Three kinds of natural fats (palm oil, lard and tallow) and four kinds of hydrogenated fats (soy-bean oil, rapeseed oil, whale oil and fish oil), for the most useful glycerides as the edible fat and for the oil industries, and their typical S3, S2U and SU2 fractions separated by solvent crystallization were studied to find the cause which will affect to the appearance, texture and creaming quality of these margarines and shortenings by means of X-ray diffraction method, microscopic melting point method and rheological method. It was found that the tendency of causing the grainy texture of margarines and shortenings of palm oil or lard depend upon their S3 fractions being α form under the thermal condition at which margarines and shortenings have been stored during the winter season and transformed into β form from α form without passing through β′ form, and thus β form gradually developed to a large crystal withlapse of time. On the other hand the S3 fraction of tallow was β′ form and hydrogenated fats had scarcely contained S3 fractions thereby tended to stabilize at β′ form. For the creaming quality it could not be investigated only from the polymorphic view, but may depend on the crystal shape or rheological property of fats.
It is possible to calculate glyceride distribution by the assumption that the group of saturated acids are distributed in 1, 3, and 2 positions of glycerides in order by variable degree, and the positions remained are occupied by the group of unsaturated acids. This “ordered distribution”, named after its arrangement of acids, covers even distribution, modified Youngs' distribution, and random distribution. A few acid distribution curves suffice to explain the glyceride type distributions of many oils. Calculated glyceride compositions of cacao butter agree well with analytical data, and those of corn oil permit to suppose that this oil may belong to even distribution, or more exactly, to strict ordered distribution.
Dextran produced by Leuconostoc mesenteroid from cane sugar is 1, 6-α-D-glucopyranose polymer. Dextran was attempted to introduce acyl groups as the first step for preparing acyl dextran sulfates. Dextran, molecular weight of 4800, was acylated with acyl chlorides at 105-110°C in pyridine-toluene solution. The chemical and physicochemical properties of acyl dextrans were examined. Oleyl dextran with 2.3-3.0 acyl groups per one glucose unit and caproyl dextran with 3.0 acyl groups were easily soluble in almost all organic solvents and insoluble in water. Both acyl dextrans depressed surface tensions of benzene, chloroform and dioxan. By dispersing of both acyl dextrans 5 % per dioxane into water-dioxan solution, stable emulsions were obtained, whereby surface tensions were depressed in the range of 1012 dyne/cm for oeyl dextran and 2027 for caproyl dextran, respectively. Hemolysis of sheep erythrocyte by both acyl dextrans could not been observed for water-dioxan emulsions containing 1 μg/ml-500 μg/ml of acyl dextrans.
In the previous paper, the isolation of 24-methylene-cycloarthanol from wheat-germ oil had been reported. In this paper, a new methylsterol named “gramisterol” having mp 169°C, [α]590+0.5° and mp 152°C, [α]590+28.1° of its acetate and formula C29H48O was isolated by repeating chromatographic separation of the more soluble fraction of the sterols. Gramisterol was precipitated with digitonin, reacted with the Liebermann-Burchard reagent very rapidly and developed blue color more deeply than Δ7-stenol (Fig. 1), and the spectrum of its color was characteristic (Fig. 2). The difference between the molecular rotation of gramisteryl-acetate and that of free gramisterol was +126°, and was obiously greater than the molecular rotation difference of any sterol series (in a narrow sense) excluding Δ5, 7-sterols. Gramisterol showed no absorption maximum of UV spectrum (above 220 mμ), and the IR spectrum (Fig. 3) showed the presences of trisubstituted olefine (6.00μ, 11.87μ, 12.05μ, 12.22μ, 12.45μ), vinylidene (3.253μ, 6.09μ, 11.29μ) and gem-dimethyl (7.33μ) groups. NMR spectrum of this sterol (Fig. 4) had two signals at τ 9.46 and τ 9.17, which were corresponded to two methyl groups connected with C-13 and C-10 respectively, and any other methyl group connected with tertiary carbon atom was not present. The doublet signals at τ 8.97 and τ 9.08 (J=6.6 cps) (at 40 Mc, τ 8.95 and τ 9.12, J=6.8 cps) seemed to indicate one methyl group connected with C-4. The orientation of the methyl group was presumed as α- or equatorial configuration, because the signal of the methyl group connected with C-10 (no 1, 3 diaxial) was appeared at normal position of τ 9.17. The doublet signals at τ 8.93 and τ 9.04 (J=6.6 cps) (at 40 Mc, τ 8.91 and τ 9.08, J=6.8 cps) would be derived from gem-dimethyl group connected with C-25, owing to vinylidene bond connected to the carbon atom. From the above results, the structure of gramisterol was presumed as 4α-methyl-Δ7, 24(28)-ergostadien-3β-ol.
The surface tension, interfacial tension, wetting power, and foaming properties of the mixtures of sucrose monostearate and avionics (sodium oleyl-N-methyltaurate, sodium dodecylbenzenesulfonate and sodium dioctylsulfosuccinate) have been investigated. The CMC values of mixtures were between those of the component surfactants. The surface tension and interfacial tension of the mixtures of sucrose monostearate and oleyl-N-methyltaurate were a little higher than those of the component surfactants at the concentrations above the CMC respectively. The surface tension and interfacial tension of the mixtures of sucrose monostearate and dodecylbenzenesulfonate or dioctylsulfosuccinate were nearly between those of the component surfactants respectively. The wetting power of sucrose monostearate has been increased by the addition of these avionics. The foaming power and foam stability of sucrose monostearate have been remarkably increased by the addition of oleyl-N-methyltaurate, but decreased by the addition of dodecylbenzenesulfonate or dioctylsulfosuccinate.
A semimicro apparatus for the cloud point test has been devised. It was found that anionic surfactants free from inorganic salts are very effective for the purpose of elevating the cloud point of the aqueous solution of polyalkylenoxide type nonionics or polyvinyl methyl ether. On the contrary, inorganic salts lowerd the cloud point.
Properties of polyoxyalkylene-glycolated polyvinyl acetate and polyvinyl alcohol were determined. Properties of these polymer were influenced by the weight ratio of polyglycol to polyvinyl acetate. They had clouding points similar to those of nonionic surfactant of polyoxyalkylene glycol series. Among the saponified products, polypropylene-glycolated polyvinyl alcohol had characteristic specialties in emulsifing property etc., but polyethylene-glycolated polyvinyl alcohols had no such special properties as they lost almost of their hydrophobic properties.
Polyvinyl alcohol having various degrees of polymerimerization was sulfated by sulfamic acid. A catalytic action was found at these sulfations for urea and for other kind of alkylamines. Purification of these sulfates was difficult. Sulfated polyvinyl alcohols were swelling easily by water and were easily soluble in water. These sulfates have good accelerative capacity for precipitation of sand, consequently for reclamation work to which these polymer surfactants may find a new application.
Calculating methods of the glyceride distributions proposed by Kartha, Youngs, and Vander Wal were simplified. Youngs' method was modified. Kartha's formulas were assumed to be approximate formulas for calculation of Vander Wal's glyceride type distribution.