• Korean Chemical Engineering Research
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• v.43 no.4
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• pp.482-486
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• 2005

The biodegradable poly(${\varepsilon}$-caprolactone)(PCL)/poly(ethylene imine)(PEI) microcapsules containing $Al_2O_3$ and fragrant oil were prepared with different PEI contents. The effects of stirring rate and concentration of the surfactant on the diameter and morphologies of microcapsules were investigated by using scanning electron microscope (SEM). Thermal behaviors were studied by using a differential scanning calorimetry(DSC), and the release behaviors of fragrant oil from microcapsule were characterized by UV/vis. spectrophotometer. As a result, the average particle size of the microcapsules decreased with increasing the stirring rate or concentration of the surfactant. The surface morphologies of the microcapsules were changed from smooth surfaces to skin-like rough surfaces as increasing the PEI content. These results were mainly due to the increased hydrophilic groups at the microcapsule surfaces, resulting in increasing the release rate of fragrant oil in the microcapsules studied.

• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.927-933
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• 2011

Conducting polyaniline-poly($\varepsilon$-caprolactone) polymer composites were synthesized via in situ deposition techniques. By dissolving different weight percentages of poly($\varepsilon$-caprolactone) (PCL) (10%, 20%, 30%, 40%, and 50%), the oxidative polymerization of aniline was achieved using ammonium persulfate as an oxidant. FTIR, UV-vis spectra, and X-ray diffraction studies support a strong interaction between polyaniline (PANI) and PCL. Structural morphology of the PANI-PCL polymer composites was studied using scanned electron microscopy (SEM) and transmittance electron microscopy (TEM), and thermal stability was analyzed by thermogravimetric analysis (TGA) technique. The temperature-dependent DC conductivity of PANI-PCL polymer composite films was studied in the range of 305-475 K, which revealed a semiconducting behavior in the transport properties of the polymer films. Conductivity increased with the increase of PCL in below critical level, however conductivity of the polymer film was decreased with increase of PCL concentration higher than the critical value.

• Polymer(Korea)
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• v.33 no.2
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• pp.137-143
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• 2009

We prepared norfloxacin (NFX)-incorporated polymeric micelle using poly ($\varepsilon$-caprolactone)/poly(ethylene glycol) (PCL/PEG, CE) diblock copolymers. Particle size was from 60 to 200 nm according to the PCL block length. Their critical association concentration (CAC) was decreased according to the increase of PCL block length. $^1H$-NMR study showed core-shell type micelle structures of CE diblock copolymers in the aqueous environment. Drug release from polymeric micelle was continued over 2 days. Duration of drug release was varied according to the PCL block length and drug contents. At antimicrobial activity test, polymeric micelle showed almost similar cytotoxicity compared to NFX itself.

• Fibers and Polymers
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• v.4 no.2
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• pp.59-65
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• 2003

PLA/LPCL/HPCL blends composed of poly(lactic acid) (PLA), low molecular weight poly($\varepsilon$-caprolactone) (LPCL), and high molecular weight poly($\varepsilon$-caprolactone) (HPCL) were prepared by melt blending for bioabsorbable fila-ment sutures. The effects of blend composition and blending time on the ester interchange reaction by alcoholysis in the PLA/LPCL/HPCL blends were studied. Their thermal properties and the miscibility due to the ester interchange reaction were investigated by $^1{H-NMR}$, DSC, X-ray, and UTM analyses. The hydroxyl group contents of LPCL in the blends decreafed by the ester interchange reaction due to alcoholysis. Thus, the copolymer was formed by the ester interchange reaction at $200^{\circ}C$ for 30-60 minutes. The thermal properties of PLA/LPCL/HPCL blends such as melting temperature and heat of fusion decreased with increasing ester interchange reaction levels. However, the miscibility among the three poly-mers was improved greatly by ester interchange reaction. Tensile strength and modulus of PLA/LPCL/HPCL blend fibers increased with increasing HPCL content, while the elongation at break of the blend fibers increased with increasing LPCL content.

• Macromolecular Research
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• v.17 no.2
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• pp.72-78
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• 2009

Size control of therapeutic carriers in drug delivery systems has become important due to its relevance to biodistribution in the human body and therapeutic efficacy. To understand the dependence of particle size on the formation condition during nanoprecipitation method, we prepared nanoparticles from biodegradable, amphiphilic block copolymers and investigated the particle size and structure of the resultant nanoparticles according to various process parameters. We synthesized monomethoxy poly(ethylene glycol)-poly($\varepsilon$-caprolactone) block copolymer, MPEG-PCL, with different MPEG/PCL ratios via ring opening polymerization initiated from the hydroxyl end group of MPEG. Using various formulations with systematic change of the block ratio of MPEG and PCL, solvent choice, and concentration of organic phase, MPEG-PCL nanoparticles were prepared through nanoprecipitation technique. The results indicated that (i) the nanoparticles have a dual structure with an MPEG shell and a PCL core, originating from self-assembly of MPEG-PCL copolymer in aqueous condition, and (ii) the size of nanoparticles is dependent upon two sequential processes: diffusion between the organic and aqueous phases and solidification of the polymer.

• Bulletin of the Korean Chemical Society
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• v.22 no.5
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• pp.467-475
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• 2001

A triblock copolymer based on $poly(\varepsilon-caprolactone)$ (PCL) as the hydrophobic part and poly(ethylene glycol) (PEG) as the hydrophilic portion was synthesized by a ring-opening mechanism of ${\varepsilon}-caprolactone$ with PEG containing a hydroxyl group at bot h ends as an initiator. The synthesized block copolymers of PCL/PEG/PCL (CEC) were confirmed and characterized using various analysis equipment such as 1H NMR, DSC, FT-IR, and WAXD. Core-shell type nanoparticles of CEC triblock copolymers were prepared using a dialysis technique to estimate their potential as a colloidal drug carrier using a hydrophobic drug. From the results of particle size analysis and transmission electron microscopy, the particle size of CEC core-shell type nanoparticles was determined to be about 20-60 nm with a spherical shape. Since CEC block copolymer nanoparticles have a core-shell type micellar structure and small particle size similar to polymeric micelles, CEC block copolymer can self-associate at certain concentrations and the critical association concentration (CAC) was able to be determined by fluorescence probe techniques. The CAC values of the CEC block copolymers were dependent on the PCL block length. In addition, drug loading contents were dependent on the PCL block length: the larger the PCL block length, the higher the drug loading content. Drug release from CEC core-shell type nanoparticles showed an initial burst release for the first 12 hrs followed by pseudo-zero order release kinetics for 2 or 3 days. CEC-2 block copolymer core-shell type nanoparticles were degraded very slowly, suggesting that the drug release kinetics were governed by a diffusion mechanism rather than a degradation mechanism irrelevant to the CEC block copolymer composition.

• Macromolecular Research
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• v.13 no.5
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• pp.397-402
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• 2005

To explore the potential of shell crosslinked micelle (SCM) as a drug carrier, the drug release behavior of poly($\varepsilon$-caprolactone)-b-poly(acrylic acid) (PCL-b-PAA) SCMs was investigated. PCL-b-PAA was synthesized by ring opening polymerization of $\varepsilon$-caprolactone and atom transfer radical polymerization of tert-butyl acrylate, followed by selective hydrolysis of tert-butyl ester groups to acrylic acid groups. The resulting amphiphilic polymer was used to prepare SCMs by crosslinking of PAA corona via amidation chemistry. The drug release behavior of the SCMs was studied, using pyrene as a model drug, and was compared with that of non-crosslinked micelles, especially below the critical micelle concentration (CMC). When the shell layers were crosslinked, the drug release behavior of the SCMs was successfully modulated at a controlled rate compared with that of the non-crosslinked micelles, which showed a burst release of drug within a short time.

• Polymer(Korea)
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• v.28 no.4
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• pp.344-351
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• 2004

Poly(ethylene glycol)-based diblock and triblock polyester copolymers stimulating to temperature were studied as injectable biomaterials in drug delivery system because of their nontoxicity, biocompatibility and biodegradability. We synthesized the diblock copolymers consisting of methoxy poly(ethylene glycol) (MPEG) (M$_{n}$=750 g/mole) and poly($\varepsilon$-caprolactone) (PCL) by ring opening polymerization of $\varepsilon$-CL with MPEG as an initiator in the presence of HCl . Et$_2$O. The aqueous solution of synthesized diblock copolymers represented sol phase at room temperature and a sol to gel phase transition as the temperature increased from room temperature to body temperature. To confirm the in vivo gel formation, we observed the formation of gel in the mice body after injection of 20 wt% aqueous solution of each block copolymer. After 2 months, we observed the maintenance of gel without dispersion in mice. In this study, we synthesized diblock copolymers exhibiting sol-gel phase transition and confirmed the feasibility as biomaterials of injectable implantation.n.

• Current Applied Physics
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• v.18 no.11
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• pp.1313-1319
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• 2018

The coil-to-globule behavior of poly{${\gamma}$-2-[2-(2methoxyethoxy)ethoxy]ethoxy-3-caprolactone} (PMEEECL) as a ${\gamma}$-substituted poly (${\varepsilon}$-caprolactone) was investigated via atomistic molecular dynamics (MD) simulation. For this purpose, radius of gyration, end-to-end distance and radial distribution function of the chain in the presence of water were calculated. Consequently, the lower critical solution temperature (LCST) of PMEEECL chain at which the coil-to-globule transition takes place, was determined in each calculated parameter curve. The simulation results indicated that the LCST of PMEEECL was occurred at close to 320 K, which is in a good agreement with previous experimental results. Additionally, the appearance of sudden change in both Flory-Huggins interaction parameter (${\chi}$) and interaction energy between the PMEEECL chain and water molecules at about 320 K confirmed the calculated LCST result. The radial distribution function (RDF) results showed that the affinity of the PMEEECL side chain to water molecules is lower than its backbone.

• Bulletin of the Korean Chemical Society
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• v.26 no.4
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• pp.523-528
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• 2005

Diblock copolymers with different poly($\varepsilon$-caprolactone) (PCL) block lengths were synthesized by ringopening polymerization of $\varepsilon$-caprolactone in the presence of monomethoxy poly(ethylene glycol) (mPEG-OH, MW 2000) as initiator. The self-aggregation behaviors of the diblock copolymer nanoparticle, prepared by the diafiltration method, were investigated by using $^1H$ NMR, dynamic light scattering (DLS), and fluorescence spectroscopy. The PEG-PCL block copolymers formed the nano-sized self-aggregate in an aqueous environment by intrsa- and/or intermolecular association between hydrophobic PCL chains. The critical aggregation concentrations (cac) of the block copolymer self-aggregate became lower with increasing hydrophobic PCL block length. On the other hand, reverse trends of mean hydrodynamic diameters were measured by DLS owing to the increasing bulkiness of the hydrophobic chains and hydrophobic interaction between the PCL microdomains. The hydrodynamic diameters of the block copolymer nanoparticles, measured by DLS, were in the range of 65-270 nm. Furthermore, the size of the nanoparticles was scarcely affected by the concentration of the block copolymers in the range of 0.125-5 mg/mL owing to the negligible interparticular aggregation between the self-aggregated nanoparticles. Considered with the fairly low cac and nanoparticle stability, the PEG-PCL nanoparticles can be considered a potential candidate for biomedical applications such as drug carrier or imaging agent.