Facilitated protamine transfer at polarized water/1,2-dichloroethane interfaces studied by cyclic voltammetry and chronoamperometry at micropipet electrodes

Analytical Chemistry
Yi Yuan, Shigeru Amemiya


Cyclic voltammetry and chronoamperometry at micropipet electrodes were applied to study the phase transfer of polypeptide protamine facilitated by complexation with charged ionophore dinonylnaphthalenesulfonate (DNNS) at polarized water/1,2-dichloroethane (DCE) interfaces, i.e., sDNNS(-) (DCE) + protamine(n+) (aq) right harpoon over left harpoon protamine-DNNS complex (DCE). Well-defined current responses based on the selective protamine transfer were obtained reproducibly even in the presence of 0.12 M NaCl. The selective and reproducible responses make this voltammetric/amperometric approach an attractive alternative to the traditional potentiometric counterpart based on mixed potential responses, for which both protamine and Na(+) need to be transferred simultaneously. Using both organic- and water-filled micropipet electrodes, the reaction mechanism was studied under different mass-transfer conditions controlled by diffusion of protamine, DNNS, and the complex in the outer solution of the pipets. Both charge number of transferred protamine, n, and complexation stoichiometry, s, were determined to be approximately 20 by chronoamperometry. With these parameters, the electrochemically irreversible voltammograms were analyzed b...Continue Reading


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