Sains Malaysiana 51(6)(2022): 1707-1724

http://doi.org/10.17576/jsm-2022-5106-09

Preparation of Molecularly Imprinted Polymer for Selective Solid-Phase Extraction and Simultaneous Determination of Five Sulfonylurea Herbicides in Cereals

(Penyediaan Polimer Teraan Molekul untuk Pengekstrakan Fasa-Pepejal Terpilih dan Penentuan Serentak Lima Herbisid Sulfonilurea dalam Bijirin)

YUAN LIU^1,2, JIAN WANG^1,2,*, FENGLI WANG¹, ZHENGZHENG HAN¹, XURAN ZHU¹, YANG LIU¹, MING CHENG¹, MENGMENG SONG¹, RUI WANG¹, TIANRUI WANG¹, YUTIAN MIAO², JIA LIU² & YONGXIN SHE¹

¹Hebei Key Laboratory of Quality & Safety Analysis-Testing for Agro-Products and Food, Hebei North University, Zhangjiakou 075000, China

²National Non-staple Food quality supervision and Inspection Center, Beijing, 102209, China

³Institute of Quality Standards & Testing Technology for Agro-Products, Chinese Academy of Agricultural Sciences, Beijing, 100081, China

Diserahkan: 25 Julai 2021/Diterima: 3 November 2021

ABSTRACT

Molecular imprinting polymer (MIP) has been increasingly employed for sulfonylurea herbicides (SUHs) detection in different matrices. A novel MIP that was effective as a highly class-selective sorbent in molecularly imprinted solid-phase extraction (MISPE) was successfully prepared for isolation and purification of SUHs, namely, metsulfuron-methyl, chlorsulfuron, chlorimuron-ethyl, prosulfuron, and pyrazosulfuron-ethyl, in rice, corn and soybean samples. The MIP was synthesized by precipitation polymerization using metsulfuron-methyl as the template, 4-vinylpyridine as the functional monomer, ethylene glycol dimethacrylate as the crosslinker, and MeCN as the porogen. The polymerization system of the MIP was optimized, and its adsorption performances were evaluated by comparing its adsorption isotherms and adsorption kinetics with those of a non-imprinted polymer (NIP). Following MISPE for extracting and enriching SUHs from rice, corn and soybean samples, high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was performed. Acceptable recoveries were observed at SUHs contaminant concentrations of 10, 20 and 40 μg/L: from 77.56 to 99.81%, with relative standard deviations of <13.8% (n = 5) for all samples. The limits of detection for the five SUHs were 0.21-0.26 μg/L. The results demonstrated that the proposed MISPE-HPLC-MS/MS method is an effective approach for the simultaneous and sensitive determination of the five SUHs in rice, corn and soybean samples.

Keywords: Cereals; HPLC-MS/MS; molecularly imprinted polymers; solid-phase extraction; sulfonylurea herbicides

ABSTRAK

Polimer teraan molekul (MIP) semakin banyak digunakan untuk pengesanan herbisid sulfonilurea (SUH) dalam matriks yang berbeza. MIP novel yang berkesan sebagai penjerap selektif kelas tinggi dalam pengekstrakan fasa pepejal teraan molekul (MISPE) telah berjaya disediakan untuk pengasingan dan penulenan SUH, iaitu, metsulfuron-metil, klosulfuron, klorimuron-etil, prosulfuron, dan pirazosulfuron-etil, dalam sampel beras, jagung dan kacang soya. MIP telah disintesis melalui pempolimeran pemendakan menggunakan metsulfuron-metil sebagai templat, 4-vinilpiridin sebagai monomer berfungsi, etilena glikol dimetakrilat sebagai penghubung silang dan MeCN sebagai porogen. Sistem pempolimeran MIP telah dioptimumkan dan prestasi penjerapannya dinilai dengan membandingkan isoterma penjerapan dan kinetik penjerapan dengan polimer tidak dicetak (NIP). Melalui penggunaan MISPE untuk mengekstrak dan memperkayakan SUH daripada sampel beras, jagung dan kacang soya, spektrometri jisim tandem kromatografi cecair berprestasi tinggi (HPLC-MS/MS) telah dilakukan. Pemulihan yang boleh diterima telah diperhatikan pada kepekatan pencemar SUH sebanyak 10, 20 dan 40 μg/L: dari 77.56 hingga 99.81%, dengan sisihan piawai relatif <13.8% (n = 5) untuk semua sampel. Had pengesanan untuk lima SUH ialah 0.21-0.26 μg/L. Keputusan menunjukkan bahawa kaedah MISPE-HPLC-MS/MS yang dicadangkan merupakan pendekatan yang berkesan untuk penentuan serentak dan sensitif lima SUH dalam sampel beras, jagung dan kacang soya.

Kata kunci: Bijirin; HPLC-MS/MS; pengekstrakan fasa pepejal; polimer teraan molekul; racun herba sulfonylurea

RUJUKAN

Alizadeh, T., Ganjali, M.R., Zare, M. & Norouzi, P. 2012. Selective determination of chloramphenicol at trace level in milk samples by the electrode modified with molecularly imprinted polymer. Food Chemistry 130(4): 1108-1114.

Asghar, N., Mustafa, G., Yasinzai, M., Al-Soud, Y.A., Lieberzeit, P.A. & Latif, U. 2019. Real-time and online monitoring of glucose contents by using molecular imprinted polymer-based IDEs sensor. Applied Biochemistry and Biotechnology 189(4): 1156-1166.

Augusto, F., Hantao, L.W., Mogollón, N.G.S. & Braga, S.C.G.N. 2013. New materials and trends in sorbents for solid-phase extraction. Trends in Analytical Chemistry 43: 14-23.

Bastide, J., Cambon, J.P., Breton, F., Piletsky, S.A. & Rouillon, R. 2005. The use of molecularly imprinted polymers for extraction of sulfonylurea herbicides. Analytica Chimica Acta 542(1): 97-103.

Bouri, M., Gurau, M., Salghi, R., Cretescu, I., Cretescu, M. & Rios, A. 2012. Ionic liquids supported on magnetic nanoparticles as a sorbent preconcentration material for sulfonylurea herbicides prior to their determination by capillary liquid chromatography. Analytical and Bioanalytical Chemistry 404(5): 529-1538.

Castro López, M.M., Cela Pérez, M.C., Dopico García, M.S., López Vilariño, J.M., González Rodríguez, M.V. & Barral Losada, L.F. 2012. Preparation, evaluation and characterization of quercetin-molecularly imprinted polymer for preconcentration and clean-up of catechins. Analytica Chimica Acta 721: 68-78.

Coyner, A., Gupta, G. & Jones, T. 2001. Effect of chlorsulfuron on growth of submerged aquatic macrophyte Potamogeton pectinatus (sago pondweed). Environmental Pollution 111(3): 453-455.

Dasgupta, S., Meisner, C., Wheeler, D., Xuyen, K. & Lam, N.T. 2007. Pesticide poisoning of farm workers-implications of blood test results from Vietnam. International Journal of Hygiene & Environmental 210(2): 121-132.

Ding, F., Liu, W., Zhang, X., Wu, L.J., Zhang, L. & Sun, Y. 2010. Identification of pyrazosulfuron-ethyl binding affinity and binding site subdomain IIA in human serum albumin by spectroscopic methods. Spectrochimica Acta Part A Molecular & Biomolecular Spectroscopy 75(3): 1088-1094.

European Commission. 2016. EU Pesticides Database. European Commission.

He, G., Tang, Y., Hao, Y., Shi, J. & Gao, R. 2016. Preparation and application of magnetic molecularly imprinted nanoparticles for the selective extraction of osthole in Libanotis buchtomensis herbal extract. Journal of Separation Science 39(12): 2313-2320.

He, Z., Liu, D.H., Li, R.H., Zhou, Z.Q. & Wang, P. 2012. Magnetic solid-phase extraction of sulfonylurea herbicides in environmental water samples by Fe3O4@dioctadecyl dimethyl ammonium chloride@ silica magnetic particles. Analytica Chimica Acta 747: 29-35.

Heine, S., Schild, F., Schmitt, W., Krebber, R., Gorlitz, G. & Preuss, T.G. 2016. A toxicokinetic and toxicodynamic modeling approach using Myriophyllum spicatum to predict effects caused by short-term exposure to a sulfonylurea. Environmental Toxicology and Chemistry 35(2): 376-384.

Hong, Y.S. & Chen, L.G. 2013. Extraction of quercetin from Herba Lysimachiae by molecularly imprinted-matrix solid phase dispersion. Journal of Chromatography B 941: 38-44.

Isarankura-Na-Ayudhya, C., Nantasenamat, C., Buraparuangsang, P., Piacham, T. & Prachayasittikul, V. 2008. Computational insights on sulfonamide imprinted polymers. Molecules 13(12): 3077-3091.

Ghobadi, M., Yamini, Y. & Ebrahimpour, B. 2015. Extraction and determination of sulfonylurea herbicides in water and soil samples by using ultra sound-assisted surfactant-enhanced emulsification microextraction and analysis by high-performance liquid chromatography. Ecotoxicology and Environmental Safety 112: 68-73.

Klaffenbach, P. & Holland, P.T. 1993. Analysis of sulfonylurea herbicides by gas-liquid chromatography III - Mass spectrometry and multiresidue determination. Biological Mass Spectrometry 22(10): 565-578.

Lee, M.H., Thomas, J.L., Su, Z.L., Zhang, Z.X., Lin, C.Y., Huang, Y.S., Yang, C.H. & Lin, H.Y. 2020. Doping of transition metal dichalcogenides in molecularly imprinted conductive polymers for the ultrasensitive determination of 17 β-estradiol in eel serum. Biosens Bioelectron150: 111901.

Liu, X., Chen, Z., Zhao, R., Shangguan, D., Liu, G. & Chen, Y. 2007. Uniform-sized molecularly imprinted polymer for metsulfuron-methyl by one-step swelling and polymerization method. Talanta 71(3): 1205-1210.

Mehdizadeh, M., Alebrahim, M.T. & Roushani, M. 2017. Determination of two sulfonylurea herbicides residues in soil environment using HPLC and phytotoxicity of these herbicides by lentil bioassay. Bulletin of Environmental Contamination & Toxicology 99(1): 1-7.

Michael, J.L. 2003. Environmental fate and impacts of sulfometuron on watersheds in the southern United States. Journal of Environmental Quality 32(2): 456-465.

M.M.O.A. (PRC) 2019. National food safety standard-maximum residue limits for pesticides in food. GB 2763-2019.

Núñez, L., Turiel, E., Martin-Esteban, A. & Tadeo, J.L. 2010. Molecularly imprinted polymer for the extraction of parabens from environmental solid samples prior to their determination by high performance liquid chromatography-ultraviolet detection. Talanta 80(5): 1782-1788.

Pei, M., Zhu, X. & Huang, X. 2018. Mixed functional monomers-based monolithic adsorbent for the effective extraction of sulfonylurea herbicides in water and soil samples. Journal of Chromatography A 1531: 13-21.

Qin, D., Zhao, M., Wang, J. & Lian, Z. 2020. Selective extraction and detection of norfloxacin from marine sediment and seawater samples using molecularly imprinted silica sorbents coupled with HPLC. Marine Pollution Bulletin 150: 110677.

Rejczak, T. & Tuzimski, T. 2015. Recent trends in sample preparation and liquid chromatography/mass spectrometry for pesticide residue analysis in food and related matrixes. Journal of AOAC International 98(5): 1143-1162.

Rico-Yuste, A., Walravens, J., Urraca, J.L., Abou-Hany, R.A.G., Descalzo, A.B., Orellana, G., Rychlik, M., De Saeger, S.M. & Moreno-Bondi, C. 2018. Analysis of alternariol and alternariol monomethyl ether in foodstuffs by molecularly imprinted solid-phase extraction and ultra-high-performance liquid chromatography tandem mass spectrometry. Food Chemistry 243: 357-364.

Sarmah, A.K. & Sabadie, J. 2002. Hydrolysis of sulfonylurea herbicides in soils and aqueous solutions: A review. Journal of Agricultural and Food Chemistry 50(22): 6253-6265.

Sellergren, B. 2001. Imprinted chiral stationary phases in high-performance liquid chromatography. Journal of Chromatography A 906(1-2): 227-252.

She, Y.X., Cao, W.Q., Shi, X.M., Lv, X.L., Liu, J.J., Wang, R.Y., Jin, F., Wang, J. & Xiao, H. 2010. Class-specific molecularly imprinted polymers for the selective extraction and determination of sulfonylurea herbicides in maize samples by high-performance liquid chromatography-tandem mass spectrometry. Journal of Chromatography B 878(23): 2047-2053.

Sofo, A., Scopa, A., Dumontet, S., Mazzatura, A. & Pasquale, V. 2012. Toxic effects of four sulphonylureas herbicides on soil microbial biomass. Journal of Environmental Science & Health Part B 47(7): 653-659.

Springer, V.H. & Lista, A.G. 2010. A simple and fast method for chlorsulfuron and metsulfuron methyl determination in water samples using multiwalled carbon nanotubes (MWCNTs) and capillary electrophoresis. Talanta 83(1): 126-129.

Svoboda, P., Sander, D., Plachká, K. & Nováková, L. 2017. Development of matrix effect-free MISPE-UHPLC-MS/MS method for determination of lovastatin in Pu-erh tea, oyster mushroom, and red yeast rice. Journal of Pharmaceutical Analysis 140: 367-376.

Tang, K., Chen, S., Gu, X., Wang, H., Dai, J. & Tang, J. 2008. Preparation of molecularly imprinted solid phase extraction using bensulfuron-methyl imprinted polymer and clean-up for the sulfonylurea-herbicides in soybean. Analytica Chimica Acta 614(1): 112-118.

Tang, K., Gu, X., Luo, Q., Chen, S., Wu, L. & Xiong, J. 2014. Preparation of molecularly imprinted polymer for use as SPE adsorbent for the simultaneous determination of five sulphonylurea herbicides by HPLC. Food Chemisty 150: 106-112.

Tranel, P.J. & Wright, T.R. 2002. Resistance of weeds to ALS-inhibiting herbicide: What have we learned? Weed Science 50(6): 700-712.

United States Department of Agriculture. 2008. Maximum Residue Limits (MRL) Database [DB/OL]. United States Department of Agriculture (USDA).

Walter, K.L., Strachan, S.D., Ferry, N.M., Albert, H.H., Castle, L.A. & Sebastian, S.A. 2014. Molecular and phenotypic characterization of Als1 and Als2 mutations conferring tolerance to acetolactate synthase herbicides in soybean. Pest Management Science 70(12): 1831-1839.

Xu, X., Liang, S., Meng, X., Zhang, M., Chen, Y., Zhao, D. & Li, Y. 2015. A molecularly imprinted polymer for the selective solid-phase extraction of dimethomorph from ginseng samples. Journal of Chromatography B 988: 182-186.

Yan, L., Jing, Z., Lin, R., Li, Y.X. & Zou, X.L. 2016. Application of solvent demulsification-dispersive liquid-liquid microextraction based on solidification of floating organic drop coupled with high performance liquid chromatography in determination of sulfonylurea herbicides in water and soil. Journal of the Brazilian Chemical Society 27: 1792-1799.

You, X.X. & Chen, L.G. 2016. Analysis of sulfonylurea herbicides in grain samples using molecularly imprinted polymers on the surface of magnetic carbon nanotubes by extraction coupled with HPLC. Analytical Methods-UK 8(5): 1003-1012.

Zhao, F., She, Y., Zhang, C., Cao, X., Wang, S., Zheng, L., Jin, M., Shao, H., Jin, F. & Wang, J. 2017. Selective solid-phase extraction based on molecularly imprinted technology for the simultaneous determination of 20 triazole pesticides in cucumber samples using high-performance liquid chromatography-tandem mass spectrometry. Journal of Chromatography B 1064: 143-150.

Zhao, Y.G., Zhou, L.X., Pan, S.D., Zhan, P.P., Chen, X.H. & Jin, M.C. 2014. Fast determination of 22 sulfonamides from chicken breast muscle using core-shell nanoring amino-functionalized superparamagnetic molecularly imprinted polymer followed by liquid chromatography-tandem mass spectrometry. Journal of Chromatography A 1345: 17-28.

Zhu, Q.Z., Haupt, K., Knopp, D. & Niessner, R. 2002. Molecularly imprinted polymer for metsulfuron-methyl and its binding characteristics for sulfonylurea herbicides. Analytica Chimica Acta 468(2): 217-227.

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