咖啡酸基聚酯的制备与性能研究.docVIP

咖啡酸基聚酯的制备与性能研究 陈明清*，李会玲，施冬健，李继航，胡娜( 江南大学化学与材料工程学院，无锡 214122 关键词：咖啡酸 石胆酸 可降解聚酯 胶束 3,4-二羟基肉桂酸（DHCA，咖啡酸）是从咖啡豆或粗咖啡中分解得到的“植物性单体”，有着独特的羟基和肉桂酸基团赋予其抗氧化和荧光等优良的性能，且在紫外光照下可发生顺/反异构化和[2+2]环加成反应。通过聚合所得到的材料具有良好的生理相容性，且代谢产物对人体无毒性，在光敏纳米材料、生物医学和环境等方面具有广阔的应用前景[1, 2]。石胆酸(LCA)是含有一个羟基和一个羧基的双官能团单体，具有刚性分子结构，作为胆甾衍生物存在于哺乳动物胆汁中，具有一定的抗癌作用[3, 4]。本文通过熔融缩聚制备了P(DHCA-co-LCA)可降解聚酯。反应过程如Scheme 1所示。 Scheme 1. Synthesis pathway of P(DHCA-co-LCA) polymers P(DHCA-co-LCA)在DMF/H2O的混合介质中自组装形成了表面光滑，粒径均一的胶束，随着聚酯溶液浓度的增大胶束平均粒径逐渐增大，Figure 1为是不同浓度P(DHCA-co-LCA)5-5（nDHCA:nLCA=5:5）溶液得到胶束的TEM图 Figure 1. TEM images of P(DHCA-co-LCA)5-5 polyester micelles formed in DMF/H2O at various solution concentrations 肉桂酰基团在λ280nm紫外光照下可以发生[2+2]环加成反应生成环丁烷，P(DHCA-co-LCA)胶束样品在紫外光源利用紫外分光光度计对不同紫外光照时间下的紫外吸收进行追踪（）。从图中可以看出，随紫外光照时间的增加，聚酯的胶束样品在特征波长326 nm处的吸光度逐渐下降。 Figure 2. UV absorbance change of P(DHCA-co-LCA)9-1 polyesters micelles with different UV irradiation time 通过LLS对P(DHCA-co-LCA)胶束表征后发现光照后的胶束平均粒径逐渐减小P(DHCA-co-LCA)9-1胶束半径分布图。 Figure 3. Radii (Rh) of P(DHCA-co-LCA)9-1 (2 mg/mL) polyesters micelles before and after UV irradiation by LLS measurements 参考文献： [1] K. Tatsuo, T. H. Thi, D. J. Shi, M. Akashi, Nat. Mater., 2006, 5(12): 996. [2] T. H. Thi, M. Matsusaki, D. J. Shi, T. Kaneko, M. Akashi, J. Biomat. Sci-Polym. E., 2008, 19(1): 75. [3] M. Matsusaki, T. H. Thi, T. Kaneko, M. Akashi, Biomaterials, 2005, 26(32): 6263. [4] K. H. Chang, L. Lee, J. Chen, W. S. Li, Chem. Commun., 2006, 6: 629. Synthesis and properties of polyesters based on coffeic acid Mingqing Chen*, Huiling Li, Dongjian Shi, Jihang Li, Na Hu School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 Abstract: Degradable P(DHCA-co-LCA) polyesters were synthesized by melt polycondensation of 3,4-dihydroxycinnamic acid (DHCA, coffeic acid) and lithocholic acid (LCA). The structure and molecular weight of P(DHCA-co-LCA) polyesters were characterized by FTIR, 1H-NMR and GPC. P(DHCA-co-LCA) micelles with different diameters were prepared by mixing N,N