• Bulletin of the Korean Chemical Society
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• 제32권5호
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• pp.1679-1684
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• 2011

Interfacial reactions kinetics often differ from kinetics of bulk reactions. Here, we describe how the density change of an immobilized reactant influences the kinetics of interfacial reactions. Self-assembled monolayers (SAMs) of alkanethiolates on gold were used as a model interface and the Diels-Alder reaction between immobilized quinones and soluble cyclopentadiene was used as a model reaction. The kinetic behavior was studied using varying concentrations of quinones. An unusual threshold density of quinones (${\Gamma}_c$ = 5.2-7.2%), at which the pseudo-first order rate constant started to vary as the reaction progressed, was observed. This unexpected kinetic behavior was attributed to the phase-separation phenomena of multi-component SAMs. Additional experiments using more phase-separated two-component SAMs supported this explanation by revealing a significant decrease in ${\Gamma}_c$ values. When the background hydroxyl group was replaced with carboxylic or phosphoric acid groups, ${\Gamma}_c$ was observed at below 1%. Also, more phase-separated thermodynamically controlled SAMs produced a lower critical density (3% < ${\Gamma}_c$ < 4.9%) than that of the less phaseseparated kinetically controlled SAMs (6.5% < ${\Gamma}_c$ < 8.9%).

• 한국응용과학기술학회지
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• 제5권1호
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• pp.41-51
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• 1988

Aliphatic aldehyde polyoxyethylene glycol acetals were synthesised through the reaction of aliphatic aldehydes such as caproic aldehyde, capryl aldehyde, capric aldehyde and lauric aldehyde with excess diethylene glycol, triethylene glycol and tetraethylene glycol, respectively. The acetal formation, in which water was azeotropically distilled by adding benzene to the reaction system, was gained a good yield of acetal type compounds. This reaction is found pseudo first order reaction at various temperatures such 70, 80, 90 and $97^{\circ}C$. Also these activation energies of reaction of acetal type products such as caproic aldehyde diethylene glycol acetal, capryl aldehyde diethylene glycol acetal, capric aldehyde diethylene glycol acetal, lauric aldehyde diethylene glycol acetal, caproic aldehyde triethylene glycol acetal and caproic aldehyde tetraethylene acetal were 17.3, 19.6, 21.2, 21.6, 15.5 and 14.7 Kcal/mole.

• Journal of Microbiology and Biotechnology
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• 제11권5호
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• pp.838-844
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• 2001

The enzyme Fuc aldolase from Methanococcus jannaschii that catalyzes the aldol condensation of DHAP and L-lactaldehyde to give fuculose-1-phosphate was inactivated by DEP. The inactivation was pseudo first-order in the enzyme and DEP, which was biphasic. A pseudo second-order rate constant of 120$M^{-1}min^{-1}$ was obtained at pH 6.0 and $25{\circ}C$. Quantifying the increase in absorbance at 240nm showed that four histidine residues per subunit were modified during the nearly complete inactivation. The statistical analysis and the time course of the modification suggested that two or three histidine residues were essential for activity. The rate of inactivation was dependent on the pH, and the pH inactivation data implied the involvement of the amino acid residue with a $pK_a$ value of 5.7. Fuc aldolase was protected against DEP inactivation by DHAP, indicating that the histidine residues were located at the active site of Fuc aldolase. DL-Glyceraldehyde, as an alternative substrate to L-lactaldehyde, showed no specific protection for the Fuc aldolase.

• 상하수도학회지
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• 제30권6호
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• pp.691-698
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• 2016

This study was carried out to investigate the characterization of iron oxide nanotubes (INTs) by anodization method and applied adsorption isotherms and kinetic models for phosphate adsorption. SEM analysis was conducted to examine the INTs surface formation. Further XRD and XPS analysis were performed to observe the crystal structure of INTs before and after phosphate adsorption. AFM analysis was conducted to determine of Fe foil surface before and after anodization. Phosphate stock solution for adsorption experiment was prepared by $KH_2PO_4$. The batch experiment was conducted using 20 ml phosphate stock solution and $40cm^3$ of INTs in 50 ml conical tube. Adsorption isotherms were applied Langmuir and Freundlich models for adsorption equilibrium test of INTs. Pseudo first order and pseudo second order models were applied for interpretation of adsorption rate by reaction time. The determination coefficient ($R^2$) values of Langmuir and Freundlich models were 0.9157 and 0.8876 respectively.

• 한국환경과학회지
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• 제28권1호
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• pp.55-64
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• 2019

The adsorption properties of $Cs^+$ and $Cu^{2+}$ ions were evaluated by using a polysulfone scoria zeolite (PSf-SZ) composite with synthetic zeolite synthesized from Jeju volcanic rocks (scoria). In order to investigate the adsorption properties, various parameters, such as pH, contact time, reaction rate, concentration, and temperature in aqueous solutions, were evaluated by tests carried out in batch experiments. The adsorption capacities of $Cs^+$ and $Cu^{2+}$ ions increased between pH 2 but achieved equilibrium at pH 4 and above. The adsorption rate increased rapidly up to the initial 24 h, after which it plateaued ; the adsorption rate then sustained at equilibrium from 48 h. The adsorption kinetics of $Cs^+$ and $Cu^{2+}$ ions were described better by the pseudo-second-order kinetic model than the pseudo-first-order kinetic model. The Langmuir model fitted the adsorption isotherm data better than the Freundlich model. The maximum adsorption capacities of $Cs^+$ and $Cu^{2+}$ ions obtained from the Langmuir model were 53.8 mg/g and 84.7 mg/g, respectively. The calculated thermodynamic parameters showed that the adsorption of $Cs^+$ and $Cu^{2+}$ ions on PSf-SZ was feasible, spontaneous and endothermic reaction.

• 한국응용과학기술학회지
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• 제24권3호
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• pp.296-300
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• 2007

This paper presents applicability of photocatalytic decomposition of methyl mercaptan using $TiO_2$. A quartz reactor was used in order to elucidate reaction pathway in photocatalytic decomposition of methyl mercaptan. Experimental results showed that more than 99.9% of methyl mercaptan was decomposed within 30 minutes. It was found that the photocatalytic decomposition of methyl mercaptan followed pseudo first order and its reaction coefficient was $0.05min^{-1}$ During 30 minutes in the photocatalytic reaction, the concentration of methyl mercaptan, dimethyl disulfide, $SO_2$, $H_2SO_4$, COS, $H_2S$ were determined. These results showed that 64% of methyl mercaptan were compensated for the increase in sulfur after 30 minutes through the mineralization. The proposed main photocatalytic decomposition pathway of methyl mercaptan was methyl $mercaptan{\rightarrow}dimethyl$ $disulfide{\rightarrow}SO_2{\rightarrow}H_2SO_4$.

• 대한화학회지
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• 제36권4호
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• pp.517-522
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• 1992

10$^{\circ}C$와 20$^{\circ}C$에서 ${\beta}$-피콜린과 치환된 벤조일클로라이드류의 반응을 압력변화에 따라 아세토니트릴용매내에서 전기전도도법으로 연구하였다. 유사 1차속도상수와 2차속도상수로부터 여러 가지 활성화파라미터들(${\Delta}V{\neq}$, ${\Delta}{\beta}{\neq}$, ${\Delta}H{\neq}$, ${\Delta}S{\neq}$ and ${\Delta}G{\neq}$)을 구하고, Hammett ${\rho}$값의 압력의존성을 설명하였다. ${\Delta}V{\neq}$, ${\Delta}{\beta}{\neq}$ 및 ${\Delta}S{\neq}$ 는 모두 음의 값을 나타내었고, 압력증가에 따라 속도상수와 Hammett ${\rho}$값은 증가하며, 결합형성이 더욱 촉진된 반응메카니즘으로 진행됨을 알 수 있었다.

• 한국환경과학회지
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• 제6권1호
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• pp.75-88
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• 1997

The rates of photodegradation, reactivities, and mechanisms of photooxidation for the aqueous solution containing with halogen derivatives of aliphatic hydrocarbons have been discussed with respect to the kinds of photocatalysts, concentration of photocatalytlc suspensions, strength of radiant power, time of illumination, changes of pH of substrate solution, wavelength of radiation, and pressure of oxygen gas saturated In the solution. These aqueous solutions suspended with 0.5 $gL^{-1}$ $TiO_2$ powder have been photodecomposed in the range of 100 and 93.8% per 1 hour if it is illuminated with wavelength (λ $\geq$ 300nm) produced from Xe-lamp(450W). The photocatalytic abilities have been increased In the order of $Fe_2O_3$ < CdS < $CeO_2$ < Y_2O_3$ <$TiO_2$, and rates of photodegradation for the solution have maldmum values in the condition of pH 6 ~ 8 and 3 psi-$O_2$ gL^{-1}$. These rates for the Photoolddation Per 1 hour were dependent on the size of molecular weight and chemical bonding for organic halogen compounds and the rates of photodegadation were increased in the order of $C_2H_5Br$ < CH_2Br_2$ < C_5H_11Cl C_2H_4Cl_2$ < tracts-$C_2H_2Cl_2$ < cis-C_2H_2Cl_2$ The T_{1/2}$ and t99% for these solutions were 5~21 and 40~90 minutes. respectively, and these values were coincided with Initial reaction kinetics(ro). It was found that reaction of photodegradation has the pseudo first-order kinetics controlled by the amount of $h^+_{VB}$ diffused from a surface of photocatalysts.

• BMB Reports
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• 제30권2호
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• pp.113-118
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• 1997

Aspartase from Hafnia alvei was inactivated by N-ethylmaleimide (NEM) and 5,5' -Dithiobis-(2-znitrobenzoic acid) (DTNB) following pseudo-first order kinetics. Their apparent reaction orders were 0.83 and 0.50 for NEM and DTNB modifications, respectively, indicating that inactivation was due to a sulfhydryl group in the active site of aspartase and participation of the sulfhydryl group in an essential step in the catalytic reaction. When aspartase was modified by DTNB, the enzyme activity was restored by dithiothreitol treatment, indicating that cysteine residuetsl islarel possibly at or near the active site. The pH-dependence of the inactivation rate by NEM suggested that an amino acid residue having pK value of 8.3 was involved in the inactivation. When aspartase was incubated with NEM and L-aspartate together, L-aspartate markedly protected the enzyme from inactivation by NEM, but the other reagents used did not.

• Journal of Pharmaceutical Investigation
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• 제11권3호
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• pp.21-26
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• 1981

The rate of decomposition of calcium thioglycollate in aqueous solution was shown to increase with increasing temperature and with diluting concentration of calcium thioglycollate. The effect of additive on oxidation rate of calcium thioglycollate was studied to prepare the more stable depilatory formula using additives, such as thiourea, mannitol, sodium thiocyanide, nicotinamide, triethanolamine and ethylenediamine. In all cases, the rate of oxidation was reduced when the additive was present in the solution, among them triethanolamine and ethylenediamine inhibited the decomposition rate remarkably. It is assumed that the decomposition reaction in aqueous solution is pseudo-first order reaction.