CAROTENOID-TO-BACTERIOCHLOROPHYLL SINGLET ENERGY TRANSFER IN CAROTENOID-INCORPORATED B850 LIGHT-HARVESTING COMPLEXES OF Rhodobacter sphaeroides R-26.1
Corresponding Author
Harry A. Frank
Department of Chemistry, University of Connecticut, Storrs, CT06269–3060, USA
*To whom correspondence should be addressed.Search for more papers by this authorRoya Farhoosh
Department of Chemistry, University of Connecticut, Storrs, CT06269–3060, USA
Search for more papers by this authorMila L. Aldema
Department of Chemistry, University of Connecticut, Storrs, CT06269–3060, USA
Search for more papers by this authorBeverly DeCoster
Department of Chemistry, Bowdoin College, Brunswick, ME 04011, USA
Search for more papers by this authorRonald L. Christensen
Department of Chemistry, Bowdoin College, Brunswick, ME 04011, USA
Search for more papers by this authorRonald Gebhard
Department of Chemistry, Gorlaeus Laboratories, Leiden University, 2300 RA Leiden, The Netherlands
Search for more papers by this authorJohan Lugtenburg
Department of Chemistry, Gorlaeus Laboratories, Leiden University, 2300 RA Leiden, The Netherlands
Search for more papers by this authorCorresponding Author
Harry A. Frank
Department of Chemistry, University of Connecticut, Storrs, CT06269–3060, USA
*To whom correspondence should be addressed.Search for more papers by this authorRoya Farhoosh
Department of Chemistry, University of Connecticut, Storrs, CT06269–3060, USA
Search for more papers by this authorMila L. Aldema
Department of Chemistry, University of Connecticut, Storrs, CT06269–3060, USA
Search for more papers by this authorBeverly DeCoster
Department of Chemistry, Bowdoin College, Brunswick, ME 04011, USA
Search for more papers by this authorRonald L. Christensen
Department of Chemistry, Bowdoin College, Brunswick, ME 04011, USA
Search for more papers by this authorRonald Gebhard
Department of Chemistry, Gorlaeus Laboratories, Leiden University, 2300 RA Leiden, The Netherlands
Search for more papers by this authorJohan Lugtenburg
Department of Chemistry, Gorlaeus Laboratories, Leiden University, 2300 RA Leiden, The Netherlands
Search for more papers by this authorAbstract
Four carotenoids, 3,4,7,8-tetrahydrospheroidene, 3,4,5,6-tetrahydrospheroidene, 3,4-dihydrospheroidene and spheroidene, have been incorporated into the B850 light-harvesting complex of the carotenoidless mutant, photosynthetic bacterium, Rhodobacter sphaeroides R-26.1. The extent of π-electron conjugation in these molecules increases from 7 to 10 carbon-carbon double bonds. Carotenoid-to-bacteriochlorophyll singlet state energy transfer efficiencies were measured using steady-state fluorescence excitation spectroscopy to be 54 ± 2%, 66 ± 4%, 71 ± 6% and 56 ± 3% for the carotenoid series. These results are discussed with respect to the position of the energy levels and the magnitude of spectral overlap between the S, (2′AJ state emission from the isolated carotenoids and the bacteriochlorophyll absorption of the native complex. These studies provide a systematic approach to exploring the effect of excited state energies, spectral overlap and excited state lifetimes on the efficiencies of carotenoid-to-bacteriochlorophyll singlet energy transfer in photosynthetic systems.
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