A Near InfraRed Emissive Chemosensor for Zn(2+) and Phosphate Derivatives Based on a Di-(2-picolyl)amine-styrylflavylium Push-Pull Fluorophore

A new Near InfraRed (NIR) fluorescent chemosensor for metal ions and anions is herein presented. The fluorophore is based on a styrylflavylium dye, a synthetic analogue of the natural anthocyanin family, with a di-(2-picolyl)amine (DPA) moiety as the metal chelating unit. The substitution pattern of the styrylflavylium core (with tertiary amines on positions 7 and 4′) shifts the optical properties of the dye towards the NIR region of the electronic spectra, due to a strong push-pull character over the π-conjugated system. The NIR chemosensor is highly sensitive to the presence of Zn(2+), which induces a strong CHelation Enhanced Fluorescence (CHEF) effect upon binding to the DPA unit (2.7 fold increase). The strongest competing ion is Cu(2+), with a complete fluorescence quenching, while other metals induce lower responses on the optical properties of the chemosensor. Subsequent anion screening of the Zn(2+)-chemosensor coordination compound has demonstrated a distinct selectivity towards adenosine 5′-triphosphate (ATP) and adenosine 5′-diphosphate (ADP), with high association constants (K ~ 10(6) M(−1)) and a strong CHEF effect (2.4 and 2.9 fold fluorescence increase for ATP and ADP, respectively). Intracellular studies with the Zn(2+)-complexed sensor showed strong luminescence in the cellular membrane of Gram(–) bacteria (E. coli) and mitochondrial membrane of mammalian cells (A659), which highlights its possible application for intracellular labelling.