In the food industry, especially conf ectionary field, the hard butter has been used in the form of solid/oil emulsion. Only practical recipe of confectionery was stuudied on the chocolate manufacturing about this emulsion, but scarce research result came to public. In the first step of this report, the viscosity of the binary system consisting of sugar and hard butter in the different conditions of oil content and temp was investigated. The viscosity reduction of this system was examined by means of adding lecithin and investigated the influence of lecithin content, 0.1% and 1.2% added to binary system. The viscosity was apt to be remarkably reduced in the range from 0.1 to 0.3% at temp, 35-60°C. But, over 0.5% of lecithin the change of viscosity was little. Hard butter from corn oil and cacao butter, too, were investigated, especially for the viscosity change during tempering of the butter, and increase of viscosity of cacao butter was tardies than the binary system of sugar and cacao butter with lecithin. On the binary system emulsion with sugar, the fine sugar particle was more viscous than the coarse.
Viscosity change of binary system, sugar and hard butter, was reported on the previous paper. From the view point of engineering, however it is necessary to determin the shear rate and shearing stress, for inductng the yield value. The yield value was obtained from graphical conclusion based on the curve indicating the relation between shearing stress and rate by the use of Brookfield viscometer. In the binary system above described there was remarkable difference in the yield value between 35% and 40% of the oil content. The yield value of 40% was about 1/2 as comparied with that of 35% of oil content. As for the influence of lecithin affecting the yield value of the solid emulsion binary system. 0.3 part per hundred emulsion reduced the viscosity to 1/2 as compared with 0.1 part of lecithin, but the influence was little to the results of yield value when the added lecithin was changed within range of 0.31.0 part. On the behavior of water content added to solid oil emulsion, the yield value increased parallel with increase of added water from 0.1 to 0.5 part, but the yield value decreased inversely at 0.8 part of the addition. This means that the partial separation of emulsion occured resulting to coagulate the wetted sugar partially.
The present report deals with the results of studies performed in consequence of the previous report to investigate the mechanism of rancid change and toxicity of waste oil. Samples of waste oil and of the noodle fried with its oil were exposed to the sun light for various periods of time. In addition, samples of the waste oil stored for 2 months at room temperature and the noodle fried with it were exposed to the sun light for various periods of time. The noodle samples were extracted with n-hexane after the exposures. The acid and peroxide values of those oil samples were determined to characterize the toxic substance. The acid values for the waste oil and the stored waste oil were 8 and 12 after the exposure for 600 hours. The acid values for the extracts of the noodle fried with the waste oil or the stored waste oil were 12 and 22 after the exposure of the noodle for 600 hours. The peroxide values for the extracts were 260 and 549 after the exposure of the noodle for 300 hours. The toxicities of the waste oil with or without storing and the extracts of the noodle were determined by peroral administration into mice. The toxicity was stronger in the extracts of the noodle than the waste oil. An acute catarrhal entertis in mice was observed from the results of pathological anatomy on the effect of these toxicities.
Samples of coconut oil (I.V. 9.9), hardened coconut oil (I.V. 1.6), and coconut oil mixed with 5 or 20% of fully hardened beef tallow (I.V. 1.4) and samples obtained by randomly interesterification among these samples were stored at 5, 15 and 30 C for 6 months, and their A.V., P.O.V. and Co.V. were measured every month. Roughness of their crystal surface was examined by electron microscope and correlation between crystal growth and change in A.V. was also examined. 1) As the criteria for judging completion of ester exchange, measurement of the melting point, S.F.I. curve and cooling differential thermal analysis were carried out. 2) No great change was seen in P.O.V. and Co.V. in the original samples and those obtained by ester exchange, but they all underwent change with the rise in storage temperature, showing that P.O.V. and Co.V. had no correlation with the glyceride composition. 3) As reported in the previous paper, the original samples showed no change when stored at 30 °C but A.V. increased by storage at 15 and 5 °C, in that order, and this change was greater in the sample mixed with hardened beef tallow. Samples obtained by interesterification showed no rise in A.V. at all the temperatures of storage tested. 4) Roughness of crystal surface under electron microscope became greater when stored at 15 and 5 °C, in that order, while the samples obtained by interesterification showed a smooth surface in all the samples kept at any of the temperatures tested. It was thereby found that low temperature deterioration characteristic to hardened coconut oil can be prevented by changing the glyceride composition.
An alkaline refined, bleached and deodorized cottonseed oil with the peroxide value of 0.35 m eq/ kg was formulated into mayonnaise. This mayonnaise was aged in the oven at the temperature of 40°C for 4 weeks. Peroxide value of the oil recovered from the aged mayonnaise was 40.0 m eq/kg. Semi-continuous deodorizer, equipped with Oldershow column, was used for the isolation of volatile decomposition products of the oil. Separations were carried out on a gas chromatograph. Various unsaturated and saturated aldehyde, ketone, alcohol and ester were identified. 2-Pentyl furan and 2-butyl furan were also identified as the components of the volatile decomposition products. Mass spectrum and infrared spectrum of the fraction, identified as 2-butyl furan, checked perfectly with the authentic 2-butyl furan which was synthesized in our laboratory.
Diethyl octenylphosphonate was prepared from oct-1-ene, by the three methods ; (1) free radical addition of PCl3, initiated with peroxide, (2) chlorophosphonation by the system of oct-1-ene-PCl3-O2 (3) Arbuzov reaction of triethylphosphite and octenyl bromide, prepared by treating oct-1-ene with N-bromo-succinic imide. The structure of these products were assigned by the spectra of IR and NMR and other analytical methods. By the method (1), diethyl oct-1-enyl-1-phosphonate was obtained in 13% yield ; by the method (2), the mixture of three types of diethyl α, β-unsaturated octenylphosphonate and diethyl octenyl-phosphonate, which was yielded by the introduction of phosphono group into the saturated part of the olefin, was obtained in 11% yield ; and by the method (3), diethyl oct-2-enylphosphonate was obtained in 70% yield.
It became an important problem to controldeterioration of fats in frozen and freeze dried foods not only to prolong their shelf lives but also to maintain their flavors. In such a study, it seems necessary to find an appropriate method or methods for detection of the onset of deterioration. Thus, a study was made to find possibility to use the conventional methods of analysis employed for fats for detection of an early stage of rancidiy of vegetable oils stored at low temperatures. Soybean oil without addition of antioxidants was stored at 25°, -5°, and -25°C and the following analyses were performed at intervals ; acid, peroxide and carbonyl values, induction periods by Warburg apparatus and the fatty acid composition of the oil by gas-liquid chromatography. The acid, peroxide and carbonyl values of the sample stored at 25°C were found to remain somewhat unchanged up to 60 days of storage; and P.V. increased thereafter and the other values increased after 120 days. Considerable variations in these values were observed with the sample stored at -5°C, and a white floculant precipitate was found to be formed after 2 months of storage. The carbonyl value of the samples stored at -25°C remained unchanged up to 180 days but its peroxide value decreased steadily until 60 days of storage and increased thereafter. No effect of temperature was observed on the apparent induction periods, but the induction periods of the samples stored for 14 days increased and those of the samples stored for 60 days decreased. Gas-liquid chromatographic analysis of the fatty acid composition showed no significant variations among the samples. The white precipitate formed most abunduntly in the sample stored at -5°C was found as triglycerides comprising a larger proportion of saturated fatty acids than that of soybean oil. These results suggest that the methods subjected to the present study are not appropriate for detection of an early stage of deterioration of the oil stored at low temperatures, and further studies are necessary.