Molecularly imprinted polymers for triazine herbicides prepared by multi-step swelling and polymerization method: Their application to the determination of methylthiotriazine herbicides in river water

Uniformly-sized, molecularly imprinted polymers (MIPs) for atrazine, ametryn and irgarol were prepared by a multi-step swelling and polymerization method using ethylene glycol dimethacrylate as a cross-linker and methacrylic acid (MAA), 2-(trifluoromethyl) acrylic acid (TFMAA) or 4-vinylpyridine either as a functional monomer or not. The MIP for atrazine prepared using MAA showed good molecular recognition abilities for chlorotriazine herbicides, while the MIPs for ametryn and irgarol prepared using TFMAA showed excellent molecular recognition abilities for methylthiotriazine herbicides. A restricted access media-molecularly imprinted polymer (RAM-MIP) for irgarol was prepared followed by in situ hydrophilic surface modification using glycerol dimethacrylate and glycerol monomethacrylate as hydrophilic monomers. The RAM-MIP was applied to selective pretreatment and enrichment of methylthiotriazine herbicides, simetryn, ametryn and prometryn, in river water, followed by their separation and UV detection via column-switching HPLC. The calibration graphs of these compounds showed good linearity in the range of 50–500 pg/mL (r > 0.999) with a 100 mL loading of a river water sample. The quantitation limits of simetryn, ametryn and prometryn were 50 pg/mL, and the detection limits were 25 pg/mL. The recoveries of simetryn, ametryn and prometryn at 50 pg/mL were 101%, 95.6% and 95.1%, respectively. This method was successfully applied for the simultaneous determination of simetryn, ametryn and prometryn in river water.