Voltammetry of the phase transfer of polypeptide protamines across polarized liquid/liquid interfaces

Using natural polypeptide protamines as the illustrating example, we observed the phase transfer of biological polyions at polarized interfaces between two immiscible electrolyte solutions (ITIES) for the first time by micropipet voltammetry. Analysis of the limiting currents indicates that each protamine carries 20 positive charges as expected from the number of arginine residues in the molecule. Also, it was shown that the shape of the voltammograms is limited by the interfacial transfer of protamines. Coupling of the transfer reactions with interfacial adsorption/desorption of protamines was also observed. ITIES will serve as a basis of amperometric sensors for biological macromolecules and also as a model for understanding potential-driven membrane transport of these molecules. Copyright © 2003 American Chemical Society.