• 대한화학회지
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• 제28권2호
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• pp.102-108
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• 1984

$ZnCe_{1+y}O_2$상에서 CO산화반응 속도가 $300{\sim}500^{\circ}C$영역에서 측정되었다. 산화반응 속도는 CO에 1차 O2에 0.5차를 나타내는 속도식에 따랐으며 격자점의 산소와 Zn 도프에 기인되어 생성된 Vo-2e' 결함이 CO 및 O2의 활성화 sites로 작용되었다. 전기전도도 데이타와 rate law로 부터 산화반응 메카니즘이 규명되었으며 율속과정이 제안되었다

• Bulletin of the Korean Chemical Society
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• 제32권4호
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• pp.1138-1142
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• 2011

Kinetic studies for the reactions of Y-aryl phenyl chlorothiophosphates with X-pyridines have been carried out in acetonitrile at $35.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles are biphasic concave upwards with a break point at X = 3-Ph, while the Hammett plots for substituent Y variations in the substrates are biphasic concave downwards (and partially upwards) with a break point at Y = H. The signs and magnitudes of the cross-interaction constant (${\rho}_{XY}$) are strongly dependent upon the nature of substituents, X and Y. The proposed mechanism is a stepwise process with a rate-limiting step change from bond breaking with the weaker electrophiles to bond formation with the stronger eletrophiles. The nonlinear free energy correlations of biphasic concave upward plots for substituent X variations in the nucleophiles are rationalized by a change in the attacking direction of the nucleophile from a backside with less basic pyridines to a frontside attack with more basic pyridines.

• Bulletin of the Korean Chemical Society
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• 제32권4호
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• pp.1187-1194
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• 2011

The hydrogen abstraction reaction of $CF_3CH_2CHO$ + OH has been studied theoretically by dual-level direct dynamics method. Two stable conformers, trans- and cis-$CF_3CH_2CHO$, have been located, and there are four distinct OH hydrogen-abstraction channels from t-$CF_3CH_2CHO$ and two channels from c-$CF_3CH_2CHO$. The required potential energy surface information for the kinetic calculation was obtained at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level. The rate constants, which were calculated using improved canonical transitionstate theory with small-curvature tunneling correction (ICVT/SCT) were fitted by a four-parameter Arrhenius equation. It is shown that the reaction proceeds predominantly via the H-abstraction from the -CHO group over the temperature range 200-2000 K. The calculated rate constants were in good agreement with the experimental data between 263 and 358 K.

• 대한화학회지
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• 제30권3호
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• pp.282-288
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• 1986

Chloropentaamminecobalt(III)의 $Cl^-$리간드와 물 分子의 置換反應에서 H$g^{2+}$ 이온 觸媒의 역할을 알기 위하여 UV分光法으로 速度論的 硏究를 하였다. 觸媒촉매가 一次일차 反應반응形式형식으로 反應반응에 관여함을 알았으며, 觸媒촉매를 考慮 했을때의 速度常數 $k_{obs}$는 3.366$l{\cdot}mol^{-1}sec^{-1}$의 값을 얻었다. 아울러 總括反應은 二次反應 임을 알았으며, $S_N2$ 反應機構로 進行되는 反應 메카니즘을 提案하였다.

• 한국생물정보학회:학술대회논문집
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• 한국생물정보시스템생물학회 2004년도 The 3rd Annual Conference for The Korean Society for Bioinformatics Association of Asian Societies for Bioinformatics 2004 Symposium
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• pp.39-49
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• 2004

When there is a lack of detailed kinetic information, dFBA(dynamic flux balance analysis) has correctly predicted cellular behavior under given environmental conditions with FBA and different ial equations. However, until now, dFBA has centered on substrate concentration, cell growth, and gene on/off, but a detailed hierarchical structure of a regulatory network has not been taken into account. For this reason, the dFBA has limited the represen tation of interactions between specific regulatory proteins and genes and the whole transcriptional regulation mechanism with environmental change. Moreover, to calculate optimal metabolic flux distribution which maximizes the growth flux and predict the b ehavior of cell system, linear programming package(LINDO) and spreadsheet package(EXCEL) have been used simultaneously. thses two software package have limited in the visual representation of simulation results and it can be difficult for a user to look at the effects of changing inputs to the models. Here, we descirbes the construction of hierarchical regulatory network with defined symbolsand the development of an integrated system that can predict the total control mechanism of regulatory elements (opero ns, genes, effectors, etc.), substrate concentration, growth rate, and optimal flux distribution with time. All programming procedures were accoplished in a visual programming environment (LabVIEW).

• 대한화학회지
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• 제48권5호
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• pp.461-466
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• 2004

고진공 및 고압에서 친핵체변화에 따른 반응을 온도변화에 따라 속도론적으로 연구하였다. 유사1차반응속도상수, 2차반응속도상수, 열역학함수 및 Hammett ${\rho}$ 값을 구하였다. ${\Delta}V^{\neq},\;{\Delta}{\beta}^{\neq}\;및\;{\Delta}S^{\neq}$는 모두 음의 값을 나타내었으며, 모든 압력 조건에서 친핵체의 치환기효과 ${\rho}$x는 음의 값을 나타내었다. 전체적인 반응은 전형적인 $S_N2$ 반응메카니즘을 따르며, 압력과 친핵체 변화에 따라 반응메카니즘에 변화가 생김을 알 수 있다.

• Bulletin of the Korean Chemical Society
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• 제24권2호
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• pp.193-196
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• 2003

Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)$ to benzylidene Meldrum's acids (BMA; $YC_6H_4CH=C(COO)_2C(CH_3)_2$) have been investigated in acetonitrile at 20.0 ℃. The rates of addition are greatly enhanced due to the abnormally high acidity of Meldrum's acid. The magnitudes of the Hammett $({\rho}_X\;and\;{\rho}_Y)$ and Bronsted $({\rho}_X$)$ coefficients are rather small suggesting an early transition state. The sign and magnitude of the cross-interaction constant, ${\rho}_{XY}$ (= -0.33), and kinetic isotope effects $(k_H/k_D\;{\stackrel}{~}{=}\;1.5-1.7)$ involving deuterated benzylamine nucleophilies $(XC_6H_4CH_2ND_2)$ are indicative of hydrogen-bonded cyclic transition state. The activation parameters, ${\Delta}H^{\neq}\;{\stackrel}{~}{=}\;4\;kcal\;mol^{-1}\;and\;{\Delta}S^{\neq}\;{\stackrel}{~}{=}\;-37\;e.u.$, are also in line with the proposed mechanism.

• Bulletin of the Korean Chemical Society
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• 제32권7호
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• pp.2339-2344
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• 2011

Kinetic studies for the reactions of O,O-dimethyl Z-S-aryl phosphorothioates with X-pyridines have been carried out in dimethyl sulfoxide at 85.0 $^{\circ}C$. The Hammett and Br$\"{o}$nsted plots for substituent X variations in the nucleophiles are biphasic concave upwards with a break point at X = H, while those for substituent Z variations in the leaving groups are linear. The negative sign of the cross-interaction constant (${\rho}_{XZ}$) implies that the reaction proceeds through a concerted mechanism for both the strongly and weakly basic pyridines. The magnitude of ${\rho}_{XZ}$ (= -0.35) for the strongly basic pyridines is greater than that (${\rho}_{XZ}$ = -0.15) for the weakly basic pyridines, indicating a change of the nucleophilic attacking direction from frontside for the strongly basic pyridines to backside for the weakly basic pyridines. The early transition state is proposed on the basis of the absence of positive deviations from both the Hammett and Br$\"{o}$nsted plots for the strong ${\pi}$-acceptor, X = 4-Ac, and small values of ${\rho}_{XZ}$ and ${\beta}_X$.

• Bulletin of the Korean Chemical Society
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• 제29권4호
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• pp.767-771
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• 2008

Second-order rate constants have been measured spectrophotometrically for the Michael-type reaction of 1-(Xsubstituted phenyl)-2-propyn-1-ones (2a-f) with amines in $H_2O$ at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. A linear Brønsted-type plot is obtained with ${\beta}_{nuc}$ = 0.25 ${\pm}$ 0.02, a typical $\beta_{nuc}$ value for reactions which proceed through a stepwise mechanism with attack of amine on the electrophilic center being the rate-determining step. Secondary alicyclic amines are found to be more reactive than isobasic primary amines. The Hammett plot for the reactions of 2a-f with morpholine is not linear, i.e., the substrate with a strong electron-donating group (e.g., 4-MeO) exhibits a negative deviation from the Hammett plot. However, the Yukawa-Tsuno plot for the same reactions exhibits an excellent linear correlation with ρ = 0.62 and r = 0.82. Thus, it has been proposed that the nonlinear Hammett plot is not due to a change in the ra te-determining step but due to ground-state stabilization through resonance interactions.

• Bulletin of the Korean Chemical Society
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• 제30권6호
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• pp.1341-1348
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• 2009

Electrocatalytic oxidation of two anti-inflammatory drugs (Mefenamic acid and Indomethacin) was investigated on a cobalt hydroxide modified glassy carbon (CHM-GC) electrode in alkaline solution. The process of oxidation and its kinetics were established by using cyclic voltammetry and chronoamperometry techniques as well as steady state polarization measurements. Voltammetric studies indicated that in the presence of under study drugs, the anodic peak current of low-valence cobalt species increased, followed by a decrease in the corresponding cathodic current. This result indicates that the drugs were oxidized via cobalt hydroxide species immobilized on the electrode surface via an E$\acute{C}$ mechanism. A mechanism based on the electrochemical generation of Co (IV) active sites and their subsequent consumption by the drugs in question was also investigated. The constants rate of the catalytic oxidation of the drugs and the electron-transfer coefficients reported.