Microchimica Acta

, Volume 171, Issue 3–4, pp 423–429 | Cite as

Molecular imprinting polymer electrosensor based on gold nanoparticles for theophylline recognition and determination

  • Xianwen Kan
  • Tingting Liu
  • Hong Zhou
  • Chen Li
  • Bin Fang
Original Paper


An electrochemical sensor for theophylline (ThPh) was prepared by electropolymerizing o-phenylenediamine on a glassy carbon electrode in the presence of ThPh via cyclic voltammetry, followed by deposition of gold nanoparticles using a potentiostatic method. The effects of pH, ratio between template molecule and monomer, number of cycles for electropolymerization, and of the solution for extraction were optimized. The current of the electro-active model system hexacyanoferrate(III) and hexacyanoferrate(IV) decreased linearly with successive addition of ThPh in the concentration range between 4.0 × 10−7 ~ 1.5 × 10−5 mol·L−1 and 2.4 × 10−4 ~ 3.4 × 10−3 mol·L−1, with a detection limit of 1.0 × 10−7 mol·L−1. The sensor has an excellent recognition capability for ThPh compared to structurally related molecules, can be regenerated and is stable.


In this paper, an electrochemical sensor for theophylline (ThPh) was prepared by electropolymerizing o-phenylenediamine (o-PD) on a glassy carbon electrode in the presence of ThPh via cyclic voltammetry, followed by deposition of gold nanoparticles to enhance the sensitivity of the sensor. Therefore, the sensor showed a high sensitivity for ThPh determining. Peak current of [Fe(CN)6]3−/[Fe(CN)6]4− varied linearly with the concentration of ThPh in the range of 4.0×10-7~1.5×10-5 mol·L-1 and 2.4×10-4~3.4×10-3 mol·L-1, and the detection limit reached 1.0×10-7 mol·L-1. Compared to structurally related molecules, the sensor also has a high recognition capability for ThPh. With excellent regeneration property and stability, the present sensor maybe provides a new class of polymer modified electrodes for sensor applications.


Molecular imprinted polymer Electrochemical sensor Au nanoparticles Theophylline Recognition 



We greatly appreciate the support of the National Natural Science Foundation of China for General program (20675001) and young program (21005002), Anhui University Provincial Natural Science Foundation Key program (KJ2010A138), Dr Start-up Fundation of Anhui Normal University (160-750834).


  1. 1.
    Riahi S, Mousavi MF, Bathaie SZ, Shamsipur M (2005) A novel potentiometric sensor for selective determination of theophylline: theoretical and practical investigations. Anal Chim Acta 548:192CrossRefGoogle Scholar
  2. 2.
    Ferapontova EE, Eva MO (2008) An RNA aptamer-based electrochemical biosensor for detection of theophylline in serum. J Am Chem Soc 130:4256CrossRefGoogle Scholar
  3. 3.
    Lai EP, Fafara A, VanderNoot VA (1998) Surface plasmon resonance sensors using molecularly imprinted polymers for sorbent assay of theophylline, caffeine, and xanthine. Can J Chem 76:265CrossRefGoogle Scholar
  4. 4.
    Saka K, Uemura K, Shintani-Ishida K, Yoshida K (2007) Acetic acid improves the sensitivity of theophylline analysis by gas chromatography–mass spectrometry. J Chromatogr B 846:240CrossRefGoogle Scholar
  5. 5.
    Pérez-Martínez I, Sagrado S, Medina-Hernández MJ (1995) A rapid procedure for the determination of caffeine, theophylline and theobromine in urine by micellar liquid chromatography and direct sample injection. Anal Chim Acta 304:195CrossRefGoogle Scholar
  6. 6.
    Tajerzadeh H, Dadashzadeh S (1995) An isocratic high-performance liquid chromatographic system for simultaneous determination of theophylline and its major metabolites in human urine. J Pharm Biomed Anal 13:1507CrossRefGoogle Scholar
  7. 7.
    Zydron M, Baranowska J, Baranowska I (2004) Sepatation, pre-concentration, and HPLC analysis of methylxanthines in urine samples. J Sep Sci 27:1166CrossRefGoogle Scholar
  8. 8.
    Brunetto MR, Gutiérrez L, Delgado Y (2007) Determination of theobromine, theophylline and caffeine in cocoa samples by a high-performance liquid chromatographic method with on-line sample cleanup in a switching-column system. Food Chem 100:459CrossRefGoogle Scholar
  9. 9.
    Şentürk Z, Erk N, Özkan SA, Akay C, Cevheroğlu Ş (2002) Determination of theophylline and ephedrine HCL in tablets by ratio-spectra derivative spectrophotometry and LC. J Pharm Biomed Anal 29:291CrossRefGoogle Scholar
  10. 10.
    Kanazawa H, Atsumi R, Matsushima Y (2000) Determination of theophylline and its metabolites in biological samples by liquid chromatography–mass spectrometry. J Chromatogr A 870:87CrossRefGoogle Scholar
  11. 11.
    Khorrami AR, Rashidpur A (2009) Design of a new cartridge for selective solid phase extraction using molecularly imprinted polymers: Selective extraction of theophylline from human serum samples. Biosens Bioelecron 25:647CrossRefGoogle Scholar
  12. 12.
    Yoshimi Y, Ohdaira R (2005) “Gate effect” of thin layer of molecularly-imprinted poly(methacrylic acid-co-ethyleneglycol dimethacrylate). Sens Actu B 73:49CrossRefGoogle Scholar
  13. 13.
    Kindschy LM, Alocilja EC (2005) A molecularly imprinted polymer on indium tin oxide and silicon. Biosens Bioelectron 20:2163CrossRefGoogle Scholar
  14. 14.
    Lee HY, Kim BS (2009) Grafting of molecularly imprinted polymers on iniferter-modified carbon nanotube. Biosens Bioelectron 25:587CrossRefGoogle Scholar
  15. 15.
    Lee E, Park DW (2008) Molecularly imprinted polymers immobilized on carbon nanotube. Colloids Surf A: Physicochem Eng Aspects 313:202CrossRefGoogle Scholar
  16. 16.
    Tominaga Y, Kubo T, Kaya K, Hosoya K (2009) Effective recognition on the surface of a polymer prepared by molecular imprinting using ionic complex. Macromolecules 42:2911CrossRefGoogle Scholar
  17. 17.
    Zhanga J, Wanga Y, Lva R, Xua L (2010) Electrochemical tolazoline sensor based on gold nanoparticles and imprinted poly-o-aminothiophenol film. Electro Acta 55:4039CrossRefGoogle Scholar
  18. 18.
    Smiechowski MF, Lvovich VF, Roy S (2006) Electrochemical detection and charanterization of proteins. Biosens Bioelectron 22:670CrossRefGoogle Scholar
  19. 19.
    Zhang YZ, Ma HY, Zhang KY (2009) An improved DNA biosensor built by layer-by-layer covalent attachment of multi-walled carbon nanotubes and gold nanoparticles. Electro Acta 54:2385–2391CrossRefGoogle Scholar
  20. 20.
    Zen JM, Yu TY (1999) Determination of theophylline in tea and drug formulation using a Nafion®:lead–ruthenium oxide pyrochlore chemically modified electrode. Talanta 50:635CrossRefGoogle Scholar
  21. 21.
    Sun HW, Qiao FX (2006) Characteristic of theophylline imprinted monolithic column and its application for determination of xanthine derivatives caffeine and theophylline in green tea. J Chromatogr A 1134:194CrossRefGoogle Scholar
  22. 22.
    Vlatakis G, Andersson LI, Muller R (1993) Drug assay using antibody mimics made by molecular imprinting. Nature 361:645CrossRefGoogle Scholar
  23. 23.
    Fang GZ, Tan J, Yan XP (2005) An ion-imprinted functionalized silica gel sorbent prepared by a surface imprinting technique combined with a sol−gel process for selective solid-phase extraction of cadmium(II). Anal Chem 77:1734CrossRefGoogle Scholar
  24. 24.
    Xie C, Liu B, Wang Z, Gao D, Guan G (2008) Molecular imprinting at walls of silica nanotubes for TNT recognition. Anal Chem 80:437CrossRefGoogle Scholar
  25. 25.
    Li Y, Yin XF, Chen FR, Yang HH (2006) Synthesis of magnetic molecularly imprinted polymer nanowires using a nanoporous alumina template. Macromolecules 39:4497CrossRefGoogle Scholar
  26. 26.
    Priego-Capote F, Ye L, Shakil S, Shamsi SA (2008) Monoclonal behavior of molecularly imprinted polymer nanoparticles in capillary electrochromatography. Anal Chem 80:2881CrossRefGoogle Scholar
  27. 27.
    Hoshina K, Horiyama S, Matsunaga H, Haginaka J (2009) Molecularly imprinted polymers for simultaneous determination of antiepileptics in river water samples by liquid chromatography–tandem mass spectrometry. J Chromatogr A 1216:4957CrossRefGoogle Scholar
  28. 28.
    Brüggemann O, Freitag R, Whitcombe MJ (1997) Comparison of polymer coatings of capillaries for capillary electrophoresis with respect to their applicability to molecular imprinting and electrochromatography. J Chromatogr A 781:43CrossRefGoogle Scholar
  29. 29.
    Ariffin MM, Miller EI, Cormack PAG, Anderson RA (2007) Molecularly imprinted solid-phase extraction of diazepam and its metabolites from hair samples. Anal Chem 79:256CrossRefGoogle Scholar
  30. 30.
    Yan H, Qiao F, Row KH (2007) Molecularly imprinted-matrix solid-phase dispersion for selective extraction of five fluoroquinolones in eggs and tissue. Anal Chem 79:8242CrossRefGoogle Scholar
  31. 31.
    Gong C, Wong KL, Lam MHW (2008) Photoresponsive molecularly imprinted hydrogels for the photoregulated release and uptake of pharmaceuticals in the aqueous media. Chem Mater 20:1353CrossRefGoogle Scholar
  32. 32.
    Riskin M, Tel-Vered R, Bourenko T, Granot E, Willner I (2008) Imprinting of molecular recognition sites through electropolymerization of functionalized Au nanoparticles: development of an electrochemical TNT sensor based on π-Donor−acceptor interactions. J Am Chem Soc 130:9726CrossRefGoogle Scholar
  33. 33.
    Xu X, Zhou G, Li H, Liu Q, Zhang S, Kong J (2009) A novel molecularly imprinted sensor for selectively probing imipramine created on ITO electrodes modified by Au nanoparticles. Talanta 78:26CrossRefGoogle Scholar
  34. 34.
    Chuang SW, Rick J, Chou TC (2009) Electrochemical characterisation of a conductive polymer molecularly imprinted with an Amadori compound. Biosens Bioelectron 24:3170CrossRefGoogle Scholar
  35. 35.
    Mazzotta E, Picc RA, Malitesta C, Piletsky SA, Piletska EV (2008) Development of a sensor prepared by entrapment of MIP particles in electrosynthesised polymer films for electrochemical detection of ephedrine. Biosens Bioelectron 23:1152CrossRefGoogle Scholar
  36. 36.
    Du D, Chen SZ, Cai J, Tao Y, Tu H, Zhang A (2008) Recognition of dimethoate carried by bi-layer electrodoposition of silver nanoparticles and imprinted poly-o-ohenylenediamne. Microchem J 53:6589Google Scholar
  37. 37.
    Zhang Z, Nie L, Yao S (2006) Electrodeposited sol–gel-imprinted sensing film for cytidine recognition on Au-electrode surface. Talanta 69:435CrossRefGoogle Scholar
  38. 38.
    Kan X, Zhao Y, Geng Z, Wang Z, Zhu JJ (2008) Composites of multiwalled carbon nanotubes and molecularly imprinted polymers for dopamine recognition. J Phys Chem C 112:4849CrossRefGoogle Scholar
  39. 39.
    Ulyanova YV, Blackwell AE, Minteer SD (2006) Poly(methylene green) employed as molecularly imprinted polymer matrix for electrochemical sensing. Analyst 131:257CrossRefGoogle Scholar
  40. 40.
    Kindschy LM, Alocilja EC (2007) Development of a molecularly imprinted biomimetic electrode. Sensors 7:1630CrossRefGoogle Scholar
  41. 41.
    Wang ZH, Kang JW, Liu XY, Ma YJ (2007) Capacitive detection of theophylline based on electropolymerized molecularly imprinted polymer. Int J Polym Anal Charact 12:131CrossRefGoogle Scholar
  42. 42.
    Liu Y, Song QJ, Wang L (2009) Development and characterization of an amperometric sensor for triclosan detection based on electropolymerized molecularly imprinted polymer. Microchem J 91:222CrossRefGoogle Scholar
  43. 43.
    Liu S, Li Y, Li J, Jiang L (2005) Enhancement of DNA immobilization and hybridization on gold electrode modified by nanogold aggregates. Biosens Bioelectron 21:789CrossRefGoogle Scholar
  44. 44.
    Sanz VC, Mena ML, González-Cortés A, Yáñez-Sedeño P, Pingarrón JM (2005) Development of a tyrosinase biosensor based on gold nanoparticles-modified glassy carbon electrodes: Application to the measurement of a bioelectrochemical polyphenols index in wines. Anal Chim Acta 528:1CrossRefGoogle Scholar
  45. 45.
    Zhang ZH, Li H (2005) Effect of the extraction method on the MIP-Sensor. Anal Lett 38:203CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  • Xianwen Kan
    • 1
  • Tingting Liu
    • 1
  • Hong Zhou
    • 1
  • Chen Li
    • 1
  • Bin Fang
    • 1
  1. 1.College of Chemistry and Materials Science, Anhui Key Laboratory of Chemo-BiosensingAnhui Normal UniversityWuhuPeople’s Republic of China

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