Detection of beeswax adulterations using concentration guide‐values

The concentrations of 102 chemical compounds (saturated and unsaturated hydrocarbons, palmitates, total and free acids, total hydroxyacids, total and free alcohols, acidic monoesters and monoesterified 1,2,3‐propanetriols) have been determined by GC/FID on white and yellow comb beeswax of Apis mellifera from different regions of Spain. Guide‐value ranges are proposed for its characterization and to discriminate adulterated foundation beeswax sheets. The concentrations of many compounds resulted to be statistically different for white and yellow beeswaxes, while the observation of concentrations out of normal in some marketed foundation beeswax sheets suggested their adulteration. However, the measurement of anomalous concentrations in foundation beeswax sheets did not imply necessarily their rejection by the bees.     

Thermal Conductivity/Diffusivity of Silicon Carbide Whisker Reinforced Mullite

The thermal conductivity and diffusivity of silicon carbide whisker reinforced mullite was shown to increase with whisker content. This effect was much greater for vapor-liquid-solid (VLS) whiskers than for rice-hull (RH) whiskers. This suggests that the thermal conductivity for the VLS whiskers was significantly higher than for the RH whiskers. Due to preferred orientation of the whiskers, thermal conductivity and diffusivity of the composite samples exhibited significant anisotropy.     

Carbohydrate type and amount alter intravascular processing and catabolism of plasma lipoproteins in guinea pigs

To test the effects of exchanging dietary complex and simple carbohydrate for fat calories on lipoprotein metabolism, guinea pigs were fed two different fat/carbohydrate ratios: 2.5∶58% (w/w) or 25∶29% (w/w) with either sucrose or starch as the carbohydrate source. Animals fed high-fat had higher plasma low-density lipoprotein (LDL) and hepatic cholesterol concentrations than animals fed low-fat diets (P<0.01). The cholesteryl ester content per particle was higher, and the number of triacylglycerol (TAG) molecules was lower in very low density lipoprotein (VLDL) and LDL from animals fed high-fat diets. Intake of high-fat/sucrose resulted in higher plasma LDL concentrations than intake of high-fat/starch, and animals fed low-fat/starch had the highest plasma TAG concentrations associated with VLDL particles containing more TAG molecules, as well as a TAG-enriched LDL. The activity of plasma lecithin cholesteryl:acyl transferase (LCAT) was highest in animals fed high-fat/sucrose, and heart lipoprotein lipase (LPL) activity was higher in animals fed high-fat diets. Hepatic apoprotein B/E (apo B/E) receptor number (B_max) was increased 21% with low-fat diets (P<0.01). These results suggest that the hypercholesterolemia induced by high-fat and by sucrose intake are associated with a higher plasma LCAT activity which results in a cholesteryl ester-enriched VLDL which, by the action of LPL, might be more readily converted to LDL through the delipidation cascade leading to downregulation of hepatic apo B/E receptors. The hypertriglyceridemia associated with low-fat intake may result from increased production of VLDL TAG, which would explain the increased TAG content and the higher TAG/CE ratio of VLDL from animals fed the low-fat/starch diet.     

Synthesis of deuterated cyclopropene fatty esters structurally related to palmitic and myristic acids

To develop a synthesis of tritiated cyclopropene fatty acids (CPFA), compounds that should prove useful for affinity labeling of desaturases in insect pheromone biosynthetic studies, a series of novel, selectively deuterated CPFA analogues was prepared and characterized. In methyl [16-²H]12,13-methylene-12-hexadecenoate, the incorporation of deuterium was achieved by treatment of the corresponding ω-chloro derivative with sodium borodeuteride in dimethylsulfoxide at 70°C for 24 h (67% yield) following conventional procedures. Alkylation of the tetrahydropyranyl derivative of 13-tridecynol in the presence of lithium diisopropylamide in tetrahydrofuran at −20°C with 1-chloro-3-iodopropane in hexamethylphosphoramide, followed by Jones oxidation of the crude product, yielded 16-chloro-12-hexadecynoic acid (54%), which was esterified to the corresponding methyl ester by treatment with potassium carbonate and methyl iodide in dimethylformamide. Treatment of this acetylenic ester with ethyldiazoacetate in the presence of activated copper-bronze as catalyst followed by hydrolysis in KOH solution at room temperature yielded 16-chloro-12,13-(carboxymethylene)-12-hexadecenoic acid. This diacid was treated with excess oxalyl chloride to give the corresponding diacyl chloride, which was decarbonylated in a diethyl ether solution with zinc chloride, and the cyclopropenium ions thus formed were added at −40°C to a methanolic sodium hydroxide solution of sodium borohydride to give methyl 16-chloro-12,13-methylene-12-hexadecenoate. Analogous procedures were followed to prepare methyl [17-²H]10,11-methylene-10-hexadecenoate, methyl [17-²H]11,12-methylene-11-hexadecenoate and methyl [17-²H]12,13-methylene-12-hexadecenoate from the corresponding diacids using sodium borodeuteride in the reduction of the cyclopropenium ions. Alternatively, methyl [2,2,3,3-²H₄]hexadecynoate, prepared by reaction of methyl 2,11-hexadecadiynoate with magnesium in deuterated methanol at room temperature, was submitted to the above cyclopropenylation and reductive decarbonylation sequence to give methyl [2,2,3,3,17-²H₅]-11,12-methylene-11-hexadecenoate. In summary, complementary methods for the selective incorporation of one to five deuterium atoms into cyclopropene fatty acids, at different sites, in moderate to high yields have been developed. The methods should easily be applicable to the preparation of the corresponding tritiated analogues.     

New N,O-containing ligands for the biomimetic copper-catalyzed polymerization of 2,6-dimethylphenol

Poly(2,6-dimethyl-1,4-phenylene ether) (PPE), which is widely used in high-performance engineering plastics, is obtained by the copper-catalyzed oxidative coupling of 2,6-dimethylphenol. The oxidative polymerizations have been carried out in acetonitrile with structurally related [copper-(N,O-containing ligand)] complexes as the catalyst precursor compounds, which appeared to be of great interest for a better understanding of the factors influencing the catalytic activities. Steric effects (influence of a methyl group close to the metal center; ligands 4–7) or electronic effects (imino versus amino group; ligands 4, 5, 8 and 6, 7, 9, respectively) on the polymerization rates have been demonstrated. The use of mono- or dinucleating ligands has strengthened the proposed mechanism of the reaction involving dinuclear active species.     

Effect of water pretreatment on CO<Subscript>2</Subscript> capture using a potassium-based solid sorbent in a bubbling fluidized bed reactor

A bubbling fluidized bed reactor was used to study CO₂ capture from flue gas by using a potassium-based solid sorbent, sorbKX35 which was manufactured by the Korea Electric Power Research Institute. A dry sorbent, sorbKX35, consists of K₂CO₃ for absorption and supporters for mechanical strength. To increase initial CO₂ removal, some amount of H₂O was absorbed in the sorbent before injecting simulated flue gas. It was possible to achieve 100% CO₂ removal for more than 10 minutes at 60°C and a residence time of 2 s with H₂O pretreatment. When H₂O pretreatment time was long enough to convert K₂CO₃ of sorbKX35 into K₂CO₃ · 1.5H₂O, CO₂ removal was excellent. The results obtained in this study can be used as basic data for designing and operating a large scale CO₂ capture process with two fluidized bed reactors. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Sulfate attack of concrete building foundations induced by sewage waters

A case history of a severe degradation of concrete foundation plinths and piers of an about-35-year-old building located in Northern Italy is described. Significant amounts of gypsum, near ettringite and/or thaumasite were detected by X-ray diffraction analyses performed on ground concrete samples. Large gypsum crystals were mainly located at the interface between the cement paste and aggregates, as observed by scanning electron microscopy coupled to energy-dispersive spectroscopy microanalysis. The degradation effects increased with decreasing the distance of concrete structures from an absorbing well located in the courtyard of the building. The well was recognized as the sulfate source due to the microorganism metabolism of sulfur compounds present in the sewage. Consequences of this attack were a very poor bond strength between cement paste and aggregates and a severe cracking of the concrete cover of the steel reinforcement.     

Preparation and characterization of trilobal activated carbon fibers

The objective of this research was to evaluate the effectiveness of several different methods for controlling the pore size and pore size distribution in activated carbon fibers. Variables studied included fiber shape, activation time, and the addition of small amounts of silver nitrate. Pure isotropic pitch and the same isotropic pitch containing 1 wt.% silver were melt spun to form fibers with round and trilobal cross sections. These fibers were then stabilized, carbonized, and activated in carbon dioxide. Field emission scanning electron microscopy (FE SEM), electron dispersive spectra (EDS), and wavelength dispersive spectra (WDS) were used to monitor the size and distribution of the silver particles in the fibers before and after activation. Each of these analyses showed that the distribution of silver particles was extremely uniform before and after activation. The fibers were also weighed before and after activation to determine the percent burn-off. The BET specific surface areas of the activated fibers were determined from N₂ adsorption isotherms measured at −196 °C. The results showed that round and trilobal fibers with equivalent cross-sectional areas yielded similar burn-off values and specific surface areas after activation. Also, activation rates were found to be independent of CO₂ flow rate. The porosity of the activated fibers depended on the total time of activation and the cross-sectional area of fibers. The N₂ adsorption measurements showed that the activated fibers had extremely high specific surface areas (greater than 3000 m²/g) and high degrees of meso- and macro-porosity. FE SEM was also used to investigate surface texture and size of pore openings on the surfaces of the activated fibers. The photos showed that silver particles generated surface macro- and mesopores, in agreement with the inferences from N₂ adsorption measurements.     

Phytotoxic properties of cnicin,a sesquiterpene lactone fromcentaurea maculosa (spotted knapweed)

Water and solvent extracts from the aerial tissues ofCentaurea maculosa, spotted knapweed, inhibited the root growth of lettuce. Column chromatography and lettuce bioassay of a chloroform extract led to the isolation of cnicin, a sesquiterpene lactone. Pure cnicin was bioassayed at 0, 1, 2, 4, 6, 8, and 10 mg/5 ml water with lettuce, created wheatgrass, bluebunch wheatgrass, rough fescue, western larch, lodgepole pine, and spotted knapweed. Germination was inhibited at one or more concentrations for all species except lodgepole pine and spotted knapweed. Growth, particularly of the roots, was retarded between 1 and 4 mg of cnicin. Lettuce, bluebunch wheatgrass, and spotted knapweed were inhibited significantly at all concentrations tested.