生物活性聚乳酸/SiO2-CaO复合薄膜的制备和表征（英文）

以聚乳酸、正硅酸乙酯和硝酸钙为原料,采用溶胶-凝胶方法制备了不同比例的聚乳酸/SiO2-CaO多孔复合薄膜.采用扫描电子显微镜和红外光谱仪对薄膜的微观结构和组成进行分析,并利用表面Zeta电位测定仪对其表面电位进行表征,通过模拟体液浸泡实验和MTT方法对薄膜的生物活性和细胞毒性进行评价.结果表明:复合薄膜在模拟体液中经过7d的浸泡,薄膜表面形成了环状结构的类骨磷灰石层;随着SiO2-CaO含量增加,复合薄膜表面微孔的孔径变小,薄膜表面Zeta电位变负,诱导类骨磷灰石沉积的能力增强;MTT实验证实复合薄膜对MG-63细胞没有毒性且有利于细胞的增殖.     

大孔孔径对含CO2-3的双相HA/β-TCP多孔陶瓷表面类骨磷灰石形成的影响

钙磷陶瓷植入生物体内后其表面首先形成一层含CO2-3的类骨磷灰石层.它对钙磷陶瓷诱导新骨的生成起非常重要的作用.本文以模拟体液SBF9#为介质,利用体外模拟装置首次研究了以新工艺制备的含CO2-3的双相HA/β-TCP多孔陶瓷其大孔孔径对表面类骨磷灰石形成的影响.结果表明该陶瓷因CO2-3的掺入导致类骨磷灰石晶体的形成时间大大缩短(从14d缩短至6d),且以300～400μm的大孔孔径最有利于类骨磷灰石晶体的形成.此外还有缺钙羟基磷灰石晶体的生成.而最不利于类骨磷灰石晶体形成的大孔孔径为400～500μm.大孔孔径的优化有利于该陶瓷材料骨诱导性的提高,进而有利于骨缺损的快速修复.     

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．     

等离子体电解氧化制备生物活性多孔纳米TiO2涂层

采用等离子体电解氧化(PEO)技术,在纯钛基体上制备了具有多孔和纳米结构并含有不同钙磷含量的氧化钛涂层.采用扫描电子显微镜和X射线衍射仪研究了涂层的显微结构和相组成.采用模拟体液浸泡实验评价涂层的生物活性.研究结果表明:涂层主要由锐钛矿和金红石相组成,涂层表面孔径小于10μm,晶粒直径约10～100nm,且涂层表面晶粒、涂层厚度、表面粗糙度和涂层中的钙磷元素含量均随着PEO过程中电流密度的增大而增加.PEO涂层在模拟体液中浸泡14 d即能够诱导类骨磷灰石在其表面沉积,显示出良好的生物活性.涂层中的钙磷含量和结晶形态对其生物活性起关键作用.     

纯钛表面立方介孔SiO2薄膜诱导沉积碳磷灰石层

采用浸渍-提拉法在预处理纯钛表面制备立方介孔SiO₂薄膜, 通过评价体外诱导类骨碳磷灰石层形成能力研究其生物活性。利用小角X射线衍射、傅立叶变换红外光谱、N₂吸附、电镜和能谱等测试技术对模板剂去除前后、模拟体液浸泡前后介孔薄膜结构、组成与形貌进行了研究; 利用固体表面Zeta电位仪研究薄膜表面荷电性质。结果表明, 介孔薄膜具有三维立方介孔结构, 在模拟体液(1.5SBF)中浸泡14 d即能诱导碳磷灰石层在其表面沉积, 显示出良好的生物活性。介孔薄膜独特的孔道结构以及孔表面Si-OH在体液中呈负电性对其生物活性起关键作用。     

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。     

大孔孔径对含CO3^2-的双相HA／β-TCP多孔陶瓷表面类骨磷灰石形成的影响

钙磷陶瓷植入生物体内后其表面首先形成一层含CO3^2-的类骨磷灰石层。它对钙磷陶瓷诱导新骨的生成起非常重要的作用。本文以模拟体液SBF9^#为介质。利用体外模拟装置首次研究了以新工艺制备的含CO3^2-的双相HA／β-TCP多孔陶瓷其大孔孔径对表面类骨磷灰石形成的影响。结果表明该陶瓷因CO3^2-的掺入导致类骨磷灰石晶体的形成时间大大缩短(从14d缩短至6d)。且以300～400μm的大孔孔径最有利于类骨磷灰石晶体的形成。此外还有缺钙羟基磷灰石晶体的生成。而最不利于类骨磷灰石晶体形成的大孔孔径为400～500μm。大孔孔径的优化有利于该陶瓷材料骨诱导性的提高，进而有利于骨缺损的快速修复。     

Ar等离子体改性纳米钛基TiO2薄膜生物活性研究

采用室温直流磁控溅射技术在纳米晶体钛表面制备TiO2薄膜,并用Ar等离子体对TiO2薄膜进行表面改性,体外模拟体液浸泡实验考察薄膜的生物活性。系统研究了Ar等离子体处理对TiO2薄膜结构、形貌、亲水性、生物活性的影响规律。结果表明:Ar等离子体处理不改变纳米晶体钛表面TiO2薄膜晶体结构(主要为金红石相),但显著改善TiO2薄膜均匀性、光滑性和亲水性。Ar等离子体处理后,TiO2薄膜在模拟体液浸泡中诱导的Ca/P层由球状团簇无定型结构转变为内联多孔网状磷灰石和磷酸八钙相结构,显示优异的生物活性。     

预钙化处理后的钛表面磷灰石涂层的形成

本研究采用碱液处理钛样品 ,并进行预钙化处理 ,在模拟体液 (SBF)中浸泡 ,能在较短时间内形成表面致密的磷灰石涂层。碱液处理使钛表面生成了钛酸钠及氧化钛等物质 ,在SBF中浸泡时 ,会发生水解而使表面形成带负电的Ti OH基团。预钙化处理使带负电的钛表面由静电引力而聚集了大量的Ca2 + 离子。Ca2 + 能吸引带负电的HPO2 -4到达表面 ,从而使表面附近能在较短时间内达到钙 磷过饱和。Ca2 + 离子又能使表面附近的pH值增大 ,Ca2 + 离子和HPO2 -4离子的活度积就增大 ,从而刺激了磷灰石晶体的成核与长大 ,最终形成表面磷灰石涂层     

生物陶瓷及其复合材料表面诱导类骨磷灰石层形成的研究

钙磷生物材料表面类骨磷灰石层的形成对其植入体内诱导新骨生成起非常重要的作用.本实验采用2倍模拟体液(2×SBF)为介质,通过仿生浸泡的方法研究了羟基磷灰石(HA)陶瓷及其复合材料羟基磷灰石/聚乳酸(HA/PLA)、羟基磷灰石/聚己內脂(HA/PCL)、羟基磷灰石/丝素(HA/SF)和羟基磷灰石/壳聚糖(HA/CS)表面诱导类骨磷灰石层形成的差异.实验结果表明,HA陶瓷及其复合材料在2×SBF溶液中仿生浸泡7d后,各样品表面均有一层厚度不同的类骨磷灰石层生成.并且该类骨磷灰石层的结晶度较低,晶粒较细(15～30nm),与人体自然骨无机物的结构非常类似.其中,在这4种复合材料中,HA/CS和HA/SF复合材料中因丝素蛋白和壳聚糖富含多种功能基团,能有效促进类骨磷灰石晶体的形核和生长,因而诱导类骨磷灰石生成的能力最强,显示其良好的生物活性.     

Chemical surface treatment of silicone for inducing its bioactivity

It has been confirmed that the apatite nucleation is induced by silanol (Si–OH) groups formed on the surfaces of materials and/or silicate ions adsorbed on them.It was previously shown that apatite nuclei are formed on organic polymers when the polymers are placed on CaO, SiO2-based glass particles soaked in a simulated body fluid (SBF) with ion concentrations nearly equal to those of human blood plasma, and that they grow spontaneously to form a dense and uniform apatite layer together with high adhesive strength to the substrates when the polymers are soaked in another solution with ion concentrations 1.5 times the SBF. In the present study, silanol groups bonded covalently to the surface of the silicone substrate were formed and its apatite-forming ability was examined. When silicone substrates were treated with 5 or 10 M NaOH with pH 7.25 at 36.5°C for more than 3 h, silanol groups were formed on the surfaces of the substrates. When thus NaOH-treated substrates were soaked in 1.5SBF at 36.5°C, a bone-like apatite was formed on the substrates in a short period. © 1998 Chapman & Hall.     

Apatite coated on organic polymers by biomimetic process: improvement in adhesion to substrate by HCl treatment

A dense, uniform and highly biologically active bone-like apatite layer can be formed in arbitrary thickness on any kind and shape of solid substance by the following biomimetic method at normal temperature and pressure: first, a substrate is set in contact with particles of CaO-SiO₂-based glass soaked in a simulated body fluid (SBF) with ion concentrations nearly equal to those of human blood plasma. Second, the substrate is soaked in another solution with ion concentrations 1.5 times those of SBF (1.5 SBF). In the present study, organic polymer substrates were treated with 1 m HCl solution, then subjected to the above mentioned biomimetic process. The induction periods for the apatite nucleation on polyethyleneterephthalate, polymethylmethacrylate, polyamide 6 and polyethersulfone substrates were reduced from 24 to 12 h with the HCl treatment. The adhesive strength of the formed apatite layer to the polyethyleneterephthalate, polymethylmethacrylate and polyamide 6 substrates were increased from 3.5 to 7.0 MPa from 1.1 to 2.8 MPa and from 0.6 to 3.1 MPa, respectively, with the HCl treatment. It is supposed that highly polar carboxyl group formed by the HCl hydrolysis reaction of ester group in polyethyleneterephthalate and polymethylmethacrylate or amide group in polyamide 6 increased the affinity of the substrates with a silicate ion to decrease the induction period, and also increased the affinity of the substrate with the apatite to increase the adhesive strength. The apatite-organic polymer composites thus obtained are expected to be useful as bone-repairing materials as well as soft-tissue-repairing materials.     

PET fiber fabrics modified with bioactive titanium oxide for bone substitutes

A rectangular specimen of polyethylene terephthalate (PET) was soaked in a titania solution composed of titanium isopropoxide, water, ethanol and nitric acid at 25 °C for 1 h. An amorphous titanium oxide was formed uniformly on the surface of PET specimen, but did not form an apatite on its surface in a simulated body fluid (SBF) within 3 d. The PET plate formed with the amorphous titanium oxide was subsequently soaked in water or HCl solutions with different concentrations at 80 °C for different periods of time. The titanium oxide on PET was transformed into nano-sized anatase by the water treatment and into nano-sized brookite by 0.10 M HCl treatment at 80 °C for 8 d. The former did not form the apatite on its surface in SBF within 3 d, whereas the latter formed the apatite uniformly on its surface. Adhesive strength of the titanium oxide and apatite layers to PET plate was increased by pre-treatment of PET with 2 wt% NaOH solution at 40 °C for 2 h. A two-dimensional fabric of PET fibers 24 μm in diameter was subjected to the NaOH pre-treatment at 40 °C, titania solution treatment at 25 °C and subsequent 0.10 M HCl treatment at 80 °C. Thus treated PET fabric formed the apatite uniformly on surfaces of individual fibers constituting the fabric in SBF within 3 d. Two or three dimensional PET fabrics modified with the nano-sized brookite on surfaces of the individual fibers constituting the fabric by the present method are believed to be useful as flexible bone substitutes, since they could be integrated with living bone through the apatite formed on their constituent fibers.     

Growth of calcium phosphate on phosphorylated chitin fibres

Calcium phosphate growth on chitin phosphorylated fibres was studied using scanning electron microscopy and energy dispersive X-ray analysis (SEM, EDX), micro-Fourier transform infrared spectroscopy (FTIR), and solid state magic angle spinning nuclear magnetic resonance (MAS NMR) techniques. The C6 chemical shift positions of 13C MAS NMR in the chitin fibres phosphorylated using urea and H3PO4 are obvious indicating that phosphorylation takes place not in the C1 but in the C6 region. Micro-FTIR and 31P MAS NMR suggested that ammonium hydrogen phosphate formed during the phosphorylation procedure. Chitin fibres phosphorylated using urea and H3PO4 and then soaked in saturated Ca(OH)2 solution at ambient temperature, which lead to the formation of thin coatings formed by partial hydrolysis of the PO4 functionalities, were found to stimulate the growth of a calcium phosphate coating on their surfaces after soaking in 1.5×SBF solution for as little as one day. The thin layer after Ca(OH)2 treatment functioned as a nucleation layer for further calcium phosphate deposition after soaking in 1.5×SBF solution. EDX-measured Ca : P ratios of the coatings of Ca(OH)2-treated phosphorylated chitin in 1.5×SBF solution suggested that calcium-deficient apatite was formed.     

Optimising the bioactivity of alkaline-treated titanium alloy

A layer of sodium titanate hydrogel on titanium alloy (Ti6Al4V) induces apatite formation in simulated body fluid (SBF). This paper seeks to determine the parameters of alkaline-treated and subsequent heat treatment which lead to the most rapid formation of apatite. Specimens were soaked in 3, 5, 10 or 15 M solutions of NaOH at temperatures of 60 or 80 °C for 1, 3 or 7 days. It was found that the optimum treatment for the Ti6Al4V alloy was a 3-day soak in 5 M NaOH solution at 80 °C. Specimens treated under these optimum conditions were subsequently heat-treated at 500, 600, and 700 °C for 1 h so as to consolidate the sodium titanate hydrogel layer and improve its bonding to the substrate. Treatment at 600 °C resulted in the best bonding and the optimum rate of apatite formation. On soaking in simulated body fluid (SBF), apatite formed within 3 days, as compared to the 7-day formation, which was the best rate previously reported. The acceleration in the rate of apatite formation is significant, as it should allow for earlier load bearing of prostheses following implantation.     

Enhancement of bonding strength by graded structure at interface between apatite layer and bioactive tantalum metal

Tantalum metal is a candidate for use as an implant material in high load-bearing bony defects, due to its attractive features such as high fracture toughness and high workability. This metal, however, does not have bone-bonding ability, i.e. bioactivity, and therefore the development of bioactive tantalum metal is highly desirable. It is known that the essential prerequisite for an artificial material to show bioactivity is to form a bonelike apatite layer on its surface in the body environment. The same type of apatite layer is formed in a simulated body fluid (SBF) with inorganic ion concentrations nearly equal to those of human blood plasma. The present authors previously showed that the apatite formation on tantalum metal in SBF was remarkably accelerated by treatment with 0.5 M-NaOH aqueous solution and subsequent firing at 300 °C, while untreated tantalum metal spontaneously formed the same apatite after a long soaking period. In the present study, the bonding strength of the apatite layer to the substrate was quantitatively evaluated in comparison with that to the untreated tantalum metal. Adhesive strength was measured as an estimation of bonding strength, and the surface microstructure of both the substrates was characterized in order to discuss the difference in the bonding strength in terms of surface structure. The apatite layer formed on the NaOH- and heat-treated tantalum metal shows higher adhesive strength than that formed on the untreated metal. The amorphous sodium tantalate layer formed on the tantalum metal by NaOH and heat treatments, has a smooth graded structure where its concentration gradually changes from the surface into the interior metal. Smooth graded structure with complex of apatite is constructed after soaking in SBF. The higher bonding strength of the apatite layer formed on the treated metal is attributed to its smooth graded structure.     

In vitro effect of magnesium inclusion in sol-gel derived apatite

Magnesium-containing apatite coatings were prepared on Ti6Al4V substrates by sol-gel dip coating method. Standard simulated body fluid (SBF) was used to evaluate the bioactivity of the coatings. A series of the coatings according to the composition (Ca_10−xMg_x)(PO₄)₆(OH)₂, where x = 0 to 2, is synthesized and immersed in the standard SBF for periods of 7 to 35 days for direct deposition of apatite layer from the SBF solution. Scanning electron microscopy (SEM) was used to examine the morphology changes of the SBF apatite layer that occurred during in vitro immersion. X-ray diffractometry, Fourier Transformation Infra-Red Spectroscopy and X-ray Photoelectron Spectroscopy were used to analyse the phases, chemical groups and composition of the sol-gel coating. Results show that as the sol-gel coating contains magnesium, this promotes deposition of apatite layer from SBF. As x ≤ 1, SBF immersion gives rise to a dense apatite layer. However, as x ? 1, selected dissolution of the deposited layer takes place, which results in serious pitting on the surface. Also, Mg ions from the dissolution of the sol-gel coating during immersion in the SBF apparently played a role in the subsequent deposition of apatite o the coating, evidence of Mg was found in the apatite layer.     

A study on mineralization behavior of amino-terminated hyperbranched polybenzimidazole membranes

Amino-bearing polymers, coated with apatite or similar minerals, have attracted significant attention for their potential in medical applications. In this study, an amino-terminated hyperbranched polybenzimidazole (HBPBI) membrane was used as a substrate for apatite growth. The membrane was soaked in solutions of CaCl₂, Na₂HPO₄ and SBF to yield an apatite coating. The structure and morphology of the layers were characterized by FTIR-ATR, XRD and FESEM. The results indicate that the high densities of amino, imide and imidazole groups on the amino-terminated HBPBI membrane provide active sites for the growth of apatite.     

Multifunctional porous titanium oxide coating with apatite forming ability and photocatalytic activity on a titanium substrate formed by plasma electrolytic oxidation

Plasma electrolytic oxidation (PEO) was used to make a multifunctional porous titanium oxide (TiO₂) coating on a titanium substrate. The key finding of this study is that a highly crystalline TiO₂ coating can be made by performing the PEO in an ammonium acetate (CH₃COONH₄) solution; the PEO coating was formed by alternating between rapid heating by spark discharges and quenching in the solution. The high crystallinity of the TiO₂ led to the surface having multiple functions, including apatite forming ability and photocatalytic activity. Hydroxyapatite formed on the PEO coating when it was soaked in simulated body fluid. The good apatite forming ability can be attributed to the high density of hydroxyl groups on the anatase and rutile phases in the coating. The degradation of methylene blue under ultraviolet radiation indicated that the coating had high photocatalytic activity.     

Composition and structure of apatite formed on organic polymer in simulated body fluid with a high content of carbonate ion

Apatite layer was formed on polyethyleneterephthalate (PET) substrate by the following biomimetic process. The PET substrate was placed on granular particles of a CaO, SiO₂-based glass in simulated body fluid (SBF) with ion concentrations nearly equal to those of human blood plasma to form apatite nuclei on their surfaces. The apatite nuclei was then grown into a continuous layer by subsequently soaking the substrate in SBF under air or CO₂ atmosphere in which CO₂ partial pressure in the ambient was adjusted to 14.8 kPa to increase the content of carbonate ion to a level nearly equal to that of blood plasma. The increase in the content of carbonate ions in SBF changed the Ca/P atomic ratio of the apatite from 1.51 to 1.63, content of CO₃ ^2- ions from 2.64 to 4.56 wt %, and lattice constants a from 94.32 to 94.23 nm and c from 68.70 to 68.83 nm, respectively. The Ca/P ratio and lattice constants of the apatite formed in SBF under CO₂ atmosphere were approximately identical to those of bone apatite, i.e. Ca/P atomic ratio 1.65, content of CO₃ ^2- ion 5.80 wt % and lattice constants a 94.20 and c 68.80 nm. This indicates that an apatite with composition and structure nearly identical to those of bone apatite can be produced in SBF by adjusting its ion concentrations including the content of carbonate ions to be equal to those of blood plasma.