Microchimica Acta

, 185:16 | Cite as

Determination of subnanomolar levels of mercury (II) by using a graphite paste electrode modified with MWCNTs and Hg(II)-imprinted polymer nanoparticles

  • Taher Alizadeh
  • Negin Hamidi
  • Mohamad Reza Ganjali
  • Faride Rafiei
Original Paper


Mercury ion-imprinted polymer nanoparticles (Hg–IP-NPs) were synthesized via precipitation polymerization by using itaconic acid as a functional monomer. A carbon paste electrode was impregnated with the synthesized Hg-IP-NPs and MWCNTs to obtain a highly sensitive and selective electrode for determination of Hg(II). Mercury ion is first accumulated on the electrode surface via an open circuit procedure. After reduction of Hg(II) ions to its metallic form at a negative pre-potential, square wave anodic stripping voltammetry was applied to generate the electrochemical signal. The high affinity of the Hg-IP-NPs for Hg(II) was substantiated by comparing of the signals of electrodes with imprinted and non-imprinted polymer. The beneficial effect of MWCNTs on the voltammetric signal is also demonstrated. Under the optimized conditions and at a typical working potential of +0.05 V (vs. Ag/AgCl), the electrode has a linear response in the 0.1–20 nmol L−1 Hg(II) concentration range and a 29 pM detection limit. The electrochemical sensitivity is as high as 1441 A·M−1·cm−2 which is among the best values known. The electrode was applied to the determination of Hg(II) in water samples.

Graphical abstract

Schematic representation of the sensor electrode modified with mercury-imprinted polymer nanoparticles, and the recognition and voltammetric determination steps.


Polymer nanoparticles Carbon nanotubes Square wave voltammetry Modified electrode Mercury ion Itaconic acid 


Compliance with ethical standards

The authors declare that they have no competing interests.

Supplementary material

604_2017_2534_MOESM1_ESM.docx (209 kb)
ESM 1 (DOCX 208 kb)


  1. 1.
    Singh DK, Mishra SH (2010) Synthesis and characterization of hg(II)-ion-imprinted polymer: kinetic and isotherm studies. Desalination 257:177CrossRefGoogle Scholar
  2. 2.
    Mergola L, Scorrano S, Bloise E, Pia Di Bello M (2016) Novel polymeric sorbents based on imprintedHg(II)-diphenylcarbazone complexes for mercury removal from drinking water. Polym J 48:73CrossRefGoogle Scholar
  3. 3.
    Khairi NS, Yusof NA, Abdullah AH, Mohammad F (2015) Removal of toxic mercury from petroleum oil by newly synthesized molecularly-imprinted polymer. Int J Mol Sci 16:10562CrossRefGoogle Scholar
  4. 4.
    Rajabi HR, Roushani M, Shamsipur M (2013) Development of a highly selective voltammetric sensor for nanomolar detection of mercury ions using glassy carbon electrode modified with a novel ion imprinted polymeric nanobeads and multi-wall carbon nanotubes. J Electroanal Chem 693:16CrossRefGoogle Scholar
  5. 5.
    Afkhami A, Madrakian T, Sabounchei SJ, Rezaei M, Samiee S, Pourshahbaz M (2012) Construction of a modified carbon paste electrode for the highly selective simultaneous electrochemical determination of trace amounts of mercury(II) and cadmium(II). Sensors Actuators B Chem 161:542CrossRefGoogle Scholar
  6. 6.
    Tuzen M, Karaman I, Citak D, Soylak M (2009) Mercury(II) and methyl mercury determinations in water and fish samples by using solid phase extraction and cold vapour atomic absorption spectrometry combination. Food Chem Toxicol 47:1648CrossRefGoogle Scholar
  7. 7.
    Detchev AA, Grobecker KH (2006) Determination of hg, cd, Mn, Pb and Sn in seafood by solid sampling Zeeman atomic absorption spectrometry. Spectrochim Acta Part B 61:454CrossRefGoogle Scholar
  8. 8.
    Leopold K, Foulkes M, Worsfold PJ (2009) Preconcentration techniques for the determination of mercury species in natural waters. Trends Anal Chem 28:426CrossRefGoogle Scholar
  9. 9.
    Butler OT, Cook M, Harrington CF, Hill SJ, Rieuwerts J, Miles DL (2007) Atomic spectrometry update. Environmental analysis. J Anal At Spectrom 22:187CrossRefGoogle Scholar
  10. 10.
    Fu J, Wang L, Chen H, Bo L, Zhou C, Chen J (2010) A selective fluorescence probe for mercury ion based on the fluorescence quenching of terbium (III)-doped cadmium sulfide composite nanoparticles. Spectrochim Acta A 77:625CrossRefGoogle Scholar
  11. 11.
    Shamsipur M, Hosseini M, Alizadeh K, Alizadeh N, Yari A, Caltagirone C, Lippolis V (2005) Novel fluorimetric bulk optode membrane based on a dansylamidopropyl pendant arm derivative of 1-aza-4,10-dithia-7-oxacyclododecane ([12]aneNS2O) for selective subnanomolar detection of hg(II) ions. Anal Chim Acta 533:17CrossRefGoogle Scholar
  12. 12.
    de Carvalho GGA, Feres MA, Ferreira JR, Kennedy VH (2010) Total and inorganic mercury determination in fish tissue by flow injection cold vapour atomic fluorescence spectrometry. Int J Environ Anal Chem 90:686CrossRefGoogle Scholar
  13. 13.
    Liang LN, Jiang GB, Liu JF, JT H (2003) Speciation analysis of mercury in seafood by using high-performance liquid chromatography on-line coupled with cold-vapor atomic fluorescence spectrometry via a post column microwave digestion. Anal Chim Acta 477:131CrossRefGoogle Scholar
  14. 14.
    Gao Y, Galan SD, Brauwere AD, Baeyens W, Leermakers M (2010) Mercury speciation in hair by headspace injection–gas chromatography–atomic fluorescence spectrometry (methylmercury) and combustion-atomic absorption. Talanta 82:1919CrossRefGoogle Scholar
  15. 15.
    Carvalho ML, Manso M, Pessanha S, Guilherme A, Ferreira FR (2009) Quantification of mercury in XVIII century books by energy dispersive X-ray fluorescence (EDXRF), J cultural. Heritage 10:435Google Scholar
  16. 16.
    Bernaus A, Gaona X, Esbrí JM, Higueras P, Falkenberg G, Valiente M (2006) Microprobe techniques for speciation analysis and geochemical characterization of mine environments: the Mercury District of Almadén in Spain. Environ Sci Technol 40:4090CrossRefGoogle Scholar
  17. 17.
    Osawa T, Hatsukawa Y, Appel PWU, Matsue H (2011) Mercury and gold concentrations of highly polluted environmental samples determined using prompt gamma-ray analysis and instrument neutron activation analysis. Nucl Inst Methods Phys Res B 269:717CrossRefGoogle Scholar
  18. 18.
    Alizadeh T, Ganjali MR, Zare M (2011) Application of an Hg2+ selective imprinted polymer as a new modifying agent for the preparation of a novel highly selective and sensitive electrochemical sensor for the determination of ultratrace mercury ions. Anal Chim Acta 689:52CrossRefGoogle Scholar
  19. 19.
    Alizadeh T, Ganjali MR, Akhoundian M, Norouzi P (2016) Voltammetric determination of ultratrace levels of cerium(III) using a carbon paste electrode modified with nano-sized cerium-imprinted polymer and multiwalled carbon nanotubes. Microchim Acta 183:1123CrossRefGoogle Scholar
  20. 20.
    Soleimani M, Afshar MG (2015) Highly selective solid phase extraction of mercury ion based on novel ion imprinted polymer and its application to water and fish samples. J Anal Chem 70:5CrossRefGoogle Scholar
  21. 21.
    Zhang Q, Wu J, Luo X (2016) Facile preparation of a novel hg(II)-ion-imprinted polymer based on magnetic hybrids for rapid and highly selective removal of hg(II) from aqueous solutions. RSC Adv 6:14916CrossRefGoogle Scholar
  22. 22.
    Luo F, Huang S, Xiong X, Lai X (2015) Synthesis and characterization of hg(II)-ion imprinted polymer and its application for the determination of mercury in water samples. RSC Adv 5:67365CrossRefGoogle Scholar
  23. 23.
    Bagheri H, Afkhami A, Khoshsafar H, Rezaei M, Shirzadmehr A (2013) Simultaneous electrochemical determination of heavy metals using a triphenylphosphine/MWCNTs composite carbon ionic liquid electrode. Sensors Actuators B Chem 186:451CrossRefGoogle Scholar
  24. 24.
    Pandit UJ, Khan I, Wankar S, Raj KK, Limaye SN (2015) Development of electrochemical method for determination of Tolvaptan at MWCNT/CPE in pharmaceutical preparations and human biological fluids, anal. Chem Lett 6:338Google Scholar
  25. 25.
    Khan I, Pandit UJ, Wankar S, Das R, Limaye SN (2017) Fabrication of electrochemical nanosensor based on polyaniline film-coated AgNP-MWCNT-modified GCE and its application for trace analysis of fenitrothion. Ionics 23:1293CrossRefGoogle Scholar
  26. 26.
    Khan I, Pandit UJ, Wankar S, Limaye SN (2017) Design of Electrochemical Sensor Based on fMWCNT-CPE decorated with TiNanofilm and its Electrocatalytic behavior towards Aminotriazole. Electrocatalysis 8:196CrossRefGoogle Scholar
  27. 27.
    Alizadeh T, Hamidi N, Ganjali MR, Norouzi P (2017) Development of a highly selective and sensitive electrochemical sensor for Bi3+ determination based on nano-structured bismuth-imprinted polymer modified carbon/carbon nanotube paste electrode. Sensors Actuators B Chem 245:605CrossRefGoogle Scholar
  28. 28.
    Alizadeh T, Rafiei F, Hamidi N, Ganjali MR (2017) A new electrochemical sensing platform for Cr(III) determination based on nano-structured Cr(III)-imprinted polymer-modified carbon composite electrode. Electrochim Acta 247:812CrossRefGoogle Scholar
  29. 29.
    Nasiri-Majd M, Taher MA, Fazelirad H (2015) Synthesis and application of nano-sized ionic imprinted polymer for the selective voltammetric determination of thallium. Talanta 144:204CrossRefGoogle Scholar
  30. 30.
    Ghanei-Motlagh M, Taher MA, Heydari A, Ghanei-Motlagh R, Gupta VK (2016) A novel voltammetric sensor for sensitive detection of mercury(II) ions using glassy carbon electrode modified with graphene-based ion imprinted polymer. Mater Sci Eng C 63:367CrossRefGoogle Scholar
  31. 31.
    Alizadeh T, Ganjali MR, Alizadeh H (2015) Competitive extraction of Gd(III) into a carbon paste electrode impregnated with a nano-sized Gd(III)-imprinted polymer as a new method for its indirect voltammetric determination. Microchim Acta 182:1205CrossRefGoogle Scholar
  32. 32.
    Alizadeh T, Amjadi S (2017) Indirect voltammetric determination of nicotinic acid by using a graphite paste electrode modified with reduced graphene oxide and a molecularly imprinted polymer. Microchim Acta 184:2687CrossRefGoogle Scholar
  33. 33.
    Alizadeh T, Azizi S (2016) Graphene/graphite paste electrode incorporated with molecularly imprinted polymer nanoparticles as a novel sensor for differential pulse voltammetry determination of fluoxetine. Biosens Bioelectron 81:198–206CrossRefGoogle Scholar
  34. 34.
    Afkhami A, Madrakian T, Soltani-Shahrivar M, Ahmadi M, Ghaedi H (2016) Selective and sensitive electrochemical determination of trace amounts of mercury ion in some real samples using an ion imprinted polymer nano-modifier. J Electrochem Soc 163:B68CrossRefGoogle Scholar
  35. 35.
    Bahrami A, Besharati-Seidani A, Abbaspour A, Shamsipur MA (2015) Highly selective voltammetric sensor for nanomolar detection of mercury ions using a carbon ionic liquid paste electrode impregnated with novel ion imprinted polymeric nanobeads. Mater Sci Eng C 48:205CrossRefGoogle Scholar
  36. 36.
    XC F, Chen X, Guo Z, Xie CG, Kong LT (2011) Stripping voltammetric detection of mercury(II) based on a surface ion imprinting strategy in electropolymerized microporous poly(2-mercaptobenzothiazole) films modified glassy carbon electrode. Anal Chim Acta 685:21CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2017

Authors and Affiliations

  • Taher Alizadeh
    • 1
  • Negin Hamidi
    • 1
  • Mohamad Reza Ganjali
    • 1
    • 2
  • Faride Rafiei
    • 1
  1. 1.Department of Analytical Chemistry, Faculty of ChemistryUniversity College of Science, University of TehranTehranIran
  2. 2.Biosensor Research Center, Endocrinology and Metabolism Molecular-Cellular Sciences InstituteTehran University of Medical SciencesTehranIran

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