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Abstract Mixed electronic-ionic conductors are crucial for various technologies, including harvesting power from humidity in a durable, self-sustainable, manner unrestricted by location or environment1,2. Biological proteins have been proposed as mixed conductors for 50 years3,4. Recently,Geobacter sulfurreducenspili filaments have been claimed to act as nanowires to generate power5,6. Here, we show that the power is generated byG. sulfurreducens-produced cytochrome OmcZ nanowires that show 20,000-fold higher electron conductivity than pili7. Remarkably, nanowires show ultrahigh electron and proton mobility (>0.25 cm2/Vs), owing to directional charge migration through seamlessly-stacked hemes and a charged, hydrogen-bonding surface, respectively. AC impedance spectroscopy and DC conductivity measurements using four-probe van der Pauw and back-gated field-effect-transistor devices reveal that humidity increases carrier mobility by 30,000-fold. Cooling halves the activation energy, thereby accelerating charge transport. Electrochemical measurements identify the voltage and mobilities required to switch pure electronic conduction to mixed conduction for power generation. The high aspect ratio (1:1000) and hydrophilic nanowire surface captures moisture efficiently to reduce oxygen reversibly, generating large potentials (>0.5 V) necessary to sustain high power. Our studies establish a new class of biologically-synthesized, low-cost and high-performance mixed-conductors and identify key design principles for improving power output using highly-tunable electronic and protein structures.
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Protein nanowires with tunable functionality and programmable self-assembly using sequence-controlled synthesis
Abstract Advances in synthetic biology permit the genetic encoding of synthetic chemistries at monomeric precision, enabling the synthesis of programmable proteins with tunable properties. Bacterial pili serve as an attractive biomaterial for the development of engineered protein materials due to their ability to self-assemble into mechanically robust filaments. However, most biomaterials lack electronic functionality and atomic structures of putative conductive proteins are not known. Here, we engineer high electronic conductivity in pili produced by a genomically-recodedE. colistrain. Incorporation of tryptophan into pili increased conductivity of individual filaments >80-fold. Computationally-guided ordering of the pili into nanostructures increased conductivity 5-fold compared to unordered pili networks. Site-specific conjugation of pili with gold nanoparticles, facilitated by incorporating the nonstandard amino acid propargyloxy-phenylalanine, increased filament conductivity ~170-fold. This work demonstrates the sequence-defined production of highly-conductive protein nanowires and hybrid organic-inorganic biomaterials with genetically-programmable electronic functionalities not accessible in nature or through chemical-based synthesis.
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- Award ID(s):
- 1749662
- PAR ID:
- 10362705
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 13
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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