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The electronic structure of the primary electron donor of reaction centers of purple bacteria at atomic resolution as observed by photo-CIDNP ¹³C NMR

Author:
Daviso, Eugenio, Prakash, Shipra, Alia, A., Gast, Peter, Neugebauer, Johannes, Jeschke, Gunnar, Matysik, Jörg
Source:
Proceedings of the National Academy of Sciences of the United States of America 2009 v.106 no.52 pp. 22281-22286
ISSN:
0027-8424
Subject:
Rhodobacter sphaeroides, absorption, cations, histidine, mutants, nitrogen, nuclear magnetic resonance spectroscopy
Abstract:
Composed of the two bacteriochlorophyll cofactors, PL and PM, the special pair functions as the primary electron donor in bacterial reaction centers of purple bacteria of Rhodobacter sphaeroides. Under light absorption, an electron is transferred to a bacteriopheophytin and a radical pair is produced. The occurrence of the radical pair is linked to the production of enhanced nuclear polarization called photochemically induced dynamic nuclear polarization (photo-CIDNP). This effect can be used to study the electronic structure of the special pair at atomic resolution by detection of the strongly enhanced nuclear polarization with laser-flash photo-CIDNP magic-angle spinning NMR on the carotenoid-less mutant R26. In the electronic ground state, PL is strongly disturbed, carrying a slightly negative charge. In the radical cation state, the ratio of total electron spin densities between PL and PM is 2:1, although it is 2.5:1 for the pyrrole carbons, 2.2:1 for all porphyrinic carbons, and 4:1 for the pyrrole nitrogen. It is shown that the symmetry break between the electronic structures in the electronic ground state and in the radical cation state is an intrinsic property of the special pair supermolecule, which is particularly attributable to a modification of the structure of PL. The significant difference in electron density distribution between the ground and radical cation states is explained by an electric polarization effect of the nearby histidine.
Agid:
2367210