title: Stereoselectivity of pigment exchange with 13(2)-hydroxylated tetrapyrroles in reaction centers of Rhodobacter sphaeroides R26.
abstract: Bacteriochlorophyll a and bacteriopheophytin a carry a stereochemically labile asymmetric carbon at position C13(2). The steric requirements of photosynthetic reaction centers from Rhodobacter sphaeroides R26 have been probed by exchange experiments with the respective epimeric 13(2)-hydroxylated pigments, in which epimerisation is blocked. (13(2)S)-13(2)-Hydroxy-bacteriochlorophyll a is accepted at both monomeric binding sites, BA,B, (13(2)S)-13(2)-hydroxy-bacteriopheophytin a exclusively at the inactive site HB. The orientation of the 13(2)-COOCH3 substituents in these pigments is the same as in the native (13(2)R)-bacteriochlorophylls and (13(2)R)-bacteriopheophytins. In no cases are the unnaturally configured 13(2)-hydroxylated (13(2)R)-epimers accepted, even if a large excess (> 95%) is offered. It is concluded that the three binding sites always require the 13(2)-COOCH3 group on the opposite side of the macrocycle (down) than the 17-propionic ester side chain (up).
authors.affiliation: Botanisches Institut, Universität München, Germany.
authors.forename: K F
authors.initials: KF
authors.lastname: Storch
authors.forename: E
authors.initials: E
authors.lastname: Cmiel
authors.forename: W
authors.initials: W
authors.lastname: Schäfer
authors.forename: H
authors.initials: H
authors.lastname: Scheer
mesh_terms: D002942:Circular Dichroism; D006900:Hydroxylation; D045342:Light-Harvesting Protein Complexes; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D045322:Photosynthetic Reaction Center Complex Proteins / Q000737:chemistry / Q000378:metabolism*; D010860:Pigments, Biological / Q000138:chemical synthesis / Q000737:chemistry* / Q000378:metabolism*; D011758:Pyrroles / Q000737:chemistry / Q000378:metabolism*; D012242:Rhodobacter sphaeroides / Q000502:physiology*; D045725:Tetrapyrroles
chemical_list: D045342:Light-Harvesting Protein Complexes; D045322:Photosynthetic Reaction Center Complex Proteins; D010860:Pigments, Biological; D011758:Pyrroles; D045725:Tetrapyrroles