• Macromolecular Research
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• 제16권3호
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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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• 제49권1호
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• pp.13-23
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• 2014

본 연구에서는 생체분해성 폴리에스터 계열의 glycolide, L-lactide 및 ${\varepsilon}$-caprolactone 단량체를 이용하여 2단계 중합법에 의한 삼원 공중합체를 제조하여, DSC를 이용한 비등온 결정화 거동을 고찰하였다. 보다 더 정확한 거동을 검토하기 위하여 Avrami 식과 Ozawa 식을 조합하여 비등온 결정화 거동을 고찰하였다. 과냉각도를 분석한 결과 PGCLA21의 값이 가장 큰 값을 보이고 있으며 L-lactide 함량이 증가함에 따라 과냉각도는 증가하는 경향을 보이고 있다. 수정된 Avrami 식을 이용하여 다양한 냉각속도에서 비등온 결정화 거동 결정화 속도 상수는 큰 경향을 보이고 있지 않는 것을 알 수 있었다. Avrami 및 Ozawa 식을 조합하여 특정한 상대적 결정화도에서의 냉각함수를 구한결과 L-lactide 함량이 증가하면서 PGCL과 비교시 결정화 속도를 향상시키는 역할을 하고 있는 것으로 여겨지는 반면 PGCLA41과 PGCLA21을 비교시 L-lactide 함량이 일정 이상 증가시 logF(T) 값이 큰 것을 확인 할 수 있는데 이는 동일한 결정을 얻는데 더 많은 냉각 속도를 필요로 한다는 것을 의미하며 결정화 속도 향상에 부정적인 영향을 미치는 것으로 판단된다.

• 폴리머
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• 제36권2호
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• pp.124-130
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• 2012

본 연구의 목적은 전기방사법을 사용하여 poly(L-lactide-$co$-${\varepsilon}$-caprolactone) (PLCL)과 marine collagen (MC)이 혼합된 나노섬유를 제조하는 것이다. 전기방사된 나노섬유의 직경과 형태는 여러 공정 변수에 의해서 변화되는데, PLCL과 MC의 혼합비, 노즐과 콜렉터와의 거리, 노즐의 직경, 용액의 방출 속도 그리고 전기장의 세기 변화에 따라 나노파이버의 직경을 주사전자현미경을 통해서 분석하였다. 또한 제조된 나노파이버의 표면변화를 확인하기 위해 물과의 접촉각을 측정하였으며, 나노파이버의 세포 친화성을 평가하기 위해 MG-63을 이용하여 생존율과 흡착형태를 주사전자현미경과 형광현미경을 통해서 관찰하였다. 이와 같은 연구 결과, 방사거리, MC의 함량, 전기장의 세기가 증가할수록 제조된 나노파이버의 평균직경은 감소하는 경향을 나타냈다. 또한 MC의 함량이 증가할수록 나노파이버의 친수성이 증가하였고 세포독성은 관찰되지 않았다. 이에 따라 해양유래 생물에서 추출한 콜라겐은 조직공학용 소재에 새롭게 사용될 수 있을 것으로 예상된다.

• Macromolecular Research
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• 제17권8호
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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.

• 방사선산업학회지
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• 제5권4호
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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.

• 폴리머
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• 제30권1호
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• pp.28-34
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• 2006

메톡시폴리에틸렌글리콜(MPEG)과 카프로락톤(CL)과 L-락타이드(LA)로 구성된 MPEG-PCLA 블록공중합체의 단량체를 다양한 비율로 $Sn(Oct)_2$의 존재 하에서 개환중합을 통해 합성하였다. MPEG-PCLA 블록공중합체의 특성은 $^1H-NMR$, GPC, DSC 그리고 XRD를 이용하여 결정하였다. 동역학적 변화를 측정하기 위하여 $Sn(Oct)_2$의 존재 하에서 MPEG-PCLA 블록공중합체의 중합 시 중합시간, 온도, 첨가하는 촉매의 양을 달리하면서 중합을 실시하였다. 그 결과 $110\;^{\circ}C$의 중합온도와 첨가하는 촉매의 양은 개시제 대비 1.2배의 경우에서 가장 높은 중합률을 보였다. 또한 합성된 블록공중합체의 수용액상에서의 시간에 따른 생분해 거동은 GPC를 이용한 분자량 분포의 비교를 통해 측정하였다. 합성된 블록공중합체의 생분해 거동을 측정한 결과 MPEG-PCLA 블록공중합체의 L-락타이드 함량이 증가할수록 생분해성도 증가하는 것을 확인하였다. 본 연구를 통해 MPEG-PCLA 블록공중합체의 $Sn(Oct)_2$의 존재 하에서 개환중합을 실시함에 있어 다양한 중합조건에 따른 중합속도를 확인하였으며 MPEG-PCLA 블록공중합체는 PCLA 블록의 PCL 대비 PLA의 함량 비율에 따라 생분해 기간을 조절할 수 있는 가능성을 확인하였다.

• Macromolecular Research
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• 제16권2호
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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.

• 폴리머
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• 제39권1호
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• pp.40-45
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• 2015

혈항혈전성 표면의 제조를 위해 간단한 비용매 휘발 방법을 통하여 고탄성체이면서 생분해성 폴리 락티드-카프로락톤 공중합체 필름의 표면상에 연잎 구조물과 유사한 마이크로 돌기를 만들어 주었다. 표면 구조와 소수성도, 항혈전 효과 등을 시험했으며, 결정화도와 탄성회복률 등의 물리적 특성도 분석하였다. 그 결과 비용매와 메틸렌클로라이드의 혼합 부피비 1:2에서 연잎표면과 유사한 최적의 효과를 얻었으며, 이때 수접촉각은 $124^{\circ}$였다. 혈소판 부착시험에서는 처리하지 않는 군에 비해 약 10%만 부착되는 효과를 확인할 수 있었다.

• 대한의용생체공학회:의공학회지
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• 제34권3호
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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.

• 방사선산업학회지
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• 제7권1호
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• pp.45-49
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• 2013

In tissue engineering application, a fibrous structure of scaffolds has been issued as an alternative system to regulate cell survival and tissue regeneration, and electrospinning technique has been popularly used to generate fibrous meshes or sheets mimicking the structure of native extracellular matrix (ECM). However, recent strategy in the scaffold development is expanded to provide the structural property as well as a biological property of native ECM, a variety of surface modification techniques have been used to introduce biological property. In this study, we developed biomimetic poly(L-lactide-co-${\varepsilon}$-caprolactone) (PLCL) nano- and micro-fibrous scaffolds as a unique platform with structural and biological properties with native ECM using electrospinning method and gamma-ray irradiation. Surface morphology of the scaffolds was observed by scanning electron microscopy, and alteration of surface property was evaluated with toluidine blue O staining, water contact angle measurement and ATR-FTIR analysis.