Enhanced Direct Electron Transfer of Fructose Dehydrogenase Rationally Immobilized on 2-Amino Anthracene Diazonium Cation Grafted Single-Walled Carbon Nanotube Based Electrode

October 11, 2018

Title

Enhanced Direct Electron Transfer of Fructose Dehydrogenase Rationally Immobilized on 2-Amino Anthracene Diazonium Cation Grafted Single-Walled Carbon Nanotube Based Electrode

Author

Paolo Bollella, Yuya Hibino, Kenji Kano, Lo Gorton, Riccarda Antiochia

Year

2018

Journal

ACS Catalysis

Abstract

In this paper, an efficient direct electron transfer (DET) reaction was achieved between fructose dehydrogenase (FDH) and a glassy carbon electrode (GCE) onto which anthracene modified single walled carbon nanotubes were deposited. The SWCNTs were in situ activated with a diazonium salt synthesized through the reaction of 2-amino anthracene with NaNO2 in acidic media (0.5 M HCl) for 5 min at 0 °C. After the in situ reaction, the 2-amino anthracene diazonium salt was electrodeposited by running cyclic voltammograms from +1000 mV to -1000 mV vs. Ag|AgClsat. The anthracene-SWCNT modified GCE was further incubated in an FDH solution to allow the enzyme to adsorb. Cyclic voltammograms of the FDH modified electrode revealed two couple of redox waves possibly ascribed to the heme c1 and heme c3 of the cytochrome domain. In the presence of 10 mM fructose two catalytic waves could clearly be seen and were correlated with two heme c:s (heme c1 and c2), with a maximum current density of 48521 µA cm-2 at 0.4 V vs. Ag|AgClsat at a sweep rate of 10 mVs-1. In contrast, for the plain SWCNT modified GCE only one catalytic wave and one couple of redox waves were observed. Adsorbing FDH directly onto a GCE showed no non-turn over electrochemistry of FDH and in the presence of fructose only a slight catalytic effect could be seen. These differences can be explained by considering the hydrophobic pocket close to heme c1, heme c2 and heme c3 of the cytochrome domain at which the anthracenyl aromatic structure could interact through π-π interactions with the aromatic side chains of the amino acids present in the hydrophobic pocket of FDH.

Instrument

J-815

Keywords

Circular dichroism, Secondary structure, Protein denaturation, Nanostructures, Materials, Biochemistry