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Z-Scheme Heterojunction Functionalized Pyrite Nanosheets for Modulating Tumor Microenvironment and Strengthening Photo/Chemodynamic Therapeutic Effects

机译:Z方案异质结官能化黄铁矿纳米片用于调节肿瘤微环境并增强光/化学动力学治疗效果

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摘要

A Z-scheme heterojunction with high electron-hole pairs separation efficacy and enhanced redox potentials exhibits tremendous potential in photonic theranostics, but still remains unexplored and challenging. Herein, novel 2D thermally oxidized pyrite nanosheets (TOPY NSs) with FeS2 core and Fe2O3 shell are fabricated combining ball grinding and two-step probe sonication assisted liquid exfoliation under different solution and air environments. The Fe2O3 shell and Fe3+/Fe2+ inside TOPY NSs can both damage the tumor microenvironment through glutathione consumption and O-2 production, and produce center dot OH by Fenton reaction. More interestingly, a direct Z-scheme heterojunction based on FeS2 core and Fe2O3 shell is constructed, in which the electrons in the conduction band (CB) of Fe2O3 are recombined with the holes in the valence band (VB) of FeS2, leaving stronger reduction/oxidation potentials in the CB of FeS2 and the VB of Fe2O3. Under irradiation of a 650 nm laser, the generation of center dot O-2(-) from O-2 and center dot OH from OH- on the CB of FeS2 and VB of Fe2O3, respectively, is largely enhanced. Furthermore, the NSs can be triggered by an 808 nm laser to generate local hyperthermia for photothermal therapy. Moreover, the fluorescent, photoacoustic, and photothermal imaging capabilities of the NSs allow multimodal imaging-guided cancer treatment.
机译:具有高电子-空穴对分离效率和增强的氧化还原电势的Z方案异质结在光子理论中具有巨大的潜力,但仍然没有被探索和挑战。在本文中,结合球磨和两步探针超声处理在不同溶液和空气环境下进行的液体剥离,制备了具有FeS2核和Fe2O3壳的新型二维热氧化硫铁矿纳米片(TOPY NSs)。 TOPY NSs内的Fe2O3壳和Fe3 + / Fe2 +既可以通过消耗谷胱甘肽和产生O-2来破坏肿瘤微环境,又可以通过Fenton反应产生中心点OH。更有趣的是,构建了基于FeS2核和Fe2O3壳的直接Z型异质结,其中Fe2O3的导带(CB)中的电子与FeS2的价带(VB)中的空穴重新结合,从而使还原更强FeS2的CB和Fe2O3的VB中的/氧化电位。在650 nm激光的照射下,分别大大增强了FeS2的CB和Fe2O3的VB上O-2产生的中心点O-2(-)和OH-产生的中心点OH。此外,NSs可以由808 nm激光触发以产生局部热疗以进行光热疗法。此外,NS的荧光,光声和光热成像功能允许进行多模态成像指导的癌症治疗。

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