Purified methyl eicosapentaenoate at considerably high degree was prepared by saponifying cuttlefish oil, esterifying the obtained fatty acids with methanol, fractionating the esters through urea adducts, distilling in vacuum the esters of highly unsaturated acids, and separating the esters by means of chromatography. It was autoxidized in the dark at 0 to 2°C. Peroxide concentrates from autoxidized methyl eicosapentaenoate were obtained by the countercurrent extraction procedure, in which the autoxidized ester was simultaneously separated from the unoxidized ester. It has the highest peroxide value (m equiv./kg) 1.19×104 of all lipids ever obtained. The ultraviolet and the infrared spectra of the peroxide concentrates were determined. From the ultraviolet spectra, it was proved that the number of conjugated diene per molecule is about 0.5, that the conjugated triene is negligible, there are no conjugated tetraene and pentaene, and that little unsaturated carbonyl groups exist. Dihydroperoxide exists from the results of infrared spectrum and peroxide value, etc. The -_??_=_??_-_??_-_??_=_??_- group probably exists in the peroxide concentrates, because the α-methylene group absorption in the infrared spectra decreased more than that of expected influences due to conjugated dienes, etc. Cis-trans conjugated diene and trans-trans conjugated diene exist, but considerable double bonds remain as cis-nonconjugated forms.
In the former paper, it was pressumed that oxidized lipids form the complexes with proteins of arterial wall, and deposits of lipids then occurred around the complexes, cause atherosclerosis. Highly unsaturated acids in the lipids of arteries are concentrated in phospholipids. And also, more highly unsaturated acids are more easily oxidized. Therefore, in this case, oxidized lipid may be concentrated in the phospholipids contained in the lipids of atheroscleotic arteries. From this point of view, lipids of atherosclerotic abdominal aorta were dialysed to separate the residue (phospholipids concentrates) and the dialysate. And then these fatty acids were obtained. From ultraviolet and infrared spectra, compositions and properties of these fatty acids were made clear. It was ascertained that oxidized lipids were concentrated in the phospholipids contained in the lipids of the atherosclerotic aorta, and that the trans-trans conjugated diene hydroperoxide existed in the oxidized lipids. After extracting the lipids from the atherosclerotic aorta, further extraction was performed to obtain residue which then was hydrolysed with alkali, and the amount of fatty acids in the residue was estimated. Thus, it was demonstrated that the atherosclerotic aorta contained lipid-protein complexes. From the infrared spectrum it became clear that oxidized lipids containing trans isomers existed in the lipids of the lipid-protein complexes.
The authors contemplated to find optimum conditions to manufacture propylene oxide and glycol by pilot plant. In manufacturing propylene chlorohydrin in circulating type column it was found that over 95% yield was achieved in continuous reaction, and that the formation of dichloride was from four to six times much as in batch reaction, and it was also recognized that the reaction temperature was kept almost constant without any cooling in continuous reaction. In manufacturing propylene oxide in the reactor having a providing net at the bottom it was found that the increase in pressure of the reactor owing to the connection to a distillation tower caused the yield worse, and the relation between the composition and the temperature in the distillation tower was also studied. Further investigations were made for the optimum condition in manufacturing propylene glycol using a multiple-type continuous reactor.
Various kinds of plasticizers such as dialkyl glycol ester were synthesized and tested as plasticizers of polyvinyl acetate films. Among these, as a result, dimethyl, diethyl glycol sebacate and dimethyl, diethyl, dibutyl glycol adipate had better plasticity effects and lower evaporation loss than the conventional dibutyl phthalate.
N-n-alkylethylenediamine have been prepared by the condensation of ethylenediamine with alkylbromides (C10C16). They were waxy, low-melting solids and combined with two equivalents of organic acids to form neutral salts which would be useful as cationic surfactants. Investigations were made on the surface activities of these salts with acetic, lactic and propionic acid. N-n-alkyl-ethylenediamine salts containing C10 and C16-alkyl group did not show good surface activities. On the other hand, N-n-dodecyl or N-n-tetradecylethylenediamine salts were found to have excellent surface activities. In respect of surface tension and penetrating power, acetates and lactates were superior, to the propionates, but inferior in foaming power.
To investigate the detergency of nonionic surfactant, following two parts of experiments were carried out for the polyoxyethylene nonylphenyl ether EO 10mole (PEG-N) by using Launder-O-meter and artificial standard soiled cotton cloth. 1) The effects of inorganic builders on soft and hard water. The concentration of PEG-N aqueous solutions was from 0.05g/l to 0.5g/l and that of inorganic builders was twice of the surfactant. The result showed that polyphosphates (hexametaphosphate, tripoly phosphate and pyrophosphate), were more effective than other builders (silicate, carbonate and neutral salts) in both soft and hard water. 2) The influence of calcium salt present in the washing water. The detergency test was carried out in water of various hardness, fixing the concentration of PEG-N aqueous solution at 0.1g/l. As a result, it was found that in the case of polyphosphate, there was certain relationship between the concentration of added builders and washing efficiency. For example, in the case of pyrophosphate, when 0.5 mole of pyrophosphate per 1mole of calcium ion was used, washing power increased remarkably.