• Bulletin of the Korean Chemical Society
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• 제17권6호
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• pp.541-544
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• 1996

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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• pp.65.1-65.1
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• 2013

Icy dust particles in interstellar clouds are considered to play a catalytic role in molecular evolution in space. Atoms and simple molecules constituting the ice mantles of dust particles may be transformed into more complex molecules under the irradiation of UV and cosmic rays. This seminar will present our recent study results for chemistry of ice surfaces, with the emphases on the mechanistic features of elementary reactions and the implications for interstellar molecular evolution. The types of reactions studied include molecule diffusion in ice, proton and hydroxide transfers, and some UV-induced reactions wih astrobiological relevance.

• Bulletin of the Korean Chemical Society
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• 제29권1호
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• pp.148-152
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• 2008

A series of lithium chloride-imidazolium chloride (LiCl-[imidazolium]Cl) melts were prepared and their catalytic activities were evaluated for the coupling reactions of propylene oxide and CO2. At the constant mole of LiCl, the catalytic activities of LiCl-[imidazolium]Cl melts increased with increasing molar ratio of [imidazolium]Cl/LiCl up to 2, but thereafter decreased rapidly. The variation of alkyl groups on the imidazolium ring showed a negligible effect on the catalytic activity, but the number of alkyl groups present on the imidazolium cation exerts a pronounced effect. Catalysis and electrospray ionization tandem mass spectral analysis results of LiCl-[imidazolium]Cl melts imply that the activity of the melt is strongly related to the amount of LiCl2- generated from the melt.

• 대한화학회지
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• 제12권3호
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• pp.121-127
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• 1968

In the oligomerization of p-aminophenol under the catalytic action of the metallic complexes, the effects of the ligands are studied. When the initial velocity of $O_2$ uptake at pH 8 using Fe(Ⅲ) as the central metal and N-hydroxylethylethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), 1,2-cyclohexanediaminetetraacetic acid(CyDTA) as the ligands respectively are compared, the velocities are as the following order: HEDTA > EDTA > DTPA > CyDTA. Further when the effect of the ligands, nitrilotriacetic acid (NTA), HEDTA, EDTA, and DTPA, on the yields of oligomers are compared, the result shows as the following order: NTA > HEDTA > EDTA > DTPA. These are nearly reverse order of the stability constants of the complexes. In order to determine the composition of the mixed complexes at the initial step, the method of continuous variation is used, and it is found that the composition ratio of Fe-EDTA complex to monomer in the mixed complexes is one at pH 5-8 range. It is also found that at pH 9 or in the more alkaline range, side reactions occur to form water soluble dimer of quinone type and the catalytic action of the metallic complex markedly decreases on account of the hydrolysis of the central metal by the $OH^-$ ion.

• Bulletin of the Korean Chemical Society
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• 제23권6호
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• pp.837-845
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• 2002

Based on ab initio calculations at the MP2(FULL)/6-31+G**//RHF/6-31G** level, we compare the energetic and mechanistic features of a model reaction for catalytic action of Δ?-3-ketosteroid isomerase (KSL,E.C.5.3,3.1) with those of a corresponding nonenzymatic reaction in aqueous solution. The results show that the two catalytic acid residues,Tyr14 and Asp99, can lower the free energy of activation by 8.6kcal/mol, which is in good agreement with the experimentally predicted~9 kcal/mol,contribution of electrophilic catalyses to the whole enzymatic rate enhancement. The dienolate intermediate formed by proton transfer from the substrate carbon acid to the catalytic base residue (Asp38) ins predicted to be stabilized by 12.0 kcal/mol in the enzymatic reaction, making its formation thermodynamically favorable. It has been argued that enzymes catalyzing the reactions of carbon acids should resolve the thermodynamic problem of stabilizing the enolate intermediate as well as the kinetic porblem of lowering the free energy of activation for porton abstraction. We find that KSI can successfully overcome the thermodynamic difficulty ingerent in the nonenzymatic reaction through the electrophilic catalyses of the two acid residues. Owing to the stabilization of dienolate intermediate, the reketonization step could influence the overall reaction rate more significantly in the KSI- catalyzed reaction than in the nonenzymatic reaction, further supporting the previous experimental findings. However, the electrophilic catalyses alone cannot account for the whole catalygic capability (12-13 kcal/mol), confiming the earlier experimental implications for the invement of additional catalytic components. The present computational study indicates clearly how catalytic residues of KSI resolve the fundamental problems associated with the entropic penalty for forming the rate-limiting transition state and its destabilization in the bulk solvation environment.

• Bulletin of the Korean Chemical Society
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• 제35권9호
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• pp.2673-2678
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• 2014

The detailed mechanisms of the efficient $\small{L}$-proline and pyrrolidine catalyzed transamidation of acetamide with benzylamine have been investigated using density functional theory (DFT) calculations. Our calculated results show: (1) the mechanisms of two catalytic cycle reactions are similar. However, the rate-determining steps of their reactions are different for the whole catalytic process. One is the intramolecular nucleophilic addition reaction of 1-COM, the other is hydrolysis reaction of 2-C. (2) COOH group of $\small{L}$-proline is essential for efficient transamidation. The computational results are in good agreement with the experiment finding and mechanism resported by Rao et al. for $\small{L}$-proline-catalyzed synthesis of amidesin good to excellent yields.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2016년도 제50회 동계 정기학술대회 초록집
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• pp.403.2-403.2
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• 2016

Porous materials play a significant role in energy storage and conversion applications such as catalyst support for polymer electrolyte membrane fuel cell. In particular, hierarchical porous materials with both micropores (poresize, ${\delta}$ < 2 nm) and regularly arranged mesopores (2 nm < ${\delta}$ < 50 nm) are known to greatly enhance the efficiency of catalytic reactions by providing enormous surface area as well as fast mass transport channels for both reactants and products from/to active sites. Although it is generally agreed that the microscopic structure of the porous materials directly affects the performance of these catalytic reactions, neither detailed mechanisms nor fundamental understanding are available at hand. In this study, we propose an atomistic model of hierarchical nanostructured porous carbons (HNPCs) in molecular dynamics simulations. By performing a systematic study, we found that structural features of the HNPC can be independently altered by tuning specific synthesis parameters, while remaining other structures unchanged. In addition, we show some structure-property relations including mechanical and gas transport properties.

• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2435-2441
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• 2007

The catalytic enantioselective electrophilic fluorinations of active methane compounds promoted chiral palladium complexes have been developed. Treatment of α-cyano acetates and α-cyanoalkylphosphonates with N-fluorobenzenesulfonimide as the fluorine source under mild reaction conditions afforded the corresponding α-cyano-α-fluorinated adducts in high yields with excellent enantiomeric excesses (up to 99% ee). These reactions can be conducted in alcoholic solvents without any precaution to exclude water and moisture.

• 한국응용과학기술학회지
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• 제7권1호
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• pp.71-76
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• 1990

Transesterification reactions (methyl methacrylate with monoethanolamine, methyl methacrylate with n-butyl alcohol, dimethylphthalate with ethylene glycol, dimethyl phthalate with monoethanolamine) were kinetically investigated in the presense of various metal acetate catalysts at $110^{\circ}C$. The amount of reactants was measured by gas and liquid chromatography, and the reaction rates also measured from the amount of reaction products and reactants upon each catalyst. The transesterification reactions were carried out under the first order conditions respect to the concentration of reactants, respectively. The overall reaction order was 2nd, Maximum reaction rates were appeared at the range of 1.4 to 1.6 in electronegativity of metal ions and maximum catalytic activities were obserbed at the range of 1.5 to 1,8 in instability constant of metal acetates.

• 대한화학회지
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• 제57권5호
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• pp.591-598
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• 2013

A series of chiral prolinamide compounds with pyridine-2, 6-dicarboxylic acid moieties derived from L-proline have been designed and synthesized, their catalytic properties for direct asymmetric aldol reactions were also studied in this article. These catalysts gave the aldol product in high yield (87%) and high enantioselectivity, up to 85%, of the anti-structure at room temperature but gave disappointing results at a lower temperature or when additive was added. Conditions, including solvents, temperature and additives were screened for the reactions. Moreover, the influence of presence of water on yield and stereoselectivity was also discussed.