Skip to main content
Log in

A novel electrochemical DNA biosensor construction based on layered CuS–graphene composite and Au nanoparticles

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

A novel CuS–graphene (CuS-Gr) composite was synthesized to achieve excellent electrochemical properties for application as a DNA electrochemical biosensor. CuS-Gr composite was prepared by a hydrothermal method, in which two-dimensional graphene served as a two-dimensional conductive skeleton to support CuS nanoparticles. A sensitive electrochemical DNA biosensor was fabricated by immobilizing single-stranded DNA (ss-DNA) labeled at the 5′ end using 6-mercapto-1-hexane (HS-ssDNA) on the surface of Au nanoparticles (AuNPs) to form ssDNA-S–AuNPs/CuS-Gr, and hybridization sensing was done in phosphate buffer. Cyclic voltammetry and electrochemical impedance spectroscopy were performed for the characterization of the modified electrodes. Differential pulse voltammetry was applied to monitor the DNA hybridization using an [Fe(CN)6]3−/4− solution as a probe. Under optimum conditions, the biosensor developed exhibited a good linear relationship between the current and the logarithm of the target DNA concentration ranging from 0.001 to 1 nM, with a low detection limit of 0.1 pM (3σ/S). The biosensor exhibited high selectivity to differentiate one-base-mismatched DNA and three-base-mismatched DNA. The results indicated that the sensing platform based on CuS-Gr provides a stable and conductive interface for electrochemical detection of DNA hybridization, and could easily be extended to the detection of other nucleic acids.

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.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Guo Y, Chen JH, Chen GN (2013) A label-free electrochemical biosensor for detection of HIV related gene based on interaction between DNA and protein. Sensors Actuators B 184:113–117

    Article  CAS  Google Scholar 

  2. Radhakrishnan S, Sumathi C, Umar A, Kim SJ, Wilson J, Dharuman V (2013) Polypyrrole-poly(3,4-ethylenedioxythiophene)-Ag (PPy-PEDOT-Ag) nanocomposite films for label-free electrochemical DNA sensing. Biosens Bioelectron 47:133–140

    Article  CAS  Google Scholar 

  3. Liu BX, Hu JP, Foord JS (2012) Electrochemical detection of DNA hybridization by a zirconia modified diamond electrode. Electrochem Commun 19:46–49

    Article  Google Scholar 

  4. Yao W, Wang L, Wang HY, Zhang XL, Li L, Zhang N, Pan L, Xing NN (2013) An electrochemiluminescent DNA sensor based on nano-gold enhancement and ferrocene quenching. Biosens Bioelectron 40:356–361

    Article  CAS  Google Scholar 

  5. Qiu SY, Li XH, Xiong WM, Xie LD, Guo LH, Lin ZY, Qiu B, Chen GN (2013) A novel fluorescent sensor for mutational p53 DNA sequence detection based on click chemistry. Biosens Bioelectron 41:403–408

    Article  CAS  Google Scholar 

  6. Huang KJ, Liu YJ, Wang HB, Wang YY, Liu YM (2014) Sub-femtomolar DNA detection based on layered molybdenum disulfide/multi-walled carbon nanotube composites, Au nanoparticle and enzyme multiple signal amplification. Biosens Bioelectron 55:195–202

    Article  CAS  Google Scholar 

  7. Li GJ, Liu LH, Qi XW, Guo YQ, Sun W, Li XL (2012) Development of a sensitive electrochemical DNA sensor by 4-aminothiophenol self-assembled on electrodeposited nanogold electrode coupled with Au nanoparticles labeled reporter ssDNA. Electrochim Acta 63:312–317

    Article  CAS  Google Scholar 

  8. Hu YW, Li FH, Han DX, Wu TS, Zhang QX, Niu L, Bao Y (2012) Simple and label-free electrochemical assay for signal-on DNA hybridization directly at undecorated graphene oxide. Anal Chim Acta 753:82–89

    Article  CAS  Google Scholar 

  9. Spain E, Keyes TE, Forster RJ (2013) DNA sensor based on vapour polymerised pedot films functionalised with gold nanoparticles. Biosens Bioelectron 41:65–70

    Article  CAS  Google Scholar 

  10. Spain E, Keyes TE, Forster RJ (2013) Polypyrrole-gold nanoparticle composites for highly sensitive DNA detection. Electrochim Acta 109:102–109

    Article  CAS  Google Scholar 

  11. Dong HF, Zhu Z, Ju HX, Yan F (2012) Triplex signal amplification for electrochemical DNA biosensing by coupling probe-gold nanoparticles-graphene modified electrode with enzyme functionalized carbon sphere as tracer. Biosens Bioelectron 33:228–232

    Article  CAS  Google Scholar 

  12. Muti M, Kuralay F, Erdem A (2012) Single-walled carbon nanotubes-polymer modified graphite electrodes for DNA hybridization. Colloids Surf B 91:77–83

    Article  CAS  Google Scholar 

  13. Yin Z, Sun S, Salim T, Wu S, Huang X, He Q, Lam YM, Zhang H (2010) Organic photovoltaic devices using highly flexible reduced graphene oxide films as transparent electrodes. ACS Nano 4:5263–5268

    Article  CAS  Google Scholar 

  14. Ghosh S, Sarker BK, Chunder A, Zhai L, Khondaker SI (2010) Position dependent photodetector from large area reduced graphene oxide thin films. Appl Phys Lett 96:163109–163109

    Article  Google Scholar 

  15. Huang KJ, Wang L, Li J, Liu YM (2013) Electrochemical sensing based on layered MoS2-graphene composites. Sensors Actuators B 178:671–677

    Article  CAS  Google Scholar 

  16. Huang J, Zhang L, Chen B, Ji N, Chen F, Zhang Y, Zhang Z (2010) Nanocomposites of size-controlled gold nanoparticles and graphene oxide: formation and applications in SERS and catalysis. Nanoscale 2:2733–2738

    Article  CAS  Google Scholar 

  17. Jiao S, Xu L, Jiang K, Xu D (2006) Well-defined non-spherical copper sulfide mesocages with single-crystalline shells by shape-controlled Cu2O crystal templating. Adv Mater 18:1174–1177

    Article  CAS  Google Scholar 

  18. Janata J, Josowicz M, DeVaney DM (1994) Chemical sensors. Anal Chem 66:207R–228R

    Article  CAS  Google Scholar 

  19. Zou J, Jiang J, Huang L, Jiang H, Huang K (2011) Synthesis, characterization and electrocatalytic activity of copper sulfide nanocrystals with different morphologies. Solid State Sci 13:1261–1267

    Article  CAS  Google Scholar 

  20. Niu SY, Sun J, Nan CC, Lin JH (2013) Sensitive DNA biosensor improved by 1,10-phenanthroline cobalt complex as indicator based on the electrode modified by gold nanoparticles and graphene. Sensors Actuators B 176:58–63

    Article  CAS  Google Scholar 

  21. Wilson J, Radhakrishnan S, Sumathi C, Dharuman V (2012) Polypyrrole-polyaniline-Au (PPy-PANi-Au) nano composite films for label-free electrochemical DNA sensing. Sensors Actuators B 171–172:216–222

    Article  Google Scholar 

  22. Li L, Wang S, Yang T, Huang SM, Wang JC (2012) Electrochemical growth of gold nanoparticles on horizontally aligned carbon nanotubes: a new platform for ultrasensitive DNA sensing. Biosens Bioelectron 33:279–283

    Article  Google Scholar 

  23. Hummers W, Offeman R (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339–1340

    Article  CAS  Google Scholar 

  24. Tian Q, Tang M, Sun Y, Zou R, Chen Z, Zhu M, Yang S, Wang J, Wang J, Hu J (2011) Hydrophilic flower-like CuS superstructures as an efficient 980 nm laser-driven photothermal agent for ablation of cancer cells. Adv Mater 23:3542–3547

    Article  CAS  Google Scholar 

  25. Du M, Yang T, Li X, Jiao K (2012) Fabrication of DNA/graphene/polyaniline nanocomplex for label-free voltammetric detection of DNA hybridization. Talanta 88:439–444

    Article  CAS  Google Scholar 

  26. Zhang W, Yang T, Zhuang X, Guo Z, Jiao K (2009) An ionic liquid supported CeO2 nanoshuttles-carbon nanotubes composite as a platform for impedance DNA hybridization sensing. Biosens Bioelectron 24:2417–2422

    Article  CAS  Google Scholar 

  27. Wang QX, Gao F, Zhang X, Zhang B, Li SX, Hu ZS, Gao F (2012) Electrochemical characterization and DNA sensing application of a sphere-like CeO2-ZrO2 and chitosan nanocomposite formed on a gold electrode by one-step electrodeposition. Electrochim Acta 62:250–255

    Article  CAS  Google Scholar 

  28. Feng KJ, Yang YH, Wang ZJ, Jiang JH, Shen GL, Yu RQ (2006) A nano-porous CeO2/chitosan composite film as the immobilization matrix for colorectal cancer DNA sequence-selective electrochemical biosensor. Talanta 70:561–565

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (U1304214) and the State Key Laboratory of Chemo/biosensing and Chemometrics (no. 2013013).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Ke-Jing Huang.

Additional information

Published in the topical collection Graphene in Analytics with guest editors Martin Pumera, Ronen Polsky, and Craig Banks.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Xu, CX., Zhai, QG., Liu, YJ. et al. A novel electrochemical DNA biosensor construction based on layered CuS–graphene composite and Au nanoparticles. Anal Bioanal Chem 406, 6943–6951 (2014). https://doi.org/10.1007/s00216-014-7904-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-014-7904-7

Keywords

Navigation