• Title/Summary/Keyword: 용매분해반응

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Enantioselective Resolution for the Preparation of Chiral para-Nitrostyrene Oxide by Microbial Epoxide Hydrolase in an Organic Solvent (미생물 에폭사이드 가수분해효소 활성을 이용한 유기용매에서의 광학활성 para-Nitrostyrene Oxide 생산)

  • 배현철;김현숙;이수정;이은열;양승택;김희숙
    • Journal of Life Science
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    • v.12 no.4
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    • pp.423-426
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    • 2002
  • Enantioselective resolution of racemic para-nitrostyrene oxide was investigated using epoxide hydrolase activity of Aspergillus niger LK for the production of optically pure (S)-para-nitrostyrene oxide. To overcome the poor solubility of the substrate, enantioselective hydrolysis in an organic solvent was attempted under optimized reaction conditions including reaction temperature and water content. (S)-para-Nitrostyrene oxide with high optical purity (> 99% ee) was obtained at 37% yield using fungal epoxide hydrolase-catalyzed enantioselective resolution.

바이오매스 구성성분 중 리그닌의 전환에 관한 연구

  • Yun, Seong-Uk;Lee, Byeong-Hak
    • 한국생물공학회:학술대회논문집
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    • 2000.11a
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    • pp.733-736
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    • 2000
  • Lignin is usable as fuels and heavy oil additives if depolymerized to monomer unit, because the chemical structures are similar to high octane materials found in gasoline. In this study, the solvent-phase thermal cracking(solvolysis) of lignin was performed at the various temperature and time in a laboratory tubular reactor. Conversion yield was measured for the properties of thermal cracking and liquefaction reaction of lignin. Highest conversion yield when acetone was used as thermal cracking solvent was 55.5% at $350^{\circ}C$, 50minutes and highest tar generation were $260{\sim}350mg/g\;{\cdot}\;lignin$ at $250^{\circ}C$, and highest conversion yield after tar removal was 76.88% at $300^{\circ}C$, 30minutes. Conversion yield, product compositions and amounts were determined by tar degradation yield.

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Solvation in Mixed Solvents (Part 6). Solvolysis of Benzyl Nitrates in Binary Aqueous Solvent Mixtures (혼합용매에서의 용매화 (제 6 보). 수용성 이성분 혼합용매계에서 Benzyl nitrates 의 가용매 분해반응)

  • Ikchoon Lee;Se Chul Sohn;Hai Whang Lee;In Chul Kim
    • Journal of the Korean Chemical Society
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    • v.31 no.5
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    • pp.419-424
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    • 1987
  • Kinetic studies on the solvolysis of para-methyl benzyl nitrate and benzyl nitrate were carried out in aqueous methanol, ethanol, acetonitrile, acetone, tetrahydrofuran and dioxane mixtures at 60$^{\circ}$C. The rates were faster in protic solvent mixtures than in aprotic solvent mixtures. This was considered in the light of transition state stabilization by hydrogen bonding solvation of protic solvent mixtures. Grunwald-Winstein equation, extended Grunwald-Winstein equation and correlation between E$_T$(30) and rate constant were applied in order to discuss the transition state variations caused by changing benzyl substituents and solvents. The results showed that strong electrophilic assistance of solvent is operative in the the water-rich solvents.

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Cooperative Effects of Solvatochromic Parameters on the Ionizations of tert-Butyl Halides in MeOH-1,1,2,2-Tetrachloroethane Mixtures (MeOH-1,1,2,2-Tetrachloroethane 혼합용매에서 tert-Butyl Halides의 이온화에 미치는 분광용매화변수들의 협동효과)

  • Yeol Sakong;Shi Choon KIm;Jae Bum Choo
    • Journal of the Korean Chemical Society
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    • v.30 no.3
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    • pp.265-272
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    • 1986
  • Kinetic studies for the methanolysis of tert-butyl halides (t-BuCl, t-BuBr, t-BuI) were carried out in MeOH-1,1,2,2-tetrachloroethane mixtures. The solvatochromic comparison method was used with six indicators to analyze solvent effects on the ionizations of tert-butyl halides. It was shown that the cooperative effect of solvent polarity-polarizability was the most important factor influenced on the methanolysis rates of tert-butyl halides, but the electrophilic assistance for halide leaving group and the nucleophilic assistance for tert-butylium ion were considerably influential, too. And it was found that the electrophilic assistance caused by hydrogen bonding and the nucleophilic assistance for carbon center were stronger for more basic leaving group ($I^-) and more polarizable leaving group(t-BuCl

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Modifications Induced by Organic Solvents to Aeromonas hydrophila IB Bct4 (유기용매에 의하여 유발된 Aeromonas hydrophila Bct4의 변형)

  • Lazaroaie, Mihaela Marilena
    • Journal of the Korean Chemical Society
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    • v.53 no.3
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    • pp.325-334
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    • 2009
  • Many bacteria that are capable to tolerate and degrade organic solvents have been isolated from seawater. However, their roles in the biodegradation of organic solvents in the marine environment have remained unknown. Aeromonas hydrophila IB$B_{ct4}$, isolated from Constanta seawater, was able to tolerate and degrade different organic solvents. Toluene, styrene, xylene isomers, ethylbenzene, with the logarithm of the partition coefficient in octanol-water mixture (log $P_{ow}$) between 2.64 and 3.17, were more toxic for bacterial cells, compared with propylbenzene, n-hexane, n-heptane, with log $P_{ow}$ between 3.69 and 4.39. There were revealed cellular and molecular modifications induced by organic solvents to Aeromonas hydrophila IB$B_{ct4}$. The study of cellular and molecular modifications induced by different organic solvents showed a complex response of bacterial cells to the presence of organic solvents in the culture media.

The Effect of Pressure on the Solvolysis of Benzylchlorides. p-Methoxybenzyl Chloride in Ethanol-Water Mixtures (염화벤질류의 가용매분해반응에 대한 압력의 영향. 에탄올-물 혼합용매내에서 p-메톡시 염화벤질의 분해반응)

  • Oh Cheun Kwun;Jin Burm Kyong;Kee Joon Choi
    • Journal of the Korean Chemical Society
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    • v.30 no.3
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    • pp.301-306
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    • 1986
  • The rate constants for the solvolysis reactions of p-methoxybenzylchloride in ethanol-water mixtures were determined at 2$^{\circ}$ and 10$^{\circ}C$ up to 1600bar. Rates of reaction were increased with increasing temperature and pressure, and decreased with increasing solvent composition of ethanol mole fraction. From the rate constants, the values of the activation parameters (${{\Delta}V_o}^{\neq},\;{\Delta}{\beta}^{\neq},\;{\Delta}H^{\neq},\;and\;{\Delta}S^{\neq}$) were evaluated. The values of ${{\Delta}V_o}^{\neq}$ and ${\Delta}{\beta}^{\neq}$ exhibit the extremum behavior at about 0.30 mole fraction of ethanol. This behavior is discussed in terms of solvent structure variation. From these results, it could be postulated that the reaction proceeds through $S_N1$ mechanism.

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Hydrogenolysis of CFC-113a$(CF_3CCl_3)$ Catalyzed by Heterogeneous Catalysts in the Liquid Phase (불균일 촉매를 이용한 CFC-113a$(CF_3CCl_3)$의 액상 가수소 분해 반응)

  • Jo, Uk Jae;Lee, Ik Mo;Kim, Hong Gon;Kim, Hun Sik
    • Journal of the Korean Chemical Society
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    • v.38 no.9
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    • pp.695-700
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    • 1994
  • Hydrogenolysis reactions of CFC-113a catalyzed by various heterogeneous catalysts $(Rh/Al_2O_3,\;Pd/C,\;Ni,\;Al_2O_3,\;Active\;carbon)$ were investigated in the liquid and gas phases. In the liquid phase reaction, different catalysts showed different activities, but all catalysts used gave high selectivities toward HCFC-123 over 95%. It was noticeable that the neutral $Al_2O_3$ showed both a high activity and a selectivity in the liquid phase reaction. In the gas phase reaction, transition metals on carbon(Pd/C, Pt/C) were so active for hydrogenolysis of CFC-113a that they even catalyzed the production reaction of overhydrogenated compounds such as $HCFC-133a(CF_3CH_2Cl)\;and\;HFC-143a(CF_3CH_3)$. $Al_2O_3$, which showed the high activity in the liquid phase reaction, did not show a remarkable activity. When $Al_2O_3$ was used in the liquid phase reaction, the hydrogenolysis of CFC-113a proceeded without any side products in THF. However, the same reaction in MeOH produced side products, such as $CH_3OCH_3\;and\;CH_3CH_2OCH_3$ from solvent. Based on this result, including heterogeneous catalysts, it was concluded that the solvent played an important role in the liquid phase reaction.

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Lipase-Catalyzed Reactions for Fats and Oils in Non-Polar Solvent (유기용매 내에서의 유지의 리파제 촉매반응)

  • Daeseok Han;Kwon, Dae-Young;Rhee, Joon-Shick
    • Microbiology and Biotechnology Letters
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    • v.16 no.3
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    • pp.250-258
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    • 1988
  • Lipases are well known as the enzymes which catalyze the hydrolysis of ester bonds combining aliphatic chains and glycerol on mono-, di- and triglycerides. Their reactions are characterized by be-ing heterogeneous and catalyzing the water-insoluble substrates. This property has been one of the Hurdles which delayed the application of lipases in fats and oils industry, However, with the development of biological reaction system of which organic solvent is introduced in part or whole as the reaction media, enzymatic manipulation of fats and oils is attracting increasing attention from the academic and industrial sectors. Trials in two-phase system and reversed micellar system to produce fatty acids through enzymatic hydrolysis of triglycerides preyed to be efficient in respect to volumetric productivity, fat hydrolysis rate, product separation, etc. In organic solvent system lipases have been found to have the ability to catalyze aminolysis, transesterification, esterification, thiotransesterification and oximolysis that are virtually impossible to catalyze in water. The organic solvent system is being extensively used in interesterifying glycerides to produce a fat with the modified physical and chemical nature.

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Study of Solvent Effects on the Ionization of tert-butyl Halide in MeOH-DMSO Mixtures (MeOH-DMSO 혼합용매중에서 tert-butyl halide의 이온화에 미치는 용매효과)

  • Yeol Sakong;Shi Choon Kim;Jin Sung Kim;Bon Su Lee
    • Journal of the Korean Chemical Society
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    • v.29 no.1
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    • pp.45-51
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    • 1985
  • Rate constants and activation parameters for the methanolysis of t-butyl halide (t-BuCl, t-BuBr, t-BuI) in various MeOH-DMSO mixtures were measured by conductometric method. Taft's solvatochromic parameters, such as polarity-polarizability(SPP's), ${\pi}^{\ast}$, hydrogen bond donor (HBD) acidity, ${\alpha}$, and hydrogen bond acceptor (HBA) basicity, ${\beta}$ of the solvents, were determined by the so called solvatochromic method using five indicators. The variation of methanolysis rate with the solvent composition was discussed on the basis of the activation parameters and the correlation of the rates with the solvatochromic parameters. It is concluded that the polarity-polarizability, HBD acidity and HBA basicity of the mixtures had an effect on the ionization of t-butyl halide cooperatively, also that the specific interaction between the leaving groups and the solvents, such as ion-dipole and hydrogen bond acceptor-donor interaction, is the most important factor of solvent effects on the stabilization of transition states.

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Hydrolysis of Phosphatidylcholine in Aerosol-OT/Isooctane Reversed Micelles by Phospholipase $A_2$ (역미셀계내에서 인지질분해효소 $A_2$에 의한 레시친의 가수분해)

  • Chang, Pahn-Shick
    • Korean Journal of Food Science and Technology
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    • v.29 no.1
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    • pp.26-31
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    • 1997
  • Bee venom (Apis mellifera) phospholipase $A_2$ solubilized in reversed micelles containing small amount of water stabilized by surfactant could catalyze the hydrolysis of dipalmitoyl phosphatidylcholine (DPPC). A sensitive and simple high performance liquid chromatographic (HPLC) methodology of phospholipase $A_2$ assay for the hydrolysis of DPPC was developed. Kinetic analysis of the phospholipase $A_2$-catalyzed reaction was found to be possible in reversed micelles. Among the surfactants and organic solvents tested, aerosol-OT and isooctane were most effective for the hydrolysis of DPPC in reversed micelles. Optimal temperature, optimal pH, $K_{m,app.},\;V_{max.,app.}$ and activation energy were determined to be $35{\sim}40^{\circ}C$, 7.0, 8.73 mM, 2.83 units/㎎ protein and 12.31 kcal/mole, respectively. The hydrolysis activity was dependent on water content and maximum activity was obtained at R value (=[water]/[aerosol-OT]) of 10.0.

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