Cell-penetrating peptides noncovalently modified red phosphorescent nanoparticles for high-efficiency imaging.

The application of long-lived phosphorescence probes in time-resolved luminescence imaging is limited by their low quantum yield in aqueous solutions. However, sensitization of thermally activated delayed fluorescence (TADF) materials can compensate for this limitation while addressing the issue of insufficient proportion of their own long lifetime. In this study, we utilized the characteristics of phosphorescence and TADF materials simultaneously by doping the receptor iridium complex PMD-Ir into the donor TADF polymer PCzDP-20 through donor-receptor doping method, and successfully prepared highly efficient red phosphorescent nanoparticles. The quantum yield of the nanoparticles obtained by this method reaches up to 30%, and the luminescence lifetime can reach several thousand nanoseconds. Additionally, due to the low concentration doping of PMD-Ir, the risk of transition metal toxicity is greatly reduced. Furthermore, we used non-covalent modification with amphiphilic cell-penetrating peptides (CPPs) to increase the cell membrane permeability of the nanoparticles. The CPPs modified nanoparticles achieve in vivo confocal imaging of zebrafish and intracellular time-resolved imaging by its significantly improved bioimaging capabilities. The functional nanoparticles designing method fully utilizes the characteristics of PMD-Ir, PCzDP-20, and CPPs, solving the problems of low quantum yield and poor membrane permeability of Ir-complex nanoparticles. This will greatly promote the development of time-resolved luminescence imaging.

2,6-Azulene-based Homopolymers: Design, Synthesis, and Application in Proton Exchange Membrane Fuel Cells.

Azulene-based homopolymers are of great interest from the point view of chemistry and material science. Herein, by means of Friedel-Crafts acylation to introduce solubilizing chains on the 1-position of azulene, we designed and synthesized two examples of 2,6-azulene-based homopolymers RP(Az-AC16) and P(Az-AC16). The arrangement of 2,6-azulene units is irregular for RP(Az-AC16), while P(Az-AC16) has head-to-head/tail-to-tail arranged 2,6-azulene units. Proton-responsive studies demonstrate that RP(Az-AC16) and P(Az-AC16) show reversible proton responsiveness in both solution and thin film. To utilize the dynamically reversible proton-responsive property of these polymers in thin films, RP(Az-AC16) and P(Az-AC16) were incorporated into a Nafion matrix as proton exchange membranes, wherein the Nafion/P(Az-AC16) composite membrane exhibits significant increases in proton conductivity relative to the Nafion membrane at different temperatures of each relative humidity (RH), which further results in a 64% improvement in hydrogen fuel cell output power under 30% RH at 80 °C. Our studies have realized the first solution synthesis of 2,6-azulene-based homopolymers and the first application of azulene-based π-systems in hydrogen fuel cells.