論文

Layered organic polymers have intercalation capabilities and dynamic properties. In classical intercalation chemistry, the interlayer guests are intercalated in the host layers via electrostatic interaction. The present work shows the organic layered materials with the host-guest interlayer interaction via hydrogen bond. Polydiacetylene (PDA) exhibits color changes from blue to red with the application of external stimuli, such as thermal and mechanical stresses. Here we report on a layered PDA containing 4,4′-bipyridyl in the interlayer space as a hydrogen-bonding guest. Whereas the layered PDA without interlayer guest shows the color transition at 65 °C, gradual color changes with two-stage reversibility are observed in the temperature range of −20–240 °C by the introduction of the hydrogen-bonding guest. The weaker interlayer interaction via the hydrogen bond promotes the dynamic motion directing the thermoresponsive color changes in a wide temperature range.

Measurement of friction force is important for safety, security, and health. Excessive friction force causes degradation of materials and biological bodies. For example, tooth enamel and gums are damaged by strong toothbrushing force. However, friction force is not easily measured by conventional materials and devices. Here, we proposed design strategies of a paper-based device for measurement of friction force. Toothbrushing force, a model of weak friction force, is the measurement target in the present work. Soft layered composites of polydiacetylene (PDA) and interlayer guest macromolecules were designed and synthesized to achieve a visible color change in response to weak friction force. A data-scientific approach assisted in the selection of the interlayer guest molecule to control the stimuli responsivity of the layered PDA. The guest polyethyleneimine (PEI) formed soft layered composites exhibiting a color change in response to weak friction force. The paper-based device of the layered PDA/PEI composite showed a gradual color change from blue to red in response to the strength and number of the applied friction force. As a model case, toothbrushing force was measured using the paper-based device. The present work shows new design strategies of molecules and materials toward measurement of a wide variety of friction forces.

Two-dimensional materials, such as layered compounds and nanosheets, have attracted interest for their characteristic structures and properties. If layered materials containing functional organic molecules are synthesized, designed nanosheets can be obtained by exfoliation. Here we show the design and synthesis of an amorphous organic layered material containing a conjugated-polymer network, its exfoliation into nanosheets, and their applications. Copolymerization of benzoquinone and pyrrole generates random stacks of the conjugated polymer layers through successive C-C bond formation and pericyclic reaction under mild conditions at 60 °C. The amorphous organic layered materials are efficiently exfoliated into nanosheets in 44.6% after 1 h. The nanosheets are used as a metal-free electrocatalyst for hydrogen evolution reaction with the overpotential 0.28 V (vs. RHE). The present approach may be applied to the design of functional nanosheets with graphene-like structures under mild conditions.

The organization states of functional molecules have a significant impact on the properties of materials. A variety of approaches have been studied to obtain well-organized molecular assemblies. The present work shows a new non-organized state of isolated and dispersed functional molecules in amorphous flexible covalent organic networks. Redox-active quinone molecules are embedded in the amorphous network polymers. Consecutive reactions between benzoquinone (BQ) and linker molecules generate random network structures through polymerization at different rates and in multiple directions. The low-crystalline stackings of the amorphous network polymers facilitate the formation of nanoflakes through exfoliation in dispersion media. Enhanced electrochemical performances, one of the highest specific capacities in recent studies, were achieved by efficient redox reactions of the quinone moiety. The present noncrystalline approach, low-crystalline stacking of designer amorphous covalent organic networks, can be applied to construct similar nanostructured polymer materials containing functional units. This journal is

Millimeter-scale mesocrystals and cross-lamellae mimicking the nanostructure of seashells were produced on a substrate through the three-dimensionally oriented assembly of c-axis-elongated calcite nanorods ∼50 nm wide and ∼500-1000 nm long by combining arrangement with evaporation-driven capillary force and alignment under an intense magnetic field.

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.

This work examined the band structure and photocatalytic activity of carbon nitride and titania nanoparticles prepared using porous silica templates with pore sizes of approximately 1 and 3 nm. The carbon nitride and titania specimens prepared in this manner exhibited absorption edge blue shifts compared to bulk samples, due to expansion of their band gap resulting from quantum size effects. The photocatalytic activity of these materials during hydrogen production from water was assessed, and the activity of carbon nitride prepared in the 1 nm pores was higher than that of the material made using 3 nm pores as well as that of the bulk carbon nitride. These results suggest that the expansion of the HOMO-LUMO energy gap contributed to increasing the catalytic performance. In contrast, the titania materials did not generate hydrogen. X-ray absorption fine structure analyses demonstrated that the titania in the silica templates had a distorted structure, which may have decreased its photocatalytic activity.

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.

Room-temperature operations of rechargeable Mg coin-cell batteries have been achieved using a Mg alloy negative electrode and a spinel MgMn2O4(MMO)-positive electrode. The present work focuses on clarifying the effects of the physiochemical properties of the MMO powder including the specific surface area (SBET) and porosity of the positive electrode on Mg battery performances in practical applications. Finally, optimal specific surface area and porosity parameters were obtained that ensured excellent battery performances as a standard coin-cell at room temperature. A typical MMO powder synthesized using a modified sol-gel method with propylene oxide-driven complex polymerization had a largeSBET> 200 m2g−1, and more than 90% porosity with a triple-tiered 3D open-channel network. Here we evaluated the discharge capacity and the cyclability for room-temperature operation as a function ofSBETin a full cell with a Mg negative electrode as well as half cells with a carbon graphite electrode. Irrespective of whether half cells or a full cell was used, the initial discharge capacity was found to depend linearly on theSBETof the porous MMO powder in a Mg tetrakis(hexafluoroisopropyl)borate/triglyme electrolyte with a wide potential window, ΔE> 3.6 V. Eventually, the maximum discharge capacity of 220 mA h g−1was realized at 25 °C in the full cell using the 3D open-channel nanostructure withSBET= 236 m2g−1. The cyclability in the full cell with the Mg alloy negative electrode, however, degraded with the increasingSBET, while no cyclability degradation was observed in the half cell with the carbon electrode. A possible mechanism is discussed regarding passivation of the Mg alloy electrode in discharge/charge cycles.

Band engineering with a quantum size effect is proposed to be utilized to design photocatalytic activity for the conversion of organic compounds. Subnanometer WO3 quantum dots (QDs) are spontaneously produced with the enhancement of the photocatalytic activity in a mesoporous silica matrix by preliminary photochemical dissolution. An appropriate upshift of the conduction band of subnanometer WO3 QDs stabilized by the coverage with the surface WO bonds promotes the efficient conversion of benzene to phenol without decomposition of the product into CO2 under ultraviolet illumination.

Exfoliation is a common route to synthesize 2D materials such as monolayered and few-layered nanosheets. However, it is not easy to control the breaking-down process. This work shows a new exfoliation strategy for generation of nanosheets from soft layered composites in high yield. Soft layered composites of inorganic hosts and organic guests are exfoliated into nanosheets in organic dispersion media. A simple yield prediction model is constructed on small-scale experimental data by sparse modeling, a data-scientific approach, combined with chemical perspective. The prediction model indicates the guest–medium combinations enabling high- and low-yield syntheses of the nanosheets. The high- and low-yield syntheses are actually achieved on different types of layered transition metal oxides in a minimum number of experiments. The number of experiments is reduced by 94%. The experimental optimization realizes further improvement of the yield, namely, shortening the exfoliation time. The present strategies can be applied to obtain a variety of 2D materials through exfoliation. Moreover, the present work suggests that combination of small experimental data, data-scientific approach, and chemical perspective, i.e., experiment-oriented materials informatics, has potentials for acceleration of materials design.

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.

The fluorescence of benzanthrone, which is a conjugated molecule bearing a carbonyl group, is activated by confinement in a pore with a diameter close to the molecular size. An intense emission originating from the aromatic character π-π∗ transition is achieved through suppression of the nonradiative n-π∗ transition by strong hydrogen bonding between carbonyl groups and silanol groups with a micropore-filling effect in the nanospace.

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.

Nanographene with various molecular sizes was synthesized and incorporated into the size-controlled pores of super-microporous silica (SMPS). It was found that when the pore diameter of the SMPS matched the molecular size of the nanographene, the fluorescence quantum yield was greatly enhanced. Furthermore, co-adsorption of water molecules improved the quantum yield. This improvement is attributed to a suppression of the interaction between the nanographene and silica walls, which lowers the quantum yield. Since nanographene is insoluble in water, it becomes surrounded by water molecules, almost like in aqueous solution. Finally, highly fluorescent solid materials were obtained by incorporating nanographene into SMPS.

The coercivity of magnetic nanoparticles is enhanced by the exchange coupling effect at the interface of ferrimagnetic and antiferromagnetic self-assembled monolayers. Antiferromagnetic Co3O4 nanocubes were regularly stacked on an ordered monolayer of ferrimagnetic Fe3O4 nanocubes by layer-by-layer manipulation using evaporation-driven self-assembly. The ordered arrangements of the ferrimagnetic and antiferromagnetic nanocubes are effective for the enhancement of the ferromagnetic character.

As children play with wooden building blocks, we would like to construct elaborate architectures through the one-by-one accumulation of nanocrystals. Recently, ordered microarrays of nanosized building blocks have attracted attention as a sophisticated bottom-up approach to fabricate adequate nanomaterials. However, their dimensions, scale, and orientations have not been strictly controlled. The present highlight article reports the potential of brickwork structures using evaporation-driven manipulation as a nanoscale architectural method. Here, the essence of controlled assembly is shown with a demonstration of 1D, 2D, and 3D brickwork structures designed with various inorganic rectangular building nanoblocks covered by stabilizing organic agents. The structures of the ordered assemblies are found to be controlled by changing several parameters, such as particle concentration and the properties of dispersion media and stabilizing agents. This brickwork technique is applicable to multicomponent systems using a library of rectangular nanoblocks. Homogeneous and heterogeneous ordered architectures with spatial and sequential control are selectively produced through the self-assembly of nanocubes and nanocuboids. These elaborate nanoscale brickwork structures are now being developed for the production of designed microstructures with novel functions.

Uniformly sized building units are generally required to construct highly elaborate architectures over a wide range. Defined nanocubes of Co3O4 evolved from deformed precursor nanograins 2-5 nm in diameter through direct oriented attachment in a nonpolar medium. Uniformly sized primary nanocubes -8 nm on a side with {100} faces were formed by adjusting the coverage of the oxide nanograins with oleic acid. Larger nanocubes 20-40 nm on a side were produced with further direct oriented attachment of the primary nanocubes. Ordered arrays, such as superlattices, were found to be constructed by the indirect oriented attachment of the primary and larger nanocubes covered with organic molecules.