• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2005년도 제17회 워크샵 및 추계학술대회
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• pp.634-637
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• 2005

Hydrogen adsorption mechanism onto the porous metal-organic frameworks (MOFs) has been studied by density functional theory calculation. The selected functionals for the predict ion of interact ion energies between hydrogen and potential adsorption sites of MOF was utilized after the evaluation with the various functionals for interaction energy of $H_2C_6H_6$ model system the adsorption energy of hydrogen molecule into MOF was investigated with the consideration of the favorable adsorption sites and the orientations. We also calculated the second favorable adsorption sites by geometry optimization using every combination of two first absorbed hydrogen molecules. Based on the calculation of first and second adsorption sites and energies, the hydrogen adsorption into MOF follows a cooperative mechanism in which the initial metal sites initiate the propagation of the hydrogen adsorption on the whole frameworks. In addition, it was found that the interaction strength between the simple benzene ring with hydrogen is significantly reinforced when the benzene ring has been incorporated into the framework of MOFs.

• 대한화학회지
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• 제68권3호
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• pp.139-145
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• 2024

This study aims to elucidate the mechanism involved in the hydrolysis of the hexacyanoferrate(III) complex ion (Fe(CN)₆^3-) and the mechanism leading to the formation of Prussian blue (Fe^III₄[Fe_II(CN)₆]₃·xH₂O, PB) in acidic aqueous solutions at moderately elevated temperatures. Hydrolysis constitutes a crucial step in generating PB through the widely used single-source or precursor method. Recent PB syntheses predominantly rely on the single-source method, where hexacyanoferrate(II/III) is the exclusive reactant, as opposed to the co-precipitation method employing bare metal ions and hexacyanometalate ions. Despite the widespread adoption of the single-source method, mechanistic exploration remains largely unexplored and speculative. Utilizing UV-vis spectrophotometry, negative-ion mode liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS), and a devised reaction, this study identifies crucial intermediates, including aqueous Fe^2+/3+ ions and hydrocyanic acid (HCN) in the solution. These two intermediates eventually combine to form thermodynamically stable PB. The findings presented in this research significantly contribute to understanding the fundamental mechanism underlying the acid-catalyzed hydrolysis of the hexacyanoferrate(III) complex ion and the subsequent formation of PB, as proposed in the sequential mechanism introduced herein. This finding might contribute to the cost-effective synthesis of PB by incorporating diverse metal ions and potassium cyanide.

• 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.

• 한국토양비료학회지
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• 제28권2호
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• pp.105-113
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• 1995

토양(土壤)의 구성성분(構成成分) 중 많은 부분(部分)을 차지하고 있는 철(鐵) 및 알루미늄의 수산화물(水酸化物)에 의한 중금속(重金屬)ion들의 흡착(吸着) mechanism을 구명(究明)하기 위하여, 무정형(無晶型) Fe 및 Al 수산화물(水酸化物), Goethite 및 Gibbsite에 의한 중금속(重金屬)ion들의 흡착(吸着) mechanism을 조사(調査)하였다. 1. 철(鐵) 및 알루미늄의 수산화물(水酸化物)에 의한 중금속(重金屬)ion들의 흡착등온선(吸着等溫線)은 Langmuir식(式)에 잘 부합되었으며, 이들의 최대흡착량(最大吸着量) 및 흡착(吸着)에너지는 무정형(無晶型) 수산화물(水酸化物)이 결정형(結晶型) 수산화물(水酸化物)보다 또 알루미늄 수산화물(水酸化物)이 철수산화물(鐵水酸化物)보다 많았다. 2. 중금속(重金屬)ion별(別) 최대흡착량(最大吸着量) 및 흡착(吸着)에너지는 Cu>Zn>Cd의 순(順)으로 CEC, 비표면적(比表面積) 및 하전밀도(荷電密度)와 정(正)의 상관(相關)이 인정(認定)되었다. 3. Goethite 및 Gibbsite에 의한 중금속(重金屬)ion들의 첫번째 흡착(吸着) mechanism은 $Cl^-$를 수반하는 nonspecific adsorption으로 1 Mole의 중금속(重金屬)ion이 흡착(吸着)되는데 대하여 표면(表面) aquo group이나 hydroxo group으로 부터 1 Mole의 H가 탈착(脫着)되었으며, 회응비율(灰應比率)은 pH가 증가(增加)할수록 감소(減少)되고 흡착(吸着)된 중금속(重金屬)ion들은 치환성양(置煥性陽)ion에 의하여 재치환(再置換)될 수 있었다. 4. Goethite 및 Gibbsite에 의한 중금속(重金屬)ion들의 두번째 흡착(吸着) mechanism은 $Cl^-$을 수반하지 않는 specific adsorption으로 1 Mole의 중금속(重金屬)ion이 흡착(吸着)되는데 대하여 표면(表面) aquo group이나 hydroxo group으로부터 2 Mole의 $H^+$가 탈착(脫着)되었으며. 흡착반응(吸着反應)의 비율(比率)은 pH가 증가(增加)할수록 증가(增加)되었으며 흡착(吸着)된 중금속(重金屬)들은 置換性 陽ion에 의하여 再置煥되지 않았다.

• Bulletin of the Korean Chemical Society
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• 제15권2호
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• pp.161-167
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• 1994

Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates (3) with alkali metal ethoxides ($EtO^-M^+$) and butane-2,3-dione monoximates ($Ox^-M^+$) in ethanol at $25^{\circ}C$. The reactivity of the alkali metal ethoxides decreases in the order $EtO^-K^+> EtO^- > EtO^-Li^+$, indicating that $K^+$ ion behaves as a catalyst and $Li^+$ ion acts as an inhibitor for all the substrates studied. For the corresponding reactions of 3 with Ox^-M^+$, $Li^+$ ion also exhibits inhibitory effect for all the substrates, while, $K^+$ ion shows catalytic or inhibitory effects depending on the nature of substituents on the acyl and phenyl moieties. A study of substituent effect on rate has revealed that both EtO^- $and Ox^-$ systems have the same reaction mechanism. The different behavior shown by $K^+$ ion for the reaction of 3 with $EtO^-$ and $Ox^-$ would be attributed to a difference in charge polarization of S=O bond in the transition state between the two systems and/or a change in conformation of Ox^-K^+$.

• Bulletin of the Korean Chemical Society
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• 제11권5호
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• pp.399-402
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• 1990

Activation parameters of the exchange between two types of glycinate groups in (nitrilotriacetato)dioxovanadate(V) ion, $[VO_2(NTA)]^{2-}$, have been determined as the results of $^{13}C$ NMR measurements over a range of temperatures between 277 and 306$^{\circ}K$. The exchange mechanism is proposed on the basis of the chelate ring opening-closing process, assuming rupture of the metal-oxygen (glycinate) bond trans to V = O bond to give a five-coordinated intermediate.

• Journal of Microbiology and Biotechnology
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• 제8권5호
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• pp.471-477
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• 1998

Taq DNA polymerase from Thermus aquaticus is very useful in the polymerase chain reaction. Taq DNA polymerase is classified in the pol I family, represented by E. coli DNA polymerase I. The three-dimensional structural alignment of 3'-5'exonuclease domains from the pol I family DNA polymerases explains why Taq DNA polymerase does not carry out proofreading in polymerase chain reactions. Three sequence motifs, Exo I, II, and III, must exist to carry out 3'-5'exonuclease activity for proof- reading by a 3'-5'exonuclease reaction, but these are abolished in Taq DNA polymerase. The key catalytic module in 3'-5'exonuclease is two metal ions chelated by four active-site carboxylic amino acids. Taq DNA polymerase was mutagenized to construct the catalytic module in the active site. The circular dichroism technique supported the formation of the catalytic module, and the radioactive assay showed that the 3'-5'exonuclease activity doubled in the mutant Taq DNA polymerase.

• 한국토양비료학회지
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• 제28권2호
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• pp.114-122
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• 1995

토양유기물(土壤有機物)에 의한 중금속(重金屬)의 흡착(吸着)현상을 구명(究明)하기 위하여 이탄토(泥炭土)에서 humic acid를 분리정제(分離精製)하여, humid acid-metal complex 생성반응(生成反應)에 대한 mechanism을 조사(調査)하였다. 1. Humic acid-metal complex의 흡광도(吸光度)는 장파장영역(長波長領域)에서 단파장영역(短波長領域)으로 갈수록 Zn-HA > Cd-HA > Cu-HA의 순(順)으로 증가(增加)하였다. 2. Humic acid의 carboxyl group과 phenolic OH group들이 중금속(重金屬) ion들과 반응(反應)하여 complex를 생성(生成)하였으며 그 생성량(生成量)은 Cu > Zn ≧ Cd의 순(順)이었다. 3. Humic acid-medal complex의 안정도(安定度) 상수(常數)는 pH가 증가(增加)함에 따라 增加하였으며 1차(次) 안정도(安定度) 상수(常數)는 Zn>Cd>Cu 순(順)이었고, 2차(次) 안정도(安定度) 상수(常數)는 Cu>Zn>Cd의 순(順)이었으며, 總安定도 常數는 Cu>Zn>Cd의 순(順)이었다. 4. Humlc acid와 중금속(重金屬)ion들 상호(相互) 간(間)의 평균결합수(平均結合數)는 pH가 증가(增加)함에 따라 Cu>Zn>Cd의 順으고 增加하였다. 5. Humic acid에 의한 중금속(重金屬) ion들의 complex생성과정(生成課程)에서 barboxyl group만이 관여(關與)하는 것과 car-boxyl gruup 및 phenolic OH group이 동시(同時)에 관여(關與)하는 두가지 흡착(吸着)mechanlsm을 제안할 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제23권11호
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• pp.1585-1589
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• 2002

Two novel calixarene-based fluoroionophores were synthesized. Their conformations were confirmed to 1,3-alternate by X-ray crystal structures. From CHEF by blocking the PET mechanism in fluorescence spectra, we observed $In^{3+}$ and $Pb^{2+}$ selectivity over other metal ions. For $In^{3+}$ion, calix[4]-bis-azacrown-5 showed about 20 times more sensitive than calix[4]-mono-azacrown-5 because the source of the binding selectivity comes from the calixarene framework and azacrown ligand by controlling the fluorescence and PET mechanisms as-sociated with the amine moiety.

• Bulletin of the Korean Chemical Society
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• 제33권3호
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• pp.881-884
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• 2012

We report a quantum chemical study of an extremely efficient nucleophilic aromatic fluorination in molten salts. We describe that the mechanism involves solvent anion interacting with the ion pair nucleophile $M^+F^-$(M = Na, K, Rb, Cs) to accelerate the reaction. We show that our proposed mechanism may well explain the excellent efficiency of molten salts for SNAr reactions, the relative efficacy of the metal cations, and also the observed large difference in rate constants in two molten salts $(n-C_4H_9)_4N^+\;CX_3SO_3^-$, (X=H, F) with slightly different sidechain ($-CH_3$ vs. $-CF_3$).