title: Femtosecond stage of electron transfer in reaction centers of the triple mutant SL178K/GM203D/LM214H of Rhodobacter sphaeroides.
abstract: Coherent processes in an initial phase of charge transfer in reaction centers (RCs) of the triple mutant S(L178)K/G(M203)D/L(M214)H of Rhodobacter sphaeroides were investigated by difference (light - dark) absorption spectroscopy with 18 fsec time resolution. Electron transfer in the B cofactor branch is activated in this mutant, while the A-branch electron transfer is slowed in comparison with native RCs of Rba. sphaeroides. A bulk of absorption difference spectra was analyzed in the 940-1060 nm range (stimulated emission of excited bacteriochlorophyll dimer P* and absorption of bacteriochlorophyll anions B(A)(-) and beta(-), where beta is a bacteriochlorophyll substituting the native bacteriopheophytin H(A)) and in the 735-775 nm range (bleaching of the absorption band of the bacteriopheophytin H(B) in the B-branch) in the -0.1 to 4 psec range of delays with respect to the moment of photoexcitation of P at 870 nm. Spectra were measured at 293 and 90 K. The kinetics of P* stimulated emission at 940 nm shows its decay with a time constant of approximately 14 psec at 90 K and approximately 18 psec at 293 K, which is accompanied by oscillations with a frequency of approximately 150 cm(-1). A weak absorption band is found at 1018 nm that is formed approximately 100 fsec after excitation of P and reflects the electron transfer from P* to beta and/or B(A) with accumulation of the P(+)beta(-) and/or P(+)B(A)(-) states. The kinetics of DeltaA at 1018 nm contains the oscillations at approximately 150 cm(-1) and distinct low-frequency oscillations at 20-100 cm(-1); also, the amplitude of the oscillations at 150 cm(-1) is much smaller at 293 than at 90 K. The oscillations in the kinetics of the 1018 nm band do not contain a 32 cm(-1) mode that is characteristic for native Rba. sphaeroides RCs having water molecule HOH55 in their structure. The DeltaA kinetics at 751 nm reflects the electron transfer to H(B) with formation of the P(+)H(B)(-) state. The oscillatory part of this kinetics has the form of a single peak with a maximum at ~50 fsec completely decaying at ~200 fsec, which might reflect a reversible electron transfer to the B-branch. The results are analyzed in terms of coherent nuclear wave packet motion induced in the P* excited state by femtosecond light pulses, of an influence of the incorporated mutations on the mutual position of the energy levels of charge separated states, and of the role of water HOH55 in the dynamics of the initial electron transfer.
authors.affiliation: Department of Photobiophysics, Belozersky Institute of Physico-Chemical Biology, Lomonosov Moscow State University, Moscow, 119991, Russia. yakov@genebee.msu.su
authors.forename: A G
authors.initials: AG
authors.lastname: Yakovlev
authors.forename: T A
authors.initials: TA
authors.lastname: Shkuropatova
authors.forename: V A
authors.initials: VA
authors.lastname: Shkuropatova
authors.forename: V A
authors.initials: VA
authors.lastname: Shuvalov
mesh_terms: D019943:Amino Acid Substitution; D001426:Bacterial Proteins / Q000737:chemistry* / Q000235:genetics; D001429:Bacteriochlorophylls / Q000737:chemistry; D004579:Electron Transport; D007700:Kinetics; D009154:Mutation; D045322:Photosynthetic Reaction Center Complex Proteins / Q000737:chemistry* / Q000235:genetics; D012242:Rhodobacter sphaeroides / Q000201:enzymology*; D013997:Time Factors
chemical_list: D001426:Bacterial Proteins; D001429:Bacteriochlorophylls; D045322:Photosynthetic Reaction Center Complex Proteins