• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2438-2442
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• 2014

A kinetic study is reported for $S_NAr$ reaction of 1-fluoro-2,4-dinitrobenzene (5a) and 1-chloro-2,4-dinitrobenzene (5b) with alkali-metal ethoxides (EtOM, M = Li, Na, K and 18-crown-6-ether complexed K) in anhydrous ethanol. The second-order rate constant increases in the order $k_{EtOLi}$ < $k_{EtO^-}$ < $k_{EtONa}$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for the reaction of 5a and $k_{EtOLi}$ < $k_{EtONa}$ < $k_{EtO^-$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for that of 5b. This indicates that $M^+$ ion behaves as a catalyst or an inhibitor depending on the size of $M^+$ ion and the nature of the leaving group ($F^-$ vs. $Cl^-$). Substrate 5a is more reactive than 5b, although the $F^-$ in 5a is ca. $10pK_a$ units more basic than the $Cl^-$ in 5b, indicating that the reaction proceeds through a Meisenheimer complex in which expulsion of the leaving group occurs after the rate-determining step (RDS). $M^+$ ion would catalyze the reaction by increasing either the nucleofugality of the leaving group through a four-membered cyclic transition state or the electrophilicity of the reaction center through a ${\pi}$-complex. However, the enhanced nucleofugality would be ineffective for the current reaction, since expulsion of the leaving group occurs after the RDS. Thus, it has been concluded that $M^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through a ${\pi}$-complex between $M^+$ ion and the ${\pi}$-electrons in the benzene ring.

• Bulletin of the Korean Chemical Society
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• 제29권1호
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• pp.117-121
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• 2008

Pseudo-first-order rate constants (kobsd) have been measured spectrophotometrically for nucleophilic substitution reactions of 5-nitro-8-quinolyl benzoate (5) with alkali metal ethoxides, EtO?M+ (M+ = Li+, Na+ and K+) in anhydrous ethanol (EtOH) at 25.0 0.1 C. The plots of kobsd vs. [EtO?M+] exhibit upward curvatures, while the corresponding plots for the reactions of 5 with EtO?Na+ and EtO?K+ in the presence of complexing agents, 15-crown-5-ether and 18-crown-6-ether are linear with rate retardation. The reactions of 5 with EtO?Na+ and EtO?Li+ result in significant rate enhancements on additions of Na+ClO4, indicating that the M+ ions behave as a catalyst. The dissociated EtO and ion-paired EtOM+ have been proposed to react with 5. The second-order rate constants for the reactions with EtO (kEtO) and EtOM+ (kEtOM+) have been calculated from ion-pairing treatments. The kEtO and kEtOM+ values decrease in the order kEtONa+ > kEtOK+ > kEtOLi+ > kEtO, indicating that ion-paired EtOM+ species are more reactive than the dissociated EtO ion, and Na+ ion exhibits the largest catalytic effect. The M+ ions in this study form stronger complex with the transition state than with the ground state. Coordination of the M+ ions with the O and N atoms in the leaving group of 5 has been suggested to be responsible for the catalytic effect shown by the alkali metal ions in this study.

• 한국환경과학회지
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• 제20권1호
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• pp.119-126
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• 2011

In this study, reaction model and reactions rate accelerated by o-iodosobenzoate ion(IB$^{\ominus}$) on hydrolysis reaction of p-nitrophenyl valate(NPV) using ethyl tri-octyl ammonium mesylate(ETAMs) for quaternary ammonium salts, the phase transfer catalysis(PTC) reagent, were investigated. The effect of IB$^{\ominus}$ on hydrolysis reaction rate constant of NPV was weak without ETAMs solutions. Otherwise, in ETAMs solutions, the hydrolysis reactions exhibit higher first order kinetics with respect to the nucleophile, IB$^{\ominus}$, and ETAMs, suggesting that reactions are occurring in small aggregates of the three species including the substrate(NPV), whereas the reaction of NPV with OH$^{\ominus}$ is not catalyzed by ETAMs. Different concentrations of NPV were tested to measure the change of rate constants to investigate the effect of NPV as substrate and the results showed that the effect was weak. This means the reaction would be the first order kinetics with respect to the nucleophile. This behavior for the drastic rate-enhancement of the hydrolysis is referred as 'Aggregation complex model' for reaction of hydrophobic organic ester with o-iodosobenzoate ion(IB$^{\ominus}$) in hydrophobic quarternary ammonium salt(ETAMs) solutions.

• Bulletin of the Korean Chemical Society
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• 제35권4호
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• pp.1001-1004
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• 2014

We have synthesized disc-like large silver nanomaterials that have nanostructured bumps on the surface using smaller nanoplate seeds. The size and shape of the bumpy nanostructures are rationally controlled by changing the concentrations of nanoplate seeds, silver ion, reductant, and citrate ion. Importantly, the synthetic mechanism of these bumpy nanostructures is remarkably similar to that of the conventional seed-mediated growth based on tiny seeds. We have further investigated the catalytic properties of the bumpy nanostructures for the reduction of 4-nitrophenol, which is associated with a concomitant color change from yellow to colorless.

• 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.

• Bulletin of the Korean Chemical Society
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• 제35권1호
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• pp.225-230
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• 2014

A kinetic study on nucleophilic substitution reactions of 4-nitrophenyl X-substituted-benzoates (7a-i) with EtOK in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$ is reported. The plots of pseudo-first-order rate constants ($k_{obsd}$) vs. [EtOK] curve upward. Dissection of $k_{obsd}$ into the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOK (i.e., $k_{EtO^-}$ and $k_{EtOK}$, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. Hammett plots for the reactions of 7a-i with the dissociated $EtO^-$ and ion-paired EtOK exhibit excellent linear correlations with ${\rho}_X$ = 3.00 and 2.47, respectively. The reactions have been suggested to proceed through a stepwise mechanism in which departure of the leaving-group occurs after the RDS. The correlation of the $k_{EtOK}/k_{EtO^-}$ ratio with the ${\sigma}_X$ constants exhibits excellent linearity with a slope of -0.53. It is concluded that the ion-paired EtOK catalyzes the reaction by increasing the electrophilicity of the reaction center rather than by enhancing the nucleofugality of the leaving group.

• Bulletin of the Korean Chemical Society
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• 제34권5호
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• pp.1525-1529
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• 2013

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reactions of 2-pyridyl thionobenzoate (5b) with alkali-metal ethoxides (EtOM, $M^+=Li^+$, $Na^+$, $K^+$, and 18-crown-6-ether complexed $K^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. $[EtOM]_o$ curve upward regardless of the nature of the $M^+$ ions, while those of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ are linear with a positive intercept. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is more reactive than the dissociated $EtO^-$, and $M^+$ ions catalyze the reactions in the order $K^+$ < $Na^+$ < $Li^+$ < 18C6-complexed $K^+$. The plot of log $k_{EtOM}$ vs. $1/r_{Stokes}$ results in an excellent linear correlation, indicating that the reactions are catalyzed by the solvated $M^+$ ions but not by the bare $M^+$ ions. The reactions of 5b with EtOM have been concluded to proceed through a six-membered cyclic TS, in which the solvated $M^+$ ions increase the electrophilicity of the reaction center and the nucleofugality of the leaving group.

• The Korean Journal of Ceramics
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• 제4권2호
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• pp.95-98
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• 1998

We have developed new type of superconducting-superionic conducting nanohybrids, $Ag_xI_wBi_2Sr_2Ca_{n-1}Cu_nO_y$ (n=1 and 2) by applying the chimie douce reaction to the superconducting Bi-based cuprates. These nanohybrids can be achieved by the stepwise intercalation whereby the $Ag^+$ ion is thermally diffused into the pre-intercalated iodine sublattice of $IBi_2Sr_2Ca_{n-1}Cu_nO_y$. According to the X-ray diffraction analysis, the Ag-I intercalates are found to have an unique heterostructure in which the superionic conducting Ag-I layer and the superconducting $IBi_2Sr_2Ca_{n-1}Cu_nO_y$ layer are regularly interstratified with a remarkable basal increment of ~7.3$\AA$. The systematic XAS studies demonstrate that the intercalation of Ag-I accompanies the charge transfer between host and guest, giving rise to a change in hole concentration of $CuO_2$ layer and to a slight $T_c$ change. The Ag K-edge EXAFS result reveals that the intercalated Ag-I has a $\beta$-AgI-like local structure with distorted tetrahedral symmetry, suggesting a mobile environment for the intercalated $Ag^+$ ion. In fact, from ac impedance analyses, we have found that the Ag-I intercalates possess a fast ionic conductivity ($\sigma_i=10^{-1.4}\sim 10^{-2.6}\Omega^{-1}\textrm{cm}^{-1}\;at\;270^{\circ}C$ with an uniform activation energy ($\DeltaE_a=0.22\pm 0.02$ eV). More interesting finding is that these intercalates exhibit high electronic conducting as well as ionic ones ($t_i$=0.02~0.60) due to their interstratified structure consisting of superionic conducting and superconducting layers. In this respect, these new intercalates are expected to be useful as an electrode material in various electrochemical devices.

• Applied Science and Convergence Technology
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• 제23권1호
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• pp.14-26
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• 2014

Copper is an important component from coin metal to electronic wire, integrated circuit, and to lithium battery. Copper oxides, mainly including $Cu_2O$ and CuO, are important semiconductors for the wide applications in solar cell, catalysis, lithium-ion battery, and sensor. Due to their low cost, low toxicity, and easy synthesis, copper oxides have received much research interest in recent year. Herein, we review the crystallization of copper oxides by designing various chemical reaction routes, for example, the synthesis of $Cu_2O$ by reduction route, the oxidation of copper to $Cu_2O$ or CuO, the chemical transformation of $Cu_2O$ to CuO, the chemical precipitation of CuO. In the designed reaction system, ligands, pH, inorganic ions, temperature were used to control both chemical reactions and the crystallization processes, which finally determined the phases, morphologies and sizes of copper oxides. Furthermore, copper oxides with different structures as electrode materials for lithium-ion batteries were also reviewed. This review presents a simple route to study the reaction-crystallization-performance relationship of Cu-based materials, which can be extended to other inorganic oxides.

• BMB Reports
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• 제29권2호
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• pp.99-104
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• 1996

Site-directed substitutions were made to change the Ile91 of restriction endonuclease EcoRV to either Val, Ala or Gly to identify the role of Ile91 in recognition and catalysis, since substitution of Ile91 with Leu afforded dramatic effects on the activity and properties of restriction endonuclease EcoRV. These changes alter the size of the hydrophobic side chain at position 91 and thus might have revealed the reason for the altered phenotype of Ile91Leu. However, the properties of Ile91Val and Ile91Ala mutants were much like wild type EcoRV, in both activity and metal ion preference. Ile91Gly had very little activity with either $Mg^{2+}$ or $Mn^{2+}$ as cofactors. To try to understand the unusual $Mn^{2+}$ profile of the Ile91Leu mutant, two double mutants, Ile91Leu;Asp90Asn and Ile91Leu;Glu45Met were created. Both double mutants were seriously disabled by the second amino acid change. Ile91Leu;Glu45Met had some residual activity in the $Mn^{2+}$ reaction buffer, whereas the Ile91Leu;Asp90Asn displayed no detectable activity.