The electronic coupling between a robust red algal photosystem I (PSI) associated with its light harvesting antenna (LHCI) and nanocrystalline n‐type semiconductors, TiO2 and hematite (α‐Fe2O3) is utilized for fabrication of the biohybrid dye‐sensitized solar cells (DSSC). PSI‐LHCI is immobilized as a structured multilayer over both semiconductors organized as highly ordered nanocrystalline arrays, as evidenced by FE‐SEM and XRD spectroscopy. Of all the biohybrid DSSCs examined, α‐Fe2O3/PSI‐LHCI biophotoanode operates at a highest quantum efficiency and generates the largest open circuit photocurrent compared to the tandem system based on TiO2/PSI‐LHCI material. This is accomplished by immobilization of the PSI‐LHCI complex with its reducing side towards the hematite surface and nanostructuring of the PSI‐LHCI multilayer in which the subsequent layers of this complex are organized in the head‐to‐tail orientation. The biohybrid PSI‐LHCI‐DSSC is capable of sustained photoelectrochemical H2 production upon illumination with visible light above 590 nm. Although the solar conversion efficiency of the PSI‐LHCI/hematite DSSC is currently below a practical use, the system provides a blueprint for a genuinely green solar cell that can be used for molecular hydrogen production at a rate of 744 μmoles H2 mg Chl−1 h−1, placing it amongst the best performing biohybrid solar‐to‐fuel nanodevices.
The monomeric photosystem I-light-harvesting antenna complex I (PSI-LHCI) supercomplex from the extremophilic red alga represents an intermediate evolutionary link between the cyanobacterial PSI reaction center and its green algal/higher plant counterpart. We show that the PSI-LHCI supercomplex is characterized by robustness in various extreme conditions. By a combination of biochemical, spectroscopic, mass spectrometry, and electron microscopy/single particle analyses, we dissected three molecular mechanisms underlying the inherent robustness of the PSI-LHCI supercomplex: (1) the accumulation of photoprotective zeaxanthin in the LHCI antenna and the PSI reaction center; (2) structural remodeling of the LHCI antenna and adjustment of the effective absorption cross section; and (3) dynamic readjustment of the stoichiometry of the two PSI-LHCI isomers and changes in the oligomeric state of the PSI-LHCI supercomplex, accompanied by dissociation of the PsaK core subunit. We show that the largest low light-treated PSI-LHCI supercomplex can bind up to eight Lhcr antenna subunits, which are organized as two rows on the PsaF/PsaJ side of the core complex. Under our experimental conditions, we found no evidence of functional coupling of the phycobilisomes with the PSI-LHCI supercomplex purified from various light conditions, suggesting that the putative association of this antenna with the PSI supercomplex is absent or may be lost during the purification procedure.
We demonstrate that controlled assembly of eukaryotic photosystem I with its associated light harvesting antenna complex (PSI-LHCI) on plasmonically active silver nanowires (AgNWs) substantially improves the optical functionality of such a novel biohybrid nanostructure. By comparing fluorescence intensities measured for PSI-LHCI complex randomly oriented on AgNWs and the results obtained for the PSI-LHCI/cytochrome c (cyt c) bioconjugate with AgNWs we conclude that the specific binding of photosynthetic complexes with defined uniform orientation yields selective excitation of a pool of chlorophyll (Chl) molecules that are otherwise almost non-absorbing. This is remarkable, as this study shows for the first time that plasmonic excitations in metallic nanostructures can not only be used to enhance native absorption of photosynthetic pigments, but also - by employing cyt c as the conjugation cofactor - to activate the specific Chl pools as the absorbing sites only when the uniform and well-defined orientation of PSI-LHCI with respect to plasmonic nanostructures is achieved. As absorption of PSI alone is comparatively low, our approach lends itself as an innovative approach to outperform the reported-to-date biohybrid devices with respect to solar energy conversion.
Photosynthetic water oxidation is catalyzed by the oxygen-evolving complex (OEC) in photosystem II (PSII). This process is energetically driven by light-induced charge separation in the reaction center of PSII, which leads to a stepwise accumulation of oxidizing equivalents in the OEC (S states, i = 0-4) resulting in O evolution after each fourth flash, and to the reduction of plastoquinone to plastoquinol on the acceptor side of PSII. However, the S-state advancement is not perfect, which according to the Kok model is described by miss-hits (misses). These may be caused by redox equilibria or kinetic limitations on the donor (OEC) or the acceptor side. In this study, we investigate the effects of individual S state transitions and of the quinone acceptor side on the miss parameter by analyzing the flash-induced oxygen evolution patterns and the S, S and S state lifetimes in thylakoid samples of the extremophilic red alga Cyanidioschyzon merolae. The data are analyzed employing a global fit analysis and the results are compared to the data obtained previously for spinach thylakoids. These two organisms were selected, because the redox potential of Q/Q in PSII is significantly less negative in C. merolae (E = - 104 mV) than in spinach (E = - 163 mV). This significant difference in redox potential was expected to allow the disentanglement of acceptor and donor side effects on the miss parameter. Our data indicate that, at slightly acidic and neutral pH values, the E of Q/Q plays only a minor role for the miss parameter. By contrast, the increased energy gap for the backward electron transfer from Q to Pheo slows down the charge recombination reaction with the S and S states considerably. In addition, our data support the concept that the S → S transition is the least efficient step during the oxidation of water to molecular oxygen in the Kok cycle of PSII.
Mitigation of man-made climate change, rapid depletion of readily available fossil fuel reserves and facing the growing energy demand that faces mankind in the near future drive the rapid development of economically viable, renewable energy production technologies. It is very likely that greenhouse gas emissions will lead to the significant climate change over the next fifty years. World energy consumption has doubled over the last twenty-five years, and is expected to double again in the next quarter of the 21st century. Our biosphere is at the verge of a severe energy crisis that can no longer be overlooked. Solar radiation represents the most abundant source of clean, renewable energy that is readily available for conversion to solar fuels. Developing clean technologies that utilize practically inexhaustible solar energy that reaches our planet and convert it into the high energy density solar fuels provides an attractive solution to resolving the global energy crisis that mankind faces in the not too distant future. Nature's oxygenic photosynthesis is the most fundamental process that has sustained life on Earth for more than 3.5 billion years through conversion of solar energy into energy of chemical bonds captured in biomass, food and fossil fuels. It is this process that has led to evolution of various forms of life as we know them today. Recent advances in imitating the natural process of photosynthesis by developing biohybrid and synthetic "artificial leaves" capable of solar energy conversion into clean fuels and other high value products, as well as advances in the mechanistic and structural aspects of the natural solar energy converters, photosystem I and photosystem II, allow to address the main challenges: how to maximize solar-to-fuel conversion efficiency, and most importantly: how to store the energy efficiently and use it without significant losses. Last but not least, the question of how to make the process of solar energy conversion into fuel not only efficient but also cost effective, therefore attractive to the consumer, should be properly addressed.
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