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Title: A new ferrocenophane surface derivatizing reagent for the preparation of nearly reversible electrodes for horse heart ferri-/ferrocytochrome c: 2,3,4,5-tetramethyl-1-((dichlorosilyl)methyl((2)-ferrocenophane

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00340a006· OSTI ID:6164034

Pt gauze electrodes functionalized with hydrolytically unstable 2,3,4,5-tetramethyl-1-((dichlorosilyl)methyl)(2)-ferrocenophane (I) exihibit persistent cyclic voltammetry waves consistent with a surface-confined redox couple, PMFc/sup +//PMFc/sup 0/, having an E/sup o'/ = +0.04 V vs. SCE in H/sub 2/O/1.0 M NaClO/sub 4/ at pH 7.0. Such electrodes will effect the one-electron reduction of horse heart ferricytochrome c (cyt c/sub ox/) to ferrocytochrome c (cyt c/sub red/ as well as the oxidation of cyt c/sub ox/, under conditions where the naked electrode does not effect such redox processes. n-type Si photoanodes functionalized with I will effect the uphill oxidation of cyt c/sub red/ upon greater than or equal to E/sub g/ illumination and will effect cyt c/sub ox/ reduction in the dark. Derivatized electrodes are durable and do not significantly lose activity with use; a 4.4mM cyt c solution can be alternately exhaustively oxidized and reduced at +0.3 or -0.3 V vs. SCE in controlled-potential electrolyses for > 10 cycles without electrode deterioration. Electrodes derivatized with I come into charge-transfer equilibrium with cyt c/sub ox//cyt c/sub red/, E/sup o'/ = +0.02 V vs. SCE, via heterogeneous electron-exchange processes involving the PMFc/sup +//PMFc/sup 0/ redox centers; such electrodes can be used as potentiometric sensors for cyt c.

Research Organization:
Massachusetts Inst. of Tech., Cambridge
OSTI ID:
6164034
Journal Information:
J. Am. Chem. Soc.; (United States), Vol. 105:2
Country of Publication:
United States
Language:
English