软刻蚀方法制备二氧化钛微图形及其相关性质研究
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摘要
深入研究仿生工程化生物材料表面的几何性质与物化性能及其生物学性能是改进和设计第三代生物材料的关键。在众多生物材料中,TiO2因其良好的生物相容性而成为人们近几年的研究热点。现有的TiO2表面微纳图形的制备技术主要包括模版法,阳极氧化法和浓碱处理法等。这些方法制备出的是不规则,无序的表面微纳结构。本研究结合微加工技术中的软刻蚀技术和溶胶凝胶法制备出规则的,有序的,单一成分的TiO2微米级沟槽,并对其物化性质和生物相容性进行研究。在软刻蚀中,用聚二甲基硅氧烷(PDMS)复制具有微图形的硅模板得到具有微沟槽PDMS弹性印章。在溶胶凝胶法中,以钛酸四丁酯为前驱体制备TiO2溶胶,经过微图形转移,最终得到锐钛矿型TiO2微沟槽。表面能检测表明具有TiO2沟槽样品比平面TiO2的表面能要小,且与微图形的尺寸相关(γ12μm<γ20μm<γ40μm<γflat surfaces)。TiO2微沟槽样品表面吸附蛋白能力要高于平板表面,且TiO2沟槽样品在整个吸附过程中具有两个解吸附的过程。诱导矿化实验表明TiO2沟槽较平面TiO2更能使磷酸钙(CaP)的形核趋于有序化,且在早期生成的晶核基本上按照微图形的趋向排列。骨细胞培养实验表明TiO2沟槽能在前期约束细胞的形貌和生长状态,使细胞按沟槽的走向生长。对于短期细胞培养(培养时间少于一个星期),微图形化TiO2表面的细胞的繁殖速率和ALP活性都低于平面样品,其趋势与表面能的趋势一致。本文研究成果对生物材料表面设计和功能应用具有一定的借鉴意义。
The effects of implant surface topography and chemistry on biomineralization and cell behavior have been a research focus because of their potential importance in orthopedic and bone replacement applications. While a vast amount of research is focusing on chemical modified surfaces and rough surfaces, little attention has been paid to the well-defined micropatterned surface effects on calcium phosphate mineralization process due to the difficulties in preparing microfabricated biomaterial surfaces. This work focus on the effects of microgrooved TiO2 surfaces on the calcium phosphate mineralization process and its biocompatibilty.
We developed a new process that can prepare microgrooved TiO2 coatings on glass substrates using the soft-lithography and sol-gel technology. TiO2 sol-gel precursor solution was prepared using a mixture of tetrabutyltitanate/ethanol/hydrochloric acid/distilled water/1,5-pentanediol with a molar ratio of 1/30/0.2/2/2. Polydimethylsiloxane (PDMS) microstamps were used to transfer micropatterns from the silicon wafer to the TiO2 gel. Then microgrooved TiO2 surfaces were used to induce Ca-P mineralization under biomimetic conditions. The results revealed that topography dominated the growth and distribution of mineralization at the initial days and then the effect of topography become weak with the extended immersion days. The surface energies of the TiO2 surfaces were in range ofγ12μm<γ20μm<γ40μm<γflat surfaces.The effect of microgrooved TiO2 surfaces on osteoblast behavior was also evaluated. Osteoblasts (MC3T3-E1) were cultured on the as-prepared microgrooved and flat TiO2 surfaces. Optical microscopy and scanning electron microscopy (SEM) were used to analyze adherent cell behavior by examining the cell morphology. Orientation angle (OA) analysis indicated that cells tended to align along with the microgrooves and this tendency was strong on the microgrooves with small width and became weak with the increase of the width. Alamar blue assay indicated that the microgrooves restricted the growth of cells and alkaline phosphatase (ALP) assay revealed that microgrooves limited the proliferation rate. This restriction increased with the decrease of the width of microgrooves. Osteoblast proliferation and differentiation on micropatterned titanium oxide surfaces was correlated with the surface energy.
The effects of implant surface topography and chemistry on biomineralization and cell behavior have been a research focus because of their potential importance in orthopedic and bone replacement applications. While a vast amount of research is focusing on chemical modified surfaces and rough surfaces, little attention has been paid to the well-defined micropatterned surface effects on calcium phosphate mineralization process due to the difficulties in preparing microfabricated biomaterial surfaces. This work focus on the effects of microgrooved TiO2 surfaces on the calcium phosphate mineralization process and its biocompatibilty.
We developed a new process that can prepare microgrooved TiO2 coatings on glass substrates using the soft-lithography and sol-gel technology. TiO2 sol-gel precursor solution was prepared using a mixture of tetrabutyltitanate/ethanol/hydrochloric acid/distilled water/1,5-pentanediol with a molar ratio of 1/30/0.2/2/2. Polydimethylsiloxane (PDMS) microstamps were used to transfer micropatterns from the silicon wafer to the TiO2 gel. Then microgrooved TiO2 surfaces were used to induce Ca-P mineralization under biomimetic conditions. The results revealed that topography dominated the growth and distribution of mineralization at the initial days and then the effect of topography become weak with the extended immersion days. The surface energies of the TiO2 surfaces were in range ofγ12μm<γ20μm<γ40μm<γflat surfaces.The effect of microgrooved TiO2 surfaces on osteoblast behavior was also evaluated. Osteoblasts (MC3T3-E1) were cultured on the as-prepared microgrooved and flat TiO2 surfaces. Optical microscopy and scanning electron microscopy (SEM) were used to analyze adherent cell behavior by examining the cell morphology. Orientation angle (OA) analysis indicated that cells tended to align along with the microgrooves and this tendency was strong on the microgrooves with small width and became weak with the increase of the width. Alamar blue assay indicated that the microgrooves restricted the growth of cells and alkaline phosphatase (ALP) assay revealed that microgrooves limited the proliferation rate. This restriction increased with the decrease of the width of microgrooves. Osteoblast proliferation and differentiation on micropatterned titanium oxide surfaces was correlated with the surface energy.
引文
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[9]徐琳,丁建宁,李伯全,程广贵.蝴蝶翅膀表面超微结构与浸润性机理分析.2009年3月第3卷.
[10]苏炳煌,李光吉,蒲侠,雷朝媛.鲨鱼皮表面微结构在高分子表面的复制方法初探.材料研究与应用2008年12月第2卷.
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[15]Hench LL, Valk CM, Meijer G, Dalmeijer RAJ, Groot K, Layrolle P. Biomimetic apatite coating applied onto dense and porous metal implants in femurs of goats. J Biomed Mater Res Part B:Appl Biomater 2003;67B:655-665.
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[17]Habibovic P, Barrere F, Groot K. Reis RL, Weiner S. New biomimetic coating technologies and incorporation of bioactive agents and proteins, in:Learning from nature how to design new implantable biomaterial. Reis, R.L.Weiner, S. (eds) Kluwer, Dordrecht.2003;105-121.
[18]Jiang H, Liu XY, Zhang G, Li Y. Cdk5 activator-binding protein C53 regulates apoptosis induced by genotoxic stress via modulating the G2/M DNA damage checkpoint. J Biolog Chem 2005;280:42061-42066.
[19]Sato K. Inorganic-organic interface interaction in hydroxyapatite mineralization processes. Topic Current Chemistry 2007; 270-127.
[20]Mitragotri S, Lahann J. Physical approaches to biomaterial design. Nature Mater 2009; 8:15-23.
[21]Lu X, Zhao ZF, Leng Y. Biomimetic calcium phosphate coatings on nitric-acid-treated titanium surfaces. Mater Sci Eng C 2007; 27:700-708.
[22]Lu X, Leng Y, Zhang XD, Xu JR, Qin L, CW. Comparative study of osteoconduction on micromachined and alkali-treated titanium alloy surfaces in vitro and in vivo. Biomaterials 2005;26:1793-1801.
[23]Kokubo T. Biomimetic modulation of crystal morphology using gel:From nano to micron-scale architectures. Mater Sci Eng C 2005; 25:97-100.
[24]Advincula MC, Rahemtulla FG, Advincula RC, Ada ET, Lemons JE, Bellis SL. Osteoblast adhesion and matrix mineralization on sol-gel-derived titanium oxide. Biomaterials 2006;27:2201-2212.
[25]Anselme K, Bigerelle M. Statistical demonstration of the relative effect of surface chemistry and roughness on human osteoblast short-term adhesion. J Mater Sci Mater Med 2006;17:471-479.
[26]Liu X, Lim JY, Donaue HJ, Dhurjati R, Mastro AM, Vogler EA. Influence of substratum surface chemistry/energy and topography on the human fetal osteoblastic cell line hFOB 1.19:Phenotypic and genotypic responses observed in vitro. Biomaterials 2007; 28:4535-4550.
[27]Anselme K, Bigerelle M. Topography effects of pure titanium substrates on human osteoblast long-term adhesion. Acta Biomaterial 2005; 1:211-222.
[28]Huang HH, Ho CT, Lee TH, Lee TL, Liao KK, Chen FL. Effect of surface roughness of ground titanium on initial cell adhesion. Biomolecu Eng 2004; 21:93-97.
[29]Khakbaznejad A, Chehroudi B, Brunette DM. Effects of titanium-coated micromachined grooved substrata on orienting layers of osteoblast-like cells and collagen fibers in culture. J Biomed Mater Res 2004; 70A:206-218.
[30]Zinger O, Zhao G, Schwartz Z, Simpson J, Wieland M, Landolt D, Boyan B. Differential regulation of osteoblasts by substrate microstructural features. Biomaterials 2005; 26:1837-1847.
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