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WIREs Nanomed Nanobiotechnol
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Multifunctional MnO2 nanoparticles for tumor microenvironment modulation and cancer therapy

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Abstract Tumor microenvironment (TME) is generally featured by low pH values, high glutathione (GSH) concentrations, overproduced hydrogen peroxide (H2O2), and severe hypoxia. These characteristics could provide an interior environment for origination and residence of tumor cells and would lead to tumor progression, metastasis, and drug resistance. Therefore, the development of TME‐responsive smart nanosystems has shown significant potential to enhance the efficacy of current cancer treatments. Manganese dioxide (MnO2)‐based nanosystems have attracted growing attentions for applications in cancer treatment as an excellent TME‐responsive theranostic platform, due to their tunable structures/morphologies, pH responsive degradation, and excellent catalytic activities. In this review, we mainly summarize the strategies of MnO2 and its nanocomposites to modulate TME, such as tumor hypoxia relief, excessive GSH depletion, glucose consumption, and tumor immunosuppressive microenvironment moderation. Such MnO2‐based TME modulation would be beneficial for a wide range of cancer therapies including photodynamic therapy, radiotherapy, sonodynamic therapy, chemodynamic therapy, starvation therapy, and immunotherapy. Next, some representative designs of MnO2‐based nanoplatforms in other tumor therapies are highlighted. Moreover, we will discuss the challenges and future perspectives of these MnO2‐based nanosystems for enhanced tumor treatment. This article is categorized under: Therapeutic Approaches and Drug Discovery > Nanomedicine for Oncologic Disease
Manganese dioxide (MnO2)‐based nanomedicine for other tumor therapies. (a) A scheme illustrating the fabrication of 2D ultrathin MnO2 nanosheets and for tumor microenvironment (TME)‐responsive magnetic resonance imaging (MRI) and photothermal therapy (PTT) against cancer. (Reprinted with permission from Liu, Zhang, et al. (2018). Copyright 2018 Elsevier) (b) Synthesis of the GSH‐activatable and O2/Mn2+‐evolving nanocomposites (GAOME NC). (c) The mechanism of the dual therapy by GAOME nanocomposites. (Reprinted with permission from He et al. (2017). Copyright 2017 Wiley‐VCH)
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Hollow manganese dioxide (MnO2) nanoplatform for enhanced cancer immunotherapy. (a) A scheme showing the preparation of PEGylated hollow manganese dioxide (H‐MnO2‐PEG) nanoparticles loaded with both Ce6 and DOX (H‐MnO2‐PEG/C&D). (b) Representative immunofluorescence images of tumor slices after hypoxia staining. The nuclei, blood vessels, and hypoxia areas were stained with DAPI (blue), anti‐CD31 antibody (red), and antipimonidazole antibody (green), respectively. (c) Tumor volume growth curves of mice after receiving various treatments. (d) A scheme illustrating the proposed mechanism of anti‐tumor immune responses induced by H‐MnO2‐PEG/C&D in combination with anti‐PD‐L1 therapy. (Reprinted with permission from Yang et al. (2017). Copyright 2017 Nature Publishing Group)
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Core‐shell gold [email protected] dioxide ([email protected]2) for oxygen‐boosted immunogenic photodynamic therapy (PDT). (a) A scheme indicating the synthesis of [email protected]2 and the applications in oxygen‐boosted immunogenic PDT. (b) Tumor growth curves of various treated groups. (c) The number of metastatic lesions received from excised lungs. (d) Photos of whole lungs (upper) and micrographs of the metastatic nodes in the lungs by H&E staining (down) collected from different treated groups. The percentage of activated CD8 T cells, CD4 T cells, and NK cells in tumors (e) and tumor draining lymph nodes (TDLN) (f) at 48 h after treatments. *p < 0.05, **p < 0.01, ***p < 0.001. (Reprinted with permission from Liang et al. (2018). Copyright 2018 Elsevier)
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Manganese dioxide (MnO2)‐based nanomedicine to enable tumor starvation therapy. (a) A scheme showing the MnO2 motor effect for starvation therapy. (b) Schematic illustration of catalyzing glucose depletion and oxygen cycle‐like supply. (c) Residual glucose after reaction with different nanoparticles in glucose solutions. (d) Relative tumor volumes of mice after receiving various treatments. (e) Tumor weights obtained from mice after day 14. (Reprinted with permission from Zhang et al. (2018). Copyright 2018 American Chemical Society) (f) Schematic illustration of the 2D MnO2 nanosheets (M‐NSs)‐mediated starvation‐enhanced photothermal therapy (PTT) in tumor cells. (g) Schematic diagram of the M‐NSs‐catalyzed glucose depletion. (Reprinted with permission from Tang, Fan, et al. (2019). Copyright 2019 Wiley‐VCH)
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Manganese dioxide (MnO2)‐based nanosystems for improving ultrasound (US)‐triggered sonodynamic therapy (SDT) and chemodynamic therapy (CDT) efficacy. (a) A scheme showing the synthesis of [email protected]‐MnOx‐RGD nanoparticles and their applications for MRI‐guided enhanced SDT against tumors. (Reprinted with permission from Zhu, Li, et al. (2018). Copyright 2018 American Chemical Society) (b) The mechanism of MnO2 as an intelligent chemodynamic agent for enhanced CDT. (c) Illustration of MnO2‐coated mesoporous silica nanoparticles ([email protected]2 NPs) for MRI‐guided chemo‐CDT. (Reprinted with permission from Lin, Song, et al. (2018). Copyright 2018 Wiley‐VCH)
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Hypoxia modulation by manganese dioxide (MnO2) nanosystems to enhance photodynamic therapy (PDT) and radioisotope therapy (RIT). (a) Schematic diagram of the fabrication of HSA‐MnO2‐Ce6&Pt (HMCP) nanoparticles. (b) Representative immunofluorescence images of tumor slices after hypoxia staining. The green and red fluorescence showed the hypoxia areas and blood vessels, respectively. (c) The relative hypoxia positive area and blood vessel density of each group in (b). (d) A scheme showing the disintegration of HMCP in the TME to improve tumor penetration of individual HSA‐based complexes. (Reprinted with permission from Chen et al. (2016). Copyright 2016 Wiley‐VCH) (e) A scheme indicating the synthesis of 131I‐HSA‐MnO2 nanosystems for enhanced RIT. (f) Photoacoustic imaging presenting the tumor oxygenation status after intravenous (i.v.) injection of HSA and HSA‐MnO2 at different time points. (g) Quantification of the oxyhemoglobin saturation in the tumor based on PA imaging results in (f). (Reprinted with permission from Tian et al. (2017). Copyright 2017 Wiley‐VCH)
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A scheme showing manganese dioxide (MnO2)‐based nanomedicine for cancer therapy through different strategies, including tumor hypoxia modulation, glutathione (GSH) depletion, glucose consumption, and others. (Reprinted with permission from Tian et al. (2017). Copyright 2017 Wiley‐VCH; Zhu et al. (2016). Copyright 2016 Wiley‐VCH; Lin, Song, et al. (2018). Copyright 2018 Wiley‐VCH; Zhu, Li, et al. (2018). Copyright 2018 American Chemical Society; Zhang et al. (2018). Copyright 2018 American Chemical Society; Liang et al. (2018). Copyright 2018 Elsevier; Wang, Guan, et al. (2019). Copyright 2019 American Chemical Society)
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