超顺磁性磷酸钙复合支架的制备及性能研究

doi:10.3724/SP.J.1077.2013.12107

摘要/Abstract

摘要：

采用共混-真空烧结方法制备了一系列超顺磁性磷酸钙复合支架, 通过SEM、EDS、XRD和VSM等手段对所制备的材料性能进行表征, 并考察了其在水中的稳定性以及Ros17/2.8细胞在材料表面的黏附生长情况。结果表明: 该方法所制备的超顺磁性复合支架具有多级连通孔结构, 磁性纳米颗粒在基体中分布均匀, 结合牢固且复合量精确可控, 在水中具有良好的稳定性。真空烧结避免了磁性纳米颗粒在烧结过程中发生氧化和相变, 使复合支架继续保持超顺磁性并具有良好的磁性能, 且该磁性支架有利于细胞的黏附和生长, 具有较好的生物相容性, 在组织工程中有潜在的应用前景。

关键词: 真空烧结, 超顺磁性四氧化三铁, 磷酸钙, 组织工程支架, 生物相容性

Abstract:

Supermagnetic calcium phosphate composite scaffold was fabricated by merging the superparamagnetic iron oxide (SPIO) into the calcium phosphate scaffold, and then sintered in vacuum. Properties of the obtained magnetic scaffold were investigated by SEM, EDS, XRD and VSM. The stability of magnetic scaffold in water was assessed and Ros17/2.8 cells were cultured on the samples to evaluate the cell adhesion on the scaffold. The results demonstrated that the magnetic scaffold had a porous structure. The magnetic nanoparticles were uniformly distributed and firmly merged into the matrix. The content of magnetic nanoparticles could be accurately tuned, and the magnetic scaffold is stable in water. The composite scaffold maintained excellent magnetic properties, as the vacuum sintering procedure avoided the oxidation and phase transition of the magnetic nanoparticles. It is proposed that the magnetic materials might be a kind of potential bone tissue engineering scaffold in the future.

Key words: vacuum sintering, superparamagnetic iron oxide, calcium phosphate, tissue engineering scaffold, biocompatibility

中图分类号:

R318

曾晓波, 胡灏, 解丽芹, 蓝芳, 吴尧, 顾忠伟. 超顺磁性磷酸钙复合支架的制备及性能研究[J]. 无机材料学报, 2013, 28(1): 79-84.

ZENG Xiao-Bo, HU Hao, XIE Li-Qin, LAN Fang, WU Yao, GU Zhong-Wei. Preparation and Properties of Supermagnetic Calcium Phosphate Composite Scaffold[J]. Journal of Inorganic Materials, 2013, 28(1): 79-84.

图/表 7

Table1 Types of magnetic scaffolds of calcium phosphate with SPIO

Name of scaffold	Type of SPIO	Mass ratio of SPIO/HA
HA	—	—
MHA0	SPIO-h	2:100
MHA1	SPIO-h	5:100
MHA2	SPIO-h	2:100
MHA3	SPIO-h	1:100
MHA4	SPIO-c	10:100
MHA5	SPIO-c	5:100
MHA6	SPIO-c	2:100

图1 MHA1(a,d,g)、MHA4(b,e,h)及HA(c,f,i)等三种陶瓷的SEM照片

Fig. 1 SEM images of MHA1 (a, d, g), MHA4 (b, e, h) and HA (c, f, i)

图2 MHA4的扫描电镜照片(a)和EDS能谱图(b) 表2 复合支架中Fe元素的质量分数与钙/磷比

Fig. 2 SEM image (a) and EDS pattern (b) of MHA4

Table 2 Fe content and Ca/P ratio of magnetic scaffolds

Name of scaffold	Theoretical content of Fe/%	Actual content of Fe /%	Theoretical Ca/P ratio	Actual Ca/P ratio
HA	Null	0	1.67	1.679
MHA0	0.85	2.87	1.67	1.658
MHA1	2.07	2.09	1.67	1.615
MHA2	0.85	0.83	1.67	1.697
MHA3	0.43	0.51	1.67	1.673
MHA4	6.58	6.60	1.67	1.676
MHA5	3.44	3.41	1.67	1.680
MHA6	1.42	1.44	1.67	1.684

图3 MHA1、MHA4、HA及HA-p四种样品的XRD图谱

Fig. 3 XRD patterns of MHA1, MHA4, HA and HA-p (HA powder before sintered)

图4 三种方法(a:真空烧结、b:空气中烧结、c:未烧结)制备的MHA1和经真空烧结的HA(d)的磁滞回线

Fig. 4 Magnetization curves of MHA1 after sintered in vacuum (a), MHA1 after sintered in air (b), MHA1 before sintered (c) and HA after sintered in vacuum (d)

图5 Ros17/2.8细胞在MHA1(a, d)、MHA5(b, e)和HA(c, f)材料表面粘附生长的SEM照片

Fig. 5 SEM micrographs of Ros17/2.8 cells grown on MHA1 (a, d), MHA5 (b, e) and HA (c, f)

参考文献 24

[1]	Bassett C A L, Schink-Ascani M, Lewis S M. Effects of pulsed electromagnetic fields on steinberg ratings of femoral head osteonecrosis. Clin. Orthop. Relat. Res., 1989, 185(246): 172-185.
[2]	Santini M T, Rainaldi G, Ferrante A, et al. Effects of a 50 Hz sinusoidal magnetic field on cell adhesion molecule expression in two human osteosarcoma cell lines (mg-63 and saos-2). Bioelectromagnetics, 2003, 24(5): 327-338.
[3]	McLeod K J, Collazo L. Suppression of a differentiation response in MC-3T3-E1 osteoblast-like cells by sustained, low-level, 30 Hz magnetic-field exposure. Radiation Research, 2000, 153(5): 706-714.
[4]	Jansen J, van der Jagt O, Punt B, et al. Stimulation of osteogenic differentiation in human osteoprogenitor cells by pulsed electromagnetic fields: an in vitro study. BMC Musculoskeletal Disorders, 2010, 23(11): 188-1-11.
[5]	Fini M, Cadossi R, Cane V, et al. The effect of pulsed electromagnetic fields on the osteointegration of hydroxyapatite implants in cancellous bone: a morphologic and microstructural in vivo study. J. Orthop. Res., 2002, 20(4): 756-763.
[6]	Zhang X Y, Xue Y, Zhang Y. Effects of 0.4 T rotating magnetic field exposure on density, strength, calcium and metabolism of rat thigh bones. Bioelectromagnetics, 2006, 27(1): 1-9.
[7]	Chang K, Chang W H. Pulsed electromagnetic fields prevent osteoporosis in an ovariectomized female rat model: a prostaglandin E2-associated process. Bioelectromagnetics, 2003, 24(3): 189-198.
[8]	Taylor K F, Inoue N, Rafiee B, et al. Effect of pulsed electromagnetic fields on maturation of regenerate bone in a rabbit limb lengthening model. J. Orthop. Res., 2006, 24(1): 2-10.
[9]	Wang L, Yang Z, Gao J, et al. A biocompatible method of decorporation: bisphosphonate-modified magnetite nanoparticles to remove uranyl ions from blood. J. Am. Chem. Soc., 2006, 128(41): 13358-13359.
[10]	Kim J, Lee J E, Lee J, et al. Magnetic fluorescent delivery vehicle using uniform mesoporous silica spheres embedded with monodisperse magnetic and semiconductor nanocrystals. J. Am. Chem. Soc., 2005, 128(3): 688-689.
[11]	Jun Y W, Huh Y M, Choi J S, et al. Nanoscale size effect of magnetic nanocrystals and their utilization for cancer diagnosis via magnetic resonance imaging. J. Am. Chem. Soc., 2005, 127(16): 5732-5733.
[12]	Wei Y, Zhang X H, Song Y, et al. Magnetic biodegradable Fe3O4/ CS/PVA nanofibrous membranes for bone regeneration. Biomedical Materials, 2011, 6(5): 055008.
[13]	Meng J, Zhang Y, Qi X, et al. Paramagnetic nanofibrous composite films enhance the osteogenic responses of pre-osteoblast cells. Nanoscale 2010, 2(12): 2565-2569.
[14]	Banobre-Lopez M, Pineiro-Redondo Y, De-Santis R, et al. Poly(caprolactone) based magnetic scaffolds for bone tissue engineering. J. Appl. Phys. , 2011, 109(7): 07B313-1-3.
[15]	Bock N, Riminucci A, Dionigi C, et al. A novel route in bone tissue engineering: magnetic biomimetic scaffolds. Acta Biomaterialia, 2010, 6(3): 786-796.
[16]	Wu Y, Jiang W, Wen X T, et al. A novel calcium phosphate ceramic-magnetic nanoparticle composite as a potential bone substitute. Biomedical Materials, 2010, 5(1): 015001.
[17]	Morrison S Roy. 赵壁英, 刘英俊译. 表面化学物理. 北京: 北京大学出版社, 1984: 238-242.
[18]	Sun S H, Zeng H. Size-controlled synthesis of magnetite nanoparticles. J. Am. Chem. Soc., 2002, 124(28): 8204-8205.
[19]	Kang Y S, Risbud S, Rabolt J F, et al. Synthesis and characterization of nanometer-size Fe3O4 and γ-Fe2O3 particles. Chemistry of Materials, 1996, 8(9): 2209-2211.
[20]	Lan F, Liu K X, Jiang W, et al. Facile synthesis of monodisperse superparamagnetic Fe3O4/PMMA composite nanospheres with highmagnetization. Nanotechnology, 2011, 22(22): 225604-1-7.
[21]	Lan F, Hu H, Jiang W, et al. Synthesis of superparamagnetic Fe3O4/PMMA/SiO2 nanorattles with periodic mesoporous shell for lysozyme adsorption. Nanoscale, 2012, 4(7): 2264-2267.
[22]	Jiang W, Wu Y, He B, et al. Effect of sodium oleate as a buffer on the synthesis of superparamagnetic magnetite colloids. J. Colloid Interface Sci., 2010, 347(1): 1-7.
[23]	Hing K A. Bioceramic bone graft substitutes: influence of porosity and chemistry. International Journal of Applied Ceramic Technology, 2005, 2(3): 184-199.
[24]	崔国文. 缺陷、扩散与烧结. 北京: 清华大学出版社: 1990: 143-175.