• Analytical Science and Technology
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• v.5 no.1
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• pp.63-71
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• 1992

Liquid chromatographic behavior of Pd(II), Ni(II) and Co(III) in N-Alkylisonitrosoacetylacetone imine(HIAA-NR) chelates was investigated by reversed phase high perfomance liquid chromatography. The optimum conditions for the separation of IAA-NR-metal chelates were examined respect to the flow rate and mobile phase strength. The metal-N-Alkylisonitrosoacetylacetone imine chelates in solution were successfully separated on Novapak $C_{18}$ column using acetonitrile/water mixture as mobile phase. The elution order of chelates is methyl>ethyl>propyl>butyl as N-alkyl group for ligand is varied. It was found that all IAA-NR-metal chelates were eluted in an acceptable range of capacity factor value($0{\leq}log\;k^{\prime}{\leq}1$). The dependence of log k' on the volume fraction of water in the binary mobile phase was examined. Also, the dependence of k' on the liquid-liquid extraction distribution ratio(Dc) in acetonitrile-water-alkane extraction system was investigated for IAA-NR-metal chelate. Both kinds of dependence are linear, which suggests that the retention of the electroneutral metal chelates on Novapak $C_{18}$ column is largely due to the hydrophobic effect.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.113-119
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• 1989

Chelating resins containing hydrazide or triethylenetetramine side chain were prepared using a commercial cation exchage resin, Diaion WK 11, and their nitrogen contents were determined by elemental analysis. The synthesized resin, and commercial chelating resins, (Diaion-CR 10 and-CR 20) were treated with various metal chelates of which metal contents were subsequently determined by chelatometry. Sectioned beads of the resin-metal chelates were also observed using electron microprobs X-ray analyzer. To examine the catalytic activity of the resin-metal chelates, they were applied to the oxidation of various hydroxy compounds and l-ascorbic acid, and found to be effective catalysts.

• Archives of Pharmacal Research
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• v.12 no.2
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• pp.119-124
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• 1989

Cotton xanthate, which was obtained by treating cotton with carbon disulfide in alkaline solution, was treated with the solution of polyvalent metal ions to produce cotton xanthate-metal chelates. This chelation reaction was readily and simply achieved, and antimicrobial agents with suitable structures could subsequently be coupled to the chelate with ease at moderate pH values and in aqueous solution. Metal ions used in present work include Cu(II), Zn(II) and Fe(III). Tetracycline, streptomycin, neomycin and pyrithion were used as antimicrobial/antifungal agents. Antibacterial activities were measured employing ditch plate method against G(+) Staphylococcus aureus, Streptococus faecalis, and G(-) Escherichia coli, Enterobacter aerogenes, and the fungus, Aspergillus niger. All the cotton xanthate-metal-antimicrobial agent chelates exhibited activities whereas the cotton xanthate-metal chelates themselves were inactive. Considering the extensive washing procedures and results from control experiments, possibility of the involvement of physical adsorption for the binding of drugs could be excluded.

• Analytical Science and Technology
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• v.13 no.1
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• pp.27-33
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• 2000

Simultaneous separation and analysis of Ni(II), Pd(II), Co(II), Cu(II) and Hg(II) in peperidinedithiocarbamate (PDTC) chelates were investigated by reversed phase liquid chromatography. The optimum conditions for the separation of PDTC metal chelates were examined with respect to the pH, extraction solvent, and mobile phase strength on Novapak $C_{18}$ column using methanol/water mixture as mobile phase. All metal PDTC chelates were eluted in an acceptable range of capacity factor value ($0{\leq}log\;k^{\prime}{\leq}1$). The linear calibration curves were obtained in the concentration range of $0{\sim}1.2{\mu}g/mL$ for five metal ions, and also good precision in the range of 1.96~3.41% RSD was obseved. Under the optimum conditions, trace metat ions in the composite water sample were successfully separated and determined with relative error of ${\pm}2.0%$.

• Analytical Science and Technology
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• v.6 no.1
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• pp.107-119
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• 1993

The purpose of this study is to investigated the elution behavior of platinoid metal acetylacetonates, which is the key to elucidate their retention mechanism and optimize their RPLC separation conditions. The retention data of four platinoid metal acetylacetonates have been measured on four different columns in methanol-water and acetonitrile-water systems. The retention of uncharged platinoid metal acetylacetonates is interpreted by solvophobic effect. The retention of platinoid metal acetylacetonates is also greatly influenced by the geometric structure of the complexes. The square planar chelates, $Pd(acac)_2$, $Pt(acac)_2$, are retained longer than the octahedral chelates, $Rh(acac)_3$, $Ir(acac)_3$. It is likely due to that square planar chelates show greater interaction with nonpolar stationary phase than octahedral chelates. The results of van't Hoff plots have shown that platinoid metal acetylacetonates is operated on the same retention mechanism in the temperature range of $25{\sim}45^{\circ}C$. The study of the retention mechanism by the enthalpy-entropy compensation phenomenon has indicated that the retention mechanism of octahedral chelates and square planar chelates do not vary with the composition change of methanol-water mobile phase, respectively. In acetonitrile-water mobile phase, however, the retention mechanism is observed to be more complicated. Optimum condition for the separation of four platinoid metal acetylacetonates is found to be 40% methanol, polymeric C18 column, and $45^{\circ}C$.

• Analytical Science and Technology
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• v.7 no.1
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• pp.103-114
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• 1994

The elution behaviors of Ni(II), Cu(II), Co(II), and Cr(II) in 1-phenyl-3-methyl-4(2-hydroxy-5-X-phenylazo)-5-pyrazolone, [Pm(2-OH)(5-X)PaPz](X=H, $CH_3$, $NO_2$, Cl) chelates have been studied by reversed phase HPLC. Thirteen metal-[Pm(2-OH)(5-X)PaPz] chelates were prepared and characterized by UV, IR, MS, and ICP spectroscopic methods. These metal-2-hydroxyarylazopyrazolone chelates were successfully separated on Novapak-$C_{18}$ column using methanol/water mixtures as a mobile phases. It was found that the chelates were eluted properly in an acceptable range of the capacity factor value($0{\leq}log\;k^{\prime}{\leq}1$). The dependence of the capacity factor(log k') on the volume fraction of water in the binary mobile phase showed a good linearity. Also, there was a good linear dependence of the capacity factor on the liquid-liquid extraction distribution ratio($D_c$) in methanol-water/n-pentadecane extraction system by the batch method. It suggested that the retention of the chelates in the reverse phase liquid chromatographic system be largely due to the solvophobic effect.

• YAKHAK HOEJI
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• v.17 no.4
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• pp.235-243
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• 1973

Determinations of the compositioin ofl chinoform metal chelates by elemental analysis and molar ratio method showed that the ratios of the ligand to metals in chinoform Cu(II) chelate, chinofrm Ni (II) chelate, and chinoform CO(II) chelate were 2:1 respectively and that the ratio in chinoform Fe(III) chelate was 3:1. It was found that diffe rential thermal values vary with the center metalic ions and that the thermal stability was in anorder of Fe>Cu>Co>Ni. The indices of over-all stability constant of chinoform Cu(II) chelate, Ni(II) chelate, Co(II) chelate, and Fe(III) chelate were 15.57, 15.16, 15.40 and 20.76, respectively, and the over-all stability was in an order of Fe>Cu>Co>Ni. The tests of the natibacterial activity in vitro of the chinoform metal chelates against Staphylococcus aureus ATCC G538, Pseudomonas aeruginosa 2131, Serratia marcescens 3357, Klebsiella pneumoniae 8899, Enterococcus 3309, Streptococcus pyogenes 507, and Escherichia coli 125 showed that the Cu(II) chelate generally had greater activity than chinoform, that it had four-fold activity particularly against Streptococcus pyogenes 507 and Staphylococcus awreus ATCC 6538, that the Ni(II) and Co(II) chelates had almost same activity, and that the Fe chelate had strong activity against Escherichia coli 125.

• Journal of the Korean Chemical Society
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• v.55 no.6
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• pp.912-918
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• 2011

Tetraaza Schiff base macrocyclic ligands, $L^1$,$L^2$ and their transition metal chelates have been synthesized and characterized by elemental analyses, IR, electronic, EPR and $^1H$ NMR spectra, TGA and magnetic measurements. The molar conductance of one milli-molar solution of the complexes measured in DMF indicates that the divalent metal complexes are nonelectrolyte while those of trivalent metal ion, are 1:1 electrolytic in the same solvent. The reduction of Racah parameter from the free ion value confirms the presence of considerable covalence of metal ligand sigma bond in the Co(II) and Mn(II) complexes. The EPR spectra of Cu(II) complexes at room temperature shows axial symmetry indicating a $d_x{^2}_{-y}{^2}$ ground state with significant covalent character. The thermal analysis suggests that the complexes do not contain water molecules because only the metal is left as residue.

• Bulletin of the Korean Chemical Society
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• v.25 no.5
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• pp.694-698
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• 2004

A new method for the simultaneous determination of seven transition metal ions in water and food by microcolumn high-performance liquid chromatography has been developed. The lead, cadmium, mercury, nickel, cobalt, silver and tin ions were pre-column derivatized with tetra-(4-aminophenyl)-porphyrin ($T_4$-APP) to form the colored chelates which were then enriched by solid phase extraction with $C_{18}$ cartridge. The enrichment factor of 50 was achieved by eluted the retained chelates from the cartridge with tetrahydrofuran (THF). The chelates were separated on a ZORBAX Stable Bound microcolumn ($2.0{\times}50\;mm,\;1.8\;{\mu}m$)with methanol-tetrahydrofuran (95 : 5, v/v, containing 0.05 mol/L pyrrolidine-acetic acid buffer salt, pH = 10.0) as mobile phase at a flow rate of 0.5 mL/min and detected with a photodiode array detector from 350-600 nm. The seven chelates were separated completely within 2.0 min. The detection limits of lead, cadmium, mercury, nickel, cobalt, silver and tin are 4 ng/L, 3 ng/L, 6 ng/L, 5 ng/L, 5 ng/L, 6 ng/L, 4 ng/L respectively in the original samples. This method was applied to the determination of the seven transition metal in water and food samples with good results.

• Journal of the Korean Chemical Society
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• v.12 no.3
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• pp.81-84
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• 1968

Stabilities of chelates of 7-nitroso-8-hydroxyquinoline-5-sulfonate have been determined for divalent transition metal ions, Mn(Ⅱ), Fe(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), and Zn(Ⅱ) by means of the Calvin-Bjerrum technique. Comparison of these stability constants with those obtained for 8-hydroxyquinoline, and 8-hydroxyquinoline-5-sulfonate shows that the observed differences are essentially the results of the lower basicity of the sulfonated group and different metal-ligand bond. The divalent metal chelate stability sequence is not in agreement with the reported metal orders for other chelating agents. The stabilities were found to follow the order Mn(Ⅱ) < Fe(Ⅱ) ${\approx}$ Co(Ⅱ) > Ni(Ⅱ) < Cu(Ⅱ) > Zn(Ⅱ).