银纳米粒子修饰的二维金属-有机框架纳米片用于光热增强银离子释放抗菌

doi:10.3866/PKU.WHXB202211043

物理化学学报 >> 2023, Vol. 39 >> Issue (7): 2211043.doi: 10.3866/PKU.WHXB202211043

银纳米粒子修饰的二维金属-有机框架纳米片用于光热增强银离子释放抗菌

赵信硕¹^,⁴, 邱海燕²^,³, 邵依¹, 王攀捷¹, 余石龙⁵, 李海⁵, 周郁斌²^,³^,*(), 周战¹^,*(), 马录芳¹^,⁴^,*(), 谭超良⁶^,⁷^,*()

¹ 洛阳师范学院化学化工学院, 河南省功能导向多孔材料重点实验室, 河南洛阳 471934
² 广东医科大学附属东莞第一医院, 广东东莞 523808
³ 广东医科大学广东天然药物研究与开发重点实验室, 药学院, 广东东莞 523808
⁴ 河南理工大学化学化工学院, 河南焦作 454000
⁵ 南京工业大学先进材料研究院, 江苏省柔性电子重点实验室, 南京 211816
⁶ 香港城市大学化学系与超金刚石及先进薄膜研究中心, 香港九龙塘, 香港特别行政区 999077
⁷ 香港城市大学深圳研究院, 广东深圳 518057

收稿日期:2022-11-23 录用日期:2023-01-06 发布日期:2023-03-06
通讯作者: 周郁斌,周战,马录芳,谭超良 E-mail:zybresearch@126.com;zhouzhan@lynu.edu.cn;mazhuxp@126.com;chaoltan@cityu.edu.hk
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(52102348);国家自然科学基金(22171123);国家自然科学基金(22005259);河南省高校科技创新人才计划(23HASTIT016);广东省基础与应用基础研究基金(2019A1515111112);广东省基础与应用基础研究基金(2021A1515011831);广东省普通高校重点领域专项(2021ZDZX2061);香港城市大学启动基金(9610495)

Silver Nanoparticle-Modified 2D MOF Nanosheets for Photothermally Enhanced Silver Ion Release Antibacterial Treatment

Xinshuo Zhao¹^,⁴, Haiyan Qiu²^,³, Yi Shao¹, Panjie Wang¹, Shilong Yu⁵, Hai Li⁵, Yubin Zhou²^,³^,*(), Zhan Zhou¹^,*(), Lufang Ma¹^,⁴^,*(), Chaoliang Tan⁶^,⁷^,*()

¹ College of Chemistry and Chemical Engineering, Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934, Henan Province, China
² The First Dongguan Affiliated Hospital, Guangdong Medical University, Dongguan 523808, Guangdong Province, China
³ Guangdong Provincial Key Laboratory of Research and Development of Natural Drugs and School of Pharmacy, Guangdong Medical University, Dongguan 523808, Guangdong Province, China
⁴ College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo 454000, Henan Province, China
⁵ Institute of Advanced Materials, Key Laboratory of Flexible Electronics, Nanjing Tech University, Nanjing 211816, China
⁶ Department of Chemistry and Center of Super-Diamond and Advanced Films (COSDAF), City University of Hong Kong, Kowloon, Hong Kong SAR 999077, China
⁷ Shenzhen Research Institute, City University of Hong Kong, Shenzhen 518057, Guangdong Province, China

Received:2022-11-23 Accepted:2023-01-06 Published:2023-03-06
Contact: Yubin Zhou, Zhan Zhou, Lufang Ma, Chaoliang Tan E-mail:zybresearch@126.com;zhouzhan@lynu.edu.cn;mazhuxp@126.com;chaoltan@cityu.edu.hk
Supported by:
the National Natural Science Foundation of China(52102348);the National Natural Science Foundation of China(22171123);the National Natural Science Foundation of China(22005259);the Science and Technology Innovation Talent Program of University in Henan Province(23HASTIT016);the Guangdong Basic and Applied Basic Research Foundation(2019A1515111112);the Guangdong Basic and Applied Basic Research Foundation(2021A1515011831);the Special Projects in Key Areas for General Colleges and Universities of Guangdong Province(2021ZDZX2061);the Start-Up Grant from City University of Hong Kong(9610495)

1. WHXB202211043-SI-10p.pdf(5117KB)

摘要/Abstract

摘要：

近年来，二维(2D)金属-有机框架(MOF)纳米复合材料被广泛的应用于生物医学领域，尤其是在抗菌方面。在此，我们通过光照诱导还银离子成功在二维MOF纳米片上生长银纳米粒子，得到了一种银纳米粒子(Ag NPs)修饰的二维Zr-Fc-MOF (MOF-Ag)纳米片，并将其用于光热增强Ag⁺释放抗菌治疗。通过水热法和超声处理合成MOF纳米片，然后通过原位光辐照诱导还原在MOF纳米片上生长Ag NPs。系列表征结果表明Ag NPs成功负载到MOF纳米片上。聚乙烯吡咯烷酮(PVP)的修饰不仅可以增强MOF-Ag在溶液中的稳定性，还可以增强它的生物相容性。在近红外激光(NIR)照射下，MOF纳米片可以在短时间升温，而温度的升高可以加速Ag NPs在溶液中氧化为银离子。通过细菌生长曲线、菌落相对数和细菌形态变化等实验表明PVP@MOF-Ag纳米片具有优异的广谱杀菌性能。此外，2D MOF纳米片良好的光热性能不仅可以增强Ag⁺的释放，还可以增强细胞膜的通透性，随后进入细菌中的Ag⁺可以诱导内源性活性氧的产生，从而引发细菌的氧化应激，实现高效抗菌。基于良好的体外抗菌性能，进一步将PVP@MOF-Ag纳米片用于小鼠伤口愈合，在此期间PVP@MOF-Ag纳米片表现出良好的治疗效果和生物安全性。我们的研究结果表明，PVP@MOF-Ag纳米片可以作为光热增强Ag⁺释放抗菌治疗和伤口愈合的有效平台。

关键词: 二维金属-有机框架材料, 二维复合材料, 银离子释放, 光热治疗, 抗菌

Abstract:

Recently, two-dimensional (2D) metal-organic framework (MOF) nanosheet-based composites have been extensively investigated as promising materials for biomedical applications, including antibacterial applications. This study reports the synthesis of silver nanoparticle (Ag NP)-modified 2D Zr-ferrocene-MOF (MOF-Ag) nanosheets by growing Ag NPs on 2D MOF nanosheets via light irradiation-induced reduction for photothermally enhanced silver ion (Ag⁺) release antibacterial treatment. The MOF nanosheets were synthesized by a hydrothermal method followed by ultrasonic treatment. Subsequently, Ag NPs were grown on the MOF nanosheets to obtain MOF-Ag nanosheets by in situ light irradiation-induced reduction. Various characterization results, including transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma-mass spectrometry (ICP-MS), showed that Ag NPs were successfully loaded onto the surface of the MOF nanosheets. Fourier transform infrared (FTIR) spectroscopy further confirmed the successful modification of the MOF-Ag surface with polyvinylpyrrolidone (PVP). The modification with of PVP not only enhanced the stability of MOF-Ag in solution, but also enhanced its biocompatibility. Under 808 nm near-infrared laser (NIR) irradiation, the MOF nanosheets exhibited good photothermal properties and photothermal conversion efficiency. The temperature increase induced by the photothermal effect accelerates the oxidation of Ag NPs to Ag⁺, and thus MOF-Ag continuously releases silver ions to kill bacteria. It was concluded that PVP-functionalized MOF-Ag (PVP@MOF-Ag) nanosheets have good antibacterial properties using experimental analyses such as bacterial growth curves, relative number of colonies, and morphological changes of bacteria. PVP@MOF-Ag nanosheets not only kills S. aureus but also inhibits E. coli growth more efficiently, exhibiting broad-spectrum bactericidal properties. Additionally, the good photothermal performance of the 2D MOF nanosheets enhanced Ag⁺ release and cell membrane permeability. Ag NPs release Ag⁺ in solution via an oxidation mechanism, and the released Ag⁺ is more likely to enter the bacteria via the cell membrane under light conditions. In bacteria, Ag⁺ induces the generation of endogenous reactive oxygen species to trigger oxidative stress, thus realizing efficient antibacterial performance. Based on the above-mentioned antibacterial mechanism and good in vitro antibacterial properties, the PVP@MOF-Ag nanosheets were used for wound healing in mice. By developing a mouse wound healing model and treating mouse wounds within a week, it was observed that PVP@MOF-Ag nanosheets have a good therapeutic effect and good biosafety during treatment. These results demonstrate that PVP@MOF-Ag nanosheets are an efficient platform for photothermally enhanced Ag⁺ release antibacterial therapy and wound healing.

Key words: 2D MOFs, 2D composites, Ag⁺ release, Photothermal therapy, Antibacterial

赵信硕, 邱海燕, 邵依, 王攀捷, 余石龙, 李海, 周郁斌, 周战, 马录芳, 谭超良. 银纳米粒子修饰的二维金属-有机框架纳米片用于光热增强银离子释放抗菌[J]. 物理化学学报, 2023, 39(7), 2211043. doi: 10.3866/PKU.WHXB202211043

Xinshuo Zhao, Haiyan Qiu, Yi Shao, Panjie Wang, Shilong Yu, Hai Li, Yubin Zhou, Zhan Zhou, Lufang Ma, Chaoliang Tan. Silver Nanoparticle-Modified 2D MOF Nanosheets for Photothermally Enhanced Silver Ion Release Antibacterial Treatment[J]. Acta Phys. -Chim. Sin. 2023, 39(7), 2211043. doi: 10.3866/PKU.WHXB202211043

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202211043

https://www.whxb.pku.edu.cn/CN/Y2023/V39/I7/2211043

图/表 5

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银纳米粒子修饰的二维金属-有机框架纳米片用于光热增强银离子释放抗菌

Silver Nanoparticle-Modified 2D MOF Nanosheets for Photothermally Enhanced Silver Ion Release Antibacterial Treatment

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