Insight into the retention mechanism on immobilized artificial membrane chromatography using two stationary phases

• Systematic comparison of IAM.PC.MG and IAM.PC.DD2 columns.
• Relationships between IAM retention factors and lipophilicity.
• Investigation of the effect of electrostatic interactions to IAM retention.

The retention behavior of sixty structurally diverse drugs on two immobilized artificial membrane (IAM) columns, IAM.PC.MG and IAM.PC.DD2 types, at two pH values, 7.4 and 5.5, was established. Extrapolated to pure aqueous phase retention factors, log kw(IAM), were determined and the role of acetonitrile as organic modifier was explored, considering the relationships with the slopes, S, of the extrapolation procedure. Good interrelations between retention factors on the two IAM stationary phases were observed, although log kw(IAM.PC.DD2) values are generally higher than log kw(IAM.PC.MG). In order to investigate the underlying retention mechanism, relationships between IAM retention factors and lipophilicity, expressed as log P or log D at pH 7.4 were established. Electrostatic interactions were considered by introducing the positively and negatively charged molecular fractions as additional parameters in the log kw(IAM)/log D relationships. The positive contribution of these fractions supported the involvement of the electrostatic interactions in the retention mechanism. Special attention was given to the retention behavior of zwitterionic compounds and for compounds with special structural characteristics.