Authors investigated the effect of tocopherol purposing for prevention of the toxicity induced by thermally oxidized oils. Rats were fed with a diet containing fresh oil and thermally oxidized soybean oils with or without tocopherol. The results obtained were as follows : 1) The rats fed with thermally oxidized oil showed growth depression and ruffled hair, whereas better growth was observed when the rats were fed on the same oil with tocopherol. 2) Amount of triglycerides in liver lipids was found to be remarkably increased in comparison with those of rats fed with thermally oxidized oil and also found as similar to those of fresh oil. 3) In the fatty acid composition, a significant difference between thermally oxidized oil and tocopherobadded group was observed. Percentage of linoleate in liver lipids and liver glycerides for the rats fed with thermally oxidized oil added with tocopherol was higher than that of tocopherol-free group. These results indicate that tocopherol has some antioxidative activity for the oxidation of essential fatty acids in liver.
In the previous papers, the authors reported that tocopherol reduced the toxicity of thermally oxidized oils. In order to compare the biological activity among tocol derivatives, rats were fed with a diet containing thermally oxidized soybean oil with tocol derivatives (dl-α-, δ-and mixed-tocopherol). The results indicated that the rats fed with thermally oxidized oil showed growth deprssion and ruffed hair, whereas better growth was observed when the rats were fed with the same oil with tocopherols, and the best growth was recognized on α-tocopherol. The liver weights and the lipid contents of liver fed with thermally oxidized oil were higher than those of the rats fed with fresh oil. However, both of them were decreased by tocol derivatives. Percentage of linoleate and linolenate in liver lipids fed with thermally oxidized oil with tocopherols was higher than that of tocopherol-free group, and the greatest antioxidative activity was recognized with mixed-tocopherol, followed by δ-tocopherol, α-tocopherol in the order.
It has long been believed that the toxicity of autoxidized oils was due to hydropcroxides. On the other hand, there are several reports that some other secondary oxidation products such as hydroxyl and carbonyl compounds make greater contribution to the toxicity than hydroperoxides. However, the major toxic compound still remains to be elucidated and despite of much research on the mechanism of the toxicity, it has not been clarified yet. Authors made some attempts in this paper to cast light on the toxic compounds and their mechanism of the toxicity. Methyl linoleate was autoxidized at 60°C and the toxicity of this deteriorated ester on mice was examined. It was found that the longer the ester was oxidized, the more toxic it became. In order to fractionate the toxic substance, this oxidized ester was molecular-distilled first for the separation of low molecular weight compounds (I). The residue was washed with dil. alkali to remove the free fatty acids (II) and then column chromatographed on silicic acid to fractionate into four fractions (III-A, B, C, D). Fractions (I), (II.), (III-A, B, C, D) were fed through stomach tube on mice to investigate the degree of toxicity. Fr. (I) was found the most toxic followed by (II), (III-D) in the order. Fr. (I) was further fractionated into six fractions (I-A, B, C, D, E, F) on silica gel. Fr. (I-D) appeared the most toxic on mice. Fr. (I-D) was identified as 4-hydroperoxy-2-en-l-al with carbon chain ranging from five to nine by means of IR, UV, elementary analysis, melting point, MS and NMR.
This paper deals the with reaction of myrcene with acetic acid-sodium acetate in the presence of a variety of palladium-catalysts under various conditions. The reaction of myrcene with acetic acid catalysed by palladuus chloride-triphenyl phosphine in benzene under nitrogen gave a mixture of linalylacetate (I), 2-acetoxy-3-methylene-7-methyl-6-octene (II), 3-acetoxymethyl-7-methyl-2, 6-octadiene (III), nerylacetate (IV) and geranylacetate (V) in a total yield of 15%.
There is no investigated report on the stable intermolecular aggregate of polysoaps in the aqueous solution. Authors prepared three anionic polysoaps (potassium salt of maleic anhydride and cetylvinyl ether copolymer) which had the molecular weights of 60.2×104 (P-1), 40.8×104 (P-2), and 6.3×104 (P-3), and with which the following results were obtained concerning the aqueous polysoap solutions by means of light scattering. (1) It is known that a polysoap simultaneously forms intermolecular aggregates besides the intramolecular micelles. Authors found out on additional fact that the molecular weight of the polysoaps gives a great influence upon the intermolecular aggregation. Namely, intermolecul araggregation increased with the decrease of the molecular weight of the polysoaps. These three polysoaps have molecular weight distributions individually, therefore, some equal molecular sire of polysoap species overlaps each other. From this point of view, the lower molecular species of P-1 would intermolecularly aggregate. The interpretation may necessarily mean the probability that the P-1 molecules are degraded while the saponification reaction from the parent copolymer, and the lower species degraded from P-1 aggregate each other. From this reason the observed Mw, would agree with the calculated value. (2) From the extension (r) of polysoap molecule per monosoap-unit, the large intermolecular aggregates of P-2 and P-3 seem to contract more than that of P-1. (3) As regards to the effect of temperature (from room temperature to 70°C) on the r values of the polysoaps, the P-1 molecule seems to expand with raise in the temperature owing to the increase of electrostatic repulsive force among charged heads, and also seems to contract reversibly to some extent with cooling down to room temperature, while either P-2 or P-3 is less temperature sensitive. Authors could understand this result by postulating an interpenetrating structure of P-2 and P-3, in which a considerable part of charged heads of the polysoap molecules is buried in the interior part of the aggregate, thereby, a small part of the charges on an outer shell of the aggregate affect the r, as was reported elsewhere.
Quaternary ammonium salts were prepared from pyridine or triethylamine and higher n-alkyl (C10-C16) monochloroacetates and their surface activities were determined. Pyridinium salts were superior than the triethylammonium salts in surface tension, foaming property and wettability, especially the salt containing C12-alkyl group showed better surface activity than other salts and the value of its surface tension was 26.9 dyne/cm in 0.2% aqueous solution. The triethylammonium salt with C16-alkyl group showed 38.2-40.8 dyne/cm in the solution of 0.05-0.5%. Pyridinium salts containing C12 and C14-alkyl groups showed good emulsifying power for benzene and kerosene and the salt with C16-alkyl group had good emulsifying power for soy bean oil. Triethylammonium salts were also found to have good emulsifying power for each of tested oils according to the choice of alkyl group as follows ; for benzene : C16H33 > C12H25 > C10H21 > C14H29 for kerosene : C12H25> C14H29 > C10C21 > C16H33 for soy bean oil : C16H33 > C12H25 > C14H29 > C10H21
Irritation intensities to the rabbit eye mucosa were examined by Ogura method and Draize method on various surface active agents including linear alkylate self onate (LAS), alpha olefin selfonate (AOS), sulfate of synthetic alcohol (syn. AS) and a formulated detergent for kitchen use, and the series of different carbon chain AOS, C10-C18, and sulfates of natural alcohol (AS), 10-C18. The observation of the minimum irritation concentration, the degree of symptoms and the period of recovery were revealed that AOS was weaker than LAS or syn.AS, no difference was observed between C10-C18 AOS, and that syn.AS was feebly stronger than AS from natural alcohol.