Selective chemical shift assignment of bacteriochlorophyll a in uniformly [13C-15N]-labeled light-harvesting 1 complexes by solid-state NMR in ultrahigh magnetic field.
Magic-angle spinning (MAS) (13)C-(13)C correlation NMR spectroscopy was used to resolve the electronic ground state characteristics of the bacteriochlorophyll a (BChl a) cofactors in light-harvesting 1 (LH1) complexes of Rhodopseudomonas acidophila (strain 10050). The BChl a (13)C isotropic chemical shifts of the LH1 complexes are compared to the (13)C chemical shifts for BChl a dissolved in acetone-d(6) and to (13)C NMR data that has been obtained for the B800 and B850 BChl molecules in Rps. acidophila peripheral light-harvesting complexes (LH2). Since both complexes contain BChl a cofactors, we can address the chemical shift variability for specific carbon responses between the two types of antennae. The global shift pattern of the LH1 BChl's resembles the shift patterns of the LH2 alpha- and beta-B850 BChl's, while some carbon responses, in particular the C3 and C3(1), show significant deviations. A comparison with density functional theory (DFT) shift calculations provides insight into the BChl concomitant structural and electronic interactions in the ground state. The differences in the LH1 BChl observed chemical shifts relative to the (13)C responses of BChl a in solution cannot be explained by local side chain interactions, such as hydrogen bonding or nonplanarity of the C3 acetyl, but appear to be dominated by protein-induced macrocycle distortion. Such shaping of the macrocycle will contribute significantly to the red shift of the BChl Q(y) absorbance band in purple bacterial light-harvesting complexes.
Pandit
Anjali
A
Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands. apandit@few.vu.nl
Buda
Francesco
F
van Gammeren
Adriaan J
AJ
Ganapathy
Swapna
S
de Groot
Huub J M
HJ
D025541:Bacteriochlorophyll A / Q000737:chemistry*; D008027:Light; D045342:Light-Harvesting Protein Complexes / Q000737:chemistry*; D008280:Magnetics; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D011789:Quantum Theory; D012241:Rhodopseudomonas / Q000737:chemistry*
D025541:Bacteriochlorophyll A; D045342:Light-Harvesting Protein Complexes