Relevance of π–π and dipole–dipole interactions for retention on cyano and phenyl columns in reversed-phase liquid chromatography

Previous work suggests that π–π interactions between certain solutes and both phenyl and cyano columns can contribute to sample retention and the selectivity of these two column types versus alkylsilica columns. Recent studies also suggest that dipole–dipole interactions are generally unimportant for retention on cyano columns. The present study presents data for 44 solutes, three columns and two different mobile phases that were selected to further test these conclusions. We find that π–π interactions can contribute to retention on both cyano and phenyl columns, while dipole–dipole interactions are likely to be significant for the retention of polar aliphatic solutes on cyano columns. When acetonitrile/water mobile phases are used, both π–π and dipole–dipole interactions are suppressed, compared to the use of methanol/water.