Articles

A retention study on perfluorophenyl silicabased stationary phase was undertaken for some organic compounds containing different polar functionalities. The dependence of the retention factor on the content of organic modifier (acetonitrile, or methanol) in mobile phase was fitted by polynomial equations. The only exception was observed for adenine, which showed a sigmoidal dependence for the retention factor versus organic modifier content. The extrapolated values of retention factor for water as mobile phase (log kw) from these dependences were well correlated with octanol–water partition constants (log Kow), excepting the values for hexachlorocyclohexane isomers and adenine. Temperature dependences of the retention factor obeyed the van’t Hoff equation with thermodynamic parameters similar to those obtained in reversed phase on C8 or C18 stationary phases, excepting two statines whose dependences of ln k on the reciprocal value of absolute column temperature were nonlinear. Again, adenine had an atypical behavior with decrease in the retention factor with the increase in column temperature, due to possible tautomeric equilibria of this compound in presence of water, in accordance with theoretical models reported by literature. Charge modeling with MarvinSketch package program revealed charged centers from analyte molecule that could interact differently with charge centers from stationary phase.

The use of a large volume injection of hydrophobic solvents as diluents for less hydrophobic solutes has already been proven for C18 and C8 stationary phases in reversed-phase liquid chromatography. The same possibility is investigated for a phenyl-hexyl stationary phase using aromatic solvents (benzene, toluene, ethylbenzene and propylbenzene) as diluents for several model analytes also containing aromatic rings. Both hydrophobic interaction and p–p stacking account for the competitive interaction of both the diluent and model analytes with the phenyl-hexyl phase. A linear decrease in analyte retention factor was observed with an increase of injection volume in the range of 1–100 mL. A moderate peak efficiency decrease was also observed, but peaks of model analytes remained undistorted with minimum band broadening up to 100 mL injection volume. A very small retention decrease was observed when changing the sample diluent in the homologous series: benzene, toluene, ethylbenzene and propylbenzene. The critical conditions for a successful large volume injection of analytes dissolved in studied hydrophobic solvents are for the analyte to have lower hydrophobicity and for the specified solutes to have proper solubility.