The methods of separation of ferulates by TLC and reversed-phase TLC and quantitative estimation of ferulates using both TLC and ultraviolet spectroscopy were investigated. The separation of ferulates from the mixture of ferulates and rice bran oil were investigated by TLC. The ferulates from the samples gave a single spot that was not found to each of the ferulates by the TLC method. However, a separation of β-sitosteryl ferulate, stigmasteryl ferulate and 24-methylenecycloartanyl ferulate was accomplished by reversed-phase TLC in the system, liquid paraffin/methanol-acetonitrile (2 : 1), thus enabling the analysis of mixtures of ferulates in rice bran oils. Also, in this way β-sitosterol, stigmasterol and 24-methylenecycloartanol were clearly separated. The double-development procedure, employing hexane-diethyl ether (9 : 1) firstly and then benzene-diethyl ether (4 : 1), was most suitable for the separation of ferulates from other components in rice bran oil. The separated ferulates in the chromatogram were extracted with ethanol. The optical density of the ethanol solution at 327 mμ was determined and the ferulate content was calculated. Since materials interfering with the ultraviolet spectroscopic analysis were eliminated by TLC, the results obtained by the method mentioned above are more accurate as compared with those determined directly by ultraviolet spectroscopic method.
Usual GLC and UV methods were examined for determination of conjugated diene content in fatty acid derivatives. Of the two methods the conjugated diene values obtained from GLC agreed well with the known concentration in good correlation, while the UV method did not agreed so well. An equation; c2= (k2/110) ×100=0.91 k2; is presently applied for determination of conjugated dienoic acid in the UV method, whereas according to the authors' experimented results a good agreement could be obtained by the use of a modified equation; c2=1.12k2; in fair correlation to the known concentration samples. (Where, k2 is absorptivity at 233mμ and is found from k2=k223-k0, where k0 is the one which is corrected for absorptions otherwise from conjugated acid such as carbonyl radical, wherein k0 is 0.07 for esters and 0.03 for fatty acids and soaps.) From the above experimented results good agreement could be seen in the UV method, too, as well in the case of GLC in the preciseness for determination of conjugated dienoic acid derivatives.
The authors are working on the liver oils of edible crabs in the Northern Ocean of Japan. In the present work α-alkyl glyceryl ethers and cholesterol were found in the solid from the unsaponifiables of the liver-oils of Chionoecetes opilio (Zuwai-kani) and Lithodes turritus (Ibara-kani). Two kinds of crystalline materials were isolated from the solid part of unsaponifiables by the fractional crystallization from methanol. One of them was identified as cholesterol by means of IR, NMR and mass spectroscopies. The other was confirmed to be the mixture of α-alkyl glyceryl ethers from the results of IR and NMR analyses. Then they were separated through GLC into C8C20 α-alkyl glyceryl ethers. The major components were α-n-hexadecyl and α-n-octadecyl glyceryl ethers. Their contents were respectively 69.0% (C. opilio), 59.0% (L. turritus) and 19.7% (C. opilio), 35.2%. (L. turritus).
In the previous paper (1), authors reported that the fat bloom of lauric hard butter is formed by polymorphism of glycerides mainly consist of lauric acid. In the present study, in order to confirm which lauric glyceride contributes to fat bloom, chocolates ware prepared from lauric hard butter which contain various synthetic glycerides, and were forced to form fat bloom under accelerated condition. The fat which was scraped off from the surface of bloomed chocolate was analyzed by gaschromatography and differential scanning calorimeter. In the bloomed fraction, C36-glyceride increased when trilaurin was added. When dilauromonocaprin was added, C34-, and C36-glyceride increased. However, dilauromonomyristin and dilauromonopalmitin did not promote the formation of fat bloom.
The authors observed that in the case of frying, especially whale meat, the frying-oil was colored and deteriorated by substances cozed out from the whale meat, for instance, by nitrogen compounds (protein, pyrrole substance) and metals (iron and copper, etc.) due to the decomposition of blood, etc. and whale oil. Also, the copper and iron in these frying oil were very often observed to be decreased during the storage. In this paper, for making clear the reason of decrease of copper and iron in frying oil, a model test on the reaction between protein and copper in the system of aqueous solution and oil was carried out. Thus the copper of different stages in the concentration was mixed with casein in water, or, mixture of casein, copper (copper sulfate) and soybean oil was heated for 1 hour at 180°C, and the amount of aduct formed with these materials was measured. The results obtained were as follows : It was confirmed that the amount of copper adduct to casein increased with the storage days in both system of aqueous solution and oil, namely, it became clear the easy formation of copper-protein complex.
Ordinarily, Schloetter's method is usual for the determination of sodium carbonate to be detected about 16 wt% in the household detergents. However, its analytical preciseness is not enough satisfactory. A determination of sodium carbonate in household detergents has been developed, in which sodium carbonate is absorbed in barium chloride as carbon dioxide and excess barium is titrated with EDTA. The carbon dioxide produced by decomposition of the sample using 30vol/vol% sulfuric acid is absorbed in a barium chloride in 0.1N-sodium hydroxide. The precipitate of barium carbonate is filtrated and the excess of barium ion in the solution is titrated with standard solution of EDTA using Eriochrome Black T as the indicator and the amount of sodium carbonate is calculated. The time required for the analysis of sample was about 11.5hrs with recovery more than 96.9 wt% and precision of recovery was 2% in coefficient of variation. Furthermore, sodium carbonate in aqueous solution could be detected by the same method.
Chlorophosphonation of α-olefins was carried out. The product mixtures were esterified with ethanol and analyzed by GLC, using 3m×3mm φ, Ucon LB 550 X column, and identified by the comparison to authentic samples synthesized by other methods. In paralell to the substitution of dichlorophosphinyl group in methylene C-H, an addition of chlorine and dichlorophosphinyl group to the double bond of α-olefin occurred. Substitution at the allylic methylene group scarcely occurred in comparison with the substituton in other methylene groups. Chlorophosphonation of saturated hydrocarbon was inhibited completely by addition of a small amount of sulfur or iodine. However the reaction of α-olefin or the mixture of α-olefin with saturated hydrocarbon did'nt be inhibited in the similar manner and the chlorophosphonated products were obtained in tolerable yields. This might be attributed to the intermediate formation of allylic hydroperoxide, which plays a role in the initiation of the radical reactions.
The author investigated the effect of water on soil deposition in nonaqueous surfactant solution systems. The deposition of carbon black and ferric oxide on cellulose, polyamide and polyethylene powders were examined in n-hexane and tetrachloroethylene solutions of sodium dioctylsulf osuccinate (AOT). The degree of soil deposition was independent of concentration of AOT, and was affected by the amount of water contained in the systems. In the case of carbon black, curves of the degree of deposition against the content of water in solution showed a maximum for cellulose and polyamide in each system, but not for polyethylene. A similar behavior was observed in the case of ferric oxide, but the maximum in the curves was not distinct. These results seem to be attributed to the amount of water adsorbed and the nature of the surface which may also adsorb the surfactant.
The fatty acid composition and the proerties of the unsaponifiable matters in acetone soluble fraction of Affinis and Hirsutus were examined. The fatty acid compositions were determined by GLC. The unsaponifiable matters were soft solids in both cases and their yields were 33.3% to the acetone soluble fraction in Affinis, and 36.4% in Hirsutus, respectively. The percentage of sterol and Δ5, 7 sterol to the unsaponifiable matters were 17.4%, 14.8% in Affinis, and 9.3%, 6.1% in Hirsutus, respectively. The main sterol was ergosterol in both cases and contained 60.5% of ergosterol to the total sterol in Affinus and 65.5% in Hirsutus by GLC. The another constituents of the unsaponifiable matters were seemed to be long chain hydrocarbons and ketoalcohols.