We unveil experimental evidence that put into question the widely held notion
concerning the impact of nanoparticles on the bioelectrocatalytic parameters of
enzymatic electrodes. Comparative studies of the bioelectrocatalytic properties
of fungal bilirubin oxidase from Myrothecium verrucaria
adsorbed on gold electrodes, modified with gold nanoparticles of
different diameters, clearly indicate that neither the direct electron transfer
rate (standard heterogeneous electron transfer rate constants were calculated
to be 31±9 s-1) nor the biocatalytic activity of the adsorbed
enzyme (bioelectrocatalytic constants were calculated to be 34±11
s-1) depends on the size of the nanoparticles, which had diameters
close to or larger than those of the enzyme molecules.
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