TADF Dye-Loaded Nanoparticles for Fluorescence Live-Cell Imaging

Thermally activated delayed fluorescence (TADF) molecules offer nowadays a powerful tool in the development of novel organic light emitting diodes due to their capability of harvesting energy from non-emissive triplet states without using heavy-metal complexes. TADF emitters have very small energy difference between the singlet and triplet excited states, which makes thermally activated reverse intersystem crossing from the triplet states back to the singlet manifold viable. This mechanism generates a long-lived delayed fluorescence component which can be explored in the sensing of oxygen concentration, local temperature, or used in time-gated optical cell-imaging, to suppress interference from autofluorescence and scattering. Despite this strong potential, until recently the application of TADF outside lighting devices has been hindered due to the low biocompatibility, low aqueous solubility and poor performance in polar media shown by the vast majority of TADF emitters. To achieve TADF luminescence in biological media, careful selection or design of emitters is required. Unfortunately, most TADF molecules are not emissive in polar media, thus complexation with biomolecules or the formation of emissive aggregate states is required, in order to retain the delayed fluorescence that is characteristic of these compounds. Herein, we demonstrate a facile method with great generalization potential that maintains the photophysical properties of solvated dyes by combining luminescent molecules with polymeric nanoparticles. Using an established swelling procedure, two known TADF emitters are loaded onto polystyrene nanoparticles to prepare TADF emitting nanomaterials able to be used in live-cell imaging. The obtained particles were characterized by optical spectroscopy and exhibited the desired TADF emission in aqueous media, due to the polymeric matrix shielding the dye from solvent polarity effects. The prepared nanoparticles were incubated with live human cancer cells and showed very low cytotoxicity and good cellular uptake, thus making fluorescence microscopy imaging possible at low dye concentrations

Kinetic Criteria for Optimal Thermally Activated Delayed Fluorescence in Photoluminescence and in Electroluminescence

A complete set of criteria for the classification, design, and selection of optimal thermally activated delayed fluorescence (TADF) emitters, for both photoluminescence and electroluminescence applications, is presently unavailable. In this work, and as a contribution toward this aim, a detailed characterization of TADF photophysical kinetics is presented, contrasting TADF in photoluminescence and TADF in electroluminescence. Two different types of TADF are identified: One-way and two-way TADF. It is shown that, for a given efficiency, one-way TADF allows lower rates of reverse intersystem crossing, an aspect that may be significant with respect to stability and roll-off issues. Graphical and quantitative indicators of singlet–triplet interconversion and photophysical efficiency are obtained and applied to the photoluminescence of eosin, coronene, and fullerenes and to the electroluminescence of several TADF emitters specifically designed for organic light emitting diodes. Relations for the photoluminescence TADF onset temperature and for the electroluminescence internal quantum efficiency are also derived