Stereospecific synthesis ofcis andtrans fatty esters

Theerythro andthreo isomers of methyl 9,10-dihydroxyoctadecanoate and thethreo isomer of methyl 12,13-dihydroxy-cis-9-octadecenoate were converted into methylcis- andtrans-9-octadecenoate and methylcis-9,rans-12-octadecadienoate, respectively, by reaction of the dihydroxy ester with triethyl orthoformate to give the 2-ethoxy-1,3-dioxolane which was thermally decomposed to the unsaturated ester.     

Fat,cholesterol, and atherosclerosis

Summary Cholesterol is a universal constituent of all animal cells and therefore occurs in all foods of animal origin. Cholesterol is the mother substance of bile acid and of sex hormones and has other important physiological roles. Cholesterol is synthesized in the body from acetate obtainable from ingested carbohydrate, fat. or protein, of animal or vegetable origin. The fate of cholesterol in the body has not been definitely established. The cause of atherosclerosis is unknown. Atherosclerosis occurs in young as well as old individuals. Atherosclerosis is the number-one killer today. Diagnosis of atherosclerosis in the healthy individual is not possible. Treatment of atherosclerosis is empirical. Reduction of blood cholesterol levels by dietary means is difficult under conditions consonant with good nutrition. A well-balanced intake of all available foods on a modified total caloric basis appears to be the practical approach to the problem of fat, cholesterol, and atherosclerosis. Presented at the 47th Annual, Meeting, American Oil Chemists’ Society, Houston, Tex., April 23–25, 1956.     

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.     

Aldol condensation of butanal over alkali metal zeolites

Alkali metal zeolites and metal oxides were used for the aldol condensation of n-butanal to 2-ethyl-2-hexenal. The order of activity at 150 °C and 1 atm. was: CsNaY > NaY > LiNaY > MgO >Al₂O₃. Selectivity to 2-ethyl-2-hexenal was 100% for both pure and mixed isomer feed. Infrared spectroscopic studies showed that stable catalysts were produced by propene pretreatments which blocked Lewis acid sites. Adsorption of ammonia and carbon dioxide on CsNaY during aldol condensation of n-butanal causes a decrease in rate. This result, along with the order of activity, suggests that the presence of both acid and basic sites produce higher activity than strongly basic MgO.Work performed at San Jose State University.     

Relation of swelling and Tg depression to the apparent free volume of a particle‐filled,epoxy‐based adhesive

The effect of hygrothermal aging on a particle‐filled, epoxy‐based adhesive was studied using a gravimetric sorption technique. This study has explored moisture sorption characteristics as well as the associated behaviors of swelling and the depression of the glass transition temperature (T_g). We observed that the diffusion of water in this adhesive has a non‐Fickian behavior, and the depression of T_g proceeds to a definite value that is independent of the final equilibrium water content of the system. Our observations suggest that water diffuses into the polymer in a dual‐sorption mode, in which water resides in two populations. In one population, water is considered to occupy apparent free volume of the adhesive, and the second population water infiltrates polymer structure and forms hydrogen‐bonded clusters. Our results show that hygrothermal aging temperature and swelling do not alter the apparent free volume of this adhesive. We conclude that the constant value of T_g depression at saturation implies that only water in the apparent free volume is responsible for the T_g depression, whereas the swelling proceeds through the formation of hydrogen bonds in the adhesive. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1436–1444, 2003     

时尚

时尚是有规律的.它不是以进步的形式运动,而是在循环中运动.外在的一致性通常会破坏内在的一致性.本文就时尚的规律、时尚的产生与运动过程、时尚与限制性规则、现代时尚的新变革等方面展开讨论.     

Very long chain PUFA in murine testicular triglycerides and cholesterol esters

Very long chain (VLC) PUFA of the n−6 and n−3 series are known to occur in mammalian testis. The aim of this work was to characterize further two testicular lipid classes with VLCPUFA, cholesterol esters (CE) and total triglycerides (TG) in rat and mouse testis. The VLCPUFA predominating in these lipids were a series of n−6 pentaenes and tetraenes with 24 to 32 carbons, including small amounts of odd-chain PUFA, 28∶5n−6 and 24∶5n−6 prevailing in CE and TG, respectively. Most of the VLCPUFA of TG were concentrated in a small fraction of TG, made up by 1-O-alkyl-2,3-DAG. This TG subclass was absent altogether from the TG of sexually immature testis. The TG and the CE with VLCPUFA only occurred in testis of adult fertile animals. The proportion of VLCPUFA in total TG and CE was higher in rodents than in other mammals. In the n−6 PUFA-rich adult mouse testis, the amounts of testicular triacylglycerols decreased significantly after consumption of fish oil for 2 wk. Whereas 18∶2n−6 was significantly reduced, the amounts of 22∶5n−6 and longer n−6 PUFA were less affected in all mamor testicular lipids including PC and PE, where they were unchanged. The 1-O-alkyl-2,3-DAG and their n−6 VLCPUFA were virtually unaffected by the diet. The VLCPUFA-containing molecular species of CE and TG may represent a form of storage of cholesterol and polyenoic FA required to sustain spermatogenesis. Via chain-shortening, VLCPUFA stored in the neutral lipids may serve as precursors of the major C₂₂ PUFA typical of cell membrane glycerophospholipids, protecting testicular cells against shifts in FA composition induced by dietary changes.     

Mediator and catalytic effects of porphyrin modified electrodes on redox LB films

In this work, the mediator and/or catalytic properties of modified ITO electrodes by oxidative electrodeposition of Ni-porphyrins have been analyzed. Thus, monolayers containing viologen or azobenzene derivatives, have been transferred onto the porphyrin modified electrodes by using the Langmuir-Blodgett (LB) technique. Following, the redox processes of these compounds forming the LB films and deposited on the modified electrode and the bare ITO have been investigated.The obtained results reveal not only the excellent mediator character of the porphyrinic electrodeposit throughout the viologen redox processes, but also its the catalytic action over the azobenzene kinetics. Specifically, for the last case, the NiTMPyP films accelerate the azobenzene kinetics up to 100 times with respect to those results obtained in absence of porphyrin.     

Pressureless low temperature sintering of nanocrystalline zirconia ceramics via dry powder processing

Pressureless sintering approaches provide a simple avenue to manufacture dense ceramic parts with minimal processing equipment, but current pressureless sintering techniques have yet to demonstrate capabilities of producing dense ceramics while maintaining sub-50 nm grain sizes. Nanocrystalline yttria stablized zirconia ceramics were process from 4 mol% yttria stablized zirconia (4YSZ) nanopowders with a crystallite size of 7.5 nm using dry cold isostatic pressing (CIP) where powders are dried immediately prior to green compact formation and CIP vacuum bagging. It is shown that CIP pressures >75 000 psi (517 MPa) effectively remove pores larger than 100 nm and that pressureless sintering occurs at reduced temperatures for green densities ≥50%. Though the sintering kinetics are shown to be similar to other zirconia nanopowder sintering studies, the small initial crystallize size and reduced sintering temperature allowed densities as high as 97.2%, while retaining a ceramic grain size at or below 40 nm. Produced nanocrystalline 4YSZ ceramics with a grain size of 30.3 nm and a density of 96.3% had Vicker's hardnesses as high as 14.2 GPa and Vicker's indentation fracture resistance of 3.43 MPa·, demonstrating that simple processing approaches can be refined to fabricate nanocrystalline ceramics while maintaining high hardness and indentation fracture resistance.     

Effect of Molybdenum on the Structure and on the Crystallization of SiO2–Na2O–CaO–B2O3 Glasses

Crystallization of the poorly durable Na₂MoO₄ phase able to incorporate radioactive cesium must be avoided in SiO₂–Al₂O₃–B₂O₃–Na₂O–CaO glasses developed for the immobilization of Mo-rich nuclear wastes. Increasing amounts of B₂O₃ and MoO₃ were added to a SiO₂–Na₂O–CaO glass, and crystallization tendency was studied. Na₂MoO₄ crystallization tendency decreased with the increase of B₂O₃ concentration whereas the tendency of CaMoO₄ to crystallize increased due to preferential charge compensation of BO₄⁻ entities by Na⁺ ions. ²⁹Si MAS NMR showed that molybdenum acts as a reticulating agent in glass structure. Trivalent actinides surrogate (Nd³⁺) were shown to enter into CaMoO₄ crystals formed in glasses.