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      • Zeaxanthin radical cation formation in minor light-harvesting complexes of higher plant antenna.

        Avenson, Thomas J,Ahn, Tae Kyu,Zigmantas, Donatas,Niyogi, Krishna K,Li, Zhirong,Ballottari, Matteo,Bassi, Roberto,Fleming, Graham R American Society for Biochemistry and Molecular Bi 2008 The Journal of biological chemistry Vol.283 No.6

        <P>Previous work on intact thylakoid membranes showed that transient formation of a zeaxanthin radical cation was correlated with regulation of photosynthetic light-harvesting via energy-dependent quenching. A molecular mechanism for such quenching was proposed to involve charge transfer within a chlorophyll-zeaxanthin heterodimer. Using near infrared (880-1100 nm) transient absorption spectroscopy, we demonstrate that carotenoid (mainly zeaxanthin) radical cation generation occurs solely in isolated minor light-harvesting complexes that bind zeaxanthin, consistent with the engagement of charge transfer quenching therein. We estimated that less than 0.5% of the isolated minor complexes undergo charge transfer quenching in vitro, whereas the fraction of minor complexes estimated to be engaged in charge transfer quenching in isolated thylakoids was more than 80 times higher. We conclude that minor complexes which bind zeaxanthin are sites of charge transfer quenching in vivo and that they can assume Non-quenching and Quenching conformations, the equilibrium LHC(N) <==> LHC(Q) of which is modulated by the transthylakoid pH gradient, the PsbS protein, and protein-protein interactions.</P>

      • Investigating energy partitioning during photosynthesis using an expanded quantum yield convention

        Ahn, T.K.,Avenson, T.J.,Peers, G.,Li, Z.,Dall'Osto, L.,Bassi, R.,Niyogi, K.K.,Fleming, G.R. Elsevier Science Publishers [etc.] 2009 Chemical physics Vol.357 No.1

        In higher plants, regulation of excess absorbed light is essential for their survival and fitness, as it enables avoidance of a build up of singlet oxygen and other reactive oxygen species. Regulation processes (known as non-photochemical quenching; NPQ) can be monitored by steady-state fluorescence on intact plant leaves. Pulse amplitude modulated (PAM) measurements of chlorophyll a fluorescence have been used for over 20 years to evaluate the amount of NPQ and photochemistry (PC). Recently, a quantum yield representation of NPQ (Φ<SUB>NPQ</SUB>), which incorporates a variable fraction of open reaction centers, was proposed by Hendrickson et al. [L. Hendrickson, R.T. Furbank, W.S. Chow, Photosynth. Res. 82 (2004) 73]. In this work we extend the quantum yield approach to describe the yields of reversible energy-dependent quenching (Φ<SUB>qE</SUB>), state transitions to balance PC between photosystems II and I (Φ<SUB>qT</SUB>), and photoinhibition quenching associated with damaged reaction centers (Φ<SUB>qI</SUB>). We showed the additivity of the various quantum yield components of NPQ through experiments on wild-type and npq1 strains of Arabidopsis thaliana. The quantum yield approach enables comparison of Φ<SUB>qE</SUB> with data from a variety of techniques used to investigate the mechanism of qE. We showed that Φ<SUB>qE</SUB> for a series of A. thaliana genotypes scales linearly with the magnitude of zeaxanthin cation formation, suggesting that charge-transfer quenching is largely responsible for qE in plants.

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