• Bulletin of the Korean Chemical Society
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• v.15 no.2
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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^+$.

• Analytical Science and Technology
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• v.6 no.5
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• pp.463-469
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• 1993

HDBPDA ion exchange resin, {(4, 5) : (13, 14)-Dibenzo-6, 9, 12-trioxa-3, 15, 21, -triazabicyclo [15. 3. 1]heneicosa-(1, 17, 19)(18, 20, 21) triene ion exchange resin : HDBPDA ion exchange resin} had a capacity of 3.8meq/g dry resin. The distribution coefficients of alkali and alkaline earth metal ions on HDBPDA and strongly acidic cation exchange resin, Dowex 50W-X8(200-400mesh) in water, and the various concentrations of hydrochloric acid were determined. Concentration of hydrochloric acid have almost not influenced on the distribution coefficients of alkali and alkaline earth metal ions for the HDBPDA ion exchange resin, but generally the distribution coefficient slightly increased with decreasing concentration of hydrochloric acid. The distribution coefficients of metal ions in water are larger than those in various hydrochloric acid concentration. The distribution coefficients of alkali and alkaline earth metal ions for the Dowex 50W-X8 ion exchange resin increased with decreasing hydrochloric acid concentration. Especially, the distribution coefficients of alkaline earth metal ions increased rapidly compared to those for alkali metal ions. The distribution coefficients of alkali and alkaline earth metal ions on HDBPDA ion exchange resin increased in a linear manner with decreasing acid concentration, and the slope, d log Kd/d log $M_{HCl}$ is about -0.2. Of the distribution cofficients of alkali metal ions on Dowex 50W-X8, at range of moderate hydrochloric acid concentration, the slope is about -1, while the slope for alkaline earth metal ions is about -2. However, at very low hydrochloric acid concentration, the linear variation between distribution coefficient and acid concentration was not occurred, but the slope was deviated from above values at low acid concentration.

• 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.12 no.1
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• pp.93-97
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• 1991

Rate constants have been measured spectrophotometrically for the reactions of alkali metal ethoxides with 4-nitrophenyl benzoate, S-4-nitrophenyl thiobenzoate and 4-nitrophenyl thionbenzoate in ethanol at 25$^{\circ}$C. Substitution of S for O in the leaving group has not affected reactivity significantly, while the effect of the similar replacement in the acyl group has led to rate decrease by a factor of 10, although pronounced rate enhancements have been expected for both systems. The replacement of O by a polarizable S has also influenced the reactivity of the esters toward alkali metal ethoxides, i.e. the reactivity decreases as the size of the metal ion decreases. The alkali metal ions have showed inhibition effect instead of catalytic effect which would have been expected for the present system. The effect of replaced sulfur atom on the reactivity for the present system is attributed to the nature of hard and soft acids and bases.

• 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.

• Macromolecular Research
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• v.13 no.2
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• pp.141-146
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• 2005

Calix[4]crown-6-2,4-bis(4-aminobutyl ether), which has a crown-6 moiety at the 1,3-position and amino function at the 2,4-position, was prepared as an intermediate for the subsequent synthesis of calix[4]crown-6-containing polyamide and polyimide using adipoyl chloride and 1,2,4,5-benzenetetracarboxylic dianhydride. The chemical structures were characterized by IR, $^{1}H NMR$ spectroscopy and elemental analysis, and some of their physical properties, including their thermal behavior, were examined. The ion binding characteristics of the monomer and polymers for alkali metal and alkali earth metal ions were measured by liquid-liquid extraction from the aqueous phase into the organic phase. It has been observed that polyamide has a high binding ability towards various metal cations as compared to polyimide, which showed cesium ion selectivity.

• Analytical Science and Technology
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• v.6 no.5
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• pp.471-477
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• 1993

The novel macrocylic ligand {(4, 5):(13, 14)-dibenzo-6, 9, 12-trioxa-3, 15, 21, -triazabicyclo [15. 3. 1]heneicosa-(1, 17, 19)(18, 20, 21) triene: HDBPDA} was synthesized, and protonable constants of the ligand and the complex stability constants with alkali metals alkaline earth metals were determined. We evaluated the resolution factor(${\Delta}$) from equation that inducing from stability constants(pK). Also, this ligand was grafted on chloromethylated styrene-divinyl benzene(Merrifield resin) for HDBPDA, ion exchanger. Alkali and alkaline earth metal ions were separated using water by the column chromatography with this ion exchanger. Selectivity(${\alpha}$) and resolution(Rs) of alkali and alkaline earth metal ions were measured from the elution curves chromatogram. The selectivity and resolution values of the various ions calculated from the elution curves were compared with those abtained from pK values. The results were in a good agreement between tow methods. Ion exchange capacity of the resin were determined using the alkali and alkaline earth metal ions and pH dependence of capacity was also discussed.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.187-187
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• 2012

Solution-processed metal-alloy oxides such as indium zinc oxide (IZO), indium gallium zinc oxide (IGZO) has been extensively researched due to their high electron mobility, environmental stability, optical transparency, and solution-processibility. In spite of their excellent material properties, however, there remains a challenging problem for utilizing IZO or IGZO in electronic devices: the supply shortage of indium (In). The cost of indium is high, what is more, indium is becoming more expensive and scarce and thus strategically important. Therefore, developing an alternative route to improve carrier mobility of solution-processable ZnO is critical and essential. Here, we introduce a simple route to achieve high-performance and low-temperature solution-processed ZnO thin film transistors (TFTs) by employing alkali-metal doping such as Li, Na, K or Rb. Li-doped ZnO TFTs exhibited excellent device performance with a field-effect mobility of $7.3cm^2{\cdot}V-1{\cdot}s-1$ and an on/off current ratio of more than 107. Also, in case of higher drain voltage operation (VD=60V), the field effect mobility increased up to $11.45cm^2{\cdot}V-1{\cdot}s-1$. These all alkali metal doped ZnO TFTs were fabricated at maximum process temperature as low as $300^{\circ}C$. Moreover, low-voltage operating ZnO TFTs was fabricated with the ion gel gate dielectrics. The ultra high capacitance of the ion gel gate dielectrics allowed high on-current operation at low voltage. These devices also showed excellent operational stability.

• Bulletin of the Korean Chemical Society
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• v.26 no.3
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• pp.393-398
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• 2005

The stability constants for the diaza-18-crown-6 ethers 2-6 and alkali metal cations ($Na^+,\;K^+,\;Rb^+\;and\;Cs^+$) were determined using potentiometry in 95% methanol. For each metal ion the stability constants of the partiallyfluorinated ligands 3-6 were larger than that of the non-fluorinated ligand 2, which might reflect an interaction between fluorine atoms and alkali metal cations. The stability constant of the ligand 4 was larger than that of the ligand 5 for each metal cation tested. This finding was also supported by the results of cation-induced chemical shifts in $^1H-,\;^{19}F$-NMR and extraction experiment. The potentiometry and NMR results as well as the X-ray crystal structures revealed that the position and number of fluorine atoms in the benzyl side arms was crucial for the enhanced interaction between a ligand and an alkali metal.

• Textile Coloration and Finishing
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• v.6 no.4
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• pp.72-76
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• 1994

The permselectivity of alkali metal chlorides through silk fibroin membrane was investigated at $25^{\circ}C$: The Permeability coefficients were found to increase in a sequence of LiCl < NaCl < KCl < CsCl. This sequence was explained by considering the partition and the hydrophilic membrane. The dependence of the permeability on the salts concentration was interpreted by means of TMS theory. The ionic mobility ratio of alkali metal chlorides through this membrane decreased with the increase of the Stokes radius. The Effectiveness of the charged density was found to depend on the ionic species. The greater the Stokes radius the larger the effective charge density of membrane.