Preparation of magnetic molecularly imprinted polymers for selective isolation and determination of kaempferol and protoapigenone in Macrothelypteris torresiana

  • Pei-shan Cai (蔡培珊)
  • Yang Zhao (赵 洋)
  • Tong-hua Yang (杨通华)
  • Jing Chen (陈 静)
  • Chao-mei Xiong (熊朝梅)
  • Jin-lan Ruan (阮金兰)


Novel uniform-sized magnetic molecularly imprinted polymers (MMIPs) were synthesized for selective recognition of active antitumor ingredients of kaempferol (KMF) and protoapigenone (PA) in Macrothelypteris torresiana (M. torresiana) by surface molecular imprinting technique in this study. Super paramagnetic core-shell nanoparticles (γ-MPS-SiO2@Fe3O4) were used as seeds, KMF as template molecule, acrylamide (AM) as functional monomer, and N, N′-methylene bisacrylamide (BisAM) as cross-linker. The prepared MMIPs were characterized by X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), transmission electron microscopy (TEM) and thermo-gravimetric analysis (TGA), respectively. The recognition capacity of MMIPs was 2.436 times of non-imprinted polymers. The adsorption results based on kinetics and isotherm analysis were in accordance with the pseudo-second-order model (R 2=0.9980) and the Langmuir adsorption model (R 2=0.9944). The value of E (6.742 kJ/mol) calculated from the Dubinin-Radushkevich isotherm model suggested that the physical adsorption via hydrogen-bonding might be predominant. The Scatchard plot showed a single line (R 2=0.9172) and demonstrated the homogeneous recognition sites on MMIPs for KMF. The magnetic solid phase extraction (MSPE) based on MMIPs as sorbent was established for fast and selective enrichment of KMF and its structural analogue PA from the crude extract of M. torresiana and then KMF and PA were detected by HPLC-UV. The established method showed good performance and satisfactory results for real sample analysis. It also showed the feasibility of MMIPs for selective recognition of active structural analogues from complex herbal extracts.

Key words

magnetic molecularly imprinted polymers magnetic solid phase extraction kaempferol protoapigenone Macrothelypteris torresiana 


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  1. 1.
    Marfe G, Tafani M, Indelicato M, et al. Kaempferol induces apoptosis in two different cell lines via Akt inactivation, Bax and SIR T3 activation, and mitochondrial dysfunction. J Cell Biochem, 2009, 106(4):643–650PubMedCrossRefGoogle Scholar
  2. 2.
    De Leo M, Braca A, Sanogo R, et al. Antiproliferative activity of Pteleopsis suberosa leaf extract and its flavonoid components in human prostate carcinoma cells. Planta Med, 2006, 72(7):604–610PubMedCrossRefGoogle Scholar
  3. 3.
    Leung HW, Lin CJ, Hour MJ, et al. Kaempferol induces apoptosis in human lung non-small carcinoma cells accompanied by an induction of antioxidant enzymes. Food Chem Toxicol, 2007, 45(10):2005–2013PubMedCrossRefGoogle Scholar
  4. 4.
    Lin AS, Chang FR, Wu CC, et al. New cytotoxic flavonoids from thelypteris torresiana. Planta Med, 2005, 71(9):867–870PubMedCrossRefGoogle Scholar
  5. 5.
    Liu HB, Jiang CY, Xiong CM, et al. DEDE, a new flavonoid induces apoptosis via a ROS-dependent mechanism in human neuroblastoma SH-SY5Y cells. Toxicol In Vitro, 2012, 26(1):16–23PubMedCrossRefGoogle Scholar
  6. 6.
    González-Pérez S, Merck KB, Vereijken JM, et al. Isolation and characterization of undenatured chlorogenic acid free sunflower (helianthus annuus) proteins. J Agric Food Chem, 2002, 50(6):1713–1719PubMedCrossRefGoogle Scholar
  7. 7.
    Molinelli A, Weiss R, Mizaikoff B. Advanced solid phase extraction using molecularly imprinted polymers for the determination of quercetin in red wine. J Agric Food Chem, 2002, 50(7):1804–1808PubMedCrossRefGoogle Scholar
  8. 8.
    Mdel López M, Cela Pérez MC, Dopico García MS, et al. Preparation, evaluation and characterization of quercetin-molecularly imprinted polymer for preconcentration and clean-up of catechins. Anal Chim Acta, 2012, 721:68–78CrossRefGoogle Scholar
  9. 9.
    Zhai HY, Li JM, Chen ZG, et al. A glass/PDMS electrophoresis microchip embedded with molecular imprinting SPE monolith for contactless conductivity detection. Microchem J, 2014, 114:223–228CrossRefGoogle Scholar
  10. 10.
    Zhu HB, Wang YZ, Yuan Y, et al. Development and characterization of molecularly imprinted polymer microspheres for the selective detection of kaempferol in traditional Chinese medicines. Anal Methods, 2011, 3:348–355CrossRefGoogle Scholar
  11. 11.
    Say R, Ersöz A, Sener I, et al. Comparison of adsorption and selectivity characteristics for 4-nitrophenol imprinted polymers prepared via bulk and suspension polymerization. Sep Sci Technol, 2005, 39(15):3471–3484CrossRefGoogle Scholar
  12. 12.
    Haginaka J, Tabo H, Ichitani M, et al. Uniformly-sized, molecularly imprinted polymers for (-)-epigallocatechin gallate, -epicatechin gallate and -gallocatechin gallate by multi-step swelling and polymerization method. J Chromatogr A, 2007, 1156(1–2):45–50PubMedCrossRefGoogle Scholar
  13. 13.
    Carter SR, Rimmer S. Aqueous compatible polymers in bionanotechnology. IEE Proc-Nanobiotechnol, 2005, 152(5): 169–176PubMedCrossRefGoogle Scholar
  14. 14.
    Haginaka J, Takehira H, Hosoya K, et al. Molecularly imprinted uniform-sized polymer-based stationary phase for naproxen comparison of molecular recognition ability of the molecularly imprinted polymers prepared by thermal and redox polymerization techniques. J Chromatogr A, 1998, 816(2):113–121CrossRefGoogle Scholar
  15. 15.
    Yoshida M, Uezu K, Goto M, et al. Metal ion imprinted microsphere prepared by surface molecular imprinting technique using water-in-oil-in-water emulsions. J Appl Polym Sci, 1999, 73(7):1223–1230CrossRefGoogle Scholar
  16. 16.
    Dai JD, Pan JM, Xu LC, et al. Preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization for the selective recognition of tetracycline from aqueous medium. J Hazard Mater, 2012, 205–206:179–188PubMedCrossRefGoogle Scholar
  17. 17.
    Wang S, Li Y, Ding MJ, et al. Self-assembly molecularly imprinted polymers of 17β-estradiol on the surface of magnetic nanoparticles for selective separation and detection of estrogenic hormones in feeds. J Chromatogr B, 2011, 879(25):2595–2600CrossRefGoogle Scholar
  18. 18.
    Zhou WH, Lu CH, Guo XC, et al. Mussel-inspired molecularly imprinted polymer coating superparamagnetic nanoparticles for protein recognition. J Mater Chem, 2010, 20:880–883CrossRefGoogle Scholar
  19. 19.
    Xie JC, Zhu LL, Luo HP, et al. Direct extraction of specific pharmacophoric flavonoids from gingko leaves using a molecularly imprinted polymer for quercetin. J Chromatogr A, 2001, 934(1–2):1–11PubMedCrossRefGoogle Scholar
  20. 20.
    Zhang ZM, Yun YB, Li CL. Preparation and adsorption performance of molecularly imprinted polymers for kaempferol. Desalin Water Treat, 2013, 51(19–21):3914–3919CrossRefGoogle Scholar
  21. 21.
    Huang CZ, Hu B. Silica-coated magnetic nanoparticles modified with γ-mercaptopropyltrimethoxysilane for fast and selective solid phase extraction of trace amounts of Cd, Cu, Hg, and Pb in environmental and biological samples prior to their determination by inductively coupled plasma mass spectrometry. Spectrochim Acta B, 2008, 63(3):437–444CrossRefGoogle Scholar
  22. 22.
    Deng YH, Yang WL, Wang CC, et al. A novel approach for preparation of thermoresponsive polymer magnetic microspheres with core-shell structure. Adv Mater, 2003, 15(20): 1729–1732CrossRefGoogle Scholar
  23. 23.
    Xiong CM, Ruan JL, Tang Y, et al. Chromatographic fingerprint analysis of Macrothelypteris Torresiana and simultaneous determination of several main constituents by LC. Chromatographia, 2009, 70:117–124CrossRefGoogle Scholar
  24. 24.
    Chen FF, Xie XY, Shi YP. Preparation of magnetic molecularly imprinted polymer for selective recognition of resveratrol in wine. J Chromatogr A, 2013, 1300:112–118PubMedCrossRefGoogle Scholar
  25. 25.
    Sun Z, Schüssler W, Sengl M, et al. Selective trace analysis of diclofenac in surface and wastewater samples using solid-phase extraction with a new molecularly imprinted polymer. Anal Chim Acta, 2008, 620(1–2):73–81PubMedCrossRefGoogle Scholar
  26. 26.
    Yu C, Mosbach K. Molecular imprinting utilizing an amide functional group for hydrogen bonding leading to highly efficient polymers. J Org Chem, 1997, 62(12):4057–4064CrossRefGoogle Scholar
  27. 27.
    Matyjaszewski K, Xia JH. Atom transfer radical polymerization. Chem Rev, 2001, 101:2921–2990PubMedCrossRefGoogle Scholar
  28. 28.
    Gu XH, Xu R, Yuan GL, et al. Preparation of chlorogenic acid surface-imprinted magnetic nanoparticles and their usage in separation of Traditional Chinese Medicine. Anal Chim Acta, 2010, 675(1):64–70PubMedCrossRefGoogle Scholar
  29. 29.
    Zhang Y, Liu RJ, Hu YL, et al. Microwave heating in preparation of magnetic molecularly imprinted polymer beads for trace triazines analysis in complicated samples. Anal Chem, 2009, 81(3):967–976PubMedCrossRefGoogle Scholar
  30. 30.
    Shea KJ, Spivac DA, Sellergren B. Polymer complements to nucleotide bases. Selective binding of adenine derivatives to imprinted polymers. J Am Chem Soc, 1993, 115(8):3368–3369CrossRefGoogle Scholar
  31. 31.
    Langumuir I. The adsorption of gases on plane surfaces of glass, mica and platinum. J Am Chem Soc, 1918, 40:1361–1403CrossRefGoogle Scholar
  32. 32.
    Freundlich HMF. Over the adsorption in solution. J Phys Chem, 1906, A57:358–471Google Scholar
  33. 33.
    Ramnani SP, Sabharwal S. Adsorption behavior of Cr(VI) onto radiation crosslinked chitosan and its possible application for the treatment of wastewater containing Cr(VI). React Funct Polym, 2006, 66(9):902–909CrossRefGoogle Scholar
  34. 34.
    Chen AH, Huang YY. Adsorption of remazol black 5 from aqueous solution by the templated crosslinked-chitosans. J Hazard Mater, 2010, 177(1–3):668–675PubMedCrossRefGoogle Scholar
  35. 35.
    Ho YS, McKay G. The sorption of lead(II) ions on peat. Water Res, 1999, 33(2):578–584CrossRefGoogle Scholar
  36. 36.
    Ho YS, McKay G. Pseudo-second order model for sorption processes. Process Biochem, 1999, 34(5):451–465CrossRefGoogle Scholar
  37. 37.
    Mehdinia A, Baradaran Kayyal T, Jabbari A, et al. Magnetic molecularly imprinted nanoparticles based on grafting polymerizatioin for selective detection of 4-nitrophenol in aqueous samples. J Chromatogr A, 2013, 1283(29):82–88PubMedCrossRefGoogle Scholar
  38. 38.
    Chang YS, Ko TH, Hsu TJ, et al. Synthesis of an imprinted hybrid organic-inorganic polymeric sol-gel matrix toward the specific binding and isotherm kinetics investigation of creatinine. Anal Chem, 2009, 81(6):2098–2105PubMedCrossRefGoogle Scholar
  39. 39.
    Yu Q, Deng SB, Yu G. Selective removal of perfluorooctane sulfonate from aqueous solution using chitosan-based molecularly imprinted polymer adsorbents. Water Res, 2008, 42(12):3089–3097PubMedCrossRefGoogle Scholar

Copyright information

© Huazhong University of Science and Technology and Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Pei-shan Cai (蔡培珊)
    • 1
  • Yang Zhao (赵 洋)
    • 1
  • Tong-hua Yang (杨通华)
    • 1
  • Jing Chen (陈 静)
    • 1
  • Chao-mei Xiong (熊朝梅)
    • 1
  • Jin-lan Ruan (阮金兰)
    • 1
  1. 1.Department of Pharmaceutical Analysis, School of Pharmacy, Tongji Medical CollegeHuazhong University of Science and TechnologyWuhanChina

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