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高等植物光系统 I-捕光复合物 I 中的俘获动力学受低能态激发态扩散与光化学电荷分离之间竞争的控制。

Trapping Dynamics in Photosystem I-Light Harvesting Complex I of Higher Plants Is Governed by the Competition Between Excited State Diffusion from Low Energy States and Photochemical Charge Separation.

机构信息

Centro Studi sulla Biologia Cellulare e Molecolare delle Piante, CNR , Via Celoria 26, 20133 Milan, Italy.

Istituto di Biologia e Biotecnologia Agraria, Consiglio Nazionale delle Ricerche , Via Bassini 15a, 20133 Milano, Italy.

出版信息

J Phys Chem B. 2017 Oct 26;121(42):9816-9830. doi: 10.1021/acs.jpcb.7b07064. Epub 2017 Oct 13.

Abstract

The dynamics of excited state equilibration and primary photochemical trapping have been investigated in the photosystem I-light harvesting complex I isolated from spinach, by the complementary time-resolved fluorescence and transient absorption approaches. The combined analysis of the experimental data indicates that the excited state decay is described by lifetimes in the ranges of 12-16 ps, 32-36 ps, and 64-77 ps, for both detection methods, whereas faster components, having lifetimes of 550-780 fs and 4.2-5.2 ps, are resolved only by transient absorption. A unified model capable of describing both the fluorescence and the absorption dynamics has been developed. From this model it appears that the majority of excited state equilibration between the bulk of the antenna pigments and the reaction center occurs in less than 2 ps, that the primary charge separated state is populated in ∼4 ps, and that the charge stabilization by electron transfer is completed in ∼70 ps. Energy equilibration dynamics associated with the long wavelength absorbing/emitting forms harbored by the PSI external antenna are also characterized by a time mean lifetime of ∼75 ps, thus overlapping with radical pair charge stabilization reactions. Even in the presence of a kinetic bottleneck for energy equilibration, the excited state dynamics are shown to be principally trap-limited. However, direct excitation of the low energy chlorophyll forms is predicted to lengthen significantly (∼2-folds) the average trapping time.

摘要

通过时间分辨荧光和瞬态吸收两种互补方法,研究了菠菜光系统 I-光捕获复合物 I 中激发态平衡和初级光化学俘获的动力学。对实验数据的综合分析表明,激发态衰减可以用两种检测方法的 12-16 ps、32-36 ps 和 64-77 ps 范围内的寿命来描述,而只有瞬态吸收才能分辨出 550-780 fs 和 4.2-5.2 ps 的更快的组分。已经开发出一种能够描述荧光和吸收动力学的统一模型。从该模型可以看出,天线色素体与反应中心之间的大部分激发态平衡在不到 2 ps 内发生,初级电荷分离态在 4 ps 左右形成,电子转移的电荷稳定在 70 ps 左右完成。与 PSI 外部天线所承载的长波长吸收/发射形式相关的能量平衡动力学也具有约 75 ps 的时间平均寿命,因此与自由基对电荷稳定反应重叠。即使存在能量平衡的动力学瓶颈,激发态动力学仍主要受到陷阱限制。然而,预测直接激发低能量叶绿素形式会显著延长平均捕获时间(约 2 倍)。

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