Magnetic hyperbranched molecularly imprinted polymers for selective enrichment and determination of zearalenone in wheat proceeded by HPLC-DAD analysis

doi:10.1016/j.talanta.2019.120555

Talanta

Volume 209, 1 March 2020, 120555

https://doi.org/10.1016/j.talanta.2019.120555 Get rights and content

Highlights

•
Magnetic surface molecularly imprinted polymers based on TAT as functional monomer was successfully prepared and applied for enrichment and determination of zearalenone in wheat.
•
The MMIPs have excellent selectivity, stability and potential reusability.
•
Established MSPE-HPLC method showed low detection-limit, good linearity and high sensitivity for zearalenone detection.

Abstract

A novel magnetic surface molecular imprinted polymers with 2, 4, 6-trisacrylamido-3, 5-triazine (TAT) as a functional monomer was successfully synthesized and used for the enrichment and determination of zearalenone. The molecular imprinting is reported herein at first time for application of zearalenone in wheat. The magnetic imprinted materials possessed excellent magnetism and uniform appearance, which were characterized by fourier transform infared spectroscopy and transmission electron microscope. The results proved the magnetic molecular imprinted polymers was successfully prepared. The magnetic molecular imprinted polymers exhibited satisfactory sensitivity, stability and potential reusability. The binding affinity was investigated by selectivity experiment, which possessed high selectivity. To obtain the optimal application conditions, the amount of adsorption, extraction time, elution solvent and time were optimized. The limited detection of zearalenone was 0.55 ng g⁻¹ and the recoveries of zearalenone were 92.1–96.0%. The relative standard deviation was lower than 5.4%. This indicated that a simple, efficient and low-cost method was established and successfully applied in spiked wheat sample.

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).

References (41)

J.N. Selvaraj et al.
Mycotoxin detection — recent trends at global level
J. Integr. Agr.
(2015)
A. Zinedine et al.
Review on the toxicity, occurrence, metabolism, detoxification, regulations and intake of zearalenone: an oestrogenic mycotoxin
Food Chem. Toxicol.
(2007)
W. Zheng et al.
Zearalenone impairs the male reproductive system functions via inducing structural and functional alterations of sertoli cells
Environ. Toxicol. Pharmacol.
(2016)
L. Luo et al.
Monitoring zearalenone in corn flour utilizing novel self-enhanced electrochemiluminescence aptasensor based on NGQDs-NH2-Ru@SiO2 luminophore
Food Chem.
(2019)
Y. Zhang et al.
Comparison of concentration and health risks of 9 Fusarium mycotoxins in commercial whole wheat flour and refined wheat flour by multi-IAC-HPLC
Food Chem.
(2019)
X. Xie et al.
Facile preparation of photonic and magnetic dual responsive protein imprinted nanomaterial for specific recognition of bovine hemoglobin
Chem. Eng. J.
(2019)
A.A. Malik et al.
Molecularly imprinted polymer for human viral pathogen detection
Mat. Sci. Eng. C-Mater.
(2017)
M. Rutkowska et al.
Application of molecularly imprinted polymers in analytical chiral separations and analysis
Trend. Anal. Chem.
(2018)
K. Qian et al.
Metal-organic frameworks supported surface-imprinted nanoparticles for the sensitive detection of metolcarb
Biosens. Bioelectron.
(2016)
C. Rui et al.
Selective extraction and enrichment of aflatoxins from food samples by mesoporous silica FDU-12 supported aflatoxins imprinted polymers based on surface molecularly imprinting technique
Talanta
(2019)

M. Jia et al.

Molecular imprinting technology for microorganism analysis

Trend. Anal. Chem.

(2018)

T. Guo et al.

Upconversion fluorescence metal-organic frameworks thermo-sensitive imprinted polymer for enrichment and sensing protein

Biosens. Bioelectron.

(2016)

A. Munawar et al.

Investigating nanohybrid material based on 3D CNTs@Cu nanoparticle composite and imprinted polymer for highly selective detection of chloramphenicol

J. Hazard Mater.

(2018)

A. Ostovan et al.

Fabrication of water-compatible superparamagnetic molecularly imprinted biopolymer for clean separation of baclofen from bio-fluid samples: a mild and green approach

Talanta

(2018)

B.B. Prasad et al.

Electrochemical sensor for folic acid based on a hyperbranched molecularly imprinted polymer-immobilized sol–gel-modified pencil graphite electrode

Sens. Actuators B Chem.

(2010)

R. Maffezzoni et al.

Stable organogels derived from triazines functionalized with chiral α-amino acid derivatives

Tetrahedron Lett.

(2008)

M. Sajid

Dendrimers based sorbents: promising materials for analytical extractions

Trend. Anal. Chem.

(2018)

A. Sorribes-Soriano et al.

Magnetic molecularly imprinted polymers for the selective determination of cocaine by ion mobility spectrometry

J. Chromatogr., A

(2018)

M. Arabi et al.

Novel strategy for synthesis of magnetic dummy molecularly imprinted nanoparticles based on functionalized silica as an efficient sorbent for the determination of acrylamide in potato chips: optimization by experimental design methodology

Talanta

(2016)

X. Liu et al.

3D hierarchical magnetic hollow sphere-like CuFe2O4 combined with HPLC for the simultaneous determination of Sudan I-IV dyes in preserved bean curd

Food Chem.

(2018)

Cited by (47)

Molecularly imprinted solid phase extraction – recent strategies, future prospects and forthcoming challenges in complex sample pretreatment process
2024, TrAC - Trends in Analytical Chemistry
This review discusses recent strategies and future challenges regarding the application of molecularly imprinted polymers (MIPs) in solid phase extraction. It highlights the advantages of imprinting technology in producing selective solid sorbents for extracting biologically important compounds. The review emphasizes the characterization of new analytical methods based on molecularly imprinted solid phase extraction (MISPE) that enable the determination of analytes in samples. Sorbent synthetic strategies are examined to highlight the microscale approaches. Additionally, the review outlines the benefits derived from applying MISPE in analysis of complex samples and identifies current challenges faced by MISPE. Moreover, commercialization capabilities and frontiers that impede the marketing of MIP-based sorbents are highlighted. Lastly, future prospects and forthcoming challenges in the field are critically examined.
Recent advances in magnetic molecularly imprinted polymers and their application in the food safety analysis
2024, Journal of Future Foods
Food safety is a worldwide concern and is directly related to human health. Therefore, convenient, effective, and economical methods and technologies for food safety analysis have been developed continuously. Magnetic molecularly imprinted polymers (MMIPs) have gained extensive attention in recent years, as they have high selectivity, high adsorption capacity, and are easy to isolate from food samples. Recently, advanced strategies for the synthesis of MMIPs have been proposed to solve problems of template leakage and non-specific adsorption, and to increase the biocompatibility, adsorption rate, as well as adsorption capacity of the imprinted materials. In this review, we focus on new attempts at modification of magnetic core and MMIPs’ surfaces, and the selection of template, functional monomer, cross-linker as well as porogen. Studies are summarized that used advanced MMIPs for the recognition and adsorption of pesticide residues, veterinary drug residues, mycotoxins, contaminants, and adulterations in foodstuffs over the last 5 years. Finally, some still existing challenges and future prospects to further promote MMIPs properties are also discussed.
Aptamer-locker probe coupling with truncated aptamer for high-efficiency fluorescence polarization detection of zearalenone
2023, Sensors and Actuators B: Chemical
Zearalenone (ZEN) is a kind of mycotoxin with estrogen-like effect. The presence of ZEN in cereals is potentially harmful to the health of humans. Herein, for the first time, the binding mechanism of ZEN aptamer with 19 bases (Z19) were systematically studied by molecular dynamics, circular dichroism and isothermal titration calorimetry. The binding driving forces, key bases of Z19 to ZEN, the conformational changes and thermodynamic information were originally found. On this basis, by employing the inherent rapid nature of fluorescence polarization and target recycling induced by Exo III, a novel fluorescence polarization aptasensor was constructed. The realized “add and measure” detection mode can be completed within one hour. Under the optimal conditions, the detection platform showed excellent analytical performance with a linear range of 0.01–100 ng/mL and a limit of detection as low as 0.004 ng/mL. Moreover, the practicability and reliability of the constructed strategy were confirmed with standard HPLC-MS method in corn and wheat samples. The established aptasensor with enhanced sensitivity broaden the application scope of fluorescence polarization technique, especially in detection targets of low molecular weight.
Molecularly imprinted polymers as the epitome of excellence in multiple fields
2022, European Polymer Journal
Molecularly imprinted polymers (MIPs) are promising receptors for a wide range of targeted molecules. In recent years, the construction of low molecular weight materials became possible based on the idea of molecular imprinting. The recent applications of MIPs are discussed with a brief computational chemistry to illustrate the design of MIPs. The different routes for the covalent and non-covalent imprinting in MIPs are highlighted in this review. The incorporation of optical, thermo-responsive, magnetic, and photocatalytic materials facilitated the development of multifunctional hybrid molecularly imprinted materials. MIPs have enormous beneficial aspects like high selectivity and specificity toward the targeted molecules. They are easy to synthesize, cost-effective, and reliable at different conditions like pH, temperature, and pressure. Additionally, the changeable properties of MIPs could be achieved by the different combinations of the templates, functional monomers, and crosslinkers. Based on these features, this review summarizes the fundamental concepts, recent advances, and applications of MIPs in multiple fields like environmental restoration, wastewater treatments, food analysis, chemical/biological sensing, targeted drug delivery, proteins recognition/purification, and hormone detoxification. The stated applications can be performed using MIPs as sorbents, stationary phases, and catalysts. Furthermore, the review features prospects and suggestions for substantial benefits from MIPs.
Electroanalytical sensors for antiretroviral drugs determination in pharmaceutical and biological samples: A review
2022, Journal of Electroanalytical Chemistry
Citation Excerpt :
Using a single layer was going to limit the imprinted cavities on the polymeric material since there were two templates now. The MIP was developed similarly to that of Prasad and coworkers [153], except that the ZDV-MIP (outer layer) was grown or prepared on the 3TC-MIP (inner layer) as shown in Fig. 17A. To quantify ZDV, the DOHCs-MIP sensor was firstly dipped into a solution of 3TC to allow its rebinding on the inner molecular cavities until saturation. This resulted in only ZDV unoccupied outer cavities.
The high human immune deficiency virus (HIV) pandemic has resulted in the discovery, development, and use of antiretroviral (ARV) drugs not only to improve patient well-being but also to reduce the risk of perinatal transmission of HIV. Due to drug-to-drug interactions, drug resistance, drug toxicity, and counterfeit drugs, there has been an urgent need for the development of portable, sensitive, selective, facile, and reliable detection strategies for ARV analysis in both pharmaceutical and clinical settings. Electroanalytical techniques are of particular interest because they offer the advantages of onsite monitoring of ARV drugs due to their flexible nature and real-time analysis compared to traditional analytical techniques. It is evident from literature dating back a decade ago that voltammetry is the most used electroanalytical technique for ARV analysis. Hence, the present review aims to discuss how detection strategies for ARV have evolved over the years and focus on recent advances in ARV analysis. Furthermore, the review will focus on different types of ARV drugs and their respective mechanisms.
Application of magnetic hydroxyapatite surface-imprinted polymers in pretreatment for detection of zearalenone in cereal samples
2022, Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences
This study is about the combination of magnetic solid phase extraction (MSPE) and high performance liquid chromatography-fluorescence detector (HPLC-FLD) for the pre-concentration and determination of Zearalenone (ZEA) in grain sample extracts. The novel sorbent (Fe₃O₄-HAP@MIPs), for selective and intelligent extraction of ZEA, was synthesized by doping Fe₃O₄ into the fibrous structure of hydroxyapatite nanoparticle (Fe₃O₄-HAP) and subsequently wrapping with molecularly imprinted polymers. The characteristic and morphology of magnetic particles were studied by infrared spectroscopy, vibrating sample magnetometer and scanning electron microscopy. The maximum adsorption capacity was 2.89 μg/mg. It could reach the adsorption equilibrium within 5 min. The adsorption isotherm of ZEA by the Fe₃O₄-HAP@MIPs were simulated. The results showed that the extraction process of ZEA with the sorbent accorded with Langmuir isotherm. The important factors affecting the extraction efficiency include elution solvent, washing solvent and the volume of them. After a serious of experiments, the optimum conditions were as follows: the volume of elution solvent was 4 mL of methanol and the washing solvent was acetonitrile–water 2:8（v/v). The calibration curve for ZEA was linear in the range of 10.00–300.00 μg/kg. The limit of detection and limit of quantitative was 2.00 μg/kg and 6.65 μg/kg, respectively. This method could provide a good reusability of 8 times and enough recoveries at three spiked levels (3, 5 and 8 ng/mL) ranging between 61.97% and 95.15% with the relative standard deviations of 1.94%∼7.44%. These results demonstrated that Fe₃O₄-HAP@MIPs could be used for separation, concentration and detection of ZEA from real samples.

View all citing articles on Scopus

View full text

Magnetic hyperbranched molecularly imprinted polymers for selective enrichment and determination of zearalenone in wheat proceeded by HPLC-DAD analysis

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Chemicals and sample

Characterization of TAT and MMIPs

Conclusions

Acknowledgments

J. Integr. Agr.

Food Chem. Toxicol.

Environ. Toxicol. Pharmacol.

Food Chem.

Food Chem.

Chem. Eng. J.

Mat. Sci. Eng. C-Mater.

Trend. Anal. Chem.

Biosens. Bioelectron.

Talanta

Trend. Anal. Chem.

Biosens. Bioelectron.

J. Hazard Mater.

Talanta

Sens. Actuators B Chem.

Tetrahedron Lett.

Trend. Anal. Chem.

J. Chromatogr., A

Talanta

Food Chem.