Computer-aided design of magnetic dummy molecularly imprinted polymers for solid-phase extraction of ten phthalates from food prior to their determination by GC-MS/MS
Magnetic dummy molecularly imprinted polymers (MDMIPs) were prepared by combining the surface imprinting technique with computer simulation for selective recognition of phthalate esters (PAEs). A computational study based on the density functional theory was performed to evaluate the template–monomer geometry and interaction energy in the prepolymerization mixture. The MDMIPs were characterized by transmission electron microscopy, scanning electron microscopy, vibrating sample magnetometry, X-ray diffraction, and Fourier transform infrared spectroscopy. They exhibited (a) high saturation magnetization of 53.14 emu g−1 (leading to fast separation), and (b) large adsorption capacity, fast binding kinetics, and high selectivity for PAEs. Subsequently, a molecularly imprinted solid-phase extraction procedure followed by GC-MS was established for selective extraction and determination of 10 PAEs in food samples. Under the optimal experimental conditions, the response (peak area) was linear in the 0.5–100 ng mL−1 concentration range. The limits of detection ranged from 0.15 to 1.64 ng g−1. The method was applied to the determination of PAEs in spiked real samples. The recoveries for 10 PAEs from various foods were in the range of 73.7%–98.1%, with relative standard deviations of 1.7%–10.2%.
KeywordsPhthalate esters Molecular simulation Quantum chemical calculations Dummy template Molecularly imprinted polymers Surface imprinting Magnetic solid-phase extraction Adsorbent Food analysis Gas chromatography-tandem mass spectrometry
This study was financially supported by the Doctoral Scientific Fund Project of the Xinjiang Production and Construction Corps (2014BB007); National Natural Science Foundation of China (21567027).
Compliance with ethical standards
The author(s) declare that they have no competing interests.
- 4.Högberg J, Hanberg A, Berglund M, Skerfving S, Remberger M, Calafat AM, Filipsson AF, Jansson B, Johansson N, Appelgren M, Hakansson H (2008) Phthalate diesters and their metabolites in human breast milk, blood or serum, and urine as biomarkers of exposure in vulnerable populations. Environ Health Perspect 116:334–339CrossRefPubMedGoogle Scholar
- 7.Benson R (2009) Hazard to the developing male reproductive system from cumulative exposure to phthalate esters-dibutyl phthalate, diisobutyl phthalate, butyl benzyl phthalate, diethylhexyl phthalate, dipentyl phthalate, and diisononyl phthalate. Regul Toxicol Pharmacol 53(2):90–101CrossRefPubMedGoogle Scholar
- 19.Nicholls IA, Andersson HS, Golker K, Henschel H, Karlsson BCG, Olsson GD, Rosengren AM, Shoravi S, Suriyanarayanan S, Wiklander JG, Wikman S (2011) Rational design of biomimetic molecularly imprinted materials: theoretical and computational strategies for guiding nanoscale structured polymer development. Anal Bioanal Chem 400:1771–1786CrossRefPubMedGoogle Scholar
- 20.Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery Jr JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, Gaussian, Inc., Wallingford CTGoogle Scholar
- 24.National Standard of the People’s Republic of China, GB/T 21911–2008Google Scholar
- 27.Yang R, Liu YX, Yan XY, Liu SM (2016) Simultaneous extraction and determination of phthalate esters in aqueous solution by yolk-shell magnetic mesoporous carbon-molecularly imprinted composites based on solid-phase extraction coupled with gas chromatography-mass spectrometry. Talanta 161:114–121CrossRefPubMedGoogle Scholar