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

Received: 25 July 2021/Accepted: 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

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^*Corresponding author; email: liuyuanwenwen1981@126.com