Cleavage of phosphodiesters and of DNA by a bis(guanidinium)naphthol acting as a metal-free anion receptor.

Phosphoric acid diesters form anions at neutral pH. As a result of charge repulsion they are notoriously resistant to hydrolysis. Nucleophilic attack, however, can be promoted by different types of electrophilic catalysts that bind to the anions and reduce their negative charge density. Although in most cases phosphodiester-cleaving enzymes and synthetic catalysts rely on Lewis acidic metal ions, some exploit the guanidinium residues of arginine as metal-free electrophiles. Here we report that a combination of two guanidines and a hydroxy group yields highly reactive receptor molecules that can attack a broad range of phosphodiester substrates by nucleophilic displacement at phosphorus in a single-turnover mode. Some stable O-phosphates were isolated and characterized further by NMR spectroscopy. The bis(guanidinium)naphthols also cleave plasmid DNA, presumably by a transphosphorylation mechanism.

Efficient upconversion fluorescence in a blue-emitting spirobifluorene-anthracene copolymer doped with low concentrations of Pt(II)octaethylporphyrin.

Upconversion-induced fluorescence in platinum-octaethylporphyrin (PtOEP)-doped thin films of a spirobifluorene-anthracene copolymer has been investigated. Upon exciting in the range of the absorption band (2.31 eV, 537 nm) of the guest molecules, blue fluorescence (2.75 eV, 450 nm) from the spirobifluorene host was observed. The intensity of the upconverted emission was found to be one order of magnitude higher than from a PtOEP doped but anthracene-free spirobifluorene copolymer and than previously reported for metallated porphyrin-doped polyfluorene samples. It is argued that the efficient upconversion originates from the triplet energy transfer from the phosphorescent dopant to the sensitive unit of the host polymer, followed by triplet-triplet annihilation and finally blue emission from the spirobifluorene host polymer backbone.