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.     

Characterization and Sintering Behavior of Alkoxide-Derived Aluminosilicate Powders

Submicrometer SiO₂-Al₂O₃ powders with compositions of 46.5 to 76.6 wt% Al₂O₃ were prepared by hydrolysis of mixed alkoxides. Phase change, mullite composition, and particle size of powders with heating were analyzed by DTA, XRD, IR, BET, and TEM. As-produced amorphous powders partially transformed to mullite and Al-Si spinel at around 980°C. The compositions of mullite produced at 1400° and 1550°C were richer in Al₂O₃ than the compositions of stable mullite solid solutions predicted from the phase diagram of the SiO₂-Al₂O₃ system. Particle size decreased with increasing Al₂O₃ content. The sintered densities depended upon the amount of SiO₂-rich glassy phase formed during sintering and the green density expressed as a function of particle size.     

Effect of Nd2O3 Concentration on the Defect Structure of CeO2–Nd2O3 Solid Solution

An extensive X-ray study of CeO₂–Nd₂O₃ solid solutions was performed, and the densities of solid solutions containing various concentrations of NdO_1.5 were measured using several techniques. Solid solutions containing 0–80 mol% NdO_1.5 were synthesized by coprecipitation from Ce(NO₃)₃ and Nd(NO₃)₃ aqueous solutions, and the coprecipitated samples were sintered at 1400°C. A fluorite structure was observed for CeO₂–NdO_1.5 solid solutions with 0–40 mol% NdO_1.5, which changed to a rare earth C-type structure at 45–75 mol% NdO_1.5. The change in the lattice parameters of CeO₂–NdO_1.5 solid solutions, when plotted with respect to the NdO_1.5 concentration, showed that the lattice parameters followed Vegard's law in both the fluorite and rare earth C-type regions. The maximum solubility limit for NdO_1.5 in CeO₂ solid solution was approximately 75 mol%. The relationship between the density and the Nd concentration indicated that the defect structure followed the anion vacancy model over the entire range (0–70 mol% NdO_1.5) of solid solution.     

Fractionation and enrichment of CLA isomers by selective esterification with Candida rugosa lipase

A commercial product of CLA contains almost equal amounts of cis-9,trans-11 (c9,t11)-CLA and trans-10,cis-12 (t10,c12)-CLA. We attempted to enrich the two isomers by a two-step selective esterification using Candida rugosa lipase that acted on c9,t11-CLA more strongly than on t10,c12-CLA. An FFA mixture containing CLA isomers was esterified with an equimolar amount of lauryl alcohol in a mixture of 20% water and the lipase. When the esterification of total FA reached 50%, two isomers were fractionated in a good yield: t10,c12-CLA was enriched in FFA, and c9,t11-CLA was recovered in lauryl esters. The FFA were esterified again to enrich t10,c12-CLA. At 27.3% esterification of total FA, the t10,c12-CLA content in FFA increased to 64.8 wt% with 89.3% recovery: The ratio of the content of t10,c12-CLA to that of two isomers was 95.9%. Lauryl esters obtained by the single esterification were employed for enrichment of c9,t11-CLA. After the esters were hydrolyzed, the resulting FFA were esterified again with lauryl alcohol. At 62.0% esterification of total FA, the c9,t11-CLA content in lauryl esters increased to 73.3 wt% with 79.4% recovery: The ratio of the content of c9,t11-CLA to that of two isomers was 95.6%. In a 600-g-scale purification, molecular distillation was effective in separating the reaction mixture into lauryl alcohol, FFA, and lauryl ester fractions.     

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.     

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.