Sensing Metal Ions with DNA Building Blocks: Fluorescent Pyridobenzimidazole Nucleosides

Abstract

We describe novel fluorescent N-deoxyribosides (1 and 2) having 2-pyrido-2-benzimidazole and 2-quino-2-benzimidazole as aglycones. The compounds were prepared from the previously unknown heterocyclic precursors and Hoffer's chlorosugar, yielding alpha anomers as the chief products. X-ray crystal structures confirmed the geometry and showed that the pyridine and benzimidazole ring systems deviated from coplanarity in the solid state by 154° and 140°, respectively. In methanol compounds 1 and 2 had absorption maxima at 360 and 370 nm, respectively, and emission maxima at 494 and 539 nm. Experiments revealed varied fluorescence responses of the nucleosides to a panel of 17 monovalent, divalent, and trivalent metal ions in methanol. One or both of the nucleosides showed significant changes with 10 of the metal ions. The most pronounced spectral changes for ligand−nucleoside 1 included red shifts in fluorescence (Au⁺, Au³⁺), strong quenching (Cu²⁺, Ni²⁺, Pt²⁺), and substantial enhancements in emission intensity coupled with red shifts (Ag⁺, Cd²⁺, Zn²⁺). The greatest spectral changes for ligand−nucleoside 2 included a red shift in fluorescence (Ag⁺), a blue shift (Cd²⁺), strong quenching (Pd²⁺, Pt²⁺), and substantial enhancements in emission intensity coupled with a blue shift (Zn²⁺). The compounds could be readily incorporated into oligodeoxynucleotides, where an initial study revealed that they retained sensitivity to metal ions in aqueous solution and demonstrated possible cooperative sensing behavior with several ions. The two free nucleosides alone can act as differential sensors for multiple metal ions, and they are potentially useful monomers for contributing metal ion sensing capability to DNAs.