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类胡萝卜素 S* 态的本质及其在植物非光化学猝灭中的作用。

The nature of carotenoid S* state and its role in the nonphotochemical quenching of plants.

机构信息

Department of Chemistry and Industrial Chemistry, University of Pisa, 56124, Pisa, Italy.

Faculty of Chemistry, University of Warsaw, 02-093, Warsaw, Poland.

出版信息

Nat Commun. 2024 Jan 29;15(1):847. doi: 10.1038/s41467-024-45090-9.

Abstract

In plants, light-harvesting complexes serve as antennas to collect and transfer the absorbed energy to reaction centers, but also regulate energy transport by dissipating the excitation energy of chlorophylls. This process, known as nonphotochemical quenching, seems to be activated by conformational changes within the light-harvesting complex, but the quenching mechanisms remain elusive. Recent spectroscopic measurements suggest the carotenoid S* dark state as the quencher of chlorophylls' excitation. By investigating lutein embedded in different conformations of CP29 (a minor antenna in plants) via nonadiabatic excited state dynamics simulations, we reveal that different conformations of the complex differently stabilize the lutein s-trans conformer with respect to the dominant s-cis one. We show that the s-trans conformer presents the spectroscopic signatures of the S* state and rationalize its ability to accept energy from the closest excited chlorophylls, providing thus a relationship between the complex's conformation and the nonphotochemical quenching.

摘要

在植物中,光捕获复合物作为天线,用于收集和传递被吸收的能量到反应中心,但也通过耗散叶绿素的激发能来调节能量传递。这个过程被称为非光化学猝灭,似乎是由光捕获复合物内的构象变化激活的,但猝灭机制仍然难以捉摸。最近的光谱测量表明类胡萝卜素 S* 暗态是叶绿素激发的猝灭剂。通过非绝热激发态动力学模拟研究叶黄素在 CP29 不同构象中的嵌入情况(植物中的一个次要天线),我们揭示了复合物的不同构象以不同的方式稳定叶黄素 s-反式构象相对于主导的 s-顺式构象。我们表明,s-反式构象呈现出 S* 态的光谱特征,并解释了它从最近的激发态叶绿素接受能量的能力,从而在复合物的构象和非光化学猝灭之间建立了关系。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cacb/11258248/933fd9545cc9/41467_2024_45090_Fig1_HTML.jpg

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