Highly selective dummy molecularly imprinted polymer as a solid-phase extraction sorbent for five bisphenols in tap and river water

• Dummy template selection via an HPLC column packed with the non-imprinted polymer.
• Highly class-selectivity for BPs of BPS-DMIP.
• Simultaneous analysis of five BPs in water using the developed DMISPE–HPLC method.
• Highly selective and sensitive method with good recovery and reproducibility.

A simple and fast method for both dummy template selection and polymer composition optimization is proposed here. A series of dummy templates for bisphenols imprinting were screened by running them on a non-imprinted polymer (NIP) column with porogen solvent as mobile phase. The tested dummy templates mainly involved bisphenol S (BPS), bromobisphenol A (TBBPA), bisphenol F (BPF), bisphenol E (BPE), bisphenol B (BPB), bisphenol AF (BPAF), 2,2′,6,6′-tetramethyl-4,4′-sulfonyldiphenol (BS-TM) and 4,4′-diaminodiphenylmethane (DADPM). Different monomers and porogens were also investigated for BPS and DADPM using the same method. BPS dummy template was finally selected with acetonitrile and 4-VP as porogen and monomer. The resulting dummy molecularly imprinted polymer (DMIP) achieved superior affinities for BPF, BPE, BPA, BPB and BPAF with imprinting factors 14.5, 13.8, 8.7, 5.7 and 4.2, respectively. An efficient method based on BPS-DMIP-SPE coupled with HPLC-UV was developed for selective extraction of BPF, BPE, BPA, BPB and BPAF in water samples. The method showed excellent recoveries (89.4–102.0%) and precision (RSD 0.3–4.8%, n = 5) for tap and river water samples spiked at three concentration levels each (40, 200 and 1000 ng L−1). The detection limits ranged between 2.2 and 3.8 ng L−1 with a sample volume of 500 mL. The result demonstrated the superiority of the optimized method for selective extraction of BPs in water samples at the ng L−1 level.