Magnetic hyperbranched molecularly imprinted polymers for selective enrichment and determination of zearalenone in wheat proceeded by HPLC-DAD analysis
Graphical abstract
Introduction
Zearalenone (ZEN) (Fig. 1) is a nonsteroidal estrogenic mycotoxin synthesized by fusarium fungi, mainly found in contaminated crops, including wheat, corn and millet [1]. Due to its good thermal stability, ZEN is difficult to be destroyed. Studies have shown that residual ZEN can cause animal infertility or miscarriage and carcinogenicity [2,3], resulting in serious economic losses in agriculture and animal husbandry. At present, ZEN has been included in food safety testing in many nation and international agencies. For instance, the European Food Safety Authority established 0.25 μg kg−1 body weight as the tolerable daily intake for ZEN [4]. The Chinese Food Safety Standards clearly stipulated that the content of ZEN in corn and wheat does not exceed 60 μg kg−1 [5]. Therefore, effective detection of ZEN is of great significance.
Nowadays, several methods for detecting ZEN have been established, including thin layer chromatography [6], enzyme-linked immunoassay (ELISA) [7], high-performance liquid chromatography (HPLC) [8], gas chromatography [9] and mass spectrometry. Although these methods were effective in most case, there are still limited such as time-consuming process, low selectivity and high cost when facing the questions of complicated sample matrices and trace concentrations of target analytes. Therefore, a simple, high selective and sensitive complex sample pretreatment were particularly important.
Molecular imprinting as a promising solid phase extraction (SPE) technology has been applied in various territories due to high selectivity, simplicity rapidity, good chemical stability and easy to prepared [[10], [11], [12], [13], [14], [15]]. So far, molecular imprinted polymers (MIPs) have been applied for the selective extraction and detection of viruses [16], microorganism [17], proteins [18] and drugs [[19], [20], [21], [22]] in complex matrices. Currently, most of the functional monomers commonly used in MIPs are small molecules such as acrylamide (AA), 4-vinyl pyridine (4-VP) and methacrylic acid (MAA). However, such MIPs are difficult to imprint macromolecular templates and prone to produce non-specific sites, resulting in low adsorption efficiency as well as selectivity, which restricts their application in the field of complex matrices analysis. 2, 4, 6-trisacrylamido-3, 5-triazine (Fig. 1) is a hyperbranched functional monomer with a triamino-triazine structure [[23], [24], [25]]. The highly symmetrical compact structure of TAT can overcome the above shortcomings. Since more functional groups are contained than small molecules functional monomers, TAT can form more chemical bonds when adsorbing target molecules, which can effectively improve adsorption selectivity and adsorption capacity of MIPs [26]. Furthermore, cross-linking of the branched structure of TAT forms regular cavities, which is more advantageous for the adsorption of target analytes.
Magnetic materials have attracted great attention owing to their magnetism and outstanding characteristics, such as low cost and simple preparation process [27,28]. Magnetic MIPs are commonly prepared by coating molecularly imprinted layers on a magnetic nanoparticle core [29]. Compared with traditional separation process, magnetic MIPs possess excellent characteristics of phase separation using an external magnetic field without additional centrifuge and filtration, simplifying the separation procedure and increasing the rate of separation [[30], [31], [32], [33]].
Here in, a novel magnetic surface molecular imprinted polymers (MMIPs) was successfully synthesized for enrichment and determination of ZEN. As a functional monomer, TAT can endow MMIPs with high selectivity and sensitivity. The MMIPs were characterized by transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FT-IR), power X-ray diffraction (XRD) and vibrating Sample Magnetometer (VSM). The synthetic TAT was characterized by elemental analysis, FT-IR and H nuclear magnetic resonance (1H NMR). The adsorption isotherms, adsorption kinetics and selective experiments were used to evaluate the adsorption behaviors of MMIPs. After optimizing the relevant conditions, a MISPE-HPLC method based on this material was established and successfully applied to the extraction and determination of ZEN in wheat extracts. As far as we know, this is first time that a magnetic molecularly imprinted material with TAT as a functional monomer has been prepared and applied to the enrichment and determination of zearalenone.
Section snippets
Chemicals and sample
Zearalenone was obtained from Saan Chemical Technology (Shanghai) Co., Ltd. Ethylene glycol dimethacrylate (EGDMA), Acrylyl chloride, melamine were purchased from Energy Chemical Co., Ltd. Fe2SO4·7H2O, FeCl3·6H2O, dimethyl sulfoxide (DMSO), triethylamine, quercetin, polyvinylpyrrolidone, acetic acid, rutin, chrysin, paracetamol, acetone were purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). 2, 2′-azobis (2-methylpropionitrile) (AIBN) was obtained from Aladdin Chemistry Co.,
Characterization of TAT and MMIPs
The 1H NMR spectrum of TAT was shown in Fig. S1. The characteristic peak of –NH– amide proton at 8.2 ppm and at 6.0 ppm confirmed protons of acryloyl groups. In addition, the area ratio of the two peaks is 1:3. The FT-IR spectrum also demonstrated the existence of functional groups of TAT (Fig. 3Aa). The characteristic peaks at 3336 cm−1 and 3207 cm−1 were corresponding to –NH asymmetric and symmetric stretching of TAT, respectively. The peaks at 1624 cm−1 and 1500 cm−1 were correspond to amide
Conclusions
In this work, we successfully synthesized a novel magnetic molecular imprinted polymers for the enrichment and determination of zearalenone combining with a functional monomer. The monomer of multifunctional groups showed more advantageous when adsorbing target molecules because of forming more chemical bonds. The MMIPs exhibited high sensitivity, stability and potential reusability. The MSPE-HPLC method based on MMIPs demonstrated the advantages of high efficiency, sensitivity, simplicity, low
Acknowledgments
This work was financially supported by the Independent Innovation Fund Project of Agricultural Science and Technology of Jiangsu Province in 2017 (NoCX (17) 1003); Guizhou Provincial Science and Technology Department Joint Fund Project (Qian Kehe LH word [2016] No. 7076).
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