Femtosecond Transient Absorption Spectroscopic Study of a Carbonyl-Containing Carotenoid Analogue, 2-(all-<i>trans</i>-Retinylidene)-indan-1,3-dione

Kusumoto, Toshiyuki; Kosumi, Daisuke; Uragami, Chiasa; Frank, Harry A.; Birge, Robert R.; Cogdell, Richard J.; Hashimoto, Hideki

doi:10.1021/jp111313f

Cited by 15 publications

(17 citation statements)

References 61 publications

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“…A nonbacteriochlorin analog ( Ret‐Ind ), derived from retinal and indan‐1,3‐dione, is shown in Chart 4 . Ret‐Ind absorbs strongly in the region near 500 nm and exhibits rapid (multistep depending on excitation energy/wavelength) excited‐state decay to the ground state in <50 ps with an overall time constant that depends on solvent polarity .…”

Section: Discussionmentioning

confidence: 99%

Photophysical Properties and Electronic Structure of Bacteriochlorin–Chalcones with Extended Near‐Infrared Absorption

Yang

Ruzié

Krayer

et al. 2013

Photochem & Photobiology

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Synthetic bacteriochlorins enable systematic tailoring of substituents about the bacteriochlorin chromophore and thereby provide insights concerning the native bacteriochlorophylls of bacterial photosynthesis. Nine free-base bacteriochlorins (eight prepared previously and one prepared here) have been examined that bear diverse substituents at the 13- or 3,13-positions. The substituents include chalcone (3-phenylprop-2-en-1-onyl) derivatives with groups attached to the phenyl moiety, a "reverse chalcone" (3-phenyl-3-oxo-1-enyl), and extended chalcones (5-phenylpenta-2,4-dien-1-onyl, retinylidenonyl). The spectral and photophysical properties (τs, Φf, Φ(ic), Φ(isc), τT, k(f), k(ic), k(isc)) of the bacteriochlorins have been characterized. The bacteriochlorins absorb strongly in the 780-800 nm region and have fluorescence quantum yields (Φf) in the range 0.05-0.11 in toluene and dimethylsulfoxide. Light-induced electron promotions between orbitals with predominantly substituent or macrocycle character or both may give rise to some net macrocycle ↔ substituent charge-transfer character in the lowest and higher singlet excited states as indicated by density functional theory (DFT) and time-dependent DFT calculations. Such calculations indicated significant participation of molecular orbitals beyond those (HOMO - 1 to LUMO + 1) in the Gouterman four-orbital model. Taken together, the studies provide insight into the fundamental properties of bacteriochlorins and illustrate designs for tuning the spectral and photophysical features of these near-infrared-absorbing tetrapyrrole chromophores.

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Section: Discussionmentioning

confidence: 99%

Photophysical Properties and Electronic Structure of Bacteriochlorin–Chalcones with Extended Near‐Infrared Absorption

Yang

Ruzié

Krayer

et al. 2013

Photochem & Photobiology

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“…This methodology was benchmarked for Cars by Kusumoto et al . 53 Using the obtained wave-functions we calculated the transition densities (custom code 54 ) within the TDC famework 32 : where and are the ground and excited state wave-functions, and define the grid size of the cube. The electronic coupling (Coulombic part only) was calculated as where Chl and Lut transition dipole moments were re-scaled to 4.49 D 55 and 0.767 D 25 , respectively.…”

Section: Methodsmentioning

confidence: 99%

Fine control of chlorophyll-carotenoid interactions defines the functionality of light-harvesting proteins in plants

Balevičius

Fox

Bricker

et al. 2017

Sci Rep

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Photosynthetic antenna proteins can be thought of as "programmed solvents", which bind pigments at specific mutual orientations, thus tuning the overall energetic landscape and ensuring highly efficient light-harvesting. While positioning of chlorophyll cofactors is well understood and rationalized by the principle of an "energy funnel", the carotenoids still pose many open questions. Particularly, their short excited state lifetime (<25 ps) renders them potential energy sinks able to compete with the reaction centers and drastically undermine light-harvesting efficiency. Exploration of the orientational phasespace revealed that the placement of central carotenoids minimizes their interaction with the nearest chlorophylls in the plant antenna complexes LHCII, CP26, CP29 and LHCI. At the same time we show that this interaction is highly sensitive to structural perturbations, which has a profound effect on the overall lifetime of the complex. This links the protein dynamics to the light-harvesting regulation in plants by the carotenoids.Photosystem I (PSI) and Photosystem II (PSII) are large, integral membrane protein super-complexes in plants and green algae 1,2 . They are the key components of the light reactions of photosynthesis. While PSII performs water oxidation to build a transmembrane proton gradient and induce electron transfer 3 , PSI primarily produces the universal redox carrier NADPH 4 . From the functional perspective, the photosystem super-complexes are divided into the core sites of actual photochemical reactions, called reaction centers (RCs), and accessory light-harvesting complexes (LHCs). Even though the RC sub-units capture light themselves, the peripheral LHC antenna proteins of the Lhcb (in PSII) and Lhca (in PSI) families are necessary to increase the absorption cross-section and ensure optimal performance 5 . The antenna complexes transfer excitation energy with remarkable efficiency, enabling near unity quantum yield of PSI/II (one photochemical reaction per one photon captured) 6 . This is due to the fine tuning of the relative positions, orientations and excitation energies of chlorophyll (Chl) cofactors coordinated by the residues, which is the reason why LHC proteins are sometimes referred to as "programmed solvent" 2 . The current precision of pigment placement resolved from the crystal structures 7-10 allows for highly detailed models, describing both the initial steps of exciton transfer 11,12 and the subsequent charge separation in the RCs 13 . However, such models largely account only for the Chls, while the second major building block of the pigment arrays, the carotenoids (Cars), are usually disregarded.Cars are typically included in photodynamic models of bacterial systems only, where they are significant light-harvesters 14 , while their light-harvesting role in plants is minor compared to the photoprotective function 15,16 . The latter is performed primarily by quenching the Chl triplet states 17 , which would otherwise sensitize molecular oxygen to form harmful singlet oxy...

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“…1-5). The validity of this method for calculating Car excited states was initially demonstrated by Kusumoto et al 44 and has previously been used to study ad hoc geometry distortions to the Car lutein 45 . We have used it extensively to parameterize models of excitation quenching in plant LHCs 14,[46][47][48] .…”

Section: Quantum Chemical Calculationsmentioning

confidence: 96%

How carotenoid distortions may determine optical properties: lessons from the Orange Carotenoid Protein

Wei

Balevičius

Polı́vka

et al. 2019

Phys. Chem. Chem. Phys.

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Femtosecond Transient Absorption Spectroscopic Study of a Carbonyl-Containing Carotenoid Analogue, 2-(all-trans-Retinylidene)-indan-1,3-dione

Cited by 15 publications

References 61 publications

Photophysical Properties and Electronic Structure of Bacteriochlorin–Chalcones with Extended Near‐Infrared Absorption

Photophysical Properties and Electronic Structure of Bacteriochlorin–Chalcones with Extended Near‐Infrared Absorption

Fine control of chlorophyll-carotenoid interactions defines the functionality of light-harvesting proteins in plants

How carotenoid distortions may determine optical properties: lessons from the Orange Carotenoid Protein

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