Operating conditions for the qualitative and quantitative determination of fatty acids and several phosphono-fatty acids were investigated by capillary-tube isotachophoresis using a potential gradient detector.
Behenoic acid-NaOH (or Na-behenoate, or K-behenoate) in methanol as a terminal electrolyte and HCl-Tris in methanol as a leading electrolyte were effective for analysis of fatty acids. The potential unit (PU) values for capillary-tube isotachophoresis depended on the molecular weight of fatty acids. The isotachophoretic sensitivities of fatty acids decreased with increasing carbon chain length of the fatty acids.
Isotachophoregrams of phosphono fatty acids showed only one zone coresponding to the secondary dissociated ion species. The results regarding phosphono-fatty acids are discussed in terms of charge.

抄録全体を表示

d-δ-Tocopherol (δ-Toc), which was dissolved in saturated and unsaturated trigiycerides, was oxidized with air under the condition of thermal oxidation. Experimental conditions and analytical methods were the same as those described in Parts I and II of this series. From the results of TLC and HPLC of the nonsaponifiable material obtained from the reaction mixture, it was assumed that the dimers of δ-Toc may be formed (Figs.-1 and 2). In order to confirm oxidative dimerization, the reaction mixture, which was obtained by the oxidation in trilaurin at 180°C for 5 h, was separated by chromatography on a silicic acid column eluted with hexane-ethyl ether mixtures, and three main oxidation products were isolated (Fig.-4). Product [I] was identified as 5- (δ-tocopheroxy) -δ- tocopherol (δ-TED), and both products [II] and [III] were identified as 5- (δ-tocopherol-5-yl) -δ-tocopherol (δ-TBD) by means of UV absorption, IR absorption, NMR and MS spectrometry (Table-1). Product [III] seems to be the atropisomer of product [II].
The decrease of δ-Toc concentration and the formation of the dimers during the course of thermal oxidation in trilaurin (Tri-La), in triolein (Tri-Ol), and in trilinolein (Tri-Li) were followed by HPLC. The decomposition of δ-Toc in Tri-Li was more rapid than that in Tri-La (Fig.-5). δ-TED was formed more abundantly than δ-TBD. The quantities of the formed dimers were greatly affected by the species of triglyceride molecules, and large amounts of dimers were obtained by the oxidation in Tri-Li. The amount of δ-TBD obtained by oxidation in Tri-Li reached a maximum within 5 h, and the quantity of this dimer formed by the oxidation at 150°C is much larger than that at 180°C (Figs.-6 and 7).

抄録全体を表示

Surface tensions (γ_s) and their surface tension components (γ_s^d, γ_s^P) of polyvinylformal (Vinylon^R, formalization degree 9.463.1 mol%), cellulose acetate (acetylation degree 38.443.8%), cellophane, and iron (III) oxinate were calculated from extended Fowkes' equation and Wu's equation. (Table-2, 3, 4)
The polar force component values (γ_s^P) from Wu's equation were a little bigger than those from extended Fowkes' equation.
The polar force components (γ_s^P) of Vinylon showed the minimum value when the formalization degree was about 35%. This indicated that the surface tension of Vinylon was minimum at the same formalization degree.
It was also revealed that the polar force components (γ_s^P) of cellulose acetate and cellophane decreased with increasing the acetylation degree whereas the surface tension (γs) decreased with increasing the acetylation degree.
The surface tension values listed in Table-2, 3, 4 may be helpful for calculating the work of adhesion (W_a) in detergency and adhesion studies.

抄録全体を表示

The adsorption characteristics of a solubilized fatty acid (nonanoic acid) on activated charcoal (Pittsburgh activated carbon) were studied for the micelles of nonionic surfactant [hexadecyl poly (oxyethylene) ether]. The adsorption isotherms obtained obeyed the Freundlich -type equation. The adsorbed amount of the fatty acid or the nonionic surfactant was found to be lower from the mixed micelles than from the single micelles in which each solute was dissolved alone.

抄録全体を表示

Thermally decomposable surfactants were prepared by the reaction of xylylenediisocyanate with polyethyleneglycol monomethyl ether acetoacetate and alcohols such as butyl, octyl, decyl, lauryl, myristyl, palmityl, and stearyl alcohols.
The properties such as the cmc, surface tension, foaming power, and wetting power of the aqueous solutions of the surfactants were measured.
Under thermal treatment of the aqueous solution, the surfactants were decomposed to water-insoluble compounds, and the surface tension of their aqueous solutions increased. This thermal decomposition was accelerated by bases such as sodium hydroxide and triethylenediamine, but suppressed by acids such as sulfuric acid and p-toluenesulfonic acid.
The dissociation temperatures of blocked isocyanates of these surfactants, measured by infrared spectroscopy according to the method of Griffin, were 90°C, which were not dependent on the length of the alkyl groups of these surfactants. On the other hand the temperatures decreased to 6570°C in the presence of triethylenediamine as a catalyst.

抄録全体を表示

Effect of the presence of fatty acid soil on removal of triglyceride soil from cotton fabrics in an alkaline builder solution was studied. Cotton fabrics were soiled with a mixture of triolein and individual fatty acids such as lauric, myristic, palmitic, stearic, and oleic acid. Triolein and individual fatty acids adhering to cotton fabrics were determined by gas-liquid chromatography (GLC) after the extraction with ethyl ether.
Triolein alone was hardly removed by a sodium carbonate (Na₂CO₃) solution, however, when triolein was mixed with individual fatty acids, its efficiency of the removal increased in the order C₁₂<C₁₄<C₁₆=C_{18 : 1}<C₁₈; the presence of long chain fatty acid was more effective than that of short chain fatty acids for the removal of triolein.
A mixture of triolein and stearic acid can be removed from cotton fabrics by a Na₂CO₃ solution more effectively than can triolein alone. This indicates that the soap formation in situ is more efficient than the action of the same soap solution for removing triolein. The removal efficiency of triolein increased with increasing amount of stearic acid and reached a constant level at the amount of stearic acid equal to that of triolein in the mixture.

抄録全体を表示

The thermal isomerizations of 2-pinene [1], 2 (10) -pinene [2], cis-pinane [3], 3-carene [4], and longifolene [5] in a mixed fused salt which were carried out under reduced pressure were investigated.
1, 8-p-Menthadiene [8] and (4E, 6Z/4E, 6E) -allocimene [IA], [11B] were obtained as three main products from [1]. The best yield of the isomerization products was 45 %, [11A plus 11B].
[8] and myrcene [12] were obtained from [2]. Especially, [12] was obtained at the highest yield (70%) among the isomerization products.
2, 4 (8) -p-Menthadiene [10], dihydromyrcene [13] and 8, 9-p-menthene [14] were obtained from [3], and [13] was obtained at the highest yield (66%).
1, 3 -Caradiene [15], p-cymene [16], 1-methyl-4-isopropenyl benzene [17] and 1-methyl-3-isopropenyl benzene [18] were obtained as four main products from [4].
Isolongifolene [19] was obtained as a main product, however, three unidentified compounds were also obtained as by-products from [5].
From these results, it is concluded that the isomerization of terpenes in an inorganic fused salt is useful in the insolubility of the reaction products and the heat-stability of the inorganic fuzed salt.

抄録全体を表示

The hydrolysis of p-nitrophenyl N-lauroyl-h-alaninate (ester (1)) was more accelated by the micelles of sodium deoxycholate than that of its D-isomer, however, the hydrolysis of p-nitrophenyl N-acetyl-phenylalaninate (ester (2)) was inhibited by the micelles and the stereo-specific effect was not observed in these systems.
The micelles of sodium N-lauroylalaninates inhibited the hydrolysis of ester (1) and ester (2), no stereo-specific effect was also observed.

抄録全体を表示