This investigation was motivated by a desire to get a deeper insight into the mechanism of carotenoiod-to-bacteriochlorophyll (Car-to-BChl) energy transfer proceeding via the carotenoid S1 state. (Here, we call the 2Ag - and 1Bu + states “the S1 and S2 states” according to the notation presently accepted.) To systematically examine the effect of the conjugation length of carotenoid on the rate and efficiency of the Car(S1)-to-BChl(Qy) energy transfer, we performed the following experiments. (1) Subpicosecond time-resolved absorption spectroscopy was employed to measure the S1-state lifetimes of lycopene (number of conjugated CC bonds, n = 11), spheroidene (n = 10), and neurosporene (n = 9), both free in n-hexane and bound to the LH2 complexes from Rhodospirillum molischianum (Rs. molischianum), Rhodobactor sphaeroides (Rb. sphaeroides) 2.4.1, and Rb. sphaeroides G1C, respectively. The lifetime of each free (bound) carotenoid was determined to be 4.7(3.4) ps for lycopene, 9.3(1.7) ps for spheroidene, and 21.2(1.3) ps for neurosporene. It was found that the rate and the efficiency of the Car(S1)-to-BChl(Qy) energy transfer increase systematically when the number of conjugated CC bonds decreases. (2) High-sensitivity steady-state fluorescence spectroscopy was used to measure the spectra of dual emission from the S2 and S1 states for the above carotenoids dissolved in n-hexane. The fluorescence data, combined with the above kinetic data, allowed us to evaluate the magnitudes of the transition-dipole moments associated with the Car(S1) emission. It was found that the S1 emissions of the above carotenoids carry noticeably large oscillator strengths (transition-dipole moments). In the case of the LH2 complex from Rs. molischianum, whose structural information is now available, the time constant of the Car(S1)-to-BChl(Qy) energy transfer (18.6 ps), which was predicted on the basis of a Car(S2)-to-BChl(Qy) full Coulombic coupling scaled by the ratio of the S1 vs S2 transition dipole moments, was in good agreement with the one spectroscopically determined (12.3 ps). The oscillator strength associated with the Car(S1) emission was discussed in terms of the state mixing between the carotenoid S2 and S1 states.
Using a novel experimental approach based on near-infrared femtosecond absorption spectroscopy, we have determined the energy of the S 1 state of the carotenoid spheroidene. The energy of this state is 13 400 ( 90 cm -1 at both 293 and 186 K, showing that there is no temperature-induced shift of the S 1 level. A discrepancy of about 800 cm -1 between the S 1 energy determined here and that obtained from previous fluorescence and resonance Raman measurements is explained in terms of the different conformational species coexisting in the S 1 excited state. Measurements of kinetics in the near-infrared region revealed that at least three relaxation processes take place after excitation of spheroidene into its S 2 state. Ultrafast S 2 fS 1 internal conversion occurs within the first 300 fs, followed by vibrational cooling in the S 1 state, which occurs on a time scale of ∼700 fs. The S 1 lifetime is 8 ps at 293 K, in good agreement with previous measurements of the S 1 f S N transition. A somewhat longer S 1 lifetime of 9.5 ps is observed at 186 K.
We review the factors that control the efficiency of carotenoid-chlorophyll excitation transfer in photosynthetic light harvesting. For this we summarize first the recently developed theory that describes electronic couplings between carotenoids and chlorophylls and we outline in particular the influence of length of conjugated system and of symmetry breaking on the couplings. We focus hereby on the structurally solved lycopene-BChl system of LH 2 from Rhodospirillum molischianum and the peridinin-Chl a system of PCP from Amphidinium carterae. In addition, we review recent spectroscopic data for neurosporene, spheroidene and lycopene, three carotenoids with different lengths of conjugated systems. On the basis of the measured energies, emission lineshapes, solution and protein environment lifetimes for their 2A ( g ) (-) and 1B ( u ) (+) states as well as of the theoretically determined couplings, we conclude that the transfer efficiencies from the 2A ( g ) (-) state are controlled by the Car(2A ( g ) (-) )-BChl(Q(g)) electronic couplings and the 2A ( g ) (-) --> 1A ( g ) (-) internal conversion rates. We suggest that symmetry breaking and geometry rather than length of conjugated system dominate couplings involving the 2A ( g ) (-) state. Differences in transfer efficiencies from the 1B ( u ) (+) state in LH 2 and PCP are found to be dominated by the differences in spectral overlap. The role of the 1B ( u ) (+) state is likely to be influenced by a lower-lying (in longer polyenes), optically forbidden 1B ( u ) (-) state.
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