Participation of spirilloxanthin in excitation energy transfer in reaction centers from purple bacteria Rhodospirillum rubrum.

The femtosecond dynamics of energy transfer from light-excited spirilloxanthin (Spx) to bacteriochlorophyll (BChl) a in the reaction centers (RCs) of purple photosynthetic bacteria Rhodospirillum rubrum was studied. According to crio-electron microscopy data, Spx is located near accessory BChl a in the B-branch of cofactors. Spx was excited by 25 fs laser pulses at 490 nm, and difference absorption spectra were recorded in the range 500-700 nm. To reveal the dynamics of individual states, we applied global analysis using different kinetic schemes. We found that the energy transfer Spx → BChl a occurs during 0.22 ps with a low efficiency of ~ 31%. The monomeric BChl a acts as the primary energy acceptor, presumably in the B-branch of cofactors. Then the energy is transferred to the BChl a dimer within 0.25 ps and subsequently used for charge separation. As a result of internal conversion in Spx, the majority (~ 69%) of the excitation energy transfers in 0.2 ps from the singlet-excited state S₂ to the states S₁ and S*, which, in turn, relax to the ground state in 1.5 and 9 ps, ​​respectively. We showed that the S₁ and S* states in Spx are not involved in energy transfer to BChl a. The found parameters of energy transfer Spx→BChl a turned out to be close to those in the light-harvesting complexes LH1 of Rhodospirillum rubrum. The sequence of events in Spx after its excitation is discussed.