The method for the determination of residualα-and β-endosulfane and endosulfane sulfate in the presence of organochlorine and chlorobenzylate pesticides was established by using gas chromatograph equipped with an electron capture detector. The activated charcoal-Florisil column chromatography wag employed for the successful cleanup, i. e., α-endosulfane was eluted in the first fraction with organochlorine insecticides, and βendosulfane and endosulfane sulfate were collected in the second fraction with chlorobenzylate pesticides (chlorobenzylate, chloropropylate, phenisobromolate, and tetradifon). The separation ofα-endosulfane from pp'-DDE, which was remain, ed so far inseparable on a gas chromatogram, could be carried out with 5% OV-17, 2% DEGS+0.5% H3PO4 and 1% QF-1 column. Furthermore, the gas chromatographic columns such as 1.5% SE-30, 5% OV-17, and 5% XE-60 were satisfactory enough for the separation ofβ-endosulfane and endosulfane sulfate from chlorobenzylate pesticides. The efficiency of the analytical method was evaluated by using 7 kinds of homogenized crops fortified with ppb level of α-and β-endosulfane and endasulfane sulfate. Average recoveries ranged from 82.7% for α-endosulfane to 92.7% for endosulfane sulfate.
Synthetic food dyes were tested for their effects on RNA synthesizing activity in nuclei isolated from rat liver and DNA dependent RNA polymerase partially purified from isolated rat liver nuclei. 1) Azo dyes (amaranth, ponceau R, ponceau 3R and orange I) highly inhibited the RNA polymerase reaction partially purified enzyme at a concentration of 1 mM. In contrast with partially purified enzyme, amaranth, ponceau R and ponceau 311, stimulated RNA synthesis in isolated rat liver nuclei. These dyes were assumed to stimulate DNA like RNA synthesis in nucleoplasm, because the stimulation of RNA synthesis by these dyes was dependent on Mn2+ ion. 2) Xanthene dyes (rose bengale, phloxine, erythrosine and eosine) highly inhibited the RNA polymerase reaction of partially purified enzyme, but acid red little effect. The results suggest that halogen atom is essential to the inhibition of RNA synthesis by xanthene dyes. Rose bengale and phloxine inhibited the RNA synthesizing reaction in rat liver nuclei at a concentration of 1 mM. 3) Triphenylmethane dyes (light green SF, acid violet 6B, brilliant blue FCF and fast green FCF) inhibited the RNA polymerase reaction of partially purified enzyme. Light green SF stimulated RNA synthesis in isolated nuclei and the stimulating activity was also dependent on Mn2+ ion. 4) Indigo carmine gave no effect on both RNA synthesizing activities.
An analytical method of piperonyl butoxide (PB) in cereals by high speed liquid chromatography (HSLC) was investigated. The HSLC used was “Hitachi 635 type. ” An adsorption column “Hitachi Gel 3010”was employed with ethanol as a mobile phase. The fluorometric detector was set existing wavelength at 290 nm and analyzed at 340nm. The ultraviolet adsorption detector was set at 290nm. Thymol was added as an internal standard. PB extracted from sample was cleaned up by the partition method using n-hexane and acetonitrile. It was necessary to clean up by the activated charcoal column chromatography in the case of the ultraviolet adsorption detector. PB injected to the column was washed with n-hexane and then eluted with a mixture of n-hexane and chloroform (1: 1). PB added to samples was recovered in the range from 79.8 to 102%
N-methylcarbamate insecticides are used in place of organochlorine insecticides, The N-nitroso derivatives of 3-methylphenyl N-methylcarbamate (MTMC, Tsumacide), 3, 4-dimethylphenyl N-methylcarbamate (MPMC, Meobal) and naphthyl N-methylcarbamate (NAC, Carbaryl), which are relatively much in the amounts of using in Japan, were crystallized, and their physico-chemical properties and stabilities were studied. It was found that these N-nitrosocarbamates were rather stable at room temperature in organic solvent in the dark but extremely unstable to light. Especially, 3-methylphenyl N-methyl N-nitrosocarbamate (NO-MTMC) and 3, 4-dimethylphenyl N-methyl-N-nitrosocarbarnate (NO-MPMC) were completely decomposed when their ethanol solutions (10mM) were exposed to sunlight through glass for 3 hr. Nitrosocarbamates were decomposed with increasing in the acidity of solution. When 20% dimethyl sulfoxide solution of NO-MTMC (10mM) was kept at 373C and pH 5.8 or 1. 2 for 1 hr, it decreased to 93 or 67% of initial amounts, respectively.
The rates of formation of nitrosocarbamates, 3-methylphenyl N-methyl-N-nitrosocarbamate (NO-MTMC) and 3, 4-dimethylphenyl N-methyl-N-nitrosocarbamate (NO-MPMC), from sodium nitrite and N-methylcarbamate insecticides, 3-methylphenyl N-methylcarbamate (MTMC) and 3, 4-dimethylphenyl N-methylcarbamate (MPMC), were studied. The initial rates of NO-MTMC formation were proportional to the concentration of MTMC and that of sodium nitrite in the ranges of 2.5-10 mM of MTMC and 25-100 mM of sodium nitrite at pH 2.0 and 37-C in aqueous solution, and the initial rates increased with increasing the acidity of reaction mixtures, being almost proportional to the hydrogen ion concentration from pH 3 to pH 1.5. The initial rate of NO-MPMC formation was almost similar to that of NO-MTMC formation at pH 2.0 and 37-C in 20% dimethyl sulfoxide (1.1 times).
Mycotoxins contamination was investigated on molds infected brown rice during longterm storage in warehouse under natural condition. The results showed that sterigmatocystin (50ppb, 450ppb), ochratoxin A (430ppb, 230ppb), and citrinin (1, 130ppb, 700ppb) were detected simultaneously in same samples. On the samples detected mycotoxins, it was found that its presence were dependent upon the infection of Pen. viridicatum and Asp. versicolor on rice grains which were limited in Hokkaido at present, and this case was also first in our country. Pen. viridicatum produced ochratoxin A and citrinin, and Asp. versicotor produced sterigmatocyetin. Detection of Pen. viridicatum having productivity of ochratoxin A and citrinin like this. Natural contamination case of ochratflxin A and citrinin in cereal grains by this species was the same. Therefore, productivity of ochratoxin A and citrinin by Pen. viridicatum was studied.
In order to make clear the pollution of the marine environment by petroleum, the present study was carried out on paraffine hydrocarbons. As one of the indices of food contaminations by petroleum, the background contents of the hydrocarbons in fishes, merts, and human adipose tissue were determined by using a modified method consisting of chromate oxidation, Florisil column chromatography and FID-gas chromatography. Paraffine hydrocarbons were detected from all of the fishes except shrimps and shortnecked clams. Sarge amount of pristane was found in sardine, mackerel-pick, and mackerel, as well as some other kinds of normal paraffine hydrocarbons. the peak patterns of the hydrocarbons in every fish and shell fish tested could be devided roughly into 4 groups. Levels of the hydrocarbon accumulation in the marine fishes were generally higher than those in the fresh ones. The peak patterns of the paraffine hydrocarbons in beef, pork, chicken, and chicken liver were characteristic, respectively, but the contents of total paraffine hydrocarbons were in the similar levels. In the meats, the paraffine hydrocarbons with higher molecular weight were detected on gas chromatograms. The peak patterns of the paraffine hydrocarbons in beef, pork, chicken, and chicken liver were characteristic, respectively, but the contents of total paraffine hydrocarbons were in the similar levels. In the meats, the paraffine hydrocarbons with higher molecular weight were detected on gas chromatograms.
We investigated the quality of frying and fats used by frying manufacturers (10 groups, 85 samples). Although there is no line of demarcation for usage in our country, we attempted to estimate the quality of frying oils and fats by reference to the limit in the Federal Republic of Germany (petroleum ether insoluble oxidized fatty acid content, <0.7%, acid value, <2.5). It is noteworthy that the usage of solid fats (saturated glyceride rich) have a tendency to rise acid values extremely, while the frying fats are not always spoiled. Referring to the contents of oxidized fatty acid, 9 samples are higher than 0.7%, and it is remarkable that in all these cases carbonyl values are higher than 50 meq/kg. the colouration of frying oils and tats are not always correspond to various indices. Carbonyl values are seemed to be more reasonable index for the quality of frying fats than peroxide values or acid values.