Ap. Doherty et al., THE EFFECT OF THE NATURE OF THE POLYMER BACKBONE ON THE STABILITY ANDTHE ANALYTICAL RESPONSE OF POLYMER-MODIFIED ELECTRODES, Electroanalysis, 7(4), 1995, pp. 333-339
The synthesis, characterization, and sensor application of the novel r
edox polymer [Os(bipy)(2)(PS)(7.5)(DMAP)(2.5)Cl]Cl, where bipy = 2, 2'
-bipyridyl, PS = polystyrene, and DMAP = poly[4-(N-methyl-N-p-vinylben
zylamino) pyridine], are described. The charge transport properties of
electrodes modified with the redox material are investigated using cy
clic voltammetry and chronoamperometry. The modified electrode behaves
as an efficient electrocatalyst for the outer-sphere reduction of Fe-
III, with the cross-exchange reaction occurring at the surface of the
polymer (Sk'') at concentrations less than 1.0 x 10(-3) mol dm(-3) Fe-
III, with a change over to the St(e) kinetic regime at higher substrat
e concentrations. Direct agreement was observed between the kinetic be
havior at rotating disk electrodes and in thin-layer flow cells. Appli
cation of the modified electrodes for the determination of iron in pha
rmaceutical formulations and the long term stability of the electrodes
are investigated. The results obtained are compared with those report
ed for the analogous metallopolymer [Os(bipy)(2)(PVP)(10)Cl]Cl, where
PVP is poly-4-vinylpyridine.