二氧化锆掺入对三维打印的硅酸二钙支架物理化学和生物学性能的影响

doi:10.15541/jim20180466

无机材料学报 ›› 2019, Vol. 34 ›› Issue (4): 444-454.DOI: 10.15541/jim20180466

所属专题：优秀作者论文集锦； 2019~2020年度优秀作者作品欣赏(六)

二氧化锆掺入对三维打印的硅酸二钙支架物理化学和生物学性能的影响

傅声扬¹,俞斌²,丁惠锋^2,³(),石国栋²,朱钰方¹()

^1. 上海理工大学材料科学与工程学院, 上海 200093
^2. 复旦大学上海医学院, 上海市公共卫生临床中心骨科, 上海 200032
^3. 上海市浦东医院复旦大学附属浦东医院 201399

收稿日期:2018-10-06 出版日期:2019-04-20 网络出版日期:2019-04-15
作者简介:FU Sheng-Yang (1994-), male, candidate for Master degree. E-mail: fushengyang@sina.com|YU Bin (1988-), male, candidate for PhD degree. E-mail: binyu13@126.com

Zirconia Incorporation in 3D Printed β-Ca₂SiO₄ Scaffolds on Their Physicochemical and Biological Property

Sheng-Yang FU¹,Bin YU²,Hui-Feng DING^2,³(),Guo-Dong SHI²,Yu-Fang ZHU¹()

^1. School of Materials Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China
^2. Department of Orthopedics, Shanghai Public Health Clinical Center, Shanghai Medical School, Fudan University, Shanghai 200032, China
^3. Department of Orthopedics, Shanghai Pudong Hospital, Fudan University Pudong Medical Center, Shanghai 201399, China

Received:2018-10-06 Published:2019-04-20 Online:2019-04-15
Supported by:
National Natural Science Foundation of China(51872185);The Science and Technology Commission of Shanghai Municipality(17060502400);The State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University(LK1616);Academic Leaders Training Program of Pudong Health Bureau of Shanghai(PWRd2017-03);Science and Technology Development Fund of Shanghai Pudong New Area(PKJ2015-Y37);"Pu Jing" Training Program of Shanghai Pudong hospital(PJ201503)

摘要/Abstract

摘要：

三维打印结合高分子前躯体制备生物陶瓷材料由于制备工艺简单, 在骨组织工程修复领域引起了极大的关注。本文成功利用三维打印技术与高分子硅胶前躯体结合, 通过填充活性CaCO₃和惰性ZrO₂制备出ZrO₂掺杂的β-Ca₂SiO₄支架。制备得到的支架具有均一、连通的大孔结构(孔隙率>67%), 随着掺杂ZrO₂含量的增加, 支架的抗压强度明显提高, 并且促进成骨细胞增殖、分化。重要的是在动物体内实验发现, 相较于纯的β-Ca₂SiO₄支架, ZrO₂的掺入明显提高了支架在骨缺损处促进新骨形成的能力。因而, 通过三维打印结合高分子前躯体技术制备掺杂ZrO₂的β-Ca₂SiO₄支架有望应用于骨组织工程。

关键词: β-Ca₂SiO₄, ZrO₂, 聚合物前驱, 三维打印, 骨组织工程

Abstract:

3D printed bioceramics derived from preceramic polymers are of great interest in bone tissue engineering due to their simplified fabrication processes. In this study, three-dimensional (3D) porous β-Ca₂SiO₄ scaffolds incorporated with ZrO₂ were fabricated from silicone resin loaded with active CaCO₃ and inert ZrO₂ fillers by 3D printing. The fabricated scaffolds possessed uniform interconnected macropores with a high porosity (> 67%). The results showed that the increase of ZrO₂ incorporation significantly enhanced the compressive strength, and stimulated cell proliferation and differentiation of osteoblasts. Importantly, the in vivo results indicated that the ZrO₂-incorporated β-Ca₂SiO₄ scaffolds improved osteogenic capacity compared to pure β-Ca₂SiO₄ scaffolds. Taken together, the ZrO₂-incorporated β-Ca₂SiO₄ scaffolds fabricated by combining polymer-derived strategy with 3D printing could be a promising candidate for bone tissue engineering.

Key words: β-Ca₂SiO₄, ZrO₂, polymer-derived, 3D printing, bone tissue engineering

中图分类号:

TQ174

傅声扬, 俞斌, 丁惠锋, 石国栋, 朱钰方. 二氧化锆掺入对三维打印的硅酸二钙支架物理化学和生物学性能的影响[J]. 无机材料学报, 2019, 34(4): 444-454.

Sheng-Yang FU, Bin YU, Hui-Feng DING, Guo-Dong SHI, Yu-Fang ZHU. Zirconia Incorporation in 3D Printed β-Ca₂SiO₄ Scaffolds on Their Physicochemical and Biological Property[J]. Journal of Inorganic Materials, 2019, 34(4): 444-454.

图/表 10

Scheme. 1 Fabrication process of the ZrO2-incorporated β-Ca2SiO4 scaffolds

Fig. 1 (A) XRD patterns of the scaffolds incorporated with different ZrO2 content sintered at 1200 ℃, (B) 15Zr-C2S scaffolds sintered at different temperature, and (C) FT-IR spectra of the β-Ca2SiO4 scaffolds incorporated with different ZrO2 content sintered at 1200 ℃.

Fig. 2 SEM images of (A) 0Zr-C2S, (B) 5Zr-C2S, (C) 10Zr-C2S and (D) 15Zr-C2S scaffolds, with SEM fracture surface images from (A3-A4) to (D3-D4)

Fig. 3 The compressive strength and porosity of the ZrO2- incorporated β-Ca2SiO4 scaffolds (n = 3; * indicated significant differences, P < 0.05)

Fig. 4 (A) pH values and (B) in vitro degradation of the ZrO2-incorporated β-Ca2SiO4 scaffolds in SBF (n = 3; *, ** and *** indicated significant differences, P < 0.05, P < 0.01 and P< 0.001), (C) FT-IR and (D) SEM images of the ZrO2- incorporated scaffold surfaces after immersed in SBF for 7 d

Fig. 5 SEM images of the attachment of rBMSCs on the ZrO2-incorporated β-Ca2SiO4 scaffolds for 1 d, (A) 0Zr-C2S; (B) 5Zr-C2S; (C) 10Zr-C2S; (D) 15Zr-C2S

Fig. 6 (A) Quantitative analysis of the proliferation of rBMSCs cultured on β-Ca2SiO4 scaffolds for 3 and 7 d (n=3); (B) ALP activity of rBMSCs cultured for 7 and 14 d on β-Ca2SiO4 scaffolds for 7 and 14 d (n = 3, * and ** indicated significant differences, P < 0.05 and 0.01)

Fig. 7 Osteogenic expression of (A) COL-1, (B) OCN, (C) RunX-2 and (D) OPN for rBMSCs cultured on β-Ca2SiO4 scaffolds by qRT-PCR analysis after 7 and 14 d (n = 3; * and ** indicated significant differences, P < 0.05 and 0.01)

Fig. 9 (A) Histological analysis with (B) quantitative analysis of newly formed bone

Fig. 8 Micro-CT evaluation of the repaired skulls at 8 weeks post-implantation

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二氧化锆掺入对三维打印的硅酸二钙支架物理化学和生物学性能的影响

Zirconia Incorporation in 3D Printed β-Ca₂SiO₄ Scaffolds on Their Physicochemical and Biological Property

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二氧化锆掺入对三维打印的硅酸二钙支架物理化学和生物学性能的影响

Zirconia Incorporation in 3D Printed β-Ca2SiO4 Scaffolds on Their Physicochemical and Biological Property

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Zirconia Incorporation in 3D Printed β-Ca₂SiO₄ Scaffolds on Their Physicochemical and Biological Property