Supramolecular chlorophyll aggregates inspired from specific light-harvesting antenna “chlorosome”: Static nanostructure, dynamic construction process, and versatile application

Matsubara, Satοshi; Tamiaki, Hitoshi

doi:10.1016/j.jphotochemrev.2020.100385

Cited by 47 publications

(24 citation statements)

References 176 publications

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“…Chlorosomes serve as an inspiration source for artificial light-harvesting complexes for new ways of solar energy utilization. This effort is motivated by their extraordinary light-harvesting properties and the fact that the formation of the pigment aggregates inside the chlorosome is based on self-assembly and can be mimicked in vitro 30 – 32 . Therefore, we also included artificial aggregates in our study.…”

Section: Introductionmentioning

confidence: 99%

Superradiance of bacteriochlorophyll c aggregates in chlorosomes of green photosynthetic bacteria

Malina

Koehorst

Bína

et al. 2021

Sci Rep

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Chlorosomes are the main light-harvesting complexes of green photosynthetic bacteria that are adapted to a phototrophic life at low-light conditions. They contain a large number of bacteriochlorophyll c, d, or e molecules organized in self-assembling aggregates. Tight packing of the pigments results in strong excitonic interactions between the monomers, which leads to a redshift of the absorption spectra and excitation delocalization. Due to the large amount of disorder present in chlorosomes, the extent of delocalization is limited and further decreases in time after excitation. In this work we address the question whether the excitonic interactions between the bacteriochlorophyll c molecules are strong enough to maintain some extent of delocalization even after exciton relaxation. That would manifest itself by collective spontaneous emission, so-called superradiance. We show that despite a very low fluorescence quantum yield and short excited state lifetime, both caused by the aggregation, chlorosomes indeed exhibit superradiance. The emission occurs from states delocalized over at least two molecules. In other words, the dipole strength of the emissive states is larger than for a bacteriochlorophyll c monomer. This represents an important functional mechanism increasing the probability of excitation energy transfer that is vital at low-light conditions. Similar behaviour was observed also in one type of artificial aggregates, and this may be beneficial for their potential use in artificial photosynthesis.

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Section: Introductionmentioning

confidence: 99%

Superradiance of bacteriochlorophyll c aggregates in chlorosomes of green photosynthetic bacteria

Malina

Koehorst

Bína

et al. 2021

Sci Rep

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“…They serve as coordination sites for molecular oxygen and carbon dioxide during cellular respiration, [1] they play a vital role as light harvesting systems in the chlorophyll photosystem,[ 2 , 3 ] and their metal binding abilities contribute to the catalytic activity of many enzymes. [ 4 , 5 ] Due to their large conjugated π‐system, they exhibit strong absorption bands in the visible region of light and are usually deeply colored, which also led to their name deriving from the Greek word πορϕύρα ( porphyra ) for purple. [6] Despite their fascinating photo‐optical properties, porphyrin‐based monomers often exhibit promiscuous assembly behavior in supramolecular polymerizations, leading to multiple aggregate types and aggregation pathways.…”

Section: Introductionmentioning

confidence: 99%

Consequences of Amide Connectivity in the Supramolecular Polymerization of Porphyrins: Spectroscopic Observations Rationalized by Theoretical Modelling

Weyandt

Filot

Vantomme

et al. 2021

Chemistry A European J

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The correlation between molecular structure and mechanism of supramolecular polymerizations is a topic of great interest, with a special focus on the pathway complexity of porphyrin assemblies. Their cooperative polymerization typically yields highly ordered, long 1D polymers and is driven by a combination of π‐stacking due to solvophobic effects and hydrogen bonding interactions. Subtle changes in molecular structure, however, have significant influence on the cooperativity factor and yield different aggregate types (J‐ versus H‐aggregates) of different lengths. In this study, the influence of amide connectivity on the self‐assembly behavior of porphyrin‐based supramolecular monomers was investigated. While in nonpolar solvents, C=O centered monomers readily assemble into helical supramolecular polymers via a cooperative mechanism, their NH centered counterparts form short, non‐helical J‐type aggregates via an isodesmic pathway. A combination of spectroscopy and density functional theory modelling sheds light on the molecular origins causing this stunning difference in assembly properties and demonstrates the importance of molecular connectivity in the design of supramolecular systems. Finally, their mutual interference in copolymerization experiments is presented.

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“…Such aggregates (tubular, lamellar, spiral) are found in chlorosomes (Figure 8), the extra-membranous peripheral antennae of green bacteria, composed of ovoidal envelope of lipid monolayer and proteins (dimensions of ≈180 nm × 60 nm × 30 nm) containing up to 2 × 10 5 BChl molecules. [24] Chlorosomes are therefore structures in which pigment-protein interactions seem to play little or no role, anchored through the so-called baseplate (a region rich in Chl-a pigments) and Fenna-Matthews-Olson (FMO) proteins to the photosynthetic membrane in which the RCs are embedded. Upon photon absorption by BChl-c aggregates, a series of excitation energy transfer reactions occurs in which each acceptor has longer wavelength maximum absorption with respect to its donor, ultimately funneling the excitation energy to the RCs.…”

Section: Spectroscopic and Electrochemical Propertiesmentioning

confidence: 99%

Chlorophylls as Molecular Semiconductors: Introduction and State of Art

Buscemi

Vona

Trotta

et al. 2021

Adv Materials Technologies

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Chlorophylls (Chls) and their derivatives are the most common pigments used for light absorption, energy transfer, and charge separation in photosynthetic organisms. Their functions change upon different aggregation states and specific pigment–protein interactions. Differences in the aromatic π‐system and substituents finely tune Chls electronic, spectroscopic, and supramolecular characteristics. The varieties of Chls species and the possibility of chemical manipulation, together with their exceptional absorption cross section, make them attractive materials for applications as sensitizer in energy conversion devices. Moreover, when deposited as thin films, Chls and their semi‐synthetic derivatives exhibit the typical behavior of molecular organic semiconductors with good charge carrier mobility and Fermi level suitable for their use in optoelectronic devices like phototransistors. This review aims at bridging the possible knowledge and language gap between biochemists and biophysicists working on Chls, and material scientists developing organic optoelectronic devices. Starting from the structural features, and proceeding towards optoelectronic devices, the review offers a critical overview on the uses of Chls as light‐responsive molecular semiconductors known so far. Exploiting the high efficiency of these renewable, biocompatible, and recyclable natural systems can pave the way for next generation biooptoelectronics, including artificial light energy converters, photodetectors, and, more in general, forward‐thinking technologies.

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Supramolecular chlorophyll aggregates inspired from specific light-harvesting antenna “chlorosome”: Static nanostructure, dynamic construction process, and versatile application

Cited by 47 publications

References 176 publications

Superradiance of bacteriochlorophyll c aggregates in chlorosomes of green photosynthetic bacteria

Superradiance of bacteriochlorophyll c aggregates in chlorosomes of green photosynthetic bacteria

Consequences of Amide Connectivity in the Supramolecular Polymerization of Porphyrins: Spectroscopic Observations Rationalized by Theoretical Modelling

Chlorophylls as Molecular Semiconductors: Introduction and State of Art

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