Nanosized diblock copolymer micelles as a scaffold for constructing a ratiometric fluorescent sensor for metal ion detection in aqueous media.

A facile strategy was employed to create a fluorescence resonance energy transfer (FRET) based ratiometric sensing system for ferric ions in all-aqueous media by using nanosized poly(ethylene oxide)-b-polystyrene micelles as the scaffold. A hydrophobic fluorescent dye nitrobenzoxadiazolyl derivative (NBD), which served as the energy transfer donor, was incorporated into the micelle core during the micelle formation; a spirolactam rhodamine derivative (SRhB-OH) was chosen as a sensitive and selective sensor for Fe(III) ions and was then 'adsorbed' into the micelle core/corona interface. A highly efficient ring-opening reaction of SRhB-OH induced by Fe(III) generates the long-wavelength rhodamine B fluorophore which can act as the energy acceptor; thus, the micelle nanoparticles can serve as a FRET-based ratiometric detection system for ferric ions. The effects of PS block length on the ion sensing performance of the micelles were investigated, and it has been found that the micelles formed by the copolymer with moderate block length (PEO(113)-b-PS(115)) were preferable as the scaffold for the FRET system and exhibited a sensitive and selective sensing capacity for Fe(III) with a detection limit of 1 microM. This nanoparticle-based sensing strategy may be utilized to construct other ratiometric chemosensors by replacing the current dyes with other suitable ones.