Silica nanoparticle-templated methacrylic acid monoliths for in-line solid-phase extraction-capillary electrophoresis of basic analytes

Polymeric ion-exchange monoliths typically exhibit low capacities due to the limited surface area on the globules of the monoliths. The ion-exchange binding of protonated weakly basic analytes on deprotonated carboxylate sites on methacrylate polymer monoliths has been increased by templating the monoliths with silica nanoparticles. The templating method is achieved by adding the nanoparticles as a suspension to the polymerisation mixture. After polymerisation, the nanoparticles are removed by washing the monolith with strong base. Monolithic columns prepared using this procedure have exhibited a 33-fold increase in ion-exchange capacity when compared to untemplated monoliths prepared and treated under similar conditions. The templating procedure does not alter the macroporous properties of the polymer monolith, confirmed through scanning electron microscopy and BET surface area analysis, but provides increased capacity predominantly through the re-orientation of more carboxylic acid groups. The resulting increase in ion-exchange capacity has proven to be useful for the preconcentration and separation of neurotransmitters by in-line solid-phase extraction–capillary electrophoresis. The increased capacity of the templated monolith allowed the injection time to be increased 10 times over that of an untemplated monolith, allowing 10 times more sample to be injected with the efficiencies and recoveries remaining unaffected. The enhancement in sensitivity for the test mixture of neurotransmitter (dopamine, norepinephrine and metanephrine) ranged 1500–1900 compared to a normal hydrodynamic injection in capillary electrophoresis. Efficiencies obtained for the neurotransmitters were 100 000–260 000 plates, typical of those obtained in capillary zone electrophoresis. The applicability of the increased capacity silica nano-templated polymer monolith was demonstrated by analysing trace levels of caffeine in biological, food and environmental samples.