Selective Coordination of Cu(2+) and Subsequent Anion Detection Based on a Naphthalimide-Triazine-(DPA)(2) Chemosensor

A new fluorescent chemosensor for copper (II) and subsequent anion sensing was designed and fully characterized. The sensor consisted of a 1,8-naphthalimide core, bearing two terminal dipicolylamine (DPA) receptor units for binding metal cations, and an ethoxyethanol moiety for enhanced water solubility. The DPA units are connected to position 4 of the fluorophore via a triazine-ethylenediamine spacer. Fluorescence titration studies of the chemosensor revealed a high selectivity for Cu(2+) over other divalent ions, the emissions were strongly quenched upon binding, and a stability constant of 5.52 log units was obtained. Given the distance from DPA chelating units and the fluorophore, quenching from the Cu(2+) complexation suggests an electron transfer or an electronic energy transfer mechanism. Furthermore, the Cu(2+)-sensor complex proved to be capable of sensing anionic phosphate derivatives through the displacement of the Cu(2+) cation, which translated into a full recovery of the luminescence from the naphthalimide. Super-resolution fluorescence microscopy studies performed in HeLa cells showed there was a high intracellular uptake of the chemosensor. Incubation in Cu(2+) spiked media revealed a strong fluorescent signal from mitochondria and cell membranes, which is consistent with a high concentration of ATP at these intracellular sites.