• Title/Summary/Keyword: nitroso compounds

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Studies on the Oxidative Rearrangement of Aziridine N-Oxides (아지리딘 N-옥시드의 酸性化 자리옮김 反應에 關한 硏究)

  • Se Chun Choi;Hyang Dong Jang
    • Journal of the Korean Chemical Society
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    • v.27 no.1
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    • pp.38-45
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    • 1983
  • Aziridine derivatives were utilized for the formation of aziridine N-oxides at low temperature, which were subject to easy decomposition and/or rearrangement like the protonated aziridines at room temperature. t-Butyl nitroso compound formed by the decomposition of N-oxide is easily characterized by its blue color and it is the major product in case that no branched alkyl groups are substituted on the carbon atoms of the aziridine ring and the stationary groups on the nitrogen are inert to rearrange the oxide such as the t-butyl group. The oxidative rearrangement products, however, are mainly formed when the substituents are methyl or ethyl group on the carbon atoms. It is interesting to see that the sigmatropic rearrangement of 2-ethyl aziridine gave only cis olefinic compound selectively in case that t-butyl group was substituted on the nitrogen, whereas N-hydroxy aziridine compounds were formed exclusively when t-butyl group was replaced with ethyl group.

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Vitrification of Highly Active Liquid Waste(I) (Thermal Decomposition of Nitrates and Additives for Glass-making)

  • Chun, Kwan-Sik;Lee, Sang-Hoon
    • Nuclear Engineering and Technology
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    • v.9 no.4
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    • pp.211-222
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    • 1977
  • The decomposition of all the individual chemicals used in the Harwell inactive vitrification pilot plant has been studied by means of a thermal balance. Weight loss curves to 110$0^{\circ}C$ have been obtained. The four materials (sodium nitrate, cesium nitrate, lithium nitrate and ruthenium nitroso-nitrate solution) showed a greater weight loss than that based on an oxide yield, and hence these compounds of their products of decomposition are volatile below 110$0^{\circ}C$. The remaining materials suffered a weight loss no more than that corresponding to a full yield of the oxide, and hence they were not volatile below 110$0^{\circ}C$. Most of chemicals begin to decompose at less than 75$^{\circ}C$ but the nitrates of cesium, strontium, barium and sodium not until 295$^{\circ}C$ to 59$0^{\circ}C$. The results obtained can be used in the analysis of process conditions in the vitrification and calcination of highly radioactive wastes and also of the thermal decomposition behaviour of mixtures containing those materials.

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Effect of the N-nitrosodimethylamine Formation in Ascorbate and Phenolic Portions from Citrus Juice (감귤류의 Ascorbate 및 Phenolic 획분이 N-nitrosodimethylamine의 생성에 미치는 영향)

  • 성낙주;송미향;이수정;신정혜;최선영
    • The Korean Journal of Food And Nutrition
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    • v.15 no.2
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    • pp.97-103
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    • 2002
  • Five citrus juices were separated into a ascorbate and phenolic portion using rep-pak C$\_$18/ cartridge, respectively, in order to elucidate the nitrite scavenging effect and N-nitrosodimethylamine(NDMA) formation in model system. The nitrite scavenging effect of ascorbate portion from citrus juices, in the different pH, when added with 5ml were 79.9 ∼98.6% under the condition of pH 2.5. 48.5∼86.3% at pH 4.2 and lower than 35.2% at pH 6.0. The nitrite scavenging effect was excellent phenolic portion rather than ascorbate portion. Particularly, the effect was more 2 times than ascorbate portion under the reaction condition of pH 6.0. When added the phenolic portion in the reaction mixture, NDMA formation was inhibited 92.8% or more in kum quat, mandarin orange and sweet orange juices. But the ascorbate portion was a negative response of the inhibition of NDMA formation. The inhibition on NDMA formation in citrus juice may be due to phenolic compounds were reacted.

Solution Phase Photolyses of Substituted Diphenyl Ether Herbicides under Simulated Environmental Conditions (모조(模造) 환경조건하(環境條件下)에서의 치환(置換) Diphenyl Ether 제초제(除草劑)의 광분해(光分解)에 관(關)한 연구(硏究))

  • Lee, Jae-Koo
    • Applied Biological Chemistry
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    • v.17 no.3
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    • pp.149-176
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    • 1974
  • Eight substituted diphenyl ether herbicides and some of their photoproducts were studied in terms of solution phase photolysis under simulated environmental conditions by using a Rayonet photochemical reactor. The test compounds absorbed sufficient light energy at the wavelength of 300 nm to undergo various photoreactions. All the photoproducts were confirmed by means of tlc, glc, ir, ms, and/or nmr spectrometry. The results obtained are summarized as follows: Solution phase photolysis of C-6989: An exceedingly large amount of p-nitrophenol formed strongly indicates the readiness of the ether linkage cleavage of this compound as the main reaction in all solvents used. Photoreduction of nitro to amino group(s) and photooxidation of trifluoromethyl to carboxyl group were recognized as minor reactions. Aqueous photolysis of p-nitrophenol: Quinone(0.28%), hydroquinone (0.66%), and p-aminophenol (0.42%) were confirmed as photoproducts, in addition to a relatively small amount of an unknown compound. The mechanisms of formation of these products were proposed to be the nitro-nitrite rearrangement via $n{\rightarrow}{\pi}^*$ excitation and the photoreduction through hydrogen abstractions by radicals, respectively. Solution phase photolysis of Nitrofen: Photochemical reduction leading to the p-amino derivative was the main reaction in n-hexane. In aqueous solution, the photoreduction of nitro to amino group and hydroxylation predominated over the ether linkage cleavage. Nucleophilic displacement of the nitro group by hydroxide ion and replacement of chlorine substituents by hydroxyl group or, to a lesser extent, hydrogen were also observed as minor reactoins. Solution phase photolysis of MO-338: Photoreduction of the nitro to amino group was marked in the n-hexane solution photolysis. In the aqueous solution, photoreduction of the nitro substituent and hydroxylation were the main reactions with replacement of chlorine substituents by the hydroxyl group and hydrogen, and cleavage of the ether linkage as minor reactions. Photolyses of MC-4379, MC-3761, MC-5127, MC-6063, and MC-7181 in n-hexane and cyclohexane: Photoreduction of the nitro group leading to the corresponding amino derivative and replacement of one of the halogen substituents by hydrogen from the solvent used were the key reactions in each compound. Aqueous photolysis of MC-4379: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, hydroxylation, and replacement of the nitro by hydroxy group were prominent with photoreduction and dechlorination as minor reactions. Aqueous photolysis of MC-3761: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, and photoreduction followed by hydroxylation were the main reactions. Aqueous photolysis of MC-5127: Replacement of carboxyethyl by hydrogen was predominant with ether linkage cleavage, photoreduction, and dechlorination as minor reactions. It was obvious that the decarboxyethylation proceeded more readily than decarboxymethylation occurring in the other compounds. Aqueous photolysis of MC-6063: Cleavage of the ether linkage and photodechlorination were the main reactions. Aqueous photolysis of MC-7181: Replacement of the carboxymethyl group by hydrogen and monodechlorination were the remarkable reactions. Cleavage of the ether linkage and hydroxylation were thought to be the minor reactions. Aqueous photolysis of 3-carboxymethyl-4-nitrophenol: The photo-induced Fries rearrangement common to aromatic esters did not appear to occur in the carboxymethyl group of this type of compound. Conversion of nitro to nitroso group was the main reaction.

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Studies on the Fermentative Production of Inosine-5′-monophosphate by Microorganisms (Part 1) Derivation of 5′-IMP Producing Mutants from Brevibacterium ammoniagenes (미생물에 의한 5′-이노신산의 생산에 관한 연구 (제1보) 5′-이노신산 생산균주의 분리)

  • Bae, Jong-Chan;Gong, Woon-Young;Son, Chung-Hong;Jang, Wook;Yoo, Ju-Hyun
    • Microbiology and Biotechnology Letters
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    • v.7 no.3
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    • pp.119-125
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    • 1979
  • As the first step of domestic developmint of the nucleic acid-related compounds, purine base required auxotrophs from Brevibacterium ammoniagenes ATCC 6872 were derived by the ultraviolet irradiation or the treatment of N-methyl-N'-nitro-N-nitroso guanidine (NTG), diethyl sulfate (DES), and ethylme-thyl sulfate (EMS). The optimum conditions of mutation by means of several mutagens were induced respectively. The yield of mutants was 0.083% by the ultraviolet irradiation, 0.67% by the NTG treatment, 1.1% by the DES treatment, and 0.45% by the EMS treatment. Six strains among 239 auxotrophs were screened out to accumulate 5'-lMP in the culture broth. Cry-stalline 5'-lMP was isolated from the culture broth of Brevifbacterium ammoniagenes adnine-guanine less mutant D-21530 by the use of anion exchange resin, Amberlite IRA-402, and it was identified physically and chemically as 5'-inosinic acid.

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Analysis Method of N-Nitrosamines in Human Urine by LC-MS/MS System (LC-MS/MS 시스템을 이용한 소변 중 N-니트로사민류 분석법 확립)

  • Park, Na-Youn;Jung, Woong;Kho, Younglim
    • Journal of the Korean Chemical Society
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    • v.61 no.2
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    • pp.51-56
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    • 2017
  • N-nitrosamines are the nitroso compounds which are produced by nitrosation reactions of the secondary amine and nitrite under acidic conditions. Approximately 300 species of N-nitrosamine have been tested for carcinogenicity in laboratory experiments, with 90% of them demonstrated carcinogenic effects different animal species, including higher primates. In 1978, IARC classified NDMA and NDEA as Group 2A, and NDPA, NDBA, NPIP, NPYR and NMOR as Group 2B. In this study, we established pretreatment and analytical method for N-nitrosamines (NDMA, NDEA, NMEA, NDPA, NDBA, NPIP, NPYR and NMOR) in human urine for biological monitoring of N-nitrosamines. The analytes were extracted using solid phase extraction (SPE), then quantitative analysis was performed by LC-(APCI)-MS/MS. The accuracies of the established method were between 85.8~108.7% and precisions were lower than 20%. The limit of detection (LOD) were between 0.0002 (NDBA) and 0.0793 (NDMA) ng/ml. The linearity obtained was satisfying for the 8 N-nitrosamines, with a coefficient of determination ($r^2$) higher than 0.999. The mean concentrations of N-nitrosamines in the urine were 2.645 mg/g creatinine for NDMA, 0.067 mg/g creatinine for NDEA, 0.009 mg/g creatinine for NMEA, 0.011 mg/g creatinine for NDBA, 0.271 mg/g creatinine for NPIP and 0.413 mg/g creatinine for NPYR. NDPA and NMOR were not detected. It can be used as a instrumental methodology for evaluation and risk assessment of human exposure to N-nitrosamines for the further research.