Preparation of N,N-p-phenylene bismethacryl amide as a novel cross-link agent for synthesis and characterization of the core–shell magnetic molecularly imprinted polymer nanoparticles

  • Saman Azodi-Deilami
  • Majid AbdoussEmail author
  • Davood Kordestani
  • Zahra Shariatinia


Novel magnetic molecularly imprinted nanoparticles (MMIPs) using N,N-p-phenylene bismethacryl amide as a cross linker and super paramagnetic core–shell nanoparticle as a supporter for use in controlled release were prepared by precipitation polymerization. Novel cross-linking agents were synthesized by the reaction of methacryloyl chloride with p-phenylenediamine. Then, the Fe3O4 nanoparticles were encapsulated with a SiO2 shell and functionalized with –CH=CH2 and MMIPs were further prepared by using methacrylic acid as a functional monomer, N,N-p-phenylene bismethacryl amide as a cross-linking agent and betamethasone as template. Magnetic non-MIPs were also prepared with the same synthesis procedure as with MMIPs only without the presence of the template. The obtained MMIPs were characterized by using transmission electron microscopy, Fourier transform infrared spectrum, X-ray diffraction, energy-dispersive X-ray spectroscopy, and the vibrating sample magnetometer. The performance of the MMIPs for the controlled release of betamethasone was assessed and results indicated that the magnetic MIPs also had potential applications in drug controlled release.


Dynamic Light Scattering Atom Transfer Radical Polymerization Molecular Imprint Polymerization Fe3O4 Nanoparticles Betamethasone 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



The authors wish to express their gratitude to Iran National Science Foundation (INSF) and Amirkabir University of Technology for their support in carrying out this project. We would also like to thank Dr. Ebadullah Asadi, Dr. Alireza Hasani and other co-workers in nano lab of Amirkabir University of Technology for their help.


  1. 1.
    Owens PK, Karlsson L, Lutz ESM, Andersson LI. Molecular imprinting for bio- and pharmaceutical analysis. Trends Anal Chem. 1999;18:146–54.CrossRefGoogle Scholar
  2. 2.
    Osmani Q, Hughes H, McLoughlin P. Probing the recognition of molecularly imprinted polymer beads. J Mater Sci. 2012;47:2218–27.CrossRefGoogle Scholar
  3. 3.
    Ho KC, Yeh WM, Tung TS, Liao JY. Amperometric detection of morphine based on poly(3,4-ethylenedioxythiophene) immobilized molecularly imprinted polymer particles prepared by precipitation polymerization. J Anal Chim Acta. 2005;542:90–6.CrossRefGoogle Scholar
  4. 4.
    Greene NT, Shimizu KD. Colorimetric molecularly imprinted polymer sensor array using dye displacement. J Am Chem Soc. 2005;127:5695–700.CrossRefGoogle Scholar
  5. 5.
    Chang L, Wu S, Chen S, Li X. Preparation of graphene oxide-molecularly imprinted polymer composites via atom transfer radical polymerization. J Mater Sci. 2011;46:2024–9.CrossRefGoogle Scholar
  6. 6.
    Vallano PT, Remcho VT. Highly selective separations by capillary electrochromatography: molecular imprint polymer sorbents. J Chromatogr A. 2000;887:125–35.CrossRefGoogle Scholar
  7. 7.
    Kamal A, Kumar BA, Arifuddin M, Dastidar SG. Synthesis of 4β-amido and 4β-sulphonamido analogues of podophyllotoxin as potential antitumour agents. Bioorg Med Chem. 2003;11:5135–42.CrossRefGoogle Scholar
  8. 8.
    Abdouss M, Azodi-Deilami S, Asadi E, Shariatinia Z. Synthesis of molecularly imprinted polymer as a sorbent for solid phase extraction of citalopram from human serum and urine. J Mater Sci Mater Med. 2012;23:1543–52.CrossRefGoogle Scholar
  9. 9.
    Chen W, Han DK, Ahn KD, Kim JM. Molecularly imprinted polymers having amidine and imidazole functional groups as an enzyme-mimetic catalyst for ester hydrolysis. Macromol Res. 2002;10:122–6.CrossRefGoogle Scholar
  10. 10.
    Suedee R, Srichana T, Martin G. Evaluation of matrices containing molecularly imprinted polymers in the enantioselective-controlled delivery of β-blockers. J Control Release. 2000;66:135–47.CrossRefGoogle Scholar
  11. 11.
    Sambe H, Hoshina K, Moadel R, Wainer W, Haginaka J. Uniformly-sized, molecularly imprinted polymers for nicotine by precipitation polymerization. J Chromatogr A. 2006;1134:88–94.CrossRefGoogle Scholar
  12. 12.
    Asadi E, Azodi-Deilami S, Abdouss M, Khaghani S. Cyproterone synthesis, recognition and controlled release by molecularly imprinted nanoparticle. Appl Biochem Biotechnol. 2012;167:2076–87.CrossRefGoogle Scholar
  13. 13.
    Azodi-Deilami S, Abdouss M, Javanbakht M. The syntheses and characterization of molecularly imprinted polymer for controlled release of bromhexine. App Biochem Biotechnol. 2011;164:133–47.CrossRefGoogle Scholar
  14. 14.
    Cirillo G, Parisi OI, Curcio M, Puoci F, Iemma F, Spizzirri UG, Picci N. Molecularly imprinted polymers as drug delivery systems for the sustained release of glycyrrhizic acid. J Pharm Pharmcol. 2010;62:577–82.Google Scholar
  15. 15.
    Lu AH, Salabas EL, Schüth F. Magnetic nanoparticles: synthesis, protection, functionalization, and application. Angew Chem Int Ed. 2007;46:1222–44.CrossRefGoogle Scholar
  16. 16.
    Ceolin G, Orban A, Kocsis V, Gyurcsanyi RE, Kezsmarki I, Horvath V. Electrochemical template synthesis of protein-imprinted magnetic polymer microrods. J Mater Sci. 2013;48:5209–18.CrossRefGoogle Scholar
  17. 17.
    Li Y, Yin XF, Chen FR, Yang HH, Zhuang ZX, Wang XR. Synthesis of magnetic molecularly imprinted polymer nanowires using a nanoporous alumina template. Macromolecules. 2006;39:4497–9.CrossRefGoogle Scholar
  18. 18.
    Tan CJ, Chua HG, Ker KH, Tong YW. Preparation of bovine serum albumin surface-imprinted submicrometer particles with magnetic susceptibility through core–shell miniemulsion polymerization. Anal Chem. 2008;80:683–92.CrossRefGoogle Scholar
  19. 19.
    Jin G, Li W, Yu S, Peng Y, Kong J. Novel superparamagnetic core–shell molecular imprinting microspheres towards high selective sensing. Analyst. 2008;133:1367–72.CrossRefGoogle Scholar
  20. 20.
    Wang X, Wang L, He X, Zhang Y, Chen L. A molecularly imprinted polymer-coated nanocomposite of magnetic nanoparticles for estrone recognition. Talanta. 2009;78:327–32.CrossRefGoogle Scholar
  21. 21.
    Lu CH, Wang Y, Li Y, Yang HH, Chen X, Wang XR. Bifunctional superparamagnetic surface molecularly imprinted polymer core–shell nanoparticles. J Mater Chem. 2009;19:1077–9.CrossRefGoogle Scholar
  22. 22.
    Chen L, Zhang X, Sun L, Xu Y, Zeng Q, Wang H, Xu H, Yu A, Zhang H, Ding L. Fast and selective extraction of sulfonamides from honey based on magnetic molecularly imprinted polymer. J Agric Food Chem. 2009;57:10073–80.CrossRefGoogle Scholar
  23. 23.
    Zhang Y, Liu R, Hu Y, Li G. Microwave heating in preparation of magnetic molecularly imprinted polymer beads for trace triazines analysis in complicated samples. Anal Chem. 2009;81:967–76.CrossRefGoogle Scholar
  24. 24.
    Chung-gi S, Kazzuo O, Masashi S, Yutaka N. Accurate method for obtaining band gaps in conducting polymers using a DFT/hybrid approach. J Phys Chem A. 1998;102:2572–8.CrossRefGoogle Scholar
  25. 25.
    Masahiro A, Tatsuo O, Yoshiko I, Kazutenu Y, Kazuo F, Haruo S. Structure of cyclothiazomycin, a unique polythiazole-containing peptide with renin inhibitory activity. Part 1. Chemistry and partial structures of cyclothiazomycin. Tetrahedron Lett. 1991;32:217–20.CrossRefGoogle Scholar
  26. 26.
    Masahiro A, Tatsuo O, Yoshiko I, Kazutenu Y, Kazuo F, Haruo S. Structure of cyclothiazomycin, a unique polythiazole-containing peptide with renin inhibitory activity. Part 2. Total structure. Tetrahedron Lett. 1991;32:221–4.CrossRefGoogle Scholar
  27. 27.
    El-Sawy NM, Elassar AZA. Some modification on radiation graft polymerization of N-vinyl-2-pyrrolidone onto low density polyethylene with α, β-unsaturated nitrile. Eur Polym J. 1998;34:1073–80.CrossRefGoogle Scholar
  28. 28.
    Rivas BL, Seguel GV. Poly(acrylic acid-co-maleic acid)–metal complexes with copper(II), cobalt(II), and nickel(II): synthesis, characterization and structure of its metal chelates. Polyhedron. 1999;18:2511–8.CrossRefGoogle Scholar
  29. 29.
    Elassar AZA, El-Sawy NM. Recent developments in the radiation grafting of N-vinyl-2-pyrrolidone onto low-density polyethylene with cinnamonitrile derivatives. J Appl Polym Sci. 2005;95:1189–97.CrossRefGoogle Scholar
  30. 30.
    Jeragh BJA, Elassar AZA, El-Dissouky A. Ligating behavior and metal uptake of N-sulphonylpolyamine chelating resins anchored on polystyrene-divinylbenzene beads. J Appl Polym Sci. 2005;96:1839–46.CrossRefGoogle Scholar
  31. 31.
    Lu Q, Singh A, Deochamps JR, Chang EL. Cu(II)-containing cross-linked polymers for the hydrolysis of 4-nitrophenyl phosphate. Inorg Chim Acta. 2000;309:82–90.CrossRefGoogle Scholar
  32. 32.
    Diab AM, El-Sonbati AZ, El-Dissouky A. Thermal degradation of poly(acryloyl chloride) and copolymers of acryloyl chloride with methyl methacrylate. Eur Polym J. 1989;25:431–4.CrossRefGoogle Scholar
  33. 33.
    Gad AM, El-Dissouky A, Abdel-Alim W. Thermal stability of poly(methacryloyl hydrazine) derivatives and their complexes with some transition metal chlorides. Polym Degrad Stab. 1995;50:163–7.CrossRefGoogle Scholar
  34. 34.
    El-Sonbati AZ, El-Dissouky A, Diab MM. Polymer complexes. V. Thermal stability of poly(acrylamido-4-aminoantipyrinyl) homopolymer and polymer complexes of acrylamido-4-aminoantipyrinyl with some transition metal salts. Acta Polym. 1989;40:112–6.CrossRefGoogle Scholar
  35. 35.
    Wang J, Chen L, Luo DB. Electrocatalytic detection of hydrogen peroxide at a Poly(m-phenylenediamine)-modified carbon paste electrode and its use for biosensing of glucose. Anal Commun. 1997;34:217–20.CrossRefGoogle Scholar
  36. 36.
    Ismail KZ, Shehata AK, El-Dissouky A. Spectroscopic and magnetic studies on some copper (II) complexes of antipyrine Schiff base derivatives. Polyhedron. 1997;16:2909–16.CrossRefGoogle Scholar
  37. 37.
    Akilah A, Moet A. Functionalized polymers and their applications. London: Chapman & Hall; 1990.Google Scholar
  38. 38.
    Patai S, Bentov M, Reichmann ME. Preparation and polymerization of aryl methacrylates and N-arylmethacrylamides. J Am Chem Soc. 1952;74:845.CrossRefGoogle Scholar
  39. 39.
    Yang D, Hu J, Fu S. Controlled synthesis of magnetite–silica nanocomposites via a seeded sol–gel approach. J Phys Chem C. 2009;113:7646–51.CrossRefGoogle Scholar
  40. 40.
    Stober W, Fink A, Bohn EJ. Controlled growth of monodisperse silica spheres in the micron size range. J Colloid Interface Sci. 1968;26:62.CrossRefGoogle Scholar
  41. 41.
    Sun H, Hong J, Meng F, Gong P, Yu J, Xue Y, Zhao S, Xu D, Dong L, Yao S. Novel core–shell structure polyacrylamide-coated magnetic nanoparticles synthesized via photochemical polymerization. Surf Coat Technol. 2006;201:250.CrossRefGoogle Scholar
  42. 42.
    Ding Y, Hu Y, Zhang L, Chen Y, Jiang X. Synthesis and magnetic properties of biocompatible hybrid hollow spheres. Biomacromolecules. 2006;7:1766–72.CrossRefGoogle Scholar
  43. 43.
    Ciardelli G, Cioni B, Cristallini C, Barbani N, Silvestri D, Giusti P. Acrylic polymeric nanospheres for the release and recognition of molecules of clinical interest. Biosens Bioelectron. 2004;20:1083–90.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2013

Authors and Affiliations

  • Saman Azodi-Deilami
    • 1
  • Majid Abdouss
    • 1
    Email author
  • Davood Kordestani
    • 2
  • Zahra Shariatinia
    • 1
  1. 1.Department of ChemistryAmirkabir University of TechnologyTehranIran
  2. 2.Department of Organic Chemistry, Faculty of ChemistryRazi UniversityKermanshahIran

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