Skip to main content
Log in

One-step solvothermal preparation of silver-ZnO hybrid nanorods for use in enzymatic and direct electron-transfer based biosensing of glucose

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

Abstract

This article describes an electrochemical glucose biosensor that is based on the immobilization of the enzyme glucose oxidase (GOx) on a glassy carbon electrode that was modified with silver-ZnO hybrid nanorods (HNRs). The HNRs containing different fractions of silver were synthesized by a one-step solvothermal method. Transmission electron microscopy, energy dispersive spectroscopy and X-ray diffraction confirmed the formation of these HNRs. FTIR spectroscopy and cyclic voltammetry demonstrated that the enzyme on the HNRs retained its native structure and bioactivity. The HNRs containing 11.26 wt% silver produced the best electrochemical response and direct electron transfer between enzyme and electrode surface. The sensor responds to glucose with two linear ranges (from 0.01 to 0.1 mM and from 0.1 to 1.5 mM). The sensitivity is 18.7 mA∙ M−1 ∙ cm−2, and the detection limit is 5 μM (at an SNR of 3). The biosensor is selective, acceptably stable, and well reproducible. It was successfully applied to the quantitation of glucose in human serum, and results were within −8.1 % and +6.5 % of data obtained with a reference method.

An electrochemical glucose biosensor was fabricated by immobilizing glucose oxidase (GOx) on silver-ZnO hybrid nanorods (Ag-ZnO HNRs), which were synthesized by a simple and low-cost one-step solvothermal route from Zn(NO3)2, AgNO3, ethanol and NaOH.

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
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Mizutani F, Yabuki S (1997) Rapid determination of glucose and sucrose by an amperometric glucosesensing electrode combined with an invertase/mutarotase-attached measuring cell. Biosens Bioelectron 12:1013

    Article  CAS  Google Scholar 

  2. Barone PW, Parker RS, Strano MS (2005) In vivo fluorescence detection of glucose using a single-walled carbon nanotube optical sensor: design, fluorophore properties, advantages and disadvantages. Anal Chem 77:7556

    Article  CAS  Google Scholar 

  3. Liu SQ, Sun YM (2007) Co-immobilization of glucose oxidase and hexokinase on silicate hybrid sol–gel membrane for glucose and ATP detections. Biosens Bioelectron 22:905

    Article  CAS  Google Scholar 

  4. Guo XS, Liang B, Jian JM, Zhang YL, Xe XS (2014) Glucose biosensor based on a platinum electrode modified with rhodium nanoparticles and with glucose oxidase immobilized on gold nanoparticles. Microchim Acta 181:519

    Article  CAS  Google Scholar 

  5. Kang XH, Wang J, Wu H, Aksay IA, Liu J, Lin YH (2009) Glucose oxidase–graphene–chitosan modified electrode for direct electrochemistry and glucose sensing. Biosens Bioelectron 25:901

    Article  CAS  Google Scholar 

  6. Meng L, Jin J, Yang GX, Lu TH, Zhang H, Cai CX (2009) Nonenzymatic electrochemical detection of glucose based on palladium − single-walled carbon nanotube hybrid nanostructures. Anal Chem 81:7271

    Article  CAS  Google Scholar 

  7. Nadzhafova O, Etienne M, Walcarius A (2007) Direct electrochemistry of hemoglobin and glucose oxidase in electrodeposited sol–gel silica thin films on glassy carbon. Electrochem Commun 9:1189

    Article  CAS  Google Scholar 

  8. Liu SQ, Ju HX (2003) Reagentless glucose biosensor based on direct electron transfer of glucose oxidase immobilized on colloidal gold modified carbon paste electrode. Biosens Bioelectron 19:177

    Article  CAS  Google Scholar 

  9. Deng SY, Jian GQ, Lei JP, Hu Z, Ju HX (2009) A glucose biosensor based on direct electrochemistry of glucose oxidase immobilized on nitrogen-doped carbon nanotubes. Biosens Bioelectron 25:373

    Article  CAS  Google Scholar 

  10. Wang W, Xie, Y.B, Wang Y, Du HX, Xia C, Tian F (2014) Glucose biosensor based on glucose oxidase immobilized on unhybridized titanium dioxide nanotube arrays. Microchim Acta 181:381.

  11. Yang ZJ, Ren YY, Zhang YC, Li J, Li HB, Huang XC, Hu XY, Xu Q (2011) Nanoflake-like SnS2 matrix for glucose biosensing based on direct electrochemistry of glucose oxidase. Biosens Bioelectron 26:4337

    Article  CAS  Google Scholar 

  12. Tian C, Zhang Q, Jiang B, Tian G, Fu H (2011) Glucose-mediated solution-solid route for easy synthesis of Ag/ZnO particles with Superior photocatalytic activity and photostability. J Alloys Compd 509:6935

    Article  CAS  Google Scholar 

  13. Wu C, Shen L, Yu H, Huang Q, Zhang YC (2011) Synthesis of Sn-doped ZnO nanorods and their photocatalytic properties. Mater Res Bull 46:1107

    Article  CAS  Google Scholar 

  14. Singh SP, Arya SK, Pandey P, Malhotra BD, Sreenivas SK, Gupta V (2007) Cholesterol biosensor based on rf sputtered zinc oxide nanoporous thin film. Appl Phys Lett 91:63901

    Article  Google Scholar 

  15. Zhu XL, Yuri I, Gan X, Suzuki I, Li G (2007) Electrochemical study of the effect of nano-zinc oxide on microperoxidase and its application to more sensitive hydrogen peroxide biosensor preparation. Biosens Bioelectron 22:1600

    Article  CAS  Google Scholar 

  16. Zhao YG, Fan XF, Yan XQ, Zhang XH, Kang Z, Zhang G, Zhang Y (2015) Nanorod arrays composed of zinc oxide modified with gold nanoparticles and glucose oxidase for enzymatic sensing of glucose. Microchim Acta 182:605

    Article  CAS  Google Scholar 

  17. Dai ZH, Shao GJ, Hong JM, Bao JC (2009) Immobilization and direct electrochemistry of glucose oxidase on a tetragonal pyramid-shaped porous ZnO nanostructure for a glucose biosensor. Biosens Bioelectron 24:1286

    Article  CAS  Google Scholar 

  18. Topoglidis E, Cass AEG, O’Regan B, Durrant JR (2001) Immobilisation and bioelectrochemistry of proteins on nanoporous TiO2 and ZnO films. J Electroanal Chem 517:20

    Article  CAS  Google Scholar 

  19. Wang YY, Chen XJ, Zhu JJ (2009) Fabrication of a novel hydrogen peroxide biosensor based on the AuNPs–C@SiO2 composite. Electrochem Commun 11:323

    Article  CAS  Google Scholar 

  20. Bai WS, Nie F, Zheng JB, Sheng QL (2014) Novel silver nanoparticle–manganese oxyhydroxide–graphene oxide nanocomposite prepared by modified dilver mirror reaction and its application for electrochemical sensing. ACS Appl Mater Interfaces 6:5439

    Article  CAS  Google Scholar 

  21. Height MJ, Pratsinis SE, Mekasuwandumrong O, Praserthdam P (2006) Ag-ZnO catalysts for UV-photodegradation of methylene blue. Appl Catal B Environ 63:305

    Article  CAS  Google Scholar 

  22. Deng Q, Duan XW, Ng DHL, Tang HB, Yang Y, Kong MG, Wu ZK, Cai WP, Wang GZ (2012) Ag nanoparticle decorated nanoporous ZnO microrods and their enhanced photocatalytic activities. ACS Appl Mater Interfaces 4:6030

    Article  CAS  Google Scholar 

  23. Wu CL, Shen L, Zhang YC, Huang QL (2013) Solvothermal synthesis of Ag/ZnO nanocomposite with enhanced photocatalytic activity. Mater Lett 106:104

    Article  CAS  Google Scholar 

  24. Georgekutty R, Seery MK, Pillai SC (2008) A highly efficient Ag-ZnO photocatalyst: synthesis, properties and mechanism. J Phys Chem C 112:13563

    Article  CAS  Google Scholar 

  25. Zheng YH, Chen CQ, Zhan YY, Lin XY, Zheng Q, Wei KM, Zhu JF (2008) Photocatalytic activity of Ag/ZnO heterostructure nanocatalyst: correlation between structure and property. J Phys Chem C 112:10773

    Article  CAS  Google Scholar 

  26. Lin CY, Lai YH, Balamurugan A, Vittal R, Lin CW, Ho KC (2010) Electrode modified with a composite film of ZnO nanorods and Ag nanoparticles as a sensor for hydrogen peroxide. Talanta 82:340–347

    Article  CAS  Google Scholar 

  27. Mishrak R, Rajanna K (2005) Metal-oxide thin film with Pt, Au and Ag nano-particles for gas sensing applications. Sens Mater 17:433–440

    Google Scholar 

  28. Willner B, Katz E, Willner I (2006) Electrical contacting of redox proteins by nanotechnological means. Curr Opin Biotechnol 17:589

    Article  CAS  Google Scholar 

  29. Wen D, Liu Y, Yang GC, Dong SJ (2007) Electrochemistry of glucose oxidase immobilized on the carbon nanotube wrapped by polyelectrolyte. Electrochim Acta 52:5312

    Article  CAS  Google Scholar 

  30. Bard J, Faulkner LR (2001) Electrochemistry methods, 2nd edn. Wiley, New York

    Google Scholar 

  31. Wu YH, Hu SS (2007) Direct electrochemistry of glucose oxidase in a colloid Au–dihexadecylphosphate composite film and its application to develop a glucose biosensor. Bioelectrochemistry 70:335

    Article  CAS  Google Scholar 

  32. Zhang JD, Feng ML, Tachikawa H (2007) Layer-by-layer fabrication and direct electrochemistry of glucose oxidase on single wall carbon nanotubes. Biosens Bioelectron 22:3036

    Article  CAS  Google Scholar 

  33. Wang YL, Liu L, Li MG, Xu SD, Gao F (2011) Multifunctional carbon nanotubes for direct electrochemistry of glucose oxidase and glucose bioassay. Biosens Bioelectron 30:107

    Article  CAS  Google Scholar 

  34. Tang WW, Li L, Zeng XP (2015) A glucose biosensor based on the synergistic action of nanometer-sized TiO2 and polyaniline. Talanta 131:417

    Article  CAS  Google Scholar 

  35. Palanisamy S, Karuppiah C, Chen SM (2014) Direct electrochemistry and electrocatalysis of glucose oxidase immobilized on reduced graphene oxide and silver nanoparticles nanocomposite modified electrode. Colloid Surface B 14:164

    Article  Google Scholar 

Download references

Acknowledgments

This work was financially supported by National Natural Science Foundation of China (21575125, 21475116, and 21275124), The Priority Academic Program Development of Jiangsu Higher Education Institution (PAPD), University Natural Science Foundation of Jiangsu Province (13KJB150039) and the Open Research Fund of State Key Laboratory of Analytical Chemistry for Life Science (SKLACLS1410). We thank also The Testing Center of Yangzhou University for all the characterizations.

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Xiaoya Hu or Zhanjun Yang.

Ethics declarations

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

Additional information

Zhanjun Yang is the first corresponding author.

Highlights

• Silver-ZnO hybrid nanorods (Silver-ZnO HNRs) were synthesized by a facile method.

• Novel electrochemical glucose biosensor is presented based on silver-ZnO HNRs.

• The glucose biosensor showed excellent analytical performance.

• These silver-ZnO HNRs provide a promising matrix for biosensing applications.

Electronic supplementary material

ESM 1

(DOC 298 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, J., Lu, M., Tan, Z. et al. One-step solvothermal preparation of silver-ZnO hybrid nanorods for use in enzymatic and direct electron-transfer based biosensing of glucose. Microchim Acta 183, 1705–1712 (2016). https://doi.org/10.1007/s00604-016-1800-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00604-016-1800-0

Keywords

Navigation