Preparation of a novel amino functionalized ion-imprinted hybrid monolithic column for the selective extraction of trace copper followed by ICP-MS detection.

In this work, a novel amino functionalized Cu(II) ion-imprinted organic-inorganic hybrid monolithic column (Cu(II)-IIHMC) was prepared via one-pot co-condensation and the combination of sol-gel and ion-imprinting techniques in a fused capillary. The Cu(II)-IIHMC was used as solid phase microextraction (SPME) matrix followed by inductively coupled plasma-mass spectrometry (ICP-MS) for the analysis of trace Cu(II). The prepared Cu(II)-IIHMC has good mechanical strength, stable imprinting sites and homogeneous structure of network skeleton with large flow-through pores by optimizing the synthesis process. Under the optimized conditions, the Cu(II)-IIHMC can selectively adsorb Cu(II) with the adsorption capacity of 3.13 mg g-1. With enrichment factor of 10-fold, the calibration curve was established in the range of 0.05-50 µg L-1 with r2 of 0.9992 and the detection limit was 0.008 µg L-1 for Cu(II). Compared with the non-imprinted hybrid monolithic column (Cu(II)-NIHMC), the Cu(II)-IIHMC possesses better selectivity, anti-interference ability and adsorption capacity. The Cu(II)-IIHMC can specifically capture the target ion in the presence of competitive ions, with the selectivity coefficients exceeding 39.4. The protocol was validated by analyzing Certified Reference Materials of standard sediment, soil and iron ore, and the results were in good agreement with certified values. Moreover, the proposed in-tube SPME procedure can not only preconcentrate trace Cu(II), but also effectively reduce the matrix effect and powerfully eliminate the interference from the main metals in real samples. Therefore, the developed SPME-ICP-MS method with facile preparation, specific selectivity, high sensitivity and efficient analysis, was applied in the determination of trace Cu(II) in environmental and mineral samples with the recoveries of 89.8-111.8% in all spiked samples.