Abstract
Ethinylestradiol (EE2) is considered an emerging pollutant with high capacity for endocrine disruption. Thus, methodologies and materials applied to the monitoring of this compound are relevant to minimize environmental impacts. In this work, a synthetic route for molecularly imprinted polymers (MIPs) was proposed, employing EE2 and methacrylic acid as template molecule and functional monomer, respectively. The synthesized material showed effective “molecular memory”, leading to selective molecular rebinding, when compared to its reference polymer: non-imprinted polymer (NIP). These results, from MIP versus NIP, were evidenced by the characterization by high-performance liquid chromatography, where the peak area was smaller for the MIP, which indicates its greater selective adsorption; and differential pulse voltammetry, where the electrochemical signal was higher for the electrode configured with MIP. Therefore, two distinct methodologies proved the presence of selective sites along the polymer matrix. For the structure of the MIP, the SEM confirms an irregular particle size, giving the material a low uniformity, and an apparent roughness. However, the IV-TF confirms the presence of different functional groups along the polymer matrix, which may contribute to the functionality of the selective sites. Given the effective synthetic proposal and the characterization of IPM, it emerges as a material potential for application in EE2 monitoring. The present work contributed with two innovations; the implementation of the evaluation of the analytical response of the washing water of the MIP using an electrochemical technique (VPD) soon shows the important process of removal of the model molecule and the availability of the selective sites; and the synthesis of an MIP for EE2.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Alizadeh T, Azizi S (2016) Graphene/graphite paste electrode incorporated with molecularly imprinted polymer nanoparticles as a novel sensor for differential pulse voltammetry determination of fluoxetine. Biosens Bioelectron 81:198–206. https://doi.org/10.1016/j.bios.2016.02.052
Alizadeh T et al (2009) A novel high selective and sensitive para-nitrophenol voltammetric sensor, based on a molecularly imprinted polymer–carbon paste electrode. Talanta 79:1197–1203. https://doi.org/10.1016/j.talanta.2009.02.051
Ansari S, Karimi M (2017) Recent progress, challenges and trends in trace determination of drug analysis using molecularly imprinted solid-phase microextraction technology. Talanta 164:612–625. https://doi.org/10.1016/j.talanta.2016.11.007
Ansell RJ (2004) Molecularly imprinted polymers in pseudoimmunoassay. J Chromatogr B 804:151–165. https://doi.org/10.1016/j.jchromb.2004.02.022
Chen L et al (2011) Recent advances in molecular imprinting technology: current status, challenges and highlighted applications. Chem Soc Rev 40:2922–2942. https://doi.org/10.1039/c0cs00084a
Chen L et al (2016) Molecular imprinting: perspectives and applications. Chem Soc Rev 45:2137–2211. https://doi.org/10.1039/C6CS00061D
Coelho MKL et al (2016) Development and application of electrochemical sensor based on molecularly imprinted polymer and carbon nanotubes for the determination of carvedilol. Chemosensors 4:1–15. https://doi.org/10.3390/chemosensors4040022
Doue M et al (2012) Molecularly imprinted polymer applied to the selective isolation of urinary steroid hormones: an efficient tool in the control of natural steroid hormones abuse in cattle. J Chromatogr A 1270:51–61. https://doi.org/10.1016/j.chroma.2012.10.067
Erdossy J et al (2016) Electrosynthesized molecularly imprinted polymers for protein recognition. TrAC-Trends Anal Chem 79:179–190. https://doi.org/10.1016/j.trac.2015.12.018
Figueiredo EC et al (2008) Impressão molecular: uma estratégia promissora na elaboração de matrizes para a liberação controlada de fármacos. Revista brasileira de ciências farmacêuticas 44:361–375. https://doi.org/10.1590/S1516-93322008000300005
Gadzala-Kopciuch R, Ricanyova J, Buszewskia B (2009) Isolation and detection of steroids from human urine by molecularly imprinted solid-phase extraction and liquid chromatography. J Chromatogr B 877:1177–1184. https://doi.org/10.1016/j.jchromb.2009.03.008
Gholivand MB, Torkashvand M (2011) A novel high selective and sensitive metronidazole voltammetric sensor based on a molecularly imprinted polymer–carbon paste electrode. Talanta 84:905–912. https://doi.org/10.1016/j.talanta.2011.02.022
Granado VLV et al (2012) Design of molecularly imprinted polymers for diphenylamine sensing. Talanta 94:133–139. https://doi.org/10.1016/j.talanta.2012.03.007
Huang YP et al (2009) Recent developments of molecularly imprinted polymer in CEC. Electrophoresis 30:155–162. https://doi.org/10.1002/elps.200800410
Jiang TH et al (2009) Molecularly imprinted solid-phase extraction for the selective determination of 17 beta-estradiol in fishery samples with high performance liquid chromatography. Talanta 78:442–447. https://doi.org/10.1016/j.talanta.2008.11.047
Li J et al (2015) One-pot synthesis of magnetic molecularly imprinted microspheres by RAFT precipitation polymerization for the fast and selective removal of 17β-estradiol. RSC Adv 5:10611–10618. https://doi.org/10.1039/c4ra11177j
Liang YM et al (2017) High sensitive and selective graphene oxide/molecularly imprinted polymer electrochemical sensor for 2,4-dichlorophenol in water. Sens Actuators B Chem 240:1330–1335. https://doi.org/10.1016/j.snb.2016.08.137
Liu ZH et al (2015) Sample-preparation methods for direct and indirect analysis of natural estrogens. Trac-Trends Anal Chem 64:149–164. https://doi.org/10.1016/j.trac.2014.09.003
Ming WN et al (2017) Magnetic molecularly imprinted polymers for the fluorescent detection of trace 17 beta-estradiol in environmental water. Sen Actuators B Chem 238:1309–1315. https://doi.org/10.1016/j.snb.2016.09.111
Motghare RV et al (2015) Voltammetric determination of uric acid based on molecularly imprinted polymer modified carbon paste electrode. Electroanalysis 27:825–832. https://doi.org/10.1002/elan.201400579
Muna GW et al (2011) Electrocatalytic oxidation of estrogenic phenolic compounds at a nickel-modified glassy carbon electrode. Electroanalysis 23:2915–2924. https://doi.org/10.1002/elan.201100406
Pauling L (1940) Theory of the structure and process offormation of antibodies. J Am Chem Soc 62:2643–2657. https://doi.org/10.1021/ja01867a018
Piscopo L et al (2002) Uniformly sized molecularly imprinted polymers (MIPs) for 17 beta-estradiol. Macromol Chem Phys 203:1532–1538. https://doi.org/10.1002/1521-3935(200207)203:10/11
Rachkov A et al (2000) Fluorescence detection of beta-estradiol using a molecularly imprinted polymer. Anal Chim Acta 405:23–29. https://doi.org/10.1016/S0003-2670(99)00743-6
Sadeghi S et al (2012) Electroanalytical determination of sulfasalazine in pharmaceutical and biological samples using molecularly imprinted polymer modified carbon paste electrode. Sens Actuators B Chem 168:336–344. https://doi.org/10.1016/j.snb.2012.04.031
Shi Y et al (2011) Selective determination of trace 17 beta-estradiol in dairy and meat samples by molecularly imprinted solid-phase extraction and HPLC. Food Chem 126:1916–1925. https://doi.org/10.1016/j.foodchem.2010.12.020
Stuart M et al (2012) Review of risk from potential emerging contaminants in UK groundwater. Sci Total Environ 416:1–21. https://doi.org/10.1016/j.scitotenv.2011.11.072
Teixeira T et al (2005) Biomimetic polymers in analytical chemistry. Part 1: preparation and applications of MIP (Molecularly Imprinted Polymers) in extraction and separation techniques. Quimica Nova 28:1076–1086. https://doi.org/10.1590/S0100-40422005000600024
Verlicchi P et al (2010) Hospital effluents as a source of emerging pollutants: an overview of micropollutants and sustainable treatment options. J Hydrol 389:416–428. https://doi.org/10.1016/j.jhydrol.2010.06.005
Viveiros R et al (2017) Green approach on the development of lock-and-key polymers for API purification. Chem Eng J 308:229–239. https://doi.org/10.1016/j.cej.2016.09.040
Viveiros R et al (2018) Green strategies for molecularly imprinted polymer development. Polymers 10:306. https://doi.org/10.3390/polym10030306
Wang X et al (2014) Novel monodisperse molecularly imprinted shell for estradiol based on surface imprinted hollow vinyl-SiO2 particles. Talanta 124:7–13. https://doi.org/10.1016/j.talanta.2014.02.040
Wei ST, Molinelli A, Mizaikoff B (2006) Molecularly imprinted micro and nanospheres for the selective recognition of 17 beta-estradiol. Biosens Bioelectron 21:1943–1951. https://doi.org/10.1016/j.bios.2005.09.017
Wong A et al (2015) Development of an electrochemical sensor modified with MWCNT-COOH and MIP for detection of diuron. Electrochim Acta 182:122–130. https://doi.org/10.1016/j.electacta.2015.09.054
Xiong H et al (2018) Switchable zipper-like thermoresponsive molecularly imprinted polymers for selective recognition and extraction of estradiol. Talanta 176:187–194. https://doi.org/10.1016/j.talanta.2017.08.019
Yadav SK et al (2013) A review on determination of steroids in biological samples exploiting nanobio-electroanalytical methods. Anal Chim Acta 762:14–24. https://doi.org/10.1016/j.aca.2012.11.037
Acknowledgements
We thank FAPEMIG, CAPES, CNPQ, and Rede Mineira de Química for the continuous support of our research.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Pereira, A.C., Braga, G.B., Oliveira, A.E.F. et al. Synthesis and characterization of molecularly imprinted polymer for ethinylestradiol. Chem. Pap. 73, 141–149 (2019). https://doi.org/10.1007/s11696-018-0557-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11696-018-0557-9