Synthesis and characterization of polyrotaxane-based polymeric continuous beds for capillary electrochromatography

Abstract

The continuous bed technique with its attractive features, such as fritless design, one-step in situ synthesis, low back pressure and no need for pressurising the electrode vessels to suppress bubble formation was applied to form polyrotaxane-based stationary phases for capillary electrochromatography (CEC). Rotaxanes are synthesized from two classes of substances, namely linear reactive monomers and inert cyclic compounds. Upon polymerisation, a gel forms with the cyclic molecules mechanically immobilized (see Fig. 1). We have employed this simple approach, using charged derivatives of cyclodextrins in order to introduce charged groups into continuous beds and thus render them appropriate for electrochromatography. The self-assembly of supramolecular structures to form rotaxanes during the synthesis of the continuous beds is treated. The electroosmotic and chromatographic properties of the various polyrotaxane-based stationary phases synthesized are discussed, as well as the synthesis of the continuous beds, including how to affect their porosity and its influence on the efficiency of the electrokinetic separation. The applicability of the rotaxane-based continuous bed is demonstrated by separation of model compounds by reversed- and normal-phase chromatography. A separation of enantiomers is also presented. This experiment is of particular interest because it indicates that the interaction with the cavity of β-cyclodextrin (β-CD) is not a fundamental requirement for enantioseparations.