2012
DOI: 10.1021/jp3110997
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Modeling of Fluorescence Quenching by Lutein in the Plant Light-Harvesting Complex LHCII

Abstract: Photoprotective non-photochemical quenching (NPQ) in higher plants is the result of the formation of energy quenching traps in the light-harvesting antenna of photosystem II (PSII). It has been proposed that this quenching trap is a lutein molecule closely associated with the chlorophyll terminal emitter of the major light-harvesting complex LHCII. We have used a combination of time-dependent density functional theory (TD-DFT) and the semiempirical MNDO-CAS-CI method to model the chlorophyll-lutein energy tran… Show more

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Cited by 76 publications
(132 citation statements)
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“…This can be interpreted as the presence of an equilibrated quencher with a slow variable quenching rate or as the transfer limited population of a strong quencher with inverted transfer kinetics. 10,34,35 Our experiments do not allow to distinguish those possibilities but the broad range of quenching rates and dwell-times up to seconds do suggest that the mechanism is indeed influenced by static disorder. 36 The fact that we observe fluorescence intermittency with a well-defined off-state (dark state) might also be caused by the fact that any underlying distribution of quenching rates that lead to an overall excited state lifetime of less than about 100 ps cannot be resolved in single molecule experiments and will just appear as a dark state.…”
Section: Discussionmentioning
confidence: 78%
“…This can be interpreted as the presence of an equilibrated quencher with a slow variable quenching rate or as the transfer limited population of a strong quencher with inverted transfer kinetics. 10,34,35 Our experiments do not allow to distinguish those possibilities but the broad range of quenching rates and dwell-times up to seconds do suggest that the mechanism is indeed influenced by static disorder. 36 The fact that we observe fluorescence intermittency with a well-defined off-state (dark state) might also be caused by the fact that any underlying distribution of quenching rates that lead to an overall excited state lifetime of less than about 100 ps cannot be resolved in single molecule experiments and will just appear as a dark state.…”
Section: Discussionmentioning
confidence: 78%
“…In the S/F regime, energy delivery to the quencher is slow (B100 ps or even slower), while the dissipation of trapped energy is fast (B10 ps). The slow (20-30 ps) transfer of energy from Chla612 to lutein 620, leading to an effective trapping time of B160 ps, followed by the rapid dissipation of the lutein S 1 excited state due to interconversion to the ground state is an example of the S/F regime 32,33 . The two regimes imply different extents of competition between photochemical and NPQ.…”
Section: Discussionmentioning
confidence: 99%
“…radical cation formation with chlorophyll (Holt et al, 2005), there are several theories explaining how lutein (and other xanthophylls) can quench excess energy, which include coherent and incoherent energy transfer pathways from chlorophyll to xanthophyll . While there is some evidence showing how zeaxanthin becomes activated as a quencher (Holt et al, 2005;Ahn et al, 2008), there are numerous reports attempting to explain the changes in protein and lutein that point to this pigment as a quencher, as well as modeling work assessing the effectiveness of this quencher in taking excess excitation energy from chlorophyll a Duffy et al, 2013aDuffy et al, , 2013bDuffy et al, , 2014Chmeliov et al, 2015). The formation of quenching chlorophyll-chlorophyll dimers has also been recently advocated .…”
Section: Change: Lhcii Rearrangements/aggregation and The Formation Omentioning
confidence: 99%