• Bulletin of the Korean Chemical Society
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• v.31 no.10
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• pp.2929-2933
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• 2010

Pseudo-first-order rate constants ($k_{obsd}$) have been measured for nucleophilic substitution reactions of 2-pyridyl benzoate 5 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol. The plots of $k_{obsd}$ vs. $[EtOM]_o$ are curved upwardly but linear in the excess presence of 18-crown-6-ether (18C6) with significant decreased $k_{obsd}$ values in the reaction with EtOK. The $k_{obsd}$ value for the reaction of 5 with a given EtONa concentration decreases steeply upon addition of 15-crown-5-ether (15C5) to the reaction medium up to ca. [15C5]/$[EtONa]_o$ = 1, and remains nearly constant thereafter, indicating that $M^+$ ions catalyze the reaction in the absence of the complexing agents. Dissection $k_{obsd}$ into $k_{EtO^-}$- and $k_{EtOM}$, i.e., the second-order rate constants for the reaction with the dissociated $EtO^-$ and the ion-paired EtOM, respectively has revealed that ion-paired EtOM is 3.2 - 4.6 times more reactive than dissociated $EtO^-$. It has been concluded that $M^+$ ions increase the electrophilicity of the reaction center through a 6-membered cyclic transition state. This idea has been examined from the corresponding reactions of 4-pyridyl benzoate 6, which cannot form such a 6-membered cyclic transition state.

• Journal of the Korean Chemical Society
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• v.28 no.6
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• pp.418-424
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• 1984

Rate constants for the hydrolysis of cinnamonitrile in the concentration range of 1 ∼ 5M of perchloric acid at 25$^{\circ}$C have been determined by UV spectrophotometry and from the Bunnett equations, hydration parameters (${\omega}$ = 9.8, ${\omega}^*$ = 0.42 & ${\phi}$=1.6) were obtained. CNDO/2 MO calculations were performed to determine relative stability, net charges, and overlap population of various conformational isomers. The results show that the (E)-planar is more stable than the (Z)-planar and protonation is favored on the nitrogen atom. On the basis of above findings, the acid hydrolysis is initiated by the protonation of the nitrogen atom of cinnamonitrile and then water molecule acting as nucleophile and as a proton transfer agent in the rate determining step. In the transition state of the acid hydrolysis, nucleophilic addition of water molecule occurs by sigma approach to the positively charged $C_7({\alpha}$) atom of the conjugate acid. As the results, we may conclude that the hydrolysis of cinnamonitrile in the strong acidic media proceeds through the A-2 type mechanism.

• Applied Chemistry for Engineering
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• v.7 no.6
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• pp.1156-1163
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• 1996

This study is related to the investigation of the characteristics of quaternary ammonium salt catalyst on the addition reaction of carbon dioxide and glycidyl methacrylate(GMA) to form(2-oxo-1,3-dioxolane-4-yl)methacrylate(DOMA). Among the salts tested, the ones with higher alkyl chain length and with more nucleophilic counter anion showed a higher catalytic activity. Mixed catalysts of NaI and 18-crown-6 showed a good yield of DOMA, but when they are used alone, they showed no catalytic activity. The DOMA monomer was obtained in low polar solvents, while poly(DOMA) could be directly synthesized in aprotic dipolar solvents. Kinetic studies carried out by measuring $CO_2$ pressure in a high pressure batch reactor showed that the reaction rate was first order to the concentration of GMA and $CO_2$ respectively. The rate constant(k) was 0.56L/mol hr and Henry's constant(H') of $CO_2$ in diglyme at $80^{\circ}C$ was $6.5{\times}10^{-4}mol/L{\cdot}kPa$.

• Membrane Journal
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• v.27 no.3
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• pp.205-215
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• 2017

Polymer membranes are cheap and easy in fabrication, and show a high permeability and selectivity, thus play pivotal roles in gas separation as well as water purification. However, polymer membranes typically exhibit the trade-off relation between permeability and selectivity; i.e. when the permeability is high, the selectivity is low and vice versa. Facilitated transport has been considered one of the solutions to address this issue. Over the last decades, facilitated transport concept had played an important role in preparing the membranes and providing ideal and various models for the transport. Understanding the nature of carrier, the mobility of matrix and the physico-chemical properties of polymer composites are crucial for facilitated transport. Depending on the mobility of carrier, facilitated transport membrane is classified into three; mobile carrier membrane, semi-mobile carrier membrane, fixed-site carrier membrane. Also, there are four types of reversible reaction between the carrier and the specific target; proton transfer reaction, nucleophilic addition reaction, p-complexation reaction and electrochemical reaction. The facilitated transport membranes have been applied in the separation of CO2, O2 and olefin (propylene or ethylene). In this review, major challenges surrounding facilitated transport membranes and the strategies to tackle these challenges are given in detail.

• The Korean Journal of Malacology
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• v.30 no.4
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• pp.399-408
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• 2014

Glutathione S-transferases (GSTs) are a superfamily of detoxification enzymes that primarily catalyze the nucleophilic addition of reduced glutathione to both endogenous and exogenous electrophiles. In this study, we isolated and characterized a full-length of alpha class GST cDNA from the abalone (Haliotis discus hannai). The abalone GST cDNA encodes a 223-amino acid polypeptide with a calculated molecular mass of 25.8 kDa and isoelectric point of 5.69. Multiple alignments and phylogenetic analysis with the deduced abalone GST protein revealed that it belongs to the alpha class GSTs and showed strong homology with disk abalone (Haliotis discus discus) putative alpha class GST. Abalone GST mRNA was ubiquitously detected in all tested tissues. GST mRNA expression was comparatively high in the mantle, gill, liver, and digestive duct, however, lowest in the hemocytes. Expression level of abalone GST mRNA in the mantle, gill, liver, and digestive duct was 182.7-fold, 114.8-fold, 4675.8-fold, 406.1-fold higher than in the hemocytes, respectively. Expression level of abalone GST mRNA in the liver was peaked at 6 h post-infection with Vibrio parahemolyticus and decreased at 12 h post-infection. While the expression level of abalone GST mRNA in the hemocytes was drastically increased at 3 h post-infection with Vibrio parahemolyticus. These results suggest that abalone GST is conserved through evolution and may play roles similar to its mammalian counterparts.

• Applied Biological Chemistry
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• v.40 no.1
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• pp.53-57
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• 1997

The rate of hydrolysis of insecticidal 1-(6-chloro-3-pyridylmethyl) -2-nitro-iminoimidazolidine (common name; imidacloprid) have been investigated in 15%(v/v) aqueous dioxane at $45^{\circ}C$. From the kinetics and non-kinetics data such as pH-effect, solvent effect(m=0.04, n=0.30 IT m<${\Delta}H^{\neq}=16.14kcal{\cdot}mol^{-1}\;&\;{\Delta}S^{\neq}=-0.03e.u.$), rate equation ($k_{obs.}=4.56{\times}10^{-3}[OH^-]$) and analysis of hydrolysis product, 1-(6-chloro-3-pyridylmethyl-2)-imidazolidinon, the hydrolysis mechanism of imidacloprid is proposed that the specific base catalyzed hydrolysis($K_{OH^-}$) through nucleophilic addition-elimination ($Ad_N-E$) mechanism proceed via intermediate, 1-(6-chloro-3- pyridylmethyl)-2-hydroxy-2-imidazolidinylisonitraminate (I) and ${\beta}$-3-(6-chloro-3-pyridylmethyl)aminoethyl-1-nitrourea(III). And the half-life(t1/2) of hydrolytic degradation at pH 8.0 and $45^{\circ}C$ was about 4.5 months.

• Applied Chemistry for Engineering
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• v.10 no.1
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• pp.129-134
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• 1999

This study is related to the investigation of the direct incorporation of $CO_2$ to polymer using quaternary ammonium salt catalysts. Quaternary ammonium salts showed good catalytic activity of $CO_2$ fixation in the synthesis of poly[(1,3-dioxolane-2-oxo-4-yl)methyl methacrylate] [poly(DOMA)] by the direct incorporation of $CO_2$ to poly(glycidyl methacrylate)[poly(GMA)]. Among the salts tested, the ones with higher alkyl chain length and with more nucleophilic counter anion showed higher catalytic activity. The yield of carbon dioxide addition increased with the reaction temperature. Kinetic study was carried out by measuring the variation of $CO_2$, pressure in a high pressure batch reactor. The reaction rate was first order to the concentration of poly(GMA) and $CO_2$, respectively. The rate constant was $0.69L/mol{\cdot}h$ and Henry's constant of $CO_2$ in DMSO at $80^{\circ}C$ was $6.8{\times}10^{-4}mol/L{\cdot}KPa$.

• Applied Biological Chemistry
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• v.42 no.4
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• pp.330-335
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• 1999

Pentachlorophenol(PCP), which is very persistent in soil and water environment, was tried to detoxify with oxidoreductive catalysts(peroxidase, laccase, tyrosinase and birnessite). To find out detoxification of PCP, the transformation of PCP through oxidative coupling was investigated in the presence of various oxidoreductive catalysts. PCP incubated with peroxidase was significantly transformed, however, in case of tyrosinase, the transformation was negligible. Using peroxidase, the optimal reaction condition was pH 5.6 and $16^{\circ}C$. The transformation of PCP was very fast in initiation step until 30 min but, that was not observed after 180 min. The transformation of PCP was increased by increasing peroacidase amount. When the effect of humic monomer was investigated as co-substrate on the transformation of PCP, the transformation of PCP was mostly decreased in the incubation with peroxidase, laccase, and birnessite. The transformation of PCP, however, was slightly increased by the incubation with tyrosinase in the presence of humic monomers as co-substrate, except catechol. On the basis of the results obtained, it may be suggested that PCP is able to be effectively detoxified through oxidative coupling mediated with oxidoreductive catalysts.

• Applied Biological Chemistry
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• v.43 no.1
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• pp.52-56
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• 2000

The influence of the 2-(4-(6-chloro-2-benzoxazolyloxy)phenoxy)-N-phenyl- propionamide derivatives on the herbicide activities against rice plant with pre-emergence and post-emergence in down land were examined and the structure activity relationship (SAR) were analyzed by Free-Wilson and Hansch method. In pre-emergence, the SAR approach is shown that the optimal, $({\pi})_{opt}=0.91$, hydrophobicity with electron donating effect of the ortho substituted mono substituents and 2,3,4-substituted three substituents were found to be contribute the herbicidal activity. Whereas, in post-emergence, the optimal, ({\pi})_{opt}=0.50$, hydrophobicity with electron withdrawing effect of meta substituted mono subsituents and 2,3-substituted two substituents were found to be contribute the herbicide activity. The herbicide activities with post-emergence more increase than that of pre-emergence. It is assumed from the SAR equations that the 2-methyl-3-methoxy-4-cyano group substituent is selected as the most lowest herbicide activity against rice plant with post-emergence in green house. The hydrolysis reaction was proceeded through nucleophilic addition-elimination (Ad_{Nu-E})$ with the orbital control between LUMO of substrate and HOMO of water molecule. And molecular electrostatic potential (MEP) of none (H) substituent was discussed.

• The Journal of the Acoustical Society of Korea
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• v.35 no.6
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• pp.473-479
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• 2016

We report a highly selective and sensitive 200 MHz Surface Acoustic Wave (SAW) sensor that can detect cyanide ion in aqueous solution using surface immobilized thioester molecules in combination with gold nanoparticles (AuNPs). To construct the sensor device, a monolayer of thioester compound was immobilized on the SAW sensor surface. At the sensor surface, hydrolysis of thioester group by nucleophilic addition of cyanide occurred and the resulting free thiol unit bound to AuNP to form thiol-AuNP conjugate. For the signal enhancement, gold staining signal amplification process was introduced subsequently with gold (III) chloride trihydrate and reducing agent, hydroxylamine hydrochloride. The SAW sensor showed a detection ability of $17.7{\mu}M$ for cyanide in aqueous solution and demonstrated a saturation behavior between the frequency shift and the concentration of cyanide ion. On the other hand, our SAW sensor had no activities for other anions such as fluoride ion, acetate ion and sulfate ion, moreover, no significant interference observed by other anions. Finally, all the experiments were carried out in-house developed sensor and fluidics modules to obtain highly reproducible results.