• Analytical Science and Technology
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• v.10 no.5
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• pp.370-377
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• 1997

The several fundamental parameters on the solvent extraction of Co(II), Cu(II) and Zn(II) with dithizone were investigated. The value of $K_{a1}/K_p$ of dithizone(at $25^{\circ}C$) between an aqueous phase and a chloroform was found to be $4.72{\times}10^{-11}$. And the mole ratios of metal ion to dithizone in its metal complexes were determined by mole ratio method. The extractibilities(%) for metal-dithizone chelates were obtained from the extraction equilibria of metal-dithizone complexes between an aqueous phase and a chloroform as follows. Co(II) : 92.3% at pH 8.0 : Cu(II) : 97.1% at pH 4.0 and Zn(II) : 99.0% at pH 7.0. And also, in optimum experimental conditions the extraction constants of Co(II), Cu(II) and Zn(II) were examined.

• Journal of the Korean Chemical Society
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• v.42 no.1
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• pp.36-41
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• 1998

In this study, the extraction of Co(Ⅱ) and Cu(Ⅱ) into chloroform solution of dithizone, distribution ratios, extractabilities and extraction rate constants of the metal complexes were compared in each case with which thiocyanate ion was or not used as the auxiliary ligand. The use of the thiocyanate ion increased threefold the distribution ratio for Co(Ⅱ) complex in a basic solution and twofold for Cu(Ⅱ) complex in a wide pH range. And the extractability was also augmented from about 90 to 99 for Co(Ⅱ) and from 95 to 99 for Cu(Ⅱ) in a given period. The extraction rate constants were $k_1\;:\;1.2{\times}10^5$, $k_2\;:\;1.34{\times}10^{17}\; mol^{-1}dm^3s^{-1}$ in case of Co(Ⅱ) and$k_1\;:\;1.1{\times}10^8$, $k_2\;:\;2.83{\times}10^{10}\; mol^{-1}dm^3s^{-1}$ in case of Cu(Ⅱ) on the extraction of dithizonate complexes into chloroform solution.

• Elastomers and Composites
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• v.40 no.3
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• pp.174-180
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• 2005

Sonochemical synthesis of fullerene oxides $[C_{70}O_n](n=1{\sim}2)$ by fullerene$[C_{70}]$ and metal hexacarbonyl complexes $M(CO)_6$(M=Cr, Mo, W) took place under air atmosphere. The reactivity of fullerene$[C_{70}]$ and several metal hexacarbonyl complexes $M(CO)_6$(M=Cr, Mo, W) under same ultrasonic condition increased in the order of $Mo(CO)_6$ > $W(CO)_6$ > $Cr(CO)_6$. The MALDI-TOF-MS, UV-visible spectra, and HPLC analysis confirmed that the products of sonochemical reaction were $[C_{70}O_n](n=1{\sim}2)$.

• Journal of the Korean Chemical Society
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• v.36 no.4
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• pp.523-535
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• 1992

The conformations of hexapeptides, their complexation with alkali cations and the inhibition of the cation transport by 5,5-diphenylhydantoin(DPH) were studied theoretically using ECEPP/2 and MM2 force field. Several low energy conformations of uncomplexed cyclic hexapepides are obtained, and they adopt compact conformations in which most amide hydrogens form intramolecular hydrogen bond to amide carbonyl oxygens. The complexation energy of the peptide with $Na^+$ ion and DPH is -60 kcaal/mol and -18 kcal/mol, respectively. However, no suitable cavity to bind metal cation exists for the local minima of the peptide, and the internal energy of the uncomplexed hexapeptide having cavity is higher than that of the uncomplexed global minimum of this work by 10 kcal/mol. Also, one of the most important amino acid residue to bind DPH is Glycine, and this can explain experimental observation that the replacement of Gly by Sarcosine (N-methyl Glycine) reduce the inhibition ability of the cation transport.

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.669-673
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• 1992

The stability constants, K for the complexation of alkali metal cations(Li^+, Na^+, K^+, Rb^+, and Cs^+) with both 4,5: 13,14-dibenzo-6,9,12-triaza-bicyclo [15,3,1] heneicosa-1 (21),7,19-trioxa-2,16-dione (DBPDA) and 6,9,12-trioxa-3,15,21-triaza bicyclo [15,3,1] heneicosa-1 (21),17,19-triene-2,16-dione (PDA) in N,N-Dimethylformamide (DMF) were determined conductomatically at various temperatures. At all the experiment temperatures, the K value sequences of the alkali metal ions with DBPDA and PDA are Cs^+ > K^+ > Rb^+ > Li^+ > Na^+ and Cs^+ > K^+ > Rb^+ > Li^+ > Na+, respectively. The K values for DBPDA are larger those of PDA for alkali metal ions. The widely recounted "hole-size-selectivity" principle is not applicable to these complexation systems. From the K values obtained at different temperatures, {\delta}H and T{\delta}S for these complexation reactions were determined. The enthalpy change plays principal important role in the complex formation by DBPDA. However, in the case of PDA, the entropy change also contributes to its complex formation.

• Journal of the Korean Chemical Society
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• v.43 no.2
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• pp.161-166
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• 1999

Transfer of lanthanide ions across the liquid/liquid interface facilitated by ionopore ETH4120 has been studied by using cyclic voltammetry (CV) and chronopotentiometry with cyclic linear current-scanning (CPCLCS) under the condition where the concentration of ETH4120 in nitrobenzene was much smaller than the concentration of lanthanide ions in aqueous solution. One cathodic current peak (transfer from aqueous to nitrobenzene phase) and two anodic current waves (transfer from nitrobenzene to aqueous phase) were observed. The cathodic wave was due to the formation of 1:1 (metal:ligand) complex and two anodic waves showed successive formation of 1:2 and 1:3 complexes in nitrobenzene solution. But there was no cathodic wave corresponding to two anodic waves. The ion transfer mechanism has also been discussed.

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.679-684
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• 1992

New Pd(IV) complexes have been prepared through the reactions of $trans-[Pd(en)_2Cl_2](ClO_4)_2 $(en = ethylenediamine) with Guanine, Adenine, or Uracil anion as purine and pyrimidine base. We identified the ratio of central metal versus ligands by $C{\cdot}H{\cdot}N$ elemental analysis and proposed the coordinating site of the base by infrared spectrum, $^1H-NMR,\; and\; ^{13}C$-NMR spectrum. Guanine or Adenine ligand coordinated at N7 site and an en ligand exchanged for $ClO_4^-$ counter ions of the starting material . As these results, the complexes showed the formula $[Pd(en)L_2(ClO_4)_2](ClO_4)_2{\cdot}(en)$, (L = Guanine, Adenine). But in the Uracil complex no exchange of the en ligand and $ClO_4^-$ occured and Uracil anion preferred the N1 to N3 as coordinating site, the complex $[Pd(en)_2(Urac)_2](ClO_4)_2(Urac = Uracil anion).$

• Journal of the Korean Chemical Society
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• v.25 no.6
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• pp.394-398
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• 1981

Two types of Ni(II)-polyethyleneimine (PEI) complexes, [Ni(PEI)]$Cl_2$ and [Ni(P-EI)$Cl_2$] were synthesized and their catalytic activities in the decomposition reaction of hydrogen peroxide were investigated. For the purpose of comparison, the corresponding monomeric complexes, $[Ni(en)_3]Cl_2$ and $[Ni(en)_2Cl_2$ were also prepared; it was observed that their activities increase in the following order; $0{\approx}[Ni(en)_3]Cl_2{\le}[Ni(en)_2Cl_2]<[Ni(PEI)]Cl_2<[Ni(PEI)Cl_2]$ On the basis of structural analysis by means of visible and infrared spectroscopy, the catalytic activiy of these Ni(II)-PEI complexes is assumed to depend on the bond strength between the ligand and the nickel ion.

• Journal of the Korean Chemical Society
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• v.14 no.1
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• pp.91-96
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• 1970

Formation of the complexes of manganese, zinc and cobaltous ions with citrate ions in aqueous, ethanol-water (20% by volume) and acetone-water (20% by volume) solutions was studied at room temperature by the equilibrium exchange technique. The pH of the solutions was controlled to 7.0-7.4, and the ionic strength of the solutions was kept at approximately 0.10. The results of the present study indicated that both $Mn^{++}\;and\;Zn^{++}$ formed one to one citrate-compexes, [M Cit]$^-$, in all the solvent systems examined, and that $Co^{++}$ formed one to one citrate-complex in aqueous solution but formed both one to one citrate-complex, [Co Cit]$^-$, and one to two citrate-complex, $[Co\;Cit_2]^{4-}$, in the mixed solvent systems mentioned above. It was also observed that the citrate-complexes of the transition metals examined were more stable in the mixed solvent systems than in water.

• Journal of the Korean Chemical Society
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• v.38 no.7
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• pp.485-495
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• 1994

Several new symmetric and asymmetric homo and hetero dinuclear complexes of the type $[Cl(dppp)(NO)_2M({\mu}-pyz)M'(NO)_2(dppp)Cl][ClO_4]_2$ and $[Cl(phen)(NO)_2M({\mu}-pyz)M'(NO)_2(dppp)Cl][ClO_4]_2$(M,M'= Mo or W; phen = 1,10-phenanthroline; dppp = 1,3-bis(diphenylphosphino)propane; pyz = 1,4-pyrazine) were synthesized in three-steps starting from $[M(NO)_2Cl_2]_n(M = Mo, W)$. The final products were purified by eluting it through silica gel column ($2{\times}20$ cm) with acetone as the eluent. Characterization of these complexes and some related complexes was accomplished through UV-vis., $^1H$-NMR, $^{13}C$-NMR and IR spectroscopies as well as elemental analysis. The infrared spectra indicate that the NO groups occupy cis-positions of the octahedral. The $^1H$ and $^{13}C-NMR$ data for the new compounds revealed a dimeric structures with bridged pyz.