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Electron spin polarization of the oxidized primary electron donor in reaction centers of photosynthetic purple bacteria

Abstract:
Fast time-resolved EPR spectroscopy is used to study electron spin polarization (ESP) in perdeuterated native, Fe2+-containing reaction centers (RCs) of photosynthetic purple bacteria. The spin-correlated radical pair(SCRP) model (previously used to simulate ESP observed in Fe-depleted RCs (Höre, P. J.; Hunter, D. A.; McKie, C. D.; Hoff, A. J. Chem. Phys. Lett. 1987, 737, 495) is extended to include the large anisotropy arising from the magnetic interactions between Fe2+ and the reduced primary electron-acceptor quinone (QA'~), which results in different quantization axes for the P+ and the (QA~Fe2+) spins. Using spectral simulations, it is shown that the ESP spectrum is solely due to the P+ part of the spin-correlated radical pair [P+(QA~Fe2+)], whereas the rapid decay of the spin-polarized signal is due to spin-lattice relaxation of the (QA~Fe2+) complex. The simulations are very sensitive to the relative orientation of the g matrices of P+ and (QA'~Fe2+). Using orientation II of the g matrix of the oxidized primary donor P+ (Klette, R.; Törring, J. T.; Plato, M.; Möbius, K.; Bönigk, B.; Lubitz, W. J. Phys. Chem. 1993, 97, 2015), the orientation of the g matrix of (QA~Fe2+) is assessed. Finally, it is shown that the ESP spectrum of perdeuterated native, Fe2+containing RCs of Rhodopseudomonas (Rps.) 'viridis is virtually identical to the spectrum obtained for perdeuterated native Rhodobacter (Rb.) sphaeroides, showing an AEA pattern (A denotes absorption and E emission). This result indicates that the magnetic axes of P+ and (QA'"Fe2+) have (nearly) the same directions relative to one another in both species. © 1996 American Chemical Society and Notes.
Publication status:
Published

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Publisher copy:
10.1021/jp952342a

Authors

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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Physical & Theoretical Chem
Role:
Author


Journal:
JOURNAL OF PHYSICAL CHEMISTRY More from this journal
Volume:
100
Issue:
6
Pages:
2430-2437
Publication date:
1996-02-08
DOI:
EISSN:
1541-5740
ISSN:
0022-3654


Language:
English
Pubs id:
pubs:45100
UUID:
uuid:09fb97a2-c184-42ed-9efb-5a060d8187df
Local pid:
pubs:45100
Source identifiers:
45100
Deposit date:
2012-12-19
ARK identifier:

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