• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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• pp.2981-2987
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• 2011

A comparative study of the photodynamic and antioxidant activities of methyl pheophorbide-a (MPa, 1) and its transition metal(II) complexes (2-5) is described. Four transition metal complexes (palladium(II): 2, zinc(II): 3, cobalt(II): 4 and copper(II): 5) of MPa were prepared by reaction between the corresponding transition metal and 1, respectively, and were characterized by $^1H$-NMR and UV-vis spectroscopic and mass spectrometric analyses. In vitro results show a photodynamic therapy (PDT) efficacy with A549 cells might be attributed to a heavy atom effect of the transition metal complexes of MPa. Among them, 4 and 5 showed higher photodynamic activity than that of 1 at the concentration of 5 ${\mu}M$ at 24 h incubation after photoirradiation. The images of morphological change for 2-5 show evidence for the PDT effect with A549 cells. And the all transition metal complexes of MPa showed higher antioxidant activity than that of MPa, in which 4 showed the highest antioxidant activity.

• 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.

• Mycobiology
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• v.35 no.3
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• pp.150-153
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• 2007

New $N_2O_2$ donor type Schiff base has been designed and synthesized by condensing acetoacetanilido-4-aminoantipyrine with 2-aminobenzoic acid in ethanol. Solid metal complexes of the Schiff base with Cu(II), Ni(II), Co(II), Mn(II), Zn(II), VO(IV), Hg(II) and Cd(II) metal ions were synthesized and characterized by elemental analyses, magnetic susceptibility, molar conduction, fast atom bombardment (FAB) mass, IR, UV-Vis, and $^1H$ NMR spectral studies. The data show that the complexes have the composition of ML type. The UV-Vis. and magnetic susceptibility data of the complexes suggest a square-planar geometry around the central metal ion except VO(IV) complex which has square-pyramidal geometry. The in vitro antifungal activities of the compounds were tested against fungi such as Aspergillus niger, Aspergillus flavus, Rhizopus stolonifer, Candida albicans, Rhizoctonia bataicola and Trichoderma harizanum. All the metal complexes showed stronger antifungal activities than the free ligand. The minimum inhibitory concentrations (MIC) of the metal complexes were found in the range of $10{\sim}31{\mu}g/ml$.

• Journal of the Korean Chemical Society
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• v.30 no.5
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• pp.456-464
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• 1986

The complex formation of branched poly(ethylene imine) (BPEI) with bivalent transition metal ions, such as Fe(II), Co(II), Ni(II) and Cu(II), have been investigated in terms of visible absorption and pH titration methods in an aqueous solution in 0.1M KCl at 30${\circ}$. The stability constants for M(II)-BPEI complexes was calculated with the modified Bjerrum method. The formation curves of M(II)-BPEI complexes showed that Fe(II), Co(II), Ni(II) and Cu(II) ions formed coordination compounds with four, two, two, and two ethylene imine group, respectively. In the case of Cu(II)-BPEI complex at pH 3.4 ∼ 3.8, ${\lambda}_{max}$ was shifted to the red region with a decrease in the acidity. The overall stability constants (log $K_2$) increased as the following order, Co(II) < Cu(II) < Ni(II) < Fe(II).

• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1801-1808
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• 2006

The interaction between whey carrier protein $\beta$-lactoglobulin type A and B (BLG-A and -B) and 2,2'-bipyridin n-hexyl dithiocarbamato Pd(II) nitrate (BPHDC-Pd(II)), a new heavy metal complex designed for anticancer property, was investigated by fluorescence spectroscopy combined with chemometry and circular dichroism (CD) techniques. A strong fluorescence quenching reaction of BPHDC-Pd(II) to BLG-A and -B was observed. Hence, BPHDC-Pd(II) complex can be bound to both BLG-A and -B, and quench the fluorescence spectra of the proteins. The quenching constant was determined using the modified Stern-Volmer equation. The binding parameters were evaluated by fluorescence quenching method. The results of binding study provided evidences presence of two and three sets of binding sites on the BLG-B and -A, respectively, for BPHDC-Pd(II) complex. Using fluorescence spectroscopy and chemometry, the ability of BLG-A and -B to form an intermediate upon interaction with BPHDC-Pd(II) complex was assessed. CD studies displayed that under influence of different concentrations of BPHDC-Pd(II) complex, the regular secondary structure of BLG-B had no significant changes, whereas for BLG-A a transition from $\alpha$-helix to $\beta$-structure was appeared. The results for both of BLG-A and -B displayed that BPHDC-Pd(II) complex can induce a conformational transition from the native form to an intermediate state with a slightly opened conformation, which is detectable with chemometry analyses.

• Textile Coloration and Finishing
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• v.8 no.6
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• pp.40-46
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• 1996

In order to investigate a practical application of fibrous absorbents to transition metals such as copper, nickel, cobalt, chrome, and iron, amidoximated fiber as a particular class of solid chelate agents were prepared from acrylic fibers treatment with hydroxylamine. The adsorption mechanisms of metal ions onto amidoximated acrylic fibers and their complexes were studied. Amidoximation of acrylic fiber with hydroxylamine is found to be first-order reaction, followed by the disappearance of infrared adsorption peaks due to nitrile groups of acrylic fibers. The uptake of metal ions onto amidoximated acrylic fiber is increased with temperature raising and the adsorption is also depended on pH of the soiutions. About 70% of metal ions can be recovered from aqueous solutions of Ni(II), Co(II), Cr(III), and Fe(II) on the concentration below 5x 10$^$^{-4}$ in the range of pH 2.1~10.0. Transition metals are adsorbed to form complex with amidoxime group by the ligand sites such as C=N, NH, NO, NHOH.OH.

• Journal of the Korean Society of Industry Convergence
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• v.7 no.1
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• pp.107-113
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• 2004

Several transition metal complexes, [$M(L)X_2$](M=Pd(II), Ni(II); X=CI, Br) are prepared with aminophosphine ligands such as 1,2-bis{(diphenylphosphino)amino}ethane{$Ph_2PNHCH_2CH_2NHPPh_2$}($L_1$), 1,2-bis{(diphenylphosphino)amino}propane{$Ph_2PNHCH(CH_3)CH_2NHPPh_2$}($L_2$), trans-1,2-bis{(diphenylphosphino)amino}cyclohexane{$Ph_2PNHC_6H_{10}NHPPh_2$}($L_3$) and 1,2-bis{(diphenylphosphino)amino}benzene{$Ph_2PNHC_6H_4NHPPh_2$}($L_4$). The properties of these complexes are characterized by optical spectroscopic methods including UV/vis spectroscopy, CD, IR, $^1H$- and $^{31}P-NMR$ together with conductometer and elemental analysis. All complexes are stable under atmospheric environment. Catalytic reactivity for C-C coupling between [$M(L)X_2$] and Grignard reagents(RMgX; R=phenyl, propyl, buthyl) by thermolysis were investigated utilizing GC/mass, $^1H$- and $^{13}C-NMR$. When mol scale is 1:20 at [$Pd(L)Cl_2$] and Grignard reagents, the high catalytic activity for C-C coupling is apparent. The [$M(L)X_2$](X=Cl, Br) complexes which have strong bond at M-P exhibit high yields for C-C coupling reactions. When the central metal ion is Pd(II), the high catalytic activity for C-C coupling is apparent. The complex coordinated with Br shows higher catalytic activity for C-C coupling reactions compared to Cl.

• Journal of the Korean Chemical Society
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• v.53 no.4
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• pp.407-414
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• 2009

The solid complexes of Cu(II), Ni(II), Co(II), Mn(II) and Fe(III) with 4-hydroxy-3-(1-{2-(2-hydroxybenzylidene)- amino phenylimino}-ethyl)-6-methy-pyran-2-one (H2L) derived from o-phenylenediamine, 3-acetyl- 6-methyl-(2H) pyran, 2,4 (3H)-dione (dehydroacetic acid or DHA) and salicylic aldehyde have been synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV-visible, IR, $^1H$-NMR spectra, X-ray diffraction, thermal analysis, and screened for antimicrobial activity. The IR spectral data suggest that the ligand behaves as a dibasic tetradentate ligand with ONNO donor atoms sequence towards central metal ion. From the microanalytical data, the stoichiometry of the complexes has been found to be 1:1 (metal: ligand). The physico-chemical data suggests square planar geometry for Cu(II) and Ni(II) complexes and octahedral geometry for Co(II), Mn(II) and Fe(III) complexes. The x-ray differaction data suggests orthorhombic crystal system for Cu(II) complex, monoclinic crystal system for Ni(II), Co(II) and Fe(III) and tetragonal crystal system for Mn(II) complex. Thermal behaviour (TG/DTA) of the complexes was studied and kinetic parameters were determined by Coats-Redfern method. The ligand and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli and fungicidal activity against Aspergillus Niger and Trichoderma.

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

• Journal of the Korean Chemical Society
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• v.65 no.2
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• pp.93-105
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• 2021

Mononuclear Cu(II), Ni(II), Co(II), Mn(II), Zn(II), Fe(III), Ru(III), and UO2(II) complexes of 2-hydroxy-4-(p-tolyldiazenyl)benzylidene)-2-(p-tolylamino)acetohydrazide (H2L) were prepared by direct method. The ligand and its complexes were isolated in solid state and characterized by analytical techniques such as elemental and thermal analyses, molar conductance, magnetic susceptibility measurements and spectroscopic techniques such as UV-Visible, IR, 1H-NMR and 13C-NMR. The spectral data indicated that the ligand acted as neutral/monobasic bidentate or monobasic/dibasic tridentate ligand bonded to the metal ions through the oxygen atom of ketonic or enolic carbonyl group, azomethine nitrogen atom and deprotonated/protonated phenolic oxygen atom forming either tetragonally distorted octahedral or octahedral. Antimicrobial activities of the ligand and its complexes were evaluated against Escherichia coli, Bacillus subtilis and Aspergillus niger by well diffusion method. The results of antifungal activity showed that the Fe(III) complex (10) exhibited higher antifungal against Aspergillus niger than the other complexes. However, the results of antibacterial activity revealed that Cu(II) complex (4) is the most active against Escherichia coli while the Cu(II) complex (5) and Fe(III) complex (10) exhibited higher antibacterial effect on Bacillus subtilis than the other complexes.