光热核壳TiN@硼硅酸盐生物玻璃纳米颗粒的降解和矿化性能

doi:10.15541/jim20220742

无机材料学报 ›› 2023, Vol. 38 ›› Issue (6): 708-716.DOI: 10.15541/jim20220742

• 研究快报 • 上一篇

光热核壳TiN@硼硅酸盐生物玻璃纳米颗粒的降解和矿化性能

吴锐¹(), 张敏慧¹, 金成韵¹, 林健¹^,²(), 王德平¹^,²

1.同济大学材料科学与工程学院, 上海 201804
2.同济大学教育部土木工程先进材料重点实验室, 上海 200092

收稿日期:2022-12-06 修回日期:2022-12-26 出版日期:2023-01-18 网络出版日期:2023-01-18
通讯作者: 林健, 教授. E-mail: lin_jian@tongji.edu.cn
作者简介:吴锐(1998-), 女, 硕士研究生. E-mail: 2030621@tongji.edu.cn

Photothermal Core-Shell TiN@Borosilicate Bioglass Nanoparticles: Degradation and Mineralization

WU Rui¹(), ZHANG Minhui¹, JIN Chenyun¹, LIN Jian¹^,²(), WANG Deping¹^,²

1. School of Materials Science and Engineering, Tongji University, Shanghai 201804, China
2. Key Laboratory of Advanced Civil Engineering Materials, Ministry of Education, Tongji University, Shanghai 200092, China

Received:2022-12-06 Revised:2022-12-26 Published:2023-01-18 Online:2023-01-18
Contact: LIN Jian, professor. E-mail: lin_jian@tongji.edu.cn.
About author:WU Rui (1998-), female, Master candidate. E-mail: 2030621@tongji.edu.cn
Supported by:
National Natural Science Foundation of China(51972232);National Key Research and Development Projects(2018YFC1106300)

摘要/Abstract

摘要：

硼硅酸盐生物玻璃以其稳定的结构和优异的生物活性而受到广泛关注, 但生物玻璃在矿化过程中活性呈现初期快而中后期慢的趋势, 造成后期的活性降低。光热可加速生物玻璃降解, 本研究制备了以氮化钛为核、生物玻璃(40SiO₂-20B₂O₃-36CaO-4P₂O₅)为壳的复合生物玻璃, 利用光热场干预生物玻璃的矿化过程。结果表明, 生物玻璃具有显著的光热效应, 光热能力随氮化钛掺杂量和激光功率密度的增加而提高；在体外浸泡中, 近红外光辐照促进了生物玻璃的降解, 浸泡7 d后模拟体液中钙、硼的含量分别增加12%~16%和8%~11%, 加速了羟基磷灰石的生成；细胞增殖活性实验表明样品有良好的生物安全性。因此, 光热场可促进生物玻璃降解和矿化, 对周围细胞影响小, 有望在保障初期生物安全的同时发挥调节作用。

关键词: 硼硅酸盐生物活性玻璃, 核壳结构, 光热性能, 矿化性能

Abstract:

Borosilicate bioglass has attracted extensive attention due to its stable structure and excellent biological activity. However, the rate of its mineralization process is fast in the initial stage and slow in the middle and late stages, which limits the application of borosilicate bioglass. As an auxiliary method, the near-infrared (NIR) laser can accelerate the degradation of bioglass. Therefore, we prepared a core-shell borosilicate bioglass with titanium nitride as the core and bioglass (40SiO₂-20B₂O₃-36CaO-4P₂O₅) as the shell, and used near-infrared laser regulation technology to intervene the mineralization process of the composite bioglass. The experimental results show that the core-shell bioglass exhibits a significant photothermal effect, and the photothermal ability increases with the increases of the doping amount of TiN NPs and the laser power density. During the in vitro immersion, near-infrared laser increased the degradation rate of bioglass. After immersion for 7 d, the contents of calcium and boron in the SBF are increased by 12%-16% and 8%-11%, respectively. Meanwhile, the formation efficiency of hydroxyapatite is significantly improved. Cell proliferation activity test shows that the sample has good biological safety. Therefore, near-infrared light can accelerate the degradation and mineralization of functional core-shell bioactive glass, which is expected to play a regulatory role.

Key words: borosilicate bioactive glass, core-shell structure, photothermal performance, mineralization

中图分类号:

TQ171

吴锐, 张敏慧, 金成韵, 林健, 王德平. 光热核壳TiN@硼硅酸盐生物玻璃纳米颗粒的降解和矿化性能[J]. 无机材料学报, 2023, 38(6): 708-716.

WU Rui, ZHANG Minhui, JIN Chenyun, LIN Jian, WANG Deping. Photothermal Core-Shell TiN@Borosilicate Bioglass Nanoparticles: Degradation and Mineralization[J]. Journal of Inorganic Materials, 2023, 38(6): 708-716.

图/表 10

Fig. 1 Preparation process of core-shell xTiN@58S-20B nanoparticles CTAB: Hexadecyl trimethyl ammonium bromide; TEOS: Tetraethyl orthosilicate; TBB: Tributyl borate

Fig. 2 Degradation of bioglass nanoparticles in vitro with and without laser irradiation

Fig. 3 Micrographs of xTiN@58S-20B (x=0, 0.02, 0.04) with insets showing the corresponding particle size distributions (a1, b1, c1) SEM images; (a2, b2, c2) TEM images; (a3, b3, c3) EDS spectra

Fig. 4 XRD patterns of xTiN@58S-20B (x=0, 0.02, 0.04), with gray shaded parts A, B, and C showing the glass peak areas, while b and c showing the strongest peak area of the TiN NPs

Fig. 5 Temperature rise diagrams of three samples in air with 1064 nm NIR laser at a power density of 1.0 W/cm2 for 60 s, with insets showing the infrared images correspondingly at each time point, X axial representing the radial distance extending to both sides from the sample center, and the Y axial representing the temperature

Fig. 6 Temperature changes of bioglass (a-c) Temperature changes of 58S-20B (a), 0.02TiN@58S-20B (b), 0.04TiN@58S-20B (c) irradiated by 1064 nm NIR laser at different power density (0.38, 0.42, 0.46, 0.50 W/cm2) for 3 min; (d)Temperature versus power density; (e) Heating curves of three samples under 1064 nm laser irradiation (1.0 W/cm2)

Fig. 7 pH changes and ions release of bioglass samples immersed in SBF at 37 ℃ for 7 d (a-c) pH changes within 7 d; (d-f) Ion release profiles of B, Ca, Si on the 7th day

Fig. 8 SEM images of borosilicate samples immersed in SBF for 7 d with insets showing corresponding EDS spectra (a1, b1, c1) Without NIR laser irradiation; (a2, b2, c2) With NIR laser irradiation

Fig. 9 XRD patterns of mineralization products of three samples with and without laser irradiation

Fig. 10 Cell proliferation activity and cell morphology analysis of control, 58S-20B, 0.02TiN@58S-20B, and 0.04TiN@58S-20B (a) CCK-8 analysis; (b) Fluorescent images of cell morphology. Blue indicates the cell nucleus and red indicates the cell cytoskeleton

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光热核壳TiN@硼硅酸盐生物玻璃纳米颗粒的降解和矿化性能

Photothermal Core-Shell TiN@Borosilicate Bioglass Nanoparticles: Degradation and Mineralization

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