Soybean oils were heated at 180°C 5 hr/day up to 2030 hr by frying the following food items with an approximately equal in surface area ; potato, chicken, soybean curd, mackerel, whale meat, and green pepper. Amounts of water depleted from each food item was kept at a level of 25ml/hr/500g oil. Polar (P) and apolar (Ap) fractions were separated by TLC by applying either oil itself or its fatty acid methyl esters (the former is called the TG and the latter the FAMe method) and both fractions were monitored directly on the plate by an UV dual wavelength thin layer chromatoscanner at 230nm. Absorbances (expressed in terms of grams of oil or FAMe used for the chromatography) of P fractions increased with increase in heating time, while those of Ap remained fairly constant at low levels. Ratios of P/Ap for fresh oils remained less than 1 by both methods. At 20 hr of heating (which is considered to be a maximum useful life of the oil under the experimental conditions) the ratios by the TG and FAMe method were 47 and 24, respectively, depending on the freshness of oils used. Of the two methods, the TG method was found to be more convenient and an amount of sample necessary for a single analysis was only 0.2mg and the time required for examination of 24 samples/plate was 12 hr.
In the catalytic reduction of oleyl oleate by palladium on carbon catalyst, it has been found that hydrogenolysis of C-O bond of alkoxy group is occurred besides the hydrogenation of double bonds. The hydrogenolysis is occurred only when the esters being reduced possess unsaturated alkoxy group. The whole reactions occurred are illustrated below : in which A1B1=oleyl oleate, A1B1=stearyloleate, A0B1=oleyl stearate, A0B0=stearyl stearate, A1H=oleic acid, A0H=stearic acid, B'H=n-octadecene and B0H=n-octadecane. Rate equation of the hydrogenolysis is seemed to be expressed as first order with respect to the reactants : d/dt ([A1H] + [A0H]) =k6 [A1B1] +k7 [A0B1] in which the rate constant k7 seems to be greater than k6. The reaction temperature has a marked effect on the hydrogenolysis, the higher the temperature the greater the extent of hydrogenolysis. Besides the palladium catalyst, rhodium, platinum, ruthenium and nickel catalysts have also tried for the catalytic reductions of oleyloleate. Of all these catalysts, palladium has an excellent hydrogenolytic activity as shown below : palladium>>rhodium>platinum>rutheniumnickel The activity of ruthenium and nickel are almost nil. The order of the activities is identical with that of the doudle bond migration in the general catalytic reduction of olefins.
The metathesis of methyl oleate with the WCl6-cocatalyst system was investigated. Tetra-n-butyl-stannane, tetraethylstannane and triethylaluminum were effective as cocatalysts. The optimum reaction condition was considerably different from that for the metathesis of internal alkene having no functional group. The addition of methyl oleate or methyl stearate depressed the various side reactions in the metathesis of alkenes having no functional group. These facts indicate that in spite of the high reaction temperature, the relatively high selectivity is obtained in the metathesis of methyl oleate owing to the existence of its ester group. Cross metathesis of methyl oleate and 1-decene was examined.
In previous papers the authors reported that browning products yielded by heating of lecithin (PC) were polymerized compounds formed of PC by aldol condensation. In this paper, catalysts and catalytic effect of the browning reaction of PC were investigated. Phosphorus and/or nitrogen containing compounds yielded by heating of PC were fractionated by solvents extraction and silicic acid column chromatography and their catalytic effects on the brown discoloration were examined. The results indicate that choline and/or phosphoric acid in PC accelerated the browning reaction. From the results obtained by the heating of PC with different solvents, it was suggested that browning reaction was accelerated mainly under anion catalytic reaction while action also showed some catalytic effect. Similar properties were noticed from both heated PC and synthetic conjugated dienone with phosphorylcholine. These results suggest that main condensing agent in browning reaction of PC is phosphorylcholine group in PC.
Some N-odd-numbered acyl-L-glutamic acids were prepared and these sodium salts were compared with the sodium salts of N-even-numbered acyl-L-glutamic acids with respect to the Krafft points, critical micelle concentrations (cmc), pH values, surface tensions, foaming powers, wetting powers and dishwashing detergencies. When the Krafft points of both odd and even monosodium salts were plotted against the carbon number of the acyl radical, a zigzag curve was obtained. As to the cmc and surface activities, this odd-even alternation was not observed.
Hydrolysis of Keratin using caustic soda was carried out. The foaming capacity of the products was found to depend on the reaction time. The reaction time of 1 hr and 20 min, at which the foaming capacity was maximum, was selected in the present study. The molecular weight distribution of the products and the average molecular weights were determined by Gel Filtrations using Sephadex G-150 and G-200. It was found that the molecular weight distribution extended over a wide range (from 5.5×103 to 1.5×105), and the number average molecular weight and the weight average molecular weight were 1.49×104 and 2.93×104, respectively.
The ζ-potential of polyacrylonitrile fiber Vonnel P was measured in aqueous acid solution (pH3) of anionic surface active agents-sodium dodecyl sulfate (SDS) and sodium tetradecyl sulfate (STS). The amounts adsorbed of surface active agents per unit area of the fiber surface were calculated from these ζ-potential values. With increasing the concentration of surface active agent, the sign of the ζ-potential value of this fiber changed from positive to negative and the amount adsorbed of surface active agent at the fiber surface increased because of the electrostatic attractive force and van der Waals' force between the fiber and those agents. The free energy of adsorption for surface active agent ΔG was calculated from the slope of the ζ-logCS (CS : the concentration of surface active agent) curve, etc.ΔG decreased with rise of temperature and with increasing the chain length of surface active agent. The heat of adsorption ΔH and the entropy of adsorption ΔS for SDS were-6.8 kcal·mol-1 and 5.3 cal·mol-1·deg-1, respectively. The corresponding parameters for STS were-6.1 kcal·mol-1 and 8.7 cal. mol-1·deg-1, respectively. These thermodynamic data indicate the importance of entropic interaction (the formation of hydrophobic bond) as a driving force to adsorption for SDS and STS at the fiber surface. From the occupied areas of surface active agent molecules on the fiber at the maximum adsorption of those agents, it was suggested that SDS and STS were coarsely adsorbed on the fiber.
The seed oil from Parthenocissus tricuspidata Planch has been studied. The dark-colored oil extracted with ether from the air-dried seeds was bleached with acid clay and then treated with acetone. The acetone-soluble oil was analyzed for its characteristics (Table-1), and the fatty acid composition was determined by GLC (Table-2). Linoleic acid constituted as high as 76.6% of the total fatty acids. The unsaponifiable matter, a light yellow solid, was separated into nine fractions by liquid chromatography on silicic acid (Table-4), and each fraction was analyzed by IR spectrometry and GLC. The main individual components identified were as follows : Nonacosane (49.8%) and heptacosane (34.2%) among hydrocarbons ; tetracosanol (32.2%) and tricosanol (28.3%) among aliphatic alcohols, a large proportion of the odd homologue (C23) being worth notice ; β-sitosterol accompained by a small amount of two other sterols, campesterol and stigmasterol, in the sterol fraction.