磷酸钙在纳米羟基磷灰石／硅橡胶复合材料表面的仿生合成

将纳米羟基磷灰石，硅橡胶复合材料浸泡于模拟体液（SBF）中仿生合成了磷酸钙，利用IR、XRD、ICP和SEM等测试手段对表面沉积物进行表征．结果表明：在模拟体液中浸泡后，复合材料表面形成了分布均匀的以羟基磷灰石为主要成分的晶粒，表面羟基磷灰石的比例得到提高，生物学性能得以进一步改善；表明纳米羟基磷灰石，硅橡胶复合材料是一种生物活性材料．     

生物活性玻璃/PLA-PEG-PLA/聚乳酸组织工程支架在SBF溶液中的降解和矿化

通过测定pH值、质量损失率、SEM、XRD和FTIR,系统研究了生物活性玻璃/聚乳酸-聚乙二醇-聚乳酸嵌段共聚物（PLA-PEG-PLA）/聚乳酸组织工程支架在模拟体液（SBF）中的降解和生物矿化性能。研究结果表明：随着支架在SBF溶液中浸泡时间的延长,SBF的pH值和支架的质量呈下降趋势;生物活性玻璃的存在使pH值升高,而PLA-PEG-PLA嵌段共聚物的存在使pH值降低。XRD、FTIR图谱和SEM图像表明：在SBF中浸泡一定时间后,有无定型或结晶不完善的磷灰石在生物活性玻璃/PLA-PEG-PLA/聚乳酸组织工程支架表面沉积形成,并且PLA-PEG-PLA共聚物降解速度比聚乳酸快;在SBF中浸泡7天后,PLA-PEG-PLA共聚物的含量已经很难通过FTIR检测出来。     

CaO-P2O5-SiO2系统溶胶-凝胶玻璃的生物矿化行为

利用体外实验方法(in vitro)以及XBD、SEM、FTIR、BET、ICP等手段研究了两种溶胶一凝胶生物活性玻璃的显微结构及其在模拟生理溶液(SBF)中的降解过程、表面反应产物和生物矿化机理．结果表明，两种生物活性玻璃都具有较高的生物活性，均具有由纳米尺寸颗粒相互连接而成的微孔结构和较大的比表面积，在模拟生理溶液(SBF)中浸泡后可形成表面类似天然骨中无机矿物的碳酸经基磷灰石层(HCA)，说明两者均具有较高的生物活性和生理环境相应特性．材料表面的硅酸凝胶层及其硅经基团的形成对碳酸经基磷灰石(HCA)微晶的成核有重要作用。     

射频磁控溅射制备 HA(+ZrO2+Y2O3)/Ti6Al4V 复合生物活性涂层

采用射频磁控溅射法制备了HA（＋ZrO2＋Y2O3）／Ti6Al4V生物复合涂层．借助于XRD、SEM、FTIR和AFM等对溅射涂层的相组成、微观形貌和界面结合进行了研究，并以模拟体液试验探讨了涂层的生物活性．实验结果表明：磁控溅射的复合涂层呈非晶态，经过退火处理，可以使其转化为晶态；复合涂层的微观表面凹凸不平，并呈现网状结构和较多的孔隙，其孔隙直径约为0．5-2．0μm，孔隙面积占涂层表面积的30％-40％；HA（＋ZrO2＋Y2O3）／Ti6Al4V复合涂层的界面结合强度随（ZrO2＋Y2O3）复合颗粒含量的增大和溅射功率的提高而增强，最高可达59．6MPa．复合涂层在模拟体液中浸泡一段时间后，表面覆盖一层新生物质—含有CO^2-3的类骨磷灰石，其晶粒非常小，它与自然骨中无机相的结构成分相似，表明复合涂层具有良好的生物活性．     

C/C复合材料的非晶SiO_2涂层制备及其生物活性

以正硅酸乙酯(TEOS)为前驱体,N_2为载气,在C/C复合材料表面通过低压化学气相沉积(LPCVD)得到非晶SiO_2涂层。研究了沉积温度对涂层成分、涂层形貌和沉积速率的影响。通过XRD、XPS、FTIR、SEM和EDS等测试手段,对涂层的成分、微观形貌以及模拟体液浸泡后材料的生物活性进行了表征和分析。实验结果表明:涂层的主要物相为非晶SiO_2;模拟体液浸泡至35天,样品表面生成类骨羟基磷灰石,与未涂层的C/C复合材料相比,表明非晶SiO_2涂层具有良好的生物活性。随着沉积温度的增加,沉积速率增大,涂层包覆更加完整;SiO_2颗粒由不规则形状转变为规则的球形,最后转变成多边形。     

钙磷硅系生物活性玻璃的溶胶-凝胶法制备与表征

采用溶胶-凝胶法制备了CaO—P2O5-SiO2生物活性玻璃，研究了原料的加入顺序的影响，确定了溶胶-凝胶生物玻璃的制备工艺；利用差热分析、X射线衍射（XRD）分析、原子吸收光谱（IR）和扫描电镜（SEM）等手段，研究了溶胶-凝胶玻璃的热演变过程及微观结构和形貌。将该生物玻璃粉与柠檬酸混合，调和固化后于模拟体液申浸泡。研究其生物活性。结果表明，所制备的生物玻璃具有良好的生物活性，能有效地诱导钙、磷离子沉积。     

生物活性玻璃/聚乳酸组织工程支架在SBF溶液中的降解和矿化性能

利用扫描电镜、X衍射仪以及红外漫反射仪,并通过对生物活性玻璃/聚乳酸组织工程支架在模拟体液（SBF）中失重率及模拟体液pH值的变化的检测,系统研究了生物活性玻璃/聚乳酸组织工程支架在SBF中的降解和矿化性能。结果发现：随着含有生物活性玻璃的聚乳酸支架在SBF溶液中浸泡时间的增长,SBF的pH值不断下降;含有生物活性玻璃...     

纳米羟基磷灰石/聚酰胺66复合材料在模拟体液(SBF)中的表面生物活性研究

通过纳米羟基磷灰石／聚酰胺66(n—HA／PA66)复合材料体外模拟体液(SBF)浸泡实验，以聚酰胺66(PA66)为对照，用IR、XRD、SEM和ICP等手段对材料的表面组成和形貌变化进行了分析，比较了PA66和n-HA／PA66复合材料的表面生物活性。结果表明，n-HA／PA66复合材料在SBF中其表面形成的HA沉积物为部分碳酸基团取代的磷灰石，而PA66在浸泡过程中Ca、P不在聚合物表面沉积；n-HA／PA66复合材料具有良好的生物活性，作为骨组织修复或替代材料具有较高的研究和应用价值。     

可注射nano HA/PAG/CS复合材料的制备与表征

通过原位聚合法制备了可注射纳米羟基磷灰石/天门冬氨酸-谷氨酸共聚物/硫酸钙复合材料(HA/PAG/CS), 采用FTIR、XRD、SEM对复合材料的组成结构、表面形貌及力学性能进行了表征, 研究了复合材料在模拟体液(SBF)中的降解性能。结果显示: 复合材料无机相羟基磷灰石、硫酸钙与有机相天门冬氨酸-谷氨酸共聚物之间存在化学相互作用, 具有良好的抗压强度; 7周后, 复合材料在SBF中完全降解, 降解方式为表面降解; 在降解过程中, 浸泡液的pH值在6.4~7.4之间变化; 复合材料在SBF中浸泡后, 其表面能够沉积磷灰石, 表明复合材料具有良好的生物活性, 有利于植入体与骨组织形成良好的界面结合。     

Ti40Zr10Cu36Pd14大块金属玻璃表面HA/TiO2涂层的制备

Ti40Zr10Cu36Pd14金属玻璃具有较好的玻璃化形成能力和可靠的生物力学性能,但生物活性较差。采用溶胶凝胶法在Ti40Zr10Cu36Pd14金属玻璃表面构建TiO2涂层,并进行水热处理使其具有锐钛矿结构;随后又在模拟体液(SBF)中进行仿生生长实验。采用扫描电子显微镜(SEM)、X射线衍射仪(XRD)和激光显微拉曼光谱仪(Raman)等观察和分析涂层表面形貌及物相组成。结果表明,TiO2涂层可改善Ti40Zr10Cu36Pd14金属玻璃试样表面生物活性;在模拟体液中浸泡7天后,覆盖TiO2涂层的金属玻璃可快速诱导磷灰石沉积,在金属玻璃基体表面形成HA/TiO2复合涂层。     

Conversion of melt-derived microfibrous borate (13-93B3) and silicate (45S5) bioactive glass in a simulated body fluid

Microfibrous bioactive glasses are showing a considerable capacity to heal soft tissue wounds, but little information is available on the mechanism of healing. In the present study, the conversion of microfibrous borate bioactive glass (diameter = 0.2–5 μm) with the composition designated 13-93B3 (5.5 Na₂O, 11.1 K₂O, 4.6 MgO, 18.5 CaO, 3.7 P₂O₅, 56.6 B₂O₃ wt%) was evaluated in vitro as a function of immersion time in a simulated body fluid (SBF) at 37 °C using structural and chemical techniques. Silicate 45S5glass microfibers (45 SiO₂, 24.5 Na₂O, 24.5 CaO, 6 P₂O₅ wt%) were also studied for comparison. Microfibrous 13-93B3 glass degraded almost completely and converted to a calcium phosphate material within 7–14 days in SBF, whereas >85 % of the silica remained in the 45S5 microfibers, forming a silica gel phase. An amorphous calcium phosphate (ACP) product that formed on the 13-93B3 microfibers crystallized at a slower rate to hydroxyapatite (HA) when compared to the ACP that formed on the 45S5 fibers. For immersion times >3 days, the 13-93B3 fibers released a higher concentration of Ca into the SBF than the 45S5 fibers. The fast and more complete degradation, slow crystallization of the ACP product, and higher concentration of dissolved Ca in SBF could contribute to the capacity of the microfibrous borate 13-93B3 glass to heal soft tissue wounds.     

Synthesis,characterization and in vitro bioactivity of sol-gel-derived SiO2–CaO–P2O5–MgO bioglass

In this study, the synthesis of SiO₂–CaO–P₂O₅–MgO bioactive glass was performed by the sol-gel method. Sol-gel-derived bioglass material was produced both in powder and in discs form by uniaxial pressing, followed by sintering at 700 °C. The obtained material was evaluated by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), thermal gravimetric analysis (TGA) and differential scanning caloremetry (DSC) analyses. The biocompatibility evaluation of the formed glass was assessed through in vitro cell culture [alkaline phosphatase (AP) activity of osteoblasts] experiments and immersion studies in simulated body fluid (SBF) for different time intervals while monitoring the pH changes and the concentration of calcium, phosphorus and magnesium in the SBF medium. The SEM, XRD and FTIR studies were conducted before and after soaking of the material in SBF. At first, an amorphous calcium phosphate was formed; after 7 days this surface consisted of deposited crystalline apatite. The present investigation also revealed that the sol-gel derived quaternary bioglass system has the ability to support the growth of human fetal osteoblastic cells (hFOB 1.19). Finally, this material proved to be non-toxic and compatible for the proposed work in segmental defects in the goat model in vivo.     

Biomimetic mineralization of partially bioresorbable glass fiber reinforced composite

The aim of this study was to investigate the biomimetic mineralization on the surface of a glass fiber reinforced composite with partially resorbable biopolymer matrix. The E-glass fibers were preimpregnated with a novel biopolymer of poly(hydroxyproline) amide, and further impregnated in the monomer system of bis-phenyl glycidyl dimethacrylate (Bis-GMA)—triethylene glycol dimethacrylate (TEGDMA), which formed interpenetrating polymer networks (IPN) with the preimpregnation polymer. After light-initiated polymerization of the monomer system, the rhombic test specimens (n = 6) were immersed in the simulated body fluid (SBF) with the bioactive glass for 24 h, and then the apatite nuclei were allowed to grow for 1, 3, 5 and 7 days in the SBF. The control test specimens (n = 3) were immersed in SBF without the bioactive glass. According to the scanning electron microscope (SEM), a mineral layer was formed on the surface of all the specimens, which were immersed with bioactive glass. The layer was thickened by the prolonged immersion time to a uniform layer. The Ca/P atomic ratio of the mineral varied between 1.30 and 1.54 as analyzed by the energy dispersive X-ray analysis (EDXA). The Fourier transform infrared spectroscopy (FT-IR) spectra gave signals for the mineral, which are characteristic of both bone-like apatite and orthocalciumphosphate. In conclusion, the mineral layer was formed on the surfaces of the specimens by biomimetic mineralization, the mineral being a mixture of bone-like apatite, orthocalciumphosphate and other calcium phosphates.     

MAS-NMR support for Hench model in the case of bioactive glass microspheres

The structural changes occurred in bioactive glass microspheres belonging to the system SiO₂–Na₂O–P₂O₅–CaO–K₂O–MgO incorporating yttrium were investigated before and after soaking in simulated body fluid (SBF) by X-ray diffraction (XRD) and ³¹P and ²⁹Si magic angle sample spinning nuclear magnetic resonance (MAS-NMR). The addition of yttrium to the bioactive glass composition induces changes in the behavior of the glass microspheres in SBF. The XRD analysis proves that after the immersion in SBF a crystalline hydroxyapatite-like phase is developed on the microspheres surface. The ²⁹Si and ³¹P MAS-NMR results show that silicate species with two and three bridging oxygens per SiO₄ tetrahedra and PO₄ monomeric units are present in the glass structure. After immersion in SBF, new silicate species with four bridging oxygens appear as result of silica-gel layer formed on microspheres surface. The formation of crystalline hydroxyapatite-type layer is reflected by the occurrence of narrow components in ³¹P MAS-NMR spectra. The NMR results support the Hench model for bioactive glasses behavior in biological environments.     

Sol-Gel生物活性玻璃降解性能及矿化沉积的体外模拟研究

本研究采用溶胶-凝胶法制备了CaO-P2O5-SiO2系统生物活性玻璃粉体,并通过成型、烧结工艺制成多孔材料,样品在体外模拟实验系统中进行材料降解性能研究.通过测量溶液pH值、Ca2 浓度及样品的XRD、SEM、FTIR测试,认为生物活性玻璃本身发生降解的同时表面有一层类骨碳酸羟基磷灰石生成.     

Investigation of emulsified,acid and acid-alkali catalyzed mesoporous bioactive glass microspheres for bone regeneration and drug delivery

Acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were successfully synthesized via combination of sol-gel and water-in-oil (W/O) micro-emulsion methods. The structural, morphological and textural properties of mesoporous bioactive glass microspheres (MBGMs) were characterized by various techniques. Results show that both MBGMs-A and MBGMs-B exhibit regularly spherical shape but with different internal porous structures, i.e., a dense microstructure for MBGMs-A and internally porous structure for MBGMs-B. ²⁹Si NMR data reveal that MGBMs have low polymerization degree of silica network. The in vitro bioactivity tests indicate that the apatite formation rate of MBGMs-B was faster than that of MBGMs-A after soaking in simulated body fluid (SBF) solution. Furthermore, the two kinds of MBGMs have similar storage capacity of alendronate (AL), and the release behaviors of AL could be controlled due to their unique porous structure. In conclusion, the microspheres are shown to be promising candidates as bone-related drug carriers and filling materials of composite scaffold for bone repair.     

含Zn、Mg生物玻璃的制备及性能研究

采用溶胶-凝胶法,在58S生物玻璃的基础上,分别用0.5wt％的氧化镁和氧化锌取代氧化钙制备了含镁和含锌的生物玻璃.压制的试样分别在600、700和800℃煅烧以做强度测试,并分析了600和800℃煅烧后的物相组成.结果表明,三种试样煅烧至800℃仍为玻璃态,而镁锌的掺入大幅度提高了生物玻璃的强度,这主要是因为Mg-O和Zn-O具有比Ca-O高的键能.模拟体液浸泡试验表明,镁和锌降低了羟基磷灰石的早期成核速度,但并不影响其后期的生长.浸泡三天后所有样品表面都被羟基磷灰石覆盖,表明了样品具有良好的生物活性.     

Bone-like apatite coating on Mg-PSZ/Al2O3 composites using bioactive systems

A biomimetic method was used to promote bioactivity on zirconia/alumina composites. The composites were composed of 80 vol% Mg-PSZ and 20 vol% Al₂O₃. Samples of these bioinert materials were immersed in simulated body fluid (SBF) for 7 days on either a bed of wollastonite ceramics or bioactive glass. After those 7 days, the samples were immersed in a more concentrated solution (1.4 SBF) for 14 days. Experiments were also performed without using a bioactive system during the first stage of immersion. A bone-like apatite layer was formed on the surface of all the materials tested, using wollastonite the bioactive layer was thicker and its morphology was close to that observed on the existing bioactive systems. A thinner apatite layer consisting of small agglomerates was obtained using bioactive glass. The thickness of the ceramic layers was within the range of 15 to 30 μm.     

Wettable arrays onto superhydrophobic surfaces for bioactivity testing of inorganic nanoparticles

Poly(l-lactic acid) superhydrophobic surfaces prepared by a phase-separation methodology were treated with 30 min exposition of UV/O₃ irradiation using hollowed masks in order to obtain patterned superhydrophilic squared-shaped areas. These wettable areas successfully confined bioactive glass nanoparticles (BG-NPs), by dispensing and drying individual droplets of BG-NPs suspensions. The obtained biomimetic chips were used to test the in vitro bioactivity of binary (SiO₂-CaO) and ternary (SiO₂-CaO-P₂O₅) nanoparticles produced using sol-gel chemistry by immersing such substrate in simulated body fluid (SBF). From SEM and EDX it was possible to conclude that the ternary system promoted an enhanced apatite deposition. This work shows the potential of using such flat disposable matrices in combinatory essays to easily evaluate the osteoconductive potential of biomaterials using small amounts of different samples.     

Characterisation of the bioactive behaviour of sol–gel hydroxyapatite–CaO and hydroxyapatite–CaO–bioactive glass composites

The fabrication and characterization of sol–gel derived hydroxyapatite–calcium oxide (HAp–CaO) material is investigated focusing on the effect of the addition of a bioactive glass on the material bioactive behaviour through the fabrication of a novel HAp–CaO (70 wt.%)–bioactive glass (30 wt.%) composite material. The bioactive behaviour of the materials was assessed by immersion studies in Simulated Body Fluid (SBF) and the alterations of the materials surfaces after soaking periods in SBF were characterized by Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR). A brittle and weakly crystalline carbonate hydroxyapatite (HCAp) layer was found to develop on the surface of all samples, few hours after immersion in SBF, confirming the high bioactivity of the material. Alterations of the morphology of the developed HCAp layer, which led to a more compact structure, were observed on the surface of composite samples after 7 days of immersion in SBF. The presence of the CaO phase seems to accelerate the formation of HCAp, while the bioactive glass affects both the morphology and cohesion of the developed layer.