ENHANCED RATES OF SUBPICOSECOND ENERGY-TRANSFER IN BLUE-SHIFTED LIGHT-HARVESTING LH2 MUTANTS OF RHODOBACTER-SPHAEROIDES

Energy transfer within various LH2 antenna complexes of the photosynth etic purple bacteria Rhodobacter sphaeroides and Rhodopseudomonas acid ophila has been studied at 77 K using tunable femtosecond and subpicos econd infrared pulses. The complexes examined include the wild-type B8 00-850 as well as three different specifically mutated complexes. The site-directed mutant strains were altered at positions 44 and 45 near the C-terminus of the cr-subunit, which introduces a spectral blue-shi ft of the 850-nm absorption band. In addition to a constant band at 80 0 nm, the mutations alpha Tyr44,Tyr45-->Phe,Tyr; -->Tyr,Phe; and -->Ph e,Leu have absorption peaks at 838, 838, and 826 nm, respectively. As the spectral overlap between the B800 and the variable bands increases , the rate of energy transfer as measured by the lifetime of the B800 excited state also increases from 2.4 +/- 0.2 to 1.8 +/- 0.2, 1.6 +/- 0.2, and 0.8 +/- 0.1 ps. This correlation between energy-transfer rate and spectral blue-shift of the B850 absorption band is in qualitative agreement with the trend predicted from Forster spectral overlap calc ulations, although the variation of the experimentally determined rate through the series of mutants is somewhat wider than what is predicte d by simulations. In addition to the decay time constants related to t he B800--> B850 energy transfer, the B800 excited state is seen to dec ay with a faster 150-500-fs component due to energy transfer between s pectrally inhomogeneous B800 molecules and possibly also vibrational r elaxation and cooling in the bacteriochlorophyll excited state.