Supramolecular imprinted polymeric stir bar sorptive extraction followed by high-performance liquid chromatography for endocrine disruptor compounds analysis

Molecular imprinted coatings based on beta-cyclodextrin (beta-CD) and acrylamide functional monomers were presented. The supramolecularly imprinted polymeric (SMIP) adsorption materials employed as the coatings of stir bar sorptive extraction (SBSE) for endocrine disruptor compounds (EDCs) analysis were proposed. A series of derivatized beta-CDs functional monomers were synthesized and characterized. The best couple of functional monomers used for SMIP was selected from the beta-CD monomers and common functional monomers, respectively. The ratio of two functional monomers was also optimized. The SMIP coatings showed good selectivity to the bisphenol A template and its structural analogs. It also provided enrichment factors ranging from 56 to 160 for bisphenols, which were 32- to 1600-fold higher than that of the commercial polyacrylate fibers (85 mu m, Supelco). Moreover, the SMIP coatings displayed better selectivity and extraction amount than the nonimprinted and both single-functional monomer-based imprinted coatings, respectively. Therefore, the SMIP coatings triggered off a synergetic recognition for target analytes. The developed SMIP-SBSE-HPLC method was successfully applied for three environmental estrogen analysis in real water samples. A recovery of 92-119% and relative standard deviation of 1.6-9.7% were obtained. Taken together, the supramolecular imprinting strategy can provide new ideas for the development of novel supramolecular polymer-based adsorption materials, and can provide an efficient analytical method for the selective analysis of trace substances in environmental water samples.