Redox-controlled, reversible rearrangement of a tris(2-pyridylthio)methyl ligand on nickel to an isomer with an “N,S-confused” 2-pyridylthiolate arm

Interchange between the nickel +2 and +3 oxidation states precisely controls the reversible rearrangement of the tris(2-pyridylthio)methanide (tptm) ligand in the organometallic nickel(II) complex [{Ni(μ-Br)-(tptm)}(2)] (2). Oxidation of 2 first gives the corresponding Ni(III) complex [{Ni(μ-Br)(tptm)}(2)][PF(6)](2) (4). However, in solution the tptm ligand in 4 slowly undergoes a rearrangement, in which the N and S atoms of one of the pyridylthiolate arms exchange Ni and C bonding partners, thereby resulting in an "N,S-confused" isomer of tptm in the product, [NiBr(bpttpm)]PF(6) (5; bpttpm= bis(2-pyridylthio)(2-thiopyridinium)-methyl). Reduction of 5 reverses this ligand rearrangement and 2 is reformed quantitatively. The individual steps involved in these unusual ligand rearrangements were investigated by a number of methods, including voltammetric analysis, and a mechanism for this process is proposed. X-ray crystal structure determinations of the key compounds 2, 4 and 5 have been obtained.     

Dynamic behaviour attributed to chiral carbohydrate substituents of N-heterocyclic carbene ligands in square planar nickel complexes

Nickel complexes having acetylated glucopyranosyl group incorporated N-heterocyclic carbene (NHC) ligands with methyl or benzyl groups as an N-substituent exhibit two kinds of dynamic behaviours in solution (1)H NMR spectroscopy. One of the dynamic behaviours is attributed to the anti- and syn-rotamers, which occur by the rotation of the unsymmetrical NHC ligands around the axes of the Ni-C bonds. The other is attributed to the diastereomers of the syn-rotamers, which occur by opposite rotation of the imidazolylidene rings and the chiral carbohydrate group incorporated into the NHC ligands. Crystallographic analysis of the nickel complex having the NHC ligand with acetylated glucopyranosyl and benzyl groups as N-substituents showed CH-π interaction between the glucopyranosyl unit of each NHC ligand and the phenyl ring of the other NHC ligand in the complex in the solid state.     

Time regularity of the solutions to second order hyperbolic equations

We consider the Cauchy problem for a second order weakly hyperbolic equation, with coefficients depending only on the time variable. We prove that if the coefficients of the equation belong to the Gevrey class g^s₀\gamma^{s_{0}} and the Cauchy data belong to g^s₁\gamma^{s_{1}}, then the Cauchy problem has a solution in  g^s₀([0,T^*];g^s₁(\mathbbR))\gamma^{s_{0}}([0,T^{*}];\gamma^{s_{1}}(\mathbb{R})) for some T ^*>0, provided 1≤s ₁≤2−1/s ₀. If the equation is strictly hyperbolic, we may replace the previous condition by 1≤s ₁≤s ₀.     

Dependence of aerodynamic characteristics and flow pattern on surface structure of a baseball

In this report, the aerodynamic characteristics, such as lift and drag, of an official rubber baseball are studied experimentally by comparing the characteristics of a sphere having a smooth surface and those of spheres having different surface structures. In addition, the flow velocity distribution is measured quantitatively using the spark tracing method. From the obtained results, the flow patterns for these baseballs and the flow mechanism around a sphere have been clarified.     

Control of Slave EDFA with Master EDFA

We have demonstrated that the AGC signals generated in a master EDFA can be used to drive a slave EDFA, thus to make the slave EDFA work in AGC mode without its own AGC control electronics. This idea can be used to reduce the amplifier costs in a WDM network node.     

Double fluorescent labeling method used for a study on liposomes

Carboxyfluorescein (CF) and Calcein (CAL) have almost the same fluorescent spectrum. However, only CAL forms a nonfluorescent chelate with the Co2+ ion. It was proven that this phenomenon can be used for the fractional determination of CF and CAL. And this fractional determination method was available for a study on liposomes.     

Laser spectroscopy and optical pumping of alkali atoms in superfluid helium

In this paper, our recent works on the alkali atoms in superfluid helim (HeII) are reported. At first we mentions the laser-sputtering method for implantation, which is simple but is very efficient to produce various kinds of neutral atoms and molecules in HeII. Secondly, we report on the laser spectroscopy of alkali atoms in HeII. Optical excitation and emission spectra are found to be roughly explained by a spherical atomic bubble model, but the spectra corresponding to the D₂ lines indicate the quadrupole oscillation of the bubble shape. Optical pumping by a circularly polarized laser beam is found to produce perfect polarization, for both electron and nuclear spins. Using the rf-optical double resonance techniques, the magnetic and hyperfine resonances are observed. It is discussed also about the phenomena which have observed in the experiments done so far but have not been fully explained.     

Core-level photoemission of the Si(1 1 1)– -Ag surface using synchrotron radiation

The evolution of Si 2p core-level photoemission during a structural conversion from the Si (1 1 1)– -Ag to the Si(1 1 1)– -Ag superstructures induced by Ag adatoms adsorption at 140 K was studied using synchrotron radiation. The component from the top-layer Si-trimer atoms on the former surface was found to split into two components in the latter surface. The result is discussed in terms of a relaxation in some of the Si trimers induced by Ag adatoms sitting on the nearby Ag triangles of the -Ag substrate. The intensity ratio between the split components is a key to exclude some structure models proposed so far for the phases.