• 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.

• Bulletin of the Korean Chemical Society
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• v.18 no.9
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• pp.1002-1006
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• 1997

1H NMR spectra of D2O solutions containing 2,2-dimethylaziridine (1) or 2-methylaziridine (2) and [SiW11COⅡO39]6- (SiW11Co) or [SiW11NiⅡO39]6- (SiW11Ni) exhibit separate signals for the free ligand and the complex, indicating that the ligand exchange is slow on the NMR time scale. Identified are two linkage isomers with the methyl group of 2 at trans or cis position with respect to the metal. The isotropic shifts of 1 and 2 coordinated to SiW11Ni originate mainly from the contact shifts, and they agree reasonably with the relative values reported for similar ligands coordinated to bis(2,4-pentanedionato)nickel(Ⅱ). The isotropic shifts for the SiW11Co complexes were separated into contact and pseudocontact contributions. The pseudocontact shifts show that (χ∥-χ⊥) is positive, while that for the SiW11Co complexes of pyridine derivatives is negative. This result indicates that the ordering of dxy and dxz, dyz orbitals in SiW11Co complexes can be reversed by ligands.

• Bulletin of the Korean Chemical Society
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• v.15 no.12
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• pp.1064-1069
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• 1994

Chlorobis(isoprene)rhodium(Ⅰ) (3), prepared by olefin-exchange reaction of chlorobis(cyclooctene)rhodium dimer (2) with isoprene, reacted with benzaldimine 4 to give iminoacylrhodium(Ⅲ) ${\eta}^3$-1,2-dimethylallyl complex 6. Ligand-promoted reductive elimination of 6 by pyridine and P(OMe)$_3$ produced ${\beta},{\gamma}$-unsaturated ketimine 8, which was readily hydrolyzed to give ${\beta},{\gamma}$-unsaturated ketone 9. Other methyl branched dienes such as 2,3-dimethylbutadiene, 3-methyl-1,3-pentadiene, 2-methyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 3-methyl-1,4-pentadiene and 2-methyl-1,4-pentadiene, were applied the synthesis of ${\beta},{\gamma}$-unsaturated ketones. In case of 2,4-dimethyl-1,3-pentadiene, only ${\gamma},{\delta}$ -unsaturated ketone 25, 1,2-addition product, was obtained, may be due to the mono-olefin coordination.

• Bulletin of the Korean Chemical Society
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• v.13 no.3
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• pp.280-285
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• 1992

Enantiomeric separation of free amino acids has been achieved by a reversed phase liquid chromatography with addition of a Cu(Ⅱ) complex of N-alkyl-L-proline (alkyl: propyl, pentyl or octyl) to the mobile phase. The amino acids eluted were detected by a postcolumn OPA system. N-alkyl-L-proline was prepared and used as a chiral ligand of Cu(Ⅱ) chelate for the enantiomeric separation. The concentration of the Cu(Ⅱ) chelate, the organic modifier and pH affect the enantiomeric separation of free amino acids. The retention behaviour, varied with change in pH and the concentration of the Cu(Ⅱ) chelate, was different compared with those of the derivatized amino acids. The elution orders between D- and L-forms were consistent except histidine showing that L-forms elute earlier than D-forms. The retention mechanism for the enantiomeric separation can be illustrated by the stereospecificity of the ligand exchange reaction and the hydrophobic interaction between the substituent of amino acids and reversed phase, $C_18$.

• 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.

• Membrane Journal
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• v.32 no.5
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• pp.348-356
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• 2022

With the development of the bio industry, membrane chromatography with a high adsorption efficiency is emerging to replace the existing column chromatography used in the downstream processes of pharmaceuticals, food, etc. In this study, through the deacetylation reaction of two commercial cellulose acetate (CA) membranes with different pore sizes, the porous regenerated cellulose (RC) supports for membrane chromatography were obtained to attach the anion exchange ligands. The adsorptive membranes for anion exchange were prepared by attaching an anion exchange ligand ([3-(methacryloylamino) propyl] trimethylammonium chloride) containing quaternary ammonium groups on the RC supports by grafting and UV polymerization. The protein adsorption capacities of the prepared membranes were obtained through both the static binding capacity (SBC) and the dynamic adsorption capacity (DBC) measurement. As a result, the membrane chromatography with the smaller the pore size, the larger the surface area showed the highest protein adsorption capacity. Membrane chromatography which was prepared by using deacetylated commercial CA support with MAPTAC ligand (i.e., RC 0.8 + MAPTAC: 43.69 mg/ml, RC 3.0 + MAPTAC: 36.33 mg/ml) showed a higher adsorption capacity compared to commercial membrane chromatography (28.38 mg/ml).

• The Korean Journal of Nuclear Medicine
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• v.16 no.2
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• pp.81-84
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• 1982

To evaluate the in-vivo and in-vitro stability of methylene diphosphonate $(MDP)-^{99m}Tc$, relative ligand exchange rates in phosphate buffer between $MDP-^{99m}Tc$ and human serum albumin (HSA), and between pyrophosphate$(PYP)-^{99m}Tc$ and HSA have been measured. Gel permeation chromatography has also been carried out to estimate relative rates of ligand exchange between polysaccharide and the $^{99m}Tc-bone$ agents. The in-vitro stability was further correlated with its specific radioactivity. The results indicated that the $MDP-^{99m}Tc$ is more stable than the $PYP-^{99m}Tc$ but less stable than $MIDA-^{99m}Tc$, $HIDA-^{99m}Tc$, and $DTPA-^{99m}Tc$ etc. in refering to other data. In stability point of view, $MDP-^{99m}Tc$ is considered to be a better bone agent than $PYP-^{99m}Tc$ since $MDP-^{99m}Tc$ can be accumulated at bone by a smooth transfer of $^{99m}Tc$ to hydroxyapatite, whereas in case of $PYP-^{99m}Tc$, most of the $^{99m}Tc$ is transferred to HSA before arriving to the hydroxyapatite.

• Analytical Science and Technology
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• v.17 no.2
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• pp.91-97
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• 2004

Cryptand ion exchange resins were synthesized with 1-aza-15-crown-5 macrocyclic ligand attached to styrene divinylbenzene (DVB) copolymer with crosslink of 1%, 2%, 5% and 10% by substitution reaction. The synthesis of these resins was confirmed by content of chlorine, element analysis, and IR-spectrum. The effects of pH, time, dielectric constant of solvent and crosslink on adsorption of uranium ($UO{_2}^{2+}$) ion were investigated. The uranium ion was showed fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in ethanol was in increasing order uranium ($UO{_2}^{2+}$), magnesium ($Mg^{2+}$), neodymium ($Nd^{3+}$) ion. The adsorption was in order of 1%, 2%, 5%, and 10% crosslink resin and adsorption of resin decreased in proportion to order of dielectric constant of solvents.

• BMB Reports
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• v.52 no.11
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• pp.659-664
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• 2019

Vav1 is a Rho/Rac guanine nucleotide exchange factor primarily expressed in hematopoietic cells. In this study, we investigated the potential role of Vav1 in osteoclast (OC) differentiation by comparing the ability of bone marrow mononuclear cells (BMMCs) obtained from Vav1-deficient ($Vav1^{-/-}$) and wild-type (WT) mice to differentiate into mature OCs upon stimulation with macrophage colony stimulating factor and receptor activator of nuclear kappa B ligand in vitro. Our results suggested that Vav1 deficiency promoted the differentiation of BMMCs into OCs, as indicated by the increased expression of tartrate-resistant acid phosphatase, cathepsin K, and calcitonin receptor. Therefore, Vav1 may play a negative role in OC differentiation. This hypothesis was supported by the observation of more OCs in the femurs of $Vav1^{-/-}$ mice than in WT mice. Furthermore, the bone status of $Vav1^{-/-}$ mice was analyzed in situ and the femurs of $Vav1^{-/-}$ mice appeared abnormal, with poor bone density and fewer number of trabeculae. In addition, Vav1-deficient OCs showed stronger adhesion to vitronectin, an ${\alpha}_v{\beta}_3$ integrin ligand important in bone resorption. Thus, Vav1 may inhibit OC differentiation and protect against bone resorption.

• 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.