Near-Infrared-Emitting Boron-Difluoride-Curcuminoid-Based Polymers Exhibiting Thermally Activated Delayed Fluorescence as Biological Imaging Probes.
Nathan R PaisleySarah V HalldorsonMichael V TranRupsa GuptaSaeid KamalW Russ AlgarZachary M HudsonPublished in: Angewandte Chemie (International ed. in English) (2021)
Near-infrared-emitting polymers were prepared using four boron-difluoride-curcuminoid-based monomers using ring-opening metathesis polymerization (ROMP). Well-defined polymers with molecular weights of ≈20 kDa and dispersities <1.07 were produced and exhibited near-infrared (NIR) emission in solution and in the solid state with photoluminescence quantum yields (ΦPL ) as high as 0.72 and 0.18, respectively. Time-resolved emission spectroscopy revealed thermally activated delayed fluorescence (TADF) in polymers containing highly planar dopants, whereas room-temperature phosphorescence dominated with twisted species. Density functional theory demonstrated that rotation about the donor-acceptor linker can give rise to TADF, even where none would be expected based on calculations using ground-state geometries. Incorporation of TADF-active materials into water-soluble polymer dots (Pdots) gave NIR-emissive nanoparticles, and conjugation of these Pdots with antibodies enabled immunofluorescent labeling of SK-BR3 human breast-cancer cells.
Keyphrases
- solid state
- energy transfer
- room temperature
- density functional theory
- light emitting
- fluorescent probe
- molecular dynamics
- single molecule
- quantum dots
- living cells
- water soluble
- fluorescence imaging
- breast cancer cells
- high resolution
- photodynamic therapy
- ionic liquid
- endothelial cells
- molecular dynamics simulations
- monte carlo
- heat shock protein
- pluripotent stem cells