• Bulletin of the Korean Chemical Society
• /
• v.31 no.8
• /
• pp.2201-2206
• /
• 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.

• Korean Journal of Crystallography
• /
• v.18 no.1_2
• /
• pp.16-20
• /
• 2007

Under hydrothermal conditions, a 2-dimensional copper(I) coordination polymer [$Cu_2Cl_2$(4,4'-dipyen)] (1) was prepared from [$Cu(OAc)_2]{\cdot}H_2O$, 4,4'-dipyen, and KCl. In polymer 1, copper atoms are linked by the 4,4'-dipyen ligands approximately along the b-axis and are also linked by the chloro ligands approximately along the a-axis to form a 2-D layer, a network of rectangles.

• Journal of the Korean Chemical Society
• /
• v.54 no.5
• /
• pp.506-514
• /
• 2010

A new series of ligands N-[(benzoylamino)-thioxomethyl]-amino acid (HL) were synthesized by reaction of benzoylisothiocyanate with various amino acids namely aspartic acid [BATA] (1), glutamic acid [BATG] (2), methionine [BATM] (3), leucine [BATL] (4), and tryptophan [BATT] (5). The ligands were characterized by elemental analysis, IR and NMR spectra. Some transition metal complexes ($ML_2$) for these ligands (6-8) were prepared; [M=Cu(II), Co(II), or Ni(II)], and characterized by elemental analysis, IR and $^1H$ NMR spectra. Antibacterial study showed that all the ligands have no antibacterial activity, whereas ($ML_2$) complexes; [M = Cu(II), Co(II), or Ni(II)] have antibacterial activity towards (Gram -ive) Escherichia (NCTC5933) and (Gram +ive) Staphylococcus (NCTC6571) and have no toxicity on (BALB/C) Albino mice.

• Korean Journal of Environmental Agriculture
• /
• v.11 no.3
• /
• pp.243-252
• /
• 1992

This research was conducted to investigate the influence of kind and concentration of organic ligands such as humic (HA) or fulvic acid (FA) on the removal of Cu or Pb from the aqueous solution employing the principles in metal-ligand complexation. Increasing HA concentration enhanced the efficiency of Cu or Pb removal, but there existed upper critical concentrations capable of forming maximum HA-metal complex. which ranged 53-289 and 42-315mg/L for Cu and Pb, respectively. At these concentrations. efficiency of removal was 70 to 95 % for Pb, but 13 to 65 % for Cu. Amounts of Cu and Pb which complexed with 100mg HA were estimated to be 7.5 and 34.1mg, respectively. FA-metal complex forming reactions were fitted significantly to the empirical models of Freundlich for Cu and Langmuir for Pb. Fulvic acid precipitated nearly 100% of Pb in solution, but formed precipitates with Cu in only 13 to 29%. Comparing organic ligands. HA had a higher removal efficiency for Cu but FA had such for Pb. Metalligand complex formation was differed from kinds and concentrations of corresponding ligands and metals. Results demonstrated that this principle has a strong potential to be employed for treating heavy metals in aqueous solution.

• Analytical Science and Technology
• /
• v.11 no.6
• /
• pp.440-447
• /
• 1998

Polydentate Schiff base ligands 5-Br-BSDT(bis(5-bromosalicylaldehyde)diethylenetriamine) having $N_3O_2$ atoms, 5-Br-BSTT(bis(5-bromosalicylaldehyde)triethylenetetramine) having $N_3O_2$ atoms, 5-Br-BSTP(bis(5-bromosalicylaldehyde)tetraethylenepentamine) having $N_3O_2$ atoms were synthesized. Stability constants of the complexes between these ligands and the metal ions such as Cu(II), Ni(II) and Zn(II) were measured in DMSO by a polarographic method. It was observed that all metal(II) ions employed in this study formed 1 : 1 complexes with Schiff base ligands. Stability constants for the ligands were in the order of Cu(II)>Ni(II)>Zn(II), and for complex formation were in the order of 5-Br-BSTP>5-Br-BSTT>5-Br-BSDT according to the increasing in the number of donor atoms. Both enthalpy and entropy changes are obtained in negative valves. Exothermicity for the complex formation indicated tight binding between the ligands and metal ions. The negative entropy change would be related to the fact that solvent molecules are strongly interacting with the metal complexes.

• Bulletin of the Korean Chemical Society
• /
• v.13 no.3
• /
• pp.256-259
• /
• 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.

• Journal of Environmental Science International
• /
• v.15 no.8
• /
• pp.799-809
• /
• 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).

• Journal of Environmental Science International
• /
• v.19 no.7
• /
• pp.849-860
• /
• 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
• /
• v.12 no.5
• /
• pp.483-487
• /
• 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
• /
• v.32 no.7
• /
• pp.2351-2357
• /
• 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.