title: Functional characteristics of spirilloxanthin and keto-bearing Analogues in light-harvesting LH2 complexes from Rhodobacter sphaeroides with a genetically modified carotenoid synthesis pathway.
abstract: Light-harvesting 2 (LH2) complexes from a genetically modified strain of the purple photosynthetic bacterium Rhodobacter (Rba.) sphaeroides were studied using static and ultrafast optical methods and resonance Raman spectroscopy. Carotenoid synthesis in the Rba. sphaeroides strain was engineered to redirect carotenoid production away from spheroidene into the spirilloxanthin synthesis pathway. The strain assembles LH2 antennas with substantial amounts of spirilloxanthin (total double-bond conjugation length N=13) if grown anaerobically and of keto-bearing long-chain analogs [2-ketoanhydrorhodovibrin (N=13), 2-ketospirilloxanthin (N=14) and 2,2'-diketospirilloxanthin (N=15)] if grown semi-aerobically (with ratios that depend on growth conditions). We present the photophysical, electronic, and vibrational properties of these carotenoids, both isolated in organic media and assembled within LH2 complexes. Measurements of excited-state energy transfer to the array of excitonically coupled bacteriochlorophyll a molecules (B850) show that the mean lifetime of the first singlet excited state (S1) of the long-chain (N≥13) carotenoids does not change appreciably between organic media and the protein environment. In each case, the S1 state appears to lie lower in energy than that of B850. The energy-transfer yield is ~0.4 in LH2 (from the strain grown aerobically or semi-aerobically), which is less than half that achieved for LH2 that contains short-chain (N≤11) analogues. Collectively, the results suggest that the S1 excited state of the long-chain (N≥13) carotenoids participates little if at all in carotenoid-to-BChl a energy transfer, which occurs predominantly via the carotenoid S2 excited state in these antennas.
authors: Photosynthetic Antenna Research Center, Washington University, St. Louis, MO 63130, USA. Electronic address: niedzwiedzki@wustl.edu.
authors: Dariusz M
authors: DM
authors: Niedzwiedzki
authors: Department of Chemistry, Washington University, St. Louis, MO 63130, USA.
authors: Preston L
authors: PL
authors: Dilbeck
authors: Department of Chemistry, University of California Riverside, Riverside, CA 92521, USA.
authors: Qun
authors: Q
authors: Tang
authors: Department of Molecular Biology and Biotechnology, University of Sheffield, Sheffield S10 2TN, UK.
authors: David J
authors: DJ
authors: Mothersole
authors: Department of Molecular Biology and Biotechnology, University of Sheffield, Sheffield S10 2TN, UK.
authors: Elizabeth C
authors: EC
authors: Martin
authors: Department of Chemistry, University of California Riverside, Riverside, CA 92521, USA.
authors: David F
authors: DF
authors: Bocian
authors: Department of Chemistry, Washington University, St. Louis, MO 63130, USA.
authors: Dewey
authors: D
authors: Holten
authors: Department of Molecular Biology and Biotechnology, University of Sheffield, Sheffield S10 2TN, UK.
authors: C Neil
authors: CN
authors: Hunter
mesh_terms: D025541:Bacteriochlorophyll A / Q000378:metabolism*; D053898:Biosynthetic Pathways; D002338:Carotenoids / Q000378:metabolism*; D007700:Kinetics; D045342:Light-Harvesting Protein Complexes / Q000378:metabolism*; D010788:Photosynthesis; D012242:Rhodobacter sphaeroides / Q000378:metabolism*; D013050:Spectrometry, Fluorescence; D013059:Spectrum Analysis, Raman; D024341:Xanthophylls / Q000737:chemistry / Q000378:metabolism
chemical_list: D025541:Bacteriochlorophyll A; D045342:Light-Harvesting Protein Complexes; D024341:Xanthophylls; D002338:Carotenoids; C055255:spirilloxanthin
keywords: Carotenoid; Diketospirilloxanthin; Energy transfer; Keto-carotenoid; LH2; Spirilloxanthin