In situ measurement of free radical formation during the thermal decomposition of grape seed oil using “spin trapping” and electron paramagnetic resonance spectroscopy

The generation of free radical intermediates as a result of the oxidative degradation of lipid molecules during the heating of grape seed oil has been established by a combination of “spin trapping” and electron paramagnetic resonance spectroscopy. The effects of temperature on the rates of formation and decomposition of the adduct with the spin trapN-t-butyl-α-phenylnitrone (PBN) have been investigated over the temperature range 105–180°C. The results show that PBN can be used for studies of free radical processes in oils in situ in the spectrometer cavity at temperatures up to 180°C.     

Time-of-day effects in maximal anaerobic leg exercise

The pathogenesis of AIDS is a complex and prolonged process that is affected by a variety of cofactors, including the abuse of both intravenous and smoked (crack) cocaine. The exact mechanisms by which cocaine facilitates this disease are yet to be proven, but likely include a combination of increased risk due to cocaine-related social behaviours, a wide-ranging capacity for cocaine to suppress the immune system, and an effect of cocaine on the infectivity and replication of HIV. While sometimes contradictory, both human and animal studies document that cocaine alters the function of natural killer (NK) cells, T cells, neutrophils and macrophages, and alters the ability of these cells to secrete immunoregulatory cytokines. In addition to these effects on the immune system, cocaine also enhances the infectivity and/or replication of HIV when tested using human cells in vitro.     

Synthesis of phosphonated styrenic copolymers and their chemical modifications

We report, for the first time, the synthesis of a phosphonated styrenic monomer dimethyl vinylbenzyl phosphonate (VBP) according to the methods described in the literature for its equivalent diethyl vinylbenzyl phosphonate, and also the monodealkylation of this monomer (VBP) to the monosalt in a neutral medium and to the corresponding monoacid via a sulfonic resin. Various statistical copolymers and statistical block copolymers of styrene and VBP were prepared with different molar percentages of these comonomers. The dealkylation of statistical copolymers was carried out in the same way as for VBP. The phosphonated statistical copolymers, prepared, were characterized by various analytical methods which show good agreement with their structures. © 2002 Society of Chemical Industry     

Modification of alkenyl chain profile in plasmalogens of rat heart mitochondria by dietary trielaidin

Effects of dietary trielaidin upon the alkenyl chain profile of plasmalogens were studied using heart mitochondria of rats fed a semi-purified diet containing 10% of fat supplement in which elaidic acid accounted for 69% of total fatty acids. Alkyl substituted dioxane (ASD) derivatives of the alkenyl groups of plasmalogens were prepared and analyzed by silver nitrate TLC and by GLC on different phases (BDS and OV-275). After two months of feeding the experimental diet, 40% of the ASD contained atrans-octadecenyl chain, suggesting that dietary elaidic acid was reduced in vivo to the corresponding alcohol and incorporated into plasmalogens. There was a simultaneous decrease in the percentage of ASD containing saturated chains, but the percentage of ASD substituted withcis-octadecenyl chains was not significantly affected. These observations suggested that elaidic acid may compete with saturated fatty acids, but not withcis-octadecenoic acids during the plasmalogen biosynthesis. Feeding trielaidin did not seem to have any significant influence on the relative proportions of plasmalogens, which accounted for 11–12%, on a phosphorus basis, of total heart mitochondria phospholipids.     

Elaboration and characterization of magnesium-substituted La5Ni19 hydride forming alloys as active materials for negative electrode in Ni-MH battery

The crystallographic structure as well as the thermodynamic and electrochemical properties of the hydrogen absorbing compounds La₅Ni₁₉ and La₄MgNi₁₉ have been determined. X-ray diffraction and microprobe analysis have shown the presence of a single hexagonal (P6₃/mmc) phase for the Mg-free binary compound whereas only one composition but two different crystallographic structures, hexagonal (P6₃/mmc) and rhombohedral (R-3m), are observed for La₄MgNi₁₉. Each phase can be described as the stacking along the c-axis of n[A₂B₄]/m[AB₅] sub-units with n = 1 and m = 3 and A = La, Mg; B = Ni. Depending on the stacking sequence, either the hexagonal or the rhombohedral phase is obtained. Thermodynamic properties toward hydrogen uptake (capacity and equilibrium pressure) and electrochemical properties (cycling behavior) in alkaline medium have been measured and are compared for these compounds with and without magnesium. It is observed that the Mg-free compound exhibits a much lower reversible hydrogen capacity than the Mg-containing one. However, despite larger capacity, this latter compound remains to be optimized in term of cycle life.     

A Flavanone and Two Phenolic Acids from Chrysanthemum morifolium with Phytotoxic and Insect Growth Regulating Activity

Leaves of Chrysanthemum morifolium cv. Ramat were extracted sequentially with hexane, ethyl acetate, and methanol. The methanol fraction, when incorporated into artificial diet was found to reduce the growth of cabbage looper (Trichoplusia ni Hubner) larvae at concentrations between 500 and 5000 ppm of diet. Fractionation of the methanol extract on a Sephadex column yielded five fractions, three of which reduced the weight of larvae relative to the control. One fraction was analyzed using high performance liquid chromatography (HPLC) and found to contain three main constituents. These compounds were purified using a combination of gel permeation chromatography on Sephadex LH20 and HPLC, and analyzed by 1H and 13CNMR as well as undergoing chemical and physical analyses. The compounds were identified as: 1, chlorogenic acid (5-O-caffeoylquinic acid); 2, 3,5-O-dicaffeoylquinic acid; and 3, 3', 4',5-trihydroxyflavanone7-O-glucuronide (eriodictyol7-O-glucuronide). At concentrations between 100 to 1000 ppm these compounds reduced both growth and photosynthesis of Lemna gibba L. with the order of efficacy being: flavanone > chlorogenic acid > 3,5-O-dicaffeoylquinic acid. Furthermore, when incorporated separately into artificial diet these compounds, at 10 to 1000 ppm, enhanced or reduced growth of the cabbage looper (Trichoplusia ni) and gypsy moth (Lymantria dispar L.).     

Kinetics of the selective catalytic reduction of NO by NH3 on a Cu-faujasite catalyst

The kinetics of the selective catalytic reduction (SCR) of NO by NH₃ in the presence of O₂ has been studied on a 5.5% Cu-faujasite (Cu-FAU) catalyst. Cu-FAU was composed of cationic and oxocationic Cu species. The SCR was studied in a gas phase-flowing reactor operating at atmospheric pressure. The reaction conditions explored were: 458<T_R<513 K, 2503 (ppm) < 4000, 12 (%) < 4. The kinetic orders were 0.8–1 with respect to NO, 0.5–1 with respect to O₂, and essentially 0 with respect to NH₃. Based on these kinetic partial orders of reactions and elementary chemistry, a wide variety of mechanisms were explored, and different rate laws were derived. The best fit between the measured and calculated rates for the SCR of NO by NH₃ was obtained with a rate law derived from a redox Mars and van Krevelen mechanism. The catalytic cycle is described by a sequence of three reactions: (i) Cu^I is oxidized by O₂ to “Cu^II-oxo”, (ii) “Cu^II-oxo” reacts with NO to yield “Cu^II-N_xO_y”, and (iii) finally “Cu^II-N_xO_y” is reduced by NH₃ to give N₂, H₂O, and the regeneration of Cu^I (closing of the catalytic cycle). The rate constants of the three steps have been determined at 458, 483, and 513 K. It is shown that Cu^I or “Cu^II-oxo” species constitute the rate-determining active center.     

Effect of addition of nanosized UV absorbers on the physico-mechanical and thermal properties of an exterior waterborne stain for wood

This study describes the effects of the addition of inorganic nanosized UV absorbers on physico-mechanical and thermal properties of an exterior commercial acrylic-based waterborne stain for wood. Electronic microscopy and water vapor (WV) permeability measurements were performed to characterize the free films of the acrylic stain and resulting nanocomposite coatings. An accelerated weathering method was used to evaluate aging behavior of the coatings on wood through appearance, T_g, abrasion resistance, adhesion strength, hardness and Young's modulus changes. In addition to improving the protection against UV, the doped TiO₂ and silica-coated ZnO nanoparticles in powder form have improved the abrasion resistance and barrier effect against water vapor diffusion of the acrylic stain. For most of nanocomposite coatings, the addition of ZnO hydrophilic nanoparticles in predispersed form has resulted in a decrease in WV permeability, while the adhesion strength and abrasion resistance of those coatings were negatively affected. The addition of ZnO nanoparticles has decreased the T_g of the acrylic stain. Finally, the accelerated weathering has induced an increase in T_g, hardness, Young's modulus (stiffness) and an increase in apparent adhesion strength and abrasion resistance of the coatings. The T_g values of the aged nanocomposite coatings were lower than that of unmodified acrylic stain.     

Effects of the nature of the doping salt and of the thermal pre-treatment and sintering temperature on Spark Plasma Sintering of transparent alumina

A slurry of α-Al₂O₃ was doped with Mg, Zr and La nitrates or chlorides, in various amounts in the range 150-500 wt ppm and then freeze-dried to produce nanosized doped powder (∼150 nm). The powder was sintered by SPS to yield transparent polycrystalline alpha alumina. The influence of the nature of the doping element and the starting salt, the thermal treatment before sintering and the sintering temperature on the transparency of the ceramics were investigated. The transparency of the ceramics of nanosized Al₂O₃ was shown to depend mainly on the way the powder was prepared, the nature of the doping salt also had an effect. Finally, a high real inline transmittance, reaching 48.1% was achieved after optimization.