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.

Cycloartenyl Ferulate Is the Predominant Compound in Brown Rice Conferring Cytoprotective Potential against Oxidative Stress-Induced Cytotoxicity.

Since brown rice extract is a rich source of biologically active compounds, the present study is aimed to quantify the major compounds in brown rice and to compare their cytoprotective potential against oxidative stress. The content of the main hydrophobic compounds in brown rice followed the order of cycloartenyl ferulate (CAF) (89.00 ± 8.07 nmol/g) >> α-tocopherol (αT) (19.73 ± 2.28 nmol/g) > γ-tocotrienol (γT3) (18.24 ± 1.41 nmol/g) > α-tocotrienol (αT3) (16.02 ± 1.29 nmol/g) > γ-tocopherol (γT) (3.81 ± 0.40 nmol/g). However, the percent contribution of CAF to the radical scavenging activity of one gram of whole brown rice was similar to those of αT, αT3, and γT3 because of its weaker antioxidant activity. The CAF pretreatment displayed a significant cytoprotective effect on the hydrogen peroxide-induced cytotoxicity from 10 µM, which is lower than the minimal concentrations of αT and γT required for a significant protection. CAF also enhanced the nuclear factor erythroid 2-related factor 2 (Nrf2) nuclear translocation coincided with the enhancement of the heme oxygenase-1 (HO-1) mRNA level. An HO-1 inhibitor, tin protoporphyrin IX (SnPP), significantly impaired the cytoprotection of CAF. The cytoprotective potential of CAF is attributable to its cycloartenyl moiety besides the ferulyl moiety. These results suggested that CAF is the predominant cytoprotector in brown rice against hydrogen peroxide-induced cytotoxicity.

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.

Layer-by-layer manipulation of anisotropic nanoblocks: orientation-switched superlattices through orthogonal stacking of a and c directions.

Nanometer-scale switching of the crystallographic orientation enables production of novel superlattices for exploration of new functions. Elaborate multilayered architectures of Mn3O4 nanocuboids were constructed by a convective self-assembly process. The nanometric cuboids were accumulated into orientation-switched superlattices on micrometric scales by controlling the a and c directions of the tetragonal crystal periodically. The orthogonal stacking of the tetragonal nanoblocks was achieved through the layer-by-layer manipulation process of two types of 2D arrays with different orientations.

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.

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.

Conductive polymer-mediated 2D and 3D arrays of Mn3O4 nanoblocks and mesoporous conductive polymers as their replicas.

Orientation-controlled 2D and 3D microarrays of Mn3O4 nanocuboids that were mediated by a conductive polymer were fabricated by evaporation-induced self-assembly of the oxide nanoblocks and subsequent polymerization of pyrrole in the interparticle spaces. Free-standing mesoporous polypyrroles (PPy) having chain- and square-grid-like nanovoid arrays were obtained as replicas of the composite assemblies by dissolving the oxide nanoblocks. The PPy-mediated manganese oxide arrays exhibited stable electrochemical performance as an ultrathin anode of a lithium-ion secondary battery.