Direct Estimation of the Surface Location of Immobilized Functional Groups for Concerted Catalysis Using a Probe Molecule

The location of active sites during concerted catalysis by a metal complex and tertiary amine on a SiO₂ surface is discussed based on the interaction between the functionalized SiO₂ surface and a probe molecule, p‐formyl phenylboronic acid. The interactions of the probe molecule with the surface functionalities, diamine ligand, and tertiary amine, were analyzed by FT‐IR and solid‐state ¹³C and ¹¹B MAS NMR. For the catalyst exhibiting high 1,4‐addition activity, the diamine ligand and tertiary amine base exist in closer proximity than in the catalyst with low activity.     

Properties of the πh_(9/2)  νi_(13/2) band in odd-odd ~(188)Au

A new rotational band has been identified and assigned to 188Au for the first time using the 173Yb(19F,4nγ) reaction at the beam energies of 86 and 90 MeV. This band is proposed to be built on the πh9/2  νi13/2 configuration by comparing the band properties with known bands in neighboring nuclei. The prolate-to-oblate shape transition through triaxial shape has been proposed to occur around 188Au for the πh9/2  νi13/2 bands in odd-odd Au isotopes on the basis of total Routhian surface (TRS) calculations.     

Detection of parametric resonance of trapped ions for micromotion compensation

We have detected excess micromotion of trapped ions by modulating the trapping voltage. This radio-frequency (rf) modulation induces parametric resonance and excites secular motion of the trapped ions when they possess excess motion. This technique has been applied to laser-cooled ions in a linear rf trap and it provides optimum values for compensating the trapping field. We found that the technique has sensitivity equal to or greater than the conventional method for detecting excess micromotion. Because any laser propagation direction can be used, this method is expected to be applied to surface-electrode traps.     

Effects of crystalline grain size and packing ratio of self-forming core/shell nanoparticles on magnetic properties at up to GHz bands

Self-forming core/shell nanoparticles of magnetic metal/oxide with crystalline grain size of less than 40 nm were synthesized. The nanoparticles were highly concentrated in an insulating matrix to fabricate a nanocomposite, whose magnetic properties were investigated. The crystalline grain size of the nanoparticles strongly influenced the magnetic anisotropy field, magnetic coercivity, relative permeability, and loss factor (tan δ=μ″/μ′) at high frequency. The packing ratio of the magnetic metallic phase in the nanocomposite also influenced those properties. High permeability with low tan δ of less than 1.5% at up to 1 GHz was obtained in the case of the nanoparticles with crystalline grain size of around 15 nm with large packing ratio of the nanoparticles.     

Mass balance method for purity assay of phthalic acid esters: development of primary reference materials as traceability sources in the Japan Calibration Service System

Purity assay of high-purity materials (HPMs) of phthalic acid esters (PAEs) was carried out by means of a mass balance method. In this method, chromatographic methods such as gas chromatography-flame ionization detector (GC-FID) and/or high-performance liquid chromatography (HPLC) in combination with other methods such as Karl-Fischer (KF) titration and vacuum evaporation (VE) were applied. The sum of the impurities estimated by these methods allowed the estimation of the purity of the main component by difference. Seven PAEs with varying side chain structures and levels of impurities were analysed on a systematic way in which impurities were classified into several groups in terms of their abundance, availability of qualitative information and availability of authentic compounds, etc. The absolute quantity of each impurity was determined by GC-FID and/or HPLC based on the calibration made by the authentic compounds of impurities whenever available. The purities in mass fraction of these PAEs were certified at the National Metrology Institute of Japan (NMIJ), and the PAEs were registered as primary reference materials playing an essential role in linking the metrological traceability of the Japan Calibration Service System (JCSS) to the International System of Units (SI).     

Solvent-induced selectivity switching: intermolecular allylsilylation, arylsilylation, and silylation of alkynes over montmorillonite catalyst

Proton-exchanged montmorillonite showed catalytic activity for intermolecular allylsilylation, arylsilylation, and terminal silylation of alkynes with allylsilanes. The reaction selectivity greatly depended on the solvent used. Reactions proceeded with various terminal alkynes and allylsilanes in good to moderate yields. The reaction pathways involving cationic Si species on the montmorillonite surface were also investigated.     

Topological aspects of excitons in artificial structure

The exciton properties of thin nanotube structures are investigated theoretically. Anisotropic size dependencies have been found in the exciton binding energy, the kinetic energy for the relative motions of an electron and a hole, and the wavefunction. These anisotropies arise from the different boundary conditions in the tube-length and circumferential directions, namely, the topological features of nanotubes. We also found that it is possible to change the topology of exciton wavefunctions by varying the tube-length and the tube-radius. These findings suggest that the optical properties of nanotubes such as oscillator strength or nonlinear susceptibilities can be controlled by tuning the structural parameters, thus yielding a novel guiding principle for designing optical functional materials.     

Structural phase transition,antiferromagnetism and two superconducting domes in LaFeAsO_(1-x)F_x(0<x≤0.75)

We report~(75) As nuclear magnetic resonance(NMR)/nuclear quadrupole resonance(NQR) and transmission electron microscopy(TEM) studies on LaFeAsO_(1-x)F_x. There are two superconducting domes in this material. The first one appears at 0.03 ≤ x ≤0.2 with T_c~(max) = 27 K, and the second one at 0.25 ≤x≤0.75 with T_c~(max) = 30 K. By NMR and TEM, we demonstrate that a C4-to-C2 structural phase transition(SPT) takes place above both domes, with the transition temperature T_s varying strongly with x. In the first dome, the SPT is followed by an antiferromagnetic(AF) transition, but neither AF order nor low-energy spin fluctuations are found in the second dome. By ~(75) As nuclear spin-lattice relaxation rate(1/T_1) measurements, we find that AF order and superconductivity coexist microscopically in LaFeAsO_(0.97) F_(0.03). In the coexisting region, 1/T_1 decreases at T_c but becomes proportional to T below 0.6 T_c, indicating gapless excitations. Therefore, in contrast to the early reports, the obtained phase diagram for x ≤ 0.2 is quite similar to the doped BaFe_2As_2 system. The electrical resistivity p in the second dome can be fitted by ρ = ρ0 + AT~n with n = 1 and a maximal coefficient A at around xopt = 0.5-0.55 at which T_s extrapolates to zero and Tc is the maximal, which suggests the importance of quantum critical fluctuations associated with the SPT. We have constructed a complete phase diagram of LaFeAsO_(1-x)F_x, which provides insight into the relationship between SPT, antiferromagnetism and superconductivity.