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Microchimica Acta

, 186:274 | Cite as

A colorimetric heparin assay based on the inhibition of the oxidase mimicking activity of cerium oxide nanoparticles

  • Hong Liao
  • Yilin Liu
  • Min Chen
  • Min Wang
  • Hua YuanEmail author
  • Lianzhe HuEmail author
Original Paper
  • 86 Downloads

Abstract

A colorimetric method is described for the sensitive detection of heparin (Hep). It is based on the finding that Hep can effectively inhibit the oxidase mimicking activity of cerium oxide nanoparticles (nanoceria). In the presence of Hep, the catalytic activity of nanoceria toward the oxidation of the chromogenic substrate 3,3′,5,5′-tetramethylbenzidine by oxygen is strongly decreased. The inhibition mechanism is attributed to the fact that Hep is adsorbed on the surface of the nanoceria. Under optimal condition, the absorbance (measured at 652 nm) decreases with increasing Hep concentrations in the range from 30 to 700 nM. The detection limit is 20 nM. The method was applied to the determination of Hep in medical injection sample and serum sample with satisfactory results.

Graphical abstract

Schematic presentation of the inhibition of oxidase-like activity of nanoceria by heparin. This allows the sensitive detection of heparin in medical injection sample and serum sample with satisfactory results.

Keywords

Nanozyme Catalysis Protamine Enzyme Polymer Peroxidase 

Notes

Acknowledgements

This work was supported by the National Natural Science Foundation of China (NSFC, 21605012 and 21802012), Chongqing Research Program of Basic Research and Frontier Technology (No. cstc2016jcyjA0432), Scientific and Technological Research Program of Chongqing Municipal Education Commission (No. KJ1600328), and Chongqing Undergraduate Training Program for Innovation and Entrepreneurship (No. 201810637022).

Compliance with ethical standards

The authors declare that they have no competing interests.

Supplementary material

604_2019_3382_MOESM1_ESM.docx (1.2 mb)
ESM 1 (DOCX 1197 kb)

References

  1. 1.
    Bromfield SM, Wilde E, Smith DK (2013) Hep sensing and binding - taking supramolecular chemistry towards clinical applications. Chem Soc Rev 42:9184–9195CrossRefGoogle Scholar
  2. 2.
    Bergamaschini L, Rossi E, Vergani C, De Simoni MG (2009) Alzheimer's disease: another target for Hep therapy. Sci World J 9:891–908CrossRefGoogle Scholar
  3. 3.
    Crowther MA, Warkentin TE (2008) Bleeding risk and the management of bleeding complications in patients undergoing anticoagulant therapy: focus on new anticoagulant agents. Blood 111:4871–4879CrossRefGoogle Scholar
  4. 4.
    Murray DJ, Brosnahan WJ, Pennell B, Kapalanski D, Weiler JM, Olson J (1997) Hep detection by the activated coagulation time: a comparison of the sensitivity of coagulation tests and Hep assays. J Cardiothorac Vasc Anesth 11:24–28CrossRefGoogle Scholar
  5. 5.
    Thiangthum S, Heyden YV, Buchberger W, Viaene J, Prutthiwanasan B, Suntornsuk L (2014) Development and validation of an ion-exchange chromatography method for Hep and its impurities in Hep products. J Sep Sci 37:3195–3204CrossRefGoogle Scholar
  6. 6.
    Sanderson P, Stickney M, Leach FE, Xia QW, Yu YL, Zhang FM, Linhardt R, Amster IJ (2018) Hep/heparan sulfate analysis by covalently modified reverse polarity capillary zone electrophoresis-mass spectrometry. J Chromatogr A 1545:75–83CrossRefGoogle Scholar
  7. 7.
    Crespo GA, Afshar MG, Bakker E (2012) Reversible sensing of the anticoagulant Hep with protamine permselective membranes. Angew Chem Int Ed 51:12575–12578CrossRefGoogle Scholar
  8. 8.
    Cheng Q, He Y, Ge Y, Zhou J, Song G (2018) Ultrasensitive detection of Hep by exploiting the silver nanoparticle-enhanced fluorescence of graphitic carbon nitride (g-C3N4) quantum dots. Microchim Acta 185:332CrossRefGoogle Scholar
  9. 9.
    Wang R, Wang X, Sun Y (2017) Aminophenol-based carbon dots with dual wavelength fluorescence emission for determination of Hep. Microchim Acta 184:187–193CrossRefGoogle Scholar
  10. 10.
    Huang J, Li F, Guo R, Chen Y, Wang Z, Zhao C, Zheng Y, Weng S, Lin X (2018) A signal-on ratiometric fluorometric Hep assay based on the direct interaction between amino-modified carbon dots and DNA. Microchim Acta 185:260CrossRefGoogle Scholar
  11. 11.
    Ding YB, Shi LL, Wei H (2015) A "turn on" fluorescent probe for Hep and its oversulfated chondroitin sulfate contaminant. Chem Sci 6:6361–6366CrossRefGoogle Scholar
  12. 12.
    Wang X, Hu Y, Wei H (2016) Nanozymes in bionanotechnology: from sensing to therapeutics and beyond. Inorg Chem Front 3:41–60CrossRefGoogle Scholar
  13. 13.
    Wei H, Wang E (2013) Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes. Chem Soc Rev 42:6060–6093CrossRefGoogle Scholar
  14. 14.
    Nasir M, Nawaz M, 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
  15. 15.
    Liu B, Liu J (2017) Surface modification of nanozymes. Nano Res 10:1125–1148CrossRefGoogle Scholar
  16. 16.
    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 2:577–583CrossRefGoogle Scholar
  17. 17.
    Lin Y, Ren J, Qu X (2014) Catalytically active nanomaterials: a promising candidate for artificial enzymes. Acc Chem Res 47:1097–1105CrossRefGoogle Scholar
  18. 18.
    Zhang Z, Zhang X, Liu B, Liu J (2017) Molecular imprinting on inorganic nanozymes for hundred-fold enzyme specificity. J Am Chem Soc 139:5412–5419CrossRefGoogle Scholar
  19. 19.
    Hu L, Liao H, Feng L, Wang M, Fu W (2018) Accelerating the peroxidase-like activity of gold nanoclusters at neutral pH for colorimetric detection of Hep and Hepase activity. Anal Chem 90:6247–6252CrossRefGoogle Scholar
  20. 20.
    Liao H, Liu G, Liu Y, Li R, Fu W, Hu L (2017) Aggregation-induced accelerating peroxidase-like activity of gold nanoclusters and their applications for colorimetric Pb2+ detection. Chem Commun 53:10160–10163CrossRefGoogle Scholar
  21. 21.
    Liao H, Hu L, Zhang Y, Yu X, Liu Y, Li R (2018) A highly selective colorimetric sulfide assay based on the inhibition of the peroxidase-like activity of copper nanoclusters. Microchim Acta 185:143CrossRefGoogle Scholar
  22. 22.
    Wang S, Cazelles R, Liao W, Vazquez-Gonzalez M, Zoabi A, Abu-Reziq R, Willner I (2017) Mimicking horseradish peroxidase and NADH peroxidase by heterogeneous Cu2+-modified graphene oxide nanoparticles. Nano Lett 17:2043–2048CrossRefGoogle Scholar
  23. 23.
    Wang X, Qin L, Zhou M, Lou Z, Wei H (2018) Nanozyme sensor arrays for detecting versatile Analytes from small molecules to proteins and cells. Anal Chem 90:11696–11702CrossRefGoogle Scholar
  24. 24.
    Wu J, Li S, Wei H (2018) Integrated nanozymes: facile preparation and biomedical applications. Chem Commun 54:6520–6530CrossRefGoogle Scholar
  25. 25.
    Wang N, Duan J, Shi W, Zhai X, Guan F, Yang L, Hou B (2018) A 3-dimensional C/CeO2 hollow nanostructure framework as a peroxidase mimetic, and its application to the colorimetric determination of hydrogen peroxide. Microchim Acta 185:417CrossRefGoogle Scholar
  26. 26.
    Wang C, Tang G, Tan H (2018) Colorimetric determination of mercury(II) via the inhibition by ssDNA of the oxidase-like activity of a mixed valence state cerium-based metal-organic framework. Microchim Acta 185:475CrossRefGoogle Scholar
  27. 27.
    Cheng H, Lin S, Muhammad F, Lin Y, Wei H (2016) Rationally modulate the oxidase-like activity of nanoceria for self-regulated bioassays. ACS Sens 1:1336–1343CrossRefGoogle Scholar
  28. 28.
    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 8:13562–13567CrossRefGoogle Scholar
  29. 29.
    Asati A, Santra S, Kaittanis C, Nath S, Perez J (2009) Oxidase-like activity of polymer-coated cerium oxide nanoparticles. Angew Chem Int Ed 48:2308–2312CrossRefGoogle Scholar
  30. 30.
    Kim M, Park K, Park H (2014) Ultrafast colorimetric detection of nucleic acids based on the inhibition of the oxidase activity of cerium oxide nanoparticles. Chem Commun 50:9577–9580CrossRefGoogle Scholar
  31. 31.
    Cao G, Jiang X, Zhang H, Croley T, Yin J (2017) Mimicking horseradish peroxidase and oxidase using ruthenium nanomaterials. RSC Adv 7:52210–52217CrossRefGoogle Scholar
  32. 32.
    Shen X, Liu W, Gao X, Lu Z, Wu X, Gao X (2015) Mechanisms of oxidase and superoxide dismutation-like activities of gold, silver, platinum, and palladium, and their alloys: a general way to the activation of molecular oxygen. J Am Chem Soc 137:15882–15891CrossRefGoogle Scholar
  33. 33.
    Pautler R, Kelly E, Huang P, Cao J, Liu B, Liu J (2013) Attaching DNA to nanoceria: regulating oxidase activity and fluorescence quenching. ACS Appl Mater Interfaces 5:6820–6825CrossRefGoogle Scholar
  34. 34.
    Montini T, Melchionna M, Monai M, Fornasiero P (2016) Fundamentals and catalytic applications of CeO2-based materials. Chem Rev 116:5987–6041CrossRefGoogle Scholar
  35. 35.
    Li J, Cheng M, Li M (2017) A luminescent and colorimetric probe based on the functionalization of gold nanoparticles by ruthenium(ii) complexes for Hep detection. Analyst 142:3733–3739CrossRefGoogle Scholar
  36. 36.
    You J, Liu Y, Lu C, Tseng W, Yu C (2016) Colorimetric assay of Hep in plasma based on the inhibition of oxidase-like activity of citrate-capped platinum nanoparticles. Biosens Bioelectron 92:442–448CrossRefGoogle Scholar
  37. 37.
    Qu F, Liu Y, Lao H, Wang Y, You J (2017) Colorimetric detection of Hep with high sensitivity based on the aggregation of gold nanoparticles induced by polymer nanoparticles. New J Chem 41:10592–10597CrossRefGoogle Scholar
  38. 38.
    Chen Z, Wang Z, Chen X, Xu H, Liu J (2013) Chitosan-capped gold nanoparticles for selective and colorimetric sensing of Hep. J Nanopart Res 15:1930–1939CrossRefGoogle Scholar
  39. 39.
    Cho Y, Ahn K (2013) Molecular interactions between charged macromolecules: colorimetric detection and quantification of Hep with a polydiacetylene liposome. J Mater Chem B 1:1182–1189CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Chongqing Key Laboratory of Green Synthesis and Applications, College of ChemistryChongqing Normal UniversityChongqingChina
  2. 2.School of Pharmaceutical SciencesChongqing UniversityChongqingChina

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