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Effects of crystal structure on the activity of MnO2 nanorods oxidase mimics

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Abstract

The crystal structures would directly affect the physical and chemical properties of the surface of the material, and would thus influence the catalytic activity of the material. α-MnO2, β-MnO2 and γ-MnO2 nanorods with the same morphology yet different crystal structures were prepared and tested as oxidase mimics using 3,3’,5,5’-tetramethylbenzidine (TMB) as the substrate. β-MnO2 that exhibited the highest activity had a catalytic constant of 83.75 μmol·m−2·s−1, 2.7 and 19.0 times of those of α-MnO2 and γ-MnO2 (30.91 and 4.41 μmol·m−2·s−1), respectively. The characterization results showed that there were more surface hydroxyls as well as more Mn4+ on the surface of the β-MnO2 nanorods. The surface hydroxyls were conducive to the oxidation reaction, while Mn4+ was conducive to the regeneration of surface hydroxyls. The synergistic effect of the two factors significantly improved the activity of β-MnO2 oxidase mimic. Using β-MnO2, a β-MnO2-TMB-GSH system was established to detect the content of glutathione (GSH) rapidly and sensitively by colorimetry. This method had a wide detection range (0.11-45 μM) and a low detection limit (0.1 μM), and had been successfully applied to GSH quantification in human serum samples.

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Acknowledgements

This work was supported by the National Key R&D Program of China (No. 2016YFA0202900), China Postdoctoral Science Foundation (No. 2018M642021), the National Natural Science Foundation of China (No. 21677095) and Minhang District Science and Technology Project of Shanghai (No. 2019MH-MS02).

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Authors and Affiliations

  1. School of Medical Instrument and Food Engineering, University of Shanghai for Science and Technology, 516 Jungong Road, Shanghai, 200093, China

    Yanxia Meng & Zhaokun Zhang

  2. School of Materials Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China

    Kunfeng Zhao & Dannong He

  3. National Engineering Research Center for Nanotechnology, 28 East Jiangchuan Road, Shanghai, 200241, China

    Kunfeng Zhao, Jing Yuan, Ting Cai & Qin Tong

  4. Shanghai University of Medicine and Health Sciences, 279 Zhouzhu Road, Shanghai, 201318, China

    Yanxia Meng, Kunfeng Zhao, Zhaokun Zhang, Gang Huang & Dannong He

  5. Ningbo Fundenergy Co., Ltd., 699 Haicheng Road, Ningbo, 315200, China

    Peng Gao

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  1. Yanxia Meng
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Meng, Y., Zhao, K., Zhang, Z. et al. Effects of crystal structure on the activity of MnO2 nanorods oxidase mimics. Nano Res. 13, 709–718 (2020). https://doi.org/10.1007/s12274-020-2680-5

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