Direct ink writing of vancomycin-loaded polycaprolactone/ polyethylene oxide/ hydroxyapatite 3D scaffolds

Novel inks were formulated by dissolving polycaprolactone (PCL), a hydrophobic polymer, in organic solvent systems; polyethylene oxide (PEO) was incorporated to extend the range of hydrophilicity of the system. Hydroxyapatite (HAp) with a weight ratio of 55–85% was added to the polymer-based solution to mimic the material composition of natural bone tissue. The direct ink writing (DIW) technique was applied to extrude the formulated inks to fabricate the predesigned tissue scaffold structures; the influence of HAp concentration was investigated. The results indicate that in comparison to other inks containing HAp (55%, 75%, and 85%w/w), the ink containing 65% w/w HAp had faster ink recovery behavior; the fabricated scaffold had a rougher surface as well as better mechanical properties and wettability. It is noted that the 65% w/w HAp concentration is similar to the inorganic composition of natural bone tissue. The elastic modulus values of PCL/PEO/HAp scaffolds were in the range of 4–12 MPa; the values were dependent on the HAp concentration. Furthermore, vancomycin as a model drug was successfully encapsulated in the PCL/PEO/HAp composite scaffold for drug release applications. This paper presents novel drug-loaded PCL/PEO/HAp inks for 3D scaffold fabrication using the DIW printing technique for potential bone scaffold applications.     

Extrusion-based 3D printing of gelatin methacryloyl with nanocrystalline hydroxyapatite

The particle shape and size distribution of inorganic fillers play a crucial role in the scaffold buildability when those are incorporated in the viscoelastic polymers. In order to address this issue, the phase pure rod-shaped nanocrystalline hydroxyapatite (HAp) powders with varying particle sizes and shapes were synthesized by a one-pot hydrothermal method without any regulatory surfactant at an initial solution pH of 9. As-synthesized nanocrystalline HAp particles (0–5 wt%) were incorporated into 15 wt% pre-cross-linked gelatin methacryloyl (GelMA) hydrogel matrix to fabricate a predesigned scaffold architecture using a custom-made 3D bioprinter. The printing parameters (nozzle diameter, extrusion pressure, and printing speed) were optimized for each composition. The biophysical properties (uniaxial compression behavior, swelling ratio, and in vitro degradation) of the composite hydrogel scaffolds were critically analyzed to unravel the role of nano-sized HAp addition. The compression strength and modulus were substantially improved, while the rate of water uptake and bio-enzymatic degradation significantly reduced with HAp content. We propose that the inorganic–organic nanocomposite hydrogel could be efficiently assembled to formulate a potential bioink for 3D bioprinting applications toward tissue regeneration.     

Phase Analysis and Thermal Stability of Hot Isostatically Pressed Zirconia–Hydroxyapatite Composites

Composites of zirconia and hydroxyapatite (OHAp) have been processed via hot isostatic pressing (HIP) or sintering in air. When the composites were sintered in air at a temperature of 950°C, decomposition of the OHAp to tricalcium phosphate occurred. Using the HIP technique, composites without any detectable degradation of the OHAp phase were produced at 1200°C. The reactivity between zirconia and OHAp was dependent on both the amount of water lost from OHAp and the geometry of the interaction. The phase composition of the materials prepared was evaluated from their powder X-ray diffraction patterns, and their microstructures were studied via electron microscopy.     

Preparation of Porous Ca10(PO4)6(OH)2 and β-Ca3(PO4)2 Bioceramics

Submicrometer-sized, pure calcium hydroxyapatite (HA, (Ca₁₀(PO₄)₆(OH)₂)) and β-tricalcium phosphate (β-TCP, Ca₃(PO₄)₂) bioceramic powders, that have been synthesized via chemical precipitation techniques, were used in the preparation of aqueous slurries that contained methyl cellulose to manufacture porous (70%–95% porosity) HA or β-TCP ceramics. The pore sizes in HA bioceramics of this study were 200–400 μm, whereas those of β-TCP bioceramics were 100–300 μm. The pore morphology and total porosity of the HA and β-TCP samples were investigated via scanning electron microscopy, water absorption, and computerized tomography.     

以葡萄糖为造孔剂制备多孔羟基磷灰石涂层

采用电泳沉积方法在钛基材表面制得羟基磷灰石(hydroxyapatite,HA)/葡萄糖复合涂层,经烧结处理得到多孔HA涂层。采用红外光谱仪、扫描电镜、X射线衍射和热重分析表征了涂层的组成、表面形貌、物相组成及热稳定性,黏结-拉伸实验测定涂层与基体的结合强度,人体模拟体液(simulated body fluid,SBF)浸泡测定涂层的生物亲合性。结果表明:经700℃烧结处理,复合涂层中的葡萄糖微粒热分解得到多孔HA涂层,孔径为2～20μm,涂层与基体的结合强度可达17.6MPa;在1.5倍SBF(各离子浓度为SBF的1.5倍)中浸泡5d后,多孔HA涂层表面碳磷灰石化,呈现良好的生物亲合性。     

无氟防龋体系浅析

牙膏无氟防龋体系应用的防龋材料主要有纳米级羟基磷灰石（HAP）、免疫球蛋白（IgY）和中药如两面针、厚朴、茶多酚和蜂胶等.纳米级羟基磷灰石可以使脱矿的牙釉质再矿化,提高牙釉质抗龋能力;免疫球蛋白对变形链球菌和牙菌斑的形成有较好的抑制作用.检测试验或临床结果表明,两面针、厚朴、茶多酚和蜂胶等中药对致龋菌和牙菌斑的形成的抑制效果也比较好,这些都可以组成效果比较好的无氟防龋体系.     

煅烧对离心雾化制备羟基磷灰石微球结构和性能的影响

在较低温度下对离心喷雾干燥所制备的羟基磷灰石微球进行煅烧,并利用X射线衍射仪、扫描电子显微镜、傅里叶红外光谱仪、比表面积分析仪以及激光粒度分析仪等分析手段,研究了煅烧对羟基磷灰石微球的相组成、微观结构以及比表面积、孔体积和粒度等性能的影响。结果表明,经400℃煅烧,微球比表面积、孔体积及其粒度均明显增大;随煅烧温度升高,比表面积和孔体积均略有降低。     

多孔ZrO2/HA医用钛合金微弧氧化复合陶瓷膜层生物力学性能研究

为了获得具有生物力学性能的陶瓷膜层材料并满足临床医学上的需要。以Ti6Al4V钛合金为基体材料,通过微弧氧化工艺方法在电解液中制备氧化锆和羟基磷灰石复合陶瓷膜层材料。利用能谱分析仪和扫描电镜分析膜层结构特点。建立并改进了多孔性膜层力学性能数学模型,利用理论计算与实验测试相结合的方法对膜层相关生物力学性能进行了研究。实验结果表明,氧化锆/羟基磷灰石医用钛合金复合陶瓷能够取得比单一的羟基磷灰石陶瓷膜层更好的生物力学性能。生物陶瓷力学性能与孔隙率及生成的新相有关,通过实验与理论模型相结合的方法能够更好的对生物陶瓷膜层力学性能进行研究,所建立数学模型科学合理,具有一定理论意义。     

Effect of the addition ZrO2–Al2O3 on nanocrystalline hydroxyapatite bending strength and fracture toughness

Nanocrystalline hydroxyapatite powder has been synthesized from a Ca(NO₃)₂·4H₂O and (NH₄)₂HPO₄ solution by the precipitation method. In the next step we prepared ZrO₂–Al₂O₃ powder. After preparation, the powder was dried at 80 °C and calcined at 1200 °C for 1 h. Various amounts (HAP–15 wt% ZA, HAP–30 wt% ZA) of powder were mixed with the hydroxyapatite by ball milling. The powder mixtures were pressed and sintered at 1000 °C, 1100 °C and 1200 °C for 1 h. In order to study the structural evolution, X-ray diffraction (XRD) was used. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were used to estimate the particle size of the powder and observe fracture surfaces. Results show that the bending strength of pressed nanocrystalline HAP was improved significantly by the addition 15 wt% of ZrO₂–Al₂O₃ powders at 1200 °C, but the fracture toughness was not changed, however when 30 wt% of ZA powders were added to nanocrystalline HAP, the bending strength and fracture toughness of the specimens decreased at all sintering temperature.     

Behaviour of bone origin hydroxyapatite at elevated temperatures and in O2 and CO2 atmospheres

In the present work the behaviour of HAp extracted from pig bones at elevated temperatures up to 1000 °C in O₂ and CO₂ atmospheres has been studied. It has been found that CO₂ atmosphere arrests HAp decomposition. Chemical analysis and infrared spectroscopy reveal that no free CaO appears and no decrease of CO₃⁻² group concentration occurs in the material calcined in CO₂ atmosphere. In the O₂ atmosphere at elevated temperatures, CaO and CO₂ are emitted from the samples, although the remaining material retains the HAp structure as indicated by the X-ray diffraction.