Iridium‐Catalyzed Coupling Reaction of Primary Alcohols with 2‐Alkynes Leading to Hydroacylation Products

A novel iridium‐catalyzed intermolecular coupling reaction of primary alcohols or aldehydes with 2‐alkynes was successfully achieved with high regioselectivity to give hydroacylation products such as α,β‐unsaturated ketones in good yields. The mechanistic investigation of the reaction strongly indicated that the coupling proceeds through the initial formation of homoallylic alcohols followed by dehydrogenation to β,γ‐unsatutated ketones and then isomerisation, which leads to the hydroacylation products.     

Bis-phosphoryl-bridged stilbenes synthesized by an intramolecular cascade cyclization

Bis-phosphoryl-bridged stilbenes have been synthesized using an intramolecular cascade cyclization. They show intense blue fluorescences at longer wavelengths with higher quantum yields compared to those of the known element-bridged stilbenes. In addition, they have much lower reduction potentials due to the inductive effect of phosphoryl groups. The incorporation of the phosphoryl moiety is an effective way for the construction of highly electron-accepting pi-conjugated systems.     

Hyperfine magnetic fields in Fe−Co alloys and their tempera ture dependences

We obtained⁵⁷Fe hyperfine field parameters from Fe₁−x-Co _x alloys (0≤x≤0.6) from 77 K to 900 K. We first discuss the origin of the low temperature hyperfine fields in terms of the 3d and 4s electrons at⁵⁷Fe atoms. The⁵⁷Fe hyperfine magnetic field (hmf) of Fe-Co alloys depends more weakly on temperature than the hmf of pure Fe. This temperature dependence occurs because the alignment of the magnetic moments at both the Fe atoms and at the Co atoms depend on temperature in the same way as the bulk magnetization of Fe-Co alloys.     

Separation of Isotopes of Lithium and Uranium by Electromigration Using Cation-Exchange Membranes

Isotope separation by chromatographic electromigration has been studied for lithium (⁶Li and ⁷Li) and uranium (²³⁵U and ²³⁸U), using cation-exchange membranes as migration media. The membranes were pulled back against the direction of the movement of isotopic cations in a countercurrent manner. In both cases of the elements the lighter isotope, ⁶Li or ²³⁵U, was concentrated at the frontal part of a migration zone; at the extreme front the ⁶Li atom % increased to 16.8% from the original value of 7.5% after 386 cm migration, and the ²³⁵ U atom % rose to 0.743% from the original value of 0.723% after 200 cm migration. Isotope separation coefficients were experimentally determined: ε = (3.7 ± 0.4) μ 10^?3 for lithium isotopes, and two slightly different values ε = (4.9 ± 1.0) μ 10^?5 and (5.4 ± 1.1) μ 10^?5 for uranium isotopes. The steep isotope accumulation was observed in a narrow boundary region. A mathematical expression for the isotope accumulation curve was derived, and the slope of the curve was assessed for each experimental result.     

Organic thin‐film transistor fabricated between flexible films by thermal lamination

We propose a novel and complementary method for fabrication of flexible electronics. This method is not based on conventional printing using inks, but is based on the application of a toner‐based method such as Xerox or laser printing, followed by a lamination process. The lamination method is a solvent‐free and material‐saving process that simultaneously seals the devices, and the fabricated flexible devices have structural durability against bending. We have also shown that thermal lamination has an oriented growth effect, and the electrical characteristics of flexible organic field‐effect transistors did not degrade under a bending radius of 1 mm.

     

First principles calculation of CH<Subscript>4</Subscript> decomposition on nickel (111) surface

The mechanism of the CH₄ decomposition on the nickel (111) surface is investigatedby first principles calculations. The activation energy of each reaction is calculatedusing nudged elastic band method. The activation energy of hydrogen dissociation from aCH₂ fragment isfound much lower than the one of a CH₃ fragment. This result is consistent with the fact,observed in our previous molecular dynamics (MD) simulations, that the CH₃ fragment is dissociated into aCH fragment and two hydrogen atoms spontaneously. The effects of finite temperatureat 1500 K on the decomposition reaction of a CH₄ molecule and its fragments are also investigated usingconstraint MD method. While the temperature effects are barely visible inCH₄ andCH₂ dissociationprocesses, they reduce the activation free energy of hydrogen dissociation fromCH₃ and CHfragments largely.     

Third-order resonant optical nonlinearity from trans–cis photoisomerization of an azo dye in a rigid matrix

 We investigated the trans–cis photoisomerization of an azo dye in a rigid matrix and the resulting third-order resonant optical nonlinearity by means of the simple theoretical prediction of a two-energy-level system, thin-layer chromatography and H-NMR studies. A methylorange (MO), a methylred (MR), congored (CR) or a Disperse Red 1 (DR1) doped polyvinyl alcohol (PVA) or silica film was used as nonlinear optical material. The existence of equi-absorbing points, or isosbestic points in the absorbance spectrum change and the remarkable stationary transmittance to be independent of the action beam intensity enabled us to confirm the photoisomerization even in a rigid matrix. Then, we measured the third-order resonant optical nonlinearity of dichroism through the polarization absorbance spectrum measurement and determined the characteristic optical parameters of the photoisomerization in the film such as the quantum yields φ_T, φ_C, the thermal reaction constant K and the photoisomerization time constant by fitting the theoretical curve of the two-energy-level system to the observed temporal transmittance change after the action beam exposure of the MO/PVA film. The quantum yields were φˉ_T=0.36 and φˉ_C=0.38, respectively. The photoisomerization time constant of MO embedded in the PVA film was a few seconds. The thermal reaction constant K depended on the excitation beam intensity. Received: 20 June 1996/Revised version: 4 October 1996     

Crystal structure and ferroelectric property of Bi4Si3O12-added Bi4−xSmxTi3O12

We synthesized Bi_4?xSm_xTi₃O₁₂ (x=0.55, 0.65, 0.80) and y mol% Bi₄Si₃O₁₂-added Bi_4?xSm_xTi₃O₁₂ (x=0.65; y=5, 10, 15, 20) by a solid-state reaction, and investigated a relationship between the ferroelectric properties and crystal structures in these samples. From the P–E hysteresis measurements, it was clarified that the Bi_3.35Sm_0.65Ti₃O₁₂ showed better ferroelectric properties than the others with different Sm content, and the sample began to exhibit larger remanent polarization by adding Bi₄Si₃O₁₂. In order to examine an effect of the Bi₄Si₃O₁₂-addition from a structural point of view, we measured synchrotron X-ray diffractions of the samples at room temperature and 1000 K, and analyzed their crystal and electronic structures with the Rietveld technique and the maximum entropy method. As a result, it was suggested that the Bi₄Si₃O₁₂-addition made distortions of the Ti-O₆ octahedra larger and had an effect on the TiO bond strengths.     

Investigation of evolution hydrocarbon species on a Si surface during methane plasma with and without substrate bias, using infrared spectroscopy in multiple internal reflection geometry

We investigated evolution of hydrocarbon species on a Si surface during methane plasma both with and without substrate bias, using infrared spectroscopy in multiple internal reflection geometry (MIR-IRAS). We found that the relative density of the sp³-CH or sp³-CH₂ species to the sp³-CH₃ species was low in the low exposure regions, but that the relative density of the sp³-CH or sp³-CH₂ species increased as the exposure was higher. Substrate temperatures rose as the plasma exposure was higher. The changes of ratios would be ascribed to the substrate heating effect by plasma exposure, which would enhance the etching and/or hydrogen abstraction effects. We also found the change of CH_1-2/CH₃ ratios was enhanced when the high substrate bias was applied. The enhancement of the ratio was due to ion effects.     

The Dimeric Form of 1,3-Diaminoisoquinoline Derivative Rescued the Mis-splicing of Atp2a1 and Clcn1 Genes in Myotonic Dystrophy Type 1 Mouse Model

Expanded CUG repeat RNA in the dystrophia myotonia protein kinase (DMPK) gene causes myotonic dystrophy type 1 (DM1) and sequesters RNA processing proteins, such as the splicing factor muscleblind-like 1 protein (MBNL1). Sequestration of splicing factors results in the mis-splicing of some pre-mRNAs. Small molecules that rescue the mis-splicing in the DM1 cells have drawn attention as potential drugs to treat DM1. Herein we report a new molecule JM642 consisted of two 1,3-diaminoisoquinoline chromophores having an auxiliary aromatic unit at the C5 position. JM642 alternates the splicing pattern of the pre-mRNA of the Ldb3 gene in the DM1 cell model and Clcn1 and Atp2a1 genes in the DM1 mouse model. In vitro binding analysis by surface plasmon resonance (SPR) assay to the r(CUG) repeat and disruption of ribonuclear foci in the DM1 cell model suggested the binding of JM642 to the expanded r(CUG) repeat in vivo, eventually rescue the mis-splicing.