Li Xinlin, Li Qi, Tan Ji, Yu Yameng, Yuan Wei, Liu Xuanyong, Zheng Yufeng, Xia Dandan
Department of Dental Materials, Peking University School and Hospital of Stomatology & National Center for Stomatology & National Clinical Research Center for Oral Diseases & National Engineering Research Center of Oral Biomaterials and Digital Medical Devices & Beijing Key Laboratory of Digital Stomatology & NHC Key Laboratory of Digital Stomatology & NMPA Key Laboratory for Dental Materials, Beijing, 100081, China.
State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China.
Acta Biomater. 2025 May 15;198:497-513. doi: 10.1016/j.actbio.2025.04.010. Epub 2025 Apr 4.
Biodegradable zinc alloys are a promising research focus for bone implants due to their excellent bioactivity and mechanical properties, but the slow biodegradation rate and poor osseointegration limit their clinical application. In this study, calcium (Ca) ions were implanted into the surface of Zn-0.1Li alloys to improve their biodegradable, osteogenic, and angiogenic properties via the plasma immersion ion implantation (PIII) technique. FE-SEM and AFM results have demonstrated that Ca ion implantation appropriately increased the surface micro-roughness of the Zn-0.1Li alloy, thereby providing a larger contact surface area for biodegradation and osseointegration. Analysis using AES, XRD, and XPS revealed that Ca existed in the form of CaO. Based on SRIM simulations and FIB/TEM cross-sectional analysis, the thickness of the Ca ion implantation layer is approximately 52.2 nm, with a peak implantation dose exceeding 3.5 × 10⁵ atoms/cm². Static and electrochemical corrosion tests demonstrated that Ca ion implantation significantly accelerated the overall degradation behaviour of the Zn-0.1Li alloy and the release of zinc ions. In vitro experiments using MC3T3-E1 cells and HUVECs showed that Ca ion implantation samples significantly increased the expression of osteogenic genes (ALP, Runx2, OCN, and Col I) and angiogenic genes (VEGF, eNOS, and FGFR), demonstrating superior osteoinductive and angiogenic properties. Finally, in vivo rat femoral implantation studies revealed that Ca ion implantation samples exhibited enhanced biodegradation and osseointegration. In conclusion, Ca ion implantation effectively improved various properties of the Zn-0.1Li alloy, broadening its potential applications in dental and orthopedic fields. STATEMENT OF SIGNIFICANCE: Zn alloys are one of the most promising biodegradable metals and have become a research hotspot in dentistry and orthopedics. However, the slow biodegradation rate and poor osteoinductivity severely limit their clinical application. In this study, we implanted Ca ions into the surface of Zn-0.1Li alloys via PIII to modulate their properties. In vitro and in vivo studies have confirmed that Ca ion implantation can effectively improve the surface micromorphology, biodegradability, osteoinductivity and angiogenic properties of Zn-0.1Li alloys, making them more prospective for use in bone implants.
由于具有优异的生物活性和力学性能，可生物降解锌合金是骨植入物领域一个很有前景的研究热点，但降解速度缓慢和骨整合不良限制了它们的临床应用。在本研究中，通过等离子体浸没离子注入（PIII）技术将钙（Ca）离子注入到Zn-0.1Li合金表面，以改善其生物可降解性、成骨和血管生成性能。场发射扫描电子显微镜（FE-SEM）和原子力显微镜（AFM）结果表明，Ca离子注入适当增加了Zn-0.1Li合金的表面微观粗糙度，从而为生物降解和骨整合提供了更大的接触表面积。俄歇电子能谱（AES）、X射线衍射（XRD）和X射线光电子能谱（XPS）分析表明，Ca以CaO的形式存在。基于SRIM模拟和聚焦离子束/透射电子显微镜（FIB/TEM）截面分析，Ca离子注入层的厚度约为52.2 nm，峰值注入剂量超过3.5×10⁵原子/cm²。静态和电化学腐蚀试验表明，Ca离子注入显著加速了Zn-0.1Li合金的整体降解行为和锌离子的释放。使用MC3T3-E1细胞和人脐静脉内皮细胞（HUVECs）进行的体外实验表明，Ca离子注入样品显著增加了成骨基因（碱性磷酸酶（ALP）、Runx2、骨钙素（OCN）和I型胶原（Col I））和血管生成基因（血管内皮生长因子（VEGF）、内皮型一氧化氮合酶（eNOS）和纤维母细胞生长因子受体（FGFR））的表达，显示出优异的骨诱导和血管生成性能。最后，大鼠股骨体内植入研究表明，Ca离子注入样品表现出增强的生物降解和骨整合。总之，Ca离子注入有效地改善了Zn-0.1Li合金的各种性能，拓宽了其在牙科和骨科领域的潜在应用。重要意义声明：锌合金是最有前景的可生物降解金属之一，已成为牙科和骨科领域的研究热点。然而，缓慢的生物降解速度和较差的骨诱导性严重限制了它们的临床应用。在本研究中，我们通过PIII将Ca离子注入到Zn-0.1Li合金表面以调节其性能。体外和体内研究证实，Ca离子注入可以有效改善Zn-0.1Li合金的表面微观形态、生物降解性、骨诱导性和血管生成性能，使其在骨植入物应用方面更具前景。
