1.1-GHz continuous-wave EPR spectroscopy with a frequency modulation method

Continuous-wave EPR spectroscopy using a frequency modulation (FM) scheme was developed. An electronically tunable resonator and an automatic tuning control (ATC) system were used. Using the FM scheme instead of magnetic field modulation, we detected EPR absorption at the first derivative mode. We used a microwave frequency of 1.1 GHz in the present experiment. Similar signal-to-noise ratios were obtained with conventional field modulation and the FM method, and a low-quality factor EPR resonator was not necessary to suppress the significant microwave reflection from the resonator. The FM method with a tunable resonator may be an alternative solution to achieving phase-sensitive detection, when the side-effects of magnetic field modulation, such as microphonic noise and mechanical vibration, are detrimental for EPR detection.     

Observation of structures of chain vortices inside anisotropic high- Tc superconductors

In order to elucidate the formation mechanism of unconventional arrangements of vortices in high- Tc superconducting thin films at an inclined magnetic field to the layer plane, we investigated the structures of vortex lines inside the films by Lorentz microscopy using our 1-MV field-emission electron microscope. Our observation results concluded that vortex lines are tilted to form linear chains in YBaCu3O(7,8). Vortex lines in the chain-lattice state in Bi2Sr2CaCu2O(8+delta), on the other hand, are all perpendicular to the layer plane, and therefore only vortices lined up along Josephson vortices form chains.     

Entropy-Driven Cooperativity in the Guest Binding of an Octaphosphonate Bis-cavitand

Uncommon entropy-driven cooperativity is reported in the guest binding of an octaphosphonate bis-cavitand. Isothermal titration calorimetry determined the thermodynamic parameters for the 1:2 host–guest binding of bis-cavitands with ammonium guests in methanol, ethanol, 2-propanol, and chloroform. Chloroform drove uncommon entropy-driven cooperative binding, whereas the alcohols resulted in enthalpy-driven noncooperative binding. ¹H NMR studies revealed that each cavity contained six water molecules in chloroform, which were liberated on guest binding. The enthalpy–entropy compensation relationship produced a large positive intrinsic entropy in chloroform, which implies that water desolvation causes a considerable entropic gain by paying an enthalpic penalty due to breaking the hydrogen-bonding networks of the water clusters.     

Implementation of visual data mining for unsteady blood flow field in an aortic aneurysm

Abstract  

This study was performed to determine the relations between the features of wall shear stress and aneurysm rupture. For this purpose, visual data mining was performed in unsteady blood flow simulation data for an aortic aneurysm. The time-series data of wall shear stress given at each grid point were converted to spatial and temporal indices, and the grid points were sorted using a self-organizing map based on the similarity of these indices. Next, the results of cluster analysis were mapped onto the real space of the aortic aneurysm to specify the regions that may lead to aneurysm rupture. With reference to previous reports regarding aneurysm rupture, the visual data mining suggested specific hemodynamic features that cause aneurysm rupture.     

High-performance liquid chromatographic determination of fluvoxamine and fluvoxamino acid in human plasma.

A high-performance liquid chromatographic (HPLC) method has been developed for the simultaneous determination of fluvoxamine and its major metabolite fluvoxamino acid in plasma. Fluvoxamine and fluvoxamino acid in plasma were extracted using a C18 bonded-solid phase cartridge, followed by C4 reversed-phase HPLC separation.Fluvoxamine, fluvoxamino acid and moperone as an internal standard were detected by ultraviolet absorbance at 254 nm. It was possible to determine both fluvoxamine and fluvoxamino acid in the concentration range of 25.0-200.0 ng/mL, respectively. The detection limits of both fluvoxamine and fluvoxamino acid were 10.0 ng/mL, respectively. The mean recoveries of fluvoxamine and fluvoxamino acid added to plasma were more than 94.0% and 96.5%, with a coefficient of variation of less than 7.6% and 8.2%, respectively. This method has been used for the simultaneous determination of steady-state plasma concentration (Css) of fluvoxamine and fluvoxamino acid in depressive patients treated with 200 mg of oral fluvoxamine dosed as 100 mg twice-daily. The Css values of fluvoxamine and fluvoxamino acid in twelve Japanese patients were showed individual variations, which were in the range of 48.3-532.9 ng/ml and 35.6-307.1 ng/ml, respectively.     

Frontispiece: Square-Planar Anionic Pt0 Complexes

A T-shaped Pt⁰ complex with a diphosphine-borane (DPB) ligand was prepared. The Pt→B interaction enhances the electrophilicity of the metal and triggers the addition of Lewis bases to give the corresponding tetracoordinate complexes. For the first time, anionic Pt⁰ complexes are isolated and structurally authenticated. X-ray diffraction analyses show the anionic complexes [(DPB)PtX]⁻ (X=CN, Cl, Br, I) to be square-planar. The d¹⁰ configuration and Pt⁰ oxidation state of the metal were unambiguously established by X-ray photoelectron spectroscopy and DFT calculations. The coordination of Lewis acids as Z-type ligands is a powerful mean to stabilize elusive electron-rich metal complexes and achieve uncommon geometry.     

Electron Spin Resonance Spectroscopy of Gamma-Irradiated Glucose Polymers

Using electron spin resonance (ESR) spectroscopy, we revealed the irradiation-induced radicals in cellulose and starch. Before gamma-ray irradiation, no ESR signals were observed in both the glucose polymers. However, after gamma-ray irradiation, a singlet at g = 2.0 was observed, and a pair of side signals appeared simultaneously. The side signals were found at the symmetric field positions at both sides of the singlet signal. The side signals were visible in cellulose but not in starch. The side signals are found to be a precise indicator for irradiation effects in cellulose. They are originated from neither the peroxide radical of glucose polymer nor the so-called cellulosic radicals. By the simulation method, we found that the side signals are originated from a triplet due to a hyperfine interaction with two protons. By the theoretical simulation, we revealed that the signal undergo the rotational motions rather than rigid limit state (or no motion).     

Selective adsorption of atomic hydrogen on a h-BN thin film

The adsorption of atomic hydrogen on hexagonal boron nitride (h-BN) is studied using two element-specific spectroscopies, i.e., near-edge x-ray absorption fine structure (NEXAFS) spectroscopy and x-ray photoelectron spectroscopy (XPS). B K-edge NEXAFS spectra show a clear change in the energy region of the π* band before and after reaction with atomic deuterium. On the other hand, N K-edge NEXAFS spectra show only a little change. B 1s XPS spectra show a distinct component at the low binding energy side of a main component, while N 1s XPS spectra show peak broadening at the high binding energy side. These experimental results are analyzed by the discrete variational Xα method with a core-hole effect and are explained by a model in which hydrogen atoms are preferentially adsorbed on the B sites of h-BN. Based on the experimental and theoretical results, we propose a site-selective property of BN material on adsorption of atomic hydrogen.