A Turn-On Luminescence Method for Phosphate Determination Based on Fast Green-Functionalized ZrO2:Yb,Er@ZrO2 Core@Shell Upconversion Nanoparticles

Anal Chem. 2019 Nov 19;91(22):14657-14665. doi: 10.1021/acs.analchem.9b03817. Epub 2019 Oct 29.

Abstract

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Erbium / chemistry
  • Erbium / radiation effects
  • Fluorescence Resonance Energy Transfer / methods
  • Infrared Rays
  • Limit of Detection
  • Luminescence
  • Luminescent Agents / chemistry*
  • Luminescent Agents / radiation effects
  • Luminescent Measurements / methods
  • Metal Nanoparticles / chemistry*
  • Metal Nanoparticles / radiation effects
  • Phosphates / analysis*
  • Proof of Concept Study
  • Rosaniline Dyes / chemistry*
  • Wastewater / analysis
  • Water Pollution, Chemical / analysis
  • Ytterbium / chemistry
  • Ytterbium / radiation effects
  • Zirconium / chemistry
  • Zirconium / radiation effects

Substances

  • Luminescent Agents
  • Phosphates
  • Rosaniline Dyes
  • Waste Water
  • Erbium
  • Fast Green
  • Zirconium
  • Ytterbium
  • zirconium oxide