均相复合羟基磷灰石/有机高分子骨组织修复材料的研制
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摘要
本文首次利用原位复合和微乳液技术制备均相复合羟基磷灰石(HAp)／壳聚糖(CS)基和HAp／聚乳酸(PLA)复合材料，探索改善HAp作为分散相在CS和PLA基体中的分布均匀性的新方法。
本论文利用磷酸钙盐在不同pH值下的溶解度差异及CS膜对离子选择性渗透原理，制备了两相分布均匀的HAp／CS基复合支架材料。考察了水化时间、CS浓度、HAp含量、胶原(Collagen)对复合材料的组成、结构、理化性能和生物活性的影响，获得了制备均相HAp／CS基复合支架材料的最佳工艺条件；同时通过细胞增殖能力试验、材料表面细胞生长形态和体内植入试验，对材料进行生物相容性评价。研究结果表明：当无机／有机比例为60／100时，水化24h后复合材料无机相为HAp。复合材料的孔隙率与孔径大小随着CS浓度增加而降低，其压缩强度随着CS浓度增加而增大；CS浓度为2％时，支架材料孔径约为200—800μm，HAp为规则的棒状颗粒，其长度均小于15μm。随着HAp含量增加，均相复合材料的压缩强度增大，其孔隙率均在85％以上。均相复合HAp／CS和HAp／CS／COL与机械共混HAp／CS复合支架材料在相同无机／有机设定投料比—60／100下，水化后前者的质量损失比后者多，而孔隙率与压缩强度均比后者大。SEM和EDS分析表明，均相复合材料中HAp晶体与CS基体紧密复合且呈均匀分布，优于机械共混HAp／CS复合材料。均相复合HAp／CS和HAp／CS／COL复合支架材料的生物活性、细胞相容性和组织相容性均优于CS支架材料和机械共混HAp／CS复合支架材料。
采用反相微乳液技术制备了纳米HAp微乳液，通过与PLA溶液复合，制备了均相复合HAp／PLA复合材料。探讨了高稳定性的纳米HAp微乳液制备方法和有机溶剂对复合材料结构的影响，获得可改善HAp在PLA基体中的分布均匀性的较优工艺条件。PLA的丙酮溶液与HAp微乳液形成均相体系，复合后材料中HAp颗粒与PLA结合紧密。初步研究证明，纳米HAp微乳液复合的两相分布均匀性优于HAp粉末复合PLA制得的复合材料。
本文为制备高性能HAp／CS和HAp／PLA复合骨组织修复材料探索了一条新途经。
In this research, in situ preparation and microemulsion techniques were originally used to prepare the Hydroxyapatite (HAp)/Chitosan (CS) and HAp/Polylactic acid (PLA) homogeneous composites. And the point was to find out the new approaches that could improve the distribution of the HAp particles in the matrix and the compatibility of the interphase boundary.
Considering the principles that calcium phosphate salts have different solubility with diverse pH value and the function of selectivity pervasion of ions of CS film, a HAp/chitosan composite scaffold was developed. The HAp particles were made in situ through a rehydration with alkaline solution and dispersed homogeneously on the porous scaffold. They bounded to the CS scaffolds very well. The effects of the rehydration time, the concentration of CS solution, the content of HAp and collagen on the composition, structure, properties and bioactivity of the composite scaffolds were studied. On the other hand, the test of the proliferation ability of cells, observation the morphology of the cells and in vivo implant test were studied to evaluate the biocompatibility. Results showed that as the ratio of inorganic/organic was 60:100, the inorganic phase of the composite was HAp after 24h rehydration. And the porosity and pore size of composite decreased while the compress strength increased as the concentration of CS solution enhanced. When the concentration of CS solution was 2%, pore size of composite was about 200-800μm, and HAp particles were claviform with 15μm in length. The compress strength of the homogeneous composite scaffolds enhanced as the content of HAp increased, as well as the porosity of the homogeneous composite scaffolds was above 85%. When the ratio of inorganic/organic was 60:100, the homogeneous composite scaffolds of HAp/CS and HAp/CS/COL had higher porosity and compress strength though higher weight loss comparing to those of the composites scaffold prepared by mechanical blending. SEM and EDS results showed that HAp particles of the homogeneous composites were not only scattered more even than the composites prepared by mechanical blending, but also bounded to the CS matrix more well. The bioactivity and biocompatibility test,
本论文利用磷酸钙盐在不同pH值下的溶解度差异及CS膜对离子选择性渗透原理，制备了两相分布均匀的HAp／CS基复合支架材料。考察了水化时间、CS浓度、HAp含量、胶原(Collagen)对复合材料的组成、结构、理化性能和生物活性的影响，获得了制备均相HAp／CS基复合支架材料的最佳工艺条件；同时通过细胞增殖能力试验、材料表面细胞生长形态和体内植入试验，对材料进行生物相容性评价。研究结果表明：当无机／有机比例为60／100时，水化24h后复合材料无机相为HAp。复合材料的孔隙率与孔径大小随着CS浓度增加而降低，其压缩强度随着CS浓度增加而增大；CS浓度为2％时，支架材料孔径约为200—800μm，HAp为规则的棒状颗粒，其长度均小于15μm。随着HAp含量增加，均相复合材料的压缩强度增大，其孔隙率均在85％以上。均相复合HAp／CS和HAp／CS／COL与机械共混HAp／CS复合支架材料在相同无机／有机设定投料比—60／100下，水化后前者的质量损失比后者多，而孔隙率与压缩强度均比后者大。SEM和EDS分析表明，均相复合材料中HAp晶体与CS基体紧密复合且呈均匀分布，优于机械共混HAp／CS复合材料。均相复合HAp／CS和HAp／CS／COL复合支架材料的生物活性、细胞相容性和组织相容性均优于CS支架材料和机械共混HAp／CS复合支架材料。
采用反相微乳液技术制备了纳米HAp微乳液，通过与PLA溶液复合，制备了均相复合HAp／PLA复合材料。探讨了高稳定性的纳米HAp微乳液制备方法和有机溶剂对复合材料结构的影响，获得可改善HAp在PLA基体中的分布均匀性的较优工艺条件。PLA的丙酮溶液与HAp微乳液形成均相体系，复合后材料中HAp颗粒与PLA结合紧密。初步研究证明，纳米HAp微乳液复合的两相分布均匀性优于HAp粉末复合PLA制得的复合材料。
本文为制备高性能HAp／CS和HAp／PLA复合骨组织修复材料探索了一条新途经。
In this research, in situ preparation and microemulsion techniques were originally used to prepare the Hydroxyapatite (HAp)/Chitosan (CS) and HAp/Polylactic acid (PLA) homogeneous composites. And the point was to find out the new approaches that could improve the distribution of the HAp particles in the matrix and the compatibility of the interphase boundary.
Considering the principles that calcium phosphate salts have different solubility with diverse pH value and the function of selectivity pervasion of ions of CS film, a HAp/chitosan composite scaffold was developed. The HAp particles were made in situ through a rehydration with alkaline solution and dispersed homogeneously on the porous scaffold. They bounded to the CS scaffolds very well. The effects of the rehydration time, the concentration of CS solution, the content of HAp and collagen on the composition, structure, properties and bioactivity of the composite scaffolds were studied. On the other hand, the test of the proliferation ability of cells, observation the morphology of the cells and in vivo implant test were studied to evaluate the biocompatibility. Results showed that as the ratio of inorganic/organic was 60:100, the inorganic phase of the composite was HAp after 24h rehydration. And the porosity and pore size of composite decreased while the compress strength increased as the concentration of CS solution enhanced. When the concentration of CS solution was 2%, pore size of composite was about 200-800μm, and HAp particles were claviform with 15μm in length. The compress strength of the homogeneous composite scaffolds enhanced as the content of HAp increased, as well as the porosity of the homogeneous composite scaffolds was above 85%. When the ratio of inorganic/organic was 60:100, the homogeneous composite scaffolds of HAp/CS and HAp/CS/COL had higher porosity and compress strength though higher weight loss comparing to those of the composites scaffold prepared by mechanical blending. SEM and EDS results showed that HAp particles of the homogeneous composites were not only scattered more even than the composites prepared by mechanical blending, but also bounded to the CS matrix more well. The bioactivity and biocompatibility test,
引文
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