• 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.

• Elastomers and Composites
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• v.49 no.1
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• pp.13-23
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• 2014

In this work, glycolide, L-lactide and ${\varepsilon}$-caprolactone monomers were polymerized into the triblock copolymers by two step polymerization method and their non-isothermal crystallization behaviors were studied by combination of modified Avrami and Ozawa formula for further analysis of their behaviors. The result showed that PGCLA21 gave the highest value for supercooling analysis and super cooling degree increased with L-lactide content. Crystallization velocity constant, however, showed no significant change. The result of cooling function in specific relative crystallization degree showed that the increase of L-lactide content made an effect on the more enhancement of crystallization velocity of the PGCLA than PGCL. The result of big logF(T) value with the L-lactide content above critical point for PGCLA41 and PGCLA21 showed that bigger cooling velocity needed to gain same crystal size compared with PGCL. This means that it gives negative effect in the increase of crystallization velocity.

• Polymer(Korea)
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• v.36 no.2
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• pp.124-130
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• 2012

The uniform nanofibers of poly(L-lactide-$co$-${\varepsilon}$-caprolactone) (PLCL) with different contents of marine collagen (MC) were successfully prepared by electrospinning method. The effects of the major parameters in electrospinning process such as tip to target distance (TTD), voltage, nozzle size and flow rate on the average diameter of the electrospun nanofiber were investigated in generating composite nanofiber. The diameter and morphology of the nanofibers were confirmed by a scanning electron microscopy (SEM). Also, we measured a water contact angle to determine the surface wettability of the nanofibers. The average diameter of the nanofibers decreased as the value of TTD, MC contents, and voltages increased in comparison with that of pristine PLCL nanofiber. In contrast, the diameter of the nanofibers increased as the flow rate and inner diameter of nozzle increased in comparison with that of pristine PLCL. In addition, the hydrophilicity of the nanofiber and attachment of MG-63 cells on the sheets increased as incorporated collagen contents increased. Therefore, the marine collagen would be a potential material to enhance cellular interactivity of synthetic materials by mimicking the natural tissue.

• Macromolecular Research
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• v.17 no.8
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• pp.575-579
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• 2009

Copolymerization of L-lactide and s-caprolactone initiated by tin (II) octoate (Sn(Oct)$_2$) was carried out in supercritical chlorodifluoromethane (R22) with varying reaction conditions (time and temperature) and amounts of monomer and catalyst, under a pressure of 250 bar. The optimum conditions were a reaction time of 10 h and a temperature of 130 $^{\circ}C$, which is similar to the temperature used in bulk copolymerization system. The conversion increased from 56% to 76% by increasing the reaction time from 1 to 10 h. The molecular weight also increased to 75,900 g.mol$^{-1}$ over the same period, while the increased monomer concentration resulted in a high molecular weight of 86,400 g.mol$^{-1}$ and a monomer conversion of 84%. Raising the reaction temperature from 90 to 130 $^{\circ}C$ increased the monomer conversion as well as the poly-L-lactide-co-${\varepsilon}$-caprolactone (PLCL) molecular weight. The variation on the stannous octoate catalyst suggested that less catalyst would decrease the caprolactone content of the polymer.

• Journal of Radiation Industry
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• v.5 no.4
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• pp.365-370
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• 2011

Electrospun nanofibers prepared with synthetic biodegradable polymer have some limitations in regulating adhesion, proliferation, and spreading of cells because of their surface hydrophobicity and absence of cell-interaction. In this study, we functionalized the electrospun poly(L-lactide-co-${\varepsilon}$-caprolactone) (PLCL) nanofibers with acrylic acid (AAc) to modulate their surface hydrophilicity using electron-beam irradiation method and then measured grafting ratio of AAc, water contact angle, and ATR-FTIR of AAc-grafted nanofibers. A grafting ratio of AAc on the nanofibers was increased as irradiation dose and AAc concentration were increased. AAc-grafted nanofibers also have higher wettability than non-modified nanofibers. In conclusion, those surface-modified nanofibers may be an essential candidate to regulate cell attachment in tissue engineering applications.

• 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.

• Macromolecular Research
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• v.16 no.2
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• pp.139-148
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• 2008

Biodegradable and elastic poly(L-lactide-co-$\varepsilon$-caprolactone) (PLCL) was electrospun to prepare nanofibers, and N-isopropylacrylamide (NIPAAm) was then grafted onto their surfaces under aqueous conditions using $^{60}Co-{\gamma}$ irradiation. The graft yield increased with increasing irradiation dose from 5 to 10 kGy and the nanofibers showed a greater graft yield compared with the firms. SEM confirmed that the PLCL nanofibers maintained an interconnected pore structure after grafting with NIPAAm. However, overdoses of irradiation led to the excessive formation of homopolymer gels on the surface of thc PLCL nanofibers. The equilibrium swelling and deswelling ratio of the PNIPAAm-g-PLCL nanofibers (prepared with 10 kGy) was the highest among the samples, which was consistent with the graft yield results. The phase-separation characteristics of PNIPAAm in aqueous conditions conferred a unique temperature-responsive swelling behavior of PNIPAAm-g-PLCL nanofibers, showing the ability to absorb a large amount of water at < $32^{\circ}C$, and abrupt collapse when the temperature was increased to $40^{\circ}C$. In accordance with the temperature-dependent changes in swelling behavior, the release rate of indomethacin and FITC-BSA loaded in PNIPAAm-g-PLCL nanofibers by a diffusion-mediated process was regulated by the change in temperature. Both model drugs demonstrated greater release rate at $40^{\circ}C$ relative to that at $25^{\circ}C$. This approach of the temperature-controlled release of drugs from PNIPAAm-g-PLCL nanofibers using gamma-ray irradiation may be used to design drugs and protein delivery carriers in various biomedical applications.

• Polymer(Korea)
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• v.34 no.2
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• pp.178-183
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• 2010

Medical metal stents inserted to patients with a cardiovascular disease associated with coronary artery system have relatively increased the survival rate. The development of new stents is, however, urgently required due to restenosis and late thrombosis generated in metal stents. To solve these problems, the biodegradable polymers such as poly(lactide-co-glycolide) (PLGA), poly(L-lactide)(PLLA), and poly ($\varepsilon$-caprolactone)(PCL) were mixed with alpha lipoic acid (ALA), which is well known to inhibit the proliferation of neointimal hyperplasia. Subsequently, the ALA-loaded polymers were coated on stainless steel by electrospray. The drug-eluting behaviors from the coated polymers were investigated according to kinds and concentrations of polymers, spray rates, and kinds of solvents. The drug-eluting rate from PCL with the lowest glass transition temperature was the fastest among three polymers and followed by PLGA and PLLA. The surface roughness increased as the spray rate was increased and also the drug-eluting rate was affected by kinds of solvents with different boiling point. It is expected that drug-eluting stent (DES) coated with ALA-loaded polymers can be applied practically for clinical applications by controlling the behavior of drug release.

• 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 Biomedical Engineering Research
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• v.34 no.3
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• pp.111-116
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• 2013

Finite element analysis(FEA) has been extensively applied in the analyses of biomechanical properties of stents. Geometrically, a closed-cell stent is an assembly of a number of repeated unit cells and exhibits periodicity in both longitudinal and circumferential directions. This study concentrates on various parameters of the FEA models for the analysis of drug-eluting biodegradable polymeric stents for application to the treatment of coronary artery disease. In order to determine the mechanical characteristics of biodegradable polymeric stents, FEA was used to model two different types of stents: tubular stents(TS) and helicoidal stents(HS). For this modeling, epigallocatechin-3-O-gallate (EGCG)-eluting poly[(L-lactide-co-${\varepsilon}$-caprolactone), PLCL] (E-PLCL) was chosen as drug-eluting stent materials. E-PLCL was prepared by blending PLCL with 5% EGCG as previously described. In addition, the effects of EGCG blending on the mechanical properties of PLCL were investigated for both types of stent models. EGCG did not affect tensile strength at break, but significantly increased elastic modulus of PLCL. It is suggested that FEA is a cost-effective method to improve the design of drug-eluting biodegradable polymeric stents.