Harnessing Molecularly Imprinted Polymers in Surface Plasmon Resonance and Quartz Crystal Microbalance for 17α-Ethinyl Estradiol Detection: A Comparative Study

Year 2024, Volume: 52 Issue: 6, 319 - 328, 12.12.2024

Meltem Okan , Memed Duman

https://doi.org/10.15671/hjbc.1533439

Abstract

Estradiol is a critical hormone for reproductive health in females and males both. Monitoring estradiol levels can aid in diagnosing various conditions such as menopause, infertility and even some cancers. Estradiol is also a type of endocrine-disrupting chemical (EDC) that has diverse impacts on ecosystems as well as human health. In can enter the environment through agricultural runoff, sewage and industrial effluents. Adapting both perspectives, establishing biosensors for estradiol detection becomes crucial. In this study, 17-α-ethinylestradiol imprinted polymeric nanoparticles (17EE-MIPs) were synthesized using mini-emulsion polymerization and characterized. Prior to consecutive Quartz Crystal Microbalance (QCM) based analysis, 17EE-MIPs were tested with Surface Plasmon Resonance (SPR), from which the equilibrium and binding kinetic analysis as well as equilibrium isotherm models were derived. Freundlich model was found to best represent the 17EE-MIP based SPR platform. Next, 17EE-MIPs were covalently attached on the QCM crystal and different 17EE concentrations were tested consecutively without regeneration steps. Both systems yielded very high linearity with R2 values of 0.9798 and 0.9895 for SPR and QCM, respectively. The limit of detection (LOD) of the SPR and QCM sensor were calculated as 11.57 and 1.335 µM, respectively. Here, two sensing platforms were employed to crosscheck the performance of the 17EE-MIPs, both verified to respond to low concentrations of 17EE with high consistency.

Keywords

17-alpha-ethinylestradiol, Molecularly Imprinted Polymers, Surface Plasmon Resonance, Quartz Crystal Microbalance, Mass Sensor

Supporting Institution

TÜBİTAK

Project Number

113Z222

References

• P.P. Waifalkar, D. Noh, P. Derashri, S. Barage, E. Oh, Role of estradiol hormone in human life and electrochemical aptasensing of 17β-estradiol: A review, MDPI, (2022).
• H. Seeger, F.P. Armbruster, A.O. Mueck, T.H. Lippert, The effect of estradiol on urodilatin production in postmenopausal women, (1998).
• M.K.L. Coelho, D.N. da Silva, A.C. Pereira, Development of electrochemical sensor based on carbonaceous and metal phthalocyanines materials for determination of ethinyl estradiol, Chemosensors, 7 (2019) Sep.
• W. Rosner, S.E. Hankinson, P.M. Sluss, H.W. Vesper, M.E. Wierman, Challenges to the measurement of estradiol: An endocrine society position statement, J. Clin. Endocrinol. Metab., 98 (2013) 1376–1387.
• X. Yang et al., Occurrence and distribution of natural and synthetic progestins, androgens, and estrogens in soils from agricultural production areas in China, Sci. Total Environ., 751 (2021).
• Y.Q. Liang et al., The progestin norethindrone alters growth, reproductive histology and gene expression in zebrafish (Danio rerio), Chemosphere, 242 (2020).
• A. Di Nisio et al., Perfluorooctanoic acid alters progesterone activity in human endometrial cells and induces reproductive alterations in young women, Chemosphere, 242 (2020).
• J.O. Ojoghoro, M.D. Scrimshaw, J.P. Sumpter, Steroid hormones in the aquatic environment, Elsevier B.V., (2021).
• L. Martín-Pozo, M.D.C. Gómez-Regalado, I. Moscoso-Ruiz, A. Zafra-Gómez, Analytical methods for the determination of endocrine disrupting chemicals in cosmetics and personal care products: A review, NLM (Medline), (2021).
• Y. Yang, J. Chen, Y.P. Shi, Determination of diethylstilbestrol in milk using carbon nanotube-reinforced hollow fiber solid-phase microextraction combined with high-performance liquid chromatography, Talanta, 97 (2012) 222–228.
• R. Mesa, A. Kabir, V. Samanidou, K.G. Furton, Simultaneous determination of selected estrogenic endocrine disrupting chemicals and bisphenol A residues in whole milk using fabric phase sorptive extraction coupled to HPLC-UV detection and LC-MS/MS, J. Sep. Sci., 42 (2019) 598–608, Jan.
• H. Zhang, Z. Cui, B. Yang, D. Fang, Y. Liu, Z. Wang, Integrated recombinant gene yeast bioassay and HPLC-MS analysis for detection of low-dose multi-component residue of hormone-like compounds in environment, Sci. Total Environ., 773 (2021) Jun.
• L. Chen, S. Xu, J. Li, Recent advances in molecular imprinting technology: Current status, challenges and highlighted applications, Chem. Soc. Rev., 40 (2011) 2922–2942, Apr.
• G. Vasapollo et al., Molecularly imprinted polymers: Present and future prospective, (2011) Sep.
• B.T.S. Bui, K. Haupt, Molecularly imprinted polymers: Synthetic receptors in bioanalysis, (2010) Nov.
• Y. Hoshino et al., Recognition, neutralization, and clearance of target peptides in the bloodstream of living mice by molecularly imprinted polymer nanoparticles: A plastic antibody, J. Am. Chem. Soc., 132 (2010) 6644–6645, May.
• Y. Ge, A.P.F. Turner, Molecularly imprinted sorbent assays: Recent developments and applications, (2009) Aug.
• D. Udomsap et al., Electrochemical molecularly imprinted polymers as material for pollutant detection, Mater. Today Commun., 17 (2018) 458–465, Dec.
• S. Lépinay, K. Kham, M.C. Millot, B. Carbonnier, In-situ polymerized molecularly imprinted polymeric thin films used as sensing layers in surface plasmon resonance sensors: Mini-review focused on 2010–2011, (2012) May.
• J. Homola, M. Piliarik, Surface Plasmon Resonance (SPR) Sensors, in Surface Plasmon Resonance Based Sensors, Springer, (2006) 45–67, ch. 2.
• J. Homola, Present and future of surface plasmon resonance biosensors, (2003) Oct.
• D. Battal, S. Akgönüllü, M.S. Yalcin, H. Yavuz, A. Denizli, Molecularly imprinted polymer-based quartz crystal microbalance sensor system for sensitive and label-free detection of synthetic cannabinoids in urine, Biosens. Bioelectron., 111 (2018) 10–17, Jul.
• S. Klangprapan, B. Choke-arpornchai, P.A. Lieberzeit, K. Choowongkomon, Sensing the classical swine fever virus with molecularly imprinted polymer on quartz crystal microbalance, Heliyon, 6 (2020) Jun.
• A.G. Ayankojo, J. Reut, R. Boroznjak, A. Öpik, V. Syritski, Molecularly imprinted poly(meta-phenylenediamine) based QCM sensor for detecting amoxicillin, Sens. Actuators B Chem., 258 (2018) 766–774, Apr.
• U. Latif, J. Qian, S. Can, F.L. Dickert, Biomimetic receptors for bioanalyte detection by quartz crystal microbalances—from molecules to cells, Sensors (Switzerland), 14 (2014) 23419–23438, Dec.
• J. Liu et al., Study on the preparation of estrone molecularly imprinted polymers and their application in a quartz crystal microbalance sensor via a computer-assisted design, Int. J. Mol. Sci., 23 (2022) May.
• E. Sari, R. Üzek, M. Duman, A. Denizli, Fabrication of surface plasmon resonance nanosensor for the selective determination of erythromycin via molecularly imprinted nanoparticles, Talanta, 150 (2016) 607–614, Apr.
• G. Aylaz, M. Andaç, Affinity-recognition-based gravimetric nanosensor for equilin detection, Chemosensors, 10 (2022) May.
• A. Minopoli et al., LSPR-based colorimetric immunosensor for rapid and sensitive 17β-estradiol detection in tap water, Sens. Actuators B Chem., 308 (2020) Apr.
• A. Makaraviciute, A. Ramanaviciene, Site-directed antibody immobilization techniques for immunosensors, (2013) Dec.
• X. Wang et al., 17β-estradiol biosensors based on different bioreceptors and their applications, Front. Media SA, (2024).
• H.H. Nguyen, S.H. Lee, U.J. Lee, C.D. Fermin, M. Kim, Immobilized enzymes in biosensor applications, MDPI AG, (2019) Jan.
• A.N. Jijana, Polyaniline entrapped water-dispersible 3MPA-ZnSe quantum dots and their application for the development of an enzymatic electrochemical nanobiosensor for the detection of 17β-estradiol, an endocrine-disrupting compound, Appl. Biochem. Biotechnol., 195 (2023) 3425–3455, May.
• D. Futra, L.Y. Heng, M.Z. Jaapar, A. Ulianas, K. Saeedfar, T.L. Ling, A novel electrochemical sensor for 17β-estradiol from molecularly imprinted polymeric microspheres and multi-walled carbon nanotubes grafted with gold nanoparticles, Anal. Methods, 8 (2016) 1381–1389, Jan.
• D.N. da Silva, A.C. Pereira, Development of a chemically modified electrode with magnetic molecularly imprinted polymer (MagMIP) for 17β-estradiol determination in water samples, Electrochem., 3 (2022) 809–819, Dec.
• D.N. da Silva, A.C. Pereira, An electrochemical sensor modified with a molecularly imprinted polymer and carbon black for 17β-estradiol detection, Anal. Methods, 14 (2022) 1208–1213, Mar.