The mass spectra of cholesteryl ferulate, campesteryl ferulate, β-sitosteryl ferulate and stigmasteryl ferulate, and of their acetyl derivatives and trimethylsilyl ether derivatives, and of a mixture of campesteryl farulate, β-sitosteryl ferulate and stigmasteryl ferulate, and of oryzanol that is a mixture of some ferulates from rice bran oil were measured. In these spectra, the molecular ion peaks of steryl ferulates and their acetyl derivatives were not observed. The base peaks were observed at m/e 368 in the spectra of free cholesteryl ferulate and its acetate, at m/e 382 in the spectra of free campesteryl ferulate and its acetate, at m/e 394 in the spectra of free stigmasteryl ferulate and its acetate, and at m/e 396 in the spectra of free β-sitosteryl ferulate and its acetate. These base peaks are corresponding to M-194 in spectra of ferulates and M- (194+42) in spectra of acetyl derivatives of ferulates. These peaks serve to distinguish a steryl ferulate from other steryl ferulates. Moreover, the characteristic ion of these steryl ferulates due to the formation of ferulic acid ion occured at m/e 194. The fragmentation patterns of the mass spectra of acetyl derivatives of steryl ferulates were similar to those of corresponding steryl ferulates, and the characteristic ions of these acetyl derivatives of the steryl ferulates were not found. In the mass spectra of trimethylsilyl ether derivatives of the steryl ferulates, the molecular ion peaks were observed for each derivative, but they were very small. Furthermore, the mass spectra of the mixture of campesteryl ferulate, β-sitosteryl ferulate and stigmasteryl ferulate, and of the oryzanol were investigated. It was found that the mass spectrum of oryzanol can be used for the qualitative analysis of the components in the mixture of ferulates from rice bran oil.
It is known that natural antioxidants are usually contained in vegetable oil and fats, and tocopherol (Toc) is the most abundant substance in those oils. Toc decomposes on heating, so it may be conceivable that the toxic effect of thermally oxidized oil (TO) is enhanced by the decrease of Toc. In the previous papers, the authors reported that Toc reduces the toxicity of TO in rats. The present paper deals with the influence of Toc on lipid component and triglyceride composition of rat tissues of rats fed fresh oil (FO) or TO. Toc-free FO was prepared by aluminium oxide column chromatography from fresh soybean oil and TO was prepared from the same oil by heating at 180°C for 50hr. Rats were fed on the diets containing FO and TO with or without Toc. The total lipids extracted from each tissue of rats were separated into neutral lipid (NL) and phospholipid fractions by column chromatography and triglyceride (TG) was isolated from (NL) fraction by thin-layer chromatography. Fatty acid distribution in TG was investigated by pancreatic lipase hydrolysis. The results indicated that total lipids and percentage of their phospholipids in liver, kidney and testicle of rats fed on Toc-free TO decreased markedly compared with those fed on FO or Toc-free FO. TG in tissues of rats fed on Toc-free TO decreased, but cholesterol increased. Significant difference on component fatty acids and 2-position of TG was observed. TG in each tissue (except kidney-TG after 30 days feeding) of rats fed on FO or Toc-free FO showed higher proportion of C18 : 2 than C18 : 1. On the contrary, C18 : 2 content in TG of rats fed on Toc-free TO was lower. The percentage of unsaturated fatty acids at the 2-position in each tissue TG was high compared to saturated fatty acids at the same position and/or component fatty acids in TG. Percentage of C18 : 1 and C18 : 2 at 2-position of TG was about 80 mole % in each tissue. C16 : 0, C18 : 0 and C18 : 1 at this position in TG of rats fed on Toc-free TO increased but C18 : 2 decreased to compare with those of FO or Toc-free FO groups. Toc was effective for prevention of toxicity induced by TO as described above, but no significant effect was not observed for FO. These results suggest that Toc has some biological antioxidative and protective activities aganist the toxicity induced by TO.
In the previous papers, the authors reported and made clear the easy formation of melanoidin-metal complex in aqueous solution and oil. As for the antioxidative effect of these materials, it was found that the rancidity of lard was the highest in the case of melanoidin (M) -metal mixture or M-metal complex. In this paper, the relationship between the binding ability of water soluble browning materials of miso (MB) with metal, and the effects of MB, tocopherol (Toc), metal and the mixture of these on the rancidification of oil were investigated. MB were prepared from water soluble browning materials in miso by Sephadex G 25 and four colored components were fractionated by DEAE-Cellulose column chromatography. MB and four fractionated materials was reacted at 50°C with some metals. From the experimental results, it was found that MB-metal complex was formed like melanoidin (M, prepared from a mixture of glycine and D-xylose by heating at 100°C for 5hr) -metal complex and the amount of MB-metal complex increased with the reaction time in aqueous solution. MB showed some antioxid ative activity, and the higher the added contents of MB, the larger the antioxidative effect in the lard was. It was also found that the rancidity of oil was seriously effected by metal and metal-Toc mixture, but in the case of MB-Toc-metal mixture, the peroxide value remained low.
The mixtures of known compositions of methyl esters of six fatty acids (C8, C10, C12, C14, C16, and C18) were analyzed collaboratively by programmed temperature gas chromatography. The experimental data were treated statistically to examine inter- and intralaboratory scattering. Moreover, the effect of the correction by correction factors was investigated. For the analysis of a sample containing esters which considerably differ in retention time, programmed temperature GLC was preferable to isothermal GLC in regard to the scattering of experimental values and the deviation from the known value. High program rate, such as 10°C/min, however, resulted in an increase of scattering in experimental values. The data from the laboratories, in which the intralaboratory CV (coefficient of variation) was so small as to be less than 3.0% for any five components of six in each sample, were corrected with correction factors which were calculated from the analytical values of other sample. The interlaboratory CV of the uncorrected values appreciably decreased compared with those of values obtained by all laboratories. The corrected values agreed very closely with the known values and the interlaboratory scattering of those corrected values considerably decreased.
Among many test methods of detergency of dishwashing detergent, the most practical method has been plate dish wash test (practical hand dish washing test). In this report, a new test method (method A) which consists of a simple operation and has sufficient accuracy was proposed. Some of the commercial dishwashing detergents were tested by method A and by plate dish wash test, and the results showed good coincidence. Moreover, sodium N-acyl-L-glutamates were evaluated by method A as surfactants for dish washing detergent. Detergencies of the mixtures of sodium N-oleoyl-L-glutamate and dimethyllaurylamine oxide or coconut fatty acid diethanolamide were better than those of the components. Detergencies of sodium N-oleoyl-L-glutamate containing organic salts were also measured.
The following three compounds, sodium N- (p-hydroxybenzyl) -fatty acid amide sulfonate (R7, R11 and R15) were prepared, _??_ R : n-C7H15 (R7), n-C11H23 (R11), n-C15H31 (R15) The physico-chemical properties of the aqueous solution of these compounds were studied by specific gravity, surface tension, electroconductivity, dispersability of CaCO3 and wettability to the cloth, etc. It was found that the surface activities of these compounds was not high except the dispersion ability of R11.
The four samples of sodium n-alkoxybenzene monosulfonates (alkyl : n-octyl, n-dodecyl, n-hexadecyl and n-octadecyl) were prepared, refined and identified. The physico-chemical studies on the properties of the aqueous solution of the above compounds (density, viscosity, surface tension, electric conductivity, wettability, emusificability and solubilizability) were carried out. From these results, it was concluded that the above compounds were inferior to ordinary surfactants in spite of the structural similarity with p-n-alkylbenzenesulfonates, well known commercial surfactants. This may be due to hydrophilic ether group located near the center of the molecule making the molecule more hydrophilic.
The cationic addition of chloromethyl methyl ether to isoprene in the presence of metal halides was investigated in order to obtain the 1, 4-adduct, 1-chloro-3-methyl-5-methoxypentene-2. It was found that the addition of small amounts of ethyl alcohol caused a large increase in the yield of the adduct, especially in the case of stannic chloride catalyst. Aliphatic glycols and esters as well as alcohols were found to be effective cocatalysts. A reaction mechanism of the cationic telomerization was discussed and the effects of the additives were attributed to the intramolecular chloride transfer in the reaction intermediate, [CH3OCH2 (C5H8)] + [SnCl5] - [ROH] x. The Grignard coupling of 1-chloro-3-methyl-5-methoxypentene-2 with methallyl chloride afforded α-isogeranyl methyl ether, a useful component of mixed perfumes.
In our previous communication the discovery of ceramide 2-aminoethylphosphonate (CAEP) in ova of a fresh-water bivalve, H. schlegelii was reported. The ova sphingolipid contained mostly 4-sphingenines which were composed of octadecasphingenine (predominant) and branched octadeca- and nonadecasphingenines. In this paper we wish to report on the characterization of the above branched compounds. A ceramide fraction derived by enzymatic degradation of CAEP was subjected to catalytic hydrogenation, hydrolyzed and separated into long-chain bases and fatty acids as described earlier. Thin-layer chromatogram of the hydrogenated long-chain bases revealed one major ninhydrin positive component with the same Rf value as that of authentic octadecasphinganine, with a very small amount of artifacts (O-methyl derivatives) (Fig. -1). The hydrogenated bases were oxidatively cleaved to aldehydes with lead tetra-acetate (this resulted in the loss of two carbon atoms from the parent carbon skeleton), and were analyzed by gas-liquid chromatography (GLC) using a 3m×3mm glass column containing 25% EGS on 6080 mesh Celite 545. Based on equivalent chain length data described by Morrison on straight and branched chain aldehydes, all of the aldehydes except Peak 3 in Fig. -2 were tentatively identified as iso-hexadecanal (Peak 1), n-hexadecanal (Peak 2), iso-heptadecanal (Peak 4) and anteiso-heptadecanal (Peak 5), respectively. For the further confirmation of the above branched chain compounds, the aldehydes were oxidized with silver oxide, and the resulting fatty acids after methylation were analyzed by GLC. Fatty acid methyl esters derived from the aldehydes of Peak 1, 2, 4 and 5 had identical retention times as iso-palmitic acid, palmitic acid, iso-margaric acid and anteiso-margaric acid (Fig. -4). However, Peak 3 in Fig. -4 did not correspond to any of the authentic saturated methyl esters available in the C14C17 range and no further characterization of this peak was made. From the gas chromatographic analyses of aldehydes and the corresponding fatty acid methyl esters, the composition of long-chain base mixtures in the ova CAEP was calculated and given as follows; iso-sphingosine (12%), sphingosine (60%), iso-nonadeca-4-sphingenine (2%), anteiso-nona-deca-4-sphingenine (22%) and unidentified long-chain base (4%). This is the first paper on the branched long-chain bases found in shellfish.
On measuring Solid Fat Index (S.F.I.) there are many defects in the usual measuring methods such as A.O.C.S. and J.O.C.S. (Part 1) tentative methods. For example, the operator cannot easily obtain the reliable data with A.O.C.S. method because the fat samples cannot be solidified below 0°C, and mercury employed in J.O.C.S. (1) method is toxic and has a disadvantage of waste water pollution. So, the authors investigated a few measuring methods free from the above-mentioned defects. The modified method that the authors have establised employs a CaCl2 aqueous dye solution (30.4wt%) as a sealing liquid and the same type of dilatometer is used as that in J.O.C.S. (1) method. In this modified method the disadvantages of water pollution are eliminated.