Abstract
The primary charge separation in photosynthetic reaction centers (RC) is carried out by an array of (bacterio)chlorophylls arranged in close proximity. The recent x-ray structures of the RC complexes from Rhodopseudomonas viridis 1–3 and Rhodobacter sphaeroides 4,5 reveal two possible electron pathways for purple bacteria, only one of which is active.6 In order to determine the environmental factors most likely to affect the direction of electron flow in the nascent charge separation, we have calculated the effects of hydrogen bonding and chemical modification (enolization) by nearby residues upon the optical spectra, reduction potentials, unpaired spin density distributions and charge densities of bacterio-chlorophylls (BChl) and -pheophytins (BPh).
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References
J. Deisenhofer, O. Epp, K. Miki, R. Huber, and H. Michel. X-ray structure analysis of a membrane protein complex. Electron density map at 3A resolution and a model of the chromophores of the photosynthetic reaction center from Rhodopseudomonas viridis, J. Mol. Biol., 180:385 (1984).
J. Deisenhofer, O. Epp, K. Miki, R. Huber, and H. Michel. Structure of the protein subunits in the reaction centre of Rhodopseudomonas viridis at 3A resolution, Nature, 318:618 (1985).
H. Michel, O. Epp, and J. Deisenhofer. Pigment-protein interactions in the photosynthetic reaction centre from Rhodopseudomonas viridis, EMBO J., 5:2445 (1986).
C.-H. Chang, D. Tiede, J. Tang, U. Smith, J. Norris, and M. Schiffer. Structure of Rhodopseudomonas sphaeroides R-26 reaction center, FEBS Lett., 205:82 (1986).
J. P. Allen, G. Feher, T. O. Yeates, H. Komiya, and D. C. Rees. Structure of the reaction center from Rhodobacter sphaeroides R-26: the cofactors, Proc. Natl. Acad. Sci. USA, 84:5730 (1987).
M. E. Michel-Beyerle, ed., “Antennas and Reaction Centers of Photosynthetic Bacteria,” Springer-Verlag, Berlin (1985).
L. K. Hanson, J. Fajer, M. A. Thompson, and M. C. Zerner. Electrochromic effects of charge separation in bacterial photosynthesis: theoretical models, J. Am. Chem. Soc., 109:4728 (1987).
A. M. Schaffer, M. Gouterman, and E. R. Davidson. Porphyrins XXVIII. Extended Hiickel calculations on metal phthalocyanines and tetrazaporphins, Theor. Chem. Acta (Berl.), 30:9 (1973).
J. Ridley and M. Zerner. An intermediate neglect of differential overlap technique for spectroscopy: pyrrole and the azines, Theor. Chim. Acta (Berl.), 32:111 (1973).
A. D. Bacon and M. C. Zerner. An intermediate neglect of differential overlap theory for transition metal complexes: Fe, Co and Cu chlorides, Theor. Chim. Acta (Berl.), 53:21 (1979).
D. F. Bocian, N. J. Boldt, B. W. Chadwick, and H. A. Frank. Nearinfrared-excitation resonance Raman spectra of bacterial photosynthetic reaction centers. Implications for path-specific electron transfer, FEBS Lett., 214:92 (1987).
M. S. Davis, A. Forman, L. K. Hanson, J. P. Thornber, and J. Fajer. Anion and cation radicals of bacteriochlorophyll and bacterio-pheophytin b. Their role in the primary charge separation of Rhodopseudomonas viridis, J. Phys. Chem., 83:3325 (1979).
M. R. Wasielewski, private communication.
J. Fajer, D. C. Brune, M. S. Davis, A. Forman, and L. D. Spaulding. Primary charge separation in bacterial photosynthesis: oxidized chlorophylls and reduced pheophytin, Proc. Natl. Acad. Sci. USA, 72:4956 (1975).
J.-L. Martin, J. Breton, A. J. Hoff, A. Migus, and A. Antonetti. Femtosecond spectroscopy of electron transfer in the reaction center of the photosynthetic bacterium Rhodopseudomonas sphaeroides R-26: direct electron transfer from the dimeric bacteriochlorophyll primary donor to the bacteriopheophytin acceptor with a time constant of 2.8±0.2 psec, Proc. Natl. Acad. Sci. USA, 83:957 (1986).
J. Breton, J.-L. Martin, A. Migus, A. Antonetti, and A. Orszag. Femtosecond spectroscopy of excitation energy transfer and initial charge separation in the reaction center of the photosynthetic bacterium Rhodopseudomonas viridis, Proc. Natl. Acad. Sci., USA, 83:5121 (1986).
C. Kirmaier, D. Holten, and W. W. Parson. Picosecond photodichroism (photoselection) measurements on transient states in reaction centers from Rhodopseudomonas sphaeroides, Rhodospirilium rubrum and Rhodopseudomonas viridis, Biochim. Biophys. Acta, 725:190 (1983).
C. Kirmaier, D. Holten, L. J. Mancino, and R. E. Blankenship. Picosecond photodichroism studies on reaction centers from the green photosynthetic bacterium Chloroflexus aurantiacus, Biochim. Biophys. Acta, 765:138 (1984).
C. Kirmaier, D. Holten, and W. W. Parson. Picosecond photodichroism studies of the transient states in Rhodopseudomonas sphaeroides reaction centers at 5K. Effects of electron transfer on the six bacteriochlorin pigments, Biochim. Biophys. Acta, 810:49 (1985).
P. Maroti, C. Kirmaier, C. Wraight, D. Holten, and R. M. Pearlstein. Photochemistry and electron transfer in borohydride-treated photosynthetic reaction centers, Biochim. Biophys. Acta, 810:132 (1985).
C. Kirmaier, D. Holten, and W. W. Parson. The question of the intermediate state P+ BChl− in bacterial photosynthesis, FEBS Lett., 185:76 (1985).
M. R. Wasielewski and D. M. Tiede. Sub-picosecond measurements of primary electron transfer in Rhodopseudomonas viridis reaction centers using near-infrared radiation, FEBS Lett., 204:368 (1986).
V. A. Shuvalov and L. N. M. Duysens. Primary electron transfer reactions in modified reaction centers from Rhodopseudomonas sphaeroides, Proc. Natl. Acad. Sci. USA, 83:1690 (1986).
V. A. Shuvalov, J. Amesz, and L. N. M. Duysens. Picosecond charge separation upon selective excitation of the primary electron donor in reaction centers of Rhodopseudomonas viridis, Biochim. Biophys. Acta, 851:327 (1986).
A. Vermeglio and R. K. Clayton. Kinetics of electron transfer between the primary and the secondary electron acceptor in reaction centers from Rhodopseudomonas sphaeroides, Biochim. Biophys. Acta, 461:159 (1977).
L. K. Hanson, M. A. Thompson, and J. Fajer. Environmental effects on the properties of chlorophylls in vivo. Theoretical models, in: “Progress in Photosynthesis Research,” Vol. I, J. Biggins, ed., Martinus Nijhoff, Dordrecht, p. 3331, (1987).
J. Fajer, K. M. Barkigia, K. M. Smith, and D. A. Goff. Consequences of electron transfer in chlorophylls, chlorins, and porphyrins. Structural and theoretical considerations, in: “Porphyrins: Excited States and Dynamics,” M. Gouterman, P. M. Rentzepis, and K. D. Straub, eds., ACS Symposium Series No. 321, p. 51 (1986).
J. Fajer, K. M. Barkigia, E. Fujita, D. A. Goff, L. K. Hanson, J. D. Head, T. Horning, K. M. Smith, and M. C. Zerner. Experimental, structural and theoretical models of bacteriochlorophylls a, d and g, in: “Antennas and Reaction Centers of Photosynthetic bacteria,” M. E. Michel-Beyerle, ed., Springer-Verlag, Berlin, p. 234 (1985).
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Hanson, L.K., Thompson, M.A., Zerner, M.C., Fajer, J. (1988). Theoretical Models of Electrochromic and Environmental Effects on Bacterio-Chlorophylls and -Pheophytins in Reaction Centers. In: Breton, J., Verméglio, A. (eds) The Photosynthetic Bacterial Reaction Center. NATO ASI Series, vol 149. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-0815-5_36
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DOI: https://doi.org/10.1007/978-1-4899-0815-5_36
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