光交联羧甲基壳聚糖水凝胶的研究-材料化学工程专业论文.docxVIP

摘 要 水凝胶是一种亲水的三维聚合物网络，它可以吸收大量水，其物理性质接近 于软组织。水凝胶有着与细胞外基质极其相似的结构与特点，具有良好的生物相 容性和生物降解性。因此，水凝胶在组织工程、药物释放等领域都获得了极大的 关注。光交联作为一种构建水凝胶的常见方式，其反应条件温和，副产物少，反 应过程容易控制，反应效率高，是构建水凝胶的良好选择。 本文拟以水溶性壳聚糖衍生物 O-羧甲基壳聚糖（CMCS）为水溶性大分子基 质，以叠氮基团的光耦合反应为交联机理构建水凝胶，旨在使得到的水凝胶不仅 具有可注射原位凝胶的性质，还具有 pH 敏感性。由于 CMCS 上含有羧基，因此， 为了避免自交联的产生，本文提出了新的 CMCS 改性方案，即先制备对叠氮苯 甲酸的活化酯，再将活化酯与 CMCS 上的氨基反应得到叠氮化羧甲基壳聚糖 （AZ-CMCS）。合成过程中对产物都进行了红外光谱（FT-IR）、核磁共振谱图 （1H-NMR）的表征。应用流变学的手段对 AZ-CMCS 水凝胶的交联过程进行了 跟踪，并对水凝胶的湿态强度进行了考察。本文将 AZ-CMCS 水凝胶制成了二维 薄膜和三维支架，分别考察了它们的理化性能和细胞相容性。 结果表明，利用对叠氮苯甲酸活化酯实现 CMCS 的叠氮化反应，可以有效避 免 CMCS 的自交联，条件容易控制。AZ-CMCS 可以在短时间完成交联，得到的 凝胶具有较好的湿态强度。AZ-CMCS 水凝胶具有良好的 pH 响应性、良好的药 物控释性能、低细胞毒性，是一种有潜力的生物医用材料。 关键词： 羧甲基壳聚糖 叠氮 光交联 水凝胶 流变学 ABSTRACT Hydrogels are networks with certain three dimensional structures, which are made up of hydrophilic polymers that are crosslinked to form water insoluble hydrogels. Today, hydrogels are widely applied in many fields. Due to their highly structural and characteristic similarity to extracellular matrix, hydrogels received remarkable interest in the field of medicine and tissue engineering. Photo-crosslinking reaction provides an effective and mild crosslinking process which involves in mild reaction conditions, minimum byproduct formation and controlling flexibility. Therefore, photo-crosslinking is a good choice for building hydrogels. In this paper, injectable hydrogels made from azidophenyl carboxymethyl chitosan derivative (AZ-CMCS) were prepared. The conjugation of azido groups to carboxymethyl chitosan chains were realized through a two step procedure. To confirm the conjugation, methods of 1H NMR and FT-IR were employed. To evaluate the photo sensitivity and mechanical properties of AZ-CMCS system, a rheological method was utilized with the help of small amplitude oscillatory shear under different conditions. To evaluate the pH sensitivity, equilibrium swelling degree was examined under a wide range of pH values. At the same time, a drug release system was set up using BSA as m