• Journal of the Korean Chemical Society
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• v.43 no.3
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• pp.257-263
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• 1999

Ln-macrocyclic([20]DOTA) complexes, [Ln([20]DPTA)(NO_{3})(H_{2}O)](NO_{3})_{2} \cdotxH_{2}O{Ln(III)=Pr, Sm, Gd, Dy}, which had been synthesized from 2, 6-diformyl-p-cresol(DFPC), was placed in methanol for 2 days, and $[Ln([20]DPTA)(NO_{3})(CH_{3}OH)]^{2+}$ was formed. The equilibrium constants(L) for the substitution of coordinated $CH_{3}OH$ in the Ln-[20]DOTA complexes by various auxiliary ligands, $L_{a}(=monodentate ligands; pyridine, imidazole, triethylamine, diethylamine, piperidine) were determined spectroscopically at $25^{\circ}C$ and 0.1M. The pKa of auxiliary ligand is in the order of pyridine < imidazole < triethylamine < diethylamine < piperidine, however the K has shown the trend of pyridine < imidzole < diethylamine < piperidine < triethylamine.

• Journal of the Korean Chemical Society
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• v.36 no.6
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• pp.840-848
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• 1992

An ionizable macrocyclic ligand, diaza-18-crown-6-diisopropionic acid(K22DAP) has been synthesized. Protonation constants of this compound and stability constants with some lanthanides were determined by potentiometric titration method. The protonation constants are log$K_1$ = 9.05, log$K_2$ = 8.37, log$K_3$ = 1.88 and log$K_4$ = 0.99. The logarithmic values of stability constants with La(III), Nd(III), Gd(III) and Lu(III) are 11.14, 11.43, 11.74 and 10.88 respectively. Extraction behavior of Ln(III) ion was investigated using TTA(thenoyltrifluoroacetone) as extractant in the presence of K22DAP as macrocyclic ionophore. It was observed that Ln(K22DAP)TTA is the dominating species in aqueous complexes of La(III) and Nd(III).

• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1747-1751
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• 2006

The dinuclear tetraazadiphenol macrocyclic nickel(II) complexes [$Ni_2$([20]-DCHDC)]$Cl_2$ (I), [$Ni_2$([20]-DCHDC)]$(ClO_4)_2{\cdot}2CH_3CN $ (II(b)) and [$Ni_2$([20]-DCHDC)$(NCS)_2$] (III) {$H_2$[20]-DCHDC = 14,29-dimethyl-3,10,18,25-tetraazapentacyclo-[25,3,1,$0^{4,9}$,$1^{12,16}$,$0^{19,24}$]ditriacontane-2,10,12,14,16(32),17,27(31), 28,30-decane-31,32-diol} have been synthesized by self-assembly and characterized by elemental analyses, conductances, FT-IR and FAB-MS spectra, and single crystal X-ray diffraction. The crystal structure of II(b) is determined. It crystallizes in the monoclinic space group P2(1)/c. The coordination geometries around Ni(II) ions in I and II(b) are identical and square planes. In complex III each Ni(II) ion is coordinated to $N_2O_2$ plane from the macrocycle and N atoms of NCS- ions occupying the axial positions, forming a square pyramidal geometry. The nonbonded Ni…Ni intermetallic separation in the complex II(b) is 2.8078(10) $\AA$. The FAB mass spectra of I, II and III display major fragments at m/z 635.1, 699.4 and 662.4 corresponding to [$Ni_2$([20]-DCHDC)(Cl + 2H)]$^+$, [$Ni_2$([20]-DCHDC)$(ClO_4\;+\;2H)]^+$ and [$Ni_2$([20]-DCHDC)(NCS) + 6H]$^+$, respectively.

• Journal of the Korean Applied Science and Technology
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• v.32 no.1
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• pp.31-39
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• 2015

The synergistic solvent extraction of rare earth elements such as europium and yttrium has been investigated by the extractant with crown ether as an additive. Macrocyclic ligand as host-guest compounds form more stable complexes with metal ions which have the similar size of the cavity of crown ether. In our previous study[14] founded that the extraction used fatty acid of the various alkyl chain length. Based on the results of the previous experiment, the synergistic separation effect of two metals investigated that the hexanoic acid had was the worst extraction effect which added a crown ether such as 18-crown-6 ether, 15-crown-5 ether, and 12-crown-4 ether. In this study, the concentrations of hexanoic acid have showed the separation effect, and then the concentrations and kind of crown ether are performed for synergistic extraction at the hexanoic acid concentration of the highest separation effect. As a results, the separation rate is the highest value of 1.72 at 0.05 M hexanoic acid, and 0.002M 15-crown-5 ether is the best value in other concentrations and kind of crown ether, it is about twice of using only hexanoic acid. Moreover, the extraction species of two metals has been founded $MLR_3{\cdot}3RH$ form when added the crown ether.

• Journal of environmental and Sanitary engineering
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• v.15 no.1
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• pp.25-33
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• 2000

The new ion exchange resin was synthesized from chloromethylated styrene-1,4-divinylbenzene(DVB) with 1-aza-15-crown-5 macrocyclic ligand by substitution reaction. The effect of pH, time, dielectric constant of solvent and cross-linked of the matrix on the adsorption for $UO_2^{2+}$, $Ca^{2}$ and $Lu^{3+}$ was investigated. The metal ion was not adsorbed on the resins below pH 3 but above pH 4 fast adsorption behavior was showed. The optimum equilibrium time for adsorption of metallic ions was two hours. The adsorption selectivity determined in ethanol matrix was in increasing order $UO_2^{2+}>Ca^{2}>Lu^{3+}$. The adsorption power was in the order of 1%, 2%, 10% and 20% -crosslinked resin, but adsorption properties of resins decreased in proportion to the order of dielectric constant of solvents used. In addition, these metal ions could be separated in the column packed with 1% crosslinked resin by pH2.5 $HNO_3$ as an eluent.

• Bulletin of the Korean Chemical Society
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• v.24 no.3
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• pp.269-273
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• 2003

The synthesis and properties of 2,13-bis(3'-pyridylmethyl) $(L^3)$, 2,13-bis(4'-pyridylmethyl) $(L^4)$, and 2,13-bis(phenylmethyl) $(L^5)$ derivatives of 5,16-dimethyl-2,6,13,17-tetraazatrcyclo$[16.4.0.^{1.18}0^{7.12}]$docosane are reported. The 3- or 4-pyridylmethyl groups of $[ML^3](ClO_4)_2\;or\;[ML^4](ClO_4)_2$ (M = Ni(Ⅱ) or Cu(Ⅱ)) are not involved in coordination, and the coordination geometry (square-planar) and ligand field strength of the complexes are quite similar to those of $[ML^5](ClO_4)_2$, bearing two phenylmethyl pendant arms. However, the complex formation reactions of $L^3\;and\;L^4$ are strongly influenced by the pyridyl groups, which can interact with a proton or metal ion outside the macrocyclic ring. The macrocycle $L^5$ exhibits a high copper(Ⅱ) ion selectivity against nickel(Ⅱ) ion; the ligand readily reacts with copper(Ⅱ) ion to form $[CuL^5]^{2+}$ but does not react with hydrated nickel(Ⅱ) ion in methanol solutions. On the other hand, $L^3\;and\;L^4$ form their copper(Ⅱ) and nickel(Ⅱ) complexes under a similar condition, without showing any considerable metal ion selectivity. The ligands $L^3\;and\;L^4$ react with copper(Ⅱ) ion more rapidly than does $L^5$ at pH 6.4. At pH 5.0, however, the reaction rate of the former macrocycles is slower than that of the latter. The effects of the 3- or 4-pyridylmethyl pendant arms on the complex formation reaction of $L^3\;and\;L^4$ are discussed.

• Bulletin of the Korean Chemical Society
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• v.12 no.5
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• pp.474-477
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• 1991

The preferential transport phenomena of neutral cation-anion moieties in neutral macrocycle-facilitated emulsion liquid membrane were described in this study. Emulsion membrane systems consisting of (1) aqueous source phase containing 0.001 M M($NO_3$)$_2(M=Mn^{2+},\;Co^{2+},\;Ni^{2+},\;Cu^{2+},\;Zn^{2+},\;Sr^{2+},\;Cd^{2+},\;and\;Pb^{2+})$ (2) a toluene membrane containing 0.01 M ligand $(DBN_3O_2$, DA18C6, DT18C6, TT18C6, HT18C6) and the surfactant span 80 (sorbitan monooleate) (3% v/v) and (3) an aqueous receiving phase containing $Na_2S_2O_3$ or $NaNO_3$ were studied with respect to the disappearence of transition metal ions from the source phase as a function of time. Cation transports for various two component or three component equimolar mixture of transition metal and $Cu^{2+}$ in a emulsion membrane system incorporating macrocyclic ligand (HT18C6) as carrier were determinded. $Cu^{2+}$ was transported higher rates than the other $M^{2+}$ in the mixture solution. Equilibrium constants for cation-source phase co-anion, cation macrocycle and cation-receiving phase reagent interaction are examined as parameters for the prediction of cation transport selectivities.

• Bulletin of the Korean Chemical Society
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• v.11 no.3
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• pp.206-208
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• 1990

Cu(II) hexaazamacrotricyclic complexes $[Cu(L)](ClO_4)_2$ and $[(Cu(L)Cl]ClO_4$, where L = 1,3,6,9,11,14-hexaazatricyclo$[12.2.1.1^{6,9}]octadecane(L_1)$ or 1,3,6,10,12,15-hexaazatricyclo$[13.3.1.1^{6,10}]eicosane(L_2)$, have been prepared by the simple template condensation reactions of triamines, diethylenetriamine for $L_1$, and N-(2-aminoethyl)-1,3-propanediamine for $L_2$, with formaldehyde in the presence of $Cu(OAc)_2\;or\;CuCl_2$. The Cu(II) complexes of $L_1$ contain two 1,3-diazacyclopentane ring moieties and those of $L_2$ contain two 1,3-diazacyclohexane ring moieties that are fused to the 14-membered macrocyclic framework. Spectra indicate that complexes $[Cu(L)](ClO_4)_2\;and\;[Cu(L)Cl]ClO_4$ have square-planar and square-pyramidal chromophores, respectively. square-planar $[Cu(L)](ClO_4)_2$ are remarkably stable against ligand dissociation in acidic aqueous solutions. Square-pyramidal $[Cu(L)Cl]ClO_4$ complexes dissociate their axial Cl-ligands easily in aqueous solutions to form $[Cu(L)H_2O]^{2+}$ species. Infrared and UV/vis absorption spectra of the Cu(II) complexes reveal that Cu-N interactions and the ligand field strengths are significantly weaker in the complexes of $L_2$ than in the complexes of $L_1$.

• Journal of the Korean Chemical Society
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• v.31 no.5
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• pp.434-443
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• 1987

The formation constants of the complexes between Ln-EDTA 1 : 1 complex and IMDA have been investigated by a potentiometric titration method at 20.0${\pm}$0.2 degree C and ${\mu}$ = 0.1 (KNO$_3$). Unusually large stability in Ln(EDTA) mixed ligand complexes was found. Trends in the formation constants vs. atomic number of the lanthanide metals were discussed on the basis of coordination number and ionic radius of the metals.

• Journal of environmental and Sanitary engineering
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• v.17 no.1
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• pp.63-68
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• 2002

Amount of styrene and divinylbenzene(DVB) was adjusted under injection of nitrogen, copolymer having crosslink of 1%, 2% and 5% was synthesized and zinc chloride was added to it. Put into benzene, swell it, add potassium iodide and 1-aza-15-crown-5 of 21.93g in toluene solution and functional resin which can adsorb heavy metal ions by stir reflex at $55^{\circ}C$ for 30 hours was synthesized. The content of divinylbenzene of this resin was increased as crosslink increase, macroporous gets smaller and the content of chlorine was reduced, which affects macrocyclic ligand in the process of substitution and content of nitrogen was also reduced. And the form of functional synthetic resin was distorted by substitution reaction of hydrogen and chlorine atoms.