• Macromolecular Research
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• v.16 no.1
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• pp.62-65
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• 2008

The morphology of the $D_2O$-induced reverse micellar structure of an amphiphilic block copolymer of poly( ethylene oxide )-b-poly(propylene oxide )-b-poly( ethylene oxide )($EO_{76}PO_{29}EO_{76}$) was investigated in hydrophobic media by small angle neutron scattering (SANS). Increasing $D_2O$ in the styrene/divinylbenzene solution of $EO_{76}PO_{29}EO_{76}$ led to a change in morphology of the reverse micelles from a short range ordered molecular aggregate to a hexagonally arranged micelle, and further to a spherical micelle.

• Macromolecular Research
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• v.10 no.2
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• pp.67-74
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• 2002

New immunoprotecting membranes were prepared by spin coating the amphiphilic random multiblock copolymers of poly(ethylene glycol) (PEG) and poly(tetramethylene ether glycol) (PTMEG) or poly(dimethyl siloxane) (PDMS) on porous Durapore(R) membrane. The copolymer coating was intended to make a biocompatible, immunoprotecting diffusional barrier and the supporting porous substrate was for mechanical stability and processability. By filling Durapore(R) membrane pores with water, the penetration of coating solution into the pores was minimized during the spin coating process. A single coating process produced a completely covered thin surface layer (~1 ${\mu}{\textrm}{m}$ in thickness) on the porous substrate membrane. The permselectivity of the coated layer was influenced by PEG block length, polymer composition, and thickness of the coating layer. A composite membrane with the coating layer prepared with PEG 2 K/PTMEG 2 K block copolymer showed that its molecular weight cut-of fat any 40 based on dextran was close to the molecular size of IgG (Mw = 150 kDa). However, IgG permeation was detected from protein permeation test, while glucose oxidase (Mw = 186 kDa) was not permeable through the coated membrane.

• 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.

• Journal of the Korean GEO-environmental Society
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• v.15 no.3
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• pp.15-19
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• 2014

Spilling pollutants and its contamination to the ground have serious impact to public resulting in various research about remediation techniques. In this study, the use of amphiphilic block copolymer for remediation was investigated with a series of laboratory tests on removal of hydrophobic contaminant in soil. Four types of amphiphilic block copolymer were developed and the efficiency of the cleaning was compared with surfactant using arbitrary diesel-contaminated soils. The results of the study show that the use of amphiphilic polymer in the soil washing process significantly enhanced the remediation of the contaminated soil and a potential of new methodology of eco-friendly remediation.

• Journal of the Society of Cosmetic Scientists of Korea
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• v.43 no.2
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• pp.165-174
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• 2017

This study reports a synthesis of an amphiphilic linear block copolymer consisting of a hydrophobic poly (lactide) (PLA) block and a hydrophilic hyperbranched polyglycerol (hbPG) block, PLA-b-hbPG. Simple chemical modification of the hbPG block with 4-hydroxycinnamic acid (CA) led to a photo-crosslinkable block copolymer, PLA-b-hbPG-CA. Nanosized micelles of the block copolyemrs were used as drug carriers for sustainable release. The hbPG shell made of a small molecular weight hbPG block showed excellent hydrophilicity, which can minimize in vivo toxicity. The UV-crosslinked PLA-b-hbPG-CA micelles loaded with drugs colud be served as a drug delivery carrier for its biocompatibility and self-assembled structures.

• 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.

• Polymer(Korea)
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• v.30 no.6
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• pp.512-518
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• 2006

A biodegradable polymer poly((R) -3-hydroxybutyric acid) (PHB) was conjugated with a hydrophilic polymer poly(ethylene glycol) (PEG) by the ttansesterification reaction to form the amphiphilic block copolymer. PHB with low molecular weight ($3000{\sim}30000$) was appropriated for the drug delivery materials. High molecular weight PHB was hydrolyzed by an acid-catalyst to produce the low molecular weight one. Amphiphilic block copolymer was formed the self-assembled polymeric micelle system in the aqueous solution that the hydrophillic PEG was wraped the hydrophobic PHB. Generally, polymeric micelle forms the small particle between $10{\sim}200nm$. These polymeric micelle systems have been widely used for the drug delivery systems because they were biodegradable, biocompatible, non-toxic and patient compliant. The hydroxyl group of PEG was substituted with carboxyl group which has the reactivity to the ester group of PHB. Amphiphilic block copolymer was conjugated between PHB, and modified PEG at $176^{\circ}C$ which was higher than the melting point of PHB. Transesterification reaction was verified with DSC, FTIR, $^1H-NMR$. In the aqueous solution, critical micelle concentration (CMC) of the mPEG-co-PHB copolymer measured by the fluororescence scanning spectrometer was $5{\times}10^{-5}g/L$. The shape and size of the nanoparticle was taken by dynamic light scattering and atomic force microscopy. The size of the nanoparticle was about 130 nm and the shape was spherical. Our polymeric micelle system can be used as the passive targeting drug delivery system.

• 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.

• Journal of Pharmaceutical Investigation
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• v.41 no.2
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• pp.95-102
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• 2011

An amphiphilic cationic branched methoxy poly (ethylene glycol)-branched polyethylenimine - poly(L-phenylalanine) (mPEG-bPEI-pPhe) block copolymer was successfully synthesized by ring-opening polymerization (ROP) of N-carboxyanhydride of L-phenylalanine (Phe-NCA) with mPEG-bPEI for the preparation of more stable polyelectrolyte complex (PEC) included a hydrophobic interaction. mPEG-bPEI was firstly prepared by the coupling of mPEG and bPEI using hexamethylene diisocyanate (HMDI). The structural properties of mPEG-bPEI-pPhe copolymers were confirmed by $^1H$ NMR. The copolymers exhibited a self-assemble behavior in water above critical aggregate concentration (CAC) in the range of 0.01-0.14 g/L. The CAC of copolymers obviously depended on the hydrophobic block content in the copolymers (the value decreased with the increase of the pPhe block content). The cationic copolymers have the ability to form multi-interaction complex (MIC) with bovine serum albumin (BSA) and plasmid DNA through multi-interaction (electrostatic and hydrophobic interaction). The physicochemical characterization of the complex was carried out by the measurement of zeta potential and particle size. Their zeta-potentials were positive (approximately +10 mV) and their sizes decreased with increasing pPhe contents in the copolymers (PPF/BSA wt% ratio = 2). The complex showed good stability at high ionic strength. Therefore, mPEG-bPEI-pPhe block copolymer was considered as a potential material to enhance the stability of complex including biotherapuetic drugs.

• Macromolecular Research
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• v.15 no.6
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• pp.587-594
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• 2007

Well defined amphiphilic diblock copolymers of poly(styrene-b-vinylbenzylphosphonic acid) (PS-b-PVBPA) were prepared by controlled radical polymerization technique, two-step hydrolysis reactions using trime-thylsilyl bromide from the corresponding phosphonic ethyl ester. By indirect, backward pH titration of the block copolymer, a good titration curve of a dibasic acid was observed. The IEC values obtained from both backward pH titration and volumetric back titration were almost identical. Thermal gravimetric analysis (TGA) of the phosphonic acid containing block copolymer showed a high thermal stability up to $400^{\circ}C$.