Preparation of poly(butyl methacrylate-co-ethyleneglyceldimethacrylate) monolithic column modified with β-cyclodextrin and nano-cuprous oxide and its application in polymer monolithic microextraction of polychlorinated biphenyls

• Poly(BMA-EDMA) monolithic column integrated with β-CD and Cu2O was prepared.
• The monolithic column was applied to the enrichment of polychlorinated biphenyls.
• The functionalized monolithic column has high preconcentration abilities for polychlorinated biphenyls.

A poly(butyl methacrylate-co-ethyleneglyceldimethacrylate) (poly(BMA-EDMA)) monolithic column was prepared with in situ polymerization method and modified with allylamine-β-cyclodextrin (ALA-β-CD) and nano-cuprous oxide (Cu2O). A polymer monolith microextraction method was developed with the modified monolithic column for the preconcentration of polychlorinated biphenyls combined with gas chromatography–electron capture detector. Various parameters affecting the extraction efficiency were investigated and optimized. Under the optimum experimental conditions, we obtained acceptable linearities, low limits of detection, and good intra-day/inter-day relative standard deviations. Because of the hydrophobic properties of β-CD and the porous nano structure of Cu2O, the enrichment capacity of the poly(BMA-EDMA) monolithic column was significantly improved. The extraction efficiency followed the order: poly(BMA-EDMA-ALA-β-CD-Cu2O) > poly(BMA-EDMA-ALA-β-CD) > poly(BMA-EDMA) > direct GC analysis. When applied to the determination of polychlorinated biphenyls in wine samples, low limits of detection (0.09 ng mL−1) were obtained under the preoptimized conditions (sample volume 1.0 mL, sample flow rate 0.1 mL min−1, eluent volume 0.1 mL, and eluent flow rate 0.05 mL min−1). In addition, the present method was employed to determine polychlorinated biphenyls in red wine samples and the accuracy was assessed through recovery experiments. The obtained recovery values were in the range of 78.8–104.1% with relative standard deviations less than 9.0%.