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A copper(II)/cobalt(II) organic gel with enhanced peroxidase-like activity for fluorometric determination of hydrogen peroxide and glucose

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Abstract

A bimetallic organic gel was prepared by mixing the bridging ligand 2,4,6-tri(4-carboxyphenyl)-1,3,5-triazine with Cu(II) and Co(II) ions at room temperature. The resulting metal-organic gel (MOG) shows enhanced peroxidase-like activity, most likely due to the synergetic redox cycling between Co(III)/Co(II) and Cu(II)/Cu(I) pairs. These accelerate interfacial electron transfer and generation of hydroxy radicals. The MOG can catalyze the reaction of H2O2 with terephthalic acid (TPA), producing a blue fluorescence product with the maximum excitation/emission at 315/446 nm. The enzyme mimic was used to design a fluorometric method for H2O2 that has a 81 nM detection limit. H2O2 is also formed by glucose oxidase-assisted oxidation of glucose by oxygen, and an assay for glucose was worked out based on the above method. It has a 0.33 μM detection limit. This study may open up a new avenue to design and synthesize nanomaterial-based biomimetic catalysts with multiple metal synergistically enhanced catalytic activity for potential applications in biocatalysis, bioassays and nano-biomedicine.

Schematic presentation of the synergic catalytic effect of Cu(II)/Co(II) bimetallic organic gel promoted by the redox cycle between Co(III)/Co(II) and Cu(II)/Cu(I) pairs. The bimetallic organic gel can catalyze the reaction of H2O2 with terephthalic acid, thereby producing a blue-fluorescent product.

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References

  1. Wei H, Wang E (2013) Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes. Chem Soc Rev 42(14):6060–6093

    Article  CAS  Google Scholar 

  2. Chen J, Chen Q, Chen J, Qiu H (2016) Magnetic carbon nitride nanocomposites as enhanced peroxidase mimetics for use in colorimetric bioassays, and their application to the determination of H2O2 and glucose. Microchim Acta 183(12):3191–3199

    Article  CAS  Google Scholar 

  3. Zhan L, Li CM, Wu WB, Huang CZ (2014) A colorimetric immunoassay for respiratory syncytial virus detection based on gold nanoparticles-graphene oxide hybrids with mercury-enhanced peroxidase-like activity. Chem Commun 50(78):11526–11528

    Article  CAS  Google Scholar 

  4. Hu AL, Deng HH, Zheng XQ, Wu YY, Lin XL, Liu AL, Xia XH, Peng HP, Chen W, Hong GL (2017) Self-cascade reaction catalyzed by CuO nanoparticle-based dual-functional enzyme mimics. Biosens Bioelectron 97:21–25

    Article  CAS  Google Scholar 

  5. Chang Q, Deng K, Zhu L, Jiang G, Yu C, Tang H (2009) Determination of hydrogen peroxide with the aid of peroxidase-like Fe3O4 magnetic nanoparticles as the catalyst. Microchim Acta 165(3–4):299–305

    Article  CAS  Google Scholar 

  6. Choleva TG, Gatselou VA, Tsogas GZ, Giokas DL (2017) Intrinsic peroxidase-like activity of rhodium nanoparticles, and their application to the colorimetric determination of hydrogen peroxide and glucose. Microchim Acta 185(1):22

    Article  Google Scholar 

  7. Wang S, Deng W, Yang L, Tan Y, Xie Q, Yao S (2017) Copper-based metal-organic framework nanoparticles with peroxidase-like activity for sensitive colorimetric detection of Staphylococcus aureus. ACS Appl Mater Interfaces 9(29):24440–24445

    Article  CAS  Google Scholar 

  8. Chen WH, Vazquez-Gonzalez M, Kozell A, Cecconello A, Willner I (2018) Cu2+-modified metal-organic framework nanoparticles: a peroxidase-mimicking Nanoenzyme. Small 14(5):1–8

    CAS  Google Scholar 

  9. Zhang Z, Zhang X, Liu B, Liu J (2017) Molecular imprinting on inorganic Nanozymes for hundred-fold enzyme specificity. J Am Chem Soc 139(15):5412–5419

    Article  CAS  Google Scholar 

  10. Huang H, Liu L, Zhang L, Zhao Q, Zhou Y, Yuan S, Tang Z, Liu X (2017) Peroxidase-like activity of ethylene diamine Tetraacetic acid and its application for ultrasensitive detection of tumor biomarkers and circular tumor cells. Anal Chem 89(1):666–672

    Article  CAS  Google Scholar 

  11. He W, Liu Y, Yuan J, Yin JJ, Wu X, Hu X, Zhang K, Liu J, Chen C, Ji Y, Guo Y (2011) Au@Pt nanostructures as oxidase and peroxidase mimetics for use in immunoassays. Biomaterials 32(4):1139–1147

    Article  CAS  Google Scholar 

  12. He W, Wu X, Liu J, Hu X, Zhang K, Hou S, Zhou W, Xie S (2010) Design of AgM bimetallic alloy nanostructures (M = au, Pd, Pt) with tunable morphology and peroxidase-like activity. Chem Mater 22(9):2988–2994

    Article  CAS  Google Scholar 

  13. Bhagat S, Srikanth Vallabani NV, Shutthanandan V, Bowden M, Karakoti AS, Singh S (2018) Gold core/ceria shell-based redox active nanozyme mimicking the biological multienzyme complex phenomenon. J Colloid Interface Sci 513:831–842

    Article  CAS  Google Scholar 

  14. Yang H, Yang R, Zhang P, Qin Y, Chen T, Ye F (2017) A bimetallic (co/2Fe) metal-organic framework with oxidase and peroxidase mimicking activity for colorimetric detection of hydrogen peroxide. Microchim Acta 184(12):4629–4635

    Article  CAS  Google Scholar 

  15. Sutar P, Maji TK (2016) Coordination polymer gels: soft metal-organic supramolecular materials and versatile applications. Chem Commun 52(52):8055–8074

    Article  CAS  Google Scholar 

  16. Lee JH, Kang S, Lee JY, Jung JH (2012) A tetrazole-based metallogel induced with ag+ in catalysis. Soft Matter 8:6557–6563

    Article  CAS  Google Scholar 

  17. Hassan HM, Näther C, Winkler HC, Janiak C (2012) Highly selective and “green” alcohol oxidations in water using aqueous 10% H2O2 and iron-benzenetricarboxylate metal-organic gel. Inorg Chim Acta 391:75–82

    Article  Google Scholar 

  18. Ke F, Li Y, Zhang C, Zhu J, Chen P, Ju H, Xu Q, Zhu J (2018) MOG-derived porous FeCo/C nanocomposites as a potential platform for enhanced catalytic activity and lithium-ion batteries performance. J Colloid Interface Sci 522:283–290

    Article  CAS  Google Scholar 

  19. Lin Q, Sun B, Yang Q-P, Fu Y-P, Zhu X, Wei T-B, Zhang Y-M (2014) Double metal ions competitively control the guest-sensing process: a facile approach to stimuli-responsive supramolecular gels. Chem Eur J 20(36):11457–11462

    Article  CAS  Google Scholar 

  20. Zhu X, Zheng H, Wei X, Lin Z, Guo L, Qiu B, Chen G (2013) Metal-organic framework (MOF): a novel sensing platform for biomolecules. Chem Commun 49(13):1276–1278

    Article  CAS  Google Scholar 

  21. TZ G, C O, Osuji JD, Forster ER, Dufresne LR (2010) Stimuli-responsive smart gels realized via modular protein design. J Am Chem Soc 132:14024–14026

    Article  Google Scholar 

  22. Okesola BO, Smith DK (2016) Applying low-molecular weight supramolecular gelators in an environmental setting-self-assembled gels as smart materials for pollutant removal. ChemSocRev 45(15):4226–4251

    CAS  Google Scholar 

  23. He L, Peng ZW, Jiang ZW, Tang XQ, Huang CZ, Li YF (2017) Novel iron(III)-based metal-organic gels with superior catalytic performance toward Luminol Chemiluminescence. ACS Appl Mater Interfaces 9(37):31834–31840

    Article  CAS  Google Scholar 

  24. Xiong Y, Qin Y, Su L, Ye F (2017) Bioinspired synthesis of Cu2+-modified covalent Triazine framework: a new highly efficient and promising peroxidase mimic. Chem EurJ 23:11037–11045

    Article  CAS  Google Scholar 

  25. Aiyappa HB, Saha S, Garai B, Thote J, Kurungot S, Banerjee R (2014) A distinctive PdCl2-mediated transformation of Fe-based Metallogels into metal-organic frameworks. Cryst Growth Des 14(7):3434–3437

    Article  CAS  Google Scholar 

  26. Roy S, Katiyar AK, Mondal SP, Ray SK, Biradha K (2014) Multifunctional white-light-emitting metal-organic gels with a sensing ability of nitrobenzene. ACS Appl Mater Interfaces 6(14):11493–11501

    Article  CAS  Google Scholar 

  27. Peng ZW, Yuan D, Jiang ZW, Li YF (2017) Novel metal-organic gels of bis(benzimidazole)-based ligands with copper(II) for electrochemical selectively sensing of nitrite. Electrochim Acta 238:1–8

    Article  CAS  Google Scholar 

  28. Kirsch PD, Ekerdt JG (2001) Chemical and thermal reduction of thin films of copper (II) oxide and copper (I) oxide. J Appl Phys 90(8):4256–4264

    Article  CAS  Google Scholar 

  29. Poulston S, Parlett PM, Stone P, Bowker M (1996) Surface oxidation and reduction of CuO and Cu2O studied using XPS and XAES. Surf Interface Anal 24:811–820

    Article  CAS  Google Scholar 

  30. Ribeiro RS, Silva AMT, Figueiredo JL, Faria JL, Gomes HT (2017) The role of cobalt in bimetallic iron-cobalt magnetic carbon xerogels developed for catalytic wet peroxide oxidation. Catal Today 296:66–75

    Article  CAS  Google Scholar 

  31. Ivanova T, Naumkin A, Sidorov A, Eremenko I, Kiskin M (2007) X-ray photoelectron spectra and electron structure of polynuclear cobalt complexes. J Electron Spectrosc Relat Phenom 156:200–203

    Article  Google Scholar 

  32. Lin JM, Shan XQ, Hanaoka SC, Yamada M (2001) Luminol Chemiluminescence in unbuffered solutions with a cobalt(II)-ethanolamine complex immobilized on resin as catalyst and its application to analysis. Analchem 73:5043–5051

    CAS  Google Scholar 

  33. Wang Y, Zhao H, Li M, Fan J, Zhao G (2014) Magnetic ordered mesoporous copper ferrite as a heterogeneous Fenton catalyst for the degradation of imidacloprid. Appl Catal B Environ 147:534–545

    Article  CAS  Google Scholar 

  34. Zhang L, Nie Y, Hu C, Qu J (2012) Enhanced Fenton degradation of rhodamine B over nanoscaled cu-doped LaTiO3 perovskite. Appl Catal B Environ 125:418–424

    Article  CAS  Google Scholar 

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Acknowledgements

The authors are grateful to the National Natural Science Foundation of China (NSFC, No. 21575117).

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Authors and Affiliations

  1. Key Laboratory of Luminescent and Real-Time Analytical Chemistry, Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, People’s Republic of China

    Ting Ting Zhao, Zhong Wei Jiang, Shu Jun Zhen, Cheng Zhi Huang & Yuan Fang Li

  2. College of Pharmaceutical Science, Southwest University, Chongqing, 400716, People’s Republic of China

    Cheng Zhi Huang

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  1. Ting Ting Zhao
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Correspondence to Cheng Zhi Huang or Yuan Fang Li.

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Zhao, T.T., Jiang, Z.W., Zhen, S.J. et al. A copper(II)/cobalt(II) organic gel with enhanced peroxidase-like activity for fluorometric determination of hydrogen peroxide and glucose. Microchim Acta 186, 168 (2019). https://doi.org/10.1007/s00604-019-3290-3

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