钛材表面微纳米结构的构建、改性及生物学评价

发布时间：2018-05-01 08:25

本文选题：钛材 + 表面改性　；参考：《重庆大学》2012年博士论文

【摘要】：生物材料的表面拓扑结构和化学成分在调节蛋白质吸附、细胞粘附、迁移、铺展、增殖和分化等生物学行为中起着至关重要的作用。随着微/纳米技术的快速发展，通过在材料表面构建微/纳米结构来调控相关生物学行为被广泛研究。同时，从仿生学角度出发，在生物医用材料表面构建微/纳复合结构可以达到与骨组织机械锁合的目的。由于其优越的理化性能，钛及钛合金已被广泛应用为骨科、牙科及心血管支架等植入体。然而，，钛材表面生物惰性，无法与周边骨组织形成有效的骨整合。因此，改善钛植入体表面性能具有重大临床应用的现实意义。适宜的表面改性不但可以保留钛材优良的力学性能，而且可以根据特定临床应用需求而改善相关性质，如生物相容性、骨整合能力、抗细菌感染和抗癌等性质。本论文主要研究钛材表面微纳米结构的构建、改性及其生物学评价，为钛材在临床骨科应用提供理论基础。本论文的主要研究内容和结论包括： 1.阳极氧化法制备二氧化钛纳米管及机理研究本文利用阳极氧化法在钛材表面原位构建了不同管径的二氧化钛纳米管，并对二氧化钛纳米管的形成机理进行了研究。首先，我们研究了不同氟电解液对二氧化钛纳米管形成的影响，结果表明0.27摩尔/升氟化铵丙三醇水溶液（丙三醇/水=1:1，体积比）作为电解液可以制备尺度可控且高度有序的二氧化钛纳米管；其次，我们研究了0.27摩尔/升氟化铵丙三醇/水电解液中水含量对二氧化钛纳米管形成的影响，结果表明该电解液体系中水的含量对二氧化钛纳米管的形成有重大影响；最后，本文以0.27摩尔/升氟化铵丙三醇水溶液（丙三醇/水=1:1，体积比）作为电解液研究了不同阳极氧化电压（10-35伏）对二氧化钛纳米管管径的影响，结果表明纳米管的管径随着阳极氧化电压的增加而增大，制备了不同管径的系列二氧化钛纳米管（27-110纳米）。当电压增加到35伏时，在该电解液条件下无法形成高度有序的二氧化钛纳米管。 2.钛材表面微/纳复合结构对骨髓间充质干细胞分化的影响为了研究钛材表面微/纳复合结构对骨髓间充质干细胞分化的影响，本文通过双酸腐蚀和阳极氧化法在钛材表面构建了三种不同结构：微米结构、二氧化钛纳米管结构和微/纳复合结构。分别以场发射扫描电子显微镜和接触角测量仪对材料进行了表征。在体外研究了不同结构对骨髓间充质干细胞增殖和分化的影响。结果表明：与未处理的钛材相比，具有微/纳复合结构的钛材提高了骨髓间充质干细胞的矿化和碱性磷酸酶的分泌。更为重要的是，骨钙素和骨桥素的表达证明了微/纳复合结构的钛材在诱导骨髓间充质干细胞分化方面具有较大的潜力。本研究为提高钛植入体的骨整合性提供了一种的潜在选择。 3.具有长效抗菌性能和良好生物相容性的钛材纳米结构的构建为研发具有长效抗菌性能的纳米结构化钛植入体，本文将3-（三甲氧基硅基）丙基-二甲基十八烷基氯化铵（季铵盐）接枝到银沉积的二氧化钛纳米管上。利用加载X射线能谱的场发射扫描电子显微镜、傅里叶变换红外分光光度计、薄膜X射线衍射仪以及接触角测量仪分别对材料进行了表征。结果表明，我们成功地制备了季铵盐修饰的银纳米颗粒加载的二氧化钛纳米管纳米结构化钛材。利用大肠杆菌抑菌圈和抗菌率实验检测了该材料的抗菌性能，并通过体外细胞实验评价了材料的细胞毒性。结果表明，季铵盐修饰的银纳米颗粒加载的二氧化钛纳米管纳米结构化钛材表现出了长效抗菌性能及良好的生物相容性。本研究为我们提供了一种有发展前景的制备抗菌钛基植入体的方法。 4.兼具抗癌和抗菌性能的钛材纳米结构的构建为研发具有抗癌和抗菌性能的纳米结构化钛植入体，本文首先通过阳极氧化法在钛材表面制备二氧化钛纳米管，然后将硒电沉积到二氧化钛纳米管中，最后用旋转涂布技术涂覆多层壳聚糖。利用配备有X射线能谱的场发射扫描电子显微镜和接触角测量仪分别对材料进行了表征。结果表明，我们成功地制备了壳聚糖多层修饰的载硒二氧化钛纳米管纳米结构化钛材。进而，以该基材体外研究其对成骨细胞与骨癌细胞生长的影响。结果表明，该壳聚糖多层修饰的载硒二氧化钛纳米管纳米结构化钛材有促进成骨细胞生长同时抑制骨癌细胞生长的巨大潜力。通过大肠杆菌的抗菌率实验检测材料的抗菌性能。结果表明，壳聚糖多层修饰的载硒二氧化钛纳米管纳米结构化钛材具有良好的抗菌性能。本文提供了一种制备临床医用抗癌抗菌钛植入体的新方法。 5.不同抛光钛材表面类金刚石薄膜的制备及细胞/血液相容性评价为提高钛材植入体的细胞相容性和血液相容性，本文首先分别用机械抛光、化学抛光和电化学抛光法对钛材表面进行处理，然后以磁控溅射法在经不同抛光处理的钛材表面制备类金刚石薄膜。利用场发射扫描电子显微镜和原子力显微镜分别对钛材表面拓扑结构和表面粗糙度进行了表征，并通过拉曼光谱研究了类金刚石薄膜的结构。结果表明，我们成功地构建了系列类金刚石薄膜沉积的不同粗糙度的钛材。利用体外成骨细胞活性和细胞增殖实验评价了材料的细胞相容性。同时，通过血小板粘附和血溶率实验检测了材料的血液相容性。体外成骨细胞实验结果表明，具有相对粗糙表面的钛材表面可促进细胞功能，如细胞活性和细胞增殖。更为重要的是，溅射了类金刚石薄膜的钛材相比未溅射类金刚石薄膜的钛材显示出了良好的血液相容性。结合细胞实验和血液相容性实验的结果发现，以化学及电化学抛光并沉积类金刚石薄膜的两种材料同时显示出了良好的细胞相容性和血液相容性。
[Abstract]:The surface topology and chemical composition of biomaterials play an important role in regulating biological behaviors such as protein adsorption, cell adhesion, migration, spreading, proliferation and differentiation. With the rapid development of micro / nano technology, the construction of micro / nano structures on the surface of materials has been widely studied. From the perspective of bionics, the construction of micro / nano composite structure on the surface of biomedical materials can achieve mechanical locking with bone tissue.
Because of its excellent physical and chemical properties, titanium and titanium alloys have been widely used as an implant in the Department of orthopedics, dental and cardiovascular stents. However, the surface inertness of the titanium material can not form an effective bone integration with the surrounding bone tissue. Therefore, it is of great significance to improve the surface properties of the titanium implants. The suitable surface modification is not only possible. To retain the excellent mechanical properties of titanium materials, and to improve the related properties according to the specific clinical application requirements, such as biocompatibility, bone integration, anti bacterial infection and anticancer. This paper mainly studies the construction, modification and bioevaluation of the micro and nano structure on the surface of titanium material, providing a theory for the application of titanium in clinical department of orthopedics. The main contents and conclusions of this paper include:
Preparation and mechanism of titanium dioxide nanotubes by 1. anodization
In this paper, titanium dioxide nanotubes with different pipe diameters were constructed on the surface of titanium by anodizing, and the formation mechanism of titanium dioxide nanotubes was studied. First, we studied the effect of different fluorine electrolyte on the formation of titanium dioxide nanotube. The results showed that 0.27 mole / liter ammonium fluoride aqueous solution (glycerol / water) =1:1, volume ratio) can be used as electrolyte to prepare scale controlled and highly ordered titanium dioxide nanotubes. Secondly, we studied the effect of water content on the formation of titanium dioxide nanotubes in 0.27 mole / HCF / hydroelectric solution. The results show that the content of water in this electrolyte system is heavy on the formation of titanium dioxide nanotubes. In the end, the effect of different anodic oxidation voltage (10-35 volts) on the tube diameter of TiO2 nanotube was studied with 0.27 mole / 0.27 HCF (10-35 volt / water =1:1, volume ratio). The results showed that the tube diameter increased with the increase of the voltage of the tube, and the series of tube diameters were prepared. Titania nanotubes (27-110 nm) can not form highly ordered titania nanotubes when the voltage increases to 35 volts.
Effect of surface micro / nano composite structure of titanium 2. on differentiation of bone marrow mesenchymal stem cells
In order to study the effect of micro / nano composite structure on the differentiation of bone marrow mesenchymal stem cells (MSCs), three different structures, microstructures, titanium dioxide nanotube structures and micro / nano composite structures were constructed on the surface of titanium by diacid corrosion and anodic oxidation. The field emission scanning electron microscope and contact angle measuring instrument were used respectively. The material was characterized. The effects of different structures on the proliferation and differentiation of bone marrow mesenchymal stem cells were investigated in vitro. The results showed that the mineralization and alkaline phosphatase secretion of bone marrow mesenchymal stem cells were improved by the titanium materials with micro / nano composite structure compared with untreated titanium materials. It is proved that the titanium materials with micro / nano composite structure have great potential in inducing bone marrow mesenchymal stem cells differentiation. This study provides a potential choice for improving the bone integration of titanium implants.
3. construction of titanium nanostructures with long-acting antibacterial properties and good biocompatibility
In order to develop a nano structured titanium implant with long-acting antibacterial properties, the 3- (trimethoxy silicyl) propyl - two methyl eighteen alkyl ammonium chloride (quaternary ammonium salt) was grafted onto silver coated titanium dioxide nanotubes. The field emission scanning electron microscopy, Fourier transform infrared spectrophotometer, and X ray film were used to load the X ray energy spectrum. The material was characterized by the diffractometer and the contact angle measuring instrument. The results showed that we successfully prepared the nanoscale titanium dioxide nanotube loaded with quaternary ammonium modified silver nanoparticles. The antibacterial properties of the material were detected by the bacteriostasis circle and the antibacterial rate of Escherichia coli, and the results were evaluated by the cell test in vitro. The results showed that the quaternary ammonium modified silver nanoparticles loaded with TiO 2 nanotube nanostructured titanium showed long effective antibacterial properties and good biocompatibility. This study provides a promising method for preparing antibacterial titanium based implant.
4. construction of titanium nanostructures with both anti-cancer and antibacterial properties
In order to develop nanostructured titanium implants with anti-cancer and antibacterial properties, titanium dioxide nanotubes were prepared by anodic oxidation on the surface of titanium. Then selenium was deposited into titanium dioxide nanotubes. Finally, the multilayer chitosan was coated with rotating coating technology. The field emission scanning electron microscopy with X ray energy spectrum was used. The material was characterized by the mirror and the contact angle measuring instrument. The results showed that we successfully prepared the chitosan multilayer modified titanium dioxide nanotube nanostructured titanium material. In addition, the effect of the substrate on the growth of osteoblasts and bone cancer cells was studied in vitro. The results showed that the chitosan multilayer modified selenium loaded two oxygen was used. The titania nanotube nanostructured titanium materials have great potential to promote osteoblast growth and inhibit the growth of bone cancer cells. The antibacterial properties of the materials are detected by the antibacterial rate test of Escherichia coli. The results show that the chitosan multilayer modified titanium dioxide nanotube nanostructured titanium materials have good antibacterial properties. A new method for preparing clinical medical anticancer antibacterial titanium implants is presented.
Preparation of 5. diamond-like carbon films on different polished titanium surfaces and evaluation of cell / blood compatibility
In order to improve the cellular compatibility and blood compatibility of the titanium implants, the surface of the titanium material was treated by mechanical polishing, chemical polishing and electrochemical polishing, and the diamond like films were prepared by magnetron sputtering on the surface of different polishing titanium materials. The field emission scanning electron microscope and atomic force microscopy were used. The surface topology and surface roughness of the titanium surface were characterized by microscope, and the structure of the diamond like film was studied by Raman spectroscopy. The results showed that we successfully constructed a series of titanium materials with different roughness deposited by a series of diamond like films. The cells were used to evaluate the cell viability and cell proliferation in vitro. At the same time, the blood compatibility of the material was detected by platelet adhesion and blood solubility test. In vitro osteoblast experimental results showed that the surface of the titanium material with relatively rough surface could promote cell function, such as cell activity and cell proliferation. The titanium materials of the stone film showed good blood compatibility. The results of cell experiments and blood compatibility experiments showed that two materials with chemical and electrochemical polishing and deposition of diamond like films showed good cytocompatibility and blood compatibility.

【学位授予单位】：重庆大学
【学位级别】：博士
【学位授予年份】：2012
【分类号】：R318.08;TB383.1

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