Insights into the Retention Mechanism for Small Neutral Compounds on Silica-Based Phenyl Phases in Reversed-Phase Liquid Chromatography
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The system constants of the solvation parameter model are used to prepare system maps for the retention of small neutral compounds on phenylhexylsiloxane- and pentafluorophenylpropylsiloxane-bonded superficially porous silica stationary phases (Kinetex Phenyl-Hexyl and Kinetex F5) for aqueous mobile phases containing 10–70% (v/v) methanol or acetonitrile. Electrostatic interactions (cation exchange) are important for the retention of weak bases for acetonitrile–water mobile phases, but virtually absent for the same compounds for methanol–water mobile phases. The selectivity of the Kinetex Phenyl-Hexyl stationary phase for small neutral compounds is similar to an octadecylsiloxane-bonded silica stationary phase with similar morphology Kinetex C-18 for both methanol–water and acetonitrile–water mobile phase compositions. The Kinetex Phenyl-Hexyl and XBridge Phenyl stationary phases with the same topology but different morphology are selectivity equivalent, confirming that solvation of the interphase region can be effective at dampening selectivity differences for modern stationary phases. Small selectivity differences observed for XTerra Phenyl (different morphology and topology) confirm previous reports that the length and type of space arm for phenylalkylsiloxane-bonded silica stationary phases can result in small changes in selectivity. The pentafluorophenylpropylsiloxane-bonded silica stationary phase (Kinetex F5) has similar separation properties to the phenylhexylsiloxane-bonded silica stationary phases, but is not selectivity equivalent. However, for method development purposes, the scope to vary separations from an octadecylsiloxane-bonded silica stationary phase (Kinetex C-18) to “phenyl phase” of the types studied here is limited for small neutral compounds. In addition, selectivity differences for the above stationary phases are enhanced by methanol–water and largely suppressed by acetonitrile–water mobile phases. For bases, larger selectivity differences are possible for the above stationary phases if electrostatic interactions are exploited, especially for acetonitrile-containing mobile phases.
KeywordsReversed-phase liquid chromatography Retention Selectivity Solvation parameter model System maps Stationary phases Phenyl phases
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Conflict of interest
Authors Atapattu and Poole have no conflict of interest. Author Praseuth is an employee of Phenomenex who manufactured the column used in this study. Authors Atapattu and Poole received no financial support from Phenomenex for this study.
This article does not contain any studies with human participants or animals performed by any of the authors.
- 1.Snyder LR, Dolan JW, Marchand DA, Carr PW (2015) The hydrophobic subtraction model of reversed-phase column selectivity. Adv Chromatogr 50:297–376Google Scholar
- 10.Stevenson PG, Mayfield KJ, Soliven A, Dennis GR, Gritti F, Guiochon G, Shalliker RA (2010) π-Selective stationary phases: (I) influence of the spacer chain length of phenyl phases on the aromatic and methylene selectivity of aromatic compounds in reversed-phase high performance liquid chromatography. J Chromatogr A 1217:5358–5364CrossRefGoogle Scholar
- 12.Stevenson PG, Soliven A, Dennis GR, Gritti F, Guiochon G, Shalliker RA (2010) π-Selective stationary phases. (III) Influence of the phenyl ligand density on the aromatic and methylene selectivity of aromatic compounds in reversed-phase liquid chromatography. J Chromatogr A 1217:5377–5383CrossRefGoogle Scholar
- 43.McDonald PD (2003) Improving our understanding of the reversed-phase separations for the 21st century. Adv Chromatogr 42:323–375Google Scholar