The incorporation of calix[6]arene and cyclodextrin derivatives into sol–gels for the preparation of stationary phases for gas chromatography

• New calix[6]arene and cyclodextrin derivatives were synthesized.
• An original method for sol–gel coating was developed.
• The sol–gel stationary phases exhibited shape selectivity.
• The thermal stabilities of the stationary phases were increased up to 280 °C.

New polyethylene-glycol-based sol–gels containing cyclodextrin or calix[6]arene derivatives have been synthesized. An original method for sol–gel preparation and capillary column coating, which consumes smaller quantities of selectors and allows for control of their amounts in the stationary phase, is reported herein. The new stationary phases exhibited excellent column efficiencies over a large range of temperatures and thermal stability up to 280 °C. The cyclodextrin derivative generally showed the best separation factors for aromatic positional isomers. The calix[6]arene derivative exhibited the best selectivity for the polychlorobiphenyl congeners and some polycyclic aromatic hydrocarbon isomers. The relationship between the structure and the chromatographic properties of the selectors is discussed. The tert-butyl groups on the upper rim of the calix[6]arene were found to possibly play an important role in the recognition of solutes. The incorporation of the cyclodextrin derivative into the sol–gel matrix did not affect its enantioselective recognition capabilities.