Inner filter effect-based upconversion fluorescence sensing of sulfide ions

Upconversion nanocrystals (UCNCs) have emerged as a new type of fluorescent probe for sensing applications. Herein, we designed a 980 nm excited upconversion luminescence system, composed of core-shell-structured NaYF₄ : Yb,Er@NaYF₄ : Yb nanocrystals (csUCNCs) and the triethylenetetramine-Cu complex (complex-I), for quantitative detection of sulfide ions. Taking advantage of the specific recognition of complex-I toward S^2-, the as-formed compound (complex-II) exhibits excellent spectral overlap not only in the range of fluorescence emissions of UCNCs but also in the excitation wavelength for UCNCs; fluorescence quenching of UCNCs occurs where the complex-II acts as the energy acceptor. Due to the electrostatic repulsion between positively charged ligand-free csUCNCs and complex-I, the fluorescence quenching is based on the primary and secondary inner filter effect rather than the fluorescence resonance energy transfer process. The detection limit of S^2- for the upconversion-based system is calculated to be 2.7 μM, exhibiting higher detection sensitivity over the single complex-I compound measured by the spectrophotometric method. Moreover, no significant variation in upconversion luminescence is observed upon the addition of other interfering ions, showing the excellent selectivity of this nanoprobe toward S^2-.