Advanced unidirectional photocurrent generation via cytochrome c as reaction partner for directed assembly of photosystem I

Stieger, Kai Ralf; Feifel, Sven C.; Lokstein, Heiko; Lisdat, Fred

doi:10.1039/c4cp00935e

Cited by 59 publications

(84 citation statements)

References 44 publications

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“…It has been shown that the isolated RC can bind (up to) 24 molecules of cyt c , 43 and the PSI RC has been shown to promote the coadsorption of electroactive cyt c to form multilayers on electrode surfaces. 21 It is likely that we have a similar semi-multilayer architecture on our electrodes.…”

Section: Resultsmentioning

confidence: 99%

“…42 This is also similar to the reported Γ cyt c on a mSAM of the same composition used in this work. 21 This ideal loading was multiplied by a reported 21-fold surface area increase for a rough silver electrode versus a flat silver electrode to obtain 320 pmol cm –2 . 36 36 …”

Section: Resultsmentioning

confidence: 99%

“…Furthermore, both works suggest that the natural binding affinity between cyt c and the RC donor side allows cyt c to effectively act as a docking site for the oriented attachment of the RC onto immobilized molecules of cyt c . 1,21 …”

Section: Introductionmentioning

confidence: 99%

“…27,28 This allows the substitution of cyt c between species as divergent as photosynthetic bacteria and mammals with negligible effects on enzyme turnover capacity. 21,27,29 In purple photosynthetic bacteria, this protein (termed cyt c 2 ) is typically located in the periplasmic space or loosely attached to the periplasmic side of the membrane 28,30 and shuttles electrons from the ubiquinol-cyt c oxidoreductase (cyt bc 1 complex) to the RC. 31 There, it reduces the photo-oxidized primary electron donor bacteriochlorophyll pair (P + ) produced by photochemical charge separation within the RC.…”

Section: Introductionmentioning

confidence: 99%

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Cytochrome c Provides an Electron-Funneling Antenna for Efficient Photocurrent Generation in a Reaction Center Biophotocathode

Friebe¹,

Millo²,

Swainsbury

et al. 2017

ACS Appl. Mater. Interfaces

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The high quantum efficiency of photosynthetic reaction centers (RCs) makes them attractive for bioelectronic and biophotovoltaic applications. However, much of the native RC efficiency is lost in communication between surface-bound RCs and electrode materials. The state-of-the-art biophotoelectrodes utilizing cytochrome c (cyt c) as a biological wiring agent have at best approached 32% retained RC quantum efficiency. However, bottlenecks in cyt c-mediated electron transfer have not yet been fully elucidated. In this work, protein film voltammetry in conjunction with photoelectrochemistry is used to show that cyt c acts as an electron-funneling antennae that shuttle electrons from a functionalized rough silver electrode to surface-immobilized RCs. The arrangement of the two proteins on the electrode surface is characterized, revealing that RCs attached directly to the electrode via hydrophobic interactions and that a film of six cyt c per RC electrostatically bound to the electrode. We show that the additional electrical connectivity within a film of cyt c improves the high turnover demands of surface-bound RCs. This results in larger photocurrent onset potentials, positively shifted half-wave reduction potentials, and higher photocurrent densities reaching 100 μA cm–2. These findings are fundamental for the optimization of bioelectronics that utilize the ubiquitous cyt c redox proteins as biological wires to exploit electrode-bound enzymes.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Cytochrome c Provides an Electron-Funneling Antenna for Efficient Photocurrent Generation in a Reaction Center Biophotocathode

Friebe¹,

Millo²,

Swainsbury

et al. 2017

ACS Appl. Mater. Interfaces

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“…It attracts growing interest for designing biophotoelectrochemical devices [7][8][9][10][11][12][13] due to its remarkable charge separation functionality and close to perfect quantum yield of almost unity. 14 The combination of PS1 and Os-complex modified redox polymers has been exploited for photocurrent generation.…”

mentioning

confidence: 99%

The Role of Hydrophobicity of Os-Complex-Modified Polymers for Photosystem 1 Based Photocathodes

Zhao

Sliozberg

Rögner

et al. 2014

J. Electrochem. Soc.

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The integration of photosystem 1 in redox hydrogels based on Os-complexes modified redox polymers on electrodes yields efficient photocathodes. The generation of high photocurrent relies on high loading in PS1 and fast electron transfer rates from the electrode to PS1. The interaction between the redox polymer and PS1 influences both the loading in protein and the electron transfer rates. Since PS1 exhibits extended hydrophobic regions, polymers with similar properties may favor attractive interactions. Here we investigate three approaches to confer hydrophobicity to the redox polymer. We demonstrate that the pyridine functionality enables to switch, via basic pH values, the polymer properties from hydrophilic to hydrophobic. The transition triggers a hydrogel collapse which allows for efficient entrapment of PS1. In addition the hydrophobic-hydrophilic balance was tuned by the addition of hydrophobic group in i) the polymer backbone and ii) as substituents at the Os-complex. The increased hydrophobicity of the backbone results in higher photocurrents from PS1 integrated in the corresponding hydrogel. On the other hand, further increasing hydrophobicity of the redox relay decreases the photocurrent due to either lower mobility of the Os-complexes or poor interaction with the hydrophilic site where the redox center of PS1 is located. This paper is part of the JES Focus Issue in Recognition of Adam Heller and His Enduring Contributions to Electrochemistry.Redox polymers play an important role in the design of enzyme modified electrodes. They serve as matrices for entrapping enzymes in their three-dimensional network, and they simultaneously transport electrons between the electrode and the enzyme's redox center. [1][2][3][4] Based on the nature of the polymer-bound redox centers, redox polymers can be designed exhibiting a wide variation in their redox potentials. This allows the redox polymers to be adjusted to the potential required for an envisaged application.5 Moreover, the properties of the polymer backbones can be tuned by changing the composition of the used monomers. 6 The overall properties of the redox hydrogel determine the performance of the corresponding enzyme modified electrode such as electron-transfer kinetics and onset potential for the biocatalytic current. Hence, redox potential as well as backbone properties of the polymer should be chosen in accordance with the specific requirement of the polymer-entrapped biocatalytic element as well as with the envisaged application.Photosystem I (PSI), a protein complex that drives photosynthesis in higher plants and cyanobacteria, represents an efficient converter for the energy of visible light into chemical energy. It attracts growing interest for designing biophotoelectrochemical devices 7-13 due to its remarkable charge separation functionality and close to perfect quantum yield of almost unity.14 The combination of PS1 and Os-complex modified redox polymers has been exploited for photocurrent generation. The highest electron transfer rate between P...

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Interprotein Electron Transfer between FeS‐Protein Nanowires and Oxygen‐Tolerant NiFe Hydrogenase

et al. 2017

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Self-assembled redox protein nanowires have been exploited as efficient electron shuttles for an oxygen-tolerant hydrogenase.Anintra/inter-protein electron transfer chain has been achieved between the iron-sulfur centers of rubredoxin and the FeSc luster of [NiFe] hydrogenases.[ NiFe] Hydrogenases entrapped in the intricated matrix of metalloprotein nanowires achieve as table,m ediated bioelectrocatalytic oxidation of H 2 at low-overpotential.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Advanced unidirectional photocurrent generation via cytochrome c as reaction partner for directed assembly of photosystem I

Cited by 59 publications

References 44 publications

Cytochrome c Provides an Electron-Funneling Antenna for Efficient Photocurrent Generation in a Reaction Center Biophotocathode

Cytochrome c Provides an Electron-Funneling Antenna for Efficient Photocurrent Generation in a Reaction Center Biophotocathode

The Role of Hydrophobicity of Os-Complex-Modified Polymers for Photosystem 1 Based Photocathodes

Interprotein Electron Transfer between FeS‐Protein Nanowires and Oxygen‐Tolerant NiFe Hydrogenase

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