Synthesis And Application Of Molecularly Imprinted Polymers Of Zearalenone In Food And Feed Analysis

In this paper,four types of zearalenone-related molecularly imprinted polymers(MIPs)were synthesized using warfarin and warfarin sodium as the dummy templates by suspension polymerization,precipitation polymerization and surface imprinting method,respectively.Single factors and orthogonal experiments were carried out to determine the optimal synthesis conditions.The obtained MIPs were used as the packing materials to prepare molecularly imprinted solid-phase extraction(SPE)column for the separation of zearalenone toxin in wheat,corn and feed samples.The washing and eluenting solution were optimized.Compared with the commercial immunoaffinity column,a sample preparation method with lower cost and better selectivity was developed.In combination with HPLC,a simple,rapid,highly effective and sensitive method for the analysis of zearalenone in food and feed was established.The main content includes the following aspects:1.Two types of MIPs(Suspension polymerized molecularly imprinted polymers and Precipitation polymerized molecularly imprinted polymers,S-MIPs and P-MIPs)were fabricated using warfarin,a structural analog of zearalenone,as the dummy template,glycidyl methacrylate as the functional monomer,divinyl benzene or ethylene glycol diacetate as the cross-linking agent and benzoyl peroxide as the initiator.Through single factor and orthogonal experiments,the optimal synthesis conditions for the two polymerization methods were obtained.In optimum conditions,the washing and eluenting solution,as well as eluenting volume of S-MIPs and P-MIPs columns were obtained.The linear range of the established method was 8-200 ng mL-1 with the limit of detection of 1.25 ng mL-1,and a limit of quantitation of 5 ng mL-1.The spiked recovery over 10-170 ng g-1 showed that S-MIPs and P-MIPs were 72.16-95.23%and 79.21-103.74%,respectively.The relative standard deviations were 1.41-7.87%and 2.19-4.48%,respectively.In real sample analysis,the results demonstrated that the performance of S-MIPs and P-MIPs columns were better than that of immunoaffinity columns,and moreover,the performance of P-MIPs column was superior than that of S-MIPs column.2.General MIPs and magnetic surface MIPs(Magnetic halloysite surface imprinted polymers,MHNTs@MIPs)for selectively binding zearalenone were synthesized by precipitation polymerization using warfarin sodium as the dummy template,a-methacrylic acid and glycidyl methacrylate as the hybrid functional monomers,ethylene glycol dimethacrylateas the cross-linking agent,and azobisisobutyronitrile as the initiator.The optimum synthesis conditions for general MIPs and magnetic surface MIPs(MHNTs@MIPs)were obtained though single factors and orthogonal experiments.These two materials were used as adsorbents for SPE and their conditions extraction,including washing and eluting solvents and eluting volume were discussed.Under optimum SPE conditions,the spiked recoveries of MIPs and MHNTs@MIPs columns were 74.75-102.37%and 79.96-104.23%in a range of 10-170 ng g-1,respectively.Besides,the relative standard deviations were 2.75-6.66%and 2.35-6.27%,respectively.The linearity of the proposed method for the MIPs column was ranging from 20 to 800 ng mL-1,the limit of detection was 3 ng mL-1,and the limit of quantitation was 8 ng mL-1;the linear range of the MHNTs@MIPs column was 10-1000 ng mL-1,with a limit of detection of 2.5 ng mL-1 and a limit of quantification of 8 ng mL"1.The results of pretreatments of real samples showed that the performance of MHNTs@MIPs column was superior than that of MIPs column and the immunoaffinity column.The contents of zearalenone in food and feed samples was determined by using a self-made column for the clean-up and preconcentration in Henan Hai Rui Zheng Detection Technology Co.,Ltd.The results showed that the column achieved the ideal effect.