Enhancement of Electrochemical Performance of Bilirubin Oxidase Modified Gas Diffusion Biocathode by Porphyrin Precursor

Pinchon, Erica; Arugula, Mary A.; Pant, Kapil; Singhal, Sameer

doi:10.1155/2018/4712547

Cited by 3 publications

(1 citation statement)

References 42 publications

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“…This electron transfer was considered as the rate limiting process in the catalytic cycle under alkaline conditions. 49 In some studies, the base electrodes were modified with aromatic amines, porphyrins, 50 surfactants, 51 pyrenes, 52 syringaldazine, 53 bilirubin, 54 and many other chemicals that could form π−π stacks with the basal planes of MWNTs to act as tethering or orienting agents for BOD. 15 Additionally, redox mediators were used to enhance the catalytic current density in prior studies.…”

Section: Discussionmentioning

confidence: 99%

Buckypaper–Bilirubin Oxidase Biointerface for Electrocatalytic Applications: Buckypaper Thickness

Walgama

Pathiranage

Akinwale

et al. 2019

ACS Appl. Bio Mater.

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Electrode materials play an important role on the electrocatalytic properties of immobilized biocatalysts. In this regard, achieving direct electronic communication between the electrode and redox sites of biocatalysts eliminates the need for additional electron transfer mediators for biocatalytic applications in fuel cells and other electrochemical energy devices. In order to increase electrocatalytic currents and power in fuel cells and metal–air batteries, conductive carbon-nanostructure-modified large surface area electrodes are quite useful. Among various electrode materials, freestanding buckypapers made from carbon nanotubes have gained significance as they do not require a solid support material and thus facilitate miniaturization. In this article, we present the effect of buckypaper (BP) thickness on the electrocatalytic properties of a bilirubin oxidase (BOD) enzyme. In this study, we prepared BPs of varying thicknesses ranging from 87 μm, the minimum thickness for suitable handling with a good stability in aqueous experiments, to 380 μm. BOD was adsorbed overnight onto the BPs, mostly via hydrophobic and π–π interactions since the nanotubes used were not chemically functionalized. Furthermore, intercalation of the BOD molecules onto the nanotubes’ multicylindrical network is feasible. We determined that the lower range BP thickness (<220 μm) exhibited better sigmoidal shaped electrocatalytic currents than the higher BP-thickness-based BOD biofilms with larger capacitive currents. An oxygen reduction current density of up to 3 mA cm–2 is achieved without the use of any redox mediators or tedious electrode modifications. Using the 87 μm thick BP as the representative case, we were able to obtain distinguishable peaks for all Cu sites of BOD and assign their types, T1, T2, and T3, based on the peak-width at half-maximum in anaerobic cyclic voltammograms. Our peak assignment is further supported by the appearance of dual electrocatalytic oxygen reduction waves at a higher scan rate region (>10 mV s–1) in oxygen-saturated buffer, which is identified to be driven by an ∼3.5 times faster electron transfer rate from the buckypaper to the T2/T3 center than the T1 Cu site. Findings from this study are significant for designing enzyme electrocatalytic systems and biosensors in general and fuel cells and aerobic energy storage devices in particular, where the cathodic oxygen reduction current is often inadequate.

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