Organic phosphorescent nanoscintillator for low-dose X-ray-induced photodynamic therapy.

X-ray-induced photodynamic therapy utilizes penetrating X-rays to activate reactive oxygen species in deep tissues for cancer treatment, which combines the advantages of photodynamic therapy and radiotherapy. Conventional therapy usually requires heavy-metal-containing inorganic scintillators and organic photosensitizers to generate singlet oxygen. Here, we report a more convenient strategy for X-ray-induced photodynamic therapy based on a class of organic phosphorescence nanoscintillators, that act in a dual capacity as scintillators and photosensitizers. The resulting low dose of 0.4 Gy and negligible adverse effects demonstrate the great potential for the treatment of deep tumours. These findings provide an optional route that leverages the optical properties of purely organic scintillators for deep-tissue photodynamic therapy. Furthermore, these organic nanoscintillators offer an opportunity to expand applications in the fields of biomaterials and nanobiotechnology.

Organic phosphorescent scintillation from copolymers by X-ray irradiation.

Scintillators that exhibit X-ray-excited luminescence have great potential in radiation detection, X-ray imaging, radiotherapy, and non-destructive testing. However, most reported scintillators are limited to inorganic or organic crystal materials, which have some obstacles in repeatability and processability. Here we present a facile strategy to achieve the X-ray-excited organic phosphorescent scintillation from amorphous copolymers through the copolymerization of the bromine-substituted chromophores and acrylic acid. These polymeric scintillators exhibit efficient X-ray responsibility and decent phosphorescent quantum yield up to 51.4% under ambient conditions. The universality of the design principle was further confirmed by a series of copolymers with multi-color radioluminescence ranging from green to orange-red. Moreover, we demonstrated their potential application in X-ray radiography. This finding not only outlines a feasible principle to develop X-ray responsive phosphorescent polymers, but also expands the potential applications of polymer materials with phosphorescence features.

Organic Room Temperature Phosphorescence Materials for Biomedical Applications.

Organic room temperature phosphorescence (RTP) materials have drawn increasing attention due to their unique features, especially the long emission lifetime for applications in biomedicine. In this review, we provide an overview of the recent developments of organic RTP materials applied in the biomedicine field. First, we introduce the basic mechanism of phosphorescence and subsequently we present various strategies of modulating the lifetime and efficiency of room temperature organic phosphorescence. Next, we summarize the progress of organic RTP materials in biological applications, including bioimaging, anti-cancer and antibacterial therapies. Finally, we provide an outlook with regard to the challenges and future perspectives in the field.

Exploiting radical-pair intersystem crossing for maximizing singlet oxygen quantum yields in pure organic fluorescent photosensitizers.

Fluorescent photosensitizers (PSs) often encounter low singlet oxygen (1O2) quantum yields and fluorescence quenching in the aggregated state, mainly involving the intersystem crossing process. Herein, we successfully realize maximizing 1O2 quantum yields of fluorescent PSs through promoting radical-pair intersystem crossing (RP-ISC), which serves as a molecular symmetry-controlling strategy of donor-acceptor (D-A) motifs. The symmetric quadrupolar A-D-A molecule PTP exhibits an excellent 1O2 quantum yield of 97.0% with bright near-infrared fluorescence in the aggregated state. Theoretical and ultrafast spectroscopic studies suggested that the RP-ISC mechanism dominated the formation of the triplet for PTP, where effective charge separation and an ultralow singlet-triplet energy gap (0.01 eV) enhanced the ISC process to maximize 1O2 generation. Furthermore, in vitro and in vivo experiments demonstrated the dual function of PTP as a fluorescent imaging agent and an anti-cancer therapeutic, with promising potential applications in both diagnosis and theranostics.

A Highly Efficient Red Metal-free Organic Phosphor for Time-Resolved Luminescence Imaging and Photodynamic Therapy.

Developing highly efficient red metal-free organic phosphors for biological applications is a formidable challenge. Here, we report a novel molecular design principle to obtain red metal-free organic phosphors with long emission lifetime (504.6 µs) and high phosphorescence efficiency (14.6%) from the isolated molecules in the crystal. Furthermore, the well-dispersed phosphorescent nanodots (PNDs) with the particle size around 5 nm are prepared through polymer-encapsulation in an aqueous solution, which show good biocompatibility and low cytotoxicity. The metal-free PNDs are successfully applied to time-resolved luminescence imaging to eliminate background fluorescence interference both in vitro and vivo as well as effective photodynamic anticancer therapy for the first time. This work will not only pave a pathway to develop highly efficient metal-free RTP materials but also expand the scope of their applications to biomedical fields.

A ferrocene∩europium assembly showing phototriggered anticancer activity and fluorescent modality imaging.

Two macrocyclic ferrocenophanes containing a coumarin fluorophore, Se2N[7]ferrocenophane (fc1), and Se4N2[7,7]ferrocenophane (fc2), construct an assembly of fc1-H+ClO4[Eu(C10H21COO)2(H2O)2(ClO4)] (fc1∩Eu) and fc2-2H+{ClO4[Eu(C10H21COO)2(H2O)2(ClO4)]}2 (fc2∩Eu) via a N-HO hydrogen bond and a coordinate bond between EuIII and ClO4-. In fc1∩Eu, UV light irradiation triggers non-covalent bond cleavage to release a ferrocenium and EuII complex, accompanying chromism and luminescence signals. Investigations through the steady-state UV-vis absorption, fluorescence, time-resolved fluorescence, femtosecond transient absorption spectra and electrochemical characterization elucidate a stepwise mechanism: firstly, an effective electron transfer occurs from a ferrocene unit to the singlet state of a coumarin unit; the following proton-coupled electron transfer (PCET) reduces EuIII and results in a non-covalent interaction cleavage. Further in vitro exploration of fc1∩Eu in HepG2 cells demonstrated phototriggered integrated cell cytotoxicity and fluorescent modality imaging.