• Title/Summary/Keyword: Carbonylation

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Synthesis of Dimethyl Carbonate by Oxidative Carbonylation of Methanol over Cu Catalysts (구리촉매 상에서의 메탄을 산화카르보닐화에 의한 디메틸카보네이트 합성)

  • Park, Jin-Seok;Suh, Young-Woong;Park, Tae-Jin;Suh, Dong-Jin
    • Clean Technology
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    • v.14 no.3
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    • pp.160-165
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    • 2008
  • The synthesis of dimethyl carbonate (DMC) with Cu catalysts was investigated in a semi-batch high-pressure reactor. DMC was synthesized via the direct oxidative carbonylation of carbon monoxide with oxygen in methanol. The corrosion rate was evaluated fie the weight change for SUS test pieces which had been added into the reactor. In order to reduce the corrosion rate without significantly losing DMC yield, various additives such as amines, olefins, and other metal salts were used. When 1-methylimidazole was used as an additive, 18.6% of DMC yield could be obtained without corrosion. If the amount of 1-methylimidazole was decreased, a high DMC yield (33.2%) could be obtained with a low corrosion rate (0.5%).

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Isothermal Vapor-Liquid Equilibria at 333.15K and Thermodynamic Excess Properties for the Binary System of Methanol+Dimethyl Carbonate (Methanol+Dimethyl Carbonate 혼합계의 333.15 K 등온 기-액 평형과 열역학 과잉 물성)

  • Han, Kyu-Jin;Park, So-Jin
    • Korean Chemical Engineering Research
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    • v.43 no.3
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    • pp.387-392
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    • 2005
  • Recently, dimethyl carbonate (DMC) is considered as an alternative of MTBE (methyl tert-butyl ether), additive for non-leaded gasoline with their fast biodegradation rate and low toxicity. DMC is usually synthesized so far by oxidative carbonylation of methanol, and recently developed synthetic process is also started with methanol. Since the phase equilibria of the system, consisted of DMC and methanol or other reaction products on different temperature and pressure is necessary for the optimum separation process design and operation. However the reported phase equilibria and physical properties for DMC mixtures in the Dortmund Data Bank (DDB; thermodynamic property data bank) are quite rare. Besides, infinitely dilute properties are not found. In this work, isothermal vapor-liquid equilibria at 333.15 K for methanol+DMC binary system and mixing properties, excess molar volume and viscosity deviation at 298.15 K are directly measured and correlated. Additionally, infinitely dilute activity coefficient of methanol in the DMC solvent at three different temperatures are measured and compared with predicted values using modified UNIFAC (Dortmund).

PHOTOCHEMICAL TRANSFORMATION OF CARBON MONOXIDE IN AQUEOUS AMMONIA

  • Kim, Hee-Jeong;Park, Hyoung-Ryun
    • Journal of Photoscience
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    • v.6 no.4
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    • pp.177-181
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    • 1999
  • The photochemical transformation of carbon monoxide in aqueous ammonia solution has been investigated at 25${\pm}$0.1$^{\circ}C$ using 184.9 nm UV light. Amination and carbonylation processes were carried out by irradiating the aqueous ammonia solution saturated with carbon monoxide, and the formation of formamide, urea, hexamethylenetetramine, formaldehyde, glyoxal and hydrazine was observed. The formation of hydrazine was affected by the presence of ammonia, and the formation of carbonyl compounds such as formaldehyde and glyoxal was influenced by the presence of carbon monoxide. The formation of formamide, urea and hexamethylenetetramine was affected by both ammonia and carbon monoxide. The initial quantum yields of the products were determined and probable mechanisms for the photochemical reaction were presented on the basis of product analysis.

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Taurine protects the antioxidant defense system in the erythrocytes of cadmium treated mice

  • Sinha, Mahua;Manna, Prasenjit;Sil, Parames C.
    • BMB Reports
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    • v.41 no.9
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    • pp.657-663
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    • 2008
  • The present study was undertaken to investigate the protective role of taurine (2-aminoethanesulfonic acid) against cadmium (Cd) induced oxidative stress in murine erythrocytes. Cadmium chloride ($CdCl_2$) was chosen as the source of Cd. Experimental animals were treated with either $CdCl_2$ alone or taurine, followed by Cd exposure. Cd intoxication reduced hemoglobin content and the intracellular Ferric Reducing/Antioxidant Power of erythrocytes, along with the activities of antioxidant enzymes, glutathione content, and total thiols. Conversely, intracellular Cd content, lipid peroxidation, protein carbonylation, and glutathione disulphides were significantly enhanced in these cells. Treatment with taurine before Cd intoxication prevented the toxin-induced oxidative impairments in the erythrocytes of the experimental animals. Overall, the results suggest that Cd could cause oxidative damage in murine erythrocytes and that taurine may play a protective role in reducing the toxic effects of this particular metal.

Transition Metal-Catalyzed Ortho-Functionalization in Organic Synthesis

  • Park, Young-Jun;Jun, Chul-ho
    • Bulletin of the Korean Chemical Society
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    • v.26 no.6
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    • pp.871-877
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    • 2005
  • Recent progress in the filed of transition-metal mediated C-H bond activation has had a great influence on organic synthesis. Among such transition-metal catalyzed reactions, ortho-functionalization via the chelationassisted strategy has been paid great attentions as one of the powerful methodologies for converting aromatic compounds into ones that are more functionalized at the exclusively ortho-position. In this context, various transition metal-catalyzed ortho-functionalizations such as alkylation, alkenylation, silylation and carbonylation are described briefly and their prospects are suggested.

Carbonylation of (Dichloromethyl)benzene Catalyzed by Cobalt Carbonyl and Iron Carbonyl under Phase Transfer Catalysis

  • Sang Chul Shiim;Chil Hoon Doh;Dong Yub Lee;Jae Goo Shim;Young Zoo Youn;Woo Hyung Park;Li Hong Jiang;Ju Hee Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.618-620
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    • 1993
  • Treatment of (dichloromethyl)benzenes with CO (1 atm) in the presence of catalytic amount of $Co_2(CO)_8,\;Fe(CO)_5$ and BTEAC under two phase systems with NaOH(_{aq}) and $PhCH_3$ containing small amount of alcohol for 20 hours at 80$^{\circ}$C gives phenylacetic acids in moderate yields.

Removal of Metallic Cobalt Layers by Reactive Cold Plasma

  • Kim, Yong-Soo;Jeon, Sang-Hwan;Yim, Byung-Joo;Lee, Hyo-Cheol;Jung, Jong-Heon;Kim, Kye-Nam
    • Proceedings of the Korean Radioactive Waste Society Conference
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    • 2004.06a
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    • pp.32-42
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    • 2004
  • Recently, plasma surface-cleaning or surface-etching techniques have been focused in respect of the decontamination of spent or used nuclear parts and equipment. In this study the removal rate of metallic cobalt surface is experimentally investigated via its surface etching rate with a $CF_4-o_2$mixed gas plasma. Experimental results reveal that a mixed etchant gas with about 80% $CF_4$-20% $O_2$ (molar) gives the highest reaction rate and the rate reaches 0.06 ${\mu}m$/min at $380^{\circ}C$ and ion-assisted etching dramatically enhances the surface reaction rate. With a negative 300 V DC bias voltage applied to the substrate, the surface reaction initiation temperature lowers and the rate increases about 20 times at $350^{\circ}C$ and up to 0.43 ${\mu}m$/min at $380^{\circ}C$, respectively. Surface morphology analysis confirms the etching rate measurements. Auger spectrum analysis clearly shows the adsorption of fluorine atoms on the reacted surface. From the current experimental findings and the results discussed in previous studies, mechanistic understanding of the surface reaction, fluorination and/or fluoro-carbonylation reaction, is provided.

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Distinct Oxidative Damage of Biomolecules by Arrays of Metals Mobilized from Different Types of Airborne Particulate Matters: SRM1648, Fine (PM2.5), and Coarse (PM10) Fractions

  • Park, Yong Jin;Lim, Leejin;Song, Heesang
    • Environmental Engineering Research
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    • v.18 no.3
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    • pp.139-143
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    • 2013
  • This study was performed to examine the in vitro toxicities which are incurred due to the mobilization metals from standard reference material (SRM) 1648, fine ($PM_{2.5}$), and coarse ($PM_{10}$) particulate matter collected in Seoul metropolitan area. DNA single strand breaks of approximately 74% and 62% for $PM_{2.5}$ and for $PM_{10}$, respectively, were observed in the presence of chelator (EDTA or citrate)/reductant (ascorbate), as compared to the control by 2% without chelator or reductant. $PM_{2.5}$ induced about 40% more carbonyl formation with proteins in the presence of EDTA/ascorbate than $PM_{10}$. Therefore, more damage to biomolecules was incurred upon exposure to $PM_{2.5}$ than to $PM_{10}$. The treatment of a specific chelator, desferrioxamine, to the reaction mixture containing chelator plus reductant decreased the extent of damage to DNA to the level of the control, but did not substantially decrease the extent of damage to proteins. This suggests that different arrays of metals were involved in the oxidation of DNA and proteins.

Iron Can Accelerate the Conjugation Reaction between Abeta 1-40 Peptide and MDA

  • Park, Yong-Hoon;Jung, Jai-Yun;Son, Il-Hong
    • Molecular & Cellular Toxicology
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    • v.5 no.2
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    • pp.108-112
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    • 2009
  • Alzheimer's disease(AD) is a neurodegenerative disorder characterized pathologically by senile plaques, neurofibrillary tangles, and synapse loss. Especially, extracellular beta-amyloid (Abeta) deposition is a major pathological hallmark of Alzheimer's disease (AD). In AD senile plaques, high level of iron and car-bonylated Abeta were detected. Iron has a Lewis acid property which can increase the electrophilicity of carbonyls, which may react catalytically with nucleophiles, such as amines. Hence, this study investigated whether or not iron could promote the carbonylation of amine with malondialdehyde (MDA) in the physiological condition. As the basic study, we examined that iron might promote the conjugation reaction between propylamine, monoamine molecule and MDA in the physiological condition. As the concentration of iron increased, the fluorescence intensity produced from the conjugation reaction increased in a dose-dependent manner. Instead of propylamine, we applied the same reaction condition to Abeta 1-40 peptide, one of major components founded in AD senile plaques for the conjugation reaction. As the result, the fluorescence intensity produced from the conjugation reaction between Abeta 1-40 peptide and MDA showed the similar trend to that of the reaction used with propylamine. This study suggests that iron can accelerate the conjugation reaction of MDA to Abeta 1-40 peptide and play an another important role in deterioration of AD brain.

Protective Effect of Fisetin (3,7,3',4'-Tetrahydroxyflavone) against γ-Irradiation-Induced Oxidative Stress and Cell Damage

  • Piao, Mei Jing;Kim, Ki Cheon;Chae, Sungwook;Keum, Young Sam;Kim, Hye Sun;Hyun, Jin Won
    • Biomolecules & Therapeutics
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    • v.21 no.3
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    • pp.210-215
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    • 2013
  • Ionizing radiation can induce cellular oxidative stress through the generation of reactive oxygen species, resulting in cell damage and cell death. The aim of this study was to determine whether the antioxidant effects of the flavonoid fisetin (3,7,3',4'-tetrahydroxyflavone) included the radioprotection of cells exposed to ${\gamma}$-irradiation. Fisetin reduced the levels of intracellular reactive oxygen species generated by ${\gamma}$-irradiation and thereby protected cells against ${\gamma}$-irradiation-induced membrane lipid peroxidation, DNA damage, and protein carbonylation. In addition, fisetin maintained the viability of irradiated cells by partially inhibiting ${\gamma}$-irradiation-induced apoptosis and restoring mitochondrial membrane potential. These effects suggest that the cellular protective effects of fisetin against ${\gamma}$-irradiation are mainly due to its inhibition of reactive oxygen species generation.