Stereospecific polymerization of isobutyl vinyl ether. III. Polymerization with VCl3 • LiCl

The polymerization of isobutyl vinyl ether by vanadium trichloride in n-heptane was studied. VCl₃ ? LiCl was prepared by the reduction of VCl₄ with stoichiometric amounts of BuLi. This type of catalyst induces stereospecific polymerization of isobutyl vinyl ether without the action of trialkyl aluminum to an isotactic polymer when a rise in temperature during the polymerization was depressed by cooling. It is suggested that the cause of the stereospecific polymerization might be due to the catalyst structure in which LiCl coexists with VCl₃, namely, VCl₃ ? LiCl or VCl₂ ? 2LiCl as a solid solution in the crystalline lattice, since VCl₃ prepared by thermal decomposition of VCl₄ and a commercial VCl₃ did not produce the crystalline polymer and soluble catalysts such as VCl₄ in heptane and VCl₃ ? LiCl in ether solution did not yield the stereospecific polymer. It was found that some additives, such as tetrahydrofuran or ethylene glycol diphenyl ether, to the catalyst increased the stereospecific polymerization activity of the catalysts. Influence of the polymerization conditions such as temperature, time, monomer and catalyst concentrations, and the kind of solvent on the formed polymer was also examined.     

Synthesis of human renin inhibitory peptides, angiotensinogen transition-state analogs containing a retro-inverso amide bond

The experimental details for the synthesis of human renin inhibitors are described. In order to avoid metabolic degradation of the Phe-His (P3-P2) amide bond in transition-state analogs, structurally modified acyl residues (P4-P3) were incorporated into the inhibitors. Compound 1a, which contained 2-(1-naphthylmethyl)-3-(N-phenethylcarbamoyl)propionyl residue (P4-P3) with a retro-inverso amide bond, L-histidine, and norstatine isoamylamide residue (P1-P1) as a transition-state mimic, had potent human renin inhibitory activity, and it lowered blood pressure when administered orally to common marmosets.     

Analysis of Quantum Rod Diffusion by Polarized Fluorescence Correlation Spectroscopy

To measure the polarization dependence of fluorescent probes, a confocal-microscope-based polarized fluorescence correlation spectroscopy system was developed, and the polarization dependence on the rotational diffusion of well-defined quantum rods (Qrods) was investigated and characterized. The rotational diffusion region of the Qrods was observed over a time range of less than 10^?5 s in a water solution, and the rotational diffusion parameters were extracted using a rotational diffusion model in which the viscosity of the solution media was varied. Our work demonstrated that polarized fluorescence correlation spectroscopy (FCS) is useful for investigating both the rotational and translational diffusion of fluorescent probes.     

Photon number squeezing of ultrabroadband laser pulses generated by microstructure fibers

To the best of our knowledge, we demonstrate for the first time the generation of photon number squeezing by spectral filtering for ultrabroadband light generated by microstructure fibers at 800 nm. A maximum squeezing of 4.6 dB is observed, corresponding to 10.3 dB after correcting for detection losses. We numerically analyzed the quantum dynamics of ultrashort laser pulse propagation through optical fibers by solving a nonlinear quantum Schr?dinger equation that included Raman scattering, especially for the quantum correlation of photon number fluctuation among frequency modes in broadband pulses.     

Imprinting modulates processing of visual information in the visual wulst of chicks

Background  

Imprinting behavior is one form of learning and memory in precocial birds. With the aim of elucidating of the neural basis for visual imprinting, we focused on visual information processing.     

Observation of D+(s)K- and evidence for D+(s)pi- final states in neutral B decays

We report the first observation of a B meson decay that is not accessible by a direct spectator process. The channel B(0)-->D(+)(s)K- is found in a sample of 85 x 10(6) BB; events, collected with the Belle detector at KEKB, with a branching fraction B(B(0)-->D(+)(s)K-)=(4.6(+1.2)(-1.1)+/-1.3) x 10(-5). We also obtain evidence for the B0-->D(+)(s)pi(-) decay with branching fraction B(B0-->D(+)(s)pi(-))=(2.4(+1.0)(-0.8)+/-0.7) x 10(-5). This value may be used to extract a model-dependent value of |V(ub)|.     

Luminescence enhancement of ZnO nanoparticles on metal surface

We have studied luminescence enhancement of zinc oxide (ZnO) nanoparticles with the average size of 30 nm on several metal surfaces at low temperatures. Bandedge luminescence originated from bound exciton (BE) annihilation is observed at 3.360 eV, and strongly depends on the kind and surface roughness of metal. The luminescence intensity is about 10 times larger for Ag surface than that for quartz surface. Furthermore, the luminescence increases remarkably when the roughness of Ag surface is almost the same as the particle size. The intensity ratio of the fast decay component to the slow one decreases for Ag surface compared with quartz. These results suggest that the luminescence enhancement is partially attributed to suppressing of the nonradiative recombination process in ZnO nanoparticles on metal surface.     

Spin Excitations in the Field-Induced Phase of the Quasi-One-Dimensional S = 1 Heisenberg Antiferromagnet NDMAP

The S = 1 quasi-one-dimensional Heisenberg antiferromagnet [Ni(C₅H₁₄N₂)₂N₃](PF₆), abbreviated as NDMAP, has been studied by electron spin resonance in a magnetic field above the critical field (H _c). We studied angular and frequency dependences of spin excitations. The angular dependence of the spin excitations in the vicinity of H _c is explained well by a phenomenological field theory, but the agreement between the experiment and the calculation is not satisfactory above 10 T. In high magnetic fields above 15 T, we obtained some characteristic spin excitations which are well explained by conventional antiferromagnetic resonance modes. These results suggest that the spin excitations change from a quantum state to a classical one due to the suppression of quantum fluctuations by high magnetic fields.     

Electronic structures of imidazolium-based ionic liquids

Electronic structures of ionic liquids formed by 1-buthyl-3-alkylimidazolium ion [C_nmim]⁺ (n = 4 and 8) with various inorganic and organic anions have been investigated by ultraviolet photoemission, X-ray photoemission, inverse photoemission and soft X-ray emission spectroscopies (SXES). The comparison of the calculated density of states with the observed spectra revealed that the molecular orbital energies of these ionic liquids are significantly affected by the electrostatic Madelung potential among the ions. The SXES results clearly show that the both highest occupied and lowest unoccupied states of [C₄mim]⁺PF₆⁻ are derived from the cation as a result of strong Madelung potential. On the other hand, the SXES results show the valence electronic structures of ionic liquids with larger anion molecules, [C_nmim]⁺Tf₂N⁻ and [C_nmim]⁺OTf⁻ are contributed from the both cation and anion.