Heme-peptide models for hemoproteins .2. N-acetylmicroperoxidase-8: Study of the pi-pi dimers formed at high ionic strength using a modified version of molecular exciton theory

AcMP8 is the Cys-14-acetylated water-soluble heme-octapeptide fragment obtained proteolytically from cytochrome c. Two successive dimerization equilibria are observed with increasing ionic strength in aqueous solution at neutral pH (part 1, preceding article). The electronic spectra of the two pi-pi dimers were extracted from the absorption envelopes at 2.01 and 4.02 M ionic strength and resolved by Gaussian analysis. The principal transitions were assigned using a tailored version of molecular exciton theory based on coupling of the main x- and y-polarized transition dipole moments of the interacting heme groups. The spectra of both pi-pi dimers indicate that the y-polarized exciton states are blue-shifted relative to the excited states of the monomer, while the x-polarized exciton states exhibit a red shift. These shifts were correctly predicted by a simple dipole-dipole coupling model. From an analysis of the resultant transition dipole moments to the exciton states with B-x(0,0) and B-y(0,0) character and the magnitudes of their red and blue exciton shifts, respectively, we have determined the dipole-dipole interaction geometries for both dimers. The principal difference between the interaction geometry in the first dimer and that in the second is a stronger interaction for the y-polarized transition dipoles and somewhat weakened interaction for the x-polarized transition dipoles. From an analysis of available crystallographic data for porphyrin and metalloporphyrin pi-pi dimers (Scheidt, W. R.; Lee, Y. J. Struct. Bonding 1987, 64, 1) and the results of our exciton model, we conclude that the origin of the coordinate system for the Soret transition dipole moments of AcMP8 is not metal-centered. Furthermore, since the true directions of the x- and y-axes of the low-symmetry heme chromophore in AcMP8 are unknown, we have not been able to determine the structures of the pi-pi dimers from a knowledge of their transition dipole-dipole interaction geometries. This study therefore highlights one of the shortfalls of molecular exciton theory.