Molecularly imprinted polymers with a streamlined mimic for zearalenone analysis.

Molecularly imprinted polymers (MIPs) with selective recognition properties for zearalenone (ZON), an estrogenic mycotoxin, and structurally related compounds have been prepared using the non-covalent imprinting approach. A rationally designed ZON analogue, cyclododecyl 2,4-dihydroxybenzoate (CDHB), that exhibits resemblance to ZON in terms of size, shape and functionality has been synthesized and used as template for MIP preparation instead of the natural toxin. Several functional monomers have been evaluated to maximize the interactions with the template molecule during the polymerization process. The polymer material prepared with 1-allylpiperazine (1-ALPP) as functional monomer, trimethyl trimethacrylate (TRIM) as cross-linker and acetonitrile as porogen (in a 1:4:20 molar ratio) displayed superior binding capacities than any other of the MIPs tested. Selectivity of this material for ZON and structurally related and non-related compounds has been evaluated using it as stationary phase in liquid chromatography. Our results demonstrate that the imprinted polymer shows significant affinity in the porogenic solvent for the template mimic (CDHB) as well as for the ZON and other related target metabolites in food samples, dramatically improving the performance of previously reported MIPs for ZON recognition. Therefore, MIPs can be an excellent alternative for clean-up and preconcentration of the mycotoxin in contaminated food samples.

[1]  C. Holst,et al.  Comparison of alternative and conventional extraction techniques for the determination of zearalenone in corn , 2003, Analytical and bioanalytical chemistry.

[2]  O. Zoller,et al.  Zearalenone in cereals for human nutrition: relevant data for the Swiss population , 2003 .

[3]  C. von Holst,et al.  Determination of zearalenone from wheat and corn by pressurized liquid extraction and liquid chromatography-electrospray mass spectrometry. , 2003, Journal of chromatography. A.

[4]  R. Krska,et al.  The state-of-the-art in the analysis of estrogenic mycotoxins in cereals , 2001, Fresenius' journal of analytical chemistry.

[5]  B. Sellergren,et al.  Determination of phenytoin in plasma by molecularly imprinted solid-phase extraction. , 2001, Journal of chromatography. A.

[6]  J. Miller,et al.  Mycotoxins in grain: compounds other than aflatoxin. , 1994 .

[7]  H. Son,et al.  Zearalenone induces male germ cell apoptosis in rats. , 2003, Toxicology letters.

[8]  Takeuchi,et al.  Atrazine-selective polymers prepared by molecular imprinting of trialkylmelamines as dummy template species of atrazine , 2000, Analytical chemistry.

[9]  J. Vanselow,et al.  Effects of the mycotoxins α- and β-zearalenol on regulation of progesterone synthesis in cultured granulosa cells from porcine ovaries , 2003 .

[10]  D. Spivak,et al.  Evidence for shape selectivity in non-covalently imprinted polymers , 2004 .

[11]  H. Seidel,et al.  Fusarial toxins and their role in animal diseases. , 2003, Veterinary journal.

[12]  R. J. Umpleby,et al.  Characterization of the imprint effect and the influence of imprinting conditions on affinity, capacity, and heterogeneity in molecularly imprinted polymers using the Freundlich isotherm-affinity distribution analysis. , 2004, Analytical chemistry.

[13]  W. Shier,et al.  Structure-activity relationships for human estrogenic activity in zearalenone mycotoxins. , 2001, Toxicon : official journal of the International Society on Toxinology.

[14]  M. Jiménez,et al.  Liquid chromatographic determination of toxigenic secondary metabolites produced by Fusarium strains. , 2002, Journal of chromatography. A.

[15]  D. Koshland,et al.  The catalytic and regulatory properties of enzymes. , 1968, Annual review of biochemistry.

[16]  R. Krska,et al.  Advances in the analysis of mycotoxins and its quality assurance , 2005, Food additives and contaminants.

[17]  J. Hajšlová,et al.  Analysis of Zearalenone in Wheat Using High-Performance Liquid Chromatography with Fluorescence Detection and/or Enzyme-Linked Immunosorbent Assay , 2001 .

[18]  J. Pestka,et al.  Analysis of zearalenone in cereal and Swine feed samples using an automated flow-through immunosensor. , 2005, Journal of agricultural and food chemistry.

[19]  P. Zöllner,et al.  Determination of zearalenone and its metabolites α- and β-zearalenol in beer samples by high-performance liquid chromatography-tandem mass spectrometry. , 2000 .

[20]  B. Sellergren,et al.  Influence of polymer morphology on the ability of imprinted network polymers to resolve enantiomers , 1993 .

[22]  Y. Ueno,et al.  Simultaneous determination of trichothecene mycotoxins and zearalenone in cereals by gas chromatography-mass spectrometry. , 2000, Journal of chromatography. A.

[23]  R. Krska,et al.  Improving methods of analysis for mycotoxins: molecularly imprinted polymers for deoxynivalenol and zearalenone , 2003, Food additives and contaminants.

[24]  C. J. Mirocha,et al.  Production of zearalenone, .alpha.- and .beta.-zearalenol, and .alpha.- and .beta.-zearalanol by Fusarium spp. in rice culture , 1985 .

[25]  M. Nielen,et al.  Confirmatory analysis method for zeranol, its metabolites and related mycotoxins in urine by liquid chromatography-negative ion electrospray tandem mass spectrometry , 2002 .

[26]  R. Krska Performance of modern sample preparation techniques in the analysis of Fusarium mycotoxins in cereals. , 1998, Journal of chromatography. A.

[27]  H. S. Hussein,et al.  Toxicity, metabolism, and impact of mycotoxins on humans and animals. , 2001, Toxicology.

[28]  K. Mosbach,et al.  Binding studies on substrate- and enantio-selective molecularly imprinted polymers , 1991 .

[29]  Wolfgang Lindner,et al.  Towards ochratoxin A selective molecularly imprinted polymers for solid-phase extraction. , 2002, Journal of chromatography. A.

[30]  P. Zöllner,et al.  Determination of zeranol, taleranol, zearalenone, α- and β-zearalenol in urine and tissue by high-performance liquid chromatography-tandem mass spectrometry , 2000 .

[31]  E. Vargas,et al.  A survey of zearalenone in corn using Romer Mycosep™ 224 column and high performance liquid chromatography , 2001, Food additives and contaminants.

[32]  B. Fazekas,et al.  Determination of zearalenone content in cereals and feedstuffs by immunoaffinity column coupled with liquid chromatography. , 2001, Journal of AOAC International.

[33]  M. Moreno-Bondi,et al.  Analysis for zearalenone and α-zearalenol in cereals and swine feed using accelerated solvent extraction and liquid chromatography with fluorescence detection , 2004 .