• Bulletin of the Korean Chemical Society
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• v.25 no.1
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• pp.85-89
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• 2004

Geometrical structures of [Pd(L)$Cl_2$] with oxathia macrocycles have been calculated using ab initio secondorder Moller-Plesset (MP2) and Density Functional Theory (DFT) methods with triple zeta plus polarization (TZP) basis set level. In optimized Pd(L)$Cl_2$ complexes, Pd(II) locates at the center surrounded by a square planar array of two sulfurs on an oxathia macrocycle and two chlorides. The endo-Pd(II) complexes with an axial (Pd${\cdots}$O) interaction are more stable than the exo-Pd(II) complexes without the interaction. In the endo-Pd(II) complexes, the atomic charge of the oxygen atom moves to Pd(II) via the axial ($Pd{\cdots}$O) interaction and then, the charge transfer from Pd(II) to the S-atoms occurs stepwise via ${\pi}$-acceptors of the empty d-orbitals.

• Journal of the Korean Chemical Society
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• v.30 no.3
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• pp.320-326
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• 1986

The antitumor properities of metal are not limited to Pt(II) complexes. Recently, it was reported that some Pt(II) and Pd(II) complexes with sulfur and nitrogen ligands had potential antitumor reactivity. Pt(II) complexes is toxic drug for anticancer. Therefore, the complexes of Pd(II) with adenine, uracil, cytosine and malonate ligands are interesting for anticancer drug. We synthesized new palladium complexes containing nucleosides. The reactions of Pd(II) with adenine, uracil, cytosine and malonate ligands have been studied in aqueous solutions. The complexes isolated from these reactions have the following formulas; $[Pd(en)(C_5H_5N_5)_2](NO_3)_2,\;[Pd(en)(C_4H_3N_2O_2)Cl],\;[Pd(en)(C_3H_2O_4)]\;and\;[Pd(en)(C_4H_5N_3O)_2](NO_3)_2{\cdot}(C_4H_5N_3O)$. The compounds have been identified by elemental analysis, mass spectra, infrared spectra and electronic spectra.

• Archives of Pharmacal Research
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• v.15 no.4
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• pp.336-342
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• 1992

Ten [$Pd^{II}$(dicarboxylato)(1, 2-diaminocyclohexane)] complexes were prepared after the antitumor-active Pt(II)1, 2-diaminocyclohexane complexes as the cisplatin analogues of palladium series. They were characterized by means of elemental analysis, IR and NMR spectroscopy. As a result, the dicarboxylate ligands were conformed to be chelated with Pd(II) within the scope studied. The stability differences beween the dicarboxylato complexes according to the chelate ring size could not be differentiated due to generally lower thermodynamic stability of the dicarboxylato Pd(II) complexes.

• 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.

• Bulletin of the Korean Chemical Society
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• v.30 no.9
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• pp.1951-1955
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• 2009

A Thermodynamic study on the interaction of bovine calf thymus DNA with new designed Pd(II) complex (Ethylendiamine- 8-hydroxyquinolinato Palladium(II) chloride) was studied by using isothermal titration calorimetry (ITC) at 27 ${^{\circ}C}$ in Tris buffer solution at pH = 7.5. The enthalpies of Pd(II) complex + DNA interaction are reported and analysed in terms of the new solvation theory. It was indicated that there are three identical and non-cooperative sites for Pd(II) complex. The binding of a Pd(II) complex is endothermic with association equilibrium constants of 428.03 m$M^{-1}$ at 27 ${^{\circ}C}$. The binding of Pd(II) complex can cause some changes in the stability of the DNA at low and high Pd(II) complex concentrations. Our results suggested that this complex might interact with DNA as an intercalator, thus interfering with DNA replication and cell proliferation.

• Membrane and Water Treatment
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• v.9 no.6
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• pp.463-471
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• 2018

The present paper deals with the liquid-liquid extraction and flat sheet supported liquid membrane studies of Pd(II) separation from nitric acid medium using a novel synthesized ligand, namely, N,N,N',N'-tetraethyl-2,2-thiodiethanthiodiglycolamide (TETEDGA). The effect of various diluents and stripping reagents on the extraction of Pd(II) was studied. The liquid-liquid extraction studies showed complete extraction of Pd(II) in ~ 5 min. The influence of nitric acid and TETEDGA concentration on the distribution of Pd(II) has been investigated. The increase in nitric acid concentration resulted in increase in extraction of Pd(II). Stoichiometry of the extracted species was found to be $Pd(NO_3)_2{\cdot}TETEDGA$ by slope analysis method. Extraction studies with SSCD solution showed negligible uptake of Pt, Cr, Ni, and Fe, thus showing very high selectivity and extractability of TETEDGA for Pd(II). The flat sheet supported liquid membrane studies showed quantitative transport of Pd(II), ~99%, from the feed ($3M\;HNO_3$) to the strippant (0.02 M thiourea diluted in $0.4M\;HNO_3$) using 0.01 M TETEDGA as a carrier diluted in n-dodecane. Extraction time was ~160 min. Parameters such as feed acidity, TETEDGA concentration in membrane phase, membrane porosity etc. were optimized to achieve maximum transport rate. Permeability coefficient value of $2.66{\times}10^{-3}cm/s$ was observed using TETEDGA (0.01 M) as carrier, at 3 M, $HNO_3$ feed acidity across $0.2{\mu}m$ PTFE as membrane. The membrane was found to be stable over five runs of the operation.

• Journal of the Korean Chemical Society
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• v.37 no.7
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• pp.662-671
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• 1993

New Ni(II) and Pd(II) complexes of isonitrosomethylacetoacetate imine derivatives, Ni(IMAA-NH)(IMAA-NH'), Ni(IMAA-NH)(IMAA-NR), $Pd(IMAA-NH)_2\;and Pd(IMAA-NR)_2(R=CH_3,\;C_2H_5,\;n-C_3H_7,\;n-C_4H_9,\;or\;CH_2C_6H_5)$, where H-IMAA-NH and H-IMAA-NR represent isonitrosomethylacetoacetate imine and N-alkylisonitrosomethylacetoacetate imine derivative, respectively, have been prepared and the structures of the complexes have been studied by elemental analyses, electronic, infrared, and $^1H-\;and\;^{13}C-NMR$ spectroscopies.

• Journal of the Korean Chemical Society
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• v.27 no.4
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• pp.268-272
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• 1983

Polyurethane foam impregnated with ${\beta}$-diphenylglyoxime has been applied to the extraction of palladium(II) from platinum(IV) and nickel(II) in aqueous solution. Palladium(II) is quantitatively extracted from $0.01{sim}0.05M$ HCl. On the other hand, platinum(Ⅳ) was slightly extracted and nickel(II) was not found to be extraction in the same experimental condition. Based on the results obtained, the selective separation, removal and recovery of Pd(II) from Pt(IV) or Ni(II) was possible by batch or elution method.

• Journal of the Korean Chemical Society
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• v.42 no.4
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• pp.369-377
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• 1998

The palladium(II) and platinum(II) complexes(where, $([M(L)_2X_2]$, M=Pd(II), Pt(II); L=isoxazole(isox), 3,5-dimethylisoxazole(3,5-diMeisox), 3-methyl, 5-phenylisoxazole(3-Me, 5-Ph-isox), and 4-amino-3,5-dimethylisoxazole (4-ADI); X=Cl, Br) with isoxazole and its derivatives were investigated on antitumor activity by MM2 and EHMO calculation. Because for all the complexes the ${\sigma}MO$ energy level $(E_{{\sigma}(M-X)})$ between $d_x^{2-}_y^2$ orbital of central metal and px orbital of halogen atom is less than ${\sigma}MO$ energy level $(E_{{\sigma}(M-N)})$ between $d_x^{2-}_y^2$ orbital of central metal and px orbital of N atom, without exception. And judging, from the lower $(E_{\'{o}(m-x)})$ value in trans, the bonding strength was found to be weaker in trans isomer than in cis. For the Pd(II) and Pt(II) complexes which have planar ligands, it was shown that for all the complexes dissociation of X-atom in the Pd(II) complexes is easier than that of X-atom in the Pt(II) complexes in both cis- and trans-complexes. Therefore it suggests that the easier dissociation of $X^-$ ion has some relations with antitumor activity, and a linear equation with correlation coefficient of 0.96 was found between ${\Delta}E_{{\sigma}(N-X)}(E_{{\sigma}(M-N)}-E_{{\sigma}(M-X)})$ and inhibitory activity coefficient, logIA.

• Nuclear Engineering and Technology
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• v.53 no.4
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• pp.1218-1223
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• 2021

A hydrophobic ionic liquid including an amino moiety ([DiOcAPmim][NTf₂]) was synthesized. Its extraction behaviors towards Pd(II), Ru(III), Rh(III) were investigated in nitric acid aqueous solution as a function of contact time, effect of concentration of nitric acid, effect of temperature, and effect of co-existing metal ions. The extraction kinetics of Pd(II) was fairly fast and extraction equilibrium can be attained within only 5 min under the [HNO₃] = 2.05 M. When [HNO₃]< 1 M, the extraction percentage of Pd(II), Ru(III), Rh(III) were all above 80%. When [HNO₃] reached 2 M, all of the extraction percentage decreased and in an order of Pd(II)>Ru(III)>Rh(III). When [HNO₃]> 2 M, the extraction performance gradually recovered. The effect of temperature can slightly affect the extraction performance of Pd(II). Furthermore, in simulated high-level liquid waste, [DiOcAPmim][NTf₂] showed a better preference towards Pd(II) under the interference of various other co-existing metal ions.