• Title/Summary/Keyword: Kinetic Constant

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Synthesis of Tetrafluoroethylene from the Pyrolysis of Chlorodifluoromethane in the Presence of Steam (과열 수증기를 이용한 클로로디플루오르메탄 열분해 반응에 의한 테트라플루오르에틸렌의 합성)

  • Han, Myungwan;Kim, Beom-Sik;Kim, Chul-Ung;Lee, Jung-Min
    • Applied Chemistry for Engineering
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    • v.10 no.2
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    • pp.190-195
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    • 1999
  • The thermal pyrolysis of chlorodifluoromethane (R22) for producting tetrafluoroethylene (TFE) has been studied using the tubular reactor designed by the authors. The reaction temperature over $600{\sim}850^{\circ}C$, residence time over 0.005~0.6 sec, and steam/R22 ratio 3 to 30 were varied through experiments to analyze the effect of these variables on the conversion of R22 and selectivity for TFE. We have provided the guidelines for the optimal operation and design for the pyrolysis reactor. With increasing the dilution ratio, not only the conversion of R22 but also the selectivity for TFE increase. The optimum range of reaction temperature was $700{\sim}750^{\circ}C$ and the residence time 0.07~0.1 sec. In the kinetic study, first order rate equation was fitted well with the experimental data. This indicates that the main reaction step is a $CF_2$ generation from R22 pyrolysis. The range of activation energy for the rate constant was obtained 44.7~48 kcal/mol.

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Effects of Glucose and Ammonium Concentrations in Continuous Culture for Poly-$\beta$-hydroxybutyrate Production (Poly-$\beta$-hydroxybutyrate 생산을 위한 연속배양에서 포도당 및 암모늄 농도의 영향)

  • 이용우;유영제
    • Microbiology and Biotechnology Letters
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    • v.20 no.5
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    • pp.597-606
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    • 1992
  • Effects of dilution rate, inlet glucose and ammonium chloride concentrations on ,he performance of continuous culture of Alcaligenes eutrQPhus for poly-p-hydroxybutyrate (PHB) production were investigated. When inlet substrate concentrations were maintained constant (inlet glucose concentration = 20 g/l, inlet ammonium chloride concentration = 2 g/l), growth rate of residual biomass and PHB production rate showed its maximum at $0.1h^{-1}$ and $0.06h^{-1}$, respectively, and washout at $0.13h^{-1}$. PHB content decreased from 50% to 25% by increasing dilution rate, while specific PHB production rate increased continuously. Cell mass and PHB concentration gave its maximum values at inlet ammonium chloride concentration of 2 g/l and thereafter decreased, which showed the existence of substrate inhibition by ammonium. When inlet glucose concentration was 30 g/l, cell mass reached its maximum value, while PHB concentration increased continuously. The parameters of kinetic model were evaluated by the graphical and parameter estimation methods. The computer simulation results for the effects of dilution rate, inlet glucose and ammonium chloride concentrations fitted the experimental data very well.

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Electrocatalytic Oxidation of NADH at the Modified Graphite Electrode Incorporating Gold Nano Particles (금 나노입자를 회합시킨 수식된 흑연전극으로 NADH의 전기촉매 산화반응)

  • Cha, Seong-Keuck;Han, Sung-Yub
    • Journal of the Korean Electrochemical Society
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    • v.10 no.1
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    • pp.1-6
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    • 2007
  • Mercaptopropionic acid(mpa) has been used to make self-assembled monolayer(SAMs) on the surface of graphite electrode incorporating gold nano particles, which are subsequently modified with dopamine(dopa). Such modified electrodes haying types of Gr(Au)/mpa-dopa were employed in the electrocatalytic oxidation of NADH. The responses of such modified electrodes were studied in terms of electron transfer kinetics and reaction procedure in the reaction. The reaction of the surface immobilized dopa with NADH was studied using the rotating disk electrode technique and a value of $5.06{\times}10^5M^{-1}s^{-1}$ was obtained for the second-order rate constant in 0.1 M phosphate buffer(pH=7.0), which was a $EC_{cat}$ and kinetic controlled procedure. But, the modified electrodes were diffusion controlled reaction having $4.64{\times}10^{-4}cm^2s^{-1}$ of the coefficient within $10^{-3}s$ after starting the reaction.

Effects of Azumolene on Ryanodine Binging to Sarcoplasmic Reticulum of Normal and Malignant Hyperthermia Sucseptible Swine Skeletal Muscles

  • Kim, Do-Han;Lee, Young-Sup
    • Animal cells and systems
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    • v.1 no.1
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    • pp.77-80
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    • 1997
  • DOantrolene is a primary specific therapeutic drug for prevention and treatment of malignant hyperthermia symptoms. The mechanisms underlying the therapeutic effects of the drug are not well understood. The present study aimed at the characterization of the effects of azumolene, a water soluble dantrolene analogue, on ryanodine binding to sarcoplasmic reticulum (SR) from normal and malign::lnt hyperthermia susceptible (MHS) swine muscles. Characteristics of $[^3H]ryanodine$ binding were clearly different between the two types of SR. Kinetic analysis of eH]ryanodine binding to SR in the presence of $2{\mu}M$ $Ca^{2+}$ showed that association constant $(K_{ryanodine}_7$ is significantly higher in MHS than normal muscle SR $(2.83 vs. 1.32{\times}10^7 M^{-1}$, whereas the maximal ryanodine binding capacity $(B_{max})$ is similar between the two types of SR. Addition of azumolene $(e.g. 400{\mu}M)$ did not significantly alter both $K_{ryanodine}$ and $B_{max}$ of $[^3H]$ryanodine binding in both types of SR, indicating that the azumolene effect was not on the ryanodine binding sites. Addition of caffeine activated $[^3H]$ ryanodine binding in both types of SR, and caffeine sensitivity was significantly higher in MHS muscle SR than normal muscle SR $(K_{caffeine}:3.24 vs. 0.82 {\times} 10^2 M^{-l}). Addition of azumolene $(e.g.400{\mu}M)$ decreased Kcaffeine without significant change in $B_{max}$ in both types of SR suggesting that azumolene competes with caffeine binding site(s). These results suggest that malignant hyperthermia symptoms are caused at least in part by greater sensitivity of the MHS muscle SR to the $Ca^{2+}$ release drug(s), and that azumolene can reverse the symptoms by reducing the drug affinity to $Ca^{2+}$ release channels.

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Effect of a Variation of a Main Duct Area on Flow Distribution of Each Branch (주덕트의 단면적 변화가 분지덕트의 유량분배에 미치는 영향)

  • Lee Jai-Ho;Kim Beom-Jun;Cho Dae-Jin;Yoon Suck-Ju
    • Korean Journal of Air-Conditioning and Refrigeration Engineering
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    • v.17 no.4
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    • pp.386-395
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    • 2005
  • With the development of a living standard, the importance of indoor air conditioning system in all kinds of buildings and vehicles has increased. A lot of researches on energy losses in a duct and various kinds of flow pattern in branches or junctions have been carried out over many years, because the primary object of a duct system used in HVAC is to provide equal flow rate in the interior of each room by minimizing pressure drop. In this study, to get equal flow distribution in each branch, a blockage is applied to the rectangular duct system. The flow analysis for flow distribution of a rectangular duct with two branches was performed by CFD. By using SIMPLE algorithm and finite volume method, flow analysis is performed in the case of 3-D, incompressible, turbulent flow. Also, the standard $k-{\varepsilon}$ model and wall function method were used for analysis of turbulent fluid flow. The distribution diagrams of static pressure, velocity vector, turbulent energy and kinetic energy in accordance with variation of Reynolds number and blockages location in a rectangular duct show that flow distribution at duct outlets is improved by a blockage. In this rectangular duct system, mean velocity and flow rate distribution in two branch outlets are nearly constant regardless of variation of Reynolds number, and a flow pattern of the internal duct has a same tendency as well.

Kinetics and Mechanism of Triethylamine Catalysed Michael Addition of Benzenethiol to 1-(2-Nitrovinyl)benzene in Acetonitrile

  • Sarathi, P.A.;Gnanasekaran, C.;Shunmugasundaram, A.
    • Bulletin of the Korean Chemical Society
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    • v.29 no.4
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    • pp.790-794
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    • 2008
  • Nucleophilic addition reaction of benzenethiols (PhSH) to 1-(2-nitrovinyl) benzenes ($\beta$ NS) in the presence of triethylamine (TEA) has been studied in acetonitrile at 25 ${^{\circ}C}$. The rate is first order with respect to [PhSH], [TEA] and [$\beta$ NS]. The reaction is found to proceed with the formation of ion-pair between benzenethiol and TEA. A suitable mechanism with the formation of an adduct between ion-pair and substrate in a slow step followed by its rearrangement to 1,2-addition product in a fast step has been proposed and corresponding rate law derived. From the rate law, the rate constants for the interaction between ion-pair and $\beta$NS have been evaluated. Interestingly, in both para-substituted substrates and benzenethiols the rate increases with the electron-withdrawing power of the substituents. The positive sign of $\rho_x$ in benzenethiols has been explained. The magnitude of cross-interaction constant, $\rho_{xy}$ is small (0.08). The magnitude of the Hammett $\rho_x$ values is higher than that of the Bronsted, $\beta_x$ values for benzenethiols. The kinetic isotope effect, $k_H/k_D$, is found to be greater than unity. A suitable transition state with simultaneous formation of $C_\beta$ -H and $B_\alpha$ -S bonds involving the ion-pair and $\beta$NS in a single concerted step has been proposed to account for these observations.

Synthesis of Selective Butyrylcholinesterase Inhibitors Coupled between α-Lipoic Acid and Polyphenols by Using 2-(Piperazin-1-yl)ethanol Linker

  • Yeun, Go Heum;Lee, Seung Hwan;Lim, Yong Bae;Lee, Hye Sook;Won, Moo-Ho;Lee, Bong Ho;Park, Jeong Ho
    • Bulletin of the Korean Chemical Society
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    • v.34 no.4
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    • pp.1025-1029
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    • 2013
  • In the previous paper (Bull. Korean Chem. Soc., 2011, 32, 2997), the hybrid molecules between ${\alpha}$-lipoic acid (ALA) and polyphenols (PPs) connected with neutral 2-(2-aminoethoxy)ethanol linker (linker-1) showed new biological activity such as butyrylcholinesterase (BuChE) inhibition. In order to increase the binding affinity of the hybrid compounds to cholinesterase (ChE), the neutral 2-(2-aminoethoxy)ethanol (linker 1) was switched to the cationic 2-(piperazin-1-yl)ethanol linker (linker 2). The $IC_{50}$ values of the linker-2 hybrid molecules for BuChE inhibition were lower than those of linker-1 hybrid molecules (except 9-2) and they also had the same great selectivity for BuChE over AChE (> 800 fold) as linker-1 hybrid molecules. ALA-acetyl caffeic acid (10-2, ALA-AcCA) was shown as an effective inhibitor of BuChE ($IC_{50}=0.44{\pm}0.24{\mu}M$). A kinetic study using 7-2 showed that it is the same mixed type inhibition as 7-1. Its inhibition constant (Ki) to BuChE is $4.3{\pm}0.09{\mu}M$.

Reaction Mode of Transglucosidase from Aspergillus niger for Production of Isomaltooligosaccharides (Aspergillus niger 유래의 Transglucosidase의 이소말토올리고당 생성반응 특성)

  • Ahn, Jang-Woo;Hong, Seung-Shu;Park, Kwan-Wha;Seo, Jin-Ho
    • Korean Journal of Food Science and Technology
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    • v.28 no.2
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    • pp.273-278
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    • 1996
  • The research was undertaken to characterize the reaction mode of transglucosidase (TG) from Aspergillus niger for the production of isomaltooligosaccharides such as isomaltose, panose and isomaltotriose. TG hydrolyzed maltose to glucose units and produced panose and glucose by transglucosylation. TG hydrolyzed panose to maltose and glucose when panose was used as an initial substrate. The reaction patterns of products when isomaltose, isomaltotriose or isomaltotetraose were used as substrates were different from the case when maltose was used as a substrate. Maltotriose and maltose showed the same formation pattern of products. TG also produced isomaltooligosaccharides from maltooligosaccharides. The production of panote by TG from maltose was mathematically described by Michaelis-Menten kinetics. The kinetic constants, $V_{max}$ (the maximum velocity) and $K_m$ (Michaelis constant), were estimated by Lineweaver-Burk plot to be 400 M/min and 21.4 mM, respectively.

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Nucleophilic Substitution Reactions of Benzoic Anhyrides with Aniline in Methanol-Acetonitrile Mixtures (메탄올-아세토니트릴 혼합용매에서 벤조산 무수물과 아닐린의 친핵성 치환반응)

  • Lee, Byung Choon;Shin, Young Kook;Lee, Seung Woo;Lee, Ik Choon;Lee, Won Heui
    • Journal of the Korean Chemical Society
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    • v.41 no.2
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    • pp.69-76
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    • 1997
  • Kinetic studies for the nucleophilic substitution reactions of the benzoic anhydrides with anilines in methanol-acetonitrile mixtures at$35.0{\circ}C$have been carried out in order to elucidate the reaction mechanism. Individual rate constants$k_{XY}$and$k_{XZ}$were decided from the ratios of the reaction products for the competitive substitution reaction at either one of the two carbonyl carbons in benzoic anhydride. Transition state structure and reaction mechanism were elucidated by the Hammett$p_x,\;p_y$and$p_z$values and cross interaction constant$p_x\;p_y$and$p_zvalues. The reaction of the benzoic anhydride has been proposed to proceed by a frontside attack$S_N2 $mechanism with four-membered ring transition state from unusually large magnitude of the$ρ_X,\;ρ_{XY},\;ρ_{XZ}$and positive$p_Y$values.

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Spectrophotometric Investigation of Oxidation of Cefpodoxime Proxetil by Permanganate in Alkaline Medium: A Kinetic Study (알칼리성 용매에서 과망간에 의한 세프포독심 프록세틸의 산화의 분광광도법적 조사: 속도론적 연구)

  • Khan, Aftab Aslam Parwaz;Mohd, Ayaz;Bano, Shaista;Siddiqi, K. S.
    • Journal of the Korean Chemical Society
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    • v.53 no.6
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    • pp.709-716
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    • 2009
  • A Kinetics pathway of oxidation of Cefpodoxime Proxetil by permanganate in alkaline medium at a constant ionic strength has been studied spectrophotometrically. The reaction showed first order kinetics in permanganate ion concentration and an order less than unity in cefpodoxime acid and alkali concentrations. Increasing ionic strength of the medium increase the rate. The oxidation reaction proceeds via an alkali-permanganate species which forms a complex with cefpodoxime acid. The latter decomposes slowly, followed by a fast reaction between a free radical of cefpodoxime acid and another molecule of permanganate to give the products. Investigations of the reaction at different temperatures allowed the determination of activation parameters with respect to the slow step of proposed mechanism and fallows first order kinetics. The proposed mechanism and the derived rate laws are consistent with the observed kinetics.