图1 几种典型的CaP陶瓷实心微球[10, 12-13]

Fig. 1 Images of typical calcium phosphate solid microspheres (a) β-TCP microsphere prepared with nitrogen liquid freeze drying method[10]; (b) HA microsphere prepared with CMCS and gel as binder[12]; (c) HA microsphere prepared with emulsion method[13]

图2 两种典型的多孔CaP微球[18, 23]

Fig. 2 Two typical porous CaP microspheres[18, 23] (a) HA microsphere prepared with alginate salt gel process[18], (b) HA microsphere prepared with spray drying method[23]

图3 以生物玻璃微球为硬模板的方式制备的CaP陶瓷空心微球工艺流程示意图[27]

Fig. 3 Scheme of calcium phosphate hollow microsphere with bioglass as hard template[27]

图4 以玻璃微球为硬模板制备的空心CaP陶瓷时, 作为模板用玻璃微球形貌(a), 空心HA微球外表面形貌(b),空心HA表面放大形貌(c), HA空心微球抛光纵切面背散射SEM观察到的形貌(d), X射线能谱显示图片(d)的含P(e)和Ca(f)元素分布 [27]

Fig. 4 SEM images of hollow HA microsphere with glass as hard template. (a) starting glass microspheres as hard template, (b) external surface of hollow HA microsphere, (c) external surface of hollow HA microsphere at high magnification. (d) SEM image in back-scattered mode of a polished cross section of a hollow hydroxyapatite microsphere, (e) and (f) X-ray maps of Ca(K) and P(K) across the planar section shown in (d)[27]

图5 分别以(a) CaCO3/Fe3O4硬模板法[32]、(b)酵母菌生物模板法[33]、(c) DCM乳液法[34]、(d) 喷雾干燥法[35]、(e) 微波水热法[37]、和(f) 电喷涂法[38]制备的几种典型的空心CaP陶瓷微球

Fig. 5 Six typical hollow calcium phosphate microspheres prepared with (a) CaCO3/Fe3O4 as hard template[32], (b) yeast as bio- template[33], (c) DCM emulsion method[34], (d) spray drying method[35], (e) microwave-hydrothermal method[37], and (f) electrosprayed method[38], respectively

图6 4种典型的花瓣状CaP陶瓷微球SEM照片, 分别是以 (a) 酒石酸氢钾[39]、(b) EDTA[40]、(c) 氟取代结合EDTA [41]和(d) 柠檬酸[42]等为模板制备而成

Fig. 6 Four typical flower-like microspheres prepared with potassium hydrogen tartrate (a)[39], EDTA[40] (b), F- substitution combined with EDTA (c) and citric acid[41] (d) as template, respectively[42]

图7 以柠檬酸为模板制备CaP陶瓷微球随pH和Ct/Ca比值的形态变化图谱[42]

Fig. 7 Morphology variation of HA crystals from solution at different pH and Ct/Ca mole ratio[42]

图8 HA微球与管状多孔HA支架及多孔圆片构建骨修复体(a)和腹膜植入(b)[45], 肌内植入3个月(c)后甲苯胺蓝染色组织切片[46]

Fig. 8 Images of (a) the HA spherules, porous HA tubes, and HA disks fabricated to assemble the novel scaffolds, (b) digital photo shows the implantation of the porous scaffolds at peritoneum pocket[45], (c) photographs of toluidine blue stained spherulite HA-positive assemble scaffold after intramuscular implantation for 3 months[46]. NB represents new bone

图9 空心CaP陶瓷微球修复大鼠颅骨6w后HE染色(a, c)和von Koss染色(b, d)组织切片, 其中(a, b)为空白对照微球, (c, d)为载1 μg BMP2微球[56]

Fig. 9 (a, c) H&E and (b, d) von Kossa stained sections of rat calvarial defects implanted for 6 weeks with (a, b) as-prepared hollow HA microspheres (without BMP2) and (c, d) hollow HA microspheres loaded with BMP2 (1 μg per defect). HB represents host (old) bone; NB represents new bone[56]