Asymmetric Hydrogenation of 3‐Amido‐2‐arylpyridinium Salts by Triply Chloride‐Bridged Dinuclear Iridium Complexes Bearing Enantiopure Diphosphine Ligands: Synthesis of Neurokinin‐1 Receptor Antagonist Derivatives

We describe a most straightforward synthetic method for preparing neurokinin‐1 (NK1) receptor antagonist derivatives by asymmetric hydrogenation of 3‐amido‐2‐arylpyridinium salts using dinuclear iridium complexes with enantiopure diphosphine ligands, affording the corresponding chiral piperidines in high cis‐diastereoselectivity (>95:5) and moderately high enantioselectivity (up to 86%). Deprotection treatments afforded the NK‐1 receptor antagonist (+)‐CP‐99,994 (83% ee). In addition, we observed unique additive effects of 10‐camphorsulfonic acid in the asymmetric hydrogenation of 3‐amido‐2‐arylpyridinium salts.

     

Iridium‐Catalyzed Asymmetric Hydrogenation of Tosylamido‐Substituted Pyrazines for Constructing Chiral Tetrahydropyrazines with an Amidine Skelton

Dinuclear triply chloro‐bridged iridium(III) complexes bearing chiral diphosphine ligands catalyze the asymmetric hydrogenation of tosylamido‐substituted pyrazines to give the corresponding chiral tetrahydropyrazines with an amidine skeleton in high yield and with high enantioselectivity. Addition of N,N‐dimethylanilinium bromide enhanced the catalytic activity of the iridium complexes and also increased the enantioselectivity of the products by trapping the hydrogenated amine products with HBr from N,N‐dimethylanilinium bromide. The amidine skeleton of the products could be transformed to give chiral piperazinones and piperazines without loss of enantioselectivity.

     

Influence of γ Irradiation on the Mechanical Strength and In Vitro Biodegradation of Porous Hydroxyapatite/Collagen Composite

Gamma irradiation treatment (GIT) is the most widely used sterilization method for biomaterials in spite of the potential to degrade polymers. The adverse effects of GIT on the mechanical properties and biological stabilities of porous hydroxyapatite/collagen (HAp/Col) composites were investigated in this study. Those properties of a porous HAp/Col composite stabilized by dehydrothermal treatment (DHT) drastically decreased by GIT in the same manner as conventional pure Col materials. DHT after GIT could partially eliminate the adverse effects, due to the introduction of cross-linkage among the degraded Col molecules.     

TETHER-LINKED [60]FULLERENE-DONOR DYADS

A series of [60]fullerene bis-adducts having a π-electron-rich aromatic ring as a donor in a face-to-face arrangement were synthesized by the bis-cyclopropanation of [60]fullerene with tether-linked bis-malonates. One of the bis-adducts showed a photoinduced intramolecular electron transfer which caused the dramatic quenching of its fluorescence in a polar solvent.     

Current control of a PWM power amplifier by an approximate 2-degree-of-freedom digital controller

There is a need for robust current control of a pulse width modulation (PWM) power amplifier whose transient response characteristics do not deteriorate with extensive load changes and/or direct-current power supply voltage changes. In this article, we propose a digital robust controller with bumpless mode switching to control the current of a PWM power amplifier to satisfy the demands and extend the range of an inductive load width. It is necessary to measure the value of the load in order to implement this bumpless mode switching automatically depending on the load range. Therefore, a method of estimating the inductive load is shown. The bumpless mode switching is automatically performed by estimating an inductive value without specifying the value of the inductive load beforehand. That is, the value of the inductive load is estimated during the DDC execution, and the control mode is automatically switched bumplessly according to this estimated value. A digital controller equipped with inductance estimation and bumpless mode switching is realized by a DSP. Some experiments show that the digital controller with the proposed bumpless mode switching can satisfy larger specifications.     

Measurements of gamma-ray emission probabilities of 241, 243Am and 239Np

Gamma-ray emission probabilities of ^{241, 243}Am and ²³⁹Np have been precisely measured with gamma- and alpha-ray spectroscopic methods. The activities of the samples were determined by measuring alpha particles using a Si semiconductor detector. Gamma rays emitted from the samples were measured with a planar type High-Purity Germanium (HPGe) detector. An efficiency curve of the HPGe detector was derived with uncertainties from 0.7% to 2.5% by combining measured efficiencies and Monte Carlo simulation. The gamma-ray emission probabilities for the major gamma rays of these nuclides were determined with uncertainties less than 1.2%.     

LAP-1 cold preservation solution for isolation of high-quality human pancreatic islets

The purpose of this study was to determine the precision of proprioceptive localization of the hand in humans. We derived spatial probability distributions which describe the precision of localization on the basis of three different sources of information: proprioceptive information about the left hand, proprioceptive information about the right hand, and visual information. In the experiment subjects were seated at a table and had to perform three different position-matching tasks. In each task, the position of a target and the position of an indicator were available in a different combination of two of these three sources of information. From the spatial distributions of indicated positions in these three conditions, we derived spatial probability distributions for proprioceptive localization of the two hands and for visual localization. For proprioception we found that localization in the radial direction with respect to the shoulder is more precise than localization in the azimuthal direction. The distributions for proprioceptive localization also suggest that hand positions closer to the shoulder are localized more precisely than positions further away. These patterns can be understood from the geometry of the arm. In addition, the variability in the indicated positions suggests that the shoulder and elbow angles are known to the central nervous system with a precision of 0.6-1.1 degrees. This is a considerably better precision than the values reported in studies on perception of these angles. This implies that joint angles, or quantities equivalent to them, are represented in the central nervous system more precisely than they are consciously perceived. For visual localization we found that localization in the azimuthal direction with respect to the cyclopean eye is more precise than localization in the radial direction. The precision of the perception of visual direction is of the order of 0.2-0.6 degrees.     

Synthesis of a Ceramic Acid of Tungstated Alumina more Active than Silica-alumina for Decompositions of Cumene, Ethylbenzene, and Toluene

A ceramics acid, calcined at temperatures above 1000 °C, was obtained by impregnating aluminum hydroxide with aqueous ammonium metatungstate followed by calcining in air at 1000–1200 °C (1–5 wt% W); its acidity and catalytic activity for decompositions of toluene, ethylbenzene, and cumene are higher than those of silica-alumina.