We synthesized 8 polymethacrylate monolithic capillary columns using laurylmethacrylate functional monomer and various cross-linking monomers differing in the polarity and size. The efficiency of monolithic columns for low-molecular compounds significantly improved with increasing number of repeat non-polar methylene groups in the cross-linker molecules, correlating with greater proportion of small pores with size less than 50 nm. The best efficiency with HETP=25 μm for alkylbenzenes was achieved for columns prepared using hexamethylene dimethacrylate (HEDMA). Columns prepared with polar (poly)oxyethylene dimethacrylate cross-linkers show also improved efficiency with increasing chain length and generally better performance in comparison to the (poly)methylene dimethacrylate cross-linkers of comparable size, however with less apparent effects of the chain lengths on the pore distribution. The monolithic columns prepared with tetraoxyethylene dimethacrylate (TeEDMA) showed the best efficiency of all the columns tested, corresponding to HETP=15 μm (approx. 70,000 theoretical plates/m), show excellent column-to-column reproducibility with standard deviations of 2.5% in retention times, good permeability and low mass transfer resistance, so that is suitable for fast separation of low-molecular compounds in 2 min or less. By modification of the fused-silica capillary inner walls pre-treatment procedure, very good long-term stability was achieved even in 0.5 mm i.d. capillary format. The TeEDMA column can be also used for size-exclusion chromatography of lower non-polar synthetic polymers, whereas it is less suitable for separations of proteins than the HEDMA column.
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