title: Orientation of the tyrosyl D, pheophytin anion, and semiquinone Q(A)(*)(-) radicals in photosystem II determined by high-field electron paramagnetic resonance.
abstract: The radical forms of two cofactors and an amino acid in the photosystem II (PS II) reaction center were studied by using high-field EPR both in frozen solution and in oriented multilayers. Their orientation with respect to the membrane was determined by using one-dimensionally oriented samples. The ring plane of the stable tyrosyl radical, Y(D)(*), makes an angle of 64 degrees +/- 5 degrees with the membrane plane, and the C-O direction is tilted by 72 degrees +/- 5 degrees in the plane of the radical compared to the membrane plane. The semiquinone, Q(A)(*)(-), generated by chemical reduction in samples lacking the non-heme iron, has its ring plane at an angle of 72 degrees +/- 5 degrees to the membrane plane, and the O-O axis is tilted by 21 degrees +/- 5 degrees in the plane of the quinone compared to the membrane plane. This orientation is similar to that of Q(A)(*)(-) in purple bacteria reaction centers except for the tilt angle which is slightly bigger. The pheophytin anion was generated by photoaccumulation under reducing conditions. Its ring plane is almost perpendicular to the membrane with an angle of 70 degrees +/- 5 degrees with respect to the membrane plane. This is very similar to the orientation of the pheophytin in purple bacteria reaction centers. The position of the g tensor with respect to the molecule is tentatively assigned for the anion radical on the basis of this comparison. In this work, the treatment of orientation data from EPR spectroscopy applied to one-dimensionally oriented multilayers is examined in detail, and improvements over previous approaches are given.
authors.affiliation: Section de Bioénergétique, Département de Biologie Cellulaire et Moléculaire, CNRS URA 2096, CEA Saclay, F-91191 Gif-sur-Yvette Cedex, France.
authors.forename: P
authors.initials: P
authors.lastname: Dorlet
authors.forename: A W
authors.initials: AW
authors.lastname: Rutherford
authors.forename: S
authors.initials: S
authors.lastname: Un
mesh_terms: D016227:Benzoquinones / Q000032:analysis* / Q000737:chemistry; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods; D045342:Light-Harvesting Protein Complexes; D010674:Pheophytins / Q000032:analysis* / Q000737:chemistry; D045322:Photosynthetic Reaction Center Complex Proteins / Q000737:chemistry*; D045332:Photosystem II Protein Complex; D010944:Plants / Q000737:chemistry; D010971:Plastoquinone / Q000031:analogs & derivatives* / Q000737:chemistry; D014443:Tyrosine / Q000031:analogs & derivatives* / Q000032:analysis* / Q000737:chemistry
chemical_list: D016227:Benzoquinones; D045342:Light-Harvesting Protein Complexes; D010674:Pheophytins; D045322:Photosynthetic Reaction Center Complex Proteins; D045332:Photosystem II Protein Complex; C100460:plastosemiquinone; C114979:tyrosyl radical YZ; C025232:semiquinone radicals; D014443:Tyrosine; D010971:Plastoquinone