Electrostatic-Driven Activity, Loading, Dynamics,
and Stability of a Redox Enzyme on Functionalized-Gold Electrodes
for Bioelectrocatalysis
Posted on 2018-11-13 - 00:00
The
oxygen reduction reaction is the limiting step in fuel cells,
and many works are in progress to find efficient cathode catalysts.
Among them, bilirubin oxidases are copper-based enzymes that reduce
oxygen into water with low overpotentials. The factors that ensure
electrocatalytic efficiency of the enzyme in the immobilized state
are not well understood, however. In this work, we use a multiple
methodological approach on a wide range of pH values for protein adsorption
and electrocatalysis to demonstrate the effect of electrostatic interactions
on the electrical wiring, dynamics, and stability of a bilirubin oxidase
adsorbed on self-assembled-monolayers on gold. We show on one hand
that the global charge of the enzyme controls the loading on the interface
and that the specific activity of the immobilized enzyme decreases
with the enzyme coverage. On the other hand, we show that the dipole
moment of the protein and the charge in the vicinity of the Cu site
acting as the entry point of electrons drive the enzyme orientation.
In case of weak electrostatic interactions, we demonstrate that local
pH variation affects the electron transfer rate as a result of protein
mobility on the surface. On the contrary, stronger electrostatic interactions
destabilize the protein structure and affect the stability of the
catalytic signal. These data illustrate the interplay between immobilized
protein dynamics and local environment that control the efficiency
of bioelectrocatalysis.
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Hitaishi, Vivek
Pratap; Mazurenko, Ievgen; Harb, Malek; Clément, Romain; Taris, Marion; Castano, Sabine; et al. (2018). Electrostatic-Driven Activity, Loading, Dynamics,
and Stability of a Redox Enzyme on Functionalized-Gold Electrodes
for Bioelectrocatalysis. ACS Publications. Collection. https://doi.org/10.1021/acscatal.8b03443
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AUTHORS (11)
VH
Vivek
Pratap Hitaishi
IM
Ievgen Mazurenko
MH
Malek Harb
RC
Romain Clément
MT
Marion Taris
SC
Sabine Castano
DD
David Duché
SL
Sophie Lecomte
MI
Marianne Ilbert
Ad
Anne de Poulpiquet
EL
Elisabeth Lojou
KEYWORDS
protein mobilityfuel cellsCu siteelectrons driveenzyme controlsFunctionalized-Gold Electrodeselectron transfer ratebilirubin oxidasesenzyme coverageenzyme orientationoxygen reduction reactioninteractionpH variationbilirubin oxidaseElectrostatic-Driven Activityprotein dynamicsprotein structureenzyme decreasesentry pointelectrocatalytic efficiencycathode catalystspH valuesRedox Enzymeprotein adsorption