Journal of Solid State Electrochemistry

, Volume 16, Issue 3, pp 857–867 | Cite as

Selective and sensitive molecularly imprinted sol–gel film-based electrochemical sensor combining mercaptoacetic acid-modified PbS nanoparticles with Fe3O4@Au–multi-walled carbon nanotubes–chitosan

  • Yufang Hu
  • Zhaohui Zhang
  • Huabin Zhang
  • Lijuan Luo
  • Shouzhuo Yao
Original Paper


A sensitive molecularly imprinted electrochemical sensor was developed for selective detection of streptomycin by combination of mercaptoacetic acid-modified PbS nanoparticles with Au-coated Fe3O4 magnetic nanoparticles dispersed multi-walled carbon nanotubes doped chitosan film. The imprinted sensor was fabricated onto the Au electrode via stepwise modification of nanocomposites and an electrodeposited thin film of molecularly imprinted polymers via sol–gel technology. The morphologies and electrochemical behaviors of the imprinted sensor were characterized by scanning electron microscope, cyclic voltammetry, and differential pulse voltammetry, respectively. The prepared sensor showed very high recognition ability and selectivity for streptomycin. Under optimal conditions, the imprinted sensor displayed good electrocatalytic activity to the redox of streptomycin. And the differential voltammetric anodic peak current was linear to the logarithm of streptomycin concentration in the range from 1.0 × 10−6 to 1.0 × 10−3 mol L−1, and the detection limit obtained was 1.5 × 10−9 mol L−1. This proposed imprinted sensor was used successfully for streptomycin determination in different injection solution samples.


Imprinted sensor Fe3O4@Au nanoparticles PbS nanoparticles Multi-walled carbon nanotubes Chitosan 



This work has been co-supported by the Nature Science Foundation China (No. 21005030), the Colonel-level Project of Jishou University of Hunan Province, China (No. 09JDY007), and the Graduate Innovation Foundation of Hunan Province, China (No. CX2010B294).


  1. 1.
    Liang RN, Zhang RM, Qin W (2009) Potentiometric sensor based on molecularly imprinted polymer for determination of melamine in milk. Sens Actuators B 141:544–550CrossRefGoogle Scholar
  2. 2.
    Blanco-López MC, Lobo-Castañón MJ, Miranda-Ordieres AJ, Tuñón-Blanco P (2003) Voltammetric sensor for vanillylmandelic acid based on molecularly imprinted polymer-modified electrodes. Biosens Bioelectron 18:353–362CrossRefGoogle Scholar
  3. 3.
    Wu N, Feng L, Tan YY, Hu JM (2009) An optical reflected device using a molecularly imprinted polymer film sensor. Anal Chim Acta 653:103–108CrossRefGoogle Scholar
  4. 4.
    Blanco-López MC, Lobo-Castañón MJ, Miranda-Ordieres AJ, Tuñón-Blanco P (2004) Electrochemical sensors based on molecularly imprinted polymers. Trends Anal Chem 23:36–48CrossRefGoogle Scholar
  5. 5.
    Hillberg AL, Brain KR, Allender CJ (2005) Molecular imprinted polymer sensors: implications for therapeutics. Adv Drug Deliv Rev 57:1875–1889Google Scholar
  6. 6.
    Wang SF, Xie F, Hu RF (2007) Carbon-coated nickel magnetic nanoparticles modified electrodes as a sensor for determination of acetaminophen. Sens Actuators B 123:495–500CrossRefGoogle Scholar
  7. 7.
    Thilwind RE, Megens M, Zon JBAD, Coehoorn R, Prins MWJ (2008) Measurement of the concentration of magnetic nanoparticles in a fluid using a giant magnetoresistance sensor with a trench. J Magn Magn Mater 320:486–489CrossRefGoogle Scholar
  8. 8.
    Salgueirino-Maceira V, Correa-Duarte MA, Spasova M, Liz-Marzán LM, Farle M (2006) Composite silica spheres with magnetic and luminescent functionalities. Adv Funct Mater 16:509–514CrossRefGoogle Scholar
  9. 9.
    Xu ZC, Hou YL, Sun SH (2007) Magnetic core/shell Fe3O4/Au and Fe3O4/Au/Ag nanoparticles with tunable plasmonic properties. J Am Chem Soc 129:8698–8699CrossRefGoogle Scholar
  10. 10.
    Deng YH, Qi D, Deng CH, Zhang XM, Zhao DY (2008) Superparamagnetic high-magnetization microspheres with an Fe3O4@SiO2 core and perpendicularly aligned mesoporous SiO2 shell for removal of microcystins. J Am Chem Soc 130:28–29CrossRefGoogle Scholar
  11. 11.
    Chen CT, Chen YC (2005) Fe3O4/TiO2 core/shell nanoparticles as affinity probes for the analysis of phosphopeptides using TiO2 surface-assisted laser desorption/ionization mass spectrometry. Anal Chem 77:5912–5919CrossRefGoogle Scholar
  12. 12.
    Chen CT, Chen WY, Tsai PJ, Chien KY, Yu JS, Chen YC (2007) Rapid enrichment of phosphopeptides and phosphoproteins from complex samples using magnetic particles coated with alumina as the concentrating probes for MALDI MS analysis. J Proteome Res 6:316–325CrossRefGoogle Scholar
  13. 13.
    Qiu JD, Xiong M, Liang RP, Peng HP, Liu F (2009) Synthesis and characterization of ferrocene modified Fe3O4@Au magnetic nanoparticles and its application. Biosens Bioelectron 24:2649–2653CrossRefGoogle Scholar
  14. 14.
    Dutta PK, Tripathi S, Mehrotra GK, Dutta J (2009) Perspectives for chitosan based antimicrobial films in food applications. Food Chem 114:1173–1182CrossRefGoogle Scholar
  15. 15.
    Bhatnagar A, Sillanpää M (2009) Applications of chitin- and chitosan-derivatives for the detoxification of water and wastewater—a short review. Adv Colloid Interface Sci 152:26–38CrossRefGoogle Scholar
  16. 16.
    Darder M, Colilla M, Ruiz-Hitzky E (2005) Chitosan–clay nanocomposites: application as electrochemical sensors. Appl Clay Sci 28:199–208CrossRefGoogle Scholar
  17. 17.
    Njagi J, Erlichman JS, Aston JW, Leiter JC, Andreescu S (2010) A sensitive electrochemical sensor based on chitosan and electropolymerized Meldola blue for monitoring NO in brain slices. Sens Actuators B 143:673–680CrossRefGoogle Scholar
  18. 18.
    MacKenzie K, Dunens O, Harris AT (2009) A review of carbon nanotube purification by microwave assisted acid digestion. Sep Purif Technol 66:209–222CrossRefGoogle Scholar
  19. 19.
    Justin J (2005) Gooding nanostructuring electrodes with carbon nanotubes: a review on electrochemistry and applications for sensing. Electrochim Acta 50:3049–3060CrossRefGoogle Scholar
  20. 20.
    Torabi M, Sadrnezhaad SK (2010) Electrochemical synthesis of flake-like Fe/MWCNTs nanocomposite for hydrogen evolution reaction: effect of the CNTs on dendrite growth of iron and its electrocatalytic activity. Curr Appl Phys 10:72–76CrossRefGoogle Scholar
  21. 21.
    Zheng DY, Hu CG, Peng YF, Hu SS (2009) A carbon nanotube/polyvanillin composite film as an electrocatalyst for the electrochemical oxidation of nitrite and its application as a nitrite sensor. Electrochim Acta 54:4910–4915CrossRefGoogle Scholar
  22. 22.
    Jiang HJ, Zhao Y, Yang H, Akins DL (2009) Synthesis and electrochemical properties of single-walled carbon nanotube–gold nanoparticle composites. Mater Chem Phys 114:879–883CrossRefGoogle Scholar
  23. 23.
    Hu KC, Liu P, Ye SJ, Zhang SS (2009) Ultrasensitive electrochemical detection of DNA based on PbS nanoparticle tags and nanoporous gold electrode. Biosens Bioelectron 24:3113–3119CrossRefGoogle Scholar
  24. 24.
    Pang LL, Li JS, Jiang JH, Le Y, Shen GL, Yu RQ (2007) A novel detection method for DNA point mutation using QCM based on Fe3O4/Au core/shell nanoparticle and DNA ligase reaction. Sens Actuators B 127:311–316CrossRefGoogle Scholar
  25. 25.
    Yang H, Wang SC, Mercier P, Akins DL (2006) Diameter-selective dispersion of single-walled carbon nanotubes using a water-soluble, biocompatible polymer. Chem Commun (13):1425–1427Google Scholar
  26. 26.
    Huang KJ, Niu DJ, Xie WZ, Wang W (2010) A disposable electrochemical immunosensor for carcinoembryonic antigen based on nano-Au/multi-walled carbon nanotubes–chitosans nanocomposite film modified glassy carbon electrode. Anal Chim Acta 659:102–108CrossRefGoogle Scholar
  27. 27.
    Xu J, Shang FJ, Luong JHT, Razeeb KM, Glennon JD (2010) Direct electrochemistry of horseradish peroxidase immobilized on a monolayer modified nanowire array electrode. Biosens Bioelectron 25:1313–1318CrossRefGoogle Scholar
  28. 28.
    Brown KR, Walter DG, Natan MJ (2000) Seeding of colloidal Au nanoparticle solutions. 2. Improved control of particle size and shape. Chem Mater 12:306–313CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Yufang Hu
    • 1
  • Zhaohui Zhang
    • 1
    • 2
  • Huabin Zhang
    • 1
  • Lijuan Luo
    • 1
  • Shouzhuo Yao
    • 2
  1. 1.College of Chemistry and Chemical EngineeringJishou UniversityHunanPeople’s Republic of China
  2. 2.State Key Laboratory of Chemo/Biosensing and ChemometricsHunanPeople’s Republic of China

Personalised recommendations