A facile chemical synthesis of cholest-4-en-3-one. Carbon-13 nuclear magnetic resonance spectral properties of cholest-4-en-3-one and cholest-5-en-3-one

This paper presents a simplified method for the chemical synthesis of cholest-4-en-3-one, which is a naturally occurring steroid and a salient intermediate in steroid chemistry. Pyridinium chlorochromate (PCC) in refluxing benzene has been found to be an effective and convenient reagent for the oxidation and concomitant isomerization of cholest-5-en-3β-ol (cholesterol) to cholest-4-en-3-one in high yield. Also described are the carbon-13 nuclear magnetic resonance spectral properties of cholest-4-en-3-one and of the isolated reaction intermediate cholest-5-en-3-one. Based on a paper presented at the Symposium on Plant and Fungal Sterols: Biosynthesis Metabolism and function held at the AOCS Annual Meeting, Baltimore, MD, April 1990.     

Sintering of the Mechanochemically Activated Powders of Hexagonal Boron Nitride

Pressureless sintering of hexagonal boron nitride (BN) was performed using a powder activated by mechano-chemical treatments. Physical properties of the sintered BN bodies depend on the type of starting powder and the conditions of the treatments. The BN body, which was obtained at 2000°C using an appropriate activated powder, was 99 wt% pure and was excellent in mechanical and physical properties, in spite of its low density (1.64 g/cm³).     

Back‐channel‐etched thin‐film transistor using c‐axis‐aligned crystal In–Ga–Zn oxide

Our crystalline In–Ga–Zn oxide (IGZO) thin film has a c‐axis‐aligned crystal (CAAC) structure and maintains crystallinity even on an amorphous base layer. Although the crystal has c‐axis alignment, its a‐axis and b‐axis have random arrangement; moreover, a clear grain boundary is not observed. We fabricated a back‐channel‐etched thin‐film transistor (TFT) using the CAAC‐IGZO film. Using the CAAC‐IGZO film, more stable TFT characteristics, even with a short channel length, can be obtained, and the instability of the back channel, which is one of the biggest problems of IGZO TFTs, is solved. As a result, we improved the process of manufacturing back‐channel‐etched TFTs.     

Effect of platelet-activating factor on lipoprotein lipase and blood lipids

We investigated the effect of platelet-activating factor (PAF) and of the PAF specific antagonist CV-6209 on plasma lipid metabolism, and particularly on post-heparin plasma lipolytic activity in male Wistar rats. Lipoprotein lipase (LPL) activity was enhanced by intravenous injection of PAF before intravenous injection of heparin when the PAF dose was low (0.2 μg/kg). PAF activated hepatic triacylglycerol lipase (HTGL) activity dose-dependently. Plasma triacylglycerols (TG) significantly decreased with the activation of LPL and/or HTGL. Plasma total cholesterol (TC) and phospholipid (PL) levels decreased at a low dose of PAF (0.2 μg/kg), but increased when higher doses were used. The PAF antagonist CV-6209 partially reversed the PAF induced effects on HTGL, TC and PL. Based on a paper presented at the Third International Conference on Platelet-Activating Factor and Structurally Related Alkyl Ether Lipids, Tokyo, Japan, May 1989.     

Liquefaction of subbituminous coals under apparently non-hydrogenative conditions

Reactivities of several coals of different ranks have been examined in degrading extractions with aromatic solvents under apparently non-hydrogenative reaction conditions. Pyrene and A240 pitch liquefied the fusible coals in high yields and the slightly-fusible coals in moderate yields, indicating the importance of fusibility in such liquefaction processes. A240-LS pitch is a powerful solvent for slightly-fusible coals. Considerable amounts of pyridine- or THF-soluble fractions were produced especially with A240-LS pitch. A240 pitch is a better solvent than pyrene for some slightly-fusible coals. However, the extent of depolymerization of liquefied coal, pyridine- or THF-solubility, was definitely inferior. Yields of such fractions are higher for lower-rank coals. The mechanism of coal liquefaction under apparently non-hydrogenative conditions is discussed with emphasis on the stabilization of thermal fragments derived from the coal.     

High-strength–high-modulus polyimide fibers II. Spinning and properties of fibers

The polyimides based on 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) described in Part I of this series were dissolved in p-chlorophenol and spun into fibers using a coagulating bath of ethanol. The fibers as spun had in general low tenacities and low moduli, but a heat treatment at 300–500°C under tension produced a remarkable increase in strength and modulus, and fibers with a tensile strength of 26 g/den (3.1 GPa) and an initial modulus higher than 1,000 g/den (120 GPa) could be obtained. Thus, the annealed fibers of polyimides are comparable to aramid fibers in mechanical properties. To heating in air and in the saturated steam, the polyimide fibers showed higher resistance than the aramid fibers. The polyimide fibers surpassed the aramid fibers in resistance to acid treatment and ultraviolet (UV) irradiation, but were inferior in resistance to alkali treatment. The annealed fibers of polyimides displayed distinct X-ray diffraction patterns. The chain repeat distance of 20.5 Å determined on the fibers of polyimide prepared from BPDA and o-tolidine, and 20.6 Å determined on the fibers of polyimide derived from BPDA and 3,4′-diaminodiphenyl ether are reasonable when the dimensions of monomeric units and the shapes of the molecular chains are considered. The X-ray reflections of both polyimide fibers were indexed satisfactorily on the basis of postulated unit cells.     

Aggregation arrestant pheromone of the German cockroach,Blattella germanica (L.) (Dictyoptera: Blattellidae): Isolation and structure elucidation of blattellastanoside-A and -B

The aggregation pheromone of the German cockroach,Blattella germanica, consists of attractant and arrestant, which can be detected by olfactometer and choice-chamber assay, respectively. Both were extracted from the frass-contaminated filter paper being used as a shelter. They were separated by solvent partition withn-butanol and water. The arrestant from then-butanol phase was purified by open column chromatography and then successive HPLC isolated two major arrestant components. Spectral evidence from SI-MS, HR-EI-MS, and NMR experiments with pulse techniques provided possible structures as 1-(6-chloro-4,5-epoxy-5-stigmast-3-yl)--d-glucopyranoside and 1-(6-chloro-5-hydroxy-5-stigmast-3-yl)--d-glu-copyranoside, denoted as blattellastanoside-A and blattellastanoside-B, respectively. They represented arrestant activity as median effective doses (ED₅₀) at 0.044 (A) and 3.2 (B) nmol on 1.0 cm² of Whatman No. 1 filter paper.     

One-step formation of ethyl methyl ketone from 1-butene and water on ultrastable Y-type zeolite catalyst

Proton exchanged ultrastable Y-type zeolite with silica/alumina = 40 showed a pronounced catalytic activity for the formation of ethyl methyl ketone directly from 1-butene and water. The formation rate of ethyl methyl ketone was much higher than those on MoO₃-based catalysts in the oxidation of 1-butene by oxygen. It was suggested that the basic site necessary for the formation of ethyl ketone directly from 1-butene and water would be the pentacoordinated Al.     

Depolymerization of poly(fluoroalkyl methacrylate-co-methyl methacrylate) as studied with thermogravimetry

Thermal behaviors of a few kinds of poly(fluoroalkyl methacrylate-co-methyl methacrylate) prepared by γ-ray copolymerization were investigated by using thermogravimetric measurements together with the intermittent analysis of the gaseous products. The thermal degradation of copolymers composed of one of fluoroalkyl methacrylates of the following structures: CH₂?C(CH₃)COOCH₂(CF₂CF₂)_nH, where n = 1,2, and 3, and methyl methacrylate proceeded according to the depolymerization mechanism reproducing the pristine component comonomers exclusively, but their thermograms in inert atmosphere showed the feature of a two-step reaction. In air, however, thermograms of copolymers did not show such a stepwise decrease in weight with the elevating temperature, and temperatures at which depolymerization was introduced shifted to a much higher region. The overall aspects of depolymerization of copolymers seemed to be much similar to that of fluoroalkyl methacrylate homopolymer previously reported, and the retardation of depolymerization by air was considered to be due mainly to the stabilization of once-formed polymer radicals by oxygen.     

Hydrophobic effects on protein/nucleic acid interaction: enhancement of substrate binding by mutating tyrosine 45 to tryptophan in ribonuclease Tl

Hydrophobic effects on binding of ribonuclease Tl to guaninebases of several ribonucleotides have been proved by mutatinga hydrophobic residue at the recognition site and by measuringthe effect on binding. Mutation of a hydrophobic surface residueto a more hydrophobic residue (Tyr45 – Trp) enhances thebinding to ribonucleotides, including mononucleotide inhibitorand product, and a synthetic substrate-analog trinudeotide aswell as the binding to dinucleotide substrates and RNA. Enhancementson binding to non-substrate ribonucleotides by the mutationhave been observed with free energy changes ranging from –2.2 to – 3 .9 kJ/mol. These changes are in good agreementwith that of substrate binding, –2.3 kJ/mol, which iscalculated from Michaelis constants obtained from kinetic studies.It is shown, by comparing the observed and calculated changesin binding free energy with differences in the observed transferfree energy changes of the amino acid side chains from organicsolvents to water, that the enhancement observed on guaninebinding comes from the difference in the hydrophobic effectsof the side chains of tyrosine and tryptophan. Furthermore,a linear relationship between nucleolytic activities and hydrophobicityof the residues (Ala, Phe, Tyr, Trp) at position 45 is observed.The mutation could not change substantially the base specificityof RNase Tl, which exhibits a prime requirement for guaninebases of substrates.