Separation of dialkyl sulfides by metallomesogenic stationary phases for complexation gas chromatography

A copper mesogenic side-chain polymer (P-C15CuC18) was cross-linked onto the capillary wall as a stationary film for gas chromatography (GC) separation of alkylsulfides. These organic sulfides are of interest for their large health impact because of their wide range of volatilities and high reactivities toward metals. Different GC parameters for optimal separation efficiency are discussed for use with a mesogenic polymer column along with flame photometric detection (FPD). Both the carrier gas flow-rate and column temperature were studied to determine the relationship of plate height to the chemical structure of the solutes, as well as to determine the morphology of the mesogenic polymer. Van ’t Hoff plots show phase transitions of the stationary mesophase as the column temperature was varied. The results reveal that the separation mechanism might be based on ligand exchange and polarity interaction between the analytes and the stationary phase, with the vapor pressure of the analytes also being important. The former interaction dominates in the lamellar crystalline phase and the latter interaction dominates in the hexagonal columnar-discotic phase. With high reproducibility for retention time (RSD ≤ 0.37%) and for peak area (RSD ≤ 5.16%), the GC–FPD system produced linear calibration graphs (r ≥ 0.9918) for the determination of 13 sulfides with a detection limit below 2.5 ng.