Molecular imprinted polymeric porous layers in open tubular capillaries for chiral separations

• New procedures used to prepare molecularly imprinted polymers in PLOT capillaries.
• These novel MIP-PLOT systems enable efficient resolution of chiral compounds.
• MIP ‘in-capillary’ polymerization based on a novel light emitting diode array.
• Parameters affecting photo-polymerization outcome have been investigated in detail.
• Polymer surface morphology investigated by scanning electron microscopy (SEM).

A new method has been developed for the preparation of molecular imprinted polymers as porous layers in open tubular (MIP-PLOT) capillary column formats for use in chiral separations by capillary liquid chromatography. The synthesis was based on ‘in-capillary’ ultraviolet (UV) initiated polymerization using light emitting diodes (LEDs) in conjunction with the continuous delivery of the pre-polymerization reagents into the polymerization zone of the capillary using an automated capillary delivery device. The relationships between exposure times, UV-light intensity and polymer layer thickness have been determined, as well as the effects of reagent delivery rate and multiple LED exposures on the layer thickness for various compositions of pre-polymerization mixtures. The polymer surface morphology was investigated by scanning electron microscopy (SEM). The non-steroidal anti-inflammatory drug S-ketoprofen was used as the template for the preparation of the MIP imprinted PLOT coatings. The separation performance with the ketoprofen racemate was investigated by capillary liquid chromatography. In contrast to alternative methods, which require the use of expensive chiral selectors, the described MIP PLOT stationary phases used non-chiral polymer precursors to create enantioselective nano-cavities through molecular self-assembly processes. The described fabrication methods provide a new avenue to tailor-make chiral MIP-PLOT capillary columns for the separation of chiral compounds present in complex or racemic analyte mixtures of chemical and biological origin.