A fluorescence chemosensor based on peptidase for detecting nickel(II) with high selectivity and high sensitivity

We report herein a new class of metal ion chemosensors and give the first example of a metal-dependent peptidase chemosensor for metal ions. The chemosensor contains the basic specific Ni(II)-dependent peptide bond hydrolysis sequence (Gly-Ala-Ser-Arg-His-Trp-Lys-Phe-Lys). The substrate was labeled with a fluorophore at the N-terminal and a quencher at the C-terminal Lys side chain. Initially, the MOCAc ((7-methoxycoumarin-4-yl)acetyl-) emission was quenched by the nearby quencher. In the presence of Ni(II), the substrate was irreversibly cleaved at the cleavage site, leading to a 20-fold increase in fluorescence intensity. The chemosensor combines the high selectivity of a peptidase (at least greater than tenfold for Ni(II) over other metal ions) with the high sensitivity of fluorescence detection limit of 50 nM and can be applied for the quantitative detection of Ni(II) over a concentration range of three orders of magnitude. Given this degree of selectivity and sensitivity, our molecular engineering design may prove useful in the future development of other peptidase-based probes for different metal ions in toxicological and environmental monitoring.