Enhancement of direct electron transfer in graphene bioelectrodes containing novel cytochrome c variants with optimized heme orientation

Izzo, Miriam; Osella, Silvio; Jacquet, Margot; Kiliszek, Małgorzata; Harputlu, Ersan; Starkowska, Alicja; Łasica, Anna M.; Ünlü, Cumhur Gökhan; Uśpieński, Tomasz; Niewiadomski, Paweł; Bartosik, Dariusz; Trzaskowski, Bartosz; Ocakoğlu, Kasım; Kargul, Joanna

doi:10.1016/j.bioelechem.2021.107818

Cited by 8 publications

(3 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…SIMS Analysis. Previous studies in our group 77,78 revealed that monolayers formed by different types of molecular wires terminated with cobalt and nickel-NTA complexes are not detectable by conventional CV on FTO or FTO/SLG surfaces when performed in an aqueous electrolyte. In order to obtain additional evidence about the presence of the different divalent cations at the molecular interface and gain a deeper insight into the metalation efficiency and homogeneity, secondary ions mass spectrometry (SIMS) analysis was performed on the covalently modified electrodes to detect the cobalt and nickel atoms (Figure 4).…”

Section: ■ Experimental Sectionmentioning

confidence: 87%

Diazonium-Based Covalent Molecular Wiring of Single-Layer Graphene Leads to Enhanced Unidirectional Photocurrent Generation through the p-doping Effect

et al. 2022

Self Cite

View full text Add to dashboard Cite

Development of robust and cost-effective smart materials requires rational chemical nanoengineering to provide viable technological solutions for a wide range of applications. Recently, a powerful approach based on the electrografting of diazonium salts has attracted a great deal of attention due to its numerous technological advantages. Several studies on graphene-based materials reveal that the covalent attachment of aryl groups via the above approach could lead to additional beneficial properties of this versatile material. Here, we developed the covalently linked metalorganic wires on two transparent, cheap, and conductive materials: fluorine-doped tin oxide (FTO) and FTO/single-layer graphene (FTO/SLG). The wires are terminated with nitrilotriacetic acid metal complexes, which are universal molecular anchors to immobilize His6-tagged proteins, such as biophotocatalysts and other types of redox-active proteins of great interest in biotechnology, optoelectronics, and artificial photosynthesis. We show for the first time that the covalent grafting of a diazonium salt precursor on two different electron-rich surfaces leads to the formation of the molecular wires that promote p-doping of SLG concomitantly with a significantly enhanced unidirectional cathodic photocurrent up to 1 μA cm–2. Density functional theory modeling reveals that the exceptionally high photocurrent values are due to two distinct mechanisms of electron transfer originating from different orbitals/bands of the diazonium-derived wires depending on the nature of the chelating metal redox center. Importantly, the novel metalorganic interfaces reported here exhibit minimized back electron transfer, which is essential for the maximization of solar conversion efficiency.

show abstract

Section: ■ Experimental Sectionmentioning

confidence: 87%

Diazonium-Based Covalent Molecular Wiring of Single-Layer Graphene Leads to Enhanced Unidirectional Photocurrent Generation through the p-doping Effect

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…Instead, metal cations-driven ET has been achieved by designing multilayered architectures on the electrode, in which metal redox centers are conveniently configured to promote the wiring between the electrode surface and redox-active proteins. [37,38] Here, we investigated the ET capabilities of the small library of cobalt biohybrids synthesized in this work. Surprisingly, we observed that, while no signal could be detected for the rest of the samples (Figure S22, Supporting Information), Co@GOx-I and Co@GOx-I/A exhibited a measurable signal starting at + 0.2 V upon the addition of glucose (Figure 3B).…”

Section: Bioelectrochemistrymentioning

confidence: 99%

Engineered Metal‐Loaded Biohybrids to Promote the Attachment and Electron‐Shuttling between Enzymes and Carbon Electrodes

Rodriguez‐Abetxuko,

Romero‐Ben,

Ontoria

et al. 2024

Adv Funct Materials

View full text Add to dashboard Cite

The inorganic content and the catalytic performance pose metal‐loaded enzyme nanoflowers as promising candidates for developing bioelectrodes capable of functioning without the external addition of a redox mediator. However, these protein‐inorganic hybrids have yet to be successfully applied in combination with electrode materials. Herein, the synthesis procedure of these bionanomaterials is reproposed to precisely control the morphology, composition, and performance of this particular protein‐mineral hybrid, formed by glucose oxidase and cobalt phosphate. This approach aims to enhance the adherence and electron mobility between the enzyme and a carbon electrode. The strategy relies on dressing the protein in a tailored thin nanogel with multivalent chemical motifs. The functional groups of the polymer facilitate the fast protein sequence‐independent biomineralization. Furthermore, the engineered enzymes enable the fabrication of robust cobalt‐loaded enzyme inorganic hybrids with exceptional protein loads, exceeding 90% immobilization yields. Notably, these engineered biohybrids can be readily deposited onto flat electrode surfaces without requiring chemical pre‐treatment. The resulting bioelectrodes are robust and exhibit electrochemical responses even without the addition of a redox mediator, suggesting that cobalt complexes promote electron wiring between the active site of the enzyme and the electrode.

show abstract

“…The PSI immobilization occurred via the organic conductive interface based on the pyr-NTA SAM into which two distinct metal redox centers were incorporated (Ni or Co) as a rational strategy to improve DET (Scheme 1). A similar approach was used before for finetuning DET (in terms of kinetics and directionality) within graphene-based bioelectrodes incorporating cyt c 553 and PSI electroactive components [38,[42][43][44][45][46]. The innovative strategy for the generation of the recombinant His6-PsaD-PSI complex was based on importing the modified nuclear-encoded His6-PsaD protein into the chloro- The innovative strategy for the generation of the recombinant His 6 -PsaD-PSI complex was based on importing the modified nuclear-encoded His 6 -PsaD protein into the chloroplast by the insertion of the chloroplast signaling peptide upstream of the 5 region of the psaD sequence, then reconstituting the His 6 -PsaD-PSI complex in vivo, i.e., during the natural PSI turnover.…”

Section: Genetic Engineering Of the C Merolae His 6 -Tagged Psad-psi Biophotocatalystmentioning

confidence: 99%

Development of a Novel Nanoarchitecture of the Robust Photosystem I from a Volcanic Microalga Cyanidioschyzon merolae on Single Layer Graphene for Improved Photocurrent Generation

Izzo

Jacquet

Fujiwara

et al. 2021

IJMS

Self Cite

View full text Add to dashboard Cite

Here, we report the development of a novel photoactive biomolecular nanoarchitecture based on the genetically engineered extremophilic photosystem I (PSI) biophotocatalyst interfaced with a single layer graphene via pyrene-nitrilotriacetic acid self-assembled monolayer (SAM). For the oriented and stable immobilization of the PSI biophotocatalyst, an His6-tag was genetically engineered at the N-terminus of the stromal PsaD subunit of PSI, allowing for the preferential binding of this photoactive complex with its reducing side towards the graphene monolayer. This approach yielded a novel robust and ordered nanoarchitecture designed to generate an efficient direct electron transfer pathway between graphene, the metal redox center in the organic SAM and the photo-oxidized PSI biocatalyst. The nanosystem yielded an overall current output of 16.5 µA·cm−2 for the nickel- and 17.3 µA·cm−2 for the cobalt-based nanoassemblies, and was stable for at least 1 h of continuous standard illumination. The novel green nanosystem described in this work carries the high potential for future applications due to its robustness, highly ordered and simple architecture characterized by the high biophotocatalyst loading as well as simplicity of manufacturing.

show abstract

Enhancement of direct electron transfer in graphene bioelectrodes containing novel cytochrome c variants with optimized heme orientation

Cited by 8 publications

References 43 publications

Diazonium-Based Covalent Molecular Wiring of Single-Layer Graphene Leads to Enhanced Unidirectional Photocurrent Generation through the p-doping Effect

Diazonium-Based Covalent Molecular Wiring of Single-Layer Graphene Leads to Enhanced Unidirectional Photocurrent Generation through the p-doping Effect

Engineered Metal‐Loaded Biohybrids to Promote the Attachment and Electron‐Shuttling between Enzymes and Carbon Electrodes

Development of a Novel Nanoarchitecture of the Robust Photosystem I from a Volcanic Microalga Cyanidioschyzon merolae on Single Layer Graphene for Improved Photocurrent Generation

Contact Info

Product

Resources

About