• Applied Chemistry for Engineering
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• v.3 no.2
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• pp.266-272
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• 1992

Azacrownoalkyl phenylphosphinic acids were synthesized and their competitive solvent extraction characteristics from water to chloroform layer were investigated. Phosphinic acids were synthesized in good yields by one step reaction of phenylphosphinate, aldehyde, and monoazacrown ether and then basic hydrolysis of the resulting phosphinate dsters. These complexing agents revealed a wide effective pH range in extraction of alkali metal ions from water to the organic phase and total metal ion loading at pH 11 was about 75%. The selectivity of the cation extraction was determined mainly by the cavity size of the azacrown ethers, showing $Na^+$ >> $K^+$ > $Rb^+$ > $Li^+$ > $Cs^+$ for the alkyl phenylphosphinic acid ${\underline{2}}$, containing monoaza-15-crown-5 and $K^+$ >> $Rb^+$ > $Na^+$ > $Cs^+$ > $Li^+$ for the alkyl phenylphosphinic acid, ${\underline{3}}$, containing monoaza-18-crown-6 moiety. Applicable pH range of these azacrown ether phosphinic acids in solvent extraction of alkali metal cations was wider than a crownether carboxylic acid with similar selectivity, showing considerable amount of metal ion loading in slightly acidic or neutral media.

• Bulletin of the Korean Chemical Society
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• v.35 no.5
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• pp.1506-1510
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• 2014

A kinetic study on nucleophilic substitution reaction of 5-nitro-8-quinolyl picolinate (6) with alkali-metal ethoxides (EtOM; M = K, Na, and Li) in anhydrous ethanol is reported. The plot of $k_{obsd}$ vs. [EtOM] curves upward in the absence of crown ethers but is linear with significantly decreased reactivity in the presence of crown ethers. 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 significantly more reactive than the dissociated $EtO^-$ (e.g., $k_{EtOM}/k_{EtO^-}$ = 33.4-141). This indicates that the reaction of 6 is catalyzed by $M^+$ ions in the order $Na^+$ > $Li^+$ > $K^+$ and the catalytic effect disappears in the presence of a proper crown ether. Picolinate ester 6 is much more reactive and is more strongly catalyzed by $M^+$ ions than 5-nitro-8-quinolyl benzoate (5). It has been concluded that $M^+$ ions catalyze the reaction of 6 by increasing electrophilicity of the reaction center through a cyclic transition state, which is structurally not possible for the reaction of 5.

• Journal of the Korean Chemical Society
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• v.31 no.3
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• pp.250-257
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• 1987

The electrical conductances for the thorium (IV) complexes with crown ethers have been measured in DMSO, and water solvents, and the oxidation-reduction reaction mechanisms, electron number and diffusion coefficients in the reversible reduction process have been examined by polarography and cyclic voltammography. The dissociation mole ratio of $Th^{4+}$ and nitrate ion are 1:1 and in aprotic solvent, and 1:4 in protic solvent like as water. The limiting molar conductances of all complexes in aprotic solvent have been found to be in the range of $92.2{\times}159$ $ohm^{-1}cm^2mol^{-1}$. In aprotic solvent, DMSO, the reduction of each complex is reversible by one electron reduction of one step, and the range of diffusion coefficients is obserbed to be $5.83\;10^{-6}{\sim}6.90{\times}10^{-6}$. The complexes which have reduction step were hydrolyzed above at 1.8volt with reference saturated calomel electrode, generating the hydrogen gas. The reaction mechanisms of thorium (IV)-crown ether complexes appear as follows. ${Th_m(IV)L_n(H_2O)_x(NO_3)_{4y}}_=^{DMSO} {\overline{{Th_m(IV)L_n(H_2O)_x(NO_3)_{4y-1}}}^+ + NO_3-$

• Nuclear Engineering and Technology
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• v.52 no.2
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• pp.328-336
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• 2020

Cesium is a major product of uranium fission, which is the most commonly existed radionuclide in radioactive wastes. Various technologies have been applied to separate radioactive cesium from radioactive wastes, such as chemical precipitation, solvent extraction, membrane separation and adsorption. Crown ethers and calixarenes derivatives can selectively coordinate with cesium ions by ion-dipole interaction or cation-π interaction, which are promising extractants for cesium ions due to their promising coordinating structure. This review systematically summarized and analyzed the recent advances in the crown ethers and calixarenes derivatives for cesium separation, especially focusing on the adsorbents based on extractants for cesium removal from aqueous solution, such as the grafting coordinating groups (e.g. crown ether and calixarenes) and coordinating polymers (e.g. MOFs) due to their unique coordination ability and selectivity for cesium ions. These adsorbents combined the advantages of extraction and adsorption methods and showed high adsorption capacity for cesium ions, which are promising for cesium separation The key restraints for cesium separation, as well as the newest progress of the adsorbents for cesium separation were also discussed. Finally, some concluding remarks and suggestions for future researches were proposed.

• The Transactions of the Korean Institute of Electrical Engineers D
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• v.52 no.5
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• pp.213-213
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• 2003

We investigated the monolayer behavior at the air-water interface with metal solution, the surface morphologies and the electrical properties such as conductivity, The calculated conductivity values of pure water subphase and its complexes with L $i^{+}$ ions are 5.6$\times$10$^{-l6}$ and 1.9$\times$10$^{-14}$ [S/cm], respectively. And the calculated barrier height D values of pure water subphase and its complexes with Li. ions are 0.70 and 0.66 [eV], respectively. We also attempted to fabricate a crown dendrimer Langmuir-Blodgett (LB) films containing functional end group that could form a complex structure with metal ions. Also, we investigated the surface activity of dendrimer films at air-water interface. In AFM images. the larger domains irregularly shaped structures on the top while the smaller ones were free from such defects. In conclusion, it is demonstrated that the metal ion around dendrimer and polymer included crown function group can contribute to make formation of network structure among crown function group and result in change of electrical properties.s.s.

• The Transactions of the Korean Institute of Electrical Engineers C
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• v.52 no.5
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• pp.213-218
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• 2003

We investigated the monolayer behavior at the air-water interface with metal solution, the surface morphologies and the electrical properties such as conductivity, The calculated conductivity values of pure water subphase and its complexes with L $i^{+}$ ions are 5.6$\times$10$^{-l6}$ and 1.9$\times$10$^{-14}$ [S/cm], respectively. And the calculated barrier height D values of pure water subphase and its complexes with Li. ions are 0.70 and 0.66 [eV], respectively. We also attempted to fabricate a crown dendrimer Langmuir-Blodgett (LB) films containing functional end group that could form a complex structure with metal ions. Also, we investigated the surface activity of dendrimer films at air-water interface. In AFM images. the larger domains irregularly shaped structures on the top while the smaller ones were free from such defects. In conclusion, it is demonstrated that the metal ion around dendrimer and polymer included crown function group can contribute to make formation of network structure among crown function group and result in change of electrical properties.s.s.

• Bulletin of the Korean Chemical Society
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• v.31 no.11
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• pp.3445-3447
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• 2010

• Journal of the Korean Chemical Society
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• v.38 no.7
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• pp.529-532
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• 1994

• Bulletin of the Korean Chemical Society
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• v.26 no.8
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• pp.1306-1308
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• 2005

• Bulletin of the Korean Chemical Society
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• v.14 no.1
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• pp.123-127
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• 1993

New lipophilic Crown-4 compounds of 16-membered rings containing furan (neutral carrier,I), tetrahydrofuran (neutral carrier,II) and lithium complex of the latter (neutral carrier,III) have been synthesized and tested as the active sensors for lithium ion in poly(vinyl chloride) (PVC) membrane electrode, in the presence and absence of an anion excluder, tetrakis(4-chloro-phenyl)borate (KTClPB), 2-nitrophenyl phenyl ether (NPPE), tris(2-ethylhexyl)phosphate (TEHP), o-nitrophenyl octyl ether (NPOE), dioctyl adipate (DOA), bis(2-ethylhexyl)adipate (BEHA), di-n-octylphenyl phosphonate (DOPP) were used as plasticizing solvent mediators. The electrode response function had a nearly Nernstian slope of 54-61 mV per decade (25$^{\circ}$C) within the concentration range of $10^{-1}-10^{-4}$ M LiCl and the detection limits for all electrodes were ca. $5{\times}10^{-4}$ M. The response time of the electrode was faster at the higher lithium concentration and the response of the electrode was stable for longer than 6 months. The sensor membranes exhibit improved response times and increased lifetimes as compared to the system described earlier.