物理化学学报 >> 2023, Vol. 39 >> Issue (12): 2212039.doi: 10.3866/PKU.WHXB202212039

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可见光激发的BiOI/ZnO纳米复合抗菌剂制备及其抗菌活性与机制

孔菁1,2, 张金贵3, 张素芬2, 奚菊群1,*(), 沈明2,3,*()   

  1. 1 扬州大学医学院,江苏 扬州 225009
    2 扬州大学化学化工学院,江苏 扬州 225002
    3 江苏汇诚医疗科技有限公司,江苏 扬州 225108
  • 收稿日期:2022-12-23 录用日期:2023-02-08 发布日期:2023-07-31
  • 通讯作者: 奚菊群,沈明 E-mail:xijq@yzu.edu.cn;shenming@yzu.edu.cn
  • 作者简介:第一联系人:

    †These authors contributed equally to this work.

  • 基金资助:
    国家自然科学基金(21673201);扬州市广陵区科技计划产业前瞻性与共性关键技术重点项目(GL202206);江苏高校品牌专业建设工程项目;江苏高校优势学科建设工程项目

Performance Improvement and Antibacterial Mechanism of BiOI/ZnO Nanocomposites as Antibacterial Agent under Visible Light

Jing Kong1,2, Jingui Zhang3, Sufen Zhang2, Juqun Xi1,*(), Ming Shen2,3,*()   

  1. 1 Medical College, Yangzhou University, Yangzhou 225009, Jiangsu Province, China
    2 College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Jiangsu Province, China
    3 Jiangsu Huicheng Medical Technology Co., Ltd., Yangzhou 225108, Jiangsu Province, China
  • Received:2022-12-23 Accepted:2023-02-08 Published:2023-07-31
  • Contact: Juqun Xi, Ming Shen E-mail:xijq@yzu.edu.cn;shenming@yzu.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(21673201);the Yangzhou Guangling District Science and Technology Plan Industry Foresight and Key Common Technology Key Project(GL202206);the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions, China (TAPP);the Priority Academic Program Development of Jiangsu Higher Education Institutions, China

摘要:

细菌感染可引发各种严重疾病,在细菌耐药性日益严重的今天开发无机抗菌药物具有重要意义。为提升氧化锌在可见光下的抗菌活性,本文设计出一系列碘氧铋与氧化锌(BiOI/ZnO)的纳米复合材料,通过常压下机械搅拌法成功合成了形状和尺寸较为均一的系列复合纳米结构。紫外-可见漫反射光谱测试结果表明此类材料具有较高的可见光吸收率和更窄的带隙。对这类新复合材料进行的抗菌活性试验表明,在可见光激发下其BiOI/ZnO-10%和BiOI/ZnO-20%样品对金黄色葡萄球菌和大肠杆菌的抗菌活性有明显增强,且光照强度可影响该类材料的抗菌活性。抗菌机制研究结果显示此类材料具有与纳米ZnO抗菌材料相似的机理:通过带正电荷的表面和强活性氧基团(•OH)的产生导致细菌细胞壁破裂和死亡,而纳米碘氧铋的复合所形成的异质结不仅使得强活性氧基团易于产生,而且使BiOI/ZnO纳米复合材料的可见光吸收增强。本研究既提出了纳米ZnO材料利用可见光激发增强抗菌活性的策略,又为纳米ZnO基复合材料的临床应用提供了实验支撑。

关键词: BiOI/ZnO纳米复合材料, 光催化, 抗菌活性, 可见光激发, 活性氧

Abstract:

Bacterial infections cause various serious diseases including tuberculosis, meningitis, and cellulitis. Moreover, there is an increase in the number of drug-resistant bacterial strains, which has caused a global health issue. Thus, it is highly essential to develop more effective antibacterial agents. Currently, zinc oxide (ZnO) is commonly used as an inorganic antibacterial agent, but with a notable limit in efficiency. In this work, to improve ZnO antibacterial activity under visible light, bismuth oxyiodide (BiOI) with a narrow bandgap of 1.8 eV was used as a suitable refinement to ZnO. Four different BiOI/ZnO nanocomposites were designed and synthesized via a simple mechanical stirring method in an atmospheric environment; these were denoted as BiOI/ZnO-2.5%, BiOI/ZnO-5%, BiOI/ZnO-10%, and BiOI/ZnO-20%. The successful synthesis of the BiOI/ZnO nanocomposites was verified through X-ray powder diffraction, energy-dispersive X-ray analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). A unique BiOI/ZnO heterojunction was also observed for the nanocomposites through high-resolution TEM, XPS, and selected area electron diffraction. Ultraviolet-visible diffuse reflectance spectroscopy revealed that all four BiOI/ZnO nanocomposites exhibited improved visible light absorption and possessed narrower bandgaps than the ZnO nanoparticles (nano-ZnO). Furthermore, the antibacterial activities of all BiOI/ZnO nanocomposites were investigated under visible light against both gram-positive and gram-negative bacteria strains. The results indicated a significant improvement in the antibacterial activities of BiOI/ZnO-10% and BiOI/ZnO-20% against both Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). Strong light exposure was found to be attributable to an increase in the antibacterial activity against S. aureus. In addition, the antibacterial mechanistic investigation was conducted upon visible light activation. The SEM images showed completely broken bacterial cell walls for both bacteria strains after treatment with the BiOI/ZnO nanocomposites. Hydroxyl radicals (•OH), which are strong reactive oxygen species, generated by the BiOI/ZnO nanocomposites under visible light, were also trapped by 5,5-dimethyl-1-pyrroline-N-oxide. Furthermore, zeta potential analysis revealed the presence of more positively charged BiOI/ZnO nanocomposite surfaces than the surfaces of nano-ZnO. The metal ions released from the BiOI/ZnO nanocomposites under visible light were also studied through inductively coupled plasma mass spectrometry. Based on the above results, BiOI/ZnO nanocomposites were found to exhibit antibacterial mechanism similar to that of nano-ZnO. In the dark, E. coli growth was only inhibited by Zn2+ released from both BiOI/ZnO nanocomposites and pure nano-ZnO. After visible light activation, •OH generated from the BiOI/ZnO nanocomposites mainly contributed to the bacterial cell death of both E. coli and S. aureus. This study proposes an effective strategy to enhance the antibacterial activity of nano-ZnO under visible light upon the formation of nanocomposites with BiOI. Besides, this study indicates that the ZnO-based nanocomposites can be used as a more effective antibacterial agent in clinical applications.

Key words: BiOI/ZnO nanocomposites, Photocatalysis, Antibacterial activity, Visible light activation, Reactive oxygen species