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Biomolecular and Biohybrid Systems for Solar Energy Conversion

A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Physical Chemistry and Chemical Physics".

Deadline for manuscript submissions: closed (30 September 2022) | Viewed by 12293

Special Issue Editors


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Guest Editor
Centre of New Technologies, University of Warsaw, Warsaw, Poland
Interests: solar-to-fuel nanodevices; biohybrid photoelectrodes; photosynthesis; photosystem I; photosystem II; cytochrome c; photoelectrochemical cells; artificial photosynthesis

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Guest Editor
Centre of New Technologies, University of Warsaw, Warsaw, Poland

Special Issue Information

Dear Colleagues,

It has been estimated that the energy captured in one hour of sunlight that reaches our planet is equivalent to the annual energy production by the human population globally. Efficiently capturing this practically inexhaustible solar energy and converting it into high energy density solar fuel is an attractive “green” alternative to running our present-day economies on rapidly depleting fossil fuels, especially in the context of the ever-growing global energy demand. Biohybrid technologies form a relatively young and dynamic field of green nanotechnology that utilizes a combination of designed synthetic and biological components. Such systems can take advantage of biological solar capture from photosynthetic organisms, such as cyanobacteria and algae; their photosynthetically active biological membranes; or the components of the photosynthetic apparatus to harness solar energy and convert it into electricity and solar fuels. Alternatively, solar energy is harvested by artificial systems, and the resulting reducing equivalents are transferred, either directly or via a suitable energy vector/mediator (e.g., H2) to a suitable organism or semi-synthetic module responsible for the synthesis of the desired chemical product. In both cases, the main advantage stems from the capacity of biology to synthesize complex products with efficiencies so far unachievable in man-made systems. This Special Issue on “Biomolecular and Biohybrid Systems for Solar Energy Conversion” will provide an up-to-date compendium on the recent advances in direct conversion of sunlight into chemicals (fuel and high-value products) using rational approaches aimed at obtaining the highest product yields and conversion efficiencies. Contributions are invited (original research papers and reviews) on the application of photosynthetic microorganisms, components of the photosynthetic apparatus, and heterotrophic microorganisms interfacing with various synthetic materials (semiconductive and conductive electrodes, graphene, molecular catalysts, bio-organic interfaces, photosynthesizers, plasmonic nanostructures, etc.) for enhanced conversion of solar light into chemicals using water, carbon dioxide, or nitrogen as substrates. Theoretical studies on developing rational approaches for minimizing wasteful back reactions and securing optimized solar-driven direct electron transfer are also welcome.

Prof. Dr. Joanna M. Kargul
Dr. Margot Jacquet
Guest Editors

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Keywords

  • direct solar conversion
  • solar-to-fuel device
  • solar-to-chemical conversion
  • biomolecular solar conversion
  • biohybrid solar systems
  • artificial photosynthesis
  • plasmonics
  • biophotoelectrode
  • photosystem I
  • photosystem II
  • light-harvesting complex
  • reaction center
  • photosensitizer
  • dye-sensitized solar cell
  • graphene

Published Papers (6 papers)

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Editorial

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3 pages, 177 KiB  
Editorial
Biomolecular and Biohybrid Systems for Solar Energy Conversion
by Joanna Kargul and Margot Jacquet
Int. J. Mol. Sci. 2023, 24(9), 7794; https://doi.org/10.3390/ijms24097794 - 25 Apr 2023
Viewed by 983
Abstract
The depletion of fossil fuels and increased amount of atmospheric/environmental pollution associated with the excessive use of fossil fuels to power our economies have intensified the efforts of academia and industry worldwide to seek sustainable technological solutions to meet the global energy demand [...] Read more.
The depletion of fossil fuels and increased amount of atmospheric/environmental pollution associated with the excessive use of fossil fuels to power our economies have intensified the efforts of academia and industry worldwide to seek sustainable technological solutions to meet the global energy demand [...] Full article
(This article belongs to the Special Issue Biomolecular and Biohybrid Systems for Solar Energy Conversion)

Research

Jump to: Editorial

19 pages, 3174 KiB  
Article
Electron Transfer in a Bio-Photoelectrode Based on Photosystem I Multilayer Immobilized on the Conducting Glass
by Sebastian Szewczyk, Alice Goyal, Mateusz Abram, Gotard Burdziński, Joanna Kargul and Krzysztof Gibasiewicz
Int. J. Mol. Sci. 2022, 23(9), 4774; https://0-doi-org.brum.beds.ac.uk/10.3390/ijms23094774 - 26 Apr 2022
Cited by 5 | Viewed by 1754
Abstract
A film of ~40 layers of partially oriented photosystem I (PSI) complexes isolated from the red alga Cyanidioschyzon merolae formed on the conducting glass through electrodeposition was investigated by time-resolved absorption spectroscopy and chronoamperometry. The experiments were performed at a range of electric [...] Read more.
A film of ~40 layers of partially oriented photosystem I (PSI) complexes isolated from the red alga Cyanidioschyzon merolae formed on the conducting glass through electrodeposition was investigated by time-resolved absorption spectroscopy and chronoamperometry. The experiments were performed at a range of electric potentials applied to the film and at different compositions of electrolyte solution being in contact with the film. The amount of immobilized proteins supporting light-induced charge separation (active PSI) ranged from ~10%, in the absence of any reducing agents (redox compounds or low potential), to ~20% when ascorbate and 2,6-dichlorophenolindophenol were added, and to ~35% when the high negative potential was additionally applied. The origin of the large fraction of permanently inactive PSI (65–90%) was unclear. Both reducing agents increased the subpopulation of active PSI complexes, with the neutral P700 primary electron donor, by reducing significant fractions of the photo-oxidized P700 species. The efficiencies of light-induced charge separation in the PSI film (10–35%) did not translate into an equally effective generation of photocurrent, whose internal quantum efficiency reached the maximal value of 0.47% at the lowest potentials. This mismatch indicates that the vast majority of the charge-separated states in multilayered PSI complexes underwent charge recombination. Full article
(This article belongs to the Special Issue Biomolecular and Biohybrid Systems for Solar Energy Conversion)
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19 pages, 25229 KiB  
Article
PEDOT-Carbon Nanotube Counter Electrodes and Bipyridine Cobalt (II/III) Mediators as Universally Compatible Components in Bio-Sensitized Solar Cells Using Photosystem I and Bacteriorhodopsin
by Alexandra H. Teodor, Stephanie Monge, Dariana Aguilar, Alexandra Tames, Roger Nunez, Elaine Gonzalez, Juan J. Montero Rodríguez, Jesse J. Bergkamp, Ricardo Starbird, Venkatesan Renugopalakrishnan, Barry D. Bruce and Claudia Villarreal
Int. J. Mol. Sci. 2022, 23(7), 3865; https://0-doi-org.brum.beds.ac.uk/10.3390/ijms23073865 - 31 Mar 2022
Cited by 6 | Viewed by 2330
Abstract
In nature, solar energy is captured by different types of light harvesting protein–pigment complexes. Two of these photoactivatable proteins are bacteriorhodopsin (bR), which utilizes a retinal moiety to function as a proton pump, and photosystem I (PSI), which uses a chlorophyll antenna to [...] Read more.
In nature, solar energy is captured by different types of light harvesting protein–pigment complexes. Two of these photoactivatable proteins are bacteriorhodopsin (bR), which utilizes a retinal moiety to function as a proton pump, and photosystem I (PSI), which uses a chlorophyll antenna to catalyze unidirectional electron transfer. Both PSI and bR are well characterized biochemically and have been integrated into solar photovoltaic (PV) devices built from sustainable materials. Both PSI and bR are some of the best performing photosensitizers in the bio-sensitized PV field, yet relatively little attention has been devoted to the development of more sustainable, biocompatible alternative counter electrodes and electrolytes for bio-sensitized solar cells. Careful selection of the electrolyte and counter electrode components is critical to designing bio-sensitized solar cells with more sustainable materials and improved device performance. This work explores the use of poly (3,4-ethylenedioxythiophene) (PEDOT) modified with multi-walled carbon nanotubes (PEDOT/CNT) as counter electrodes and aqueous-soluble bipyridine cobaltII/III complexes as direct redox mediators for both PSI and bR devices. We report a unique counter electrode and redox mediator system that can perform remarkably well for both bio-photosensitizers that have independently evolved over millions of years. The compatibility of disparate proteins with common mediators and counter electrodes may further the improvement of bio-sensitized PV design in a way that is more universally biocompatible for device outputs and longevity. Full article
(This article belongs to the Special Issue Biomolecular and Biohybrid Systems for Solar Energy Conversion)
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14 pages, 2351 KiB  
Article
Improving Photostability of Photosystem I-Based Nanodevice by Plasmonic Interactions with Planar Silver Nanostructures
by Marcin Szalkowski, Dorota Kowalska, Julian David Janna Olmos, Joanna Kargul and Sebastian Maćkowski
Int. J. Mol. Sci. 2022, 23(6), 2976; https://0-doi-org.brum.beds.ac.uk/10.3390/ijms23062976 - 10 Mar 2022
Cited by 1 | Viewed by 1687
Abstract
One of the crucial challenges for science is the development of alternative pollution-free and renewable energy sources. One of the most promising inexhaustible sources of energy is solar energy, and in this field, solar fuel cells employing naturally evolved solar energy converting biocomplexes—photosynthetic [...] Read more.
One of the crucial challenges for science is the development of alternative pollution-free and renewable energy sources. One of the most promising inexhaustible sources of energy is solar energy, and in this field, solar fuel cells employing naturally evolved solar energy converting biocomplexes—photosynthetic reaction centers, such as photosystem I—are of growing interest due to their highly efficient photo-powered operation, resulting in the production of chemical potential, enabling synthesis of simple fuels. However, application of the biomolecules in such a context is strongly limited by the progressing photobleaching thereof during illumination. In the current work, we investigated the excitation wavelength dependence of the photosystem I photodamage dynamics. Moreover, we aimed to correlate the PSI–LHCI photostability dependence on the excitation wavelength with significant (ca. 50-fold) plasmonic enhancement of fluorescence due to the utilization of planar metallic nanostructure as a substrate. Finally, we present a rational approach for the significant improvement in the photostability of PSI in anoxic conditions. We find that photobleaching rates for 5 min long blue excitation are reduced from nearly 100% to 20% and 70% for substrates of bare glass and plasmonically active substrate, respectively. Our results pave promising ways for optimization of the biomimetic solar fuel cells due to synergy of the plasmon-induced absorption enhancement together with improved photostability of the molecular machinery of the solar-to-fuel conversion. Full article
(This article belongs to the Special Issue Biomolecular and Biohybrid Systems for Solar Energy Conversion)
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13 pages, 2114 KiB  
Article
The Interplay of Conjugation and Metal Coordination in Tuning the Electron Transfer Abilities of NTA-Graphene Based Interfaces
by Magdalena Kaźmierczak, Bartosz Trzaskowski and Silvio Osella
Int. J. Mol. Sci. 2022, 23(1), 543; https://0-doi-org.brum.beds.ac.uk/10.3390/ijms23010543 - 04 Jan 2022
Cited by 1 | Viewed by 1816
Abstract
An artificial leaf is a concept that not only replicates the processes taking place during natural photosynthesis but also provides a source of clean, renewable energy. One important part of such a device are molecules that stabilize the connection between the bioactive side [...] Read more.
An artificial leaf is a concept that not only replicates the processes taking place during natural photosynthesis but also provides a source of clean, renewable energy. One important part of such a device are molecules that stabilize the connection between the bioactive side and the electrode, as well as tune the electron transfer between them. In particular, nitrilotriacetic acid (NTA) derivatives used to form a self-assembly monolayer chemisorbed on a graphene monolayer can be seen as a prototypical interface that can be tuned to optimize the electron transfer. In the following work, interfaces with modifications of the metal nature, backbone saturation, and surface coverage density are presented by means of theoretical calculations. Effects of the type of the metal and the surface coverage density on the electronic properties are found to be key to tuning the electron transfer, while only a minor influence of backbone saturation is present. For all of the studied interfaces, the charge transfer flow goes from graphene to the SAM. We suggest that, in light of the strength of electron transfer, Co2+ should be considered as the preferred metal center for efficient charge transfer. Full article
(This article belongs to the Special Issue Biomolecular and Biohybrid Systems for Solar Energy Conversion)
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18 pages, 5281 KiB  
Article
Development of a Novel Nanoarchitecture of the Robust Photosystem I from a Volcanic Microalga Cyanidioschyzon merolae on Single Layer Graphene for Improved Photocurrent Generation
by Miriam Izzo, Margot Jacquet, Takayuki Fujiwara, Ersan Harputlu, Radosław Mazur, Piotr Wróbel, Tomasz Góral, C. Gokhan Unlu, Kasim Ocakoglu, Shinya Miyagishima and Joanna Kargul
Int. J. Mol. Sci. 2021, 22(16), 8396; https://0-doi-org.brum.beds.ac.uk/10.3390/ijms22168396 - 05 Aug 2021
Cited by 7 | Viewed by 2349
Abstract
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, [...] Read more.
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. Full article
(This article belongs to the Special Issue Biomolecular and Biohybrid Systems for Solar Energy Conversion)
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