钽离子注入对镍钛合金表面生物学性能的影响

doi:10.15541/jim20220140

无机材料学报 ›› 2022, Vol. 37 ›› Issue (11): 1217-1224.DOI: 10.15541/jim20220140

钽离子注入对镍钛合金表面生物学性能的影响

吴凌¹^,²(), 谭继¹, 钱仕¹^,³, 葛乃建⁴, 刘宣勇¹^,²^,³()

1.中国科学院上海硅酸盐研究所高性能陶瓷与超微结构国家重点实验室, 上海 200050
2.中国科学院大学材料科学与光电工程中心, 北京 100049
3.慈溪生物材料表面工程中心, 宁波 315300
4.海军军医大学东方肝胆外科医院, 上海 200438

收稿日期:2022-03-13 修回日期:2022-04-18 出版日期:2022-05-07 网络出版日期:2022-05-07
通讯作者: 刘宣勇, 研究员. E-mail: xyliu@mail.sic.ac.cn
作者简介:吴凌(1997-), 男, 硕士研究生. E-mail: 18373153250@163.com
基金资助:
国家自然科学基金面上项目(31971249);上海市基础研究重点项目(19JC1415500);宁波市高层次人才和高端创新创业团队引进计划(2018A-09-C)

Biological Property Investigation of Nitinol Surface Implanted with Tantalum

WU Ling¹^,²(), TAN Ji¹, QIAN Shi¹^,³, GE Naijian⁴, LIU Xuanyong¹^,²^,³()

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Science, Beijing 100049, China
3. Cixi Center of Biomaterials Surface Engineering, Ningbo 315300, China
4. Eastern Hepatobilialy Surgery Hospital, Naval Medical University, Shanghai 200438, China

Received:2022-03-13 Revised:2022-04-18 Published:2022-05-07 Online:2022-05-07
Contact: LIU Xuanyong, professor. E-mail: xyliu@mail.sic.ac.cn
About author:WU Ling (1997-), male, Master candidate. E-mail: 18373153250@163.com
Supported by:
National Natural Science Foundation of China(31971249);The Key Project of Fundamental Research of Shanghai(19JC1415500);High-level Talents and Innovative and High-end Entrepreneur Team Introduction Plan of Ningbo(2018A-09-C)

摘要/Abstract

摘要：

镍钛合金血管支架植入后可引发血栓和支架再狭窄, 且对损伤的血管内壁无修复作用, 需进行表面改性赋予其抗凝血和促内皮化生物学功能。本研究采用等离子体浸没离子注入与沉积(PIII&D)技术将钽(Ta)注入至镍钛合金, 研究Ta离子注入对镍钛表面理化特性及生物学性能的影响规律。结果表明, 调控Ta离子注入时间, 可在镍钛表面分别构建含Ta、Ta/Ta₂O₅、Ta/Ta₂O_5-_x/Ta₂O₅三种不同组分的改性层。各种改性样品中, 含Ta/Ta₂O_5-_x/Ta₂O₅的改性镍钛表面亲水性均更好, 可提供更多细胞附着位点, 促进人脐静脉内皮细胞早期粘附和铺展, 并提高其增殖能力。相比仅含单质Ta的改性镍钛表面, 含Ta/Ta₂O_5-_x/Ta₂O₅改性镍钛表面的血液相容性更高, 血小板粘附数量显著减少, 且基本保持为未被激活的球形状态; 各组改性表面的溶血率远低于5%阈值, 均未发生明显溶血现象。上述结果说明, Ta离子注入改性镍钛血管支架在降低血栓形成、加速内皮化方面具有潜在应用。

关键词: 镍钛合金, 钽, 离子注入, 血液相容性

Abstract:

Nitinol vascular stent can trigger thrombosis and restenosis, but lacks the ability to rehabilitate with injury still to the blood vessel wall. Thus, surface modification to the stent is indispensable for nitinol surfaces to realize biological functions of anticoagulation and accelerate endothelialization. Here, tantalum ions were implanted into nitinol surfaces by plasma immersion ion implantation and deposition (PIII&D). Physicochemical and biological characteristics of the modified nitinol surfaces were analyzed. The results show that the Ta, Ta/Ta₂O₅, and Ta/Ta₂O_5-_x/Ta₂O₅-containing modified layers are formed on nitinol surfaces with extension of implantation time. Among all samples, the modified surface containing Ta/Ta₂O_5-_x/Ta₂O₅ phase possesses better hydrophilicity and provides more sites for cell attachment to promote initial cell adhesion and proliferation. Compared with the solely Ta-bearing surface, the modified surface containing Ta/Ta₂O_5-_x/Ta₂O₅ shows superior hemocompatibility, on which fewer adhered platelets are observed, maitaining an inactive and original spherical shape. Besides, the hemolysis rates of all samples are far below the threshold value of 5%, indicating that hemolysis hardly happens. The results indicate that Ta ion implantation modified nitinol stent has a potential application in reducing thrombosis and accelerating endothelialization.

Key words: nitinol, tantalum, ion implantation, hemocompatibility

中图分类号:

TQ174

吴凌, 谭继, 钱仕, 葛乃建, 刘宣勇. 钽离子注入对镍钛合金表面生物学性能的影响[J]. 无机材料学报, 2022, 37(11): 1217-1224.

WU Ling, TAN Ji, QIAN Shi, GE Naijian, LIU Xuanyong. Biological Property Investigation of Nitinol Surface Implanted with Tantalum[J]. Journal of Inorganic Materials, 2022, 37(11): 1217-1224.

图/表 11

表1 钽等离子体浸没离子注入与沉积工艺参数

Table 1 Process parameters of tantalum plasma immersion ion implantation and deposition

Parameters	Target	Cathodic arc
Voltage pulse duration/μs	500	800
Pulsing frequency/Hz	10	10
Implantation voltage/kV	-15	-
Implantation time/min	30, 60, 120	-

图1 样品表面形貌的SEM照片

Fig. 1 SEM images of surface morphologies of different samples

图2 样品的XRD图谱

Fig. 2 XRD patterns of different samples

图3 (a)样品表面的XPS全谱和(b~d)Ta4f 高分辨图谱

Fig. 3 (a) XPS full spectra and (b-d) Ta4f high-resolution XPS spectra detected from samples’ surfaces The color figures can be obtained from online edition.

图4 样品的接触角

Fig. 4 Contact angles of various samples The color figures can be obtained from online edition (**: p<0.01)

图5 样品在生理盐水中的极化曲线

Fig. 5 Polarization curves of various samples in physiological saline. The color figure can be obtained from online edition

表2 样品的腐蚀电位与腐蚀电流

Table 2 Corrosion potentials and corrosion currents of various samples

Sample	E_corr/V	I_corr/(A∙cm^-2)
NiTi	-0.288	5.65×10^-6
30Ta-NiTi	-0.288	6.37×10^-6
60Ta-NiTi	-0.261	6.69×10^-6
120Ta-NiTi	-0.251	6.62×10^-6

图6 HUVECs在样品表面培养1、4、24 h的荧光照片

Fig. 6 Fluorescent images of HUVECs adhered to various samples at 1, 4, and 24 h The color figures can be obtained from online edition

图7 样品表面培养4 d的HUVECs的活/死细胞染色荧光图像

Fig. 7 Live (green)/dead (red) cell staining fluorescent images of HUVECs seeded on samples for 4 d The color figures can be obtained from online edition

图8 HUVECs在样品表面培养1、4、7 d的细胞活性

Fig. 8 Cell viability of HUVECs cultured on sample surfaces for 1, 4 and 7 d The color figures can be obtained from online edition *: p<0.05, *: p<0.01, ***: p<0.001

图9 (a)样品表面的血小板粘附SEM照片和(b)各组样品的溶血率

Fig. 9 (a) SEM images of adhered platelets on sample surfaces and (b) hemolysis rate of various samples Arrows indicate the stimulated platelets; The color figures can be obtained from online edition

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钽离子注入对镍钛合金表面生物学性能的影响

Biological Property Investigation of Nitinol Surface Implanted with Tantalum

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