Spectroscopic evidence for triplet excitation energy transfer among carotenoids in the LH2 complex from photosynthetic bacterium <Emphasis Type="Italic">Rhodopseudomonas palustris</Emphasis>

The LH2 complex from Rhodopsudomonas (Rps.) palustris is unique in the heterogeneous carotenoid compositions. The dynamics of triplet excited state Carotenoids (³Car* has been investigated by means of sub-microsecond time-resolved absorption spectroscopy both at physiological temperature (295 K) and at cryogenic temperature (77K). Broad and asymmetric T _n ←T ₁ transient absorption was observed at room temperature following the photo-excitation of Car at 532 nm, which suggests the contribution from various carotenoid compositions having different numbers of conjugated C=C double bonds (N_c=c). The triplet absorption bands of different carotenoids, which superimposed at room temperature, could be clearly distinguished upon decreasing the temperature down to 77 K. At room temperature the shorter-wavelength side of the main T_n04T₁ absorption band decayed rapidly to reach a spectral equilibration with a characteristic time constant of ∽1 μs, the same spectral dynamics, however, was not observed at 77 K. The aforementioned spectral dynamics can be explained in terms of the triplet-excitation transfer among heterogeneous carotenoid compositions. Global spectral analysis was applied to the time-resolved spectra at room temperature, which revealed two spectral components peaked at 545 and 565 nm, and assignable to the T_n04 T₁ absorption of Cars with Nc=c=11 and Nc=c=13, respectively. Surprisingly, the decay time constant of a shorter-conjugated Car, i.e. 0.72 ώs (aerobic) and 1.36 ώs (anaerobic), is smaller than that of a longer-conjugated Car, i.e. 2.12 us (aerobic) and 3.75 ώs (anaerobic), which is contradictory to the general rule of carotenoids and relative polyenes. The results are explained in terms of triplet-excitation transfer among different types of Cars. It is postulated that two Cars with different conjugation lengths coexist in an α, β-subunit in the LH2 complex.