Molecularly imprinted polymers on silica: selective supports for high-performance ligand-exchange chromatography

Abstract

Thin coatings of molecularly imprinted, metal-complexing polymers have been grafted to activated silica beads suitable for high-performance liquid chromatography (HPLC). Propylmethacrylate-activated silica particles were coated by copolymerization with a metal-chelating monomer, Cu^(2+)-[N-(4-vinylbenzyl)-imino]diabetic acid, a metal-coordinating (imidazole) template, and ethylene glycol dimethacrylate. After extraction to remove the template and re-loading with metal, the composite materials re-bind the templates with which they were prepared and exhibit selectivities comparable to bulk-polymerized imprinted materials. The strong Cu^(2+)-imidazole interaction, desirable for creating a high-fidelity imprint, leads to excessive retention in elution chromatography. By replacing the copper in the imprinted metal-complexing polymers with weaker-binding Zn^(2+), these novel ligand-exchange supports can effect partial to complete chromatographic separation of their bis-imidazole templates from other, highly similar imidazole-containing substrates. This “bait-and-switch” approach can significantly enhance the performance of molecularly imprinted materials. Scatchard plots of equilibrium binding data show a significant degree of heterogeneity in the imprinted binding sites of material prepared with a bis-imidazole template, but not with a mono-imidazole template. The best chromatographic separations are observed with small sample sizes, where the substrates occupy the strongest (highest-fidelity) sites.