含锶磷灰石骨水泥浆体的pH值及其固化体的体外细胞毒性评价

在线测量了自制含锶羟基磷灰石骨水泥(Sr-CPC)浆体在水化过程中的pH值实时变化以及各固化体在培养液中浸泡不同时间后其浸提液的pH值,并利用MTT比色法评价了该水泥固化体的体外细胞毒性.XRD与FTIR分析表明,固化体在SBF中浸泡24h后,水化产物为锶钙羟基磷灰石固溶体,而且该固溶体中含有与骨磷灰石类似的CO₃^2-;各水泥浆体pH值的在线测量表明,不同含锶量水泥浆体的pH基本在6.5-7.8之间变化,接近中性;体外细胞毒性试验表明,不同含锶量水泥固化体的细胞毒性为0或1级,且细胞毒性与各水泥固化体浸提液的浓度、作用时间有一定的关联性.     

不同含锶量羟磷灰石无机骨水泥的制备及其对可注射性的影响

采用碳酸钙、碳酸锶和磷酸氢钙为起始原料,经高温固相反应合成制备了不同含锶量(0、5%、10%、15%和20%(原子分数))的羟磷灰石无机骨水泥粉剂,以丙烯酸-衣康酸共聚液和柠檬酸的混合液为骨水泥固化液,探讨不同含锶量对骨水泥可注射性的影响。结果表明,0、5%、10%和15%(原子分数)含锶量试样组的物相结构为含锶的羟磷灰石和α-TCP。20%(原子分数)含锶量试样组的物相结构则为含锶的羟磷灰石和β-TCP,并且不具有水化凝固的特性。随着含锶量的增加,骨水泥的注射性能也变得更好。当粉液比采用1.8g/g时,0、5%、10%和15%(原子分数)试样组骨水泥的可注射率分别达到46%、74%、100%和100%,由此表明锶的掺入可以明显提高羟磷灰石无机骨水泥的可注射性。     

氧化锌对纳米羟基磷灰石/壳聚糖复合骨水泥理化性能的影响

质量比为70∶30的n-HA/CS复合材料与适量ZnO粉末的共混物为固相,选用合适的固化液,按照适当的固/液比例进行调和,制备出一种在空气、生理盐水及血液或体液中均可快速固化的新型n-HA/CS复合骨水泥,考查了ZnO含量对该骨水泥理化性能的影响.结果表明:当ZnO与复合材料质量比为1∶8、固化液与固相粉末比例(L/P)为1.2ml/g时,所制备的复合骨水泥抗压强度和固化时间均较佳,能够满足临床操作的需要.ZnO/复合材料质量比分别为1∶8和1∶5的骨水泥在生理盐水中的pH值随浸泡时间的延长而逐渐升高,前者在第20d时pH值维持在7.28左右,而后者在第20d时的pH值接近7.40,均与人体的pH环境相近.当ZnO/复合材料质量比为1∶8时,骨水泥对水的接触角最小,表明其具有良好的润湿性能.ZnO含量越高,骨水泥的吸水率越低,这对于保持骨水泥植入体内后的体积稳定性具有重要价值.SEM观察发现,固化后的骨水泥中含有大量微孔,有利于营养物质的传递及代谢废物的排泄,并利于新生骨组织的长入及爬行替代.     

氧化石墨烯增强磷酸钙生物水泥

为了提高磷酸钙水泥(CPCs)的强度,将纳米片状的氧化石墨烯(GO)与CPCs复合。首先,以α-Ca₃(PO₄)₂、CaHPO₄和CaCO₄物质的量之比为1:1:1的CPCs为固相、不同浓度的GO水分散液为固化液,二者按一定的固/液比混合并固化成型,制得GO/CPCs;然后,探讨GO添加量对GO/CPCs力学强度的影响,测量固化时间、在模拟体液中浸泡后的降解率及浸提液的pH,以XRD检测其物相,并通过SEM观察其显微形貌。结果显示:GO添加量对CPCs的抗压强度有显著影响,最佳添加量为0.0500wt%;随老化时间的延长,不同GO添加量的CPCs的抗压强度均明显提高,尤其是在早期阶段;与不加GO的对照组相比,老化2 h和24 h后,0.0500wt% GO/CPCs的抗压强度分别提高了200%和67%。GO/CPCs在模拟体液中的降解率升高且浸提液pH下降。GO/CPCs在同期水化反应中可获得更多的羟基磷灰石相,结晶有序、均匀且细小。所得结论表明掺加GO可以显著改善CPCs的抗压强度。      

磷酸钙/BMP复合生物活性骨水泥水化性能及诱导成骨特性研究

采用微细α-磷酸三钙(α-TCP)粉料、辅助料与冻干牛骨形态发生蛋白(BMP)预先固相混合制备了新型磷酸钙(CPC)/BMP复合生物骨水泥.通过水化、凝固性能研究优化了配料成分、调和液和促凝剂组成;通过大鼠肌袋种植实验研究了骨水泥的异位成骨性能.结果表明:以α-TCP:CaHPO₄:CaO(0.95:0.025:0.025)为固相配料,以0.25mol/LNaH₂PO₄/Na₂HPO₄混合液([P]_T=0.5mol/L)作为调合液可制备性能优异的骨水泥材料,骨水泥初凝时间为6min,终凝时间为30min,固化强度达33MPa,达到临床手术的要求;α-TCP粉料粒度对骨水泥凝固性能影响显著,实验选用α-TCP粉料粒径d₅₀为1.3μm;骨水泥在Hank’s溶液中浸泡5天抗压强度可达最大值;骨水泥块经浸泡后内部生成针状羟基磷灰石晶体的网状结构.新型CPC/BMP复合骨水泥异位成骨作用明显,4周即能快速形成板层骨结构,证明该新型复合材料具有较强的诱导成骨活性.该生物活性骨水泥复合材料可望成为一类新型组织工程骨修复材料.     

温度对含模拟α-高放核废液的磷酸镁水泥固化体性能的影响

利用磷酸镁水泥(Magnesium potassium phosphate cement,MPC)对模拟α-高放核废液(HLW)进行固化,研究温度对固化体力学性能、物相组成、微观形貌及核素Cs~+浸出率的影响。BET、XRD、SEM及AAS等测试结果表明,室温下MgO、KH2PO4与高放核废液反应形成致密结构;随着温度的升高,固化体脱水,400℃时孔道结构增多,平均孔径增大,抗压强度降低,Cs~+浸出率增加;温度继续升高,磷酸镁水泥烧结陶瓷化,平均孔径逐渐减小,抗压强度增大;900℃时固化体表现出良好的陶瓷结构特征,晶粒完全熔融,晶粒间没有明显界线,Cs~+的28d浸出率为7.21×10~(-6) g/(cm~2·d)。不同温度下高放核废液的磷酸镁水泥固化体核素Cs~+的浸出率均能达到玻璃固化体的性能要求,表明磷酸镁水泥用于固化高放核废液具有明显优势。     

可注射镁基磷酸钙骨水泥的研究

采用MgO、KH₂PO₄、β-TCP、葡萄糖作为骨水泥的固相, 磷酸溶液作为液相, 制备可注射镁基磷酸钙骨水泥(IMPC)。考察液固比(LPR)、MgO含量、葡萄糖含量变化对IMPC胶凝性能和力学性能的影响。实验结果显示: 液固比和缓凝剂葡萄糖含量增大均会导致凝结时间变长和抗压强度下降, 但有益于可注射性; 随MgO含量增大, 凝结时间缩短, 可注射率降低, 但抗压强度提高。采用正交实验法确定MgO含量26wt%, 液固比0.30 mL/g, 葡萄糖含量6wt%时得到的IMPC综合性能良好, 水化过程缓和, 放热量低。该IMPC有望成为一种新型骨粘结材料。     

原料粒度对磷酸钙骨水泥性能的影响

以等质量的部分结晶磷酸钙(PCCP)和磷酸氢钙(DCPA)的混合物组成的磷酸钙骨水泥(CPC)粉体作为研究对象,采用单因素实验,研究了PCCP和DCPA粒度变化对骨水泥抗压强度、孔隙率、凝结时间、水化产物物相组成和结晶形貌的影响.结果发现:在0.4的液固比下,固定PCCP的粒度,减小DCPA的粒径,骨水泥的抗压强度呈先升高后减小的趋势,存在一最大值为34.6MPa;而PCCP的粒度变化对骨水泥性能的影响较大,随着PCCP粒径的减小,所需调和液的比例增到0.5,抗压强度也存在一最大值为19.7MPa.而孔隙率随这两种原料粒度变化的规律都与强度的变化规律相反,随原料粒径的减小,均存在一最小值.DCPA的粒度变化对骨水泥的凝结时间影响不大;而随PCCP颗粒粒径的减小,骨水泥的凝结时间变短.所生成的水化产物都为弱结晶的羟基磷灰石(HA),但当DCPA颗粒较粗时,固化体中有微量的DCPA残余;而当PCCP颗粒过细时,固化体中有较多的DCPA残余.     

氧化石墨烯对磷酸钙骨水泥的水化行为的影响

将氧化石墨烯(GO)分散液作为固化液,研究了该固化液对磷酸钙骨水泥(CPC)的水化行为的影响。利用维卡仪、万能压力试验机和热导式等温量热仪等研究了GO浓度对CPC骨水泥的凝结时间、抗压强度和水化行为的影响。利用X射线衍射和扫描电子显微镜等技术研究了GO浓度对CPC骨水泥固化体的晶相组成和断面形貌的影响。研究结果表明,固化液中加入GO,对骨水泥的断面形貌和水化产物均有影响,同时可以使CPC骨水泥的凝结时间由(36±4)min大幅度延长到(67±2)min,抗压强度由(20.1±1.7)MPa增加到(25.6±2.7)MPa。     

磷酸钙/纤维蛋白胶复合支架材料的结构及力学性能分析

用可吸收磷酸钙骨水泥和纤维蛋白胶按一定比例体外构建复合支架材料,通过XRD、SEM、抗压实验和空隙率测试等方法对其结构及力学性能进行分析.结果发现:由于加入纤维蛋白胶,复合支架材料在一定程度上延长了磷酸钙骨水泥的初凝时间,但并不影响磷酸钙骨水泥的终凝时间;同时,加入纤维蛋白胶改变了骨水泥固化体的微观结构,提高了骨水泥的抗压强度,其最大抗压强度达到14MPa,弹性模量在96.64～269.39MPa之间,空隙率为38.8%.与在同样条件下制备的磷酸钙骨水泥比较,复合支架材料的抗压强度增强了55.6%,而空隙率仅仅下降了6.9%;XRD分析显示,复合支架材料并不影响磷酸钙骨水泥的最终的转化,其结晶结构仍是羟基磷灰石结构,是更好的骨组织工程支架材料.     

Physicochemical properties and cytotoxicities of Sr-containing biphasic calcium phosphate bone scaffolds

This study demonstrates a new biomaterial system composed of Sr-containing hydroxyapatite (Sr-HA) and Sr-containing tricalcium phosphate (Sr-TCP), termed herein Sr-containing biphasic calcium phosphate (Sr-BCP). Furthermore, a series of new Sr-BCP porous scaffolds with tunable structure and properties has also been developed. These Sr-BCP scaffolds were obtained by in situ sintering of a series of composites formed by casting various Sr-containing calcium phosphate cement (Sr-CPC) into different rapid prototyping (RP) porous phenol formaldehyde resins, which acted as the negative moulds for controlling pore structures of the final scaffolds. Results show that the porous Sr-BCP scaffolds are composed of Sr-HA and Sr-TCP. The phase composition and the macro-structure of the Sr-BCP scaffold could be adjusted by controlling the processing parameters of the Sr-CPC pastes and the structure parameters of the RP negative mould, respectively. It is also found that both the compressive strength (CS) and the dissolving rate of the Sr-BCP scaffold significantly vary with their phase composition and macropore percentage. In particular, the compressive strength achieves a maximum CS level of 9.20 ± 1.30 MPa for the Sr-BCP scaffold with a Sr-HA/Sr-TCP weight ratio of 78:22, a macropore percentage of 30% (400–550 μm in size) and a total-porosity of 63.70%, significantly higher than that of the Sr-free BCP scaffold with similar porosity. All the extracts of the Sr-BCP scaffold exhibit no cytotoxicity. The current study shows that the incorporation of Sr plays an important role in positively improving the physicochemical properties of the BCP scaffold without introducing obvious cytotoxicity. It also reveals a potential clinical application for this material system as bone tissue engineering (BTE) scaffold.     

Study on injectable and degradable cement of calcium sulphate and calcium phosphate for bone repair

Injectable calcium sulphate/phosphate cement (CSPC) with degradable characteristic was developed by introduction of calcium sulphate (CS) into calcium phosphate cement (CPC). The setting time, compressive strength, composition, degradation, cells and tissue responses to the CSPC were investigated. The results show that the injectable CSPC with optimum L/P ratio exhibited good injectability, and had suitable setting time and mechanical properties. Furthermore, the CSPC had good degradability and its degradation significantly faster than that of CPC in Tris–HCl solution. Cell culture results indicate that CSPC was biocompatible and could support MG63 cell attachment and proliferation. To investigate the in vivo biocompatibility and osteogenesis, the CSPC were implanted in the bone defects of rabbits. Histological evaluation shows that the introduction of CS into CPC enhanced the efficiency of new bone formation, and CSPC exhibited good biocompatibility, degradability and osteoconductivity with host bone in vivo. It can be concluded that the injectable CSPC had a significant clinical advantage over CPC, and might have potential to be applied in orthopedic, reconstructive and maxillofacial surgery, especially for minimally invasive techniques.     

Development of an octocalcium phosphate cement

From previous studies it is known that alpha-tertiary calcium phosphate and dicalcium phosphate form a cement upon mixing with water. In this study this cement was optimized in terms of the milling of the constituents, their molar ratio, the amount of hydroxyapatite added and the water/powder ratio. The optimum Ca/P molar ratio of the cement mixture was 1.36±0.03. X-ray diffraction showed the reaction product to be octocalcium phosphate. Addition of precipitated hydroxypatite of over 3% diminished the final strength of the cement significantly. However, admixtures of only 2% of precipitated hydroxyapatite (a) kept the final compressive strength at 30±5 MPa after soaking in Ringers solution at 37°C, (b) diminished the initial setting time from 27.5 to 10 min and the final setting time from 65 to 40 min, (c) diminished the time in which the final strength was reached from 36 to less than 14 h. The tensile strength of this cement is 19±1% of its compressive strength. The optimum water/powder ratio as found in this study was 0.30 g/g.     

Development of strong and bioactive calcium phosphate cement as a light-cure organic–inorganic hybrid

In this research, light cured calcium phosphate cements (LCCPCs) were developed by mixing a powder phase (P) consisting of tetracalcium phosphate and dicalcium phosphate and a photo-curable resin phase (L), mixture of hydroxyethylmethacrylate (HEMA)/poly acrylic-maleic acid at various P/L ratios of 2.0, 2.4 and 2.8?g/mL. Mechanical strength, phase composition, chemical groups and microstructure of the cured cements were evaluated at pre-set times, i.e. before and after soaking in simulated body fluid (SBF). The proliferation of Rat-derived osteoblastic cells onto the LCCPCs as well as cytotoxicity of cement extracts were determined by cell counting and 3-{4,5-dimethylthiazol-2yl}-2,5-diphenyl-2H-tetrazolium bromide assay after different culture times. It was estimated from Fourier transforming infrared spectra of cured cements that the setting process is ruled by polymerization of HEMA monomers as well as formation of calcium poly-carboxylate salts. Microstructure of the cured cements consisted of calcium phosphate particles surrounded by polymerized resin phase. Formation of nano-sized needlelike calcium phosphate phase on surfaces of cements with P/L ratios of 2.4 and 2.8?g/mL was confirmed by scanning electron microscope images and X-ray diffractometry (XRD) of the cured specimen soaked in SBF for 21?days. Also, XRD patterns revealed that the formed calcium phosphate layer was apatite phase in a poor crystalline form. Biodegradation of the cements was confirmed by weight loss, change in molecular weight of polymer and morphology of the samples after different soaking periods. The maximum compressive strength of LCCPCs governed by resin polymerization and calcium polycarboxylate salts formation was about 80?MPa for cement with P/L ratio of 2.8?g/mL, after incubation for 24?h. The strength of all cements decreased by decreasing P/L ratio as well as increasing soaking time. The preliminary cell studies revealed that LCCPCs could support proliferation of osteoblasts cultured on their surfaces and no cytotoxic effect was observed for the extracts of them.     

Microwave assisted preparation of magnesium phosphate cement (MPC) for orthopedic applications: A novel solution to the exothermicity problem

There are two interesting features of this paper. First, we report herein a novel microwave assisted technique to prepare phosphate based orthopedic cements, which do not generate any exothermicity during setting. The exothermic reactions during the setting of phosphate cements can cause tissue damage during the administration of injectable compositions and hence a solution to the problem is sought via microwave processing. This solution through microwave exposure is based on a phenomenon that microwave irradiation can remove all water molecules from the alkaline earth phosphate cement paste to temporarily stop the setting reaction while preserving the active precursor phase in the formulation. The setting reaction can be initiated a second time by adding aqueous medium, but without any exothermicity. Second, a special emphasis is placed on using this technique to synthesize magnesium phosphate cements for orthopedic applications with their enhanced mechanical properties and possible uses as drug and protein delivery vehicles.The as-synthesized cements were evaluated for the occurrences of exothermic reactions, setting times, presence of Mg-phosphate phases, compressive strength levels, microstructural features before and after soaking in (simulated body fluid) SBF, and in vitro cytocompatibility responses. The major results show that exposure to microwaves solves the exothermicity problem, while simultaneously improving the mechanical performance of hardened cements and reducing the setting times. As expected, the cements are also found to be cytocompatible. Finally, it is observed that this process can be applied to calcium phosphate cements system (CPCs) as well. Based on the results, this microwave exposure provides a novel technique for the processing of injectable phosphate bone cement compositions.     

Penetration resistance and electrical resistivity of cement paste with superplasticizer

The purpose of this paper is to investigate the setting process and evolution of electrical resistivity of Portland cement pastes with constant water to cement ratio (w/c) of 0.3 and with different dosages of naphthalene superplasticizer (SP) from 0 to 1.2 %. The setting process of cement paste was monitored by the Vicat needle test. The depth of penetration was recorded and used to calculate the shear resistance generated by the cement paste. Electrical resistivity was measured by a non-contacting electrical resistivity apparatus. The hyperbolic curve of electrical resistivity versus time was plotted to determine the ultimate electrical resistivity. The results show that the addition of SP to the pastes with a fixed w/c can cause longer setting time and delay the evolution of electrical resistivity. The final setting time (t _f) and the occurring time of maximum rate of electrical resistivity (t _r) were both delayed when the dosage of SP was increased. This may indicates that the electrical resistivity measurement can be used to monitor the setting process of cement. The compressive strength at 28 days and the ultimate electrical resistivity show a same tendency for the cement pastes with different dosages of SP. Thus, it would be possible to predict the compressive strength of hardened cement paste by its ultimate electrical resistivity.     

纳米Fe2O3水泥基复合材料制备的响应曲面研究

配制三种常用高效减水剂溶液,观察纳米Fe_2O_3在三种溶液中的分散效果;基于响应曲面正交旋转组合设计,并考虑纳米Fe_2O_3掺量(Nano-Fe_2O_3content,NFC)、聚羧酸减水剂母液掺量(Polycarboxylate superplasticizer content,PSC)、水胶比(Water-binder rational,WBR)三因素,研究水泥硬化浆体的配比参数与强度间的响应曲面,分析各参数对强度的影响规律。结果表明:纳米Fe_2O_3在聚羧酸高性能减水剂母液溶液中分散效果最好;当配比参数NFC=0.027、PSC=0.017 5、WBR=0.28时,水泥硬化浆体具有较高的强度;从统计学与实践角度来看,响应曲面方程具有较高的可靠性和精度;抗压强度随PSC的增大先增大后减小,随WBR的增大而减小,随NFC的增大而增大;最佳数值附近存在最适宜配方和掺量,使水泥基复合材料具有较好的强度和施工性;响应曲面法(Response surface methodology,RSM)可广泛应用于新型水泥基复合材料的研发领域,发展前景广阔。     

Calcium–phosphate–silicate composite bone cement: self-setting properties and in vitro bioactivity

In this study, a novel low temperature setting calcium phosphate–silicate cement was obtained by mixing CaHPO₄ · 2H₂O (DCPD) and Ca₃SiO₅ (C₃S) with 0.75 M sodium phosphate buffers (pH = 7.0) as liquid phase. The self-setting properties of the obtained DCPD/C₃S paste with liquid to powder ratio (L/P) of 0.6 ml/g, such as setting times, injectability, degradability and compressive strength were investigated and compared with that of DCPD/CaO cement system. The results indicated that, with the weight ratio of C₃S varied from 20% to 40%, the workable DCPD/C₃S pastes could set within 20 min, and the hydrated cement showed significantly higher compressive strength (around 34.0 MPa after 24 h) than that of the DCPD/CaO cement system (approximately 10.0 MPa). Furthermore, the in vitro pH value of the cements was investigated by soaking in simulated body fluid (SBF) for 12 h, and the result indicated that the DCPD/C₃S did not induce significant increase or decrease of pH value in SBF. Additionally, the composite cement possesses better ability to support and stimulate cell proliferation than the DCPD/CaO cement. With good hydraulic properties, improved biocompatibility and moderate degradability, the novel DCPD/C₃S bone cement may be a potential candidate as bone substitute.     

磷酸钙骨粘合剂的研究

在柠檬酸中添加壳聚糖配成的固化液与磷酸钙骨水泥(CPC)调和制备的骨修复材料具有类似口香糖的胶状特性, 可应用于碎骨粘结, 称之为磷酸钙骨粘合剂(CPCBA)。本研究考察了柠檬酸的含量对抗压强度、固化时间、水化产物和粘结强度的影响, 同时对该体系进行了初步的体外生物学评价。结果显示, 加入柠檬酸可以缩短固化时间并且时间可以通过柠檬酸的含量进行调控, 同时也改善了抗水性能。壳聚糖可以与骨水泥中的钙离子发生螯合作用, 可以增加界面的粘结强度。小鼠原成骨细胞(MC3T3-E1)在其表面粘附良好, 该体系骨水泥有望取代PMMA成为新的骨粘结剂。