Pulsed ENDOR at 95 GHz on the primary acceptor ubisemiquinone Q in photosynthetic bacterial reaction centers and related model systems

Rohrer, M., MacMillan, F., Prisner, T.F., Gardiner, A.T., Möbius, K. and Lubitz, W. (1998) Pulsed ENDOR at 95 GHz on the primary acceptor ubisemiquinone Q in photosynthetic bacterial reaction centers and related model systems. The Journal of Physical Chemistry B, 102 (23). pp. 4648-4657. ISSN 1089-5647

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Davies-type pulsed H electron nuclear double resonance (ENDOR) measurements were performed at a magnetic field of 3.4 T and a microwave (MW) frequency of 95 GHz (W-band). By taking advantage of the increased electron Zeeman interaction at high field, the small g-anisotropy of the semiquinone anion radicals could be resolved in frozen solutions. Hence, the W-band ENDOR spectra could be taken at the well-separated canonical peaks of the powder electron paramagnetic resonance (EPR) spectra, thereby becoming highly orientation-selective with respect to the relative orientation of the radicals to the external magnetic field. The measurements were performed on various randomly oriented semiquinone anion radicals in frozen alcoholic solution and on the primary ubiquinone anion radical, Q, frozen photosynthetic bacterial reaction centers (RCs) of Rhodobacter sphaeroides in which the Fe was replaced by Zn (ZnRC). A simulation program was used to obtain magnitudes and orientations of the hyperfine tensors. The W-band ENDOR spectra of the immobilized radicals show not only hyperfine couplings (HFC) of local protons of the semiquinones, but also those of protons from the environment. These are, for example, involved in hydrogen bonds between the amino acid surrounding and the quinone carbonyl groups. For Q in ZnRCs, a particularly large H-bond HFC was obtained from which direction and distance of the H-bond could be estimated. These data were compared with those measured for the respective ubisemiquinone radical, UQ-10, in protonated and deuterated 2-propanol, where two H-bonds of comparable strength but different directions could be detected. Comparison of H ENDOR spectra of the 2,3,5,6-tetra-methyl-1,4-benzoquinone anion radical in frozen solution, performed both at W-band and at X-band frequency, demonstrated the limitations of achieving orientation selected ENDOR spectra from X-band experiments on systems with small g-anisotropy.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
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Depositing User: Pure Connector
Date Deposited: 21 Jan 2015 11:48
Last Modified: 04 Jun 2020 23:44
URI: https://ueaeprints.uea.ac.uk/id/eprint/51857
DOI: 10.1021/jp9805104

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