Skip to content
BY-NC-ND 3.0 license Open Access Published by De Gruyter Open Access October 14, 2015

Magnetic molecular imprinted polymers as a tool for isolation and purification of biological samples

Katarzyna Kwaśniewska , Renata Gadzała-Kopciuch and Bogusław Buszewski
From the journal Open Chemistry


Technology of molecularly imprinted polymers (MIP) has become very popular in recent decades. MIPs are primarily used in medical diagnostics, chromatographic separation and solid phase extraction (SPE); also as sensors and catalysts. In recent years there have been reported benefits of combining molecular imprinted polymers with additional features, e.g. magnetic properties, through the build-up of this type of material on magnetite particles (Magnetic Molecularly Imprinted Polymer – MMIP). This method produces a multifunctional material which has high selectivity and the ability to isolate the analyte from biological and environmental samples, allowing effective purification from such interferents as proteins and fats. This developing branch of new materials for the preparation and purification of complex sample matrices is an interesting alternative to materials routinely used to date, particularly with regard to the immunosorbents. This paper summarizes recent reports regarding MMIP preparation and their application for purification and isolation of compounds from biological matrices.

Graphical Abstract


[1] Smith F. E., Arsenault, E. A., Microwave-assisted sample preparation in analytical chemistry, Talanta, 1996, 43, 1207-1268. 10.1016/0039-9140(96)01882-6Search in Google Scholar

[2] Barcelo D., Petrovic M., Eljarrat E., Lopez de Alda M.J., Kampioti A., Environmental analysis, In: Heftmann E. (Ed.), Chromatography: Fundamentals and applications of chromatography and related differential migration methods-Part B: Applications, J. Chromatogr. Library, vol. 69B; 6th ed., Elsevier, Amsterdam, 2004. Search in Google Scholar

[3] Buszewski B., Szultka M., Gadzała-Kopciuch R., Sorbent chemistry, evolution, In: Pawliszyn J. (Ed.), Comprehensive sampling and sample preparation, Analytical Techniques for Scientists, Elsevier, Amsterdam, 2012. 10.1016/B978-0-12-381373-2.00040-5Search in Google Scholar

[4] Simpson N. J., Solid-phase extraction: principles, techniques, and applications, CRC Press Taylor & Francis Group, Phillipsburg, New Jersey, 2000. Search in Google Scholar

[5] Chen L., Xu S., Li J., Recent advances in molecular imprinting technology: current status, challenges and highlighted applications, Chem. Soc. Rev. 2011, 40, 2922-2944. Search in Google Scholar

[6] Gadzała-Kopciuch R., Cendrowski K., Cesarz A., Kiełbasa P., Buszewski B., Determination of zearalenone and its metabolites in endometrial cancer by coupled separation techniques, Anal. Bioanal. Chem., 2011, 401, 2069-2078. 10.1007/s00216-011-5206-xSearch in Google Scholar

[7] Ansell R. J., Mosbach K., Magnetic molecularly imprinted polymer beads for drug radioligand binding assay, Analyst, 1998, 123, 1611-1616 . 10.1039/a801903gSearch in Google Scholar

[8] in Vol. 25.09.2015 Search in Google Scholar

[9] Haupt K., Mosbach K., Molecularly imprinted polymers and their use in biomimetic sensors, Chem. Rev., 2000, 100, 2495-2504. 10.1021/cr990099wSearch in Google Scholar

[10] Pardeshi S., Dhodapkar R., Kumar A., Molecularly imprinted microspheres and nanoparticles prepared using precipitation polymerisation method for selective extraction of gallic acid from Emblica officinalis, Food Chem., 2014, 146, 385-398. 10.1016/j.foodchem.2013.09.084Search in Google Scholar

[11] Ho K-C., Yeh W-M., Tung T-S., Liao J-Y., Amperometric detection of morphine based on poly (3, 4-ethylenedioxythiophene) immobilized molecularly imprinted polymer particles prepared by precipitation polymerization, Anal. Chim. Acta, 2005, 542, 90-96. 10.1016/j.aca.2005.02.036Search in Google Scholar

[12] Pérez N., Whitcombe M.J., Vulfson E.N., Molecularly imprinted nanoparticles prepared by core-shell emulsion polymerization, J. Appl. Polym. Sci., 2000, 77, 1851-1859. 10.1002/1097-4628(20000822)77:8<1851::AID-APP23>3.0.CO;2-JSearch in Google Scholar

[13] Chen P-Y., Vittal R., Nien P-C., Liou G-S., Ho K-C., A novel molecularly imprinted polymer thin film as biosensor for uric acid, Talanta, 2010,80,1145-1151. 10.1016/j.talanta.2009.08.041Search in Google Scholar

[14] Herrero-Hernández E., Carabias-Martínez R., Rodríguez-Gonzalo E., Behavior of Phenols and Phenoxyacids on a Bisphenol-A Imprinted Polymer. Application for Selective Solid-Phase Extraction from Water and Urine Samples, Intern. J. Mol. Sci., 2011, 12, 3322-3339. 10.3390/ijms12053322Search in Google Scholar

[15] Qiao J., Wang M., Yan H., Yang G., Dispersive Solid-Phase Extraction Based on Magnetic Dummy Molecularly Imprinted Microspheres for Selective Screening of Phthalates in Plastic Bottled Beverages, J. Agric. Food Chem. 2014, 62, 2782-9. Search in Google Scholar

[16] Hu C., Deng J., Zhao Y., Xia L., Huang K., Ju S., et al. A novel core–shell magnetic nano-sorbent with surface molecularly imprinted polymer coating for the selective solid phase extraction of dimetridazole, Food Chem. 2014, 158, 366-73. Search in Google Scholar

[17] Gao R., Kong X., Wang X., He X., Chen L., Zhang Y., Preparation and characterization of uniformly sized molecularly imprinted polymers functionalized with core-shell magnetic nanoparticles for the recognition and enrichment of protein, J. Mater. Chem. 2011, 21, 17863-71. Search in Google Scholar

[18] Bouri M., Lerma-García M.J., Salghi R., Zougagh M., Ríos A., Selective extraction and determination of catecholamines in urine samples by using a dopamine magnetic molecularly imprinted polymer and capillary electrophoresis, Talanta, 2012, 99, 897-903. 10.1016/j.talanta.2012.07.053Search in Google Scholar PubMed

[19] Dramou P., Zuo P., He H., Pham-Huy L.A., Zou W., Xiao D., et al. Development of novel amphiphilic magnetic molecularly imprinted polymers compatible with biological fluids for solid phase extraction and physicochemical behavior study, J. Chromatogr. A, 2013, 1317, 110-20. 10.1016/j.chroma.2013.07.075Search in Google Scholar PubMed

[20] Fan L., Zhang Y., Li X., Luo C., Lu F., Qiu H., Removal of alizarin red from water environment using magnetic chitosan with Alizarin Red as imprinted molecules, Coll. Surf. B, 2012, 91, 250-257. 10.1016/j.colsurfb.2011.11.014Search in Google Scholar PubMed

[21] Liu J., Wang W., Xie Y., Huang Y., Liu Y., Liu X., et al., A novel polychloromethylstyrene coated superparamagnetic surface molecularly imprinted core-shell nanoparticle for bisphenol A, J. Mater. Chem. 2011, 21, 9232-9238. Search in Google Scholar

[22] Chen L., Liu J., Zeng Q., Wang H., Yu A., Zhang H., et al., Preparation of magnetic molecularly imprinted polymer for the separation of tetracycline antibiotics from egg and tissue samples, J. Chromatogr. A, 2009, 1216, 3710-3719. 10.1016/j.chroma.2009.02.044Search in Google Scholar PubMed

[23] Su X., Li X., Li J., Liu M., Lei F., Tan X., et al., Synthesis and characterization of core–shell magnetic molecularly imprinted polymers for solid-phase extraction and determination of Rhodamine B in food, Food Chem., 2015, 171, 292-297. 10.1016/j.foodchem.2014.09.024Search in Google Scholar PubMed

[24] Hu Y., Li Y., Liu R., Tan W., Li G., Magnetic molecularly imprinted polymer beads prepared by microwave heating for selective enrichment of β-agonists in pork and pig liver samples, Talanta, 2011, 84, 462-470. 10.1016/j.talanta.2011.01.045Search in Google Scholar PubMed

[25] Zhang Z., Yang X., Chen X., Zhang M., Luo L., Peng M., et al., Novel magnetic bovine serum albumin imprinted polymers with a matrix of carbon nanotubes, and their application to protein separation, Anal. Bioanal. Chem., 2011, 401, 2855-2863. 10.1007/s00216-011-5373-9Search in Google Scholar PubMed

[26] Ma G., Chen L., Development of magnetic molecularly imprinted polymers based on carbon nanotubes – Application for trace analysis of pyrethroids in fruit matrices, J. Chromatogr. A, 2014, 1329, 1-9. 10.1016/j.chroma.2013.12.079Search in Google Scholar PubMed

[27] Wang X., Pan J., Guan W., Zou X., Huo P., Yan Y., et al., Selective recognition of sesamol using molecularly imprinted polymers containing magnetic wollastonite, J. Sep. Sci. 2011, 34, 3287-3294. Search in Google Scholar

[28] Pan J., Xu L., Dai J., Li X., Hang H., Huo P., et al., Magnetic molecularly imprinted polymers based on attapulgite/Fe3O4 particles for the selective recognition of 2,4-dichlorophenol, Chem. Eng. J., 2011,174, 68-75. 10.1016/j.cej.2011.08.046Search in Google Scholar

[29] You Q., Zhang Y., Zhang Q., Guo J., Huang W., Shi S., et al., High-capacity thermo-responsive magnetic molecularly imprinted polymers for selective extraction of curcuminoids, J. Chromatogr. A 2014, 1354, 1-8. 10.1016/j.chroma.2014.05.040Search in Google Scholar PubMed

[30] Ji Y., Yin J., Xu Z., Zhao C., Huang H., Zhang H., et al., Preparation of magnetic molecularly imprinted polymer for rapid determination of bisphenol A in environmental water and milk samples, Anal. Bioanal. Chem. 2009, 395, 1125-33. Search in Google Scholar

[31] Pawliszyn J., Sampling and sample preparation for field and laboratory, fundamentals and new directions in sample preparation, Elsevier Science B.V., 2002. Search in Google Scholar

[32] Qiao L., Gan N., Hu F., Wang D., Lan H., Li T., et al., Magnetic nanospheres with a molecularly imprinted shell for the preconcentration of diethylstilbestrol, Microchim. Acta, 2014, 181, 1341-1351. 10.1007/s00604-014-1257-ySearch in Google Scholar

[33] Rao W., Cai R., Zhang Z., Yin Y., Long F., Fu X., Fast separation and determination of erythromycin with magnetic imprinted solid extraction coupled with high performance liquid chromatography, RSC Adv., 2014, 4, 18503-18511. 10.1039/c3ra47249cSearch in Google Scholar

[34] Liu Y., Huang Y., Liu J., Wang W., Liu G., Zhao R., Superparamagnetic surface molecularly imprinted nanoparticles for water-soluble pefloxacin mesylate prepared via surface initiated atom transfer radical polymerization and its application in egg sample analysis, J. Chromatogr. A, 2012, 1246, 15-21. 10.1016/j.chroma.2012.01.045Search in Google Scholar PubMed

[35] Xu S., Guo C., Li Y., Yu Z., Wei C., Tang Y., Methyl parathion imprinted polymer nanoshell coated on the magnetic nanocore for selective recognition and fast adsorption and separation in soils, J. Haz. Maters 2014, 264, 34-41. 10.1016/j.jhazmat.2013.10.060Search in Google Scholar PubMed

[36] Qi S., Zhang H., Zhu Q., Chen H., Dong Y., Zhou L., Ren C., Chen X., Off-line hyphenation of molecularly imprinted magnetic nanoparticle-based extraction with large volume sample stacking capillary electrophoresis for high-sensitivity detection of trace chloro-phenols, Anal. Meth., 2014, 6, 1219-1226. 10.1039/c3ay41606bSearch in Google Scholar

[37] Madrakian T., Ahmadi M., Afkhami A., Soleimani M., Selective solid-phase extraction of naproxen drug from human urine samples using molecularly imprinted polymer-coated magnetic multi-walled carbon nanotubes prior to its spectrofluorometric determination, Analyst, 2013, 138, 4542-4549. 10.1039/c3an00686gSearch in Google Scholar PubMed

[38] Karimi M., Aboufazeli F., Zhad HRLZ., Sadeghi O., Najafi E., Determination of Sulfonamides in Chicken Meat by Magnetic Molecularly Imprinted Polymer Coupled to HPLC-UV, Food Anal. Meth., 2014, 7, 73-80. 10.1007/s12161-013-9600-1Search in Google Scholar

[39] Azodi-Deilami S., Najafabadi A.H., Asadi E., Abdouss M., Kordestani D., Magnetic molecularly imprinted polymer nanoparticles for the solid-phase extraction of paracetamol from plasma samples, followed its determination by HPLC, Microchim. Acta, 2014 , 181, 1823-1832. 10.1007/s00604-014-1230-9Search in Google Scholar

[40] Behbahani M., Bagheri S., Amini M.M., Sadeghi Abandansari H., Reza Moazami H., Bagheri A., Application of a magnetic molecularly imprinted polymer for the selective extraction and trace detection of lamotrigine in urine and plasma samples, J. Sep. Sci., 2014, 37, 1610-1616. 10.1002/jssc.201400188Search in Google Scholar PubMed

[41] Zhang Z., Tan W., Hu Y., Li G., Simultaneous determination of trace sterols in complicated biological samples by gas chromatography–mass spectrometry coupled with extraction using β-sitosterol magnetic molecularly imprinted polymer beads, J. Chromatogr. A., 2011, 1218, 4275-4283. 10.1016/j.chroma.2011.05.022Search in Google Scholar PubMed

[42] Wang S., Wang R., Wu X., Wang Y., Xue C., Wu J., et al., Magnetic molecularly imprinted nanoparticles based on dendritic-grafting modification for determination of estrogens in plasma samples, J. Chromatogr., B 2012, 905, 105-112. 10.1016/j.jchromb.2012.08.009Search in Google Scholar PubMed

[43] Azodi-Deilami S., Abdouss M., Asadi E., Hassani Najafabadi A., Sadeghi S., Farzaneh S., Asadi S., Magnetic molecularly imprinted polymer nanoparticles coupled with high performance liquid chromatography for solid‐phase extraction of carvedilol in serum samples, J. Appl. Polym. Sci., 2014, 131, 41209 (1-10). 10.1002/app.41209Search in Google Scholar

[44] Lan H., Gan N., Pan D., Hu F., Li T., Long N., et al., Development of a novel magnetic molecularly imprinted polymer coating using porous zeolite imidazolate framework-8 coated magnetic iron oxide as carrier for automated solid phase microextraction of estrogens in fish and pork samples, J. Chromatogr. A, 2014, 1365,35-44. 10.1016/j.chroma.2014.08.096Search in Google Scholar PubMed

[45] Du X., Lin S., Gan N., Chen X., Cao Y., Li T, et al., Multi‐walled carbon nanotube modified dummy‐template magnetic molecularly imprinted microspheres as solid‐phase extraction material for the determination of polychlorinated biphenyls in fish, J. Sep. Sci., 2014, 37, 1591-1600. 10.1002/jssc.201400146Search in Google Scholar PubMed

[46] Lin S., Gan N., Zhang J., Chen X., Cao Y., Li T., A novel reductive graphene oxide-based magnetic molecularly imprinted poly(ethylene-co-vinyl alcohol) polymers for the enrichment and determination of polychlorinated biphenyls in fish samples, J. Mol. Recogn. 2015, 28, 359-368. Search in Google Scholar

[47] Zhang Y., Li Y., Hu Y., Li G., Chen Y., Preparation of magnetic indole-3-acetic acid imprinted polymer beads with 4-vinylpyridine and β-cyclodextrin as binary monomer via microwave heating initiated polymerization and their application to trace analysis of auxins in plant tissues, J. Chromatogr. A, 2010, 1217, 7337-7344. 10.1016/j.chroma.2010.09.059Search in Google Scholar PubMed

[48] Madrakian T., Afkhami A., Mahmood-Kashani H., Ahmadi M., Superparamagnetic surface molecularly imprinted nanoparticles for sensitive solid-phase extraction of tramadol from urine samples, Talanta, 2013, 105, 255-261. 10.1016/j.talanta.2012.12.039Search in Google Scholar PubMed

[49] Zou W., Dramou P., Ai Pham-Huy L., Zhang K., He J., Pham-Huy C., et al., Simultaneous extraction of anthracyclines from urine using water-compatible magnetic nanoparticles with a dummy template coupled with high performance liquid chromatography, Anal. Meth., 2014, 6, 4421-4429. 10.1039/C4AY00232FSearch in Google Scholar

[50] Duan H., Li L., Wang X., Wang Y., Li J., Luo C., A sensitive and selective chemiluminescence sensor for the determination of dopamine based on silanized magnetic graphene oxide-molecularly imprinted polymer, Spectrochim. Acta Part A: Mol. Biomol. Spectrosc., 2015, 139, 374-379. 10.1016/j.saa.2014.12.051Search in Google Scholar PubMed

[51] Turner N.W., Jeans C.W., Brain K.R., Allender C.J., Hlady V., Britt D.W., From 3D to 2D: A review of the molecular imprinting of proteins, Biotechnol. Progr., 2006, 22, 1474-1489. 10.1002/bp060122gSearch in Google Scholar

[52] Kan X., Zhao Q., Shao D., Geng Z., Wang Z., Zhu J-J., Preparation and recognition properties of bovine hemoglobin magnetic molecularly imprinted polymers, J. Phys. Chem. B, 2010, 114, 3999-4004. 10.1021/jp910060cSearch in Google Scholar PubMed

[53] Gai Q-Q., Qu F., Zhang T., Zhang Y-K., The preparation of bovine serum albumin surface-imprinted superparamagnetic polymer with the assistance of basic functional monomer and its application for protein separation, J. Chromatogr. A, 2011, 1218, 3489-3495. 10.1016/j.chroma.2011.03.069Search in Google Scholar PubMed

Received: 2015-1-8
Accepted: 2015-8-30
Published Online: 2015-10-14

© 2015 Katarzyna Kwaśniewska et al.

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

Downloaded on 30.11.2022 from
Scroll Up Arrow