【作者】 姜金华；

【导师】 徐家宁； 张萍；

【作者基本信息】 吉林大学 ， 无机化学， 2011， 博士

【摘要】 本论文致力于合成具有特殊结构、形貌或特定性质的几种多孔无机生物材料,探讨材料作为药物缓/控释体系的缓释性能,探索其在药物缓/控方面的应用。第一章介绍了无机生物材料的性能优势、介孔分子筛的结构特点和合成路线、具有介观结构和多孔结构的几种无机生物材料的合成及应用。在第二章中,选用生物相容性较好的系列脂肪酸为结构导向剂,合成了具有介观结构的多级层状羟基磷灰石,其层间距可随脂肪酸链的增长而增大,表明层间距可调控。第三章中,采用一步法(one-pot)合成了中空介孔壳二氧化硅材料,该方法不仅具有简单快速的特点,而且是绿色合成,不会对环境造成污染；同时,采用微乳液法合成了中空碳酸钙球,并考察了合成条件对产物形貌的影响。在第四章中,引入发光离子制得光功能化的介孔生物活性玻璃球形颗粒,探讨了其做为药物载体的缓释能力以及进行光学监测的可能性。在第五章中,以四氧化三铁颗粒为核使钙、磷物种在其外围生长,得到两种具有磁力性能的磷酸钙样品,两种样品均具有纳米孔道。本论文较详细地讨论了多种无机生物材料的制备和性能,为无机生物材料的进一步研究应用打下基础。更多还原

【Abstract】 Inorganic biomaterials have been the subject of considerable attention due to their good stability in body, high mechanical strength, biocompatibity and hydrophilicity, acid or alkali resist, and innoxiousness. Winter has investigated the relationship between bioactivity in vitro and component, porous structure of inorganic biomaterials, the result implies that component and porous structure are important. The bioactivity in vitro would improve obviously when increasing the surface area and pore volume. Moreover, with porocity, a sharp fall of the rigidity of materials would happen, this is beneficial to the interface stress conduction and necessity achieving the stabile interface of materials. Ordered mesoporous materials are of great interest because of their periodic ordered regular channels, extremely high surface areas and pore volume, high thermal and hydrothermal stability, controllable morphology, and easily functionalized surface. After the addition of luminescent, magnetic substances or organic functional molecule, the mesoporous materials can be applied in target-drug delivery or selective adsorption/ separation of protein etc.. Recently, according to the designed strategy and synthetic method of mesoporous materials, large numbers of novel inorganic biomaterials were synthesized, such as mesoporous hydroxyapatite, mesoporous calcium carbonate, and mesoporous bioactive glass. These porous biomaterials offer an ideal platform for the main potential application in biology field such as remedy, therapy and bone repair.In this thesis, we prepared several mesostructured biomaterials as following:(1) synthesis and characterization of multi-lamellar mesostructured hydroxyapatites; (2) exploiting a simple, rapid and green route to fabricate hollow mesoporous silica; (3) synthesis of hollow calcium carbonate; (4) synthesis and characterization of a luminescent europium-doped inorganic porous bioglass sphere; (5) synthesis of magnetic particle-calcium phosphates. The obtained hollow mesoporous silica and europium-doped inorganic porous bioglass sphere were used as drug carriers to investigate the drug storage/release properties using ibuprofen (IBU) as a model drug.Learning from the study of Liang etc., there is meaningful relation between lamellar structure and mechanical property. Lamellar materials have an advantage of application in biology. Many researchers have paid attention to synthesize lamellar hydroxyapatite with innoxious surfactants as directing agents. To date, fatty acids have rarely been applied to produce mesostructured hydroxyapatite. Five familiar natural fatty acids were employed to prepare five lamellar mesostructured hydroxyapatites in alcohol/water mixed solvent. The results indicates that the interlayer spacing of HAs can be controlled and HAs with suitable interlayer spacing can be provided to accommodate functional molecules for further applications.Calcium carbonate is friendly to environment and organism because of the biocompatibility and biodegradability. There have been several reports on synthesizing hollow porous silica with calcium carbonate as hard template. However, most of the preparations require many tedious and time consuming synthetic steps, usually the hard template should be prapared firstly, following the centrifugation. washing and dispersion repeatly. A facile and rapid approach was exploited to synthesize hollow mesoporous silica materials. Ca(OAc)2 and NaHCO3 solution were mixed rapidly, then TEOS was dropped into the reaction mixture immediately, CTAB was used as second template to form prous structure in the silica shells. After the remove of inoranic CaCO3 and organic CTAB at alcohol/acid solution with ultrasonic assistant, a hollow mesoporous silica was obtained. A great of -OH were maintained by this template removing method, which performed an ideal platform for the adsorption of ibuprofen. This composite showed sustained release profile with ibuprofen as the model drug.Hollow calcium carbonate can be effectively used in the carry of large molecules owing to its biodegradable and large hollow structure. A series of hollow calcium carbonate have been reported, only a few hollow calcium carbonate with the particle size less than 500 nm were fabricated, of which the amount of product usually low. In view of these findings, we prepared hollow calcium carbonate (250nm-450nm) in the water/ glycol emulsion system. The morphology of products transformed from sphere to ellipsoid with the increase of amount of glycol.Mesoporous bioactive glass has been applied to repair bone defective and lost bone for decades. These days, researchers have paid attention to the synthesis of materials with specifical morphology and property. Mesoporous europium-doped bioactive glass spheres were successfully synthesized by a two-step acid-catalyzed selfassembly process in an inorganic-organic system. The results revealed that the IBU-loaded samples still showed red luminescence of Eu3+ under UV irradiation, and the emission intensities of Eu3+ in the drug carrier system varied with the released amount of IBU. The system demonstrates a great potential in the drug delivery and disease therapy fields.Calcium phosphate system has attracted significant interest for the good biodegradable. Many investigations displayed the original structure and functional property, however, there was few research focusing on porous-magnetic calcium phophate. Two Fe3O4 particles were prepared as magnetic core to react with Ca2+ and PO43-, giving the magnetic materials covering with calcium phosphate shell. Interestly, there are nanopores in both of the samples which can been separated easily at magnetic field. It is anticipated that the porous-magnetic calcium phophates may find advanced applications in target-drug delivery or selective adsorption/ separation of drugs etc.更多还原