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Nano Research 2020, 13(3): 709-718 https://doi.org/10.1007/s12274-020-2680-5
Research Article | Issue | Published: 22 February 2020

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

Show Author's Information Yanxia Meng1,4,  Kunfeng Zhao2,3,4( ),  Zhaokun Zhang1,4,  Peng Gao5( ),  Jing Yuan3,  Ting Cai3,  Qin Tong3,  Gang Huang4,  Dannong He2,4( )
School of Medical Instrument and Food Engineering, University of Shanghai for Science and Technology, 516 Jungong Road, Shanghai 200093, China
School of Materials Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China
National Engineering Research Center for Nanotechnology, 28 East Jiangchuan Road, Shanghai 200241, China
Shanghai University of Medicine and Health Sciences, 279 Zhouzhu Road, Shanghai 201318, China
Ningbo Fundenergy Co., Ltd., 699 Haicheng Road, Ningbo 315200, China
Keywords:
MnO2, glutathione, crystal phase structure, oxidase mimics, surface hydroxyls, 3, 3', 5, 5'-tetramethylbenzidine (TMB)
Topics:
Catalyst activityCrystal structureMorphologyNanorodsPeptides
Cite this article:
Meng Y, Zhao K, Zhang Z, et al. Effects of crystal structure on the activity of MnO2 nanorods oxidase mimics. Nano Research, 2020, 13(3): 709-718. https://doi.org/10.1007/s12274-020-2680-5
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Abstract Full text Electronic supplementary material About this article

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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Electronic supplementary material
About this article

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

Show Author's information Yanxia Meng1,4, Kunfeng Zhao2,3,4( ), Zhaokun Zhang1,4, Peng Gao5( ), Jing Yuan3, Ting Cai3, Qin Tong3, Gang Huang4, Dannong He2,4( )
School of Medical Instrument and Food Engineering, University of Shanghai for Science and Technology, 516 Jungong Road, Shanghai 200093, China
School of Materials Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China
National Engineering Research Center for Nanotechnology, 28 East Jiangchuan Road, Shanghai 200241, China
Shanghai University of Medicine and Health Sciences, 279 Zhouzhu Road, Shanghai 201318, China
Ningbo Fundenergy Co., Ltd., 699 Haicheng Road, Ningbo 315200, China

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.

Keywords: MnO2, glutathione, crystal phase structure, oxidase mimics, surface hydroxyls, 3, 3', 5, 5'-tetramethylbenzidine (TMB)

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Acknowledgements

Publication history

Received: 21 November 2019
Revised: 18 January 2020
Accepted: 22 January 2020
Published: 22 February 2020
Issue date: March 2020

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020

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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