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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
引用本文: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):2211043-0.
作者姓名: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
作者单位: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 4719342 广东医科大学附属东莞第一医院, 广东 东莞 5238083 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 5238084 河南理工大学化学化工学院, 河南 焦作 4540005 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 2118166 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 9990777 香港城市大学深圳研究院, 广东 深圳 518057
基金项目: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)
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  
收稿时间:2022-11-23

Silver Nanoparticle-Modified 2D MOF Nanosheets for Photothermally Enhanced Silver Ion Release Antibacterial Treatment
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.
Keywords:2D MOFs  2D composites  Ag+ release  Photothermal therapy  Antibacterial  
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