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聚(D,L-丙交酯-共-ε-己内酯)-聚(乙二醇)-聚(D,L-丙交酯-共-ε-己内酯)的表征、降解及机械强度

Characterization, degradation, and mechanical strength of poly(D,L-lactide-co-epsilon-caprolactone)-poly(ethylene glycol)-poly(D,L-lactide-co-epsilon-caprolactone).

作者信息

Bramfeldt Hanna, Sarazin Pierre, Vermette Patrick

机构信息

Laboratoire de Bioingénierie et de Biophysique de l'Université de Sherbrooke, Department of Chemical Engineering, Université de Sherbrooke, 2500, blvd de l'Université, Sherbrooke, Quebec, Canada J1K 2R1.

出版信息

J Biomed Mater Res A. 2007 Nov;83(2):503-11. doi: 10.1002/jbm.a.31300.

Abstract

A series of three biocompatible P(CL-co-LA)-PEG-P(CL-co-LA) copolymers were synthesized using ring-opening polymerization and characterized by 1H-NMR, gel permeation chromatography, DSC, dynamic-mechanical analysis, and X-ray diffraction. The number of monomer units was kept constant, while the D,L-LA fraction was varied so as to constitute 0, 30, or 70% of the end segments. The molecular weights were sufficiently high to eventually permit 3D scaffold preparation. A degradation study was carried out over 26 weeks, and the effect of monomer composition on the rate of degradation as well as on changes in mechanical strength was investigated. Pure polycaprolactone (PCL)-poly(ethylene glycol) (PEG)-PCL copolymer, P(100/0), was a crystalline material displaying no measurable mass loss, a 30% reduction in mean molecular weight (Mn), and only very slight changes in tensile strength. The random incorporation of 30 and 70% D,L-LA into the end sections of the polymer chain, produced more and more amorphous materials, exhibiting increasingly high rates of degradation, mass loss, and loss of tensile strength. Compared with random P(CL-co-LA), the presence of the PEG block was found both to improve hydrophilicity and thus the rate of degradation and to infer a stabilizing quality, thereby pacing the decrease in tensile strength during degradation. The tested copolymers range from materials exhibiting low mechanical strength and high rate of degradation to slow-degrading materials with high mechanical strength suitable, e.g., for three-dimensional scaffolding.

摘要

通过开环聚合法合成了一系列三种生物相容性的聚(己内酯-共-丙交酯)-聚乙二醇-聚(己内酯-共-丙交酯)共聚物,并通过1H-NMR、凝胶渗透色谱、差示扫描量热法、动态力学分析和X射线衍射对其进行了表征。单体单元的数量保持恒定,同时改变D,L-丙交酯的比例,使其占末端链段的0%、30%或70%。分子量足够高,最终可以制备三维支架。进行了为期26周的降解研究,研究了单体组成对降解速率以及机械强度变化的影响。纯聚己内酯(PCL)-聚乙二醇(PEG)-PCL共聚物P(100/0)是一种结晶材料,没有可测量的质量损失,平均分子量(Mn)降低了30%,拉伸强度只有非常轻微的变化。在聚合物链的末端随机掺入30%和70%的D,L-丙交酯,产生了越来越多的无定形材料,表现出越来越高的降解速率、质量损失和拉伸强度损失。与无规聚(己内酯-共-丙交酯)相比,发现PEG嵌段的存在既能提高亲水性,从而提高降解速率,又能赋予一种稳定质量,从而减缓降解过程中拉伸强度的下降。测试的共聚物范围从机械强度低、降解速率高的材料到机械强度高、降解缓慢的材料,例如适用于三维支架。

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