Voltammetry and Single-Molecule in Situ Scanning Tunneling Microscopy of Laccases and Bilirubin Oxidase in Electrocatalytic Dioxygen Reduction on Au(111) Single-Crystal Electrodes

Climent, Vı́ctor; Zhang, Jingdong; Friis, Esben P.; Østergaard, Lars; Ulstrup, Jens

doi:10.1021/jp2086285

Cited by 60 publications

(106 citation statements)

References 80 publications

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“…[47] A clearer situation was obtained upon immobilization of Mv BOD on gold single-crystal electrodes. [158,177] CV coupled to QCM and AFM experiments at various SAMs confirmed that hydrophilic interfaces, and especially negative interfaces, were more favorable for T1 interaction and electrocatalysis of O 2 reduction. A different orientation on bare gold vs. SAM-modified gold was suggested.…”

Section: Multicopper Oxidases (Mcos)mentioning

confidence: 84%

“…[157] In MCOs, the T1 Cu center situated 7-8 from the surface of the enzyme is targeted for fast interfacial electron-transfer rate. [64] In LACs the charge of the pocket near T1 Cu center in which the substrate binds depends on the origin of the enzyme, [158][159] but the binding pocket is essentially hydrophobic. [160] In contrast to LACs, the binding pocket in BODs is mainly hydrophilic.…”

Section: Chemelectrochem Reviews Wwwchemelectrochemorgmentioning

confidence: 99%

“…CHEMELECTROCHEM REVIEWS www.chemelectrochem.org situ scanning tunneling microscopy, [158] and quartz crystal microbalance (QCM) with dissipation (QCM-D). [37,141,169] All these methods help in the understanding of the behavior of the enzyme upon immobilization and to address key issues such as enzyme release, enzyme denaturation, enzyme reorientation, structural rearrangement under electric field, and substrate access, with ultimate progress toward single-molecule science.…”

Section: Tools To Study Orientationmentioning

confidence: 99%

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Biohydrogen for a New Generation of H₂/O₂ Biofuel Cells: A Sustainable Energy Perspective

et al. 2014

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Among sustainable alternatives to fossil fuel, proton exchange membrane fuel cells are promising devices that deliver electricity from hydrogen and oxygen, producing only water. The transformation of the fuel and oxidant however relies on rare‐metal catalysts. H2/O2 enzymatic biofuel cells thus emerge as sustainable biotechnological devices in which chemical catalysts are replaced by hydrogenases at the anode and multicopper oxidases at the cathode. This review discusses the recent breakthroughs and the limitations in all the components of H2/O2 biofuel cells: 1) Catalytic mechanisms involved in multicopper oxidases and hydrogenases, in addition to the new potential of enzymes from the biodiversity pool, which exhibit outstanding properties. 2) The molecular basis for oriented enzyme immobilization on the electrochemical interfaces as a prerequisite for a fast direct electron‐transfer rate. 3) The requirement for 3D networks to enhance current densities. 4) The production of H2 from biomass. 5) The history of H2/O2 biofuel cells and recent devices, which also highlights the remaining issues that will allow the use of such devices in low‐power applications.

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Section: Multicopper Oxidases (Mcos)mentioning

confidence: 84%

Section: Chemelectrochem Reviews Wwwchemelectrochemorgmentioning

confidence: 99%

Section: Tools To Study Orientationmentioning

confidence: 99%

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Biohydrogen for a New Generation of H₂/O₂ Biofuel Cells: A Sustainable Energy Perspective

et al. 2014

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“…0.4 V vs. NHE [27]. Wellpronounced DET-based bioelectrocatalytic reduction of O 2 on bare and modified Au(111) single-crystal electrodes modified with immobilized Lc from different sources has been reported [25]. The voltammetric behaviour of surface-immobilized composite Lc is exceedingly sensitive to the general state of both the electrode surface and the enzymes.…”

mentioning

confidence: 95%

“…Denaturation (protein unfolding) of the enzymes on bare Au surface can also account for the observed effects. The bioelectrocatalytic reduction of O 2 by laccase on modified Au electrodes [24][25] including nanoparticle modified Au electrodes [26] has been described. The catalytic reduction of O 2 by laccase supported on a nanoporous gold film modified electrode has been described, however at low potentials of ca.…”

mentioning

confidence: 99%

Direct electron transfer of Trametes hirsuta laccase adsorbed at unmodified nanoporous gold electrodes

Salaj-Kośla

Pöller

Schuhmann

et al. 2013

Bioelectrochemistry

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The enzyme Trametes hirsuta laccase undergoes direct electron transfer at unmodified nanoporous gold electrodes, displaying a current density of 28 A/cm 2 . The response indicates that ThLc was immobilised at the surface of the nanopores in a manner which promoted direct electron transfer, in contrast to the absence of a response at unmodified polycrystalline gold electrodes. The bioelectrocatalytic activity of ThLc modified nanoporous gold electrodes was strongly dependent on the presence of halide ions. Fluoride completely inhibited the enzymatic response, whereas in the presence of 150 mM Cl -, the current was reduced to 50% of the response in the absence of Cl -. The current increased by 40% when the temperature was increased from 20°C to 37°C. The response is limited by enzymatic and/or enzyme electrode kinetics and is 30% of that observed for ThLc co-immobilised with an osmium redox polymer. Keywords: Laccase, direct electron transfer, nanoporous gold 2 IntroductionElectron transfer (ET) reactions are ubiquitous in nature. Controlling the rate of these reactions can be of significant benefit in developing biochemical systems that utilise redox proteins and enzymes and in particular, in applications that provide power for implanted or portable electronic devices. ET can be achieved directly (direct electron transfer, DET) or by the use of mediators (mediated electron transfer, MET) to shuttle electrons between the redox centre of the enzyme and the electrode. However, mediators are unselective and can also give rise to interfering effects [1][2][3]. DET-based devices offer high selectivity and sensitivity due to the absence of mediators. In addition, devices based on DET operate at potentials close to the redox potential of the enzyme, maximising the potential difference between the cathode and anode for biofuel cell applications [2]. Moreover, DET can be used to provide detailed information on the kinetics and thermodynamics of the ET process. However, the low stability of the enzyme layer together with the long distances over which ET occurs, represent major obstacles for DET based devices. In addition, the shielding mechanism of the enzymatic redox centre by the protein shell can disrupt DET [2,4]. One approach in optimizing and enabling rapid DET is to design the electrode surface with an architecture which promotes efficient rates of ET. In this way the electrode morphology ensures the most efficient orientation of the enzymatic redox centre and facilitates communication with the electroactive surface. Porous electrodes can be used to encapsulate the enzyme within a network of cavities, shortening the distance for electron transfer to the redox active site, which will promote more efficient and rapid rates of electron transfer [5]. However, the number of redox enzymes capable of interacting directly with the electrode while catalyzing the enzymatic reaction is limited, with estimates of approximately 5% of all enzymes exhibiting such a response [6].DET in enzymes was first described in 1978 fo...

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Retrospective and Prospective Views of Electrochemical Electron Transfer Processes: Theory and Computations

Nazmutdinov

Ulstrup

2021

Atomic‐Scale Modelling of Electrochemical Systems

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Voltammetry and Single-Molecule in Situ Scanning Tunneling Microscopy of Laccases and Bilirubin Oxidase in Electrocatalytic Dioxygen Reduction on Au(111) Single-Crystal Electrodes

Cited by 60 publications

References 80 publications

Biohydrogen for a New Generation of H₂/O₂ Biofuel Cells: A Sustainable Energy Perspective

Biohydrogen for a New Generation of H₂/O₂ Biofuel Cells: A Sustainable Energy Perspective

Direct electron transfer of Trametes hirsuta laccase adsorbed at unmodified nanoporous gold electrodes

Retrospective and Prospective Views of Electrochemical Electron Transfer Processes: Theory and Computations

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Voltammetry and Single-Molecule in Situ Scanning Tunneling Microscopy of Laccases and Bilirubin Oxidase in Electrocatalytic Dioxygen Reduction on Au(111) Single-Crystal Electrodes

Cited by 60 publications

References 80 publications

Biohydrogen for a New Generation of H2/O2 Biofuel Cells: A Sustainable Energy Perspective

Biohydrogen for a New Generation of H2/O2 Biofuel Cells: A Sustainable Energy Perspective

Direct electron transfer of Trametes hirsuta laccase adsorbed at unmodified nanoporous gold electrodes

Retrospective and Prospective Views of Electrochemical Electron Transfer Processes: Theory and Computations

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Product

Resources

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Biohydrogen for a New Generation of H₂/O₂ Biofuel Cells: A Sustainable Energy Perspective

Biohydrogen for a New Generation of H₂/O₂ Biofuel Cells: A Sustainable Energy Perspective