Extração de pesticidas em amostras de alimentos através de sorção em ponteiras descartáveis
Oliveira T.C., Lanças F.M.
Keywords: Disposable Pipette Tip Extraction, DPX, sample preparation, pesticides in food
Abstract: Over the years, the agricultural market is facing a growing competition, and the search for increased production, quality, and pest control makes the use of pesticides increasingly necessary. The toxicity of these substances and potential health risks generate a constant charge to society for the presence of pesticide residues in food. Chromatographic techniques are widely used in the identification and quantification of these substances. Because they are present in complex matrices and low concentrations, the sample preparation becomes fundamental for the adequacy of the analytes for instrumental analysis.
Miniaturized techniques based on extracting phases are being used more and more, as they provide high performance and reduce the amount of solvent, sample, and time consumed. Among the most recent techniques, disposable pipette extraction (DPX) stands out, which uses sorbent material contained in pipette tips for extraction and concentration of the analytes present in the matrix.
The present work presents a review of the fundamentals of the DPX technique and its recent applications in the area of pesticides in food matrices.
 Ribeiro ML, Lourencetti C, Polese L, Navickiene S OL. Pesticidas: Usos e Riscos para o Meio Ambiente. Holos Environ. 2008;8(1):53–71.
 Pinto IP de, Pedroso MP. Microextração em gota única (SDME): fundamentos e aplicações. Sci Chromatogr . 2015;7(3):183–98.
 Luque de Castro MD, Priego-Capote F. Soxhlet extraction: Past and present panacea. J Chromatogr A. abril de 2010;1217(16):2383–9.
 Rezaee M, Yamini Y, Faraji M. Evolution of dispersive liquid–liquid microextraction method. J Chromatogr A. abril de 2010;1217(16):2342–57.
 Barrionuevo WR, Lanças FM. Extração em fase sólida (SPE) e micro extração em fase sólida (SPME) de piretróides em água. Quim Nova. abril de 2001;24(2):172–5.
 Arthur CL, Pawliszyn J. Solid phase microextraction with thermal desorption using fused silica optical fibers. Anal Chem. outubro de 1990;62(19):2145–8.
 Andrade MA, Lanças FM. Estado-da-arte na análise cromatográfica de Ocratoxina A em amostras de alimentos. Sci Chromatogr. 2015;7(1):31–52.
 Kremser A, Jochmann MA, Schmidt TC. PAL SPME Arrow—evaluation of a novel solid-phase microextraction device for freely dissolved PAHs in water. Anal Bioanal Chem. 16 de janeiro de 2016;408(3):943–52.
 Ghiasvand A, Yazdankhah F, Nouriasl K, Hajipour S. Extraction and determination of residual organic solvents in pharmaceutical products by SPME method using a new nanocomposite fiber. US Patent 10 , 258 , 963 B2; 2019.
 Baltussen E, Sandra P, David F, Cramers C. Stir bar sorptive extraction (SBSE), a novel extraction technique for aqueous samples: Theory and principles. J Microcolumn Sep. 1999;11(10):737–47.
 Abdulra’uf LB, Tan GH. Review of SBSE Technique for the Analysis of Pesticide Residues in Fruits and Vegetables. Chromatographia. 6 de janeiro de 2014;77(1–2):15–24.
 Ridgway K, Lalljie SPD, Smith RM. Sample preparation techniques for the determination of trace residues and contaminants in foods. J Chromatogr A. junho de 2007;1153(1–2):36–53.
 Abdel-Rehim M. (54). Method and apparatus for sample preparation using solid phase microextraction. US Patent Application Publication 2004 / 0231417 A1; 2004.
 Fumes BH. Emprego de materiais baseados em grafeno como sorventes em técnicas de preparo de amostra. Tese [Doutorado em Ciências]. São Carlos- USP; 2012.
 Pereira J, Gonçalves J, Alves V, Câmara JS. Microextraction using packed sorbent as an effective and high-throughput sample extraction technique: Recent applications and future trends. Sample Prep. 2013;1:38–53.
 Ruiz del Castillo ML, Rodríguez-Valenciano M, Flores G, Blanch GP. New method based on Solid Phase Microextraction and Multidimensional gas chromatography-mass spectrometry to determine pesticides in strawberry jam. LWT. janeiro de 2019;99:283–90.
 Pang Y, Zang X, Li H, Liu J, Chang Q, Zhang S, et al. Solid-phase microextraction of organophosphorous pesticides from food samples with a nitrogen-doped porous carbon derived from g-C3N4 templated MOF as the fiber coating. J Hazard Mater. outubro de 2019;121430.
 Ma J-K, Huang X-C, Wei S-L. Preparation and application of chlorpyrifos molecularly imprinted solid-phase microextraction probes for the residual determination of organophosphorous pesticides in fresh and dry foods. J Sep Sci. agosto de 2018;41(15):3152–62.
 Zheng S, He M, Chen B, Hu B. Porous aromatic framework coated stir bar sorptive extraction coupled with high performance liquid chromatography for the analysis of triazine herbicides in maize samples. J Chromatogr A. novembro de 2019;460728.
 Ochiai N, Sasamoto K, David F, Sandra P. Solvent-assisted stir bar sorptive extraction by using swollen polydimethylsiloxane for enhanced recovery of polar solutes in aqueous samples: Application to aroma compounds in beer and pesticides in wine. J Chromatogr A. julho de 2016;1455:45–56.
 Simon I, Miclean M, Cadar O, Senila L. Determination of the organochlorine pesticide residues contents in grapes by SBSE-TD-GC-ECD analysis. Stud Univ Babes-Bolyai Chem. 2016;61(3TOM2):431–40.
 Sun T, Fan Y, Fan P, Geng F, Chen P, Zhao F. Use of graphene coated with ZnO nanocomposites for microextraction in packed syringe of carbamate pesticides from juice samples. J Sep Sci. 9 de junho de 2019;42(12):2131–9.
 Di Ottavio F, Della Pelle F, Montesano C, Scarpone R, Escarpa A, Compagnone D, et al. Determination of Pesticides in Wheat Flour Using Microextraction on Packed Sorbent Coupled to Ultra-High Performance Liquid Chromatography and Tandem Mass Spectrometry. Food Anal Methods. 25 de junho de 2017;10(6):1699–708.
 Fumes BH, Andrade FN, Neto ÁJ dos S, Lanças FM. Determination of pesticides in sugarcane juice employing microextraction by packed sorbent followed by gas chromatography and mass spectrometry. J Sep Sci. julho de 2016;39(14):2823–30.
 Bordin DCM, Alves MNR, De Campos EG, De Martinis BS. Disposable pipette tips extraction: Fundamentals, applications and state of the art. J Sep Sci. 2016;39(6):1168–72.
 Barker SA, Long AR, Short CR. Isolation of drug residues from tissues by solid phase dispersion. J Chromatogr A. janeiro de 1989;475(2):353–61.
 Lanças FM. Extração em Fase Sólida (SPE). 1o ed. São Carlos: RiMa; 2004.
 Anastassiades M, Lehotay SJ., Štajnbaher D., Schenck FJ. Fast and Easy Multiresidue Method Employing Acetonitrile Extraction/Partitioning and “Dispersive Solid-Phase Extraction” for the Determination of Pesticide Residues in Produce. J AOAC Int. 2003;86(2):412–31.
 Cabrera L da C, Martins ML, Primel EG, Prestes OD, Adaime MB, Zanella R. Extração em Fase Sólida Dispersiva na determinação de resíduos e contaminantes em alimentos. Sci Chromatogr. 2012;4(3):227–40.
 Brewer WE. Disposable Pipette Extraction. US Patent 6,566,145 B2; 2003.
 Yuan Y, Wang M, Jia N, Zhai C, Han Y, Yan H. Graphene/multi-walled carbon nanotubes as an adsorbent for pipette-tip solid-phase extraction for the determination of 17β-estradiol in milk products. J Chromatogr A. 2019;1600:73–9.
 Hashemi SH, Ziyaadini M, Kaykhaii M, Keikha AJ, Naruie N. Separation and determination of ciprofloxacin in seawater, human blood plasma and tablet samples using molecularly imprinted polymer pipette-tip solid phase extraction and its optimization by response surface methodology. J Sep Sci. 2019;98(54):1–24.
 Mastrianni KR, Kemnitzer WE, Miller KWP. A Novel, Automated Dispersive Pipette Extraction Technology Greatly Simplifies Catecholamine Sample Preparation for Downstream LC-MS/MS Analysis. SLAS Technol. 2019;24(1):117–23.
 Kaewsuya P, Brewer WE, Wong J, Morgan SL. Automated QuEChERS tips for analysis of pesticide residues in fruits and vegetables by GC-MS. J Agric Food Chem. 2013;61(10):2299–314.
 Pinto MAL, Queiroz MEC. Extração em ponteiras descartáveis: fundamentos teóricos e aplicações. Sci Chromatogr. 2015;7(2):101–8.
 Turazzi FC, Morés L, Carasek E, Merib J, De Oliveira Barra GM. A rapid and environmentally friendly analytical method based on conductive polymer as extraction phase for disposable pipette extraction for the determination of hormones and polycyclic aromatic hydrocarbons in river water samples using high-performance l. J Environ Chem Eng. 2019;7(3):103156.
 Hashemi SH, Kaykhaii M, Jamali Keikha A, Mirmoradzehi E. Box-Behnken design optimization of pipette tip solid phase extraction for methyl orange and acid red determination by spectrophotometry in seawater samples using graphite based magnetic NiFe 2 O 4 decorated exfoliated as sorbent. Spectrochim Acta – Part A Mol Biomol Spectrosc. 2019;213:218–27.
 Deng Q, Sun L, Zhu T. Preparation of porous aromatic framework modified graphene oxide for pipette-tip solid-phase extraction of theophylline in tea. Electrophoresis. 2019;2954–61.
 Yan H, Yang C, Sun Y, Row KH. Ionic liquid molecularly imprinted polymers for application in pipette-tip solid-phase extraction coupled with gas chromatography for rapid screening of dicofol in celery. J Chromatogr A. 2014;1361:53–9.
 Sadeghi S, Olieaei S. Nanostructured polyaniline based pipette tip solid phase extraction coupled with high-performance liquid chromatography for the selective determination of trace levels of three sulfonamides in honey and milk samples with the aid of experimental design met. Microchem J. 2019;146(November 2018):974–85.
 Springer V, Jacksén J, Ek P, Lista AG, Emmer Å. Determination of fluoroquinolones in bovine milk samples using a pipette-tip SPE step based on multiwalled carbon nanotubes prior to CE separation. J Sep Sci. janeiro de 2014;37(1–2):158–64.
 İlktaç R, Aksuner N, Henden E. Selective and sensitive fluorimetric determination of carbendazim in apple and orange after preconcentration with magnetite-molecularly imprinted polymer. Spectrochim Acta Part A Mol Biomol Spectrosc. março de 2017;174:86–93.
 Wang Z, Wang Y, Gong F, Zhang J, Hong Q, Li S. Biodegradation of carbendazim by a novel actinobacterium Rhodococcus jialingiae djl-6-2. Chemosphere. outubro de 2010;81(5):639–44.
 Augusto Santos Aguiar Júnior C, Leandro Rodrigues dos Santos A, Marcio de Faria A. Disposable pipette extraction using a selective sorbent for carbendazim residues in orange juice. Food Chem. 2019;125756.
 Ma Y, Liu L, Tang W, Zhu T. Sulfonated poly(styrene-divinylbenzene) modified with amines and the application for pipette-tip solid-phase extraction of carbendazim in apples. J Sep Sci. 2017;40(20):3938–45.
 Zhang H, Li Y, Zhu J, Li H, Li D, Liu Z, et al. Disposable Pipette Extraction (DPX) Coupled with Liquid Chromatography–Tandem Mass Spectrometry for the Simultaneous Determination of Pesticide Residues in Wine Samples. Food Anal Methods. 2019;12(10):2262–72.
 Shi Z, Li Q, Xu D, Huai Q, Zhang H. Graphene-based pipette tip solid-phase extraction with ultra-high performance liquid chromatography and tandem mass spectrometry for the analysis of carbamate pesticide residues in fruit juice. J Sep Sci. 2016;39(22):4391–7.
 LI Kai;LIU Yong-qiang;ZHANG Jin-ling;PAN Yu-xiang;TIAN Guo-ning;SUN Jun;Weifang Entry-Exit Inspection and Quarantine Bureau; Application of DPX-Q tips for analysis of 102 pesticide residues in fruits and vegetables by GC-MS. Chinese J Anal Lab. 2015;(2):28.
 Fernandes VC, Domingues VF, Mateus N, Delerue-Matos C. Comparison of disposable pipette extraction and dispersive solid-phase extraction in the QuEChERS method for analysis of pesticides in strawberries. J Chromatogr Sci. 2014;52(10):1–7.
 Microsep W, Co B. Determination of 9 kinds of pesticide residues in fruits and vegetables using disposable pipette extraction and gas chromatography–tandem mass spectrometry. J Food Saf Qual. 2019;10(10):3017–23.
 Song S, Zhang C, Chen Z, He F, Wei J, Tan H, et al. Simultaneous determination of neonicotinoid insecticides and insect growth regulators residues in honey using LC–MS/MS with anion exchanger-disposable pipette extraction. J Chromatogr A. 2018;1557:51–61.
 Chen L, Dang X, Ai Y, Chen H. Preparation of an acryloyl β-cyclodextrin-silica hybrid monolithic column and its application in pipette tip solid-phase extraction and HPLC analysis of methyl parathion and fenthion. J Sep Sci. 2018;41(18):3508–14.
 Wang M, Yan H, Yuan Y, Han Y. Pipette-tip solid-phase extraction by use of a sol-gel hybrid adsorbent: a new pretreatment strategy for rapid screening of cucumbers for cyanazine and atrazine. Anal Bioanal Chem. 2015;407(4):1231–9.
 Yang C, Lv T, Yan H, Wu G, Li H. Glyoxal-Urea-Formaldehyde Molecularly Imprinted Resin as Pipette Tip Solid-Phase Extraction Adsorbent for Selective Screening of Organochlorine Pesticides in Spinach. J Agric Food Chem. 2015;63(43):9650–6.
 Du T, Cheng J, Wu M, Wang X, Zhou H, Cheng M. An in situ immobilized pipette tip solid phase microextraction method based on molecularly imprinted polymer monolith for the selective determination of difenoconazole in tap water and grape juice. J Chromatogr B Anal Technol Biomed Life Sci. 2014;951–952(1):104–9.
 Podhorniak L V. The Use of Dispersive Pipet Extraction (DPX) Tips for the Sample Cleanup of Apples, Pears, and Oranges in the Analysis of Formetanate HCl. J AOAC Int. 1 de maio de 2014;97(3):942–5.
 Cabrices OG, Schreiber A, Brewer WE. Automated Sample Preparation and Analysis Workfl ows for Pesticide Residue Screenings in Food Samples using DPX-QuEChERS with LC/MS/MS. AN/2013. 2013;8:1–10.
 Li Z, Li Y, Liu X, Li X, Zhou L, Pan C. Multiresidue analysis of 58 pesticides in bean products by disposable pipet extraction (DPX) cleanup and gas chromatography-mass spectrometry determination. J Agric Food Chem. 2012;60(19):4788–98.
 Guan H, Brewer WE, Garris ST, Morgan SL. Disposable pipette extraction for the analysis of pesticides in fruit and vegetables using gas chromatography/mass spectrometry. J Chromatogr A. 2010;1217(12):1867–74.
 Koesukwiwat U, Lehotay SJ, Miao S, Leepipatpiboon N. High throughput analysis of 150 pesticides in fruits and vegetables using QuEChERS and low-pressure gas chromatography-time-of-flight mass spectrometry. J Chromatogr A. 2010;1217(43):6692–703.
 Guan H, Brewer WE, Garris ST, Craft C, Morgan SL. Multiresidue analysis of pesticides in fruits and vegetables using disposable pipette extraction (DPX) and micro-luke method. J Agric Food Chem. 2010;58(10):5973–81.
 Guan H, Brewer WE, Morgan SL. New approach to multiresidue pesticide determination in foods with high fat content using disposable pipette extraction (DPX) and gas chromatography-mass spectrometry (GC-MS). J Agric Food Chem. 2009;57(22):10531–8.
 Guan H, Brewer WE, Morgan SL, Stuff JR, Whitecavage JA, Foster FD. Automated Multi-Residue Pesticide Analysis in Fruits and Vegetables by Disposable Pipette Extraction (DPX) and Gas Chromatography/Mass Spectrometry. AN/2009. 2009;1:1–7.