Micellar Nanoparticles of Coil-Rod-Coil Triblock Copolymers for Highly Sensitive and Ratiometric Fluorescent Detection of Fluoride Ions

We report on the fabrication of a novel type of ratiometric fluorescent polymeric probes for fluoride ions (F–) based on self-assembled micellar nanoparticles of P(MMA-co-NBDAE)-b-PF-b-P(MMA-co-NBDAE) coil–rod–coil triblock copolymer, where MMA, NBDAE, and PF are methyl methacrylate, 4-(2-acryloyloxyethylamino)-7-nitro-2,1,3-benzoxadiazole, and polyfluorene, respectively. Blue-emitting conjugated PF block and green-emitting NBDAE moieties with F– turn-off characteristics within the PMMA block serve as fluorescence resonance energy transfer (FRET) donors and switchable acceptors, respectively. For coil–rod–coil triblock copolymer in a good solvent such as THF, the blue emission of PF block dominates due to unimolecularly dissolved state associated with ineffective FRET process. The addition of F– ions only leads to ∼2.92-fold decrease of fluorescence intensity ratio, I515/I417, of characteristic NBDAE and PF emission bands. In acetone, the triblock copolymer spontaneously self-assembles into micelles posse...

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