具有球形形貌的羟基磷灰石纳米颗粒的合成研究

发布时间：2017-12-27 00:22

本文关键词：具有球形形貌的羟基磷灰石纳米颗粒的合成研究　出处：《哈尔滨理工大学》2017年硕士论文　论文类型：学位论文

【摘要】：羟基磷灰石与人体硬组织的化学成分和晶体结构极为相似,具有独特的生物活性和生物相容性,植入体内安全、无毒,并能与骨中胶原蛋白形成良好的化学键合,被广泛的用于组织工程、骨的修复与替代和牙科材料等。近年来,随着药物与基因载体研究的发展,人们逐渐扩展了纳米HAP的许多其他新用途,如作为蛋白质、基因、药物、生长因子的控制释放载体。目前,制备规整形貌和不同空间结构的羟基磷灰石微纳米颗粒,成为了生物材料领域研究的热点。本研究的目的在于采用模板法制备出单分散球形的羟基磷灰石纳米颗粒。本文中,首先探索采用表面活性剂十六烷基三甲基溴化铵(CTAB)在水热条件下诱导HAP的成核与生长,并研究不同CTAB浓度和反应温度对产物粒径和形貌的影响。借助X射线衍射、红外分析、扫描电镜、透射电镜、能谱分析、N2吸附-脱附等检测手段对产物进行表征。采用水热法合成的产物为高结晶度的HAP颗粒,但是形貌不规整,颗粒间发生不可避免的团聚现象。为了改善产物的形貌与分散性,开创性的首次将碳量子点(CQDs)引入合成体系中,以其为核诱导磷酸钙盐在其表面均相沉积,从而获得规整形貌的HAP颗粒,在此过程中考察CQDs浓度、CTAB用量、反应物用量、溶液p H、反应温度、反应时间和不同添加剂对产物形貌和粒径的影响。通过上述的检测手段对合成产物进行分析。透射电镜结果表明引入的CQDs平均粒径约5 nm、呈球形、高度分散。然后以CQDs作为核,在其表面吸附表面活性剂CTAB分子层,随后PO43-通过静电引力在CQDs的表面形成PO43-吸附层,与之后引入的钙源反应,生成磷酸钙盐涂层,调整反应条件使得磷酸钙盐均匀的包覆在CQDs的表面从而得到规整形貌的HAP颗粒。实验结果表明:最佳反应条件为溶液p H为10,CTAB:Na3PO4的摩尔比为1:1,加入环己烷,在80℃下反应8 h。在最佳条件下合成产物为准球形的HAP纳米颗粒,粒径约60 nm,颗粒分散性较高。产物Ca/P摩尔比为1.61,略低于HAP中Ca/P的化学计量比1.67。比表面积、BJH吸附孔径和孔容分别为93.5 m2/g,25 nm和0.5682 ml/g,介孔来源于颗粒间堆积产生的空隙。
[Abstract]:The chemical composition and crystal structure of hydroxyapatite and the hard tissues of the human body is very similar, with unique compatibility and bioactivity in vivo, safe, non-toxic, and can form a good chemically bonded with bone collagen, is widely used in tissue engineering, bone repair and replacement and dental materials etc.. In recent years, with the development of drug and gene carrier research, people have gradually expanded many other new uses of nano HAP, such as the controlled release carrier as protein, gene, drug and growth factor. At present, the preparation of hydroxyapatite micronanoparticles with regular morphology and different spatial structures has become a hot topic in the field of biomaterials. The purpose of this study is to prepare monodisperse spherical hydroxyapatite nanoparticles by template method. In this paper, we first explored the nucleation and growth of HAP under hydrothermal conditions by using surfactant sixteen alkyl three methyl ammonium bromide (CTAB), and studied the effect of different CTAB concentration and reaction temperature on the particle size and morphology of the product. The products were characterized by X ray diffraction, infrared analysis, scanning electron microscopy, transmission electron microscopy, energy spectrum analysis and N2 adsorption desorption. The products synthesized by hydrothermal method are HAP particles with high crystallinity, but the morphology is not regular, and the inevitable agglomeration occurs between the particles. In order to improve the dispersion and the morphology of the product, groundbreaking for the first time the carbon quantum dots (CQDs) into the synthesis system, the induction of calcium phosphate on the surface of sedimentary facies, to obtain HAP regular particles morphology, in this process, the effects of CQDs concentration, CTAB dosage, dosage, reaction effect P H solution, reaction temperature, reaction time and different additives on the morphology and particle size. The synthetic products were analyzed by the above methods. The results of transmission electron microscopy showed that the average particle size of CQDs introduced was about 5 nm, and it was spherical and highly dispersed. Then take the CQDs as the core, on the surface adsorption of surfactant CTAB molecular layer, then PO43- through electrostatic attraction on the surface of the CQDs formation of PO43- adsorption layer, and after the introduction of the source of calcium reaction, formation of calcium phosphate coating, coated calcium phosphate salt makes the adjustment of the reaction conditions to obtain uniform regular particles morphology in CQDs HAP the surface. The experimental results show that the optimum reaction condition is that the solution P H is 10, the molar ratio of CTAB:Na3PO4 is 1:1, and cyclohexane is added, and the reaction is 8 h at 80. Under the best conditions, the synthetic products are quasi spherical HAP nanoparticles, with a particle size of about 60 nm and a high particle dispersion. The molar ratio of the product Ca/P is 1.61, which is slightly lower than the stoichiometric ratio of Ca/P in HAP by 1.67. The specific surface area, BJH pore size and pore volume are 93.5 m2/g, 25 nm and 0.5682 ml/g, respectively. The mesoporous pores are derived from the gap between particles.
【学位授予单位】：哈尔滨理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：R318;TB383.1

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