Synthesis of redox-active, intramolecular charge-transfer chromophores by the [2+2] cycloaddition of ethynylated 2H-cyclohepta[b]furan-2-ones with tetracyanoethylene

Ethynylated 2H-cyclohepta[b]furan-2-ones 5-15 have been prepared by Pd-catalyzed alkynylation of 3-iodo-5-isopropyl-2H-cyclohepta[b]furan-2-one (2) with the corresponding ethynylarenes or the reaction of 2-iodothiophene with 3-ethynyl-5-isopropyl-2H-cyclohepta[b]furan-2-one (4) under Sonogashira-Hagihara conditions. Compounds 5-15 reacted with tetracyanoethylene in a formal [2+2] cycloaddition reaction, followed by ring opening of the initially formed [2+2] cycloadducts, cyclobutenes, to afford the corresponding 1,1,4,4-tetracyanobutadienyl (TCBD) chromophores 16-26 in excellent yields. The intramolecular charge-transfer interactions between the 2H-cyclohepta[b]furan-2-one ring and TCBD acceptor moiety were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the novel TCBD derivatives 16-26 was examined by cyclic voltammetry and differential pulse voltammetry, which revealed multistep electrochemical reduction properties, depending on the number of TCBD units in the molecule. Moreover, a significant color change was observed by UV/Vis spectroscopy under electrochemical reduction conditions.     

Production of a positron microprobe using a transmission remoderator.

A production method for a positron microprobe using a beta+-decay radioisotope (22Na) source has been investigated. When a magnetically guided positron beam was extracted from the magnetic field, the combination of an extraction coil and a magnetic lens enabled us to focus the positron beam by a factor of 10 and to achieve a high transport efficiency (71%). A 150-nm-thick Ni(100) thin film was mounted at the focal point of the magnetic lens and was used as a remoderator for brightness enhancement in a transmission geometry. The remoderated positrons were accelerated by an electrostatic lens and focused on the target by an objective magnetic lens. As a result, a 4-mm-diameter positron beam could be transformed into a microprobe of 60 microm or less with 4.2% total efficiency. The S parameter profile obtained by a single-line scan of a test specimen coincided well with the defect distribution. This technique for a positron microprobe is available to an accelerator-based high-intensity positron source and allows 3-dimensional vacancy-type defect analysis and a positron source for a transmission positron microscope.     

A new reforming process based on CH4 decomposition using a hydrogen-permeating membrane reactor

A new reforming process was studied using Ni/SiO₂ with a hydrogen-permeating membrane reactor. Nickel catalyst supported on SiO₂ is highly active for CH₄?H₂O?O₂ reaction in membrane reactor and the reaction close to CH₄+0.35O₂+1.3H₂O→CO₂+3.3H₂ proceeds at 873 K. Since the selectivity to carbon and CO₂ increased and decreased with decreasing contact time respectively, it is considered that the reaction was started by decomposition of CH₄ followed by oxidation of C and water shift reaction. Therefore, the reaction mechanism was different from so-called autothermal reforming (ATR) reaction.     

Complex formation of amphiphilic polymers with azo dyes and their photoviscosity behavior

The hydrophobic interaction of amphiphilic copolymers, which contain 2-hydroxyethyl methacrylate(HEMA) and 1vinyl-2-pyrrolidone (VPy), with Methyl Orange (MO) was compared with that of HEMA-acrylamide (AAm) copolymers to deduce the correlation between their complexation ability in a photochromic azo dye and the photoviscosity effect in aqueous copolymer/dye complex solution. On the basis of the dialysis data and fluorometric analysis it appeared that the complexation dependence on HEMA content in the copolymers was due to the hydrophobic interaction between the polymer and the dye. For a comparable HEMA content AAm copolymers bound less MO than VPy copolymers. It was confiied by photoviscosity measurements that the conformation of the complex composed of photochromic azo dye and HEMA copolymer changed reversibly in response to the photo- and thermal isomerization of the dye. In HEMA-AAm copolymer systems the photoviscosity effect was small compared with that of HEMA-VPy copolymer systems. From these results it was concluded that the complexation ability of polymers due to the hydrophobic interaction was an important factor in producing a large photoinduced conformational change in water.     

An experimental study on effects of solid concentration and ζ-potential on pseudoplastic flow of suspensions

The pseudoplastic flow of suspensions, alumina or styrene-acrylamide copolymer particles in water or an aqueous solution of glycerin has been studied by the step-shear-rate method. The relation between the shear rate,D, and the shear stress,, in the step-shear-rate measurements, where the state of dispersion was considered to be constant, was expressed as = AD ^1/2 +CD. The effective solid volume fraction,ø _F, andA were dependent on the shear rate and expressed byø _F =aD ^b andA = D . Combining the above relations, the steady flow curve was expressed by = D ^{1/2 +} + ₀ (1 – a D ^b/0.74)^–1.85 D, where ₀ is the viscosity of the medium.With an increase in solid volume fraction and a decreases in the absolute value of the-potential, the flow behavior of the suspensions changed from Newtonian ( = = b = 0), slightly pseudoplastic ( = b = 0), pseudoplastic ( = 0) to a Bingham-like behavior.The change in viscosity of the medium had an effect on the change in the effective volume fraction.     

A highly stereocontrolled total synthesis of dysiherbaine

A total synthesis of dysiherbaine, a potent agonist of AMPA-KA type glutamate receptors, has been accomplished in completely stereocontrolled manner starting from tri-O-acetyl-D-galactal in 25 steps and in 3% overall yield.     

Peumusolide A, unprecedented NES non-antagonistic inhibitor for nuclear export of MEK

A new polyketide peumusolide A was disclosed as an unprecedented NES non-antagonistic inhibitor for nuclear export of MEK, a promising scaffold for antitumor agents with novel mechanism of action, from Peumus boldus Molina. The absolute stereostructure as well as optical purity was established by use of the two synthesized enantiomeric model lactones. In addition, the Δε values in their CD spectra were demonstrated to be the conclusive index for determination of not only configuration at C-3 but also optical purity of natural congeneric polyketides. Peumusolide A was revealed to show NES non-antagonistic action by the biotinylated probe and to inhibit proliferation of MEK-activated tumor cells selectively.     

Analytic non-integrable Hamiltonian systems and irregular singularity

We study a C ^∞-Liouville-integrable and analytic non-integrable Hamiltonian system. We will show that an irregular singular character plays a crucial role in the analytic non-integrability of the system. Partially supported by Grant-in-Aid for Scientific Research (No. 11640183), Ministry of Education, Science and Culture, Japan.