Enhancement of Aggregation-Induced Emission in Dye-Encapsulating Polymeric Micelles for Bioimaging

Three amphiphilic block copolymers are employed to form polymeric micelles and function as nanocarriers to disperse hydrophobic aggregation‐induced emission (AIE) dyes, 1,1,2,3,4,5‐hexaphenylsilole (HPS) and/or bis(4‐(N‐(1‐naphthyl) phenylamino)‐phenyl)fumaronitrile (NPAFN), into aqueous solution for biological studies. Compared to their virtually non‐emissive properties in organic solutions, the fluorescence intensity of these AIE dyes has increased significantly due to the spatial confinement that restricts intramolecular rotation of these dyes and their better compatibility in the hydrophobic core of polymeric micelles. The effect of the chemical structure of micelle cores on the photophysical properties of AIE dyes are investigated, and the fluorescence resonance energy transfer (FRET) from the green‐emitting donor (HPS) to the red‐emitting acceptor (NPAFN) is explored by co‐encapsulating this FRET pair in the same micelle core. The highest fluorescence quantum yield (∼62%) could be achieved by encapsulating HPS aggregates in the micelles. Efficient energy transfer (>99%) and high amplification of emission (as high as 8 times) from the NPAFN acceptor could also be achieved by spatially confining the HPS/NPAFN FRET pair in the hydrophobic core of polymeric micelles. These micelles could be successfully internalized into the RAW 264.7 cells to demonstrate high‐quality fluorescent images and cell viability due to improved quantum yield and reduced cytotoxicity. Highly efficient fluorescence probes are achieved through the encapsulation of aggregation‐induced emission molecules, 1,1,2,3,4,5‐hexaphenylsilole (HPS) and/or bis(4‐(N‐(1‐naphthyl) phenylamino)‐phenyl)fumaronitrile (NPAFN) in the core of polymeric micelles. Bright fluorescence cell images are shown with tunable colors of green directly from HPS aggregates and red through efficient fluorescence resonance energy transfer (FRET) from HPS aggregates to NPAFN aggregates.