High-Sensitive Spatiotemporal Distribution Imaging of Compression Stresses Based on Time-Evolutional Responsiveness.

Mechanoresponsive materials have been studied to visualize and measure stresses in various fields. However, the high-sensitive and spatiotemporal imaging remain a challenging issue. In particular, the time evolutional responsiveness is not easily integrated in mechanoresponsive materials. In the present study, high-sensitive spatiotemporal imaging of weak compression stresses is achieved by time-evolutional controlled diffusion processes using conjugated polymer, capsule, and sponge. Stimuli-responsive polydiacetylene (PDA) is coated inside a sponge. A mechanoresponsive capsule is set on the top face of the sponge. When compression stresses in the range of 6.67-533 kPa are applied to the device, the blue color of PDA is changed to red by the diffusion of the interior liquid containing a guest polymer flowed out of the disrupted capsule. The applied strength (F/N), time (t/s), and impulse (F·t/N s) are visualized and quantified by the red-color intensity. When a guest metal ion is intercalated in the layered structure of PDA to tune the responsivity, the device visualizes the elapsed time (τ/min) after unloading the stresses. PDA, capsule, and sponge play the important roles to achieve the time evolutional responsiveness for the high-sensitive spatiotemporal distribution imaging through the controlled diffusion processes.

Construction of Millimeter-Wide Monolayers of Ordered Nanocubes as a Stain of "Wineglass Tears" Driven by the Marangoni Flow.

We constructed millimeter-wide monolayers consisting of tetragonally ordered BaTiO3 (BT) nanocubes through the liquid film formation caused by the Marangoni flow in a toluene-hexane binary liquid containing oleic acid. A thin liquid film containing BT nanocubes was overspread on a standing silicon substrate through the condensation of toluene at the advancing front after the preferential evaporation of hexane. Then, the oscillatory droplet formation like "wineglass tears" occurred on the substrate. Finally, two-dimensionally ordered BT nanocubes were observed as a stain of "wineglass tears" on the substrate after the liquid film receded through evaporation. The presence of a thin liquid film in the binary system is essential for the production of millimeter-wide monolayers on the substrate because multilayer deposition occurs without the formation of a thin liquid film in monocomponent systems. We improved the regularity of the ordered arrays of nanocubes by adjusting the liquid component and evaporation conditions.

Self-Assembly of 2D Nematic and Random Arrays of Sterically Stabilized Nanoscale Rods with and without Evaporation.

The adequate manipulation of nanometer-scale building blocks using dispersion systems is regarded as a fundamental technique to fabricate elaborate microstructures. Although a liquid flow with evaporation is generally regarded as an essential factor for the self-assembly of floating blocks, experimental evidence has not been sufficient to clarify the importance of the flow in the dispersion systems. In the present study, 2D nematic layers of sterically stabilized nanoscale calcite rods were achieved in a millimeter-scale region on a solid substrate via the very slow recession of an organic dispersion with evaporation. 2D random arrays of the nanorods were obtained via recession of the liquid in the same system without evaporation. When the nanorods were not sterically stabilized, 3D random arrays were formed even with evaporation. We demonstrated that the evaporation-driven flow of sterically stabilized nanorods to a confined space at the air-liquid-solid interface is essential for the formation of 2D nematic structures on a substrate.

Solid-State Low-Temperature Thermoresponsive and Reversible Color Changes of Conjugated Polymer in Layered Structure: Beyond Infrared Thermography.

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.

Spinel-Type MgMn2O4 Nanoplates with Vanadate Coating for a Positive Electrode of Magnesium Rechargeable Batteries.

Spinel-type MgMn2O4 nanoplates ∼10 nm thick were prepared as a positive electrode for magnesium rechargeable batteries by the transformation of metal hydroxide nanoplates. Homogeneous coating with a vanadate layer thinner than 3 nm was achieved on the spinel oxide nanoplates via coverage of the precursor and subsequent mild calcination. We found that the spinel oxide nanoplates with the homogeneous coating exhibit improved electrochemical properties, such as discharge potential, capacity, and cyclability, due to the enhanced insertion and extraction of magnesium ions and suppressed decomposition of electrolytes. The nanometric platy morphology of the spinel oxide and the vanadate coating act synergistically for the improvement of the electrochemical performance.

Supermicroporous Silica Nanograins: Synthesis and Application.

Supermicroporous silicas having micropores 1-2 nm in diameter were miniaturized to 30-40 nm in diameter using a combination of binary organic agents: cationic surfactant as a porogen and polyethylene glycol as a growth suppressor in a concentrated system. The miniaturized nanograins of the porous silica were effective as a porous and transparent matrix for WO3 quantum dots that exhibit enhanced photocatalytic activity.

Evolution of Co3O4 Nanocubes through Stepwise Oriented Attachment.

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.

Modifications in coordination structure of Mg[TFSA]2-based supporting salts for high-voltage magnesium rechargeable batteries.

To achieve a sustainable-energy society in the future, next-generation highly efficient energy storage technologies, particularly those based on multivalent metal negative electrodes, are urgently required to be developed. Magnesium rechargeable batteries (MRBs) are promising options owing to the many advantageous chemical and electrochemical properties of magnesium. However, the substantially low working voltage of sulfur-based positive electrodes may hinder MRBs in becoming alternatives to current Li-ion batteries. We proposed halide-free noncorrosive ionic liquid-based electrolytes incorporating Mg[TFSA]2 for high-voltage MRB applications. Upon the complexation of Mg[TFSA]2 with tetraglyme (G4) and strict control of the liquid states, the electrolytes achieved excellent anodic stability up to 4.1 V vs. Mg2+/Mg even at 100 °C. The modest electrochemical activities for magnesium deposition/dissolution in the [Mg(G4)][TFSA]2/ionic liquid electrolyte can be improved by certain modifications to the coordination state of [TFSA]-. Dialkyl sulfone was found to be effective in changing the coordination state of [TFSA]- from associated to isolated (free). This coordination change successfully promoted magnesium deposition/dissolution reactions, particularly in the coexistence of ether ligand. By contrast, the coordination of Mg2+ by strongly donating agents such as dimethyl sulfoxide and alkylimidazole led to the complexes inactive electrochemically, suggesting that interaction between Mg2+ and coordination agents predominates the fundamental electrochemical activity. We also demonstrated that an enhancement in the electrochemical activity of electrolytes contributed to improvements in the cycling ability of magnesium batteries with 2.5 V-class MgMn2O4 positive electrodes.

Nanoscale Mosaic Works: Tetragonal Lattices of Iso-Oriented Heterogeneous Nanocubes.

Tetragonal 2D lattices are spontaneously formed by the self-assembly of homogeneous nanocubes. However, ordered arrays consisting of differently sized rectangular nanoblocks have not been achieved because the regulation of the assembly is weakened by the combination of binary units. In the present work, ordered arrays comprising binary nanocubes were investigated using the combination of 10 nm Pt nanocubes and 20 nm BaTiO3 nanocubes. Heterogeneous but ordered 2D tetragonal lattices were successfully produced using differently sized rectangular nanoblocks. The highly ordered self-assembly in the heterogeneous system requires the matching of the size ratio of binary nanocubes with the buffer effect of oleic acid covering the building units.

Layer-by-Layer Manipulation of Heterogeneous Rectangular Nanoblocks: Brick Work for Multilayered Structures with Specific Heterojunction.

The combination of heterogeneous inorganic nanocrystals provides novel nanometer-scale architectures for exploration of novel functions. In the present study, heterogeneous bilayers, such as BaTiO3-Fe3O4 and Mn3O4-CeO2, are fabricated via layer-by-layer stacking of several rectangular nanoblocks 5-23 nm in size by evaporation-driven self-assembly. Specific heterojunctions between inorganic crystals are constructed by nanoscale simple brick work through spontaneous adjustment of the crystallographic orientations of the nanoblocks in the lower and upper layers.

Ultrasensitive Detection of Methylmercaptan Gas Using Layered Manganese Oxide Nanosheets with a Quartz Crystal Microbalance Sensor.

Methylmercaptan (MM) is a marker of periodontal disease; however, the required sensitivity for MM is parts per billion, which has been challenging to realize with a simple sensor. Here, we report the capability to detect MM at concentrations as low as 20 ppb using layered manganese oxide nanosheets with a quartz crystal microbalance sensor. The sensing capabilities of the manganese oxide nanosheets are promoted by adsorbed water present on and between the nanosheets. The strong adsorption of MM to the sensor, which is necessary for the high sensitivity, leads to significant hysteresis in the response on cycling due to irreversible adsorption. However, the sensor can be readily reset by heating to 80 °C, which leads to highly reproducible response to MM vapor at low concentrations. A key aspect of this sensor design is the high selectivity toward MM in comparison to other compounds such as ethanol, ammonia, acetaldehyde, acetic acid, toluene, and pyridine. This layered nanosheets design for high-sensitivity sensors, demonstrated here for dilute MM, holds significant promise for addressing needs to identify sulfur compounds associated for environmental protection and medical diagnostics.

Oriented Attachment of Calcite Nanocrystals: Formation of Single-Crystalline Configurations as 3D Bundles via Lateral Stacking of 1D Chains.

The formation of single-crystalline configurations by the oriented attachment of calcite was experimentally demonstrated as 3D bundles in a nonaqueous system. In the initial stage, 1D short chains elongated in the c direction were formed through the primary oriented attachment of calcite nanoblocks ∼30 nm in diameter. The 3D bundles were then produced through subsequent side-by-side oriented attachment of the 1D chains in the progressive stage. Finally, micrometer-sized single-crystalline architectures were constructed via large-scale oriented attachment of the nanoscale building blocks with a decrease in repulsion force due to the surface charge.

Significant Increase in Band Gap and Emission Efficiency of In2O3 Quantum Dots by Size-Tuning around 1 nm in Supermicroporous Silicas.

The size of In2O3 quantum dots (QDs) is tuned from 0.57 to 1.80 nm by using supermicroporous silicas (SMPSs) as a template. The band gap energy and photoluminescence quantum yields of In2O3-QDs increase remarkably when their size is decreased below 1 nm.

Spatial Control of Crystallographic Direction in 2D Microarrays of Anisotropic Nanoblocks on Trenched Substrates.

Elaborate two-dimensional (2D) microarrays of tetragonal Mn3O4 nanocuboids 10-20 nm in size were constructed with parallel trenches 500 nm wide and 500 nm deep on a silicon substrate. By adjusting the conditions, including the dispersion medium, particle concentration, and evaporation rate, the a-face and c-face 2D arrays were selectively deposited on the upper and lower stages of the trenches, respectively. The crystallographic direction of the tetragonal crystal was alternately switched in the 2D microarrays under these specific conditions at the optimal particle concentration and evaporation rate. Spatial switching of their crystallographic direction was achieved via interaction of the anisotropic nanoblocks and the specifically shaped surfaces.

Orientation-Selective Alignments of Hydroxyapatite Nanoblocks through Epitaxial Attachment in a and c Directions.

Nanometric rods of hydroxyapatite (HA) were aligned in selective crystallographic directions by the alternation of adsorbing molecules. The side and end faces of HA nanorods elongated in the c direction were covered with oleic acid (OA) and tetraoctylammonium (TOA) ions, respectively. Alignment in the c direction of the OA-modified nanorods was produced through epitaxial attachment of the bare end faces in toluene because the side faces were hydrophobized with the negatively charged modifier. Another alignment-in the a direction of the TOA-modified HA nanorods-was obtained through the epitaxial attachment of the bare side faces in ethanol due to stabilization of the end faces with the positively charged modifier. Controlled alignments of the nanorods in the a and c directions were achieved through oriented attachment with the selective coverage of the c and a faces with the specific modifiers.

Hierarchical CaCO3 chromatography: a stationary phase based on biominerals.

In biomineralization, acidic macromolecules play important roles for the growth control of crystals through a specific interaction. Inspired by this interaction, we report on an application of the hierarchical structures in CaCO3 biominerals to a stationary phase of chromatography. The separation and purification of acidic small organic molecules are achieved by thin-layer chromatography and flash chromatography using the powder of biominerals as the stationary phase. The unit nanocrystals and their oriented assembly, the hierarchical structure, are suitable for the adsorption site of the target organic molecules and the flow path of the elution solvents, respectively. The separation mode is ascribed to the specific adsorption of the acidic molecules on the crystal face and the coordination of the functional groups to the calcium ions. The results imply that a new family of stationary phase of chromatography can be developed by the fine tuning of hierarchical structures in CaCO3 materials.

Formation of Monocrystalline 1D and 2D Architectures via Epitaxial Attachment: Bottom-Up Routes through Surfactant-Mediated Arrays of Oriented Nanocrystals.

Monocrystalline architectures with well-defined shapes were achieved by bottom-up routes through epitaxial attachment of Mn3O4 nanocrystals. The crystallographically continuous 1D chains elongated in the a axis and 2D panels having large a or c faces were obtained by removal of the organic mediator from surfactant-mediated 1D and 2D arrays of Mn3O4 nanocrystals, respectively. Our basal approach indicates that the epitaxial attachment through the surfactant-mediated arrays is utilized for fabrication of a wide variety of micrometric architectures from nanometric crystalline units.

Surface-functionalized monolayered nanodots of a transition metal oxide and their properties.

Lateral size, surface chemistry, and properties are varied in inorganic monolayers based on a transition metal-oxide. A variety of inorganic monolayers with their emergent properties have been studied in recent decades. However, it is not easy to tune the lateral size, surface chemistry, and dispersibility of monolayers by typical synthetic methods. In the present work, a new approach is developed for the simultaneous surface functionalization and exfoliation of the precursor nanocrystals in a nonpolar organic medium. We obtained monolayered nanodots of a titanium oxide less than 5 nm in lateral size with surface functionalization by an alkylamine (C14H29NH2) and dihydroxynaphthalene (DHN) in toluene. The bandgap energy of the monolayers was changed by the lateral size and surface functionalization. The present study suggests versatile potentials of the monolayers with tuned size, surface chemistry, and properties.

Direction control of oriented self-assembly for 1D, 2D, and 3D microarrays of anisotropic rectangular nanoblocks.

Micrometric linear chains (1D arrays), monolayers (2D arrays), and superstructures (3D arrays) of anisotropic Mn3O4 nanocuboids were selectively produced by oriented self-assembly through evaporation of a dispersion. The 1D arrays were basically formed on a substrate via oriented self-assembly of the rectangular crystals in the ⟨100⟩ direction. The 2D and 3D microarrays were obtained by adjusting the particle concentration of the dispersion. The [001] direction of tetragonal crystal was controlled to be parallel and perpendicular to the substrate by changing the polarity of the medium.

An experimental study on the processes of hierarchical morphology replication by means of a mesocrystal: a case study of poly(3,4-ethylenedioxythiophene).

The processes for the synthesis of polymers in a mesocrystal structure were studied for understanding of the mechanisms. The mesocrystal structure has the nanoscale pores between the unit crystals for incorporation of guest molecules. The monomers can be incorporated and polymerized in the nanospace of the mesocrystals. In the present work, a sea urchin spine and poly(3,4-ethylenedioxythiophene) (PEDOT) were adopted as a model of the original mesocrystal and replicated polymer material, respectively. A sea urchin spine, as an original material, has the hierarchical architectures based on the mesocrystal structure consisting of the oriented carbonate nanocrystals. The monomers were introduced in the nanoscale pores. The composite of the original carbonate and PEDOT was obtained after the incorporation and the polymerization. After dissolution of the original carbonate, the resultant PEDOT architecture showed the hierarchical morphologies similar to those of the original sea urchin spine. The morphology replication processes were compared with those of the different polymers. The important factors for the morphology replication are studied. The present work suggests that the approach can be applied to morphogenesis of a variety of polymer materials.