure by electroless plating in an aqueous medium.

Mesocrystals of MgCo2O4 spinel oxide exhibiting porous and single-crystalline structures were synthesized by the reaction of magnesium ions with calcite-type CoCO3 mesocrystal precursors grown in micrometer-sized agar gels. The mesocrystals consisted of single-crystalline porous grains measuring 200–300 nm in diameter with iso-oriented subunits of approximately 10 nm. The single-crystalline porous framework structure of the MgCo2O4 mesocrystals enhanced the discharge capacity and positively shifted the discharge potential compared with MgCo2O4 nanoparticles prepared by the inverse co-precipitation method. These enhancements were attributed to a combination of the high specific surface areas of the mesocrystals and the high connectivity of the magnesium ion diffusion paths in the solid-phase.

Stimuli-responsive properties of soft materials originate from dynamic structure changes. Layered polydiacetylene (PDA) shows color-change properties with the application of external stimuli, such as thermal and mechanical stresses. Layered organic materials possessing intercalation capabilities and dynamic properties have potentials for tuning their structures and properties by the intercalated guests. A variety of sensing and imaging devices can be developed by control of the stimuli responsivity. Here, the key structures, processes, and mechanisms for tuning the stimuli-responsive color-change properties of layered PDA are studied by in situ analyses with heating and cooling. The in situ analyses indicate that heating initiates thermal motion of the alkyl side chains of the PDA main chain in the host layers around 60 °C, regardless of the type of intercalated guests. Further heating induces torsion of the PDA main chain leading to color changes at different temperatures, depending on the types of the intercalated guest. Then, the layered structure is irreversibly deformed with lowering the crystallinity. The results indicate that the stimuli-responsive color-change properties are controlled by the rigidity of the layered structures consisting of the host layers and guests. The control strategy based on rigidity tuning can be applied to a variety of soft materials with stimuli responsivity.

Two-dimensional nanomaterials have attracted much interest for their anisotropic structures and emergent properties. Whereas a variety of inorganic nanosheets are prepared by exfoliation, design and synthetic strategies of organic nanosheets are still developing. Here we report on crystal-controlled synthesis of conductive and redox-active organic polymer nanosheets with tunable thickness and lateral size. Although the nanosheets consist of classical conductive polymers, such as polypyrrole (PPy) and poly(3,4-ethylenedioxythiophene) (PEDOT), a new crystal-controlled polymerization approach provides 2D nanomaterials with enhanced and characteristic properties. Oxidative polymerization proceeds on the crystal surface of organic oxidants, such as quinone derivatives, with diffusion of the monomer vapor at low temperature under ambient pressure. The present method affords the control of lateral size and thickness of the nanosheets. The resultant nanosheets show the characteristic and enhanced properties originating from a 2D nature, such as the high structure anisotropy with aspect ratio around 104, enhanced conductivity 287 S cm-1, and specific charge-discharge capacitance 523 F g-1 at the current density of 18 A g-1. The organic nanosheets with conductivity and redox activity can be used as a building block for development of functional materials and devices. ©

A variety of inorganic and organic nanosheets with characteristic structures and properties can be synthesized through exfoliation of layered materials. However, in general, immense time and efforts are required for exploration of exfoliation conditions and characterization of nanosheets. In addition, it is challenging to improve the yield of nanosheets obtained through exfoliation. Here a materials-informatics-assisted high-yield synthesis of nanosheets is proposed, which does not require experience and intuition. Layered composites containing inorganic layers and interlayer organic guests are delaminated into nanosheets in a variety of dispersion media. First, an experimental screening is performed to find efficient exfoliation conditions and obtain a training dataset for the informatics approach. Sparse modeling is then used facilitating the extraction of important factors predicting the yield of nanosheets. High-yield (up to ≈50%) synthesis of nanosheets is demonstrated in unknown systems in a minimum number of experiments. The yield is higher than those typically reported for layered materials. It is expected that the effective combination has potentials for not only discovery of compounds but also structure control of materials.

A variety of organic and inorganic layered compounds are exfoliated into 2D nanomaterials in liquid phase. Improvement of exfoliation yield is a significant challenge for further applications of 2D nanomaterials. However, yield of transition-metal-oxide nanosheets is not so high, such as around 5% for 240 h and 15% for 120 h, in previous exfoliation methods. Here we show a new exfoliation approach to high-yield synthesis of nanosheets. A layered composite of cobalt hydroxide and guest quinone derivative was exfoliated into nanosheets through redox reactions of the interlayer guests in the yield 1657% for 1 h under mild conditions. The redox reactions of the guest molecules on the layer facilitate efficient exfoliation through improvement of the affinity between the guest and dispersion medium. The present redox-mediated exfoliation approach can be applied to efficient synthesis of a variety of 2D nanomaterials from layered composites.

Quantitative detection of external stimuli, such as light, heat, and force, is an important challenge for sensing materials. Near-infrared (NIR) light is used in a variety of fields, such as biological, physical, medical, and engineering applications. Visualization and quantitative detection of invisible NIR are significant for its safe use. Here we fabricate a paper-based device coated with polypyrrole (PPy) and layered polydiacetylene (PDA). As PPy induces evolution of heat with irradiation of NIR, the effective conjugation length of the layered PDA is changed by the dynamic structure changed through the heat conduction. The visible color change from blue to red proceeds on the paper device. The red-color intensity has a relationship with the irradiation power of NIR. These facts suggest that the irradiation time and power of NIR are quantified by the color. Moreover, the results indicate that layered PDA can be applied to the quantification of external stimuli through conversion from the desired stimulus to the detectable one.

Visualization and quantification of invisible lights, such as microwaves, are significant for their safe use. In general, a sensitizer material combined with a transistor is used as electronic devices for the measurement. Here, we developed a thermoresponsive color-change hydrogel of poly(N-isopropylacrylamide) (PNIPAAm) cross-linked by a layered organic composite based on polydiacetylene (PDA) for visualization and colorimetric quantification of microwaves. The layered PDA in the PNIPAAm hydrogel showed the temperature-dependent gradual color change with heating. Irradiation of microwaves induced the color change of PDA through heating of water in the hydrogel and subsequent volume shrinkage. The color of the gel was applied to visualize the temperature distribution with increasing irradiation time of microwaves. Moreover, the power of the irradiated microwave was quantified by time to the complete color change of the gel. The results indicate that the stimulus conversion process has potentials for development of a variety of imaging and quantification devices based on the layered PDA.

2D materials exhibit emergent properties originating from their characteristic nanostructures. In general, monolayered and few-layered nanosheets are obtained by exfoliation of the precursor layered materials. However, lateral-size distribution of the nanosheets is not easily controlled through the exfoliation because of the unpredictable down-sizing processes. The present work shows selective syntheses of transition-metal-oxide nanosheets with the monodisperse and polydisperse lateral sizes by the assistance of machine learning on small experimental data. The precursor layered composites of host transition-metal oxides and interlayer organic guests are exfoliated into the surface-modified nanosheets in organic dispersion media. A prediction model of the size distribution is constructed by sparse modeling, a method of machine learning, on the experimental data. The host-guest-medium combinations achieving the monodisperse and polydisperse lateral sizes are recommended by the prediction model. Therefore, the nanosheets with the controlled lateral-size distribution are selectively obtained in a limited number of the experiments. Moreover, self-assembly of the polydispersed nanosheets forms the homogeneous thin film exhibiting interference color. The prediction model and its construction method can be applied to the other 2D materials. Moreover, the present work implies that sparse modeling is an effective approach for small-data-driven materials science.

Emergence of thermoresponsive and reversible color changes at low temperature is a challenging target. In general, it is not easy to induce sufficient dynamic motion of rigid molecules including chromophore at a lower temperature. The present work shows unusually low-temperature color-change properties originating from the dynamic motion of rigid conjugated polymer in solid state. The layered composites of polydiacetylene (PDA) and guest l-arginine (L-Arg) (PDA-(L-Arg)) exhibit temperature-responsive gradual color changes with reversibility in the range of 123–333 K in solid crystalline state. The dynamic properties are induced by gradual and reversible distortion of the π-conjugated main chain in response to temperature. The tuned flexibility of the layered structure facilitates motion of the rigid π-conjugated molecule at low temperature. The PDA-(L-Arg)-coated substrates are applied to visualization and quantification of 2D and 3D temperature distributions generated by cooling with liquid nitrogen. These thermographic devices afford to image lower temperature range than typical infrared thermography. The present work indicates potentials of layered architectures with tunable flexibility for emergence of dynamic properties.

Yield-prediction models were studied for efficient exfoliation of soft layered materials stackedviavan der Waals interactions with the assistance of machine learning on small experimental data. High-yield exfoliation of graphite and layered organic polymer was achieved under the conditions guided by the models in a limited number of experiments.

A phase-segregated composite of polystyrene (PSt) and layered polydiacetylene (PDA) was formed through simultaneous polymerization and crystallization. As the motion of PSt chains with glass transition is transferred to that of PDA, the color change was achieved by the shortening of the conjugation length with deformation of the layered structure.