• Journal of the Korean Chemical Society
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• v.53 no.5
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• pp.499-504
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• 2009

Metals have often played important roles to some enzymatic reactions that are essential to biological processes. Therefore many scientists have studied the reaction mechanisms of catalytic reactions in metaloenzymes for many years. Methane MonoOxygenase (MMO) is an enzyme that oxidize methane to methyl alcohol. Recently Tolman et al. studied a model reaction for MMO, which is a hydroxide transfer reaction in Bis-($\mu$-oxo)-dicopper complex, and suggested several possible mechanisms. Later a two-step mechanism, which is hydrogen transfer followed by hydroxide rebound, was proposed from theoretical studies. In this study we calculated the reactant, product, and the transition state structures, and energetics of the first hydrogen transfer reaction using various DFT methods including recently developed the MO6 family of DFT, namely, MO6, MO6L, and MO6-2X. We found that the M06/6-31G(d,p)/LANL2DZ method reproduce the experimental XRD structure of reactants very well. The TS structures, barrier heights, and reaction energies depend very much on the size of the basis sets.

• Journal of Korean Society on Water Environment
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• v.18 no.3
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• pp.271-282
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• 2002

The sonochemical process has been applied as a treatment method to investigate its effect on the decomposition of humic substances (HS). The reaction kinetics and mechanisms in the process of sonochemical treatment for humic substances in wastewater have also been discussed. It was observed that the metal ions such Fe(II) and Mn(II) showed catalytic effects, while Al(III), Ca(II), and Mg(II) had inhibitory effects on the decomposition of humic substances in sonochemical reaction with hydrogen peroxide. Experimental results also showed factors such as hydrogen peroxide dose affected the formation of disinfection by-products. Two trihalomethanes, chloroform and dichlorobromomethane were formed as major disinfection by-products during chlorination. The depolymerization and the radical reaction of HS radicals appear to occur simultaneously. The final step of the reaction is the conversion of organic acids to carbon dioxide.

• Journal of the Korean Chemical Society
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• v.40 no.5
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• pp.302-307
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• 1996

Diethanolamine dithiocarbamate is known to react with dichlorobis(ethylenediamine)cohalt(Ⅲ) chloride to form [Co(dtc)3](dtc=diethanolamine dithiocarbamate) in which two sulfur atoms of the dithiocarbamate are bound to cobalt. The complex is moderately soluble in acetone, but sparingly soluble in carbon disulfide. Kinetics and mechanisms of the reaction of dichlorobis(ethylenediamine)cobalt(Ⅲ) chloride with diethanolamine dithiocarbamate have been studied in aqueous solution. Activation parameters have been calculated from the kinetic data for the reaction and from these results a possible mechanism for the reaction has been proposed.

• International Journal of Automotive Technology
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• v.7 no.3
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• pp.261-267
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• 2006

Understanding the mechanism of carbon oxidation is important for the successful modeling of diesel particulate filter regeneration. Carbon oxidation characteristics were investigated by temperature programmed oxidation(TPO) method as well as constant temperature oxidation(CTO) with a flow reactor including porous bed. The activation energy of carbon oxidation was increasing with temperature and had two different constant values in the early and the later stage of the oxidation process respectively in TPO experiment. Kinetic constants were derived and the reaction mechanisms were assumed from the experimental results and a simple reaction scheme was proposed, which approximately predicted the overall oxidation process in TPO as well as CTO.

• Journal of Sensor Science and Technology
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• v.28 no.3
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• pp.139-145
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• 2019

Precautionary detection of chemical warfare agents (CWAs) has been an important global issue mainly owing to their toxicity. To achieve proper detection, many studies have been conducted to develop sensitive gas sensors for CWAs. In particular, metal-oxide semi-conductors (MOS) have been investigated as promising sensing materials owing to their abundance in nature and excellent sensitivity. In this review, we mainly focus on various MOS-based gas sensors that have been fabricated for the detection of two specific CWA simulants, 2-chloroethyl ethyl sulfide (2-CEES) and dimethyl methyl phosphonate (DMMP), which are simulants of sulfur mustard and sarin, respectively. In the case of 2-CEES, we mainly discuss $CdSnO_3-$ and ZnO-based sensors and their reaction mechanisms. In addition, a method to improve the selectivity of ZnO-based sensors is mentioned. Various sensors and their sensing mechanisms have been introduced for the detection of DMMP. As the reaction with DMMP may directly affect the sensing properties of MOS, this paper includes previous studies on its poisoning effect. Finally, promising sensing materials for both gases are proposed.

• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1177-1180
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• 1999

The ab initio SCF MO and density functional theory (DFT) studies are carried out on the electrophilic (1a) and electron transfer (1b) addition reactions to the vinyl double bond of aryl vinyl sulfides and ethers. In the electrophilic addition processes, a double bond shift from C3 = C4 to X = C3 occurs with occupation number (1.97) close to the normal two. Due to this shift direct conjugation between the cationic center, X = S or O, and the para electron-donor substituent becomes impossible so that the reaction energies (or log K) are correlated with σ rather than σ+. By contrast, radical cation formation leads to delocalization of the SOMO, a lone-pair πorbital on X, with four major resonance structures in which cationic charge as well as spin density is delocalized over C4 , X and C7 atoms. As a result, partial πbonds are formed over C1 -X and C3 - C4 with occupation numbers (0.82) lower than one. In two of the cannonical structures, III(Ⅹ) and III(X+), direct conjugation between the cationic center, X, and the para substituent is achieved so that a better correlation with σ+ rather than σis obtained. The SCF MO energies at the HF/3-21G* and HF/6-31G* levels lead to very much inferior Hammett correlations in the σ/ σ+ diagnostic criterion. In contrast, the ρvalues evaluated with the DFT energies can give reliable diagnostic distinction between the two addition mechanisms.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.21 no.9
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• pp.1174-1184
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• 1997

Extinction characteristics of pure hydrogen-oxygen diffusion flames, at high pressures in the neighborhood of the critical pressure of oxygen, is numerically studied by employing counterflow diffusion flame as a model flame let in turbulent flames in rocket engines. The numerical results show that extinction strain rate increases almost linearly with pressure up to 100 atm, which can be explained by comparison of the chain-branching-reaction rate with the recombination-reaction rate. Since contributions of the chain-branching reactions, two-body reactions, are found to be much greater than those of the recombination reactions, three-body reactions, extinction is controlled by two-body reactions, thereby resulting in the linearity of extinction strain rate to pressure. Therefore, it is found that the chemical kinetic behaviors don't change up to 100 atm. Consideration of the pressure fall-off reactions shows a slight increase in extinction strain rate, but does not modify its linearity to pressure. The reduced kinetic mechanisms, which were verified at low pressures, are found to be still valid at high pressures and show good qualitative agreement in prediction of extinction strain rates. Effect of real gas is negligible on chemical kinetic behaviors of the flames.

• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1706-1712
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• 2014

The OH($X^2{\Pi}$, ${\upsilon}^{\prime\prime}=0,1$) internal state distribution following the reaction of electronically excited oxygen atom ($O(^1D_2)$) with cyclo-$C_3H_6$ has been measured using laser-induced fluorescence, and compared with that following the reaction of $O(^1D_2)$ with $C_3H_8$. The overall characteristics of the OH internal energy distributions for both reactions were qualitatively similar. The population propensity of the ${\Pi}(A^{\prime})$ ${\Lambda}$-doublet sub-level suggested that both reactions proceeded via an insertion/elimination mechanism. Bimodal rotational population distributions supported the existence of two parallel mechanisms for OH production, i.e., statistical insertion and nonstatistical insertion. However, detailed analysis revealed that, despite the higher exoergicity of the reaction, the rotational distribution of the OH following the reaction of $O(^1D_2)$ with $C_3H_8$ was significantly cooler than that with cyclo-$C_3H_6$, especially in the vibrational ground state. This observation was interpreted as the effect of the flexibility of the insertion complex and faster intramolecular vibrational relaxation (IVR).

• The Transactions of The Korean Institute of Electrical Engineers
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• v.65 no.1
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• pp.65-72
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• 2016

This paper presents the analysis of the analysis of thrust characteristics of linear induction motors(LIMs) according to secondary reaction plate. LIMs are well known as high speed transport systems, which can obtain thrust directly without gears and links, or auxiliary mechanisms. A simple structure, easy maintenance, and less environmental pollution are advantages of LIMs. In transport systems using LIMs, the secondary reaction plate is an important design factor, because it has considerable impact on the cost of the railway as well as the performance of the LIMs. This paper deals analyzed the characteristics of linear induction motor used for moving the vehicle of container scanner. Thrust, efficiency and load characteristic were interpreted with FEM regarding two models whose material of secondary reaction plate was copper and aluminum. It suggested the interpretation of thrust, efficiency and power factor characteristic along slip and compared the operation ability of linear induction motor through characteristics analysis along the load.

• Korean Journal of Fisheries and Aquatic Sciences
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• v.19 no.1
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• pp.45-51
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• 1986

Equimolar aqueous solutions of D-glucose and glycine were heated at $50^{\circ}C\;and\;95^{\circ}C$ at pH 6.7. The headspace volatiles and the ether extracts from the reaction mixture were analyzed by gas chromatography and gas chromatography-mass spectrometry using a fused silica capillary column. The major components formed were identified as diacetyl, three furfurals, two pyrroles, one furanone, two pyranones and two amides. In order to elucidate the formation mechanisms of the amides formed front amino-carbonyl reaction, two model systems were adopted. N-butylacetamide were formed as major components from diacetyl-butylamine ana glyoxal-butylamine systems, respectively. The results obtained suggest that such ${\alpha}-dicarbonyls$ as 3-deoxy-D-erythro-2,3-hexodiulose and diacetyl generated in the amino-carbonyl reaction react with amino compounds, amides then being formed by cleavage of the C-C bond in the ${\alpha}-dicarbonyls$.