基于可降解镁合金的 Cu(Ga)@ZIF-8-MAO 复合涂层的制备及其抗菌性能研究

镁合金因其独特的可降解性、良好的力学性能和生物相容性，在植入器械领域具有广阔的应用前景。然而，临床上镁合金仍面临着降解速度过快和缺乏体内抗菌性能等问题。基于此，本文在WE43镁合金表面微弧氧化(MAO)涂层的基础上，基于ZIF-8 的载体特性和Cu、Ga元素的抗菌功能，在镁合金表面构建Cu@ZIF-8-MAO和Ga@ZIF-8-MAO复合涂层。

(1) 利用室温原位生长法，在含Zn(NO3 )2，CuSO4和二甲基咪唑的无水甲 醇 混 合 溶 液 中 反 应 1 ， 6 ， 12 和 24 h 分 别获得 Cu@ZIF-8-MAO(1h) ，Cu@ZIF-8-MAO(6h) ， Cu@ZIF-8-MAO(12h) 和 Cu@ZIF-8-MAO(24h) 样品。利用SEM，EDS和XRD对样品进行表征，结果显示所有样品表面均分布着尺寸为1.5~2.8 μm、由十二面体几何结构的颗粒构成的Cu@ZIF-8涂层。Cu@ZIF-8-MAO涂层由MgO和Cu掺杂的ZIF-8构成，厚度12.5 ~78.0 μm。除Cu@ZIF-8-MAO (24h)涂层呈现较多的孔洞外，其它涂层质量较好。浸泡实验(离子溶出)和电化学腐蚀研究(动电位极化曲线，开路电位，EIS阻抗 谱 ) 结 果 显 示 ， 样 品 的 腐 蚀 降 解 速 率 依 次 为 Cu@ZIF-8-MAO(12h) Cu@ZIF-8-MAO(1h)外，其他样品对E.coli和S.aureus的抗菌率均为100%。

(2) 利 用 室 温 原 位 生 长 法 和 离 子 交 换 法 ，在含Zn(NO3 )2，Hmim和Ga(NO3 )3 的 无 水 甲 醇 混 合 溶 液 中 反 应 分 别 获 得 Ga@ZIF-8-MAO(1h) ，Ga@ZIF-8-MAO(2h) 和 Ga@ZIF-8-MAO(3h) 样 品 。 结 果 显 示 ， 所 有Ga@ZIF-8-MAO样品表面均分布着尺寸约为500 nm的正十二面体颗粒组成的Ga@ZIF-8涂层。涂层由MgO和Ga掺杂的ZIF-8构成，厚度11.2 ~12.8 μm。电化学研究显示，Ga@ZIF-8-MAO比MAO和ZIF-8-MAO样品的耐腐蚀性能略有降低，但其降解速率仍显著低于未处理镁合金。在Ga掺杂的样品中，Ga@ZIF-8-MAO(3h)样品表现出最佳的耐腐蚀性能。抗菌研究结果显示所有Ga@ZIF-8-MAO样品对E.coli和S.aureus的抗菌率均为100%。(3) 在 本 文 制 备 的 样 品 中 ， Cu@ZIF-8-MAO (12h) 、 Cu@ZIF-8-MAO(6h)以及Ga@ZIF-8-MAO(3h)样品在涂层质量、耐腐蚀及抗菌性能方面表现出优异的综合性能，在植入器械领域具有潜在的应用前景。

Magnesium alloys have large potential for the application in the implantable devices fields due to their unique biodegradability, favorable mechanical properties, and biocompatibility. However, in the clinic, these alloys still face challenges such as rapid degradation and a lack of antibacterial property in the human body. To address these issues, Cu@ZIF-8-MAO and Ga@ZIF-8-MAO composite coatings were introduced to the surface of WE43 magnesium alloys on our previous microarc oxidation (MAO) layer in this study, considering the carrier characteristics of ZIF-8 and the antibacterial capabilities of Cu and Ga elements.

(1) Cu@ZIF-8-MAO samples were prepared by using an in-situ growth method at room temperature in an anhydrous methanol containing Zn(NO₃)₂, CuSO₄, and Hmim. After 1, 6, 12, and 24 h of reaction, Cu@ZIF-8-MAO (1h), Cu@ZIF-8-MAO(6h), Cu@ZIF-8-MAO(12h), and Cu@ZIF-8-MAO(24h) samples were formed, respectively. SEM, EDS, and XRD results revealed that all samples surfaces were composed of uniformly distributed dodecahedral Cu@ZIF-8 particles with the size of 1.5 to 2.8 μm. Cu@ZIF-8-MAO coatings consisted of MgO and Cu-doped ZIF-8, with the thicknesses ranging from 12.5 to 78.0 μm. Apart from the Cu@ZIF-8-MAO (24h) coating showing many corrosion pores, the other Cu doped coatings revealed good quality. Immersion tests (ion release) and electrochemical corrosion studies (potentiodynamic polarization curves, open circuit potential, EIS impedance spectroscopy) showed the degradation rate of the samples in the following order: Cu@ZIF-8-MAO(12h) < Cu@ZIF-8-MAO(6h) < Cu@ZIF-8-MAO(1h) < Cu@ZIF-8-MAO(24h) < MAO < untreated magnesium alloy. Antibacterial assessments (plate counting method, live/dead staining, and SEM) indicated that all Cu-doped samples except Cu@ZIF-8-MAO(1h) achieved a 100% antibacterial efficiency against both E. coli and S. aureus.

(2) Ga@ZIF-8-MAO samples were synthesized by a combination of in-situ growth at room temperature and ion exchange in an anhydrous methanol solution containing Zn(NO₃)₂, Hmim, and Ga(NO₃)₃. The formed samples were abbreviated as Ga@ZIF-8-MAO(1h), Ga@ZIF-8-MAO(2h), and Ga@ZIF-8-MAO(3h) samples. The results revealed that all Ga@ZIF-8-MAO samples were uniformly coated with approximately dodecahedral Ga@ZIF-8 particles at the size of 500 nm. These coatings consisted of MgO and Ga-doped ZIF-8, with the thicknesses ranging from 11.2 to 12.8 μm. Electrochemical studies suggested a slight reduction in corrosion resistance for Ga@ZIF-8-MAO compared to MAO and ZIF-8-MAO samples. However, their degradation rates were still significantly lower than those of the untreated magnesium alloys. Among the Ga-doped samples, Ga@ZIF-8-MAO(3h) demonstrated the best corrosion resistance. Antibacterial studies indicated a 100% antibacterial rate against both E. coli and S. aureus for all the Ga@ZIF-8-MAO samples.

(3) All in all, Cu@ZIF-8-MAO (12h), Cu@ZIF-8-MAO (6h), and Ga@ZIF-8-MAO (3h) exhibited excellent overall performance in terms of coating quality, corrosion resistance, and antibacterial activity among all the samples in this study, showing potential applications as implantable devices in the future.

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