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Title: Pyrene hydrogel for promoting direct bioelectrochemistry: ATP-independent electroenzymatic reduction of N2

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C8SC01638K· OSTI ID:1438937

Enzymatic bioelectrocatalysis often requires an artificial redox mediator to observe significant electron transfer rates. The use of such mediators can add a substantial overpotential and obfuscate the protein's native kinetics, which limits the voltage of a biofuel cell and alters the analytical performance of biosensors. Herein, we describe a material for facilitating direct electrochemical communication with redox proteins based on a novel pyrene-modified linear poly(ethyleneimine). This method was applied for promoting direct bioelectrocatalytic reduction of O2 by laccase and, by immobilizing the catalytic subunit of nitrogenase (MoFe protein), to demonstrate the ATP-independent direct electroenzymatic reduction of N2 to NH3.

Research Organization:
Fulcrum BioScience, Inc., Salt Lake City, UT (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Manufacturing Office
Grant/Contract Number:
SC0017845
OSTI ID:
1438937
Alternate ID(s):
OSTI ID: 1466824
Journal Information:
Chemical Science, Journal Name: Chemical Science Vol. 9 Journal Issue: 23; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United Kingdom
Language:
English
Citation Metrics:
Cited by: 42 works
Citation information provided by
Web of Science

References (40)

Direct electron transfer of cytochrome c and its biosensor based on gold nanoparticles/room temperature ionic liquid/carbon nanotubes composite film journal January 2008
Electron-Transfer Communication in Glutathione Reductase Assemblies: Electrocatalytic, Photocatalytic, and Catalytic Systems for the Reduction of Oxidized Glutathione journal February 1994
Anthracene-modified pyrenes immobilized on carbon nanotubes for direct electroreduction of O2 by laccase journal September 2013
Electron transfers in chemistry and biology journal August 1985
Nature of biological electron transfer journal February 1992
Fe Protein-Independent Substrate Reduction by Nitrogenase MoFe Protein Variants journal April 2015
Cross-linked redox gels containing glucose oxidase for amperometric biosensor applications journal February 1990
Electrical communication between redox centers of glucose oxidase and electrodes via electrostatically and covalently bound redox polymers journal March 1989
Direct, Electrocatalytic Oxygen Reduction by Laccase on Anthracene-2-methanethiol-Modified Gold journal July 2010
Kinetics of Redox Polymer-Mediated Enzyme Electrodes journal July 2008
Bioelectrocatalysis of Oxygen Reduction Reaction by Laccase on Gold Electrodes journal July 2004
Conducting Polymer Enzyme Alloys: Electromaterials Exhibiting Direct Electron Transfer journal June 2010
Enhanced direct electron transfer between laccase and hierarchical carbon microfibers/carbon nanotubes composite electrodes. Comparison of three enzyme immobilization methods journal November 2012
Photoswitchable Electrical Communication of Glucose Oxidase and Glutathione Reductase with Electrode Surfaces through Photoisomerizable Redox Mediators journal August 1995
Efficient direct oxygen reduction by laccases attached and oriented on pyrene-functionalized polypyrrole/carbon nanotube electrodes journal January 2013
Nitrogenase: a general hydrogenator of small molecules journal January 2013
Complex electrochemistry of flavodoxin at carbon-based electrodes: results from a combination of direct electron transfer, flavin-mediated electron transfer and comproportionation journal March 1996
Covalent electropolymerization of glucose oxidase in polypyrrole. Evaluation of methods of pyrrole attachment to glucose oxidase on the performance of electropolymerized glucose sensors journal August 1993
Multicopper Oxidases and Oxygenases journal January 1996
Enzyme catalysed biofuel cells journal January 2008
Direct Electrochemistry of Redox Enzymes as a Tool for Mechanistic Studies journal July 2008
A Crosslinked Microperoxidase-11 and Nitrate Reductase Monolayer on a Gold Electrode: An Integrated Electrically Contacted Electrode for the Bioelectrocatalyzed Reduction of NO3− journal June 1998
High-Sensitivity Amperometric Biosensors Based on Ferrocene-Modified Linear Poly(ethylenimine) journal July 2009
Impact of substrate diffusion and enzyme distribution in 3D-porous electrodes: a combined electrochemical and modelling study of a thermostable H 2 /O 2 enzymatic fuel cell journal January 2017
Improving the microenvironment for enzyme immobilization at electrodes by hydrophobically modifying chitosan and Nafion® polymers journal March 2008
STRUCTURE: Nitrogenase Reveals Its Inner Secrets journal September 2002
Anthracene-Modified Multi-Walled Carbon Nanotubes as Direct Electron Transfer Scaffolds for Enzymatic Oxygen Reduction journal October 2011
Mediated electron transfer in gluthathione reductase organized in self-assembled monolayers on gold electrodes journal December 1992
Microperoxidase-11-mediated reduction of hemoproteins: electrocatalyzed reduction of cytochrome c, myoglobin and hemoglobin and electrocatalytic reduction of nitrate in the presence of cytochrome-dependent nitrate reductase journal June 1997
Electrochemical Studies of Intramolecular Electron Transfer in Laccase fromTrametes versicolor journal November 2007
Chemical/Biochemical Preparation of New Polymeric Bionanocomposites with Enzyme Labels Immobilized at High Load and Activity for High-Performance Electrochemical Immunoassay journal January 2010
Mechanism of Molybdenum Nitrogenase journal January 1996
Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid journal April 2016
Bioelectrochemical Haber-Bosch Process: An Ammonia-Producing H 2 /N 2 Fuel Cell journal February 2017
Self-assembly of gold nanoparticles to carbon nanotubes using a thiol-terminated pyrene as interlinker journal January 2003
Uncoupling Nitrogenase: Catalytic Reduction of Hydrazine to Ammonia by a MoFe Protein in the Absence of Fe Protein-ATP journal September 2010
ATP-Uncoupled, Six-Electron Photoreduction of Hydrogen Cyanide to Methane by the Molybdenum–Iron Protein journal May 2012
Amperometric biosensor based on direct communication between glucose oxidase and a conducting polymer inside the pores of a filtration membrane journal January 1991
Nitrogenase bioelectrocatalysis: heterogeneous ammonia and hydrogen production by MoFe protein journal January 2016
Bioelectrochemical Haber-Bosch Process: An Ammonia-Producing H 2 /N 2 Fuel Cell journal February 2017

Cited By (8)

Electrochemical Characterization of Isolated Nitrogenase Cofactors from Azotobacter vinelandii journal October 2019
Pyrene‐Based Noncovalent Immobilization of Nitrogenase on Carbon Surfaces journal January 2020
Strategies for Bioelectrochemical CO 2 Reduction journal September 2019
Templating Porphyrin Anisotropy via Magnetically Aligned Carbon Nanotubes journal February 2019
Intracellular dark-field imaging of ATP and photothermal therapy using a colorimetric assay based on gold nanoparticle aggregation via tetrazine/trans-cyclooctene cycloaddition journal July 2019
Interfacing nature’s catalytic machinery with synthetic materials for semi-artificial photosynthesis journal October 2018
The progress and outlook of bioelectrocatalysis for the production of chemicals, fuels and materials journal January 2020
Direct bioelectrocatalysis by redox enzymes immobilized in electrostatically condensed oppositely charged polyelectrolyte electrode coatings journal January 2020

Figures / Tables (6)


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