Microchimica Acta

, 186:525 | Cite as

A glassy carbon electrode modified with silver nanoparticles and functionalized multi-walled carbon nanotubes for voltammetric determination of the illicit growth promoter dienestrol in animal urine

  • Manoel M. S. Lima Filho
  • Alessandra A. Correa
  • Francisco D. C. Silva
  • Francisco A. O. Carvalho
  • Lúcia H. Mascaro
  • Thiago M. B. F. OliveiraEmail author
Original Paper


An electroanalytical method for determining dienestrol (DNL) in bovine urine samples is described. A glassy carbon electrode (GCE) modified with silver nanoparticles and functionalized multi-walled carbon nanotubes was used as working sensor. The modified GCE displays substantial analytical improvements including an amplified signal, fast electron transfer kinetics, and resistance to fouling. The irreversible oxidation signal of DNL is pH-dependent. Best reactivity is found at pH 3.0, where a typical anodic peak is recorded at 0.8 V (vs. Ag/AgCl). Square-wave voltammetry revealed a 8.4 nM detection limit (1.9 μg L−1), good repeatability and reproducibility (RSDs <5.0%), and good accuracy (93.2–99.4% recovery from spiked samples). The modified electrode is highly stable even in the presence of ions (Na+ and K+), urea and uric acid. The electrochemical sensor fulfills all requisites to be used as forensic device in surveillance of illegal livestock practices.

Graphical abstract

Schematic presentation of the construction of a glassy carbon electrode modified with silver nanoparticles and functionalized multi-walled carbon nanotubes. This sensor exhibited a remarkable performance for voltammetric detection of the illicit growth promoter dienestrol in animal urine.


Growth promoters Dienestrol Multi-walled carbon nanotubes Silver nanoparticles Electrochemical sensors Forensic analysis 



The authors gratefully acknowledge the funding provided by the following Brazilian agencies: Coordination for the Improvement of Higher Education Personnel (CAPES; proc. 88881.140821/2017-01 and Finance code 001) and National Council for Scientific and Technological Development (CNPQ; proc. 420261/2018-4 and 407891/2018-8). M.M.S. Lima Filho also thanks CAPES for the grant.

Compliance with ethical standards

The author(s) declare that they have no competing interests.

Supplementary material

604_2019_3645_MOESM1_ESM.docx (75 kb)
ESM 1 (DOCX 75 kb)


  1. 1.
    FAO, IFAD, UNICEF, WFP, WHO (2018) The state of food security and nutrition in the world. Building climate resilience for food security and nutrition. FAO, Rome, p 2018Google Scholar
  2. 2.
    Robinson TP, Thornton PK, Franceschini G, Kruska RL, Chiozza F, Notenbaert A, Cecchi G, Herrero M, Epprecht M, Fritz S, You L, Conchedda G, See L (2011) Global livestock production systems. Food and Agriculture Organization of the United Nations (FAO) and International Livestock Research Institute (ILRI), RomeGoogle Scholar
  3. 3.
    Enahoro D, Lannerstad M, Pfeifer C, Dominguez-Salas P (2018) Contributions of livestock-derived foods to nutrient supply under changing demand in low- and middle-income countries. Glob Food Sec 19:1–10. CrossRefGoogle Scholar
  4. 4.
    Marselis SM, Feng K, Liu Y, Teodoro JD, Hubacek K (2017) Agricultural land displacement and undernourishment. J Clean Prod 161:619–628. Scholar
  5. 5.
    Tullo E, Finzi A, Guarino M (2019) Review: environmental impact of livestock farming and precision livestock farming as a mitigation strategy. Sci Total Environ 650:2751–2760. CrossRefPubMedGoogle Scholar
  6. 6.
    Boxall ABA (2018) Contamination from the agricultural use of growth promoters and medicines. In: Dellasala DA, Goldstein MI (eds) Encyclopedia of the Anthropocene. Elsevier, Oxford, pp 257–262CrossRefGoogle Scholar
  7. 7.
    Yopasá-Arenas A, Fostier AH (2018) Exposure of Brazilian soil and groundwater to pollution by coccidiostats and antimicrobial agents used as growth promoters. Sci Total Environ 644:112–121. CrossRefPubMedGoogle Scholar
  8. 8.
    Corsini E, Ruffo F, Racchi M (2018) Steroid hormones, endocrine disrupting compounds and immunotoxicology. Curr Opin Toxicol 10:69–73. CrossRefGoogle Scholar
  9. 9.
    Parr T, Mareko MHD, Ryan KJP, Hemmings KM, Brown DM, Brameld JM (2016) The impact of growth promoters on muscle growth and the potential consequences for meat quality. Meat Sci 120:93–99. CrossRefPubMedGoogle Scholar
  10. 10.
    Ronquillo MG, Hernandez JCA (2017) Antibiotic and synthetic growth promoters in animal diets: review of impact and analytical methods. Food Control 72:255–267. CrossRefGoogle Scholar
  11. 11.
    Silvestre BS, Monteiro MS, Viana FLE, De Sousa-Filho JM (2018) Challenges for sustainable supply chain management: when stakeholder collaboration becomes conducive to corruption. J Clean Prod 194:766–776. CrossRefGoogle Scholar
  12. 12.
    Schrippe P, Ribeiro JLD (2019) Preponderant criteria for the definition of corporate sustainability based on Brazilian sustainable companies. J Clean Prod 209:10–19. CrossRefGoogle Scholar
  13. 13.
    Neethirajan S, Tuteja SK, Huang S-T, Kelton D (2017) Recent advancement in biosensors technology for animal and livestock health management. Biosens Bioelectron 98:398–407. CrossRefPubMedGoogle Scholar
  14. 14.
    Oliveira TMBF, Ribeiro FWP, Nascimento JM, Soares JES, Freire VN, Becker H, Lima-Neto P, Correia NA (2012) Direct electrochemical analysis of dexamethasone endocrine disruptor in raw natural waters. J Braz Chem Soc 23:110–119. CrossRefGoogle Scholar
  15. 15.
    Oliveira TMBF, Morais S (2018) New generation of electrochemical sensors based on multi-walled carbon nanotubes. Appl Sci 8(10):1925. CrossRefGoogle Scholar
  16. 16.
    Xiao D, Jiang Y, Bi Y (2018) Molecularly imprinted polymers for the detection of illegal drugs and additives: a review. Microchim Acta 185(4):247. CrossRefGoogle Scholar
  17. 17.
    Regiart M, Pereira SV, Spotorno VG, Bertolino FA, Raba J (2013) Nanostructured voltammetric sensor for ultra-trace anabolic drug determination in food safety field. Sensors Actuators B Chem 188:1241–1249. CrossRefGoogle Scholar
  18. 18.
    Dickson LC, MacNeil JD, Reid J, Fesser ACE (2003) Validation of screening method for residues of diethylstilbestrol, dienestrol, hexestrol, and zeranol in bovine urine using immunoaffinity chromatography and gas chromatography/mass spectrometry. J AOAC Int 86:631–639PubMedGoogle Scholar
  19. 19.
    Arikan OA, Rice C, Codling E (2008) Occurrence of antibiotics and hormones in a major agricultural watershed. Desalination 226:121–133. CrossRefGoogle Scholar
  20. 20.
    Goulart LA, Gonçalves R, Correa AA, Pereira EC, Mascaro LH (2018) Synergic effect of silver nanoparticles and carbon nanotubes on the simultaneous voltammetric determination of hydroquinone, catechol, bisphenol a and phenol. Microchim Acta 185:1–12. CrossRefGoogle Scholar
  21. 21.
    Goulart LA, De Moraes FC, Mascaro LH (2016) Influence of the different carbon nanotubes on the development of electrochemical sensors for bisphenol a. Mat Sci Eng C – Mater 58:768–773. CrossRefGoogle Scholar
  22. 22.
    Miller JN, Miller JC (2005) Statistics and chemometrics for analytical chemistry. Pearson Prentice Hall, HarlowGoogle Scholar
  23. 23.
    Paiva WDA, Oliveira TMBF, Sousa CP, Lima-Neto P, Correia AN, Morais S, Silva DR, Castro SSL (2018) Electroanalysis of imidacloprid insecticide in river waters using functionalized multi-walled carbon nanotubes modified glassy carbon electrode. J Electrochem Soc 165:B431–B435. CrossRefGoogle Scholar
  24. 24.
    De Moura MR, Mattoso LHC, Zucolotto V (2012) Development of cellulose-based bactericidal nanocomposites containing silver nanoparticles and their use as active food packaging. J Food Eng 109:520–524. CrossRefGoogle Scholar
  25. 25.
    Chen X, Ma Y, Chen D, Ma M, Li C (2015) Electrochemical fabrication of polymerized imidazole-based ionic liquid bearing pyrrole moiety for sensitive determination of hexestrol in chicken meat. Food Chem 180:142–149. CrossRefPubMedGoogle Scholar
  26. 26.
    Séquaris J-M, Fritz J (1992) Voltammetric detection and analysis of the behavior of diethylstilbestrol oxidation products. Electroanalysis 4:121–127. CrossRefGoogle Scholar
  27. 27.
    Lee JHQ, Koh YR, Webster RD (2017) The electrochemical oxidation of diethylstilbestrol (DES) in acetonitrile. J Electroanal Chem 799:92–101. CrossRefGoogle Scholar
  28. 28.
    Santos MJR, Medeiros MC, Oliveira TMBF, Morais CCO, Mazzetto SE, Martínez-Huitle CA, Castro SSL (2016) Electrooxidation of cardanol on mixed metal oxide (RuO2-TiO2 and IrO2-RuO2-TiO2) coated titanium anodes: insights into recalcitrant phenolic compounds. Electrochim Acta 212: 95–101. 2016.06.145
  29. 29.
    Bard AJ, Faulkner LR (1980) Electrochemical methods: fundamentals and applications. Wiley, New YorkGoogle Scholar
  30. 30.
    Liao S, Wu X, Xie Z (2005) Determination of some estrogens by flow injection analysis with acidic potassium permanganate–formaldehyde chemiluminescence detection. Anal Chim Acta 537:189–195. CrossRefGoogle Scholar
  31. 31.
    Gao F, Liu J, Lu W, Li J, Liu H (2018) Determination of four phenolic estrogens in water samples by pressure-assisted electrokinetic injection coupled with capillary electrophoresis. Chin J Chromatogr 36:573–577CrossRefGoogle Scholar
  32. 32.
    Qin Y, Zhang J, Li Y, Han Y, Zou N, Jiang Y, Shan J, Pan C (2016) Multiplug filtration cleanup method with multi-walled carbon nanotubes for the analysis of malachite green, diethylstilbestrol residues, and their metabolites in aquatic products by liquid chromatography–tandem mass spectrometry. Anal Bioanl Chem 408:5801–5809. CrossRefGoogle Scholar
  33. 33.
    Socas-Rodrígues B, Herrera-Herrera V, Hernández-Borges J, Rodríguez-Delgado MÁ (2017) Multiresidue determination of estrogens in different dairy products by ultra-high-performance liquid chromatography triple quadrupole mass spectrometry. J Chromatogr A 1496:58–67. CrossRefGoogle Scholar
  34. 34.
    D’Orazio G, Hernández-Borges J, Herrera-Herrera AV, Fanali S, Rodríguez-Delgado MÁ (2016) Determination of estrogenic compounds in milk and yogurt samples by hollow-fibre liquid-phase microextraction-gas chromatography-triple quadrupole mass spectrometry. Anal Bioanal Chem 408:7447–7459. CrossRefPubMedGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Faculdade de Química, Instituto de Ciências ExatasUniversidade Federal do Sul e Sudeste do ParáMarabáBrazil
  2. 2.Departamento de QuímicaUniversidade Federal de São CarlosSão CarlosBrazil
  3. 3.Centro de Ciência e TecnologiaUniversidade Federal do CaririJuazeiro do NorteBrazil

Personalised recommendations