钛表面聚多巴胺钝化掺锶黑磷纳米片复合涂层的构建及性能

王丙乾; 李美婷; 崔艺严; 曾辉; 黄硕; 郭芳; 刘昌奎

doi:10.16490/j.cnki.issn.1001-3660.2025.22.020

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表面技术 ›› 2025, Vol. 54 ›› Issue (22) : 208-215. DOI: 10.16490/j.cnki.issn.1001-3660.2025.22.020

表面功能化

钛表面聚多巴胺钝化掺锶黑磷纳米片复合涂层的构建及性能

王丙乾^1,2, 李美婷², 崔艺严², 曾辉², 黄硕², 郭芳², 刘昌奎^1,2*

作者信息 +

Preparation and Performance of In-situ Deposition of Titanium Scaffolds with Polydopamine Passivated Europium-doped Black Phosphorus Nanosheets

WANG Bingqian^1,2, LI Meiting², CUI Yiyan², ZENG Hui², HUANG Shuo², GUO Fang², LIU Changkui^1,2*

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文章历史 +

摘要

目的为克服钛合金（Ti-6Al-4V,Ti）样品表面生物惰性的弊端,通过在其表面引入聚多巴胺钝化掺锶（Sr）黑磷纳米片（Black Phosphorus Nanosheets,BPNs）涂层对其改性,以期提高Ti样品生物活性和骨整合能力。方法采用扫描电镜（SEM）、能谱仪（EDS）、X射线光电子能谱（XPS）、Zeta电位、拉曼光谱对改性前后的Ti表面进行表征。通过体外矿化实验和细胞黏附实验评价涂层对矿化能力和对细胞生长情况的影响。结果 SEM显示,Ti-PDA样品表面可见球形颗粒状聚集体分布,引入BPNs和Sr²⁺后,可观察到大量纳米片被PDA纳米颗粒所包裹;EDS及XPS分析显示,涂层中具有明显的P、Sr、N元素分布;Zeta电位结果显示BPNs、BP+Sr和PDA@(BP+Sr)电势分别为（-20.30±1.64）mV,（-5.76±1.07）mV,（-12.73± 0.42） mV;拉曼光谱图中PDA@(BP+Sr)组显示出二维材料BPNs中的特征拉曼吸收峰（A¹_g、B_2g、A²_g）,且相比纯BPNs组仅有轻微的位移,说明Ti-PDA@(BP+Sr)复合样品成功制备。体外矿化实验表明,Ti-PDA@BP与Ti-PDA@(BP+Sr)组表面有更多的颗粒沉积,富集一定的钙盐,证明涂层的引入提升了样品表面的矿化能力;细胞实验结果显示,PDA@(BP+Sr)涂层处理样品表面细胞增多,单个细胞铺展面积大。结论在Ti样品表面构建PDA@(BP+Sr)涂层,可有效提高样品表面生物活性,利于细胞铺展,为克服纯Ti样品常见的表面生物惰性提供了一种新策略,可增强其在骨缺损修复重建等领域的应用潜力。

Abstract

The work aims to solve the defects of bioinertness on the surface of titanium alloy (Ti-6Al-4V) bone tissue engineering scaffold. The titanium alloy was modified by inserting a coating of strontium-doped black phosphorus nanoparticle with polydopamine on its surface, which improved the biological activity and bone integration ability of the Ti scaffold. Titanium alloy (Ti-6Al-4V) was designed and prepared as the substrate for the biological scaffold of bone tissue engineering. The black phosphorus nanosheets were covalently bonded with bioactive strontium by polyelectrolyte complex method. Through a simple oxidative self-polymerization reaction of dopamine (DA), polydopamine (PDA) was carried out on the surface of the scaffold, and a hierarchical structure with a composite monolayer of PDA was also obtained. At the same time, PDA@(BP+Sr) functional biological coating was successfully constructed on the surface of Ti-PDA through the secondary reaction function of PDA coating. The titanium surface before and after modification was characterized and analyzed by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectrometer (XPS), Zeta potentiometer and Raman spectrometer. The effects of the coating on mineralization ability and cell growth were evaluated by in vitro mineralization experiment and cell adhesion experiment. The prepared Ti scaffold coated with PDA@(BP+Sr) was tested, and the results showed that it had better biological activity and bone integration ability. SEM showed that the surface of the Ti scaffold was relatively smooth. Through oxidation and self-polymerization of PDA, spherical particle aggregates were uniformly distributed on the surface of the titanium PDA scaffold. After loading of BPNs and Sr²⁺, a large number of nanosheets were observed to be wrapped by PDA nanoparticles. EDS analysis and XPS analysis showed that P, Sr and N elements in the coating were obviously distributed. The zeta potentials of BPNs, BP+Sr and PDA@(BP+Sr) were (-20.30±1.64) mV, (-5.76±1.07) mV and (-12.73±0.42) mV, respectively, which indicated that the Ti-PDA@(BP+Sr) composite scaffold was successfully prepared. The Raman spectra of PDA@(BP+Sr) group showed characteristic Raman absorption peaks (A¹_g, B_2g, A²_g) in the two-dimensional material BPNs, indicating that the preparation of PDA@(BP+Sr) did not change the original lattice structure of BPNs, and retained its good characteristics as a carrier. In vitro mineralization experiments showed that the surface of Ti-PDA@BP and Ti-PDA@(BP+Sr) groups had more particle deposition and enriched some calcium salts, which proved that the combination of phosphate and calcium ions generated by BPNs degradation improved the mineralization ability of the scaffold. The surface of the scaffold was seeded with bone marrow mesenchymal stem cells (BMSCs) for 4 h. SEM showed that the number of cells on the surface of the scaffold treated with PDA@(BP+Sr) coating increased, the area of single cells spread larger, and the number of adherent cells extending out of the synapse was significantly better than that of the Ti group. The experimental results show that the PDA@(BP+Sr) coating on the surface of the Ti scaffold can effectively improve the biological activity of the scaffold and promote cell adhesion and proliferation, which will provide a new strategy for overcoming the common surface biological inertia of pure Ti scaffolds, so as to enhance its application potential in bone defect repair and reconstruction.

导出引用

王丙乾, 李美婷, 崔艺严, 曾辉, 黄硕, 郭芳, 刘昌奎. 钛表面聚多巴胺钝化掺锶黑磷纳米片复合涂层的构建及性能[J]. 表面技术. 2025, 54(22): 208-215 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.22.020

WANG Bingqian, LI Meiting, CUI Yiyan, ZENG Hui, HUANG Shuo, GUO Fang, LIU Changkui. Preparation and Performance of In-situ Deposition of Titanium Scaffolds with Polydopamine Passivated Europium-doped Black Phosphorus Nanosheets[J]. Surface Technology. 2025, 54(22): 208-215 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.22.020

中图分类号： TG335.86 R318.08

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