Electronic spectra and electronic structures of some antimicrobials derived from proflavine

The shifts in the absorption and fluorescence spectra of 3-aminoacridine, proflavine, acridine orange, and acridine yellow were employed to show that the singly charged cations, the predominant species at biological pH, exist in the ground state in the amino form. In the lowest excited singlet state, however, the monocations of the diaminoacridines have the imino structure, a conclusion supported by the relative ground- and excited-state pKa values of the reactions of the monocation with H-+. The ground-state amino structure has its positive charge concentrated at the heterocyclic nitrogen atom, a fact that is of primary importance in determining the geometry of binding to DNA.