Energy dissipative photoprotective mechanism of carotenoid spheroidene from the photoreaction center of purple bacteria Rhodobacter sphaeroides

Literature Information

Publication Date 2015-08-04
DOI 10.1039/C5CP03089G
Impact Factor 3.676
Authors

Sundaram Arulmozhiraja, Naoki Nakatani, Akira Nakayama


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Abstract

Carotenoid spheroidene (SPO) functions for photoprotection in the photosynthetic reaction centers (RCs) and effectively dissipates its triplet excitation energy. Sensitized cis-to-trans isomerization was proposed as a possible mechanism for a singlet–triplet energy crossing for the 15,15′-cis-SPO; however, it has been questioned recently. To understand the dissipative photoprotective mechanism of this important SPO and to overcome the existing controversies on this issue, we carried out a theoretical investigation using density functional theory on the possible triplet energy relaxation mechanism through the cis-to-trans isomerization. Together with the earlier experimental observations, the possible mechanism was discussed for the triplet energy relaxation of the 15,15′-cis-SPO. The result shows that complete cis-to-trans isomerization is not necessary. Twisting the C15–C15′ bond leads to singlet–triplet energy crossing at ϕ(14,15,15′,14′) = 77° with an energy 32.5 kJ mol−1 (7.7 kcal mol−1) higher than that of the T1 15,15′-cis minimum. Further exploration of the minimum-energy intersystem crossing (MEISC) point shows that triplet relaxation could occur at a less distorted structure (ϕ = 58.4°) with the energy height of 26.5 KJ mol−1 (6.3 kcal mol−1). Another important reaction coordinate to reach the MEISC point is the bond-length alternation. The model truncation effect, solvent effect, and spin–orbit coupling were also investigated. The singlet–triplet crossing was also investigated for the 13,14-cis stereoisomer and locked-13,14-cis-SPO. We also discussed the origin of the natural selection of the cis over trans isomer in the RC.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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