title: Origin of optical activity in the purple bacterial photoreaction center.
abstract: The photoreaction center (RC) of purple bacteria contains four bacteriochlorophyll (Bch) and two bacteriopheophytin (Bph) molecules as prosthetic groups. Their optical activity, as measured by circular dichroism (CD) spectroscopy, is largely increased in situ as compared to organic solutions. The all-exciton hypothesis posits that this enhanced optical activity is entirely due to excitonic interactions between the electronic transitions of all six bacteriochlorin molecules. Using the simple exciton theory, this model predicts that the near-infrared CD spectra should be conservative. The fact that they are not, whether the special pair of Bch (SP) that constitutes the primary electron donor is reduced or oxidized, has been explained by hyperchromic effects. The present work tests this hypothesis by successively eliminating the absorption and, therefore, the optical activity of the Bphs and of the non-special-pair (non-SP) Bchs. This was accomplished by trapping these pigments in their reduced state. RC preparations with the four non-SP bacteriochlorins trapped in their reduced state and, therefore, with an intact SP displayed conservative CD spectra. RC preparations with only the electronic transitions of SP and of one non-SP Bch also showed conservative CD spectra. These conservative CD spectra and their corresponding absorption spectra were simulated using simple exciton theory without assuming hyperchromic effects. Bleaching half of the 755-nm absorption band by phototrapping one of the two Bph molecules led to the complete disappearnce of the corresponding CD band. This cannot be explained by the all-exciton hypothesis. These results suggest that the optical activity of the SP alone, or with one non-SP Bch, is due to excitonic interactions.(ABSTRACT TRUNCATED AT 250 WORDS)
authors.affiliation: Département de Biochimie, Université de Montréal, Québec, Canada.
authors.forename: T
authors.initials: T
authors.lastname: Mar
authors.forename: G
authors.initials: G
authors.lastname: Gingras
mesh_terms: D001205:Ascorbic Acid; D001429:Bacteriochlorophylls / Q000737:chemistry / Q000528:radiation effects; D002841:Chromatiaceae / Q000737:chemistry / Q000528:radiation effects; D002942:Circular Dichroism; D004227:Dithionite; D004579:Electron Transport; D045342:Light-Harvesting Protein Complexes; D055095:Optics and Photonics; D010084:Oxidation-Reduction; D010674:Pheophytins / Q000737:chemistry / Q000528:radiation effects; D010777:Photochemistry; D045322:Photosynthetic Reaction Center Complex Proteins / Q000737:chemistry* / Q000528:radiation effects*; D013053:Spectrophotometry
chemical_list: D001429:Bacteriochlorophylls; D045342:Light-Harvesting Protein Complexes; D010674:Pheophytins; D045322:Photosynthetic Reaction Center Complex Proteins; D004227:Dithionite; C006678:bacteriopheophytin; D001205:Ascorbic Acid