Sorption of Cationic Surfactants to Artificial Cell Membranes: Comparing Phospholipid Bilayers with Monolayer Coatings and Molecular Simulations

Abstract

This study reports the distribution coefficient between phospholipid bilayer membranes and phosphate buffered saline (PBS) medium (D_MW,PBS) for 19 cationic surfactants. The method used a sorbent dilution series with solid supported lipid membranes (SSLMs). The existing SSLM protocol, applying a 96 well plate setup, was adapted to use 1.5 mL glass autosampler vials instead, which facilitated sampling and circumvented several confounding loss processes for some of the cationic surfactants. About 1% of the phospholipids were found to be detached from the SSLM beads, resulting in nonlinear sorption isotherms for compounds with log D_MW values above 4. Renewal of the medium resulted in linear sorption isotherms. D_MW values determined at pH 5.4 demonstrated that cationic surfactant species account for the observed D_MW,PBS. Log D_MW,PBS values above 5.5 are only experimentally feasible with lower LC-MS/MS detection limits and/or concentrated extracts of the aqueous samples. Based on the number of carbon atoms, dialkylamines showed a considerably lower sorption affinity than linear alkylamine analogues. These SSLM results closely overlapped with measurements on a chromatographic tool based on immobilized artificial membranes (IAM-HPLC) and with quantum-chemistry based calculations with COSMOmic. The SSLM data suggest that IAM-HPLC underestimates the D_MW of ionized primary and secondary alkylamines by 0.8 and 0.5 log units, respectively.