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Biochemistry (Moscow). Papers in Press. Published on May 6, 2019 as Manuscript BM19-039.

Algorithm for Extracting Weak Bands Kinetics from the Transient Absorption Spectra of the Rhodobacter sphaeroides Reaction Center

R. A. Khatypov1,a*, A. M. Khristin1, L. G. Vasilyeva1, and V. A. Shuvalov1,2

1Institute of Basic Biological Problems, Pushchino Scientific Center for Biological Research, Russian Academy of Sciences, 142290 Pushchino, Moscow Region, Russia

2Semenov Institute of Chemical Physics, Russian Academy of Sciences, 119991 Moscow, Russia

*To whom correspondence should be addressed.

Received February 15, 2019; Revised March 21, 2019; Accepted March 21, 2019
An algorithm to extract kinetics of the ion radical bands from the strong absorption background in the transient absorption spectra of the Rhodobacter sphaeroides reaction centers upon femtosecond excitation of the primary electron donor is suggested. The rising kinetics of the transient absorption band at 1020 nm and the bleaching kinetics of the 545-nm band constructed using the proposed method are adequately fitted by the kinetic equations for sequential electron transfer from the excited primary donor to the BA (monomeric bacteriochlorophyll) molecule, and then to the HA (bacteriopheophytin serving as an electron acceptor) molecule with the rate constants of 3.5 ± 0.2 and 0.8 ± 0.1 ps, respectively. The kinetics of the bacteriochlorophyll absorption band at 600 nm shows both the ultrafast bleaching of the P870 dimer and slower bleaching of the BA monomer due to its transition to the anion radical. The plotted kinetics of the ion radical bands is in agreement with the concentration profiles of the charge-separated states produced by the global target analysis of experimental data using the model of sequential electron transfer in the reaction centers.
KEY WORDS: femtosecond spectroscopy, bacterial reaction centers, electron transfer