• Korean Chemical Engineering Research
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• v.50 no.6
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• pp.1064-1067
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• 2012

Recently, there is a growing interest in vegetable oils, cheap and abundant renewable natural resources. Vegetable oils can be used as raw materials for ecofriendly biodegradable polymer materials. In this study, poly(${\beta}$-amino esters) were synthesized by polymerization reaction of acrylated epoxidized soybean oil (AESO) and 2-aminoethanol. Various polymer films were prepared by changing the molar ratio of AESO to 2-aminoethanol. The formation of C-N bonds in poly(${\beta}$-amino ester) was confirmed using FT-IR. Gel contents higher than 98% confirmed the synthesis of crosslinked polymer networks. Tensile strengths and elongation at breaks of polymer films ranged from 0.3 to 1.3 MPa and 32 to 55%, respectively. Polymer films degraded 2 to 7% of the initial weight in 35 days in phosphate buffer solution (pH 7.2) containing lipase enzyme.

• Macromolecular Research
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• v.15 no.5
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• pp.437-442
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• 2007

Poly(ethylene glycol) methyl ether (PEG)-poly(${\beta}$-amino ester) (PAE) block copolymers were synthesized using a Michael-type step polymerization, and the construction of pH-sensitive polymeric micelles (PM) investigated. The ${\beta}$-amino ester block of the block copolymers functioned as a pH-sensitive moiety as well as a hydrophobic block in relation to the ionization of PAE, while PEG acted as a hydrophilic block, regardless of ionization. The synthesized polymers were characterized using $^1H-NMR$, with their molecular weights measured using gel permeation chromatography. The $pK_b$ values of the pH-sensitive polymers were measured using a titration method. The pH-sensitivity and critical micelle concentration (CMC) of the block copolymers in PBS solution were estimated using fluorescence spectroscopy. The pH dependent micellization behaviors with various bisacrylate esters varied within a narrow pH range. The critical micelle concentration at pH 7.4 decreased from 0.032 to 0.004 mg/mL on increasing the number of methyl group in the bisacrylate from 4 to 10. Also, the particle size of the block copolymer micelles was determined using dynamic light scattering (DLS). The DLS results revealed the micelles had an average size below 100 nm. These pH-sensitive polymeric micelles may be good carriers for the delivery of an anticancer drug.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.263-263
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• 2006

Poly (ethylene glycol)(PEG) - Poly (${\varepsilon}-caprolactone(CL)$) - Poly (D,L lactide(LA) (PCLA-PEG-PCLA) was synthesized by ring-opening polymerization to form temperature sensitive hydrogel triblock copolymer. The triblock copolymer was acrylated by acryloyl chloride. ${\beta}-amino$ ester was used as a pH sensitive moiety, in this study ${\beta}$- amino ester obtained from 1,4-butandiol diacrylate, and 4, 4' trimethylene dipiperidine, it have pKb around 6.6. pH/temperature sensitive penta-block copolymer (PAE-PCL-PEG-PCL-PAE) was synthesized by addition polymerization from acrylated triblock copolymer, 1,4-butandiol diacrylate, and 4, 4' trimethylene dipiperidine. Their physicochemical properties of triblock and penta-block copolymers were characterized by $^1H-NMR$ spectroscopy and gel permeation spectroscopy. Sol-gel phase transition behavior of PAE-PCL-PEG-PCL-PAE block copolymers were investigated by remains stable method. Aqueous media of the penta-block copolymer (at 20 wt%) changed from a sol phase at pH 6.4 and $10^{\circ}C$ to a gel phase at pH 7.4 and $37^{\circ}C$. The sol-gel transition properties of these block copolymers are influenced by the hydrophobic/hydrophilic balance of the copolymers, block length, hydrophobicity, stereo-regularity of the hydrophobic of the block copolymer, and the ionization of the pH function groups in the copolymer depended on the changing of environmental pH, respectively. The degradation and the stabilization at pH 7.4 and $37^{\circ}C$, and the stabilization at pH 6.4 and $10^{\circ}C,\;5^{\circ}C,\;0^{\circ}C$, of the gel were determined. The results of toxicity experiment show that the penta block copolymer can be used for injection drug delivery system. The sol?gel transition of this block copolymer also study by in vitro test ($200{\mu}l$ aqueous solution at 20wt% polymer was injected to mouse). Insulin loading and releasing by in vitro test was investigated, the results showed that insulin can loading easily into polymer matrix and release time is around 14-16days. The PAE-PCL-PEG-PCL-PAE can be used as biomaterial for drug, protein, gene loading and delivery.

• Polymer(Korea)
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• v.36 no.6
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• pp.822-830
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• 2012

We used dipodal type bis[3-(trimethoxysilyl)propyl]amine (BTMA) silane coupling agent to modify silica nanoparticles to introduce secondary amino groups on the silica surface. These N-H groups were reacted with three different molecular weights (M.W. = 258, 575, and 700) of poly(ethylene glycol) diacrylates to introduce different attached layer thicknesses on the silica surface by Michael addition reaction. After Michael addition reaction, we used several analytical techniques such as fourier transform infrared spectroscopy (FTIR), elemental analysis (EA) and solid state $^{13}C$ cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance spectroscopy to characterize introduced structures. We found almost complete Michael addition reaction of both two acrylate groups of PDGDA with N-H groups of BTMA modified silica to form ${\beta}$-amino acid esters. Between equimolar ratio of pure BTMA and pure PEGDA reaction, only one acrylate group of two acrylate groups of PEGDA reacted with N-H groups of pure BTMA to form ${\beta}$-amino acid ester and the other remaining acrylate group can be used to form a polymer later.

• Macromolecular Research
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• v.14 no.1
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• pp.117-120
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• 2006

• Polymer(Korea)
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• v.35 no.6
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• pp.558-564
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• 2011

The biocompatibility and biodegradability of poly(amino acid) make them ideal candidates for many bio-related applications. Poly(aspartic acid), PASP, is one of synthetic water-soluble polymers with proteinlike structure, and has been extensively explored for the potential industrial and biomedical applications due to its biodegradable, biocompatible and pH-responsive properties. In this work, amino acid-conjugated PASPs were prepared by aminolysis reaction onto polysuccinimide (PSI) using ${\gamma}$-aminobutylic acid(GABA) and ${\beta}$-alanine methyl ester and a subsequent hydrolysis process. Their chemical gels were prepared by crosslinking reaction with ethylene glycol diglycidyl ether (EGDE). The hydrogels were investigated for their basic swelling behavior, hydrolytic degradation and morphology. The crosslinked gels showed a responsive swelling behavior, which was dependent on pH and salt concentration in aqueous solution, and relatively fast hydrolytic degradation.

• Macromolecular Research
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• v.13 no.2
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• pp.147-151
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• 2005

The main objective of this study was to modulate pH-sensitive polymers (poly($\beta-amino esters$)) by controlling their molecular weight during their synthesis. These pH-sensitive and biodegradable polymers were synthesized by Michael-type step polymerization. 1,4-Butane diol diacrylate was used as the unsaturated carbonyl compound and piperazine as the nucleophilic compound. Various molecular weight polymers were obtained by varying the mol ratio of piperazine/1,4-butane diol diacrylate. The synthesized polymers were characterized by $^{1}H-NMR$ and their molecular weights were measured by gel permeation chromatography(GPC). The dependence of the molecular weight on the mol ratio was evaluated by the titration method. Also, the pH dependent turbidity of the polymers was determined by UV-Vis spectrophotometry. This pH dependent property of the polymers could be very useful for preparing drug carriers that are sensitive to pH.

• Macromolecular Research
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• v.17 no.2
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• pp.99-103
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• 2009

We evaluated the efficacy of pH-sensitive micelles, formed by methoxy poly(ethylene glycol)-b-poly($\beta$)-amino ester) (PEG-PAE), as carriers for paclitaxel (PIX), a drug currently used to treat various cancers. PTX was successful encapsulated by a film hydration method. Micelles encapsulated more than 70% of the PTX and the size of the PTX-encapsulated micelles (PTX-PM) was less than 150 nm. In vitro experiments indicated that the micelles were unstable below pH 6.5. After encapsulation of PTX within the micelles, dynamic light scattering (DLS) studies indicated that low pH had a similar demicellization effect. An in vitro release study indicated that PTX was slowly released at pH 7.4 (normal body conditions) but rapidly released under weakly acidic conditions (pH 6.0). We demonstrated the safety of micelles from in vitro cytotoxicity tests on HeLa cells and the in vivo anti-tumor activity of PTX-PM in B16F 10 tumor-bearing mice. We concluded that these pH-sensitive micelles have potential as carriers for anti-cancer drugs.