• Macromolecular Research
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• v.14 no.3
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• pp.255-256
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• 2006

• 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.

• Macromolecular Research
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• v.17 no.5
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• pp.301-306
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• 2009

This work has demonstrated that a novel amphiphilic poly(epichlorohydrine)-graft-polystyrene (PECH-g-PS) copolymer at 34:66 wt% was synthesized via atom transfer radical polymerization (ATRP) of styrene using PECH as a macroinitiator. The structure of the graft copolymer was characterized by nuclear magnetic resonance ($^1H$ NMR) and FTIR spectroscopy, demonstrating that the "grafting from" method using ATRP was successful. The self-assembled graft copolymer was used as a template film for the in-situ growth of silver nanoparticles from $AgCF_3SO_3$ precursor under UV irradiation. The in situ formation of silver nanoparticles with 6-8 nm in average size in the solid state template film was confirmed by transmission electron microscopy (TEM), UV-visible spectroscopy and wide angle X-ray scattering (WAXS). Differential scanning calorimetry (DSC) also displayed the selective incorporation and the in situ formation of silver nanoparticles within the hydrophilic PECH domains, probably due to stronger interaction of the silvers with the ether oxygens of PECH backbone than that with hydrophobic PS side chains.

• Archives of Pharmacal Research
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• v.20 no.4
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• pp.324-329
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• 1997

AB-type amphiphilic copolymers (abbreviated as LE) composed of poly (L-leucine) (PLL) as the A component and poly (ethylene oxide) (PEO) as the B component were synthesized by the ring-opening polymerization of L-leucine N-carboxy-anhydride initiated by methoxy polyoxyethylene amine $(Me-PEO-NH_2)$ and characterized. Core-shell type nanoparticles were prepared by the diafiltration method. Particle size distribution obtained by dynamic light scattering was dependent on PLL composition and the size for LE-1, LE-2 and LE-3 was $369.6{\pm}267$, $523.4{\pm}410$ and $561.2{\pm}364 nm$, respectively. Shapes of the nanoparticies observed by transmission electron microscope (TEM) were almostly spherical. The critical micelle concentration (CMC) of the nanoparticles determined by a fluorescence probe technique was dependent on the composition of hydrophobic PLL, and the CMC for LE-1, LE-2 and LE-3 was $2.0{\times}10^{-6},1.7{\times}10^{-6}$ and $1.5{\times}10^{-6}(mol/l) $, respectively. Clonazepam release from core-shell type nanoparticles in vitro was dependent on PLL composition and drug loading content.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.262-262
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• 2006

Biodegradable and amphiphilic di-block and tri-block copolymers, prepared with monomethoxy poly ethylene glycol (MPEG) and ${\varepsilon}-caprolactone\;({\varepsilon}-CL)$, were used for the application of W1/O/W2 multi- emulsion capsules. The effects of topology and the ratio of hydrophilic moiety of PCL-based polymers on the encapsulation efficiency of the $W_{1}/O/W_{2}$ multi-emulsion capsules containing Ascorbic Acid-2-Glucoside (AA-2-G) were investigated. The ratio of PEG and PCL was 1:0.5, 1:0.75, 1:1, and 1:1.25. PEG-PCL block copolymers were added to the first step of the preparation of $W_{1}/O$ emulsions. The dispersion stability, the particle size, the morphology of the $W_{1}/O/W_{2}$ multi-emulsion capsules were observed using an on-line turbidity meter, dynamic light scattering (DLS), a confocal microscopy (with FITC) and an optical microscopy. Biodegradable behavior of the PEG-PCL block copolymers and release behavior of AA-2-G were also observed by Gel Permeation Chromatography (GPC) and High Performance Liquid Chromatography (HPLC).

• Macromolecular Research
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• v.15 no.4
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• pp.385-391
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• 2007

Block copolymer micelles are generally formed via the self-assembly of amphiphilic block copolymers in an aqueous medium. The hydrophilic and hydrophobic blocks form shell and core micelles, respectively. The block copolymers of methoxy poly(ethylene glycol) (MPEG)-b-poly(2-diisopropylamino)ethyl methacrylate (PDPA) were synthesized via atom transfer radical polymerization, with the macro initiator synthesized by the coupling of 2-bromoisobutyryl bromide with MPEG in the presence of a triethyl amine base catalyst. The atom transfer radical polymerization of 2-diisopropylamino)ethyl methacrylate was performed in conjunction with an N,N,N',N",N"-pentamethyl-diethylenetriamine/copper bromide catalyst system, in DMF, at $70^{\circ}C$. The pH induced micellization/demicellization was studied using fluorescence, with a pyrene probe. Furthermore, the pH dependent micellization was confirmed using the microviscosity method, with a dipyme fluorescence probe. The pH dependant micelle size distribution was studied using dynamic light scattering. The characterization of the synthesized polymers was established using gel permeation chromatography and from the $^1H-nuclear$ magnetic resonance spectroscopy.

• Korean Chemical Engineering Research
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• v.52 no.2
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• pp.209-213
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• 2014

A graft copolymer of poly(vinyl chloride)-g-poly(oxyethylene methacrylate) (PVC-g-POEM) was synthesized via atom transfer radical polymerization (ATRP) and used as a structure-directing agent to prepare $Al@Fe_2O_3$ core-shell nanocomposites through a sol-gel process. The amphiphilic property of PVC-g-POEM allows for good dispersion of Al particles and leads to specific interaction with iron ethoxide, a precursor of $Fe_2O_3$. Secondary bonding interaction in the sol-gel composites was characterized by Fourier transform-infrared (FT-IR) spectroscopy. The well-organized morphology of $Al@Fe_2O_3$ core-shell nanocomposites was observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Energy dispersive X-ray (EDX) and X-ray diffraction (XRD) were used to analyze the elemental composition and crystallization structure of the composites.

• Journal of the Korean Ceramic Society
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• v.45 no.5
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• pp.297-302
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• 2008

To direct the evolution of nanostructure and immobilize ${\gamma}-Al_2O_3$ catalyst, nanocrystalline La-doped-$Al_2O_3$ powder were prepared by the sol-gel process with addition of an amphiphilic block copolymer template (pluronic P123: $(poly(ethyleneoxide)_{20}-poly(propyleneoxide)_{70}-poly(ethyleneoxide)_{20})$. The dried gel is amorphous, whereas heating at temperature above $700^{\circ}C$ leads to the formation of nanocrystalline ${\gamma}$ and ${\delta}-Al_2O_3$ and these two phases is kept until $1100^{\circ}C$. ${\alpha}-A1_2O_3 $starts to form at $1200^{\circ}C$ with $LaAl_{11}O_{18}$. The surface morphology and crystal structure has been observed by field emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD). Solid state $^{27}Al$ MAS NMR indicates two types of local environment, i.e. octahedral and tetrahedral sites. The surface area and pore size was compared among these powders using the BET nitrogen adsorption measurements.

• Macromolecular Research
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• v.11 no.4
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• pp.283-290
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• 2003

Organic drugs including aspirin, omeprazole, and naproxen with three different levels of octanol/water partition coefficient were examined for their release behavior from the amphiphilic PCL-b-PEO-b-PCL (PCEC) matrix. Scanning electron micrograph (SEM) of PCEC illustrated a well defined two-phase morphology consisted of dispersed poly(ethylene oxide) (PEO) domain and continuous polycaprolactone (PCL) phase. Differential scanning calorimetry (DSC) and X-ray diffractometry (XRD) experiments veri tied that three model drugs are dissolved as a molecular dispersion in PCEC matrix. The release of hydrophilic aspirin closely followed the water absorption profile of the matrix indicating that its major fraction is present in PEO domain. However, substantial amount of aspirin present in less hydrophilic region displayed discontinuous biphasic release pattern. In the case of omeprazole with intermediate hydrophobicity consistent release behavior was observed for a period of 24 hrs after the rapid liberation of ca. 10% of the drug presumably partitioned in PEO phase. It was ascribed to the fact that the progressive hydration of PCEC matrix gradually increased the chance of drug/water exposure to compensate the exhaustion of device. Naproxen with the highest octanol/water distribution coefficient among three model drugs exhibited a limited release of 35% for 24 hrs. Finally, hydroxypropyl methylcellulose phthalate (HPMCP)/PCEC blend matrix demonstrated an accelerated and quantitative release of hydrophobic naproxen by generating high porosity and thereby expanding polymer/water interface.

• Macromolecular Research
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• v.13 no.4
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• pp.344-351
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• 2005

pH-sensitive block copolymers were synthesized by coupling reaction of sulfamethazine and amphiphilic diblock copolymer, and their micellization-demicellization behavior was investigated. Sulfamethazine (SM), a derivative of sulfonamide, was introduced as a pH responsive moiety while methoxy poly(ethylene glycol)poly(D,L-lactide) (MPEG-PDLLA) and methoxy poly(ethylene glycol)-poly($D,L-lactide-co-{\varepsilon}-caprolactone$) (MPEG-PCLA) were used as biodegradable amphiphilic diblock copolymers. After the sulfamethazine was carboxylated by the reaction with succinic anhydride, the diblock copolymer was conjugated with sulfamethazine by coupling reaction in the presence of DCC. The critical micelle concentration (CMC) and mean diameter of the micelles were examined at various pH conditions through fluorescence spectroscopy, dynamic light scattering and transmission electron microscopy. For MPEG-PDLLA-SM and MPEG-PCLA-SM solutions, the pH-dependent micellization-demicellization was achieved within a narrow pH band, which was not observed in the MPEG-PDLLA and MPEG-PCLA solutions. The micelle showed a spherical morphology and had a very narrow size distribution. This pH-sensitive block copolymer shows potential as a site-targeted drug carrier.