• Bulletin of the Korean Chemical Society
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• 제31권8호
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• pp.2201-2206
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• 2010

To improve the separation property and stability of metal chelate Cu(II) column, three new kinds of multidentate aminocarboxy silica columns with cation-exchange properties were synthesized using glutamic acid (Glu), glutamic acidbromoacetic acid (Glu-BAA), glutamic acid-bromosuccinic acid (Glu-BSUA) as ligands and silica gel as matrix. The standard proteins were separated with prepared chromatographic columns. The stationary phases exhibited the metal chelate property after fixing copper ion (II) on the synthesized multidentate ligand silica columns. The binding capacity of immobilized metal ion was related with the dentate number of multidentate ligands. Chromatographic behavior of proteins and the leakage of immobilized metal ion on multidentate chelate Cu(II) columns were affected by the dentate number of multidentate ligands and competitive elution system directly. The results showed that quinquedentate Glu-BSUA-Cu(II) column exhibited better chromatographic property and stability as compared with tridentate Glu-Cu(II) column, tetradentate Glu-BAA-Cu(II) column and commonly used IDA-Cu(II) column.

• 한국결정학회지
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• 제18권1_2호
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• pp.16-20
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• 2007

수열 반응 조건 하에서, [$Cu(OAc)_2]{\cdot}H_2O$, 4,4-dipyen, 그리고 KCl로부터 2차원 구리 배위 고분자 [$Cu_2Cl_2$(4,4'-dipyen)] (1)이 합성되었다. 고분자 1 내에서, 구리 원자들이 4,4-dipyen 리간드들로 대략 b-축 방향으로 연결되고, 또한 Cl 리간드들로 대략 a-축 방향으로 연결되어 직사각형 그물 망 형태의 2차원 층이 형성된다.

• 대한화학회지
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• 제54권5호
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• pp.506-514
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• 2010

benzoylisothiocyanate 와 아스파르트산 [BATA] (1), 글루탐산 [BATG] (2), 메티오닌 [BATM] (3), 루신 [BATL] (4), 및 트립토판 [BATT] (5) 등의 다양한 아미노산을 반응시켜 일련의 새로운 리간드인 N-[(benzoylamino)-thioxomethyl]-amino acid (HL)를 합성하였다. 이들 리간드의 특성을 원소분석, IR 및 NMR로 규명하였다. 이러한 리간드 (6-8)의 몇가지 전이금속 착물을 제조하여[M = Cu(II), Co(II), 또는 Ni(II)] 원소분석, IR 및 $^1H$ NMR을 통하여 특성을 규명하였다. 항균성에 대한 연구 결과 모든 리간드가 항균 활성을 보이지 않는 반면, ($ML_2$) 착물; [M=Cu(II),Co(II), 또는 Ni(II)]은 (Gram -ive) Escherichia (NCTC5933) 및 (Gram +ive) Staphylococcus (NCTC6571)에 대해 항균 활성을 보였으며 또한 (BALB/C) 알비노 쥐에 대해 독성을 보이지 않았다.

• 한국환경농학회지
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• 제11권3호
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• pp.243-252
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• 1992

금속-유기리간드 착염형성반응을 이용한 중금속 제거 방법을 연구하기 위하여, 리간드의 종류 및 농도가 침전형성량에 미치는 영향을 알아보았다. 부식산의 처리농도 증가는 금속과의 복합체 형성을 통해 Cu, Pb의 제거효율을 높였으나, 부식산의 일정 농도에서 최대의 침전형성을 보였다. 최대의 침전을 형성할 수 있는 부식산의 농도는 Cu의 경우 $53{\sim}289$, Pb의 경우 $42{\sim}315mgC/L$로 비슷한 수준이었으나. 제거 효율은 금속을 $200{\sim}1000{\mu}\;M$ 처리시 Cu가 $13{\sim}65%$인데 반해, Pb은 $70{\sim}95%$로 높았다. l00mg의 부식산으로 제거할 수 있는 최대량은 Cu가 7.5mg($11.8{\mu}\;mol$)이었고, Pb은 34.1mg($16.5{\mu}\;mol$) 정도였다. 훌브산의 농도와 중금속과의 복합체형성의 관계는 Cu는 Freundlich model에 Pb는 Langmuir model에 유의성있게 부합되었다. 훌브산은 용액중의 Pb을 거의 100% 제거할 수 있었으나 Cu의 제거효율은 $13{\sim}29%$에 불과했다. 중금속 제거효율을 비교해 볼때. 부식산, 훌브산 모두는 Cu보다는 Pb를 효율적으로 제거 하였다. 유기리간드의 종류를 비교해 볼때 Cu의 경우 부식산, Pb의 경우 훌브산에 의한 제거효율이 유의성있게 높았다. 실험결과를 통해, 중금속-리간드 복합체형성반응은 유기리간드의 종류, 농도, 중금속의 종류에 따라 다르며, 복합체 형성 후 분리방법 등에 관한 연구 보완이 이뤄진다면, 유기리간드를 이용하여 수용액으로부터 중금속을 제거할 수 있는 가능성은 크다고 사료된다.

• 분석과학
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• 제11권6호
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• pp.440-447
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• 1998

브롬 치환기를 가지는 여러자리 시프염기인 5-Br-BSDT(bis(5-bromosalicylaldehyde)diethy- lenetriamine), 5-Br-BSTT(bis(5-bromosalicylaldehyde)triethylenetetramine)와 5-Br-BSTP(bis(5-bromosalicylaldehyde)tetraethylenepentamine)를 합성하여 DMSO 용매에서 이들 리간드들과 구리(II), 니켈(II) 및 아연(II) 등의 전이금속과의 안정도 상수값을 폴라로그래피를 이용하여 구하였다. 이때 금속과 리간드는 1 : 1착물을 형성하였고, 안정도 상수값은 금속으로서는 Cu(II)>Ni(II)>Zn(II) 순서로, 리간드로서는 5-Br-BSTP>5-Br-BSTT>5-Br-BSDT 순서로 나타남으로서 주개 원자수의 증가에 의존한다는 사실을 알았다. 엔탈피와 엔트로피는 모두 음의 값을 나타내었는데 흡열반응으로서 금속이온과 리간드가 매우 강하게 결합하고 있음을 알 수 있고 극성을 가지는 금속착물이 생성되어 용매인 DMSO와 아주 강한 상호작용을 함으로써 큰 음의 엔트로피 값을 가진 것으로 생각된다.

• Bulletin of the Korean Chemical Society
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• 제13권3호
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• pp.256-259
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• 1992

The 14-membered tetraaza macrocyclic ligand 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradeca-4,11-diene(B) can be synthesized as its dihydroperchlorate salt by the one-pot reaction of 2-ethylaminoethylamine, methylvinyl ketone, and perchloric acid in absolute ethanol. The reaction of Ni(II) or Cu(II) ion and the salt yields $[M(B)]^{2+}$ (M = Ni(II) or Cu(II)), which reacts with $NaBH_4$ to produce $[M(D)]^{2+}$ (D = 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradecane). The complexes $[M(L)]^{2+}$ (L = B or D) have planar geometry and contain two ethyl groups at the donor nitrogen atoms of the ligands. The red solids $[Cu(B)](X)_2(X)$ = $ClO_4-$ or $PF_6^-$) react with water molecules of atmospheric moisture to produce the purple solids in which water molecules are coordinated to the metal ion. Synthesis, characterization, and the properties of the new N-ethylated macrocyclic ligands and their Ni(II) and Cu(II) complexes are reported.

• 한국환경과학회지
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• 제15권8호
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• pp.799-809
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• 2006

Hydrobromic acid salts of new N, N, O tridentate ligands containing phenol, 2-[(2-Methylamino- ethyl- amino)-methyl]-phenol(H-MMP. 2HBr), 5-Bromo-2-[(2-Methylamino-ethylamino)-methyl]-phenol (Br- MMP. 2HBr), 5-Chloro-2-[(2-Methylamino-ethylamino)-methyl]-phenol(Cl-MMP. 2HBr), 5-Methyl-2-[(2-Methylamino-ethylamino)-methyl]-phenol(Me-MMP. 2HBr), 5-Methoxy-2-I(2-Methylamino-ethylamino)- methyl]-phenol(MeO- MMP. 2HBr) and. 1-[(2-Methylamino-ethylamino)- methyl]-naphthalen-2-ol(Nap- MMP. 2HBr) were synthesized. The synthesized ligands were confirmed by C. H. N. atomic analysis, UV-visible and IR spectroscopies, $^1$H NMR, $^{13}$C NMR and mass analysis. The potentiometry study revealed that the proton dissociation constants(logK$_n^H$) of the synthesized ligands and stability constants (logK$_{ML}$, logK$_{LM2}$) of transition metal complexes of Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) ions occurred in three steps and the order of the calculated overall proton dissociation constants(log$\beta_p$) and stability constants (logK$_{ML}$) of ligands was Br-MMP. 2HBr < Cl-MMP 2HBr < H-MMP. 2HBr < Nap-MMP. 2HBr < Me-MMP. 2HBr < MeO-MMP. 2HBr. The order showed a similar trend to that of Hammett substituent constants($\delta_p$). The synthesized ligands usually form 2:1(ML$_2$) complexes with transition metal ions. The order of the stability constants of each transition metal ions was Co(II) < Ni(II) < Cu(II) ;> Zn(II) ;> Cd(II) ;> Pb(II).

• 한국환경과학회지
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• 제19권7호
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• pp.849-860
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• 2010

A new $N_3O_2$ pentadentate ligand, N,N'-Bis(2-hydroxybenzyl)-ethylenetriamine(H-BHET 3HCl) was synthesized. The hydrochloric acid salts of Br-BHET 3HCl, Cl-BHET 3HCl, $CH_3O$-BHET 3HCl and $CH_3$-BHET 3HCl containing Br-, Cl-, H-, $CH_3O-$ and $CH_3-$ groups at the para-site of the phenol group of the H-BHEP were synthesized. The structures of the ligands were confirmed by C. H. N. atomic analysis and $^1H$ NMR, $^{13}C$ NMR, UV-visible and mass spectra. The calculated stepwise protonation constants(${\logK_n}^H$) of the synthesized $N_3O_2$ ligands showed six steps of the proton dissociation. The orders of the overall protonation constants($\log{\beta}_p$) of the ligands were Br-BHET < Cl-BHET < H-BHET < $CH_3O$-BHET < $CH_3$-BHET. The orders agreed well with that of para Hammett substituent constants(${\delta}_p$). The calculated stability constants($\logK_{ML}$) between the ligands and heavy metal ions (Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II)) agreed well with the order of the overall proton dissociation constants of the ligands but they showed a reverse order in para Hammestt substituent constants(${\delta}_p$). The order of the stability constants between the heavy metal ions with the synthesized ligands were Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II).

• Bulletin of the Korean Chemical Society
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• 제12권5호
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• pp.483-487
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• 1991

The tetraaza macrocyclic ligand 3,14-dimethyl-2,6,13,17-tetraazatricyclo $[14,4,0^{1.18} ,0^{7.12}]$docosa-2,12-diene(B), that contains two cyclohexane rings, has been prepared as its dihydroperchlorate salt by the nontemplate condensation of methyl vinyl ketone with 1,2-diaminocyclohexane and perchloric acid. Reduction of B with sodium borohydride produces 3,14-dimethyl-2,6,13,17-tetraazatricyclo$[14,4,0^{1.18},0^{7.12}]$docosane(C). Square planar Ni(Ⅱ) and Cu(Ⅱ) complexes of B and C have been prepared by the reaction of the metal ions and the ligands. Synthesis, characterization, and the properties of the ligands and their metal complexes are reported.

• Bulletin of the Korean Chemical Society
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• 제32권7호
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• pp.2351-2357
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• 2011

Three new metal-organic copper(II) complexes, $[Cu(H_2PZTC)_2]_n{\cdot}2nH_2O$ (1), $[Cu(HPZTC){\cdot}2H_2O]_n{\cdot}2nH_2O$ (2), and $Cu_2[(PZHD)(OH)(H_2O)_2]_n$ (3) ($H_3PZTC$ = pyrazine-2,3,5-tricarboxylic acid, $PZHD^{3-}$ = 2-hydroxypyrazine-3,5-dicarboxylate), have been synthesized from $Cu(II)/H_3PZTC$ system under different synthetic conditions, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. In complexes 1 and 2, $H_3PZTC$ ligands loose one and two protons, which were transformed into $H_2PZTC^-$ anion and $HPZTC^{2-}$ dianion under different preparation condition, respectively. Furthermore, two ligands coordinate with Cu(II) cations in different modes, leading to the formation of the different chain structures. In complex 3, $H_3PZTC$ ligand was converted into a new ligand-PZHD by in situ decarboxylation and hydroxylation under a higher pH value than that for complexes 1 and 2. PZHD ligands link the Cu(II) cations to form a 2D layer structure. These results demonstrate that the preparation conditions, including pH value and reaction temperature etc, play an important role in the construction of complexes based on $H_3PZTC$ ligand.