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Microchimica Acta

, 186:354 | Cite as

Colorimetric evaluation of the hydroxyl radical scavenging ability of antioxidants using carbon-confined CoOx as a highly active peroxidase mimic

  • Hongwei Song
  • Xin Li
  • Yanfang He
  • Yinxian PengEmail author
  • Jianming Pan
  • Xiangheng NiuEmail author
  • Hongli Zhao
  • Minbo LanEmail author
Original Paper
  • 10 Downloads

Abstract

The authors present a colorimetric method for the evaluation of the hydroxyl radical scavenging capability of antioxidants by exploiting carbon-confined mixed cobalt oxide nanoparticles (denoted as C-confined CoOx NPs) as a novel peroxidase mimic. The nanozyme can be prepared from the metal-organic framework ZIF-67 by calcination at a moderate temperature. It exhibits peroxidase-mimicking activity and catalyzes the oxidation of colorless 3,3′,5,5′-tetramethylbenzidine (TMB) to form a blue product in the presence of H2O2 via generation of hydroxyl radicals. However, in the presence of an antioxidant, the color reaction is suppressed due to scavenging of hydroxyl radicals by the antioxidant. Based on this principle, the hydroxy radical scavenging ability of glutathione (GSH), cysteine (Cys), tannic acid (TA) and tea polyphenols (TP) was assessed. It was found that these antioxidants can scavenge hydroxyl radicals in the following decreasing order: TA>Cys>GSH>TP. The assay was also used to quantify the antioxidative power of common fruit extracts.

Graphical abstract

Schematic presentation for evaluating the hydroxyl radical scavenging ability of different antioxidants using carbon-confined mixed cobalt oxide nanoparticles (denoted as C-confined CoOx NPs) as a highly active peroxidase mimic. With excellent activity, the C-confined CoOx NPs together with the visible peroxidase reaction can be employed as a powerful tool to rapidly screen appropriate antioxidants from natural samples and measure their activity for guiding their usage in related products.

Keywords

Nanozyme Co-based materials ROS Colorimetric detection Hydroxyl radicals Antioxidant activity POx Fruit extracts 

Notes

Acknowledgements

The authors appreciated the supports from the National Natural Science Foundation of China (Nos. 21605061 and 31601549), the Natural Science Foundation of Jiangsu Province (No. BK20160489), the Open Fund from the Shanghai Key Laboratory of Functional Materials Chemistry (No. SKLFMC201601), the Open Fund from the State Key Laboratory of Bioreactor University, and the Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. KYCX18_2341).

Compliance with ethical standards

The author(s) declare that they have no competing interests.

Supplementary material

604_2019_3488_MOESM1_ESM.docx (1.9 mb)
ESM 1 (DOCX 1898 kb)

References

  1. 1.
    Pisoschi AM, Pop A (2015) The role of antioxidants in the chemistry of oxidative stress: a review. Eur J Med Chem 97:55–74CrossRefPubMedGoogle Scholar
  2. 2.
    Ames BN, Shigenaga MK, Hagen TM (1993) Oxidants, antioxidants, and the degenerative diseases of aging. Proc Natl Acad Sci U S A 90:7915–7922CrossRefPubMedPubMedCentralGoogle Scholar
  3. 3.
    Halliwell B (1996) Antioxidants in human health and disease. Annu Rev Nutr 16:33–50CrossRefPubMedGoogle Scholar
  4. 4.
    Zang S, Tian SZ, Jiang J, Han DD, Yu XY, Wang K, Li D, Lu DY, Yu AM, Zhang ZW (2017) Determination of antioxidant capacity of diverse fruits by electron spin resonance (ESR) and UV-vis spectrometries. Food Chem 221:1221–1225CrossRefPubMedGoogle Scholar
  5. 5.
    Peng XY, Xiong YL, Kong BH (2009) Antioxidant activity of peptide fractions from whey protein hydrolysates as measured by electron spin resonance. Food Chem 113:196–201CrossRefGoogle Scholar
  6. 6.
    Guo SS, Deng QC, Xiao JS, Xie BJ, Sun ZD (2007) Evaluation of antioxidant activity and preventing DNA damage effect of pomegranate extracts by chemiluminescence method. J Agric Food Chem 55:3134–3140CrossRefPubMedGoogle Scholar
  7. 7.
    Giokas DL, Vlessidis AG, Evmiridis NP (2007) On-line selective detection of antioxidants free-radical scavenging activity based on co(II)/EDTA-induced luminol chemiluminescence by flow injection analysis. Anal Chim Acta 589:59–65CrossRefPubMedGoogle Scholar
  8. 8.
    Oliveira GKF, Tormin TF, Sousa RMF, Oliveira AD, Morais SALD, Richter EM, Munoz RAA (2016) Batch-injection analysis with amperometric detection of the DPPH radical for evaluation of antioxidant capacity. Food Chem 192:691–697CrossRefPubMedGoogle Scholar
  9. 9.
    Prieto-Simón B, Cortina M, Campàs M, Calas-Blanchard C (2008) Electrochemical biosensors as a tool for antioxidant capacity assessment. Sensors Actuators B Chem 129:459–466CrossRefGoogle Scholar
  10. 10.
    Bener M, Özyürek M, Güçlü K, Apak R (2010) Development of a low-cost optical sensor for cupric reducing antioxidant capacity measurement of food extracts. Anal Chem 82:4252–4258CrossRefPubMedGoogle Scholar
  11. 11.
    López-Alarcón C, Denicola A (2013) Evaluating the antioxidant capacity of natural products: a review on chemical and cellular-based assays. Anal Chim Acta 763:1–10CrossRefPubMedGoogle Scholar
  12. 12.
    Wei H, Wang EK (2013) Nanomaterials with enzyme-like characterics (nanozymes): next-generation artificial enzymes. Chem Soc Rev 42:5981–6202CrossRefGoogle Scholar
  13. 13.
    Nasir M, Nawaz MH, Latif U, Yaqub M, Hayat A, Rahim A (2017) An overview on enzyme-mimicking nanomaterials for use in electrochemical and optical assays. Microchim Acta 184:323–342CrossRefGoogle Scholar
  14. 14.
    Nagvenkar AP, Gedanken A (2016) Cu0.89Zn0.11O, a new peroxidase-mimicking nanozyme with high sensitivity for glucose and antioxidant detection. ACS Appl Mater Interfaces 8:22301–22308CrossRefPubMedGoogle Scholar
  15. 15.
    Han L, Liu P, Zhang HJ, Li F, Liu AH (2017) Phage capsid protein-directed MnO2 nanosheets with peroxidase-like activity for spectrometric biosensing and evaluation of antioxidant behavior. Chem Commun 53:5216–5219CrossRefGoogle Scholar
  16. 16.
    Xie JX, Cao HY, Jiang H, Chen YJ, Shi WB, Zheng HZ, Huang YM (2013) Co3O4-reduced graphene oxide nanocomposite as an effective peroxidase mimetic and its application in visual biosensing of glucose. Anal Chim Acta 796:92–100CrossRefPubMedGoogle Scholar
  17. 17.
    Liu JB, Hu XN, Hou S, Wen T, Liu WQ, Zhu X, Wu XC (2011) Screening of inhibitors for oxidase mimics of au@Pt nanorods by catalytic oxidation of OPD. Chem Commun 47:10981–10983CrossRefGoogle Scholar
  18. 18.
    Niu XH, He YF, Li X, Song HW, Zhang WC, Peng YX, Pan JM, Qiu FX (2017) Trace iodide dramatically accelerates the peroxidase activity of VOx at ppb-concentration levels. ChemistrySelect 2:10854–10859CrossRefGoogle Scholar
  19. 19.
    Barreto JC, Smith GS, Strobel NH, McQuillin PA, Miller TA (1995) Terephthalic acid: a dosimeter for the detection of hydroxyl radicals in vitro. Life Sci 56:89–96Google Scholar
  20. 20.
    Chen FF, Zhu YJ, Xiong ZC, Sun TW (2017) Hydroxyapatite nanowires@metal-organic framework core/shell nanofibers: templated synthesis, peroxidase-like activity and their derived flexible recyclable test paper. Chem Eur J 23:3328–3337CrossRefPubMedGoogle Scholar
  21. 21.
    Ortiz-Gómez I, Salinas-Castillo A, García AG, Álvarez-Bermejo JA, de Orbe-Payá I, Rodríguez-Diéguez A, Capitán-Vallvey LF (2018) Microfluidic paper-based device for colorimetric determination of glucose based on a metal-organic framework acting as peroxidase mimetic. Microchim Acta 185:47CrossRefGoogle Scholar
  22. 22.
    Dong WF, Zhuang YX, Li SQ, Zhang XD, Chai HX, Huang YM (2018) High peroxidase-like activity of metallic cobalt nanoparticles encapsulated in metal-organic frameworks derived carbon for biosensing. Sensors Actuators B Chem 255:2050–2057CrossRefGoogle Scholar
  23. 23.
    Nirala NR, Prakash R (2018) Quick colorimetric determination of choline in milk and serum based on the use of MoS2 nanosheets as a highly active enzyme mimetic. Microchim Acta 185:224CrossRefGoogle Scholar
  24. 24.
    Zhu F, Zhao G, Dou W (2018) Voltammetric sandwich immunoassay for Cronobacter sakazakii using a screen-printed carbon electrode modified with horseradish peroxidase, reduced graphene oxide, thionine and gold nanoparticles. Microchim Acta 185:45CrossRefGoogle Scholar
  25. 25.
    Niu XH, He YF, Pan JM, Li X, Qiu FX, Yan YS, Shi LB, Zhao HL, Lan MB (2016) Uncapped nanobranch-based CuS clews used as an efficient peroxidase mimic enable the visual detection of hydrogen peroxide and glucose with fast response. Anal Chim Acta 947:42–49CrossRefPubMedGoogle Scholar
  26. 26.
    He YF, Niu XH, Shi LB, Zhao HL, Li X, Zhang WC, Pan JM, Zhang XF (2017) Photometric determination of free cholesterol via cholesterol oxidase and carbon nanotube supported Prussian blue as a peroxidase mimic. Microchim Acta 184:2181–2189CrossRefGoogle Scholar
  27. 27.
    Song YJ, Qu KG, Zhao C, Ren JS, Qu XG (2010) Graphene oxide: intrinsic peroxidase catalytic activity and its application to glucose detection. Adv Mater 22:2206–2210CrossRefPubMedGoogle Scholar
  28. 28.
    Niu XH, He YF, Zhang WC, Li X, Qiu FX, Pan JM (2018) Elimination of background color interference by immobilizing Prussian blue on carbon cloth: a monolithic peroxidase mimic for on-demand photometric sensing. Sensors Actuators B Chem 256:151–159CrossRefGoogle Scholar
  29. 29.
    Zhang WC, Niu XH, Li X, He YF, Song HW, Peng YX, Pan JM, Qiu FX, Zhao HL, Lan MB (2018) A smartphone-integrated ready-to-use paper-based sensor with mesoporous carbon-dispersed Pd nanoparticles as a highly active peroxidase mimic for H2O2 detection. Sensors Actuators B Chem 265:412–420CrossRefGoogle Scholar
  30. 30.
    Zhang WC, Niu XH, Meng SC, Li X, He YF, Pan JM, Qiu FX, Zhao HL, Lan MB (2018) Histidine-mediated tunable peroxidase-like activity of nanosized Pd for photometric sensing of ag+. Sensors Actuators B Chem 273:400–407CrossRefGoogle Scholar
  31. 31.
    Li X, Pu ZL, Zhou H, Zhang WC, Niu XH, He YF, Xu XC, Qiu FX, Pan JM, Ni L (2018) Synergistically enhanced peroxidase-like activity of Pd nanoparticles dispersed on CeO2 nanotubes and their application in colorimetric sensing of sulfhydryl compounds. J Mater Sci 53:13912–13923CrossRefGoogle Scholar
  32. 32.
    He YF, Qi F, Niu XH, Zhang WC, Zhang XF (1021) J.M. Pan JM (2018) Uricase-free on-demand colorimetric biosensing of uric acid enabled by integrated CoP nanosheet arrays as a monolithic peroxidase mimic. Anal Chim Acta:113–120CrossRefPubMedGoogle Scholar
  33. 33.
    The natural HRP (100 mg, 300 U/mg) purchased from Shanghai Macklin biochemical co., ltd. costs ~$70, so the cost of the natural HRP is ~$2.5 per kU. The commercial prices of the co(NO3)2·6H2O (100 g) and 2-MI (100 g) precursors are ~$20 and ~$10, respectively. After considering the cost of other reagents including PVP, the cost of all raw materials is calculated to be ~$35 to obtain 25 g C-confined CoOx NPs. Taking ~$30 as the cost for the preparation of C-confined CoOx NPs, the total cost of 25 g C-confined CoOx NPs is determined to be ~$65. According to the k cat value, the enzymatic activity of C-confined CoOx NPs is estimated to be about 20 U/mg. So, the cost of the C-confined CoOx NPs nanozyme is ~$0.13 per kU, which is much lower than that of natural HRP (~$2.5 per kU)Google Scholar
  34. 34.
    Zhao J, Dong WF, Zhang XD, Chai HX, Huang YM (2018) FeNPs@Co3O4 hollow nanocages hybrids as effective peroxidase mimics for glucose biosensing. Sensors Actuators B Chem 263:575–584CrossRefGoogle Scholar
  35. 35.
    Li X, Kong CY, Chen ZB (2019) Colorimetric sensor array for antioxidant discrimination based on the inhibition of oxidation reaction between 3,3′,5,5′-tetramethylbenzidine and hydrogen peroxides. ACS Appl Mater Interfaces 11:9504–9509CrossRefPubMedGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Environmental and Chemical EngineeringJiangsu University of Science and TechnologyZhenjiangChina
  2. 2.Institute of Green Chemistry and Chemical Technology, School of Chemistry and Chemical EngineeringJiangsu UniversityZhenjiangChina
  3. 3.Shanghai Key Laboratory of Functional Materials Chemistry, School of Chemistry and Molecular EngineeringEast China University of Science and TechnologyShanghaiChina

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