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HYDROXYMETHYLFERROCENE MODIFIED TIN OXIDE ELECTRODES AND THEIR APPLICATIONS TO THE OXIDATIVE ELECTROCATALYSIS OF FERROCYTOCHROME C AND NICOTINAMIDE ADENINE DINUCLEOTIDE REDUCED FORM

ARTHUR LORING CORDRY, University of Nebraska - Lincoln

Abstract

Hydroxymethylferrocene was chemically bonded to tin oxide glass film electrodes by two different sulfonyl compounds, p-carboxybenzenesulfonyl chloride and 4,4' biphenyldisulfonyl chloride. Plots of peak current versus scan rate was found to be linear which is what would be expected for a surface process. The anodic peak potential for the hydroxymethylferrocene electrode at moderate scan rates were found to range from .37 to .39 V versus Ag/AgCl in .1 M Tris HC10(,4) pH7 supporting electrolyte. The anodic peak width at half the height range from 70 to 100 millivolts for linked with p-carboxybenzenesulfonylchloride. Hydroxymethylferrocene linked with 4,4' biphenyldisulfonylchloride showed anodic peak width at half the height to range from 120 to 167 millivolts. Surface coverage of the p-carboxybenzenesulfonylchloride linked electrode was found to be 6.4 x 10('-10) moles/cm('2) by chronocoulometry and 6.9 x 10('-10) moles/cm('2) by copy cut and weigh method. The surface coverage of hydroxymethylferrocene electrodes linked with 4,4' biphenyldisulfonylchloride was found to be 1.3 x 10('-9) moles/cm('2) by chronocoulometry and 1.1 x 10('-9) by the copy cut and weigh method. Chemically bonding of electroactive components to electrodes using these sulfonyl compounds proved to be simpler than other bonding techniques currently being used. The electrode response is what would be expected for surface bound electrochemistry. The bound hydroxymethylferrocene had some nonideal characteristics but were consistent with current theory and published data of other ferrocene electrodes. These hydroxymethylferrocene electrodes were found to catalyze the oxidation of ferrocytochrome c and nicotinamide adenine dinucleotide reduced form (NADH). The oxidation of NADH in the presence of solution xanthine oxidase was catalyzed at +0.4V versus Ag/AgCl. During the oxidation of ferrocytochrome c, water was also found to oxidize to protons and dioxygen. This reaction occurred at a potential of .554 versus Ag/AgCl which is very near the potential calculated for the oxidation of water by cytochrome c oxidase and cytochrome c in biological systems.

Subject Area

Analytical chemistry

Recommended Citation

CORDRY, ARTHUR LORING, "HYDROXYMETHYLFERROCENE MODIFIED TIN OXIDE ELECTRODES AND THEIR APPLICATIONS TO THE OXIDATIVE ELECTROCATALYSIS OF FERROCYTOCHROME C AND NICOTINAMIDE ADENINE DINUCLEOTIDE REDUCED FORM" (1983). ETD collection for University of Nebraska-Lincoln. AAI8412298.
https://digitalcommons.unl.edu/dissertations/AAI8412298

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