Biomimetic strengthening polylactide scaffold materials for bone tissue engineering

In this paper, a new polylactide (PLA)-based scaffold composite by biomimetic synthesis was designed. The novel composite mainly consists of nano-hydroxyapatite (n-HA), which is the main inorganic content in natural bone tissue for the PLA. The crystal degree of the n-HA in the composite is low and the crystal size is very small, which is similar to that of natural bone. The compressive strength of the composite is higher than that of the PLA scaffold. Using the osteoblast culture technique, we detected cell behaviors on the biomaterial in vitro by SEM, and the cell affinity of the composite was found to be higher than that of the PLA scaffold. The biomimetic three-dimensional porous composite can serve as a kind of excellent scaffold material for bone tissue engineering because of its microstructure and properties. Translated from Journal of Hunan University (Natural Sciences), 2006, 33(2) (in Chinese)     

Preparation and characterization of calcium hydroxyapatite and balloon-like calcium phosphate particles from forced hydrolysis of Ca(OH)2–triphosphate solution

Calcium phosphate particles were prepared by aging a solution of dissolved Ca(OH)₂ and sodium triphosphate (sodium tripolyphosphate, Natpp: Na₅P₃O₁₀) at 100–150 °C for 18 h in a Teflon-lined screw-capped Pyrex test tube. Large spherical and/or small aggregated spherical particles were precipitated with an extremely fast rate of reaction under 100 °C. The large spherical particles were amorphous and the small aggregated ones were α-CaNa₂P₂O₇^.4H₂O. The former amorphous ones crystallized to β-Ca₂P₂O₇ after being calcined above 600 °C. Calcium hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, Hap), with rod-like and ellipsoidal or spherical aggregated shapes, was successfully produced using polyphosphates as a source of orthophosphate ions. Time resolved TEM measurement revealed that the crystallization of Hap particles takes place on the surface of tiny amorphous particles precipitated before aging. The tiny particles played the role of nuclei for Hap crystallization. The aging temperature drastically varied the particle shape under conditions for producing uniform amorphous spherical particles; solid spherical particles were produced with an aging temperature of up to 120 °C, whilst transparent balloon-like hollow spheres were precipitated at 125 °C. Finally, fully transparent balloon-like hollow spheres were produced with mere trace amounts of small rod-like particles after aging the solution above 127 °C. The time resolved TEM observation and ICP-AES measurements revealed that the balloon-like hollow spheres were produced by dissolving the interior of solid spherical particles after reinforcing their shell by the adsorption of unhydrolyzed tpp and/or pyrophosphate (pp) ions, which are the hydrolysis product of tpp. The balloon-like hollow spheres of calcium phosphate may have the potential use as drug delivery vehicles and have biocompatibility advantages.     

Pd-Cu/羟磷灰石的制备及常温常湿CO催化氧化性能

通过溶胶-凝胶法(SG)和水热法(HT)合成了羟磷灰石载体(HAP-SG, HAP-HT), 以浸渍法制备负载型Pd-Cu/HAP催化剂(PC-SG, PC-HT), 并考察其常温常湿条件下CO催化氧化反应性能. 采用电感耦合等离子体发射光谱(ICP-OES)、 N₂物理吸附-脱附、 X射线衍射(XRD)、 傅里叶变换红外光谱(FTIR)、 H₂程序升温还原(H₂-TPR)、 CO₂程序升温脱附(CO₂-TPD)、 X射线光电子能谱(XPS)和CO原位漫反射傅里叶变换红外光谱(in-situ DRIFTS)等手段对Pd-Cu/HAP催化剂进行了表征. 结果表明, 相比于PC-SG, PC-HT具有较大比表面积和孔容, 含有较多的Cu₂Cl(OH)₃物种且与Pd物种和载体直接产生了较强的相互作用; 而且PC-HT表面含有较强CO活化能力的Pd⁺物种和更多具有较强氧化还原性质的Cu⁺物种, 以及较少数量和较低强度的碱性位点, 因而表现出更加优异的常温常湿条件下CO催化氧化性能.     

HA/ZnO/SiO2梯度涂层材料的制备及其体外抗菌活性测试

采用区带电泳法电泳羟基磷灰石（HA）、壳聚糖（CS）、ZnO和SiO₂悬浊液,接着施予反向电场进行电泳沉积从而在钛基材表面获得HA/CS/ZnO/SiO₂复合涂层材料,而后经710℃焙烧2 h后得到HA/ZnO/SiO₂涂层材料（Z1）。同时也仅用电泳沉积法直接制得HA/ZnO/SiO₂涂层材料（E1）作为对比。X射线能谱分析发现Si和Zn两种元素在Z1的径向上均呈现梯度分布,初步说明Z1具有一定的梯度。结合扫描电子显微镜、粉末X射线衍射、傅里叶红外光谱等手段对2种材料进行表征,发现Z1的各种性能较E1更为优异,主要表现在Z1与钛基材表面的结合强度达31.2 MPa,且在HEPES模拟体液中培养14 d后Z1表面碳磷灰石化程度更加完全。另外,抑菌实验发现Z1粉末对大肠杆菌和金黄色葡萄球菌的抑菌率分别为81.7%和89.4%。     

Electrophoretic Deposition of Hydroxyapatite Coatings on Metal Substrates: A Nanoparticulate Dual-Coating Approach

Hydroxyapatite coatings can be readily deposited on metal substrates by electrophoretic deposition. However, subsequent sintering is highly problematic owing to the fact that temperatures in excess of 1100°C are required for commercial hydroxyapatite powders to achieve high density. Such temperatures damage the metal and induce metal-catalysed decomposition of the hydroxyapatite. Furthermore, the firing shrinkage of the hydroxyapatite coating on a constraining metal substrate leads to severe cracking. The present study has overcome these problems using a novel approach: the use of aged nanoparticulate hydroxyapatite sols (lower sintering temperature) and a dual coating strategy that overcomes the cracking problem. Dual layers of uncalcined hydroxyapatite (HAp) powder were electrophoretically coated on Ti, Ti6Al4V and 316L stainless steel metal substrates, sintered at 875–1000°C, and characterised by SEM and XRD, and interfacial shear strength measurement. Dual coatings on stainless steel had an average high bond strength (about 23 MPa), and dual coatings on titanium and titanium alloy had moderate strengths (about 14 and 11 MPa, respectively), in comparison with the measured shear strength of bone (35 MPa). SEM and XRD demonstrated that the second layer blended seamlessly with the first and filled the cracks in the first. The superior result on stainless steel is attributed to a more appropriate thermal expansion match with hydroxyapatite, the thinner oxide layer, or a combination of these factors.     

铒掺杂羟基磷灰石的荧光及其生物矿化性能

通过共沉淀法制备铒掺杂羟基磷灰石（Er-HAP）颗粒,应用Materials Studio模拟与X射线衍射、扫描电镜-能量色散谱、X射线光电子能谱和荧光光谱分析对其晶体结构、表面化学成分及其荧光性能进行表征。结果表明,离子半径稍小的Er³⁺会竞争性占据HAP晶格中一个Ca²⁺位点,在340 nm波长激发下,Er-HAP颗粒能在419 nm（紫色）、458 nm（蓝色）、501 nm（绿色）和535 nm（绿色）处发出很强的特征荧光,光致发光显示的4个发光带相应归属于⁴F_3/2→⁴I_15/2、⁴F_5/2→⁴I_15/2、⁴F_7/2→⁴I_15/2和⁴S_3/2→⁴I_15/2过渡态。相比掺杂量（物质的量分数）1% 的Er-HAP,掺杂量9% 的Er-HAP颗粒表面矿化速度和成骨性能均明显下降,即当Er掺杂量在约1% 时,其Er-HAP生物矿化能力相对较强。     

载银羟基磷灰石抗菌粉体和陶瓷的制备及抗菌性能

采用水热法一步合成载银羟基磷灰石抗菌粉体(Ag-HA),并将其应用于抗菌陶瓷的制备。研究结果表明水热条件下HA实际载银量与AgNO₃加入量存在较好的线性关系。XRD和TEM分析结果显示Ag-HA与HA具有相同的晶体结构,水热条件下Ag⁺取代Ca²⁺在HA晶体中的位置,生成Ag_xCa_10-x(PO₄)₆(OH)₂。Ag-HA长度随Ag⁺掺入量的增加而增大,当Ag⁺掺入量增加至1.50%时,Ag-HA由棒状生长为晶须状。选择4.50% Ag-HA作为抗菌粉体,其掺入量为9wt%时,陶瓷的抗菌率>99.9%,此时釉料中Ag₃PO₄含量为0.56%,低于目前研究中釉料中Ag₃PO₄添加量(2wt%~4wt%),不但在一定程度上解决了抗菌陶瓷产品成本较高的问题,而且满足JC/T 897-2002(抗菌陶瓷制品抗菌性能)对抗菌陶瓷抗菌性能的要求。     

改性羟基磷灰石/聚乳酸(PLLA)复合材料的制备及细胞毒性

制备了一种表面接枝聚(γ-苄基-L-谷氨酸)的改性纳米羟基磷灰石(PBLG-g-HA),利用红外光谱(FT-IR)、X射线光电子能谱(XPS)证明了聚(γ-苄基-L-谷氨酸)(PBLG)成功的接枝在羟基磷灰石表面,TGA结果显示PBLG的接枝量为33.6%。通过溶剂复合法制得了PBLG-g-HA/PLLA复合材料,并通过MTT法对所制备的复合材料的细胞毒性进行了研究。结果表明,PBLG-g-HA/PLLA复合材料具有良好的生物相容性、能够促进成骨细胞增殖。更多还原     

羟基磷灰石/活性炭复合吸附剂的制备及其除氟性能研究

采用羟基磷灰石(HAP)和活性炭(AC)共混,经过活化烧结制得HAP/AC复合吸附剂.考察了HAP/AC质量比、聚乙烯醇(PVA)浓度、焙烧时间和焙烧温度等因素对吸附剂去除水中氟离子的影响.实验结果表明:HAP/AC质量比为4∶1、PVA浓度3wt;、焙烧温度350 ℃、焙烧时间3.5 h,吸附剂对氟离子的去除效率达到最大值为70.69;.将HAP/AC复合吸附剂用于对模拟含氟废水的吸附研究,通过静态吸附实验和动态柱吸附实验考察了吸附剂对模拟含氟废水的吸附性能,对其吸附机理进行了探讨.结果表明Langmuir等温吸附模型更优于Freundlich模型,且吸附剂对氟离子的吸附主要以表面单分子层吸附为主,吸附过程中具有离子交换能力的活性中心起主导作用.最后将HAP/AC复合吸附剂应用于地氟病区实际含氟废水的处理,以探讨其实际运用的可行性.     

改性羟基磷灰石晶须牙科复合树脂材料的制备及研究

采用硅胶对制备的HAP晶须进行表面改性形成SiO2颗粒附着,然后以硅胶改性的HAP晶须为填料混合甲基丙烯酸酯制备复合树脂材料.二氧化硅对晶须改性是通过形成凝胶颗粒与晶须结合并通过热处理形成牢固的结合.通过XRD、FT-IR光谱和SEM以表征微结构、键性质以及表面相组成.结果表明:经硅胶改性的HAP晶须表面有SiO2小颗粒附着,随着煅烧温度的增加,SiO2颗粒的数量明显增多,尺寸有变大的趋势.复合树脂材料的弯曲强度随改性晶须煅烧温度的增加而增加,以600 ℃煅烧的改性晶须为原料制备的树脂样品,其弯曲强度最高,达到89.46 MPa.