Development of nickel-selective molecularly imprinted polymers

Abstract

A series of eight novel bidentate ligands, designed for use in the construction of nickel-selective molecularly imprinted polymers (MIP's), have been prepared. The synthetic pathway was established by retrosynthetic analysis of the target molecules to the readily available precursors, pyridine-2-carbaldehyde (or 6-methylpyridine-2-carbaldehyde) and ethyl bromoacetate. The ligands were designed to contain an allyl group for co-polymerisation and amine and pyridyl nitrogen donors, located to permit the formation of 5-membered nickel chelates. The eight novel ligands and their respective precursors were characterized by elemental (high-resolution MS) and spectroscopic (IR and ¹H and ¹³C NMR) analysis. High resolution electron-impact mass spectrometry has also been used, together with B/E linked scan data, to explore the fragmentation patterns of selected ligands. The various nickel(ll) complexes were analyzed using spectroscopic techniques and, in some cases, elemental analysis; computer modelling has also been used to explore conformational effects and complex stability. Numerous MIP's, containing nickel(II) complexes of the bidentate ligands, have been prepared, using ethylene glycol dimethylacrylate (EGDMA) as the cross-linker, azobis(isobutyronitrile) (AlBN) as the polymerization initiator and MeOH as the porogenic solvent. The template nickel(II) ions were leached out with conc. HCI, and the nickel(II) selectivity [in the presence of Fe(Ill)] of the nickel-imprinted polymers was examined by ICP-MS analysis. The ICP-MS data indicate that the MIP's examined exhibit extremely high selectivity for nickel over iron.,KMBT_363,Adobe Acrobat 9.54 Paper Capture Plug-in