Microchimica Acta

, Volume 182, Issue 5–6, pp 1123–1129 | Cite as

Ultrasensitive and selective voltammetric aptasensor for dopamine based on a conducting polymer nanocomposite doped with graphene oxide

  • Wenting Wang
  • Wei Wang
  • Jason J. Davis
  • Xiliang Luo
Original Paper


We describe an aptasensor for the determination of dopamine in human serum and with ultrahigh sensitivity and selectivity. The sensor is based on a nanocomposite consisting of reduced graphene oxide (rGO) and the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT). The PEDOT/rGO interface was prepared by electrochemical polymerization of EDOT using graphene oxide as the dopant which is later electrochemically reduced to form rGO. Subsequent covalent modification of the high surface area composite with a selective aptamer enables highly sensitive and selective detection by differential pulse voltammetry. The calibration plot established at a working voltage of 160 mV displays a linear response in the 1 pM to 160 nM concentration range and an unprecedented detection limit of 78 fM. The sensor is fairly selective in not responding to common interferents, and is reusable after regeneration with a 7 M solution of urea. It was successfully applied to (spiked) serum samples and gave recoveries ranging from 98.3 to 100.7 %.

Graphical Abstract

A highly sensitive and selective biosensor for dopamine was developed based on an aptamer-modifed conducting polymer (PEDOT) doped with reduced graphene oxide.


Aptamer Conducting polymer Dopamine Graphene oxide Poly(3,4-ethylenedioxythiophene) 



This research was supported by the National Natural Science Foundation of China (No. 21275087, 21175077), the Natural Science Foundation of Shandong Province of China (ZR2012BM008), and the Taishan Scholar Program of Shandong Province, China.


  1. 1.
    Jose PA, Eisner GM, Felder RA (1998) Renal dopamine receptors in health and hypertension-effects of ouabain and certain endogenous ouabain-like factors in hypertension. Pharmacol Ther 80:149–182CrossRefGoogle Scholar
  2. 2.
    Kim YR, Bong S, Kang YJ, Yang Y, Mahajan RK, Kim JS, Kim H (2010) Elecrochemical detection of dopamine in the presnce of ascorbic acid using graphene modified electrodes. Biosens Bioelectron 25:2366–2369CrossRefGoogle Scholar
  3. 3.
    Perry M, Li Q, Kennedy RT (2009) Review of recent advances in analytical techniques for the determination of neurotransmitters. Anal Chim Acta 653:1–22CrossRefGoogle Scholar
  4. 4.
    Noelker C, Hampel H, Dodel R (2011) Blood-based protein biomarkers for diagnosis and classification of neurodegenerative diseases: current progress and clinical potential. Mol Diagn Ther 15:83–102CrossRefGoogle Scholar
  5. 5.
    Päivi U, Ruut R, Kirsi H, Petteri P, Raimo AK, Risto K (2009) Analysis of intact glucuronides and sulfates of serotonin, dopamine, and their phase I metabolites in rat brain microdialysates by liquid chromatography-tandem mass spectrometry. Anal Chem 81:8417–8425CrossRefGoogle Scholar
  6. 6.
    Moghadam MR, Dadfarnia S, Shabani AMH, Shahbazikhah P (2011) Chemometric-assisted kinetic-spectrophotometric method for simultaneous determination of ascorbic acid, uric acid, and dopamine. Anal Biochem 410:289–295CrossRefGoogle Scholar
  7. 7.
    Huang HM, Lin CH (2005) Methanol plug assisted sweeping-micellar electrokineric chrimatography for the determination of dopamine in urine by violet light emitting diode-induced fluorescence detection. J Chromatogr B 816:113–119CrossRefGoogle Scholar
  8. 8.
    Seçkin ZE, Volkan M (2005) Flow injection fluorescene determination of dopamine using a photoinduced electron transfer (PET) boronic acid derivative. Anal Chim Acta 547:104–108CrossRefGoogle Scholar
  9. 9.
    Kong B, Zhu AW, Luo YP, Tian Y, Yu YY, Shi GY (2011) Sensitive and selective colorimetric visualization of cerebral dopamine based on double molecular recognition. Angew Chem 50:1877–1880CrossRefGoogle Scholar
  10. 10.
    Sanghavi BJ, Wolfbeis OS, Hirsch T, Swami NS (2015) Nanomaterial-based electrochemical sensing of neurological drugs and neurotransmitters. Microchim Acta 182:1–43. doi: 10.1007/s00604-014-1308-4
  11. 11.
    Wang Y, Li YM, Tang LH, Lu J, Li JH (2009) Application of graphene-modified electrode for selective detection of dopamine. Electrochem Commun 11:889–892CrossRefGoogle Scholar
  12. 12.
    Li Y, Du J, Yang J, Liu D, Lu X (2012) Electrocatalytic detection of dopamine in the presence of ascorbic acid and uric acid using single-walled carbon nanotubes modified electrode. Colloids Surf B: Biointerfaces 97:32–36CrossRefGoogle Scholar
  13. 13.
    Jia D, Dai JY, Yuan HY, Lei L, Xiao D (2011) Selective detection of dopamine in the presence of uric acid using a gold nanoparticles-poly(luminol) hybrid film and multi-walled carbon nanotubes with incorporated β-cyclodextrin modified glassy carbon electrode. Talanta 85:2344–2351CrossRefGoogle Scholar
  14. 14.
    Ellington AD, Szostak JW (1990) In vitro selection of RNA molecules that bind specific ligands. Nature 346:818–822CrossRefGoogle Scholar
  15. 15.
    Tuerk C, Gold L (1990) Systematic evolution of ligands by exponential en-richment:RNA ligands to bacteriophage T4 DNA polymerase. Science 249:505–510CrossRefGoogle Scholar
  16. 16.
    Hu XG, Mu L, Wen JP, Zhou QX (2012) Covalently synthesized graphene oxide-aptamer nanosheets for efficient visible-light photocatalysis of nucleic acids and proteins of viruses. Carbon 50:2772–2781CrossRefGoogle Scholar
  17. 17.
    Iliuk AB, Hu L, Tao WA (2011) Aptamer in bioanalytical applications. Anal Chem 83:4440–4452CrossRefGoogle Scholar
  18. 18.
    Song SP, Wang LH, Li J, Fan CH, Zhao JL (2008) Aptamer-based biosensors. Trends Anal Chem 27:108–117CrossRefGoogle Scholar
  19. 19.
    Zhou L, Li DJ, Gai L, Wang JP, Li YB (2012) Electrochemical aptasensor for the detection of tetracycline with multi-walled carbon nanotubes amplification. Sensors Actuators B 162:201–208CrossRefGoogle Scholar
  20. 20.
    Mucic RC, Storhoff JJ, Mirkin CA, Letsinger RL (1998) DNA-directed synthesis of binary nanoparticle network materials. J Am Chem Soc 120:12674–12675CrossRefGoogle Scholar
  21. 21.
    Liu Y, Matharu Z, Howland MC, Revzin A, Simonian AL (2012) Affinity and enzyme-based biosensors: recent advances and emerging applications in cell analysis and point-of-care testing. Anal Bioanal Chem 404:1181–1196CrossRefGoogle Scholar
  22. 22.
    Zhou L, Wang M, Wang J, Ye Z (2011) Application of Biosensor Surface Immobilization Methods for Aptamer. Chin J Anal Chem 39:432–438CrossRefGoogle Scholar
  23. 23.
    He P, Shen L, Cao Y, Li D (2007) Ultrasensitive electrochemical detection of proteins by amplification of aptamer-nanoparticle bio bar codes. Anal Chem 79:8024–8029CrossRefGoogle Scholar
  24. 24.
    Huang YC, Ge B, Sen D, Yu HZ (2008) Immobilized DNA switches as electronic sensors for picomolar detection of plasma proteins. J Am Chem Soc 130:8023–8029CrossRefGoogle Scholar
  25. 25.
    Zheng Y, Wang Y, Yang X (2011) Aptamer-based colorimetric biosensing of dopamine using unmodified gold nanoparticles. Sensors Actuators B 156:95–99CrossRefGoogle Scholar
  26. 26.
    Farjami E, Campos R, Nielsen JS, Gothelf KV, Kjems J, Ferapontova EE (2013) RNA aptamer-based electrochemical biosensor for selective and label-free analysis of dopamine. Anal Chem 85:121–128CrossRefGoogle Scholar
  27. 27.
    Liu S, Xing X, Yu J, Lian W, Li J, Cui M, Huang J (2012) A novel label-free electrochemical aptasensor based on graphene-polyaniline composite film for dopamine determination. Biosens Bioelectron 36:186–191CrossRefGoogle Scholar
  28. 28.
    Wang WT, Xu GY, Cui XT, Sheng G, Luo XL (2014) Enhanced catalytic and dopamine sensing properties of electrochemically reduced conducting polymer nanocomposite doped with pure graphene oxide. Biosens Bioelectron 58:153–156CrossRefGoogle Scholar
  29. 29.
    Luo XL, Killard AJ, Smyth MR (2007) Nanocomposite and nanoporous polyaniline conducting polymers exhibit enhanced catalysis of nitrite reduction. Chem Eur J 13:2138–2143CrossRefGoogle Scholar
  30. 30.
    Bryan T, Luo XL, Forsgren L, Morozova-Roche LA, Davis JJ (2012) The robust electrochemical detection of a Parkinson’s disease marker in whole blood sera. Chem Sci 3:3468–3473CrossRefGoogle Scholar
  31. 31.
    Deng C, Chen J, Nie Z, Wang M, Chu X, Chen X, Xiao X, Lei C, Yao S (2009) Impedimetric aptasensor with femtomolar sensitivity based on the enlargement of surface-charged gold nanoparticles. Anal Chem 81:739–745CrossRefGoogle Scholar
  32. 32.
    Xu D, Yu X, Liu Z, He W, Ma Z (2005) Label-free electrochemical detection for aptamer-based array electrodes. Anal Chem 77:5107–5113CrossRefGoogle Scholar
  33. 33.
    Xu MY, Luo XL, Davis JJ (2013) The label free picomolar detection of insulin in blood serum. Biosens Bioelectron 39:21–25CrossRefGoogle Scholar
  34. 34.
    Liu Y, Qu X, Guo H, Chen H, Liu B, Dong S (2006) Facile preparation of amperometric laccase biosensor with multifunction based on the matrix of carbon nanotubes-chitosan composite. Biosens Bioelectron 21:2195–2201CrossRefGoogle Scholar
  35. 35.
    Inhwa J, Dmitriy AD, Richard DP, Rodney SR (2008) Tunable electrical conducitivity of individual graphene oxide at “low” temperatures. Nano Lett 8:4283–4287CrossRefGoogle Scholar
  36. 36.
    Mo JW, Ogorevc B (2001) Simultaneous measurement of dopamine and ascorbate at their physiological levels using voltammetric microprobe based on overoxidized poly(1,2-phenylenediamine)-coated carbon fiber. Anal Chem 73:1196–1202CrossRefGoogle Scholar
  37. 37.
    Yu S, Luo C, Wang L, Peng H, Zhu Z (2013) Poly (3,4-ethylenedioxythiophene)-modified Ni/silicon microchannel plate electrode for the simultaneous determination of ascorbic acid, dopamine and uric acid. Analyst 138:1149–1155CrossRefGoogle Scholar
  38. 38.
    Song MJ, Lee SK, Kim JH, Lim DS (2012) Dopamine sensor based on a boron-doped diamond electrode modified with a polyaniline/Au nanocomposites in the presence of ascorbic acid. Anal Sci 28:583–587CrossRefGoogle Scholar
  39. 39.
    Jiang X, Lin X (2005) Immobilization of DNA on carbon fiber microelectrodes by using overoxidized polypyrrole template for selective detection of dopamine and epinephrine in the presence of high concentrations of ascorbic acid and uric acid. Analyst 130:391–396CrossRefGoogle Scholar
  40. 40.
    Zhuang Z, Li J, Xu R, Xiao D (2011) Electrochemical detection of dopamine in the presence of ascorbic acid using overoxidized polypyrrole/graphene modified electrodes. Int J Electrochem Sci 6:2149–2161Google Scholar
  41. 41.
    Zeng Y, Zhou Y, Kong L, Zhou T, Shi G (2013) A novel composite of SiO2-coated graphene oxide and molecularly imprinted polymers for electrochemical sensing dopamine. Biosens Bioelectron 45:25–33CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Wien 2014

Authors and Affiliations

  1. 1.Key Laboratory of Sensor Analysis of Tumor Marker, Ministry of Education, College of Chemistry and Molecular EngineeringQingdao University of Science and TechnologyQingdaoChina
  2. 2.Department of ChemistryUniversity of OxfordOxfordUK

Personalised recommendations