• Title/Summary/Keyword: 전이금속(Ni, Zn)

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Potentiometric Study of Transition Metal Ions Complexes of Hexadentate($N_4$, $O_2$) Ligands (질소-산소계 여섯 자리 리간드들의 전이금속이온 착물에 대한 전위차법 연구)

  • Kim, Sun-Deuk;Kim, Jun-Kwang;Lee, Woo-Sik
    • Journal of the Korean Chemical Society
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    • v.44 no.6
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    • pp.518-525
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    • 2000
  • The open-chain hexadentate N$_4$, O$_2$ ligands 1,13-bis(2-hydroxybenzyl)-2,5,9,12-tetraazatridecane-tetrahydrochloride (BSATD${\cdot}$4HCl) and 1,14-bis (2-hydroxybenzyl)-2,6,9,12-tetraazatetradecane-tetrahydrochloride (BSATED${\cdot}$ 4HCl) have been synthesized as their tetrahydrochloride salt and characterized by EA, IR, NMR and Mass. Their proton dissociation constants(log$K^{n}_{H}$) and stability constants(log$K_{ML}$) for Cu(II), Ni(II), Co(II), and Zn(II) ions were determined in aqueous solution by potentiometry and compared with those of analogous N$_4$, O$_2$ ligands contain ethylenic spacers or propylenic spacers, which make six-membered chelate rings between the aliphatic nitrogen atoms. Synthesis and characterization of [Cu(BSATD)]ClO$_4$ and [Cu(BSATED)](ClO$_4$)$_2$ complexes are described.

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Biogeochemistry of Metal and Nonmetal Elements in the Surface Sediment of the Gamak Bay (가막간 표층퇴적물 중의 금속 및 비금속 원소의 생지화확적 분포특성)

  • Kim, Pyoung-Joong;Shon, Sang-Gyu;Park, Soung-Yun;Kim, Sang-Soo;Jang, Su-Jeong;Jeon, Sang-Baek;Ju, Jae-Sik
    • Journal of the Korean Society of Marine Environment & Safety
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    • v.18 no.2
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    • pp.67-83
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    • 2012
  • In order to evaluate die geochemical characteristics of sediment in a semi-enclosed bay used as shellfish and fish farming area, the concentrations of metallic(V, Cr, Mn, Fe, Co. Ni, Cu, Zn, Ag, Cd, Hg, Ph, As) and non-metallic(P, Se) elements and uranium were measured in the surface sediment samples collected from 19 stations of Gamak Bay in April 2010. Metal contamination status in the sediments were also evaluated using the sediment quality guidelines(SQGs) proposed by the National Oceanic and Atmospheric Administration(NOAA) and the enrichment factor(EF). The concentrations of elements in sediment were mainly controlled by quartz-dilution effect(V, Cr, Fe, Co and Ni), the dilution effect of organic matter(Cd and U), and metal redistribution by the decomposition of organic matter(Mn, Ag, As, and Se). The concentrations of metals, except As and Ni, in sediments from all sampling stations were lower than ERL values of NOAA. Conclusively, the surface sediment of Gamak Bay was slightly polluted with Ni, Ag, Cd, and Cd but was not polluted with other elements on the basis of EF results. Our results suggest that the surface sediment in Gamak Bay is not polluted by metallic elements.

The Study on Thermal Analysis and Thermodynamic Characteristics of Spinel Compounds(ZnCo2O4, NiCo2O4) (스피넬 구조를 가지는 전이금속화합물(ZnCo2O4, NiCo2O4)의 열적 분석 및 열역학적 특성 연구)

  • Kim, Jae-Uk;Ji, Myoung-Jin;Cha, Byung-Kwan;Kim, Chul-Hyun;Jang, Won-Cheoul;Kim, Jong-Gyu
    • Journal of the Korean Chemical Society
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    • v.54 no.2
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    • pp.192-197
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    • 2010
  • The spinel compound was obtained by the thermal decomposition of Zn-Co and Zn-Ni gel prepared by sol-gel method using oxalic acid as a chelating agent. The formation of spinel compound has been comfirmed by thermogravimetric analysis (TGA), x-ray powder diffraction (XRD) and infrared spectroscopy (IR). The particle size of 13 nm~16 nm was calculated by Scherrer's equation. The sol-gel method provides a practicable and effective route for the synthesis of the spinel compound at low temperature ($350^{\circ}C$). The kinetic parameters such as activation energy (Ea) and pre-exponential factor (A) for each compound were found by means of the Kissinger method and Arrhenius equation. The decomposition of spinel compound has an activation energy about 155 kJ/mol. Finally, the thermodynamic parameters (${\Delta}G^{\varphi}$, ${\Delta}H^{\varphi}$, ${\Delta}S^{\varphi}$) for decomposition of spinel compound was determined.

Synthesis of new N2O2 tetradentate ligands and the substituent effect on the stability constants of the transition metal complexes (새로운 산소-질소(N2O2)계 네 자리 리간드의 합성과 전이금속 착물 안정도상수에 대한 치환기 효과)

  • Kim, Sun Deuk;Jin, Gyoung Rok
    • Analytical Science and Technology
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    • v.19 no.2
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    • pp.131-141
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    • 2006
  • Hydrobromic acid salt of a $N_2O_2$ tetradentate ligand, N,N'-bis(2-hydroxybenzyl)-ethylene-diamine ($H-BHE{\cdot}2HBr$) was synthesized. $Br-BHE{\cdot}2HBr$, $Cl-BHE{\cdot}2HBr$, $CH_3-BHE{\cdot}2HBr$ and $CH_3O-BHE{\cdot}2HBr$ having Br, Cl, $CH_3$ and $CH_3O$ substituents at 5-position of the phenol group of $H-BHE{\cdot}2HBr$ were also synthesized. $Nap-BHE{\cdot}2HBr$ having naphthalen-2-ol instead of the phenol group was also synthesized. The potentiometry study in aqueous solution revealed that the proton dissociations of the synthesized ligands occurred in four steps and the order of the calculated overall proton dissociation constants (${\log}{\beta}_p$) of each ligand was Br-BHE < Cl-BHE < H-BHE < Nap-BHE < $CH_3$-BHE < $CH_3O$-BHE. The order showed a similar trend to that of Hammett substituent constants(${\sigma}_P$). The order of the stability constants (${\log}K_{ML}$) was CO(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II). The order in their stability constants (${\log}K_{ML}$) of each transition metal complex agreed well with that of the overall proton dissociation constants (${\log}{\beta}_p$).

Complex Formation of 1,15-Diaza-3,4:12,13-dibenzo-5,8,11-trioxacycloheptadecane with Some Transition Metal Ions (전이금속이온과 1,15-Diaza-3,4:12,13-dibenzo-5,8,11-trioxacycloheptadecane과의 착물형성)

  • Cheul-Gyu Chang;Young-Kook Shin;Si-Joong Kim
    • Journal of the Korean Chemical Society
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    • v.30 no.6
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    • pp.526-531
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    • 1986
  • The stability constants of 1,15-diaza-3,4:12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdien H$_4$, L) with transition metal ions such as $Co^{2+},\;Ni^{2+},\;Cu^{2+},\;and\;Zn^{2+}$ have been determined by potentiometry in 95% methanol solution at 25$^{\circ}$C. The complex formation of the NenOdien $_4$ with the transition metal ions depends on the basicity of the donor atoms. The order of complex stability was Co(II) < Ni(II) < Cu(II) > Zn(II). The geometries of the complexes in solid state were discussed by visible-near infrared and infrared spectrophotometry, elemental analysis and electro-conductivity. The results suggest that the geometries of the solid complexes are octahedral for $[CoL_2(OH_2)Cl]Cl{\cdot}2H_2O$, $[NiL_2(OH_2)Cl]Cl{\cdot}2H_2O$, and $[ZnLCl_2]{\cdot}\frac{1}{2}H_2O$ and square pyramidal for [CuLCl]Cl, respectively.

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Biological activities of some organometalic compounds as artificial nuclease (인공핵산 분해효소로서 몇 가지 유기금속 화합물들의 생물활성)

  • Sung, Nack-Do;Kim, Dae-Whang;Kwon, Byung-Mok;Kim, Tae-Young;Suh, Il-Hwan
    • The Korean Journal of Pesticide Science
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    • v.4 no.1
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    • pp.32-37
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    • 2000
  • A series of transition metal complexes of 3,6-bis(6'-methyl-2'-pyridyl)pyridazine ($L^{1}$) and 3,6-bis(2'-pyridyl)pyridazine ($L^{2}$) as artificial nuclease, $1{\sim}8$ were synthesized. After determining of X-ray crystal structure, hydrolysis rate constants of phosphates, as DNA model compound and biological activities were confirmed. $L^{2}$-Zn(II) complex, 8 was shown the best hydrolysis rate constant. The $L^{2}$-Ni(II) complex, 5 and $L^{2}$-Co(II) complex, 6 showed the highest herbicidal activity against SCP (Scriptus Juncoids) with excellent tolerance to rice, ORY (Oryzae sativa L.). And the $L^{1}$-Co(II) complex, 2, $L^{1}$-Zn(II) complex, 4 and ligand ($L^{1}$ amp; $L^{2}$) displayed above 90% fungicidal activity against MAG (Magnaporthe grisea).

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The Stability Constant of Transition and Lanthanide Metal Ions Complexes with 15 Membered Macrocyclic Azacrown Ligands (거대고리 아자크라운화합물과 전이금속 및 란탄족금속이온의 착물의 안정도)

  • Hong, Choon-Pyo;Choi, Yong-Gu;Choppin, G.R.
    • Journal of the Korean Chemical Society
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    • v.48 no.6
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    • pp.577-582
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    • 2004
  • The azacrown compounds, 1,4-dioxa-7,10,13-triazacyclopentadecane-N,N',N''-triacetic acid, $N-ac_3[15]aneN_3O_2(II_a)$ and 1,4-dioxa-7,10,13-triazacyclopentadecane-N,N',N''-tripropioc acid, $N-pr_3[15]aneN_3O_2(II_b)$ were synthesized by modified methods. Potentiometry was used to determine the protonation constant of the $N-ac_3[15]aneN_3O_2\;and\;N-pr_3[15]aneN_3O_2$. The stability constants of complexes of the trivalent metal ions of $Ce^{3+},\;Eu^{3+},Gd^{3+},and\;Yb^{3+}$ and divalent metal ions of $Co^{2+},\;Ni^{2+},\;Cu^{2+},\;and\;Zn^{2+}$ with the ligands $N-ac_3[15]aneN_3O_2\;and\;N-pr_3[15]aneN_3O_2$ have been determined at $25{\pm}0.1^{\circ}C$ in 0.1 M $NaClO_4$ solution by potentiometric methods. The metal ion affinities of the two triazamacrocyclic ligands with three pendant acetate or propionate groups are compared to those obtained for the similar ligands, 1,7-dioxa-4,10,13-triazacyclopentadecane-N,N',N''-triacetic acid, and 1,7-dioxa-4,10,13- triazacyclopentadecane-N,N',N''-tripropioc acid. The trends in stability of complexes for different metal ions due to changes in the nitrogen position of the donor atoms of the ligand are discussed.

Spectrophotometric, pH-metric and Conductometric Studies on Some 3-Arylhydrazone Derivatives of (2-Thenoyl) Ethylpyruvate) (2-Thenoyl Ethylpyruvate의 몇 가지 3-Arylhydrazone 유도체에 대한 분광광도법, pH 및 전도도법 연구)

  • El-Dossoki, F. I.;El-Seify, F. A.
    • Journal of the Korean Chemical Society
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    • v.50 no.2
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    • pp.99-106
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    • 2006
  • The electronic absorption spectra of [3-(2-thenoyl) 3-(p-NO2-phenylhydrazone) ethyl pyruvate] (I), p-Br (II) and p-CH3 (III) were studied in ethanol and the spectra comprise four absorption bands which assigned to the corresponding electronic transition. The pK values of these compounds have been determined spectrophotometrically and pH-metrically, the results shown that the interval range for color change of compound (I) is (8-10) similar to that of phenolphethalin indicator, indicating that this compound can be used as acid-base indicator. The successive stability constants of the compounds under study with some transition elements (Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), UO2(II), La(III) and Zr(IV) have been determined pH- metrically. Stoichiometric complexes with ratios 1:1 and 1:2 (M: L) were formed for all metals. The pK of the three derivatives and the values of the stability constant (logK) of the complexes have the order; III > II > I. Also conductometric titrations have been carried out and the results show that this titration can be used for determination of both the metal ion and the ligand concentrations by each others.

Synthesis of New N2O Tridentate Ligands and Their Stability Constants of Transition Metal Complexes (새로운 N2O계 세 자리 리간드의 합성과 전이금속 착물 안정도상수)

  • Kim, Sun-Deuk;Park, Young-Sik
    • Journal of the Korean Chemical Society
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    • v.47 no.6
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    • pp.569-577
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    • 2003
  • Ligands, Br-PEMP, Cl-PEMP and $CH_3O-PEMP$ having Br, Cl and $CH_3O$ substituents at 5-position of the $N_2O$ tridentate ligand, 2-[(2-pyridine-2-ethylamio)-methyl]-phenol (H-PEMP) containing pyridine and phenol were synthesized. Another ligand, Naph-PEMP having pyridine and 2-hydroxy-1-naphthalene was also synthesized. The ligands were characterized using elemental analysis, UV-visible, IR, $^1H\;NMR\;and\;^{13}C$ NMR spectroscopy and mass analysis. The potentiometric titration study in aqueous solution revealed that the proton dissociation of the ligands occurred in three steps and the order of overall proton dissociation constants (log${\beta}$) was $CH_3O-PEMP$ > Naph-PEMP > H-PEMP > Cl-PEMP > Br-PEMP. The order of stability constants (logML and log$ML_2$) of their transition metal complexes was Co(II) < Ni(II) < Cu(II) > Zn(II). The order in their stability constants values of each transition metal complex agreed well with that in overall proton dissociation constant value of the ligands.

Synthesis of Schiff-Base Ligands and Determination of Stability Constants of Their Transition Metal(II) Complexes (질소-산소계 시프염기 리간드의 합성과 전이금속(II) 착물의 안정도상수결정)

  • Kim, Seon Deok;Song, Chan Ik;Kim, Jun Gwang;Kim, Jeong Seong
    • Journal of Environmental Science International
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    • v.13 no.9
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    • pp.835-843
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    • 2004
  • N,N-bis(2-salicylaldehyde)dipropylenetriamine(5- Hsaldipn), N,N-bis( 5-bromosalicyl-aldehyde) dipropylenetriamine (5-Brsaldipn), N,N-bis(5-chlorosalicy laldehyde )dipropylene-triamine(5-Clsaldipn), N,N-bis(2-hydroxy- $5-methoxy-benzaldehyde)dipropylenetriamine(5-OCH_3saldipn)$ and N,N-bis (2-hydroxy-5-nitrobenzaldehyde)dipropylenetriamine $(5-NO_2saldipn)$ were synthesized and characterized by elemental analysis, infrared spectrometry, NMR spectrometry and mass spectrometry. Their proton dissociation constants were determined in 70% dioxane/30% water solution by potentiometric. Stability constants of the complexes between these ligands and the metal ions such as Cu(II), Ni(II) and Zn(II) were measured in dimethyl sulfoxide by a polarographic method. Stability constants for the ligands were in the order of $5-OCH_3$ > 5-H > 5-Br > 5-Cl > $5-NO_2$ saldipn. Enthalpy and entropy changes were obtained in negative values.