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Dendritic Mesoporous Silica Nanoparticle-Tuned High-Affinity MnO2 Nanozyme for Multisignal GSH Sensing and Target Cancer Cell Detection

  • Yuan Zhang
    Yuan Zhang
    Institute of Environmental Science, and School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
    More by Yuan Zhang
  • Weina Meng
    Weina Meng
    Institute of Environmental Science, and School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
    More by Weina Meng
  • Xiao Li
    Xiao Li
    Innovation Research Institute of Traditional Chinese Medicine, Shandong University of Traditional Chinese Medicine, Jinan 250355, China
    More by Xiao Li
  • Dong Wang
    Dong Wang
    Institute of Environmental Science, and School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
    More by Dong Wang
  • Shaomin Shuang
    Shaomin Shuang
    Institute of Environmental Science, and School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
    More by Shaomin Shuang
  • , and 
  • Chuan Dong*
    Chuan Dong
    Institute of Environmental Science, and School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
    *Email: [email protected]. Phone/Fax: +86-351-7018613.
    More by Chuan Dong
Cite this: ACS Sustainable Chem. Eng. 2022, 10, 18, 5911–5921
Publication Date (Web):April 28, 2022
https://doi.org/10.1021/acssuschemeng.2c00259
Copyright © 2022 American Chemical Society

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    Abstract

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    Development of multifunctional enzymatic nanomaterials with rapid and sensitive characteristics for glutathione determination is extremely urgent for early cancer diagnosis. Herein, a core–shell ultrasensitive nanozyme (denoted as CPT/DM-FA) for triple-mode glutathione sensing and specific in vitro cancer detection is constructed. The dendritic mesoporous silica nanoparticle (DMSN) core not only acts as a camptothecin carrier, but also offers the nanoplatform to synthesize the MnO2 shell. Due to the DMSN-regulated high dispersion of MnO2, the atomic utilization efficiency of MnO2 is surprisingly enhanced, and leads to notable enzymatic activity with Km 0.136 μM and Vmax 0.59 μM/s. In addition, by integrating the quenching ability based on fluorescence resonance energy transfer and oxidase-mimic-mediated 1O2, O2 generation of MnO2, the fluorescence, UV–vis, and colorimetric method for glutathione sensing is established with a comprehensive linear range from 2 to 250 μM and a limit of detection of 0.654 μM. Besides, after surface folic acid modification, the CPT/DM-FA could also specifically detect cancer cells from 25 to 1 50 000 through the color reaction of 3,3′,5,5′-tetramethylbenzidine. We believe this nanozyme could afford a potential strategy to amplify the nanozyme activity for further biomedical applications.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.2c00259.

    • UV–vis spectrums of CPT-loaded nanoparticles, sensing parameters optimization, nanozyme′s stability in different pH environment, impact of temperature to the nanozyme′s activity, color parameters of colorimetric sensing, catalytic activity of MnO2, fluorescence of SOSG, ESR spectrum, overlapped fluorescence spectrum and lifetime, stability of nanozyme in DMEM, live/dead fluorescence images and data tables of N2 absorption/desorption, concentrations of the investigated interferents, GSH determination results in serum samples and the comparative cancer cell detection study (PDF)

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    Cited By

    This article is cited by 10 publications.

    1. Ruimiao Li, Yu Zhu, Lin Gong, You Fan, Jianan Zhang, Sheng Wu, Kui Luo, Xiaohua Zhu, Meiling Liu, Youyu Zhang, Shouzhuo Yao. Synthesis and Catalytic Performance of Cu-CeO2 Nanoparticles and the Application in Cr(VI) Detection: Third-Year Undergraduate Comprehensive Laboratory Experiment. Journal of Chemical Education 2023, 100 (10) , 3945-3954. https://doi.org/10.1021/acs.jchemed.3c00548
    2. Hengjia Zhu, Bangxiang Liu, Jinjin Liu, Jianming Pan, Panwang Hu, Lizhang Xu, Xiangheng Niu. MnOx In Situ Growth-Induced Luminescence and Oxidase-Like Feature Bimodulation of CePO4:Tb Nanorods: Toward Ascorbic Acid-Related Bioanalysis in a “One-Stone-Two-Birds” Manner. Inorganic Chemistry 2023, 62 (37) , 15215-15225. https://doi.org/10.1021/acs.inorgchem.3c02404
    3. Yan-Wen Mao, Juan Zhang, Rui Zhang, Jia-Qi Li, Ai-Jun Wang, Xiao-Cheng Zhou, Jiu-Ju Feng. N-Doped Carbon Nanotubes Supported Fe–Mn Dual-Single-Atoms Nanozyme with Synergistically Enhanced Peroxidase Activity for Sensitive Colorimetric Detection of Acetylcholinesterase and Its Inhibitor. Analytical Chemistry 2023, 95 (22) , 8640-8648. https://doi.org/10.1021/acs.analchem.3c01070
    4. Guoyuan Ren, Mingju Lu, Zhiqiang Zhao, Fengjuan Qin, Kai Li, Wenxing Chen, Yuqing Lin. Cobalt Single-Atom Nanozyme Co-Administration with Ascorbic Acid Enables Redox Imbalance for Tumor Catalytic Ablation. ACS Biomaterials Science & Engineering 2023, 9 (2) , 1066-1076. https://doi.org/10.1021/acsbiomaterials.2c01301
    5. Xuyang Chen, Haizhen Tao, Yuqi Guo, Zichao Wang, Ruifang Li, Yingyuan Zhao, Chuan Liu, Xuanping Zhao, Xueqin Wang, Shaofeng Duan. Anti-CD44 antibodies grafted immunoaffinity Fe3O4@MnO2 nanozymes with highly oxidase-like catalytic activity for specific detection of triple-negative breast cancer MDA-MB-231 cells. Analytica Chimica Acta 2023, 1249 , 340947. https://doi.org/10.1016/j.aca.2023.340947
    6. Wei Duan, Jinling Wang, Xiaomeng Peng, Shoufu Cao, Jingjing Shang, Zhiwei Qiu, Xiaoqing Lu, Jingbin Zeng. Rational design of trimetallic AgPt–Fe3O4 nanozyme for catalyst poisoning-mediated CO colorimetric detection. Biosensors and Bioelectronics 2023, 223 , 115022. https://doi.org/10.1016/j.bios.2022.115022
    7. Neeraj Sohal, Banibrata Maity, Soumen Basu. Transformation of bulk MnO2 to fluorescent quantum dots for selective and sensitive detection of ferric ions and ascorbic acid by turn-off-on strategy. Journal of Photochemistry and Photobiology A: Chemistry 2023, 434 , 114280. https://doi.org/10.1016/j.jphotochem.2022.114280
    8. Xiaohuan Sun, Fei Guo, Qianyun Ye, Jinfeng Zhou, Jie Han, Rong Guo. Fluorescent Sensing of Glutathione and Related Bio-Applications. Biosensors 2023, 13 (1) , 16. https://doi.org/10.3390/bios13010016
    9. Qiong Liu, Xinxin Ren, Yufang Hu, Jieying Zhou. Versatile Electrochemical Platform for GSH Detection and its Boolean Logic Application in Related Biological Pathways. Journal of The Electrochemical Society 2022, 169 (12) , 127516. https://doi.org/10.1149/1945-7111/aca8d7
    10. Zhibo Tong, Tong Wang, Yunheng Cai, Jingquan Sha, Tai Peng. Oxygen-powered flower-like FeMo 6 @CeO 2 self-cascade nanozymes: a turn-on enhancement fluorescence sensor. Journal of Materials Chemistry B 2022, 10 (34) , 6425-6432. https://doi.org/10.1039/D2TB01466A

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