Five kinds of 4-methyl sterol and also their oxo, acetoxy (OAc), trifluoracetoxy (TFA) and trimethylsiloxy (TMS) derivatives at the position of C-3 were prepared from cholesterol. Relationship between the molecular structure of 4-methyl sterols and their retention time has been studied. The retention data were expressed as the relative retention time and the methylene unit value (Table-2, 3). The increment of the retention time due to the introduction of 4-methyl group was shown in Table-4 as retention factor. Main results obtained were as follows. 1) The retention times of 4-methyl sterols and their derivatives were found to be larger than those of the corresponding non-methylated sterols and their derivatives. 2) The retention factor of 4-methyl group was affected by its number and stereochemical configuration, the nature of C-3 functional group and unsaturated bond adjacent to the 4-methyl group. 3) The retention times for the derivatives at C-3 functional group were in the following increasing order : TFA<hydroxyl<TMS<OAc on SE-30; TFA<TMS<hydroxyl<OAc on OV-17. The change of C-3 functional group from hydroxyl to oxo resulted in an increase in retention time for 4α-methyl compound, while it decreased for 4β-methyl-, 4, 4-dimethyl- and 4, 4-dimethyl-Δ5 compounds. 4) 4α- and 4β-methyl compounds could be separated each other finely well on SE-30 and on OV-17, and the latter was eluted after the former, while the both isomers with oxo and TMS group at C-3 exhibited almost equal retention times. 5) The retention time of the compounds with 4, 4-dimethyl group was smaller than might be expected, especially 4, 4-dimethyl-Δ5-cholesten-3-one was eluted faster than the corresponding non-methylated Δ5-cholesten-3-one.
The composition of a standard mixture containing methyl esters of C12, C14, C16 and C18 fatty acids was determined by a gas chromatograph with a flame ionization detector and an electronic integrator by changing the flow rate of the carrier gas, and the influence of the variation on the weight response of the components were examined. It was observed that the variation of the flow rate of the carrier gas had significant influence on the weight response of the components, especially on those of C12-Me and C18-Me. Then the programmed temperature operation was carried out using a standard mixture of six components from C8-Me to C18-Me to examine if the correct analytical values would be obtained by this operation. The deviation of the analytical values from the known values was decreased by temperature programming, but not diminished. The weight response of the components increased as the carbon number increased, and the rate of the increase from C8-Me to C10-Me was significant. Therefore, authors believe that the influence of the carbonyl group in the molecule on the weight response of C8-Me and C10-Me is not negligible.
Soybean oil was heated at 180°C for 35 and 50 hours. Fresh soybean oil and thermally oxidized oils were fed to rats in a diet containing 15% of oil. The contents of the lipids, tocopherol and protein and amino acids composition in liver, blood and testicle were determined. The results indicated that the rats fed with thermally oxidized oil showed growth depression and ruffled hair as reported in previous papers. The weights and the lipids content in liver of rats fed with thermally oxidized oils were higher than those of rats fed fresh oil. On the contrary, the decrease of weight and of lipids content in testicle was observed. The decrease of protein content was observed in the liver, blood and testicle of rats fed thermally oxidized oils. A significant difference in the liver amino acid composition was observed between rats fed with fresh oil and thermally oxidized oils. Namely, tyrosine, histidine, iso-leucine, serine, cystine, proline and lysine etc. were less detected in those fed with thermally oxidized oils.
1) A number of methyl linoleate derivatives, all highly purified, were examined on their toxicities for the mice and the chick embryos. Each substance was administered to the mice with a gastric tube or to the yolk sacs of the chick embryos through the egg shells with an injector. The results obtained from both animals were quite similar. 2) The compounds used in this experiment were as follows; methyl hydroperoxyoctadecadienoate (HPO), methyl hydroxyoctadecadienoate (HO), methyl ketooctadecadienoate (K), methyl hydroperoxyepoxyoctadecenoate (HE), methyl trihydroxyoctadecenoate (T), methyl octadecadienoate (trans, trans-conjugated) (t-C), methyl epoxyoctadecenoate (α-unsaturated) (E α), methyl epoxyoctadecenoate (β-unsaturated) (E β), methyl linoleate (ML), and methyl ricinolate (MR). Five compounds from the top of the aboves, especially HE, proved to have strong toxicities as compared with methyl linoleate. When the relation between the radicals in these compounds and their toxicities was investigated, the toxic strength came in the order of -OOH>-CO>-OH. 3) The characteristic disorders were found in all the mice administered with toxic substances, in more or less degree. Those were atrophy of the spleen, marked dilatation of the intestine, several histological changes in the lymphatic system, and decrease in the leucocyte count in the blood. 4) It was shown that the toxic lesions in the mice induced by these compounds were quite the same as those by the rancid edible oils seen previously. These results indicate that the toxicity of rancid edible oils is the sum of the toxicities of numerous oxidation products.
Crude high density lipoprotein of egg yolk was fractionated by rate zonal ultracentrifugation. Rate zonal ultracentrifugation was carried out with zonal rotor RPZ-43T (660ml) in density gradient d. 1.00-1.40 by sodium bromide at 40000rpm. By the ultracentrifugation for four hours, the separation of high density lipoprotein (HDL) from low density lipoprotein (LDL) was observed, but HDL was completely purified only by the second ultracentrifiugation for twenty four hours after the first procedure. The purified HDL shows only one peak in the schlieren pattern of the analytical ultracentrifugation.
Properties of the floweroil of Seiyotanpopo (Taraxacum officinale Weber) and Mizugiku (Inula cilialis Maxim) and their fatty acid and unsaponifiable components were studied. The conjugated polyenoic acid contents of these two flower-oils were similiar (Table-4), but the total unsaturated fatty acid contents were very high in Seiyotanpopo as compared to Mizugiku as showed in Table-5. It seems characteristic that the contents of unsaponifiable matters of both samples are very high (about 30%). The unsaponifiable matters of both samples are presumably consisted of long chained hydrocarbons, triterpenealcohols and β-sitosterol.
Gas chromatograms of mixtures of fatty acid methyl esters containing positional and/or geometrical isomers, were obtained using capillary columns (BDS and Apiezon L). The samples prepared by hydrazine reduction of linoleic and linolenic acids were separated into 4 and 8 peaks by BDS column, respectively and the sample obtained by isomerization of methyl linoleate in the presence of nitrous acid gave only two peaks. Chromatograms of fatty acid methyl esters of hydrogenated soybean and linseed oil were also obtained by the same column. The methyl esters from those oils were fractionated into mono- and diene fractions by preparative GLC using EGS column, and then each fraction was run by Apiezon L. Monoene fraction was separated into much more peaks than diene fraction was.
In the study of the organic composition of Chionoecetes opilio, Chionoecetes opilio oil was obtained from the dried material of Chionoecetes opilio (Zuwai-kani, _??_), liver oil from the liver, and body oil from the dried material of the body parts excluding the liver. The characteristics and the composition of fatty acids of each oil were examined. Greater parts of the oils obtained from Chionoecetes opilio were stored in the liver. Of the three kinds of oil mentioned above, fatty acids of an odd number of carbon were identified besides those of even number of carbon. From the Chionoecetes opilio oil, 21 kinds of fatty acids were proven to exist, of which the principal acids were C14, C16, C18, C16 : 1, C18 : 1, C20 : 1, C20 : 3 and C22 : 3. Among these fatty acids, about 63% of the whole mixture consisted of C16, C18 : 1 and C22 : 1. The body oil contained as many as 23 kinds of fatty acids, though little in the quantity, about 88% of which consisted of C14, C16, C16 : 1, C18 : 1, C20 : 1, C20 : 3, C22 : 1 and C22 : 2. On the contrary, the liver oil contained considerably much quantities of fatty acids, which were separated into only 14 kinds. A 95 percent of these acids consisted of C14, C16, C16 : 1, C18 : 1 and C20 : 1. C18 : 1 (oleic acid) covered nearly one half of this percentage.