Abstract—Illumination of purple phototrophic bacteria in the carotenoid absorption band of light harvesting complexes often leads to low energy efficiency of absorbed light. This is due to singlet–triplet fission of carotenoid excitation. In the present study, the nature of this process was explored with a phototrophic bacterium Thermochromatium tepidum as an example. It was demonstrated by time-resolved EPR spectroscopy and magnetic field modulation of the fluorescence yield that the concept of intramolecular excitation fission that was developed in several publications was not confirmed experimentally. Evidence of the intermolecular character of excitation fission that involves two carotenoid molecules of the light-harvesting pigment–protein complexes, LH1-RC and LH2, has been obtained. The advantages of intermolecular excitation fission for application in photovoltaic solar energy converters are discussed.
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REFERENCES
B. Ke, Photosynthesis. Photobiochemistry and Photobiophysics (Kluwer, Dordrecht, 2001).
H. Hashimoto, Y. Sugai, C. Uragami, et al., J. Photochem. Photobiol. C 25, 46 (2015).
R. J. Cogdell, A. T. Gardiner, A. W. Roszak, et al., Photosynth. Res. 81, 207 (2004).
R. J. Cogdell and H. A. Frank, Biochim. Biophys. Acta 895, 63 (1987).
A. A. Krasnovsky, Biofizika 22 (5), 927 (1977).
A. A. Krasnovsky, Photochem. Photobiol. 29, 29 (1979).
H. A. Frank and R. J. Cogdell, in Carotenoids in Photosynthesis (Springer, 1993), Chap. 8, pp. 252–326.
T. Polivka and V. Sundstrom, Chem. Rev. 104, 2021 (2004).
D. Niedzwiedzki, J. F. Koscielecki, H. Cong, et al., J. Phys. Chem B. 111, 5984 (2007).
C. C. Gradinaru, J. T. M. Kennis, E. Papagiannakis, et al., Proc. Natl. Acad. Sci. U. S. A. 98 (5), 2364 (2001).
E. Papagiannakis, J. T. M. Kennis, I. H. M. van Stokkum, et al., Proc. Natl. Acad Sci. U. S. A. 99, 6017 (2002).
M. B. Smith and J. Michl, Chem. Rev. 110, 6891 (2010).
M. B. Smith and J. Michl, Annu. Rev. Phys. Chem. 64, 361 (2013).
M. C. Hanna and A. J. Nozik, J. Appl. Phys. 100 (7), 074510-1 (2006).
I. B. Klenina, Z. K. Makhneva, A. A. Moskalenko, et al., Dokl. Biochem. Biophys. 441, 290 (2011).
J. Yu, L.-M. Fu, L.-J. Yu, et al., J. Am. Chem. Soc. 139, 15984 (2017).
I. B. Klenina, A. A. Gryaznov, Z. K. Makhneva, et al., Dokl. Biochem. Biophys. 485 (2), 135 (2019).
I. B. Klenina, Z. K. Makhneva, A. A. Moskalenko, et al., Biophysics (Moscow) 58 (1), 43 (2013).
A. Ashikhmin, Z. Makhneva, and A. Moskalenko, Photosynth. Res. 119, 291(2014).
A. Angerhofer, F. Bornhauser, A. Gall, et al., Chem. Phys. 194, 259 (1995).
K. Bhattacharyya, D. Dey, and A. Datta, J. Phys. Chem. C 123, 4749 (2019)
M. Tuan Trinh, Yu Zhong, Qishui Chen, et al., J. Phys. Chem. C 119, 1312 (2015).
G. McDermott, S. M. Prince, A. A. Freer, et al., Nature 374, 517 (1995).
V. Cherezov, J. Clogston, M. Z. Papiz, et al., J. Mol. Biol. 357, 1605 (2006).
P. Tavan and K. Shulten, Phys. Rev. B 36, 4337 (1987).
I. B. Klenina, Z. K. Makhneva, A. A. Moskalenko, et al., Biochemistry (Moscow) 79 (3), 235 (2014)
R. E. Merrifield, Pure Appl. Chem. 27 (3), 481 (1971).
C. E. Swenberg and N. E. Geacintov, in Organic Molecular Photophysics, Ed. by J. B. Birks (Wiley, London, 1973), pp. 489–564.
D. M. Niedzwiedzki, M. Kobayashi, and R. E. Blankenship, Photosynth. Res. 107, 177 (2011).
H. Rademaker, A. J. Hoff, R. van Grondelle, et al., Biochim. Biophys. Acta 592, 240 (1980).
Funding
The work on the isolation of pigments from Th. tepidum and their analysis (see “Materials and methods”) was carried out with partial financial support from The Russian Foundation for Basic Research, project no. 17-04-00929_a; the other results were obtained within the framework of the State Assignment, no. AAAAA-A17-117030110140-5.
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Abbreviations: BChl, bacteriochlorophyll; Car, carotenoid; EPR, electron paramagnetic resonance; SZF, splitting in zero field.
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Gryaznov, A.A., Klenina, I.B., Makhneva, Z.K. et al. The Singlet–Triplet Fission of Carotenoid Excitation in Light-Harvesting Complexes from Thermochromatium tepidum. BIOPHYSICS 64, 847–852 (2019). https://doi.org/10.1134/S0006350919060083
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DOI: https://doi.org/10.1134/S0006350919060083