A novel
ratiometric fluorescent method for the detection of copper
ions (Cu2+) based on the stimulus-responsive dual-ligand
lanthanide luminol-Tb-GMP coordination polymer nanoparticle (CPNP)
fluorescent probe is reported in this study. The luminol-Tb-GMP CPNPs
are composed of Tb3+ as the center metal ions and ligand
of GMP together with the cofactor luminol ligands as the bridging
ligands. In the presence of Cu2+, the fluorescence of GMP-Tb
as the response moiety is dynamically quenched, while the fluorescence
of luminol used as the reference remains constant. Hence, ratiometric
fluorescent monitoring of Cu2+ can be achieved by measuring
the ratio of the fluorescence at the 430 nm (F430) wavelength
of luminol to the 547 nm (F547) wavelength of Tb3+ in the fluorescent spectra of the luminol-Tb-GMP CPNPs suspension.
In this sensing approach, when Cu2+ coordinates with a
luminol/GMP unit, the fluorescence of the Tb3+ units located
in the vicinity Cu2+ will also be quenched. Thus, the sensing
sensitivity is highly improved due to the large number of luminol/GMP
units in CPNPs. The obtained Cu2+ detection limit is as
low as 4.2 nM (S/N = 3), which is approximately 3 orders of magnitude
lower than that for the single ligand GMP-Tb CPNPs (3.5 μM)
without luminol doping. The linear range is from 0.01 to 80 μM.
Because luminol is directly linked to the CPNP molecule, which serves
as a strong chelating reagent for Cu2+, the common disturbances
of Hg2+ and Ag+ are almost completely eliminated,
highly improving the selectivity for practical application with little
interference. The present method has been successfully applied in
the detection of Cu2+ in river water, ascites, and urine
samples, indicating that luminol-Tb-GMP CPNPs can be used to detect
Cu2+ in environmental water and complexed biological samples.