Determination of polymer log D distributions by micellar and microemulsion electrokinetic chromatography

• Characterization of polymer hydrophobicity.
• Determination of polymer log D distributions.
• Applications to cationic polylysines derivatives.
• Comparison between MEKC and MEEKC.

The characterization of the hydrophobicity of polymer compounds in solution remains a challenging issue of importance, especially for biomedical or pharmaceutical applications. To our knowledge, there is no data of polymer hydrophobicity (log D) in the literature. In this work, for the first time, the log D distributions of cationic polymers were characterized using micellar or microemulsion electrokinetic chromatography at physiological pH. The log D distributions of the polymer samples were obtained from the electrophoretic/chromatographic retardation of the polymer derivatives in presence of neutral micelles (or neutral microemulsion), using small cationic molecules for calibration. Separating electrolytes were based on a TRIS–chloride buffer containing a neutral surfactant (polyoxyethyleneglycol dodecyl ether) for the formation of micelles (in water) or microemulsion (in water/n-pentanol mixture). The log D distributions obtained at pH 7.4 using this method were in good agreement with the chemical structures of cationic polypeptides: poly(lys, phe) 1:1 > poly(lys, tyr) 1:1 > poly(lys, trp) 4:1 > poly(lys, ser) 3:1 > poly(l-lysine), where x:y represents the molar ratio of each amino acid in the copolymer. Weight average octanol–water log D values and the dispersion of the log D distribution were also defined and determined for each polymer sample.