Oligo(trimethylene carbonate)-based supramolecular biomaterials
Oligo(trimethylene carbonate)-based supramolecular biomaterials
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DOI：
10.1021/ma061078o
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发表时间：
2006-12-12
期刊：
影响因子：
5.5
通讯作者：
Meijer, E. W.
中科院分区：
文献类型：
--
作者：
Dankers, Patricia Y. W.;Zhang, Zheng;Meijer, E. W.
提出了一种超分子聚合物体系，其中相对短的三亚甲基碳酸酯（TMC）预聚物通过可逆的四重氢键脲基嘧啶酮（UPy）部分连接。合成了几种UPy改性的双官能和三官能TMC聚合物。通过将不同的三官能UPy-TMC与双官能UPy-TMC聚合物混合来实现机械和热性能的可调谐性。UPy基团的浓度影响材料的结晶行为。UPy改性的TMC聚合物显示熔融吸热，这是由UPy单元聚集成小微晶引起的。据推测，UPy二聚体由于氨基甲酸酯氢键而在横向方向上堆叠。原子力显微镜证实了纤维状堆栈的存在。这些微晶赋予材料机械强度，并防止材料在加工成3D支架后流动。更重要的是，这些聚合物可以在稍微升高的温度下非常容易地加工。由于氢键的可逆性质的强温度依赖性，它们的熔体粘度低，而在低于50 ℃的温度下，由于超分子物理交联，发现优异的机械性能。UPy-TMC聚合物显示出生物相容性，并且成纤维细胞在UPy-TMC的滴铸膜上增殖良好。因此，这些新的超分子UPy-TMC聚合物是非常有前途的，生物相容的，可调的，易于加工的生物材料的应用，如组织工程。
A supramolecular polymer system is presented in which relatively short trimethylene carbonate (TMC) prepolymers are linked via reversible quadruple hydrogen bonding ureidopyrimidinone (UPy) moieties. Several UPy-modified bifunctional and trifunctional TMC polymers were synthesized. Tunability of the mechanical and thermal properties was achieved by mixing different trifunctional UPy-TMC with bifunctional UPy-TMC polymers. The concentration of UPy groups influenced the crystallization behavior of the materials. The UPy-modified TMC polymers displayed melting endotherms, which are caused by aggregation of the UPy units into small crystallites. It is assumed that the UPy dimers stack in the lateral direction due to urethane hydrogen bonding. Atomic force microscopy confirmed the presence of fiberlike stacks. These crystallites give the material its mechanical strength and prevent flowing of the material after processing into 3D scaffolds. More importantly, these polymers can be processed quite easily at slightly elevated temperatures. Because of the strong temperature dependence of the reversible nature of the hydrogen bonds, their melt viscosities are low, while at temperatures below 50 C excellent mechanical properties are found as a result of supramolecular, physical cross-linking. The UPy-TMC polymers are shown to be biocompatible and fibroblasts proliferate well on drop cast films of UPy-TMC. Thus, these novel supramolecular UPy-TMC polymers are very promising, biocompatible, tunable, and easily processable biomaterials for applications such as tissue engineering.