Аннотация:Measurement of photosensitized luminescence of singlet oxygen has been applied to studies of singlet oxygen generation
and quenching by C40
carotenoids (neurosporene, lycopene, rhodopin, and spirilloxanthin) with long chain of conjugated
double bonds (CDB) using hexafluorobenzene as a solvent. It has been found that neurosporene, lycopene, and rhodopin
are capable of the low efficient singlet oxygen generation in aerated solutions upon photoexcitation in the spectral region of
their main absorption maxima. The quantum yield of this process was estimated to be (1.5–3.0) × 10−
2. This value is near
the singlet oxygen yields in solutions of ζ-carotene (7 CDB) and phytoene (3 CDB) and many-fold smaller than in solutions
of phytofluene (5 CDB) (Ashikhmin et al. Biochemistry (Mosc) 85:773–780, https:// doi. org/ 10. 1134/ S0006 29792 00700 56,
2020, Biochemistry (Mosc) 87:1169–1178, 2022, https:// doi. org/ 10. 1134/ S0006 29792 21001 082022). Photogeneration of
singlet oxygen was not observed in spirilloxanthin solutions. A correlation was found between the singlet oxygen yields and
the quantum yields and lifetimes of the fluorescence of the carotenoid molecules. All carotenoids were shown to be strong
physical quenchers of singlet oxygen. The rate constants of 1O2 quenching by the carotenoids with long chain of CDB (9–13)
were close to the rate constant of the diffusion-limited reactions ≈1010 M−
1 s−
1, being many-fold greater than the rate constants
of 1O2 quenching by the carotenoids with the short chain of CDB (3–7) phytoene, phytofluene, and ζ-carotene studied in prior papers of our group (Ashikhmin et al. 2020, 2022). To our knowledge, the quenching rate constants of rhodopin and
spirilloxanthin have been obtained in this paper for the first time. The mechanisms of 1O2 photogeneration by carotenoids in solution and in the LH2 complexes of photosynthetic cells, as well as the efficiencies of their protective action are discussed.
Keywords Neurosporene · Rhodopin · Lycopene · Spirilloxanthin · Singlet oxygen ---Photosensitization · Quenching · Light harvesting
complex