A practical preparation of highly versatile N-acylpyrroles from 2,4,4-trimethoxybutan-1-amine

A novel method for the preparation of N-acylpyrrole is described. The method involves condensation of carboxylic acids with 2,4,4-trimethoxybutan-1-amine, followed by acid-mediated cyclization to form the pyrrole ring. The preparative procedure is highly tolerant of a variety of functional groups.     

Simulation of metal-ligand self-assembly into spherical complex m(6)l(8)

Molecular dynamics simulations were performed to study the self-assembly of a spherical complex through metal-ligand coordination interactions. M(6)L(8), a nanosphere with six palladium ions and eight pyridine-capped tridentate ligands, was selected as a target system. We successfully observed the spontaneous formation of spherical shaped M(6)L(8) cages over the course of our simulations, starting from random initial placement of the metals and ligands. To simulate spontaneous coordination bond formations and breaks, the cationic dummy atom method was employed to model nonbonded metal-ligand interactions. A coarse-grained solvent model was used to fill the gap between the time scale of the supramolecular self-assembly and that accessible by common molecular dynamics simulation. The simulated formation process occurred in the distinct three-stage (assembly, evolution, fixation) process that is well correlated with the experimental results. We found that the difference of the lifetime (or the ligand exchange rate) between the smaller-sized incomplete clusters and the completed M(6)L(8) nanospheres is crucially important in their supramolecular self-assembly.     

Creation of high-refractive-index amorphous titanium oxide thin films from low-fractal-dimension polymeric precursors synthesized by a sol-gel technique with a hydrazine monohydrochloride catalyst

Amorphous titanium dioxide (TiO(2)) thin films exhibiting high refractive indices (n ≈ 2.1) and high transparency were fabricated by spin-coating titanium oxide liquid precursors having a weakly branched polymeric structure. The precursor solution was prepared from titanium tetra-n-butoxide (TTBO) via the catalytic sol-gel process with hydrazine monohydrochloride used as a salt catalyst, which serves as a conjugate acid-base pair catalyst. Our unique catalytic sol-gel technique accelerated the overall polycondensation reaction of partially hydrolyzed alkoxides, which facilitated the formation of liner polymer-like titanium oxide aggregates having a low fractal dimension of ca. (5)/(3), known as a characteristic of the so-called "expanded polymer chain". Such linear polymeric features are essential to the production of highly dense amorphous TiO(2) thin films; mutual interpenetration of the linear polymeric aggregates avoided the creation of void space that is often generated by the densification of high-fractal-dimension (particle-like) aggregates produced in a conventional sol-gel process. The mesh size of the titanium oxide polymers can be tuned either by water concentration or the reaction time, and the smaller mesh size in the liquid precursor led to a higher n value of the solid thin film, thanks to its higher local electron density. The reaction that required no addition of organic ligand to stabilize titanium alkoxides was advantageous to overcoming issues from organic residues such as coloration. The dense amorphous film structure suppressed light scattering loss owing to its extremely smooth surface and the absence of inhomogeneous grains or particles. Furthermore, the fabrication can be accomplished at a low heating temperature of <80 °C. Indeed, we successfully obtained a transparent film with a high refractive index of n = 2.064 (at λ = 633 nm) on a low-heat-resistance plastic, poly(methyl methacrylate), at 60 °C. The result offers an efficient route to high-refractive-index amorphous TiO(2) films as well as base materials for a wider range of applications.     

Survey meter combining CVD diamond and silicon detectors for wide range of dose rates and high accumulated doses

We have developed a prototype of a survey meter combining a CVD diamond detector and silicon detectors to appropriately take temporal measurements of γ-ray radiations over a wide range of the dose rates and to measure high accumulated doses of γ-ray radiations. In order to carry out this, at first, we have studied the radiation hardness of diamond detectors suitably fabricated with high-quality single-crystalline CVD diamond films to confirm that such CVD diamond detectors have greatly superior radiation hardness, compared with commercially available silicon detectors. It is evidenced that the performance of the CVD diamond detector did not significantly change even after heavy γ-ray irradiation of 0.7 MGy while the silicon detectors have a remarkable increase in the dark current, a detection peak shift to the low energy side, and a decrease in detection counts for 5.486-MeV α particles. Due to a size limitation of the CVD diamond detector, such a CVD diamond detector was combined with six commercially available silicon detectors to fabricate a survey meter which can appropriately work under severe irradiation conditions, or, at accumulated doses larger than at least 0.5 MGy and which can cover a wide range of the dose rates from 1 μGy/h to at least 1 kGy/h. The prototype survey meter had a practically useful linearity in this dose rate range. Thus, we have confirmed that such a diamond-Si combined survey meter can be put into practical use.     

A vapoluminescent Eu-based metallo-supramolecular polymer

An Eu-based metallo-supramolecular polymer (polyEu) was prepared by self-assembly coordination polymerization. Unique vapoluminescence property of polyEu triggered by acid-base vapor was found and a photoluminescence display in switchable imaging by acid-base vapor was fabricated.     

Efficient dynamic kinetic resolution of racemic secondary alcohols by a chemoenzymatic system using bifunctional iridium complexes with C-N chelate amido ligands

The combined catalyst system of bifunctional amidoiridium complexes derived from benzylic amines with CALB was found to provide a range of chiral acetates from racemic secondary alcohols in excellent yields with nearly perfect enantioselectivities via dynamic kinetic resolution.