• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.573-576
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• 2009

The reaction of $(en)Pd(NO_3)_2$ (en = ethylenediamine) with 1,4-bis(dimethyl-4-pyridylsilyl)benzene (L) affords cyclodimer, $[(en)Pd(L)]_2(NO_3)_4$, whereas the reaction of $(tmeda)Pd(NO_3)_2$ (tmeda = N,N,N’,N’-tetramethylethylenediamine) with L gives cyclotrimer, $[(tmeda)Pd(L)]_3(NO_3)_6$. Both complexes exist as catenane in water. The catenated cyclodimer is rigid whereas the catenated cyclotrimer is dynamic in water. The catenated cyclotrimers afford hydrogel containing 98.5% water below 2 ${^{\circ}C}$. The hydrogel changes to its sol around 38 ${^{\circ}C}$, and to its clear solution at 78 ${^{\circ}C}$. Such a notable difference between $[(en)Pd(L)]_2(NO_3)_4$ and $[(tmeda)Pd(L)]_3(NO_3)_6$ might be explained by their different dynamic behavior via ring size effects.

• Bulletin of the Korean Chemical Society
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• v.9 no.5
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• pp.292-295
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• 1988

Macrocyclic ligands have been studies as cation carriers in a bulk liquid membrane system. $Cu^{2+}$ has been transported using nitrogen substituted macrocycles as carriers and several transition metal ions($M^{n+}\;=\;Mn^{2+},\;Co^{2+},\;Ni^{2+},\;Cd^{2+},\;Pb^{2+}\;and\;Ag^{+}$) have been transported using $DBN_3O_2,\;DBN_2O_2,\;Me_6N_414C4$ and DA18C6 as carriers in a bulk liquid membrane system. Competitive $Cu^{2+}-M2^+$ transport studies have also been carried out for the same system. In single cation transport experiments, the best macrocyclic ligand for transport is a ligand that gives a moderately stable rather than very stable complex in the extraction. However, when both cations are present in the source phase, the cation which forms the most stable complex with carrier is favored in transport over other cations. Generally, the nitrogen substiituted macrocycles transport $Cu^{2+}$ selectively over $Mn^+$. Ligand structure, equilibrium constant (or stability constant) for complex formation, source phase pH and carrier concentration are also important parameters in transport experiments.

• Journal of the Korean Chemical Society
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• v.39 no.6
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• pp.440-445
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• 1995

The chemical compositions and stability constants, thermodynamic parameters for the neodymium(Ⅲ) complexes of substituted benzo-1,4,7,10,13-pentaoxacyclopentadecane(B15C5) have been determined by spectrophotometry and conductometry in methanol solution at various temperatures. As substituents, CH3, Br, CHO, NO2, and 3,4-(NO2)2 were used. In methanol solution the ratios of neodymium(Ⅲ) to the ligands in the complexes are 1 : 1. The stability constants were increased in order of B15C5-3,4-(NO2)2 < B15C5-NO2 < B15C5-CHO < B15C5-Br < B15C5 < B15C5-CH3. This observation can be explained in terms of the substituent effect. The order of stability constants was dimethylsulfoxide < acetone < acetonitrile in solution and the magnitudes were found to be inversely proportional to the solvents donicities. These results could be understood in terms of solvent basicity, ligand basicity, solvation of the cation, and entropy changes of complex formation.

• Korean Journal of Materials Research
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• v.11 no.3
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• pp.185-190
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• 2001

The effect of neutral ligand(L) on the precursor characteristics of (hfac)Cu(I)-L and on Cu MOCVD Process was studied. The neutral ligands of (hac)Cu(I)-L$_{x}$, such as ATMS(allytrimethylsilane), VTMS(vinyltrimethylsilane), VCH(vinylcyclohexane), MP(4-methyl-1-pentene), ACP(allylcyclopentane), and DMB(3,3-dimethyl-1-butene) were investigated. When the dissociation temperature of Cu(I)-L bond is low, low temperature deposition below $100^{\circ}C$ is possible and the resistivity of the film is low. But thermal stability of the precursor is low in this case. The resistivity is almost the same regardless of L at the deposition temperature range of $125~175^{\circ}C$. The resistivity is increased as the molecular weight of L becomes higher above $225^{\circ}C$ The vapor pressure of the precursor was closely related to the boiling point of L, the lower the boiling point of L, the higher the vapor pressurere.

• Korean Journal of Environmental Agriculture
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• v.14 no.3
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• pp.263-271
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• 1995

Chemical assessment of soil pollution with heavy metals was made by analyzing the changes in pH, ionic strength, cationic concentration and chemical species in the soil solution. Saturated pastes of the unpolluted soils were made by adding solutions containing Cu or Cd and the final Cu or Cd concentrations were in the range of 0 to 400 mg/kg. After equilibrating for 24 hours at $25^{\circ}C$, the soil solution was extracted from the saturated pastes by the vacuum extraction method and analyzed for pH, electrical conductivity, Cu, Cd, cations and inorganic ligands. Chemical species in soil solution were calculated by the GEOCHEM-PC program employing the input variables of pH, ionic strength(${\mu}$), molar concentrations of cations and ligands. Increasing Cu or Cd additions lowered pH of the soil solution but increased concentrations of Ca, Mg and K resulting in increases of ${\mu}$ of the soil solution. Effects of Cu on lowering pH and increasing ${\mu}$ were greater than those of Cd. Concentrations of Cu or Cd in soil solution were relatively very low as compared to those of additions, but increased linearly with increasing additions representing that concentrations of Cu were higher than those of Cd. At 400 mg/kg additions, concentrations of Cu were in the range of 0.51 to 11.70 mg/L but those of Cd were 34.4 to 88.5 mg/L. Major species of Ca, Mg and K were free ions and these species were equivalent to greater than 95 molar % of the existing respective molar concentrations. These cationic species were not changed by Cu or Cd additions. Major species of Cu in lower pH soils such as SiCL and SL were free $Cu^{2+}$ (>95 molar %), but those in LS having a higher pH were free $Cu^{2-}$ and Cu-hydroxide complex. At 100 mg Cu/kg treatment, $Cu^{2+}$ and Cu-hydroxide complex were equivalent to 73 and 22.4 molar %, respectively. These respective percentages were decreased and increased correspondingly with increasing Cu treatments. Major species of Cd in soil solution were free $Cd^{2+}$ and Cd-chloride complex, representing 79 to 85 molar % for $Cd^{2+}$ and 13 to 20% for Cd-chloride complex at 10 mg Cd/kg treatment. With increasing Cd additions to 400 mg/kg, $Cd^{2+}$ species decreased to $40{\sim}47%$ but Cd-chloride complexes increased to $53{\sim}60$ molar %. These results demonstrated that soil contamination with heavy metals caused an adverse effect on the plant nutritional aspects of soil solution by lowering pH, increasing cations temporarily, and increasing free metal concentrations and species enough to be phytotoxic.

• Journal of the Korean Chemical Society
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• v.38 no.1
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• pp.41-49
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• 1994

Exchange reaction mechanisms of the Pb(II) ion for the complexes between Pb(II) ion and nitrogen oxygen donor macrocyclic ligands, such as 1,13-diaza-3,4 : $1011-dibenzo-59-dioxacyclohexa-decane(NtnOtnH_4)$, 1,15-diaza-3,4 : $1213-dibenzo-5811-trioxacycloheptadecane(NenOdienH_4)$, and 1,15-diaza-3,4 : $1213-dibenzo-5811-trioxacyclooctadecane(NtnOdienH_4)$, were studied by $^{207}Pb-NMR$ spectroscopy in N,N'-dimethylformamide(DMF) solutions. The associative-dissociative mechanism dominated in $NtnOtnH_4-Pb(II)$ and $NtnOdienH_4-Pb(II)$ system. For $NenOdienH_4-Pb(II)$ system, the bimolecular exchange mechanism prevailed below $-5^{\circ}C$, and both bimolecular exchange and associative-dissociative mechanism dominated above $+5^{\circ}C.$ The order of activation energies for dissociation was $NtnOdienH_4\;<\;NtnOtnH_4\;<\;NenOdienH_4$ which was reverse to the order of stabilities.

• Journal of the Korean Chemical Society
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• v.33 no.4
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• pp.366-370
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• 1989

A new macrocyclic ligand 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-cycloeicosane (NdienOdien$H_4$ = $N_3O_3$) has been synthesized and identified by element analysis, NMR and IR spectrophotometry. Stepwise protonation constants of ligand are determined by potentiometry in 95% methanol solution(I = 0.1 mol $dm^{-3}$, $Me_4$NCl). log $K_1$;log $K_2$;log $K_3$ = 9.1;8.1;3.6.The kinetics of the acid-promoted dissociation reactions of complex cations of nickel(II) and copper(III) with NdienOdien and NdienOen macrocyclic ligands having, respectively, 17 and 20 ring members, have been studied spectrophotometrically in HCl$O_4$ NaCl$O_4$ aqueous solutions. From the temperature effect on kinetic constant ($k_{obs}$), the parameters of activation(${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$) of dissociation reaction for $ML^{2+}$ with $H^+$ ion have been determined. We have proposed the possible mechanism of the reaction from the data obtained.

• Molecules and Cells
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• v.38 no.12
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• pp.1064-1070
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• 2015

Translocator protein 18 kDa (TSPO) is a mitochondrial outer membrane protein and is abundantly expressed in a variety of organ and tissues. To date, the functional role of TSPO on vascular endothelial cell activation has yet to be fully elucidated. In the present study, the phorbol 12-myristate 13-acetate (PMA, 250 nM), an activator of protein kinase C (PKC), was used to induce vascular endothelial activation. Adenoviral TSPO overexpression (10-100 MOI) inhibited PMA-induced vascular cell adhesion molecule-1 (VCAM-1) and intracellular cell adhesion molecule-1 (ICAM-1) expression in a dose dependent manner. PMA-induced VCAM-1 expressions were inhibited by Mito-TEMPO ($0.1-0.5{\mu}m$), a specific mitochondrial antioxidants, and cyclosporin A ($1-5{\mu}m$), a mitochondrial permeability transition pore inhibitor, implying on an important role of mitochondrial reactive oxygen species (ROS) on the endothelial activation. Moreover, adenoviral TSPO overexpression inhibited mitochondrial ROS production and manganese superoxide dismutase expression. On contrasts, gene silencing of TSPO with siRNA increased PMA-induced VCAM-1 expression and mitochondrial ROS production. Midazolam ($1-50{\mu}m$), TSPO ligands, inhibited PMA-induced VCAM-1 and mitochondrial ROS production in endothelial cells. These results suggest that mitochondrial TSPO can inhibit PMA-induced endothelial inflammation via suppression of VCAM-1 and mitochondrial ROS production in endothelial cells.