We report the directed assembly of quantum dots (QDs) within wellordered photonic nanocomposites using a family of (polynorbornene-graf tpoly(styrene))-block-(polynorbornene-graf t-poly(ethylene oxide)) (PS-b-PEO) brush block copolymers (BBCPs). Cadmium selenide (CdSe) nanoparticles (NPs) modified with 11-mercaptoundecylhydroquinone are selectively incorporated within the PEO domains of the self-assembled BBCPs via strong hydrogen-bonding interactions between the ligands on QDs and PEO brushes of the BBCPs. Wellordered QD arrays were readily created within a periodic lamellar polymer matrix, or one-dimensional photonic crystal, with a widely tunable lattice spacing ranging from 46.2 to up to 145 nm. The loading concentration of the QDs can be up to 30 wt % (15 vol %) while maintaining a well-ordered lamellar morphology, providing an optical gain material platform for the systematic investigation of optical properties. Strong photoluminescence and third harmonic generation from the well-ordered QD arrays were observed via multiphoton excitation using femtosecond (fs) laser light at several optical wavelengths from 700 to 1550 nm.
We discovered a unique fluorescent enhancement of dye encapsulated polymeric nanoparticles, which strongly depended on the polymeric matrix. Interestingly, the polymer nanoparticles containing a NIR emissive dye exhibited remarkable enhancement of emission encapsulated by the polymer amphiphilic polymer containing polystyrene (PS) moiety, whereas the nanoparticles showed weak fluorescence when using other polymer encapsulation. The highest fluorescent quantum yield of nanoparticles can reach 27% by using PS-PEG encapsulation, where the strong NIR fluorescence can be observed. These ultra-bright fluorescence nanoparticles also possess a strong three-photon fluorescence and show a good candidate for in vivo vascular three-photon fluorescence imaging of mouse brain and ear under 1550 nm fs laser excitation. A fine three-dimensional (3D) reconstruction with an imaging depth of 635 and 180 µm was achieved, respectively. We further demonstrate that these nanoparticles can effectively target the sentinel lymph node (SLN) of mice.
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