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Issue
J. Chim. Phys.
Volume 96, Number 4, April 1999
Page(s) 665 - 684
DOI http://dx.doi.org/10.1051/jcp:1999164
DOI: 10.1051/jcp:1999164


J. Chim. Phys. Vol. 96, N°4  p. 665-684

Voltammetry of 6,6'-dithiodinicotinic acid on a self-assembled phospholipid monolayer prive

R. Herrero1, T. Vilariño1, J.L. Barriada1, M.E. Sastre de Vicente1, J.M. López-Fonseca2 and M.R. Moncelli3

1  Departamento de Química Fundamental e Industrial, Facultad de Ciencias, University of La Coruña, La Coruña 15071, Spain
2  Departamento de Química Física y Analítica, Facultad de Química, University of Oviedo, Oviedo, Spain
3  Dipartimento di Chimica, University of Florence, Florence 50121, Italy

Abstract
This paper reports a voltammetric study of 6,6'-dithiodinicotinic acid (CPDS) across a biomimetic membrane system consisting of a monolayer of dioleoylphosphatidylcholine, deposited on mercury. Because of the low solubility of this compound and its potential decomposition in alkaline media, estimation of pK values for the carboxyl and amino groups of the pyridine ring of the CPDS entailed using the Hammett equation. UV spectra seem to confirm the presence of the dianionic form of CPDS above $\rm pH=3-4$. Differential capacity and cyclic voltammetry measurements were made in order to characterize the voltammetric behavior directly on mercury and through a monolayer of dioleoylphosphatidylcholine. Estimation of the CPDS hydrophobicity degree from the partition coefficient in octanol/ water suggests no penetration of the dianion into the monolayer and supports the fact that the named dianion undergoes protonation at the phospholipid/solution interface to give a neutral specie which penetration into the phospholipid region, favored by its higher hydrophobicity, is followed by electrochemical reduction at the mercury surface.

Résumé
Nous avons étudié par voltampérométrie le comportement de l'acide 6,6'-dithiodinicotinique (CPDS) sur l'électrode de mercure couverte par une monocouche de dioleoyl-phosphatidylcholine. La caractérisation électrochimique a été effectuée par des mesures de la capacité différentielle et par voltamétrie cyclique au dessus d'un pH 3-4. Le spectre UV paraît confirmer la présence de la forme dianionique du CPDS. Cependant les données expérimentales associées à une estimation de l'hydrophobicité de la forme dianionique suggèrent que seule la forme neutre du CPDS peut être réduite sur la surface de l'électrode.


Key words: 6,6'-dithiodinicotinic acid -- phospholipid monolayer -- voltammetry
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