近红外光响应的双相抗菌介孔生物活性玻璃复合支架的制备及抗菌性能研究

doi:10.15541/jim20250030

无机材料学报 ›› 2025, Vol. 40 ›› Issue (10): 1137-1144.DOI: 10.15541/jim20250030

近红外光响应的双相抗菌介孔生物活性玻璃复合支架的制备及抗菌性能研究

张博¹(), 付一敏¹, 陈政¹^,², 石澳¹, 朱敏¹()

¹ 上海理工大学材料与化学学院, 上海 200050
² 泰州学院医药与化学化工学院, 泰州 225300

收稿日期:2025-01-20 修回日期:2025-02-24 出版日期:2025-07-16 网络出版日期:2025-07-16
通讯作者: 朱敏, 副研究员. E-mail: mzhu@usst.edu.cn
作者简介:张博(1999-), 男, 硕士研究生. E-mail: 15993162824@163.com
基金资助:
国家自然科学基金(52072246)

Near-infrared Responsive Biphasic Antibacterial Mesoporous Bioactive Glass Composite Scaffolds: Preparation and Antibacterial Performance

ZHANG Bo¹(), FU Yimin¹, CHEN Zheng¹^,², SHI Ao¹, ZHU Min¹()

¹ School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200050, China
² School of Pharmacy and Chemical Engineering, Taizhou University, Taizhou 225300, China

Received:2025-01-20 Revised:2025-02-24 Published:2025-07-16 Online:2025-07-16
Contact: ZHU Min, associate professor, E-mail: mzhu@usst.edu.cn
About author:ZHANG Bo (1999-), male, Master candidate. E-mail: 15993162824@163.com
Supported by:
National Natural Science Foundation of China(52072246)

摘要/Abstract

摘要：

骨植入材料易感染且具有高发性、迟发性和复发性。然而, 目前常见的抗菌手段通常缺乏选择性, 容易在杀菌的同时对正常组织和细胞造成损害。基于此, 本研究以介孔生物活性玻璃(MBG)为原料, 结合S-NO键的近红外(NIR)光热响应释放NO自由基及Cu²⁺抗菌性能, 采用氨基化偶联S-亚硝基硫醇(RSNO)制备了MBG-RSNO粉体以供给NO·, 并通过多巴胺聚合及Cu²⁺螯合合成了PMBG@Cu粉体。将上述两种粉体材料经3D打印得到PMBG@Cu/MBG-RSNO复合抗菌支架。该支架具有NIR光热响应特性, 在808 nm激光脉冲辐照条件下, 支架持续释放的一氧化氮自由基(NO·)含量高达113.71 μg/100 mg MBG-RSNO, 且光热作用将温度升高至约40 ℃, 有利于实现高效灭菌。进一步使用金黄色葡萄球菌(S. aureus)和大肠杆菌(E. coli) 评估复合支架在有/无外部NIR刺激条件下的抗菌效果。实验结果显示, PMBG@Cu/MBG-RSNO复合支架对两种菌种的抗菌效率均达到了99.9%。综上所述, PMBG@Cu/MBG-RSNO复合支架为解决骨植入材料的感染问题并实现骨缺损修复提供了一种潜在的解决方案。

关键词: 介孔生物活性玻璃, 抗菌, 一氧化氮, 光热效应

Abstract:

Bone implant-related infections are characterized by a high risk of delayed incidence or recurrence. Current antibacterial strategies often lack selectivity, leading to collateral damage to normal tissues and cells during bacterial eradication. To address this, mesoporous bioactive glass (MBG) was used as a base material in this study. By leveraging the near-infrared (NIR) photothermal response of S-NO bonds to release NO radicals and the antibacterial properties of Cu²⁺, MBG-RSNO powder was synthesized through amino-functionalized conjugation of S-nitrosothiols (RSNO) for nitric oxide free radicals (NO·) delivery, while PMBG@Cu powder was prepared via dopamine polymerization and Cu²⁺ chelation. These two powder materials were further processed through 3D printing to fabricate a PMBG@Cu/MBG-RSNO composite antibacterial scaffold. This scaffold demonstrated a strong NIR photothermal response, with pulsed 808 nm laser irradiation enabling the sustained release of NO· up to 113.71 μg per 100 mg of MBG-RSNO and increasing the temperature to approximately 40 ℃, facilitating efficient bacterial elimination. Antibacterial performance of the scaffold was evaluated using Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) as representative Gram-positive and Gram-negative bacteria, respectively, with and without external NIR stimulation. The results revealed that the PMBG@Cu/MBG-RSNO composite scaffold achieved an antibacterial efficiency of 99.9% against both bacterial strains. In summary, the PMBG@Cu/MBG-RSNO composite scaffold offers a promising solution to address infection challenges in bone implant materials and supports bone defect repair.

Key words: mesoporous bioactive glass, antibacterial, nitric oxide, photothermal effect

中图分类号:

TQ171

张博, 付一敏, 陈政, 石澳, 朱敏. 近红外光响应的双相抗菌介孔生物活性玻璃复合支架的制备及抗菌性能研究[J]. 无机材料学报, 2025, 40(10): 1137-1144.

ZHANG Bo, FU Yimin, CHEN Zheng, SHI Ao, ZHU Min. Near-infrared Responsive Biphasic Antibacterial Mesoporous Bioactive Glass Composite Scaffolds: Preparation and Antibacterial Performance[J]. Journal of Inorganic Materials, 2025, 40(10): 1137-1144.

图/表 7

图1 PMBG@Cu/MBG-RSNO复合支架的制备及抗菌机理示意图

Fig. 1 Schematic diagram of preparation and antimicrobial mechanism of PMBG@Cu/MBG-RSNO composite scaffold

图2 MBG及其改性粉体的理化性能表征

Fig. 2 Physicochemical properties of MBG and modified powders (a) TEM image of MBG; (b) FT-IR spectra; (c) N2 adsorption-desorption isotherm curves; (d) Pore size distributions

图3 PMBG@Cu/MBG-RSNO复合支架在不同放大倍数下的SEM照片

Fig. 3 SEM images of PMBG@Cu/MBG-RSNO composite scaffold at different magnifications

图4 PMBG@Cu/MBG-RSNO复合支架的光热响应性能

Fig. 4 Photothermal response performance of PMBG@Cu/MBG-RSNO composite scaffold (a, b) Photothermal curves in (a) dry state environment and (b) wet state environment; (c) Photothermal cycling curves under 1.00 W/cm2 laser irradiation in dry state environment; (d-f) Thermal images under dry state environment at power densities of (d) 0.50, (e) 0.75 and (f) 1.00 W/cm2

图5 PMBG@Cu/MBG-RSNO复合支架释放NO·的性能分析

Fig. 5 Analysis of NO· release from PMBG@Cu/MBG-RSNO composite scaffold (a) EPR spectra under continuous illumination for 15 and 60 min; (b) EPR spectra with a cumulative total illumination time of 15 min within 60 min under pulsed illumination; (c) Released content of NO·

图6 PMBG@Cu/MBG-RSNO复合支架的体外抗菌效果及光热温度分析

Fig. 6 In vitro antibacterial effect and photothermal temperature analysis of PMBG@Cu/MBG-RSNO composite scaffold (a, b) Photos of (a) S. aureus group and (b) E. coli group; (c, d) OD values of (c) S. aureus and (d) E. coli under UV-Vis with asterisks indicating statistically significant difference of treatments vs. untreated culture (*** indicates p < 0.001); (e, f) The highest temperature of (e) S. aureus and (f) E. coli under 5 times pulsed illumination by 808 nm laser at a power density of 1.00 W/cm2

图7 PMBG@Cu/MBG-RSNO复合支架在有/无NIR照射下的抗菌性能及SEM照片

Fig. 7 Antimicrobial properties and SEM images of PMBG@Cu/MBG-RSNO composite scaffold with and without NIR illumination (a, b) Confocal images of (a) SYTO-9 and (b) PI staining for the blank group of S. aureus; (d, e) Confocal images of (d) SYTO-9 and (e) PI staining for PMBG@Cu/MBG-RSNO group of S. aureus; (g, h) Confocal images of (g) SYTO-9 and (h) PI staining for PMBG@Cu/ MBG-RSNO+NIR group of S. aureus; (c, f, i) SEM images of PMBG@Cu/MBG-RSNO composite scaffold with and without NIR illumination

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近红外光响应的双相抗菌介孔生物活性玻璃复合支架的制备及抗菌性能研究

Near-infrared Responsive Biphasic Antibacterial Mesoporous Bioactive Glass Composite Scaffolds: Preparation and Antibacterial Performance

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