The
development of practical and sensitive tools for detecting
phosphate deficiency could facilitate engineering approaches to enhance
crop yield and quality in phosphate-stressed environments, reducing
the misuse of nonrenewable fertilizers and their consequent ecological
impact. Herein, a 975 nm-activated method based on ZrO2:Yb,Er@ZrO2 core@shell upconversion nanoparticles is presented
for rapid visualization and determination of the phosphate ions in
aqueous solutions and extracts. At optimized thickness, the nondoped
ZrO2 shell not only enhances the emission of the ZrO2:Yb,Er but also provides an active surface for the intense
interaction with the phosphate group, allowing a “label-free”
determination that avoids the use of additional phosphate-recognizing
elements like ligands or antibodies. According to the experimental
evidence, the optical output of the ZrO2:Yb,Er@ZrO2 nanoparticles specifically matches with the absorption spectrum
of the fast green alimentary dye (FG) electrostatically attached to
the nanoparticle surface, activating the Förster resonance
energy transfer (FRET) and thereby the upconversion luminescence quenching.
Upon addition of the phosphate ions and the covalent interaction with
the ZrO2:Yb,Er@ZrO2–FG nanocomplex, the
FG is gradually removed, displaying a fast and reproducible “turn-on”
luminescence which allows measurements in a few minutes. This rapid
response is due to the stronger coordination between the ZrO2 shell and the phosphate compared to the FG molecules (−31.97
and −5.99 eV, respectively). The detection method was then
effectively modulated in a 20–1000 nM linear response range
without interfering effects of commonly coexisting ions, achieving
a detection limit up to 15 times lower than that obtained with the
conventionally used colorimetric methods.