Insights into the Retention Mechanisms on Perfluorohexylpropylsiloxane-Bonded (Fluophase-RP) and Octadecylsiloxane-Bonded (Betasil C18) Stationary Phases Based on the Same Silica Substrate in RP-LC |
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Authors: | C F Poole H Ahmed W Kiridena C DeKay W W Koziol |
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Institution: | (1) Department of Chemistry, Wayne State University, Detroit, MI 48202, USA;(2) North America Analytical and Physical Sciences Laboratory, Flint Group, 4600 Arrowhead Drive, Ann Arbor, MI 48105, USA |
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Abstract: | The solvation parameter model is used to elucidate the retention mechanism on a perfluorohexylpropylsiloxane-bonded (Fluophase
RP) and octadecylsiloxane-bonded (Betasil C18) stationary phases based on the same silica substrate with acetonitrile–water
and methanol–water mobile phase compositions. Dewetting affects the retention properties of Fluophase RP at mobile phase compositions
containing less than 20% (v/v) acetonitrile or 40% (v/v) methanol. It results in a loss of retention due to an unfavorable change in the phase ratio as well as changes in specific
intermolecular interactions. Steric repulsion reduces retention of bulky solutes on fully solvated Betasil C18 with methanol–water
(but not acetonitrile–water) mobile phase compositions but is not important for Fluophase RP. The retention of weak bases
is affected by ion-exchange interactions on Fluophase RP with acetonitrile–water, and to a lesser extent, methanol-water mobile
phases but these are weak at best for Betasil C18. The system constants of the solvation parameter model and retention factor
scatter plots are used to compare selectivity differences for Fluophase RP, Betasil C18 and a perfluorophenylpropylsiloxane-bonded
silica stationary phase Discovery HS F5 for conditions where incomplete solvation, steric repulsion and ion-exchange do not
significantly contribute to the retention mechanism. Lower retention on Fluophase RP results from weaker dispersion and/or
higher cohesion moderated to different extents by polar interactions since solvated Fluophase RP is a stronger hydrogen-bond
acid and more dipolar/polarizable than Betasil C18. Retention factors for acetonitrile–water mobile phases are highly correlated
for Fluophase RP and Betasil C18 except for compounds with a large excess molar refraction and weak hydrogen-bonding capability.
Selectivity differences are more significant for methanol–water mobile phases. Retention factors on Fluophase RP are strongly
correlated with those on Discovery HSF5 for acetonitrile–water mobile phases while methanol–water mobile phases retention
on Fluophase RP is a poor predictor of the retention order on Discovery HS F5. |
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Keywords: | Column liquid chromatography Solvation parameter model Fluophase RP Betasil C18 Steric repulsion Ion exchange |
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