应用于骨修复的明胶-CaO-SiO_2-TiO_2生物活性杂化材料的合成及其性能(英文)

Synthesis and characterization of gelatin-CaO-SiO2-TiO2 bioactive hybrid applied in bone repairing

背景:有研究表明,材料生物活性是由材料表面的Si-OH或Ti-OH等基团和体液中的钙离子共同作用的结果,可否将明胶链与Si-O-Ti无机网络共价结合合成一种新的有机-无机杂化材料?目的: 合成一种能应用于骨修复的明胶-CaO-SiO2-TiO2生物活性杂化材料,并观察其结构及生物活性。设计:随机对照观察。单位:陕西科技大学材料科学与工程学院实验室。材料:明胶(国药集团上海化学试剂有限公司),钛酸异丙酯(固安恒业精细化工有限公司),γ- 环氧丙基氧丙基三甲氧基硅烷 (荆州市江汉精细化工有限公司),硝酸钙(天津市博迪化工有限公司)。方法:实验于2006-04/08在陕西科技大学材料科学与工程学院实验室完成,通过溶胶-凝胶法以明胶、γ-(2,3环氧丙基氧丙基)三甲氧基硅烷、钛酸四异丙酯及硝酸钙为初始原料合成了一种新的有机-无机杂化材料。①材料的结构分析:材料的结构用傅立叶红外光谱、X射线衍射及扫描电子显微镜观察分别进行分析。②生物活性评价:样品Ti15Ca0和Ti15Ca20进行模拟体液浸泡实验,通过薄膜X射线衍射分析,扫描电子显微照片分析其表面组或和形貌。主要观察指标:材料的结构分析及其生物活性。结果:①材料呈完全无定形态,表面近乎均一,有机成分与无机成分之间以共价键结合,傅立叶红外光谱分析证明了Si-OH基团和Si-O-Si键的存在,并且钛酸四异丙酯的加入引入了Si-O-Ti键。②该材料在SBF中浸泡后产生磷灰石晶体, 其形貌与生物玻璃和其它生物活性材料相似,记明其具有体外生物活性。结论: 通过溶胶-凝胶法将明胶链与Si-O-Ti无机网络共价结合合成了一种新的有机-无机杂化材料。样品Ti15Ca20在模拟体液中浸泡后其表面生成大量磷灰石和透钙磷石晶体,充分证明了材料的生物活性。

BACKGROUND ： It has been reported that bioactivity is found to be favored by the co-operative behavior of silanol （Si-OH） or Ti-OH etc. groups on the material surface and the involved calcium ions, To confirm the hypothesis that a new family of organic-inorganic hybrid materials, which incorporate gelatin chains covalently into Si-O-Ti network, is synthesized through sol-gel procedure. OBJECTIVE： To synthesize a hybrid of gelatin and CaO-SiO2-TiO2 system which is used for bone repairing, and observe its structure and bioactivity. DESIGN ： Randomized control observation SETTING ： the laboratory, School of Material Science and Engineering, Shaanxi University of Science and Technology MATERIALS： Gelatin （Sinopharm Chemical Reagent Co., Ltd）, titanic acid isopropyl ester （Gu＇an Hengye Fine Chemicals Co., Ltd）, γ-glycidoxy propyl trimethoxy silane （Jingzhou Jianghan Fine Chemicals Co., Ltd）, calcium nitrate （Tianjin Bodi Chemicals Co., Ltd） METHODS： The experiment was carried out in the laboratory, School of Materials Sciences and Engineering, Shaanxi University of Science and Technology between April and August in 2006. A new type of bioactive organic-inorganic hybrid was synthesized through sol-gel processing starting from gelatin, γ-（2,3-glycidoxypropyl）trimethoxysilane （GPSM）, Tetraisopropyltitanate （TiPT） and calcium nitrate. ①Structure of the hybrid： The structures of the products were investigated with Fourier transformed infrared （FT-IR） diffusive reflection spectroscope, X-ray diffraction （XRD） instrument and scanning electron microscope （SEM） respectively.②Bioactivity： The products Ti15Ca0 and Ti15Ca20 were soaked in a stimulated body fluid （SBF） to evaluate the morphology of the surfaces by SEM and thin-film XRD. MAIN OUTCOME MEASURES ： The structure and bioactivity of the hybrid RESULTS：①The hybrid was completely amorphous and its surface was almost homogenous, which implied the covalent bonding between the organic component and inorganic component. FT-IR spectra result verified the occurrence of Si-OH group and Si-O-Ti bond, as well as the addition of TiPT supplied Si-O-Ti bond.②There were lots of apatite crystallines formed on the surface of hybrid Ti15Ca20 after soaked in SBF for 7 days, which confirmed their in vitro bioactivity. These apatite particles were similar to the bioglass and other bioactive materials in the patterns. CONCLUSION ： A new type of organic-inorganic hybrid material, which incorporates gelatin chains covalently into Si-O-Ti network, is synthesized through sol-gel procedure. There are lots of apatite and brushite crystals formed on the surface of the product Ti15Ca20 after soaking in SBF for 7 days, which obviously proves the bioactivity of the hybrid.