Atherosclerosis is caused by deposits of lipids in the arteries. Lipids containing oxidized unsaturated fatty acids and protein form complexes which have strong linkages unable to be separated by solvent extraction. If oxidized lipids form the complexes with protein of arterial wall, deposits of cholesterol and its esters of fatty acids may occur around the complexes. In this case oxidized lipids may be detected in the lipids of arteries. From this point of view, lipids were extracted from atherosclerotic artery with methanol-chloroform (1 : 2) at room temperature. Fatty acids, and then methyl esters were obtained from the lipids. All procedures were performed at room temperature under the atmosphere of nitrogen. Fatty acids composition was calculated from the results of ultra-violet spectrum analysis. It became clear that trans-trans conjugated diene hydroperoxide exists in the methyl ester from the infra-red spectrum. No hydroperoxides were found in the lipids of normal artery.
In the previous paper, a cacao butter like fat, based on melting point, was obtained from palm kernel oil by fractional crystalization. In this paper, the products from palm kernel oil were examined on the fatty acid composition, cooling curve, micropenetration, solid content index and stability tests. The fatty acid composition of the fractionated palm kernel oil was compared with those of the original palm kernel oil. The linoleic acid and caprilic acid were reduced to zero, oleic acid and capric acid were decreased, and on the contrary myristic acid and palmitic acid were increased. Cooling curve, micropenetration and solid content index of the fractionated palm kernel oil showed that the products have a narrow melting range and melt sharply. Accordingly the products could be regarded to have a good quality as cacao butter like fat. The AOM stability test showed that the fractionated palm kernel oil was more stable than cacao butter. From the above results, the fractionated palm kernel oil has a satisfactory quality as cacao butter like fat.
The condition of making chocolate using fractionated palm kernel oil, and the qualities of the products were investigated. The results were as follows : 1) When making bitter type chocolate, mixing the fractionated palm kernel oil in cacao butter caused melting point lowering, but it was proved that the cacao butter could be replaced with fractionated palm kernel oil up to 40 per cent. 2) In case of cacao type chocolate, a chocolate was prepared by fractionated palm kernel oil only. The products was of good quality with higher melting point compared with that using cacao butter only. It showed virtually very good quality as summer chocolate. It was noticed that the fractionated palm kernel oil did not necessiate the tempering which is one of the most difficult operations in chocolate making.
The ultra-violet absorption spectra of n-hexane solutions of some oils deacidified by means of the usual anion exchange resin (Amberlite IRA-401-OH type) and the substances absorbed by it were investigated. The remarkable deviation of the spectra of the deacidified rice bran oil from the crude oil was observed while little deviation of them was found in the case of soybean oil. From the spectra of the same solution of the absorbed substances, the existence of the considerable amount of oryzanol which had already been found by Tsuchiya, was confirmed and unknown component having the absorption at 280mμ was assumed in the rice bran oil. In the soybean oil some components which have maxima of the absorption spectra near 260, 269, 280, 300 and 315mμ respectively were also assumed.
On account of obtaining optimum condition to recover oryzanol efficiently from rice bran oil, which was dissolved into some kinds of organic solvents (methanol, benzene etc.), then passed through the alternative resins. The ultra-violet absorption spectra of n-hexane solution of the absorbed substances were measured. The behavior of oryzanol was followed with the coefficient of absorbancy at 315mμ which was obtained from the ultra-violet absorption spectra of n-hexane solution of the component from rice bran oil. It was found that the strongly basic anion exchange resins (OH type) were most effective for the recovery of oryzanol.
Some ferulates as phenolic substances have been confirmed to occur in the soapstock of rice bran oil. These ferulic acid esters are resemble to that of rice germ oil. The unsaponifiable fractions from these ferulates were confirmed to consist mainly of two tri-terpenoid alcohols (cycloartenol C30H50O and 24-methylene-cycloartanol C31H52O) and sterol C28H48O.
Authors reported in the previous paper that aqueous solution of nonionic surfactant of polyethenoxy ether becomes reddish and turdid when aqueous iodine-potassium iodide solution is added dropwise and that the quantity of iodine solution required to produce the turbidity is related with the number of moles of ethylene oxide added in the surfactant. In this report, it was found that the maximum wavelength in the absorption spectrum of aqueous iodine-potassium iodide solution, when a nonionic surfactant is added into this solution, remained at constant of 350mμ in the lower concentration, but bigan to shift towards the longer wavelength at a definite concentration, and above this concentration it reached at 363374mμ and became constant (Fig. 1). The relation between the concentration of the surfactant and the wavelength of absorption maximum is shown in Fig. 3 and the concentration at which the shift of wavelength will begin can be obtained from this graph. It is believed that this dues to the molecular dispersion at low concentration of surfactant and micelle begins to form when it reaches to a certain concentration and that this micelle forms complex with iodine and begins to discolor (Fig. 4). It is assummed that the concentration at which this discoloration, or the shift of wavelength begins, is the CMC of this surfactant. Hence, a series of solutions which contain various quantities of nonionic surfactant in a definite quantiy of iodine-potassium iodide were prepared, then their spectra were measured and the concentration “Cm” at which the shift of absorption maximum wavelength began was determined (Fig. 57). From these results, it was found that Cm is correlated with n, the number of moles of ethylene oxide added (Table 1), and that the shift begins at higher concentration with the increase in number of moles aded (Fig. 8). Further, between “n” and “Cm” in the unit of 10-4mole/liter, there are linear relations as below. OP-series logCm=0.012n+0.31 NP-series logCm=0.0125n-0.18 C-series logCm=0.010n-0.65 In connection with this study, Ross et al. and Becker reported recently, independently from the authors' research, that CMC has been obtained from the change in extinction at 360mμ of the colored complex of iodine and surfactant micelle. However, the color of the complex has a tendency to fade (cf. Fig. 1 and 2) and its use in determination of CMC will introduce uncertainty. On the contrary, as the maximum wavelength used in this report does no change with time, its use for determination of CMC is considered to be quite reasonable. On the other hand, in case of polyethylene glycol solution the concentration at which the maximumm wavelength begins to shift is considerably high (10 g/100 ml, for carbowax 400), and in the case of carbowax 4, 000 the absorption disappears occassionally (Fig. 9). It is considered that in the case of polyethylene glycol micelle is not formed, but the shift of absorption maximum dues, rather, to the solvent effect (Fig. 10).
The authors contemplated to manufacture propylene glycol by catalytic and high pressure process. In the high pressure procss, it was found that impurities contained in the propylene oxide have acidified the crude propylene glycol solution. In the catalytic process, the optimum catalyst concentration was at 0.02%. For continuous catalytic hydrolysis of propylene oxide to propylene glycol, using a multi-type reactor, four vessels were required to complete the reaction, and the catalyst was completely neutralized with alkali within 30 minutes at 90°C.
Applications of dicarboxy alkylamine and alkyl-β-alanine type ampholytic surface active agents as dyeing assistants and antistatic agents were studied. Surface tension, wetting power and dye dispersing power of the former is better, while the latter has better effect on the rate of absorption of dyes. The two ampholytics showed equally good migration, but antistatic effect of alkyl-β-alanine type is better in all cases, especially for Tetron, wool and acetate.
Polyoxyethylene derivatives (1, 5, 10 and 20 moles of ethylene oxide, E, in a molecule) of polyoxypropylene cetyl ethers (1, 2, 4 and 8 moles of propylene oxide, P, in a molecule, respectively) were prepared and the change in properties of these 16 kinds of alkylene oxide derivatives, varying the number of moles of P and E was studied. (1) Solubility : Increase in hydrophobic property was observed with increase of the mole number of P in these derivatives and at the same time, a tendency to decrease the affinity against oil, having low polarity, was observed. (2) Surface tension of aqueous solution : A tendency to lower the concentration, at which reduction in surface tension will occur, was observed with increase of the mole number of P in a molecule. Except certain samples, the lowering power of surface tension was reduced with increase of the added mole number of E in a molecule, at a definite concentration. (3) Foaming power of aqueous solution : Foaming power of aqueous solution of these derivatives became larger according to the increase in added mole number of E in the molecule. By increasing the mole number of P, foaming power decreased for the cases of the derivatives having 1 and 20 moles of E in their molecules, and for the cases of those having 10 moles of E it increased contrary. (4) Foam stability of aqueous solution : Foam stability generally became worse with increase of the mole number of P. And it is expected to exist an optimum mole number of E which will show a good stability among the derivatives of E from 1 to 20 moles. (5) Wetting power of aqueous solution : With increase of the mole number of P, wetting power became greater for the derivatives having 20 moles of E and became lower for those having 10 moles of E.
The fatty alcohol was prepared from methyl α-eleostearate by Bouveault et Blanc reduction which is quite different from the case of nonconjugated fatty acid esters. The yield of the fatty alcohol was only 83% of theory. The fatty alcohol was separated by liquid chromatography into dienoic (D-part) and trienoic (T-part) alcohols. The infrared absorbtion curves of these two parts showed cis, trans cojugated diene and isolated trans ethylene, not corresponding to that of original methyl α-eleostearate. The ultraviolet absorbtion curves of these two samples, entirely independent from that of the original ester, showed that D-part is mainly composed of conjugated diene and T-part contains less conjugation than D-part. The paper chromatography of oxidation products by potassium permanganate in acetone was studied for the purpose of determining the double bond position of fatty alcohols. It came to conclusion that D-part is a mixture of 10, 12-octadecadiene-1-ol and 11-octadecene-1-ol, and trienoic component of T-part is a mixture of some positional isomers, namely 9, 12, 15-, 9, 12, 14-, 9, 11, 13-octadecatriene-1-ol which were consequently formed by the shift of double bonds. The mechanism of double bonds shift and isomer formation was discussed.
The authors have studied on the hydrogenation of acetylene contained in a small amount in a mixed gas of hydrogen and carbon monoxide (H2 : CO=2 : 1) using copper-chromium-manganese oxide catalyst of granular form. It is found that the acetylene is completely hydrogenated to ethylene, ethane and other hydrocarbons, such as butene and but butane, none of the carbon monoxide being hydrogenated to methane at the temperatures between 80200°C and S.V. (space velocity) 1, 000 to the volume of the catalyst.
For improvement of oil-solubility, authors have studied about the preparative methods of resol and rosin-modified phenolics using the resol as follows : 1) Phenol resol was obtained by the reaction of acid condensation at pH 15 and at 50°C for eight to ten hours from the methylolated phenol which was prepared by the reaction of phenol (1mol) with formaldehyde (0.83.0mol) in the presence of sodium hydroxide (0.2mol, 45% concentration) at room temperature for a day. Average composition of the resol is shown by the _??_OH CH2 OH CH2OH formula in case of the mole-ratio of phenol to formaldehyde being 1 : 1. 2) Some kinds of rosin-modified phenolics were prepared by heating rosin, resol and glycerine, and the relations of oil-solubility and softening point of the resins to the properties and contents of the resol were examined. Oil-solubility of the rosin-modified phenolics prepared is solely affected by the resol content and is independent for the kinds of the resol prepared under various conditions. The limit of resol content allowing oil-solubility is 25% by weight. When the resol to be used is left for more than ten days, the lowering of softening point of the resins can be seen, compared with the case using the resol soon after the preparation. The rosin-modified phenolics prepared here have shown excellent oil-solubility inspite of their high softening points (140180°C).