Carotenoids as a Shortcut for Chlorophyll Soret‐to‐Q Band Energy Flow

Götze, Jan P.; Kröner, Dominik; Banerjee, Shiladitya; Karasulu, Bora; Thiel, Walter

doi:10.1002/cphc.201402233

Cited by 29 publications

(44 citation statements)

References 67 publications

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“…448 Later, the site energies of CP43 were refined from structure-based calculations based on electrostatic shift calculations, suggesting different mutations of potential interest that could shed further light in the assignment of the excited states in the complex. 449,450 Several quantum chemical studies have also addressed the role of the xanthophyll carotenoids in the light harvesting capability of LHCII, [451][452][453] indicating for example that carotenoids can provide a shortcut for the chlorophylls Soret-to-Q bands energy flow. 453 Moreover, the role of the xantophylls is believed to be central to the ability of LHCII to dissipate the excess energy through NPQ.…”

Section: Lhc Familymentioning

confidence: 99%

“…449,450 Several quantum chemical studies have also addressed the role of the xanthophyll carotenoids in the light harvesting capability of LHCII, [451][452][453] indicating for example that carotenoids can provide a shortcut for the chlorophylls Soret-to-Q bands energy flow. 453 Moreover, the role of the xantophylls is believed to be central to the ability of LHCII to dissipate the excess energy through NPQ. Several quantum chemical studies have investigated the molecular basis of the predominant NPQ component, the rapidly reversible energy quenching triggered by the pH difference across the thylakoid membrane.…”

Section: Lhc Familymentioning

confidence: 99%

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Quantum Chemical Studies of Light Harvesting

2016

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The design of optimal light-harvesting (supra)molecular systems and materials is one of the most challenging frontiers of science. Theoretical methods and computational models play a fundamental role in this difficult task, as they allow the establishment of structural blueprints inspired by natural photosynthetic organisms that can be applied to the design of novel artificial light-harvesting devices. Among theoretical strategies, the application of quantum chemical tools represents an important reality that has already reached an evident degree of maturity, although it still has to show its real potentials. This Review presents an overview of the state of the art of this strategy, showing the actual fields of applicability but also indicating its current limitations, which need to be solved in future developments.

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Section: Lhc Familymentioning

confidence: 99%

Section: Lhc Familymentioning

confidence: 99%

Quantum Chemical Studies of Light Harvesting

2016

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“…It is well known that the quantum chemical description of the electronic excitations in carotenoids is extremely challenging due to the specific character of the different π − π * excited states. Indeed, from theoretical studies comparing single-and multi-reference approaches, [24][25][26][27] it comes out that contributions from multiple excitations are crucial for the description of the lowest (dark) excited state, whereas the (bright) second state is dominated by single excitations. 28 For that excitation, Time Dependent Density Functional Theory (TDDFT) has shown to be a valid approach especially when used in combination with optimized long-range corrected hybrid density functionals.…”

mentioning

confidence: 99%

The Dynamic Origin of Color Tuning in Proteins Revealed by a Carotenoid Pigment

Loco

Buda

Lugtenburg

et al. 2018

J. Phys. Chem. Lett.

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Understanding the microscopic origin of the color tuning in pigment-protein complexes is a challenging yet fundamental issue in photoactive biological systems. Here, we propose a possible interpretation by using a state-of-the-art multiscale strategy based on the integration of quantum chemistry and polarizable atomistic embeddings into a dynamic description. By means of such a strategy we are able to resolve the long-standing dispute over the coloration mechanism in the crustacyanin protein. It is shown that the combination of the dynamical flexibility of the carotenoid pigments (astaxanthin) with the responsive protein environment is essential to obtain quantitative predictions of the spectral tuning. The strong linear correlation between the excitation energies and the bond length alternation in the long-chain carotenoids modulated by the dynamical protein environment is a novel finding explaining the high color tunability in crustacyanin.

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“…If only LHCII is present in solution, the excitation process pumps electrons from the ground state to the excited states of Soret band or Q band. The excitation of the Soret band is followed by internal conversion and ultrafast excitation energy transfer (EET) to the Q band with assistance of carotenoids contained in LHCII trimer, as was proposed and verified by a theoretical modeling . Thus all the fluorescence emissions from LHCIIs were at 683 nm, corresponding to a radiative relaxation of the electrons from the excited Q band to the ground state.…”

Section: Resultsmentioning

confidence: 69%

Plasmonic Enhancement of Biosolar Cells Employing Light Harvesting Complex II Incorporated with Core–Shell Metal@TiO₂ Nanoparticles

Yang

Gobeze

D’Souza

et al. 2016

Adv Materials Inter

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photosynthetic complexes in artifi cial phototovoltaic (PV) devices as "green" light harvesting antennas was proposed in hopes to use their extraordinarily efficient light absorption and energy transfer properties. Measurable photocurrent was initially achieved using a self-assembled membrane of RCs, [ 2,3 ] LHCI-RC core complexes, [ 4 ] or whole photosystems (PSI or PSII) [ 3,5 ] on conductive electrodes. The power conversion effi ciency (PCE) was increased notably after incorporating the photosynthetic complexes into the PV cells. [ 6,7 ] Light-harvesting complex II (LHCII) extracted from green plants is the major antenna complex in photosystem II (PSII). As a subunit, LHCII has much simpler structure and smaller size than the composite photosystems. It accounts for about half of the chlorophylls (Chls) in the thylakoid. The natural form of LHCII is a trimer consisting of three monomers each of which comprises a polypeptide of about 232 amino-acid residues, some light-absorbing pigments (8 Chl a , 6 Chl b , and 3-4 carotenoids) and one phospholipid. [ 8 ] The protein structure precisely confi nes the pigments in proper positions to generate strong coupling with each other, which enables high effi ciency in harvesting and transfering solar energy. [ 9 ] A LHCII layer inserted at the heterojunction of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid (PCBM) in a solid-state PV cell has claimed to show ≈30% enhancement in the photocurrent and the internal quatum effi ciency. [ 10 ] Other studies have utilized LHCII trimers as photosensitizers to interface with semiconductive TiO 2 fi lm in fabricating economic and environment-friendly dye-sensitized solar cells (DSSCs). [ 7,11 ] The operation of such DSSCs mimics natural photosynthesis, with photons captured by the dye sensitizers in analogue to LHCs and charge separation occuring between sensitizer-TiO 2 interface in analogue to the RCs. Therefore DSSCs can be used as a model artifi cial device to exploit the energy conversion processes in photosynthetic proteins. Our previous work on assembling LHCII aggregates in a thin-fi lm DSSC has demostrated that the formation of charge transfer (CT) states in the aggregated LHCIIs can facilitate faster electron injection from LHCII to TiO 2 , leading to higher electron collection effi ciency of the PV system. [ 12 ] Here the study of effects of plasmonic nanoparticles (PNPs) conjugated with natural extract light-harvesting complex II (LHCII) is reported. Three types of core-shell metal@TiO 2 PNPs with distinct surface plasmonic resonance are prepared. The plasmonic adsorption of the metal core provides strong photon capture and enhances the LHCII excitation through plasmon-induced resonance energy transfer (PIRET). More effi cient charge separation is facilitated at LHCII/TiO 2 interface as revealed by quenching of the fl uorescence and reduction of the fl uorescence lifetime of LHCII after adsorbing on PNPs. Femtosecond transient absorption provides further conclusive proof for charge injection from exci...

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Carotenoids as a Shortcut for Chlorophyll Soret‐to‐Q Band Energy Flow

Cited by 29 publications

References 67 publications

Quantum Chemical Studies of Light Harvesting

Quantum Chemical Studies of Light Harvesting

The Dynamic Origin of Color Tuning in Proteins Revealed by a Carotenoid Pigment

Plasmonic Enhancement of Biosolar Cells Employing Light Harvesting Complex II Incorporated with Core–Shell Metal@TiO₂ Nanoparticles

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Carotenoids as a Shortcut for Chlorophyll Soret‐to‐Q Band Energy Flow

Cited by 29 publications

References 67 publications

Quantum Chemical Studies of Light Harvesting

Quantum Chemical Studies of Light Harvesting

The Dynamic Origin of Color Tuning in Proteins Revealed by a Carotenoid Pigment

Plasmonic Enhancement of Biosolar Cells Employing Light Harvesting Complex II Incorporated with Core–Shell Metal@TiO2 Nanoparticles

Contact Info

Product

Resources

About

Plasmonic Enhancement of Biosolar Cells Employing Light Harvesting Complex II Incorporated with Core–Shell Metal@TiO₂ Nanoparticles