以双(三羟甲基)丙烷与氯甲酸乙酯为原料制备双六元环状碳酸酯(BTB),并以其为交联剂制备聚三亚甲基碳酸酯/聚己内酯(PTMC/PCL)三维网络聚合物,考察BTB的交联效果;以疏棉状嗜热丝孢菌脂肪酶为降解介质,研究PTMC/PCL三维网络聚合物的体外酶解性能。结果表明:BTB可有效促使PTMC或PCL发生交联反应,得到性能良好的三维网络聚合物,且PCL三维网络聚合物的酶解明显快于PTMC三维网络聚合物。
Bis(trimethylene carbonate) was synthesized from di(trimethylolpropane) and ethyl chloroformate to be used as crosslinker to form stable polymeric networks.The enzymatic degradation behavior of the obtained networks was investigated in lipase from Thermomyces lanuginosus at 37℃.The results showed that BTB had high reactivity and efficiency to crosslink poly (trimethylene carbonate) and poly(ε-caprolactone) and formed stable networks.Due to the preferred cleavage of ester bonds,the enzymatic degradation rate of poly(ε-caprolactone) networks was much faster than that of poly (trimethylene carbonate) networks in lipase.
[1] Lendlein A,Langer R.Biodegradable,elastic shape-memory polymers for potential biomedical applications[J].Science,2002,296(5565):1673-1676.
[2] Langer R,Tirrell D A.Designing materials for biology and medicine[J].Nature,2004,42(6982):487-492.
[3] Bostman O,Pihlajamäki H.Clinical biocompatibility of biodegradable orthopaedic implants for internal fixation:a review[J].Biomaterials,2000,21(24):2615-2621.
[4] Burkhart S S.The evolution of clinical applications of biodegradable implants in arthroscopic surgery[J].Biomaterials,2000,21(24):2631-2634.
[5] Zhang Z,Foks M A,Grijpma DW,et al.PTMC and MPEG-PTMC microparticles for hydrophilic drug delivery[J].Journal of Controlled Release 2005,101(1-3):392-394.
[6] Zhang Y,Zhuo R X.Synthesis and drug release behavior of poly (trimethylene carbonate)-poly (ethylene glycol)-poly (trimethylene carbonate) nanoparticles[J].Biomaterials,2005,26(14):2089-2094.
[7] Fabre T,Schappacher M,Bareille R,et al.Study of a (trimethylenecarbonate-co-ε-caprolactone) polymer-Part 2:in vitro cytocompatibility analysis and in vivo ED1 cell response of a new nerve guide[J].Biomaterials,2001,22(22):2951-2958.
[8] Kokai L E,Ghaznavi A M,Marra K G.Incorporation of double-walled microspheres into polymer nerve guides for the sustained delivery of glial cell line-derived neurotrophic factor[J].Biomaterials,2010,31(8):2313-2322.
[9] Bat E,Kothman B H,Higuera GA,et al.Ultraviolet light crosslinking of poly(trimethylene carbonate) for elastomeric tissue engineering scaffolds[J].Biomaterials,2010,31(33):8696-8705.
[10] Song Y,Wennink J W,Kamphuis M M,et al.Dynamic culturing of smooth muscle cells in tubular poly (trimethylene carbonate) scaffolds for vascular tissue engineering[J].Tissue Engineering Part A,2011,17(3-4):381-387.
[11] Yang L,Li J,Zhang W,et al.The degradation of poly(trimethylene carbonate) implants:the role of molecular weight and enzymes[J].Polymer Degradation and Stability,2015,122:77-87.
[12] Zhang Z,Kuijer R,Bulstra S K,et al.The in vivo and in vitro degradation behavior of poly(trimethylene carbonate)[J].Biomaterials,2006,27(9):1741-1748.
[13] Sachlos E,Czernuszka J T.Making tissue engineering scaffolds work.Review:the application of solid freeform fabrication technology to the production of tissue engineering scaffolds[J].European Cells and Materials,2003,5:29-40.
[14] Karp J M,Shoichet M S,Davies J E.Bone formation on two-dimensional poly(D,L-lactide-co-glycolide)(PLGA) films and three-dimensional PLGA tissue engineering scaffolds in vitro[J].Journal of Biomedical Materials Research Part A,2003,64(2):388-396.
[15] Sun H,Mei L,Song C,et al.The in vivo degradation,absorption and excretion of PCL-based implant[J].Biomaterials,2006,27(9):1735-1740.
[16] Yang L,Meng S,Liu D H,et al.Potential biodegradable implants from ε-caprolactone and D,L-Lactide copolymers:synthesis,properties,and in vivo degradation[J].International Journal of Polymer Analysis and Characterization,2014,19(5):422-440.
[17] Yang L Q,Yang D,Guan Y M,et al.Random copolymers based on trimethylene carbonate and ε-caprolactone for implant applications:synthesis and properties[J].Journal of Applied Polymer Science,2012,124(5):3714-3720.
[18] Yang L,Li J,Meng S,et al.The in vitro and in vivo degradation behavior of poly (trimethylene carbonate-co-ε-caprolactone) implants[J].Polymer,2014,55(20):5111-5124.
[19] Albertsson A C,Eklund M.In vitro degradation of poly(trimethylene carbonate),poly(trimethylene carbonate-co-caprolactone),and poly(adipic anhydride)[J].Journal of Applied Polymer Science,1995,57(1):87-103.
基金资助
“十三五”国家重点研发计划(2016YFC1000902);国家自然科学基金(51503093);沈阳市科技攻关项目(F16-205-1-37);辽宁省博士科研启动基金(201501116);辽宁省自然科学基金(20170540491)