In the previous papers the authors obseved that the amount of metal adduct to casein increased with the longer storage days in the system of aqueous solution and oil. It was also found that the rancidity of oil was seriously effected by metal as compared with casein or metal-casein complex. In this paper, authors investigated the relation between the binding ability of inorganic metalfood constituent complexes and the effect of the inorganic metal, food constituents and these complexes on the racidification of oil. Some inorganic metals (copper sulfate, ferric chloride, zinc nitrate) were mixed with non-fat casein, albumin, gluten, soluble starch, and some free fatty acids in soybean oil or aqueous solution. Thus, the amount of adduct formed with these materials and the variation of peroxid value were measured during storage periods. The results obtained were as follows : It was found that the rancidity of oil was seriously effected by metal, starch, unsaturated fatty acids and copper-fatty acid mixture, therefore, the increase of peroxide value was the most highest in the case of copper-fatty acid mixture as compared with free copper and iron-fatty acid mixture system. Namely, it became clear that the easy formation of metal-protein complex and the metalprotein complex thus formed did not promote the rancidity of oil. A correlation existed between the binding ability of inorganic metal-protein complex and rancidity ratios of oil. On the other hand, the marked difference seen between the case of copper-fatty acid mixture and iron-fatty acid mixture systems on the rancidity of oil is not yet clarified. This phenomenon can be considered from only fact that fatty acids reacted with metals (copper and iron). These reaction products were detected as metallic soaps by thin-layer chromatography. It was concluded that the cupric stearate (purchased from Yoneyama Yakuhin Co.) apparently promoted the rancidity of oil, but ferric stearate did not promote the rancidity of oil.
The reactions of ethylene oxide (EO) with p-hydroxybenzenesulfonamide (HBSA), benzenesulfonamide, and phenol were carried out in the presence of small amounts of NaOH as a catalyst in an autoclave at 80°C. In order to remove poly-EO and to reduce the width of molecular weight distribution of crude addition polymerisates of EO the gel filtration and countercurrent distribution extraction were perfomed and these separated samples were analyzed by thin layer chromatography, infrared spectroscopy and nuclear magnetic resonance. From the synthetic results described above and those of addition polymerisation products of EO to p-hydroxybenzamide (HBCA) published in our previous paper, authors noticed that HBSA reacted more easily with EO than HBCA, and so the addition reaction of EO to HBSA was accompanied by the formation of more minute quantity of poly-EO and unreacted amide than in the case of HBCA, resulting the longer EO chain length of etho-HBSA. From the physico-chemical studies on the aqueous solutions of the samples, it was recognized that the increase of specific gravity, wettability and the decrease of surface tension in the aqueous solutions of etho-HBSA were greater than those of etho-HBCA.
Although it has already been reported that anionic detergents (AD) strongly inhibited the activity of lipase, scarce data is available on their influence in the presence of surface active agents (PSA). This report deals the influence of PSA on detergent tolerance of lipases. Three microbial lipases of Achromobacter sp., Candida sp. and Mucor sp., and an animal lipase of hog pancreas were used. Anionic detergents included sodium dodecyl benzene sulfonate (DBS), sodium dodecyl sulfonate (SDS) and sodium stearate (SOAP). 12 kinds of surface active agents selected from cationic, nonionic and amphoteric surface active agents were tested for their protection of lipases. The influence of PSA were examined by assaying the residual lipase activity according to modified Dole's method after the contact of lipase solution with the mixture of AD and PSA. Results obtained were as follows : 1. The inhibition of microbial lipase activity by DBS and SDS was protected by the addition of nonionic PSA such as Tween and Emulgen (polyoxyethylene nonylphenylether), but in case of animal lipase, Ameate was the only PSA which was found to be effective to protect the activity. On the contrary, the inhibition of microbial lipase activity by SOAP was not protected by any PSA but most of the nonionic PSA protected animal lipase. 2. This protective effect of PSA, with some exception, increased as concentration of lipase and PSA increased and decreased along the increse of the concentration of AD. The temperature and the time at the contract reversely affected to their protective effect. 3. Lipases of Candida sp. and Mucor sp. were unstable in the presence of salts which are usually used as bilders, whereas lipases of hog pancreas and Achromobacter sp. were comparatively stable. Tolerance of lipase activity in commercial detergents also increased by the addition of PSA.
A series of sodium polyoxypropylated cyclohexyl and phenyl phosphates was synthesized. The change in their surface activities, such as lowering of surface tension, foaming properties, wetting power, dispersing power and emulsifying power, with variation of the number of moles of propylene oxide added was discussed. Influence of cyclohexyl and phenyl group attached to the end of hydrophobic group on the surface activities was also studied. The results obtained are as follows. The aqueous solution of cyclohexanol derivatives have lower surface tension than those of phenol derivatives, while the wetting power and dispersing power of phenol derivatives are superior than those of cyclohexanol derivatives. The foaming properties and emulsifying power of both derivatives are slight, and the lowering of surface tension, wetting power and dispersing power are improved by increasing the number of moles of propylene oxide added.
A rapid method for the determination of moisture in liquid and granulated detergents by nearinfrared spectroscopy was established. Using DMF as the solvent, water has strong absorption at 1.93μ in the near-infrared region. The linear relationship is obtained between the absorbance value at 1.93μ and water content. Further, water in detergent is dissolved or extracted readily by DMF. Based on these facts, in this method, detergent sample (containing 0.20.3g of the water) was weighed into 50ml volumemetric flask, DMF was added until marked line, and the flask was shaken. The spectrum of the solution was mesured from 1.7μ to 2.2μ in 1cm silica cell. And the absorbance value was obtained from peak-height of the band at 1.93μ by the baseline method. The moisture content was obtained from the absorbance value and the calibration curve. By this method, the moisture content in liquid and granulated detergent can be determination with a standard diviation of 0.94% as contrasted to Karl Fischer method.
The relation between the replacement ratio of the air in flask (300ml) with nitrogen and flow rate, flow time and the position of nitrogen inlet was studied under the condition of peroxide value measurement according to Lea's method. The composition of nitrogen and oxygen was determined on the basis of the peak intensities of their molecular ions in mass spectra. The results showed that the value of the replacement ratio is higher when flow rate is faster, flow time is longer and also the position of nitrogen inlet is deeper. In case of 300ml flask used, the following condition is necessary for the concentration of residual oxygen to be below 5% : the position of nitrogen inlet is more than 6cm in depth, flow rate is faster than 100ml/min and flow time is longer than 7min.
Hydrolyses of α, α, α, γ-tetrachloroalkanes (1 : 1 adducts of carbontetrachloride with α-olefins) by fuming nitric acid were carried out under various conditions and it was found that β-chlorocarboxylic acids were prepared from corresponding α, α, α, γ-tetrachloroalkanes in an yield of 7080 mol%. α, α, α, γ-Tetrachloroalkanes were obtained in high yields by the telomerization reaction of carbon tetrachloride with α-olefins using initiator of ligand transfer type.