• Journal of the Korean Chemical Society
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• v.34 no.1
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• pp.76-84
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• 1990

Optical isomers of dansyl amino acids were separated by a chiral mobile phase addition method. Two metha and para isomers of xylenyl-L-proline were prepared and used as the ligands of copper(Ⅱ) chelate to resolve the dansyl amino acids. Their elution behaviors were similar to those obtained from the addition of copper (Ⅱ) benzyl-L-proline chelate. The matrix effect of the mobile phase such as pH, concentration of buffer and compositions of organic solvent acetonitrile affected the optical resolution. The separation mechanism could be explained by a cis-trans effect of the ligand exchange reaction and hydrophobic interaction between the ternary complex and the stationary phase.

• Journal of the Microelectronics and Packaging Society
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• v.23 no.3
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• pp.15-20
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• 2016

In an effort to overcome the weakness of aerogel, polymer aerogels have been prepared by copolymerizing the different types of monomers through sol-gel process. Polymerizing the successive phase of a high internal phase emulsion, which has interconnected porous structure, porous polymer aerogel can be manufactured. In this paper, we use the styrene/divinylbenzene chain as a basic monomer structure, and additionally use 2-ethylhexyl methacrylate (2-EHMA) or 2-ethylhexyl acrylate (2-EHA) as monomers for distinguishing the visible mechanical properties of synthesized polymer aerogel. We can observe the different tendency of polymer aerogels by kinds of monomer or ratio. Flexibility and microstructure can be changed by the types of monomer. EHA polymer aerogel shows high flexibility and thin microstructure, and EHMA polymer aerogel shows high hardness and thick microstructure. EHA/EHMA polymer aerogel shows the intermediate nature between them. By utilizing the mechanical properties of three types of polymer aerogels to adequate situation or environment, polymer aerogels could be used as drug agent, ion exchange resin, oil filter and insulator, and so on.

• Bulletin of the Korean Chemical Society
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• v.11 no.5
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• pp.411-415
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• 1990

The dabsylation of amino acids has been applied to resolve their optical isomers with the use of chiral mobile phase in high performance liquid chromatography. The dabsyl amino acids were successfully separated on reversed phase column($C_{18}$) by adding a chiral L-benzylproline-Cu(II) chelate to the mobile phase. The separation selectivity of the dabsyl amino acid enantiomers was not less than that of dansyl amino acids. The retention order of the dabsyl amino acid enantiomers was as those of the dansyl amino acid enantiomers except dabsyl threonine. The optical selectivity of the dabsyl amino acids increase with pH of the mobile phase and concentration of the chelate, but slightly decreases with concentration of buffer and organic solvent composition. However serine, methionine, valine, and leucine showed a slight decrease in the optical selectivity with increase in pH. The retention times of the dabsyl amino acids decreases with increasing pH and acetonitrile concentration but increases with the concentration of the chiral chelate added. The mechanism of the optical resolution is based on a stereospecific interaction including a intramolecular hydrophobic effect and SN-2 reactivity of the ligand exchange chromatography.It is advantageous to detect absorption at 436 nm, which is less interferent them the other detection systems. The derivatized dabsyl amino acids are stable for a month.

• Analytical Science and Technology
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• v.11 no.6
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• pp.460-468
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• 1998

Schiff base ligands such as $SOPDH_2$, $SNDH_2$, $EBNH_2$, and $PBNH_2$ and their Co(II) complexes such as [$Co(II)(SND)(H_2O)_2$], [$Co(II)(SOPD)(H_2O)_2$], [$Co(II)(EBN)(H_2O)$], and [$Co(II)(PBN)(H_2O)$] have been synthesized. The mole ratio of Shiff base ligand to cobalt(II) for the Co(II) complexes was found to be 1:1. Also these complexes have been configurated with hexa-coordination. Reduction of dioxygen was investigated by cyclic voltammetry at glassy carbon electrodes modified with Schiff base Co(II) complexes in 1 M KOH aqueous solution. At modified glassy carbon electrode with Schiff base Co(II) complexes, reduction peak current of oxygen was increased and peak potential was shifted to more positive direction compared to bare glassy carbon electrode. The electrokinetic parameters such as number of electron and exchange rate constant were calculated from the results of cyclic voltammogrms. The reduction of dioxygen at glassy carbon electrode has been $2e^-$ reaction pathway. Exchange rate constant at glassy carbon electrode modified with Co(II) complexes was increased 2~10 times compared to bare electrode.

• Journal of the Korean Chemical Society
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• v.34 no.2
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• pp.143-158
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• 1990

Metal complexes were prepared by reacting uranium (Ⅵ), thorium (Ⅳ) and rare earth metal (Ⅲ) ions including Nd (Ⅲ), Sm (Ⅲ) and Ho (Ⅲ) with macrocyclic ligands including five crown ethers, nine crownands and one cryptand ligands, and subjected to NMR studies in order to examine coordination sites of the ligands and compositions of the complexes formed. Among the marcocyclic ligands, crown ethers and crownand ligands have shown down-field shifts of the methylene protons of the lcigands by forming stable complexes with all the metal ions and the differences of chemical shifts were decreased as increasing of the cavity-size of crown ethers for the same metal ions and decreasing of the atomic number of the rare earth metals for the same ligands. It has been found that crownand 22 gave a stable complex with uranium(Ⅵ) ion by the coordination through both oxygen and nitrogen atoms of the ligand whereas no complex was formed with the rare earth metal(Ⅲ) ions, which on the other hand were found to form stable complexes with cryptand 221. The rest of the crowand ligands have also been found to form stable complexes with uranium(Ⅵ) ion by coordinating through all the oxygen and nitrogen atoms of the ligands whereas no complexes were formed with the rare earth metal(Ⅲ) ions. It has also been shown by 1H-NMR study that uranium(Ⅵ), thorium(Ⅳ) and rare earth metal(Ⅲ) ions formed 1:1 complexes with the macrocyclic ligands except for thorium(Ⅳ) complex of 12C4 in which the mole ratio of metal to ligand is 1:2. More stable metal complexes show larger changes in chemical shifts of the coordinated ligand protons. Finally, the rare earth metal(Ⅲ) complexes of 18C6 have shown ligand exchange reaction with the solvent molecules in acetylacetone solution, which was not observed for the uranium (Ⅵ) complexes.

• Progress in Superconductivity
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• v.9 no.1
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• pp.85-90
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• 2007

Lanthanum aluminate($LaAlO_3$) film has been prepared on single crystal and metal substrates by dip coating method. Lanthanum acetate and aluminum were prepared via ligand exchange starting from lanthanum nitrate hexahydrate and aluminum nitrate hexahydrate in acetate glacial acetic acid solution after being refluxed. Coating solution was obtained by diluting the gel with methanol and 2-methoxyethanol to adjust the total cation concentration to 0.67 M. Precursor coated film was prepared by dip-coating with a speed of 25 mm/min on various substrates such as $LaAlO_3$ (001), MgO(001), $SrTiO_3$(001) single crystal, LMO/MgO/Ni-alloy. Thin films have been obtained by heat treating the precursor film at various temperatures from $600^{\circ}C{\sim}900^{\circ}C$ and various heating rate from $0.83^{\circ}C/min{\sim}1.25^{\circ}C/min$ under $Ar/O_2$ mixture containing 1000ppm oxygen. The films have been characterized by scanning electronic microscopy (SEM) and X-ray diffraction (XRD). XRD analysis for the prepared film showed that $LaAlO_3$ thin films with a preferred orientation of (100) plane parallel to substrate surface were obtained at $800^{\circ}C(1.11\;^{\circ}C/min)$ on LMO/MgO/Ni-alloy substrate, but the intensity decreased with the increase of heat treatment temperature.

• Journal of Microbiology and Biotechnology
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• v.16 no.1
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• pp.77-83
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• 2006

A gene encoding a $\gamma-butyrolactone$ autoregulator receptor was cloned from Saccharopolyspora erythraea, and the biochemical characteristics, including the autoregulator specificity, were determined with the purified recombinant protein. Using primers designed for the conserved amino acid sequence of Streptomyces $\gamma-butyrolactone$ autoregulator receptors, a 120 bp S. erythraea DNA fragment was obtained by PCR. Southern and colony hybridization with the 120 bp fragment as a probe allowed to select a genomic clone of S. erythraea, pESG, harboring a 3.2 kb SacI fragment. Nucleotide sequencing analysis revealed a 615 bp open reading frame (ORF), showing moderate homology (identity, $31-34\%$; similarity, $45-47\%$) with the $\gamma-butyrolactone$ autoregulator receptors from Streptomyces sp., and this ORF was named seaR (Saccharopolyspora erythraea autoregulator receptor). The seaR/pET-3d plasmid was constructed to overexpress the recombinant SeaR protein (rSeaR) in Escherichia coli, and the rSeaR protein was purified to homogeneity by DEAE-Sephacel column chromatography, followed by DEAE-ion-exchange HPLC. The molecular mass of the purified rSeaR protein was 52 kDa by HPLC gel-filtration chromatography and 27 kDa by SDS-polyacrylamide gel electrophoresis, indicating that the rSeaR protein is present as a dimer. A binding assay with tritium-labeled autoregulators revealed that rSeaR has clear binding activity with a VB-C-type autoregulator as the most effective ligand, demonstrating for the first time that the erythromycin producer S. erythraea possesses a gene for the $\gamma-butyrolactone$autoregulator receptor.

• Journal of Microbiology and Biotechnology
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• v.15 no.5
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• pp.1047-1053
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• 2005

Cyclosporin A binding protein type-19 kDa peptidyl-prolyl cis/trans isomerase (PPIases, EC 5.2.1.8) of Euglena gracilis was purified and some of its biochemical characters were elucidated. Purification of the PPIase was achieved by employing a series of steps involving ammonium sulfate precipitation, Superdex G-75 gel filtration chromatography, Mono­Q anion and Mono-S cation exchange chromatographies, and Superdex S-200 gel filtration chromatography on FPLC. Purified PPIase had a specific activity of 8,250 units/mg, showing a 27-fold increase compared with that of cell-free extract of Euglena gracilis. The enzyme consisted of a single polypeptide chain with a molecular mass of 19 kDa. It showed high substrate specificity to succinyl-Ala-Ala-Pro-Phe-p-nitroanilide, and $k_{car}/K_{m}$, for this substrate was found to be $61.19{\times}10^5/sec$. The isomer distributions were investigated at an equilibrium of seven different peptide substrates, varying Xaa in Suc-Ala-Xaa-Pro-Phe-p-nitroanilide in dimethylsulfoxide. The cis/trans equilibrium constants were estimated to be from 0.14 (Ile) to 0.63 (Gly), which correspond to $12.00\%\;to\;38.52\%$ of the cis population, respectively, under experimental condition. The enzyme was highly sensitive to the immunosuppressive ligand cyclosporin A, but not to other immunosuppressants such as FK506 and rapamycin. Thus, it appears to belong to the class of cyclophilin.

• Journal of the Korean Chemical Society
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• v.30 no.2
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• pp.216-223
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• 1986

Separation of optical isomers of DNS derivatized amino acids by a reversed-phase high-performance liquid chromatography has been studied by adding a complex of an optically active amino acid (L-arginine) with the metal ion (Cu(II), Zn(II), Cd(II), Ni(II)) to the mobile phase. The separations are affected by the concentrations of acetonitrile, chelate and buffer. They are also affected by the pH and the kinds of metal and buffer. A separation mechanism, which is based on steric effect of the ligand exchange reaction for the formation of ternary complexes by the D,L-DNS-amino acids and the chiral additive associated with the stationary phase, is proposed to interpret the elution behaviors of D, L-dansyl-amino acids.

• Macromolecular Research
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• v.14 no.5
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• pp.573-578
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• 2006

Three different, polymer-platinum conjugates (hydrogels, microparticles, and nanoparticles) were synthesized by complexation of cis-dichlorodiammineplatinum(II) (cisplatin) with partially succinylated glycol chitbsan (PSGC). Succinic anhydride was used as a linker to introduce cisplatin to glycol chitosan (GC). Succinylation of GC was investigated systematically as a function of the molar ratio of succinic anhydride to glucosamine, the methanol content in the reaction media, and the reaction temperature. By controlling the reaction conditions, water-soluble, partially water-soluble, and hydrogel-forming PSGCs were synthesized, and then conjugated with cisplatin. The complexation of cisplatin with water-soluble PSGC via a ligand exchange reaction of platinum from chloride to the carboxylates induced the formation of nano-sized aggregates in aqueous media. The hydrodynamic diameters of PSGC/cisplatin complex nano-aggregates, as determined by light scattering, were 180-300 nm and the critical aggregation concentrations (CACs), as determined by a fluorescence technique using pyrene as a probe, were $20-30{\mu}g/mL$. The conjugation of cisplatin with partially water-soluble PSGC, i.e., borderline between water-soluble and water-insoluble PSGC, produced micro-sized particles $<500{\mu}m$. Cisplatin-complexed PSGC hydrogels were prepared from water-insoluble PSGCs. All of the cisplatin-incorporated, polymer matrices released platinum in a sustained manner without any significant initial burst, suggesting that they may all be useful as slow release systems for cisplatin. The release rate of platinum increased with the morphology changes from hydrogel through microparticle to nanoparticle systems.