Skip to main content
Log in

Mn3O4 nanoparticles decorated porous reduced graphene oxide with excellent oxidase-like activity for fast colorimetric detection of ascorbic acid

  • Original Paper
  • Published:
Microchimica Acta Aims and scope Submit manuscript

Abstract

Mn3O4 nanoparticles composed of porous reduced graphene oxide nanosheets (Mn3O4@p-rGO) with enhanced oxidase-like activity were successfully fabricated through an in-situ approach for fast colorimetric detection of ascorbic acid (AA). The residual Mn2+ in the GO suspension of Hummers method was directly reused as the manganese source, improving the atom utilization efficiency. Benefiting from the uniform distribution of Mn3O4 nanoparticles on the surface of p-rGO nanosheets, the nanocomposite exhibited larger surface area, more active sites, and accelerated electron transfer efficiency, which enhanced the oxidase-like activity. Mn3O4@p-rGO nanocomposite efficiently activate dissolved O2 to generate singlet oxygen (1O2), leading to high oxidation capacity toward the substrate 3,3′,5,5′–tetramethylbenzidine (TMB) without the extra addition of H2O2. Furthermore, the prominent absorption peak of the blue ox-TMB at 652 nm gradually decreased in the presence of AA, and a facile and fast colorimetric sensor was constructed with a good linear relationship (0.5–80 μM) and low LOD (0.278 μM) toward AA. Owing to the simplicity and excellent stability of the sensing platform, its practical application for AA detection in juices has shown good feasibility and reliability compared with HPLC and the 2, 4-dinitrophenylhydrazine colorimetric method. The oxidase-like Mn3O4@p-rGO provides a versatile platform for applications in food testing and disease diagnosis.

Graphical Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Chen Q, Espey MG, Sun AY, Pooput C, Kirk KL, Krishna MC, Khosh DB, Drisko J, Levine M (2008) Pharmacologic doses of ascorbate act as a prooxidant and decrease growth of aggressive tumor xenografts in mice. P Natl Acad Sci USA 105(32):11105–11109

    CAS  Google Scholar 

  2. Padayatty SJ, Riordan HD, Hewitt SM, Katz A, Hoffer LJ, Levine M (2006) Intravenously administered vitamin C as cancer therapy: three cases. Can Med Assoc J 174(7):937–942

    Google Scholar 

  3. Padayatty SJ, Katz A, Wang Y, Eck P, Kwon O, Lee J-H, Chen S, Corpe C, Dutta A, Dutta SK, Levine M (2003) Vitamin C as an Antioxidant: Evaluation of Its Role in Disease Prevention. J Am Coll Nutr 22(1):18–35

    CAS  PubMed  Google Scholar 

  4. Sönmez M, Türk G, Yüce A (2005) The effect of ascorbic acid supplementation on sperm quality, lipid peroxidation and testosterone levels of male Wistar rats. Theriogenology 63(7):2063–2072

    PubMed  Google Scholar 

  5. Massey LK, Liebman M, Kynast-Gales SA (2005) Ascorbate increases human oxaluria and kidney stone risk. J Nutr 135(7):1673–1677

    CAS  PubMed  Google Scholar 

  6. Nováková L, Solich P, Solichová D (2008) HPLC methods for simultaneous determination of ascorbic and dehydroascorbic acids. Trac-trend Anal Chem 27(10):942–958

    Google Scholar 

  7. Ma Y, Zhou M, Jin X, Zhang B, Chen H, Guo N (2002) Flow–injection chemiluminescence determination of ascorbic acid by use of the cerium(IV)–Rhodamine B system. Anal Chim Acta 464(2):289–293

    CAS  Google Scholar 

  8. He P, Niu Y, Mei Z-h, Bao J-f, Sun X-m (2010) Measurement of ascorbic acid in single rat peritoneal mast cells using capillary electrophoresis with electrochemical detection. J Chromatogr B 878(15):1093–1097

    CAS  Google Scholar 

  9. Cheng H, Wang X, Wei H (2015) Ratiometric electrochemical sensor for effective and reliable detection of ascorbic acid in living brains. Anal Chem 87(17):8889–8895

    CAS  PubMed  Google Scholar 

  10. Arabi M, Ostovan A, Wang Y, Mei R, Fu L, Li J, Wang X, Chen L (2022) Chiral molecular imprinting-based SERS detection strategy for absolute enantiomeric discrimination. Nat Commun 13(1):5757

    CAS  PubMed  PubMed Central  Google Scholar 

  11. Arabi M, Chen L (2022) Technical challenges of molecular-imprinting-based optical sensors for environmental pollutants. Langmuir 38(19):5963–5967

    CAS  PubMed  Google Scholar 

  12. Arabi M, Ostovan A, Zhang Z, Wang Y, Mei R, Fu L, Wang X, Ma J, Chen L (2021) Label-free SERS detection of Raman-Inactive protein biomarkers by Raman reporter indicator: Toward ultrasensitivity and universality. Biosens Bioelectron 174:112825

    CAS  PubMed  Google Scholar 

  13. Li X, Zhu H, Liu P, Wang M, Pan J, Qiu F, Ni L, Niu X (2021) Realizing selective detection with nanozymes: Strategies and trends. Trac-trend Anal Chem 143:116379

    CAS  Google Scholar 

  14. Liang M, Yan X (2019) Nanozymes: from new concepts, mechanisms, and standards to applications. Accounts Chem Res 52(8):2190–2200

  15. Chong Y, Liu Q, Ge C (2021) Advances in oxidase-mimicking nanozymes: classification, activity regulation and biomedical applications. Nano Today 37:101076

    CAS  Google Scholar 

  16. Attar F, Shahpar MG, Rasti B, Sharifi M, Saboury AA, Rezayat SM, Falahati M (2019) Nanozymes with intrinsic peroxidase-like activities. J Mol Liq 278:130–144

    CAS  Google Scholar 

  17. Chen Z-J, Huang Z, Sun Y-M, Xu Z-L, Liu J (2021) The most active oxidase-mimicking mn2o3 nanozyme for biosensor signal generation. Chem A Europ J 27(37):9597–9604

    CAS  Google Scholar 

  18. Fu R, Zhou J, Wang Y, Liu Y, Liu H, Yang Q, Zhao Q, Jiao B, He Y (2021) Oxidase-like nanozyme-mediated altering of the aspect ratio of gold nanorods for breaking through H2O2-supported multicolor colorimetric assay: application in the detection of acetylcholinesterase activity and its inhibitors. ACS Appl Bio Mater 4(4):3539–3546

    CAS  PubMed  Google Scholar 

  19. Liu J, Meng L, Fei Z, Dyson PJ, Zhang L (2018) On the origin of the synergy between the Pt nanoparticles and MnO2 nanosheets in Wonton-like 3D nanozyme oxidase mimics. Biosens Bioelectron 121:159–165

    CAS  PubMed  Google Scholar 

  20. Liu B, Huang Z, Liu J (2016) Boosting the oxidase mimicking activity of nanoceria by fluoride capping: rivaling protein enzymes and ultrasensitive F detection. Nanoscale 8(28):13562–13567

    CAS  PubMed  Google Scholar 

  21. Li D, Liu B, Huang P-JJ, Zhang Z, Liu J (2018) Highly active fluorogenic oxidase-mimicking NiO nanozymes. Chem Commun 54(88):12519–12522

    CAS  Google Scholar 

  22. Wang L, Ye K, Pan J, Song H, Li X, Niu X (2019) A catalytic reaction-based colorimetric assay of alkaline phosphatase activity based on oxidase-like MnO2 microspheres. Anall Methods 11(42):5472–5477

    CAS  Google Scholar 

  23. Wang J, Tao H, Lu T, Wu Y (2021) Adsorption enhanced the oxidase-mimicking catalytic activity of octahedral-shape Mn3O4 nanoparticles as a novel colorimetric chemosensor for ultrasensitive and selective detection of arsenic. J Colloid Interf Sci 584:114–124

    CAS  Google Scholar 

  24. Ganganboina AB, Doong R-a (2018) The biomimic oxidase activity of layered V2O5 nanozyme for rapid and sensitive nanomolar detection of glutathione. Sensor Actuat B-Chem 273:1179–1186

    CAS  Google Scholar 

  25. Zhang T, Xing Y, Song Y, Gu Y, Yan X, Lu N, Liu H, Xu Z, Xu H, Zhang Z, Yang M (2019) AuPt/MOF-graphene: a synergistic catalyst with surprisingly high peroxidase-like activity and its application for H2O2 Detection. Anal Chem 91(16):10589–10595

    CAS  PubMed  Google Scholar 

  26. Chen C, Xie M, Kong L, Lu W, Feng Z, Zhan J (2020) Mn3O4 nanodots loaded g-C3N4 nanosheets for catalytic membrane degradation of organic contaminants. J Hazard Mater 390:122146

    CAS  PubMed  Google Scholar 

  27. Li Z, Yang X, Yang Y, Tan Y, He Y, Liu M, Liu X, Yuan Q (2018) Peroxidase-mimicking nanozyme with enhanced activity and high stability based on metal-support interactions. Chem-Eur J 24(2):409–415

    CAS  PubMed  Google Scholar 

  28. Ahmed SR, Takemeura K, Li T-C, Kitamoto N, Tanaka T, Suzuki T, Park EY (2017) Size-controlled preparation of peroxidase-like graphene-gold nanoparticle hybrids for the visible detection of norovirus-like particles. Biosens Bioelectron 87:558–565

    CAS  PubMed  Google Scholar 

  29. Chen X, Zhai N, Snyder JH, Chen Q, Liu P, Jin L, Zheng Q, Lin F, Hu J, Zhou H (2015) Colorimetric detection of Hg2+ and Pb2+ based on peroxidase-like activity of graphene oxide–gold nanohybrids. Anall Methods 7(5):1951–1957

    CAS  Google Scholar 

  30. Darabdhara G, Boruah PK, Das MR (2018) Colorimetric determination of glucose in solution and via the use of a paper strip by exploiting the peroxidase and oxidase mimicking activity of bimetallic Cu-Pd nanoparticles deposited on reduced graphene oxide, graphitic carbon nitride, or MoS2 nanosheets. Microchim Acta 186(1):13

    Google Scholar 

  31. Borthakur P, Boruah PK, Das MR (2021) CuS and NiS nanoparticle-decorated porous-reduced graphene oxide sheets as efficient peroxidase nanozymes for easy colorimetric detection of Hg(II) ions in a water medium and using a paper strip. ACS Sustain Chem Eng 9(39):13245–13255

    CAS  Google Scholar 

  32. Wang Q, Zhang X, Huang L, Zhang Z, Dong S (2017) One-pot synthesis of Fe3O4 nanoparticle loaded 3D porous graphene nanocomposites with enhanced nanozyme activity for glucose detection. ACS Appl Mater Interfaces 9(8):7465–7471

    CAS  PubMed  Google Scholar 

  33. Borthakur P, Darabdhara G, Das MR, Boukherroub R, Szunerits S (2017) Solvothermal synthesis of CoS/reduced porous graphene oxide nanocomposite for selective colorimetric detection of Hg(II) ion in aqueous medium. Sensor Actuat B-Chem 244:684–692

    CAS  Google Scholar 

  34. Chu Z, Xiao M, Dong Q, Li G, Hu T, Zhang Y, Jiang Z (2023) Porous reduced graphene oxide for ultrasensitive detection of nitrogen dioxide. Chin Chem Lett 34(1):107197

  35. Zhang N, Ning X, Chen J, Xue J, Lu G, Qiu H (2022) Photocatalytic degradation of tetracycline based on the highly reactive interface between graphene nanopore and TiO2 nanoparticles. Micropor Mesopor Mat 338:111958

    CAS  Google Scholar 

  36. Chen Z, Li Z, Chen J, Tan H, Wu J, Qiu H (2022) Selective adsorption of rare earth elements by Zn-BDC MOF/graphene oxide nanocomposites synthesized via in situ interlayer-confined strategy. Ind Eng Chem Res 61(4):1841–1849

    CAS  Google Scholar 

  37. Wu J, Li Z, Tan H, Du S, Liu T, Yuan Y, Liu X, Qiu H (2021) Highly selective separation of rare earth elements by Zn-BTC metal–organic framework/nanoporous graphene via in situ green synthesis. Anal Chem 93(3):1732–1739

    CAS  PubMed  Google Scholar 

  38. Song L, Zhang H, Cai T, Chen J, Li Z, Guan M, Qiu H (2019) Porous graphene decorated silica as a new stationary phase for separation of sulfanilamide compounds in hydrophilic interaction chromatography. Chin Chem Lett 30(4):863–866

    CAS  Google Scholar 

  39. Chen J, Wang L, Huang Y, Li Z, Zhang H, Chand Ali M, Liu J, Chen X, Qiu H (2019) Fabrication of nanoporous graphene/cuprous oxide nanocomposite and its application for chemiluminescence sensing of NADH in human serum and cells. Sensor Actuat B-Chem 290:15–22

    CAS  Google Scholar 

  40. Hummers WS Jr, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80(6):1339–1339

    CAS  Google Scholar 

  41. Jiangying Q, Feng G, Quan Z, Zhiyu W, Han H, Beibei L, Wubo W, Xuzhen W, Jieshan Q (2013) Highly atom-economic synthesis of graphene/Mn3O4 hybrid composites for electrochemical supercapacitors. Nanoscale 5(7):2999–3005

    PubMed  Google Scholar 

  42. Li Y, Qu J, Gao F, Lv S, Shi L, He C, Sun J (2015) In situ fabrication of Mn3O4 decorated graphene oxide as a synergistic catalyst for degradation of methylene blue. Appl Catal B-Environ 162:268–274

    CAS  Google Scholar 

  43. Bharath G, Arora N, Hai A, Banat F, Savariraj D, Taher H, Mangalaraja RV (2020) Synthesis of hierarchical Mn3O4 nanowires on reduced graphene oxide nanoarchitecture as effective pseudocapacitive electrodes for capacitive desalination application. Electrochim Acta 337:135668

    CAS  Google Scholar 

  44. Cheng C, Huang Y, Wang N, Jiang T, Hu S, Zheng B, Yuan H, Xiao D (2015) Facile fabrication of Mn2O3 nanoparticle-assembled hierarchical hollow spheres and their sensing for hydrogen peroxide. ACS Appl Mater Interfaces 7(18):9526–9533

    CAS  PubMed  Google Scholar 

  45. Nana L, Ruiyi L, Qinsheng W, Yongqiang Y, Xiulan S, Guangli W, Zaijun L (2021) Colorimetric detection of chlorpyrifos in peach based on cobalt-graphene nanohybrid with excellent oxidase-like activity and reusability. J Hazard Mater 415:125752

    PubMed  Google Scholar 

  46. Wang T, Le Q, Guo X, Huang M, Liu X, Dong F, Zhang J, Zhang YX (2019) Preparation of porous graphene@Mn3O4 and its application in the oxygen reduction reaction and supercapacitor. ACS Sustain Chem Eng 7(1):831–837

    CAS  Google Scholar 

Download references

Funding

The work was supported by the National Natural Science Foundation of China (21964003), the Science and Technology Project of the Education Department of Jiangxi Province (490042), the Double Thousand Talents Program of Jiangxi Province (jxsq2019102009), and the College Students’ Innovation and Entrepreneurship Projects of Gannan Normal University (CX220058).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Hongdeng Qiu.

Ethics declarations

Conflict of interest

The authors declare no competing interests.

Additional information

Publisher's note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 2126 KB)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Peng, D., Que, M., Deng, X. et al. Mn3O4 nanoparticles decorated porous reduced graphene oxide with excellent oxidase-like activity for fast colorimetric detection of ascorbic acid. Microchim Acta 190, 243 (2023). https://doi.org/10.1007/s00604-023-05822-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00604-023-05822-y

Keywords

Navigation