• Title/Summary/Keyword: Kinetic Parameters

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Kinetics of Intracellular Adenosine Deaminase to Substrate Analogs and Inhibitors in Aspergillus oryzae (Aspergillus oryzae의 세포내 효소인 Adenosine Deaminase의 기질 유사체와 억제물질에 대한 반응속도론적 분석)

  • Choi, Hye-Seon
    • Korean Journal of Microbiology
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    • v.32 no.1
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    • pp.84-90
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    • 1994
  • Kinetic parameters of various substrates and inhibitors were measured to elucidate the binding requirements of the active site of intracellular adenosine deaminase (ADA) in Aspergillus oryzae. 3'-Deoxyadenosine was the best substrate according to the value of relative kcat/$K_m$. Purine riboside was found to be the strongest inhibitor with the $K_i$ value of $3.7{\times}10^{-5}$M. Adenine acted neither as a substrate nor as an inhibitor, suggesting the presence of ribose at N-9 of adenosine was crucial to binding. ADA also catalyzed the dechlorination of 6-chloropurine riboside, generating inosine and chloride ions. Substrate specificity of 6-chloropurine riboside was 0.86% of adenosine. Purine riboside, a competitive inhibitor of ADA, inhibit the dechlorination with similar $K_i$ value, suggesting that the same binding site was involved in deamination and dechlorination. Among the sulfhydryl group reagents, mercurials, pchloromercuribenzoate (PCMB), mersalyl acid and $HgCl_2$ inactivated the enzyme. Mersalyl acid-inactivated ADA was reactivated by thiol reagents, but PCMB-inactivated enzyme was not. When ADA was treated with the mercurial reagents, the inhibition constants and inhibition patterns were determined. Each inhibition was competitive with substrate. The $K_i$ values of these mercurial reagents were lower in 10 mM phosphate buffer than in 100 mM phosphate buffer, showing phosphate dependency.

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Studies of Solvolyses of Di-n-butyl Phosphorochloridate by Extended Grunwald-Winstein Equation (확장된 Grunwald-Winstein 식에 의한 Di-n-butyl Phosphorochloridate의 가용매 분해반응 연구)

  • Kang, Min Sung;Kim, Cheul Ju;Kang, Suk Jin;Koh, Han Joong
    • Journal of the Korean Chemical Society
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    • v.59 no.5
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    • pp.373-378
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    • 2015
  • The solvolysis rate constants of di-n-butyl phosphorochloridate ((CH3CH2CH2CH2O)2POCI, 1) in 28 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale and YCl solvent ionizing scale, with the sensitivities values of 1.40 and 0.42 for l and m, respectively. These l and m values can be considered to support an SN2 reaction pathway. This interpretation is further supported by the activation parameters, i.e., relatively small positive ΔH (8.0 to 15.9 kcal·mol−1 ) values and large negative ΔS (−25.8 to −53.1 cal·mol−1 ·K−1 ) values, the Kivinen’s n values (0.9~1.7), and the solvent kinetic isotope effect (1.62).

Determination of the Langmuir and Temkin Adsorption Isotherms of H for the Cathodic H2 Evolution Reaction at a Pt/KOH Solution Interface Using the Phase-Shift Method

  • Chun Jang-H.;Jeon Sang-K.;Chun Jin-Y.
    • Journal of the Korean Electrochemical Society
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    • v.9 no.1
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    • pp.19-28
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    • 2006
  • The phase-shift method for determining the Langmuir, Frumkin, and Temkin adsorption isotherms ($\theta_H\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at a Pt/0.1 M KOH solution interface has been proposed and verified using cyclic voltammetric, differential pulse voltammetric, and electrochemical impedance techniques. At the Pt/0.1 M KOH solution interface, the Langmuir and Temkin adsorption isotherms ($\theta_H\;vs.\;E$), the equilibrium constants ($K_H=2.9X10^{-4}mol^{-1}$ for the Langmuir and $K_H=2.9X10^{-3}\exp(-4.6\theta_H)mol^{-1}$ for the Temkin adsorption isotherm), the interaction parameters (g=0 far the Langmuir and g=4.6 for the Temkin adsorption isotherm), the rate of change of the standard free energy of $\theta_H\;with\;\theta_H$ (r=11.4 kJ $mol^{-1}$ for g=4.6), and the standard free energies (${\Delta}G_{ads}^{\circ}=20.2kJ\;mol^{-1}$ for $k_H=2.9\times10^{-4}mol^{-1}$, i.e., the Langmuir adsorption isotherm, and $16.7<{\Delta}G_\theta^{\circ}<23.6kJ\;mol^{-1}$ for $K_H=2.9\times10^{-3}\exp(-4.6\theta_H)mol^{-1}$ and $0.2<\theta_H<0.8$, i.e., the Temkin adsorption isotherm) of H for the cathodic HER are determined using the phase-shift method. At intermediate values of $\theta_H$, i.e., $0.2<\theta_H<0.8$, the Temkin adsorption isotherm ($\theta_H\;vs.\;E$) corresponding to the Langmuir adsorption isotherm ($\theta_H\;vs.\;E$), and vice versa, is readily determined using the constant conversion factors. The phase-shift method and constant conversion factors are useful and effective for determining the Langmuir, Frumkin, and Temkin adsorption isotherms of intermediates for sequential reactions and related electrode kinetic and thermodynamic data at electrode catalyst interfaces.

A Kinetic Study on the Esterification of Oleic Acid with Methanol in the Presence of Amberlyst-15 (Amberlyst-15 촉매의 존재 하에서 올레산과 메탄올의 에스테르화 반응 속도식 연구)

  • Kim, Young-Joo;Kim, Deog-Keun;Rhee, Young Woo;Park, Soon-Chul;Lee, Jin-Suk
    • Korean Chemical Engineering Research
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    • v.43 no.5
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    • pp.621-626
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    • 2005
  • The esterification reaction of free fatty acid with methanol was investigated in the presence of catalyst, Amberlyst-15, producing fatty acid methyl ester, namely, biodiesel. In this paper, the effects of the reaction parameters such as reaction temperature, mole ratio of alcohol to oleic acid and mass of catalyst on the catalytic activity have been examined. The results showed that the reaction rate increased about twice as the temperature increased every $20^{\circ}C$ in the reaction temperature range from 333 K to 373 K. The equilibrium conversion rate of oleic acid increased with the feed mole ratio of alcohol to acid ranging from 6:1 to 44:1. When the feed mole ratio was higher than 44:1, all the results were similar to that of 44:1. As for the influence of the mass of catalyst, the initial reaction rate increased from 1.2 to 1.3 times as the mass of catalyst doubles in the range of the catalyst weight from 5 to 20 wt%. The experiment data obtained were well described by the second reaction rate using a pseudo-homogeneous model.

Channel and Gate Workfunction-Engineered CNTFETs for Low-Power and High-Speed Logic and Memory Applications

  • Wang, Wei;Xu, Hongsong;Huang, Zhicheng;Zhang, Lu;Wang, Huan;Jiang, Sitao;Xu, Min;Gao, Jian
    • JSTS:Journal of Semiconductor Technology and Science
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    • v.16 no.1
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    • pp.91-105
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    • 2016
  • Carbon Nanotube Field-Effect Transistors (CNTFETs) have been studied as candidates for post Si CMOS owing to the better electrostatic control and high mobility. To enhance the immunity against short - channel effects (SCEs), the novel channel and gate engineered architectures have been proposed to improve CNTFETs performance. This work presents a comprehensive study of the influence of channel and gate engineering on the CNTFET switching, high frequency and circuit level performance of carbon nanotube field-effect transistors (CNTFETs). At device level, the effects of channel and gate engineering on the switching and high frequency characteristics for CNTFET have been theoretically investigated by using a quantum kinetic model. This model is based on two-dimensional non-equilibrium Green's functions (NEGF) solved self - consistently with Poisson's equations. It is revealed that hetero - material - gate and lightly doped drain and source CNTFET (HMG - LDDS - CNTFET) structure can significantly reduce leakage current, enhance control ability of the gate on channel, improve the switching speed, and is more suitable for use in low power, high frequency circuits. At circuit level, using the HSPICE with look - up table(LUT) based Verilog - A models, the impact of the channel and gate engineering on basic digital circuits (inverter, static random access memory cell) have been investigated systematically. The performance parameters of circuits have been calculated and the optimum metal gate workfunction combinations of ${\Phi}_{M1}/{\Phi}_{M2}$ have been concluded in terms of power consumption, average delay, stability, energy consumption and power - delay product (PDP). In addition, we discuss and compare the CNTFET-based circuit designs of various logic gates, including ternary and binary logic. Simulation results indicate that LDDS - HMG - CNTFET circuits with ternary logic gate design have significantly better performance in comparison with other structures.

A Study on the Kinetics of Copper Ions Reduction and Deposition Morphology with the Rotating Disk Electrode (RDE를 이용한 구리이온의 환원속도 및 전착형태에 관한 고찰)

  • Nam, Sang Cheol;Um, Sung Hyun;Lee, Choong Young;Tak, Yongsug;Nam, Chong Woo
    • Applied Chemistry for Engineering
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    • v.8 no.4
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    • pp.645-652
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    • 1997
  • Electrochemical characteristics and kinetic parameters of copper ion reduction were investigated with a platinum rotating disk electrode (RDE) in a diffusion controlled region. Reduction of Cu(II) in sulfate had one-step two-xelectron process, while the reduction of Cu(II) in chloride solution was involved two one-electron processes. The transfer coefficient of Cu(II) in sulfate solution was lowest, and the transfer coefficient of Cu(I) in halide solutions had the value of nearly one. In chloride solutions, electrodeposition rate of Cu(II) was about one hundred times faster than Cu(I). Diffusion coefficient increased in the order of Cu(II) in chloride solution, Cu(I) in the iodide, bromide, chloride solution, Cu(II) in sulfate solution. The calculated ionic radii and activation energy for diffusion decreased in the same order as above. Morphological study on the copper electrodeposition indicated that the electrode surface became rougher as both concentration and reduction potential increases, and the roughness of the surface was analyzed with UV/VIS spectrophotometer.

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Free-Radical Polymerization and Copolymerization of N-Acetyl ${\alpha}$-Aminoacrylic Acid (N-Acetyl ${\alpha}$-aminoacrylic Acid의 자유라디칼 중합 및 혼성중합)

  • Il Hyun Park;Chong Kwnag Lee;Jae Ho Choi;Jung-Il Jin
    • Journal of the Korean Chemical Society
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    • v.26 no.4
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    • pp.235-246
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    • 1982
  • The free radical polymerization and copolymerization of N-acetyl ${\alpha}$-aminoacrylic acid were investigated. From the result of kinetic investigation of N-acetyl ${\alpha}$-aminoacrylic acid in DMF at $60^{\circ}C$, a rate equation of $R_p$ = $k_p[M]^{0.97}[I]^{0.59}$ was obtained. The overall activation energy for the polymerization was found to be 25.2 kcal/mole. Copolymerization of N-acetyl ${\alpha}$-aminoacrylic acid with acrylic acid and styrene was carried out for the determination of monomer reactivity ratios. The monomer reactivity ratios for the monomer pairs determined at 70.0{\pm}0.1^{\circ}C$ using benzoyl peroxide as an initiator are; $r_1$(N-acetyl ${\alpha}$-aminoacrylic acid) = 0.49, $r_2$(acrylic acid) = 1.41, $r_1$(N-acetyl ${\alpha}$-aminoacrylic acid) = 0.44, $r_2$(styrene) = 0.91. The values of Alfrey-Price's Q and e parameters for N-acetyl ${\alpha}$-aminoacrylic acid were calculated to be 0.51 and 0.16 for the both systems. Differential thermal analysis and thermogravimetry showed that acrylic acid copolymers have poorer thermal stability as compared with the homopolymer of N-acetyl ${\alpha}$-aminoacrylic acid.

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Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures (압력변화에 따른 퀴놀린 유도체와 p-치환 염화벤조일류의 속도론적 연구)

  • Jong-Wan Lim;Se-Kyong Kim
    • Journal of the Korean Chemical Society
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    • v.47 no.3
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    • pp.206-212
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    • 2003
  • The reaction rates of substituted quinolines (6-Clqui., qui.) with p-substituted benzoylchlorides $(p-CH_3,\;p-H,\;p-NO_2)$ have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10, 15, 20, $25^{\circ}C$) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters $(Ea,\;{\Delta}V^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}, \;{\Delta}G^{\neq})$and the pressure dependence of Hammett ρ values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron acceptor substituents in substrate $(p-NO_2)$ with quinoline. The activation volume and the activation entropy are all negative. And the Hammett p values are negative for nucleophile ${\rho}_X$ and positive for the substrate ${\rho}_Y$ over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed through a typical $S_N2$ reaction mechanism and "associative $S_N2$" favoring bond formation with increasing pressures.

The Effect of Pyrolysis Pressure on Combustion Reactivity of Coal Char (열분해 압력이 석탄 촤의 연소반응성에 미치는 영향)

  • Park Ho Young;Kim Young Ju;Kim Tae Hyung;Seo Sang Il
    • Journal of Energy Engineering
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    • v.14 no.1
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    • pp.1-10
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    • 2005
  • The combustion reactivity of char depending on the pyrolysis pressure was investigated with Pressurized Thermogravimetric Analyser. The amounts of volatiles released at pyrolysis pressure of 1, 8 and 15 atm were, first, measured with Alaska, Adaro and Denisovsky coals. Reactivities of chars produced at var-ious pyrolysis pressure were evaluated at atmospheric pressure and 500℃, and analysed in terms of char crystal structure, surface area, pore characteristics and chemical composition of char. Finally, the combustion reactivities of three chars were examined at pressure of 1 atm, 8 atm and 15 atm. From this study, it was recognized that the amount of volatiles released decreases with increase in pyrolysis pressure, and reaction rate of char produced at higher pyrolysis pressure was lower than that at lower pyrolysis pressure. It might be resulted from the difference in char surface area and pore characteristics rather than char crystal structure and chemical characteristics. At 15 atm, kinetic parameters of Alaska char were obtained with the grain model, and these were 56.8 KJ/mole for activation energy and 222.34 (1/min) for frequency factor.

Characterization of Enzymatic Properties of Streptomyces albus Amylase Expressed in Recombinant Bacillus subtilis (재조합 Bacillus subtilis 에서 발현된 Streptomyces albus 유래 amylase 의 효소공학적 특성)

  • Park, Geun-Woo;Kim, Myoung-Dong;Ahn, Jang-Woo;Kim, Young-Bae;Seo, Jin-Ho
    • Korean Journal of Food Science and Technology
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    • v.30 no.6
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    • pp.1426-1431
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    • 1998
  • The research was undertaken to characterize enzymatic properties of Streptomyces albus amylase expressed in recombinant Bacillus subtilis. Molecular weight and pI of the purified enzyme were estimated to be 50 kD by SDS-PAGE and 4.3 by isoelectric focusing. The optimum temperature and optimum pH were $45^{\circ}C$ and 6.0, respectively. D-and Z-value were estimated to measure thermostability of the purified enzyme. The Z-value was estimated $17.7^{\circ}C$, which is lower than typical amylase. Maltotetraose was produced as a major component from soluble starch in the early state of reaction but gradually degraded to maltose. Thin layer chromatography was also performed to analyze the reaction products. The parameters involved in Michaelis-Menten enzyme kinetics were found to be the maximum velocity of 0.37 mM/min and the Michaelis constant of 0.13%, respectively.

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