Model Systems For The Investigation Of The Opsin Shift In Bacteriorhodopsin

Donor-acceptor Substituted styrenes and phenylbutadienes with substituents varying in donor and acceptor strength and as reconstituted chromophore-protein complexes were investigated as model compounds for the protonated Schiff base chromophore in bacteriorhodopsin (bR) both experimentally and theoretically. Charge distribution, donor-acceptor strength, and the shift of the absorption energy are correlated. The effect of the external electrostatic field was tested with a compound carrying an additional nonconjugated charge. The concept of overpolarization by the external charge, that is, the reversal of the relative importance of the two main resonance structures in S-0 and S-1, has been emphasized and related to a simple qualitative 2 x 2 interaction model. The variable donor approach is a new way for a better understanding of the Opsin shift in Bacteriorhodopsin.