Dihemic c4-type cytochrome acting as a surrogate electron conduit: Artificially interconnecting a photosystem I supercomplex with electrodes

Feifel, Sven C.; Stieger, Kai Ralf; Hejazi, Mahdi; Wang, Xie; Ilbert, Marianne; Zouni, Athina; Lojou, Élisabeth; Lisdat, Fred

doi:10.1016/j.elecom.2018.05.006

Cited by 6 publications

(9 citation statements)

References 45 publications

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“…30,31 Mediated electron transfer was achieved via redox polymers, 12,16 small redox molecules, 32,33 and different cytochromes. 9,34,35 In recent years, significant efforts have been devoted to increasing the efficiency of photobioelectrodes based on PSI. 5,36 These electrodes can be constructed on different flat 2D electrodes.…”

Section: Introductionmentioning

confidence: 99%

Scalable Three-Dimensional Photobioelectrodes Made of Reduced Graphene Oxide Combined with Photosystem I

Morlock

Subramanian

Zouni

et al. 2021

ACS Appl. Mater. Interfaces

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Photobioelectrodes represent one of the examples where artificial materials are combined with biological entities to undertake semi-artificial photosynthesis. Here, an approach is described that uses reduced graphene oxide (rGO) as an electrode material. This classical 2D material is used to construct a three-dimensional structure by a template-based approach combined with a simple spin-coating process during preparation. Inspired by this novel material and photosystem I (PSI), a biophotovoltaic electrode is being designed and investigated. Both direct electron transfer to PSI and mediated electron transfer via cytochrome c from horse heart as redox protein can be confirmed. Electrode preparation and protein immobilization have been optimized. The performance can be upscaled by adjusting the thickness of the 3D electrode using different numbers of spin-coating steps during preparation. Thus, photocurrents up to ∼14 μA/cm2 are measured for 12 spin-coated layers of rGO corresponding to a turnover frequency of 30 e– PSI–1 s–1 and external quantum efficiency (EQE) of 0.07% at a thickness of about 15 μm. Operational stability has been analyzed for several days. Particularly, the performance at low illumination intensities is very promising (1.39 μA/cm2 at 0.1 mW/cm2 and −0.15 V vs Ag/AgCl; EQE 6.8%).

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Section: Introductionmentioning

confidence: 99%

Scalable Three-Dimensional Photobioelectrodes Made of Reduced Graphene Oxide Combined with Photosystem I

Morlock

Subramanian

Zouni

et al. 2021

ACS Appl. Mater. Interfaces

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“…It rather tends to assemble into isotropic, heterogeneous monolayers and multilayers, which is detrimental to BPV performance . Recent studies have investigated anisotropic monolayers that use various linker strategies to modify the surface of the electrode, ,− coupling to plasmonically active metallic nanowires, short peptides developed by phage display, or conductive interlayers ,− to bias the orientation of PSI. Even perfectly oriented PSI, however, must also be free of traps and electronically coupled to the electrode or else the electron/hole pairs will recombine before they can be extracted. − Thus, an ideal strategy for controlling the orientation of PSI must also modify the electrode–protein interface for optimal alignment between the energy levels of P 700 or F A /F B sites and the work function of the electrode.…”

Section: Introductionmentioning

confidence: 99%

Fullerenes Enhance Self-Assembly and Electron Injection of Photosystem I in Biophotovoltaic Devices

et al. 2021

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This paper describes the fabrication of microfluidic devices with a focus on controlling the orientation of photosystem I (PSI) complexes, which directly affects the performance of biophotovoltaic devices by maximizing the efficiency of the extraction of electron/hole pairs from the complexes. The surface chemistry of the electrode on which the complexes assemble plays a critical role in their orientation. We compared the degree of orientation on self-assembled monolayers of phenyl-C 61 -butyric acid and a custom peptide on nanostructured gold electrodes. Biophotovoltaic devices fabricated with the C 61 fulleroid exhibit significantly improved performance and reproducibility compared to those utilizing the peptide, yielding a 1.6-fold increase in efficiency. In addition, the C 61 -based devices were more stable under continuous illumination. Our findings show that fulleroids, which are well-known acceptor materials in organic photovoltaic devices, facilitate the extraction of electrons from PSI complexes without sacrificing control over the orientation of the complexes, highlighting this combination of traditional organic semiconductors with biomolecules as a viable approach to coopting natural photosynthetic systems for use in solar cells.

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“…[6][7][8] To enable DET, monolayers of PSI protein complexes have been coupled with various linking molecules and proteins, which help minimize the electrodeprotein separation distance and also provide an energetically favorable pathway for electron transfer. [7,[14][15][16][17][18][19][20][21][22][23][24] Most notably, the cytochrome complex (cyt c) has been used to attach PSI onto a variety of electrode materials. [7,[14][15][16][17][18][19][20][21][22][23][24] Alternatively, significant improvements in mediated photocurrent generation have been achieved by drop-casting thick multilayer films of PSI onto silicon, gold, and graphene electrodes.…”

Section: Introductionmentioning

confidence: 99%

“…[7,[14][15][16][17][18][19][20][21][22][23][24] Most notably, the cytochrome complex (cyt c) has been used to attach PSI onto a variety of electrode materials. [7,[14][15][16][17][18][19][20][21][22][23][24] Alternatively, significant improvements in mediated photocurrent generation have been achieved by drop-casting thick multilayer films of PSI onto silicon, gold, and graphene electrodes. [5,[25][26][27] Applying thicker films of PSI improves overall light absorption by providing a higher areal protein loading and increasing the total amount of converted mediator.…”

Section: Introductionmentioning

confidence: 99%

“…Many strategies have been explored with aims of maximizing electron transfer between PSI and its host electrode . To enable DET, monolayers of PSI protein complexes have been coupled with various linking molecules and proteins, which help minimize the electrode‐protein separation distance and also provide an energetically favorable pathway for electron transfer . Most notably, the cytochrome complex (cyt c) has been used to attach PSI onto a variety of electrode materials …”

Section: Introductionmentioning

confidence: 99%

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Photosystem I Multilayers within Porous Indium Tin Oxide Cathodes Enhance Mediated Electron Transfer

et al. 2019

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Understanding and improving charge transfer pathways between extracted Photosystem I (PSI) protein complexes and electrodes is necessary for the development of low‐cost PSI‐based devices for energy conversion. We incorporated PSI multilayers within porous indium tin oxide (ITO) electrodes and observed a greater mediated photocurrent in comparison to multilayers on planar ITO. First, the mediated electron transfer (MET) pathway in the presence of 2,6‐dichlorophenolindophenol (DCPIP) and ascorbate (AscH) was studied via photochronoamperometry on planar ITO. ITO nanoparticles were then used to fabricate two porous electrode morphologies; mesoporous (20–100 nm pores) and macroporous (5 μm pores). PSI multilayers within macroporous ITO cathodes produced 42±5 μA cm−2 of photocurrent, three times the photocurrent produced by mesoporous ITO. Additionally, macroporous cathodes are able to utilize twice as much active surface area, when compared to mesoporous cathodes. Our findings show that MET within PSI multilayers is greater in 5 μm macropores than mesoporous ITO due to both an increase in electrode surface area and the location of PSI complexes within the pores. Improving MET in PSI‐based bioelectrodes has applications including improving the total charge transfer achieved in PSI‐based photoelectrochemical cells or even incorporation in bio‐photocatalytic cells.

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Dihemic c4-type cytochrome acting as a surrogate electron conduit: Artificially interconnecting a photosystem I supercomplex with electrodes

Cited by 6 publications

References 45 publications

Scalable Three-Dimensional Photobioelectrodes Made of Reduced Graphene Oxide Combined with Photosystem I

Scalable Three-Dimensional Photobioelectrodes Made of Reduced Graphene Oxide Combined with Photosystem I

Fullerenes Enhance Self-Assembly and Electron Injection of Photosystem I in Biophotovoltaic Devices

Photosystem I Multilayers within Porous Indium Tin Oxide Cathodes Enhance Mediated Electron Transfer

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