SpringerLink
Log in

Pipette-tip solid-phase extraction using polypyrrole as efficient adsorbent for extraction of avermectins and milbemycins in milk

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

In this work, we developed a HPLC method for the multidetermination of avermectins (AVM) (abamectin—ABA 1b and ABA 1a, eprinomectin—EPR, and ivermectin—IVM) and milbemycins (moxidectin—MOX) in milk samples using polypyrrole (PPy) as adsorbent material in pipette-tip solid-phase extraction (PT–PPy–SPE). PPy was characterized by scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and X-ray diffraction and the data agreed with the literature. The sample preparation included the clean-up of the milk by protein precipitation (PP) with acetonitrile and extraction of the analytes by PT–PPy–SPE. The chromatographic method was developed in reverse phase and isocratic mode with flow rate at 1.2 mL min−1 and ultraviolet detection at 250 nm. The mobile phase composition was acetonitrile:methanol:water (55:25:20, v/v/v). The studied parameters and the optimized conditions for the sample preparation were washing solvent (300 μL water), volume and type of eluent (500 μL methanol), volume and pH of sample (1 mL and pH 10), amount of adsorbent material (50 mg PPy), and without addition of salt (NaCl). The method was linear over the concentration range from 20 to 3000 ng mL−1 with coefficients of correlation (r) ≥ 0.99 for all analytes and recoveries around 100%. The method developed and validated was used for the analyses of real milk samples from cow treated with Ivomec® (IVM 3.5%), in which were found 21.51 ± 2.94 ng mL−1 of IVM. Finally, the results proved that PT–PPy–SPE coupled to HPLC–UV was economical, simple, and easy-to-perform technique.

Pipette-tip solid phase extraction using polypirrole as adsorbent material for determination of avermectins and milbemycins in milk

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price includes VAT (Spain)

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Ivermectine DM. Ann Dermatol Venereol. 2004;131:561–70.

    Article  Google Scholar 

  2. Burg RW, Miller BM, Baker EE, Birnbaum J, Currie SA, Hartman R, et al. Avermectins, new family of potent anthelmintic agents: producing organism and fermentation. Antimicrob Agents Chemother. 1979;15:361–7.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  3. Prichard R, Ménez C, Moxidectin LA. The avermectins: consanguinity but not identity. Int J Parasitol Drugs Drug Resist. 2012;2:134–53.

    Article  PubMed  PubMed Central  Google Scholar 

  4. Lespine A, Alvinerie M, Vercruysse J, Prichard RK, Geldhof P. ABC transporter modulation: a strategy to enhance the activity of macrocyclic lactone anthelmintics. Trends Parasitol. 2008;24:293–8.

    Article  CAS  PubMed  Google Scholar 

  5. Council Directive 96/23/Ec. Measures to monitor certain substances and residues thereof in live animals and animal products and repealing. Directives 85/358/EEC and 86/469/EEC and Decisions 89/187/EEC and 91/664/EEC. 2012;127:10–31.

    Google Scholar 

  6. Brasil, Ministério da Agricultura, Pecuária e Abastecimento, Secretaria de Defesa Agropecuária, Instrução Normativa n° 46 22/11/2016.

  7. Shipp JL, Wang K, Ferguson G. Residual toxicity of avermectin b1 and pyridaben to eight commercially produced beneficial arthropod species used for control of greenhouse pests. Biol Control. 2000;17:125–31.

    Article  CAS  Google Scholar 

  8. Colwell DD. Presistant activity of moxidectin pour-on and injectable against sucking and biting louse infestations of cattle. Vet Parasitol. 2002;140:319–26.

    Article  Google Scholar 

  9. Gomes LVC, Lopes WDZ, Cruz BC, Teixeira WF, Felippelli G, Maciel WG, et al. Acaricidal effects of fluazuron (2.5 mg/kg) and a combination of fluazuron (1.6 mg/kg) + ivermectin (0.63 mg/kg), administered at different routes, against Rhipicephalus (Boophilus) microplus-parasitizing cattle. Exp Parasitol. 2015;153:22–8.

    Article  CAS  PubMed  Google Scholar 

  10. Danaher M, Howells LC, Cerkvenik-Flajs V, O’keeffe M. Review of methodology for the determination of macrocyclic lactone residues in biological matrices. J Chromatogr B. 2006;844:175–203.

    Article  CAS  Google Scholar 

  11. Szprengier-Juszkiewicz T, Jedziniak P, Olejnik M, Żmudzki J. Control of residues of five macrocyclic lactones in cow milk by liquid chromatography with fluorescence detection. Bull Vet Inst Pulawy. 2012;56:595–9.

    Article  Google Scholar 

  12. Janer EC, Klafke GM, Capurro ML, Schumaker TT. Cross-resistance between fipronil and lindane in Rhipicephalus (Boophilus) microplus. Vet Parasitol. 2015;210:77–83.

    Article  CAS  Google Scholar 

  13. Cruz BC, Lopes WDZ, Maciel WQ, Felippellia G, Fávero FC, Teixeira WFP, et al. Susceptibility of Rhipicephalus (Boophilus) microplus to ivermectin (200, 500 and 630 μg/kg) in field studies in Brazil. Vet Parasitol. 2015;207:309–17.

    Article  CAS  PubMed  Google Scholar 

  14. Nasrel-Bahy M, Eman K, Hazem IB, Shaheen M. Efficacy of deltamethrin, diazinon, and ivermectin on Boophilus annulatus ticks (in vitro and in vivo study). Parasitol Res. 2015;114:29–36.

    Article  Google Scholar 

  15. Souza LHO, Garcia MV, Barros JC, Koller WR, Andreotti R. Evaluation of Rhipicephalus (Boophilus) microplus (Acari: Ixodidae) resistance to different acaricide formulations using samples from Brazilian properties. Braz J Vet Parasitol. 2016;25:163–71.

    Article  Google Scholar 

  16. Zhana J, Yub XJ, Zhong YY, Zhang ZT, Cui XM, Peng JF, et al. Generic and rapid determination of veterinary drug residues and other contaminants in raw milk by ultra-performance liquid chromatography–tandem mass spectrometry. J Chromatogr B. 2012;906:48–57.

    Article  CAS  Google Scholar 

  17. Anastasio A, Esposito M, Amorena M, Catellani P, Serpe L, Cortesi ML. Residue study of ivermectin in plasma, milk, and mozzarella cheese following subcutaneous administration to buffalo (Bubalus bubalis). J Agric Food Chem. 2002;50:5241–5.

    Article  CAS  PubMed  Google Scholar 

  18. Ortelli D, Cognard E, Jan P, Edder P. Comprehensive fast multiresidue screening of 150 veterinary drugs in milk by ultra-performance liquid chromatography coupled to time of flight mass spectrometry. J Chromatogr B. 2009;877:2363–74.

    Article  CAS  Google Scholar 

  19. Boscher A, Guignard C, Pellet T, Hoffmann L, Bohn T. Development of a multi-class method for the quantification of veterinary drug residues in feedingstuffs by liquid chromatography–tandem mass spectrometry. J Chromatogr A. 2010;(41):6394–404.

  20. Kaufmann P. Multi-residue quantification of veterinary drugs in milk with a novel extraction and clean up technique: salting out supported liquid extraction (SOSLE). Anal Chem. 2014;820:56–68.

    CAS  Google Scholar 

  21. Zarzycki PK, Zarzycka MB, Ślączka MM, Clifton VL. Acetonitrile, the polarity chameleon. Anal Bioanal Chem. 2010;397:905–8.

    Article  CAS  PubMed  Google Scholar 

  22. Chen M, Ding S, Wen K, **e S, Wang Q, Pei X, et al. Development of a fluorescence-linked immunosorbent assay for detection of avermectins using a fluorescent single-domain antibody. Anal Methods. 2015;7:3728–35.

    Article  CAS  Google Scholar 

  23. Oka H, Ikai Y, Hayakawa J, Harada KI, Suzuki M, Shimizu A, et al. Separation of ivermectin components by high-speed counter-current chromatography. J Chromatogr A. 1996;723:61–8.

    Article  CAS  Google Scholar 

  24. Kolberg DIS, Presta MA, Wickert C, Adaime MB, Zanella R. Rapid and accurate simultaneous determination of abamectin and ivermectin in bovine milk by high performance liquid chromatography with fluorescence detection. J Braz Chem Soc. 2009;20:1220–6.

    Article  CAS  Google Scholar 

  25. Danaher M, Radeck W, Kolar L, Keegan J, Cerkvenik-Flajs V. Recent developments in the analysis of avermectin and milbemycin residues in food safety and the environment. Curr Pharm Biotechnol. 2012;13:936–51.

    Article  CAS  PubMed  Google Scholar 

  26. Durden DA. Positive and negative electrospray LC–MS–MS methods for quantitation of the antiparasitic endectocide drugs, abamectin, doramectin, emamectin, eprinomectin, ivermectin, moxidectin and selamectin in milk. J Chromatogr A. 2007;850:134–57.

    CAS  Google Scholar 

  27. Ferrer I, Thurman E. Analysis of 100 pharmaceuticals and their degradates in water samples by liquid chromatography/quadrupole time-of-flight mass spectrometry. J Chromatogr A. 2012;1259:148–57.

    Article  CAS  PubMed  Google Scholar 

  28. Yoshii K, Kaihara A, Tsumura Y, Ishimitsu S, Tonogai Y. Liquid chromatographic determination of emamectin, milbemectin, ivermectin and abamectin in crops and confirmation by liquid chromatography–mass spectrometry. J Chromatogr A. 2000;896:75–85.

    Article  CAS  PubMed  Google Scholar 

  29. Andrade RT, da Silva RCS, Pereira AC, Borges KB. Self-assembly pipette tip-based cigarette filters for micro-solid phase extraction of ketoconazole cis-enantiomers in urine samples followed by high performance liquid chromatography/diode array detection. Anal Methods. 2015;7:7270–80.

    Article  CAS  Google Scholar 

  30. da Silva RCS, Mano V, Pereira AC, de Figueiredo EC, Borges KB. Development of pipette tip-based on molecularly imprinted polymer micro-solid phase extraction for selective enantioselective determination of (−)-(2S,4R) and (+)-(2R,4S) ketoconazole in human urine samples prior to HPLC-DAD. Anal Methods. 2016;8:4075–85.

    Article  CAS  Google Scholar 

  31. de Oliveira HL, Anacleto SS, da Silva AT, Pereira AC, Borges WS, de Figueiredo EC, et al. Molecularly imprinted pipette-tip solid phase extraction for selective determination of fluoroquinolones in human urine using HPLC-DAD. J Chromatogr B. 2016;1033-1043:27–39.

    Article  CAS  Google Scholar 

  32. da Silva ATM, de Oliveira HL, Silva CF, Fonseca MC, Pereira TFD, Nascimento Jr CS, et al. Efficient molecularly imprinted polymer as a pipette-tip solid-phase sorbent for determination of carvedilol enantiomers in human urine. J Chromatogr B. 2017;1061-1062:399–410.

    Article  CAS  Google Scholar 

  33. Borges KB, de Figueiredo EC, Queiroz MEC (2015) Preparo de amostras para análise de compostos orgânicos, first ed., LTC−Livros Técnicos Científicos Editora Ltda, Rio de Janeiro.

  34. Bagheri H, Saraji M. Conductive polymers as new media for solid-phase extraction: isolation of chlorophenols from water sample. J Chromatogr A. 2003;986:111–9.

    Article  CAS  PubMed  Google Scholar 

  35. Dutra FVA, Pires BC, Nascimento TA, Mano V, Borges KB. Polyaniline-deposited cellulose fiber composite prepared via in situ polymerization: enhancing adsorption properties for removal of meloxicam from aqueous media. RSC Adv. 2017;7:12639–49.

    Article  Google Scholar 

  36. Nascimento TA, Dutra FVA, Pires BC, Tarley CRT, Mano V, Borges KB. Preparation and characterization of a composite based on polyaniline, polypyrrole and cigarette filters: adsorption studies and kinetics of phenylbutazone in aqueous media. RSC Adv. 2016;6:64450–60.

    Article  CAS  Google Scholar 

  37. Pires BC, Dutra FVA, Nascimento TA, Borges KB. Preparation of PPy/cellulose fibre as an effective potassium diclofenac adsorbent. React Funct Polym. 2017;113:40–9.

    Article  CAS  Google Scholar 

  38. Meng J, Bu J, Deng C, Zhang X. Preparation of polypyrrole-coated magnetic particles for micro solid-phase extraction of phthalates in water by gas chromatography–mass spectrometry analysis. J Chromatogr A. 2011;(12):1585–91.

  39. Khalilian F, Rezaee M, Gorgabi MK. Magnetic polypyrrole/Fe3O4 particles as an effective sorbent for the extraction of abamectin from fruit juices using magnetic solid-phase extraction combined with dispersive liquid–liquid microextraction. Anal Methods. 2015;7:2182–90.

    Article  CAS  Google Scholar 

  40. Martínez-Villalba A, Vaclavik L, Moyano E, Galceran MT, Hajslova J. Direct analysis in real time high-resolution mass spectrometry for highthroughput analysis of antiparasitic veterinary drugs in feed and food. Rapid Commun Mass Spectrom. 2013;27:467–75.

    Article  CAS  PubMed  Google Scholar 

  41. VICH GL 49, Studies to evaluate the metabolism and residue kinetics of veterinary drugs in food-producing animals: validation of analytical methods used in residue depletion studies. http://www.vichsec.org/guidelines/pharmaceuticals/pharma-safety/metabolism-and-residue-kinetics.html, 2015 (accessed 08 June 2017).

  42. Turnipseed S, Roybal J, Andersen W, Kuck L. Analysis of avermectin and moxidectin residues in milk by liquid chromatography–tandem mass spectrometry using an atmospheric pressure chemical ionization/atmospheric pressure photo ionization source. Anal Chem. 2005;529:159–65.

    CAS  Google Scholar 

  43. Boix C, Ibáñez M, Sancho JV, León N, Yusá V, Hernández F. Qualitative screening of 116 veterinary drugs in feed by liquid chromatography–high resolution mass spectrometry: potential application to quantitative analysis. Food Chem. 2014;160:313–20.

    Article  CAS  PubMed  Google Scholar 

  44. Ozdemir N, Kahraman T. Rapid confirmatory analysis of avermectin residues in milk by liquid chromatography tandem mass spectrometry. J Food Drug Anal. 2016;24:90–3.

    Article  CAS  PubMed  Google Scholar 

  45. Cheng C, Liua LC. On-line solid-phase extraction coupled liquid chromatography-ESI-ion trap-mass spectrometry for analysis of abamectin and ivermectin residues in milk. Anal Methods. 2014;6:1581–90.

    Article  CAS  Google Scholar 

  46. Frenich AG, Aguilera MDM, Vidal JLM, Romero-González R. Comparison of several extraction techniques for multiclass analysis of veterinary drugs in eggs using ultra-high pressure liquid chromatography–tandem mass spectrometry. Anal Chem. 2010;(2):150–60.

  47. Priscila MS, Maia B, Rezende DF, Annibal D, Netto FP, Marques FC. An alternative derivatization reaction to the determination of doramectin in bovine milk using spectrofluorimetry. Spectrochim Acta A Mol Biomol Spectrosc. 2015;100:127–30.

    Google Scholar 

  48. León N, Roca M, Igualada C, Martins CPB, Pastor A, Yusá V. Widerange screening of banned veterinary drugs in urine by ultra-high liquid chromatography coupled to high-resolution mass spectrometry. J Chromatogr A. 2012;1258:55–65.

    Article  CAS  PubMed  Google Scholar 

  49. Imperiale FA, Busetti MR, Suarez VH, Lanusse CE. Milk excretion of ivermectin and moxidectin in dairy sheep: assessment of drug residues during cheese elaboration and ripening period. J Agric Food Chem. 2009;20:6205–11.

    Google Scholar 

  50. Campillo N, Viñas P, Férez-Melgarejo G, Hernández-Córdoba M. Dispersive liquid–liquid microextraction for the determination of macrocyclic lactones in milk by liquid chromatography with diode array detection and atmospheric pressure chemical ionization ion-trap tandem mass spectrometry. J Chromatogr A. 2013;1282:20–6.

    Article  CAS  PubMed  Google Scholar 

  51. Cerkvenik-Flajsa V, Milcinski L, Süssingera A, Hodosceka L, Danaherb M, Antonica J. Trace analysis of endectocides in milk by high performance liquid chromatography with fluorescence detection. Anal Chim Acta. 2010;633:165–71.

    Article  CAS  Google Scholar 

  52. Rúbies A, Antkowiak S, Granados M, Companyó R, Centrich F. Determination of avermectins: a QuEChERS approach to the analysis of food samples. Food Chem. 2015;151:57–63.

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors would like to thank the Brazilian agencies CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico), CAPES (Coordenação de Aperfeiçoamento de Pessoal de Nível Superior), FAPES (Fundação de Amparo à Pesquisa e Inovação do Espírito Santo), and FAPEMIG (Fundação de Amparo à Pesquisa do Estado de Minas Gerais) for financial support. This study is also part of the project involving the Rede Mineira de Química (RQ-MG) supported by FAPEMIG (Project: REDE-113/10; Project: CEX-RED-0010-14).

Author information

Authors and Affiliations

  1. Departamento de Ciências Naturais, Universidade Federal de São João del-Rei, Campus Dom Bosco, Praça Dom Helvécio 74, Fábricas, São João del-Rei, Minas Gerais, 36301-160, Brazil

    Diego Hernando Ângulo Florez, Roseane Andrade Teixeira, Ricky Cássio Santos da Silva, Bruna Carneiro Pires, Flávia Viana Avelar Dutra & Keyller Bastos Borges

Authors
  1. Diego Hernando Ângulo Florez
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Roseane Andrade Teixeira
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ricky Cássio Santos da Silva
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Bruna Carneiro Pires
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Flávia Viana Avelar Dutra
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Keyller Bastos Borges
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Keyller Bastos Borges.

Ethics declarations

All studies involving animals are reported in accordance with the ARRIVE guidelines and approved by the institutional ethics board committee.

Conflict of interest

The authors declare that they have no conflict of interest.

Electronic supplementary material

ESM 1

(PDF 296 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Florez, D.H.Â., Teixeira, R.A., da Silva, R.C.S. et al. Pipette-tip solid-phase extraction using polypyrrole as efficient adsorbent for extraction of avermectins and milbemycins in milk. Anal Bioanal Chem 410, 3361–3374 (2018). https://doi.org/10.1007/s00216-018-1031-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-018-1031-9

Keywords

Search

Navigation