Synthesis and application of imprinted polyvinylimidazole-silica hybrid copolymer for Pb2+ determination by flow-injection thermospray flame furnace atomic absorption spectrometry Original Research Article

A novel ion imprinted polyvinylimidazole-silica hybrid copolymer (IIHC) was synthesized and used as a selective solid sorbent for Pb2+ ions preconcentration using an on-line solid phase extraction (SPE) system coupled to TS-FF-AAS. The ionic hybrid sorbent was prepared using 1-vinylimidazole and 3-(trimethoxysilyl)propylmethacrylate as monomers, Pb2+ ions as template, tetraethoxysilane as reticulating agent and 2,2′-azobis-isobutyronitrile as initiator. The best on-line SPE conditions concerning sorption behavior, including sample pH (6.46), buffer concentration (9.0 mmol L−1), eluent (HNO3) concentration (0.5 mol L−1) and preconcentration flow rate (4.0 mL min−1), were optimized by means of full factorial design and Doehlert matrix. The analytical curve ranged from 2.5 to 65.0 μg L−1 (r = 0.999) with limit of detection of 0.75 μg L−1; the precision (repeatability) calculated as relative standard deviation (n = 10) was 5.0 and 3.6% for Pb2+ concentration of 10.0 and 60.0 μg L−1, respectively. From on-line breakthrough curve, column capacity was 3.5 mg g−1. Preconcentration factor (PF), consumptive index (CI) and concentration efficiency (CE) were 128.0, 0.16 mL and 25.6 min−1, respectively. The selective performance of the sorbent, based on relative selectivity coefficient, was compared to NIC (non imprinted copolymer) for the binary mixture Pb2+/Cd2+, Pb2+/Cu2+ and Pb2+/Zn2+. The results showed that ion imprinted polyvinylimidazole-silica hybrid polymer had higher selectivity for Pb2+ than NIC at 64.9, 16.0 and 8.8 folds. The developed method was successfully applied for highly sensitive and selective Pb2+ determination in different kinds of water samples, parenteral solutions and urine. Accuracy was also assessed by analyzing certified reference fish protein (DORM-3) and marine sediment (MESS-3 and PACS-2) with satisfactory results.