• Title/Summary/Keyword: 2,4-dinitrophenylhydrazine

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Structural Characterization and Thermal Behavior of a Novel Energetic Material: 1-Amino-1-(2,4-dinitrophenylhydrazinyl)-2,2-dinitroethylene

  • Ren, Xiaolei;Zuo, Xiangang;Xu, Kangzhen;Ren, Yinghui;Huang, Jie;Song, Jirong;Wang, Bozhou;Zhao, Fengqi
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2267-2273
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    • 2011
  • A novel energetic material, 1-amino-1-(2,4-dinitrophenylhydrazinyl)-2,2-dinitroethylene (APHDNE), was synthesized by the reaction of 1,1-diamino-2,2-dinitroethylene (FOX-7) and 2,4-dinitrophenylhydrazine in N-methyl pyrrolidone (NMP) at 110 $^{\circ}C$. The theoretical investigation on APHDNE was curried out by B3LYP/6-311+$G^*$ method. The IR frequencies analysis and NMR chemical shifts were performed and compared with the experimental results. The thermal behavior of APHDNE was studied by DSC and TG/DTG methods, and can be divided into two crystal phase transition processes and three exothermic decomposition processes. The enthalpy, apparent activation energy and pre-exponential factor of the first exothermic decomposition reaction were obtained as -525.3 kJ $mol^{-1}$, 276.85 kJ $mol^{-1}$ and $10^{26.22}s^{-1}$, respectively. The critical temperature of thermal explosion of APHDNE is 237.7 $^{\circ}C$. The specific heat capacity of APHDNE was determined with micro-DSC method and theoretical calculation method, and the molar heat capacity is 363.67 J $mol^{-1}K^{-1}$ at 298.15 K. The adiabatic time-to-explosion of APHDNE was also calculated to be a certain value between 253.2-309.4 s. APHDNE has higher thermal stability than FOX-7.

Analytical method for analyzing formaldehyde using 2, 4-DNPH and gas chromatography/FID, NPD (2,4-DNPH와 가스크로마토그래프를 이용한 포름알데히드 분석방법)

  • Jeong, Jee Yeon;Park, Seung Hyun;Yi, Gwang Yong;Oh, Se Min
    • Journal of Korean Society of Occupational and Environmental Hygiene
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    • v.10 no.1
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    • pp.126-146
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    • 2000
  • To develop and evaluate formaldehyde measurement method using 2,4-dinitro-phenylhydrazine (2,4-DNPH) coated sampler and gas chromatography, laboratory test and field test were conducted. Results of this study are as follows. Limit of detection(LOD) of measurement methods, HPLC-UVD, GC-NPD and GC-FID, is $0.008{\mu}g/m{\ell}$ $0.060{\mu}g/m{\ell}$, $0.472{\mu}g/m{\ell}$ respectively. Coefficiency of measurement methods, HPLC-UVD, GC-NPD and GC-FID, is 0.008, 0.009, 0.020 respectively. Desorption efficiency of sep-pak xposure aldehyde sampler and sorbent sample tube is 1.05(range : 0.99 - 1.12), 1.02(range : 0.99 - 1.06) respectively. Samples of sorbent sample tube and sep-pak xposure aldehyde sampler turned out to be stored at refrigerator, according to storage test results. Measurement methods of HPLC-UVD, GC-NPD, GC-FID, according to results of precision for the combined sampling and analytical procedure, became acceptable to OSHA evaluation standard. Field test using exposure chamber met the NIOSH overall uncertainty recommendation(less than 25%). Overall uncertainty of Sepak-HPLC(UVD), Tube-GC(NPD), Tube-GC(FID) is 11.0% - 17.0%. Consequently gas chromatography(GC-NPD, GC-FID) and high performance liquid chromatography(EPA TO-11) using 2,4-DNPH coated sampler for formaldehyde measurement turned out to be suitable to measure personal formaldehyde exposure at workplaces.

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Analysis of Carbonyl Compounds using DNPH Cartridge with LC-MS (DNPH cartridge/LC-MS 방법에 의한 카르보닐화합물 분석에 관한 연구)

  • Cho Deok-Hee;Song Il-Seok
    • Journal of Korean Society for Atmospheric Environment
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    • v.22 no.2
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    • pp.201-208
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    • 2006
  • Several carbonyl compounds are important because of their irritant and toxic properties, mutagenicity and carcinogenicity. Therefore, they are regulated in korean odor emission standard. In this study, atmospheric pressure ionization-mass spectrometry(API-MS) is used for the analysis of carbonyl compounds after derivatization with 2, 4-dinitrophenylhydrazine (DNPH) and liquid chromatographic separation. In the negative ion mode, the $[M-H]^-$ pseudomolecular ions are most abundant for the carbonyls. Analytical parameters such as linearity, repeatability and minimum detection limit were evaluated. The linearities ($r^2$) for carbonyls were $0.9977{\sim}0.9999$ when analyte concentration ranges from $25\;to\;250{\mu}g/L$(n=6). The relative standard deviations (%RSD) for carbonyls were $0.55{\sim}3.51%$ for concentration of $100{\mu}g/L$(n=5). The minimum detection limit (MDL) was $1.88{\mu}g/L$(0.27 ppb) for i-valeraldehyde. It was shown that LC-MS method has a great potential for carbonyl compounds analysis.

Vitamin C Intake and Serum Leverls in Smoking College Students (흡연대학생의 비타민 C 섭취량과 혈청수준)

  • 박정아
    • Journal of Nutrition and Health
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    • v.29 no.1
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    • pp.122-133
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    • 1996
  • As ciarette smoking adversely affects vitamin C metabolism in humans, smokers need substantially more vitamin C intake than do non-smokers to achieve similar serum vitamin C concentration. To provide the basic information currently available for the determination of vitamin C requirement for Korean smokers, we investigated the differences the serum vitamin C values between smokers(n=53) and non-smokers(n=62) in relation to their intake of the vitamin through diet in 115 male college students, who had not been using vitamin C supplements. Dietary intakes of vitamin C were determined by a 24-hour recall, and serum vitamin C was determined using the 2, 4-dinitrophenylhydrazine method. The mean vitamin C intakes of smokers and non-smokers were consuming less than 75% of the Koeran RDA for vitamin c in their diet. Smokers consumed yellow and green leafy vegetables more often (P=0.02) and fresh fruits less often(P=0.006) than non-smokers. The mean serum vitamin C concentration of smokers consuming the same amounts of vitamine C as non-smokers, 64.3 umol/1, were 20% lower than for non-smokers, 80.1 umol/l(P<0.05). The risk of low serum vitamin C concentration (LoC) among smokers were 3.8% compared with 1.6% in non-smokers, and the odd ratio for LoC risk was 2.43. There were no correlations between dietary and serum vitamin C for smokers and non-smokers. It was concluded that smokers might require at least 20% more vitamin C to reach the same concentration comparable to non-smokers.

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Measurement of Carbonyl Compounds in Ambient Air using a DNPH Cartridge coupled with HPLC Method (DNPH 카트리지와 HPLC를 이용한 대기 중 카르보닐화합물의 농도측정)

  • 황윤정;박상곤;백성옥
    • Journal of Korean Society for Atmospheric Environment
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    • v.12 no.2
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    • pp.199-209
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    • 1996
  • The purpose of this study is to evaluate analytical method for the measurement of carbonyl compounds and to apply method to the measurement of indoor and outdoor concentrations of these compounds at public facilities. For sampling, 2.4-dinitrophenylhydrazine (DNPH) coated DNPH-Silica cartridges were uwed in this study. DNPH reacts with carbonyl compounds and forms carbonyl hydrazone, The carbonyl hydarzone was eluted from the cartridge with acetonitrile and analyzed by reverse-phase HPLC with UV detection. Possible interference caused by ozone during sampling was eliminated by using KI trap commected in series with the DNPH-Silica cartridge. A number of experimental studies were undertaken to evaluate and validate the analytical method, including collection efficiency, recovery, repeatability, lower limits of detection, and effect of ozone. Indoor and outdoor measurements of carbonyl compounds were simultaneously carried out at 14 public facilities located in Taegu city and Kyungsan city from June to July, 1995. Except for one or two sites, the indoor concentrations were found to be higher than the outdoor concentrations for carbonyl compounds. And the concentrations of carbonyl compounds measured in the morning and afternoon were showed higher than the concentrations measured in the evening.

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Reaction of Potassium 2-Thexyl-1,3,2-dioxaborinane Hydride with Selected Organic Compounds Containing Representative Functional Groups

  • Jin Soon Cha;Sung Eun Lee
    • Bulletin of the Korean Chemical Society
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    • v.13 no.5
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    • pp.531-537
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    • 1992
  • The approximate rates and stoichiometry of the reaction of excess potassium 2-thexyl-1,3,2-dioxaborinane hydride(KTDBNH) with 55 selected compounds containing representative functional groups under standardized conditions (tetrahydrofuran, TEX>$0^{\circ}C$, reagent : compound=4 : 1) was examined in order to define the characteristics of the reagent for selective reductions. Benzyl alcohol and phenol evolve hydrogen immediately. However, primary, secondary and tertiary alcohols evolve hydrogen slowly, and the rate of hydrogen evolution is in order of $1^{\circ}$> $2^{\circ}$> $3^{\circ}$. n-Hexylamine is inert toward the reagent, whereas the thiols examined evolve hydrogen rapidly. Aldehydes and ketones are reduced rapidly and quantitatively to give the corresponding alcohols. Cinnamaldehyde is rapidly reduced to cinnamyl alcohol, and further reduction is slow under these conditions. The reaction with p-benzoquinone dose not show a clean reduction, but anthraquinone is cleanly reduced to 9,10-dihydro-9,10-anthracenediol. Carboxylic acids liberate hydrogen immediately, further reduction is very slow. Cyclic anhydrides slowly consume 2 equiv of hydride, corresponding to reduction to the caboxylic acid and alcohol stages. Acid chlorides, esters, and lactones are rapidly and quantitatively reduced to the corresponding carbinols. Epoxides consume 1 equiv hydride slowly. Primary amides evolve 1 equiv of hydrogen readily, but further reduction is slow. Tertiary amides are also reduced slowly. Both aliphatic and aromatic nitriles consume 1 equiv of hydride rapidly, but further hydride uptake is slow. Analysis of the reaction mixture with 2,4-dinitrophenylhydrazine yields 64% of caproaldehyde and 87% of benzaldehyde, respectively. 1-Nitropropane utilizes 2 equiv of hydride, one for hydrogen evolution and the other for reduction. Other nitrogen compounds examined are also reduced slowly. Cyclohexanone oxime undergoes slow reduction to N-cyclohexylhydroxyamine. Pyridine ring is slowly attacked. Disulfides examined are reduced readily to the correponding thiols with rapid evolution of 1 equiv hydrogen. Dimethyl sulfoxide is reduced slowly to dimethyl sulfide, whereas the reduction of diphenyl sulfone is very slow. Sulfonic acids only liberate hydrogen quantitatively without any reduction. Finally, cyclohexyl tosylate is inert to this reagent. Consequently, potassium 2-thexyl-1,3,2-dioxaborinane hydride, a monoalkyldialkoxyborohydride, shows a unique reducing characteristics. The reducing power of this reagent exists somewhere between trialkylborohydrides and trialkoxyborohydride. Therefore, the reagent should find a useful application in organic synthesis, especially in the field of selective reduction.

A novel nanocomposite as adsorbent for formaldehyde removal from aqueous solution

  • Hejri, Zahra;Hejri, Mehri;Omidvar, Maryam;Morshedi, Sadjad
    • Advances in nano research
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    • v.8 no.1
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    • pp.1-11
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    • 2020
  • In order to develop a new adsorbent for removal of formaldehyde from aqueous solution, surface modification of TiO2 nanoparticles was performed with 2,4-Dinitrophenylhydrazine (DNPH) that have a strong affinity to the formaldehyde. Sodium dodecyl sulfate (SDS) surfactant was used to improve the DNPH grafting to TiO2 surface. Modified adsorbents were characterized by SEM, TEM, XRD, EDX and FTIR. Since the COD level in wastewaters including formaldehyde is considerable, it is necessary to determine the COD content of the synthetic wastewater. In order to determine the optimal removal conditions, the effect of contact time (60-210 min), pH (4-10) and adsorbent dosage (0.5-1.5 g/L) on adsorption and COD removal efficiencies were studied, using response surface method. EDX and FTIR analysis confirmed the presence of nitrogen-containing functional groups on the modified TiO2 surface. The maximum formaldehyde adsorption and COD removal efficiencies by modified TiO2 were about 15.65 and 7.35% higher than the unmodified nanoparticles respectively. Therefore, the grafting of nano-TiO2 with DNPH would greatly improve its formaldehyde adsorption efficiency. The optimum conditions determined for a maximum formaldehyde removal of 99.904% and a COD reduction of 94.815% by TiO2/SDS/DNPH nanocomposites were: adsorbent dosage 1.100 g/L, pH 7.424 and the contact time 183.290 min.

7-Ketocholesterol Induces Vascular Smooth Muscle Cell Apoptosis via Akt Degradation (7-Ketocholesterol에 의한 Akt 감소와 혈관평활근세포의 세포자멸사)

  • Seo, Kyo Won;Kim, Chi Dae;Lee, Won Suk
    • Journal of Life Science
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    • v.26 no.2
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    • pp.226-233
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    • 2016
  • Vascular smooth muscle cell (VSMC) apoptosis has been identified in various vascular diseases, including atherosclerosis and restenosis after angioplasty, and has been known to precipitate atherosclerotic plaque instability and rupture. Oxysterols are known as inducers of apoptosis in VSMC, and 7-ketocholesterol (7KC) is the major nonenzymically formed oxysterol in atherosclerotic lesions. The precise mechanism underlying VSMC apoptosis is still poorly understood. In this study, we investigated whether 7KC causes apoptosis, and characterized its apoptotic mechanisms in primary cultured rat aortic VSMC. Cell viability was assessed by MTT assay and trypan blue assay. Apoptosis was assessed by flow cytometry, immunofluorescence, immunoprecipitation, and Western blot analyses. 7KC markedly decreased the VSMC viability in a time- and concentration-dependent manner, and increased the production of 4-hydroxynonenal (HNE), a major end-product of lipid peroxidation, which also decreased the VSMC viability. Pretreatment with 2,4-dinitrophenylhydrazine, a well-known reagent of lipid peroxidation-derived aldehydes, significantly restored the 7KC-decreased viability of VSMC. Furthermore, HNE, as well as 7KC, reduced the level of total Akt, a major mediator of cell survival. The 7KC-decreased level of total Akt was significantly restored by pretreatments with 2,4-dinitrophenylhydrazine and N-acetylcysteine. Lactacystin, a proteasome inhibitor, protected VSMC against apoptosis and Akt degradation, but did not inhibit HNE production. In the immunoprecipitation assay, 7KC increased HNE-modified Akt. From the results, it seems that, in atherosclerotic lesions, 7KC induces HNE production in VSMC, and this HNE binds to Akt, proceeding to proteasomal degradation of Akt, through which mechanism the atherosclerotic plaque instability may be facilitated.

The Change of Vitamin C Content and Effect of Galacturonic Acid Addition during Kimchi Fermentation (김치 숙성중(熟咸中)의 비타민 C 함량(含量)의 소장(消長) 및 Galacturonic Acid의 첨가(添加) 효과(效果))

  • Lee, Tae-Young;Lee, Joung-Won
    • Applied Biological Chemistry
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    • v.24 no.2
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    • pp.139-144
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    • 1981
  • Modified radish Kimchi and radish-root juice were fermented under $N_2$ atmosphere at $22{\sim}23^{\circ}C$ and $37^{\circ}C$, respectively and their changes of vitamin C content. were determined by dinitrophenylhydrazine and indophenol methods. In the earlier period of the fermentation, vitamin C content decreased temperarily and then began to increase. When the flavor of Kimchi was most acceptable, vitamin C showed the maximum value which eras equivalent to or more than the initial, after which vitamin C content decreased gradually. The increase of vitamin C content seemed to come from the biosynthesis of the vitamin owing to the enzymatic action occurred in radish-root. The addition of galacturonic acid to Kimchi and to radish-root juice elevated the vitamin C content, which suggested galacturonic acid was a good substrate for the synthesis of vitamin C. The optimum pH of the Kimchi fermentation for the better vitamin C content ranged 4.0 to 4.5.

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Trapping of Methylglyoxal by Sieboldin from Malus baccata L. and Identification of Sieboldin-Methylglyoxal Adducts Forms

  • Kim, Ji Hoon;Zhang, Kaixuan;Lee, Juhee;Gao, En Mei;Lee, Yun Jung;Son, Rak Ho;Syed, Ahmed Shah;Kim, Chul Young
    • Natural Product Sciences
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    • v.27 no.4
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    • pp.245-250
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    • 2021
  • The methylglyoxal (MGO) trapping constituents from Malus baccata L. were investigated using incubation of MGO and crude extract under physiological conditions followed by HPLC analysis. The peak areas of MGO trapping compounds decreased, and their chemical structures were identified by HPLC-ESI/MS. Sieboldin was identified as a major active molecule representing MGO-trapping activity of the crude extract. After reaction of sieboldin and MGO, remaining MGO was calculated by microplate assay method using imine (Schiff base) formation of 2,4-dinitrophenylhydrazine (DNPH) and aldehyde group. After 4 h incubation, sieboldin trapped over 43.8% MGO at a concentration of 0.33 mM and showed MGO scavenging activity with an RC50 value of 0.88 mM for the incubation of 30 min under physiological conditions. It was also confirmed that sieboldin inhibited the production of advanced glycation end products (AGE) produced by bovine serum albumins (BSA)/MGO. Additionally, MGO trapping mechanism of sieboldin was more specifically identified by 1H-, 13C-, 2D NMR and, confirm to be attached to the position of C-3' (or 5').