201. Exciton Origin of Color-Tuning in Ca2+-Binding Photosynthetic Bacteria
- Author
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Arvi Freiberg, Alexandra Lehtmets, Liina Kangur, Margus Rätsep, Zheng-Yu Wang-Otomo, and Kõu Timpmann
- Subjects
QH301-705.5 ,Exciton ,Light-Harvesting Protein Complexes ,spectral red-shift ,010402 general chemistry ,Photosynthesis ,01 natural sciences ,Purple bacteria ,Catalysis ,Article ,Ca2+-binding bacteria ,Inorganic Chemistry ,Absorbance ,chemistry.chemical_compound ,Pigment ,Algae ,Bacterial Proteins ,0103 physical sciences ,Physical and Theoretical Chemistry ,Biology (General) ,Molecular Biology ,QD1-999 ,Bacteriochlorophylls ,Spectroscopy ,molecular excitons ,photosynthesis ,010304 chemical physics ,biology ,Bacteria ,Organic Chemistry ,General Medicine ,biology.organism_classification ,light-harvesting ,0104 chemical sciences ,Computer Science Applications ,Chemistry ,chemistry ,Chemical physics ,visual_art ,visual_art.visual_art_medium ,Calcium ,Bacteriochlorophyll ,Photosynthetic bacteria - Abstract
Flexible color adaptation to available ecological niches is vital for the photosynthetic organisms to thrive. Hence, most purple bacteria living in the shade of green plants and algae apply bacteriochlorophyll a pigments to harvest near infra-red light around 850–875 nm. Exceptions are some Ca2+-containing species fit to utilize much redder quanta. The physical basis of such anomalous absorbance shift equivalent to ~5.5 kT at ambient temperature remains unsettled so far. Here, by applying several sophisticated spectroscopic techniques, we show that the Ca2+ ions bound to the structure of LH1 core light-harvesting pigment–protein complex significantly increase the couplings between the bacteriochlorophyll pigments. We thus establish the Ca-facilitated enhancement of exciton couplings as the main mechanism of the record spectral red-shift. The changes in specific interactions such as pigment–protein hydrogen bonding, although present, turned out to be secondary in this regard. Apart from solving the two-decade-old conundrum, these results complement the list of physical principles applicable for efficient spectral tuning of photo-sensitive molecular nano-systems, native or synthetic.
- Published
- 2021