Spectroscopic evidence for triplet excitation energy transfer among carotenoids in the LH2 complex from photosynthetic bacterium Rhodopseudomonas palustris  

作　　者：FENG Juan, WANG Qian, ZHANG Xujia, HUANG Youguo, Al Xicheng, ZHANG Xingkang & ZHANG JianpingState Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China National Laboratory of Biomacromolecules, Institute of Biophysics, Chinese Academy of Sciences, Beijing 100101, China 

出　　处：《Science China Chemistry》2004年第1期80-90,共11页中国科学（化学英文版）

基　　金：This work was supported by the National Natural Science Foundation of China(Grant Nos.20273077 and 39890390);the State Key Basic Research and Development Plan(Grant No.G1998010100).

摘　　要：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 (Nc=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 Tn04T1 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 Tn04 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 ?s (aerobic) and 1.36 ?s (anaerobic), is smaller than that of a longer-conjugated Car, i.e. 2.12 us (aerobic) and 3.75 ?s (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.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 (77 K). Broad and asymmetric Tn←T1 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 (NC=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 Tn←T1 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 Tn←T1 absorption of Cars with NC=C=11 and NC=C=13, respectively. Surprisingly, the decay time constant of a shorter-con- jugated Car, I.e. 0.72 μs (aerobic) and 1.36 μs (anaerobic), is smaller than that of a longer-con- jugated Car, I.e. 2.12 μs (aerobic) and 3.75 μs (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.

关 键 词：PURPLE PHOTOSYNTHETIC bacteria  carotenoid  excited-state  TIME-RESOLVED spectroscopy. 

分 类 号：O657.3[理学—分析化学]