Extração em fase sólida magnética (MSPE): Fundamentos e aplicações
Silva, Amandha Kaiser da; Sobieski Neto, Eduardo; Viana, Luiz Henrique; Lanças, Fernando M.; Nazariob, Carlos Eduardo Domingues
Palavras-chave: preparo de amostra, MSPE, nanopartículas magnéticas, análise de traços.
Resumo: Diversas estratégias de preparo de amostras têm sido desenvolvidas com o objetivo de diminuir a tempo de análise e a manipulação da amostra, e maximizar a pré- concentração dos analitos em matrizes complexas. O uso da tecnologia de separação magnética tem se destacado para esta finalidade pela simplificação das etapas de preparo de amostra. Neste conceito, a extração em fase sólida magnética (MSPE) baseia-se na manipulação de nanopartículas magnéticas para promover a separação das fases. Além da simplicidade e alta eficiência de extração, a MSPE supera alguns inconvenientes da SPE e d-SPE convencional. Nesta revisão, são discutidos os conceitos e estratégias de síntese das partículas magnéticas modificadas com diversos recobrimentos (sílica, MIP, surfactantes, líquidos iônicos, grafeno e derivados) para a extração e pré-concentração dos analitos em diversas matrizes.
 Fumes BH, Silva MR, Andrade FN, Nazario CED, Lanças FM. Recent advances and future trends in new materials for sample preparation. TrAC – Trends Anal Chem. 2015;71:9-25.
 Socas-Rodríguez B, Herrera-Herrera A V, Asensio-Ramos M, Hernández-Borges J. Dispersive Solid-Phase Extraction. In: Analytical Separation Science. Wiley-VCH; 2015. p. 1525–70.
 González-Sálamo J, Herrera-Herrera AV, Fanali C, Hernández-Borges J. Magnetic nanoparticles for solid-phase extraction. LCGC Eur. 2016;29(4):180–93.
 Deng Y, Qi D, Deng C, Zhang X, Zhao D. Superparamagnetic High-Magnetization Microspheres with an Fe3O4@SiO2 Core and Perpendicularly Aligned Mesoporous SiO2 Shell for Removal of Microcystins. J Am Chem Soc. American Chemical Society; 2008 Jan 1;130(1):28–9.
 Towler PH, Smith JD, Dixon DR. Magnetic recovery of radium, lead and polonium from seawater samples after preconcentration on a magnetic adsorbent of manganese dioxide coated magnetite. Anal Chim Acta. 1996;328(1):53–9.
 Šafaříková M, Šafařík I. Magnetic solid-phase extraction. J Magn Magn Mater. 1999;194(1):108–12.
 Francisquini E, Schoenmaker J, Souza JA. Nanopartículas magnéticas e suas aplicações. In p. 269–89.
 Dowling A, Clift R, Grobert N, Hutton D, Oliver R, O’neill O, et al. Nanoscience and nanotechnologies: opportunities and uncertainties. The Royal Society. 2004. 618-618 p.
 Beveridge JS, Stephens JR, Williams ME. The use of magnetic nanoparticles in analytical chemistry. Annu Rev Anal Chem. 2011;4:251–73.
 Rocío-Bautista P, Pino V. Extraction Methods Facilitated by the use of Magnetic Nanoparticles. In: Analytical Separation Science. Wiley-VCH; 2015. p. 1681–723.
 Cornell RM, Schwertmann U. 2nd ed. Wiley-VCH; 2003. 705 p.
 Wu W, Wu Z, Yu T, Jiang C, Kim W-S. Recent progress on magnetic iron oxide nanoparticles: synthesis, surface functional strategies and biomedical applications. Sci Technol Adv Mater. 2015;16(2):1–43.
 Knobel M, Nunes WC, Socolovsky LM, Biasi E De, Vargas JM, Denardin JC. Superparamagnetism and other magnetic features in granular materials: a review on ideal and real systems. J Nanosci Nanotechnol. 2008;8(4):2836–57.
 Wu W, He Q, Jiang C. Magnetic iron oxide nanoparticles: Synthesis and surface functionalization strategies. Nanoscale Res Lett. 2008;3(11):397–415.
 Tavengwa NT, Cukrowska E, Chimuka L. Synthesis, adsorption and selectivity studies of N-propyl quaternized magnetic poly(4- vinylpyridine) for hexavalent chromium. Talanta. 2013;116:670–7.
 Naghizadeh M, Taher MA, Behzadi M, Hassani Moghaddam F. Simultaneous preconcentration of bismuth and lead ions on modified magnetic core–shell nanoparticles and their determination by ETAAS. Chem Eng J. 2015;281:444–52.
 Shi H, Yang J, Zhu L, Yang Y, Yuan H, Yang Y, et al. Removal of Pb2+, Hg2+, and Cu2+by Chain-Like Fe3O4@SiO2@ Chitosan Magnetic Nanoparticles. J Nanosci Nanotechnol. 2016;16(2):1871–82.
 Pirbazari AE, Saberikhah E, Gorabi NGA. Fe3O4 nanoparticles loaded onto wheat straw: an efficient adsorbent for Basic Blue 9 adsorption from aqueous solution. Desalin Water Treat. 2014;1–12.
 Lai L, Xie Q, Chi L, Gu W, Wu D. Adsorption of phosphate from water by easily separable Fe3O4@SiO2 core/shell magnetic nanoparticles functionalized with hydrous lanthanum oxide. J Colloid Interface Sci. 2016;465:76–82.
 Rajput S, Pittman CU, Mohan D. Magnetic magnetite (Fe3O4) nanoparticle synthesis and applications for lead (Pb2+) and chromium (Cr6+) removal from water. J Colloid Interface Sci. 2016;468:334–46.
 Bao S, Tang L, Li K, Ning P, Peng J, Guo H, et al. Highly selective removal of Zn(II) ion from hot-dip galvanizing pickling waste with amino-functionalized Fe3O4@SiO2 magnetic nano-adsorbent. J Colloid Interface Sci. 2016;462:235–42.
 Teja AS, Koh P. Synthesis, properties, and applications of magnetic iron oxide nanoparticles. 2009;55:22–45.
 Zhang C, Yu Z, Zeng G, Huang B, Dong H, Huang J, et al. Phase transformation of crystalline iron oxides and their adsorption abilities for Pb and Cd. Chem Eng J 2016;284:247–59.
 Lu AH, Salabas EL, Schüth F. Magnetic nanoparticles: Synthesis, protection, functionalization, and application. Angew Chemie – Int Ed. 2007;46(8):1222–44.
 Jamshaid T, Neto ETT, Eissa MM, Zine N, Kunita MH, El-Salhi AE, et al. Magnetic particles: From preparation to lab-on-a-chip, biosensors, microsystems and microfluidics applications. TrAC – Trends Anal Chem. 2015;79:344–62.
 González-Sálamo J, Socas-Rodríguez B, Hernández-Borges J, Rodríguez-Delgado MÁ. Core-shell poly(dopamine) magnetic nanoparticles for the extraction of estrogenic mycotoxins from milk and yogurt prior to LC-MS analysis. Food Chem. 2017;215:362–8.
 Yu X, Yang H. Pyrethroid residue determination in organic and conventional vegetables using liquid-solid extraction coupled with magnetic solid phase extraction based on polystyrene-coated magnetic nanoparticles. Food Chem. 2016;217:303–10.
 Wang P, Wang X, Yu S, Zou Y, Wang J, Chen Z, et al. Silica coated Fe3O4 magnetic nanospheres for high removal of organic pollutants from wastewater. Chem Eng J. 2016;306:280–8.
 Philipse AP, Bruggen MPB Van, Pathmamanoharan C. Magnetic Silica Dispersions: Preparation and Stability of SurfaceModified Silica Particles with a Magnetic Core. Langmuir. 1994;10(17):92–9.
 Lu Y, Yin Y, Mayers BT, Xia Y. Modifying the Surface Properties of Superparamagnetic Iron Oxide Nanoparticles through a Sol-Gel Approach. Nano Lett. 2002;2(3):183–6.
 Andrade AL, Souza DM, Pereira MC, Fabris JD, Domingues RZ. Synthesis and characterization of magnetic nanoparticles coated with silica through a sol-gel approach. Ceramica. 2009;55:420–4.
 Im SH, Herricks T, Lee YT, Xia Y. Synthesis and characterization of monodisperse silica colloids loaded with superparamagnetic iron oxide nanoparticles. Chem Phys Lett. 2005;401(1–3):19–23.
 Deng YH, Wang CC, Hu JH, Yang WL, Fu SK. Investigation of formation of silica-coated magnetite nanoparticles via sol-gel approach. Colloids Surfaces A Physicochem Eng Asp. 2005;262(1–3):87–93.
 Zheng J, Yu Z, Ji G, Lin X, Lv H, Du Y. Reduction synthesis of FexOy@ SiO2 core – shell nanostructure with enhanced microwave-absorption properties. J Alloys Compd. 2014;602:8–15.
 Kobayashi Y, Horie M, Konno M, Rodriguez-Gonzalez B, Liz-Marzan LM. Preparation and properties of silica-coated cobalt nanoparticles. J Phys Chem B. 2003;107(30):7420–5.
 Tago T, Shibata Y, Hatsuta T, Miyajima K, Kishida M, Tashiro S, et al. Synthesis of silica-coated rhodium nanoparticles in reversed micellar solution. J Mater Sci. 2002;37(5):977–82.
 Dobson J, Tan W, Santra S, Tapec R, Theodoropoulou N, Dobson J. Synthesis and Characterization of Silica-Coated Iron Oxide Nanoparticles in Microemulsion: The Effect of Nonionic Surfactants Synthesis and Characterization of Silica-Coated Iron Oxide Nanoparticles in Microemulsion : The Effect of Nonionic. 2015;2900–6.
 Ding H, Zhang Y, Wang S, Xu J, Xu SC, Li G. Fe3O4@SiO2 core/shell nanoparticles: the silica coating regulations with a singlecore for different core sizes and shell thicknesses. Chem M. 2012;24:4572–80.
 Sonmez M, Georgescu M, Alexandrescu L, Gurau D, Ficai A, Ficai D, et al. Synthesis and applications of Fe3O4/SiO2 core-shell materials. Curr Pharm Des. 2015;21(37):5324–35.
 Jiang C, Sun Y, Yu X, Gao Y, Zhang L, Wang Y, et al. Application of C18-functional magnetic nanoparticles for extraction of aromatic amines from human urine. J Chromatogr B Anal Technol Biomed Life Sci. 2014;947–948:49–56.
 Ma J, Yan F, Chen F, Jiang L, Li J, Chen L. C 18 -Functionalized Magnetic Silica Nanoparticles for Solid Phase Extraction of Microcystin-LR in Reservoir Water Samples Followed by HPLC-DAD Determination. J Liq Chromatogr Relat Technol. 2015;38(6):655–61.
 Mahmoud ME, Amira MF, Zaghloul AA, Ibrahim GAA. Microwave-enforced sorption of heavy metals from aqueous solutions on the surface of magnetic iron oxide-functionalized-3-aminopropyltriethoxysilane. Chem Eng J. 2016;293:200–6.
 Peng X, Zhang W, Gai L, Jiang H, Tian Y. Thiol-functionalized Fe3O4/SiO2 microspheres with superparamagnetism and their adsorption properties for Au(III) ion separation. Russ J Phys Chem A. 2016;90(8):1656–64.
 Tadjarodi A, Abbaszadeh A, Taghizadeh M, Shekari N, Asgharinezhad AA. Solid phase extraction of Cd(II) and Pb(II) ions based on a novel functionalized Fe3O4@ SiO2 core-shell nanoparticles with the aid of multivariate optimization methodology. Mater Sci Eng C. 2015;49:416–21.
 Ma S, He M, Chen B, Deng W, Zheng Q, Hu B. Magnetic solid phase extraction coupled with inductively coupled plasma mass spectrometry for the speciation of mercury in environmental water and human hair samples. Talanta. 2016;146:93–9.
 Hussain S, Khan S, Gul S, Pividori MI, Del Pilar Taboada Sotomayor M. A novel core@shell magnetic molecular imprinted nanoparticles for selective determination of folic acid in different food samples. React Funct Polym. 2016;106:51–6.
 Wang W, Ma R, Wu Q, Wang C, Wang Z. Magnetic microsphere-confined graphene for the extraction of polycyclic aromatic hydrocarbons from environmental water samples coupled with high performance liquid chromatography-fluorescence analysis. J Chromatogr A. 2013;1293:20–7.
 Chen S, Chen J, Zhu X. Solid phase extraction of bisphenol A using magnetic core-shell (Fe3O4@SiO2) nanoparticles coated with an ionic liquid, and its quantitation by HPLC. Microchim Acta. 2016;183(4):1315–21.
 Chen J, Wang Y, Ding X, Huang Y, Xu K. Magnetic solid-phase extraction of proteins based on hydroxy functional ionic liquidmodified magnetic nanoparticles. Anal Methods. 2014;6(20):8358–67.
 Martín-Esteban A. Molecularly-imprinted polymers as a versatile, highly selective tool in sample preparation. TrAC Trends Anal Chem. 2013;45:169–81.
 Marsh KN, Boxall JA, Lichtenthaler R. Room temperature ionic liquids and their mixtures – A review. Fluid Phase Equilib. 2004;219(1):93–8.
 Yue C, Fang D, Liu L, Yi TF. Synthesis and application of task-specific ionic liquids used as catalysts and/or solvents in organic unit reactions. J Mol Liq. 2011;163(3):99–121.
 Casado-Carmona FA, Alcudia-León M del C, Lucena R, Cárdenas S, Valcárcel M. Magnetic nanoparticles coated with ionic liquid for the extraction of endocrine disrupting compounds from waters. Microchem J. 2016;128:347–53.
 Hummers WS, Offeman RE. Preparation of Graphitic Oxide. J Am Chem Soc. 1958;80(6):1339–1339.
 Su S, Chen B, He M, Hu B, Xiao Z. Determination of trace/ultratrace rare earth elements in environmental samples by ICP-MS after magnetic solid phase extraction with Fe 3O4@SiO2@polyaniline-graphene oxide composite. Talanta. 2014;119:458–66.
 Wu L, Yu L, Ding X, Li P, Dai X, Chen X, et al. Magnetic solid-phase extraction based on graphene oxide for the determination of lignans in sesame oil. Food Chem. 2017;217.
 Ding X, Wang Y, Wang Y, Pan Q, Chen J, Huang Y, et al. Preparation of magnetic chitosan and graphene oxide-functional guanidinium ionic liquid composite for the solid-phase extraction of protein. Anal Chim Acta. 2015;861:36–46.
 Sha Y, Huang D, Zheng S, Deng C. Development of magnetic graphene as an adsorbent and matrix for selective enrichment and detection of crotonaldehyde in saliva by MALDI-TOF-MS. Anal Methods. 2013;5(18):4585–90.
 Gupta S, Tai N-H. Carbon materials as oil sorbents: a review on the synthesis and performance. J Mater Chem A. Royal Society of Chemistry; 2016;4(5):1550–65.
 Augusto F, Carasek E, Silva RGC, Rivellino SR, Batista AD, Martendal E. New sorbents for extraction and microextraction techniques. J Chromatogr A. 2010;1217(16):2533–42.
 Deng X, Guo Q, Chen X, Xue T, Wang H, Yao P. Rapid and effective sample clean-up based on magnetic multiwalled carbon nanotubes for the determination of pesticide residues in tea by gas chromatography-mass spectrometry. Food Chem. 2014;145:853–8.
 Tian J, Xu J, Zhu F, Lu T, Su C, Ouyang G. Application of nanomaterials in sample preparation. J Chromatogr A. 2013;1300:2– 16.
 Pena-Pereira F, Duarte RMBO, Trindade T, Duarte AC. Determination of anionic surface active agents using silica coated magnetite nanoparticles modified with cationic surfactant aggregates. J Chromatogr A. 2013;1299:25–32.
 He H, Yuan D, Gao Z, Xiao D, He H, Dai H, et al. Mixed hemimicelles solid-phase extraction based on ionic liquid-coated Fe3O4/SiO2 nanoparticles for the determination of flavonoids in bio-matrix samples coupled with high performance liquid chromatography. J Chromatogr A. 2014;1324:78–85.
 Manafi MH, Allahyari M, Pourghazi K, Amoli-Diva M, Taherimaslak Z. Surfactant-enhanced spectrofluorimetric determination of total aflatoxins from wheat samples after magnetic solid-phase extraction using modified Fe3O4 nanoparticles. Spectrochim Acta – Part A Mol Biomol Spectrosc. 2015;146:43–9.
 Abdolmohammad-Zadeh H, Talleb Z. Speciation of As(III)/As(V) in water samples by a magnetic solid phase extraction based on Fe3O4/Mg-Al layered double hydroxide nano-hybrid followed by chemiluminescence detection. Talanta. 2014;128:147–55.
 Xie L, Guo J, Zhang Y, Shi S. Efficient determination of protocatechuic acid in fruit juices by selective and rapid magnetic molecular imprinted solid phase extraction coupled with HPLC. J Agric Food Chem. 2014;62(32):8221–8.
 Binellas CS, Stalikas CD. Magnetic octadecyl-based matrix solid-phase dispersion coupled with gas chromatography with mass spectrometry in a proof-of-concept determination of multi-class pesticide residues in carrots. J Sep Sci. 2015;38(20):3575–81.
 Chai W, Wang H, Zhang Y, Ding G. Preparation of polydopamine-coated magnetic nanoparticles for dispersive solid-phase extraction of water-soluble synthetic colorants in beverage samples with HPLC analysis. Talanta. 2016;149:13–20.
 Fasih Ramandi N, Shemirani F. Selective ionic liquid ferrofluid based dispersive-solid phase extraction for simultaneous preconcentration/separation of lead and cadmium in milk and biological samples. Talanta. 2015;131:404–11.
 Bagheri A, Taghizadeh M, Behbahani M, Akbar Asgharinezhad A, Salarian M, Dehghani A, et al. Synthesis and characterization of magnetic metal-organic framework (MOF) as a novel sorbent, and its optimization by experimental design methodology for determination of palladium in environmental samples. Talanta. 2012;99:132–9.
 Tian M, Feng W, Ye J, Jia Q. Preparation of Fe3O4@TiO2/graphene oxide magnetic microspheres for microchip-based preconcentration of estrogens in milk and milk powder samples. Anal Methods. 2013;5(16):3984.
 Asgharinezhad AA, Rezvani M, Ebrahimzadeh H, Shekari N, Ahmadinasab N, Loni M. Solid phase extraction of Cd(II) and Pb(II) ions based on a novel functionalized Fe3O4@ SiO2 core-shell nanoparticles with the aid of multivariate optimization methodology. Anal Methods. 2015;7:10350–8.
 Zhang L, Wu H, Liu Z, Gao N, Du L, Fu Y. Ionic Liquid-Magnetic Nanoparticle Microextraction of Safranin T in Food Samples. Food Anal Methods. 2015;8(3):541–8.
 Aboufazeli F, Zhad HRLZ, Sadeghi O, Karimi M, Najafi E. Novel ion imprinted polymer magnetic mesoporous silica nanoparticles for selective separation and determination of lead ions in food samples. Food Chem. 2013;141(4):3459–65.
 Abolhasani J, Hosseinzadeh Khanmiri R, Babazadeh M, Ghorbani-Kalhor E, Edjlali L, Hassanpour A. Determination of Hg(II) ions in sea food samples after extraction and preconcentration by novel Fe3O4@SiO2@polythiophene magnetic nanocomposite. Environ Monit Assess. 2015;187(9):554.
 Asgharinezhad AA, Ebrahimzadeh H. A simple and fast method based on mixed hemimicelles coated magnetite nanoparticles for simultaneous extraction of acidic and basic pollutants. Anal Bioanal Chem. 2016;408(2):473–86.
 Zhang S, Yao W, Ying J, Zhao H. Polydopamine-reinforced magnetization of zeolitic imidazolate framework ZIF-7 for magnetic solid-phase extraction of polycyclic aromatic hydrocarbons from the air-water environment. J Chromatogr A. 2016;1452:18–26.
 Rashidi Nodeh H, Wan Ibrahim WA, Ali I, Sanagi MM. Development of magnetic graphene oxide adsorbent for the removal and preconcentration of As(III) and As(V) species from environmental water samples. Environ Sci Pollut Res. 2016;23(10):9759–73.
 Zhang S, Luo H, Zhang Y, Li X, Liu J, Xu Q, et al. In situ rapid magnetic solid-phase extraction coupled with HPLC-ICP-MS for mercury speciation in environmental water. Microchem J. 2016;126:25–31.
 Abd Ali LI, Wan Ibrahim WA, Sulaiman A, Kamboh MA, Sanagi MM. New chrysin-functionalized silica-core shell magnetic nanoparticles for the magnetic solid phase extraction of copper ions from water samples. Talanta. 2016;148:191–9.
 Camba M, Romero V, Lavilla I, Bendicho C. In situ growth of Fe 3 O 4 nanoparticles for dispersive magnetic micro-solid phase extraction of cadmium followed by ETAAS detection. Anal Methods. 2015;7(3):1154–60.
 Esmaeili-Shahri E, Es’haghi Z. Superparamagnetic Fe3O4@SiO2 core-shell composite nanoparticles for the mixed hemimicelle solid-phase extraction of benzodiazepines from hair and wastewater samples before high-performance liquid chromatography analysis. J Sep Sci. 2015;38(23):4095–104.
 Dimpe KM, Nyaba L, Magoda C, Ngila JC, Nomngongo PN. Synthesis, modification, characterization and application of AC@ Fe2O3@MnO2 composite for ultrasound assisted dispersive solid phase microextraction of refractory metals in environmental samples. Chem Eng J. 2016;308:169–76.
 Diniz KM, Tarley CRT. Speciation analysis of chromium in water samples through sequential combination of dispersive magnetic solid phase extraction using mesoporous amino-functionalized Fe3O4/SiO2 nanoparticles and cloud point extraction. Microchem J. 2015;123:185–95.
 Sheykhaghaei G, Hosaini M, Khanahmadzadeh S. Synthesis and characterization of the core-shell magnetic molecularly imprinted polymer nanoparticles for selective extraction of tizanidine in human plasma. Bull Mater Sci. 2016;39(3):647–53.
 Yan H, Gao M, Yang C, Qiu M. Ionic liquid-modified magnetic polymeric microspheres as dispersive solid phase extraction adsorbent: A separation strategy applied to the screening of sulfamonomethoxine and sulfachloropyrazine from urine. Anal Bioanal Chem. 2014;406(11):2669–77.
 Bagheri H, Daliri R, Roostaie A. A novel magnetic poly(aniline-naphthylamine)-based nanocomposite for micro solid phase extraction of rhodamine B. Anal Chim Acta. 2013;794:38–46.
 Ding J, Mao LJ, Guo N, Yu L, Feng YQ. Determination of endogenous brassinosteroids using sequential magnetic solid phase extraction followed by in situ derivatization/desorption method coupled with liquid chromatography-tandem mass spectrometry. J Chromatogr A. 2016;1446:103–13.
 Mahpishanian S, Sereshti H. Graphene oxide-based dispersive micro-solid phase extraction for separation and preconcentration of nicotine from biological and environmental water samples followed by gas chromatography-flame ionization detection. Talanta 2014;130:71–7.