Indirect Detection of Alkaline Earth Ions by the Voltammetric Response of Ferricyanide Anion at a Glassy Carbon Electrode Anodized in 1-Octanol

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The suppressed voltammetric respones of Fe(CN)^<3->_6 at a glassy carbon (GC) electrode anodized in 1-octanol is restored by addition of alkaline earth ions and this can be applied to the detection of such cations. A good dependence of the cathodic currents of Fe(CN)^<3->_6 at a 1-octanol-modified GC electrode on the concentration of each cation (Ca^<2+>, Mg^<2+>, Sr^<2+>. Ba^<2+>) is obtained over the range 10 μM-1 mM. The slight increase in enhanced voltammetric response of Fe(CN)^<3->_6 in the presence of Ca^<2+> following added MeOH ruled out an ion-extraction mechanism for the observed phenomena. The effects of Ca^<2+> upon the voltammetric behavoir of Fe(CN)^<4->_6 and IrCl^<2->_6 as well as Fe/(CN)^<3->_6 at a 1-octanol-modified GC electrode were compared with those previously reported at a carbon microelectrode, suggesting that the suppression of the cathodic reaction of Fe(CN)^<3->_6 and its elimination by the addition of alkaline earth ions are brought about through transformation of a macroelectrode into a pseudo-microelectrode by anodization in 1-octanol. This is strongly supported by the fact that similar phenomena occur at other chemically modified electrodes, providing that modification is controlled to give an effective surface area corresponding to that of a pseudo-microelectrode.
公益社団法人日本薬学会の論文
1996-03-15