• Title/Summary/Keyword: Kinetic studies

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Kinetic Studies for the Reaction of p-Methylphenacyl Arenesulfonates with Pyridine under High Pressures (고압하에서 p-Methylphenacyl Arenesulfonate와 피리딘과의 반응메카니즘)

  • Yoh Soo-Dong;Park Heon-Young;Park Jong-Hwan;Hwang Jeong-Ui
    • Journal of the Korean Chemical Society
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    • v.35 no.1
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    • pp.64-69
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    • 1991
  • Kinetics of the reaction of p-methylphenacyl arenesulfonates with pyridine in acetonitrile were investigated by an electric conductivity method at 1∼2000 bars and 35∼55$^{\circ}C$. The rates of these reactions were increased with raising pressures and temperatures. The activation enthalpy(${\Delta}H^{\neq}$), entropy(${\Delta}S^{\neq}$) and activation volume(${\Delta}V^{\neq}$) of the reaction were obtained with the rate constants. Activation volume and entropy were both negative valued, and activation enthalpy was positive. The acteivation parameters (${\Delta}V^{\neq}$ and ${\Delta}S^{\neq}$) were decreased with increasing pressure. From all of the above results, it was found that this reaction proceeds on the S$_N$2 in which C${\cdots}$O bond breaking is more advanced as pressure increases.

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Kinetic Studies on the Nucleophilic Addition of 3-Mercaptopropionic Acid to ${\beta},\;{\beta}$-Diethoxycarbonylstyrene Derivatives (${\beta},\;{\beta}$-Diethoxycarbonylstyrene 유도체에 대한 3-Mercaptopropionic Acid의 친핵성첨가반응에 관한 반응속도론적 연구)

  • Tae-Rin Kim;Yun-Chung Choi;Myung-Sook Chung
    • Journal of the Korean Chemical Society
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    • v.33 no.1
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    • pp.127-134
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    • 1989
  • The rate constants of the nucleophilic addition reaction of 3-mercaptopropionic acid to the ${\beta},\;{\beta}$-diethoxycarbonylstryene derivatives (H, p-OCH$_3$, 3,4,5-(OCH$_3)_3$, 3,4-methylenedioxy) were determined by ultraviolet spectrophotometry, and rate equation which could be applied over a wide pH range was obtained. On the basis of pH-rate profile and the presence of general base catalysis, a plausible mechanism of this addition reaction was propound:Below pH 6.0 the reaction was initiated by the addition of neutral 3-mercaptopropionic acid molecule, and in the range of pH 6.0∼8.0, a neutral 3-mercaptopropionic acid molecule and a sulfide anion competitively attacked to the double bond. Above pH 8.0, the reaction proceeded through the addition of a sulfide anion.

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Rates and Mechanism of the Reduction of Vanadium(V) by Benzyl Alcohol in Aqueous Dimethylformamide (DMF 수용매에서 벤질알코올에 의한 바나듐(V)의 환원반응속도와 메카니즘)

  • Chang-Su Kim;Woo-Sik Lee
    • Journal of the Korean Chemical Society
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    • v.32 no.3
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    • pp.179-185
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    • 1988
  • The reaction of VO_2\;^+$ with benzyl alcohol in perchloric acid and aqueous dimethylformamide leads to the formation of $VO^{2+}$ and benzaldehyde. The products, $VO^{2+}$ and benzaldehyde, are identified by infrared spectroscopy and gas chromatography. Kinetic studies on the reaction of VO_2\;^+$ with benzyl alcohol have been carried out using visible spectroscopy. The empirical rate equation can be expressed as $-d[VO_2\;^+]/dt=2\{\\{k_O+k_H[HClO_4]\}\[VO_2\;^+][C_6H_5CH_2OH]$ The rate determining step for the reaction is the process for the formation of $VO^{2+}$ and $C_6H_5CHOH$. The activation parameters are ${\Delta}H^{\neq}=13.32{\pm}1.73\;kcalmol^{-1}$ and ${\Delta}S^{\neq}=-31.02{\pm}0.09\;calmol^{-1}K^{-1}$ for the oxidation of benzyl alcohol in aqueous dimethylformamide.

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Kinetic Studies on Halogen Exchange of Substituted Benzenesulfonylbromides

  • Kim, Jaerok
    • Nuclear Engineering and Technology
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    • v.5 no.4
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    • pp.321-333
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    • 1973
  • The rates and activation parameters for the halide exchange reactions of substituted benzenesulfonylbromides (R-C$_{6}$H$_4$SO$_2$Br, R=p-MeO, p-$CH_3$, p-H, p-NO$_2$) in dry acetone at two temperatures were determined. It was found that the nucleophilicity order of Cl->I-$\geq$Br- for strong electron withdrawing-, and mild electron donating group, and of I-$\geq$Cl->Br- for strong electron donating group, Hammett plots showed slightly convoked characteristics which is similar to the plots of substituted benzenesulfonylchlorides, but contrary to the concaved nature for the halide exchange reactions of substituted benzyl chlorides. The rate of halogen exchange between benzenesulfonylbromide and lithium bromide decreased in the order of solvent : ($CH_3$)$_2$CO>$CH_3$CN》MeOH. The rates and activation parameters were also compared with those already known in the substituted benzenesulfonylchlorides. Theses were explained in terms of the structural properties of the transition state, and discussed the reaction mechanisms.s.

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Inhibitory actions of the antidepressant/antipanic drug phenelzine on brain GABA transaminase

  • Yoo, Byung-Kwon;Hong, Joung-Woo;Suk, Jae-Wook;Ahn, Jee-Yin;Yoo, Jeong-Suk;Lee, Kil-Soo;Cho, Sung-Woo;Choi, Soo-Young
    • Archives of Pharmacal Research
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    • v.19 no.6
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    • pp.480-485
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    • 1996
  • Brain GABA transaminase is inactivated by preincubation with antidepressant/antipanic drug pheneizine (${\beta}$ethylphenylhydrazine) (mixing molar ratio 10:1) at pH 7.4. The reaction of enzyme with phenelzine was monitored by absorption and fluorescence spectroscopic methods. The inactive enzyme was fully reconstituted by addition of cofactor pyridoxal-5-phosphate. This result implies that the blocking of 1 mol of pyridoxal-5-phosphate per enzyme dimer is needed for inactivation of the enzyme. The time course of the reaction is significantly affected by the substrate .alpha.-ketoglutarate, which afforded complete protection against the loss of catalytic activity. The kinetic studies shows that phenelzine reacts with the cofactor of enzyme with a second-order rate constant of $2.1{\times}10^3M^{-1}s^{-1}$. It is postulated that the antidepressant/antipanic drug phenelzine is able to elevate the neurotransmitter GABA levels in central nervous system by inhibitory action on GABA degradative enzyme GABA transaminase.

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PILOT INJECTION OF DME FOR IGNITION OF NATURAL GAS AT DUAL FUEL ENGINE-LIKE CONDITIONS

  • MORSY M. H.;AHN D. H.;CHUNG S. H.
    • International Journal of Automotive Technology
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    • v.7 no.1
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    • pp.1-7
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    • 2006
  • The ignition delay of a dual fuel system has been numerically investigated by adopting a constant volume chamber as a model problem simulating diesel engine relevant conditions. A detailed chemical kinetic mechanism, consisting of 28 species and 135 elementary reactions, of dimethyl ether (DME) with methane ($CH_{4}$) sub-mechanism has been used in conjunction with the multi-dimensional reactive flow KIVA-3V code to simulate the autoignition process. The start of ignition was defined as the moment when the maximum temperature in the combustion vessel reached to 1900 K with which a best agreement with existing experiment was achieved. Ignition delays of liquid DME injected into air at various high pressures and temperatures compared well with the existing experimental results in a combustion bomb. When a small quantity of liquid DME was injected into premixtures of $CH_{4}$/air, the ignition delay times of the dual fuel system are longer than that observed with DME only, especially at higher initial temperatures. The variation in the ignition delay between DME only and dual fuel case tend to be constant for lower initial temperatures. It was also found that the predicted values of the ignition delay in dual fuel operation are dependent on the concentration of the gaseous $CH_{4}$ in the chamber charge and less dependent on the injected mass of DME. Temperature and equivalence ratio contours of the combustion process showed that the ignition commonly starts in the boundary at which near stoichiometric mixtures could exists. Parametric studies are also conducted to show the effect of additive such as hydrogen peroxide in the ignition delay. Apart from accurate predictions of ignition delay, the coupling between multi-dimensional flow and multi-step chemistry is essential to reveal detailed features of the ignition process.

Effects of the Hip Internal Rotation Gait on Gluteal and Erector Spinae Muscle Activity (고관절 내회전 보행이 둔부 근육과 척추 기립근의 근활성도에 미치는 영향)

  • Kwon, Oh-Yun;Won, Jong-Hyuck;Oh, Jae-Seop;Lee, Won-Hwee;Kim, Soo-Jung
    • Physical Therapy Korea
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    • v.13 no.1
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    • pp.24-31
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    • 2006
  • The purpose of this study was to identify the effect of the hip internal rotation on gluteal and erector spinae muscle electromyographic (EMG) activity during treadmill walking. Eleven healthy subjects were recruited. All subjects performed treadmill walking while maintaining the hip in neutral position (condition 1) and in internal rotation (condition 2). Surface EMG activity was recorded from four muscles (gluteus maximus (GM), gluteus medius (GMED), tensor fascia latae (TFL), and erector spinae (ES)) and the hip internal rotation angle was measured using a three dimensional motion analysis system. The gait cycle was determined with two foot switches, and stance phase was normalized as 100% stance phase (SP) for each condition using the MatLab 7.0 program. The normalized EMG activities according to the hip rotation (neutral or internal rotation) were compared using a paired t-test. During the entire SP of treadmill walking, the EMG activities of GM in condition 1 were significantly greater than in condition 2 (p<.05). The EMG activities of TFL and ES in condition 2 were significantly greater than in condition 1 (p<.05). The EMG activities of the GMED in condition 1 were significantly greater than in condition 1 (p>.05) except for 80~100% SP. Further studies need randomized control trials regarding the effect of hip internal rotation on the hip and lumbar spine muscle activity. Kinetic variables during gait or going up and down stairs are also needed.

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The Effect to Drug Metabolizing Enzyme Cytochrome P450 3A4 by Chungyulyak (청열약 수종의 Cytochrome P450 3A4 효소활성도에 미치는 영향)

  • Jo, Hee-Chan;Shin, Yong-Cheol;Ko, Seong-Gyu
    • Journal of Society of Preventive Korean Medicine
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    • v.12 no.3
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    • pp.99-113
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    • 2008
  • In this study, the author experimented the influence of five herbal medicines, which are Lonicera japonica Thunb, Paeonia suffruticosa Andr., Fraxinus rhynchophylla Hance, Gardenia jasminoides Ellis, Scutellaria baicalensis George which are called 'Chungyulyak(淸熱藥)' on drug metabolizing enzyme cytochrome P450 3A4 in Human Liver Microsome. Above all, the reason for this study is that herbal medicines can be assumed that herbs might have interactions with drugs, other herbs, alcohol and chemicals whether those are much better synergy effects than expected effects when the medicine was treated alone or not. As a result, we showed that all of five traditional herbal medicines had no CYP 3A4 inhibition effect on 10, 20, 30, 40, $50{\mu}g/m{\ell}$ doses in Human Liver Microsome. However, this result are mostly not enough to prove that PMT has a CYP 3A4 inhibition effect. Moreover, it is not that those rates showed that those herbal medicines have CYP 3A4 induction effect. In conclusion, the result could support that those herbal medicines are more safe than chemical drugs even if this is the basic step to prove that result. Therefore, more specific studies to support this result, which are Kinetic study, cell and animal study then finally until clinical research, are required.

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The Effect to the Hepatic Metabolic Enzume that Uses Human Liver Microsome Caused by a Bariety of Yigiyak (Human Liver Microsome을 이용한 수종 이기약의 간대사효소에 미치는 영향)

  • Kim, Hyun-Ho;Shin, Yong-Cheol;Ko, Seong-Gyu
    • Journal of Society of Preventive Korean Medicine
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    • v.12 no.2
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    • pp.37-49
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    • 2008
  • In this study, we experimented the influence of three herbal medicines, which are Saussurea lappa Clarke, Poncirus trifoliata Rafin, Citrus aurantium Linne, which are called 'Yigiyak(理氣藥)' on drug metabolizing enzyme cytochrome P450 3A4 in Human Liver Microsome. Above all, the reason for this study is that herbal medicines can be assumed that herbs might have interactions with drugs, other herbs, alcohol and chemicals whether those are much better synergy effects than expected effects when the medicine was treated alone or not. As a result, we showed that all of five traditional herbal medicines had no CYP 3A4 inhibition effect on 10, 20, 30, 40, $50{\mu}g/m{\ell}$ doses in Human Liver Microsome even Saussurea lappa Clarke showed a little inhibition as about 93% and 79% inhibition rate of control. However, this result are mostly not enough to prove that SLC has a CYP 3A4 inhibition effect. Moreover, it is not that those rates showed that those herbal medicines have CYP 3A4 induction effect. In conclusion, the result could support that those herbal medicines are more safe than chemical drugs even if this is the basic step to prove that result. Therefore, more specific studies to support this result, which are Kinetic study, cell and animal study then finally until clinical research, are required.

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Adsorption Studies of Nickel(II) Ions onto Amorphous Alumina (무정형 알루미나에서의 니켈(II) 이온의 흡착에 관한 연구)

  • Park, Yeong Jae;Suh, Moo Yul;Park, Kyoung Kyun;Choi, Kwang Soon;Jee, Kwang Yong;Kim, Won Ho
    • Analytical Science and Technology
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    • v.13 no.4
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    • pp.433-439
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    • 2000
  • Adsorption behaviors of Ni(II) ions were investigated using amorphous alumina as adsorbent. In the adsorption kinetic study, it was observed that Ni(II) ions were bound to the alumina surface in two adsorption stages, the rapid and slow adsorption stages. The rapid adsorption proceeded within 1 hr, thereafter the slow adsorption occurred. The results of adsorption isotherm experiments showed that the Ni(II) adsorption obeyed the Langmuir-Freundlich isotherm, and that the adsorption enhanced with increasing pH. The change in ionic strength did not exhibit a conspicuous trend in Ni(II) adsorption, thereby suggesting that the adsorption occurs through surface complexation rather than electrostatic interactions. The amounts of adsorption were measured with varying pH at three different Ni(II) concentrations under the condition of constant ionic strength, showing that with increasing Ni(II) concentration, the percentage of adsorption decreased and the adsorption edge was shifted to a higher pH value.

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