System maps for retention of small neutral compounds on a biphenylsiloxane-bonded silica stationary phase in reversed-phase liquid chromatography

•System maps for a Kenetex Biphenyl column with acetonitrile- and methanol-water mobile phases.•Intermolecular interactions responsible for retention are characterized.•The biphenyl stationary phase chemistry has complementary selectivity to octadecylsiloxane-bonded silica stationary phase chemistry.•The biphenyl stationary phase chemistry has similar selectivity to the ether-linked alkylphenylsiloxane-bonded silica stationary phase chemistry.•The biphenyl stationary phase chemistry has dissimilar selectivity to pentafluorophenylsiloxane-bonded silica stationary phase chemistry.

The system constants of the solvation parameter model are used to prepare system maps for the retention of small neutral compounds on a biphenylsiloxane-bonded superficially porous silica stationary phase (Kinetex Biphenyl) for aqueous-organic solvent mobile phases containing 10-70% (v/v) methanol or acetonitrile. The retention properties of the biphenylsiloxane-bonded phase are shown to be complementary to an octadecylsiloxane-bonded silica (Kinetex C-18) and a pentafluorophenylpropylsiloxane-bonded silica stationary phases (Discovery HS F5). The retention properties of the Kinetex Biphenyl column are similar to an ether-linked phenylpropylsiloxane-bonded silica phase (Synergi Polar RP) with only small differences in relative retention.