A facile approach for cupric ion detection in aqueous media using polyethyleneimine/PMMA core–shell fluorescent nanoparticles

A facile approach was developed to produce a dye-doped core-shell nanoparticle chemosensor for detecting Cu(2+) in aqueous media. The core-shell nanoparticle sensor was prepared by a one-step emulsifier-free polymerization, followed by the doping of the fluorescent dye Nile red (9-diethylamino- 5H-benzoalpha phenoxazine-5-one, NR) into the particles. For the nanoparticles, the hydrophilic polyethyleneimine (PEI) chain segments serve as the shell and the hydrophobic polymethyl methacrylate (PMMA) constitutes the core of the nanoparticles. The non-toxic and biocompatible PEI chain segments on the nanoparticle surface exhibit a high affinity for Cu(2+) ions in aqueous media, and the quenching of the NR fluorescence is observed upon binding of Cu(2+) ions. This makes the core-shell nanoparticle system a water-dispersible chemosensor for Cu(2+) ion detection. The quenching of fluorescence arises through intraparticle energy transfer (FRET) from the dye in the hydrophobic PMMA core to the Cu(2+)/PEI complexes on the nanoparticle surface. The energy transfer efficiency for PEI/PMMA particles with different diameters was determined, and it is found that the smaller nanoparticle sample exhibits higher quenching efficiency, and the limit for Cu(2+) detection is 1 microM for a nanoparticle sample with a diameter of approximately 30 nm. The response of the fluorescent nanoparticle towards different metal ions was investigated and the nanoparticle chemosensor displays high selectivity and antidisturbance for the Cu(2+) ion among the metal ions examined (Na(+), K(+), Mg(2+), Ca(2+), Zn(2+), Hg(2+), Mn(2+), Fe(2+), Ni(2+), Co(2+) and Pb(2+)). This emulsifier-free, biocompatible and sensitive fluorescent nanoparticle sensor may find applications in cupric ion detection in the biological and environmental areas.