title: Iron-sulfur-based single molecular wires for enhancing charge transport in enzyme-based bioelectronic systems.
abstract: When redox enzymes are wired to electrodes outside a living cell (ex vivo), their ability to produce a sufficiently powerful electrical current diminishes significantly due to the thermodynamic and kinetic limitations associated with the wiring systems. Therefore, we are yet to harness the full potential of redox enzymes for the development of self-powering bioelectronics devices (such as sensors and fuel cells). Interestingly, nature uses iron-sulfur complexes ([Fe-S]), to circumvent these issues in vivo. Yet, we have not been able to utilize [Fe-S]-based chains ex vivo, primarily due to their instability in aqueous media. Here, a simple technique to attach iron (II) sulfide (FeS) to a gold surface in ethanol media and then complete the attachment of the enzyme in aqueous media is reported. Cyclic voltammetry and spectroscopy techniques confirmed the concatenation of FeS and glycerol-dehydrogenase/nicotinamide-adenine-dinucleotide (GlDH-NAD(+)) apoenzyme-coenzyme molecular wiring system on the base gold electrode. The resultant FeS-based enzyme electrode reached an open circuit voltage closer to its standard potential under a wide range of glycerol concentrations (0.001-1M). When probed under constant potential conditions, the FeS-based electrode was able to amplify current by over 10 fold as compared to electrodes fabricated with the conventional pyrroloquinoline quinone-based composite molecular wiring system. These improvements in current/voltage responses open up a wide range of possibilities for fabricating self-powering, bio-electronic devices.
authors.affiliation: Department of Biological and Agricultural Engineering, Texas A&M University, 303C Scoates Hall, College Station, TX 77843, USA.
authors.forename: Aishwarya
authors.initials: A
authors.lastname: Mahadevan
authors.affiliation: Department of Biological and Agricultural Engineering, Texas A&M University, 303C Scoates Hall, College Station, TX 77843, USA.
authors.forename: Teshan
authors.initials: T
authors.lastname: Fernando
authors.affiliation: Department of Biological and Agricultural Engineering, Texas A&M University, 303C Scoates Hall, College Station, TX 77843, USA. Electronic address: sfernando@tamu.edu.
authors.forename: Sandun
authors.initials: S
authors.lastname: Fernando
mesh_terms: D001674:Bioelectric Energy Sources; D015374:Biosensing Techniques / Q000295:instrumentation; D006046:Gold / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D009243:NAD / Q000737:chemistry; D036103:Nanotechnology; D010084:Oxidation-Reduction; D013401:Sugar Alcohol Dehydrogenases / Q000737:chemistry; D013440:Sulfides / Q000737:chemistry*
chemical_list: D013440:Sulfides; D009243:NAD; D006046:Gold; D007501:Iron; D013401:Sugar Alcohol Dehydrogenases; C020672:glycerol dehydrogenase
keywords: Bioanode; Bioelectronics; Enzyme immobilization; Molecular wire; Redox enzymes; Self-assembled monolayers