ACE C18-PFP column introduces III-PFP separation mechanism
The ACE C18-PFP phase exhibits multiple retention mechanisms including hydrophobicity, π-π interaction, dipole-dipole, hydrogen bonding, and shape selectivity.
While the following sections provide approximations of relative intensities, the advantages of each retention mechanism are determined by the physical/chemical properties of the solute, its structure, and the chromatographic conditions employed.
Î -Ï€ interaction
The PFP ring adds aromatic character to the surface of the phase.
However, the PFP phase is different from the phenyl phase because the electronegative fluorine atom produces an electron-deficient benzene ring, so that the PFP phase can function as a Lewis acid.
This will interact with an analyte that is capable of giving electrons (ie, a Lewis base).
This is in contrast to the phenyl phase, which contains electron-rich aromatic rings (due to the absence of electron withdrawing groups), so they can function as Lewis bases.
Dipole-dipole and hydrogen bonding
The carbon-fluorine bond in the PFP ring has a strong polarity.
Thus, the PFP phase can additionally retain the analyte by dipole-dipole or hydrogen bonding interactions that occur between the analyte and the electronegative fluorine atom.
Any such interaction will result in an increase in retention.
Shape selectivity
PFP has a rigid ring structure that, when combined with other possible retention mechanisms, imparts excellent shape selectivity to the PFP phase.
The ACE C18-PFP phase shows a multiple retention mechanism for the PFP phase, and chromatographers may use these mechanisms to resolve mixtures that are difficult, if not impossible, to separate in the traditional C18 phase (which relies primarily on hydrophobic retention mechanisms).
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