Journal of Molecular Modeling

, Volume 15, Issue 7, pp 829–836 | Cite as

A computational approach to studying monomer selectivity towards the template in an imprinted polymer

  • Siavash Riahi
  • Farrin Edris-Tabrizi
  • Mehran Javanbakht
  • Mohammad Reza Ganjali
  • Parviz Norouzi
Original Paper


A computational approach was proposed to study monomer–template interactions in a molecularly imprinted polymer (MIP) in order to gain insight at the molecular level into imprinting polymer selectivity, regarding complex formation between template and monomer at the pre-polymerisation step. This is the most important step in MIP preparation. In the present work, chlorphenamine (CPA), diphenhydramine (DHA) and methacrylic acid (MAA), were chosen as the template, non-template, and monomer, respectively. The attained complexes were optimised, and changes in the interaction energies, atomic charges, IR spectroscopy results, dipole moment, and polarisability were studied. The effects of solvent on template–monomer interactions were also investigated. According to a survey of the literature, this is the first work in which dipole moment and polarisability were used to predict the types of interactions existing in pre-polymerisation complexes. In addition, the density functional tight-binding (DFTB) method, an approximate version of the density functional theory (DFT) method that was extended to cover the London dispersion energy, was used to calculate the interaction energy.


Chlorphenamine Computational chemistry Density functional theory Molecularly imprinted polymer Monomer-template interactions 



We gratefully acknowledge the generous allocation of computing time from the Institute of Petroleum Engineering, University of Tehran for Advanced Computing and Supercomputing Facilities.


  1. 1.
    Wu L, Li Y (2004) Study on the recognition of templates and their analogues on molecularly imprinted polymer using computational and conformational analysis approaches. J Mol Recognit 17:567–574CrossRefGoogle Scholar
  2. 2.
    Haginaka J, Sanbe H (2001) Uniformly sized molecularly imprinted polymer for (S)-naproxen—retention and molecular recognition properties in aqueous mobile phase. J Chromatogr A 913:141–146CrossRefGoogle Scholar
  3. 3.
    Chianella I, Karim K, Piletska EV et al (2006) Computational design and synthesis of molecularly imprinted polymers with high binding capacity for pharmaceutical applications-model case: adsorbent for abacavir. Anal Chim Acta 559:73–78CrossRefGoogle Scholar
  4. 4.
    Haupt K, Mosbach K (2000) Molecularly imprinted polymers and their use in biomimetic sensors. Chem Rev 100:2495–2504CrossRefGoogle Scholar
  5. 5.
    Ciardelli G, Cioni B, Cristallini C et al (2004) Acrylic polymeric nanospheres for the release and recognition of molecules of clinical interest. Biosens Bioelectron 20:1083–1090CrossRefGoogle Scholar
  6. 6.
    Donato L, Figoli A, Drioli E (2005) Novel composite poly (4-vinylpyridine)/polypropylene membranes with recognition properties for (S)-naproxen. J Pharm Biomed Anal 37:1003–1008CrossRefGoogle Scholar
  7. 7.
    Sambe H, Hoshina K, Moaddel R et al (2006) Uniformly-sized, molecularly imprinted polymers for nicotine by precipitation polymerization. J Chromatogr A 1134:88–94CrossRefGoogle Scholar
  8. 8.
    Ozcan L, Sahin Y (2007) Determination of paracetamol based on electropolymerized-molecularly imprinted polypyrrole modified pencil graphite electrode. Sens Actuators B 127:362–369CrossRefGoogle Scholar
  9. 9.
    Gomez-Caballero A, Unceta M, Goicolea MA et al (2007) Evaluation of the selective detection of 4,6-dinitro-o-cresol by a molecularly imprinted polymer based microsensor electrosynthesized in a semiorganic media. Sens Actuators, B. 130:713–722CrossRefGoogle Scholar
  10. 10.
    Holthoff EL, Bright FV (2007) Molecularly templated materials in chemical sensing. Anal Chim Acta 594:147–161CrossRefGoogle Scholar
  11. 11.
    Piletsky SA, Karim K, Piletska EV et al (2001) Recognition of ephedrine enantiomers by molecularly imprinted polymers designed using a computational approach. Analyst 126:1826–1830CrossRefGoogle Scholar
  12. 12.
    Dong W, Yan M, Zhang M et al (2005) A computational and experimental investigation of the interaction between the template molecule and the functional monomer used in the molecularly imprinted polymer. Anal Chim Acta 542:186–192CrossRefGoogle Scholar
  13. 13.
    Dineiro Y, Menendez MI, Blanco-Lopez MC et al (2006) Computational predictions and experimental affinity distributions for a homovanillic acid molecularly imprinted polymer. Biosens Bioelectron 22:364–371CrossRefGoogle Scholar
  14. 14.
    Liu Y, Wang F, Tan TW et al (2007) Study of the properties of molecularly imprinted polymers by computational and conformational analysis. Anal Chim Acta 581:137–146CrossRefGoogle Scholar
  15. 15.
    Monti S, Cappelli C, Bronco S et al (2006) Towards the design of highly selective recognition sites into molecular imprinting polymers: a computational approach. Biosens Bioelectron 22:153–163CrossRefGoogle Scholar
  16. 16.
    Riahi S, Ganjali MR, Norouzi P et al (2008) Application of GA-MLR, GA-PLS and the DFT quantum Mechanical (QM) calculations for the prediction of the selectivity coefficients of a histamine-selective electrode. Sens Actuators B 132:13–19CrossRefGoogle Scholar
  17. 17.
    Riahi S, Norouzi P, Bayandori-Moghaddam A et al (2007) Theoretical and experimental report on the determination of electrode potentials of dihydroxyanthracene and thioxanthens derivatives. Chem Phys 337:33–38CrossRefGoogle Scholar
  18. 18.
    Riahi S, Ganjali MR, Bayandori-Moghaddamb A et al (2008) Structural study of 2-(1-oxo-1 H-inden-3-yl)-2H-indene-1,3-dione by ab initio and DFT calculations, NMR and IR spectroscopy. Spectrochim Acta, Part A 70:94–98CrossRefGoogle Scholar
  19. 19.
    Riahi S, Ganjali MR, Bayandori-Moghaddam A et al (2006) Determination of the electrode potentials for substituted 1,2-dihydroxybenzenes in aqueous solution: theory and experiment. J Mol Struct (THEOCHEM) 774:107–111CrossRefGoogle Scholar
  20. 20.
    Chen W, Liu F, Zhang X et al (2001) The specificity of a chlorphenamine-imprinted polymer and its application. Talanta 55:29–34CrossRefGoogle Scholar
  21. 21.
    Haginaka J, Kawaga C (2002) Uniformly sized molecularly imprinted polymer for d-chlorpheniramine - Evaluation of retention and molecular recognition properties in an aqueous mobile phase. J Chromatogr A 948:77–84CrossRefGoogle Scholar
  22. 22.
    Haginaka J, Kawaga C (2004) Retentivity and enantioselectivity of uniformly sized molecularly imprinted polymers for d-chlorpheniramine and -brompheniramine in hydro-organic mobile phases. J Chromatogr B 804:19–24CrossRefGoogle Scholar
  23. 23.
    Mahato SB, Sahu NP, Maitra SK (1986) Simultaneous determination of chlorpheniramine and diphenhydramine in cough syrups by reversed-phase ion-pair high-performance liquid chromatography. J Chromatogr 351:580–584CrossRefGoogle Scholar
  24. 24.
    Riahi S, Ganjali MR, Moghaddam AB (2008) Experimental and quantum chemical study on the IR, UV and electrode potential of 6-(2,3-dihydro-1,3-dioxo-2-phenyl-1H-inden-2-yl)-2,3-dihydroxybenzaldehyde. Spectrochim Acta, Part A 71:1390–1396CrossRefGoogle Scholar
  25. 25.
    Ganjali MR, Norouzi P, Faridbod F et al (2007) Determination of Vanadyl ions by a New PVC Membrane Sensor Based on N, N'-bis-(salicylidene)-2,2-dimethylpropane-1,3-diamine. IEEE Sens J 7:544–550CrossRefGoogle Scholar
  26. 26.
    Ganjali MR, Norouzi P, Mirnaghi FS (2007) Lanthanide recognition: monitoring of praseodymium(III) by a novel praseodymium (III) microsensor based on N-(pyridine-2-ylmethylene) benzohydrazide. IEEE Sens J 7:1138–1144CrossRefGoogle Scholar
  27. 27.
    Faridbod F, Ganjali MR, Larijani B (2007) Lanthanide recognition: an asymetric erbium microsensor based on a hydrazone derivative. Sensors 7:3119–3135CrossRefGoogle Scholar
  28. 28.
    Faridbod F, Ganjali MR, Dinarvand R (2008) Schiff’s bases and crown ethers as supramolecular sensing materials in construction of the potentiometric membrane sensors. Sensors 8:1645–1703CrossRefGoogle Scholar
  29. 29.
    HyperChem™ (1997) Molecular Modeling System, Release 5.1 Pro for Windows, Hypercube Inc, Gainesville, FLGoogle Scholar
  30. 30.
    Frisch MJ, Trucks GW, Schlegel HB et al (1998) Gaussian Inc, Pittsburgh, PAGoogle Scholar
  31. 31.
    Schimdt MW et al (1993) J Comput Chem 14:1347–1355CrossRefGoogle Scholar
  32. 32.
    Wu L, Zhu K, Zhao M et al (2005) Theoretical and experimental study of nicotinamide molecularly imprinted polymers with different porogens. Anal Chim Acta 549:39–44CrossRefGoogle Scholar
  33. 33.
    Elstner M, Hozba P, Frauenheim T et al (2001) Hydrogen bonding and stacking interactions of nucleic acid base pairs: a density-functional-theory based treatment. J Chem Phys 114:5149–5155CrossRefGoogle Scholar
  34. 34.
    Spivak A (2005) Adv Drug Deliver Rev 57:1779CrossRefGoogle Scholar
  35. 35.
    Karim K, Breton F, Rouillon R et al (2005) Adv Drug Deliver Rev 57:1795CrossRefGoogle Scholar
  36. 36.
    Schwenke DW, Truhlar DG (1985) J Chem Phys 82:2418–2423CrossRefGoogle Scholar
  37. 37.
    Frisch MJ, Del Bene JE, Binkley JS et al (1986) Extensive theoretical studies of the hydrogen-bonded complexes (H2O)2, (H2O)2H+, (HF)2, (HF)2H+, F2H, and (NH3)2. J Chem Phys 84:2279–2289CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2008

Authors and Affiliations

  • Siavash Riahi
    • 1
    • 2
  • Farrin Edris-Tabrizi
    • 3
  • Mehran Javanbakht
    • 3
  • Mohammad Reza Ganjali
    • 2
  • Parviz Norouzi
    • 2
  1. 1.Institute of Petroleum Engineering, Faculty of EngineeringUniversity of TehranTehranIran
  2. 2.Center of Excellence in Electrochemistry, Faculty of ChemistryUniversity of TehranTehranIran
  3. 3.Department of ChemistryAmirkabir University of TechnologyTehranIran

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