{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T03:29:20Z","timestamp":1760239760483,"version":"build-2065373602"},"reference-count":41,"publisher":"MDPI AG","issue":"24","license":[{"start":{"date-parts":[[2020,12,20]],"date-time":"2020-12-20T00:00:00Z","timestamp":1608422400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia (FCT), Portugal","award":["UID\/FIS\/00068\/2019","Bilateral Project entitled \u201cDete\u00e7\u00e3o de Estrog\u00e9nio- um Contaminante Emergente - em Corpos H\u00eddricos\u201d within the scope of \u201cCoopera\u00e7\u00e3o Transnacional_FCT (Portugal)-CAPES (Brazil) 2018\u201d","PD\/BD\/142767\/2018"],"award-info":[{"award-number":["UID\/FIS\/00068\/2019","Bilateral Project entitled \u201cDete\u00e7\u00e3o de Estrog\u00e9nio- um Contaminante Emergente - em Corpos H\u00eddricos\u201d within the scope of \u201cCoopera\u00e7\u00e3o Transnacional_FCT (Portugal)-CAPES (Brazil) 2018\u201d","PD\/BD\/142767\/2018"]}]},{"name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia (FCT), Portugal,","award":["PTDC\/FIS-NAN\/0909\/2014"],"award-info":[{"award-number":["PTDC\/FIS-NAN\/0909\/2014"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Sensors"],"abstract":"<jats:p>Hormones have a harmful impact on the environment and their detection in water bodies is an urgent matter. In this work, we present and analyze a sensor device able to detect traces of the synthetic hormone 17\u03b1-ethinylestradiol (EE2) below 10\u22129 M in media of different complexities, namely, ultrapure, mineral and tap waters. This device consists of solid supports with interdigitated electrodes without and with a polyethylenimine (PEI) and poly (sodium 4-styrenesulfonate) (PSS) layer-by-layer film deposited on it. Device response was evaluated through capacitance, loss tangent and electric modulus spectra and the data were analyzed by principal component analysis method. While the three types of spectra were demonstrated to be able to clearly discriminate the different media, loss tangent spectra allow for the detection of EE2 concentration, with a sensitivity of \u22120.072 \u00b1 0.009 and \u22120.44 \u00b1 0.03 per decade of concentration, for mineral and tap water, respectively. Detection limits values were found to be lower than the ones present in the literature and presenting values of 8.6 fM (2.6 pg\/L) and of 7.5 fM (22.2 pg\/L) for tap and mineral waters, respectively. Moreover, the obtained response values follow the same behavior with EE2 concentration in any medium, meaning that loss tangent spectra allow the quantification of EE2 concentration in aqueous complex matrices.<\/jats:p>","DOI":"10.3390\/s20247324","type":"journal-article","created":{"date-parts":[[2020,12,21]],"date-time":"2020-12-21T01:01:08Z","timestamp":1608512468000},"page":"7324","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Detecting Traces of 17\u03b1-Ethinylestradiol in Complex Water Matrices"],"prefix":"10.3390","volume":"20","author":[{"given":"Paulo M","family":"Zagalo","sequence":"first","affiliation":[{"name":"CEFITEC, Departamento de F\u00edsica, Faculdade de Ci\u00eancias e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9665-7610","authenticated-orcid":false,"given":"Paulo A","family":"Ribeiro","sequence":"additional","affiliation":[{"name":"CEFITEC, Departamento de F\u00edsica, Faculdade de Ci\u00eancias e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4710-0693","authenticated-orcid":false,"given":"Maria","family":"Raposo","sequence":"additional","affiliation":[{"name":"CEFITEC, Departamento de F\u00edsica, Faculdade de Ci\u00eancias e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2020,12,20]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"2165","DOI":"10.1002\/etc.5620201005","article-title":"Characterization of estrogenic compounds in water samples collected from United Kingdom estuaries","volume":"20","author":"Thomas","year":"2001","journal-title":"Environ. Toxicol. Chem."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"3649","DOI":"10.1021\/es035342u","article-title":"A model to estimate influent and effluent concentrations of estradiol, estrone, and ethinylestradiol at sewage treatment works","volume":"38","author":"Johnson","year":"2004","journal-title":"Environ. Sci. Technol."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"531","DOI":"10.1897\/03-192","article-title":"Sorption of steroid estrogens to soils and sediments","volume":"23","author":"Yu","year":"2004","journal-title":"Environ. Toxicol. Chem."},{"key":"ref_4","doi-asserted-by":"crossref","unstructured":"Wang, Y., Hu, L., Wang, Q., Lu, G., and Li, Y. (2014). Adsorption Behaviors of 17 \u03b1-ethinylestradiol in sediment-water system in northern taihu lake, China. Sci. World J.","DOI":"10.1155\/2014\/371075"},{"key":"ref_5","doi-asserted-by":"crossref","unstructured":"Clouzot, L., Haguenauer, C., and Vanrolleghem, P.A. (2020). An extended ecosystem model for understanding EE2 indirect effects on a freshwater food web and its ecosystem function resilience. Water, 12.","DOI":"10.3390\/w12061736"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"385","DOI":"10.1016\/j.ecoenv.2007.01.009","article-title":"Daphnia magna responses to a vertebrate estrogen receptor agonist and an antagonist: A multigenerational study","volume":"67","author":"Clubbs","year":"2007","journal-title":"Ecotoxicol. Environ. Saf."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"107","DOI":"10.1016\/j.envint.2016.12.010","article-title":"Environmental impact of estrogens on human, animal and plant life: A critical review","volume":"99","author":"Adeel","year":"2017","journal-title":"Environ. Int."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"4705","DOI":"10.1021\/acs.est.7b00606","article-title":"Re-evaluating the Significance of Estrone as an Environmental Estrogen","volume":"51","author":"Ankley","year":"2017","journal-title":"Environ. Sci. Technol."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"12016","DOI":"10.3390\/ijerph121012016","article-title":"Simultaneous degradation of estrone, 17\u03b2-estradiol and 17\u03b1-ethinyl estradiol in an aqueous UV\/H2o2system","volume":"12","author":"Ma","year":"2015","journal-title":"Int. J. Environ. Res. Public Health"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"447","DOI":"10.1007\/s00128-016-1873-9","article-title":"Estrogen as an Environmental Pollutant","volume":"97","author":"Shore","year":"2016","journal-title":"Bull. Environ. Contam. Toxicol."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"777","DOI":"10.1080\/01496395.2011.644618","article-title":"Removal of Estrone (E1), 17\u03b2-Estradiol (E2) and 17\u03b1-Ethinylestradiol (EE2) During Soil Aquifer Treatment of a Model Wastewater","volume":"47","author":"Essandoh","year":"2012","journal-title":"Sep. Sci. Technol."},{"key":"ref_12","doi-asserted-by":"crossref","unstructured":"Mukhopadhyay, S., and Mason, A. (2013). Emerging Organic Contaminants in Groundwater. Smart Sensors for Real-Time Water Quality Monitoring. Smart Sensors, Measurement and Instrumentation, Springer.","DOI":"10.1007\/978-3-642-37006-9"},{"key":"#cr-split#-ref_13.1","unstructured":"Vella, K. (2018). Commission Implementing Decision"},{"key":"#cr-split#-ref_13.2","unstructured":"(EU) 2018\/840 of 5 June 2018. Off. J. Eur. Union, 1-4. Available online: http:\/\/data.europa.eu\/eli\/dec_impl\/2018\/840\/oj."},{"key":"ref_14","first-page":"e00056715","article-title":"Regulation of the synthetic estrogen 17\u03b1-ethinylestradiol in water bodies in Europe, the United States, and Brazil","volume":"32","author":"Bila","year":"2016","journal-title":"Cadernos de Sa\u00fade P\u00fablica"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"122687","DOI":"10.1016\/j.matchemphys.2020.122687","article-title":"Electrochemical quantification of 17\u03b1\u2014Ethinylestradiol in biological samples using a Au\/Fe3O4@TA\/MWNT\/GCE sensor","volume":"244","author":"Nodehi","year":"2020","journal-title":"Mater. Chem. Phys."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"431","DOI":"10.1016\/j.apsusc.2018.07.035","article-title":"Ultrasensitive biosensor based on polyvinylpyrrolidone\/chitosan\/reduced graphene oxide electrospun nanofibers for 17\u03b1\u2013Ethinylestradiol electrochemical detection","volume":"458","author":"Pavinatto","year":"2018","journal-title":"Appl. Surf. Sci."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"126728","DOI":"10.1016\/j.snb.2019.126728","article-title":"Determination of a natural (17\u0392-estradiol) and a synthetic (17A-ethinylestradiol) hormones in pharmaceutical formulations and urine by adsorptive stripping voltammetry","volume":"297","author":"Valenzuela","year":"2019","journal-title":"Sens. Actuators B Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1016\/j.jelechem.2015.08.002","article-title":"Layer-by-Layer assembled films of chitosan and multi-walled carbon nanotubes for the electrochemical detection of 17\u03b1-ethinylestradiol","volume":"755","author":"Pavinatto","year":"2015","journal-title":"J. Electroanal. Chem."},{"key":"ref_19","doi-asserted-by":"crossref","unstructured":"Magro, C., Mateus, E., Raposo, M., and Ribeiro, A.B. (2018). Overview of electronic tongue sensing in environmental aqueous matrices: Potential for monitoring emerging organic contaminants. Environ. Rev.","DOI":"10.1139\/er-2018-0019"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1277","DOI":"10.1088\/0022-3727\/20\/10\/010","article-title":"AC admittance of the metal\/insulator\/electrolyte interface","volume":"20","author":"Taylor","year":"1987","journal-title":"J. Phys. D Appl. Phys."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"24","DOI":"10.1016\/j.snb.2019.01.023","article-title":"Insight into the sensing mechanism of an impedance based electronic tongue for honey botanic origin discrimination","volume":"285","author":"Elamine","year":"2019","journal-title":"Sens. Actuators B Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"239","DOI":"10.1021\/la011017d","article-title":"Artificial taste sensor: Efficient combination of sensors made from Langmuir-Blodgett films of conducting polymers and a ruthenium complex and self-assembled films of an azobenzene-containing polymer","volume":"18","author":"Riul","year":"2002","journal-title":"Langmuir"},{"key":"ref_23","doi-asserted-by":"crossref","unstructured":"Rocha Neto, J.B.M., Soares, A.C., Bataglioli, R.A., Carr, O., Costa, C.A.R., Oliveira, O.N., Beppu, M.M., and Carvalho, H.F. (2020). Polysaccharide Multilayer Films in Sensors for Detecting Prostate Tumor Cells Based on Hyaluronan-CD44 Interactions. Cells, 9.","DOI":"10.3390\/cells9061563"},{"key":"ref_24","unstructured":"Macdonald, J.R. (1987). Theory, John Wiley and Sons Inc."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1737","DOI":"10.1002\/polb.1995.090331205","article-title":"Dielectric relaxation spectroscopy in poly(hydroxyethyl acrylates)\/water hydrogels","volume":"33","author":"Kyritsis","year":"1995","journal-title":"J. Polym. Sci. Part B Polym. Phys."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"443","DOI":"10.1016\/j.snb.2016.01.067","article-title":"Study of the humidity-sensing mechanism of CaCu3Ti4O12","volume":"228","author":"Li","year":"2016","journal-title":"Sens. Actuators B Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"4439","DOI":"10.1016\/j.physb.2010.08.011","article-title":"Impedance spectroscopy study of dehydrated chitosan and chitosan containing LiClO4","volume":"405","author":"Costa","year":"2010","journal-title":"Phys. B Condens. Matter"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"160","DOI":"10.1007\/BFb0116302","article-title":"Fine-Tuning of the film thickness of ultrathin multilayer films composed of consecutively alternating layers of anionic and cationic polyelectrolytes","volume":"89","author":"Decher","year":"2007","journal-title":"Prog. Colloid Polym. Sci."},{"key":"ref_29","unstructured":"Jackson, J., and Edward, A. (2003). Users Guide to Principal Components, John Wiley& Sons."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"6095","DOI":"10.1021\/ma970228f","article-title":"Kinetics of Adsorption of Poly(o-methoxyaniline) Self-Assembled Films","volume":"30","author":"Raposo","year":"1997","journal-title":"Macromolecules"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"41","DOI":"10.1002\/(SICI)1521-396X(199905)173:1<41::AID-PSSA41>3.0.CO;2-Q","article-title":"Non-equilibrium adsorbed polymer layers via hydrogen bonding","volume":"173","author":"Pontes","year":"1999","journal-title":"Phys. Status Solidi A Appl. Res."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"2839","DOI":"10.1021\/la990945y","article-title":"Energies of adsorption of poly(o-methoxyaniline) layer-by-layer films","volume":"16","author":"Raposo","year":"2000","journal-title":"Langmuir"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"10167","DOI":"10.3390\/s130810167","article-title":"Nano-molar deltamethrin sensor based on electrical impedance of PAH\/PAZO layer-by-layer sensing films","volume":"13","author":"Ribeiro","year":"2013","journal-title":"Sensors"},{"key":"ref_34","doi-asserted-by":"crossref","unstructured":"Magro, C., Zagalo, P., Pereira-da-Silva, J., Pires Mateus, E., Branco Ribeiro, A., Ribeiro, P., and Raposo, M. (2020). Polyelectrolyte Based Sensors as Key to Achieve Quantitative Electronic Tongues: Detection of Triclosan on Aqueous Environmental Matrices. Nanomaterials, 10.","DOI":"10.3390\/nano10040640"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"8103","DOI":"10.1021\/la049872v","article-title":"Counterions in poly(allylamine hydrochloride) and poly(styrene sulfonate) layer-by-layer films","volume":"20","author":"Ribeiro","year":"2004","journal-title":"Langmuir"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"26","DOI":"10.1016\/j.jcis.2007.04.040","article-title":"Counterions in layer-by-layer films-Influence of the drying process","volume":"313","author":"Ribeiro","year":"2007","journal-title":"J. Colloid Interface Sci."},{"key":"ref_37","doi-asserted-by":"crossref","unstructured":"Magro, C., Mateus, E.P., Paz-Garc\u00eda, J.M., S\u00e9rio, S., Raposo, M., and Ribeiro, A.B. (2019). Electronic tongue coupled to an electrochemical flow reactor for emerging organic contaminants real time monitorin. Sensors, 19.","DOI":"10.3390\/s19245349"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"142","DOI":"10.1016\/j.apsusc.2016.12.170","article-title":"Detection of Traces of Triclosan in Water","volume":"421","author":"Marques","year":"2017","journal-title":"Appl. Surf. Sci."},{"key":"ref_39","unstructured":"Osborne, J.W., and Costello, A.B. (2010). Sample size and subject to item ratio in principal components analysis. J. Biom. Biostat., 1."},{"key":"ref_40","doi-asserted-by":"crossref","unstructured":"Giacometti, J.A., Shimizu, F.M., Carr, O., and Oliveira, O.N. (November, January 30). A Guiding Method to Select and Reduce the Number of Sensing Units in Electronic Tongues. Proceedings of the 2016 IEEE Sensors, Orlando, FL, USA.","DOI":"10.1109\/ICSENS.2016.7808663"}],"container-title":["Sensors"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1424-8220\/20\/24\/7324\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T10:47:34Z","timestamp":1760179654000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1424-8220\/20\/24\/7324"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,12,20]]},"references-count":41,"journal-issue":{"issue":"24","published-online":{"date-parts":[[2020,12]]}},"alternative-id":["s20247324"],"URL":"https:\/\/doi.org\/10.3390\/s20247324","relation":{},"ISSN":["1424-8220"],"issn-type":[{"type":"electronic","value":"1424-8220"}],"subject":[],"published":{"date-parts":[[2020,12,20]]}}}