Synthesis of monodispersed silica nanoparticles with high concentration by the Stöber process

Silica nanoparticles with high concentration were prepared by the sol–gel process based on the Stöber method using tetraethoxysilane as a starting material. It was found that silica sol with about 4 wt% in concentration and with a diameter of about 10 nm was obtained by controlling the reaction conditions in the Stöber process. By removing the solvent under a reduced pressure, the particle concentration was increased up to 15 wt% without aggregation.     

Macrocyclic Metal Complexes Bearing Rigid Polyaromatic Ligands: Synthesis and Catalytic Activity

We synthesised palladium and platinum complexes possessing cyclic and acyclic pincer‐type polyaromatic ligands and investigated their structural effect on the catalysis. The pincer‐type bis(6‐arylpyridin‐2‐yl)benzene skeleton was constructed via Kröhnke pyridine synthesis under transition metal‐free conditions on gram‐scale quantity. Ligand structure significantly influenced catalytic activity toward the platinum‐catalysed hydrosilylation of diphenyl acetylenes, despite the ligand‐independence of the conformations and electronic properties of these complexes.     

Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two-Step Iron(II) Spin Crossover Switchable by Temperature,Light, and Pressure

A two-step hysteretic Fe^II spin crossover (SCO) effect was achieved in programmed layered Cs{[Fe(3-CNpy)₂][Re(CN)₈]}⋅H₂O ( 1 ) (3-CNpy=3-cyanopyridine) assembly consisting of cyanido-bridged Fe^II-Re^V square grid sheets bonded by Cs⁺ ions. The presence of two non-equivalent Fe^II sites and the conjunction of 2D bimetallic coordination network with non-covalent interlayer interactions involving Cs⁺, [Re^V(CN)₈]³⁻ ions, and 3-CNpy ligands, leads to the occurrence of two steps of thermal SCO with strong cooperativity giving a double thermal hysteresis loop. The resulting spin-transition phenomenon could be tuned by an external pressure giving the room-temperature range of SCO, as well as by visible-light irradiation, inducing an efficient recovery of the high-spin Fe^II state at low temperatures. We prove that octacyanidorhenate(V) ion is an outstanding metalloligand for induction of a cooperative multistep, multiswitchable Fe^II SCO effect.     

Effect of suspended particles on spreading of volatile droplet on solid substrate

Abstract  

We have been interested in behaviors of suspended particles in a volatile droplet placed on a smooth substrate. It is known that the particles gather and deposit in the vicinity of the macroscopic contact line of the droplet, which is generally called ‘coffee stain problem’. A convective flow induced by non-uniform evaporation through the interface brings suspended particles toward the pinned contact line in the drying droplet, which forms a ring stain. We have focused on the dynamics of the droplet with/without suspended particles spreading on the solid substrate and on the behaviors of particles in the evaporating droplet. Spreading process of the droplet is significantly affected by the suspended particles. We indicate flow patterns in the droplet, in which the flow exhibits a modal structure with a mode number in the azimuthal direction, and indicate particles depositions after the dryout of the droplet. Three-dimensional particle tracking velocimetry is applied to reconstruct such unique flow patterns in the spreading process of the droplet. Resultant patterns of the particles depositing on the substrate are introduced.     

Experimental study on the influences of grain boundary scattering on the charge and heat transport in gold and platinum nanofilms

The electrical and thermal conductivities of polycrystalline gold and platinum nanofilms have been measured simultaneously using a direct current heating method from 60 to 300 K. The measured electrical and thermal conductivities are greatly decreased from the corresponding bulk values. And it is found that the reduction increases as the temperature decreases. The deviation from the bulk value is due to the effect of grain boundary scattering. Furthermore, the experimental results indicate that the grain boundary scattering effect imposes greater influence to the charge transport than to the heat transport. Consequentially, the Lorentz number is several times larger than that of bulk materials, leading to the violation of the Wiedemann–Franz law. The reflection coefficient R (0.86 in platinum, 0.42 in gold) at grain boundaries is obtained based on the Mayadas-Shatzkes theory and Matthiessen’s rule, which agrees well with the previous experiments.     

What we have learned from studies on chemical properties of amorphous alloys?

Amorphous alloys have many attractive characteristics including extremely high corrosion resistance if the sufficient amounts of corrosion-resistant elements are added. The superiority of amorphous alloys is based on the homogeneous single phase nature without any chemical and physical heterogeneities. Although there are processing limitations to avoid the formation of heterogeneous crystalline structure in addition to no welding technology without crystallization, the application of corrosion-resistant amorphous alloys is expected particularly to the very aggressive environments, where any conventional crystalline metallic materials cannot be used. Some amorphous bulk alloys showed zero corrosion mass loss due to spontaneous passivation even in 12 M HCl. Production of amorphous bulk alloys became possible for selected compositions. The homogeneous single phase nature is also effective to form useful catalysts with unique composition and structure. An example of catalysts is for carbon dioxide methanation useful for supply of renewable energy in the form of methane.     

A microfluidic chip integrated with a microoptical lens fabricated by femtosecond laser micromachining

We report on the integration of microlens and microfluidic channels in fused silica glass chip using femtosecond laser micromachining. The main process includes three procedures: (1) femtosecond laser scanning for forming a hemispherical surface and a Y-shaped channel in the fused silica glass; (2) chemical etching of the sample for removal of the modified areas; and (3) oxyhydrogen (OH) flame polish for smoothening the surface of the microlens. In addition, we demonstrate that the fabricated microlens exhibits good imaging performance with a 5× magnification, showing great potential in future lab-on-a-chip applications.     

Mitigation of lunar dust adhered to mechanical parts of equipment used for lunar exploration

A unique cleaning system has been developed utilizing electrostatic force to remove lunar dust adhered to the mechanical parts of equipment used for lunar exploration. A single-phase voltage is applied to parallel electrodes printed on a flexible substrate to remove the dust. More than 90% of adhered dust was repelled from the surface of the slightly inclined device in a vacuum, and the cleaning performance of the system would be further improved in the low-gravity environment of the Moon. This technology is expected to increase the reliability of equipment used in long-term manned and unmanned activities on the lunar surface.     

Cross‐Conjugated Hexaphyrins and Their Bis‐Rhodium Complexes

A cross‐conjugated hexaphyrin that carries two meso‐oxacyclohexadienylidenyl (OCH) groups 9 was synthesized from the condensation of 5,10‐bis(pentafluorophenyl)tripyrrane with 3,5‐di‐tert‐butyl‐4‐hydroxybenzaldehyde. The reduction of 9 with NaBH₄ afforded the Möbius aromatic [28]hexaphyrin 10 . Bis‐rhodium complex 11 , prepared from the reaction of 10 with [{RhCl(CO)₂}₂], displays strong Hückel antiaromatic character because of the 28 π electrons that occupy the conjugated circuit on the enforced planar structure. The oxidation of 11 with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) yielded complexes 12 and 13 depending upon the reaction conditions. Both 12 and 13 are planar owing to bis‐rhodium metalation. Although complex 12 bears two meso‐OCH groups at the long sides and is quinonoidal and nonaromatic in nature, complex 13 bears 3,5‐di‐tert‐butyl‐4‐hydroxyphenyl and OCH groups and exhibits a moderate diatropic ring current despite its cross‐conjugated electronic circuit. The diatropic ring current increases upon increasing the solvent polarity, most likely due to an increased contribution of an aromatic zwitterionic resonance hybrid.     

Reduction Reaction of the Copper(II) Complex Bearing 1,3-Di(pyridine-2-carboxaldimino)propane (pitn) by Decamethylferrocene in Acetonitrile

The reduction reaction of the Cu(II)–pitn complex (pitn = 1,3-di(pyridine-2-carboxaldimino)propane) by decamethylferrocene [Fe(Cp*)₂] was examined in acetonitrile. The observed pseudo-first-order rate constants exhibited saturation kinetics with increasing excess amount of [Fe(Cp*)₂]. Detailed analyses revealed that the reaction is controlled by a structural change prior to the electron transfer step, rather than a conventional bimolecular electron transfer process preceded by ion pair (encounter complex) formation. The rate constant for the structural change was estimated to be 275 ± 13 s^?1 at 298 K (?H* = 33.3 ± 1.0 kJ·mol^?1, ?S* = 86 ± 5 J·mol^?1·K^?1), which is the fastest among gated reactions involving CuN₄ complexes. It was confirmed by EPR measurement and Conflex calculations that the dihedral angle between the two N–N planes is significantly large (40°) in solution whereas it is merely 17.14° in the crystal.