Oligodeoxyfluorosides: Strong Sequence Dependence of Fluorescence Emission.

We describe the properties of a series of oligomeric polyfluorophores assembled on the DNA backbone. The eleven oligomers (oligodeoxyfluorosides, ODFs), 4 to 7 monomers in length, were composed of only two fluorescent monomers and a spacer in va ried sequences, and were designed to test how fluorescent nucleobases can interact electronically to yield complexity in fluorescence emission. The monomer fluorophores were deoxyribosides of pyrene and perylene, which emit light in violet and blue wavele ngths respectively. The experiments show that simple variation of sequence and spacing can dramatically change fluorescence, yielding emission maxima ranging from 380 to 557 nm and visible colors from violet to orange-red. Fluorescence lifetimes data, excitation spectra, and absorption data point to a number of multi-fluorophore electronic interactions, including pyrene-pyrene and perylene-perylene excimers, pyrene-perylene exciplexes, as well as monomer dye emissions, contributing to the final spectral outcomes. Thus, two simple fluorophores can be readily combined to give emissions over much of the visible spectrum, all requiring only a single excitation. The results demonstrate that fluorescent nucleobases in oligomeric form can act cooperatively as electronic units, and that fluorophore sequence in such oligomers is as important as fluorophore composition in determining fluorescence properties.