Department of Chemical Physics and Optics, Faculty of Mathematics and Physics , Charles University , Ke Karlovu 3 , 121 16 Prague 2 , Czech Republic.
Protein Crystallography, Faculty of Biology and Biotechnology , Ruhr-University Bochum , D-44780 Bochum , Germany.
J Phys Chem B. 2018 Sep 27;122(38):8834-8845. doi: 10.1021/acs.jpcb.8b06751. Epub 2018 Sep 17.
Chlorophyll (Chl) triplet states generated in photosynthetic light-harvesting complexes (LHCs) can be quenched by carotenoids to prevent the formation of reactive singlet oxygen. Although this quenching occurs with an efficiency close to 100% at physiological temperatures, the Chl triplets are often observed at low temperatures. This might be due to the intrinsic temperature dependence of the Dexter mechanism of excitation energy transfer, which governs triplet quenching, or by temperature-induced conformational changes. Here, we report about the temperature dependence of Chl triplet quenching in two LHCs. We show that both the effects contribute significantly. In LHC II of higher plants, the core Chls are quenched with a high efficiency independent of temperature. A different subpopulation of Chls, which increases with lowering temperature, is not quenched at all. This is probably caused by the conformational changes which detach these Chls from the energy-transfer chain. In a membrane-intrinsic LHC of dinoflagellates, similarly two subpopulations of Chls were observed. In addition, another part of Chl triplets is quenched by carotenoids with a rate which decreases with temperature. This allowed us to study the temperature dependence of Dexter energy transfer. Finally, a part of Chls was quenched by triplet-triplet annihilation, a phenomenon which was not observed for LHCs before.
叶绿素(Chl)三重态在光合作用光捕获复合物(LHCs)中产生,可被类胡萝卜素猝灭以防止活性单线态氧的形成。尽管在生理温度下,这种猝灭的效率接近 100%,但在低温下经常观察到 Chl 三重态。这可能是由于激发能量转移的 Dexter 机制的固有温度依赖性,即三重态猝灭,或由温度诱导的构象变化引起的。在这里,我们报告了两种 LHCs 中 Chl 三重态猝灭的温度依赖性。我们表明,这两种效应都有很大的贡献。在高等植物的 LHC II 中,核心 Chls 以与温度无关的高效率猝灭。随着温度降低而增加的不同的 Chls 亚群根本不会被猝灭。这可能是由于构象变化将这些 Chls 从能量转移链上分离出来。在原生质膜的甲藻 LHC 中,也观察到了类似的两种 Chl 亚群。此外,类胡萝卜素还以随温度降低而降低的速率猝灭 Chl 三重态的另一部分。这使我们能够研究 Dexter 能量转移的温度依赖性。最后,一部分 Chls 被三重态-三重态湮灭猝灭,这是以前在 LHCs 中未观察到的现象。