• Journal of the Korean Chemical Society
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• v.35 no.2
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• pp.119-127
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• 1991

The protonation and the metal ion complexation of 15 to 18 membered diaza crown ether such as 1,12-diaza-3, 4 : 9, 10-dibenzo-5, 8-dioxacyclopentadecane(NtnOenH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-hydroxy-5,9-dioxacyclohexadecane(NtnOtnH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-15-hydroxy-5,9-dioxacyclohexadecane(Ntn(OH)OtnH$_4$), 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdienH$_4$) and 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane(NtnOdienH$_4$) were studlied by potentiometry and NMR spectroscopy. The protonation constants were used to predict basicity of crown ethers. The sequence of the basicity was NenOdienH$_4$ < Ntn(OH)OtnH$_4$ < NtnOenH$_4$ < NtnOtnH$_4$ < NtnOdienH$_4$. Changes on the basicity were explained in terms of the effects of substituents and the degree of twistness of the macrocyclic ring. The sequence of the complex stabilities were Co(II) < Ni(II) < Cu(II) < Zn(II) for the transition metal complexes and Cd(II) < pb(II) < Hg(II) for the post-transition metal complexes. These changes on the stabilities were dependent on the basicity of the ligand and cavity size of the ring. For the heavy post-transiton metal complexes and Zn(Ⅱ) complex, the former factor was predominent and for the other transition metal complexes, the latter was affected on the stabilities. $^1$H and $^{13}$C-NMR studies for heavy post-transition metal complexes indicated that the nitrogen atom has greater affinity on metal ions than oxygen atom and the planarity of the rings was losed by the complexation with metal ions.

• Analytical Science and Technology
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• v.14 no.6
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• pp.530-534
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• 2001

Effect of stripping solutions on the Duolite GT-73 chelating resin for ten elements, Ag(I), Al(III), Ca(II), Cd(II), Cu(II), Fe(II), Hg(II), Mn(II), Pb(II), and Zn(II), was investigated. Relation between affinities of the metal ions and solubility products of metal sulfides was studied. The smaller the solubility product of metal sulfideis, the larger the affinitie with the ionsis. The ions which have the solubility products larger than $10^{-23}$ could be effectively desorbed with nitric acid. Complexation with chloride ion enhanced the desorption efficiencies of the ions having moderately strong affinity with the resin. The ions which have very strong affinity by the chelating resin can be desorbed by complextion with thiourea and hydrochloric acid.

• Journal of the Korean Chemical Society
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• v.41 no.2
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• pp.77-81
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• 1997

The transport rates of transition metal cations were increased in order of Ni(II)$(NtnOenH_4)$and 1,12,15-triaza-3,4;9,10-dibenzo-5,8-dioxacyclo-heptadecane$(NdienOenH_4)$as carriers. The transport rates of transition metal cations was found to be of first order to the salt concentrations. It was also found that the dissociation process in the transport process is rate determining step. From the measurements of the transport rates at various temperatures, the partition free energies of hydration$({\Delta}G_p)$for the transition metal cations were calculated. The results showed that the order of transport rates of transition metal cations was found to be proportional to the magnitudes of negative value of the partition free energies of hydration$({\Delta}G_p)$.

• Journal of the Korean Chemical Society
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• v.26 no.5
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• pp.265-273
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• 1982

The effect of ${\pi}$ bonds on the calculated dipole moments for square planar and tetrahedral [M(II)$O_2S_2$]] type complexes has been investigated by two different approaches. One is the approximate molecular orbital method based on the assumption that the mixing coefficient CM of the valence basis sets for the central metal ion and the appropriate ligand orbitals is equal for all ${\sigma}$ and ${\pi}$ bonding molecular orbitals. The other is the more refined calculation based on the semiempirical LCAO-MO method. If ${\sigma}$ bonds only are assumed to be formed, the calculated dipole moments for square planar and tetrahedral complexes are lower than those of the experimental values. If the contribution of ${\pi}$ bonds to the calculated dipole moments are fully considered, the calculated dipole moments for both square planar and tetrahedral [M(II)$O_2S_2$]] type complexes are higher than the experimental values. However if ${\pi}$ bonds are assumed to be delocalzed, the calculated dipole moments for tetrahedral [M(II$O_2S_2$]] type complexes fall in the range of the experimental values, but those for square planar complexes deviate from the experimental values. These results suggest that [M(II)$O_2S_2$]] type complexes may have the tetrahedral structure in inert solvent solution. This structure is in agreement with the experimental one. The calculated dipole moments for tetrahedral [M(II)$O_2S_2$]] type complexes indicate that the contribution of ${\pi}$ bonds to the calculated dipole moments may not be neglected.

• Journal of the Korean Chemical Society
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• v.32 no.1
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• pp.22-29
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• 1988

The reaction of methanol-water mixture to $CO_2$ and $H_2$ on alkaline earth metal-copper-zinc oxide has been studied in the temperature range of 150 ${\sim}\;300^{\circ}C$. Generally the addition of the alkaline earth metal to Cu/ZnO resulted in an enhancement of selectivity for $CO_2$ formation and a reduction of catalytic activity. Measurable activities were found from 150$^{\circ}C$, 200$^{\circ}C$, and 250$^{\circ}C$ on Mg/Cu/ZnO, Ca/Cu/ZnO, and Ba/Cu/ZnO respectively. However, the highest selectivity for $CO_2$ formation was observed in Ba/Cu/ZnO catalyst at 250$^{\circ}C$. The effect of alkaline earth metal or ZnO on the reactivity was investigated using temperature programmed desorption of $CO_2$ or temperature programmed reduction with $H_2$ over catalysts respectively. It was found that $CO_2$ interacts more strongly in the sequence of MgO < CaO < BaO and ZnO decereases the reduction temperature of CuO. From the results, it was suggested that ZnO activates $H_2$ in the redox process of Cu component and alkaline earth metals adsorbs $CO_2$ in the catalytic process.

• Journal of the Korean Chemical Society
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• v.65 no.2
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• pp.93-105
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• 2021

Mononuclear Cu(II), Ni(II), Co(II), Mn(II), Zn(II), Fe(III), Ru(III), and UO2(II) complexes of 2-hydroxy-4-(p-tolyldiazenyl)benzylidene)-2-(p-tolylamino)acetohydrazide (H2L) were prepared by direct method. The ligand and its complexes were isolated in solid state and characterized by analytical techniques such as elemental and thermal analyses, molar conductance, magnetic susceptibility measurements and spectroscopic techniques such as UV-Visible, IR, 1H-NMR and 13C-NMR. The spectral data indicated that the ligand acted as neutral/monobasic bidentate or monobasic/dibasic tridentate ligand bonded to the metal ions through the oxygen atom of ketonic or enolic carbonyl group, azomethine nitrogen atom and deprotonated/protonated phenolic oxygen atom forming either tetragonally distorted octahedral or octahedral. Antimicrobial activities of the ligand and its complexes were evaluated against Escherichia coli, Bacillus subtilis and Aspergillus niger by well diffusion method. The results of antifungal activity showed that the Fe(III) complex (10) exhibited higher antifungal against Aspergillus niger than the other complexes. However, the results of antibacterial activity revealed that Cu(II) complex (4) is the most active against Escherichia coli while the Cu(II) complex (5) and Fe(III) complex (10) exhibited higher antibacterial effect on Bacillus subtilis than the other complexes.

• Korean Journal of Environmental Agriculture
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• v.6 no.1
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• pp.25-30
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• 1987

This study was conducted to find out the effect of several improvers such as triple super phosphate, slaked lime, wollastonite and gypsum for reducing Cd content in brown rice. Several improvers were applied to two different types of soils which are contaminated with copper-zinc mine wasted and sludge.(Soil I contained Cd : 7.88, Cu : 57.9, Zn : 175.0 ppm, Soil II contained Cd : 3.95, Cu : 30.2, Zn :124.0 ppm) In general, effects of improvers on reducing content of Cd, Cu and Zn in brown rice were greater in soil I than soil II. In soil I, the Cd content of brown rice was reduced to 0.4ppm below by application of triple superphosphate, fused phosphate, slaked lime and gypsum, 98, 225, 190 and 276Kg/10a, respectively. Triple superphosphate was more effective than fused phosphate in reducing uptake of Cd, Cu and Zn by applying them as an equal amount of phosphorous, also to equal alkalinity, slaked lime had the highest effect. Negatively linear effect was found between soil pH and Cd and Zn content in brown rice. As to above results, it was no doubt that triple superphosphate, fused phosphate and slaked lime would be applied to reduced heavy metals in brown rice. The slaked lime, triple super phosphate and fused phosphate were available to reduce uptake of Cd, Cu and Zn by rice plant grown in the soil contaminated with mine waste and sludge.

• Journal of the Korean Chemical Society
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• v.8 no.2
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• pp.62-64
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• 1964

The cation exchange chromatographic studies for the analysis of transition metals have been described. The quantitative separation of a mixture of Fe(Ⅲ), Cu(II), Zn(II), Ni(II), Cd(II), Co(II) and Mn(II) has been obtained by elution, through a 28cm column of the resin, Dowex 50 ${\times}$ 4 (100∼200 mesh), using 0.45 M $NaNO_3$+0.05 M Na-tartrate solution as eluent, starting with the eluent of pH 3.5, followed stepwise by pH 4.0 and 4.5. A comparison between the calculated and the observed peak positions in the elution curve has been shown. The relative stability constants for tartrate complexes of some transition metals have been calculated by using distribution ratios obtained in this separation procedure.

• Bulletin of the Korean Chemical Society
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• v.34 no.10
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• pp.2900-2904
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• 2013

We present the synthesis and characterization of DTPA-bis(histidylamide) (1a), DTPA-bis(aspartamide) (1b), and their gadolinium complexes of the type $[Gd(L)(H_2O)]$ (2a:L = 1a; 2b:L = 1b). Thermodynamic stabilities and $R_1$ relaxivities of 2a-b compare well with Omniscan$^{(R)}$, a well-known commercial, extracellular (ECF) MRI CA which adopts the DTPA-bis(amide) framework for the chelate: $R_1$ = 5.5 and 5.1 $mM^{-1}$ for 2a and 2b, respectively. Addition of the Cu(II) ion to a solution containing 2b triggers relaxivity enhancement to raise $R_1$ as high as 15.3 $mM^{-1}$, which corresponds to a 300% enhancement. Such an increase levels off at the concentration beyond two equiv. of Cu(II), suggesting the formation of a trimetallic ($Gd/Cu_2$) complex in situ. Such a relaxivity increase is almost negligible with Zn(II) and other endogenous ions such as Na(I), K(I), Mg(II), and Ca(II). In vivo MR images and the signal-to-noise ratio (SNR) obtained with an aqueous mixture of 2b and Cu(II) ion in an 1:2 ratio demonstrate the potentiality of 2 as a copper responsive MRI CA.

• YAKHAK HOEJI
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• v.5 no.1
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• pp.3-5
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• 1960

Trace elements in deer horn have been determined Ca, Mg, Fe, Cu, Zn, Mn, Al and as were detected by partition paper chromarography and spectroscopic method.