Aggregation-Induced Emission from Fluorophore–Quencher Dyads with Long-Lived Luminescence

Aggregation-induced emission (AIE) is an important photophysical phenomenon in molecular materials and has found broad applications in optoelectronics, bioimaging, and chemosensing. Currently, the majority of reported AIE-active molecules are based on either propeller-shaped rotamers or donor–acceptor molecules with strong intramolecular charge-transfer states. Here, we report a new design motif, where a fluorophore is covalently tethered to a quencher, to expand the scope of AIE-active materials. The fluorophore–quencher dyad (FQD) is nonemissive in solutions due to photoinduced electron-transfer quenching but becomes luminescent in the solid state. The intrinsic emission lifetimes are found to be within the microseconds domain at both room and low temperatures. We performed single-crystal X-ray diffraction measurement for each of the FQDs as well as theoretical calculations to account for the possible origin of the long-lived AIE. These FQDs represent a new class of AIE-active molecules with potential applications in organic optoelectronics

Oxygen Sensing Difluoroboron β‑Diketonate Polylactide Materials with Tunable Dynamic Ranges for Wound Imaging

Difluoroboron β-diketonate poly­(lactic acid) materials exhibit both fluorescence (F) and oxygen sensitive room-temperature phosphorescence (RTP). Introduction of halide heavy atoms (Br and I) is an effective strategy to control the oxygen sensitivity in these materials. A series of naphthyl-phenyl (nbm) dye derivatives with hydrogen, bromide, and iodide substituents were prepared for comparison. As nanoparticles, the hydrogen derivative was hypersensitive to oxygen (0–0.3%), while the bromide analogue was suited for hypoxia detection (0–3% O₂). The iodo derivative, BF₂nbm­(I)­PLA, showed excellent F to RTP peak separation and a 0–100% oxygen sensitivity range, unprecedented for metal-free RTP emitting materials. Due to the dual emission and exceptionally long RTP lifetimes of these O₂ sensing materials, a portable, cost-effective camera was used to quantify oxygen levels via lifetime and red/green/blue (RGB) ratiometry. The hypersensitive H dye was well matched to lifetime detection; simultaneous lifetime and ratiometric imaging was possible for the bromide analogue, whereas the iodide material, with intense RTP emission and a shorter lifetime, was suited for RGB ratiometry. To demonstrate the prospects of this camera/material design combination for bioimaging, iodide boron dye-PLA nanoparticles were applied to a murine wound model to detect oxygen levels. Surprisingly, wound oxygen imaging was achieved without covering (i.e., without isolating from ambient conditions, air). Additionally, wound healing was monitored via wound size reduction and associated oxygen recovery, from hypoxic to normoxic. These single-component materials provide a simple tunable platform for biological oxygen sensing that can be deployed to spatially resolve oxygen in a variety of environments

Oxygen Sensing Difluoroboron β‑Diketonate Polylactide Materials with Tunable Dynamic Ranges for Wound Imaging

Difluoroboron β-diketonate poly­(lactic acid) materials exhibit both fluorescence (F) and oxygen sensitive room-temperature phosphorescence (RTP). Introduction of halide heavy atoms (Br and I) is an effective strategy to control the oxygen sensitivity in these materials. A series of naphthyl-phenyl (nbm) dye derivatives with hydrogen, bromide, and iodide substituents were prepared for comparison. As nanoparticles, the hydrogen derivative was hypersensitive to oxygen (0–0.3%), while the bromide analogue was suited for hypoxia detection (0–3% O₂). The iodo derivative, BF₂nbm­(I)­PLA, showed excellent F to RTP peak separation and a 0–100% oxygen sensitivity range, unprecedented for metal-free RTP emitting materials. Due to the dual emission and exceptionally long RTP lifetimes of these O₂ sensing materials, a portable, cost-effective camera was used to quantify oxygen levels via lifetime and red/green/blue (RGB) ratiometry. The hypersensitive H dye was well matched to lifetime detection; simultaneous lifetime and ratiometric imaging was possible for the bromide analogue, whereas the iodide material, with intense RTP emission and a shorter lifetime, was suited for RGB ratiometry. To demonstrate the prospects of this camera/material design combination for bioimaging, iodide boron dye-PLA nanoparticles were applied to a murine wound model to detect oxygen levels. Surprisingly, wound oxygen imaging was achieved without covering (i.e., without isolating from ambient conditions, air). Additionally, wound healing was monitored via wound size reduction and associated oxygen recovery, from hypoxic to normoxic. These single-component materials provide a simple tunable platform for biological oxygen sensing that can be deployed to spatially resolve oxygen in a variety of environments

Oxygen Sensing Difluoroboron β‑Diketonate Polylactide Materials with Tunable Dynamic Ranges for Wound Imaging

Difluoroboron β-diketonate poly­(lactic acid) materials exhibit both fluorescence (F) and oxygen sensitive room-temperature phosphorescence (RTP). Introduction of halide heavy atoms (Br and I) is an effective strategy to control the oxygen sensitivity in these materials. A series of naphthyl-phenyl (nbm) dye derivatives with hydrogen, bromide, and iodide substituents were prepared for comparison. As nanoparticles, the hydrogen derivative was hypersensitive to oxygen (0–0.3%), while the bromide analogue was suited for hypoxia detection (0–3% O₂). The iodo derivative, BF₂nbm­(I)­PLA, showed excellent F to RTP peak separation and a 0–100% oxygen sensitivity range, unprecedented for metal-free RTP emitting materials. Due to the dual emission and exceptionally long RTP lifetimes of these O₂ sensing materials, a portable, cost-effective camera was used to quantify oxygen levels via lifetime and red/green/blue (RGB) ratiometry. The hypersensitive H dye was well matched to lifetime detection; simultaneous lifetime and ratiometric imaging was possible for the bromide analogue, whereas the iodide material, with intense RTP emission and a shorter lifetime, was suited for RGB ratiometry. To demonstrate the prospects of this camera/material design combination for bioimaging, iodide boron dye-PLA nanoparticles were applied to a murine wound model to detect oxygen levels. Surprisingly, wound oxygen imaging was achieved without covering (i.e., without isolating from ambient conditions, air). Additionally, wound healing was monitored via wound size reduction and associated oxygen recovery, from hypoxic to normoxic. These single-component materials provide a simple tunable platform for biological oxygen sensing that can be deployed to spatially resolve oxygen in a variety of environments