Bench-Top Type In Vivo EPR Spectrometer for Estimating the Renal Reducing Ability of a Rat

A main electromagnet optimized for electron paramagnetic resonance (EPR) measurements of rats by using a surface loop resonator with a loop diameter of 10?mm was designed. The fabricated main electromagnet was ca. 420?mm in diameter, ca. 240?mm in width, and ca. 60?kg in weight. When a static magnetic field of 25?mT was generated at the center of the main electromagnet, its deviation in a sphere space with a diameter of 10?mm was <0.02?mT. In this condition, the temperature elevation on the surface of the magnet was negligible for the measurement time assumed for in vivo study. Using this magnet, a bench-top type in vivo EPR spectrometer could be obtained, which made it possible to perform EPR measurements for estimating the renal reducing ability of a rat.     

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.     

Phase behavior of aqueous solutions of copolymers of N,N'-diisopropylfumaramide and N-isopropylacrylamide: effect of the density of side chains

This letter describes the phase behavior of aqueous solutions of an N-isopropylacrylamide (NIPAM) homopolymer and copolymers of N,N'-diisopropylfumaramide (DIPFAM) and NIPAM as studied by transmittance measurements, infrared spectroscopy, and differential scanning calorimetry to reveal the effect of the density of N-isopropylamide side chain upon the phase behavior. The clouding-point and clearing-point temperatures decreased with increasing the mole fraction of DIPFAM (x(D)). It was noteworthy that only an extra side chain per ca. 7 NIPAM units had a remarkable effect on the phase behavior; the interactions between side chains were stronger, the intrapolymer contraction was less favorable, and the cooperativity of phase transition was lower at x(D) = 0.15 presumably because of the steric hindrance of dense side chains.     

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.     

Fluorescence imaging of potassium ions in living cells using a fluorescent probe based on a thrombin binding aptamer-peptide conjugate

When a biotinylated FRET probe based on a peptide-thrombin binding aptamer conjugate was introduced together with streptavidin and biotinylated nuclear export signal peptide into HeLa cells, the resulting ternary complex enabled visualization of K(+) concentration changes in the cell.     

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.     

Characterization of inclusion complex of vitamin E compound with 2,6-di-O-methylated β-cyclodextrin as the solubility enhancer and its kinetic determination for radical scavenging ability

The structure of the inclusion complex of α-tocopherol (vitamin E compound) with 2,6-di-O-methylated β-cyclodextrin (DM-β-CD) was characterized by 2D ROESY NMR measurements, suggesting that DM-β-CD includes the side-chain moiety of α-tocopherol. The inclusion complexation of DM-β-CD showed the usefulness of water solubilizer for the radical scavenging assay of vitamin E compounds in aqueous solution. Using the electron paramagnetic resonance (EPR) competitive spin trapping method, we determined the oxygen radical (RO^?) scavenging abilities of seven vitamin E compounds (tocopherols and tocotrienols), which were solubilized by DM-β-CD in water. The order of the RO^? radical scavenging abilities for vitamin E compounds solubilized by DM-β-CD are α- > β- ≈ γ- > δ-, which is in agreement with the oxidation potential values of antioxidants. It is noted that the RO^? radical scavenging abilities of tocotrienols are comparable to those of tocopherols. Based on the results, the mechanism of the antioxidant reaction of vitamin E compounds with the RO^? radical is discussed.     

FMO‐MD Simulations on the Hydration of Formaldehyde in Water Solution with Constraint Dynamics

Full‐quantum mechanical fragment molecular orbital‐based molecular dynamics (FMO‐MD) simulations were applied to the hydration reaction of formaldehyde in water solution under neutral conditions. Two mechanisms, a concerted and a stepwise one, were considered with respect to the nucleophilic addition and the proton transfer. Preliminary molecular orbital calculations by means of polarized continuum model reaction field predicted that the hydration prefers a concerted mechanism. Because the calculated activation barriers were too high for free FMO‐MD simulations to give reactive trajectories spontaneously, a More O’Ferrall–Jencks‐type diagram was constructed from the statistical analysis of the FMO‐MD simulations with constraint dynamics. The diagram showed that the hydration proceeds through a zwitterionic‐like (ZW‐like) structure. The free energy changes along the reaction coordinate calculated by means of the blue moon ensemble for the hydration and the amination of formaldehyde indicated that the hydration proceeds through a concerted process through the ZW‐like structure, whereas the amination goes through a stepwise mechanism with a ZW intermediate. In inspection of the FMO‐MD trajectories, water‐mediated cyclic proton transfers were observed in both reactions on the way from the ZW‐like structure to the product. These proton transfers also have an asynchronous character, in which deprotonation from the nucleophilic oxygen atom (or nitrogen atom for amination) precedes the protonation of the carbonyl oxygen atom. The results showed the strong advantage of the FMO‐MD simulations to obtain detailed information at a molecular level for solution reactions.     

Mechanofluorochromism of carbazole-type D–π–A fluorescent dyes

We have newly designed and synthesized unsymmetrical carbazole-type D–π–A fluorescent dyes. The dyes show a bathochromic shift-type mechanofluorochromism (MFC): grinding of as-recrystallized dyes induces a bathochromic shift of fluorescent color and the fluorescent color is recovered by heating or exposure to solvent vapor. In order to clarify the MFC mechanism for the carbazole-type D–π–A fluorescent dyes, time-resolved fluorescence spectroscopy, X-ray powder diffractometry, single-crystal X-ray structural analysis, IR spectroscopy, and differential scanning calorimetry are performed before and after grinding of the solids. On the basis of experimental results and semi-empirical molecular orbital calculations (AM1 and INDO/S), we have revealed that the MFC is attributed to a reversible switching between crystalline and amorphous states with changes of intermolecular hydrogen bonding and π–π interaction.