Journal
BIOCHIMICA ET BIOPHYSICA ACTA-BIOENERGETICS
Volume 1797, Issue 8, Pages 1410-1420Publisher
ELSEVIER
DOI: 10.1016/j.bbabio.2010.02.026
Keywords
Femtosecond pump-probe spectroscopy; Photosystem I; Reaction center; Electron transfer; Radical pairs
Categories
Funding
- Russian Foundation for Basic Research [09-04-01657-a, 08-04-00888, 08-03-00728]
- Ministry of Education and Science of the Russian Federation [MIPT 2.1.1.8102]
- Russian Academy of Sciences
- Russian Federation [SS-4525.2008.4]
- Federal Agency for Science and Innovation [02.512.11.2286, 02.740.11.0293]
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The ultrafast (<100 fs) conversion of delocalized exciton into charge-separated state between the primary donor P700 (bleaching at 705 nm) and the primary acceptor A(0) (bleaching at 690 nm) in photosystem I (PSI) complexes from Synechocystis sp. PCC 6803 was observed. The data were obtained by application of pump-probe technique with 20-fs low-energy pump pulses centered at 720 nm. The earliest absorbance changes (close to zero delay) with a bleaching at 690 nm are similar to the product of the absorption spectrum of PS I complex and the laser pulse spectrum, which represents the efficiency spectrum of the light absorption by PS I upon femtosecond excitation centered at 720 nm. During the first similar to 60 fs the energy transfer from the chlorophyll (Chl) species bleaching at 690 nm to the Chl bleaching at 705 nm occurs, resulting in almost equal bleaching of the two forms with the formation of delocalized exciton between 690-nm and 705-nm Chls. Within the next similar to 40 fs the formation of a new broad band centered at similar to 660 nm (attributed to the appearance of Chl anion radical) is observed. This band decays with time constant simultaneously with an electron transfer to A(1) ( phylloquinone). The subtraction of kinetic difference absorption spectra of the closed (state P700(+) A(0)A(1)) PS I reaction center (RC) from that of the open (state P700A(0)A(1)) RC reveals the pure spectrum of the P700(+)A(0)(-) ion-radical pair. The experimental data were analyzed using a simple kinetic scheme: An* (k1)-> [(PA(0))*A(1) (<100fs)-> P(+)A(0)(-)A(1)] (k2)-> P(+)A(0)A(1)(-), and a global fitting procedure based on the singular value decomposition analysis. The calculated kinetics of transitions between intermediate states and their spectra were similar to the kinetics recorded at 694 and 705 nm and the experimental spectra obtained by subtraction of the spectra of closed RCs from the spectra of open RCs. As a result, we found that the main events in RCs of PSI under our experimental conditions include very fast (<100 fs) charge separation with the formation of the P700(+)A(0)(-)A(1) state in approximately one half of the RCs, the similar to 5-ps energy transfer from antenna Chl* to P700A(0)A(1) in the remaining RCs, and similar to 25-ps formation of the secondary radical pair P700(+)A(0)A(1)(-). (C) 2010 Elsevier B.V. All rights reserved.
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