• Korean Membrane Journal
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• v.9 no.1
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• pp.57-63
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• 2007

Amphiphilic graft copolymer from poly(vinylidene fluoride) (PVDF) was synthesized using atom transfer radical polymerization (ATRP) for composite nanofiltration membranes. Direct initiation of the secondary fluorinated site of PVDF facilitates grafting of tert-butyl methacrylate (tBMA). Amphiphilic PVDF-g-PMAA graft copolymer with a 51:49 wt ratio was obtained by hydrolyzing poly(tert-butyl methacrylate) (PtBMA) to poly(methacrylic acid) (PMAA). Wide angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC) confirmed the decrease of crystallinity of PVDF upon graft copolymerization. Composite nanofiltration membranes were prepared from PVDF-g-PMAA as a top layer coated onto PVDF ultrafiltration (UF) support membrane. The morphology and hydrophilicity of membranes were characterized using scanning electron microscopy (SEM) and contact angle measurement. The rejections of composite membranes were 80.2% for $Na_2SO_4$ and 28.4% for NaCl, and the solution flux were 9.5 and $14.5\;L/m^2\;h$ at 1.0 MPa pressure.

• Journal of the Korean Vacuum Society
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• v.8 no.1
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• pp.63-69
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• 1999

The characteristic parameters of high density plasma source (Helical Resonator) have been measured with Langmuir probe to get the plasma density electron temperature, ion current density, etc. Optical emission spectra of Si and SiCl have been analyzed in $Cl_2$$/poly-Si system to elucidate etching mechanism. In this system, the main reaction to remove silicon atoms on the surface is proceeding mostly through chemical reaction, not pure physical reaction. The emission intensity of SiCl (chemical etching product) increases much faster than Si (pure physical etching product) with increasing the concentration of impurities (P). This is due to the electron transfer from substrate to the surface via Si-Cl bond. As a result, Si-Cl bond becomes more ionic and mobile, therefore the Cl-containing etchant forms $SiCl_x$ with surface more easily. Consequently, for the removal of Si atom from poly silicon surface, the chemical etching is more favorable than physical etching with increasing P concentrations.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2271-2278
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• 2007

Electron transfer of a redox protein at a bare gold electrode is too slow to observe the redox peaks. A novel Nafion-riboflavin functional membrane was constructed during this study and electron transfer of cytochrome c, superoxide dismutase, and hemoglobin were carried out on the functional membrane-modified gold electrode with good stability and repeatability. The immobilized protein-modified electrodes showed quasireversible electrochemical redox behaviors with formal potentials of 0.150, 0.175, and 0.202 V versus Ag/AgCl for the cytochrome c, superoxide dismutase and hemoglobin, respectively. Whole experiment was carried out in the 50 mM MOPS buffer solution with pH 6.0 at 25 oC. For the immobilized protein, the cathodic transfer coefficients were 0.67, 0.68 and 0.67 and electron transfer-rate constants were evaluated to be 2.25, 2.23 and 2.5 s?1, respectively. Hydrogen peroxide concentration was measured by the peroxidase activity of hemoglobin and our experiment revealed that the enzyme was fully functional while immobilized on the Nafion-riboflavin membrane.

• 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.22 no.2
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• pp.86-94
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• 1978

The crystal and molecular structure of theophylline hydrochloride has been determined from X-ray data by Patterson techniques. The structure has been refined by block-diagonal least-squares and Fourier synthesis on three dimensional data. The unit cell is orthorhombic, space group $P_{na21}$, with a = 14.01, b = 11.49, c = 6.77${\AA}$, and contains four molecules. The final R value based on 743 observed reflexions is 12.2%. The intramolecular distances are similar to those in other compounds containing a purine or pyrimidine group. The molecules are nearly planar and are stacked in layers parallel to the (001)plane. The chlorine atom is coordinated to N(1) atom at a distance of 3.06${\AA}$. The structure is stabilized mainly by van der Waals interactions; however, a short N${\cdot}{\cdot}{\cdot}$Cl contact of length $3.06\AA$, which is slightly less than the expected van der Waals separation, suggest that weak charge transfer interaction may be present. The relationship between this structure and the known structures of theophylline monohydrate and caffeine monohydrate are discussed.

• Polymer(Korea)
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• v.37 no.3
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• pp.332-341
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• 2013

H-shaped amphiphilic pentablock copolymers $(PSt)_2-b-PCL-b-PEO-b-PCL-b-(PSt)_2$ was synthesized via chemoenzymatic method by combining enzyme-catalyzed ring-opening polymerization (eROP) of ${\varepsilon}$-caprolactone (${\varepsilon}$-CL) and atom transfer radical polymerization (ATRP) of styrene. By this process, we obtained copolymers with controlled molecular weight and low polydispersity. The structure and composition of the obtained copolymers were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and infrared spectroscopy analysis (IR). The crystallization behavior of the copolymers was analyzed by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The crystallization behavior of the H-shaped block copolymers demonstrated a PCL dominate crystallization. The self-assembly behavior of the copolymers was investigated in aqueous media. The hydrodynamic diameters of the copolymer micelles in aqueous solution were measured by dynamic light scattering (DLS). The morphology of the copolymer micelles was observed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The hydrodynamic diameters of spherical micelles declined gradually with the increase of the hydrophobic chain lengths of the copolymers. The critical micelle concentration (CMC) values were determined from fluorescence emission, and it was found that the CMCs decreased with an increase of PSt hydrophobic block lengths.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.226-226
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• 2006

Ethylene was polymerized with a catalyst having sterically hindered pentamethylcyclopentadienyl ligand, $Cp^{\ast}_{2}ZrCl_{2}/MAO$, and the polymerization mixture were treated with dry oxygen (oxidative workup) to produce hydroxyl-terminated polyethylenes (PE-OH). Polyethylene-block-Poly (${\Box}-caprolactone$) was synthesized from PE-OH and ${\cdot}\^{A}-caprolactone$A by using stannous octoate as a catalyst for ring opening polymerization of ${\cdot}\^{A}-caprolactone$. Polyethylene-block-Poly(methyl methacrylate) was obtained by transforming the hydroxyl-terminated polyethylenes to macroinitiators for atom transfer radical polymerization (ATRP) and by reacting them with MMA.

• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.1071-1073
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• 2011

The reactions of 4-nitrobenzenesulfenyl chloride with substituted benzylamines proceed through three pathways, the uncatalyzed ($k_2$) and catalyzed ($k_3$) paths including solvolysis ($k_o$) by the solvent. The large value of primary normal kinetic isotope effects imply that the proton transfer occurs concurrently from benzylamine to Cl atom of the substrate. The ${\beta}_x$ and ${\rho}_x$ values for the catalyzed path, $k_3$, are greater than those for the uncatalyzed path, indicating that greater degree of bond formation in the catalyzed TS compared to the uncatalyzed TS.

• Membrane Journal
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• v.21 no.3
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• pp.222-228
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• 2011

Poly(vinyl chloride)-g-poly(oxyethylene methacrylate) (PVC-g-POEM) graft copolymer was synthesized via atom transfer radical polymerization (ATRP) and used as an electrolyte for electrochromic device. Plasticized polymer electrolytes were prepared by the introduction of propylene carbonate (PC)/ethylene carbonate (EC) mixture as a plasticizer. The effect of salt was systematically investigated using lithium tetrafluoroborate ($LiBF_4$), lithium perchlorate ($LiClO_4$), lithium iodide (LiI) and lithium bistrifluoromethanesulfonimide (LiTFSI). Wide angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC) measurements showed that the structure and glass transition temperature ($T_g$) of polymer electrolytes were changed due to the coordinative interactions between the ether oxygens of POEM and the lithium salts, as supported by FT-IR spectroscopy. Transmission electron microscopy (TEM) showed that the microphase-separated structure of PVC-g-POEM was not greatly disrupted by the introduction of PC/EC and lithium salt. The plasticized polymer electrolyte was applied to the electrochromic device employing poly(3-hexylthiophene) (P3HT) conducting polymer.

• Bulletin of the Korean Chemical Society
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• v.14 no.4
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• pp.439-444
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• 1993

The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.