Journal of the American Chemical Society p. 2379 - 2386 (1981)
Update date:2022-08-11
Topics:
Bresnahan, William T.
Elving, Philip J.
The title reduction was investigated at pH 9.1 in several base electrolytes of varying surface activity in order to elucidate the role of adsorption of NAD+, its free radical, and the resulting dimer at the aqueous solution/mercury electrode interface.In the presence of electrolytes of low activity, NAD+ is adsorbed at potentials positive to its 1-e reduction (ca. -0.9 V vs.SCE); the electrochemically generated dimer, (NAD)2, is adsorbed positive of -1.20 and -1.32 V in 0.06 and 0.4 M KCl solutions, respectively.NAD+ undergoes both diffusion- and adsorption-controlled reduction; the former predominates on slow time scale experiments and the latter on fast time scales.From low concentration surfactant (0.06 and 0.1 M tetraethylammonium (Tea+) chloride) solutions, NAD+ is only adsorbed positive of -0.65 V and an adsorption-controlled prewave appears, indicating that an adsorbed layer of NAD. and/or (NAD)2 is formed on reduction of dissolved NAD+.From a high concentration (0.4 M) Tea+ solution, NAD+ is adsorbed positive of -0.66 V, but the adsorption-controlled prewave is suppressed and the reduction is entirely diffusion controlled.Under diffusion control, the heterogeneous rate constant for the title reduction is ca. 0.1 cm s-1 and the rate constant for dimerization of NAD. is ca. 3E6 M-1 s-1.
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