The anthers studied on the Unsaponifiable matter of the lipid of crustacean plankton, Calanus plumchrus. Calanus plumchrus belongs to the pelagic species living in cold sea, and it is distributed in the Kurile Current area of North Hokkaido, Sea of Okhotsk and Bering Sea. The unsaponifiable matter was liquid of reddish brown color contained ca. 50% in the lipid, and its characteristics were as follows : n25D 1.4620, I.V. 98.7, and sterol content 2.0%. The unsaponifiable matter was resolved into several constituents on silicic acid chromatography and these were analyzed. It contained ca. 80% of fatty alcohol, ca. 2% of pristane and ca. 2% of sterol. The fatty alcohols consisted of saturated alcohols (hexadecanol predominantly, octadecanol and eicosanol) and lower unsaturated alcohols (hexadecenol, octadecenol, eicosenol and docosenol). Higher unsaturated alcohols were contained in a small amount or not. Specific gravity (d154) of the lipid of Calanus plumchrus is 0.880.89 as previously reported, which is smallar than that of other genus of plankton and many marine fishes. The lowness of this value of the lipid depends upon the presence of 50% of unsaponifiable matter which contains 80% of fatty alcohols. As one of the authers already discussed about the ecological functions of these lipid, the reason for the high content of fatty alcohols seems probably that their functions are related to the plankton moving vigorously and especially vertically with depth, namely may be for buoyancy in such plankton. Sperm whale and the sharks living in deep sea have the lipids rich in fatty alcohols and hydrocarbons respectively. It seems that the formation and presence of such non-glyceride constituents as fatty alcohols and hydrocarbons are related to the ecological or physiological functions common to the marine organisms living in deep sea. Recently, Nevenzel et al. and Mori et al. reported on the lipid of deep-sea fishes. They found that wax esters constituted greater part of the lipids from muscle. This finding is in accordance with our informations on the lipid rich in fatty alcohols. Hydrocarbons in the lipid of plankton have been reported by Blumer. They have found that the hydrocarbon pristane occared in unusually high concentration (1 to 3% of the body fat) in the three copepods Calanus finmarchicus, C. glacialis, and C. hyperboreus, and considered that these planktonic crustaceans appear to be the primary source of the pristane in liver oil of sharks and whales. Authers also found 2% of pristane in the unsaponifiable matter of the lipid of Calanus plumchrus.
A series of experiments are being carried out by authers on the correlation between the melting point and polymorphism of edible solid fat. In the present of work, the same experiments were carried out on three kinds of hardened fish oil, one kind of hardened whale oil and one kind of hardened rape seed oil which contain larger amount of higher fatty acids above C20 than the usual oils. The same experiment was also carried out on mixing oil containing coconut oil which has a drastically different molecular chain. 1) All the three samples of hardened fish oil with different degree of hardening, I.V. 40.8 (#40), 52.7 (#50) and 69.2 (#70), showed approximately similar tendency in the open-capillary melting point when left at 0°C and 10°C, but showed a great difference in the melting point when left at 30°C. Changes according to the period of standing was also great in the latter case. 2) The polymorphism of the hardened fish oil when left at 0°C and 10°C is a β' type, but that of #70 when left at 30°C was β'-3 type, showing advanced transition. 3) Open-capillary melting point of hardened whale oil (I.V. 59.9) showed hardly any difference when left at 0°C or 10°C, but a great difference of about 3°C was found when left at 20°C. Its polymorphism was generally β' type when left at 0° and 10°C, but was β'-3 type when left at 30°C. 4) The hardened rape seed oil (I.V. 69.9) showed small difference in open-capillary melting point according to the temperature of standing. Polymorphism was β'-3 type even when left at 0°C, showing a more rapid transition than hardened fish or whale oil. 5) A mixture of coconut oil and hardened fish oil showed different segregation according to the ratio of mixing, and the open-capillary melting point was scattered.
In connection with studies on the correlation between the melting point and polymorphism, the same experiments as before were carried out on samples of hardened soybean oil mixed with six kinds of liquid vegetable oil in proportion of 20, 50 or 80%. In X-ray diffraction, measurement of long spacing was made by the modified apparatus for small-scattering X-ray diffraction of reflection besides that of side spacing by the existing wide-scattering X-ray diffraction. 1) Open-capillary melting point of samples compounded with corn oil or rice oil showed greater changes with lapse of time than that of the samples compounded with soybean oil, cotton seed oil or safflower oil. S.F.I. value at 30°C, 1hr, was greater than that at 10°C, 1hr, and its changes with lapse of time were greater. 2) Melting point and S.F.I. of a sample compounded with rape seed oil showed the same tendency as that of the samples compounded with corn oil or rice oil, indicating the rapid rate of crystallization. 3) Side spacing of the samples allowed to stand at 20°C for 2 days showed a type when not containing liquid oil; β' type in those with 20% oil, β'-3 type in those with 50% oil, and β type in those with 80% oil. There was no difference according to the kind of oil used. Therefore, such minute difference does not allow comparison of melting point and S.F.I. by merely measuring the side spacing. 4) Result of long spacing measurement by the apparatus for small scattering X-ray diffraction of reflection showed that samples compounded with corn oil or rice oil, which showed greater changes in melting point and S.F.I., had larger diffraction intensity than the samples compounded with soybean oil, etc. The greater diffraction intensity signifies promoted crystallization, and this is the reason why there was a marked change in the melting point and a large value of S.F.I..
Examinations are being made on the low-temperature deterioration of hardened coconut oil series, and in the present series, examinations were made on the addition of liquid oil or various heattreatment as a means of preventing such deterioration. 1) In some cases, fully hardened beef tallow is added in order to obtain a high melting coconut oil but this accelerates deterioration. Addition of 5, 10 or 20% of fully hardened beef tallow to hardened coconut oil or hardened palm kernel oil, with further addition of 5 or 50% of liquid soybean oil, enabled prevention of A.V. increase, almost without lowering the melting point. 2) Electron microscopic observation of the crystal surface showed that the surface becomes rather rough when fully hardened beef tallow is added. In the product added with liquid oil, the single crystal is small and amorphous ones are also observed, the surface becoming smooth. 3) When the oil is solidified by rapid cooling, then heat-treated at 30°C, and allowed to stand at 15°C, the increase of A.V. became extremely small. Crystal surface is composed of large single crystal but their layering is thin and the surface is smooth. Consequently, pretreatment rather than mere solidification with rapid cooling makes it possible to prevent deterioration.
Transalkylation reaction of tertiary amines having hydroxyalkyl groups with dodecyl alcohol was studied at 300°C for 3hrs under 20kg/cm2 of hydrogen, using commercially available copper chromite as catalyst. The reaction of 2- (diethylamino) ethanol with dodecyl alcohol gave 43% yield of N, N-diethyldodecylamine (based on the alcohol used) and small amounts of N-ethyl-N-dodecylethanolamine, accompanied by self-condensation reaction and hydrogenolysis of the ethanolamine which respectively afforded large quantities of N, N'-diethylpiperazine (20% based on the ethanolamine used) and diethylamine, ethylamine, etc. The reaction with N-ethyldiethanolamine gave 8% of N-dodecyl N-ethylethanolamine, 5% of N-ethyldodecylamine (based on the alcohol), and 26% of N, N'-diethylpiperazine (based on the diethanolamine). While, the reaction with triethanolamine did not afford any N-dodecyl derivative, but gave only the products from self-condensation reaction and hydrogenolysis of triethanolamine. The reaction of 3- (diethylamino) propanol, or 2- (diethylamino) ethyl 2-hydroxyethyl ether which gave only hydrogenolysis products, and the condensation reaction of triethylamine with mono- or diethylene glycol which gave a good yield of 2- (diethylamino) ethanol or N-ethyl morpholine, were also studied. The reaction scheme of transalkylation of ethanolamine was discussed.
The removal processes of natural sebum and its model oily soil adhered on twisted yarn and fiber filament in washing solutions were observed by means of the microscope technique. The various behaviors of soil removal were odserved by the combinations of fiber and soil, and also by the structures of substrate on which soil adhered. With respect to cotton, oleic acid adhered on fiber filament was immediately removed after contacting to the detergent solution, but was gradually removed with the formation of droplet and myelinic figure from twisted yarn. Liquid paraffin adhered on cotton twisted yarn was partly removed with the formation of droplet, but without the formation of myelinic figure. With respect to wool, oleic acid adhered on fiber filament formed the unduloid-type droplet, and then was removed with the formation of myelinic figure, but the removal of oleic acid from twisted yarn was not observed. The removal processes of natural sebum from twisted yarn are affected by the compositions of soil, including water-soluble components, and besides by the adhering states of natural sebum. These results were discussed from the view of the following items. (1) The affinity between soil and fiber which appears through the assembly mode of fiber. (2) The phase of the concentrated solution consisted of soil and surfactant.
The relations between oily soil removal efficiency and kinds of fabric and oily soil were studied from the side of viscosity, contact angle of oily soil and interfacial tension of oily soil/washing solution interface. The degrees of the change of contact angle of oily soil with the kinds of polymer film and oily soil decreased in the order : Triolein>olive oil>oleic acid>squalene>liquid paraffin>tetradecane for oily soils; and polypropylene>cellulose>nylon_??_treated polyethylene>polyester, for polymers, respectively. The contact angles of the mixed soil of liquidparaffin and n-octadecane for treated polyethylene, polypropylene, and nylon films increased with the increase of liquid paraffin/n-octadecane ratio. For the mixed soil of liquid paraffin and oleic acid, the contact angles for treated polyethylene and polyester decreased to a constant value with the increase of oleic acid, for cellulose increased gradually, and for polypropylene it increased through a minimum. The detergency of the mixed soil of liquid paraffin and n-octadecane depends on the viscosity and the interfacial tension of the mixed soil, but that of the mixed soil of liquid paraffin and oleic acid cannot be explained only by the viscosity and the interfacial tension of the mixed soil.