• 대한화학회지
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• 제36권2호
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• pp.191-196
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• 1992

$CHCl_3,\;CHCl_3 : CH_2Cl_2$(1:1) 및 $CH_2Cl_2$ 용매 중에서 N,N-dimethylaniline(N,N-DMA)과 iodine간의 반응을 전도도법을 이용하여 속도론적으로 조사하였다. 유사 1차반응 속도상수($k_{obs}$) 및 2차반응 속도상수($k_{obs}$/[N,N-DMA])가 N,N-DMA 농도 의존성을 보였다. 실험적으로 구한 2차반응 속도상수는 N,N-DMA 농도 증가와 더불어 증가하였다. 이러한 결과를 반응 중간 생성물로서 charge tranfer complex의 생성에 기인하는 것으로 보고, 반응 scheme의 설정과 속도상수식의 유도로부터 complex 생성에 따른 평형상수와 변환에 따른 활성화 파라미터를 계산하였다. 평형상수는 용매의 유전상수의 증가와 더불어 감소하였으며, 1.9${\sim}$4.2$M^{-1}$의 값을 보였다. 또한 변환의 빠르기는 용매의 극성에 크게 의존하였으며, ${\Delta}H^{\neq}$값은 6.3-12.6kJ/mol, ${\Delta}S^{\neq}$값은 약 -234J/mol K의 큰 음의 값을 나타내었다.

• 한국환경과학회지
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• 제26권6호
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• pp.719-728
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• 2017

In order to investigate the adsorption characteristics for Sr ion using the Na-X zeolite synthesized from coal fly ash, batch tests and response surface analyses were carried out. The adsorption kinetic data for Sr ions, using Na-X zeolite, fitted well with the pseudo-second-order model. The uptake of Sr ions followed the Langmuir isotherm model, with a maximum adsorption capacity of 196.46 mg/g. Thermodynamic studies were conducted at different reaction temperatures, with the results indicating that Sr ion adsorption by Na-X zeolite was an endothermic (${\Delta}H^o$>0) and spontaneous (${\Delta}G^o$<0) process. Using the response surface methodology of the Box-Behnken method, initial Sr ion concentration ($X_1$), initial temperature ($X_2$), and initial pH ($X_3$) were selected as the independent variables, while the adsorption of Sr ions by Na-X zeolite was selected as the dependent variable. The experimental data fitted well with a second-order polynomial equation by multiple regression analysis. The value of the determination coefficient ($R^2=0.9937$) and the adjusted determination coefficient (adjusted $R^2=0.9823$) was close to 1, indicating high significance of the model. Statistical results showed the order of Sr removal based on experimental factors to be initial pH > initial concentration > temperature.

• BMB Reports
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• 제32권3호
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• pp.294-298
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• 1999

Myo-inositol monophosphate phosphatase is a key enzyme in the phosphoinositide cell-signaling system. Incubation of myo-inositol monophosphate phosphatase from porcine brain with N-bromosuccinimide (NBS) resulted in a time-dependent loss of enzyme activity. The inactivation followed pseudo-first-order kinetics with the second-order rate constant of $3.8{\times}10^3\;M^{-1}min^{-1}$. The time course of the reaction was significantly affected by the substrate myo-inositol-1-phosphate, which afforded complete protection against the loss of catalytic activity. Spectrophotometric studies indicated that about one oxindole group per molecule of enzyme was formed following complete loss of enzymatic activity. It is suggested that the catalytic function of myo-inositol monophosphate phosphatase is modulated by the binding of NBS to a specific tryptophan residue at or near the substrate binding site of the enzyme.

• 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.

• 한국응용약물학회:학술대회논문집
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• 한국응용약물학회 1995년도 춘계학술대회
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• pp.75-75
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• 1995

Succinic semialdehyde reductase, one of key enzyme of GABA shunt in CNS, is inactivated by o-phthalaldehyde, The inactivation followed pseudo first-order kinetics, and the second-order rate constant for the inactivation process was 28 M$\^$-1/s$\^$-1/ at pH 7.4 and 25$^{\circ}C$. The absorption spectrum(λ$\_$max/=377nm), fluorescence exitation(λ$\_$max/=340nm) and fluorescence emission spectra (λ$\_$max/=409nm) were consistent with the formation of an isoindole derivative in the catalytic site between a cysteine and a lysine residues about 3${\AA}$ apart. The substrate, succinic semialdehyde, did not protect the enzymatic activity against inactivation, whereas the coenzyme, NADPH, protected against o-phthalaldehyde induced inactivation of the enzyme. About 1 isoindole group per moi of the enzyme was formed following complete loss of the enzymatic activity. These results suggest that the amino acid residues of the enzyme participating in reaction with o-phthalaldehyde more likely residues at or near the coenzyme binding site.

• Nuclear Engineering and Technology
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• 제54권2호
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• pp.456-461
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• 2022

Heavy metal pollution is caused due to anthropogenic activities and is considered as a serious environmental problem which endangers human health and environment. The present study deals with biosorption, an eco-friendly technique for the removal of heavy metal Zn(II) from aqueous medium. Various natural materials have been explored for the uptake of metal ions, where most of them are physically or chemically enhanced. Dry cowdung powder (DCP) has been utilized as a low-cost, environmentally friendly humiresin without any pre-treatment, thus demonstrating the concept of Green Chemistry. Batch biosorption studies using ⁶⁵Zn(II) tracer were performed and the impact of different experimental parameters was studied. Results revealed that at pH 6, 94 ± 2% of Zn(II) was effectively biosorbed in 5 min, at 303 K. The process was spontaneous and exothermic, following pseudo-second-order reaction. The mechanism of heavy metal biosorption employing green adsorbent was therefore elucidated in order to determine the optimal method for removing Zn(II) ions. DCP has a lot of potential in the wastewater treatment industry, as seen by its ability to meet 3A's affordability, adaptability, and acceptability criteria. As a result, DCP emerges as one of the most promising challengers for green chemistry and the zero-waste idea.

• 대한화학회지
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• 제48권2호
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• pp.195-202
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• 2004

미셀 촉매 작용은 이론과 실험 화학 교과내용에서 중요한 부분이다. 산성 용액에서 도데실황산 나트륨(SDS)을 촉매로 한 글리신과 과망가니즈산 칼륨의 반응은 미셀 촉매 작용을 보여주는 반응속도론적 실험으로 적합하며, 고등학교와 대학 학부과정의 물리화학실험에서 사용할 수 있다. 본 연구에서는 이 반응이 계면활성제 존재하에서 반응속도가 빨라지는 것을 관찰하기 위하여 SDS를 넣지 않은 경우와 넣은 경우 모두 실험을 진행하였고, 얻어진 k를 [SDS]에 대하여 도시하였다. SDS의 임계 미셀 농도 이하에서부터 계면활성제에 의한 촉매 효과가 관찰되었는데, 이 선-미셀 촉매 효과는 양의 협동효과에 의한 것임을 알 수 있다. 얻어진 양의 협동지수(n)는 2.37이다. 또한 기질과 산화제의 농도에 따른 반응속도 변화도 논의하였다. 반응은 유사 일차 반응으로 진행되었으며, 글리신과 과망가니즈산 이온의 농도에 각각 일차 반응으로 나타나 전체 반응 차수는 이차 반응이었다. 반응 시간은 3~4시간으로 한 실험 시간에 몇 개의 실험 데이터를 얻을 수 있다. 용액 제조와 실험 과정에 대해서 자세히 기술하였으며, 또한 계면활성제에 의한 촉매 작용의 이론도 논의하였다.

• Bulletin of the Korean Chemical Society
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• 제31권2호
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• pp.303-308
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• 2010

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl benzoate (5a), 4-nitrophenyl 4-methoxybenzoate (5b), and 4-nitrophenyl 4-hydroxybenzoate (5c) with alkali metal ethoxides, $EtO^-M^+$ ($M^+=Li^+$, $Na^+$ and $K^+$) in anhydrous ethanol (EtOH) at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [$EtO^-M^+$] exhibit upward curvatures in all cases, indicating that $M^+$ ions catalyze the reactions and ionpaired $EtO^-M^+$ species are more reactive than dissociated $EtO^-$. Second-order rate constants for reactions with dissociated $EtO^-$ and ion-paired $EtO^-M^+$ (i.e., $k_{EtO^-}$ and $k_{EtO^-M^+}$, respectively) have been calculated from ion-pair treatment for the reactions of 5a and 5b. However, such ion-pair treatment has failed to determine $k_{EtO^-}$ and $k_{EtO^-M^+}$ values for the reactions of 5c. It has been concluded that reactions of 5a and 5b are catalyzed by one metal ion, which increases electrophilicity of the reaction center through coordination on the carbonyl oxygen. In contrast, reactions of 5c have been suggested to involve two metal ions, i.e., the one coordinated on the carbonyl oxygen increases the electrophilicity of the reaction center while the other one associated on the phenoxy oxygen decreases the charge repulsion between the anionic reagents (i.e., $EtO^-$ and deprotonated 5c). It has been found that the rate equation derived from the mechanism involving two metal ions fits nicely to the kinetic results obtained for the reactions of 5c.

• 청정기술
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• 제23권4호
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• pp.413-420
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• 2017

화력발전소에서 발생되는 석탄비산재로부터 합성한 제올라이트 X를 이용한 Cs 흡착의 회분식 실험 및 반응표면분석법(Response Surface Methodology, RSM)을 적용하여 결과를 분석하였다. Cs 흡착 실험에 적용된 회귀 방정식은 반응변수의 함수로 나타낼 수 있었다. 결정계수($r^2$)가 0.9630으로서 이 모델은 높은 상관성을 가졌다. pH > Cs 농도 > 온도와 같은 실험적 요인의 순서로 Cs의 제거효율에 영향을 준다는 것을 통계적인 결과로부터 확인하였다. 흡착속도는 유사 2차 모델에 의해 보다 정확하게 표현되었다. Langmuir 등온선 모델로부터 계산된 최대 흡착용량은 293 K에서 $151.52mg\;g^{-1}$이었다. 또한, Vant Hoff 식에 의해 계산된 열역학 파라미터에 의거하여 흡착반응이 흡열반응이며, 자발적인 과정임을 확인할 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제35권1호
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• pp.177-181
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• 2014

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the reactions of Y-substituted-phenyl benzoates (5a-j) with potassium ethoxide (EtOK) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [EtOK] curve upward regardless of the electronic nature of the substituent Y in the leaving group. Dissection of $k_{obsd}$ into the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOK (i.e., $k_{EtO^-}$ and $k_{EtOK}$, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. The Br${\phi}$nsted-type plots for the reactions with the dissociated $EtO^-$ and ion-paired EtOK exhibit highly scattered points with ${\beta}_{lg}$ = -$0.5{\pm}0.1$. The Hammett plots correlated with ${\sigma}^o$ constants result in excellent linear correlations, indicating that no negative charge develops on the O atom of the leaving Y-substituted-phenoxide ion in transition state. Thus, it has been concluded that the reactions with the dissociated $EtO^-$ and ion-paired EtOK proceed through a stepwise mechanism, in which departure of the leaving group occurs after the RDS, and that $K^+$ ion catalyzes the reactions by increasing the electrophilicity of the reaction center through a four-membered cyclic TS structure.