Autoxidation of ethyl eicosapentaenoate and docosahexaenoate

The extent of oxidation of ethyl esters of eicosapentaenoic (EPA) and docosahexaenoic acids (DHA) was compared quantitatively with that of ethyl linoleate (Lo) and ethyl linolenate (Ln) by oxygen uptake and formation of conjugated diene, hydroperoxide and secondary oxidation products. EPA and DHA esters were oxidized rapidly even at 5 C in the dark after an induction period of 3–4 days, while the induction periods of Ln and Lo esters were 20 days and more than 60 days, respectively. Oxygen uptake of EPA and DHA esters after the induction period was 5.2 and 8.5 times faster than that of ethyl Ln, respectively. Hydroperoxides of EPA and DHA esters are much less stable than those of ethyl Lo. The peroxide value is not necessarily a good indication of oxidation in these polyenoic acids because a considerable amount of secondary products is formed at the early stage of oxidation. Polymers were found to be major secondary products in these polyenoic esters.     

Pervaporation membranes for ethanol–water mixture prepared by plasma polymerization. III. Perfluorocarbon membranes

Pervaporation membranes for the ethanol–water mixture were prepared by plasma polymerization of tetrafluoroethylene, perfluoropropane, and perfluoropropylene onto porous substrates. The influence of the monomers on the elemental ratio (F/C) of the polymer depositions by X-ray photoelectron spectroscopy was rather small compared with that of the W/FM parameter (W = wattage for plasma excitation, FM = mass flow rate of a monomer). The optical emission spectroscopy indicated the similarity of gaseous species formed in the plasmas. The membranes were found ethanol-permselective, showing separation coefficients (α_EtOH) around 4–7 and a wide range of permeation rates (J), 10–10^?2 kg/m² h, for the 4.8 wt % ethanol solution at 40°C. The α_EtOH of the membranes with thicker depositions could be correlated to the F/C ratios as a measure of membrane hydrophobicity. It was thought that, by making a plot α_EtOH against J values for the perfluorocarbon membranes, they could be classified into three groups on thickness of deposition. The ethanol-separation mechanisms for each group, which may contain four kinds of mass transfer schemes, i.e., distillation through larger pores, flow of sorption layer at the liquid–membrane interface, and diffusions through deposition or substrate, were also discussed.     

Thraustochytrid as a potential source of carotenoids

Thraustochytrids, marine protists whose dominant genera are Thraustochytrium and Schizochytrium, belong to the kingdom Chromista and are known as an industrial source of DHA. We describe here that thraustochytrid strain KH105, isolated as a DHA producer, also accumulates significant levels of β-carotene and xanthophylls including canthaxanthin and astaxanthin. A4-d cultivation using a medium composed of 10% glucose and less than 0.3% of nitrogen sources in a half-concentration of seawater gave an astaxanthin production up to 6.1 mg/L, and canthaxanthin content reached more than 10 mg/L under conditions where a higher concentration of nitrogen sources (6%) was employed. It might be advantageous in mass production systems for these carotenoids to be extracted readily by simply suspending the cells with organic solvents such as acetone and chloroform. Analyses on the morphological and life history features of the KH105 strain revealed that it belongs to the genus Schizochytrium. This particular species of thraustochytrids is thus considered to be a promising source of xanthophylls as well as DHA for use in the food industry.     

Antioxidant effects of chlorophyll and pheophytin on the autoxidation of oils in the dark. II. The mechanism of antioxidative action of chlorophyll

To understand the mechanism of the antioxidant effect of chlorophyll on the autoxidation of oils in the dark, antioxidant activities of several derivatives of chlorophyll were compared. Antioxidant activities were observed in chlorophyll derivatives such as protopor-phyrin methyl ester and its magnesium chelated compound. Porphyrin seems to be an essential chemical structure for the antioxidant activity of chlorophyll. Chlorophyll did not decompose the hydroperoxides, but reduced free radicals such as 1,1-diphenyl-2-picrylhydrazyl. Electron spin resonance spectrum of the π-cation radical was recorded during the oxidation of chlorophyll in methyl linoleate solution. These observations suggest that chlorophyll may act as a hydrogen donor to break the chain reaction.     

The oxidative coupling of methane on alkali- and alkaline earth-phosphate catalysts

The oxidative coupling of methane has been tested over alkali- and alkaline earth-phosphate catalysts at 700 and 775 °C with and without the introduction of a small quantity of tetrachloromethane (TCM) to the feedstream. In general, the conversion of methane was enhanced by the addition of TCM but the effect on selectivity was dependent on the catalyst being examined. The selectivity to C₂ and higher hydrocarbons and that to oxidation products have been shown to have a dependence on the cation radius/charge ratio.     

Porous poly(L‐lactic acid)/poly(ethylene glycol) blend films

Poly(L ‐lactic acid) (PLLA: M_w = 19.4 × 10⁴)/poly(ethylene glycol) (PEG: M_w = 400) blend films were formed by use of a solvent‐cast technique. The properties and structures of these blend films were investigated. The Young's modulus of the PLLA decreased from 1220 to 417 MPa with the addition of PEG 5 wt %, but the elongation at break increased from 19 to 126%. The melting point of PLLA linearly decreased with increases in the PEG content (i.e., pure PLLA: 172.5°C, PLLA/PEG = 60/40 wt %: 159.6°C). The PEG 20 wt % blend film had a porous structure. The pore diameter was 3–5 μm. The alkali hydrolysis rate of this blend film was accelerated due to its porous structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 965–970, 2004     

Thermal and flammability properties of a silica–poly(methylmethacrylate) nanocomposite

PMMA, poly(metheylmethacrylate), nanocomposites were made by in situ radical polymerization of MMA, methylmethacrylate, with colloidal silica (ca. 12 nm) to study the effects of nanoscale silica particles on the physical properties and flammability properties of PMMA. Transparent samples resulted and the dispersity of the particles was examined by transmission electron microscopy and atomic force microscopy. The addition of nanosilica particles (13% by mass) did not significantly change the thermal stability, but it made a small improvement in modulus, and it reduced the peak heat release rate roughly 50%. Last, the flame‐retardant mechanism provided by the addition of nanosilica particles in PMMA is discussed. Published 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2072–2078, 2003     

Thermal Response and Oxidation of Tyranno™-Fiber-Reinforced Si-Ti-C-O Matrix Composites for a Thermal Protection System in High-Enthalpy Dissociated Air

The thermal response and oxidation of Tyranno™ Lox-M fiber-reinforced Si-Ti-C-O matrix composites in high-enthalpy dissociated air was investigated in an arc jet facility (an arc wind tunnel). The maximum surface temperature reached 1310–1670°C. Catalytic recombination of oxygen and nitrogen on the composite surface under dissociated air was not significant. Surface recession was insignificant below 1600°C surface temperatures and above 5 kPa of oxygen partial pressure at the stagnation point. Passive-to-active oxidation transition of the composite agreed with Balat's theory for monolithic silicon carbide. A glass sealant prevented active oxidation of the composite for short-time exposures.     

Formation and transformation of cubic 3PbO·2Ta2O5 solid solution

The formation of lead tantalates in the PbO-rich region is studied using the powders prepared by the simultaneous hydrolysis of lead and tantalum alkoxides. Cubic 3PbO · 2Ta₂O₅ solid solutions crystallize at low temperatures from amorphous materials between 60 and 75 mol% PbO. The lattice parameter,a, increases linearly from 1.0545 to 1.0705 nm with increasing PbO. At higher temperatures the solid solutions above 66.67 mol% PbO are transformed into those of rhombohedral 2PbO · Ta₂O₅. Rhombohedral 5PbO · 2Ta₂O₅ is formed at 850 to 900 °C by transformation of 2PbO·Ta₂O₅ solid solution corresponding to 71.43 mol% PbO. The existence of previously reported 3PbO·Ta₂O₅ is not confirmed.     

Isolation kernel: the X factor in efficient and effective large scale online kernel learning

Large scale online kernel learning aims to build an efficient and scalable kernel-based predictive model incrementally from a sequence of potentially infinite data points. Current state-of-the-art large scale online kernel learning focuses on improving efficiency. Two key approaches to gain efficiency through approximation are (1) limiting the number of support vectors, and (2) using an approximate feature map. They often employ a kernel with a feature map with intractable dimensionality. While these approaches can deal with large scale datasets efficiently, this outcome is achieved by compromising predictive accuracy because of the approximation. We offer an alternative approach that puts the kernel used at the heart of the approach. It focuses on creating a sparse and finite-dimensional feature map of a kernel called Isolation Kernel. Using this new approach, to achieve the above aim of large scale online kernel learning becomes extremely simple—simply use Isolation Kernel instead of a kernel having a feature map with intractable dimensionality. We show that, using Isolation Kernel, large scale online kernel learning can be achieved efficiently without sacrificing accuracy.