摘要
天然高分子材料可用于组织工程等医学领域,研究其自身因素对降解过程的影响和机理,设计降解可控的生物材料是亟待解决的问题。本文主要研究海藻酸钠、纳米莲纤维为基材的多孔材料制备及表征,重点对其降解性能进行深入探讨。
(1)蜂窝状海藻酸盐多孔材料的制备及表征。通过理化性质表征发现海藻酸钠易于加工成型,Mw=3.0×105海藻酸盐多孔材料成膜性能最佳,应根据需要选择合适的分子量以改善其性能。采用冷冻干燥技术、-10℃预冻可构建出蜂窝状多孔材料(孔隙率为92.06%),改变预冻温度可以调控孔隙结构。随着海藻酸钠用量增多,多孔材料的孔隙率降低,孔径减小,吸水率先上升而后下降；而拉伸强度、断裂伸长率均增加。以上研究为构建降解可控的海藻酸盐多孔材料奠定了基础。
(2)氧化海藻酸钠制备及海藻酸盐多孔材料的降解性能调控。对海藻酸钠进行醛基化改性并表征其化学组成、氧化度及降解性能；再分别用氯化钙、羧甲基壳聚糖进行交联,研究其降解性能。氯化钙交联后海藻酸盐多孔材料降解速率与氧化度的增加成正比,最高达61.71%。海藻酸盐多孔材料降解液pH值下降,亦与氧化度成正比。羧甲基壳聚糖交联氧化海藻酸钠制备的多孔材料降解速率提升,14天降解82.12%-100.00%。随着羧甲基壳聚糖用量提高,降解液pH值趋于上升,说明调整组分摩尔比可以控制材料的降解速率及pH值。
(3)纳米莲纤维/海藻酸盐多孔材料的制备及降解性能调控。采用TEMPO/NaClO/NaBr体系对预处理过的莲纤维进行羧基改性,所得纳米莲纤维直径为15nm,其羧基含量随着氧化时间的增加而升高。对照组纤维素粉降解缓慢；纳米莲纤维降解速率与羧基含量成正相关,而降解液pH值随羧基含量上升呈下降趋势。氯化钙交联的纳米莲纤维/海藻酸盐多孔材料降解速率较小(40.20%),而羧甲基壳聚糖交联的纳米莲纤维/海藻酸盐多孔材料拥有优异的降解性能(59.16%),以及高孔隙率(87.10%)、高吸水率(1813.33%)、较好的拉伸性能(0.36MPa/7.73%),为构建皮肤组织工程支架提供研究基础。
Natural polymer materials could be used in the field of tissue engineering and other medicine domain. To study the effect of its own factors on the degradation process and mechanism and design degradation of controllable of biological materials were the key issue to be solved. In this paper, we studied preparation and characterization of porous materials by sodium alginate and lotus nanofibers, and their degradation performance were discussed.
(1) Preparation and characterization of spongy alginate porous materials. According to physicochemical characterization, sodium alginate was easy to processing molding. Alginate (Mw=3.0×105) was conducive to forming membranes. So, suitable molecular weight should be selected in order to improve their performance. With freeze-drying technology and pre-freezing at-10℃, we have builded the honeycomb materials (Porousity=92.06%). Changing the pre-freezing temperature can regulate pore structure to some extent. With the increased dosage of sodium alginate, the porosity and the pore size of the materials were reduced, while tensile strength and elongation at break increased. Water absorption performance of the materials was good. The above studies lay a foundation for construction of controllable degradation alginate porous materials.
(2) The preparation of oxidized sodium alginate and controllable degradation study of alginate porous materials. Sodium alginate was aldehyde-modified and characterization of its chemical structure, the degree of oxidation and biodegradation. Then, oxidized sodium alginate was crosslinked respectively with calcium chloride and carboxymethyl chitosan, with their degradation performance studied.
It was found that the non-oxidized alginate porous materials degrade slowly. The degradation rates of oxidized alginate were faster, which was up to61.71%. Thus, degradation rates of calcium chloride crosslinked porous materials increased while pH values of liquid decreased, which was proportional to the degree of oxidation. The oxidized alginate materials crosslinked with carboxymethyl chitosan degraded faster than non-oxidized one, with degradation rates decreased82.12%-100.00%during14days. Increasing dosage of carboxymethyl chitosan, the pH values tended to rise, which indicated that adjusting component mole ratio may control the material degradation rates and pH values.
(3) Preparation of lotus nanofibers/alginate porous materials and controlled degradation studies. First, lotus fibers were carboxyl-modified with TEMPO/NaClO/NaBr system and got lotus nanofibers whose diameter reached15run. The carboxyl content of lotus nanofibers increased with the increase of oxidation time. Unmodified cellulose degradation rates were very slow. But degradation rates of lotus nanofibers were positively correlated with the carboxyl content and pH values were opposite.
The degradation rates of the lotus nanofibers/alginate materials crosslinked with calcium chloride were slow (40.20%). In contrast, the materials crosslinked with carboxymethyl chitosan owned better performance such as porosity (87.10%), water absorption ration (1813.33%), mechanical properties (0.36MPa/7.73%) and in vitro degradation (59.16%). So, the materials crosslinked with carboxymethyl chitosan are expected to be used in medical fields such as skin tissue engineering.
引文
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