Dynamics of Energy Transfer from Lycopene to Bacteriochlorophyll in Genetically-Modified LH2 Complexes of Rhodobacter sphaeroides

Abstract

LH2 complexes from Rb. sphaeroides were modified genetically so that lycopene, with 11 saturated double bonds, replaced the native carotenoids which contain 10 saturated double bonds. Tuning the S1 level of the carotenoid in LH2 in this way affected the dynamics of energy transfer within LH2, which were investigated using both steady-state and time-resolved techniques. The S1 energy of lycopene in n-hexane was determined to be approximately 12 500 +/- 150 cm(-1), by direct measurement of the S1-S2 transient absorption spectrum using a femtosecond IR-probing technique, thus placing an upper limit on the S1 energy of lycopene in the LH2 complex. Fluorescence emission and excitation spectra demonstrated that energy can be transferred from lycopene to the bacteriochlorophyll molecules within this LH2 complex. The energy-transfer dynamics within the mutant complex were compared to wild-type LH2 from Rb. sphaeroides containing the carotenoid spheroidene and from Rs. molischianum, in which lycopene is the native carotenoid. The results show that the overall efficiency for Crt --> B850 energy transfer is approximately 80% in lyco-LH2 and approximately 95% in WT-LH2 of Rb. sphaeroides. The difference in overall Crt --> BChl transfer efficiency of lyco-LH2 and WT-LH2 mainly relates to the low efficiency of the Crt S(1) --> BChl pathway for complexes containing lycopene, which was 20% in lyco-LH2. These results show that in an LH2 complex where the Crt S1 energy is sufficiently high to provide efficient spectral overlap with both B800 and B850 Q(y) states, energy transfer via the Crt S1 state occurs to both pigments. However, the introduction of lycopene into the Rb. sphaeroides LH2 complex lowers the S1 level of the carotenoid sufficiently to prevent efficient transfer of energy to the B800 Q(y) state, leaving only the Crt S1 --> B850 channel, strongly suggesting that Crt S1 --> BChl energy transfer is controlled by the relative Crt S1 and BChl Q(y) energies.

Energetics and Dynamics of the Low-Lying Electronic States of Constrained Polyenes: Implications for Infinite Polyenes

“…For example, for the N = 11 polyene, lycopene (N = 11) and β-carotene (N = 11), the 2 1 Ag − lifetimes are 6.1, 4.0, and 8.1 ps, respectively. 98,99 …”

Ultrafast S1 and ICT state dynamics of a marine carotenoid probed by femtosecond one- and two-photon pump-probe spectroscopy

“…The S 1 -S n transient absorption shows a peak shift at early delay times. This has been explained by the vibrational relaxation in S 1 evidenced by a slow rise on the red side and a fast decay on the blue side of the main S 1 -S n transient absorption during vibrational relaxation [40,41]. A time constant of vibrational relaxation was determined to be 320720 fs by fitting to the kinetic traces.…”

Comparison of transient grating signals from spheroidene in an organic solvent and in pigment-protein complexes fromRhodobacter sphaeroides2.4.1

“…acidophila 10 050 are about 50%. [4][5][6]25,48 This difference is explained by the number of the energy-transfer channels in operation in the different cases. Namely, when the number of conjugation double bonds of the carotenoid is n Ն 11, only excitation energy transfer from S 2 to Q x takes place and the transfer rate from S 1 to Q y becomes very low, resulting in an overall low efficiency.…”