Synthesis of a lignan skeleton via nickel- and palladium-phosphine complex catalyzed grignard coupling reaction of halothiophenes

A lignan skeleton is prepared in good yield through desulfurization of 3,4-dibenzyl-thiophene or 2,5-diaryl-3,4-dimethylthiophenes which are obtained by the nickel- or palladium-phosphine complex catalyzed Grignard cross-coupling reaction of halothiophenes.     

Crystallinity of bulk polyacetylene

The fine structure of bulk trans-polyacetylene (PA) was investigated by x-ray diffraction. The degree of crystallinity 0.81, determined by Ruland's method, was significantly higher than the value for linear polyethylene. The disorder parameter k was 5, which is much larger than the value for polyethylene. These results led us to propose that PA crystals are more disordered than PE crystals owing to the higher rigidity of PA chains. Small-angle x-ray diffraction indicated that the crystal morphology is of the extended-chain type rather than lamellar. All results obtained in this work showed that the fine structure of PA bulk is such as to facilitate electrical conduction of bulk PA.     

Effects of extension on the gas permeability of hard elastic polypropylene film

Permeabilities of He, N₂, O₂, Ar, and CO₂ in stretched hard-elastic polypropylene film exhibiting extraordinarily high elasticity were measured as functions of temperature, pressure, and extension ratio. The permeability decreases slightly for strains of 10% or less, increases abruptly for strains from 15% to 30%, and then increases gradually for strains up to 100%. In recovery from extension, changes in permeability are similar to those in extension. The gas permeation mechanism is of the solution-diffusion type for extensions less than 15%. Above 15% extension, the mechanism involves permeation through voids created during deformation. The apparent mean pore size, estimated from the gas permeation, is very large at comparatively small extensions, and decreases with increasing extension. The change in specific volume accompanying extension of the sample indicates that only a very small fraction of the voids are interconnected to form channels that traverse the thickness of the film.     

Composite lattice pattern formation in a wide-aperture thin-slice solid-state laser with imperfect reflective ends

We observed self-formations of multiple lasing channels and two-dimensional lasing patterns consisting of composite local modes having different lasing frequencies in a laser-diode-pumped wide-aperture thin-slice solid-state laser with imperfect reflective end surfaces. Global patterns resembling higher-order Hermite-Gaussian modes or possessing N-fold rotational symmetries were experimentally shown to appear due to the standard polished surface roughness of closely spaced reflective ends and nonlinear modal interactions.     

Estimation of the orientation of heme in cytochrome C immobilized on a carboxylate-terminated alkanethiol monolayer on a au electrode by the use of electroreflectance spectroscopy with polarized light incidence

Electroreflectance (ER) spectroscopy was used for the estimation of the orientation of heme in a horse heart cytochrome c molecule immobilized on a self-assembled monolayer of 11-mercaptoundecanoic acid on both polycrystalline gold (Au) and single crystalline Au(111) electrodes. The intensity ratio of the ER signal of p-polarized incident light against s-polarized incident light as a function of the incident angle of the light was analyzed in two ways: a doubly degenerate transition for the Soret absorption band of the heme was assumed in one, and the anisotropy of the two orthogonal transitions was taken into account in the other. The doubly degenerate model failed in the expression of the experimental data, pointing to the existence of the anisotropy. Two orthogonal in-plane linear electric dipoles with different magnitudes were assumed to be responsible for the Soret band absorption in a new analysis procedure. This enabled us to fit the experimental data closely to the simulated data. The result revealed that the heme plane is near-vertical to the electrode surface. The need of clarification of the anisotropic heme transition was invoked.     

Conductive polymer-carbon-imidazolium composite: a simple means for constructing solid-state dye-sensitized solar cells

A clay-like conductive material comprising polyaniline-loaded carbon black particles and an ethyleneoxide-substituted imidazolium iodide was prepared. The material was sandwiched between dye-coated porous TiO2 and counter-electrode to form a solid-state dye-sensitized solar cell, which works with overall conversion efficiencies of 3.48% and 4.07% for AM 1.5, 100 mW cm(-2) and 23 mW cm(-2) irradiation, respectively.     

Heteropolynuclear complexes of 3,5-dimethylpyrazolate [Pt2M4(Me2pz)8] (M = Ag, Cu). Highly luminescent character of the triplet excited state based on mixed-metal cores

The platinum dimer and heteropolynuclear platinum complexes of 3,5-dimethylpyrazolate, [Pt2M4(mu-Me2pz)8] [M = H (1), Ag (2), Cu (3)], were synthesized and structurally characterized. They exhibit yellow, sky-blue, and orange luminescence, respectively, in the solid state. The absorption bands of 2 and 3 are mainly assigned to the combination of the metal-metal-to-ligand charge-transfer and [Pt2 --> Pt2M4] transitions by the time-dependent density functional theory (DFT) method. DFT calculations also indicate that the emissive states of 2 and 3 are 3[Pt2 --> Pt2Ag4] and 3[Cu(d) --> Pt2Cu4], respectively.     

Hybrid molecular material exhibiting single-molecule magnet behavior and molecular conductivity

Two unique materials based on Mn4 single-molecule magnet (SMM) clusters (ST=9) and integer or non-integer average valent platinum maleonitriledithiolate (mnt2-) complexes, [{MnII2MnIII2(hmp)6(MeCN)2}{Pt(mnt)2}2][Pt(mnt)2]2.2MeCN (1) and [{MnII2MnIII2(hmp)6(MeCN)2}{Pt(mnt)2}4][Pt(mnt)2]2 (2), were synthesized by the material diffusion method and electrochemical oxidation, respectively (hmp-=2-hydroxymethylpyridinate). 1 and 2 are comprised of four and six [Pt(mnt)2]n- units, respectively, in addition to a common MnII2MnIII2 double-cuboidal unit, [MnII2MnIII2(hmp)6(MeCN)2]4+ (hereinafter [Mn4]4+). Among the [Pt(mnt)2]n- units, two units in 1 and four units in 2 are coordinated with the [Mn4]4+ unit, forming a 1D chain of {-[Mn4]-[Pt(mnt)2]2-} for 1 and a discrete subunit of {[Pt(mnt)2]2-[Mn4]-[Pt(mnt)2]2} for 2. The other two [Pt(mnt)2]n- units, occupying void space of the packing, form a stacking column with the coordinating [Pt(mnt)2]n- units, finally constructing hybrid frames of aggregates consisting of [Mn4]4+ units and [Pt(mnt)2]n- units. Electronic conductivity measurements revealed that 1 is an insulator and 2 is a semiconductor with sigma=0.22 S.cm(-1) at room temperature and an activation energy of 136 meV. Detailed magnetic measurements proved that the [Mn4]4+ units in 1 and 2 behave as SMMs with an ST=9 ground state at low temperatures. There is no significant interaction between [Mn4]4+ units and [Pt(mnt)2]n- units, but interactions between localized spins of [Pt(mnt)2]n- were detected even in 2 at low temperatures where the conductivity is electronically insulated. 2 is the first example of a hybridized material exhibiting SMM behavior and electronic conductivity.     

Catalytic behavior of tris(2,2'-bipyridine)iron(II) complex in chemiluminescence reaction of luminol in reversed micellar medium of cetyltrimethylammonium chloride

Tris(2,2'-bipyridine) complex of iron(II) was found to cause an increase in the chemiluminescence (CL) emission of luminol dispersed in the reversed micellar medium of cetyltrimethylammonium chloride (CTAC) in 1:1 (v/v) dichloromethane-cyclohexane/water, when the iron(II) complex in dichloromethane was mixed directly with the reversed micellar solution containing luminol. Visible absorption measurements showed that, when dispersed in the CTAC reversed micellar medium, the iron(II) complex dissociates easily. In the reverse micelle, subsequently the free iron(II) ion produced may catalyze the CL oxidation of luminol even in the absence of hydrogen peroxide. The CL emission produced under the optimized experimental conditions was detectable at a minimum iron(II) concentration of 1.0 x 10(-9) M using a flow injection system.