可降解<strong>Zn</strong>表面金属<strong>-</strong>多酚载药涂层骨生成和抗菌性能

doi:10.11900/0412.1961.2023.00035

金属学报

2024, Vol. 60

Issue (11): 1545-1558 DOI: 10.11900/0412.1961.2023.00035

研究论文

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可降解Zn表面金属-多酚载药涂层骨生成和抗菌性能

林雪¹^,², 钱军余¹^,², 张文泰¹^,², 王鹏¹^,², 万国江¹^,²(

)

1 西南交通大学医学院材料先进技术教育部重点实验室成都 610031
2 西南交通大学材料科学与工程学院成都 610031

Osteogenic and Antibacterial Metal-Polyphenol Drug-Loaded Coating on Biodegradable Zinc for Orthopedic Implants Application

LIN Xue¹^,², QIAN Junyu¹^,², ZHANG Wentai¹^,², WANG Peng¹^,², WAN Guojiang¹^,²(

)

1 Key Laboratory of Advanced Technologies of Materials (Ministry of Education), College of Medicine, Southwest Jiaotong University, Chengdu 610031, China
2 School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu 610031, China

引用本文:

林雪, 钱军余, 张文泰, 王鹏, 万国江. 可降解Zn表面金属-多酚载药涂层骨生成和抗菌性能[J]. 金属学报, 2024, 60(11): 1545-1558.
Xue LIN, Junyu QIAN, Wentai ZHANG, Peng WANG, Guojiang WAN. Osteogenic and Antibacterial Metal-Polyphenol Drug-Loaded Coating on Biodegradable Zinc for Orthopedic Implants Application[J]. Acta Metall Sin, 2024, 60(11): 1545-1558.

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摘要:

Zn及其合金因其适中的降解速率和潜在的生物功能性在骨植入体领域展现出广泛的应用前景。然而，其降解过程中存在Zn²⁺释放过快导致促骨生成能力不足、不均匀腐蚀造成力学性能失效以及较差的抗菌性能等问题，限制了其应用。本工作采用交替沉积法，利用活性金属离子与单宁酸螯合并负载二甲双胍在Zn表面制备金属-多酚载药功能涂层。结果表明，该涂层结构致密，提高了Zn基底的抗腐蚀能力，改善了腐蚀降解模式，延缓Zn²⁺释放并调控二甲双胍的释放；体外前成骨细胞(MC3T3-E1)培养证实该涂层具有优异的促骨生成能力；抗菌实验结果表明该涂层具有优异的抗菌效果。

关键词 ：可降解Zn, 活性金属离子, 金属-多酚载药涂层, 促骨生成, 抗菌性能

Abstract：

Biodegradable metallic Zn materials are being considered for orthopedic implant applications because of their moderate degradation rate and potential bio-functionalities. Nevertheless, their clinical use is limited due to inadequate osteogenic properties owing to Zn²⁺ burst release, premature mechanical failure caused by non-uniform corrosion, and poor antibacterial ability. Therefore, to overcome these issues, a metal-polyphenol drug-loaded coating was functionalized on the surface using an alternating chemical deposition method out of tannic acid/metformin molecules and active metallic ions via coordination/chelation reactions. The coating was characterized by homogeneous compactness, which enhanced the corrosion resistance of the Zn substrate, adjusted the corrosion mode, suppressed the release of Zn²⁺, and regulated metformin release. The in vitro pre-osteoblasts (MC3T3-E1) culture results showed that the coated Zn samples exhibited excellent osteogenic ability. The antibacterial assays with coated Zn samples demonstrated strong antibacterial efficiency.

Key words： biodegradable Zn active metallic ion metal-polyphenol drug-loaded coating osteogenesis antibacterial property

收稿日期: 2023-02-02

ZTFLH:

TG146.1

基金资助:国家重点研发计划项目(2016YFC1102500);四川省科技计划项目(2020YFH0077);四川省科技计划项目(2024YFHZ0310);材料腐蚀与防护四川省重点实验室开放基金项目(2022CL07)

通讯作者: 万国江，guojiang.wan@home.swjtu.edu.cn，主要从事可降解金属材料及表面改性的研究

Corresponding author: WAN Guojiang, professor, Tel: (028)87600723, E-mail: guojiang.wan@home.swjtu.edu.cn

作者简介: 林雪，女，1996年生，硕士

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图1 纯Zn、多酚载药涂层(TA/Met)、金属-多酚载药涂层(Cu-TA/Met、Fe-TA/Met、Mg-TA/Met和Sr-TA/Met)表面形貌的SEM像

图2 纯Zn、TA/Met、Cu-TA/Met、Fe-TA/Met、Mg-TA/Met和Sr-TA/Met的FTIR谱

图3 TA/Met、Cu-TA/Met、Fe-TA/Met、Mg-TA/Met和Sr-TA/Met的高分辨XPS

表1 样品表面元素含量 (atomic fraction / %)

图4 Zn、TA/Met、Cu-TA/Met、Fe-TA/Met、Mg-TA/Met和Sr-TA/Met样品在(37 ± 0.5)℃下Hank's溶液中的动电位极化曲线，自腐蚀电位和自腐蚀电流密度，Nyquist和拟合等效电路图，及Bode-阻抗和Bode-相位角图

表2 EIS拟合结果

图5 Zn、TA/Met、Cu-TA/Met、Fe-TA/Met、Mg-TA/Met和Sr-TA/Met在(37 ± 0.5)℃下Hank's溶液中浸泡21 d后表面形貌的SEM像

图6 纯Zn、TA/Met、Cu-TA/Met、Fe-TA/Met、Mg-TA/Met和Sr-TA/Met在(37 ± 0.5)℃下Hank's溶液中浸泡21 d后的XRD谱、Zn2+累计释放量、pH累计变化量和二甲双胍累计释放量

图7 Zn、TA/Met、Cu-TA/Met、Fe-TA/Met、Mg-TA/Met和Sr-TA/Met在(37 ± 0.5)℃下Hank's溶液中浸泡21 d去除腐蚀产物后表面形貌的SEM像

图8 MC3T3-E1在不锈钢(SS)、Zn、TA/Met、Cu-TA/Met、Fe-TA/Met、Mg-TA/Met和Sr-TA/Met样品表面培养1 d后的荧光图像

图9 MC3T3-E1在SS、Zn、TA/Met、Cu-TA/Met、Fe-TA/Met、Mg-TA/Met和Sr-TA/Met样品表面培养1 d后的细胞黏附数量和碱性磷酸酶(ALP)活性定量结果

图10 MC3T3-E1在SS、Zn、TA/Met、Cu-TA/Met、Fe-TA/Met、Mg-TA/Met和Sr-TA/Met样品表面培养14 d后的ALP染色结果

图11 金黄色葡萄球菌(S.aureus)和大肠杆菌(E.coli)在SS、Zn、TA/Met、Cu-TA/Met、Fe-TA/Met、Mg-TA/Met和Sr-TA/Met表面孵育1 d的菌落数和抗菌率

图12 金属-多酚载药涂层的构建机制

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