As a means for purity discrimination of sesame oil or olive oil, continuous cooling and heating differential thermal analysis (DTA) was carried out in a low-temperature range of from 0°C to -100°C. The samples used were three kinds of pure sesame oil, three kinds of pure olive oil; and soybean oil, cotton-seed oil, kapok oil, rape-seed oil, peanut oil, and linseed oil for 6 references. 1) Cooling DTA curve of sesame oil showed three exothermic peaks at -16, -38, and -64°C, the size and height of these peaks being the same. Heating DTA curve showed endothermic peaks, small ones at -71 and -33°C and a large sharp one at -17°C. 2) Cooling DTA curve of olive oil showed small exothermic peaks at -19 and -32°C and a very large and sharp peak at -42°C. Its heating DTA curve had a broad endothermic peak at -37°C and a very sharp and large peak at -1°C. 3) When more than 20% of soybean oil, peanut oil or linseed oil is added to sesame oil, their presence can be discriminated from the characteristics of the cooling DTA curve. Presence of rapeseed oil in over 20% can also be discriminated from either heating or cooling curve, but such discrimination is difficult in the case of cotton-seed oil. 4) Addition of more than 20% of soybean oil, cotton-seed oil or peanut oil in olive oil can be discriminated from either cooling or heating DTA curve. Presence of above 10% of kapok can be known, but that of rape-seed oil cannot be judged from the DTA curve. 5) Because the DTA analysis is rapid as comparing with other chemical methods, it was found to be more useful and adequate to the discrimination, if combined with other analytical methods such as GLC of fatty acid composition.
The auther studied on the unsaponifiable matter of the lipid of crustacean plankton, Themisto japonica. The unsaponifiable matter was liquid of yellowish brown color, contained 26.2% in the lipid, and its characteristics were as follows : n20D 1.4779, I.V. 108.9, and sterol content 19.35%. The unsaponifiable matter was resolved into several constituents on alumina chromatography and these were analyzed. It contained ca. 50% of fatty alcohol (hexadecanol, octadecanol, eicosanol, and C1822 lower unsaturated alcohols), ca. 20% of sterol (predominantly cholesterol) and small amount of glyceryl ether (predominantly chimyl alcohol). The unsaponifiable matter of the lipid of plankton, Themisto japonica, is distinguished from that of the marine fish, in which unsaponifiable matter of the lipid is generally contained only in small amount in the lipid and is predominantly composed of cholesterol.
In the previous papers, authors reported the existance of many ferulates in rice bran oil. In the course of detailed gas chromatographic investigation of unsaponifiable matters from these ferulates, existance of matters with RRT of 2.74 (X), 3.08 (Y) and 3.64 (Z) was found in the outer field of cyclobranol with RRT of 2.54 (RRT of cholesterol : 1.00, as reference). These 3 fractions were isolated from the residue of extraction of cyclobranol by means of column chromatography, digitonin treatment and repeated recrystallisation. Every fraction was confirmed as a saturated new triterpenoid, according to inspection of IR spectrum, TLC, Liebermann-Burchard reaction and X-ray diffraction pattern. Physical data were as follows : X : C30H52O2, mp 181.5°C, [α] D+48.7, Y : C32H56O2, mp 109.0°C, [α] D+47.7 and Z : C32H56O2, mp 151.0°C, [α] D+42.7. The newly isolated triterpenoids were presumed as 25-hydroxy cycloartanol, 25-ethoxy cycloartanol and 24-methyl-24-methoxy cycloartanol.
In order to confirm chemical structure of three components entitled, authors invenstigated mass and NMR spectra. As a result, it was found that they are tetracyclic triterpene alcohols, which only differ in the character of their side chains at 20-C of cycloartanol. In comparing with the reference compound, it was confirmed that X component has an OH-group at 25-carbon, Y has CH3CH2O-group at 25-C and Z has CH3-and CH3O-groups at 24-C. From those observation, it is reasonable to define X as 25-hydroxy cycloartanol, Y as 25-ethoxycycloartanol and Z as 24-methyl-24-methoxy cycloartanol.
Linseed oil fatty acid ethyl ester was heated at 190, 230, and 270°C for 25 hours in the stream of nitrogen. Volatile compounds produced were collected in the ice trap and dry ice-methanol trap. The volatile compounds were analyzed by gas-liquid chromatography. As a result, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-tridecane, valeric aldehyde, caproic aldehyde, pelargonic aldehyde, capric aldehyde and lauric aldehyde were detected. And these volatile compounds were observed about 8% in the residual ester in the case of 190°C heating and about 5% in the case of 230°C and 270°C heating.
A series of experiments on the low-temperature deterioration of hardened coconut oil series showed that this phenomenon relates to their crystal structure. In the present series of work, relation of permeability and sorption of water to crystal structure was examined. 1) Permeability through a thin fat membrane was greater at 15°C than at 5°C, and greater in hardened palm kernel oil than in hardened coconut oil, the order being reverse of that of deterioration. Examination of the permeation curve showed that, in contrast to hardened beef tallow, the time to reach a steady state was slow and that there was a point of inflexion. 2) Sorption of water decreased in the order of hardened palm kernel oil, hardened coconut oil and hardened cotton seed oil, and sorption of water seemed to beccome easier with decreasing permeability. While hardened cotton seed oil was able to desorb completely, hardened palm kernel oil and hardened coconut oil had difficulty in desorption, indicating the high hygroscopicity. 3) Specific surface area, obtained by the BET method, decreased in the order of hardened palm keanel oil, hardened coconut oil, and hardened cotton seed oil.
Ordinarily, the household detergents contain about 1% of sodium carboxymethyl cellulose (CMC) to prevent redeposition of soil. For the determination of CMC itself, nitric acid-methanol method is usual. This method is not applicable for the determination of CMC in household detergents, as the components which are insoluble in 80% methanol solution are added to CMC. Anthrone or naphthalenediol method is used for the determination of CMC in household detergents. In the both methods, however, intensity of color development is influenced by the degree of substitution of hydrogen of hydroxy radicals by carboxymethyl radicals. If the degree of substitution isunknown, the content of CMC can not be found unless the degree of substitution is assumed. Furthermore, intensity of color development is influenced by ingredients of detergent. Authors noted that intensity of color development of these methods indicate reverse relationship with the degree of substitution, and found that combination of these two method is available to determine both the content and the degree of substitution. At the same time, the measuring conditions were investigated for. As a result, this method is useful for the determination of CMC in household detergents.
Detergency of fabrics soiled with natural sebum that was extracted with ethyl ether from soiled under-shirts has been studied. Detergency of natural sebum for fabrics decreases in the order as follows. Cotton≥wool>polyester>polypropylene Detergency of the components of natural sebum for respective fabric decreases in the order as follows. For cotton : other residues (fatty alcohols, waxes, hydrocarbons, and so on) >free fatty acids>glycerides≥steroids_??_squalene For polyester : free fatty acids>steroids_??_other residues>squalene>glycerides For wool : free fatty acids_??_other residues>steroids>glycerides_??_squalene For polypropylene : free fatty acids>steroids_??_other residues_??_squalene>glycerides The relation between the detergency of oleic-1-14C or triolein-1-14C contained within natural sebum and cycles of soiling and laundering shows that oleic acid-1-14C accumulates considerably for cotton and wool but scarcely for nylon and polyester, on the other hand, triolein-1-14C accumlates considerably for polyester, cotton, and wool but comparatively scarcely for nylon.
Surface active properties of binary aqueous solutions of dodecyl pyridinium chloride (DPC) -metal soap were investigated. Metal soaps used were ricinoleates and laurates of manganese, copper, cobalt etc., which were prepared by metatheses of the corresponding sodium salts with metal halides in alcoholic solution. The molar mixing ratios of DPC to metal soap were 5 and 10 to 1. Manganese, cobalt, zinc soaps etc. were solubilized in DPC solution in molar ratio of 1 : 31 : 10 with regard to the latter, while other metal soaps, especially iron, chromium, lead soaps etc. were less soluble. The values of surface tension and contact angle against chromium plate of the mixed aqueous solutions of laurates and of ricinoleates reached down to 24 and 30dyne/cm, and 15 and 22°θ, respectively. The specific conductances of the mixed solutions were higher than those of the solution of DPC alone and especially cobalt and zinc soap solutions showed high values. In wetting power, most remarkable synergistic effect was shown. The sinking time against felt and cotton cloth reached to 13 seconds in the case of manganese and cobalt laurate solutions. A noticeable synergistic effect was shown in foaming characteristics, too. Excellent foaming power was shown in all soap solutions, and in the foam stability every laurate and manganese ricinoleate solutions were better than the remainders. In emulsifying characteristics, emulsifying power was not so good in general, however, every laurate and manganese ricinoleate solutions were suited to kerosene which was not suitable for DPC. The rust-preventive power of mixed solutions against soft iron and brass was not so good in general, while better effects were obtained with almost soap solutions against aluminium at the higher concentrations. In anti-bacterial action, cadmium, cobalt and manganese soap solutions were effective against R. japonicus, S. cerevisiae etc. Though the effect of metal soap varies considerably with the kind of properties measured, the best effect obtained in this study was nearly equal to that caused by barium soap which was most effective among several soaps used in the previous reports.