Title
Circular dichroism and resonance Raman spectroscopies of bacteriochlorophyll b-containing LH1-RC complexes
Author
Y. Kimura, T. Yamashita, R. Seto, M. Imanishi, M. Honda, S. Nakagawa, Y. Saga, S. Takenaka, L.-J. Yu, M. T. Madigan & Z.-Y. Wang-Otomo
Year
2021
Journal
Photosynthesis Research (2021)
Abstract
The core light-harvesting complexes (LH1) in bacteriochlorophyll (BChl) b-containing purple phototrophic bacteria are characterized by a near-infrared absorption maximum around 1010 nm. The determinative cause for this ultra-redshift remains unclear. Here, we present results of circular dichroism (CD) and resonance Raman measurements on the purified LH1 complexes in a reaction center-associated form from a mesophilic and a thermophilic Blastochloris species. Both the LH1 complexes displayed purely positive CD signals for their Qy transitions, in contrast to those of BChl a-containing LH1 complexes. This may reflect differences in the conjugation system of the bacteriochlorin between BChl b and BChl a and/or the differences in the pigment organization between the BChl b- and BChl a-containing LH1 complexes. Resonance Raman spectroscopy revealed remarkably large redshifts of the Raman bands for the BChl b C3-acetyl group, indicating unusually strong hydrogen bonds formed with LH1 polypeptides, results that were verified by a published structure. A linear correlation was found between the redshift of the Raman band for the BChl C3-acetyl group and the change in LH1-Qy transition for all native BChl a- and BChl b-containing LH1 complexes examined. The strong hydrogen bonding and π–π interactions between BChl b and nearby aromatic residues in the LH1 polypeptides, along with the CD results, provide crucial insights into the spectral and structural origins for the ultra-redshift of the long-wavelength absorption maximum of BChl b-containing phototrophs.
Instrument
J-1500, NRS-7100
Keywords
Light-harvesting, Reaction center, Hydrogen bond π–π interaction, Redshift/ultra-redshift