• Polymer(Korea)
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• v.36 no.3
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• pp.309-314
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• 2012

To control degradation rate of biodegradable poly(lactide)s (PLA), the stereochemical PLAs with different ratios of $d$-lactide and $l$-lactide units were synthesized by the ring open polymerization and a degradation behavior was measured by a Langmuir film balance. Degradation rates of mixture monolayers on alkaline subphase were investigated as a function of optical purity of mixture component, 100, 99, 97 and 95%. As increasing their optical purity, melting temperatures of mixtures from stereocomplexation increased. The degradation rate of mixture monolayer with 100% optical purity was much slower than that of each homopolymer one and the others showed 2 step degradation behaviors. In the first step, the degradation which is faster than that of each homopolymer occurs in the uncomplexed region, and secondly, the degradation occurred in the complexed region which showed similar degradation rate to that of 100% optical purity. These results indicate that the alkaline degradation of stereochemical PLAs could be controlled by stereochemistry and stereocomplexation between enantiomer PLAs.

• Macromolecular Research
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• v.16 no.3
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• pp.231-237
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• 2008

Biodegradable poly($\varepsilon$-caprolactone-co-L-lactide)-b-poly(ethylene glycol) (PCLA-b-PEG) copolymers were synthesized via solution polymerization by varying the feed composition of $\varepsilon$-caprolactone ($\varepsilon$-CL) and L-lactide (LLA) ($\varepsilon$-CL: LLA= 10:0, 7:3, 5:5, 3:7, 0: 10). The feed ratio based on weight is in accordance with the copolymer composition except for the case of $\varepsilon$-CL: LLA=3:7 (C3L7), which was verified by $^1H$-NMR. Two different approaches were used for the exceptional case, which is an extension of the reaction time or the sequential introduction of the monomer. A copolymer composition of $\varepsilon$-CL: LLA=3:7 could be obtained in either case. The chemical microstructure of PCLA-b-PEG was determined using the $^{13}C$-NMR spectra and the effect of the sequential structure on the thermal properties and crystallinity were examined. Despite the same composition ratio of the copolymer, the microstructure can differ according to the reaction conditions.

• Polymer(Korea)
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• v.30 no.1
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• pp.28-34
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• 2006

A series of methoxypoly(ethylene glycol) $(MPEG)-poly(\varepsilon-co-L-lactide)$ (PCLA) diblock copolymers were synthesized by ring-opening polymerization of a mixture of $\varepsilon-caprolactone$ and L-lactide with different ratios in the presence of $Sn(Oct)_2$. The characterization of MPEG-PCLA diblock copolymers were examined by $^1H-NMR$, GPC, DSC, and XRD. Kinetic study on ring-opening polymerization of monomer mixtures was carried out in various conditions such as a variation with polymerization time, amount of catalyst, and temperature. The highest conversion obtained in 1.2 ratic of initiator venn catalyst at $110\;^{\circ}C$. The biodegradable characterization of MPEG-PCLA diblock copolymers in aqueous solution was carried out by using GPC for $1\~14$ weeks. The biodegradability of MPEG-PCLA diblock copolymers increased as the L-lactide content of diblock copolymers increased. In conclusion, we confirmed the dependence of polymerization rate according to various conditions. In addition, we can control the biodegradability of MPEC-PCLA diblock copolymers by changing the ratio of PCL and PLA block segment.

• Journal of Adhesion and Interface
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• v.3 no.2
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• pp.17-29
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• 2002

Interfacial properties and microfailure degradation mechanisms of the bioabsorbable composites for implant materials were investigated using micromechanical technique and measurement of surface wettability. As hydrolysis time increased, the tensile strength, the modulus and the elongation of poly(ester-amide) (PEA) and bioactive glass fibers decreased, whereas those of chitosan fiber almost did not change. Interfacial shear strength (IFSS) between bioactive glass fiber and poly-L-lactide (PLLA) was much higher than PEA or chitosan fiber/PLLA systems using dual matrix composite (DMC) specimen. The decreasing rate of IFSS was the fastest in bioactive glass fiber/PLLA composites whereas that of chitosan fiber/PLLA composites was the slowest. Work of adhesion, $W_a$ between bioactive glass fiber and PLLA was the highest, and the wettability results were consistent with the IFSS. Interfacial properties and microfailure degradation mechanisms can be important factors to control bioabsorbable composite performance.

• Polymer(Korea)
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• v.36 no.5
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• pp.593-598
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• 2012

Solution polymerization behaviors of L-lactide using single and mixed aluminium catalyst systems were studied. Triisobutylaluminium (TIBA) was a reference catalyst for mixing. For the $Al(O-i-Pr)_3$/TIBA catalytic systems, the molecular weight of the resulting polylactide (PLA) decreased as the composition of $Al(O-i-Pr)_3$ increased. The higher molecular weight shoulder was revealed in their GPC curve. At TIBA of 80 mol% a bimodal GPC curve was shown. The conversion in the trimethylaluminium (TMA)/TIBA catalysts system decreased as the composition of TMA in the mixed catalyst increased. The conversion in the trioctylaluminium (TOA)/TIBA catalysts system decreased as the composition of TOA in the mixed catalyst increased. The unimodal molecular weight distribution was observed with the TOA/TIBA catalyst systems. The Al compounds-mixed catalyst could produce a higher molecular weight shoulder in the GPC curve.

• Journal of Adhesion and Interface
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• v.4 no.1
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• pp.18-27
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• 2003

Interfacial properties and microfailure degradation mechanisms of the oxygen-plasma treated biodegradable poly(p-dioxanone) (PPDO) fiber/poly(L-lactide) (PLLA)composites were investigated for the orthopedic applications as implant materials using micromechanical technique and surface wettability measurement. PPDO fiber reinforced PLLA composite can provide good mechanical performance for long hydrolysis time. The degree of degradation for PPDO fiber and PLLA matrix was measured by thermal analysis and optical observation. IFSS and work of adhesion, $W_a$ between PPDO fiber and PLLA matrix showed the maximum at the plasma treatment time, at 60 seconds. Work of adhesion was lineally proportional to the IFSS. PPDO fiber showed ductile microfailure modes at We initial state, whereas brittle microfailure modes appeared with elapsing hydrolysis time. Interfacial properties and microfailure degradation mechanisms can be important factors to control bioabsorbable composites performance because IFSS changes with hydrolytic degradation.

• KSBB Journal
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• v.26 no.4
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• pp.333-340
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• 2011

In this study, gemcitabine-loaded methoxy poly(ethylene glycol)-b-poly(L-lactide) (MPEG-PLLA) microparticles with different PEG block lengths were prepared by a W/O/W double emulsion technique. The present study focuses on the investigation of the influence of various preparative parameters such as the ratio of internal water phase and oil phase, polymer concentration, solvent composition of organic phase and salt concentration of external water phase on the morphology and encapsulation efficiency of the microparticles. The microparticles fabricated at high volume ratios of internal water phase to oil phase and at high polymer concentrations showed a relatively high encapsulation efficiency and low porosity. When a dichloromethane/ethyl acetate mixture was used as solvent, both the encapsulation efficiency and drug loading of the microparticles decreased as the level of ethyl acetate increased. The addition of a salt (NaCl) to the external water phase significantly improved the encapsulation efficiency up to 40%, and the microparticles became more spherical with their size and porosity decreased.

• Macromolecular Research
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• v.14 no.2
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• pp.209-213
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• 2006

The ring-opening polymerization of D,L-lactide initiated by tin(II) 2-ethylhexanoate $(Sn(Oct)_2)$ on the surface-initiated magnetite $(Fe_{3}O_4)$ nanoparticles was performed at $130^{\circ}C$. The effects of the polymer molar mass and concentration on the amount of surface polymer were investigated. The number average molecular weights, $M_n$, obtained by both NMR and GPC methods fit well within the accuracy of the applied methods and ranged from 1,100 to $4,040g\;mol^{-1}$. A surface functionalization density of up to 625 initiation sites per particle was obtained. The composition of various core-shell particles was determined by TGA, with results indicating magnetite $(Fe_{3}O_4)$ contents, ${\mu}m$, between 17 and 59 wt%. Under the influence of a magnetic field, the heating generated by superparamagnetic core-shell particles suspended in toluene presented guidelines for an optimization of magnetic particle systems with respect to an application for hyperthermia.

• Macromolecular Research
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• v.15 no.4
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• pp.330-336
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• 2007

Luminescent CdSe/ZnS QDs, with emission in the red region of the spectrum, were synthesized and encapsulated in poly(ethylene glycol)-poly(D,L-lactide) diblock copolymer micelles, to prepare water-soluble, bio-compatible QD micelles. PEG-PLA diblock copolymers were synthesized by ring opening polymerization of D,L-lactide, in the presence of methoxy PEG as a macro initiator. QDs were encapsulated with PEG-PLA polymers using a solid dispersion method in chloroform. The resultant polymer micelles, with encapsulated QDs, were characterized using various analytical techniques, such as UV- Vis measurement, light scattering, fluorescence spectroscopy, transmission electron microscopy (TEM) and atomic forced microscopy (AFM). The polymer micelles, with encapsulated QDs, were spherical and showed diameters in the range of 20-150 nm. The encapsulated QDs were highly luminescent, and have high potential for applications in biomedical imaging and detection.

• Macromolecular Research
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• v.17 no.12
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• pp.1010-1014
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• 2009

Monodispersed microparticles with a poly(D,L-lactide-co-glycolide) (PLGA) core and a poly(ethyl 2-cyanoacrylate) (PE2CA) shell were prepared by Shirasu porous glass (SPG) membrane emulsification to reduce the initial burst release of doxorubicin (DOX). Solution mixtures with different weight ratios of PLGA polymer and E2CA monomer were permeated under pressure through an SPG membrane with $1.9\;{\mu}m$ pore size into a continuous water phase with sodium lauryl sulfate as a surfactant. Core-shell structured microparticles were formed by the mechanism of anionic interfacial polymerization of E2CA and precipitation of both polymers. The average diameter of the resulting microparticles with various PLGA:E2CA ratios ranged from 1.42 to $2.73\;{\mu}m$. The morphology and core-shell structure of the microparticles were observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The DOX release profiles revealed that the microparticles with an equivalent PLGA:E2CA weight ratio of 1:1 exhibited the optimal condition to reduce the initial burst of DOX. The initial release rate of DOX was dependent on the PLGA:E2CA ratio, and was minimized at a 1:1 ratio.