Cysteine adds to lipid hydroperoxide

Cysteine reacts with linoleic acid hydroperoxide to yield several products, some of which were identified as fatty acid-cysteine adducts. The addition was catalyzed by ferric chloride (10⁻⁵ M) by initiating free radical reactions. When isomerically pure 13-hydroperoxy-cis-9,trans-11-octadecadienoic acid and cysteine were reacted in 80% ethanol under N₂, the major adducts were 9-S-cysteine-13-hydroxy-10-ethoxy-trans-11-octadecenoic acid (I) and 9-S-cysteine-10,13-dihydroxy-trans-11-octadecenoic acid (II). When the reaction included both isomers of the hydroperoxide (13-and 9-hydroperoxide) and air, an adduct of 9-oxononanoic acid and cysteine also was isolated. Additional experiments gave information about possible mechanisms of I and II formation.     

Inclined hot-wire response equations for a flow field having a dominant tangential velocity component

Modified sets of response equations have been derived for a single inclined hot-wire probe introduced in various orientations in a flow field having a dominant tangential velocity component. By means of these equations, the components of the three dimensional mean velocity vectors, the turbulence intensity and the Reynolds stresses can be easily determined at any location in a swirling flow which is stationary with time. This method is particularly applicable to the characterization of the flow field in chemical processing equipment where this type of swirling flow is increasingly being used. It has been successfully applied to a study of the flow field in a spray-drying chamber, in the course of which good reproducibility and consistency of results were obtained.     

Effects of the nitrification inhibitor N-Serve on the utilization of fall-applied urea by wheat

Four-year microplot tests were performed to study the utilization by wheat, in the presence and absence of the nitrification inhibitor N-Serve, of¹⁵N labeled urea spread in fall. The percentages of fertilizer nitrogen taken up by winter wheat (grains and straw) were 18 to 37 percent when urea was spread in fall, 33 to 45 percent when urea plus N-Serve was applied in fall, and 36 to 49 percent when urea was spread in spring. In the 0–30 cm layer of soil there were found, for the treatments listed above, 15 to 23 percent, 24 to 45 percent, and 15 to 47 percent of urea nitrogen after the harvesting of winter wheat. Application of urea plus N-Serve in fall and of urea alone in spring resulted in similar amounts of fertilizer nitrogen being taken up by spring wheat to those taken up by winter wheat. Of the urea nitrogen applied in fall, 20 to 28 percent and 47 to 50 percent were not recovered from the plants and 0–30 cm soil layer with and without additional N-Serve treatment, respectively. The utilization by winter wheat of urea nitrogen spread, with no additional N-Serve, in fall from mid-October onward was considerably lower in those cases where, after fertilizing, weather conditions were such as to favour both nitrification and leaching. On heavy and loamy soil such influences of weather were offset by application of N-Serve.     

Pressure reaction of maleic esters with vegetable oils

The reaction of dimethyl maleate and some related dienophiles with vegetable oils under pressure has been studied successfully. When safflower oil reacts with 100% excess maleate, sulfur dioxide catalyst, and hydroquinone inhibitor at 290° for 1hr., 80 to 90% yields of adduct fraction, based on linoleate, are obtained. Under the same conditions almost equally good yields result with either linseed or soybean oils. With safflower oil, dimethyl fumarate gave slightly lower yields. Di-n-butyl maleate gave even poorer yields, and much residue was formed. Paper II in a series entitled, “Reactions of Dienophiles with Vegetable Oils”. Presented at annual meeting, American Oil Chemists' Society, St. Louis, Mo., May 1–3, 1961. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S. Department of Agriculture.     

Thermal analysis and calorimetry of some fatty acid sodium soaps

Transition temperatures and enthalpies and some phase diagrams of pure odd and even sodium soaps have been determined by means of dif-ferential thermal analysis and scanning calorim-etry. Branched sodium soaps have been added for comparison. No essential difference has been found between the number, type, and enthalpy of the transitions of the neighboring odd and even soaps. The total enthalpy and entropy of transition are consider-ably lower than those of the corresponding par-affins and fatty acids. The entropy of the subneat-neat and perhaps of the neat isotropic transition has an alternating character, which suggests a different methyl end-group packing for even and odd soap. These two facts suggest that the melted soap is still in an organized state. Presented at the AOCS Meeting, New Orleans, May 1967.     

Determination of tocopherol in autoxidizing methyl esters of fatty acids

Summary Autoxidizing methyl esters of fatty acids interfered with the determination of α-tocopherol by ultraviolet spectrophotometry or by the bipyridine colorimetric method. Interference with the colorimetric method was removed by sulfuric acid treatment, but spectrophotometry was applicable only when the tocopherol was completely separated from oxidized fat. This separation could not be obtained by sulfuric acid treatment but was accomplished by room temperature saponification in an alcohol-petroleum ether system protected by pyrogallol. The sensitivity of the spectrophotometric method was increased by oxidizing tocopherol quantitatively to thep-quinone with 2N nitric acid. N. R. C. No. 4053. Presented in part at meeting of American Oil Chemists’ Society, Minneapolis, Minn., Oct. 11–13, 1954.     

Esters of hydroxystearic acids as primary low-temperature plasticizers for a vinyl chloride—Vinyl acetate copolymer

Summary Thirty-one acyloxy or aryloxy esters prepared from hydroxystearic acids have been evaluated as plasticizers for a vinyl chloride-vinyl acetate copolymer (95∶5). Many of them were found to be primary plasticizers, having outstanding low-temperature performance when employed at the 35% level. Formulations with these compounds compared quite favorably in tensile properties with those containing the di-2-ethylhexyl esters of phthalic, sebacic, azelaic, and adipic acids. Volatility losses were similar to those of the four di-2-ethylhexyl esters. The loss of plasticizer through migration was equal to or less than that from compositions containing the esters of sebacic, azelaic, and adipic acids but was greater than that of the phthalate ester. A mechanistic scheme of plasticizer-polymer interaction has been presented, proposing that the rate of diffusion of plasticizer through the polymer mass is a controlling factor in both good low-temperature performance and the resulting high migration losses. Methyl esters, some aromatic esters, and esters containing three or more polar centers have improved permanence but show a more rapid change in torsional modulus as the temperature is lowered during the determination of the Clash-Berg stiffening temperature. Eastern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Possible use of methylbenzenes as electrolyte additives for improving the overcharge tolerances of Li-ion batteries

Based on the voltammetric behaviour of a series of methyl-substituted benzenes in 1M LiPF₆/EC-DMC electrolyte, xylene was selected and tested as an electrolyte additive for overcharge protection of Li-ion batteries. From the overcharge curves, CV behaviour and SEM observations of the cells in the presence of xylene, it was found that the additive can polymerize at the overcharged voltage to form a dense layer of isolating polymer film at the cathode surface, which blocks off further oxidation of the electroactive material and electrolyte and, therefore, improves the overcharge tolerance of the Li-ion battery. In addition, the xylene additive has shown only a slight influence on the cycling behaviour.     

Thermal properties of poly(tetramethyl-p-silphenylene siloxane) and (tetramethyl-p-silphenylene siloxane-dimethyl siloxane) copolymers

Some physical properties of poly(tetramethyl-p-silphenylene siloxane) homopolymer and random block copolymers of tetramethyl-p-silphenylene siloxane-dimethyl siloxane have been determined and correlated with polymer structure. Differential scanning calorimetry (d.s.c.), differential thermal analysis (d.t.a.), density gradient column measurements and optical hot stage melting point determination and diluent techniques were used. The thermodynamic melting temperature of the homopolymer was estimated to be 160°C and its heat of fusion, ΔH_u, found to be 54.4 J/g (13 cal/g or 2710 cal/mol of monomer repeat units). Its limiting glass transition temperature, T_g, was ?20°C. T_g of the copolymer was found to vary almost monotonically with increasing dimethyl siloxane (DMS) content ranging from ?20° (0% DMS) to just above ?123°C, for pure DMS polymer. The copolymer melting temperature was found to increase as the fraction of the crystalline (hard) TMPS constituent was increased. Based upon copolymer theory and extrapolated melting point data, it was estimated that the block size of soft DMS component in the copolymer most probably consists of twelve monomer units distributed amongst TMPS sequences of varying length.