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Label-free fluorescence detection of hydrogen peroxide and glucose based on the Ni-MOF nanozyme–induced self-ligand emission

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Abstract

A bifunctional Ni-MOF nanosheet was synthesized and developed for label-free fluorescent detection of H2O2 and glucose. The Ni-MOF exhibited intrinsic peroxidase-like activity and its catalytic activity was demonstrated to be originated from the hydroxyl radicals (•OH) produced in catalytic process. Since the generated •OH enabled terephthalic acid, the non-fluorescent organic ligand of Ni-MOF, to form a strongly fluorescent 2-hydroxy terephthalic acid, the Ni-MOF nanozyme was endowed with dual-function properties of mimicking peroxidase and emitting fluorescence. Based on this bifunctional Ni-MOF nanozyme, the proposed label-free fluorescence sensing strategy was applied to detecting H2O2 and glucose with wide linear ranges of 0.1–20 mM and 8–30 μM, and low detection limits of 4.0 × 10−5 M and 4.0 × 10−6 M, respectively. Furthermore, the bifunctional Ni-MOF-based label-free sensing platform was successfully used for the glucose detection in human serum samples, showing good reproducibility and high accuracy. This strategy provides a green and sensitive method for the determination of small biomolecules in practical applications by the combination of enzyme cascade reaction.

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References

  1. Sun H, Jiao X, Han Y, Jiang Z, Chen D (2013) Synthesis of Fe3O4-Au nanocomposites with enhanced peroxidase-like activity. Eur J Inorg Chem 2013:109–114

    Article  CAS  Google Scholar 

  2. Mu J, Zhang L, Zhao M, Wang Y (2014) Catalase mimic property of Co3O4 nanomaterials with different morphology and its application as a calcium sensor. ACS Appl Mater Interfaces 6:7090–7098

    Article  CAS  PubMed  Google Scholar 

  3. Zhang W, Li X, Cui T, Li S, Qian Y, Yue Y, Zhong W, Xu B, Yue W (2021) PtS2 nanosheets as a peroxidase-mimicking nanozyme for colorimetric determination of hydrogen peroxide and glucose. Microchim Acta 188(5):1–9

    Article  Google Scholar 

  4. Wu G, Shen Y, Shi X, Deng H, Zheng X, Peng H, Liu A, **a X, Chen W (2017) Bimetallic Bi/Pt peroxidase mimic and its bioanalytical applications. Anal Chim Acta 971:88–96

    Article  CAS  PubMed  Google Scholar 

  5. Lin Y, Ren J, Qu X (2014) Catalytically active nanomaterials: a promising candidate for artificial enzymes. Acc Chem Res 47:1097–1105

    Article  CAS  PubMed  Google Scholar 

  6. Huang Y, Liu C, Pu F, Liu Z, Ren J, Qu X (2017) GO-Se nanocomposite as an antioxidant nanozyme for cytoprotection. Chem Commun 53:3082–3085

    Article  CAS  Google Scholar 

  7. Wei H, Wang E (2013) Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes. Chem Soc Rev 42:6060–6093

    Article  CAS  PubMed  Google Scholar 

  8. Zhu J, Luo G, ** X, Wang Y, Selvaraj JN, Wen W, Zhang X, Wang S (2021) Cu2+-modified hollow carbon nanospheres: an unusual nanozyme with enhanced peroxidase-like activity. Microchim Acta 188:8

    Article  CAS  Google Scholar 

  9. Wu Y, Ma Y, Xu G, Wei F, Ma Y, Song Q, Wang X, Tang T, Song Y, Shi M, Xu X, Hu Q (2017) Metal-organic framework coated Fe3O4 magnetic nanoparticles with peroxidase-like activity for colorimetric sensing of cholesterol. Sens Actuators B Chem 249:195–202

    Article  CAS  Google Scholar 

  10. Qiu H, Guan Y, Luo P, Wang Y (2017) Recent advance in fabricating monolithic 3D porous graphene and their applications in biosensing and biofuel cells. Biosens Bioelectron 89:85–95

    Article  CAS  PubMed  Google Scholar 

  11. Wan H, Wang Y, Chen J, Meng HM, Li Z (2021) 2D Co-MOF nanosheet-based nanozyme with ultrahigh peroxidase catalytic activity for detection of biomolecules in human serum samples. Microchim Acta 188(4):1–8

    Article  Google Scholar 

  12. Darabdhara G, Sharma B, Das MR, Boukherroub R, Szunerits S (2017) Cu-Ag bimetallic nanoparticles on reduced graphene oxide nanosheets as peroxidase mimic for glucose and ascorbic acid detection. Sens Actuators B Chem 238:842–851

    Article  CAS  Google Scholar 

  13. Zhou X, Wang S, Zhang C, Lin Y, Lv J, Hu S, Zhang S, Li M (2021) Colorimetric determination of amyloid-β peptide using MOF-derived nanozyme based on porous ZnO-Co3O4 nanocages. Microchim Acta 188(2):1–10

    Article  Google Scholar 

  14. Guo J, Wang Y, Zhao M (2018) 3D flower-like ferrous (II) phosphate nanostructures as peroxidase mimetics for sensitive colorimetric detection of hydrogen peroxide and glucose at nanomolar level. Talanta 182:230–240

    Article  CAS  PubMed  Google Scholar 

  15. Lu K, Aung T, Guo N, Weichselbaum RR, Lin W (2018) Nanoscale metal-organic frameworks for therapeutic, imaging, and sensing applications. Adv Mater 30:1707634

    Article  Google Scholar 

  16. Wu Y, Gao Y, Du J (2019) Bifunctional gold nanoclusters enable ratiometric fluorescence nanosensing of hydrogen peroxide and glucose. Talanta 197:599–604

    Article  CAS  PubMed  Google Scholar 

  17. Zhang X, Ge C, Zhang N, Duan Y, Wang Y, Zhao L, Zhuang X, Li J, Wu J, Yang Q (2019) A MOF material based on zinc (II) and mixed ligands: synthesis, structure and luminescence behavior. Inorg Chim Acta 496:119035

    Article  CAS  Google Scholar 

  18. Yang H, Liu J, Feng X, Nie F, Yang G (2021) A novel copper-based metal-organic framework as a peroxidase-mimicking enzyme and its glucose chemiluminescence sensing application. Anal Bioanal Chem 1–10

  19. Shi M, Xu M, Gu Z (2019) Copper-based two-dimensional metal-organic framework nanosheets as horseradish peroxidase mimics for glucose fluorescence sensing. Anal Chim Acta 1079:164–170

    Article  CAS  PubMed  Google Scholar 

  20. Let S, Samanta P, Dutta S, Ghosh SK (2020) A Dye@ MOF composite as luminescent sensory material for selective and sensitive recognition of Fe (III) ions in water. Inorganica Chim Acta 500:119205

    Article  CAS  Google Scholar 

  21. Cai S, Fu Z, **ao W, **ong Y, Wang C, Yang R (2020) Zero-dimensional/two-dimensional AuxPd100–x nanocomposites with enhanced nanozyme catalysis for sensitive glucose detection. ACS Appl Mater Interfaces 12:11616–11624

    Article  CAS  PubMed  Google Scholar 

  22. Chen Y, Chen T, Wu X, Yang G (2019) CuMnO2 nanoflakes as pH-switchable catalysts with multiple enzyme-like activities for cysteine detection. Sens Actuators B Chem 279:374–384

    Article  CAS  Google Scholar 

  23. Guo J, Wu S, Wang Y, Zhao M (2020) A label-free fluorescence biosensor based on a bifunctional MIL-101(Fe) nanozyme for sensitive detection of choline and acetylcholine at nanomolar level. Sens Actuators B Chem 312:128021

    Article  CAS  Google Scholar 

  24. Hu Z, Jiang X, Xu F, Jia J, Long Z, Hou X (2016) Colorimetric sensing of bithiols using photocatalytic UiO-66(NH2) as H2O2-free peroxidase mimics. Talanta 158:276–282

    Article  CAS  PubMed  Google Scholar 

  25. Ai L, Li L, Zhang C, Fu J, Jiang J (2013) MIL-53 (Fe): a metal-organic framework with intrinsic peroxidase-like catalytic activity for colorimetric biosensing. Chem Eur J 19:15105–15108

    Article  CAS  PubMed  Google Scholar 

  26. Li D, Zhang S, Feng X, Yang H, Nie F, Zhang W (2019) A novel peroxidase mimetic Co-MOF enhanced luminol chemiluminescence and its application in glucose sensing. Sens Actuators B Chem 296:126631

    Article  CAS  Google Scholar 

  27. Hu S, Yan J, Huang X, Guo L, Lin Z, Luo F, Qin B (2018) A sensing platform for hypoxanthine detection based on amino-functionalized metal organic framework nanosheet with peroxidase mimic and fluorescence properties. Sens Actuators B Chem 267:312–319

    Article  CAS  Google Scholar 

  28. ** T, Li Y, **g W, Li Y, Fan L, Li X (2020) Cobalt-based metal organic frameworks: a highly active oxidase-mimicking nanozyme for fluorescence “turn-on” assays of biothiol. Chem Commun 56:659–662

    Article  CAS  Google Scholar 

  29. Chen WH, Vázquez-González M, Kozell A, Cecconello A, Willner I (2018) Cu2+-modified metal-organic framework nanoparticles: a peroxidase-mimicking nanoenzyme. Small 14:1703149

    Article  Google Scholar 

  30. Garner RC, Walpole AL, Rose FL (1975) Testing of some benzidine analogues for microsomal activation to bacterial mutagens. Cancer Lett 1:39

    Article  CAS  PubMed  Google Scholar 

  31. Chen J, Shu Y, Li H, Xu Q, Hu X (2018) Nickel metal-organic framework 2D nanosheets with enhanced peroxidase nanozyme activity for colorimetric detection of H2O2. Talanta 189:254–261

    Article  CAS  PubMed  Google Scholar 

  32. Lin T, Qin Y, Huang Y, Yang R, Hou L, Ye F, Zhao S (2018) A label-free fluorescence assay for hydrogen peroxide and glucose based on the bifunctional MIL-53 (Fe) nanozyme. Chem Commun 54:1762–1765

    Article  CAS  Google Scholar 

  33. Lin YH, Zhao AD, Tao Y, Ren J, Qu X (2013) Ionic liquid as an efficient modulator on artificial enzyme system: toward the realization of high-temperature catalytic reactions. J Am Chem Soc 135:4207–4210

    Article  CAS  PubMed  Google Scholar 

  34. Gao L, Zhuang J, Nie L, Zhang J, Zhang Y, Gu N, Wang T, Feng J, Yang D, Perrett S, Yan X (2007) Intrinsic peroxidase-like activity of ferromagnetic nanoparticles. Nat Nanotechnol 2:577–583

    Article  CAS  PubMed  Google Scholar 

  35. **a C, Huang W, Kang X, Chen P, You L, Guo L (2022) Salt-template preparation of Mo5N6 nanosheets with peroxidase- and catalase-like activities and application for colorimetric determination of 4-aminophenol. Microchim Acta 189:1

    Article  CAS  Google Scholar 

  36. Fan Y, Zhang W, Liu Y, Zeng Z, Quan X, Zhao H (2019) Three-dimensional branched crystal carbon nitride with enhanced intrinsic peroxidase-like activity: a hypersensitive platform for colorimetric detection. ACS Appl Mater Interfaces 11:17467–17474

    Article  CAS  PubMed  Google Scholar 

  37. Song C, Ding W, Zhao W, Liu H, Wang J, Yao Y, Yao C (2020) High peroxidase-like activity realized by facile synthesis of FeS2 nanoparticles for sensitive colorimetric detection of H2O2 and glutathione. Biosens Bioelectron 151:111983

    Article  CAS  PubMed  Google Scholar 

  38. Yang X, Xu X, Xu J, Han Y (2013) Iron oxychloride (FeOCl): an efficient fenton-like catalyst for producing hydroxyl radicals in degradation of organic contaminants. J Am Chem Soc 135:16058–16061

    Article  CAS  PubMed  Google Scholar 

  39. Guo J, Wang Y, Zhao M (2019) Target-directed functionalized ferrous phosphate-carbon dots fluorescent nanostructures as peroxidase mimetics for cancer cell detection and ROS-mediated therapy. Sens Actuators B Chem 297:126739

    Article  CAS  Google Scholar 

  40. Alizadeh N, Salimi A, Hallaj R (2019) Mimicking peroxidase-like activity of Co3O4-CeO2 nanosheets integrated paper-based analytical devices for detection of glucose with smartphone. Sens Actuators B Chem 288:44–52

    Article  CAS  Google Scholar 

  41. Tao Y, Ju E, Ren J, Qu X (2015) Bifunctionalized mesoporous silica-supported gold nanoparticles: intrinsic oxidase and peroxidase catalytic activities for antibacterial applications. Adv Mater 27:1097–1104

    Article  CAS  PubMed  Google Scholar 

  42. Su L, Qin W, Zhang H, Rahman ZU, Ren C, Ma S, Chen X (2015) The peroxidase/catalase-like activities of MFe2O4 (M = Mg, Ni, Cu) MNPs and their application in colorimetric biosensing of glucose. Biosens Bioelectron 63:384–391

    Article  CAS  PubMed  Google Scholar 

  43. Liu Q, Yang Y, Li H, Zhu R, Shao Q, Yang S, Xu J (2015) NiO nanoparticles modified with 5, 10, 15, 20-tetrakis (4-carboxyl pheyl)-porphyrin: promising peroxidase mimetics for H2O2 and glucose detection. Biosens Bioelectron 64:147–153

    Article  CAS  PubMed  Google Scholar 

  44. Liu YL, Zhao XJ, Yang XX, Li YF (2013) A nanosized metal-organic framework of Fe-MIL-88NH2 as a novel peroxidase mimic used for colorimetric detection of glucose. Analyst 138:4526–4531

    Article  CAS  PubMed  Google Scholar 

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Funding

This work was supported by the National Natural Science Foundation of China (No. 31470489).

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, 150001, China

    **g**g Guo, Yangyang Liu, Zhao Mu, Shu Wu & Yan Wang

  2. Key Laboratory of Nanobiotechnology of Hebei Province, Yanshan University, Qinhuangdao, 066004, China

    **g**g Guo

  3. College of Life Science, Northeast Forestry University, Harbin, 150040, China

    Jueyu Wang, Yue Yang & Min Zhao

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  1. **g**g Guo
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  2. Yangyang Liu
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  3. Zhao Mu
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  7. Min Zhao
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  8. Yan Wang
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Correspondence to Yan Wang.

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Guo, J., Liu, Y., Mu, Z. et al. Label-free fluorescence detection of hydrogen peroxide and glucose based on the Ni-MOF nanozyme–induced self-ligand emission. Microchim Acta 189, 219 (2022). https://doi.org/10.1007/s00604-022-05313-6

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