• Journal of the Korean Society of Industry Convergence
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• v.6 no.3
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• pp.165-169
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• 2003

To extract alkali metal ions and heavy metal ions, search for crown ether model compounds (4a-b, 5a-b, 6a-b) bearing side arm has led to achieve in 5~6 steps starting from 2,6-dimethylaniline. The determination of structure in their compound derivatives were on the basis of melting point and nuclear magnetic resonance spectroscopy. In the solvent extraction of metal ions from the synthesized derivatives, we observed that silver ion has only high selectivity for synergistic ligation of crown ether.

• Journal of Environmental Health Sciences
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• v.22 no.3
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• pp.81-87
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• 1996

The purpose of this research is to examine the utilization of oyster shells for neutralization and removal of heavy metal ions in plating wastewater, because oyster shells have been known to be very porous, to have high specific surface area and to have alkaline minerals such as calcium and magnesium. The results obtianed from this research showed that oyster shells had a buffer capacity to neutralize an acidic.alkali system in plating wastewater. Generally, it could be showed that the removal efficiencies of heavy metal ions were very influenced by reaction times and oyster shell dosages. In point of ocean waste, if oyster shells substituted for a valuable adsorbent such as actviated carbon, they could look forward to an expected economical effect.

• Bulletin of the Korean Chemical Society
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• v.29 no.7
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• pp.1295-1296
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• 2008

• Bulletin of the Korean Chemical Society
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• v.23 no.5
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• pp.688-692
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• 2002

The aminomethylation of phenols with para-substituents by the Mannich reaction has successfully been accomplished to produce the Mannich bases 2-6. The compounds 7-8 have also been synthesized in order to identify the effect of the side arms and t he macrocycle in the complex formation. Protonation constants and stability constants of the double armed diaza-18-crown-6 ethers 2-7 with metal ions have been determined by potentiometric method at 25 $^{\circ}C$ in 95 % methanol solution. Under a basic condition (pH > 8.0), the double-armed crown ethers 2-6 revealed stronger interaction with divalent metal ions than the simple diazacrown ether 1. The stability constants with these metal ions were Co 2+ < Ni2+ < Cu2+ > Zn 2+ in increasing order, which are in accordance with the order of the Williams-Irving series. The stability constants with alkali earth metal ions were Ca 2+ < Sr 2+ < Ba 2+ in increasing order, which may be explained by the concept of size effect. It is noteworthy that the hosts 2-6, which have phenolic side arms and a macrocycle, bind stronger with metal ions than the hosts 1 and 7. On the other hand, the host 8, which has phenolic side arms with a pyperazine ring,provided comparable stability constants to those with the host 3. These facts demonstrate that phenolic side arms play a more important role than the azacrown ether ring in the process of making a complex with metal ions especially in a basic condition. In particular, the log KML values for complexation of divalent metal ions with the hosts 2-6 had the sequence, i.e., 2 (R=OCH3) < 3 (R=CH3) < 4 (R=H) < 5 (R=Cl) < 6 (R=CF3). The stability constants of the hosts 5 and 6 containing an electron-withdrawing group are larger than those of the hosts 2 and 3 containing an electron-donating group. This substituent effect is attributed to the solvent effect in which the aryl oxide with an electron-donating group has a tendency to be tied strongly with protic solvents.

• Bulletin of the Korean Chemical Society
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• v.16 no.8
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• pp.716-720
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• 1995

• Bulletin of the Korean Chemical Society
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• v.18 no.12
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• pp.1311-1313
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• 1997

• Journal of the Korean Chemical Society
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• v.37 no.5
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• pp.491-495
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• 1993

Synthesis of polymer-supported azacrown ether ion exchanger, {(4,5): (13,14)-dibenzo-6,9,12-trioxa-3,15,21-triazazabicyclo[15.3.1]heneicosa-1(21),17,19-triene-2,16-dione : DBPDA ion exchanger}, and its ion binding ability to alkali metal $(Li^+,\;Na^+,\;K^+)$ picrates were studied. The binding constants $(K_b)$ of DBPDA ion exchanger to the alkali metal picrates in ether type solvents were obtained by spectrophotometry. Binding constants of alkali metal ions were in the order to Li < Na < K, and alkali metal ions were formed 1 : 1 complexes with ligands of DBPDA ion exchanger. Also, $K_b$ was found to depend on the variables such as solvent and temperature. The binding constants for the complexes were obtained in the ranges of $2{\times}10^3{\sim}4{\times}10^4M^{-1}$. In order to obtain the enthalpy (${\Delta}$H) and entropy changes (${\Delta}$S)n the complexation process, Kb were plotted against the temperature in the ranges of 10∼40$^{\circ}C$ according to the van't Hoff theory. Enthalphy and entropy changes were found in the ranges of -2.71∼-3.79 kcal/mol, and -16.52∼-20.57 eu, respectively.

• Bulletin of the Korean Chemical Society
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• v.34 no.5
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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.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1951-1956
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• 2011

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate 5 and isonicotinate 6 with alkali metal ethoxide EtOM (M = K, Na, and Li) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. Plots of pseudo-first-order rate constant $k_{obsd}$ vs. EtOM concentration exhibit upward curvature for the reactions of 5 and 6 with EtOK and EtONa but are almost linear for those with EtOLi. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has shown that $k_{EtOK}$ ${\geq}$ $k_{EtONa}$ > $k_{EtO^-}$ but $k_{EtOLi}$ < $k_{EtO^-}$. It has been concluded that $K^+$ and $Na^+$ ions catalyze the reactions by increasing the electrophilicity of the carbonyl carbon atom through formation of a 4-membered cyclic transition state $TS_3$ or $TS_4$. However, $M^+$ ion catalysis has been found to be much less significant for the reactions of 5 and 6 than for the corresponding reactions of 4-nitrophenyl picolinate 4, which was reported to proceed through a 5-membered cyclic transition state $TS_2$. Although 5 and 6 are significantly more reactive than 4-nitrophenyl benzoate 3, the reactions of 5 and 6 result in smaller $k_{EtOK}/k_{EtO^-}$ ratios than those of 3. The electron-withdrawing ability of the nitrogen atom in the acyl moiety of 5 and 6 has been suggested to be responsible for the increase in reactivity and the decrease in the $k_{EtOK}/k_{EtO^-}$ ratio.

• Bulletin of the Korean Chemical Society
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• v.19 no.2
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• pp.207-211
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• 1998

Potentiometric characteristics of DOS plasticized PVC-based membranes containing upper-rim calix[4]crown neutral carrier to various metal cations and protonated alkylamines have been examined. Although the calix[4]crown-based membrane electrodes exhibited substantial emf responses to alkali and alkaline earth metal cations, their high detection limits (- log[Cs+]=4.5) and sub-Nernstian response slopes (48 mV/pCs+) to the most selective cation, cesium, indicate that the metal cation complexing ability of calix[4]crown is much weaker than that of macrocyclic crown ethers. However, the calix[4]crown-based membrane electrodes exhibited near-Nernstian response slopes (56 mV/decade for hexylNH3+) with low detection limits (log[hexylNH3+]= - 6.7) to most alkylammonium ions compared to those of blank (DOS plasticized PVC membrane with no ionophore) or crown ether-based membranes. While the selectivity patterns of blank and crown ether-based membranes are determined primarily by the lipophilicity of alkylammonium ions, the membranes doped with calix[4]crown ionophore could effectively discriminate the steric shapes of nonpolar alkyl groups of alkylammonium ions.