Mn/nHA涂层CF/PEEK复合材料的制备及体外成骨活性评价

doi:10.15541/jim20250078

无机材料学报 ›› 2025, Vol. 40 ›› Issue (10): 1145-1152.DOI: 10.15541/jim20250078

Mn/nHA涂层CF/PEEK复合材料的制备及体外成骨活性评价

李正浩¹^,²(), 李婧鸣¹^,², 章玉祥¹^,², 袁波¹^,², 张凯¹^,², 朱向东¹^,²()

¹ 四川大学 1. 国家生物医学材料工程技术研究中心
² 生物医学工程学院, 成都 610064

收稿日期:2025-02-23 修回日期:2025-03-25 出版日期:2025-04-15 网络出版日期:2025-04-15
通讯作者: 朱向东, 研究员. E-mail: zhu_xd1973@scu.edu.cn
作者简介:李正浩(2000-), 男, 硕士研究生. E-mail: 2022223100034@stu.scu.edu.cn
基金资助:
国家重点研发计划(2022YFC2406102)

Preparation and in vitro Osteogenic Activity Evaluation of Mn/nHA Coated CF/PEEK Composite

LI Zhenghao¹^,²(), LI Jingming¹^,², ZHANG Yuxiang¹^,², YUAN Bo¹^,², ZHANG Kai¹^,², ZHU Xiangdong¹^,²()

¹ National Engineering Research Center for Biomaterials, Sichuan University, Chengdu 610064, China,
² College of Biomedical Engineering, Sichuan University, Chengdu 610064, China

Received:2025-02-23 Revised:2025-03-25 Published:2025-04-15 Online:2025-04-15
Contact: ZHU Xiangdong, professor. E-mail: zhu_xd1973@scu.edu.cn
About author:LI Zhenghao (2000-), male, Master candidate. E-mail: 2022223100034@stu.scu.edu.cn
Supported by:
National Key R&D Program of China(2022YFC2406102)

摘要/Abstract

摘要：

碳纤维/聚醚醚酮(Carbon Fiber Polyetheretherketone, CF/PEEK)在骨修复领域已得到了广泛应用, 但生物惰性致使其骨整合性较弱, 极大地影响了临床应用的长期稳定性和骨修复效果。本研究基于无机纳米粒子液相自组装策略, 在CF/PEEK表面构筑了锰掺杂纳米羟基磷灰石(Mn/nHA)涂层, 以期改善其生物活性和骨整合性。实验结果表明, Mn/nHA和nHA涂层均可显著改善CF/PEEK表面粗糙度和提升亲水性。体外研究发现, Mn/nHA和nHA两组涂层改性材料与大鼠骨髓间充质干细胞(BMSCs)共培养7 d后, 相对细胞存活率分别高达180%和159%, 均表现出显著的促增殖效果。此外, 茜素红染色和逆转录-聚合酶链式反应(RT-PCR)检测发现两种涂层均能增强细胞在材料表面的矿化和成骨分化能力, 且Mn/nHA涂层呈现出更强的促进作用。

关键词: 羟基磷灰石, 锰, 碳纤维/聚醚醚酮, 成骨活性

Abstract:

Carbon fiber/polyetheretherketone (CF/PEEK) has been widely used in the field of bone repair. However, its bio-inert nature results in poor osseointegration, which significantly limits its long-term stability and bone repair efficacy in clinical applications. Here, a manganese-doped nano-hydroxyapatite (Mn/nHA) coating was constructed on the surface of CF/PEEK using a liquid-phase self-assembly strategy of inorganic nanoparticles. The experimental results demonstrated that both Mn/nHA and nHA coatings significantly improved the surface roughness and hydrophilicity of CF/PEEK. Further in vitro studies revealed that after co-culturing with rat mesenchymal stem cells (BMSCs) for 7 d, the relative cell viability of the Mn/nHA- and nHA-coated materials reached as high as 180% and 159%, respectively, indicating a pronounced pro-proliferative effect. Additionally, alizarin red staining and reverse transcription-polymerase chain reaction (RT-PCR) analysis showed that both coatings enhanced cell mineralization and osteogenic differentiation on the material surface, with the Mn/nHA coating exhibiting a stronger promoting effect.

Key words: hydroxyapatite, manganese, carbon fiber/polyetheretherketone, osteogenic activity

中图分类号:

R318

李正浩, 李婧鸣, 章玉祥, 袁波, 张凯, 朱向东. Mn/nHA涂层CF/PEEK复合材料的制备及体外成骨活性评价[J]. 无机材料学报, 2025, 40(10): 1145-1152.

LI Zhenghao, LI Jingming, ZHANG Yuxiang, YUAN Bo, ZHANG Kai, ZHU Xiangdong. Preparation and in vitro Osteogenic Activity Evaluation of Mn/nHA Coated CF/PEEK Composite[J]. Journal of Inorganic Materials, 2025, 40(10): 1145-1152.

图/表 11

表1 RT-PCR中所用引物序列

Table 1 Primers utilized for RT-PCR amplification

For GAPDH
F: 5ʹ-GGCACAGTCAAGGCTGAGAATG-3ʹ R: 5ʹ-ATGGTGGTGAAGACGCCAGTA-3ʹ
For BMP
F: 5ʹ-TGACTGGATCGTGGCACCTC-3ʹ R: 5ʹ-CAGAGTCTGCACTATGGCATGGTTA-3ʹ
For OPG
F: 5ʹ-AACCGCACCCACAACCGA-3ʹ R: 5ʹ-CACCTGAGAAGAACCCATCCG-3ʹ
For RUNX-2
F: 5ʹ-TGGCCGGGAATGATGAGAAC-3ʹ R: 5ʹ-TTGAACCTGGCCACTTGGTT-3ʹ
For OCN
F: 5ʹ-TCTGAGTCTGACAAAGCCTTCAT-3ʹ R: 5ʹ-AAGTCCATTGTTGAGGTAGCG-3ʹ
For ALP
F: 5ʹ-CATCGCCTATCAGCTAATGCACA-3ʹ R: 5ʹ-ATGAGGTCCAGGCCATCCAG-3ʹ
For BSP
F: 5ʹ-GACCAGTTATGGCACCACGA-3ʹ R: 5ʹ-CGCAGTGTTGTACTCGTTGC-3ʹ

图1 材料表面形貌的SEM照片

Fig. 1 SEM images for surface morphology of various material samples (a, d) CF/PEEK; (b, e) nHA-CF/PEEK; (c, f) 5%Mn/nHA-CF/PEEK

图2 CF/PEEK (a, d)、nHA-CF/PEEK (b, e)和5%Mn/nHA-CF/PEEK (c, f)表面形貌的AFM图像(a-f)和粗糙度(g)

Fig. 2 AFM images (a-f) and roughness (g) for surface topographies of CF/PEEK (a, d), nHA-CF/PEEK (b, e) and 5%Mn/ nHA-CF/PEEK (c, f) (a-c) 3D images; (d-f) 2D images; (g) Roughness

图3 CF/PEEK、nHA-CF/PEEK和5%Mn/nHA-CF/PEEK表面的水接触角

Fig. 3 Water contact angles of CF/PEEK, nHA-CF/PEEK and 5%Mn/nHA-CF/PEEK

图4 CF/PEEK表面nHA和5%Mn/nHA涂层样品的FT-IR光谱图

Fig. 4 FT-IR spectra of nHA and 5%Mn/nHA coated on CF/PEEK samples

图5 CF/PEEK表面nHA和5%Mn/nHA涂层样品的XRD图谱

Fig. 5 XRD patterns of nHA and 5%Mn/nHA coated on CF/PEKK samples

图6 CF/PEEK表面nHA和5%Mn/nHA涂层样品的XPS谱图

Fig. 6 XPS spectra of nHA and 5%Mn/nHA coated on CF/PEKK samples (a) XPS full spectra; (b) Mn, (c) P and (d) Ca element valence analyses

表2 材料表面涂层的元素组成(原子分数)

Table 2 Elemental composition of the surface coating (in atom)

Sample	O/%	Ca/%	P/%	Mn/%
nHA	63.96±2.55	21.38±1.24	14.67±1.22	-
5%Mn/nHA	69.41±3.15	17.05±1.74	12.36±1.24	1.18±0.15

图7 在CF/PEEK、nHA-CF/PEEK及5%Mn/nHA-CF/PEEK表面培养1、4和7 d的BMSCs增殖情况

Fig. 7 BMSCs growth and proliferation on CF/PEEK, nHA-CF/PEEK and 5%Mn/nHA-CF/PEEK after culturing for 1, 4 and 7 d (a) CLSM images; (b) MTT analysis. Colorful figures are available on website

图8 在SCF/PEEK、nHA-CF/PEEK及5%Mn/nHA- CF/PEEK表面培养4、7和14 d的BMSCs矿化能力

Fig. 8 BMSCs mineralization ability on SCF/PEEK, nHA-CF/ PEEK and 5%Mn/nHA-CF/PEEK after culturing for 4, 7 and 14 d (a) Alizarin red stained images; (b) Semi-quantitative analysis. Colorful figures are available on website

图9 BMSCs在CF/PEEK、nHA-CF/PEEK及5%Mn/nHA-CF/PEEK表面培养4 d的成骨相关基因表达

Fig. 9 Osteogenic gene expressions of BMSCs cultured on CF/PEEK, nHA-CF/PEEK and 5%Mn/nHA-CF/PEEK for 4 d

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Mn/nHA涂层CF/PEEK复合材料的制备及体外成骨活性评价

Preparation and in vitro Osteogenic Activity Evaluation of Mn/nHA Coated CF/PEEK Composite

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