Bioinspired Luminescent Europium-Based Probe Capable of Discrimination between Ag+ and Cu

Abstract

Due to their similar coordination properties, discrimination of Cu⁺ and Ag⁺ by water-soluble luminescent probes is challenging. We have synthesized LCC4^Eu, an 18 amino acid cyclic peptide bearing a europium complex, which is able to bind one Cu⁺ or Ag⁺ ion by the side chains of two methionines, a histidine and a 3-(1-naphthyl)-l-alanine. In this system, the naphthyl moiety establishes a cation-π interaction with these cations. It also acts as an antenna for the sensitization of Eu³⁺ luminescence. Interestingly, when excited at 280 nm, LCC4^Eu behaves as a turn-on probe for Ag⁺ (+150% Eu emission) and as a turn-off probe for Cu⁺ (-50% Eu³⁺ emission). Shifting the excitation wavelength to 305 nm makes the probe responsive to Ag⁺ (+380% Eu³⁺ emission) but not to Cu⁺ or other physiological cations. Thus, LCC4^Eu is uniquely capable of discriminating Ag⁺ from Cu⁺. A detailed spectroscopic characterization based on steady-state and time-resolved measurements clearly demonstrates that Eu³⁺ sensitization relies on electronic energy transfer from the naphthalene triplet state to the Eu³⁺ excited states and that the cation-π interaction lowers the energy of this triplet state by 700 and 2400 cm^-1 for Ag⁺ and Cu⁺, respectively. Spectroscopic data point to a modulation of the efficiency of the electronic energy transfer caused by the differential red shift of the naphthalene triplet, deciphering the differential luminescence response of LCC4^Eu toward Ag⁺ and Cu⁺.