Phosphorescent sensor for phosphorylated peptides based on an iridium complex

Abstract

A bis[(4,6-difluorophenyl)pyridinato-N,C2']iridium(III) picolinate (FIrpic) derivative coupled with bis(Zn2+-dipicolylamine) (ZnDPA) was developed as a sensor (1) for phosphorylated peptides, which are related to many cellular mechanisms. As a control, a fluorescent sensor (2) based on anthracene coupled to ZnDPA was also prepared. When the total negative charge on the phosphorylated peptides was changed to -2, -4, and -6, the emission intensity of sensor 1 gradually increased by factors of up to 7, 11, and 16, respectively. In contrast, there was little change in the emission intensity of sensor 1 upon the addition of a neutral phosphorylated peptide, non-phosphorylated peptides, or various anions such as CO32-, NO3-, SO42-, phosphate, azide, and pyrophosphate. Furthermore, sensor 1 could be used to visually discriminate between phosphorylated peptides and adenosine triphosphate in aqueous solution under a UV-vis lamp, unlike fluorescent sensor 2. This enhanced luminance of phosphorescent sensor 1 upon binding to a phosphorylated peptide is attributed to a reduction in the repulsion between the Zn 2+ ions due to the phenoxy anion, its strong metal-to-ligand charge transfer character, and a reduction in self-quenching. © 2014 American Chemical Society.