磷酸钙骨水泥大孔径多孔组织工程支架的制备及其纤维增强

采用粒子溶出造孔法, 用棒状谷氨酸钠晶体作为造孔粒子, 制备磷酸钙骨水泥多孔支架, 研究了造孔粒子含量和多孔支架孔隙率之间的关系, 并加入甲壳素纤维来改善支架材料的力学性能. 结果表明, 支架材料的孔隙率可达(79.8±2.3)%,孔隙直径100～600μm; 复合纤维后支架的强度提高了3～4倍, 断裂应变显著提高, 可作为非承重部位骨缺损修复的骨组织工程支架材料.     

多孔 n2 HA/ PA26复合材料的制备及性能

采用注塑方法制备了多孔纳米磷灰石/聚酰胺26 (n2 HA/ PA26) 复合材料 , 采用 SEM、XRD、IR、 力学性能测试考察了多孔材料的性能。结果发现 : 多孔纳米磷灰石/聚酰胺26复合材料的孔隙分布均匀 , 贯通性良好 , 孔的尺寸约为 100～700μm , 平均孔径约 300～500μm , 大孔壁上有丰富的微孔 ; 所得多孔复合材料的孔隙率可控 , 总孔隙率最高可达 881 6 %; 多孔材料的总孔隙率降低 , 则开孔率随之降低 ; 多孔纳米磷灰石/聚酰胺26 复合材料的抗压强度为 1. 1～15. 6 MPa , 压缩模量为 0. 4～1. 4 GPa ; 在总孔隙率相近的条件下 , 多孔材料的抗压强度随 n2 HA质量分数增加而升高; 发泡剂和发泡过程对组成纳米磷灰石/聚酰胺26复合材料的两组元材料的性质和结构无影响。这种多孔材料可望作为人体非承重部位的植入骨修复体和组织工程支架使用。     

纳米羟基磷灰石/聚酰胺多孔支架材料的制备及性能研究

使用多种致孔剂采用粒子沥滤法制备了纳米羟基磷灰石／聚酰胺多孔支架材料，用IR、XRD、SEM等手段对多孔复合材料的组成结构及形貌进行了表征，并检测了其物理性能指标。结果表明，复合材料中两相分散均匀，且发生了界面结合；材料的孔隙率与致孔剂的含量成正比，支架中大孔与微孔并存且相互贯通；以NaCl作致孔剂且孔隙率达到80％左右时的支架材料可以同时满足组织工程对孔隙率和力学强度的双重要求。     

超临界CO2中制备聚乳酸/羟基磷灰石复合支架材料

利用盐析/超临界CO2复合方法制备了一系列的PDLLA/HA三维多孔支架材料.利用这种方法可以避免使用有机溶剂、较高温度和降低常规气体发泡法所需的较长时间.制备的三维多孔支架的孔隙率最高达91%,孔与孔之间相互连通,孔分布均匀,孔径大小为100～300μm,抗压强度明显增加.详细研究了CO2压力、温度、浸润时间以及致孔剂含量等条件的变化对复合材料形貌和孔隙率的影响.     

骨组织工程用纳米羟基磷灰石/ 壳聚糖多孔支架材料的制备及性能表征

以16.7%(质量分数)的柠檬酸水溶液作溶剂,通过粒子沥滤法制备了 n HA/CS多孔材料,并对其进行了IR、XRD、SEM、孔隙率及力学性能测试。结果表明n HA/CS复合材料中羟基磷灰石呈弱结晶状态,复合前后两组分的化学组成未发生显著变化,但两相间发生了相互作用。多孔材料呈高度多孔结构,孔壁上富含微孔,孔间贯通性高;复合材料/致孔剂质量比为1时,多孔材料的孔隙率为 53%,其抗压强度可达17 MPa左右,可以满足组织工程支架材料的要求。     

PLA-PEG共聚物三维多孔支架的制备及表征

将D,L-丙交酯(D,L-LA)与聚乙二醇(PEG)共聚制备了一系列共聚物,并用IR、GPC和1H-NMR对其进行了表征.在此基础上,采用溶剂浇铸-柱子沥滤技术和层叠技术制备了具有一定空间形状的三维多孔组织工程支架,并研究了致孔剂颗粒尺寸及其用量对多孔支架的孔径、孔隙率的影响.结果表明,PLA-PEG共聚物的分子量随着原料中PEG含量的增加而减小;以PLA-PEG共聚物为原料制备多孔支架时,孔径的大小与致孔剂颗粒尺寸有一定的对应关系,孔隙率随着致孔剂用量的增加而增加;采用层叠技术制备的具有一定形状的三维多孔支架符合组织工程对支架材料的一般要求.     

浆料粘度对纳米羟基磷灰石/聚酰胺66复合支架孔结构与力学性能的影响

浆料粘度是热诱导相分离法制备支架材料的关键因素,采用不同粘度的纳米羟基磷灰石/聚酰胺66(n-HA/PA66)复合浆料制备了相应的n-HA/PA66多孔支架,并对不同粘度浆料制备支架材料的泡孔结构和力学性能等进行了对比研究。结果表明,浆料粘度对n-HA/PA66复合多孔支架的孔径、孔径分布、孔隙率、开孔率、力学强度等性能有显著的影响。随着浆料粘度的增大,制备支架的孔径、孔隙率、开孔率逐渐减小,而力学强度却逐渐增大。当浆料粘度为330Pa.s时,制备出的n-HA/PA66复合多孔支架综合性能最好,其孔径主要分布在200～500μm,平均孔径(324±67.1)μm,孔隙率为(75±1.6)%,开孔率为(59±2.5)%,抗压强度为(2.12±0.90)MPa,能够较好地满足骨组织工程支架材料对孔径、孔隙率和力学性能的要求。     

凝胶成型法制备多孔羟基磷灰石生物陶瓷及其性能研究

介绍了一种新型的凝胶成型法来制备多孔羟基磷灰石支架材料.利用体视显微镜等对制备的多孔羟基磷灰石孔洞结构进行观察.结果表明这种方法可以很好地控制多孔支架材料的孔洞结构与大小.孔分布均匀且内部连通,孔径在300μm～500μm之间.体外模拟试验表明羟基磷灰石具有良好的生物相容性,这种孔洞结构的特点更有利于骨细胞的生长.对压缩性能和孔隙率的测定结果表明,压缩强度和孔隙率随不同工艺参数的变化而变化.     

有机泡沫法制备多孔羟基磷灰石生物支架

采用有机泡沫法制备了多孔羟基磷灰石(HA)支架,考察了水解预处理工艺、粘结剂聚乙烯醇(PVA)和固相HA的含量对孔隙率的影响,利用扫描电子显微镜(SEM)观察了支架的孔结构.研究结果表明,采用有机泡沫法可获得孔径均匀的多孔HA支架;有机泡沫(海绵)模板经过水解处理后,其挂浆量增加;支架的孔隙率随PVA含量的增加而增大;浆料中固相HA含量在70%左右为宜,此时材料的孔隙率最大.     

软骨修复用 HA/PU多孔支架材料的制备与表征

研制了用于软骨的组织工程的HA／PU多孔支架材料，采用气体发泡法制备了三维贯通的多孔HA／PU支架材料，通过XRD、IR对其结构组成进行了分析，用DSC测量了玻璃化转变温度，用SEM观察了微观形貌和孔径尺寸，并计算了孔隙大小和孔隙率的分布．通过燃烧试验分析了HA／PU复合材料中HA的百分含量，并对力学性能进行了评估．结果表明，多孔HA／PU复合支架材料，其大小孔道相互贯通，孔径范围在100-800μm，大孔中含有微孔，孔隙率可达到78％-80％，HA含量达到30wt％，力学强度达到271kPa．多孔HA／PU复合材料具有一定的弹性，是一类性能很好的可望用于软骨修复的支架材料．     

骨组织工程用硅胶/掺锶β-磷酸三钙/硫酸钙复合多孔支架的制备与性能研究

以掺锶β-磷酸三钙/硫酸钙为原料,利用搅拌喷雾干燥法制备出掺锶β-磷酸三钙/硫酸钙复合小球,再将硅胶与制备的复合小球复合,通过在模具中堆垛聚集的方法,制备出硅胶/掺锶β-磷酸三钙/硫酸钙复合生物支架。采用XRD,SEM,FT-IR等方法分析制得复合多孔支架的成分、形貌以及结构特征,并研究复合生物支架的降解性、孔隙率、力学性能和细胞毒性等。结果表明:该复合多孔生物支架具有一定的不规则孔洞结构,小球与小球之间的孔隙约为0.2~1mm,而每个小球上也有大量的微孔,孔径在50~200μm之间,且平均孔隙率达到62%,基本能满足骨组织工程支架对孔隙率的要求;该复合多孔支架无细胞毒性,其降解周期约为80天,抗压强度约为0.1MPa,因此该支架在非承重骨组织修复方面具有良好的应用前景。     

Sol–gel method to fabricate CaP scaffolds by robocasting for tissue engineering

Highly porous calcium phosphate (CaP) scaffolds for bone-tissue engineering were fabricated by combining a robocasting process with a sol–gel synthesis that mixed Calcium Nitrate Tetrahydrate and Triethyl Phosphite precursors in an aqueous medium. The resulting gels were used to print scaffolds by robocasting without the use of binder to increase the viscosity of the paste. X-ray diffraction analysis confirmed that the process yielded hydroxyapatite and β-tricalcium phosphate biphasic composite powders. Thus, the scaffold composition after crystallization of the amorphous structure could be easily modified by varying the initial Ca/P ratio during synthesis. The compressive strengths of the scaffolds are ~6 MPa, which is in the range of human cancellous bone (2–12 MPa). These highly porous scaffolds (~73 vol% porosity) are composed of macro-pores of ~260 μm in size; such porosity is expected to enable bone ingrowth into the scaffold for bone repair applications. The chemistry, porosity, and surface topography of such scaffolds can also be modified by the process parameters to favor bone formation. The studied sol–gel process can be used to coat these scaffolds by dip-coating, which induces a significant enhancement of mechanical properties. This can adjust scaffold properties such as composition and surface morphology, which consequently may improve their performances.     

Morphological,mechanical, and biocompatibility characterization of macroporous alumina scaffolds coated with calcium phosphate/PVA

In bone tissue engineering, a highly porous artificial extracellular matrix or scaffold is required to accommodate cells and guide the tissue regeneration in three-dimension. Calcium phosphate (CaP) ceramics are widely used for bone substitution and repair due to their biocompatibility, bioactivity, and osteoconduction. However, compared to alumina ceramics, either in the dense or porous form, the mechanical strength achieved for calcium phosphates is generally lower. In the present work, the major goal was to develop a tri-dimensional macroporous alumina scaffold with a biocompatible PVA/calcium phosphate coating to be potentially used as bone tissue substitute. This approach aims to combine the high mechanical strength of the alumina scaffold with the biocompatibility of calcium phosphate based materials. Hence, the porous alumina scaffolds were produced by the polymer foam replication procedure. Then, these scaffolds were submitted to two different coating methods: the biomimetic and the immersion in a calcium phosphate/polyvinyl alcohol (CaP/PVA) slurry. The microstructure, morphology and crystallinity of the macroporous alumina scaffolds samples and coated with CaP/PVA were characterized by X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM/EDX) analysis. Also, specific surface area was assessed by BET nitrogen adsorption method and mechanical behavior was evaluated by axial compression tests. Finally, biocompatibility and cytotoxicity were evaluated by VERO cell spreading and attachment assays under SEM. The morphological analysis obtained from SEM photomicrograph results has indicated that 3D macroporous alumina scaffolds were successfully produced, with estimated porosity of over 65% in a highly interconnected network. In addition, the mechanical test results have indicated that porous alumina scaffolds with ultimate compressive strength of over 3.0 MPa were produced. Concerning to the calcium phosphate coatings, the results have showed that the biomimetic method was not efficient on producing a detectable layer onto the alumina scaffolds. On the other hand, a uniform and adherent inorganic–organic coating was effectively formed onto alumina macroporous scaffold by the immersion of the porous structure into the CaP/PVA suspension. Viable VERO cells were verified onto the surface of alumina porous scaffold samples coated with PVA–calcium phosphate. In conclusion, a new method was developed to produce alumina with tri-dimensional porous structure and uniformly covered with a biocompatible coating of calcium phosphate/PVA. Such system has high potential to be used in bone tissue engineering.     

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.     

原位自发泡制备磷酸钙/聚氨酯复合骨修复支架

磷酸钙/聚氨酯(CaP/PU)复合骨修复支架制备过程中随着材料体系粘度逐渐增大, 后期加入的发泡剂难于均匀分散, 影响支架孔隙率及孔结构均匀性。本研究在CaP/PU材料合成过程中将发泡剂水以磷酸氢钙结晶水合物(DCPD)的形式均匀复合在材料中, 在一定条件下释放结晶水与聚氨酯(PU)中的异氰酸根反应生成CO₂, 实现自发泡成型。实验结果显示, 90 ℃条件下自发泡制备的CaP/PU支架孔隙率高、孔结构均匀、贯通性好。将90 ℃发泡成型的CaP/PU多孔支架在110 ℃再熟化处理, 可提高支架的力学性能高达1倍以上。该方法简便易行, 为聚氨酯基多孔支架的制备提供了新思路。     

Preparation of flexible bone tissue scaffold utilizing sea urchin test and collagen

Gonads of sea urchin are consumed in Japan and some countries as food and most parts including its tests are discarded as marine wastes. Therefore, utilization of them as functional materials would reduce the waste as well as encourage Japanese fishery. In this study, magnesium containing calcite granules collected from sea urchin tests were hydrothermally phosphatized and the obtained granules were identified as approximately 82% in mass of magnesium containing β-tricalcium phosphate and 18% in mass of nonstoichiometric hydroxyapatite, i.e., a biphasic calcium phosphate, maintaining the original porous network. Shape-controlled scaffolds were fabricated with the obtained biphasic calcium phosphate granules and collagen. The scaffolds showed good open porosity (83.84%) and adequate mechanical properties for handling during cell culture and subsequent operations. The MG-63 cells showed higher proliferation and osteogenic differentiation in comparison to a control material, the collagen sponge with the same size. Furthermore, cell viability assay proved that the scaffolds were not cytotoxic. These results suggest that scaffold prepared using sea urchin test derived calcium phosphate and collagen could be a potential candidate of bone void fillers for non-load bearing defects in bone reconstruction as well as scaffolds for bone tissue engineering.     

Approaches to the fabrication of calcium phosphate-based porous materials for bone tissue regeneration

This paper reviews advances in the fabrication of calcium phosphate materials for injured bone tissue regeneration. We examine the key features of rapid prototyping for the fabrication of porous ceramic scaffolds with tailored architectures, the technology of biopolymer-based composite materials reinforced with calcium phosphate particles, and the fabrication of porous scaffolds via cement route.     

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.     

In Vitro Characterizations of PLLA/β-TCP Porous Matrix Materials and RMSC-PLLA-β-TCP Composite Scaffolds

To develop a novel degradable poly (L-lactic acid)/β-tricalcium phosphate (PLLA/β-TCP) bioactive materials for bone tissueengineering, β-TCP powder was produced by a new wet process. Porous scaffolds were prepared by three steps, i.e. solventcasting, compression molding and leaching stage. Factors influencing the compressive strength and the degradation behaviorof the porous scaffold, e.g. weight fraction of pore forming agent-sodium chloride (NaCl), weight ratio of PLLA: β-TCP,the particle size of β-TCP and the porosity, were discussed in details. Rat marrow stromal cells (RMSC) were incorporatedinto the composite by tissue engineering approach. Biological and osteogenesis potential of the composite scaffold weredetermined with MTT assay, alkaline phosphatase (ALP) activity and bone osteocalcin (OCN) content evaluation. Resultsshow that PLLA/β-TCP bioactive porous scaffold has good mechanical and pore structure with adjustable compressive strengthneeded for surgery. RMSCs seeding on porous PLLA/     

Study on β-TCP Coated Porous Mg as a Bone Tissue Engineering Scaffold Material

Three-dimensional honeycomb-structured magnesium (Mg) scaffolds with interconnected pores of accurately controlled pore size and porosity were fabricated by laser perforation technique. Biodegradable and bioactive β-tricalcium phosphate (β-TCP) coatings were prepared on the porous Mg to further improve its biocompatibility, and the biodegradation mechanism was simply evaluated in vitro. It was found that the mechanical properties of this type of porous Mg significantly depended on its porosity. Elastic modulus and compressive strength similar to human bones could be obtained for the porous Mg with porosity of 42.6%-51%. It was observed that the human osteosarcoma cells (UMR106) were well adhered and proliferated on the surface of the β-TCP coated porous Mg, which indicates that the β-TCP coated porous Mg is promising to be a bone tissue engineering scaffold material.