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Syntheses of New Nitrogen-Oxygen Multidentate Ligands and Their Stability Constants of Transition Metal(Ⅱ) Ions (새로운 질소-산소계 여러 자리 리간드의 합성 및 전이금속(Ⅱ)이온 착물의 안정도상수)

  • Kim, Sun Deuk;Jang, Ki Ho;Kim, Jun Kwang
    • Journal of the Korean Chemical Society
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    • v.42 no.5
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    • pp.539-548
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    • 1998
  • Multidentate N,O-containing ligands, such as N,N'-bis(2-hydroxybenzyl)-ethylenediamine(BHED), N,N'-bis(2-hydroxybenzyl)-propylenediamine(BHPD), N,N'-bis(2-hydroxybenzyl)-diethylenetriamine(BHDT), N,N'-bis(2-hydroxybenzyl)-triethylenetriamine(BHTT) and N,N'-bis(2-hydroxybenzyl)-tetraethylenepentaamine (BHTP) were synthesized by reduction of the imine group of Bis(salicylidene)-ethylendiamine(BSED), Bis (salicylidene)-propylenediamine(BSPD), Bis(salicylidene)-diethylentriamine(BSDT), Bis(salicylidene)-triethylenetetraamine(BSTT) and Bis(salicylidene)-tetraethylenepentaamine(BSTP). Proton dissociation constants of the ligands and stability constants of transition metal(Ⅱ) ion complexes with BHED, BHPD, BHDT, BHTT, and BHTP were determined by potentiometic titration. The sequence of stability constants $(logK_{ML})$ of complex increases as BHED Zn(Ⅱ) which follows the Irving-Williams series.

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Protonation State of Norfloxacin and Their Interaction with DNA (pH에 따른 Norfloxacin의 형태 및 DNA와의 상호작용에 관한 연구)

  • Yeo, Jeong-Ah;Son, Gwan-Su;Kim, Jong-Moon;Moon, Hyung-Rang;Jun, Eun-Duk;Cho, Tae-Sub
    • Journal of the Korean Chemical Society
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    • v.44 no.1
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    • pp.4-9
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    • 2000
  • We investigated the self-association and protonation state of norfloxacin, a member of quinokme antibiotics, using electric absorption and potentiom,etric titration. Both nitrogen at the piperazine ring and carboxylic acid were protonated at a low pH (cationic norfloxacin), and deprotonated at a high pH (anionic norfloxacin). In the intermediate pH range, a neutral species was dominant with the possibility of forming a zwitter ion. We also observed that nortloxacin molecules can be sracked to form a dimer at an intermediate pH, The equilibrium constant of the norfloxacin-DNA complex formation, which was measured by Stem-Volmermethod, increases as the pH of the system is lowered. This observation indicates that it is the cationic nortloxacin that forms a complex with DNA among various norfloxacin species in aqueous solution.

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Hg(II) ion- Selective Electrodes with Neutral Carriers of Macrocycles (거대고리 중성 운반체를 갖는 Hg(II)이온 선택성 전극)

  • 정오진
    • Journal of Environmental Science International
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    • v.5 no.2
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    • pp.211-220
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    • 1996
  • New thin-and diselena-crown ethers containing two suffer and selenium donor atoms have been prepared. And then, mercury ($Hg^{2+}$) ion-selective electrodes with PVC-plasticizer (STPB) based on some macrocycles as neutral carriers were also made. The electrochemical selectivities for various ions, and the effects for macrocycles, matrix of membranes, ratio of plasticizer to macrowcles, concentration and pH of test solution were investigated on the $Hg^{2+}$ ion-selective electrodes. The 1, 10-diselena-18-crown-6-PVC-STPB (sodium tetraphenylborate) exhibited good linear responses of ${28.2}\pm{0.6}$ decade-1 for $Hg^{2+}$ ion in the conientration ranges of $10^{-2}~10^{-6}$ M $Hg^{2+}$ ion. This electrode exhibited comparatively good selectivities for $Hg^{2+}$ ion in comparison with alkali and alkaline earth metal ions, some heavy metal ions and rare earth metal ion in the range of pH 2.5~6.0. In addition, this electrode was applied as a sensor in the titration of $Hg^{2+}$ ion with $1^-$ ion in water.

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중금속이온과 포단드와의 착물형성에 관한 연구

  • Choi, Kyu Seong;Kang, Dong Hyun;Kim, Yong Seong;Lee, Shim Sung;Huh, Whang
    • Journal of the Korean Chemical Society
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    • v.45 no.2
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    • pp.131-137
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    • 2001
  • The protonation and stability constants of complexation of Zn(II), Cd(II) and Pb(II), Hg(II) ion with sulfur-containing podand ligands such as tri(phenylthio-2-ethy1)amine (Podand N$_1$S$_3$)tetra(phenylthio-2-ethyl)ethylenediamine (Podand N$_2$S$_4$) , tris(1-benzylaminoethyl)amine (Podand N$_4$) have been determined by potentiometric titration in 95% methanol at variable temperatures, From these studies, we observed that podand N$_4$ ligand showed the largest protonation constant. Protonation constant, stability constant, enthalpy, entropy of Zn(II), Cd(II) and Pb(II), Hg(II),ions increased with the following order podand N$_1$S$_3$$_2$S$_4$$_4$.

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Synthesis of Tridentate Poly-amine Ligands and Determination of Stability Constants of Transition Metal Complexes (세자리 폴리아민리간드의 합성과 양성자 해리상수 및 전이금속과의 착물 안정도상수의 결정)

  • Kim, Sun-Deuk;Kim, Jun-Kwang;Ko, Moon-Soo
    • Analytical Science and Technology
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    • v.15 no.2
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    • pp.135-141
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    • 2002
  • The new tridentate poly-amine ligands, N,N-Bis(2-amino-ethyl)-methyl amine${\cdot}$2HBr (BAMA${\cdot}$2HBr), N,N-Bis(2-amino-ethyl)-ethylamine${\cdot}$2HBr (BAEA${\cdot}$2HBr), N,N-Bis(2-amino-ethyl)-propylamine${\cdot}$2HBr (BAPA${\cdot}$2HBr) and N,N-Bis(2-amino-ethyl)-butylamine${\cdot}$2HBr (BABA${\cdot}$2HBr) were synthesized as their dihydrobromic-salt and characterized by EA, IR, NMR and Mass spectroscopy. The protonation constants of the ligands and stability constants of transition metal(II) complexes were determined in aqueous solutions by potentiometry and compared with diethylenetriamine. Stability constants for transition metal complexes of ligands are in the order of BAMA < BAEA < BAPA > BABA. The larger value of stability constants of BAPA compared to these BABA, may be attributed to the more distorted structure of the complex due to the increased steric crowding caused by the presence of the bulky N-butyl group.

A rapid determination of chloride in saturated paste extracts of salt-affected soils using EC change upon AgCl precipitation (AgCl 침전 전후 전기전도도 변화를 이용한 염해지 포화침출액의 염소 이온 신속 정량)

  • Lee, Yehun;Kim, Jeeyoon;Lee, Jeongsu;Pros, Khok;Park, Jee Won;Han, Gwang Hyun
    • Journal of Applied Biological Chemistry
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    • v.60 no.3
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    • pp.279-282
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    • 2017
  • Chloride is known as the most important anion in salt-affected soils. We observed the degree of EC change upon AgCl precipitation was quantitatively related with the chloride concentration. Method validation and intercomparison with ion chromatography revealed the proposed method can provide rapid and moderately precise chloride concentrations in salt-affected soils.

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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Prediction of Chemical Species of Copper and Cadmium in Natural Waters (천연수중 구리 및 카드뮴의 화학종 예측)

  • Chung Kil Park;Un Sik Kim
    • Journal of the Korean Chemical Society
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    • v.29 no.6
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    • pp.637-645
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    • 1985
  • To predict speciation of copper and cadmium in natural waters, the stability constant of complexes formed between copper or cadmium and natural organic ligands have been determined by the ion selective electrodes at pH 6. The stability constants for copper and cadmium, log $K'_{CuL} = 5.80\;and\;log K'_{CdL}=3.82$, were incorporated inot MINEQL computer program and prediction of chemical species of copper and cadmium in a model fresh water system was made by using this computer program. The natural organic ligands form complex with cupric ions at the concentration of $10^{-6}$ moles/l and with cadmium ions at the concentration of $10^{-5}$ moles/l. This result showed that prediction of chemical species of heavy metals in natural waters was not possible without taking into account the presence of the natural organic ligands.

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A Study on Complexation of Cu(Ⅱ) Ion with Hydrazide Schiff Base Lignads (Cu(Ⅱ) 이온과 Hydrazide Schiff Base 리간드와의 착물형성에 관한 연구)

  • Cho, Hwee Kyung;Cha, Bun Hee;Hur, Young Ae;Choi, Kyu Seong
    • Journal of the Korean Chemical Society
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    • v.39 no.4
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    • pp.281-287
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    • 1995
  • Copper(Ⅱ) complexes with N,N'-oxalylbis(salicylaldehydehydrazone), N,N'-malonylbis(salicylaldehydehydrazone) and N,N'-succinylbis(salicylaldehydehydrazone) have been prepared in 95% DMF. Their protonation and stability constants were investigated by potentiometric titration. We observed that MBSH ligand showed the largest protonation constant. The values of the protonation constants among three different ligands were increased as following order SBSH < OBSH < MBSH. However, the increasing order of stability constants was somewhat different such as Cu(Ⅱ)-SBSH < Cu(Ⅱ)-MBSH < Cu(Ⅱ)-OBSH. In addition, thermodynamic parameters, ΔH and ΔS of Cu(Ⅱ) complexes have been studied. As a result, we found the SBSH ligand produced the best stable copper (Ⅱ) complex.

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Analysis of Chloride Content in Aqueous Solution and Mortar using Laser Induced Breakdown Spectroscopy (LIBS를 활용한 수용액과 모르타르 내 염화물량 분석)

  • Ryu, Hwa-Sung;Park, Won-Jun
    • Journal of the Korea Institute of Building Construction
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    • v.21 no.3
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    • pp.189-194
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    • 2021
  • LIBS has been attracting attention as an analytical method capable of real-time measurement without sample preparation. In this study, a Lab. scale LIBS device was fabricated to examine the applicability and reproducibility of LIBS in the analysis of chloride contents in mortar. The existing analysis method and LIBS analysis were performed simultaneously on the mortar test specimen with the chloride content adjusted. Compared to the chloride content condition of the mortar, the XRF and Potentiometric Titration results also showed a similar trend. As a result of LIBS analysis, chlorine ions were detected at a wavelength of 837.59 nm according to the chloride content condition. In order to improve the precision in various concentration ranges, the LIBS signal amplification of about 50 times through the electric field enhancement was implemented. Through the verification of the aqueous solution-based reproducibility, a high correlation between the LIBS signal strength and the Cl concentration was confirmed, and the possibility of applying LIBS to the durability diagnosis of concrete damage by chloride was confirmed.