多壳层化中空微球两相陶瓷生物材料制备研究

doi:10.3724/SP.J.1077.2014.13501

无机材料学报 ›› 2014, Vol. 29 ›› Issue (6): 650-656.DOI: 10.3724/SP.J.1077.2014.13501 CSTR: 32189.14.SP.J.1077.2014.13501

多壳层化中空微球两相陶瓷生物材料制备研究

杨永祝¹, 张雷², 杨国敬², 高长有¹, 苟中入¹

(1. 浙江大学浙江加州国际纳米技术研究院, 杭州310058; 2. 温州医科大学附属第三医院, 瑞安 325200)

收稿日期:2013-09-30 修回日期:2013-11-14 出版日期:2014-06-20 网络出版日期:2014-05-27
作者简介:杨永祝(1988-), 男, 硕士研究生. E-mail: 21126035@zju.edu.cn
基金资助:
国家自然科学基金(51372218, 51102211, 81271956);浙江省自然科学基金(Q14H060011);浙江省科技厅公益性项目(2011C3-3049, 2012C23067)

Preparation and Characterization of Multi-shell Hollow Biphase Bioceramic Microsphere Composites

YANG Yong-Zhu¹, ZHANG Lei², YANG Guo-Jing², GAO Chang-You¹, GOU Zhong-Ru¹

(1. Zhejiang-California International Nanosystems Institute, Zhejiang University, Hangzhou 310058, China; 2. Rui’an People’s Hospial & the 3rd Affiliated Hospital to Wenzhou Medical University, Rui’an 325200, China)

Received:2013-09-30 Revised:2013-11-14 Published:2014-06-20 Online:2014-05-27
About author:YANG Yong-Zhu. E-mail: 21126035@zju.edu.cn
Supported by:
National Natural Science Foundation of China (51372218, 51102211, 81271956);Zhejiang Provincial Natural Science Foundation of China (Q14H060011);Science and Technology Department Foundation of Zhejiang Province (2011C33049, 2012C23067)

摘要/Abstract

摘要：

利用硅灰石(CaSiO₃)和β-磷酸三钙(β-TCP)在骨损伤环境中降解速率存在显著性差异的基本特性, 以海藻多糖凝胶球为模板, 运用层-层包裹方法构建CaSiO₃、β-TCP交替包裹的多壳层化中空微球。首先, 将海藻酸钠与硅酸钠的混合水溶胶逐滴加入到温和搅拌的硝酸钙水溶液中, 形成由水合硅酸钙盐为壳层的海藻多糖基复合微球, 然后将该复合微球依次浸入到含β-TCP的海藻酸钠溶液和含CaSiO₃的海藻酸钠溶液中, 温和搅拌后将微球悬浮液分离, 再经真空冷冻干燥和850℃煅烧处理, 从而获得以CaSiO₃为最内壳层并具有双壳层或三壳层的中空微球。按类似步骤也可以制备以β-TCP为最内壳层的多壳层中空微球。运用SEM、EDX、XRD和FTIR对该类微球的微结构和组成进行了分析。运用弱酸性Tris缓冲液(pH=5.2)对双壳层中空微球的降解。实验证明, 缓冲液中硅、磷浓度变化特征与其外壳层、内壳层化学组成(即β-TCP或CaSiO₃)密切相关。本研究结果对构建降解速率阶段可调的复合陶瓷多孔生物材料以及研究原位骨再生效率与孔道网络演化规律之间关系等具有重要学术价值。

关键词: 降解性可调, 多壳层化中空微球, 硅灰石, β-磷酸三钙, 生物活性陶瓷

Abstract:

A series of hollow bioceramic microspheres with two or three shell layers were fabricated via alginate microsphere template and layer-by-layer coating techniques. The Na₂SiO₃-alginate mixture hydrosol beads were firstly injected into the Ca(NO₃)₂ aqueous solution under mild stirring to form calcium silicate hydrate-coated alginate microspheres. The composite microspheres were dispersed into the beta-tricalcium phosphate (β-TCP) -containing alginate hydrosol and wollastonite (CaSiO₃)-containing alginate hydrosol in turn while gently stirring. The microspheres were filtered, dried in vacuum and finally calcined at 850℃ for 2 h to obtain the multi-shell hollow bi-phase ceramic microspheres. The microstructure and chemical composition of the microspheres were characterized by SEM, EDX, XRD and FTIR analysis. In vitro biodegradation behavior of the two-shell hollow microspheres was tested in weak acidic Tris buffer and confirmed a unique controlled release characteristic for the silicate and phosphate groups. These results suggest that the rational design of the two- or multi-shell layer allows the preparation of bioceramic composites composed of β-TCP and CaSiO₃ with stage adjustable biodegradation and these biomaterials are potential candidates for improving bone regeneration and repair.

Key words: stage adjustable degradation, multi-shell hollow microspheres, wollastonate, β-TCP, bioceramics

中图分类号:

TQ174

杨永祝, 张雷, 杨国敬, 高长有, 苟中入. 多壳层化中空微球两相陶瓷生物材料制备研究[J]. 无机材料学报, 2014, 29(6): 650-656.

YANG Yong-Zhu, ZHANG Lei, YANG Guo-Jing, GAO Chang-You, GOU Zhong-Ru. Preparation and Characterization of Multi-shell Hollow Biphase Bioceramic Microsphere Composites[J]. Journal of Inorganic Materials, 2014, 29(6): 650-656.

图/表 7

图1 中空微球合成技术方案以及中空微球微结构示意图

Fig. 1 Proposed multi-shell hollow microspheres preparation process and the superstructures of the ceramic microspheres

图2 单壳层微球形貌和微结构照片

Fig. 2 Photographs of the microspheres before drying (a), after drying (b) and after calcination (c) and SEM images (d,e) of the superstructures of the single-shell CaSi microspheres

图3 中空双层壳微球形貌与微结构照片及壳层EDX能谱图

Fig. 3 Morphology before drying (a), microstructrue (b-d) and EDX spectra (e, f) of the two-shell CaSi@CaP hollow microspheres after calcination.

图4 中空三壳层微球形貌和微结构照片

Fig. 4 Macromorphology before drying (a) and SEM images (b-f) of the three-shell CaSi@CaP@CaSi hollow microspheres showing the crosssection microstructures (b) and the three shell layers after calcination (c-f)

图5 不同样品的XRD图谱

Fig. 5 XRD patterns of the as-calcined CaAlg microspheres (a), single-shell CaSi hollow microspheres (b), and two-shell CaSi@CaP hollow microspheres (c)

图6 不同煅烧样品的FTIR图谱

Fig. 6 FTIR spectra of the pure β-TCP (a), single-shell CaSi hollow microspheres (b) and two-shell CaSi@CaP hollow microspheres (c)

图7 中空双壳层CaSi@CaP微球(a)和CaP@CaSi微球(b)在pH 5.2的Tris溶液中降解过程Ca、Si、P浓度变化

Fig. 7 Changes in Ca, P, and Si concentrations in the Tris buffer with initial pH 5.2 during soaking the two-shell CaSi@CaP (a) and CaP@CaSi (b) hollow ceramic microspheres

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多壳层化中空微球两相陶瓷生物材料制备研究

Preparation and Characterization of Multi-shell Hollow Biphase Bioceramic Microsphere Composites

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