类骨磷灰石的结构分析与形成机制研究

采用在模拟体液(SBF)中浸泡材料的方法,在致密羟基磷灰石(HA)表面形成类骨磷灰石层,利用XRD和FT-IR分析表面相结构,SEM观察表面形貌,X光电子能谱分析表面化学组成及其价态.结果表明,表面新生相为含PO43-、CO32-和OH-的低结晶度的类骨磷灰石微晶.其形成机制属于溶解-沉淀型,HA陶瓷浸泡与SBF液中,首先产生表面溶解,使表面附近Ca2+、PO43-等离子浓度升高,然后通过静电吸引,在其表面吸附、成核、长大,形成类骨磷灰石新相.     

磷酸钙陶瓷在不同动物的模拟体液中类骨磷灰石的形成研究

根据人、狗、猪、猴和兔五种动物体液的钙离子浓度和pH值的差异,配制了不同组分的模拟体液,将孔壁致密和有微孔的多孔磷酸钙陶瓷分别浸泡在这些模拟体液中,研究陶瓷孔隙表面类骨磷灰石的形成情况.结果表明:在模拟体液中浸泡14天后,孔壁致密的材料未见有类骨磷灰石层形成;有微孔的多孔磷酸钙陶瓷,材料孔壁表面(包括陶瓷表面较深孔隙)有类骨磷灰石层的形成,这与体内植入实验观察到的类骨磷灰石层形成和诱导成骨情况相似,可以推论类骨磷灰石层的形成的确是骨诱导的先决条件.随着钙离子浓度的增加,其孔壁表面类骨磷灰石层的形成也更为均匀,但类骨磷灰石生长快慢顺序与动物组织学观察到的骨诱导性高低的次序不完全一致.     

PMMA/HA-GF复合材料在模拟体液中表面类骨磷灰石的形成

主要讨论了在聚甲基丙烯酸甲酯(PMMA)/无机玻璃纤维(GF)复合材料表面涂覆羟基磷灰石(HA)并经过处理后,在模拟体液中材料表面的接触角、类骨磷灰石的形成及表面微结构和形貌的变化.实验结果表明:增加PMMA/HA-FG复合材料表面的粗糙,可降低材料表面的接触角,使材料具有良好的润湿性;将材料在模拟体液中浸泡15d后,材料表面易形成团簇的、不连续的球状类骨磷灰石沉积物,主要成分为能与人体组织有良好结合的碳酸羟基磷灰石.     

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。     

羟基磷灰石纳米棒的合成及其体外生物活性研究

在没有任何表面活性剂存在的情况下，利用水热法合成了尺寸分布均匀的羟基磷灰石（HAp）纳米棒，其长度和直径分别为0．5～1．51am和45～60nm。通过模拟体液（SBF）浸泡实验，研究了其体外生物活性。结果显示，浸泡10d后的羟基磷灰石纳米棒直径变为60～140nm，表面有新的羟基磷灰石层的形成，表明了该羟基磷灰石纳米棒具有良好的生物活性．     

等离子体表面改性的双相磷酸钙陶瓷在SBF中类骨磷灰石形成的研究

由于材料表面类骨磷灰石的形成是材料是否具有生物活性的关键因素。因此,本文研究了等离子体活化改性的双相钙磷陶瓷(HA／TCP)在模拟体液(SBF)中形成类骨磷灰石的表面形貌、组成和结构,并探讨活化和沉积的机理。结果发现等离子体处理的HA／TCP更容易形成类骨磷灰石。其机理是等离子体中的高能、高活性的粒子轰击HA／TCP,使其表面刻蚀和粗化,也使HA／TCP晶体产生畸变活化,从而增加了钙磷陶瓷的溶解性,易使局部钙、磷离子浓度达到过饱和,有利于类骨磷灰石的成核和生长。表明等离子体表面改性提高了材料的活性。有利于促进骨的形成和生长。     

玻璃基生物骨水泥内部纳米羟基磷灰石的形成研究

以CaO-SiO2-P2O5系统生物玻璃和磷酸铵调和液混合制得玻璃基生物骨水泥(GBC),利用XRD、FTIR和SEM对GBC的产物晶相、化学组成和内部显微结构进行了分析,并对其力学性能进行了测试。实验结果表明,随着浸泡时间的增加GBC中的玻璃相逐步向羟基磷灰石(HAP)微晶转化,生成的磷灰石为弱结晶度的类骨状碳酸羟基磷灰石微晶,这些微晶主要分布于玻璃粉末的界面之间,端面尺寸在30～50nm,这表明GBC中所生成的HAY晶体与人体骨有很大的相似性,因而会具有良好的生物活性。对力学性能测试的结果表明,随着浸泡时间的增加GBC的抗压强度逐步增加,在30天时可达到80MPa。因而GBC不仅具有良好的生物活性,而且具有一定的力学强度。     

致密磷酸钙陶瓷在动态SBF中类骨磷灰石层形成研究

磷酸钙陶瓷植入体内后其表面类骨磷灰石层的形成是诱导成骨的先决条件．本实验在模拟体液(ｓｉｍｕｌａｔｅｄ ｂｏｄｙ ｆｌｕｉｄ,ＳＢＦ)以人体骨骼肌组织内体液的正常生理流率(２ｍＬ/１００ｍＬ·ｍｉｎ)和偏离正常生理流率流动的动态条件下,研究在动态ＳＢＦ中影响致密磷酸钙陶瓷表面类骨磷灰石层形成的因素．结果表明:在生理流率条件下,材料的粗糙表面有利于类骨磷灰石的形成,加大ＳＢＦ中Ｃａ^２＋、ＨＰＯ_４^２－离子浓度,类骨磷灰石层的形成速度加快．比起通常使用的静态浸泡试验,ＳＢＦ以生理流率流动的动态试验能够更好地模拟类骨磷灰石生长的体内环境．动态ＳＢＦ对了解类骨磷灰石形成,进而了解磷酸钙陶瓷在体内诱导成骨机理是十分有用的．     

人血清浸泡纳米羟基磷灰石及其聚酰胺复合材料的表面生物活性研究

对n-HA及n-HA／PA66复合材料在人血清中的浸泡行为进行了研究。通过ICP、FT-IR、XRD、SEM等检测手段,分析了n-HA及n-HA／PA66复合材料浸泡前后表面化学组成、结晶结构及表面形貌等的变化。结果表明,n-HA及n-HA／PA66复合材料表面均能吸附蛋白质,并在材料表面生成了与骨磷灰石相似的类骨磷灰石层。这对材料植入体内与骨组织形成骨性键合有着重要意义。同时,也说明了n-HA／PA66复合材料具有优异的生物活性。     

纳米羟基磷灰石/聚碳酸酯复合生物材料Ⅱ:体外生物活性

研究了纳米羟基磷灰石/聚碳酸酯(n-HA/ PC)生物复合材料在模拟体液(SBF)中的表面变化,并用傅里叶红外光谱(FTIR) 、X射线衍射仪(XRD)和扫描电子显微镜(SEM)对材料的表面变化进行了分析。结果表明,n-HA/PC生物复合材料在模拟体液(SBF)中浸泡后,表面会沉积碳酸化羟基磷灰石(CHA),随着浸泡时间的延长,沉积层变厚,CHA晶体形貌变得规整。对n-HA/PC复合材料进行了细胞实验,通过四唑盐(MTT)检测和扫描电镜观察,表明n-HA/PC复合材料无细胞毒性,细胞形态正常,是一种有应用前景的可承力骨修复替代材料。      

Process of formation of bone-like apatite layer on silica gel

It has been proposed that a hydrated silica plays an important role in forming a biologically active apatite layer on the surfaces of bioactive glasses and glass-ceramics in the body. Recent experiments have shown that a silica hydrogel actually induces apatite formation on its surface in a simulated body fluid (SBF). In the present study the process of apatite formation on silica gel was investigated by means of thin-film X-ray diffraction, Fourier-transformed infrared reflection spectroscopy and scanning electron microscopic observation of the surface of the silica gel, as well as the measurement of changes in the ion concentration of the fluid. It was found that the induction period for the apatite nucleation on the surface of the silica gel was about 6 days. Once the apatite nuclei were formed they grew, taking a spherulitic form by consuming the calcium and phosphate ions from the surrounding fluid. Each spherulite consisted of a lot of flake that clustered into a petal-like morphology. The flake was carbonate-containing hydroxyapatite of small-crystallites and/or defective structure. The Ca/P ratio of the apatite was estimated as 1.5–1.6. Thus, the apatite formed was able to induce secondary nucleation of the apatite.     

Biomimetic formation of crystalline bone-like apatite layers on spongy materials templated by bile salts aggregates

Since the trabecular bone exhibit sponge-like bicontinuity there is a growing interest in the synthesis of spongy-like sieves for the construction of bio-active implantable materials. Here, we propose a one step sol–gel method for the synthesis of bicontinuous pore silica materials using different bile salts aqueous mixtures as templates. The influences of the type and amount of bile salt on the synthesis processes are investigated and correlated with the final material morphology. As a final point, their structural properties are interrelated with their ability to induce a bone-like apatite layer in contact with simulated body fluid (SBF). We have confirmed that under specific template conditions, the synthesized material has an open bio-active macropore structure that is blanched in a 3D-disordered sponge-like network similar than those existed in trabecular bone.     

Preparation of a bone-like apatite foam cement

The preparation of a porous bone-like calcium deficient apatite implant material was investigated. A novel cement system composed of an equimolar mixture of Ca₄(PO₄)₂O, Ca(H₂PO₄)₂{H₂O, and CaCO₃ was used. At a liquid/powder ratio of 0.83 ml/g low density open framework foam cements were formed due to the rapid evolution of CO₂. The initial product of the reactants was CaHPO₄{2H₂O which then reacted with Ca₄(PO₄)₂O, forming a calcium deficient carbonated apatite, upon soaking of the cement blocks in SBF. Foam-like cements were composed of a plate-like apatite due to epitaxial overgrowth and conversion of the brushite plate precursor. Cylinders of the foam cement were reinforced with an outer layer of a solid apatite cement to form a material suitable for application as a bone-section implant. © 2001 Kluwer Academic Publishers     

Ultraviolet-accelerated formation of bone-like apatite on oxidized Ti-24Nb-4Zr-7.9Sn alloy

A novel method has been developed to rapidly deposit bone-like apatite with the assistance of ultraviolet （UV） light irradiation on the nanostructured titania in the simulated body fluid （SBF）. The process has three main steps： Ti-24Nb-4Zr-7.9Sn alloy was heated at 650℃ for 3 h, UV-light illumination in air for 4 h and soaking in the SBF for 3 d. A titania coating consisted of main rutile formed on the thermal oxidized Ti-24Nb-4Zr- 7.9Sn alloy. The UV not only converted the futile surface from hydrophilic to hydrophobic but also stimulated high surface activity. After 4 h UV illumination, the contents of Ti3＋ and hydroxyl groups on the oxidized sample were increased, while that of lattice O decreased. After 3 d of soaking in the SBF, a compact and uniform layer of carbonated hydroxyapatite （CHA） particles was formed on the UV-illuminated rutile surface whereas there was a few of HA to be viewed on the surface of as-oxidized Ti-24Nb-4Zr-7.9Sn alloy. Our study demonstrates a simple, fast and cost-effective technique for growing bone-like apatite on titanium alloys.     

The mechanism of biomineralization of bone-like apatite on synthetic hydroxyapatite: an in vitro assessment.

The mechanism of biomineralization of bone-like apatite on synthetic hydroxyapatite (HA) has been investigated in vitro, in which the HA surface was surveyed as a function of soaking time in simulated body fluid (SBF). In terms of surface structure by transmission electron microscopy with energy-dispersive X-ray spectrometry, the HA whose Ca/P atomic ratio was 1.67 revealed three different characteristic soaking periods in SBF, i.e. the first soaking period, in which the HA surface increased the Ca/P ratio up to 1.83 to form an amorphous phase of Ca-rich calcium phosphate; the second soaking period, in which the HA surface decreased the Ca/P ratio up to 1.47 to form an amorphous phase of Ca-poor calcium phosphate; and the third soaking period, in which the HA surface gradually increased the Ca/P ratio up to 1.65 to eventually produce the bone-like nano-cerystallites of apatite, which grew forming complex crystal assemblies with a further increase in immersion time. Analysis using electrophoresis spectroscopy indicated that, immediately after immersion in SBF, the HA revealed a highly negative surface potential, which increased to reach a maximum positive value in the first soaking period. The surface potential then decreased to again reach a negative value in the second soaking period and thereafter converge to a constant negative value in the third soaking period. This implies that the HA induces biomineralization of apatite by smartly varying its surface potential to trigger an electrostatic interaction, first with positive calcium ions and second with negative phosphate ions in the SBF.     

Combinatorial design of calcium meta phosphate poly(vinyl alcohol) bone-like biocomposites

The incidence of degenerative diseases and the ageing population have added to the growing demand for bone grafts. Although autologous bone continues to be the gold standard, limited yield and potential morbidity of the donor site pose considerable challenges. Currently, clinically used synthetic grafts based on calcium phosphates are mechanically brittle and not compliant hence composite scaffolds are expected to be provide viable solutions. In this study we report composites of calcium meta phosphate-poly (vinyl alcohol) with tunable mechanical properties, low swelling and excellent biocompatibility. The elastomeric nature of the composites resist brittle fracture and the scaffolds can be easily shaped to the bone defect by the surgeon. Testing on bone plug shaped specimens of the scaffolds, exhibited superior mechanical properties compared to currently commercially available bone plugs with additional advantages being the ability to increase porosity without compromising properties in compression and degree of swelling, which make these composites promising synthetic alternatives for bone grafts and bone tissue engineering.     

The role of amorphous phase in nucleating bone-like apatite on plasma-sprayed hydroxyapatite coatings in simulated body fluid

Abstracts are not published in this journal This revised version was published online in November 2006 with corrections to the Cover Date.