• Bulletin of the Korean Chemical Society
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• v.27 no.9
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• pp.1405-1417
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• 2006

The geometrical structures, potential energy surfaces, and energetics for the ligand exchange reactions of tetracoordinated platinum $(PtY_2L_2\;:\;Y,\;L=Cl^-,\;OH^-,\;OH_2,\;NH_3)$ complexes in the ligand-solvent interaction systems were investigated using the ab initio Hartree-Fock (HF) and Density Functional Theory (DFT) methods. The potential energy surfaces for the ligand exchange reactions used for the conversions of $(PtCl_4\;+\;H_2O)^{^\ast_\ast}\;to\;[PtCl_3(H_2O)\;+\;Cl^-]$ and $[Pt(NH_3)_2Cl_2\;+\;H_2O]$$[Pt(NH_3)_2Cl_2\;+\;H_2O]$ to $[Pt(NH_3)_2Cl(H_2O)\;+\;Cl^-] $ were investigated in detail. For these two exchange reactions, the transition states $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime])^{^\ast_\ast} $ correspond to complexes such as $(PtCl_4{\cdot}{\cdot}{\cdot}H_2O)^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$, respectively. In the transition state, $([PtCl_4{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]]^{^\ast_\ast})$ have a kind of 6-membered $(Pt-Cl{\cdot}{\cdot}{\cdot}HOH{\cdot}{\cdot}{\cdot}Cl)$ and $(Pt-OH{\cdot}{\cdot}{\cdot}Cl{\cdot}{\cdot}{\cdot}HN)$ interactions, respectively, wherein a central Pt(II) metal directly combines with a leaving $Cl^-$ and an entering $H_2O$. Simultaneously, the entering $H_2O$ interacts with a leaving $Cl^-$. No vertical one metal-ligand interactions $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime]) $ are found at the axial positions of the square planar $(PtY_2L_2)$ complexes, which were formed via a vertically associative mechanism leading to $D_{3h}$ or $C_{2v}$-transition state symmetry. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes are also examined quantitatively. Schematic diagrams for the dissociation reactions of {PtCl4(H2O)n(n=2,4)} into {$PtCl_3(H_2O)_{(n-2)}\;+\;Cl^-(H_2O)_2$} and the binding energies {$PtCl_4(H_2O)_n$(n = 1-5)} of $PtCl_4$ with water molecules are drawn.

• Bulletin of the Korean Chemical Society
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• v.8 no.6
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• pp.476-479
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• 1987

The macrocyclic nickel complex of the molecular formula[Ni($C_{32}H_{26}N_4$)] has been synthesized from the template condensation reaction between 1-benzoylacetone and o-phenylenediamine in the presence of nickel acetate. Protonation and deuterium exchange reactions of the demetallated macrocyclic ligand and the nickel complex have been carried out. The infrared, electronic and proton magnetic resonance spectral data of both compounds are compared and discussed; protonation of the macrocyclic ligand take place at the nitrogen atoms and all the amine protons undergo very rapid deuterium exchange while the methine protons undergo very slow exchange. On the other hand, protonation of the nickel complex occurs at the nitrogen atoms and only amine protons undergo rapid deuterium exchange. Protonation and deprotonation of the nickel complexes proceed reversibly.

• Bulletin of the Korean Chemical Society
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• v.29 no.3
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• pp.627-640
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• 2008

The geometrical structures, atomic charges, and relative energies of tetracoordinated Pd complexes [PdCl3Z (Z = Cl-, Br-, OH?-, H2O, NH3, PH3), PdCl2Z2 (Z = Br-, OH?-, H2O, NH3, PH3), PdZ?2X (Z = Cl-, OH?-, H2O, NH3, PH3; X = oxalate, O2-?CCO2-), and PdZ2Y (Z = Cl?-, OH?-, H2O, NH3, PH3; Y = succinate, CO2-?CHCHCO2-?)] and the ligand exchange reactions of the Pd complexes were investigated using the ab initio second order Mller-Plesset perturbation (MP2) and Density Functional Theory (DFT) methods. The geometrical characteristics of the tetracoordinated Pd(II) complexes with mono- and bidentate ligands, the effects of the atomic charges for the charged and uncharged ligands, the (dz2-p ) interactions between the dz2-orbital of Pd(II) and the p -orbital of bidentates, and the relative stabilities between the isomers of PdCl2Z2 and PdZ2Y were investigated in detail. The potential energy surfaces for the ligand exchange reactions used for the conversions of {[PdCl2(NH3)2] + H2O} to {[PdCl(NH3)2(H2O)]+ + Cl?-?} and {[PdCl2(PH3)2] + H2O} to {[PdCl(PH3)2(H2O)]+ + Cl?-?]} were investigated. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes were also examined quantitatively.

• Journal of Environmental Science International
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• v.6 no.5
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• pp.505-512
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• 1997

The Interfacial characteristics between various heavy metals and hydrous FeS were investigated. Heavy metals which have lower sulfide solubilities than FeS undergoes the lecttice exchange reaction when these metal tons contact FeS In the aqueous phase. For heavy metals which have higher suede solubilities than FeS, these metal ions adsorb on the surface of FeS. Such characteristic reactions were interpreted by the soled solution formation theory. The presence of ligand such as EDTA reduced largely metal removal efficiency due to formation of metal-ligand complex In the solution. In an attempt to elucidate the Interfacial characteristics, zeta potential of the hydrous FeS In the absence and In the presence of various metal loons were measured and analyzed.

• Bulletin of the Korean Chemical Society
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• v.31 no.11
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• pp.3118-3122
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• 2010

The water soluble redox polymer, poly(N-vinylimidazole) complexed with Os(4,4'-dichloro-2,2'-bipyridine)$_2Cl]^+$ (PVI-[Os(dCl-bpy)$_2Cl]^+$), was electrodeposited on the surface of a glassy carbon electrode by applying cycles of alternating square wave potentials between 0.2 V (2 s) and 0.7 V (2 s) to the electrode in a solution containing the redox polymer. The coordinating anionic ligand, $Cl^-$ of the osmium complex, became labile in the reduced state of the complex and was substituted by the imidazole of the PVI chain. The ligand substitution reactions resulted in crosslinking between the PVI chains, which made the redox polymer water insoluble and caused it to be deposited on the electrode surface. The deposited film was still electrically conducting and the continuous electrodeposition of the redox polymer was possible. When cycles of square wave potentials were applied to the electrode in a solution of bilirubin oxidase and the redox polymer, the enzyme was co-electrodeposited with the redox polymer, because the enzymes could be bound to the metal complexes through the ligand exchange reactions. The electrode with the film of the PVI-[Os(dCl-bpy)$_2Cl]^+$ redox polymer and the co-electrodeposited bilirubin oxidase was employed for the reduction of $O_2$ and a large increase of the currents was observed due to the electrocatalytic $O_2$ reduction with a half wave potential at 0.42 V vs. Ag/AgCl.

• Bulletin of the Korean Chemical Society
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• v.7 no.1
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• pp.45-50
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• 1986

Separation of optical isomers of some derivatives of amino acids by reversed-phase HPLC has been accomplished by adding a chelate of an optically active amino acid to copper(Ⅱ) to the mobile phase. Cu(Ⅱ) complexes of L-proline and L-hydroxyproline in the mobile phase showed different degrees of separation. Optical isomers of DNS derivatives of amino acids are selectively separated, but those of several other derivatives are not at all. The kinds of buffer agents, the pH, and the concentrations of acetonitrile and the Cu(Ⅱ) ligand all affect the separations. The elution behavior between D and L DNS-amino acids appears to depend on the alkyl side chain of the amino acids. A chromatographic mechanism is proposed that is based on a stereospecificity of the formation of ternary complexes by the D, L-DNS-amino acids and the chiral additive associated with the stationary phase. The steric effects of the ligand exchange reactions are related with the feasibility of cis and/or trans attack of the amino acids to the binary chiral chelate retained on the stationary phase.

• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.223-229
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• 1992

Mechanistic studies on the metal-exchange reactions of sparteine copper(II) dichloride [$SpCuCl_2$] with Hg(II) ion and Hg(0) metal have been carried out with the aid of Cyclic Voltammetry and UV-visible spectrophotometry. The metal exchange reaction of $SpCuCl_2$ with both Hg(II) ion and Hg(0) metal follows pseudo-first order kinetics. Rate constants and activation parameters of metal exchange reaction have been evaluated and reported. Experimental results indicate that the rate determining step for the exchange reaction is the cleavage of Cu(II)-N bond in the transient binuclear complex of Cu(II) and mercury(II) bound to sparteine ligand.

• Proceedings of the Korean Society of Applied Pharmacology
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• 2000.04a
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• pp.17-19
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• 2000

Heterotrimeric G Proteins transduce ligand binding to a wide variety of seven transmembrane cell surface receptors into intracellular signals. The currently accepted model for the activation of G protein suggests that ligand-activated receptor accelerates GDP-GTP exchange reactions on the ${\alpha}$ subunit of the heterotrimeric G protein. At least seventeen distinct isoforms of the G${\alpha}$ subunit protein have been identified in mammalian organisms. Among them, the G${\alpha}$q family consists of five members whose ${\alpha}$ subunits show different expression patterns. G${\alpha}$q and G${\alpha}$11 seem to be almost ubiquitously expressed, whereas G${\alpha}$14 is predominantly expressed in spleen, lung, kidney and testis. G${\alpha}$16 and its murine counterpart G${\alpha}$15 are expressed in hematopoietic cells and has been shown to couple a wide variety of receptors to phosphoinositide-specific phospholipase C activity. Beta-isoforms of phospholipase C were shown to be activated by all members of G${\alpha}$q family, i.e., G${\alpha}$q, G${\alpha}$11, G${\alpha}$l4 and G${\alpha}$16 subunits either in reconstitution system. or in experiments using cDNA transfection with intact Cos-7 cells.

• Journal of Powder Materials
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• v.30 no.1
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• pp.53-64
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• 2023

Atomic layer etching (ALE) is a promising technique with atomic-level thickness controllability and high selectivity based on self-limiting surface reactions. ALE is performed by sequential exposure of the film surface to reactants, which results in surface modification and release of volatile species. Among the various ALE methods, thermal ALE involves a thermally activated reaction by employing gas species to release the modified surface without using energetic species, such as accelerated ions and neutral beams. In this study, the basic principle and surface reaction mechanisms of thermal ALE?processes, including "fluorination-ligand exchange reaction", "conversion-etch reaction", "conversion-fluorination reaction", "oxidation-fluorination reaction", "oxidation-ligand exchange reaction", and "oxidation-conversion-fluorination reaction" are described. In addition, the reported thermal ALE processes for the removal of various oxides, metals, and nitrides are presented.

• Journal of the Korean Magnetic Resonance Society
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• v.21 no.4
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• pp.135-138
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• 2017

Titanium phenoxide and titanium carboxylate derivatives were prepared by ligand exchange of titanium tetraisopropoxide with the corresponding phenol and carboxylic acids. The substitution reactions were analyzed by NMR focused in the liberation of isopropylalcohol. The chemical shift of secondary proton of isopropyl group shifted to upfield after liberation; from 4.47 ppm at titanium-bound to 4.1~4.3 ppm at free alcohol state in $CDCl_3$. The substitution reaction of titanium tetraisopropoxide with carboxylic acid was applied to form dye-Ti complex for dye-sensitized solar cell.