摘要
钛具有良好的生物相容性,被广泛用作硬组织替换材料。但是,钛是生物惰性材料,植入人体内易被当做异物。对医用钛进行表面改性,赋予医用钛理想的耐腐性能、生物活性和抗菌性,可有效改善其植入效果。本论文利用银/氮二元离子注入对钛进行表面改性,探查了银/氮二元离子注入顺序对钛表面的纳米硬度、耐腐能力和抗菌能力的影响。结合水热法和等离子体浸没离子注入技术,对医用钛进行表面改性,探查了改性钛表面的纳米结构、生物活性、抗菌性能和细胞相容性。此外,初步探讨了溶胶凝胶法制备聚乳酸(PLA)/CaO-Si02复合薄膜的生物活性和生物相容性。取得的主要研究成果如下：
1.利用等离子体浸没离子注入技术将银/氮二元离子按不同顺序(即先银后氮、先氮后银和银氮共注)注入钛的表面。银/氮二元离子注入钛表面的银以单质形式存在,而氮以氮化钛的形式存在。不同的银/氮二元注入顺序对改性后钛的耐腐性、纳米硬度和抗菌性能均有影响。银/氮二元离子共注钛表面的耐腐性能和硬度均优于先氮后银和先银后氮注入钛表面,这是因为银/氮二元共注导致的热效应使钛表面生成的氮化层最厚。银/氮二元注入样品对大肠杆菌和金黄色葡萄球菌均具有良好的抗菌作用。细胞实验表明,银/氮二元注入样品对细胞没有明显毒性,且有利于细胞的增殖和分化。
2.采用双氧水水热法在钛表面预先构建元素主要成份为Ti和O的不同纳米结构。利用等离子体浸没离子注入技术将银负载在双氧水水热处理钛表面,注银后样品表面纳米结构仍然保留完好。相对于纯钛片,注银前后钛基材的耐腐能力均获得了明显的改善。模拟体液浸泡实验显示,注银前后钛表面均具有良好的生物活性。注银样品对大肠杆菌和金黄色葡萄球菌繁殖具有明显抑制作用,显示出良好的抗菌性。细胞毒性实验表明,水热处理72小时钛表面注银前后对小鼠成骨细胞的繁殖和分化均具有良好的促进作用。
3.以氢氧化钠和双氧水作为反应介质,在钛表面构建了四种纳米结构,采用等离子体浸没离子注入技术将银负载在纳米结构表面。模拟体液浸泡实验显示,注银前后钛表面均显示良好的生物活性。注银表面对大肠杆菌和金黄色葡萄球菌均具有良好的抗菌能力。细胞毒性实验表明,除氢氧化钠水热处理并注银样品外,其它三种水热处理并注银钛表面对小鼠成骨细胞的增殖和分化具有较好的促进作用。
4.制备了不同比例的PLA/CaO-Si02多孔复合薄膜。在模拟体液浸泡7天的薄膜表面形成环状结构的类骨磷灰石层,显示良好生物活性。随着CaO-SiO2含量增加,复合薄膜表面微孔的孔径变小,薄膜表面zeta电位变负,诱导类骨磷灰石沉积的能力增强；MTT实验证实复合薄膜对MG-63细胞没有毒性且有利于细胞的增殖。
Titanium has been widely used as hard tissue implant material because of its good biocompatibility. However, titanium implant in human body is often repulsed as a foreign object due to its bioinertia. Thus, it is necessary to carry out surface modification for titanium to obtain implant with ideal performances on corrosion resistance, bioactivity and antibacterial ability. In this work, titanium surface was modified by sliver (Ag) and nitrogen (N) dual ions implantation, the depending properties of titanium, such as corrosion resistance, hardness and antibacterial ability, on Ag/N dual ion implantation sequence was investigated. To enhance the bioactivity and antibacterial activity, titanium was treated by surface modification combining chemical method (hydrothermal method) and physical method (plasma immersion ion implantation), and then its microstructure, bioactivity, antibacterial ability and cell cytotoxicity were studied. The poly (Lactic Acid)(PLA)/CaO-SiO2composite membranes were synthesized by sol-gel method, and the bioactivity and biocompatibilty of these composite membranes were examined. The results obtained are described as follows:
1. Silver (Ag) and nitrogen (N) dual ions were sequentially implanted into titanium via plasma immersion ion implantation (PⅢ) technology at different implantation sequence, including PIII-Ag-N (Ag ions prior to N implantation), PIII-N-Ag (N prior to Ag ions implantation) and PIII-Ag+N (Ag/N dual ions co-implantation). Sliver and nitrogen in all modified titanium were existence of metallic sliver and titanium nitride. The Ag/N dual ions implantation sequences play an important role on the corrosion resistance and hardness of the modified samples. The results showed that the properties of samples via Ag/N dual ion co-implantation mentioned above are better than PⅢ-Ag-N and PⅢ-N-Ag, which is ascribed to the thickness of titanium nitrogen layer caused by thermal spikes effect during implantation process. The antibacterial experiments indicated Ag/N dual ions implanted titanium exhibit high antibacterial ability against Escherichia coli and Staphylococcus aureus. The cytotoxicity experiments showed the Ag/N dual ions implanted titanium can promote cell proliferation.
2. Hydrogen peroxide hydrothermal method was used to modify the surface of titanium plates. The nanostructural layer consisting of Ti and O was formed on the surface of hydrothermal-treated titanium. Then, sliver was introduced into hydrothermal-treated titanium by plasma immersion ion implantation. The surface morphology of titanium as above can be remained at nano-scale level after Ag ion implantation. The corrosion resistance of hydrothermal-treated titanium before and after Ag ion implantation is better than pure titanium, while the SBF test also indicated these samples before and after sliver ion implantation exhibit well bioactivity. The Ag ion implanted samples exhibit well antibacterial ability against Escherichia coli and Staphylococcus aureus. The hydrothermal-treated titanium samples before and after Ag ion implantation are of good cytocompatibility.
3. Titanium plates were hydrothermal treated in a mixture solution of hydrogen peroxide and sodium. Silver was introduced into the hydrothermal-treated titanium by plasma immersion ion implantation. The SBF test indicated the hydrothermal-treated titanium before and after sliver ion implantation exhibit good bioactivity. The Ag implanted into titanium pretreated by hydrothermal method exhibited well antibacterial ability against Escherichia coli and Staphylococcus aureus, and can promote cell proliferation except the samples pretreated by sodium hydroxide solution.
4. A novel porous PLA/CaO-SiO2(nSiO2/nCao=1) composite membrane is synthesized by sol-gel method. After soaked in simulated body fluids for7days, the surfaces of the PLA/CaO-SiO2composite membranes are covered by apatite layer with orderly ring structure. With the increase of CaO-SiO2content in the composite membrane, the size of the pores on the surface of composite membrane becomes smaller, the surface zeta potentials decreases and the bioactivity become better. MTT experiments showed the composite membranes are not of cytotoxcity to MG-63cells and support cell proliferation.
引文
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